Article

Journal of Elastomers & Plastics

2020, Vol. 52(1) 3–28
Incorporation of ª The Author(s) 2019
Article reuse guidelines:

a recycled rubber sagepub.com/journals-permissions

DOI: 10.1177/0095244318819213

compound from the shoe journals.sagepub.com/home/jep

industry in polystyrene:
Effect of SBS compatibilizer
content
Carlos Bruno Barreto Luna , Edcleide Maria Araújo,
Danilo Diniz Siqueira, Dayanne Diniz de Souza Morais,
Edson Antônio dos Santos Filho and Marcus Vinı́cius Lia Fook

Abstract
This research aimed to evaluate the influence of styrene–butadiene–styrene (SBS)
compatibilizer in the polystyrene blends properties with a recycled styrene–butadiene
rubber compound. The SBS content was 5, 7.5, and 10%. Commercial high-impact
polystyrene (HIPS) was used for comparison. The results indicated that the viscosity
of the blends was higher than that of HIPS. The blends compatibilized with 5 and 7.5%
had the same level of impact strength as HIPS, while the one with 10% obtained a gain of
80% in relation to HIPS. The flexural strength, hardness, heat deflection temperature,
and Vicat softening temperature properties were similar to those of HIPS, which was
attributed to the presence of inorganic fillers, minimizing losses in these properties. By
atomic force microscopy, two distinct phases were observed, and in the morphology
analyzed through scanning electron microscopy, a typical characteristic of immiscible
blends was observed.

Keywords
Polystyrene, rubber recycled, shoe industry, polymer blends, compatibilizer

Department of Materials Engineering, Federal University of Campina Grande, Av. Aprı́gio Veloso, Paraı́ba,
Brazil

Corresponding author:
Carlos Bruno Barreto Luna, Department of Materials Engineering, Federal University of Campina Grande, Av.
Aprı́gio Veloso, 882 – Bodocongó, ZIP CODE 58429-140 Campina Grande, Paraı́ba, Brazil.
Email: brunobarretodemaufcg@hotmail.com
4 Journal of Elastomers & Plastics 52(1)

Introduction
The worldwide advance in the consumption of industrialized products has caused an
increase in the generation of solid waste that causes serious environmental impacts, a
challenge for the management and final destination of garbage in large cities.1 The
production of rubber from the footwear and tire industries grows annually, resulting in
a large amount of waste discarded or incinerated, implying an aggression to the
environment.2,3 Reuse has been encouraged to overcome the environmental impacts
caused by this kind of waste and, consequently, contributing to a sustainable envi-
ronmental cycle.4–6
The reuse of postconsumer and postindustrial rubber waste is a major challenge,
particularly in the tire and footwear industries, since they are mostly vulcanized. One of
the main obstacles in the recycling of vulcanized rubbers is the fact that these materials
have cross-links in their structure, preventing their melt and reprocessing.7–9 One of the
technologies used for the rubber waste reuse is its mixture with thermoplastics, such as
the development of polymer blends. In this case, the rubber waste ground into particle
form is mixed with a polymer matrix during processing, acting as flexible fillers. In
general, rubber residues are added to thermoplastic polymers with brittle mechanical
behavior to toughening them.10–12 In this sense, research has been carried out to analyze
the effects of adding footwear or ground tire residues in polystyrene (PS) matrix com-
positions, according to the literature13–16 as a way to generate materials that have good
properties, are economically advantageous, and have increased impact strength.
Vulcanized rubber waste from tires and footwear is usually made of a complex
mixture containing fillers, processing additives, curing agents, pigments, and stabilizers,
and when improperly discarded into the environment, some of these ingredients that
have low molar mass may contaminate the soil and the groundwater over time.17–21
Furthermore, nowadays, the recycling of vulcanized rubbers is even more difficult as the
industries improve rubber compositions with new additives in the blends aiming to
increase their performance and lifetime. Also, the actual composition is unknown
because it is an industrial secret. Therefore, there is clear justification for research that
encourages the possibility of reusing rubber residues from the industries, making it
possible to obtain materials with good elastic properties and adding value to a material
that would be otherwise discarded.
There are several studies in the literature22–31 on the development of thermoplastic
blends with residues of rubber tires and footwear, being reinforced mainly with carbon
black filler, resulting in dark-colored materials. However, studies using white rubber
vulcanized styrene–butadiene (SBR) in the development of blends with PS as polymer
matrixes are practically nonexistent. Therefore, it is convenient to study this SBR waste
and, consequently, to analyze the real technological potential of this recycled compound
as an elastomeric filler.
The aim of this study is to evaluate the influence of the styrene–butadiene–styrene
(SBS) compatibilizer content on the development of PS blends with a white recycled
rubber compound and to compare their properties with those of commercial high-impact
polystyrene (HIPS).
Luna et al. 5

Table 1. Compositions of ternary and binary blends and HIPS.

Materials PS (% wt.) SBRr (%wt.) SBS (%wt.) HIPS (%wt.)

HIPS — — — 100
PS/SBRra 50 50 — —
PS/SBRr/SBSa 47.5 47.5 5 —
PS/SBRr/SBSa 46.25 46.25 7.5 —
PS/SBRr/SBSa 45 45 10 —

HIPS: high-impact polystyrene; PS: polystyrene; SBRr: recycled styrene–butadiene rubber; SBS: styrene–
butadiene–styrene.
a
All components were mixed simultaneously in a single extrusion step.

Materials and methods

Materials
The blends were prepared from PS crystal, commercialized with the code U288® and with a
melt flow index (MFI) ¼ 3 g/10 min (200 C/5 kg), supplied as pellets and manufactured by
Unigel S.A. (Brazil). A recycled compound of vulcanized styrene–butadiene rubber (called
SBRr) in the form of white powder from the shoe industry of São Paulo Alpargatas S.A.,
based in the city of Campina Grande (in the state of Paraı́ba – PB), was used as the filler or
dispersed phase. The compatibilizing agent used was the SBS linear triblock copolymer in
the form of pellets, commercialized with the code D1101B®, containing 31% styrene and a
MFI lower than 1 g/10 min (200 C/5 kg), supplied by Activas S.A. (Brazil).
For the purposes of comparison with blends, the study used HIPS, commercialized
under the code Styron 478®, with an MFI ¼ 6 g/10 min (200 C/5 kg), provided in pellets,
and manufactured by Dow Plastics (São Paulo, Brazil).

Blend preparation
Before the preparation of the blends, the industry-recycled rubber compound was sieved
in 18-mesh sieve (1 mm) and the sieved powder was used. Table 1 shows the mass
proportions (%) of the compositions that were used in the development of ternary and
binary blends and HIPS.
The binary and ternary blends were dry-mixed and subsequently processed in a modular
co-rotational twin screw extruder, model Zweiwelliger SchneckenKneter (ZSK) (D ¼ 18
mm and L/D ¼ 40) from Coperion Werner & Pfleiderer (Stuttgart-Feuerbach, Germany),
with a temperature of 190 C in zones 1 and 2, and 200 C in the other zones, screw rotation
speed of 250 r min1, and controlled feed rate of 4 kg h1 with screw profile configured
with distributive and dispersive mix elements (Figure 1). After the blends were processed
by extrusion, the material was granulated and dried in a vacuum heating oven for 24 h at a
temperature of 60 C and, then, in a vacuum oven at the same temperature for 24 h. HIPS
was processed under the same conditions of the blends.
HIPS and extruded blends were molded by means of injection in an Arburg All-
rounder 207C Golden Edition injector (ARBURG Technology Center, Kaiserstr,
6 Journal of Elastomers & Plastics 52(1)

Figure 1. Extruder thread profile used with distribution and dispersion mixing elements.

Radevormwald, Germany) to produce specimens. Molding temperature was at 200 C in

all zones, 20 s of injection time, and mold temperature at 20 C.

Characterization of the recycled rubber

Granulometric distribution. Particle size distribution of the recycled SBRr compound was
carried out according to ASTM D5644 from a 300 g sample of milled material, which
was sieved and stirred for 20 min with a set of overlapping sieves and openings of 18, 20,
25, 35, 40, 60, 80, 120, and 200 mesh.

Morphological analysis with energy-dispersive spectrum. Morphology of SBRr was deter-

mined by means of scanning electron microscopy (SEM) in a VEGAN 3 TESCAN
equipment, with a voltage of 30 kV and under high vacuum. The analysis of the fillers in
the SBRr was determined by means of energy-dispersive spectrum (EDS) following SEM.

Fourier transform infrared spectroscopy. Fourier transform infrared (FTIR) spectroscopy

was performed on a PerkinElmer Spectrum 400 FTIR/ATR spectrometer, with scans
ranging from 4000 cm1 to 650 cm1.

Thermogravimetry. Thermogravimetry (TG) of the recycled rubber, HIPS, and blends was
obtained by employing a TA Instruments (New Castle, DE, USA) SDT-Q600 Simul-
taneous TGA/Differential Scanning Calorimeter (DSC)/Differential Thermal Analysis
(DTA) equipment and about 5 mg of sample, heating rate of 10 C min1, and gas flow
rate of 100 mL min1, starting from a temperature at 30 C up to 1000 C inside a nitrogen
atmosphere.

Gel content. Gel content was determined from the recycled rubber powder. Three samples
were analyzed by introducing approximately 1 g of filter paper–based material into toluene
for 24 h at atmospheric pressure inside a volumetric flask, which was kept boiling.
Analysis of the gel content determined the soluble (sol) and insoluble (reticulated material/
gel) portions of the SBRr, according to the difference in sample weight before and after
extraction. After extraction, the material was dried in a vacuum oven at 60 C for 48 h.

Characterizations of blends and HIPS

Rheological characterization
Torque rheometry. Rheological curves were obtained by a Thermo Scientific (Wal-
tham, MA, USA) HAAKE PolyLab QC mixer with roller-type rotors at 200 C and 50 r
min1 rotor speed inside an air atmosphere for 10 min.
Luna et al. 7

Mechanical properties
Impact test. Izod impact strength test was performed on notched specimens in
accordance with ASTM D256, on a CEAST Resil 5.5 J device operating with 2.75 J
hammer at room temperature. The results were analyzed with an average of 10 test
specimens.
Flexural testing. Flexural tests were performed by an EMIC DL 2000 universal test
machine (Instron, Norwood, MA, USA) in accordance with ASTM D790, operating in a
three-point bending mode at a speed of 1.6 mm min1 and separation between 80 mm
supports and 2 kN load cell. Tests were conducted at room temperature and results
analyzed with an average of six test specimens.
Shore D hardness test. Determination of the penetration resistance was performed in
accordance with ASTM D2240 in a Shore-Durometer Hardness Type “D” equipment
(Politerm measuring instruments Ltd., São Paulo, Brazil), with 1kN load controlled by
springs calibrated using durometer-standardized indenters. The indenter was pressed
onto the sample for 15 s at five random points.

Thermomechanical properties
Heat deflection temperature. Heat deflection temperature (HDT) was obtained in
accordance with ASTM D648 in a CEAST HDT 6 VICAT equipment (Instron, Norwood,
MA, USA), with a 455 kPa load and heating rate of 120 C h1 (method A). Temperature
was determined after deflecting the sample by 0.25 mm. The results were analyzed with an
average of three test specimens.
Vicat softening temperature. Vicat softening temperature test was performed in
accordance with ASTM D1525 on a CEAST HDT 6 VICAT equipment (Instron, Norwood,
MA, USA) at a heating rate of 120 C h1. Temperature was determined after the needle
penetrated 1 mm into the specimens. Results were analyzed with an average of three test
specimens.

Morphology characterization
Atomic force microscopy. Atomic force microscopy (AFM) morphology was analyzed
by Shimadzu equipment. The scanning mode adopted was either intermittent contact or
tapping mode in air with a cantilever whose tip oscillated on the surface of the samples
extracted from Izod impact test specimens.
Scanning electron microscopy. SEM analyses were performed on the fracture surface of
the specimens submitted to the impact test. A VEGAN 3 TESCAN SEM was used under
a 30 kV voltage and high vacuum (8000 and 25,000 magnifications). An SSX 550
Superscan–Shimadzu (Barueri, Brazil) scanning electron microscope was used under a
30 kV voltage and high vacuum (40 magnifications). Fractured impact sample tests
were used, their surfaces were gold coated using a Shimadzu sputter IC 50, operating
with a 4 mA current for a period of 2 min, and it was done to avoid negative charge
accumulation.
8 Journal of Elastomers & Plastics 52(1)

Table 2. Particle size distribution for the recycled SBRr rubber compound.

Sieve size

Mesh mm % Retained

18 1 11.04 + 0.4
20 0.84 13.66 + 0.3
25 0.71 16.37 + 0.6
35 0.5 19.15 + 0.5
40 0.42 9.88 + 0.3
60 0.25 15.35 + 0.4
80 0.177 8.94 + 0.7
120 0.125 3.72 + 0.6
200 0.074 1.89 + 0.3
% of the used rubber powder (0.84–0.074 mm) 88.96%

SBRr: recycled styrene–butadiene rubber.

Results and discussion

Characterization of the recycled rubber powder
Granulometric distribution. Particle size distribution for the recycled SBRr rubber com-
pound is shown in Table 2.
Table 2 shows that the recycled SBRr compound powder has a broad particle size
distribution, with particle sizes ranging from 0.84 mm to 0.074 mm. Results also evi-
denced that the average particle size is between 25 and 35 mesh (0.71 to 0.5 mm), which
corresponds to 35.52%.

Morphological analysis with EDS. Figure 2(a) shows the SEM micrographs for the SBRr
powder, while Figure 2(b) represents the SEM and the EDS of the sintered SBRr powder
for 1 h up to 600 C.
Figure 2(a) shows that the SBRr powder presents a significant surface roughness with
particles of irregular shape probably resulting from milling to which the recycled rubber
is exposed. Additionally, the presence of fillers adhered to the rubber phase was suc-
cessfully verified. The presence of calcium (Ca), silicon (Si), magnesium (Mg), zinc
(Zn), and titanium (Ti) can be seen in the sintered SBRr powder following semi-
quantitative EDS analysis according to Figure 2(b), associated with the presence of
calcium carbonate (CaCO3), silica (SiO), talc (Mg3H2Si4O12), zinc oxide (ZnO), and
titanium dioxide (TiO2). All the fillers mapped on the EDS are white, being calcium
carbonate, zinc oxide, and talc are considered inactive charges differently from silica,
which acts as an active reinforcing filler. Calcium carbonate and talc are generally used
as fillers in rubber compounds. On the other hand, zinc oxide is a typical vulcanization
activator. The presence of titanium dioxide, probably in its rutile, polymorphic form, was
added to the rubber compound to provide protection against ultraviolet radiation.32
Luna et al. 9

Figure 2. (a) SEM micrographs with 100 and 5000 magnification of recycled rubber powder;
(b) SEM and EDS of the sintered recycled SBRr rubber powder. SEM: scanning electron micro-
scopy; SBRr: recycled styrene–butadiene rubber; EDS: energy-dispersive spectrum.

FTIR spectroscopy. Figure 3 shows the FTIR spectrum of the recycled rubber compound
powder (SBRr).
The spectrum analysis of Figure 3 shows different absorption bands occurring groups:
(1) 1,4 cis-butadiene (754.8 cm1); (2) 1,4 trans-butadiene (965.1 cm1); (3) 1,2-butadiene
units (909.9 cm1); (4) and (5) elongation of CH groups in styrene aromatic rings (2919.2
and 2849.9 cm1), respectively; (6) vibration of stretches in CH2 and CH3 groups (1600
cm1); (7) and elongation of the CC groups of aromatic rings (980 cm1), such absorptions
are typical of the SBR.33 The main bands of calcium carbonate are also found in (8) and (9)
at approximately 1445.4 and 875.2 cm1 (CO32 group elongation and CO32 off-plane
deformation, respectively); of silica (10) and (11) at 3450 and 1026.8 cm1 attributed to
the elongation of the SiO group19; of talc (12) and (13) in 3696.36 and 3384 cm1
associated with the Mg3OH group34; (14) 1080 cm1 symmetric C-S-C group stretching
vibrations in the two C-S bonds4; and of titanium dioxide (15) in typical 680 cm1
vibration of the TiO group.35 In general, the bands presented in the FTIR spectrum cor-
roborate with the EDS analysis. The band that characterizes ZnO was not visualized as it
appears in the range from 400 cm1 to 600 cm1, and the equipment used in this research
starts scanning at 650 cm1.

Thermogravimetry. Figure 4 shows the TG curve for the recycled SBRr rubber compound
powder.
The recycled rubber compound has three well-known thermal decomposition steps.
The first mass loss below 320 C refers to the presence of plasticizers, antidegradants,
10 Journal of Elastomers & Plastics 52(1)

3,0
(11)
(7)
2,5

(2)
2,0 (3)
Absorbance (a.u)

(14)
1,5 (4) (15)
(12)
(10) (8)
1,0 (5)
(13) (6) (9)
(1)
0,5

0,0

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber (cm )

Figure 3. FTIR spectrum of recycled rubber powder (SBRr). FTIR: Fourier-transform infrared;
SBRr: recycled styrene–butadiene rubber.

(1) (2) (3) (4)

100

90
Weight Loss (%)

80

70

60

50

40

30
100 200 300 400 500 600 700 800 900 1000
Temperature (°C)

Figure 4. TG curve of recycled rubber powder in a N2 atmosphere. TG: thermogravimetry.

accelerators, and notably, extender oils. The use of these oils favors the processing,
ensuring a good final surface and assisting the vulcanization process.36 The second mass
loss, in the range of 320–470 C, refers to the degradation of SBR chains. The third
verified loss is probably associated with the decomposition of calcium carbonate.
Luna et al. 11

Table 3. Determination of the gel content.

Samples Initial mass (g) Final mass (g) Variation (g) %Mextracted

1 1.001 0.928 0.073 7.293

2 1.002 0.925 0.077 7.685
3 1.001 0.926 0.075 7.492

Average 7.49 + 0.16

%Mextracted %Mresidual % of polymer material Gel content (%)

7.49 35.6 11.6 88.4

A residual material content of 35.6% at the end of the process is also observed at 1000 C,
resulting from the presence of fillers typically used in SBR formulations of the footwear
industry, which were confirmed by EDS and FTIR analysis.

Gel content (%). The procedure of calculating gel content was the same adopted in the
literature,37 as provided by equations (1) and (2).
ð%Mextracted Þ
% of polymer material ¼  100 ð1Þ
ð100  %Mresidual Þ
where Mextracted ¼ Percentage mass extracted from the gel determination test; Mresidual ¼
Residual percentage mass obtained in TG analysis.
Therefore:
Gel content ¼ 100  % of polymer material ð2Þ
The results obtained by extracting the gel content are shown in Table 3.
The recycled rubber compound (SBRr) has 88.4% of cross-linked material and 11.6%
of soluble material (oils/additives from rubber were solubilized in toluene, and/or there
were small amounts of polymer chains that were not cured), which is consistent with the
behavior observed in the TG analysis of the SBRr sample.

Characterizations of blends and HIPS

Torque rheometry. Figure 5(a) and (b) illustrates the torque versus time curves, as well as
the mechanical work performed during the whole process by HIPS, PS/SBRr blend (50/
50%), and ternary blends according to the content of SBS compatibilizer, respectively.
The PS torque curve was added to check the influence of the recycled rubber powder on
the PS matrix viscosity.
Figure 5(a) shows the loading peak of the material corresponding to the entry of solid
material into the mixing chamber in the first minutes of mixing, promoting a resistance
against the free spin of rotors, thus increasing the torque. Afterward, torque tends to drop
because of the heat transfer being sufficient to melt HIPS, PS, and blends. After 3 min of
12 Journal of Elastomers & Plastics 52(1)

(a) 25 (b) 40
HIPS
PS/SBRr (50/50%) 35
20 PS/SBRr/SBS (5%)
PS/SBRr/SBS (7.5%)
PS/SBRr/SBS (10%) 30
15 PS
Torque (N.m)

TEnd - TStart
25
10
20

5 15

0 10

0 2 4 6 8 10 HIPS 50/50%) BS (5%) S (7,5%) S (10%) PS

BRr ( S/SBRr/S BRr/SB /SBRr/SB
Time (min) PS/S P PS/S PS

Figure 5. (a) Torque versus time curves; (b) temperature variation inside chamber of HIPS, PS,
binary PS/SBRr blends, and ternary ones with 5, 7.5, and 10% of the SBS copolymer. HIPS: high-
impact polystyrene; PS: polystyrene; SBRr: recycled styrene–butadiene rubber; SBS: styrene–
butadiene–styrene.

process, the torque value for HIPS, PS, binary, and ternary blends tends to remain
constant, with small oscillations. This behavior indicates viscosity stability happened for
the used process conditions, that is, speed of 50 r min1 and temperature at 200 C. It is
important to point out that when adding a recycled rubber in the PS matrix, it provided a
greater stability to the processing in relation to the PS. Moreover, HIPS presented the
lowest torque value, that is, a lower viscosity when compared to the blends and PS,
possibly due to the higher MFI presented by HIPS.
In relation to the binary PS/SBRr blend, 50% of recycled rubber (SBRr) presented an
increase in torque in relation to PS, which means an increase in viscosity. Ciro et al.38
correlates the elevation of viscosity with the increase of content in an elastomeric tire
residue (SBR) inserted in a polypropylene matrix as SBR under vulcanization failed to
melt. Therefore, the increase in viscosity of binary blends (PS/SBRr) in relation to the PS
can also be attributed to the presence of 50% recycled rubber (SBRr) vulcanized in
powder, which acts as a filler, causing an increase in blend viscosity. This hypothesis is
confirmed by the gel content and FTIR (C-S band of vulcanized rubber).
Analyzing the behavior of PS/SBRr/SBS blends containing 5, 7.5, and 10 (% in
weight) of SBS, Figure 5(a) shows that there is an increase in torque for the compati-
bilized blends in relation to the PS as the content of the SBS compatibilizer increases.
This is due to the increased miscibility among similar chemical groups, such as the
styrene blocks found in SBS and in the PS and SBRr chains. In addition, the viscosity
increases in the PS/SBRr/SBS blends compared to the PS can be associated with the low
melt flow rate (higher viscosity) of the SBS. However, the increase in torque was only
more significant for the blends containing 7.5 and 10% SBS compared to the non-
compatibilized blend, while the composition with 5% was practically at the same level as
the binary blend (PS/SBRr). The approximate variation between 3.5 min and 5.5 min
Luna et al. 13

shows that blends containing 7.5 and 10% of SBS presented a very evident increase in
curves, which suggests a strong interface among the constituents of the referred blends in
accordance with the mechanical properties under impact.
Scuracchio et al.39 evaluated the influence of 1.25, 2.5 and 3.75% by weight of the
compatibilizer SBS in the viscosity of PS blends with the SBR rubber on a torque
rheometer. It was observed that the increase of SBS compatibilizer content caused the
torque to increase as well, which also increased the viscosity of the blends. They
attributed such increase in viscosity to the possible interactions between SBR and SBS.
The addition of 2.5% SBS in the SBR/SBS mixture increased the torque 25% over the
pure SBR. However, when developing PS/SBS blends, the addition of only 2.5% SBS
practically did not change the viscosity related to the pure PS. Therefore, a double effect
may be occurring to increase the viscosity of PS/SBRr/SBS blends, namely the action of
a vulcanized filler and possible interactions between the SBRr and SBS chemical groups.
Figure 5(b) shows the difference between the final and initial temperatures of HIPS,
PS, binary, and ternary blends inside the process chamber, reflecting the mechanical
work done by the blends. PS and HIPS both presented the lowest temperature variation
during processing, represented by a smaller mechanical work when compared to the
blends. The binary blend imposed the greatest mechanical work among all materials,
probably due to the greater presence of recycled rubber (50%), thus hindering the flow of
the PS matrix. However, ternary blends presented a superior mechanical work during
processing in relation to PS and HIPS. On the other hand, the presence of SBS com-
patibilizer helped the ternary blends to reduce the mechanical work against the non-
compatibilized blend (PS/SBRr), which indicates that the compatibilizer improved the
processability of the PS/SBRr/SBS blends. Also, by increasing the torque of blends with
the SBS copolymer (Figure 5(a)), the mechanical work of the blends tends to be higher.
Therefore, it seems that the increase in torque is followed by a higher viscosity of the
blends, indicating a greater mechanical work to overcome the higher levels of molecular
entanglements of the more viscous blends. Blend containing 7.5% of SBS showed a
temperature variation close to the blends with 10% SBS, suggesting that the mechanical
work of these blends is similar, presenting viscosities close by the end of the process.

Impact tests. Figure 6 shows the impact strength of HIPS, binary blends, and ternary
blends with 5, 7.5, and 10% of the SBS compatibilizer, respectively.
The literature40,41 shows that the impact strength of PS is often increased by adding an
elastomeric phase, that is, the rubber phase aids in the toughening of PS. To incorporate a
recycled rubber compound into a polymer matrix, the particle size of the rubber and the
adhesion between the matrix and the rubber are the main factors in the mechanical
performance of the blends.42
Results from Izod impact strength for PS/SBRr binary blends in Figure 6 show that
the mechanical mixing of 50% SBRr in PS did not produce a significant increase in
impact strength over commercial HIPS, indicating that it is an incompatible blend. Also,
the noncompatibilized blend presented mechanical performance under impact lower than
the blends compatibilized with SBS, which is an indication of low interfacial adhesion
between the direct PS blend and the recycled SBRr compound, inducing a lower stress
14 Journal of Elastomers & Plastics 52(1)

Impact strength (J/m) 200

150

100

50

HIPS 50/50
%) (5%) (7,5%
)
(10%
)
BRr ( SBS SBS SBS
PS/S BRr/ BRr/ BRr/
PS/S P S / S P S / S

Figure 6. Impact strength of HIPS, binary blends, and ternary blends with 5, 7.5, and 10% of SBS
compatibilizer, respectively. HIPS: high-impact polystyrene; SBS: styrene–butadiene–styrene.

transfer from the PS matrix to SBRr particles. The lower performance of PS/SBRr blends
is corroborated by a wide distribution of SBRr particles (see Table 2), as the smaller
particles tend to aggregate on the larger particles, forming agglomerates and thus
reducing the stress distribution.43 The lower impact performance of such PS/SBRr blend
is confirmed by morphological analysis (Figure 13(a)).
A significant increase in the impact strength of all PS/SBRr samples compatibilized
with SBS was observed. It was also observed an increase of such property with the increase
of SBS content. For example, by adding 5% of the SBS copolymer, there was a consid-
erable increase in impact strength, up to a gain of 54.5% compared to the PS/SBRr blend,
while the mixture containing 7.5% SBS presented a sharp increase, equivalent to
approximately 62.1%. On the other hand, the comparison of compositions with 5 and 7.5%
SBS verifies close values. In this case, within the experimental margin of error, similar
mechanical impact properties were obtained. The behavior of the blends containing 10%
SBS has to highlighted due to their significant impact strength, which was close to 200%
when compared to the noncompatibilized blend. According to the literature,44,45 the
compatibilizer reduces the interfacial stress difference among the phases, by refining the
average particle size, strengthening the interface system, and improving the mechanism of
stress transfer among the phases, increasing the values of this property. Additionally, the
data from impact strength in Figure 6 corroborate with the results from torque rheometry,
where the presence of SBS may be favoring greater interactions between SBRr and PS,
thus increasing the overall compatibility of the system. Results from impact strength of the
compatibilized blends are according to the obtained morphology, where smaller and well-
distributed SBRr particles were observed, as well as a greater adhesion among the phases.
Luna et al. 15

(a) (b) 50
2500
45
40

Flexural Strength (MPa)

2000
35
Elastic Modulus (MPa)

30
1500
25
20
1000
15
10
500 5
0
0 HIPS 50/50%) %) %)
BS (5 /SBS (7,5 r/SBS (10
%)
HIPS 50/50%) BS (5%) S (7,5%) S (10%) BRr ( S/SBRr/S BRr BR
PS/S P P S /S P S /S
BRr ( S/SBRr/S B
BRr/S PS/SBRr
/SB
PS/S P PS/S

Figure 7. (a) Elastic modulus; (b) flexural strength of HIPS, binary PS/SBRr blends, and ternary
blends with 5, 7.5, and 10% of the SBS copolymer, respectively. HIPS: high-impact polystyrene; PS:
polystyrene; SBRr: recycled styrene–butadiene rubber; SBS: styrene–butadiene–styrene.

Moreover, there is the increase of PS/SBRr blend compatibility with 10% SBS in
relation to commercial HIPS, which presented a significant gain after reaching values of
80.5%. Results from impact strength for PS/SBRr/SBS blends can be considered tech-
nologically interesting as they were developed with a high concentration of recycled
rubber and can be considered toughened at room temperature when compared to com-
mercial HIPS.

Flexural testing. The elastic modulus and the flexural strength of HIPS, PS/SBRr binary
blends, and ternary ones with 5, 7.5, and 10% of SBS compatibilizer, respectively, are
shown in Figure 7(a) and (b).
As can be seen in Figure 7(a), there was a reduction in the values of elastic modulus
for mixtures in relation to the HIPS reference sample. Adding high concentrations of a
flexible rubber (SBRr) in blends makes them more flexible, resulting in losses of these
properties. Also, when 50% SBRr was added to the binary blend, a significant decrease
of the elastic modulus occurred among all blends. The literature46 states that the addition
of vulcanized rubber, particulate filler, to a thermoplastic reduces mechanical properties
as a consequence of the poor adhesion among phases and the concentration of stresses
around the particles of the rubber powder.
Zhang et al.13 suggest that the addition of a compatibilizer may increase adhesion
between the PS matrix and the recycled powder domains of vulcanized rubber by
modifying the interface, improving stress transfer, and increasing mechanical properties.
Figure 7(a) shows a progressive decrease in the elastic modulus with the increase of SBS
compatibilizer concentration, which is easier when using 10% SBS. On the other hand,
the addition of SBS copolymer increased the performance of elastic modulus under
flexion when compared to the noncompatibilized blend. It is also interesting to note that
16 Journal of Elastomers & Plastics 52(1)

80

70

60
Shore D Hardness

50

40

30

20

10

HIPS 0/50%
)
(5%) (7,5%
)
(10%
)
Rr (5 SBS SBS SBS
/ S B BRr/ BRr/ BRr/
PS PS/S PS/S PS/S

Figure 8. Shore D hardness of HIPS, binary PS/SBRr blends, and ternary ones with 5, 7.5, and 10%
of the SBS copolymer, respectively. HIPS: high-impact polystyrene; PS: polystyrene; SBRr: recycled
styrene–butadiene rubber; SBS: styrene–butadiene–styrene.

the values of the modulus under flexion are close to the commercial HIPS. Again, blends
containing SBS show signs of good interaction, reinforcing the idea of a greater interface
favoring a greater adhesion among phases and, consequently, reducing the probability of
interface flaws.
Figure 7(b) shows that all blends had a lower flexural strength compared to the more
rigid HIPS. There is also a decrease in strength with the increase of the SBS compati-
bilizer content, which shows a greater reduction at 10% SBS. Blends containing 7.5 and
10% SBS are at the same level of this property considering the limit of the experimental
error. In relation to the blends without compatibilizer (PS/SBRr), a lower performance in
the flexural strength was observed when compared to the blends containing SBS. This is
also an indication that there was compatibilization in PS/SBRr/SBS mixtures, leading to
a reduction in interfacial stress among phases and increasing the ability to support the
stress transfer from the PS matrix. Bending results are consistent with the impact
behavior of the blends.

Shore D hardness test. Figure 8 shows the Shore D hardness of HIPS, binary PS/SBRr
blends, and ternary ones with 5, 7.5, and 10% of the SBS compatibilizer, respectively.
HIPS presented the highest hardness, in other words, the highest resistance to
penetration. In general, the values obtained for all blends had lower hardness values than
HIPS. This behavior of blends is due to the incorporation of the rubber compound in the
PS matrix, which gives the material greater flexibility and causes a reduction of the
Shore D hardness. Also, SBS compatibilized blends showed a decrease in Shore D
Luna et al. 17

PS/SBRr
100
PS/SBRr/SBS (5%)
PS/SBRr/SBS (7.5%)
PS/SBRr/SBS (10%)
80 HIPS
Weigth Loss (%)

60

40

20

0
0 200 400 600 800 1000
Temperature (°C)

Figure 9. TG curves of HIPS and blends in a N2 atmosphere at 10 C/min. TG: thermogravimetry;
HIPS: high-impact polystyrene.

hardness as the compatibilizer content increased. A different behavior for PS/SBRr

blends can be seen with a superior performance in hardness when compared to com-
patibilized blends. The literature47,48 reports that the hardness is related to the polymer
matrix and the presence of inorganic fillers, indicating that the hardness depends on the
surface characteristics of the blends and, therefore, overlaps the effect of the interfacial
adhesion that justifies the different behavior of the PS/SBRr blend for this particular
property. The PS/SBRr blend is made of the highest concentration (50%) of recycled
rubber compound (SBRr), which probably favored a greater amount of dispersed mineral
fillers on the surface of the blend, increasing the hardness in relation to compatibilized
blends. However, blends containing SBS, being a thermoplastic elastomer that does not
have mineral fillers in its composition, acted to make the surfaces of the compatibilized
blends softer, reducing the penetration resistance when compared to the PS/SBRr blends.
The behavior of blends in Shore D hardness is consistent with the amount of inorganic
fillers presented in results from the TG analysis, as well as in line with the AFM analysis.
In general, the incorporation of a recycled rubber powder in large quantities decreases
the hardness of the developed materials. However, whenever there is a need to consider
the addition of a recycled material in contents of up to 50% by weight in the PS, this
reduction is acceptable, as it did not significantly compromise the Shore D hardness,
once it is close to the commercial HIPS prepared by graphitization.

Thermogravimetry. Figure 9 shows the TG curves of HIPS, binary blends (PS/SBRr), and
ternary ones containing 5, 7.5, and 10% of the compatibilizer SBS, respectively.
HIPS presents a single decomposition step initiated at approximately 350 C, inducing
the primary bonds rupture process due to thermal energy and causing degradation of the
18 Journal of Elastomers & Plastics 52(1)

Table 4. Residual mass obtained by TG of HIPS and of the blends.

Composition Residual mass at 1000 C (mg)

HIPS 0
PS/SBRr (50/50%) 24.7
PS/SBRr/SBS (5%) 16.1
PS/SBRr/SBS (7.5%) 14.8
PS/SBRr/SBS (10%) 14.0

TG: thermogravimetry; HIPS: high-impact polystyrene; PS: polystyrene; SBRr: recycled styrene–butadiene
rubber; SBS: styrene–butadiene–styrene.

material. In general, all blends presented a thermal stability lower than HIPS and curves
showed a slight decrease. PS/SBRr, PS/SBRr/SBS (5%), and PS/SBRr/SBS (7.5%)
blends presented three stages of thermal decomposition, while the PS/SBRr/SBS mixture
(10%) presented two mass losses. The first one is below 320 C, which is due to plas-
ticizers, antidegradants, accelerators, processing aids, stearic acid, and, mainly, extender
oils. The second mass loss, ranging from 320 C to 480 C, refers to the degradation of the
SBR; as well as a slight loss between 480 C and 600 C, probably associated with the
decomposition of calcium carbonate. This loss was not verified for the blend containing
10% SBS. By the end of the process at 1000 C, a residual material content in the blends
can be observed, much more significant in the mixture containing 50% SBRr. This is due
to the greater presence of recycled rubber. The presence of residual material is attributed
to the presence of fillers typically used in SBR formulations for the footwear industry,
which corroborates with previously reported results in EDS, TG, and FTIR of the rubber.
Table 4 shows the residual content of inorganic fillers found in the blends. Interest-
ingly, the higher the recycled rubber content added to the PS, the greater the residual
mass amount found at the end of the process. The PS/SBRr blend presented the highest
amount of residual inorganic fillers when compared to the other blends, which explains
the greater hardness presented by the PS/SBRr blend. However, blends compatibilized
with 7.5 and 10% SBS had practically the same content of residual material in line with
the behavior of Shore hardness, which were similar.

Heat deflection temperature. Figure 10 shows the HDT behavior of HIPS, binary blends,
and ternary ones containing 5, 7.5, and 10% of the SBS compatibilizer, respectively.
Figure 10 shows that the maximum HDT value was of 85 C for HIPS and the lowest
value was of 76 C for the PS/SBRr binary mixture. Thermomechanical analysis of HDT
can be used to evaluate the compatibility of the polymer systems in a manner similar to
the mechanical properties.49 A moderate increase in HDT was observed following the
increase of the SBS compatibilizer content, indicating that the compatibilizing agent had
a positive effect on HDT properties of the ternary mixtures compared to the non-
compatibilized PS/SBRr mixture, an effect that was highly evidenced in the mixture
compatibilized with 10% SBS. All blends presented a HDT below HIPS, probably due to
the high concentration of SBRr, making the systems more flexible, generating a loss in
Luna et al. 19

90

80

70

60
HDT (°C)

50

40

30

20

10

HIPS 50/50
%) ( 5%) (7,5%
)
(10%
)
BRr ( SBS SBS SBS
PS/S BRr/ BRr/ BRr/
PS/S P S / S P S / S

Figure 10. HDT of HIPS, binary PS/SBRr and ternary blends with 5, 7.5, and 10% of the SBS
copolymer, respectively. HDT: heat deflection temperature; HIPS: high-impact polystyrene; PS:
polystyrene; SBRr: recycled styrene–butadiene rubber; SBS: styrene–butadiene–styrene.

the behavior of HDT when compared to HIPS that is typically formulated with 6–10% by
rubber mass.50 However, it is interesting to note that the PS/SBRr blends and those
compatible with SBS have an important technological contribution, as the use of a
recycled compound, SBRr, in high concentrations favors the development of materials
with HDT close to commercial HIPS. The addition of a recycled rubber compound
(SBRr) with cross-linking and mineral fillers in the PS matrix is suggested, which sig-
nificantly contributes to keep the HDT of blends at higher levels, even higher than
engineering polymers such as polyamide (approximately 55 C). Additionally, values
observed for PS/SBRr/SBS (10%) blends are relevant, as a decrease of 6% of HDT was
obtained when compared to commercial HIPS, as well as a considerable increase in
impact strength, once considering that it was formulated with 45% recycled rubber.

Vicat softening temperature. Figure 11 shows the behavior of the Vicat softening tem-
perature of HIPS, binary blend (PS/SBRr), and ternary ones containing 5, 7.5, and 10%
of the SBS compatibilizer, respectively.
The incorporation of rubber into polymers tends to decrease the hardness and con-
tributes to a drop in the Vicat softening temperature. Figure 11 shows that HIPS pre-
sented the highest Vicat softening temperature, a fact attributed to its higher stiffness,
thus requiring a higher temperature to allow needle penetration. On the other hand, there
is a reduction in the Vicat softening temperature of all blends when compared to HIPS,
regardless of whether the blend is compatibilized or not. Adding flexible filler in the PS
20 Journal of Elastomers & Plastics 52(1)

100

80
Vicat Softening Temperature (°C)

60

40

20

0
HIPS %) S (5%
)
(7,5%
)
(10%
)
50/50 Rr/SB r/SBS
S / S BRr ( / S B S B R r/SBS / S B R
P P S PS/ PS

Figure 11. Vicat softening temperature of HIPS, binary blend (PS/SBRr), and ternary ones with 5,
7.5, and 10% of the SBS compatibilizer, respectively. HIPS: high-impact polystyrene; PS: poly-
styrene; SBRr: recycled styrene–butadiene rubber; SBS: styrene–butadiene–styrene.

matrix assumes a reduction in hardness, resulting in less resistance to penetration as

temperature rises. Also, as the content of SBS compatibilizer increases, Vicat softening
temperature tends to drop, with the stronger effect much more evidenced at the con-
centration containing 10% of the compatibilizer. However, the noncompatibilized blend
showed a distinct behavior, presenting a higher Vicat softening temperature when
compared to SBS compatibilized blends. This property is mostly dependent on surface
characteristics and, therefore, adding 50% by mass of a recycled compound of vulca-
nized rubber with mineral fillers has the potential to delay the penetration of the needle,
increasing the softening temperature in relation to compatible blends. In general, Vicat
softening temperature results are consistent with the Shore D hardness behavior and the
residual mass obtained by TG.

Atomic force microscopy. AFM is a tool of great relevance in the study of polymers, as it
allows the study of the surface morphology and phase distribution by either topography
or difference of the elastic modulus. Additionally, the study enables the detection of
variations among the different components of a polymer blend, as well as the phase
distribution of these materials.51
Figure 12(a) to (d) shows the images obtained by AFM of PS/SBRr blends and ternary
blends with 5, 7.5, and 10% SBS, respectively. The images presented correspond to the
topography of samples from impact test specimens.
Luna et al. 21

Figure 12. AFM micrographs of the blends: (a) PS/SBRr (50/50%), (b) PS/SBRr/SBS (5%), (c) PS/
SBRr/SBS (7.5%), and (d) PS/SBRr/SBS (10%). AFM: atomic force microscopy; PS: polystyrene;
SBRr: recycled styrene–butadiene rubber; SBS: styrene–butadiene–styrene.

The analysis of the topographic images of Figure 12(a) to (d) demonstrated that all
blends are composed of two distinct phases, one dark and one clear, indicating the
existence of a heterogeneous system and, in this case, of immiscible blends. The liter-
ature52 states that authors associate these darker regions with rigid phases, indicating
phases of low elasticity, that is, PS and possible mineral fillers that might have migrated
to the surface. On the other hand, the clear phases correspond to the elastomeric phase.
Also, when using the content of 50% of SBRr in the binary blend (Figure 12(a)), there is
a chance that the surface becomes more rigid, as it tends to become darker when
compared to ternary blends. This indicates a higher penetration resistance for the PS/
SBRr blends and corroborating with the results from the hardness test, as well as the
presence of fillers previously observed by FTIR, TG, and EDS. The comparison of the
compatibilized blends morphologies evidenced that as the SBS compatibilizer content
increases, the surface tends to become lighter, which is more evident when using 10%
SBS. In this case, there is an indication of a greater distribution at the surface of the
elastomeric phase, which favors the softening of blends and induces a lower hardness,
thus corroborating with the results presented in Figure 8.

Scanning electron microscopy. Figure 13(a) to (d) shows SEM photomicrographs from the
fracture surface of binary (PS/SBRr) and ternary blends with 40 and 8000 magni-
fication, respectively.
22 Journal of Elastomers & Plastics 52(1)

Figure 13. SEM micrographs of the samples fracture surfaces with a 40 and 8000 magnifi-
cation, respectively: (a) PS/SBRr (50/50%), (b) PS/SBRr/SBS (5%), (c) PS/SBRr/SBS (7.5%), and (d)
PS/SBRr/SBS (10%). Images (a, b, c, d): Magnification of 40. Images (a-1, b-1, c-1, d-1): Magnifi-
cation of 8000. SEM: scanning electron microscopy; PS: polystyrene; SBRr: recycled styrene–
butadiene rubber; SBS: styrene–butadiene–styrene.
Luna et al. 23

Figure 14. SEM micrograph of PS/SBRr/SBS blends (10%) with 25,000 magnification. SEM:
scanning electron microscopy; PS: polystyrene; SBRr: recycled styrene–butadiene rubber; SBS:
styrene–butadiene–styrene.

The micrographs of all blends, as shown in Figure 13(a) to (d), reveal a typically
morphological surface of immiscible blends, as well as the phase separation of PS and
SBRr. Also, a high index of plastic deformation is observed in all morphologies, in
which the dispersed phase is not easily verified. There is evidence of a ductile fracture
mechanism, that is, with a visible plastic deformation. Regarding the morphology
refinement, no conclusions can be made because of the impossibility to distinguish the
phases from the presented SEM micrographs (40 magnification).
The morphology of the PS/SBRr binary blend as seen in Figure 13(a) shows the
presence of many voids caused by the pullout of SBRr particles during the impact test,
indicating a low interfacial adhesion among phases, as well as incompatibility. Also,
smooth surfaces are visualized without roughness and delamination process (Figure
13(a)), which strengthens the assumption of poor adhesion among phases, thus causing a
reduction in the stress transfer of the PS matrix to SBRr particles. The incompatibility
between PS and SBRr phase corroborates with the low mechanical property of this
system. However, the effects of the SBS compatibilizer concentration produce different
surface characteristics compared to the noncompatibilized blend.
Figure 13(b) to (d) shows a reduction in the number of voids in the morphology of the
compatibilized blends when compared to the binary blend, which is assumed to have a higher
adhesion among blend constituents. This is corroborated by the literature53 that reports the
compatibilizer tends to diffuse to the interface, increasing the adhesion of the phases,
avoiding the formation of agglomerates, and improving stress transfer imposed to the system.
The SBS addition with content from 5% tends to stabilize the morphology of PS/SBRr
blend, thus reducing interfacial stress and the number of voids and delamination. The
24 Journal of Elastomers & Plastics 52(1)

morphology of blends containing SBS corroborates with a higher performance of the

properties of these mixtures. There is a chance that the miscibility of SBS with PS and
SBRr caused this copolymer to migrate to the interface of PS/SBRr/SBS blends,
strengthening the adhesion and inducing a greater stress transfer from the PS rigid matrix
to SBRr particles. The good interaction of this SBS compatibilizer is visualized in Figure
13(d) to (1) and Figure 14 (photomicrography with 25000 magnification), where the
rubber particle is strongly adhered to the PS phase (white arrow), indicating that the
interface did not fracture, which is important for a greater performance under impact.
Considering the size of the particles, apparently, the breaking down of some particles
of SBRr occurred. According to the literature,54–56 this breakage could be due to two
possibilities: (1) there were small amounts of polymer chains that were not cured or (2)
the operating conditions, especially the speed of rotation (250 r min1). According to
Sousa et al.,57 the screw speed influences the size of the rubber particles. The authors
found that the size of the rubber particles decreased with increasing screw speed. At a
speed of 250 r min1, the mixture presented smaller size and smaller particle size
distributions.

Conclusions
The compatibilization of PS blends with a recycled rubber compound from the footwear
industry and SBS copolymer was studied and compared to commercial HIPS. Results
evidenced that even with all difficulties to reuse vulcanized rubbers, it is possible to
obtain a material with good properties, by reducing production costs when developing a
product and obtaining a material with good aesthetic appearance. Considering that it is
made of recycled white rubber, thus allowing to boost the development of materials from
recycling and contributing to reduce environmental degradation, as well as favoring a
more efficient environmental cycle. Besides, landfill disposal expenses are avoided. The
composition of these rubbers is complex and may contain stabilizers, flame retardants,
and plasticizers of low molar mass, which may contaminate groundwater over time. The
development of PS blends with a white rubber compound could boost new advances in
the production of materials that contribute to an environmentally sustainable cycle.
Mainly, when reusing these vulcanized materials, their incineration are highly aggressive
to both environment and humans and is to be avoided, as their structure presents sulfur
that once released by burning reacts with oxygen forming sulfur dioxide, which may
cause damage to ecosystems and human health. These results illustrate that new mate-
rials with good properties can be obtained with this recycled rubber compound, sur-
passing even the HIPS in applications that require a toughened material at room
temperature. Thus, it is possible to value an industrial waste that would rather be dis-
posed and to avoid aggression to ecosystems, by reducing the waste.

Acknowledgement
The authors thank UFCG, CERTBIO, CAPES/PNPD, MCTI/CNPq, CNPq, and São Paulo Alpar-
gatas/PB for the supply of the recycled rubber compound.
Luna et al. 25

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship,
and/or publication of this article.

Funding
The author(s) disclosed receipt of the following financial support for the research, authorship, and/
or publication of this article: The authors acknowledge the financial support given by Conselho
National Council for Scientific and Technological Development (CNPq).

ORCID iD
Carlos Bruno Barreto Luna https://orcid.org/0000-0002-2441-7439

References
1. Asaro L, Gratton M, Seghar S, et al. Recycling of rubber wastes by devulcanization. Res
Conserv Recycl 2018; 133: 250–262.
2. Aodia K, Azem S, Hocine NA, et al. Recycling of waste tire rubber: microwave devulcani-
zation and incorporation in a thermoset resin. Waste Manag 2017; 60: 471–481.
3. Nuzaimah M, Sapuan SM, Nadlene R, et al. Recycling of waste rubber as fillers: a review. IOP
Conf Ser Mater Sci Eng 2018; 368: 1–9.
4. Garcia PS, Sousa FDB, Lima JÁ, et al. Devulcanization of ground tire rubber: physical and
chemical changes after different microwave exposure times. Exp Polym Lett 2015; 9(11):
1015–1026.
5. Costa HM, Ramos VD, Silva WS, et al. Otimização de propriedades mecânicas de misturas
ternárias de polipropileno (PP)/Borracha de etileno-propileno-dieno (EPDM)/Pó de pneus
(SRT) sob tração e impacto usando a metodologia da superfı́cie de resposta (MSR). Polı´meros
2012; 22(1): 27–33.
6. Yang JN, Nie SB, Huang XH, et al. Thermoplastic blends of PP and waste rubber powder:
effects of compatibilizer on tensile properties, thermal behavior and decomposition kinetics.
Int Polym Proc 2018; 33(4): 460–470.
7. Ramara S, Khalid M, Ratman CT, et al. Waste tire rubber in polymer blends: a review on the
evolution, properties and future. Prog Mater Sci 2015; 72: 100–140.
8. Zanchet A, Carli LN, Giovanela M, et al. Characterization of microwave-devulcanized
composites of ground SBR scraps. J Elastom Plast 2009; 41(6): 497–507.
9. Shi Y, Liu F, and Wang Z. Mullins effect and its reversibility for compatibilised thermoplastic
elastomers based on high-density polyethylene/waste ground rubber tyre powder under
compression mode. Plast Rubber Compos 2018; 47(8): 1–8.
10. Araújo EM, Carvalho LH, Fook MVL, et al. Propriedades mecânicas de blendas de PS/resı́duo
de borracha - Influência da concentração, granulometria e método de moldagem. Polı´meros
1997; 7(3): 45–52.
11. Yepes WU, Vásquez NC, Restrepo SMV, et al. Revisión - Caracterización de compuestos de
caucho com residuos de cuero posindustrial. Prospect 2017; 15(2): 13–25.
12. Dung NT, Hanh LTM, Lan PT, et al. Properties of polymer blends based on devulcanized
waste rubber powder (d-WRP)/EPDM/P. Vietnam J Chem. 2018; 56(2): 237–243.
13. Zhang J, Chen H, Zhou Y, et al. Compatibility of waste rubber powder/polystyrene blends by
the addition of styrene grafted styrene butadiene rubber copolymer: effect on morphology and
properties. Polym Bull 2013;70(10): 2829–2841.
26 Journal of Elastomers & Plastics 52(1)

14. Macsiniuc A, Rochette A, Brisson J, et al. Polystyrene/recycled SBR powder compounds

produced in an internal batch mixer. Prog Rubber Plast Recycl Technol 2014; 30(4): 186–210.
15. Rosas RM and Juan XR. Electrical application of polystyrene (PS) reinforced with old tire
rubber (GTR): dielectric, thermal, and mechanical properties. Sci Eng Compos Mater 2013;
20(3):1–12.
16. Veilleux J and Rodrigues D. Properties of recycled PS/SBR blends: effect of SBR pretreat-
ment. Prog Rubber Plast Recycl Technol 2016; 32(3): 111–128.
17. Scuracchio CH, Waki DA, and Silva MLCP. Thermal analysis of ground tire rubber devul-
canized by microwaves. J Therm Anal Calorim 2007; 87(3):893–897.
18. Kocsis JK, Mészáros L, and Bárány T. Ground tyre rubber (GTR) in thermoplastics, ther-
mosets, and rubbers. J Mater Sci 2013; 48(1): 1–38.
19. Baeta DA, Zattera JA, Oliveira MG, et al. The use of styrene-butadiene rubber waste as a
potential filler in nitrile rubber: order of addition and size of waste particles. Braz J Chem Eng
2009; 26(1): 23–31.
20. Nunes AT, Santos RE, Pereira JS, et al. Characterization of waste tire rubber devulcanized in
twin-screw extruder with thermoplastics. Prog Rubber Plast Recycl Technol 2018; 34(3):
143–157.
21. Song P, Li S, and Wang S. Interfacial interaction between degraded ground tire rubber and
polyethylene. Polym Degrad Stab 2017; 143: 85–94.
22. Pittolo M and Burford RP. Recycled rubber crumb as a toughener of polystyrene. Rubber
Chem Technol 1985; 58(1): 97–106.
23. Wang Z, Zhang Y, Du F, et al. Thermoplastic elastomer based on high impact polystyrene/
ethylene-vinyl acetate copolymer/waste ground rubber tire powder composites compatibilized
by styrene-butadiene-styrene block copolymer. Mater Chem Phys 2012; 136(2–3): 1124–1129.
24. Zhao J, Wei D, and Wang Z. Thermoplastic elastomers based on high-impact polystyrene/
waste styrene butadiene rubber powder blends enhanced by styrene–butadiene–styrene block
copolymer and aromatic Oil. J Macromol Sci B 2015; 54(3): 262–274.
25. Montagna LS, Bento LS, Silveira MRS, et al. Evaluation of the effect of the incorporation of
rubber tire waste particles on the properties of PP, HIPS and PP/HIPS matrices. Polı´meros
2013; 23(2): 169–174.
26. Costa HM, Ramos VD, Silva WS, et al. Analysis and optimization of polypropylene (PP)/
ethylene–propylene–diene monomer (EPDM)/scrap rubber tire (SRT) mixtures using RSM
methodology. Polym Test 2012; 29(5): 572–578.
27. Hernández EH, Gámez JFH, Cepeda LF, et al. Sulfuric acid treatment of ground tire rubber
and its effect on the mechanical and thermal properties of polypropylene composites. J Appl
Polym Sci 2017; 134(21): 1–7.
28. El-Nemr KF, Khalil AM, and Fathy ES. Thermoplastic elastomers based on waste rubber and
expanded polystyrene: role of devulcanization and ionizing radiation. Int J Polym Anal
Character 2017; 23(1):58–69.
29. Karahrodi MH, Jazani OM, Paran SMR, et al. Modification of thermal and rheological char-
acteristics of bitumen by waste PET/GTR blends. Constr Build Mater 2017; 134: 157–166.
30. Moghaddamzadeh S and Rodrigue D. The effect of polyester recycled tire fibers mixed with
ground tire rubber on polyethylene composites. II Prog Rubber Plast Recycl Technol 2018;
34(3):128–142.
31. Cosnita M, Cazan C, and Duta A. Effect of waste polyethylene terephthalate content on the
durability and mechanical properties of composites with tire rubber matrix. J Compos Mater
2016; 51(3): 357–372.
Luna et al. 27

32. Smijs TG and Pavel S. Titanium dioxide and zinc oxide nanoparticles in sunscreens: focus on
their safety and effectiveness. Nanotechnol Sci Appl 2011; 4: 95–112.
33. Rocha TLAC, Schuster RH, Jacobi MM, et al. Estudo da modificação quı́mica de polidienos
do tipo SBR e BR. Polı´meros 2004; 14(5): 318–321.
34. Castillo LA, Barbosa SE, Maiza P, et al. Surface modifications of talcs. Effects of inorganic
and organic acid treatments. J Mater Sci 2011; 46: 2578–2586.
35. Kauffman CMF. Sı´ntese e caracterização estrutural, mecaˆnica e o´ptica de materais com-
pósitos restauradores. PhD Thesis, Federal University of Pernambuco, Brazil, 2011.
36. Bhowmick AK and Stephens HL. Handbook of elastomers. 2nd ed. New York: Marcel
Dekker, 2000, p. 944.
37. Massarotto M, Crespo JS, Zattera AJ, et al. Characterization of ground SBR scraps from shoe
industry. Mat Res 2008; 11: 81–84.
38. Ciro E, Parra J, Zapata M, et al. Effect of the recycled rubber on the properties of recycled
rubber/recycled polypropylene blends. Ing Cienc 2015; 11(22): 173–188.
39. Scuracchio CH, Bretas RES, and Isayev AI. Blends of PS with SBR devulcanized by ultra-
sound: rheology and morphology. J Elastom Plast 2004; 36(1): 45–75.
40. Coutinho FMB, Costa MPM, Guimarães MJOC, et al. Preparation and characterization of
high-impact polystyrene using different types of polybutadiene. J Appl Polym Sci 2008;
108(1): 406–413.
41. Cai GD, Yang HY, Zhu LD, et al. Toughening polystyrene by core–shell grafting copolymer
polybutadiene-graft-polystyrene with potassium persulfate as initiator. J Ind Eng Chem 2013;
19(3): 823–828.
42. Costa HM, Ramos VD, Silva WS, et al. Analysis and optimization of polypropylene (PP)/
ethylene–propylene–diene monomer (EPDM)/scrap rubber tire (SRT) mixtures using RSM
methodology. Polym Test 2010; 29(5): 572–578.
43. De SK, Isayev AI, and Khait K. Rubber recycling. 1st ed. New York: Taylor & Francis Group,
2005, p. 528.
44. Koning C, Duin MV, Pagnoulle C, et al. Strategies for compatibilization of polymer blends.
Prog Mater Sci 1998; 23(4): 707–757.
45. Libio IL, Grass VG, Dal Pizzol MF, et al. Toughened polystyrene with improved photo-
resistance: effects of the compatibilizers. J Appl Polym Sci 2012; 126(1): 179–185.
46. Lee SH, Balasubramanian M, and Kim JK. Dynamic reaction inside co-rotating twin screw extruder.
I. Truck tire model material/polypropylene blends. J Appl Polym Sci 2007; 106(5): 3193–3208.
47. Higazy AA, Afifi H, Khafagy AH, et al. Ultrasonic studies on polystyrene/styrene butadiene
rubber polymer blends filled with glass fiber and talc. Ultrasonics 2006; 44(suppl):1439–1445.
48. Schneider AC, Mendonça MJ, Rodrigues RB, et al. Influência de três modos de fotopoli-
merização sobre a microdureza de três resinas compostas. Polı´meros 2016; 26: 37–42.
49. Araújo EM, Júnior HÁ, and Carvalho AJF. Compatibilização de blendas de poliamida 6/ABS
usando os copolı́meros acrı́licos reativos MMA-GMA e MMA-MA. Parte 2: Comportamento
termomecânico e morfológico das blendas. Polı´meros 2004; 14(1): 22–30.
50. Rovere J, Correa CA, Grassi VG, et al. Role of the rubber particle and polybutadiene cis
content on the toughness of high impact polystyrene. J Mater Sci 2008; 43(3): 952–959.
51. Herrmann PSP, Silva MAP, Bernades R, et al. Microscopia de varredura por força: uma
ferramenta poderosa no estudo de polı́meros. Polı´meros 1997; 7(4): 51–61.
52. Lee SH, Balasubramanian M, and Kim JK. Dynamic reaction inside co-rotating twin screw
extruder. II. Waste ground rubber tire powder/ polypropylene Blends. J Appl Polym Sci 2007;
106(5): 3209–3219.
28 Journal of Elastomers & Plastics 52(1)

53. Konig C, Duin MV, Pagnoulle C, et al. Strategies for compatibilization of polymer blends.
Prog Polym Sci 1998; 23(4): 707–757.
54. Bilgili E, Arastoopour H, and Bernstein B. Pulverization of rubber granulates using the
solid-state shear extrusion (SSSE) process: Part I. Process concepts and characteristics.
Powder Technol 2001; 115(3): 265–276.
55. Tozzi KA, Canto LB, and Scuracchio CH. Regeneração de resı́duo de borracha expandida
através de extrusão no estado sólido e incorporação em copolı́mero de estireno-butadieno
(SBR) vulcanizado – avaliação das propriedades mecânicas. In: Antonio Eduardo Martinelli,
Clodomiro Alves Junior Dulce Maria de Araújo Melo, et al. (eds) CBCIMat - congresso
brasileiro de engenharia e cieˆncia dos materiais, Natal, Brasil, 06 November 2016, paper no.
416–025, pp. 1–14.
56. Saiwari S, van Hoek J, Dierkes W, et al. Upscaling of a batch de-vulcanization process for
ground car tire rubber to a continuous process in a twin screw extruder. Materials 2016:
9(9): 724.
57. Sousa FDB, Scuracchio CH, Hu GH, et al. Effects of processing parameters on the properties
of microwave-devulcanized ground tire rubber/polyethylene dynamically revulcanized
blends. J Appl Polym Sci 2016; 133(23): 1–11.