materials

Review
Waste Rubber Recycling: A Review on the Evolution
and Properties of Thermoplastic Elastomers
Ali Fazli and Denis Rodrigue *
Department of Department of Chemical Engineering, Université Laval, Quebec, QC G1V 0A6, Canada;
[email protected]
* Correspondence: [email protected]; Tel.: +1-418-656-2903




Received: 19 November 2019; Accepted: 5 February 2020; Published: 8 February 2020


Abstract: Currently, plastics and rubbers are broadly being used to produce a wide range of products
for several applications like automotive, building and construction, material handling, packaging,
toys, etc. However, their waste (materials after their end of life) do not degrade and remain for
a long period of time in the environment. The increase of polymeric waste materials’ generation
(plastics and rubbers) in the world led to the need to develop suitable methods to reuse these waste
materials and decrease their negative effects by simple disposal into the environment. Combustion
and landfilling as traditional methods of polymer waste elimination have several disadvantages such
as the formation of dust, fumes, and toxic gases in the air, as well as pollution of underground water
resources. From the point of energy consumption and environmental issues, polymer recycling is the
most efficient way to manage these waste materials. In the case of rubber recycling, the waste rubber
can go through size reduction, and the resulting powders can be melt blended with thermoplastic resins
to produce thermoplastic elastomer (TPE) compounds. TPE are multi-functional polymeric materials
combining the processability of thermoplastics and the elasticity of rubbers. However, these materials
show poor mechanical performance as a result of the incompatibility and immiscibility of most polymer
blends. Therefore, the main problem associated with TPE production from recycled materials via melt
blending is the low affinity and interaction between the thermoplastic matrix and the crosslinked rubber.
This leads to phase separation and weak adhesion between both phases. In this review, the latest
developments related to recycled rubbers in TPE are presented, as well as the different compatibilisation
methods used to improve the adhesion between waste rubbers and thermoplastic resins. Finally, a
conclusion on the current situation is provided with openings for future works.

Keywords: rubber; recycling; waste polymers; thermoplastic elastomer; compatibilisation

1. Introduction
Rubber, as an elastomeric material, has the ability of reversible deformation (between 100 up
to 1000%), which is significantly influenced by its chemical structure and molecular weight (MW).
Ideally, rubber chains should return to their original shape after removing the applied force (stress).
The macromolecular chains of rubber are long and oriented without large substituents, which makes
them capable of moving and rotating around chemical bonds at low temperatures because of their low
glass transition temperature (Tg). Increasing irregularities in the polymer chains or the presence of
large substituents (styrene-butadiene rubbers (SBR)) leads to higher rubber Tg.
The production of high-quality rubber at a large scale with a low cost substantially increased
with the development of efficient vulcanisation processes. Vulcanisation is defined as the irreversible
crosslinking reaction via curing agents (sulfur or peroxide materials) to form a three-dimensional
(3D) network between the rubber macromolecules. Several parameters must be controlled in the
rubber vulcanisation process such as curing time, temperature, and fillers having a direct effect on the

Materials 2020, 13, 782; doi:10.3390/ma13030782 www.mdpi.com/journal/materials

Materials 2020, 13, 782 2 of 31

chemical, mechanical, and physical properties of crosslinked rubbers. Incorporation of vulcanizing

agents into an unsaturated rubber improves the rubber strength due to the crosslinked structure
created. Therefore, vulcanized rubber as an elastic, insoluble, and infusible thermoset material cannot
be directly reprocessed. This is an important limitation for material recycling, especially after the
end of life of a part. Depending on the final application, different rubbers are mixed with different
components and additives. For instance, stabilisers, anti-oxidants, and anti-ozonants are being used in
rubber formulation to make tires extremely resistant to severe outdoor conditions (chemical reagents,
high temperatures, radiations, and shear stress) during their lifetime [1–3].
Tires as the main application of rubber industries are complex materials containing several
components suitable to operate in a wide range of environment. Rubber is the main component used
for tire manufacturing, which can be classified into natural rubber (NR), SBR, nitrile-butadiene rubber
(NBR), and ethylene–propylene–diene-monomer rubber (EPDM). However, the presence of reinforcing
fillers, antioxidants, antiozonants, and curating agents in tire formulation makes them resistant to
biodegradation, photochemical decomposition, and high temperatures [2,4]. Therefore, waste tires’
management is an important issue with respect to the global growth of tire industries. This paper
reviews the progress of waste tire recycling focused on melt blending of ground tire rubber (GTR) with
thermoplastic matrix. Furthermore, this review presents developments in surface modification and
devulcanisation of GTR and compatibilisation of thermoplastic elastomer (TPE) blends to improve the
interfacial adhesion of GTR and thermoplastic matrix.

1.1. Microstructural Composition

1.1.1. Elastomers
NR is extensively used in rubber production as an elastomer component. NR with high MW
and long chain branches has the ability to crystallize quickly under stretching, leading to high tensile
strength and tear growth resistance. Usually, NR is mixed with other synthetic rubbers such as
butadiene rubber (BR), hydrogenated nitrile-butadiene rubber (HNBR), SBR, NBR, and EPDM to
further improve its properties (tensile strength and tear growth resistance) in tire manufacturing [5].

1.1.2. Fillers
Different fillers such as carbon black (CB), precipitated silica, and clay have been used in rubber
formulation to improve the rubber strength. This is done via the formation of a flexible filler network
and strong polymer-filler interactions [6]. Stiffening fillers (CB and silica) improve rubber stiffness,
tensile and tear strength, hardness, and rupture modulus as a result of increased chain entanglements
and shear strength between the polymer chains. Montmorillonite, synthetic mica, and saponite
are clay-based fillers used in rubber production due to better mechanical properties’ improvement
compared to CB [7]. For example, Okada [8] reported the positive effect of 10 vol.% of organoclay in
NBR to achieve similar tensile strengths as rubber formulations with 40 vol.% CB. However, the rubber
microstructure might be affected by the size, shape, and molecular structure of the fillers [9].

1.1.3. Other Additives

Several materials have been used to increase the durability and accelerate the crosslinking reaction
of rubber compounds. For instance, zinc oxide has been used as an activator during vulcanisation.
Mild extract solvate (MES), naphthenic oil, treated distillate aromatic extract (TDAE), and paraffinic
oils are being used to improve the rubber’s processability [9]. Nevertheless, the type and level of filler
addition strongly depend on the rubber matrix being used.

1.2. Rubbers Types

Rubbers can be categorized into different groups: saturated/unsaturated, natural/synthetic, etc.
However, according to the application and properties required, there are general rubbers and special
Materials 2020, 13, x FOR PEER REVIEW 3 of 31

rubbers. General rubbers are relatively low-cost materials produced and consumed in large volume,
while
Materialsspecial
Materials 2020,13,
2020, xrubbers
13,782FOR PEERhave special
REVIEW properties such as thermal stability/fire resistance, aging 33 of 31
31
resistance, chemical resistance, and swelling resistance in non-polar oils, as well as their elastic
rubbers. General
properties. Some rubbers are relatively
of the most low-cost
used rubber materials
materials in produced
industriesand are consumed
described in tolarge
get avolume,
better
rubbers. General
while special of rubbers
rubbers are relatively
have special low-cost materials produced and consumed
properties such as thermal stability/fire resistance, in large volume,
aging
understanding their properties and applications.
while specialchemical
resistance, rubbers have specialand
resistance, properties
swellingsuch as thermal
resistance in stability/fire
non-polar oils, resistance,
as wellaging resistance,
as their elastic
chemical resistance,
properties.
1.2.1. Natural Some
Rubberofand
theswelling
most usedresistance
rubber in materials
non-polar in oils, as well asare
industries their elastic properties.
described to get a Somebetter
of the most used rubber materials in industries
understanding of their properties and applications. are described to get a better understanding of their
NR isand
properties a biopolymer
applications.based on cis-1,4-polyisoprene with a vegetable origin obtained from Hevea
brasiliensis (Figure 1). NR is an unsaturated rubber with long, regular, flexible, and linear
1.2.1. Natural Rubber
1.2.1. Natural Rubber
macromolecules, as well as high elastic properties (Tg ~ −70 °C). Unvulcanised NR can be reversibly
NR is a biopolymer based on cis-1,4-polyisoprene
elongated under high deformation up to 800–1000% with due atovegetable
its highly origin obtained
resilient from Hevea
characteristics.
NR is a biopolymer based on cis-1,4-polyisoprene with a vegetable origin obtained from
brasiliensisseveral
Although (Figure 1). NR
curing is are
agents an available,
unsaturated NR rubber
is almost with
alwayslong, regular, by
vulcanized flexible, and linear
sulfur-containing
Hevea brasiliensis (Figure 1). NR is an unsaturated rubber with long, regular, flexible, and linear
macromolecules,
curing as well aspoor
systems. Despite high chemical
elastic properties
resistance(Tgand
~ −70processability,
°C). Unvulcanised NR NR
showscan be
good reversibly
elastic
macromolecules, as well as high elastic properties (Tg ~ −70 ◦ C). Unvulcanised NR can be reversibly
elongated under high deformation up to 800–1000% due to its highly
properties, resilience, and damping. The low aging resistance of NR is due to its poor stability resilient characteristics.
elongated under high deformation up to 800–1000% due to its highly resilient characteristics. Although
Although
towards several
ozone andcuring
oxygen.agents are available,
This rubber is mainlyNRused
is almost
for thealways vulcanized
production of tires,by sulfur-containing
gloves, toys, elastic
several curing agents are available, NR is almost always vulcanized by sulfur-containing curing
curing systems. Despite poor chemical
bands, erasers, and sports equipment [10–12]. resistance and processability, NR shows good elastic
systems. Despite poor chemical resistance and processability, NR shows good elastic properties,
properties, resilience, and damping. The low aging resistance of NR is due to its poor stability
resilience, and damping. The low aging resistance of NR is due to its poor stability towards ozone and
towards ozone and oxygen. This rubber is mainly used for the production of tires, gloves, toys, elastic
oxygen. This rubber is mainly used for the production of tires, gloves, toys, elastic bands, erasers, and
bands, erasers, and sports equipment [10–12].
sports equipment [10–12].

Figure 1. Chemical structure of isoprene and natural rubber (NR) (polyisoprene). Adapted with
permission from [12]; copyright 2019 Elsevier Ltd.
Figure 1. Chemical structure of isoprene and natural rubber (NR) (polyisoprene). Adapted with
1.2.2.permission
Synthetic
Figure from [12];structure
Rubbers
1. Chemical copyrightof
2019 Elsevier
isoprene Ltd.natural rubber (NR) (polyisoprene). Adapted with
and
permission from [12]; copyright 2019 Elsevier Ltd.
1.2.2. Synthetic Rubbers
1.2.2.1. Styrene-Butadiene Rubber
1.2.2. Synthetic Rubbers
Styrene-Butadiene Rubber
SBR is made from the copolymers of styrene and butadiene (Figure 2), but its properties are
mainly affected by
SBRStyrene-Butadienethe polymer
is made from the copolymers chains’ of structure
styrene andand styrene (Figure
butadiene content.2),
SBR
butcannot crystallize
its properties under
are mainly
1.2.2.1. Rubber
stress and
affected byisthe
mostly vulcanized
polymer chains’bystructure
sulfur agents. Currently,
and styrene free radical
content. copolymerisation
SBR cannot in emulsion
crystallize under stress
SBR is made from the copolymers of styrene and butadiene (Figure 2),
and is mostly vulcanized by sulfur agents. Currently, free radical copolymerisation in emulsion SBR
and anionic copolymerisation in solution are the main copolymerisation but its properties
methods for are
and
mainly copolymerisation
anionic affected
preparation. SBRby the
has lowpolymer chains’
inmechanical
solution structure
arestrength,
the and styrene
mainmaking content.
it necessary
copolymerisation SBRreinforcing
to add
methods cannot
for crystallize under
fillers into
SBR preparation. its
SBR
stress
has and
formulation. is mostly vulcanized
SBR hasstrength,
low mechanical been used by sulfur
in automotive
making agents.
it necessary Currently,
industries, free radical copolymerisation
especially fillers
to add reinforcing for carinto
tires,
itsbecause in emulsion
of its high
formulation. SBR
and
abrasionanionic copolymerisation
resistance, thermal in
stability, solution
and are
resistance the main
against copolymerisation
crack formation (better
has been used in automotive industries, especially for car tires, because of its high abrasion resistance,methods
than NR for
and SBR
BR).
preparation.
However, SBRSBRis has
less low mechanical
chemically reactive strength,
with making
slow curing it necessary
kinetics, to
whichadd reinforcing
requires
thermal stability, and resistance against crack formation (better than NR and BR). However, SBR is less more fillers into
accelerators its
formulation.
[12,13].
chemically SBR has been used in automotive industries, especially for
reactive with slow curing kinetics, which requires more accelerators [12,13]. car tires, because of its high
abrasion resistance, thermal stability, and resistance against crack formation (better than NR and BR).
However, SBR is less chemically reactive with slow curing kinetics, which requires more accelerators
[12,13].

Figure 2. Chemical structure of styrene-butadiene rubber (SBR). Adapted with permission from [12];
copyright 2019 Elsevier Ltd.
Materials 2020, 13, x FOR PEER REVIEW 4 of 31
Materials 2020, 13, x FOR PEER REVIEW 4 of 31
Figure 2. Chemical structure of styrene-butadiene rubber (SBR). Adapted with permission from [12];
copyright
Figure 2019 Elsevier
2. Chemical Ltd. of styrene-butadiene rubber (SBR). Adapted with permission from [12];
structure
copyright
Materials 2020, 13,2019
782 Elsevier Ltd. 4 of 31
1.2.2.2. Nitrile-Butadiene Rubber
1.2.2.2.
AsNitrile-Butadiene
shown in FigureRubber 3 NBR is made from the copolymers of acrylonitrile and butadiene via
Nitrile-Butadiene
radical Rubber in emulsion at low temperature (5–30 °C). NBR does not crystallize under
copolymerisation
As shown in Figure 3 NBR is made from the copolymers of acrylonitrile and butadiene via
stressAsand
radical shownhas low
copolymerisationtensile
in Figure strength,
3 in
NBR but
is made
emulsion shows
atfrom
low the good resistance
copolymers
temperature to non-polar
of acrylonitrile
(5–30 °C). NBR doesandsolvents,
butadiene
not fats,via
crystallizeoils, and
radical
under
motor andfuel.has
copolymerisationOillow
resistance
intensile
emulsionis directly dependent
at lowbut
temperature on(5–30
the ◦ C). NBR does
acrylonitrile content. The NBR
not crystallize structure
under is
stress
stress strength, shows good resistance to non-polar solvents, fats, oils, and
determined
and
motor hasfuel.
lowOilby its
tensile preparation
strength,
resistance method
but shows
is directly and changes
good resistance
dependent from linear to
to non-polarcontent.
on the acrylonitrile highly branched
solvents,The
fats,NBR molecules
oils,structure
and motor is
according
fuel.
determined to by
the its
Oil resistance copolymerisation
ispreparation temperature.
directly dependent
method onand Swellingfrom
the acrylonitrile
changes resistance
content. intonon-polar
linearThe agentsisand
NBR structure
highly branched Tg both
determined
molecules
increase
by
according with
its preparation
to theincreasing
methodacrylonitrile
copolymerisationand changes content. NBRtohas
from linear
temperature. Swelling been
highly widely
branched
resistance used foragents
molecules
in non-polar sealing
according
and tubes, oil
Tgtoboth
the
transport equipment,
copolymerisation
increase with increasing and other
temperature. devices
Swelling
acrylonitrile with
content.oil resistance
resistance
NBRinhas [12].
non-polar agentsused
been widely and Tgforboth increase
sealing tubes,with
oil
increasing acrylonitrileand
transport equipment, content.
other NBR haswith
devices beenoil
widely used [12].
resistance for sealing tubes, oil transport equipment,
and other devices with oil resistance [12].

Figure 3.3.Monomers
Figure Monomers andand polymer
polymer structure
structure of nitrile-butadiene
of nitrile-butadiene rubberAdapted
rubber (NBR). (NBR). with
Adapted with
permission
permission
Figure
from from [12]
3. copyright
[12]; Monomers ; copyright
2019and 2019
polymer
Elsevier Elsevier Ltd.
Ltd.structure of nitrile-butadiene rubber (NBR). Adapted with
permission from [12]; copyright 2019 Elsevier Ltd.
Ethylene-Propylene-Diene Monomer
1.2.2.3. Ethylene-Propylene-Diene Monomer
1.2.2.3.
EPDMEthylene-Propylene-Diene
is aa terpolymer
terpolymer of Monomerpropylene,
of ethylene,
ethylene, propylene, and a non-conjugated
non-conjugated diene with residualresidual
unsaturation in
EPDM is a the the side chain.
side chain.
terpolymer This synthetic
This synthetic
of ethylene, rubber with
rubberand
propylene, with a non-polar backbone shows
a non-conjugated diene with residual better
resistance
unsaturation to heat, light,
in the sideand ozone
chain. compared
This syntheticto unsaturated
rubber withrubbers (NR orbackbone
a non-polar SBR). One of thebetter
shows most
most
important grades of EPDM
EPDM is
is with
with 5-ethylidene-2-norborene
5-ethylidene-2-norborene (ENB) as
as aa diene
diene (Figure
(Figure
resistance to heat, light, and ozone compared to unsaturated rubbers (NR or SBR). One of the most 4).
4). EPDM’s
EPDM’s
properties depend
dependofon
important grades on the
the ethylene
EPDM is with and
ethylene and propylene
propylene content.
content. The
5-ethylidene-2-norborene most
(ENB) assignificant properties
a diene (Figure of the
4). EPDM’s
vulcanized EPDM are ◦ C.
properties depend on the
theexcellent
ethyleneresistance to atmospheric
and propylene aging,
content. The oxygen,
most and ozone
significant up to 150
properties °C.
of the
EPDM can be
vulcanized curedare
EPDM bythe
peroxide or resistance
excellent sulfur systems, and these aging,
to atmospheric rubbersoxygen,
are extensively
and ozone used
up as
to sealing
150 °C.
materials
materials
EPDM can[12,14,15].
[12,14,15].
be cured Despite peroxidic
by peroxide curing,
or sulfur sulfurand
systems, vulcanisation of EPDM
these rubbers shows complex
are extensively used as reactions
sealing
induced
materialsby sulfur during
[12,14,15]. Despitecrosslinking, and sulfur
peroxidic curing, a few vulcanisation
kinetic numerical models
of EPDM showsarecomplex
available on the
reactions
accelerated sulfur
induced by sulfur vulcanisation
sulfurvulcanisation of EPDM
of EPDMand
during crosslinking, [16,17].
[16,17].
a few kinetic numerical models are available on the
accelerated sulfur vulcanisation of EPDM [16,17].

Chemical structure
Figure 4. Chemical structure of
of ethylene-propylene-diene
ethylene-propylene-diene monomer (EPDM)
(EPDM) containing
containing 5-ethylidene-
5-ethylidene-
2-norborene (ENB) as a diene. Adapted
Adapted with
with permission
permission from
from [15];
[15] ; copyright 2019 John Wiley and
Figure 4. Chemical structure of ethylene-propylene-diene monomer (EPDM) containing 5-ethylidene-
Sons Ltd.
2-norborene (ENB) as a diene. Adapted with permission from [15]; copyright 2019 John Wiley and
Sons Ltd.
Polyurethane
1.2.2.4. Polyurethane
PUPolyurethane
1.2.2.4. is produced by the polyaddition of diisocyanates and polyols (an alcohol having two or
more hydroxyl groups) (Figure 5). PU can be obtained in various chemical structures and different
properties because of the types of monomers, composition ratios, and reaction conditions. PU has
several advantages such as good abrasion and tear resistance, tensile strength, oxygen and ozone
hydroxyl groups)
Materials 2020, (Figure
13, x FOR 5). PU can be obtained in various chemical structures and different
PEER REVIEW 5 of 31
properties because of the types of monomers, composition ratios, and reaction conditions. PU has
severalPUadvantages
is producedsuchby theas polyaddition
good abrasion and tear resistance,
of diisocyanates tensile(an
and polyols strength, oxygentwo
alcohol having andorozone
more
resistance, and a low(Figure
hydroxyl groups) friction5).
coefficient.
PU can be Theobtained
largest application
in variousofchemical
PU is in automotive industries
structures and differentas
dampers,
properties
Materials flexible
2020, 13, 782 connections,
because of the types and
of electric lines composition
monomers, [18]. ratios, and reaction conditions. PU 5 ofhas
31
several advantages such as good abrasion and tear resistance, tensile strength, oxygen and ozone
resistance, and a low friction coefficient. The largest application of PU is in automotive industries as
resistance, and a low friction coefficient. The largest application of PU is in automotive industries as
dampers, flexible connections, and electric lines [18].
dampers, flexible connections, and electric lines [18].

Figure 5. Schematic representation of polyurethane (PU) and its monomers. Adapted with permission
from [18]; copyright 2019 RSC Publishing.
Figure 5. Schematic representation of polyurethane (PU) and its monomers. Adapted with permission
1.2.2.5. Silicone
Figure
from
Rubber 2019 RSC Publishing.
5. Schematic
[18]; copyright representation of polyurethane (PU) and its monomers. Adapted with permission
from [18]
Silicon ; copyright
rubber, also 2019
knownRSCasPublishing.
siloxanes, polyorganosiloxanes, or polysiloxanes, is produced by
Silicone Rubber
multilevel hydrolysis and subsequent condensation of dimethyldichlorosilane in an acid medium or
1.2.2.5. Silicone
Silicon Rubber
rubber, also known of ascyclotetrasiloxane,
siloxanes, polyorganosiloxanes, or polysiloxanes, is produced by
by ring opening polymerisation catalyzed by strong acids or bases. The polymer
multilevel
backbone
Silicon ishydrolysis
based and
rubber,onalso subsequent
a chain
known of siliconcondensation
and oxygen
as siloxanes, of dimethyldichlorosilane
atoms rather than
polyorganosiloxanes, carbon andin anhydrogen
or polysiloxanes, acid medium
atoms.
is produced or
by
by ring
Silicone opening
multilevelrubbers polymerisation
with aand
hydrolysis of cyclotetrasiloxane,
verysubsequent
flexible structure show high
condensation catalyzed by strong acids or
stability over a wide range
of dimethyldichlorosilane bases.
in anof acid The polymer
temperatures
medium or
backbone
(−70 tois250
°C opening
by ring based
°C) on a chain
[19]. of of
As shown
polymerisation silicon and oxygen
in Figure 6, thereatoms
cyclotetrasiloxane, rather
are four
catalyzed bythan
primary carbon
strong acids and
groups hydrogen
oridentified
bases. atoms.
Thebypolymer
letters
Silicone
forming rubbers
a typical with a very flexible
polysiloxane. structure
Silicon rubbersshow
are high
also stability
resistant over
to a
oxygen wideand
backbone is based on a chain of silicon and oxygen atoms rather than carbon and hydrogen atoms. range
ozone of temperatures
ageing, so this
(−70 ◦ C to 250 ◦ C) [19]. As shown in Figure 6, there are four primary groups identified by letters
rubber
Siliconeisrubbers
mainly with
used afor theflexible
very manufacture of tubing
structure for ozone
show high transport.
stability Finally,
over a wide rangesilicon rubbers are
of temperatures
forming
highly atotypical
(−70 °Cadhesive, 250 °C)polysiloxane.
hydrophobic,
[19]. As shownSilicon
and rubbers6,are
biocompatible,
in Figure also
making
there resistant
are to oxygen
this primary
four rubber and ozone
angroups
ideal material ageing,
identified forbyso this
medical
letters
rubber
implants is mainly
and used
other for
devicesthe manufacture
biocompatible of tubing
with human for ozone
organismstransport.
[10,14]. Finally,
forming a typical polysiloxane. Silicon rubbers are also resistant to oxygen and ozone ageing, so thissilicon rubbers are
highly adhesive, hydrophobic, and biocompatible, making this rubber an ideal material
rubber is mainly used for the manufacture of tubing for ozone transport. Finally, silicon rubbers are for medical
implants and other
highly adhesive, devices biocompatible
hydrophobic, with human
and biocompatible, organisms
making [10,14].
this rubber an ideal material for medical
implants and other devices biocompatible with human organisms [10,14].

Figure 6. The four groups making polysiloxanes: “M” is trimethylsiloxychlorosilanes (Me3 SiO), “D”
Figure
Me2 SiO6.2 , The
“T” four
MeSiOgroups
3 , andmaking polysiloxanes:
“Q” silicate (SiO4 ). For“M”
“P”,isreplace
trimethylsiloxychlorosilanes (Me3SiO),
Me by phenyl side groups, while“D”
for
Me2SiO
“V”, 2, “T”
replace MeMeSiO 3, and
by vinyl “Q”
side silicate
groups. (SiO4). with
Adapted For “P”, replace from
permission Me by phenyl
[12]; side groups,
copyright whileLtd.
2019 Elsevier for
“V”, replace Me by vinyl side groups. Adapted with permission from [12]; copyright 2019 Elsevier
2. Recycling
Ltd.
Figure 6. The four groups making polysiloxanes: “M” is trimethylsiloxychlorosilanes (Me3SiO), “D”
ItMeis2SiO
well known
2, “T” MeSiOthat polymer
3, and decomposition
“Q” silicate (biodegradation)
(SiO4). For “P”, takes side
replace Me by phenyl a long timewhile
groups, and for
causes
2. Recycling
harmful“V”, replace Me by vinyl side groups. Adapted with permission from [12]; copyright 2019 Elsevierissue.
environmental effects. Therefore, polymer wastes’ disposal is a serious environmental
Tires Itcontaining
Ltd. almostthat
is well known 50% polymer
rubber are polymeric materials.
decomposition The global production
(biodegradation) takes a long of time
rubber
andmaterials
causes
in 2017 was about 26.7 Mtons divided into 12.31 Mtons of NR and 14.46 Mtons of synthetic
harmful environmental effects. Therefore, polymer wastes’ disposal is a serious environmental issue. rubber [9].
2. Recycling
Discarded rubber almost
pipes, belts,
Tires containing 50% and shoes
rubber areare various types
polymeric of waste
materials. Therubber
globalproducts.
production However, the
of rubber
tire industries, as the main application of rubbers (65% of the global production), generate the largest
It is well known that polymer decomposition (biodegradation) takes a long time and causes
amounts of rubber waste materials. Therefore, rubber recycling is often defined as tire recycling.
harmful environmental effects. Therefore, polymer wastes’ disposal is a serious environmental issue.
Currently, 1.5 Bn tires/year are discarded worldwide containing up to 90% of vulcanized rubber that
Tires containing almost 50% rubber are polymeric materials. The global production of rubber
cannot be easily recycled (reprocessed) due to their complex crosslinked structure [9]. Vulcanized
rubbers are being used in tires manufacturing since these thermoset materials can sustain severe
mechanical and thermal conditions while their properties do not change with temperature. The
Materials 2020, 13, 782 6 of 31

chemical composition of tires influences their mechanical behavior and lifespan. As shown in Table 1,
the typical tire compositions for passenger cars (7.5–9 kg) and trucks (50–80 kg) are different based on
the rubber type, as well as the other components [20].

Table 1. Typical compositions of tires [1,2,21,22].

Material Cars/Passenger (wt.%) Trucks (wt.%)

Rubber 41–48 41–45
Carbon Black 22–28 20–28
Metal 13–16 20–27
Textile 4–6 0–10
Additives 10–12 7–10

Waste tires are rich materials due to their composition and properties and thus the sources of
valuable raw materials. Waste tires can be categorized as worn tires or end of life tires in which
some of these worn tires are still suitable for on the road use. However, end of life tires cannot be
used for tire manufacture. The incorporation of different additives such as stabilisers, antioxidants,
and anti-ozonants into the vulcanized rubber compounds make them resistant to biodegradation,
photochemical decomposition, chemical reagents, and thermal degradation. Due to this complex
formulation, finding practical methods at a suitable cost for waste tires’ recycling is a serious dilemma
for the tire industries. Landfilling is the easiest approach to get rid of waste tires. However, there are
several drawbacks. For instance, impermeable discarded tires might keep water for a long period of
time and support sites for mosquito larva breeding, which cause deadly diseases such as dengue and
malaria [1]. Several works have been reported on recycling end of life tires for energy recovery [23]
and pyrolysis [24]. Waste tires, which contain more than 90% organic materials with a heat value of
32.6 MJ/kg (the heat value of coal is 18.6–27.9 MJ/kg), have been used for energy recovery purposes [1].
For example, waste tires are used as a fuel source in cement kilns, which is more environmentally
friendly compared to coal combustion. Moreover, waste tires are used as fuel for the production of
steam, electrical energy, pulp, paper, lime, and steel. However, burning tires as fuel releases hazardous
gases and only recovers 25% of the energy used for the rubber production [25]. Furthermore, the
pyrolysis of waste tires decomposes the rubber component to produce carbon black, zinc, sulphur,
steels, oils, and gas. However, the high operating costs of the pyrolysis plants limit the wide application
of this method [26]. Some environmentally friendly recycling techniques have been developed such as
triboelectric separation, froth flotation, and laser-induced breakdown spectroscopy. However, these
methods are expensive, and the obtained recycled rubbers vary in cleanliness, size, shape, and surface
topography quality [21,27,28]. Although vulcanized waste rubbers are difficult to recycle, they are very
durable, strong, and flexible materials, which can be used as ideal fillers in composite production [9].
Therefore, an interesting option is to blend waste tires with plastics (by the action of heat and
pressure) to decrease the final costs of the products due to a lower amount of virgin material being used.
Waste tires need to be shredded (grinding) into smaller particles (downsizing) for easier incorporation
into plastic matrices. Usually, pneumatic separators and electromagnets are used for the separation
of textiles and steels from waste tires, respectively [1]. Several methods of waste tire downsizing
processes are presented in Table 2, resulting in different surface characteristics and the size of GTR.
Cryogenic processes lead to clean granulates without surface oxidation. Shredded tires can be used
in virgin/fresh polymers such as rubbers, thermoplastics, and thermoset blends for civil engineering,
automotive applications, sports equipment, and others. Blends of rubber with thermoplastics are
consuming a large amount of waste tires, as discussed in the next section [1,29].
Materials 2020, 13, 782 7 of 31

Table 2. General methods of waste tire downsizing [1,2,22].

Methods Description Advantages Disadvantages

Temperature could rise up
Repeated grinding following shredder,
Ambient (0.3 mm rough, to 130 ◦ C
mills, knife, granulators, and High surface area and volume ratio
irregular) Oxidation on the surface of
rolling mills
granulates
Cooling needed to prevent
combustion
Grinding suspension of shredded Lower level of degradation on Requires drying step and
Wet ambient (100 µm rough,
rubber using grindstone granulates shredding of tires before
irregular)
Water cools granulates and grindstone High surface area and volume grinding
Used for large sized tires (trucks and
Environmentally safe, energy saving, Requires high pressure and
Water jet (rough, irregular) tractors)
low level of noise, and no pollutants trained personnel
Water jet of >2000 bar pressure and
high velocity used to strip rubber
Combines a rolling mill with a
Berstoff’s method Small grain size, large specific area,
specially designed twin screw extruder Not disclosed
(rough, irregular) and low humidity
in a line.
Cryogenic (75 µm sharp Rubber cooled in liquid nitrogen and No surface oxidation of granulates High cost of liquid nitrogen
edge flat/smooth) shattered using impact type mill and cleaner granulates High humidity of granulates

3. Thermoplastic Elastomers
Thermoplastic resins are being broadly used for melt blending with waste rubber powder to form
TPE compounds. TPE are composed of an elastomeric component as a soft fraction and a non-elastomeric
material as a hard segment, which is a thermodynamically incompatible system. TPE compounds benefit
from the processability of thermoplastics and the properties of glassy/semi-crystalline thermoplastics
combined with soft elastomers. TPE compounds can be prepared by extrusion through the dissociation
of hard domains at high temperature and shear followed by cooling and solidifying the polymer melt.
TPE materials are categorized into thermoplastic olefin (TPO), thermoplastic natural rubber (TPNR),
thermoplastic vulcanizate (TPV), thermoplastic polyurethane (TPU), styrene block copolymer (SBC),
polyether block amide (PEBA), and copolyester (COPE) [30].

3.1. TPE Structure

TPE compounds can be obtained by three different structures and morphologies as:

• Block copolymers consisting of elastic and non-elastic blocks;

• Rubber/thermoplastic blends;
• Dynamically vulcanized rubber/thermoplastic blends.

3.1.1. Block Copolymers

TPE based on block copolymers consist of multi-block copolymers for which the end of these
blocks can be crystallized and linked together, forming a crosslinked network. The main fraction of
block copolymers is the amorphous phase with rubber-like properties. Several copolymers have been
used in this category such as TPU, SBC, PEBA, and COPE. Figure 7 resents a schematic representation of
a TPE copolymer illustrating the rigid crystalline segments and rubbery blocks as a continuous domain
of soft rubbery chains. Under deformation, the hard blocks remain crystalline and never deform, so
TPE deformation is governed by the soft rubber domains. Going through the melt temperature, the
copolymer chains start to flow, and the material can be processed like all thermoplastic polymers [31,32].
 used in this category such as TPU, SBC, PEBA, and COPE. Figure 7 resents a schematic representation
deform,
of a TPEso TPE deformation
copolymer is the
illustrating governed by the soft
rigid crystalline rubber and
segments domains. Going
rubbery through
blocks the melt
as a continuous
temperature,
domain of soft therubbery
copolymer chains
chains. Understart to flow, and
deformation, the material
the hard can be
blocks remain processed
crystalline like
and all
never
thermoplastic polymers [31,32].
deform, so TPE deformation is governed by the soft rubber domains. Going through the melt
temperature, the copolymer chains start to flow, and the material can be processed like all
Materials 2020, 13, 782 8 of 31
thermoplastic polymers [31,32].

Figure 7. Morphology of a block copolymer thermoplastic elastomer (TPE). Adapted with permission
from [33]; copyright 2020 Elsevier Ltd.
Figure 7. Morphology of a block copolymer thermoplastic elastomer (TPE). Adapted with permission
Figure 7. Morphology of a block copolymer thermoplastic elastomer (TPE). Adapted with permission
3.1.2.from [33]; copyright 2020 Elsevier
Rubber/Thermoplastic Blends Ltd.
from [33]; copyright 2020 Elsevier Ltd.
3.1.2.Typical TPE compounds
Rubber/Thermoplastic are prepared by direct melt blending of an elastomer with a
Blends
3.1.2. Rubber/Thermoplastic Blends
thermoplastic by internal mixing (batch) or extrusion (continuous). TPO is a well known type of TPE
Typical TPE compounds are prepared by direct melt blending of an elastomer with a thermoplastic
basedTypical
on meltTPE blending
compoundsof a rubber and a polyolefin
are prepared by direct such asblending
polypropylene (PP), low-density
by internal mixing (batch) or extrusion (continuous). TPO ismelt
a well known type of an elastomer
of TPE based onwithmelta
polyethylene
thermoplastic (LDPE),
by linear
internal low-density
mixing (batch) polyethylene
or extrusion (LLDPE),
(continuous). and
TPOHDPE.
is a As
well shown
known in Figure
type of TPE8,
blending of a rubber and a polyolefin such as polypropylene (PP), low-density polyethylene (LDPE),
the thermoplastic
based is the continuous
on melt blending phase,
of a rubber andbuta the morphologysuchofasTPO is not fixed as(PP),
the rubber phase
linear low-density polyethylene (LLDPE), and polyolefin
HDPE. As shown inpolypropylene low-density
Figure 8, the thermoplastic is the
shape and
polyethylene size might
(LDPE), change
linear by coalescence
low-density or rupture
polyethylene during
(LLDPE), high
and shear
HDPE. processing.
As shown inSince
Figure the8,
continuous phase, but the morphology of TPO is not fixed as the rubber phase shape and size might
dispersed
the rubber phase
thermoplastic is the is not crosslinked
continuous phase, with
but themorphology
the thermoplastic,
of TPOiscan
TPO not be easily
fixed as prepared
the rubber atphase
low
change by coalescence or rupture during high shear processing. Since the dispersed rubber phase
cost.
shape TPOandhave
sizebeen
mightextensivelyby used in the transportation sector including automotive exteriors and
is not crosslinked with change coalescence
the thermoplastic, TPOor rupture
can during
be easily high at
prepared shear
low processing.
cost. TPO have Sincebeenthe
interior
dispersed fascia [31,32].
rubber phase is not crosslinked with the thermoplastic, TPO can be easily prepared at low
extensively used in the transportation sector including automotive exteriors and interior fascia [31,32].
cost. TPO have been extensively used in the transportation sector including automotive exteriors and
interior fascia [31,32].

Figure 8. Morphology of rubber/plastic blend thermoplastic elastomer (TPE). Adapted with permission
Figure 8. copyright
from [32]; Morphology
2020of rubber/plastic
Elsevier Ltd. blend thermoplastic elastomer (TPE). Adapted with
permission from [32]; copyright 2020 Elsevier Ltd.
TPE
Figurecompounds are mostly
8. Morphology prepared from
of rubber/plastic blendheat resistant rubbers
thermoplastic such(TPE).
elastomer as EPDM. NR with
Adapted has been
TPE
introduced compounds
in the TPE are mostly
production prepared from
especially after
permission from [32]; copyright 2020 Elsevier Ltd.
heat
the resistant
developmentrubbers
of such
dynamic as EPDM. NR
vulcanisationhas been
through
introduced in the TPE
phenolic curatives. TPEproduction
containingespecially
NR as theafter the development
elastomer componentofmeltdynamic vulcanisation
blended through
with thermoplastics
phenolic
are known curatives.
TPE compounds TPE containing
as TPNR. Usually, TPNR
are mostly NR as the elastomer
compounds
prepared from heat component
are melt blended
resistant melt blended
via internal
rubbers with thermoplastics
mixer orNR
such as EPDM. co-rotating
has been
are
twinknown
screwas
introduced in TPNR.
the TPEUsually,
extruders. SeveralTPNR
production compounds
thermoplastics
especially such
after areasdevelopment
the melt blendedof
polystyrene via
(PS) internal mixer or6co-rotating
[34], polyamide
dynamic vulcanisation(PA6) [35],
through
twin screw extruders.
ethylene-vinyl acetate Several
(EVA) thermoplastics
[36], and such
poly(methyl as polystyrene
methacrylate) (PS)
(PMMA) [34], polyamide
[37] are 6
reported
phenolic curatives. TPE containing NR as the elastomer component melt blended with thermoplastics (PA6)
to be [35],
used
in
areTPNR
known production. Furthermore,
as TPNR. Usually, TPNRdifferent polyolefins
compounds (PP,
are melt LDPE,via
blended HDPE) havemixer
internal been or
broadly used
co-rotating
for
twinTPNR
screwpreparation [38]. For
extruders. Several example, meltsuch
thermoplastics blending of NR and
as polystyrene HDPE
(PS) [34],results in a combination
polyamide 6 (PA6) [35],
of the excellent processing properties of HDPE and the elastic properties of NR to produce TPNR
for automobile components. Since HDPE and NR are nonpolar materials with totally different melt
viscosity and MW, they show poor interfacial adhesion. Not only compatibilisers have been reported
to enhance interaction between both phases, but also processing oils have been used for their softening
ability (plasticizing), processability improvement (lubrication), and elastic recovery [39,40].
different melt viscosity and MW, they show poor interfacial adhesion. Not only compatibilisers have
been reported to enhance interaction between both phases, but also processing oils have been used
for their softening ability (plasticizing), processability improvement (lubrication), and elastic
recovery [39,40].
Materials 2020, 13, 782 9 of 31
3.1.3. Thermoplastic Vulcanizates

3.1.3.TPV compoundsVulcanizates
Thermoplastic are based on melt blending of the elastomer with the thermoplastic at high
temperature and shear through dynamic vulcanisation or an in situ crosslinking process. The
TPV compounds are based on melt blending of the elastomer with the thermoplastic at high
dynamic vulcanisation process crosslinks the elastomer component dispersed in the continuous
temperature and shear through dynamic vulcanisation or an in situ crosslinking process. The dynamic
thermoplastic phase, even if its volume fraction is above 50%. The dispersed particles’ (rubber phase)
vulcanisation process crosslinks the elastomer component dispersed in the continuous thermoplastic
size directly affects the physical properties of TPV with 1 μm being the optimum rubber particles size
phase, even if its volume fraction is above 50%. The dispersed particles’ (rubber phase) size directly
(Figure 9) [32].
affects the physical properties of TPV with 1 µm being the optimum rubber particles size (Figure 9) [32].

Figure 9. Thermoplastic vulcanizates (TPV) morphology with continuous plastic phase and discrete
Figure 9. Thermoplastic
rubber particles. vulcanizates
Adapted (TPV)from
with permission morphology with continuous
[32]; copyright plastic
2020 Elsevier Ltd. phase and discrete
rubber particles. Adapted with permission from [32]; copyright 2020 Elsevier Ltd.
The preparation of TPV compounds is expensive and requires complex processing since the
The preparation
dispersed rubber phaseofneeds TPV tocompounds
be crosslinkedis expensive and requires
during mixing. The highcomplex
amount processing
of rubber (>50since the
wt.%)
dispersed rubber phase needs to be crosslinked during mixing. The high amount
with high crosslinking density leads to high elasticity and rubber being the continuous phase, while of rubber (>50 wt.%)
with high crosslinking
the uniformly dispersed density
rubberleads
phase to is
high elasticity
essential for and rubber being
the desired the continuous
mechanical propertiesphase,
of TPV.while
On
the uniformly
the other hand,dispersed
a continuousrubber phase
plastic is essential
phase for the
is required for desired mechanical
appropriate properties
processability. of TPV. the
Altogether, On
the other hand, a continuous plastic phase is required for appropriate processability.
phase inversion of the rubber phase from a continuous phase (in the premix) to a dispersed phase Altogether, the
phase
(in theinversion
TPV) shows of the rubber phase
a dominant rolefrom
in thea continuous
preparationphaseof TPV(incompounds.
the premix) toAsa shown
dispersed phase (in
in Figure 10,
the TPV)
a high showsof
amount a dominant role in
rubber (50–80 the preparation
wt.%) of TPV
is melt blended compounds.
with As shown
the thermoplastic in Figure
(20–50 wt.%)10,ata high
high
amount
temperature of rubber
and shear (50–80 wt.%)
stress. is melt
Dynamic blended with
vulcanisation the thermoplastic
is performed after adding(20–50 wt.%)
the curing at high
agents and
temperature
other additives and shear
into stress. Dynamic
the premixed vulcanisation
blends under the sameisprocessing
performedconditions
after adding the curing
to crosslink agents
the rubber
and other
phase. additives
Rubber into theand
crosslinking premixed
breakingblends under
up occur the same processing
simultaneously, conditions
so the phase inversion to occurs.
crosslink the
Then,
rubber phase. Rubber crosslinking and breaking up occur simultaneously, so
intensive mixing is required to achieve uniform dispersion of rubber particles in the thermoplastic the phase inversion
occurs.
matrix. Then, intensive
Since the mixing
vulcanized is required
rubber domain to andachieve uniformmatrix
thermoplastic dispersion
show of rubber
poor particles
interfacial in the
adhesion,
thermoplastic matrix. Since the vulcanized rubber domain and thermoplastic
compatibilisation is required to achieve TPV with good overall properties and mechanical strength. matrix show poor
interfacial adhesion,
Compatibilisers compatibilisation
can improve is required
the interfacial to achieve
adhesion TPV with
by decreasing thegood overall
surface properties
tension of the TPVand
mechanical
Materials
components2020, strength.
13, Compatibilisers
x FOR PEER
[41,42]. REVIEW can improve the interfacial adhesion by decreasing the surface 10 of 31
tension of the TPV components [41,42].

Figure 10. Processing steps to produce thermoplastic vulcanizates (TPV) compounds. Adapted with
Figure 10. Processing
permission steps to produce
from [42]; copyright thermoplastic
2019 Elsevier Ltd. vulcanizates (TPV) compounds. Adapted with
permission from [42]; copyright 2019 Elsevier Ltd.
4. Compatibility
4. Compatibility
Melt blending of waste rubber with a thermoplastic resin is an upcycling process and adequate
technique for wasteoftires’
Melt blending wasterecycling. However,
rubber with interfacialresin
a thermoplastic incompatibility between
is an upcycling both
process phases
and is a
adequate
technique for waste tires’ recycling. However, interfacial incompatibility between both phases is a
critical issue in melt blending processes. Thermodynamically, due to large unfavorable enthalpy, the
incompatibility of polymer blends leads to phase separation, weak interfacial adhesion, and poor
mechanical properties. Therefore, controlling the morphology and interfacial tension plays an
important role in determining the properties of polymer blends. Miscibility and compatibility in
Materials 2020, 13, 782 10 of 31

critical issue in melt blending processes. Thermodynamically, due to large unfavorable enthalpy,
the incompatibility of polymer blends leads to phase separation, weak interfacial adhesion, and
poor mechanical properties. Therefore, controlling the morphology and interfacial tension plays an
important role in determining the properties of polymer blends. Miscibility and compatibility in
polymer blends are closely related and are often confused since both terms contribute to the morphology
and properties. Generally, miscibility results in one phase, while compatibility creates a disperse phase
(interphase) for which its size and stability is determined by interfacial interactions [43].
The basic thermodynamic relationship controlling mixtures is:

∆Gm = ∆Hm − T ∆Sm (1)

where ∆Gm is the free energy of mixing, ∆Hm is the enthalpy of mixing, and ∆Sm is the entropy of
mixing at the temperature T.
The miscibility theory for polymer blends was introduced by Flory and Huggins [44]. Based on
this theory, ∆Sm is the entropy factor and corresponds to the disorder or randomness value that is
always positive; so, it is favorable to mixing or miscibility. In polymer-polymer mixtures, the entropy
of mixing has a negligible value, and the enthalpy of mixing (∆Hm ) is the dominant factor to determine
miscibility. ∆Gm will be negative if and only if ∆Hm is negative: exothermic mixing requiring specific
interactions between the components of the blend.
Incorporation of additives is a common method to improve the miscibility of polymer blends by
decreasing their interfacial tension, which is called compatibilization. In fact, the main objectives of
compatibilization are:

• Lowering the interfacial tension,

• Controlling the morphology by size reduction and stabilisation of the dispersed droplets to prevent
their coalescence,
• Increasing the interfacial adhesion between the phases, leading to better stress transfer and
mechanical properties [45].

Physical and chemical compatibilisation methods are two main strategies for blend
compatibilisation. For example, Iyer and Schiraldi [46] reported that the functional groups of additives
(copolymers or nanoparticles) can interact with one or both of the polymers, thereby improving the
compatibility of polymer blends.
Physical compatibilisation of polymer blends is based on applying external energy. Generally,
the crosslinked structure of the vulcanized rubber is destroyed with energy sources to create
physical entanglements and increase the interaction between the thermoplastic and rubber molecules.
Physical compatibilisation (mechanical or thermo-mechanical stresses assisted by oil), high energy
radiation (microwave or γ radiation), and ultrasonics (ultrasonic waves) are conventional physical
compatibilisation methods.
Chemical compatibilisation of polymer blends is conducted through non-reactive and reactive
approaches using chemical agents [47]. In non-reactive methods, a block or graft copolymers with
chain units similar to the blend components are used. Kumar et al. [48] studied an immiscible blend of
GTR/LLDPE and used SBR, NR, and EPDM to improve the compatibility of polymer blends. According
to their results, the blends containing EPDM showed the highest mechanical properties (almost 60–70%
improvement in tensile strength) as a result of improved interaction and compatibility between the
components. Recently, inorganic nanoparticles (NP) have been used as compatibilisers since they can
bridge immiscible polymers and offer compatibility.
In reactive compatibilisation, copolymers are generated in situ during the melt blending process.
Copolymers’ formation might occur by reaction between the end-groups of the first polymer with
the end-groups or pendant groups of a second polymer [45]. Furthermore, dynamic vulcanisation
involving the immobilisation of the dispersed phase via crosslinking can also improve the blend
compatibility between the components. Recently, inorganic nanoparticles (NP) have been used as
compatibilisers since they can bridge immiscible polymers and offer compatibility.
In reactive compatibilisation, copolymers are generated in situ during the melt blending process.
Copolymers’ formation might occur by reaction between the end-groups of the first polymer with
the end-groups or pendant groups of a second polymer [45]. Furthermore, dynamic vulcanisation
Materials 2020, 13, 782 11 of 31
involving the immobilisation of the dispersed phase via crosslinking can also improve the blend
compatibility. Usually, the vulcanized rubber as the dispersed phase is a crosslinked component
distributed in the
compatibility. continuous
Usually, thermoplastic
the vulcanized phase
rubber [42].dispersed phase is a crosslinked component
as the
distributed in the continuous thermoplastic phase [42].
4.1. Copolymers
4.1. Copolymers
Copolymers are extensively used as compatibilisers in immiscible polymer blends, and their
efficiency is determined
Copolymers by their
are extensively usedcomposition, chain in
as compatibilisers length, and configuration
immiscible polymer blends, (Figure 11).
and their
Copolymers
efficiency need to have
is determined by segments that can interact
their composition, with and
chain length, eachconfiguration
polymer in the blend11).
(Figure [45].
Copolymers
need to have segments that can interact with each polymer in the blend [45].

Figure 11. Different structures of linear copolymers: (a) alternating, (b) random, (c) gradient, and
Figure
(d) 11.copolymers.
block Different structures
Adapted of linear
with copolymers:
permission from(a) alternating,
[45]; copyright(b) random,
2019 (c)Ltd.
Elsevier gradient, and (d)
block copolymers. Adapted with permission from [45]; copyright 2019 Elsevier Ltd.
For instance, Shanmugharaj et al. [49] used polypropylene grafted maleic anhydride (PP-g-MA)
as a compatibiliser in PP/GTR blends
For instance, Shanmugharaj et al.by using
[49] usedallylamine grafted
polypropylene GTR maleic
grafted and reported 10–20%
anhydride tensile
(PP-g-MA)
strength improvement
as a compatibiliser of the PP-g-MA
in PP/GTR blends bycontaining compound
using allylamine compared
grafted GTR andwith unmodified
reported 10–20% blends
tensile
as a result
strength of enhancedofcompatibility
improvement the PP-g-MAand interaction
containing between
compound all the components.
compared with unmodifiedFurthermore,
blends as
Kim et al.
a result of[50] compatibilized
enhanced acrylamide
compatibility (AAm) modified
and interaction between allGTR/HDPE blendsFurthermore,
the components. with PP-g-MA Kimand
et
reported impact strength
al. [50] compatibilized improvements
acrylamide (AAm) of modified
the AAm-grafted
GTR/HDPE powder-filled composite
blends with PP-g-MA compared with
and reported
those
impact ofstrength
the unmodified powder-filled
improvements system and due
of the AAm-grafted to the bonding
powder-filled effect between
composite rubber
compared withpowders
those of
and the compatibiliser (Figure 12). Similar studies also focused on using copolymers
the unmodified powder-filled system and due to the bonding effect between rubber powders and the as compatibilisers
in Materials
TPE 2020, [51–54].
blends
compatibiliser 13, x FOR PEER
(Figure REVIEW studies also focused on using copolymers as compatibilisers
12). Similar 12 in
of 31

TPE blends [51–54].

Figure 12. Notched Izod impact strength of high-density polyethylene (HDPE)/ground tire rubber
Figure 12. Notched Izod impact strength of high-density polyethylene (HDPE)/ground tire rubber
(GTR) composites as a function of rubber content. Adapted with permission from [50]; copyright 2019
(GTR) composites as a function of rubber content. Adapted with permission from [50]; copyright 2019
John Wiley and Sons Ltd.
John Wiley and Sons Ltd.

4.2. Nanoparticles (NP)

More recently, inorganic NP with a large specific surface area and high aspect ratio such as
graphene (specific surface area 2600 m2/g and aspect ratio 200–1000) [55], single walled CNT (specific
surface area 1315 m2/g and aspect ratio >1000) [56], and nanoclay (natural montmorillonite clay
specific surface area 750 m2/g and aspect ratio 200–1000) [57] have been used as compatibilisers in
Materials 2020, 13, 782 12 of 31

4.2. Nanoparticles (NP)

More recently, inorganic NP with a large specific surface area and high aspect ratio such as
graphene (specific surface area 2600 m2 /g and aspect ratio 200–1000) [55], single walled CNT (specific
surface area 1315 m2 /g and aspect ratio >1000) [56], and nanoclay (natural montmorillonite clay
specific surface area 750 m2 /g and aspect ratio 200–1000) [57] have been used as compatibilisers in
polymer melt blending in addition to their application for improving the mechanical, thermal, and
barrier properties [58–60]. The Flory–Huggins thermodynamics theory of mixing clarifies the phase
separation in a ternary system containing two polymers and NP. However, droplet stabilisation against
coalescence is not clearly understood. There are different mechanisms for the NP compatibilisation
effect in polymer blends. Based on thermodynamics compatibility, the large specific surface area and
high aspect ratio of inorganic NP adsorb the polymer chains on their surface to increase the stabilizing
energy leading to the negative overall free energy of mixing and a thermodynamically compatible
system. On the other hand, kinetics compatibility is related to the selective localisation of the NP at the
polymers interface by decreasing the interfacial tension and preventing droplet coalescence during
melt blending. The compatibilisation efficiency of NP is affected by their migration and localisation
in phases during melt blending, which can be determined by processing parameters (compounding
sequence, melt compounding time, and shear rate) [61]. Moreover, blend morphology depends on
the viscosity ratio and the interfacial tension between the polymer phases. For instance, a finer
morphology is achieved in polymer blends as the viscosity ratio between the matrix and dispersed
phases is closer to one [62], as well as low interfacial tension between the blend components [63]. NP
are recognized as appropriate compatibilisers to decrease the interfacial tension of polymer blends and
stabilize the morphology depending on their localisation. If the nanofillers migrate to one phase of the
co-continuous blend, they form a percolated particle network in one phase and prevent coarsening
related to the increased viscosity [64]. On the other hand, selective localisation of NP at the interface
of polymer blends can stabilize the co-continuous structure. NP jammed at the interface are more
effective than percolated particle networks within one of the two phases by suppressing the coarsening
phenomena [65]. NP localisation can be predicted by measuring its wetting coefficients (ω) defined as:
h  i
ω= γNP/x − γNP/y /γx/y (2)

where γNP/x , γNP/y , and γx/y are the interfacial energies (or interfacial tensions) between NP–polymer
(x), NP–polymer (y), and polymer (x)–polymer (y), respectively. All these interfacial energies can be
theoretically calculated based on the Owens–Wendt equation [66] by measuring the dispersive (γd )
and polar (γp ) part of the surface energies:
" #
  1  p p 1
γxy = γx + γ y − 2 γdx γdy 2 + γx γ y 2 (3)

Based on Equation (2), if the wetting coefficient is higher than one (ω > 1), the NP
thermodynamically prefer to stay in the polymer (y), while NP locate in the polymer (x) when
ω < −1. Ideally, NP migrate to the interface between both phases when −1 < ω < 1 (Figure 13b) and
act as smart/functional barriers inhibiting droplets’ coalescence [58,61].
Several inorganic NP have been used for both reinforcing and compatibilisation effects in
immiscible polymer blends. However, the main challenge in using NP for blend compatibilisation is
their poor dispersion in the polymer matrix due to particle agglomeration, limiting their efficiency [45].
 𝛾 =𝛾 +𝛾 −2 𝛾 𝛾 + 𝛾 𝛾 (3)

Based on Equation (2), if the wetting coefficient is higher than one (ω > 1), the NP
thermodynamically prefer to stay in the polymer (y), while NP locate in the polymer (x) when ω < −1.
Ideally, NP migrate to the interface between both phases when −1 < ω < 1 (Figure 13b) and13act
Materials 2020, 13, 782
as
of 31
smart/functional barriers inhibiting droplets’ coalescence [58,61].

Figure 13.The
Figure13. Thethree possible
three cases
possible for nanoparticles’
cases (NP) localisation
for nanoparticles’ in an immiscible
(NP) localisation binary polymer
in an immiscible binary
blend: (a) in the dispersed phase, (b) at the interface (ideal case), or (c) in the continuous phase.
polymer blend: (a) in the dispersed phase, (b) at the interface (ideal case), or (c) in the continuous
Adapted with permission
phase. Adapted from [58];
with permission copyright
from 2019 Elsevier
[58]; copyright Ltd.
2019 Elsevier Ltd.
5. Rubber Modification
Several inorganic NP have been used for both reinforcing and compatibilisation effects in
Severalpolymer
immiscible methods, suchHowever,
blends. as graft the
polymerisation,
main challenge radiation-induced
in using NP for blend modification, and gasis
compatibilisation
modification, have beeninproposed
their poor dispersion to modify
the polymer matrixrubbers.
due toCurrently, rubber surface modification
particle agglomeration, limiting theirtechniques
efficiency
have
[45]. been performed at the laboratory scale. The purpose of rubber modification is to introduce oxygen
functional groups (peroxy, hydroperoxy, hydroxyl, and carbonyl) on the rubber surface to interact with
polar polymers
5. Rubber or reactive compatibilisers to improve the interfacial adhesion between the polymer and
Modification
rubber. Conventional oxidizing agents including potassium permanganate (KMnO4 ) [67], nitric acid
Several methods, such as graft polymerisation, radiation-induced modification, and gas
(HNO3 ) and hydrogen peroxide (H2 O2 ) [68], and sulphuric acid (H2 SO4 ) [69] have been used. Moreover,
modification, have been proposed to modify rubbers. Currently, rubber surface modification
grafting monomers onto rubber particles through free-radical initiation or photo-initiation can prevent
techniques have been performed at the laboratory scale. The purpose of rubber modification is to
particles’ agglomeration, leading to smaller particle size and more homogeneous distribution within
introduce oxygen functional groups (peroxy, hydroperoxy, hydroxyl, and carbonyl) on the rubber
the continuous polymer matrix to achieve better blend properties [1,27,70].
surface to interact with polar polymers or reactive compatibilisers to improve the interfacial adhesion
between theand
Reclamation polymer and rubber. Conventional oxidizing agents including potassium permanganate
Devulcanisation
(KMnO4) [67], nitric acid (HNO3) and hydrogen peroxide (H2O2) [68], and sulphuric acid (H2SO4) [69]
haveVulcanized
been used.rubbers
Moreover,are infusible
grafting and insoluble
monomers materials
onto rubberwith a 3D crosslinked
particles structure (100%
through free-radical gel
initiation
content), which are difficult
or photo-initiation to process
can prevent and reprocess
particles’ for further
agglomeration, compound
leading production.
to smaller particleTherefore,
size and these
more
rubbers need to be partially soluble with lower crosslink density, which
homogeneous distribution within the continuous polymer matrix to achieve better blend can be achieved byproperties
partially
destroying
[1,27,70]. the initial crosslinked structure, giving more chain mobility (molecular freedom). The soluble
fraction can interact and bond with the polymer matrix chains. Thermomechanical, thermochemical,
ultrasonic, and microwave
5.1. Reclamation are common techniques for partial breakup of the crosslinked structure of
and Devulcanisation
vulcanized rubbers. Regardless of the method used, there are two concepts related to the process of
Vulcanized
destroying rubbers are
the crosslinked infusible
structure and insoluble
of rubber includingmaterials with a 3D
devulcanisation andcrosslinked
reclamation.structure (100%
Reclamation
gel content), which are difficult to process and reprocess for further
is based on the scission of C–C bonds in the rubber backbone to reduce the MW and obtain some compound production.
Therefore,On
plasticity. these rubbers
the other need
hand, to be partiallyis soluble
devulcanisation withcleavage
the specific lower crosslink
of S–S and density, which
C–S bonds, can be
partially
achieved by partially destroying the initial crosslinked structure, giving
destroying the 3D network to produce plasticity. In an ideal devulcanisation process, the rubber more chain mobility
(molecularshould
backbone freedom).
not be The soluble fraction
damaged. However, canselective
interact breakup
and bond of with the polymer
the crosslinked matrix chains.
structure inside
Thermomechanical, thermochemical, ultrasonic, and microwave are common
vulcanized rubber is not possible without damaging some C–C bonds in the backbone. Table 3 reports techniques for partial
breakup of the crosslinked structure of vulcanized rubbers. Regardless of the method
the energy required for breaking the different bonds of crosslinked rubbers. In general, reclamation used, there are
two concepts related to the process of destroying the crosslinked structure
and devulcanisation might occur at the same time, making their differentiation difficult in a specificof rubber including
devulcanisation
process (Figure 14) and
[1].reclamation. Reclamation is based on the scission of C–C bonds in the rubber
backbone to reduce the MW and obtain some plasticity. On the other hand, devulcanisation is the
specific cleavage Tableof 3.
S–S and C–S
Energy bonds,
required for partially destroying
cleaving typical bondsthe 3D network
in vulcanized to produce
rubbers [71]. plasticity. In

Type of Bond Energy Required for Cleavage (kJ/mol)

C–C 348
C–S–C 285
C–S–S–C 268
C–Sx –C 251
 Table 3. Energy required for cleaving typical bonds in vulcanized rubbers [71].

Type of Bond Energy Required for Cleavage (kJ/mol)

C–C 348
C–S–C 285
Materials 2020, 13, 782 14 of 31
C–S–S–C 268
C–Sx–C 251

Figure 14. Schematic

Figure 14. Schematic representation
representation of
of the
the devulcanisation
devulcanisation and
and reclamation
reclamation process.
process. Adapted
Adapted with
with
permission from [1]; copyright 2020 Elsevier Ltd.
permission from [1]; copyright 2020 Elsevier Ltd.
6. TPE Compatibilisation
6. TPE Compatibilisation
Vulcanized and reclaimed rubber are exposed to severe conditions (shear stress, thermal and
Vulcanized and reclaimed rubber are exposed to severe conditions (shear stress, thermal and
chemical degradation, radiation) in their lifetime and recycling processes, so the properties of the
chemical degradation, radiation) in their lifetime and recycling processes, so the properties of the
resulting TPE differ from compounds based on virgin materials. Furthermore, rubbers contain several
resulting TPE differ from compounds based on virgin materials. Furthermore, rubbers contain
fillers that might limit possible improvement of blend properties. TPE compounds based on polyolefin
several fillers that might limit possible improvement of blend properties. TPE compounds based on
(especially PE) have received a great deal of attention because they are easy to process, and the
polyolefin (especially PE) have received a great deal of attention because they are easy to process,
materials are easily available at low costs. However, the performance of these blends depends on the
and the materials are easily available at low costs. However, the performance of these blends depends
nature and concentration of each component, as well as their interaction. The compounds need to
on the nature and concentration of each component, as well as their interaction. The compounds need
show at least 100% elongation at break and compression set lower than 50% to be recognized as good
to show at least 100% elongation at break and compression set lower than 50% to be recognized as
TPE materials [72]. It is known that polymer blend properties significantly depend on the interfacial
good TPE materials [72]. It is known that polymer blend properties significantly depend on the
adhesion between both phases and the size of the dispersed phase inside the continuous matrix. Poor
interfacial adhesion between both phases and the size of the dispersed phase inside the continuous
interfacial adhesion between the rubber and thermoplastic phases leads to low mechanical properties.
matrix. Poor interfacial adhesion between the rubber and thermoplastic phases leads to low
In fact, the vulcanized rubber molecules do not have enough freedom to entangle with the thermoplastic
mechanical properties. In fact, the vulcanized rubber molecules do not have enough freedom to
molecules to create strong bonding. Therefore, the interfacial adhesion and morphological behavior of
entangle with the thermoplastic molecules to create strong bonding. Therefore, the interfacial
TPE blends are important parameters to control/optimize the composition and processing conditions
adhesion and morphological behavior of TPE blends are important parameters to control/optimize
for high performance compounds [1,70].
the composition and processing conditions for high performance compounds [1,70].
6.1. Effect of Rubber Particles’ Size and Loading
6.1. Effect of Rubber Particles’ Size and Loading
Considering the size of the dispersed phase, small rubber particles usually show better mechanical
Considering
properties the particles
than larger size of due
the to
dispersed phase, small
a lower probability rubber particles
of failure/crack usually
formation. show
Ismail better
et al. [73]
mechanical properties than larger particles due to a lower probability of failure/crack
studied the effect of three different GTR sizes (250–500 µm, 500–710 µm, and 710 µm–1 mm) on the formation.
Ismail et al.properties
mechanical [73] studied the effect
of PP/GTR of three
blends. different
They GTR
reported thatsizes (250–500
blends μm, smaller
containing 500–710GTR
μm, particles
and 710
μm–1 mm) on the mechanical properties of PP/GTR blends. They reported that blends containing
(250–500 µm) showed higher equilibrium torque due to high friction associated with the higher surface
area of the smaller GTR particles. As shown in Figure 15, the blends containing small GTR particles
also showed the highest elongation at break (20%). However, the values were low because of the
crosslinked structure of the GTR particles and poor adhesion with the PP matrix, resulting in easy
crack initiation and rapid crack propagation.
Sonnier et al. [67] used three different rubber particle sizes (380–1200 µm) in GTR/LDPE compounds.
They did not achieve a significant difference in the mechanical properties of GTR/LDPE (50/50 wt.%)
blends (impact energy ~2.6 kJ/m2 for all blends with different rubber particle sizes). Therefore, they
suggested that controlling the GTR particles’ size is not the only parameter to achieve significant
mechanical properties’ improvement. It has been reported that the effective rubber particle size to
improve the mechanical properties of TPE is around 500 µm or less (Figure 16). However, at high rubber
 Materials 2020, 13, 782 15 of 31

Figure 15. Elongation at break as a function of composition for ground tire rubber
concentration (above 50 wt.%), the effect of rubber particle size is less important since low interfacial
(GTR)/polypropylene (PP) blends. Adapted with permission from [73]; copyright 2019 Taylor &
adhesion is the dominant parameter controlling the mechanical properties. In fact, substantial drops
Francis2020,
Materials Ltd.
in 13,
thextensile strength
FOR PEER and impact strength of TPE compounds filled with vulcanized rubbers are
REVIEW 15 of 31
related to low interfacial adhesion, rubber particles’ agglomeration, and void formation at the interface
between the rubber and thermoplastic phases. Due to a mismatch in polarity, melt viscosity, and MW
Sonnier
smaller GTRetparticles
al. [67](250–500
used three different
μm) showed higherrubber particle
equilibrium sizes
torque due(380–1200 μm)associated
to high friction
of both materials, the interfacial adhesion is weak. Poor interface quality leads to high interfacial
in GTR/LD
with the tension
compounds. higher
They and surface
did areaagglomeration,
notparticle
GTR achieve of athe smaller
significant GTR particles.
difference
facilitating voids’ in As
the
formation shown
mechanical
around in Figure
the rubber 15,Asthe of
properties
particles. blends
GTR/LD
containing
(50/50 small
wt.%)shown
blends GTR
in Figure particles also
17, increasing
(impact energy showed
the rubber the2 for
highest
concentration
~2.6 kJ/m elongation
resulted
all at different
in the formation
blends with break (20%).
of more defectsHowever,
rubberand the siz
particle
cracks
values were in GTR/EVA
low because of compounds. A
thecontrolling clear indication
crosslinked structure of low interfacial adhesion is confirmed by the
Therefore, they
cleansuggested that
and easy removal of rubber particlesthe GTR of
(pull-outs)
the GTR particles
particles’
from the EVAsize
matrix
and
is[74].
not thepoor
onlyadhesion
parameterwith to
theachi
PP matrix, resulting in easy crack initiation and rapid crack propagation.
significant mechanical properties’ improvement. It has been reported that the effective rubber part
size to improve the mechanical properties of TPE is around 500 μm or less (Figure 16). However
high rubber concentration (above 50 wt.%), the effect of rubber particle size is less important si
low interfacial adhesion is the dominant parameter controlling the mechanical properties. In f
substantial drops in the tensile strength and impact strength of TPE compounds filled w
vulcanized rubbers are related to low interfacial adhesion, rubber particles’ agglomeration, and v
formation at the interface between the rubber and thermoplastic phases. Due to a mismatch
polarity, melt viscosity, and MW of both materials, the interfacial adhesion is weak. Poor interf
quality leads to high interfacial tension and GTR particle agglomeration, facilitating voids’ format
around the rubber particles. As shown in Figure 17, increasing the rubber concentration resulted
the formation of more defects and cracks in GTR/EVA compounds. A clear indication of l
interfacial adhesion is confirmed by the clean and easy removal of rubber particles (pull-outs) fr
the EVA matrix Figure
[74]. 15. Elongation at break as a function of composition for ground tire rubber (GTR)/polypropylene
Figure 15.(PP) Elongation
blends. Adaptedatwith
break as from
permission a function of2019
[73]; copyright composition
Taylor & Francisfor
Ltd. ground tire rubber
(GTR)/polypropylene (PP) blends. Adapted with permission from [73]; copyright 2019 Taylor &
Francis Ltd.

Sonnier et al. [67] used three different rubber particle sizes (380–1200 μm) in GTR/LDPE
compounds. They did not achieve a significant difference in the mechanical properties of GTR/LDPE
(50/50 wt.%) blends (impact energy ~2.6 kJ/m2 for all blends with different rubber particle sizes).
Therefore, they suggested that controlling the GTR particles’ size is not the only parameter to achieve
significant mechanical properties’ improvement. It has been reported that the effective rubber particle
size to improve the mechanical properties of TPE is around 500 μm or less (Figure 16). However, at
high rubber concentration (above 50 wt.%), the effect of rubber particle size is less important since
low interfacial adhesion is the dominant parameter controlling the mechanical properties. In fact,
substantial drops in the tensile strength and impact strength of TPE compounds filled with
vulcanized rubbers are related to low interfacial adhesion, rubber particles’ agglomeration, and void
formation at the interface between the rubber and thermoplastic phases. Due to a mismatch in
Figure 16. Effect of ground tire rubber (GTR) particle size on the mechanical properties of thermoplastic
polarity, melt blends.
viscosity, and MW of both materials, the interfacial adhesion is weak. Poor interface
Adapted with permission from [1]; copyright 2020 Elsevier Ltd.
quality leads to high interfacial tension and GTR particle agglomeration, facilitating voids’ formation
around the rubber particles. As shown in Figure 17, increasing the rubber concentration resulted in
the formation of more defects and cracks in GTR/EVA compounds. A clear indication of low
interfacial adhesion is confirmed by the clean and easy removal of rubber particles (pull-outs) from
the EVA matrix [74].
Materials 2020, 13, x FOR PEER REVIEW 16 of 31

Figure 16. Effect of ground tire rubber (GTR) particle size on the mechanical properties of
Materials 2020, 13, 782 blends. Adapted with permission from [1]; copyright 2020 Elsevier Ltd.
thermoplastic 16 of 31

Figure 17. SEM micrographs of ethylene-vinyl acetate (EVA) blends with different ground tire rubber
Figurecontents:
(GTR) 17. SEM micrographs
(a) 10 wt.%,of(b)
ethylene-vinyl acetate
20 wt.%, (c) 50 wt.%,(EVA) blends
and (d) with different
70 wt.%. Adaptedground tire rubber
with permission
(GTR) contents: (a) 10 wt.%, (b) 20 wt.%, (c) 50
from [74]; copyright 2019 SAGE Publications Ltd. wt.%, and (d) 70 wt.%. Adapted with permission from
[74]; copyright 2019 SAGE Publications Ltd.
6.2. Non-Reactive Compatibilisation
6.2. Non-Reactive Compatibilisation
It is also possible to improve the interfacial adhesion of immiscible polymers blends via
compatibilisation methods.
It is also possible The addition
to improve of compatibilising
the interfacial adhesion of aids (copolymers
immiscible or nanoparticles),
polymers blends via
surface modification
compatibilisation of the materials,
methods. The additionas wellofascompatibilising
a variety of devulcanisation
aids (copolymers methods or and processing
nanoparticles),
aids (solvents)
surface are conventional
modification techniques
of the materials, to enhance
as well the compatibility
as a variety of TPEmethods
of devulcanisation blends. Incorporation
and processing of
block or graft copolymers
aids (solvents) into polymer
are conventional blends
techniques todecreases
enhance the the compatibility
interfacial tension andblends.
of TPE promotes interaction
Incorporation
between
of block or polymers. Differentinto
graft copolymers compatibilisers
polymer blends suchdecreases
ethylene-acrylic acid copolymer
the interfacial tension and (EAA) [75],
promotes
chlorinated polyethylene (CPE) [76], PE-g-MA [77], ethylene-co-glycidyl
interaction between polymers. Different compatibilisers such ethylene-acrylic acid copolymer (EAA) methacrylate copolymer
(E-GMA) [78], epoxydised
[75], chlorinated NR [79], (CPE)
polyethylene styrene-butadiene-styrene
[76], PE-g-MA [77], blockethylene-co-glycidyl
copolymer (SBS) [80], methacrylate
and EVA [30]
have been used
copolymer in TPE
(E-GMA) compounds.
[78], epoxydisedFor NRexample, PE-g-MA showed good
[79], styrene-butadiene-styrene efficiency
block copolymer for improving
(SBS) [80],
the
and mechanical
EVA [30] have properties
been used ofinTPOTPEcompounds
compounds. as Foraexample,
result ofPE-g-MA
a reaction between
showed good the anhydride
efficiency for
groups
improvinggrafted
the onto polyethylene
mechanical (PE) with
properties of TPOhydroxyl groups/unsaturated
compounds as a result bonds on the GTR
of a reaction particles’
between the
surface.
anhydride Therefore, using PE-g-MA
groups grafted as a compatibiliser
onto polyethylene (PE) with can reducegroups/unsaturated
hydroxyl the interfacial tension, bonds improve
on the
the
GTRdispersed
particles’phase uniformity,
surface. Therefore, decrease the domain
using PE-g-MA as size, and maintaincan
a compatibiliser thereduce
blends’the morphology
interfacial
stability [81]. Esmizadeh
tension, improve et al. [77]
the dispersed phase studied the effect
uniformity, of reactive
decrease compatibilisation
the domain on the mechanical
size, and maintain the blends’
and morphological
morphology stabilityproperties of TPVetblends
[81]. Esmizadeh al. [77]containing
studied theHDPE/reclaimed
effect of reactive rubber (RR). Theyon
compatibilisation used
the
PE-g-MA
mechanical and
and peroxide as the compatibiliser
morphological properties of TPV and blends
vulcanizing agent,HDPE/reclaimed
containing respectively. Analysis rubberof(RR).
the
torque
They usedvalues showedand
PE-g-MA increasing
peroxidetrendsas theof the plateau region
compatibiliser (equilibrium
and vulcanizing value)
agent, with increasing
respectively. RR
Analysis
content due to the
of the torque restricted
values showed chain mobility trends
increasing and difficult
of thedispersion of crosslinked
plateau region rubbervalue)
(equilibrium particles
within
HDPE. A similar
increasing observation
RR content due towasthereported by Ismail
restricted et al. [73] and
chain mobility in which the stabilized
difficult dispersion torque increased
of crosslinked
from
rubber4 Nm to 8 Nm
particles in with
HDPE. increasing
A similar GTR content from
observation was 20reported
wt.% to 60 bywt.%Ismaildueettoal.
a good
[73] indispersion
which the of
hard crosslinked rubber particles in PP (Figure 18).
 Materials 2020, 13, x FOR PEER REVIEW 17 of 31
Materials 2020, 13, x FOR PEER REVIEW 17 of 31

Materials 2020, 13,

stabilized 782 increased from 4 Nm to 8 Nm with increasing GTR content from 20 wt.% to17
torque 60ofwt.%
31
stabilized torque increased from 4 Nm to 8 Nm with increasing GTR content from 20 wt.% to 60 wt.%
due to a good dispersion of hard crosslinked rubber particles in PP (Figure 18).
due to a good dispersion of hard crosslinked rubber particles in PP (Figure 18).

Figure
Figure 18.18. Torque
Torque evolution
evolution forfor polypropylene
polypropylene (PP)/waste
(PP)/waste tire
tire dust
dust (WTD)
(WTD) blends
blends (250–500
(250–500 μm).
µm).
18. Torque evolution for polypropylene (PP)/waste tire dust (WTD) blends (250–500 μm).
Adapted
Adapted with permission from [73]; copyright 2019 Taylor & Francis Ltd.
Adapted with
with permission
permission from
from [73];
[73];copyright
copyright2019
2019Taylor
Taylor&&Francis
FrancisLtd.
Ltd.

Furthermore, reactive
Furthermore, compatibilisation and dynamic vulcanisation can the
increase the torque
Furthermore,reactive
reactivecompatibilisation
compatibilisation andanddynamic vulcanisation
dynamic can increase
vulcanisation can increase torque
the plateau
torque
dueplateau
to the due to theviscosity
increased increasedofviscosity
the systemof the system
[77]. [77]. Generally,
Generally, TPE TPE compounds
compounds show a show a shear-
shear-thinning
plateau due to the increased viscosity of the system [77]. Generally, TPE compounds show a shear-
thinning (pseudo-plastic)
(pseudo-plastic) behavior,
behavior, behavior,
and their andand their
viscosity viscosity decreases withshear
increasing shear rate. Sae-Oui
thinning (pseudo-plastic) their decreases with increasing
viscosity decreases rate.shear
with increasing Sae-Ouirate.etSae-Oui
al. [82]
et al. [82]
reported thereported the pseudo-plastic
pseudo-plastic behaviour ofbehaviour
NR/HDPE ofcompounds
NR/HDPE since
compounds
the since the
complex complex
viscosity viscosity
decreased
et al. [82] reported the pseudo-plastic behaviour of NR/HDPE compounds since the complex viscosity
decreased
with increasingwith increasing angular frequency (Figure 19). Obviously, increasing complex viscosity
decreased with angular
increasing frequency
angular(Figure
frequency19). (Figure
Obviously,
19). increasing
Obviously,complex viscosity
increasing complex wasviscosity
directly
was
related directly related
to the related
was directly
to
NR concentration the NR concentration
(complex viscosity
to the NR concentration
(complex viscosity
(NR/HDPE):
(complex viscosity90/10 > 80/20 > 70/30
(NR/HDPE):
(NR/HDPE): 90/10 >> 60/40)
90/10 > 80/20 >
80/20 >since
70/30
70/30the> >
60/40) since
fully the fully NR vulcanized structure restricted flowability.
60/40)NR vulcanized
since the fullystructure restricted
NR vulcanized flowability.
structure restricted flowability.

Figure 19. Complex viscosity as a function of angular frequency for thermoplastic natural rubber
Figure 19. Complex viscosity as a function of angular frequency for thermoplastic natural rubber
Figure 19.
(TPNR) Complex
based viscosity
on different as a rubber
natural function of angular frequency
(NR)/high-density for thermoplastic
polyethylene natural
(HDPE) ratios. rubber
Adapted
(TPNR) based on different natural rubber (NR)/high-density polyethylene (HDPE) ratios. Adapted
(TPNR)
with based onfrom
permission different natural rubber
[82]; copyright (NR)/high-density
2019 Elsevier Ltd. polyethylene (HDPE) ratios. Adapted
with permission from [82]; copyright 2019 Elsevier Ltd.
with permission from [82]; copyright 2019 Elsevier Ltd.
Moreover, the storage modulus (G’) as a function of angular frequency increased because of less
Moreover,
time Moreover,
available for the storage relaxation
modulus (G’) as a function of angular frequency increased atbecause of less
themolecular
storage modulus (G’)(Figure 20). Furthermore,
as a function G’ increased
of angular frequency morebecause
increased higher NR
of less
time available
content (NR/HDPE for= molecular relaxation
90/10) because of the (Figure 20).and
crosslinked Furthermore, G’ NR
highly elastic increased more
content, which at gave
higher NR
rise
time available for molecular relaxation (Figure 20). Furthermore, G’ increased more at higher NR
to content (NR/HDPE
a stronger = 90/10)
elastic =response because of
(slope reductionthe crosslinked
in Figureandand highly elastic NR content, which gave
20).highly elastic NR content, which gave rise rise
content (NR/HDPE 90/10) because of the crosslinked
to a stronger elastic response (slope reduction in Figure 20).
to a stronger elastic response (slope reduction in Figure 20).
Materials 2020, 13, 782 18 of 31
Materials 2020, 13, x FOR PEER REVIEW 18 of 31

0 ) as a function of angular frequency for thermoplastic natural rubber

Figure 20.Storage
Figure20. Storagemodulus
modulus(G (G′) as a function of angular frequency for thermoplastic natural rubber
(TPNR)
(TPNR) based on different naturalrubber
based on different natural rubber(NR)/high-density
(NR)/high-densitypolyethylene
polyethylene(HDPE)
(HDPE)ratios.
ratios.Adapted
Adapted
with permission from [82]; copyright 2019 Elsevier Ltd.
with permission from [82]; copyright 2019 Elsevier Ltd.

Table 4 compares the mechanical strength of compatibilized compounds showing that

Table 4 compares the mechanical strength of compatibilized compounds showing that
compatibiliser addition led to higher interfacial adhesion between RR and HDPE. It is clear that a
compatibiliser addition led to higher interfacial adhesion between RR and HDPE. It is clear that a
very small amount of vulcanizing agent (0.2 wt.%) is more effective than compatibilisers to improve
very small amount of vulcanizing agent (0.2 wt.%) is more effective than compatibilisers to improve
the mechanical properties. Figure 21 shows that Figure 21. Hardness of high-density polyethylene
the mechanical properties. Figure 21 shows that Figure 21. Hardness of high-density polyethylene
(HDPE) decreased with increasing RR content, which was attributed to the higher concentration
(HDPE) decreased with increasing RR content, which was attributed to the higher concentration of
of the elastomeric component in the TPE. Furthermore, increased hardness of the compatibilized
the elastomeric component in the TPE. Furthermore, increased hardness of the compatibilized and
and dynamically vulcanized blends were related to better interaction between the materials induced
dynamically vulcanized blends were related to better interaction between the materials induced by
by the compatibiliser and the formation of a stronger crosslinked structure (increased rigidity),
the compatibiliser and the formation of a stronger crosslinked structure (increased rigidity),
respectively [77].
respectively [77].
Table 4. Tensile properties of high-density polyethylene (HDPE)/reclaimed rubber (RR) blends. Adapted
Table 4. Tensile properties of high-density polyethylene (HDPE)/reclaimed rubber (RR) blends.
with permission from [77]; copyright 2019 Springer Nature Ltd.
Adapted with permission from [77]; copyright 2019 Springer Nature Ltd.
Sample Code Tensile Strength (MPa) Tensile Modulus (MPa) Elongation at Break (%)
Sample Code Tensile Strength (MPa) Tensile Modulus (MPa) Elongation at Break (%)
H-R30
H-R30 ± 0.1± 0.1
11.0 11.0 ± 7.3 ± 7.3
166.7166.7 2.7 ± 2.7
31.5 ±31.5
H-R50
H-R50 6.0
6.0 ± 0.6 ± 0.6 101.4
101.4 ± 2.8 ± 2.8 61.3 ± 5.5 ± 5.5
61.3
H-R70
H-R70 2.3
2.3 ± 0.1 ± 0.1 26.3
26.3 ± 5.8 ± 5.8 6.2 ± 6.2
125 ± 125
H-R90 0.6 ± 0.2 1.6 ± 0.7 149 ± 4.3
H-R90 0.6 ± 0.2 1.6 ± 0.7 149 ± 4.3
H-R30-C 12.2 ± 4.1 218.4 ± 6.1 45.1 ± 5.7
H-R30-C 12.2 ± 4.1 218.4 ± 6.1 45.1 ± 5.7
H-R50-C 7.3 ± 3.2 122.4 ± 3.8 78.9 ± 7.1
H-R50-C
H-R70-C
7.3 ±3.0
3.2± 0.7 122.4 29.8
± 3.8± 1.8 78.9 ±138.6
7.1 ± 2.4
H-R70-C
H-R90-C 3.0 ± 0.7
0.9 ± 0.2 29.8 ± 1.8
2.1 ± 0.9 138.6 ± 2.4 ± 4.9
183
H-R90-C
H-R30-P 0.9 ± 0.2
13.5 ± 5.1 2.1 ± 0.9
346.6 ± 7.4 183 ± 4.9
58 ± 8.2
H-R30-P
H-R50-P 13.5 ±9.4
5.1± 2.6 346.6184.9
± 7.4 ± 5.8 58 ± 8.2
94.1 ± 3.4
H-R50-P
H-R70-P 9.4 ±6.0
2.6± 1.7 184.9 36.5
± 5.8± 2.7 94.1 ±152.2
3.4 ± 1.5
H-R90-P
H-R70-P 1.7± 0.8
6.0 ±2.7 36.5 ±2.82.7± 1.5 ± 1.5 ± 6.1
152.2 213.5
H-R90-P
H: HDPE, 2.7compatibiliser
R: reclaimed rubber, C: ± 0.8 (PE-g-MA), P:2.8 ± 1.5 (liquid peroxide with
peroxide 213.5 ± 6.1
trade name DHBP
(2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane)).
H: HDPE, R: reclaimed rubber, C: compatibiliser (PE-g-MA), P: peroxide (liquid peroxide with trade
name DHBP (2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane)).
Kakroodi et al. [83] used PE-g-MA as a matrix to produce TPE compounds filled with high GTR
contents (50–90 wt.%) and compared their mechanical strength with HDPE/GTR compounds. The
results showed that TPE containing 50–70 wt.% of GTR in PE-g-MA had very good elongation at break
(εb = 465%) and tensile strength (σy = 32.7 MPa) at 50 wt.% GTR, while these properties decreased with
increasing GTR content to 90 wt.% (εb = 219% and σy = 4.6 MPa). Furthermore, the tensile properties
of HDPE/GTR compounds, with and without PE-g-MA as a coupling agent, were significantly lower
Materials 2020, 13, 782 19 of 31

than for the blends with PE-g-MA as the matrix. Therefore, PE-g-MA was shown to be a good matrix
Materials 2020, 13, x FOR PEER REVIEW 19 of 31
to produce TPE with high tensile properties.

Figure 21. Hardness of high-density polyethylene (HDPE) as a function of reclaimed rubber (RR)
Figure 21.
content: (1)Hardness
H-R10, (2)ofHR10-C,
high-density polyethylene
(3) H-R10-P. (HDPE)
Adapted withas a functionfrom
permission of reclaimed rubber2019
[77]; copyright (RR)
content: Nature
Springer Ltd. (2) HR10-C, (3) H-R10-P. Adapted with permission from [77]; copyright 2019
(1) H-R10,
Springer Nature Ltd.
Wang et al. [84] worked on the production of TPE compounds based on recycled PE (R-PE)/GTR
and investigated
Kakroodi etthe al. effect of Engage
[83] used PE-g-MA 8180asand Vestenamer
a matrix 8012 copolymers
to produce TPE compounds on thefilled
morphological and
with high GTR
mechanical properties. They reported better compatibilising efficiency
contents (50–90 wt.%) and compared their mechanical strength with HDPE/GTR compounds. The of Engage 8180 on R-PE/GTR
compounds
results showed thanthatVestenamer 8012. This
TPE containing behavior
50–70 wt.% was attributed
of GTR to the interaction
in PE-g-MA had very good and entanglement
elongation at
of R-PE(εand
break b = GTR
465%) molecular
and tensilechains due to the
strength (σy compatibilising
= 32.7 MPa) at effect of the
50 wt.% ethylene-octene
GTR, while thesecopolymer
properties
(main component
decreased of EngageGTR
with increasing 8180). In fact,
content to 90thewt.%
ethylene
(εb =part
219%was
andcompatible withFurthermore,
σy = 4.6 MPa). R-PE, while the the
octene
tensile segment
properties showed entanglement
of HDPE/GTR with SBR
compounds, with(main part of GTR).
and without PE-g-MAEven as though,
a couplingthey reported
agent, were
improved
significantlyelongation
lower than at break
for theofblends
compounds with 10 as
with PE-g-MA wt.%
the Engage 8180 up toPE-g-MA
matrix. Therefore, 76%. However,
was shownthe
values
to be awere
goodstill lower
matrix tothan 100%,TPE
produce which
withimplies the need
high tensile to do more research on the compatibilisation
properties.
of highly
Wang filled TPE
et al. [84]compounds,
worked on especially whenofrecycled
the production thermoplastic
TPE compounds based resins are usedPE
on recycled as(R-PE)/GTR
the matrix.
and investigated the effect of Engage 8180 and Vestenamer 8012 copolymers on the morphological
6.3.
andReactive Compatibilisation
mechanical properties. They reported better compatibilising efficiency of Engage 8180 on R-
PE/GTR
In general, better than
compounds Vestenamer
interaction between8012.
the This behaviorleads
components was toattributed to theofinteraction
the reduction the dispersedand
entanglement
phase of R-PE
particle size and GTR molecular
and compatibility chains In
improvement. due to the blending,
reactive compatibilising
block or effect
graftofcopolymers
the ethylene-as
octene copolymer
compatibilisers are(main
formed component of Engage
in situ during mixing. 8180). In fact,
These the ethyleneimprove
compatibilisers part wasbonding
compatible with
through
R-PE, while
covalent the octene
reactions between segment showed entanglement
the functionalized componentswith SBR (main
in polymers. part of
Grafting GTR). melt
through Evenblending
though,
theybereported
can done byimproved
a two-rollelongation
mill, internalat break
mixer,ofandcompounds
twin screw with 10 wt.%
extruder. KimEngage
et al. 8180 up to 76%.
[50] worked on
However, the values were still lower than 100%, which implies the need
the surface modification of GTR via grafting of AAm and melt blending of surface modified GTR to do more research on the
compatibilisation of highly filled TPE compounds, especially when recycled
with HDPE. They used PP-g-MA to induce the reaction between maleic anhydride (MA) and surface thermoplastic resins are
used as the
modified GTRmatrix.
powders to increase the compatibility between the phases. Both blends containing
AAm-grafted GTR and unmodified GTR showed decreasing tensile stress and tensile strain with
6.3. Reactive
increasing Compatibilisation
rubber content. However, the HDPE/AAm-GTR systems showed higher tensile stress and
tensileInstrain. The AAm-GTR
general, better filled between
interaction blends containing 10 wt.%leads
the components and 20to wt.% rubber did
the reduction ofnot
thebreak and
dispersed
elongated up tosize
phase particle 300%andand 400%, respectively
compatibility (Figure 22).
improvement. In reactive blending, block or graft copolymers
Furthermore, Patel et al. [85] studied the reactive
as compatibilisers are formed in situ during mixing. These blending of LDPE/NR
compatibilisers and LDPE/NBR
improve using
bonding through
acrylic
covalentacid (AA) andbetween
reactions MA. Thethe reaction mechanism
functionalized for LDPE/NR
components in modified
polymers.with MA isthrough
Grafting presented in
melt
Figure 23, while similar reactions are expected for AA-grafted LDPE/NBR. Dicumyl
blending can be done by a two-roll mill, internal mixer, and twin screw extruder. Kim et al. [50] peroxide (DCP)
was used on
worked as an
theinitiator
surfacetomodification
generate the offreeGTR
radical
via sites on the
grafting ofLDPE
AAmchains.
and melt blending of surface
modified GTR with HDPE. They used PP-g-MA to induce the reaction between maleic anhydride
(MA) and surface modified GTR powders to increase the compatibility between the phases. Both
blends containing AAm-grafted GTR and unmodified GTR showed decreasing tensile stress and
tensile strain with increasing rubber content. However, the HDPE/AAm-GTR systems showed higher
 Materials 2020, 13, x FOR PEER REVIEW 20 of 31

tensile stress and tensile strain. The AAm-GTR filled blends containing 10 wt.% and 20 wt.% rubber
Materials 2020, 13, 782 20 of 31
did not break and elongated up to 300% and 400%, respectively (Figure 22).

Figure 22. Tensile stress-strain curves of high-density polyethylene (HDPE) and HDPE/ground tire
rubber (GTR) compounds. Adapted with permission from [50]; copyright 2019 John Wiley and Sons
Ltd.

Furthermore, Patel et al. [85] studied the reactive blending of LDPE/NR and LDPE/NBR using
acrylic acid (AA) and MA. The reaction mechanism for LDPE/NR modified with MA is presented in
Figure 23, while similar reactions are expected for AA-grafted LDPE/NBR. Dicumyl peroxide (DCP)
was used
Figure 22.asTensile
an initiator to generate
stress-strain curves the free radicalpolyethylene
of high-density sites on the (HDPE)
LDPE chains.
and HDPE/ground tire
Figure 22. Tensile stress-strain curves of high-density polyethylene (HDPE) and HDPE/ground tire
rubber (GTR) compounds. Adapted with permission from [50]; copyright 2019 John Wiley and Sons Ltd.
rubber (GTR) compounds. Adapted with permission from [50]; copyright 2019 John Wiley and Sons
Ltd.

Furthermore, Patel et al. [85] studied the reactive blending of LDPE/NR and LDPE/NBR using
acrylic acid (AA) and MA. The reaction mechanism for LDPE/NR modified with MA is presented in
Figure 23, while similar reactions are expected for AA-grafted LDPE/NBR. Dicumyl peroxide (DCP)
was used as an initiator to generate the free radical sites on the LDPE chains.

Figure 23. Reaction mechanism for low-density polyethylene (LDPE)/natural rubber (NR) modified
with maleic anhydride (MA). Adapted with permission from [85]; copyright 2019 Taylor & Francis Ltd.

The hardness results showed that ungrafted compounds had lower values (Table 5). In fact,
the grafting method increased the hardness of both NR and NBR compounds up to 98 Shore A for
LDPE/NBR (80/20) blends modified with MA-grafted particles. Moreover, based on tensile results,
the strength decreased after aging (air oven at 70 ◦ C for 16 h) due to the degradation of the elastomer
phase. After aging, the ungrafted compounds showed a 20% reduction in tensile strength, while the
Materials 2020, 13, 782 21 of 31

grafted compounds showed only 1–5% reduction in tensile strength, which indicated their higher
stability due to grafting [85].

Table 5. Hardness (Shore A) of low-density polyethylene (LDPE)/natural rubber (NR) and

LDPE/nitrile-butadiene rubber (NBR) with and without particle modification. Adapted with permission
from [85]; copyright 2019 Taylor & Francis Ltd.

LDPE/NBR LDPE/NR Ungrafted Acrylic Acid (AA) Grafted Maleic Anhydride (MA) Grafted
- 80/20 90 97 95
- 60/40 82 90 85
- 40/60 65 70 69
- 20/80 55 57 58
80/20 - 95 97 98
60/40 - 85 86 87
40/60 - 65 70 72
20/80 - 55 58 56

6.4. Effect of NP Incorporation

In recent years, anisotropic nanofillers such as nanoclays, CNT, and graphene, with large
specific surface area and high aspect ratio, have been used to modify the interfacial adhesion of
immiscible polymer blends [58,59]. Incorporation of small amount of NP leads to strong interfacial
interaction between the components, improving the mechanical strength and thermal stability of
TPE nanocomposites.
Mehta et al. [86] studied the effect of nanoclays on the morphology of PP/EPDM (70/30) blends.
They showed important size reduction of the dispersed phase by increasing the nanoclays’ concertation.
Generally, the final morphology was influenced by the filler distribution, the viscosity ratio between the
components, and the affinity of the filler toward the polymers. Naderi et al. [87] studied the effect of the
matrix viscosity and NP content on the mechanical properties and morphology of PP/EPDM/nanoclay
compounds. XRD analysis was used to study clays’ exfoliation into nanolayers in the polymer blends.
As shown in Figure 24, the addition of 3 wt.% nanoclays (Cloisite 15A) increased the interlayer spacing
from 30.44
Materials 2020,Å
13,for PP/EPDM
x FOR (80/20) to 34.62 Å for TPE nanocomposite (PP/EPDM/nanoclays).
PEER REVIEW 22 This
of 31
behavior was attributed to the intercalation of polymer chains inside the silicate layers. They used
adomain
fixed NP sizes of the dispersed
concentration phase wereitssignificantly
since increasing concertationinfluenced by the
led to difficult presence of
penetration of the
NPpolymer
and the
viscosity ratio between both polymers [87].
chains through the silicate layers and decreased interlayer spacing of the nanoclays.

Figure 24. X-ray diffraction patterns of: (a) Cloisite 15A and TPE nanocomposites based on
Figure 24. X-ray diffraction patterns of: (a) Cloisite 15A and TPE nanocomposites based on
polypropylene (PP) with: (b) 60%, (c) 40%, and (d) 20% ethylene-propylene-diene monomer (EPDM).
polypropylene (PP) with: (b) 60%, (c) 40%, and (d) 20% ethylene-propylene-diene monomer (EPDM).
Adapted with permission from [87]; copyright 2019 John Wiley and Sons Ltd.
Adapted with permission from [87]; copyright 2019 John Wiley and Sons Ltd.
Furthermore, they reported the effect of the viscosity ratio on the size of the rubber domain in
PP/EPDM (60/40) blends. The results showed that the rubber droplet sizes decreased with increasing
Materials 2020, 13, 782 22 of 31

the viscosity of the PP phase. As mentioned before, a fine dispersion is achieved when the viscosity
ratio of the plastic/rubber is close to one. Furthermore, they showed the effect of nanoclays on breaking
up the rubber droplets. Increasing the rubber concertation increased the dispersed rubber phase size
in the compounds without nanoclays (Figure 25a,c), which indicated the effect of NP on preventing
Figure 24. X-ray diffraction patterns of: (a) Cloisite 15A and TPE nanocomposites based on
coalescence and reducing the dispersed phase sizes. Therefore, the distribution and domain sizes
polypropylene (PP) with: (b) 60%, (c) 40%, and (d) 20% ethylene-propylene-diene monomer (EPDM).
of the dispersed phase were significantly influenced by the presence of NP and the viscosity ratio
Adapted with permission from [87]; copyright 2019 John Wiley and Sons Ltd.
between both polymers [87].

25. SEM
Figure 25.
Figure SEM micrographs
micrographsofofTPE based
TPE on:on:
based (a)(a)
unfilled polypropylene
unfilled (PP)/ethylene-propylene-diene
polypropylene (PP)/ethylene-propylene-
monomer (EPDM) (60/40), (b) nanoclay-filled PP/EPDM (60/40), (c) unfilled
diene monomer (EPDM) (60/40), (b) nanoclay-filled PP/EPDM (60/40), (c) unfilled PP/EPDM (40/60),
PP/EPDM and
(40/60),
(d) nanoclay-filled PP/EPDM (40/60) blends. Adapted with permission from [87]; copyright 2019 John
and (d) nanoclay-filled PP/EPDM (40/60) blends. Adapted with permission from [87]; copyright 2019
Wiley and Sons Ltd.
John Wiley and Sons Ltd.

In another study, Lopattananon et al. [88] investigated the effect of sodium montmorillonite
In another study, Lopattananon et al. [88] investigated the effect of sodium montmorillonite (Na-
(Na-MMT) concentration on the mechanical and morphological properties of TPV based on NR/PP
MMT) concentration on the mechanical and morphological properties of TPV based on NR/PP
(60/40). According to the results, the two phase-separated morphology of the blends changed to a
(60/40). According to the results, the two phase-separated morphology of the blends changed to a
droplet-like structure upon addition of 2–5 phr (parts per hundred resin) nanoclays as a result of a
droplet break-up effect.

6.5. GTR Surface Modification and Devulcanisation

Another compatibilisation technique is the surface modification of GTR particles via oxidation to
improve the interaction between the components. Colom et al. [89] used various acids such as H2 SO4 ,
HNO3 , and perchloric acid (HClO4 ) for the surface treatment of GTR for melt blending with HDPE.
They reported improved rubber interaction with HDPE and higher stiffness for the TPE compounds as
a result of rubber rigidification after the acid treatment. As shown in Figure 26, the smooth surface of
HClO4 treated particles (b) is similar to the surface of untreated particles (Figure 26), which is evidence
of poor adhesion. However, HNO3 and H2 SO4 (Figure 26c,d) provided a rough surface with several
 Another compatibilisation technique is the surface modification of GTR particles via oxidation
to improve the interaction between the components. Colom et al. [89] used various acids such as
H2SO4, HNO3, and perchloric acid (HClO4) for the surface treatment of GTR for melt blending with
HDPE. They reported improved rubber interaction with HDPE and higher stiffness for the TPE
compounds as a result of rubber rigidification after the acid treatment. As shown in Figure 26, the
Materials 2020, 13, 782 23 of 31
smooth surface of HClO4 treated particles (b) is similar to the surface of untreated particles (Figure
26), which is evidence of poor adhesion. However, HNO3 and H2SO4 (Figure 26c,d) provided a rough
surface
micro-poreswithand several
cavitiesmicro-pores andthecavities
that enhanced thatcontact
interfacial enhanced the interaction
area and interfacial between
contact the
area and
rubber
interaction between the
and the thermoplastic rubber
matrix. and
The the thermoplastic
micro-roughness matrix. The
topography wasmicro-roughness
related to the acidtopography was
treatment with
related
sulphuric to acid,
the acid treatment
which led to awith sulphuric
decrease in theacid,
numberwhich led to abonds
of double decrease in tire
in the the chemical
number of double
structure
bonds in the
due to the tire chemical
degradation structure
process due to theand
of polybutadiene degradation process hydrocarbon
other unsaturated of polybutadiene andchains
polymer other
unsaturated hydrocarbon polymer chains (diene) on the GTR surface.
(diene) on the GTR surface.

SEMofofthe
Figure 26. SEM theground
groundtiretirerubber
rubber (GTR)
(GTR) particles
particles surface:
surface: (a) (a) untreated
untreated andand treated
treated with:
with: (b)
(b) perchloric acid (HClO ), (c) nitric acid (HNO ), and (d)
perchloric acid (HClO4), 4(c) nitric acid (HNO3),3 and (d) sulphuricsulphuric acid (H
(H22 44). Adapted with
SO ). Adapted
permission
permission from
from [89];
[89];copyright
copyright2019
2019Elsevier
ElsevierLtd.
Ltd.

In another
In anotherwork,work,Liu
Liuet al.
et [90] investigated
al. [90] the oxidation
investigated of EPDM
the oxidation powderpowder
of EPDM by KMnO by4 to generate
KMnO 4 to
hydroxyl hydroxyl
generate groups bygroups
breakingby unsaturated C=C bonds
breaking unsaturated C=Cin the rubber.
bonds in theThe addition
rubber. The of surfaceof
addition modified
surface
EPDM intoEPDM
modified PP containing
into PPa containing
small amount of MA amount
a small grafted chains
of MAshowed
graftedsignificant elongation
chains showed at break
significant
improvement.
elongation It was
at break explained that
improvement. polar
It was groups on
explained thatthe EPDM
polar surface
groups reacted
on the EPDMwith MA to
surface form
reacted
covalent bonds, improving the interaction between the rubber and matrix. Several
with MA to form covalent bonds, improving the interaction between the rubber and matrix. Several methods are known
to improve
methods arethe polarity
known to (oxygen
improveconcentration) of the rubber
the polarity (oxygen surface such
concentration) as high-energy
of the rubber surfacetechniques
such as
like plasma, corona discharge, and electron beam [27]. Sonnier et al. [67] studied
high-energy techniques like plasma, corona discharge, and electron beam [27]. Sonnier et al. [67] the production
of compatible
studied GTR/HDPE
the production compounds
of compatible using surface
GTR/HDPE treated using
compounds rubbersurface
particles. They
treated usedparticles.
rubber KMnO4
as a common oxidizing agent and γ irradiation for which the energy can induce
They used KMnO4 as a common oxidizing agent and γ irradiation for which the energy can induce macromolecular
chain scission and
macromolecular free-radical
chain scission formation, havingformation,
and free-radical the possibility
havingto react with the oxygen
the possibility to reactinwith
air and
the
create polar groups. However, the surface oxidation of GTR was not efficient enough to improve the
mechanical properties of HDPE/PE-g-MA/GTR compounds (elongation at break ~24% for all blends
with different modified rubber particle sizes).
It should be mentioned that the polarity of an elastomer can influence the interfacial adhesion
between GTR and the thermoplastic matrix. Li et al. [30] studied HDPE/GTR blends using EVA and
ethylene-octene copolymer (POE) as polar and non-polar compatibilisers, respectively. According to the
results, the impact strength and elongation at break of the HDPE/GTR/POE (60/20/20) compounds were
417 J/m and 129%, both of which were higher than 175 J/m and 82% for the HDPE/GTR/EVA (60/20/20)
compounds. After morphological analysis, this behavior was explained by better homogeneity and
encapsulation of the GTR particles by non-polar copolymers, helping the thermoplastic matrix to
between GTR and the thermoplastic matrix. Li et al. [30] studied HDPE/GTR blends using EVA and
ethylene-octene copolymer (POE) as polar and non-polar compatibilisers, respectively. According to
the results, the impact strength and elongation at break of the HDPE/GTR/POE (60/20/20) compounds
were 417 J/m and 129%, both of which were higher than 175 J/m and 82% for the HDPE/GTR/EVA
(60/20/20) compounds. After morphological analysis, this behavior was explained by better
Materials 2020, 13, 782 24 of 31
homogeneity and encapsulation of the GTR particles by non-polar copolymers, helping the
thermoplastic matrix to deform under applied forces. Furthermore, Formela et al. [80] investigated
the effects
deform of non-polar
under elastomer
applied forces. (partially crosslinked
Furthermore, Formela et al.butyl
[80]rubber and SBSthe
investigated block copolymers)
effects of non-polaron
the morphological
elastomer (partiallyand mechanical
crosslinked properties
butyl rubber of LDPE/GTR
and SBS blockblends. GTR particles
copolymers) were encapsulated
on the morphological and
by the elastomer phase, which was compatible with the thermoplastic phase,
mechanical properties of LDPE/GTR blends. GTR particles were encapsulated by the elastomer phase, improving the
interfacial
which was adhesion
compatible with thethe
with LDPE matrix. Asphase,
thermoplastic shownimproving
in Figure 27,
thesmall GTR adhesion
interfacial particles showed
with thehigher
LDPE
interfacial
matrix. As adhesion as a result
shown in Figure of better
27, small encapsulation
GTR particles showedofhigher
the GTR particles
interfacial by theas elastomer.
adhesion a result of
Moreover,
better the compounds
encapsulation containing
of the GTR SBSby(branched
particles Kraton
the elastomer. 1184) showed
Moreover, up to 125%
the compounds elongation
containing SBSat
break, which
(branched is twice
Kraton the
1184) value of
showed upLDPE/GTR (50/50), indicating
to 125% elongation betteriscompatibility
at break, which with
twice the value of both LDPE
LDPE/GTR
and GTR.
(50/50), indicating better compatibility with both LDPE and GTR.

Figure
Figure 27. Compatibilisation mechanism
27. Compatibilisation mechanism of
of thermoplastic/ground
thermoplastic/ground tire
tire rubber
rubber (GTR)
(GTR) blends
blends using
using an
an
elastomer as a modifier. Adapted with permission from [80]; copyright 2019 Elsevier Ltd.
elastomer as a modifier. Adapted with permission from [80]; copyright 2019 Elsevier Ltd.

Reclamation and devulcanisation of rubber have also been used to improve the compatibility and
Reclamation and devulcanisation of rubber have also been used to improve the compatibility
processability of TPE. In fact, destroying the crosslinked rubber structure, as well as co-crosslinking at
and processability of TPE. In fact, destroying the crosslinked rubber structure, as well as co-
the interface enhanced polymer chains mobility and the mechanical strength of the resulting compounds.
crosslinking at the interface enhanced polymer chains mobility and the mechanical strength of the
Furthermore, the presence of RR short chains and processing oil enhanced the processability and
resulting compounds. Furthermore, the presence of RR short chains and processing oil enhanced the
elongation at break of RR containing compounds due to a plasticisation effect. The crosslinked gel part
processability and elongation at break of RR containing compounds due to a plasticisation effect. The
of recycled rubber particles acts as stress concentration points, so increasing the rubber concentration
crosslinked gel part of recycled rubber particles acts as stress concentration points, so increasing the
(gel content) in the blends leads to increased crosslink density, producing lower tensile strength
rubber concentration (gel content) in the blends leads to increased crosslink density, producing lower
and elongation at break [1]. Sripornsawat et al. [91] studied the devulcanisation reaction time and
tensile strength and elongation at break [1]. Sripornsawat et al. [91] studied the devulcanisation
temperature through a relation between the soluble fraction (sol) and crosslink density. According
reaction time and temperature through a relation between the soluble fraction (sol) and crosslink
to their results, it was required to perform the devulcanisation process in a short time to prevent
density. According to their results, it was required to perform the devulcanisation process in a short
recombination of free-radicals to form new covalent bonds. Furthermore, increasing the reaction time
time to prevent recombination of free-radicals to form new covalent bonds. Furthermore, increasing
leads to the generation of more reactive radicals forming new links and increasing the crosslink density.
the reaction time leads to the generation of more reactive radicals forming new links and increasing
As shown in Figure 28, the optimum devulcanisation time is 4 min to obtain the maximum tensile
the crosslink density. As shown in Figure 28, the optimum devulcanisation time is 4 min to obtain
strength (3.7 MPa) and elongation at break (57%) for these samples. The authors also investigated the
the maximum tensile strength (3.7 MPa) and elongation at break (57%) for these samples. The authors
effect of devulcanisation on the mechanical and morphological properties of TPV based on blends of
also investigated the effect of devulcanisation on the mechanical and morphological properties of
COPE with devulcanized rubber (DR) and undevulcanised rubber (UDR). It was expected that DR
TPV based on blends of COPE with devulcanized rubber (DR) and undevulcanised rubber (UDR). It
had more unsaturated and uncrosslinked chains to participate in dynamic vulcanisation. As shown in
Figure 29, the polar functional groups on the surface of DR domains interacted with the COPE matrix
and showed better interfacial adhesion. High interfacial adhesion induced compatibility between the
components, leading to improved tensile strength and elongation at break of TPV containing DR.
vulcanisation. As shown in Figure 29, the polar functional groups on the surface of DR domains
was expected that DR had more unsaturated and uncrosslinked chains to participate in dynamic
interacted with the COPE matrix and showed better interfacial adhesion. High interfacial adhesion
vulcanisation. As shown in Figure 29, the polar functional groups on the surface of DR domains
induced compatibility between the components, leading to improved tensile strength and elongation
interacted with the COPE matrix and showed better interfacial adhesion. High interfacial adhesion
at break of TPV containing DR.
induced compatibility between the components, leading to improved tensile strength and elongation
Materials 2020, 13, 782 25 of 31
at break of TPV containing DR.

Figure 28. Tensile strength and elongation at break of dynamically cured devulcanized rubber
(DR)/copolyester (COPE)
Figure 28. Tensile blends
strength andaselongation
a function at
of the devulcanisation
break time
of dynamically at 180
cured °C. Adaptedrubber
devulcanized with
Figure 28. Tensile strength and elongation at break of dynamically cured devulcanized rubber
permission from [91]
(DR)/copolyester ; copyright
(COPE) blends2019
as aElsevier
functionLtd.
of the devulcanisation time at 180 ◦ C. Adapted with
(DR)/copolyester (COPE) blends as a function of the devulcanisation time at 180 °C. Adapted with
permission from [91]; copyright 2019 Elsevier Ltd.
permission from [91]; copyright 2019 Elsevier Ltd.

Figure 29. Schematic representation of the microstructure differences between the thermoplastic
Figure 29. Schematic
vulcanizates representation
(TPV) based of the
on devulcanized microstructure
rubber differences
(DR)/copolyester (COPE)between the thermoplastic
and undevulcanised rubber
vulcanizates (TPV)(COPE)
(DR)/copolyester based blends.
on devulcanized rubber
Adapted with (DR)/copolyester
permission (COPE) and
from [91]; copyright undevulcanised
2019 Elsevier Ltd.
Figure 29. Schematic representation of the microstructure differences between the thermoplastic
rubber (DR)/copolyester (COPE) blends. Adapted with permission from [91]; copyright 2019 Elsevier
vulcanizates (TPV) based on devulcanized rubber (DR)/copolyester (COPE) and undevulcanised
Crosslinked polymers do not dissolve in solvents due to their chemically bonded hydrocarbon
Ltd.
rubber (DR)/copolyester (COPE) blends. Adapted with permission from [91]; copyright 2019 Elsevier
chains. However, these links do not prevent the swelling of crosslinked polymers. Polymer swelling is
Ltd.
Crosslinked
defined as a volumepolymers doofnot
increase thedissolve in solvents
gel fraction dueortoatheir
by a liquid chemically
gas [91]. bonded
Macsiniuc et al. hydrocarbon
[92] proposed
chains. However,ofthese
a pre-treatment rubberlinks do notinprevent
particles a solvent the
to swelling
improve ofthecrosslinked
compatibilitypolymers.
betweenPolymer
rubber and swelling
plastic
Crosslinked polymers do not dissolve in solvents due to their chemically bonded hydrocarbon
isfor
defined as a volume increase of the gel fraction by a liquid or a gas [91]. Macsiniuc
TPE preparation. This method is based on swelling the rubber chains by a solvent, improving et al. [92]
chains. However, these links do not prevent the swelling of crosslinked polymers. Polymer swelling
proposed a pre-treatment
the penetration of rubber
of the dissolved particles matrix
thermoplastic in a solvent to improve
molecules into the the compatibility
crosslinked rubberbetween
network.
is defined as a volume increase of the gel fraction by a liquid or a gas [91]. Macsiniuc et al. [92]
rubber and et
Macsiniuc plastic forstudied
al. [92] TPE preparation.
the swelling This methodofisSBR
behavior based on swelling
particles thepenetration
and the rubber chains by a
of matrix
proposed a pre-treatment of rubber particles in a solvent to improve the compatibility between
solvent,
moleculesimproving the penetration
in the crosslinked of the dissolved
rubber structure. thermoplastic
They reported matrix molecules
increased Young’s modulus (468 intotothe
652
rubber and plastic for TPE preparation. This method is based on swelling the rubber chains by a
MPa), tensile strength (5.14 to 9.39 MPa), and impact strength (35.2 to 50.1 J/m). These mechanical
solvent, improving the penetration of the dissolved thermoplastic matrix molecules into the
properties’ improvement was attributed to the effect of swelling SBR particles in tetrahydrofuran
(THF), which allowed the PS molecules to enter the pores/voids. Consequently, interfacial adhesion of
PS/SBR was enhanced by chain entanglement with a PS matrix. However, immersion time and solvent
efficiency affected the swelling and penetration. Similarly, Veilleux and Rodrigue [93] investigated
Materials 2020, 13, 782 26 of 31

the properties of compounds based on virgin PS with recycled SBR powders (0–94% wt.) using a
pre-treatment in solution (toluene) to improve the compatibility between the phases. According to
the results of extraction tests and thermogravimetric analysis (TGA), the solution treatment allowed
inserting about 7.5% wt. of virgin PS inside the SBR particles, which was lower than the value obtained
in a similar work on recycled PS (10.5% wt.) [94]. This difference was attributed to the lower MW
of recycled PS, favoring its diffusion into the solvent and the swollen rubber particles. As expected,
incorporation of more elastomeric particles (up to 62% SBR) into PS decreased the hardness to 76 Shore
A (six units lower than neat PS). Furthermore, the addition of SBR into the rigid PS matrix decreased
both the rigidity (modulus) and strength (stress) of the compounds. Furthermore, the incorporation of
62% SBR into PS led to higher impact strength (up to 38 J/m form 22 J/m) due to the presence of more
elastomer in the compounds to absorb the impact energy [94].

7. Conclusions
Disposal of waste plastic and rubber is a significant issue from an environmental point of view
since the natural degradation of these materials takes several years. Vulcanized rubbers are extensively
used in a wide range of applications (mainly the tire industries) because of their mechanical strength,
excellent durability, abrasion resistance, and low cost.
The recycling of discarded tires as the main fraction of waste rubbers has attracted increasing
attention due to the large amounts of waste tires as an environmental issue. However, the complex
crosslinked structure and the presence of various additives in the tire composition make their
(re)processing difficult. In fact, vulcanized rubber (crosslinked structure) cannot be melted, making tire
recycling very difficult. Therefore, it is required to develop technologically possible and cost-effective
methods for recycling the waste rubber from scrap tires.
The most straightforward and environmentally friendly method is shredding/grinding waste tires
into ground tire rubber (GTR) and using the material (different particle sizes) as fillers in thermosets,
virgin rubbers, or thermoplastics (especially recycled resins) to produce thermoplastic elastomer
(TPE) compounds. The most convenient size of rubber particles for blending with thermoplastic
resins is less than 500 µm since smaller rubber particles are more efficient for improving the TPE
mechanical strength. TPE have the combined mechanical properties of thermoplastic/elastomer and easy
processability of thermoplastics. Styrene-butadiene rubber (SBR), ethylene propylene diene monomer
(EPDM), and natural rubber (NR) are the most used recycled rubber particles for melt blending with
thermoplastics to prepare TPE materials. Melt blending of waste rubber particles with recycled plastic
is an environmentally friendly and sustainable approach not only for higher consumption of waste
polymers, but also because of more economical/eco-friendly advantages. However, low compatibility
and weak interfacial adhesion between the rubbers and thermoplastics leads to the low mechanical
properties of TPE. Poor interfacial adhesion between the rubber and thermoplastic is more dominant
at higher rubber concentration (above 50 wt.%), which significantly deteriorates the mechanical
properties of the blends (especially elongation at break and toughness). Therefore, modification
techniques are required to obtain recycle-based TPE compounds with appropriate properties. Several
compatibilisation methods such as non-reactive and reactive approaches using chemical agents
(copolymer/nanoparticles, NP), as well as rubber surface modification through oxidizing agents or
reclamation/devulcanisation process and radiation-induced modification were presented here. There
is also the possibility of solution treatment using more environmentally friendly (green) solvents. The
main objective of these modification techniques is to improve the interfacial adhesion between the
rubber particles and thermoplastic matrices to achieve TPE compounds with appropriate mechanical
and morphological properties.
It is expected that in the near future, industrial and academic research will focus on the development
of green and cost-effective TPE compounds based on recycled polymers. The production of TPE from
recycled materials reduces the negative effects of these waste materials’ disposal. It also leads to the
production of materials with lower costs. The TPE market is expected to grow significantly in the near
Materials 2020, 13, 782 27 of 31

future due to increased demand for green and low-cost compounds obtained from waste polymers.
Even though the incorporation of recycled rubber (NR and SBR) into thermoplastics has been widely
studied, more studies should be done using different types of rubber such as EPDM since this rubber
is widely recycled due to its high cost. However, due to variability in the composition of polymer
wastes and difficult conditions during their service life, the performance of recycled compounds varies
compared to virgin compounds, which needs to be improved. Thermoplastic elastomers seem to be
one of the most promising fields of study, and several research works have been conducted on the
mechanical and morphological properties of TPE compounds. However, the lack of literature about
the thermal, dynamic mechanical, and aging behavior of these compounds highlights the need for
more research on TPE preparation and their characterisation.

Author Contributions: Writing—original draft preparation, A.F.; writing—review and editing, D.R.; supervision,
D.R.; project administration, D.R.; funding acquisition, D.R. All authors have read and agreed to the published
version of the manuscript.
Funding: This research was funded by the Natural Sciences and Engineering Research Council of Canada.
Acknowledgments: The authors gratefully acknowledge the financial support of the Natural Sciences and
Engineering Research Council of Canada.
Conflicts of Interest: The authors declare no conflict of interest.

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