Journal Pre-proof

Recycled tires shreds based polyurethane binder: Production and

characterization

Fatima-Zahra Semlali Aouragh Hassani , Wafa Ouarhim ,

Mounir El Achaby , Youssef Tamraoui ,
Mohammed-Ouadi Bensalah , Denis Rodrigue , Rachid Bouhfid ,
Abou el kacem Qaiss

PII: S0167-6636(19)30738-0
DOI: https://doi.org/10.1016/j.mechmat.2020.103351
Reference: MECMAT 103351

To appear in: Mechanics of Materials

Received date: 1 September 2019

Revised date: 28 January 2020
Accepted date: 8 February 2020

Please cite this article as: Fatima-Zahra Semlali Aouragh Hassani , Wafa Ouarhim ,
Mounir El Achaby , Youssef Tamraoui , Mohammed-Ouadi Bensalah , Denis Rodrigue ,
Rachid Bouhfid , Abou el kacem Qaiss , Recycled tires shreds based polyurethane
binder: Production and characterization, Mechanics of Materials (2020), doi:
https://doi.org/10.1016/j.mechmat.2020.103351

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Highlights

 Valorization of used tire to solve the environmental problems that resulted.

 Used tire based a new composite with high mechanical performance
 Halogenation treatment has been used to improve adhesion at the interface.

1
 Recycled tires shreds based polyurethane binder: Production and
characterization

Fatima-Zahra Semlali Aouragh Hassani1,2, Wafa Ouarhim1,2, Mounir El Achaby3, Youssef

Tamraoui3, Mohammed-Ouadi Bensalah2, Denis Rodrigue4, Rachid Bouhfid1, Abou el
kacem Qaiss1*

1
Moroccan Foundation for Advanced Science, Innovation and Research (MAScIR), Composites and
Nanocomposites Center, Rabat, Morocco
2
Mohammed V-Rabat, University, Faculty of Science, Mechanics of Materials Laboratory, Rabat
Marocco.
3
Materials Science and Nanoengineering Department (MSN), Mohammed VI Polytechnic University
(UM6P), Lot 660 – Hay Moulay Rachid, 43150 Benguerir, Morocco
4
Department of Chemical Engineering and CERMA, Université Laval, Québec, Canada

2
ABSTRACT

End-of-life tires are known to have negative economic and environmental impacts due to
their difficult disposal and recycling. Thus, the use of recycled waste tire rubber particles
mixed with an elastomeric polyurethane resin dyed in the mass has emerged as a
potentially sustainable solution to this environmental issue. Indeed, they can be used for
the manufacture of damping tiles for playgrounds and sports fields, which limit the risks
associated with falling. This is a product that interests town halls, businesses and
individuals. In this study, the recycled waste tire rubber particles and their fibers
byproducts are introduced into a new binder based on commercial polyurethane
adhesive (Vinyprene P2006) blended with a polyisocyanate hardener to elaborate a low-
cost composite. Also, halogenation is proposed as a surface modification to improve the
interfacial adhesion between the binder and the particles. The samples were produced
with two densities and characterized using SEM and FTIR, as well as bonding,
compression, relaxation and residual deformation. The results show that the chemical
treatment increased the rubber surface roughness which improved the binder ability, and
on the other hand, the rubber composites exhibit higher compression properties than the
rubber mixed the fiber by product composites.

Keywords

Waste tire rubber; Polyurethane binder; Halogenation; Composites; Morphological

analysis; Mechanical properties; compression; relaxation; residual deformation.

3
 1. Introduction

Solid waste management is the most important problem in the world, especially for tires
(Karakurt, 2015). Over time, the number of used and end-of-life tires has substantially
increased with automotive development (Zhang et al., 2012). So, the accumulation of
large amounts of waste tires has brought serious environmental problems, leading
scientists to intense research on finding ways to recover and revalorize these residues
(Shanmugharaj et al., 2005; Xiaowei et al., 2017)

Generally, a worn tire can be considered as a source of secondary raw material even if it
contains a high number of different chemicals with potential energy recovery. However,
tire recycling results in the production of three streams: rubber particles, steel inserts
and synthetic yarn fibers (textiles). Each of these materials can be recovered separately
leading to massive energy and raw materials savings (Bulei et al., 2018). Today, several
technical solutions have been developed for tire recycling, but mechanical recycling,
including the separation of metal, textile and rubber parts, remains the most interesting
(Lucignano et al., 2012). As a worn tire is composed of up to 48 wt.% of a soft
elastomeric rubber phase, this led to different ways to reuse, revalorize and recycling the
rubber particles after grinding (Bulei et al., 2018). One of the most common approaches
for using these rubber particles is to mix them with a polymeric binder to produce
composite materials (Kim and Lee, 2000; Plesuma et al., 2013). Furthermore, fiber
addition to these rubber composites, such as those recovered from the tire byproduct,
may also be an interesting alternative to improve the mechanical properties. The
resulting composites would combine the advantages of rubbers and rubber particles
(flexibility and elasticity) with the fibers (stiffness and strength) (Jacob et al., 2004). But
to improve the interactions between the rubbers/fibers with the matrix and achieve better
composite properties, the use of chemical treatment and compatibilizing agents has
been investigated (Colom et al., 2007; Moghaddamzadeh and Rodrigue, 2018a, 2018b).

The properties of rubber composites may change as a result of ageing, eventually to the
point where the material is no longer able of satisfying its function. Ageing depends on
several factors including formulation, polymer type and environmental conditions. The
latter generally takes place under normal ambient temperatures because increasing the

4
temperature accelerates the rate of these degradation processes. For example,
elastomers lose their rubber-like properties and sealability at low temperatures (Jacob et
al., 2006). It is important to note that rubber composites are often operating under
conditions where factors such as fatigue, creep, stress relaxation and chemical attack
are significant. Such materials can fail by progressive degradation resulting in
hardening, softening, crack growth or fracture (Jacob et al., 2006). Consequently, the
determination of mechanical properties remains important. Moreover, experiments such
as compression are time-dependent and cannot provide a complete idea about the time-
dependent viscoelastic nature of polymers. Hence, to give insight into the real properties
of polymers, long-term properties, such as stress relaxation and residual deformation,
need to be analyzed to get a complete picture (Jacob et al., 2006).

In this study, the elaboration of a new low-cost composite with high mechanical
performance is performed using compression molding at room temperature. This is done
by using a new binder based on a commercial polyurethane adhesive (Vinyprene
P2006) blended with a polyisocyanate hardener, before the recycled waste tire rubber
particles and their fibers byproduct are added. Also, the effect of particle halogenation is
investigated to improve the interfacial adhesion. Finally, as the properties of rubber
composites may change as a result of ageing, the determination of mechanical
properties at short (compression) and long (stress relaxation and residual deformation)
terms are determined.

2. EXPERIMENTAL DETAILS
2.1. Materials

The rubber particles (1.18 g/cm3) were obtained by grinding automobile tires (Figure 1)
in our laboratory with the following composition: the plasticizer (8 Wt.%), rubber
hydrocarbon (65 Wt.%), carbon black (25 Wt.%) and ash content (2 Wt.%). While, the
short fibers (1.49 g/cm3) were the tire byproducts. As the composite binder, a
commercial polyurethane adhesive Vinyprene P2006 (Intercolle, Casablanca, Morocco)
was mixed with the polyisocyanates hardener (Intercolle, Casablanca, Morocco). The
other chemical products used are the halogen powder and solvent based on

5
Trichloroisocyanuric Acid (1,3,5-trichloro-1,3,5-triazine-2,4,6-trione) supplied by
Intercolle, Casablanca, Morocco.

Figure 1: Schematic representation of the tire composition.

2.2. Used tire processing

A scrap tire process can be simplified in three main steps: grinding, sieving and particles
separation as illustrated in Figure 2. For the whole tire, only the rubber parts (shreds)
can be ground and the parts of the radial steel tire are discarded. The first step is to cut
and sort out the tire shreds. For grinding, rubber pieces are fed into a Pulverisette-19
grinder (Fritsch GmbH, Germany) with a sieve opening of 4 mm, thus obtaining a
mixture of rubber particles and fibers of approximately 87.5:12.5 wt.%. Then, to get rid of
smaller rubber particles, the material (rubber+ fibers) is sieved through a 3 mm opening.
To recover only the rubber particles, the mixture was blended with water and subjected
to mechanical mixing in a tank. Under high-speed stirring, mechanical separation
allowed the fibers suspension to float on the water surface while the solid rubber
particles sank to the bottom. To determine the rubber particle sizes, a picture with about
200 particles was taken using a digital camera (Nikon D5300, Japan) under continuous
white LED backlight illuminator with dimensions of (114x114 mm2) (Opto Engineering,

6
Italy), and image analysis was done by the ImageJ software (National Institutes of
Health, USA) (Figure 3(a)). It is worth noting that the waste tire fibers were initially long
woven fibers integrated in the rubber, but the fiber length obtained was 3.0±0.5 mm due
to the grinding process. To determine the fiber diameters, optical microscopy (Nikon
Eclipse LV100ND microscope, Japan) was performed using about 50 fibers (Figure
3(b)). The results gave an average length of 3.00±1.25 mm and a fiber diameter of
90±10 µm as shown in Figure 3(a) and (b).

Figure 2: Schematic representation of the process starting with used tires to obtain the
rubber particles and fibers.

7
 Figure 3: Characterization of: (a) the rubber particle (R) sizes and (b) the fiber (RF)
diameters.

2.3. Particle surface modification

Chemical modification was used to improve the adhesion between the binder and the
particles. Both materials (R and RF) were chemically surface-treated by immersion in a
halogenated solvent containing 2 wt.% of halogen powder for 10 min at room
temperature under stirring. The treated materials were then rinsed with distilled water
and oven dried for 1 h at 60 °C (see Figure 2). Finally, the treated rubber particles size
was determined via the same technique used for the untreated ones giving an average
size of 2.16±0.85 mm (Figure 4).

Figure 4: Characterization of the treated rubber particle sizes.

2.4. Composites preparation

The treated and untreated materials (R and RF) were manually blended with the mixture
of binder and hardener according to the proportions in Table 1. The compounds were
compression molded in a square mold (100×100×10 mm3) using a semi-automatic press
(Carver Inc., USA) at room temperature for 72 h as illustrated in Figure 5. It is important
to note that the treated and untreated composites RFC/UT, RFC/T, RC/UT and RC/T

8
were manufactured at two different densities (0.7 g/cm3 and 0.9 g/cm3) following the bulk
density (b) defined as:

(2)

where m and V denote the composites mass and volume, respectively. So a total of 8
composites were produced (Table 1). All the samples were processed under the same
thermal history. Finally, the molded samples were cut according to the dimensions
needed for their characterization.

Figure 5: Composites preparation process.

9
 Table 1: Formulations used for the composites preparation.

Specimen Density Rubber Fibers Binder Hardener

Description Halogenation 3
code (g/cm ) (wt.%) (wt.%) (wt.%) (wt.%)
Untreated rubber
RC/UT 0.9 composites at No 0.98 70 0 27 3
d=0.9
Treated rubber
RC/T 0.9 composites at Yes 0.99 70 0 27 3
d=0.9
Untreated
(rubber + fiber)
RFC/UT 0.9 No 0.89 61.25 8.75 27 3
composites at
d=0.9
Treated (rubber
+ fiber)
RFC/T 0.9 Yes 0.92 61.25 8.75 27 3
composites at
d=0.9
Untreated rubber
RC/UT 0.7 composites at No 0.72 70 0 27 3
d=0.7
Treated rubber
RC/T 0.7 composites at Yes 0.76 70 0 27 3
d=0.7
Untreated
(rubber + fiber)
RFC/UT 0.7 No 0.69 61.25 8.75 27 3
composites at
d=0.7
Treated (rubber
+ fiber)
RFC/T 0.7 Yes 0.71 61.25 8.75 27 3
composites at
d=0.7

3. Characterization
3.1. Morphological analysis

The composites roughness after the halogenation was first obtained by observing the
morphology of the treated and untreated particles surface under a scanning electron
microscope (SEM) model FEI Quanta 200-ESEM (USA). The samples were coated with
a thin conductive gold layer to avoid charging under an accelerating voltage of 15 kV.
Then, a circular section (15 mm) was cut from the waste tire shreds and seen under the
optical microscopy (Nikon Eclipse LV100ND microscope, Japan).

3.2. FTIR analysis

Fourier Transform Infrared (FTIR) spectra were obtained by means of an ABB Bomem
FTLA 2000-102 spectrometer (Attenuated Total Reflectance (ATR): Specac Golden
Gate) for the treated rubber particles, untreated rubber particles and the halogen

10
powder. Each spectrum was obtained by the accumulation of 16 consecutive scans with
a resolution of 4 cm-1.

3.3. Porosity measurement

The composites porosity was calculated using the real and bulk densities. The real
densities (r) were determined using a Micrometrics AccuPyc II 1340 Gas Pycnometer
(USA), while the bulk densities (b) were calculated from the masses and volumes of the
samples. The porosity (P) was calculated as:

(2)

3.4. Mechanical testing

3.4.1. Bonding

Bonding tests were performed on a Tinius Olsen Horizon H10KT universal testing
machine operated in the tensile mode at a crosshead speed of 5 mm/min using a 5 kN
load cell. The samples were cut from tire shreds into rectangular specimens (20x60x5
mm3), then a section of (20x25 mm²) was considered to glue the specimens with the
binders, as shown in Figure 6. An average of three specimens was used to report
representative results.

Figure 6: Representative illustration of the bonding test.

11
 3.4.2. Compression

Compression tests were performed on a Tinius Olsen Horizon H10KT universal testing
machine at a crosshead speed of 5 mm/min using a 5 kN load cell. The elastic modulus
of the samples was determined from the stress/strain curve obtained from the
compressive test. For all the compositions, the molded samples were cut into prismatic
specimens (33x33x10 mm3). The compression properties are reported as the average of
three specimens.

3.4.3. Relaxation testing

In a relaxation test, performed on a Tinius Olsen Horizon H10KT universal test machine
at a crosshead speed of 5 mm/min using a 5 kN load cell, the composite is compressed
at a predetermined cross-head speed to a desired strain level (strain=30%) and the load
is measured, at which point the cross-head motion is stopped. The specimen continues
to strain inelastically under the action of the load applied. When the material is non-
elastically compressed, the applied load is relaxed according to the elastic compliance of
the specimen and load strain. From the compressive test, the relaxation time, relaxation
speed and relaxation rate (t/0) were determined from the time/stress curve as shown
in Figure 7. For all the compositions, the molded samples were cut into prismatic
specimens (33x33x10 mm3). The relaxation properties are reported as the average of
three specimens.

Figure 7: Typical curve of stress relaxation under compression.

12
 3.4.4. Residual deformation at compression state

The residual deformation test is intended to measure the ability of rubber composites to
retain their elastic properties after prolonged action of compressive stresses. Specimen
preparation and determination of the residual deformation under constant deflection
(25%) were carried out according to ASTM D395 (D 395 – 02 and Standard, 2003). The
set-up includes 2 compression plates, spacers and a clamping device as shown in
Figure 8. Cylindrical specimens with a diameter of 29 mm were introduced between two
steel plates with the spacer bars on each side and then compressed according to the
spacer thickness to maintain a constant deflection. Then, the set-up is left for 72 h in an
oven at 55 °C. Finally, the residual deformation is measured 30 min after specimen
demolding and cooling via:

(2)

where C denotes the residual deformation, t0 and ti are the original and final thickness of
the specimen respectively, and tn refers to the spacer bar thickness.

Figure 8: Schematic representation of the residual deformation test.

13
 4. Results and discussion
4.1. Morphological analysis

SEM and microscopic images of the treated and untreated rubber particles are
presented in Figure 9. It can be easily seen that untreated particles have a smooth
surface (Figure 9 (a, a‘,c)) which is not suitable for good mechanical adhesion with the
matrix. On the other hand, the particles have a much rougher surface after chemical
treatment (halogenation) (Figure 9 (b, b‘,d)), including the formation of micropores and
cavities improving mechanical interlocking with the matrix. This increase in surface
roughness is associated to the halogenation treatment being able to degrade and
remove some specific components of the tire formulation (Colom et al., 2007; Sivaraos
et al., 2013).

14
Figure 9: SEM images of waste tire rubber particles: (a) untreated rubber particles
(R/UT) and (b) treated rubber particles (R/T); (b) at 500X; (a‘) R/UT and (b‘) R/T at
1000X. Microscope images: (c) untreated rubber and (d) treated rubber

15
 4.2. FTIR analysis

Chemical changes produced by the halogenation treatment can also be determined by

FTIR spectroscopy. Figure 10 shows the spectra in the 600-4000 cm-1 region for the
halogen powder, and the untreated and treated rubber particles. The ATR-IR spectra of
the halogen powders show the absorption bands due to N–H (3300, 1154, 700, and 800
cm-1) of isocyanuric acid created by the powder reaction with the environmental moisture
(García-Martín et al., 2010). The bands at 2275 and 1361 cm-1 are assigned to N=C=O
and C–N successively. While the picks at 1738 and 1668 appear due to C=O stretching
(García-Martín et al., 2010).

In the IR spectrum of R/T, the band at 3220 cm−1 is assigned to the O–H stretching
vibration, while at 3111 and 1710 cm−1 the –CH stretching vibration of ring hydrogens
present in the styrene group and the C=O stretching vibration in the carboxylic groups
are respectively seen (Khan et al., 2017; Shanmugharaj et al., 2005). The strong band at
1640 cm−1 corresponds to the polyisoprene C=C backbone, while the weak band at
1540 cm−1 is related to zinc stearate (Colom et al., 2007). The lower intensity of the
bands at 1430 and 875 cm−1 and the appearance of new bands at 1402 and 1121 cm−1
is an indication of the O=S=O stretching absorption (Colom et al., 2007). The peak at
680 cm−1 represents the –C-C– stretching in the –C-CH3 group and a ring deformation
vibration of styrene (Shanmugharaj et al., 2005). A weak band at 1739 cm−1 is observed
in the R/UT spectra associated with the thermal oxidation due to surface exposure to
oxygen leading to the formation of an oxidation skin made of carbonyl groups (Colom et
al., 2007). Finally, the band at 1026 cm−1, present in both spectra, is assigned to carbon
black (Colom et al., 2007).

16
 Figure 10: FTIR spectra of the treated (R/T) and untreated (R/UT) waste tire rubber
particles.

4.3. Porosity measurement

Figure 11 reports on the porosity of all the samples. It can be seen that increasing the
density from 0.7 to 0.9 g/cm3 significantly decreases the porosity. It can be observed
that the porosity decrease by 47% for the untreated (rubber + fiber) composites
(RFC/UT) and by 80% for the untreated rubber composites (RC/UT). This is consistent
with the fact that a higher content of recycled rubber fills up more voids, thus lowering
the sample porosity and forming a more compact composite with less pores upon curing
(Murray et al., 2014). On the other hand, the chemical modification of the materials
surface for both densities (0.7 and 0.9) increases the porosity. This can probably be
explained by the decrease in the particle size distribution (from 3.0 to 2.2 mm) of the
rubber crumb after chemical modification (Mahzan et al., 2010).

17
 Figure 11: Porosity of the composites.

4.4. Mechanical testing

4.4.1. Bonding test

Figure 12 shows that the treated materials have a very high bonding strength compared
to the untreated one under the same conditions. In the former case, the section where
the materials are glued remained intact, while a tear of the rubbery part was observed
(Figure 12b). On the other hand, an unsteady peel-off was observed for the untreated
materials (Figure 12a). As reported in the morphological analysis, the chemical
treatment increased the rubber surface roughness which improved the binder ability to
interact with all the components (Jacob et al., 2004).

Figure 12: Bonding test of: (a) untreated and (b) treated materials.

18
 4.4.2. Compression testing

Figure 13 shows the mechanical properties of the samples at both densities in terms of
the compression modulus, strain at yield and compressive strength. The first observation
is that increasing the density from 0.7 to 0.9 g/cm3 leads to a significant improvement in
all the properties (compression modulus, strain at yield and compressive strength). As
reported before in the porosity measurements, higher density is related to lower porosity
and the formation of a more compact composite (less voids/defects) with higher internal
cohesion and interaction between all components (Murray et al., 2014).

On the other hand, the rubber composites exhibit higher compression properties than
the rubber/fiber composites. The compression modulus (Figure 13 a,b) decreases by
15% and 20% for the untreated and treated composites at 0.7 g/cm 3, compared with
20% and 23% at 0.9 g/cm3, respectively. This observation may be attributed to better
interaction provided by the rubber particles with the binder compared to the fibers. In
fact, the hydrophobic nature of rubber particles enhances the interface adhesion with the
binder leading to better compression properties (Subramaniyan et al., 2013). But lower
strain at break (Figure 13 a‘,b‘) indicates that the fiber addition decreases the
composites resilience and toughness due higher rubber molecules mobility restriction
(Ismail et al., 2002; Jacob et al., 2004). Finally, the lower compressive strength (Figure
13 a‘‘,b‘‘) is due to the presence of fibers between the rubber particles disrupting the
regular conformation and interaction between the rubber molecules, thereby causing a
loss of its crystallization capacity. In general, rubbers inherently have high strengths due
to strain-induced crystallization. So when fiber reinforced rubber composites is subjected
to load, the fibers act as carriers of load and stress is transferred from matrix along the
fibers leading to effective and uniform stress distribution which results in a composite
having good mechanical properties. In our case, the fibers are not capable of
transferring load to one another and stress gets accumulated at certain points of
composite due to the low levels of fiber loading, thus leading to low tensile strength.
(Jacob et al., 2004). Also, the fibers generally tend to tear the structure/network wall
leading to the bonding system losing its strength (Subramaniyan et al., 2013).

19
It is also important to emphasize that the chemical treatment drastically increased the
compression properties (modulus, strain at yield and strength). As observed from the
bonding tests, the halogenation increased the rubber and fiber surface roughness,
hence improving the interfacial contact areas and mechanical interactions in the
composites (Jacob et al., 2004).

Figure 13: Compression modulus, strain at yield and compression strength for the
composites at: (a, a‘ and a‘‘) d=0.7 g/cm3 and (b, b‘ and b‘‘) d=0.9 g/cm3.

20
 4.4.3. Relaxation test

Generally, when a constant strain is applied to a rubber composite, the force necessary
to maintain this strain is not constant but decreases with time; this behavior is called
‗‗stress relaxation‘‘(Amin et al., 2006). The term ―relaxation‖ denotes a process of
tending towards a statistic equilibrium in a physical or physico-chemical system and the
rate depends upon the probability of transition from one state of equilibrium to another
(Amin et al., 2006). Two distinct causes for stress relaxation are known: physical and
chemical. Under normal conditions, both processes can occur simultaneously (Amin et
al., 2006). At high temperatures and/or long time periods, chemical processes are
dominant while at ambient to low temperatures and/or short time periods, stress
relaxation is dominated by physical processes (Amin et al., 2006). The main difference
between them, in terms of their impact on rubber compression set properties, is that
specific physical processes such as entanglements, diffusion of chain ends or cell wall
buckling have the potential to recover with time while all chemical relaxation processes
are non-recoverable (irreversible) (Jacob et al., 2006). Figure 14 presents the variation
of relaxation time, relaxation speed and relaxation ratio for the composites at both
densities (d=0.7 and 0.9 g/cm3). It can be seen that increasing the composite density
increases the relaxation properties in terms of relaxation time, speed and rate. This can
be explained by the formation of a more compact material with higher internal cohesion
and interaction due to lower porosity, as explained before (Murray et al., 2014). On the
other hand, it was observed that fiber addition to the rubber composites decreases the
relaxation properties. As expected, the complete relaxation in rubber composites is due
to the rubber molecules alone. But when fibers are added, the relaxation process is
hindered due to the fiber-fiber and fiber-rubber interface and thus decreasing the
relaxation (Jacob et al., 2006). Figure 14 also depicts a decrease of relaxation time and
rate with chemical modification. This can be attributed to better adhesion in treated
composites. For untreated materials, interfacial adhesion is leading to particles being
easily pulled-out from the matrix leaving behind gaps/cavities without possible stress
transfer. But treated fibers break and are not fully extracted from the matrix (Jacob et al.,
2006).

21
 Figure 14: Relaxation time, relaxation speed and relaxation rate for the composites

at d=0.7 g/cm3 and d=0.9 g/cm3.

4.4.4. Residual deformation testing

Generally, residual deformation is associated with plastic deformation and the formation
of voids or cavitation (structural changes). Also, material deformation to a specific strain
level should leads to voids creation (Kikuchi et al., 1991). On the other hand, the matrix
bonding the rubber particles is prevented from yielding and maintains an equivalent
stress, within the elastic limit which can be called the "elastic domain". The elastic
domains should act as an adhesive to connect the rubber particles providing a
mechanism for the strain recovery of two-phase systems. On the other hand, when this
two-phase system is further stretched, the domains start to yield resulting in limited
strain recovery; i.e. large residual strain (Kikuchi et al., 1991). The residual deformations
for the composites produced are in good agreement with the bonding (Figure 12),
compression (Figure 13) and relaxation (Figure 14) trends. As reported in Figure 15,
halogenation for composites at 0.7 g/cm3 have much lower residual deformation (66%)
for the rubber composites compared with only 18% for the rubber/fiber composites. As
the chemical treatment improves the interfacial compatibility, applying a certain strain
level to the composites will make it difficult to create voids owing to the strong bonds
formed between the binder and the reinforcements resulting in better crush performance
(Kikuchi et al., 1991). For the composites at 0.9 g/cm3, it has been observed that

22
halogenation increases the residual deformation. Generally, rubbers are composed of
long chains connecting filler particles together: a network resulting from the chemical
crosslinking of the rubber, and a ―van der Waals‖ type of network arising from the filler-
matrix interactions, both producing a reinforcing effect (F. Clement, L. Bokobza, 2001).
Thus increasing the reinforcement content (0.9 g/cm3) and adhesion by the chemical
treatment may lead the reinforcements acting as stress concentrators and promoting a
large number of micro-cracks and plastic deformations when the specimen was
compressed for 72 h at 55 °C. Micro-cracks initiation and propagation can lead to voids
formation consuming more energy and resulting in more limited strain recovery
(significant residual strain) (Tang et al., 2011).

Figure 15: Residual deformation of the composites.

5. Conclusion

This work presented a new hybrid composite from recycled waste tire rubber particles
and their fibers byproducts, introduced into a new matrix based on commercial
polyurethane adhesive (Vinyprene P2006) blended with a polyisocyanate hardener. The
aim of the elaborated material is to produce a low-cost composite for the manufacture of
damping tiles for playgrounds and sports fields. Thus, the samples were produced by
compression molding at room temperature. In particular, two parameters were

23
investigated: particle surface treatment via halogenation and final composite density (0.7
and 0.9 g/cm3). The results showed that both parameters had a substantial effect on the
composites mechanical performances. In fact, higher density led to lower porosity and
more interactions between the components while the chemical treatment was found to
increase the particle surface roughness improving the interfacial contact area and
possible mechanical interlocking between all the components in the composites.

Conflict of interest

This statement is to certify that all authors have seen and approved the manuscript
being submitted. We warrant that the article is the authors‘ original work. We warrant
that the article has not received prior publication and is not under consideration for
publication elsewhere. On behalf of all co-authors, the corresponding author shall bear
full responsibility for the submission

The authors declare that there is no conflict of interest.

ACKNOWLEDGMENTS

This work was supported by MAScIR; Moroccan Foundation for Advanced Science,
Innovation and Research, MESRSFC and CNRST, Morocco Grant no.1970/15. The
authors would like to thank Mr. Mehdi Ait Dahi for his fruitful technical support and
assistance.

24
References

Amin, A.F.M.S., Lion, A., Sekita, S., Okui, Y., 2006. Nonlinear dependence of viscosity
in modeling the rate-dependent response of natural and high damping rubbers in
compression and shear: Experimental identification and numerical verification. Int.
J. Plast. 22, 1610–1657. https://doi.org/10.1016/j.ijplas.2005.09.005

Bulei, C., Todor, M.P., Heput, T., Kiss, I., 2018. Directions for material recovery of used
tires and their use in the production of new products intended for the industry of civil
construction and pavements. Mater. Sci. Eng. 294, 1–9.
https://doi.org/10.1088/1757-899X/294/1/012064

Cao, W., 2007. Study on properties of recycled tire rubber modified asphalt mixtures
using dry process. Constr. Build. Mater. 21, 1011–1015.
https://doi.org/10.1016/j.conbuildmat.2006.02.004

Colom, X., Carrillo, F., Can, J., 2007. Composites reinforced with reused tyres : Surface
oxidant treatment to improve the interfacial compatibility. Compos. Part A 38, 44–
50. https://doi.org/10.1016/j.compositesa.2006.01.022

D 395 – 02, Standard, 2003. Standard Test Methods for Rubber Property —
Compression Set1. ASTM Stand. 98, 1–22.

F. Clement, L. Bokobza, L.M., 2001. On the mullins effect in silica-filled

polydimethylsiloxane networks. RUBBER Chem. Technol. 74, 847–870.
https://doi.org/10.5254/1.3547657

García-Martín, C., Andreu-Gómez, V., Miguel Martín-Martínez, J., 2010. Surface

modification of vulcanized styrenebutadiene rubber with trichloroisocyanuric acid
solutions of different active chlorine contents. Int. J. Adhes. Adhes. 30, 550–558.
https://doi.org/10.1016/j.ijadhadh.2010.06.004

Ismail, H., Shuhelmy, S., Edyham, M.R., 2002. The effects of a silane coupling agent on
curing characteristics and mechanical properties of bamboo fibre filled natural
rubber composites. Eur. Polym. J. 38, 39–47. https://doi.org/10.1016/S0014-

25
 3057(01)00113-6

Jacob, M., Jose, S., Thomas, S., Varughese, K.T., 2006. Stress relaxation and thermal
analysis of hybrid biofiber reinforced rubber biocomposites. J. Reinf. Plast. Compos.
25, 1903–1917. https://doi.org/10.1177/0731684406069919

Jacob, M., Thomas, S., Varughese, K.T., 2004. Mechanical properties of sisal/oil palm
hybrid fiber reinforced natural rubber composites. Compos. Sci. Technol. 64, 955–
965. https://doi.org/10.1016/S0266-3538(03)00261-6

Karakurt, C., 2015. Microstructure properties of waste tire rubber composites: an

overview. J. Mater. Cycles Waste Manag. 17, 422–433.
https://doi.org/10.1007/s10163-014-0263-9

Khan, T.A., Rahman, R., Khan, E.A., 2017. Adsorption of malachite green and methyl
orange onto waste tyre activated carbon using batch and fixed-bed techniques:
isotherm and kinetics modeling. Model. Earth Syst. Environ. 3, 37–50.
https://doi.org/10.1007/s40808-017-0284-1

Kikuchi, Y., Fukui, T., Okada, T., Inoue, T., 1991. Elastic-Plastic Analysis of the
Deformation Mechanism of PP-EPDM Thermoplastic Elastomer: Origin of Rubber
Elasticity. Polym. Eng. Sci. 31, 1029–1032. https://doi.org/10.1002/pen.760311406

Kim, J.I.N.K.U.K., Lee, S.H.Y.O., 2000. New Technology of Crumb Rubber

Compounding for Recycling of Waste Tires. Appl. Polym. Sci. 78, 1573–1577.

Lucignano, C., Gugliemotti, A., Quadrini, F., 2012. Compression Moulding of Rubber
Powder from Exhausted Tyres. Polym. Plast. Technol. Eng. 51, 340–344.
https://doi.org/10.1080/03602559.2011.625378

Mahzan, S., Zaidi, A.M.A., Arsat, N., Hatta, M.N.M., Ghazali, M.I., Mohideen, S.R., 2010.
Study on Sound Absorption Properties of Coconut Coir Fibre Reinforced Composite
with Added Recycled Rubber. Integr. Eng. 2, 29–34.

Moghaddamzadeh, S., Rodrigue, D., 2018a. The effect of polyester recycled tire fibers
mixed with ground tire rubber on polyethylene composites. Part I. Prog. Rubber,

26
 Plast. Recycl. Technol. 34, 200–220. https://doi.org/10.1177/1477760618798267

Moghaddamzadeh, S., Rodrigue, D., 2018b. The effect of polyester recycled tire fibers
mixed with ground tire rubber on polyethylene composites. Part II. Prog. Rubber,
Plast. Recycl. Technol. 34, 128–142. https://doi.org/10.1177/1477760618798268

Murray, C.A., Snyder, K.S., Marion, B.A., 2014. Characterization of permeable

pavement materials based on recycled rubber and chitosan. Constr. Build. Mater.
69, 221–231. https://doi.org/10.1016/j.conbuildmat.2014.07.047

Plesuma, R., Megne, A., Malers, L., 2013. Mechanical Properties of the Composite
Material Based on Modified Scrap Tires and Polymer. Plast. Recycl. Technol. 29,
177–187. https://doi.org/10.1177/147776061302900304

Shanmugharaj, A.M., Kim, J.K., Ryu, S.H., 2005. UV surface modification of waste tire
powder: Characterization and its influence on the properties of polypropylene/waste
powder composites. Polym. Test. 24, 739–745.
https://doi.org/10.1016/j.polymertesting.2005.04.006

Sivaraos, Yap, T.C., Qumrul, Amran, M.A., Anand, T.J.S., Izamshah, R., Aziz, A.A.,
2013. Friction performance analysis of waste tire rubber powder reinforced
polypropylene using pin-on-disk tribometer. Procedia Eng. 68, 743–749.
https://doi.org/10.1016/j.proeng.2013.12.248

Subramaniyan, S.K., Mahzan, S., Ghazali, M.I., Ismon, M., Mujahid, A., Zaidi, A., 2013.
Mechanical Behavior of Polyurethane Composite Foams from Kenaf Fiber and
Recycled Tire Rubber Particles 315, 861–866.
https://doi.org/10.4028/www.scientific.net/AMM.315.861

Tang, Y., Deng, S., Ye, L., Yang, C., Yuan, Q., Zhang, J., Zhao, C., 2011. Effects of
unfolded and intercalated halloysites on mechanical properties of halloysite–epoxy
nanocomposites. Compos. Part A 42, 345–354.
https://doi.org/10.1016/j.compositesa.2010.12.003

Xiaowei, C., Sheng, H., Xiaoyang, G., Wenhui, D., 2017. Crumb waste tire rubber

27
 surface modification by plasma polymerization of ethanol and its application on oil-
well cement. Appl. Surf. Sci. 409, 325–342.
https://doi.org/10.1016/j.apsusc.2017.03.072

Zhang, J.L., Chen, H.X., Ke, C.M., Zhou, Y., Lu, H.Z., Wang, D.L., 2012. Graft
polymerization of styrene onto waste rubber powder and surface characterization of
graft copolymer. Polym. Bull. 68, 789–801. https://doi.org/10.1007/s00289-011-
0586-9

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Figure Captions:

Figure 1: Schematic representation of the tire composition.

Figure 2: Schematic representation of the process starting with used tires to get the
rubber particles and fibers.

Figure 3: Characterization of: (a) the rubber particle (R) sizes and (b) the fiber (RF)
diameters.

Figure 4: Characterization of the treated rubber particle sizes.

Figure 5: Composites preparation process.

Figure 6: Representative illustration of the bonding test.

Figure 7: Typical curve of stress relaxation under compression.

Figure 8: Schematic representation of the residual deformation test.

Figure 9: SEM images of waste tire rubber particles: (a) R/T and (b) R/UT (b) at 500X;
(a‘) R/T and (b‘) R/UT at 1000X.

Figure 10: FTIR spectra of the treated (R/T) and untreated (R/UT) waste tire rubber
particles.

Figure 11: Porosity of the composites.

Figure 12: Bonding test of: (a) untreated and (b) treated materials.

Figure 13: Compression modulus, strain at yield and compression strength for the
composites at: (a, a‘ and a‘‘) d=0.7 g/cm3 and (b, b‘ and b‘‘) d=0.9 g/cm3.

Figure 14: Relaxation time, relaxation speed and relaxation rate for the composites at
d=0.7 g/cm3 and d=0.9 g/cm3.

Figure 15: Residual deformation of the composites.

29