Rubber/Thermoplastic Blends: Micro

and Nano Structured

Cristina Cazan and Anca Duta

Abstract Research on recycling, scarcely visible only a few decades ago, is now a
very active, fastgrowing discipline, particularly focusing on wastes re-use as
second raw materials. This chapter presents an overview on the state-of- art in
recycling, the most recent technologies, and recent developments. Rubber and PET
are the most frequently recycled polymers, and are particularly addressed to within
this chapter. Recent results are presented on rubber/thermoplastic-based micro/
nano blends, along with their manufacturing and characterization methods. There
are described methods to obtain the rubber-PET composites, based on ground
discarded tires as a matrix composites, using as fillers plastic materials (PET,
HDPE, and LDPE) and inorganic oxides (CaO, ZnO, and fly ash). Based on the
structural and output properties and the chapter outlines the role of various
components in the polymer composites. It is demonstrated that inorganic materials
in the polymer composites allow obtaining performances unrecorded by pure
polymer composites. However, the control of the inorganic material (type, quan-
tity, particle size, and molecular structure) dispersed in polymeric matrix is
essential in achieving the expected performance. Using different recipes, the
composites can be tailored for various indoor and outdoor applications, as building
materials as paving slabs, as thermal and electrical insulators, etc.

C. Cazan (&)
A. Duta

Faculty Product Design and Environment, Transilvania University of Brasov,
500036 Brasov, Romania
e-mail: [email protected]; [email protected]
A. Duta
e-mail: [email protected]

P. M. Visakh et al. (eds.), Advances in Elastomers I, 183

Advanced Structured Materials 11, DOI: 10.1007/978-3-642-20925-3_7,
 Springer-Verlag Berlin Heidelberg 2013
184 C. Cazan and A. Duta

1 Introduction to Thermoplastic Blends

Polymers play a vital role in the field of material science nowadays. In perfor-
mance characteristics, applications and diversity, they offer a degree of versatility,
not found with any other kind of materials. Depending on the mechanical behavior,
polymers are generally classified into three main categories: rubbers or elasto-
mers, thermoplastics and thermoset resins.
Thermoplastics are resins that repeatedly soften when heated and harden when
cooled. This is associated with the absence of chemical cross-links in their
structure. Many are soluble in specific solvents and burn to some degree. Com-
pared with thermosets, thermoplastics generally offer higher impact strength,
easier processing and better adaptability to complex designs [1]. The thermoplastic
can be sub-divided into two classes, commodity plastics (e.g. polyethylene PE,
polypropylene PP, polystyrene PS) and engineering plastics (e.g. polyoxymeth-
ylene POM, polyamide PA, polycarbonate PC).
Most thermoplastics are relatively soft and ductile, consisting of linear and
branched polymers with flexible chains. Thermoplastics may be (re)fabricated a
number of times by the simultaneous application of heat and pressure without
major changes in their properties. As the temperature increases, secondary bonding
forces are diminished by increased molecular motion so that the relative move-
ment of adjacent chain is facilitated when stress is applied. However, irreversible
degradation occurs whenever the temperature of melting thermoplastics is raised to
a point at which molecular vibrations become large enough to break the primary
covalent bonds [2, 3].
Thermoplastic polymer composites are falling under increasing scrutiny due to
their potential to be easily repaired and/or reshaped, making them easier to recycle
and reuse compared with thermosetting matrix composites.

2 Introduction to Rubber: Thermoplastic Blends

A polymer blend such as rubber—thermoplastic can be obtained either when

rubber-rich mixtures form soft thermoplastic elastomers, or when plastic-rich
blends produce rubber toughened thermoplastic. Rubber toughened thermoplastics
with flexible and high impact properties can be used as economical alternatives for
ordinary plastic materials.
The market for these materials has grown dramatically because of their ability
to be recycled and reprocessed, using conventional thermoplastic machinery.
However, many studies show that the additions of rubber to a thermoplastic matrix
results in a significant overall deterioration in mechanical properties [4, 5].
The properties of rubber-thermoplastic blends are reported to be depend on the
type of rubber/thermoplastic used in the composition and on the adhesion between
the phases. Further, the adhesion between the materials depends on the melt
Rubber/Thermoplastic Blends 185

viscosity of the matrix phase, the shape and size of the dispersed phase, and the
processing conditions. In addition, blend properties also vary with the moulding
techniques used to make test samples [6].
Rubber-thermoplastic blends can be broadly classified into three types:
1. Impact resistant rubber toughened thermoplastics;
2. Blends of vulcanizable rubbers, which contain various amounts of resins that
can act as reinforcing or stiffening agents;
3. Blends showing thermoplastic elastomeric behavior, commonly known as
thermoplastic elastomers (TPEs) [7, 8].
Microstructured polymer blends represents one of the most interesting field of
research in material science. In this context, the development of the first ther-
moplastic elastomers (TPEs) in the 1950s [9] provided a new dimension to the
field of polymer science and technology.

2.1 Classification of TPEs

TPEs may be rationally divided into the following classes according to their
chemistry and morphology:
1. (Soft) triblock copolymers; e.g., styrene–butadiene–styrene (S–B-S) or styrene-
ethylenebutylene-styrene (S-EB-S);
2. (Hard) multiblock copolymers; e.g., thermoplastic polyurethane (TPU), ther-
moplastic polyamide (TPA);
3. Blends of rubbers with thermoplastics subject of dynamic vulcanization; e.g.,
polypropylene/ethylene propylene diene rubber (PP/EPDM), un-crosslinked or
partially or fully crosslinked.
The field of TPEs based on polyolefin rubber—thermoplastic compositions, has
grown along two distinctly different product-lines or classes: one class consists of
simple blends and is commonly designated as thermoplastic elastomeric olefins
(TEO) according to ASTM D 5593 [10]. In the other group, the rubber phase is
dynamically vulcanized, giving rise to a thermoplastic vulcanizate (TPV) or
dynamic vulcanizate (DV) according to ASTM D 5046 [11]. Numerous literature
data are available on this subject [12–14], especially on thermoplastic vulcanizates
(TPVs) or dynamic vulcanizates (DV).
Morphologically, TPVs are characterized by the presence of finely dispersed
cross-linked rubber particles distributed in a continuous thermoplastic matrix [15].
If the rubber particles are sufficiently vulcanized, the physical and chemical
properties of the blend are generally improved.
TPEs have both advantages and disadvantages in their practical use over con-
ventional vulcanized rubbers [16, 17]. They are as follows:
186 C. Cazan and A. Duta

Fig. 1 Processing scheme of vulcanized rubbers (a) and thermoplastic elastomers

(b) disadvantages

Advantages:
• No vulcanization and very little compounding are required.
• Amenable to methods of thermoplastic processing, like injection molding, blow
molding, thermoforming, heat welding etc., which are unsuitable for conven-
tional rubbers; short mixing and processing cycles and low energy consumption.
A common processing scheme for vulcanized rubbers and for TPEs is presented
in Fig. 1.
• Scrap can be recycled and reused without significant performance deterioration;
• Properties can easily be manipulated by changing the ratio of the components;
• Better quality control;
• Good colorability;
• TPEs soften or melt at elevated temperature above which they lose their
mechanical properties;
• Rubbery behavior;
• TPEs show creep behavior on extended use.

3 Rubber: Thermoplastic Based Micro Blends

In recent years, TPEs and TPVs have replaced conventional rubber in a variety of
applications including appliance, automotive, medical, engineering, etc.
TPEs are obtained by copolymerization and by blending thermoplastics with
rubber component. TPVs, on the other hand, are obtained by dynamically vulca-
nizing the rubber component in a rubber—thermoplastic blend during mixing.
Both materials are processed like thermoplastics and are recyclable [18].
In most cases, TPEs are block copolymers consisting of soft and mobile
‘rubbery’ blocks with a low glass transition temperature (Tg), and rigid or hard
‘glassy’ blocks with a high melting temperature (Tm) and/or high Tg.
Rubber/Thermoplastic Blends 187

The rubber—thermoplastic blends are immiscible and their structure and

morphology depend on many factors among which the flow history and the
interfacial properties are the most important. At high dilutions and at low flow
rates the morphology of polymer blends is controlled by three dimensionless
microrheological parameters. Thus, the interfacial and rheological properties are
the keys for the morphology development in polymer blends, which in turn is the
controlling factor for their performance.
To improve performance of immiscible blends, usually they need to compati-
bilize. There are three aspects for compatibilization:
• Reduction of the interfacial tension that facilities fine dispersion;
• Stabilization of morphology against destructive modification during the sub-
sequent high stress and strain processing;
• Enhancement of adhesion between phases in the solid state, facilitating the
stress transfer, hence improving the mechanical properties of the product.
To insure compatibility as well as strong interfacial adhesion between the
plastic and rubber phases still remains a major challenge in producing high per-
formance TPE. The compatible and miscibility in a blend is not easy to achieve
due to the different characteristics of each component that represents a separate
phase with low attraction force along the phase boundaries. However, some
miscible blends have been reported and variously interpreted as results of specific
interaction, such as hydrogen bonding, dipole–dipole interaction, ion–dipole
interaction or repulsive interaction. Some of the blends are also produced from
chemical reaction, such as transesterification and the formation of covalent bonds
within the constituents of the blends. Thus to improve the tensile properties of such
blends, it is important to develop a proper control of phase morphology and better
interfacial adhesion between the blend constituent via chemical or process
approach by using compatibilizing agents or by dynamic vulcanization. There are
three ways to do this by physical, technological or chemical compatibilization.

3.1 Physical Compatibilization

The major factors that control the compatibility in physical blend are the polymer
chain entanglement, the high material viscosity at low processing temperature and
by controlling the shear rate. Increased processing temperature may influence the
thermodynamic miscibility. Increased shearing rate will decrease the size domain
within the limits allowed by melt viscosity. However, extreme shearing force
especially at low temperature and high viscosity may break polymer molecules
into reactive macroradicals. Cross-combination of these radicals can then produce
block or grafted polymers and prepare for the later technological compatibiliza-
tion, [19].
188 C. Cazan and A. Duta

3.2 Technological Compatibilization

Technological compatibilization of polymer blends can be produced or enhanced

by simple physical addition of monomeric or polymeric material without expecting
spontaneous chemical reactions to produce the desired properties. Addition of
monomeric materials includes solvent(s), plasticizer(s), surfactant(s), and fillers
which have been reported able to increase compatibility.
Another method of controlling the technological compatibilization is the
addition of polymeric ingredients, based on the use of suitable block or grafted
copolymer which are located at the interface between the phases of an immiscible
blend and acted as emulsifying agent. However, this method cannot be applied for
all types of polymer blends; it is based on the in situ formation of block or graft
copolymer at the interface due to chemically reactions during melt mixing; this
method is also called reactive compatibilization [20].
Reactive compatibilization of immiscible or incompatible blend can also be
performed by the proper selection of blending ingredients, where third component
addition is obviously miscible with one of the blend components and reactive with
the other blend component. As a result, the emulsifier is produced in-situ and
located at interface, and interacts with the phases via chain entanglement. High
physicochemical affinity at both phases can strongly modify the morphology,
interfacial adhesion, and final mechanical properties of the blends.

3.3 Chemical Compatibilization

Polymer blends are usually prepared by melt mixing process. Only a few of the
available basic polymers are able to perform compatible blend in practical
blending environment, without any chemical reaction. Thus, polymer modification
during original polymerization reaction or modification after polymerization (post
polymerization reaction) could be conducted in order to prepare such materials for
compatibilization via block copolymerization, random copolymerization, attach-
ment of terminal functional group and control of molecular weight [21].

4 Rubber/Thermoplastic Based Nano-Blends

The definition of nanocomposite materials has expanded significantly to encom-

pass a variety of systems, such as the one-dimensional, two-dimensional, three-
dimensional and amorphous materials, made up of separate components combined
at nanoscale. Significant efforts have been concentrated for the control of nano
structures through innovative synthetic approach. The properties of nanocom-
posites depend not only on the components properties, but also on the morphology
and interface properties.
Rubber/Thermoplastic Blends 189

This area continuously generates the development of novel materials, with

surprising properties. These properties result from combining the properties of
primary components in a single material, most of the time expecting synergic
effects. Experimental work showed that virtually all types and classes of nano-
composite materials lead to improved properties compared to their macrocom-
pozite lines, and can be synthesized using rather simple and inexpensive
techniques. Therefore, nanocomposites promise new applications in many sectors:
low-mass components and mechanical properties improved non-linear optics,
cathode ion batteries, nano-wires, sensors and other systems.
Nanotechnology is now one of the most promising opportunities for techno-
logical development in the 21st century. For research materials, development of
polymer nanocomposites is rapidly becoming a multidisciplinary activity whose
results may broaden the application of polymers, with benefits for many industries.
Polymer nanocomposites (PCN) have a polymer matrix (thermoplastics, ther-
mosetting or elastomer) consolidated or reinforced with small amounts of nano-
particles (less than 5 % by weight). Nanocomposites are referred in this context to
polymer systems containing inorganic particles with sizes in the nanometer range.
Polymer nanocomposites have been developed in the late 80s, both in private
research organizations and academic laboratories.
Most commercial applications focused on thermoplastics. Thermoplastics can
be divided into two categories: frequently used resins (low cost) and high per-
formance resins (expensive). Embedding nano-particles in a low cost matrix can
provide low/average cost composite resins, with similar or better properties,
comparing to the high-cost resins.
Thermoplastics combined with nanoscale materials may differ in properties
from the bulk conventional composites (micro-sized or higher dimensions of the
dispersed phase). Some properties of the nanocomposites, such as increased tensile
strength can be obtained using a larger amount of conventional fillers, with the risk
of an increased weight. Other nanocomposites properties, such as clarity or
improved barrier properties can be obtained only by using the appropriate fillers,
with the appropriate dimensions.
Rubber/thermoplastic based nano-blends are a new class of nanocomposites,
which are particle-filled polymers for which at least one dimension of the dis-
persed particles is in the nanometer range. One can distinguish three types of
nanocomposites, depending on how many dimensions of the dispersed particles are
in the nanometer range [22].
• When the three dimensions are in the order of nanometers, we are dealing with
isodimensional nanoparticles, such as spherical silica nanoparticles obtained by
in situ sol gel methods.
• When two dimensions are in the nanometer scale and the third is larger, forming
an elongated structure, we speak about nanotubes or whiskers as, for example,
carbon nanotubes or cellulose whiskers which are extensively studied as rein-
forcing nanofillers yielding materials with exceptional properties.
190 C. Cazan and A. Duta

• The third type of nano-fillers is characterized by only one dimension in the

nanometer range. In this case the filler is present in the form of sheets of one to a
few nanometer thick to hundreds to thousands nanometers long. This family of
composites can be gathered under the name of polymer-layered nanocomposites
(as example silica layers—polymer composites).
Owing to the nanometer-size particles obtained by dispersion, these nano-
composites exhibit markedly improved mechanical, thermal, optical and physical–
chemical properties when compared with the pure polymer or conventional
(microscale) composites.

5 Recent Studies on Rubber/Thermoplastic Based

Micro-Blends

Polymer blending provides another path for developing new materials, leading to a
significant number of thermoplastic—elastomeric products (TPE), commercialized
during mid to late of 1980s [23].
The improved interfacial adhesion, morphology and mechanical properties of
the blends are believed to be the result of the in situ formation of copolymer(s), at
the interface of two immiscible polymers caused by energy treatment with or
without the use of any chemicals. Recently, the blends of isotactic polypropylene
(iPP) and uncured ethylene–propylene diene rubber (EPDM) treated by high power
ultrasonic waves during extrusion have been investigated by Feng and Isayev [24].
The yield strength, elongation at break, tensile strength, and toughness of
ultrasonically treated PP/EPDM blends were improved at certain conditions of
ultrasonic treatment compared to those of untreated blends. These blends has been
commercialized with trade name such as Santoprene and Geolast which posses
high TPE oil resistance and performs with the versatility of rubber properties [25].
For some of the immiscible blends, with technological compatibilizations, the
addition of small amount of compatibilizing agent in the blend during melts mixing
could improve mechanical properties. It acts as a macromolecular surfactant and
allows the formation of very small droplet of elastomer that will become small
particles of vulcanized rubber when cured with dynamic vulcanization. There are
limited publications concerning compatibilizing immiscible blends of TPE.
Natural rubber (NR)/HDPE are typically immiscible blends and to achieve NR/
HDPE blend with practical value, various compatibilizers were used. The use of
modified phenolic resin as a compatibilizer improved the mechanical properties of
NR/HDPE blends due to chemical reactions between HDPE and the phenolic
molecules [26]. Supri and Ismail [27] also reported, that the use of glycidyl
methacrylate (GMA) on recycle polyvinyl chloride/acrylonitrile butadiene rubber
blends (GMA ? rPVC/NBR) has improved the mechanical properties and thermal
stability, leading to a low swelling index. On the other hand, EPDM/nylon blends
with maleic anhydride grafted EPR (MAH-g-EPR) also show better mechanical
Rubber/Thermoplastic Blends 191

performance than other compatibilizing agent containing acid group due to better
interfacial adhesion [24]. This again shows the beneficial effect of compatibilizer
to the immiscible TPE blend.
There are many papers presenting results on the addition of functional polymers
as compatibilizers. Basically, a polymer chemically identical to one of the blend
components is modified to contain functional or reactive units. These functional
units have some affinity for the second blend component, and have the ability to
chemically react with it. However, other types of interaction such as ionic are also
possible. The functional modification may be achieved in a reactor or via an
extrusion modification process. Functionalised polymers (usually maleic anhy-
dride or acrylic acid grafted polyolefins) are commercially available at acceptable
cost to be used as compatibilizers. For example, the grafting of maleic anhydride
(or similar compounds) to polyolefins, results in the formation of pendant carboxyl
group which have the ability to form a chemical bridge with polyamides, via their
terminal amino groups [28].
Papke and Karger-Kocsis [29] have studied the compatibilizing effect of eth-
ylene/propylene rubber grafted with glycidyl methacrylate (EPR-g-GMA) in the
thermoplastics elastomers/poly(ethylene terephthalate) blends. It was found that
the blend compatibility with PET is strongly improved when the EPR-g-GMA is
used as compatibilizer in the blends.
Papadopoulou and Kalfoglou [30] have studied the efficiency of maleic anhy-
dride modified polyolefins on the PET/PP blend. Aravind [31] have studied the
compatibilizing effect of maleic anhydride grafted ethylene propylene rubber
(EPMg- MA) in ethylene propylene diene rubber/Poly(trimethylene terephthalate)
(PPT) blends. It was found that the addition of EPM-g-MA reduces the domain
size of the dispersed phase followed by a leveling off at higher concentrations of
the compatibilizer. The addition of EPM-g-MA to the blends tends to decrease the
free volume showing its compatibilizing effect.
Ethylene vinyl acetate copolymer (EVA) is obtained through chemical modifi-
cation of polyethylene (PE) with vinyl acetate as co-monomer which reduces the PE
crystallinity. Thus it has many characteristic of thermoplastic elastomers, which
depends on the vinyl acetate content. EVA provides good mechanical properties,
excellent ozone resistance, good weather resistance and relatively lower material
cost [32, 33]. Epoxidized natural rubber (ENR) is a modified natural rubber having
properties resembling those of synthetic rubber rather than natural rubber. ENR has
unique properties such as good oil resistance, low gas permeability, improved wet
grip and rolling resistance, coupled with high strength [34, 35].
There are several references on EVA blends with different types of rubbers such
as nitrile rubber (NBR) [36], natural rubber (SMR 10) [37], styrene butadiene
rubber (SBR) and etc. having potential use in various applications such as films,
footwear, tubes and hoses.
Macaúbas and Demarquette [38] added styrene–butadiene–styrene (SBS) and
styrene–ethylene/butylene–styrene (SEBS) triblock copolymers as compatibilizers
in polypropylene/polystyrene system. The addition of compatibilizers to the PS
phase resulted in a reduction of the interfacial tension following an emulsion
192 C. Cazan and A. Duta

curve. It was shown that for both compatibilizers the concentration at which the
interfacial tension essentially levels off is smaller than the concentration at which
the average radius of the dispersed phase essentially levels off.
The morphological, viscosity and interfacial tension results showed that SEBS
is a better compatibilizer for the PP/PS blend than is SBS. Chen et al. [39]
have investigated the compatibilization effect of triblock copolymers of
poly[styrene-b- (ethylene-co-butylene)-b-styrene] and the diblock copolymer
of poly[styrene-b- (ethylene-co-butylene)] in high density polyethylene/syndio-
tactic polystyrene (sPS) blends. Morphology observation showed that phase
amount of dispersed sPS particles was significantly reduced on addition of the
copolymers and the interfacial adhesion between the two phases was dramatically
enhanced. Tensile strength of the blends increased at lower copolymer content but
decreased with increasing the copolymer content. The elongation at break of the
blends sharply increased with copolymers addition.

6 Recent studies on Rubber/Thermoplastic Based

Nano-Blends

The nanoscale of dimensions is the transition zone between the macrolevel and the
molecular level. Recent interest in polymer matrix based nanocomposites has
emerged initially with interesting observations involving exfoliated clay and more
recent studies with carbon nanotubes, carbon nanofibers, exfoliated graphite
(graphene), nanocrystalline metals and a host of additional nanoscale inorganic
filler or fiber modifications.
While the reinforcement aspects of nanocomposites are the primary area of
interest, a number of other properties and potential applications are important
including barrier properties, flammability resistance, electrical/electronic proper-
ties, membrane properties, polymer blend compatibilization.
The structure–property relationships of thermoplastic olefin (TPO)-based
nanocomposites prepared by melt processing are reported with a main focus on the
ratio of maleic anhydride-grafted polypropylene (PP-g-MA) to organoclay. The
morphological observations by transmission electron microscopy, atomic force
microscopy, along with X-ray diffraction are presented in conjunction with the
mechanical and rheological properties of these nanocomposites, [40].
The effect of different nanofillers and compatibilizers (maleic anhydride-grafted-
polypropylene and maleic anhydride-grafted-ethylene propylene diene terpolymer
rubber) on the morphology, mechanical, mechanodynamical and thermal charac-
teristics of thermoplastic olefins based on polypropylene and ethylene propylene
diene terpolymer rubber blends has been analyzed. A better affinity with the matrix
and a better dispersion of the nanoparticles is observed in rubber rich matrices. The
maleic anhydride-grafted-ethylene propylene diene terpolymer rubber is a better
compatibilizer for organo-clay nanocomposites based on rubber rich matrices [41].
Rubber/Thermoplastic Blends 193

Mirzadeh et al. [42] describe the effects of different polypropylene-g-maleic

anhydride polymers, as compatibilizers, on the degree of exfoliation and co-con-
tinuity of thermoplastic elastomer (TPE) nanocomposites based on polypropylene/
ethylene-propylene-diene monomer (PP/EPDM). X-ray diffractometry patterns
and transmission electron microscopy (TEM) micrographs show nanocomposites
range from an intercalated structure to a coexistence of intercalated tactoids
(relatively ordered stacks) and exfoliated layers. The significant increase in
crystallization temperature (*20 C) could be beneficial for molding applications
because of the faster solidification and shorter cycle time. The relaxation time
obtained by stress relaxation experiments shows that the key parameter that
determines the dispersion level in nanocomposites is the mobility of the
compatibilizer.
Thermoplastic elastomer nanocomposites (TPE nanocomposites) based on
PA6/NBR/Cloisite 30B were prepared through a direct melt mixing process in an
internal mixer by Mahallati et al. [43]. The effects of NBR content (10, 30 and 50
wt. %) and nanoclay loading (3, 5 and 7 wt. %) on morphology and mechanical
properties of the nanocomposites have been studied and compared with unfilled
PA6/NBR blends as well. The TPE nanocomposites were characterized by X-ray
diffraction (XRD), transmission electron microscopy (TEM), scanning electron
microscopy (SEM), differential scanning calorimeter (DSC) and mechanical
properties. Results suggested that the nanoclay is exfoliated into the TPE nano-
composite matrix. By adding the nanoclay, improved modulus of the prepared TPE
nanocomposites was achieved.
Ganguly and Bhowmick [44] used atomic force microscopy for qualitative
phase morphological mapping as well as quantitative investigation of surface
forces measured at constituting blocks and clay regions of a thermoplastic elas-
tomeric nanocomposite based on triblock copolymer: poly(styrene-ethylene-co-
butylene- styrene) (SEBS) and organically modified nano-clay. The roughness and
power spectral density analyses of surface topography provided the increment in
random roughness of the nanocomposite surface compared to pristine SEBS sur-
face. The same surfaces were examined by means of single point force-distance,
and force-volume measurements. Large adhesive force of 25 nN and contact force
of 260 nN were found in soft polyethylene (PEB) segments and higher cantilever
deflection of 210 nm was found for clay regions of SEBS-clay nanocomposite.
There has been a great discussion on tribomaterials of polymeric nanocom-
posites in recent years. However, little study has been done to develop triboma-
terials suitable for micro size devices with sufficient balances between tribological
and mechanical properties. A study was conducted to develop new tribomaterials
with high performance for micro mechanic and electric devices, made by blending
vapor grown carbon fiber filled polybutylene terephthalate with various func-
tionalized thermoplastic elastomer (TPE) based on styrene butadene elastomer.
The tribological and mechanical properties of these injection-molded polymer
blends were examined by Nishitani et al. [45], using three types of TPE based on
styrene butadiene elastomer.
194 C. Cazan and A. Duta

Excellent improvement in mechanical properties like tensile strength, elonga-

tion at break, and modulus was observed on incorporation of the nanofillers in the
rubber/thermoplastic based nano blends. When the nanofillers were added to the
plastic phase, the mechanical reinforcement is comparatively poorer due to partial
destruction of the crystallinity.

7 Different Manufacturing Methods of Rubber/

Thermoplastic Based Micro-Blends

Rubber—thermoplastic blends have become technologically interesting for

obtaining thermoplastic elastomers. Thermoplastic elastomers have many prop-
erties of the rubber, but can be processed as thermoplastics [46]. They do not need
to be vulcanized during fabrication or finishing. Due to its unique fabrication
ability and properties, they offer designers new flexibility in applications requiring
soft-touch features, seals against fluid environment, impact protection and
improved ergonomics. In addition, their general reputation of light weight, recy-
clability or reproducibility, chlorine free as well as environmental friendly
behavior, they attracted special interest as alternative materials in several fields,
such as cap and closures in house wares, sport appliances, wires and cables in
automotive, electrical and electronic industries, footwear, wheels, etc. [47].
Thermoplastic vulcanisates (TPVs) are a particular family of TPEs, which are
produced via dynamic vulcanization of non-miscible blends of rubber and ther-
moplastics, i.e. the selective crosslinking of the rubber with simultaneous mixing
with the thermoplastic melt [48].
Bhowmick et al. [49] considered that the plastic acts as a continuous phase and
allows the melt of the TPEs, whereas the dispersed rubber phase is responsible for the
rubber elasticity. Various types of thermoplastics are used to prepare TPEs. These
include polypropylene, low-density polyethylene, ultra-low-density polyethylene,
linear low-density polyethylene, chlorinated polyethylene, polystyrene, polyamide,
ethylene vinyl acetate (EVA) copolymer and poly(methyl methacrylate).
The first step in the design of a rubber—thermoplastic composite material is an
appropriate choice of the fabrication method. There are many widely used methods
to prepare rubber—thermoplastic composite materials, several of which are out-
lined below.

7.1 Injection Molding

Injection molding is by far the most used technique in TPE processing due to its
high productivity and because it is a clean process with no waste formation.
Injection molding is the process by which flow state plastic is brought under
Rubber/Thermoplastic Blends 195

adequate pressure and then is introduced into a mold. It is used in a large variety of
applications, ranging from tubes or foams to finished articles; it can be applied to
the co- or insert-injection. The use of hot runner methods in injection molding was
reviewed by Lachmann [50] and this is an interesting diversification of the con-
ventional technique; it maintains the flow ability of the melt during transportation
to the individual cavities or to the individual gates. During injection molding,
TPEs behave as the other thermoplastics in hot runner, without major problems.

7.2 Compression Molding

Compression molding is less used than injection molding. Compression modeling

applied pressure on the exact dosage pressed powder, locked in a heated mold,
when under heat influence runs a continuous polycondensation process and results
in the products’ stiffening, [51, 52].

7.3 Extrusion

Extrusion is the continuous processing whereby materials in the plastic state are
forced to pass through a channel that gives them shape.
The extrusion of TPEs was reviewed by Knieps [53]. This processing technique
is essential in the shaping of many different profiles; the use of single-screw
extruders is predominant, but some other extruders are also used, such as those
equipped with three-section or barrier screws. Extrusion is also applied to other
shapes: foams, tubes, sheets, etc.

7.4 Blow Processings

The blow processing is a method that uses a gas (air, N2) to expand a hot preform
against a mold pattern to produce a hollow object.
Extrusion and injection blow molding of TPEs are particularly important
whatever the shape: bottles, boots, etc. They were reviewed by Nagaoka [54], who
showed that the parameters controlling the processing are similar to those which
control extrusion and injection molding. Blow processes are also used to prepare
TPE foams.
196 C. Cazan and A. Duta

7.5 Thermoforming

Thermoforming represents shaping of a hot plastic sheet or plate, usually to obtain

a desired object shape. The number of references relative to the thermoforming of
TPEs drastically increases, particularly in the last three years; most of them are
patents and apparently this TPE processing technique did not yet reached its
maturity [55].

7.6 Calendering

Calendering is a process of rolling the material in plastic state, among warmed up

cylinders that rotate in opposite direction. The distance between the cylinders
regulates the sheet thickness.

8 Different Manufacturing Methods of Rubber/

Thermoplastic Based Nano-Blends

One of the barriers in the design and production control of nanomaterials with
predefined properties is the lack of understanding of fundamental processes at
nanoscale. To develop new materials by nano-level design should be able to define
the relationship between the (bulk) molecular structure and how they behave in
reality (surface, boundary). This requires understanding how small changes affect
the macroscopic properties and the ability to reproduce these models in strictly
controlled samples. The polymer nanocomposites properties are mainly depending
on the polymer-nanofiller interface and on the nanofiller volume fraction.
Diverse manufacturing technologies of these materials involve machines and
processes for: the procurement of the polymeric matrix, preparing the reinforcing
components, fibers/fillers impregnation or treatment, making the reinforcement
(network, netting, web, etc.), making the adequate composition through injection,
extrusion, compression—molding, other proceedings. Basically, for every type of
polymeric nanocomposite material a distinct technology, with specific operations
and devices is necessary. Nanocomposite materials procurement technologies are a
lot more different than the ones applied in the case of classic materials (metals,
glass, ceramic, etc.). The choice of the optimum technology is made according to
the shape and size of the pieces, the size of the fabricated products, and the nature
of polymeric matrix, along with the product’s quality and costs, [56].
Rubber/Thermoplastic Blends 197

9 Characterization Methods of Rubber/Thermoplastic

Based Micro-Blends

The preparation of TPEs is closely related to the structure and morphology control,
as they are structurally complex systems, requiring accurate, efficient, and rapid
investigation techniques. The characterization techniques are grouped into ana-
lytical branches, but it is essential to keep in mind that most of them are relevant
when associated.

9.1 Chromatography

For a long time, the use of chromatography was mainly limited to molecular weight
determination and to the qualitative estimation of the samples heterogeneity. At
present, it is a highly efficient technique, giving very accurate values [57, 58].
Copolymers are complex macromolecular systems, characterized by two distribu-
tions in molecular weight and chemical composition; liquid chromatography used
at the critical point of adsorption allows the determination of the molecular het-
erogeneities (chemical and molecular weight distributions) [32]. The association of
chromatography with other techniques allows, for instance, the analysis of the
molecular mass distribution of each block, in one run, as well as the respective
chemical distribution.

9.2 Spectrometric Techniques

FT-IR spectroscopy allows establishing the structure of an unknown compound,

outlining different groups of atoms and their mobility restrictions. Chemical
structure problems can be solved based on the characteristic vibration frequency of
certain groups of atoms, which change in a relatively small extent under the
influence of neighboring atoms and bonds. FT-IR spectroscopy is often associated
with NMR [59] or X-ray diffraction [60].
NMR spectroscopy is essential in TPE characterization; it is often associated
with other techniques. This technique allows a deep insight in the structure of the
block copolymer chains. NMR is often used as a routine technique because it is
efficient in the control of the TPE purity. The evaluation of accurate values of the
copolymers molecular weights and their distribution, as well as of the functionality
of di-functional oligomers remains a difficult problem. NMR is probably one of the
most efficient tools in the evaluating the end-group concentration. In some cases,
the end-units are converted into groups, which are fluorescent or adsorbing in the
visible or UV light; sometimes they are converted into chemically titratable
groups.
198 C. Cazan and A. Duta

9.3 Scattering Techniques

X-ray diffraction is an important tool in assessing the crystalline composition, for

instance in the investigation of the semicrystalline [61] or liquid-crystalline blocks
[62] and of the stretching behavior of TPEs [63, 64].

9.4 Microscopies

Atomic force microscopy (AFM) has an important development in the structural

analysis of TPEs. It was applied to different problems: thermo-oxidative stability
and morphology, copolymers with arborescent blocks, thermoplastic vulcanizates,
blends and morphology and orientation during deformation studied both by AFM
[65–67].
Transmission electron microscopy (TEM) is most useful to characterize the
structure and morphology of TPEs. It is almost always associated with other
techniques, (Atomic Force Microscopy, AFM). TEM is used in studies of inter-
penetrating networks, morphology and crystallinity of hard blocks, structural
evolution of segmented copolymers under strain, and blends [68–70].

9.5 Thermal Techniques

Differential scanning calorimetry (DSC) and other thermal analyses are frequently
used in TPE characterization, often as routine methods. DSC is a powerful tech-
nique to improve the knowledge of the microphase structure. DSC and thermo-
mechanical analysis (TMA) are often complementarly used to other techniques
(particularly spectroscopic analyses) or for providing additional information.

9.6 Contact Angle Measurements

The study of the interfacial phenomena is important for composite materials

because the interface is a frequent cause of damages that compromises the com-
posites reliability. The evaluation of the surface energy (polar and non-polar
components) can be done by contact angle measurements.
An important role in optimal adhesion is played by the chemical properties of
the solid surface, influencing the surface tension, [71]. Surface tension, contact
angle and surface properties are a consequence of the intermolecular interactions
on the surface of the uncompensated condensed phase (S, L) with a fluid (liquid,
vapor or gas). The surface tension depends on both participants.
Rubber/Thermoplastic Blends 199

10 Characterization Methods of Rubber/Thermoplastic

Based Nano-Blends

In order to characterize the properties of the polymer nanocomposites and

understand their responses to external stimuli, such as stress, thermal or concen-
tration gradients, it is important to have an insight into their structure and mor-
phology. The properties of rubber—thermoplastic nanocomposites are mostly
governed by two major factors:
• Dispersion and distribution of the nanofillers within the polymer matrix;
• Interactions between the polymer chains and nanofillers.
Both factors play important roles in deciding on possible applications for the
final product. Over the years, various techniques have been devised to investigate
the nanocomposites structure. A list of the commonly used techniques that are
widely used in nanocomposites studies are further presented [72]:
(a) Structural property characterization
• Scattering techniques: X-ray scattering, small angle light scattering, small
angle neutron scattering;
• Microscopic techniques: electron microscopy, atomic force microscopy;
• Spectroscopic techniques: FTIR, UV–VIS, nuclear magnetic resonance;
• Chromatography: gel-permeation chromatography.
(b) Bulk property characterization:
• Melt state rheometry: shear rheology, extensional rheology
• Solid state analysis: mechanical testing, barrier properties, optical properties.
(c) Thermal property characterization:
• Calorimetry and others: differential scanning calorimetry, thermal gravimetric
analysis, heat distortion temperatures.
Those characterization methods can also be meet at micro-level characteriza-
tion of the polymer composites.

11 Applications

Disposal of used rubber into landfills has become increasingly prohibitive due to
high cost, legislative pressures, public opinion, especially high environmental
stress. Researchers pay much attention to recycling. Many rubber products are now
recycled, such as used tires.
One important step is processing or reduction of whole tires into useful parts.
Sadhan [18] noted that the processes used for rubber grinding are based on cutting,
200 C. Cazan and A. Duta

shearing, or impact, depending on the equipment and the grinding conditions.

There are mentioned: cutting, milling, extrusion, ambient and wet grinding,
cryogenic grinding, etc.
Shredded tires are used as fillers in highways construction because they increase
the abrasion resistance and enhance the resilience. Concentrations of tire rubber
used for these purposes range from 10 to 20 % [18].
The best way to recycle rubber products would be to devulcanize and reuse
them in the rubber industry. Processes for devulcanization, including chemical,
thermal, thermomechanical, and ultrasonic, have been worked out, but they are
costly and not always suitable for commercial application, particularly in manu-
facturing highly engineered produces like tires.
Sadhan [18] summed up that another alternative is to blend the crumb or ground
rubber with a material having the ability to flow under heat and pressure, so that it
can be shaped into useful articles at a reasonable cost. This can be accomplished
by mixing finely ground rubber with plastics, along with necessary additives.
A rubber—thermoplastic composite is one of the most important materials and
prevails in a wide region. In rubber composites products such as tires, belts, and so
on, fibers are used as reinforcements. Among all fiber reinforcing materials, PET
seems to be a promising material because it has good mechanical properties,
particularly in high-modulus and low shrinkage. However, PET fiber is a relatively
inert polymer, and as a result, it merely possesses insufficient adhesion to rubbers.
Therefore, a third component is necessary to enhance adhesion between PET fibers
and rubber [50].
Good interfacial adhesion and reduced interfacial tension between the com-
ponents can be obtained for compatibilized PET and rubber materials. The com-
patibility can be obtained by the addition of other polymers, such as high density
polyethylene (HDPE), low density polyethylene (LDPE) and/or inorganic com-
pounds (TiO2). Inorganic oxides (CaO, ZnO and fly ash) were also tested for
enhancing the mechanical properties.
Using different recipes, the composites can be tailored for various indoor and
outdoor applications. The chapter presents composites (in terms of physical,
chemical and mechanical properties) for applications as building materials as
paving slabs, as thermal and electrical insulators, etc.

11.1 Development of Novel Nanocomposites:

PET—Rubber—Metal Oxides

Composites with inorganic structures embedded in the polymer matrix represent a

new class of materials with very interesting specific properties. It is demonstrated
that inorganic materials in polymer composites result in performances unrecorded
by pure polymer composites. However, inorganic material type, quantity, particle
size and molecular structure when dispersed in polymeric matrix are essential in
Rubber/Thermoplastic Blends 201

achieving the expected performance [73, 74]. Thus, inorganic oxides (CaO, ZnO)
of nanoscale dimensions can be used; as an oxide mixture, another waste, fly ash,
was also tested.
Composites based on recycled materials, obtained by compression molding
were investigated; the sample composition was rubber:polyethylene:HDPE:metal
oxide = 59.75:35:5:0.25.
Differences occurring between the samples with different fillers are related to
their influence on the interface and on the thermo-oxidative stability. Specific
characteristics recorded during mechanical testing proved the superiority of the
composites containing CaO. Tensile tests, compression and impact resistance
show that samples containing CaO develop significant organic–inorganic physical
interactions, without forming any new chemical species.
The fly ash collected from the electro-filters of a CPH has no significant
influence on the thermal behavior of the samples, without modifying the transition
temperatures, but the presence of a porous, heterogeneous structure can be noticed
as an advantage in further developing good organic–inorganic interfaces.

11.2 Obtaining Rubber: PET Composites

‘‘Blending of recycled wastes for developing materials with controlled properties,

embedded in novel products represents a process which has both, economic and
environmental advantages. The main focus is to find solutions for recycling those
polymeric wastes that are traditionally difficult to use in re-processing, as PET.
Therefore, rubber—PET composites represent a tempting alternative. Tire rubber is
a low cost second raw material that can easily act as matrix, but the amount of PET
able to be mixed with rubber is limited by the low compatibility between these two
components, as result of the low intermolecular forces between the non-polar
rubber and polar PET macromolecular chains. These structural differences have
also consequences on the different thermal behavior (significantly different Tg and
Tt), therefore process optimization represents another issue to be solved. Many
studies were done aiming at improving the PET-rubber compatibility. Obvious
compatibility agents are low molecular compounds with hydrophilic-hydrophobic
dual behavior; although efficient, these are expensive and toxic, increasing the costs
and the environmental burden. Therefore we propose to test various other poly-
meric wastes as compatibility agents, up to a high PET content, [75]’’.
To obtain composites based on recycled materials there were used:
• Poly-ethylene terephthalate (PET)—obtained from soft drink bottles;
• Rubber—from tires and bicycle tubes;
• High density polyethylene (HDPE)—from yogurt containers, etc.;
• Low density polyethylene (LDPE)—from packaging.
The mechanical properties and the environmental behavior can be tailored by
dispersing different oxide powders. Efficient dispersing occurs when the powders
202 C. Cazan and A. Duta

Fig. 2 The composition of composites based on recycled rubber

are in the range of nano- or mezzo- scale, resulting hybrid inorganic–organic

composites. Therefore, blends were developed using:
• TiO2 powder (Degussa P25), with an average size of 21 nm primary and specific
surface 50 m2/g TiO2 nanoparticles consisting of 75 % anatase and 25 % rutile.
• CaO powder (Reagent Bucharest, Romania, purity [90 %)
• ZnO powder (Scharlau, purity [99 %)
• fly ash powder with the following composition: SiO2 (53.32 %), Al2O3
(22.05 %), Fe2O3 (8.97 %), CaO (5.24 %), MgO (2.44 %), K2O (2.66 %), Na2O
(0.63 %), TiO2 (1.07 %), MnO (0.08 %), the rest being unburned carbon, (CPH
Brasov, Romania)
It is important to notice that these effects are obvious if the nano-particles do
not agglomerate, forming micro- sized clusters.

11.3 Composites Structure

These materials have different roles in the composites, as shown in Fig. 2

11.4 The production Method of Composites

To obtain rubber—PET composites based on recycled materials, there have been

followed the steps outlined in Fig. 3:
• Cleaning by washing the recycled rubber and plastics, to remove impurities and
labels;
Rubber/Thermoplastic Blends 203

Fig. 3 Steps to obtain samples

• Grinding materials: grinding was performed using cutting tools (guillotines,

shears) to obtain pellets about 1–2 mm size and further using a centrifugal mill
ZM 200 to obtain particulate sizes of 0.5–1 mm.
• Components mixing, dosed by various recipes and strengthening using
additives;
• Forming composite—produced by compression molding, resulting in samples of
rectangular shape (10 9 10 9 120 mm3);
• Cooling—for completion the samples shape;
• Removal of the mold from the samples;
• Product packaging.

11.5 Techniques for Characterization of Rubber—PET

Composites Laboratory

The samples were tested and analyzed in the Department for Renewable Energy
Systems and Recycling within the Transilvania University of Brasov, following
the characterization methods included in Fig. 4.
The samples were analyzed in terms of:
• Physico-chemical properties, by FTIR and contact angle measurements, DSC,
XRD and AFM analysis, following the structural changes and possible physical

Fig. 4 Techniques for characterization of composites

204 C. Cazan and A. Duta

and chemical interactions at interface matrix—filling material, with proper

amendments;
• Mechanical properties—measuring the tensile strength, the compression resis-
tance and the impact resistance.
For each experiment three samples were tested, considering the value obtained
by mediating three test results.

11.6 Steps to Optimize Experimental Parameters

Composition and Technological Parameters

The optimal conditions for obtaining composites based on recycled rubber and
plastic products were identified by studying the influence of the following
parameters:
• composition parameters—the type of recycled rubber, PET percentage of
composite, additives used, percentage of oxide in the inorganic—organic
composites;
• process parameters—molding duration, temperature, distribution patterns of the
composite components.
The composition and process parameters, were investigated in the following
sequence:
• Optimization the composites composition, using rubber as matrix;
• Establishing the optimum molding duration;
• Choice of the recycled rubber type;
• Distribution of the components in composite;
• Molding temperature;
• Maximal PET percentage in the rubber—PET—HDPE composites;
• Choice of the additive;
• Optimizing TiO2 percentage in inorganic—organic composites;
• Development of rubber—PET—HDPE—metal oxides composites (TiO2, CaO,
ZnO, fly ash).
Optimizing the composites composition with recycled rubber matrix was done by
testing several sets of samples:rubber—PET, rubber- HDPE and rubber—PET—
HDPE. The initial composition was considered:rubber:PET:HDPE = 85:10:5.
Starting from this composition, molding duration for obtaining the samples
was optimized. The study was conducted on samples obtained in a temperature
domain ranging from 180 to 260 C, at processing durations of 45 min and,
respectively of 60 min. Obtaining samples from recycled material requires a
longer compounding duration (60 min.) allowing the material to turn from the
solid into a high-elastic state; the optimal temperature depends on the recycled
materials and mainly on their transition temperatures (Tg, Tm). For the three
Rubber/Thermoplastic Blends 205

recycled materials (rubber, PET and HDPE) the optimal temperatures range from
220 to 260 C. Samples with 85 % of rubber have as optimal the temperature of
220 C.
Recycled rubber can result from different products, with different compositions
(mainly with a different content of sulfur, oxides, etc.). Due to these micro-ele-
ments, the rubber matrix behavior can be very different. Therefore, the type of
rubber was selected by preserving the previously optimized parameters, using two
different waste sources: from the tires and from bicycle tubes. Following the EDX
analysis, the sulfur content was found higher in the tires. The samples were
mechanically tested, proving that samples with high content of sulfur and zinc
(rubber from tires) obtained at temperatures above 220 C, show high tensile
strength and compression resistance, as result of crosslinking processes. Study on
the influence of rubber type on mechanical properties of PET-rubber composites
indicates that certain fillers present in the recycled rubber (S, Si, Zn, carbon black)
must be controlled, typically because of their crosslinking potential, actually
sometimes unwanted. According to the mechanical properties obtained, compos-
ites based on rubber tires, can be used as construction materials, such as paving
slabs, while the rubber composites, with lower sulfur content (more elastic) can be
used as sound/noise absorbing materials, for road impact damping places or for
children playgrounds.
To test the influence of the components distribution in the composite on the
mechanical properties, two sets of samples were developed—randomly mixed and
layered. For the layered samples there were recorded high levels of compression
forces however, the risk of delamination is high, so these composites can be
recommended as pavement materials for indoor dry spaces, while randomly mixed
composites can be used for outdoor applications.
The effect of additives on the rubber—PET interface was investigated based on
the interface properties, preserving the processing conditions. Samples were
obtained with the rubber composition:PET:additive = 70:25:5, testing as additives
polymers (HDPE, LDPE) and inorganic fillers (TiO2). Based on the experiments, it
was found that HDPE’s develops stronger interfaces comparing to other additives,
and the composites can be used as construction materials [76].
While rubber recycling has numerous technological variants, PET recycling for
product development raises plenty of questions because re-processing is quite
limited. Therefore, embedding a higher amount of PET in the composite represents
a target set for the next studies. Various samples with a different PET percentage in
the composites were prepared with a PET content ranging from 10 to 45 %. Stable
composites were obtained, which show no delamination, by integrating up to 35 %
PET in the rubber matrix, using HDPE as a compatibility agent. These composites
can be used as construction and insulating materials.
It was aimed at optimizing the percentage of TiO2 in inorganic—organic
composites with the generic composition:rubber:PET:HDPE:TiO2 = (60-
x):35:5:(x \ 2), considering the well known experience from rubber processing,
where inorganic fillers strongly improve the mechanical properties [77]. Samples
with low TiO2 content (0.25–0.5 %) were obtained with improved mechanical
206 C. Cazan and A. Duta

properties, being thus recommended for building materials like paving slabs for
outdoor landscaping, courtyards, protection pillars, etc.
Based on these results, different samples were obtained with the composition
rubber:PET:HDPE:metal oxide = 59.75:35:5:0.25. Differences which arise
between samples obtained with different fillers can be attributed to their nature,
primarily their influence on the interface. The thermal analysis run on these
samples shows that nano-fillers have a favorable effect on the thermo-oxidative
stability of the polymeric composites. The specific characteristics recorded during
the mechanical testing show that the highest tensile strength corresponds to
composites containing CaO. If metal oxides addition has a beneficial effect, adding
a complex of oxides could preserve this effect. Therefore, another waste was tested
as additive—the fly ash resulted from coal burning.
Fly ash is a mixture of crystalline, polycrystalline and amorphous oxides with
carbon black. Adding fly ash in the composite does not significantly influence the
thermal behavior of the samples, but promotes the development of porous, het-
erogenous structures, with voids having an irregular distribution. Considering the
outstanding records for these samples containing only recyclable materials, we
recommend their use as paving material in indoor applications.

11.7 The Influence of Environmental Factors on Polymer

Composites with Inorganic Fillers

Environmental factors may influence, alone or associated the functional properties

of the composite materials both on microscopic and macroscopic level; they cause
the composite ‘‘aging’’ and shorten their lifetime at a minimal level of perfor-
mance. The aging process involves chemical bond cleavage as a result of oxidation
reactions, cross-linking, polymerization/depolymerization, decomposition [78].
Accelerated aging tests are designed to estimate the relative resistance of the
composites over time. Assessment of the aging rate is done by maintaining the
composites under a controlled amount/flow of aging factor(s) for limited durations,
after which the main properties are measured and compared with those corre-
sponding to the samples kept in non-aggressive media.
The most influential factor in changing the thermal transitions of the polymer
nanocomposites is the interaction between the filler/additive and the polymer
matrix that influences the spatial constraints or the confinement. By reducing the
vacant volume of the interface matrix rubber—additive, a decrease in the chain
flexibility will result, having as effect a reduction in the glass transition temper-
ature. As result, the accelerated aging tests will target these interactions which can
be more easily destroyed by an energy input (thermal, UV, etc.).
The polymer composites optimized with inorganic filler material (rub-
ber:PET:HDPE:inorganic additive = 59.75:35:5:0.25) were maintained in harsh
environments: temperature variations, UV irradiation and salty mist. Their
Rubber/Thermoplastic Blends 207

characterization has been done by FTIR analysis (bond formation/constraints), dif-

ferential scanning calorimetry (phase transitions), X-ray diffraction (crystalline
phase amount and structure), atomic force microscopy (morphology), contact angle
measurements (surface charge); the results were confirmed by mechanical tests.
The materials used were composites, having:
• The matrix—recycled rubber powder (rubber from tires, 0.5 mm);
• Organic filler material—PET powder (0.5–1 mm);
• Additive—HDPE powder (0.5–1 mm);
• Inorganic filler material—metal oxide nanoparticles—TiO2, ZnO, CaO and fly
ash respectively.

11.7.1 Influence of Low Temperatures

The fillers in the polymer nanocomposites structure have as effect an increase in

the thermal stability of the composite material. Interactions between polymer and
inorganic filler materials are powerful and increase the molecular cohesion energy
and hence the heat needed to activate the mechanism of thermal degradation [78].
Four series of composite material were developed, based on rubber, HDPE and
PET and one oxide was added as inorganic filler: CaO, ZnO, TiO2 or fly ash.
Samples marked with K-1 (TiO2), K-2 (CaO), K-3 (ZnO), K-4 (fly ash) were
analyzed. For each test three samples were analyzed and the representative results
were considered. The samples were kept in the laboratory at low temperatures
between -40 and -10 C for 500 h, then tested and analyzed following physico-
chemical and mechanical properties. The results were compared with samples kept
at room temperature, considered standard.

FTIR Analysis

The series of samples were analyzed, the bands’ values obtained from the analysis
were compared with those of the samples kept at room temperature and those of
the individual components, including the filling agents.
The IR spectra of the composite material containing TiO2 showed displace-
ments of several bands: from 1,720 to 1,714 cm-1—corresponds to C=O
stretching vibration and indicates the presence of oxidation components on rubber
surface; 1,524–1,537 cm-1—attributed to stretching vibrations of C=C of aro-
matic nucleus; 1,411–1,410 cm-1—C=O group vibration resulting from the
polymers oxidation; 1,376–1,375 cm-1; 1,341–1,342 cm-1—are due to bond-
stretching vibration of –C–C– from –CH3 and to the deformation and vibration of
the styrene nuclei; 907 cm-1 la 906 cm-1 existing bands due to deformation
vibration of carbon-hydrogen bond to the aromatic nuclei; 730 cm-1 la
729 cm-1—predominant PET bands in this period are moved to lower wave
numbers, corresponding to weaker bonds.
208 C. Cazan and A. Duta

For samples containing CaO there were recorded bands’ shifting from 1,261 to
1,260 cm-1 and from 869 to 865 cm-1 (C–C valence vibration). No bands were
noted at the wave numbers: 1,714, 1,219, 1,494, and 1,862 cm-1; they formed a
band with low intensity at 1,409 cm-1 corresponding to the strain in the plane of
the group –OH alcohol resulting from the oxidative degradations of composite
material components.
For samples containing ZnO, due to possible chemical interactions between the
components, new bands were registered: 1,587 cm-1 (assigned to the stretching
vibrations of C=C of aromatic nucleus) 1,492 cm-1, and band shift were recorded,
from 2,117 to 2,113 cm-1; from 1,263 to 1,257 cm-1; from 723 to 719 cm-1 as
result of the physical interactions between the components in the composite
material.
For samples containing fly ash some characteristic bands were no longer
recorded: at wave numbers of 1,302, 1,141 cm-1 (CH deformation in plane C–C
valence vibration) and a new band was formed at 1,720 cm-1 corresponding to
aldehyde C=O group vibration. Also bands shift from 932 to 958 cm-1 can be
obtained (corresponding to the deformation vibration of carbon-hydrogen bond to
the aromatic nucleus).
All these aspects indicate interactions developing bonds, ranging from chemical
(strong) to physical (weak) that contribute to the interfaces formation; the strongest
interfaces correspond to the samples with CaO and ZnO, while the samples with
TiO2 have developed pure physical interfaces.

Differential Scanning Calorimetry

The comparative Differential Scanning Calorimetry (DSC) study on the thermal

behavior of the samples without and with TiO2 is presented in Table 1, for the
samples kept at low temperatures. The results show that the melting temperatures
(Tt) are slightly changed by incorporating the inorganic filler. The heats of fusion,
however, decrease when adding the fillers. This change is explained by the lower
degree of crystallinity and by the increase in the crystallites size, indicating a
possible supra-organization around the oxide powder.

X-ray Diffraction

The X-ray diffraction spectra of the samples containing TiO2, kept at low tem-
peratures are presented in Fig. 5 and present a typical halo, characteristic to the

Table 1 Thermophysical parameters for the samples kept at low temperatures

Thermophysical properties Tm (8C) DHm (J/g) vc Tg (8C) DCp (J/g*8C)
Composites with TiO2 122.84 2.50 0.08 -35.61 1.158
247.73 5.14
Rubber/Thermoplastic Blends 209

Fig. 5 Diffractometry for

samples containing TiO2 kept
Tlow

amorphous phase, given mainly by rubber; the crystalline phase is mostly related
to the other components in the composite.
No new peaks were observed (supplementary to those corresponding to the
single components forming the composite assembly), proving that the interface
does not contain new crystalline compounds. The crystallites sizes were calculated
using the Scherrer equation (241 nm) and the crystalline degree was evaluated at
0.1, which is consistent with DSC analysis result. There is an increase of the
crystallites sizes from 154.13 nm (samples kept at room temperature) to 276 nm
(samples kept at low temperatures).

Atomic Force Microscopy

The surface characteristics of the composites were evaluated based on Atomic

Force Microscopy (AFM) analysis Fig. 6. Rather inhomogeneous surfaces are
resulting, which is expected considering the initial dimensions of the component
pellets, also reflected by the high average roughness. It is important to notice that
in performing AFM on composites with components having initial dimensions
much larger than the scanning area, special attention must be devoted in choosing
the analysis spot. Otherwise, results without any significance are actually obtained.

Contact Angle Measurements

Contact angle measurements were made using water and 3.5 % NaCl solution, for
10 min, at a liquid flow into the droplet of 1lL/s; the recorded data are presented
in the Figs. 7 and 8.
210 C. Cazan and A. Duta

Fig. 6 AFM images for

samples kept Tlow

Fig. 7 Hwater angle variation

with time for samples kept at
low temperatures

A linear dependence of the water contact angle could be observed, with the
specific fitting parameters presented in Table 2. Two types of kinetics were
checked in the water/composite heterogeneous systems and, for all samples, the
pseudo-second order kinetics is predominant, resulting in high values of the rate
constants, k.
A comparative analysis on the contact angle values of the samples kept at low
temperatures and at room temperature shows higher values for the latest. This
means that at low temperatures changes have occurred, as confirmed by the AFM
analysis, increasing the roughness (from 699.54 nm for samples at room temper-
ature to 1364 nm for samples kept at low temperatures). With decreasing tem-
perature, the materials tend to develop a glassy phase, the main component
responsible being rubber (which crystallizes at about -25 C).
Rubber/Thermoplastic Blends 211

Fig. 8 Hsalt angle variation

with time for samples kept at
low temperatures

Table 2 Linear dependence of specific fitting parameters hapa for samples from Tlow
Type samples First-order pseudo-kinetics Second-order pseudo-kinetics
k R2 k2 he R2
K-1 0.0003 0.9705 0.1030 52 0.9983
K-2 0.0266 0.9768 0.0678 32 0.9958
K-3 0.0114 0.9996 0.0654 83 0.9995
K-4 0.0106 0.9979 0.0831 70 0.9996

Table 3 Surface energy values for nanocomposites

Composites with Surface tension Dispersive component Polar component
(mN/m) (mN/m) (mN/m)
TiO2 68.81 0.65 63.16
CaO 53.26 21.79 31.47
ZnO 16.21 4.29 11.92
Fly ash 66.28 65.32 0.95

In the contact angle measurement using NaCl solution, the values are lower,
proving slightly polar surfaces (low charged). It is not only the surface charge but
also the surface pores/voids responsible for these values. The samples with ZnO
and CaO have an uneven surface, favoring a fast absorption/adsorption.
Surface energies were estimated using the contact angles values and the specific
surface tensions of the two liquids, Table 3. Surface energy data confirms the
predominant influence of polarity on the contact angle value; ash containing
composites have a significant amount of surface energy, almost exclusively as
result of the dispersive interactions, once again confirming the low surface polarity
as result of a good mixing of the fly ash in the composite bulk. On the other hand,
212 C. Cazan and A. Duta

Fig. 9 Adhesion work diagram for the sample containing ZnO kept at Tlow

the TiO2 composite has a high value of the polar component indicating a surface
segregation. These data confirm that even in the absence of active interfaces, the
presence of inorganic components produces reorganizations of polymeric com-
ponents and a different behavior at low temperatures.
The work of adhesion of the liquid on the solid phases was estimated based on
the polar and dispersive contributions of the surface tensions of the two testing
liquids, Fig. 9. For the samples containing ZnO, with a low surface energy, the
adhesion work diagram was plotted. The chart shows that the two liquids are not
within tolerance lines (red lines) so no liquid wet the surface, confirming the high
values of the contact angles (h [ 90).
According to the mechanical properties, it can be concluded that the best
resistance at low temperatures was exhibited by the samples containing fly ash,
with compression forces up to 8,000 N and impact resistance of 9.92 kJ/m2. This
composite material can be used as building material as plates/slabs/paving mats
outdoors in winter.

11.7.2 The High Temperatures Influence

Aging can also be the result of high temperatures action. The samples were kept at
temperatures between 10 and 50 C, in laboratory conditions for 500 h, in order to
monitor the physico-chemical and mechanical changes and for choosing the
optimal applications. In the samples analyzed were contained following fillers:
TiO2, CaO, ZnO, and fly ash.
Rubber/Thermoplastic Blends 213

FT-IR Analysis

The FTIR spectra show no new bands and no missing peaks, only low energy
bands shift proving that, in this range, temperature does not strongly affects the
bulk and interface bonds.

DSC Thermal Analysis

The DSC thermogram was developed for the sample with TiO2. Two melting
temperatures can be identified, similarly with the low temperatures behaviour,
corresponding to HDPE and PET in the composite, Table 4. Compared to the
standard sample (kept at room temperature), there is a variation of the transitions
energies and a correspondent increase in the crystallinity degree, as result of
possible structural reorganizations, without developing new types of structures and
associations.

X-ray Diffraction

These data are confirmed by the XRD pattern of the samples containing TiO2,
Fig. 10, where no changes are observed in the peaks position, allowing the con-
clusion that this average temperature domain (usually corresponding to summer
temperatures) has no strong impact on the composite structure.

AFM Analysis

If not the temperature as such, the thermal treatment duration (500 h) could be an
aging cause. A change in the microphase morphology resulted in a decrease in the
average roughness (RMS) at values down to 430 nm, Fig. 11. The possible
mechanisms may include macromolecular chains rearrangements, forming denser
structures. The sample has a porous structure, mainly as result of the TiO2
nanoparticles agglomeration.

Contact Angle Measurements

Interaction between the liquid and the surface was estimated by contact angle
measurements. Values of the h angle recorded for 10 min are presented in Figs. 12
Table 4 Thermophysical properties of samples containing TiO2 kept Thigh
Thermophysical properties Tm (8C) DHm (J/g) vc Tg (8C) DCp (J/g*8C)
Composites TiO2 123.03 12.08 0.67 -45.01 0.764
243.78 9.41
214 C. Cazan and A. Duta

Fig. 10 Diffractometry for

samples containing TiO2 kept
at Thigh

Fig. 11 Images of atomic

force microscopy for samples
kept at Thigh

and 13. It is observed the linear dependence of the water angle and the high values,
over 908 indicating that wetting is not a likely mechanisms because of the surface
energy and/or uniformity and/or compact structure of the samples. Exceptions are
the samples containing with ZnO and 77.5 angle, having a porous surface, making
wetting possible. This sample presents however a high value of the contact angle
when using NaCl solution, (96.78), confirming the bulk infiltration of the ZnO
nanoparticles.
Compared with the samples preserved at room temperature, the samples tested
at higher temperatures show: higher hwater values for samples with CaO, TiO2 and
lower values for those containing ash and ZnO and higher hsalt values for samples
with CaO, ash, ZnO and lower values for those containing TiO2. As in all
Rubber/Thermoplastic Blends 215

Fig. 12 Hwater angle

variation with time for
samples kept at high
temperatures

Fig. 13 Hsalt angle variation

with time for samples kept at
high temperatures

investigated cases, this behavior is caused, obviously, by the surface energy which
is influenced by at least two factors:
1. Surface composition: the oxide powder increases the surface energy and
emphasizes the wetting phenomenon, while migration/agglomeration of pow-
ders in the composite volume leaves free a hydrophobic surface with low
energy.
2. Surface roughness: a rough surface, fractured, with edges and corners has a
great(er) surface energy and a more hydrophilic/less hydrophobic behavior
compared with a less rough surface.
216 C. Cazan and A. Duta

Table 5 Linear dependence of specific fitting parameters hwater for the specimens kept at Thigh
Composite with First-order pseudo-kinetics Second-order pseudo-kinetics
k R2 k2 he R2
TiO2 0.0117 0.9986 0.0631 83 0.9995
CaO 0.0103 0.9982 0.0695 85 0.9996
ZnO 0.0273 0.9738 0.0410 59 0.9968
Fly ash 0.0094 0.9984 0.0786 82 0.9996

Table 6 Surface energy values for specimens kept Thigh

Composites with Surface tension Dispersive component Polar component
(mN/m) (mN/m) (mN/m)
TiO2 67.4 58.18 9.22
CaO 100.56 98.25 2.32
ZnO 78.56 68.51 10.05
Fly ash 22.48 0.04 22.44

The specific fitting parameters for the linear dependence of the contact angle
versus time are presented in Table 5. From the slope values the rate constants are
calculated and prove that, for samples containing ZnO, the adsorption/absorption
phenomena are faster than for the other composites, mainly because the samples
have a more porous aspect. Pseudo-second order and pseudo-first order kinetics are
parallel mechanisms and the first one is faster, the contribution of first-order
pseudo-kinetics mechanisms being much lower (10–15 %).
The surface energy for the samples kept at higher temperatures are presented in
Table 6. It is noted that for the samples containing TiO2, ZnO and CaO the
dispersive component prevails, confirming the predominant hydrophobic surface,
in agreement with the contact angle values. For the samples containing fly ash, a
surface charge is obvious, resulting from possible interactions between the active
centers of fly ash and parts of the polymeric components.
With the inorganic fillers in the composite materials, increased values of
mechanical strength are observed, the oxide particles acting as nucleation agents
that can lead to a size decrease of spherulite and hence the increase system
packing. Samples containing CaO showed the best mechanical strength under the
test conditions (impact resistance being 11.86 kJ/m2). As result of their properties,
these composite materials can be used as construction materials (mats, paving
slabs, impact parapets, etc.) resistant to temperatures up to 50 C, both for indoor
environments and for outdoor use.

11.7.3 Influence of UV Radiation

Aging tests were conducted by assessing the composites behavior under UV

radiation. Samples with fillers: TiO2, CaO, ZnO, fly ash, were subjected to
Rubber/Thermoplastic Blends 217

Scheme 1 The process of polymer degradation under UV exposure

accelerated aging tests, for 500 h using a fotoreactor with three lamps (F18 W-P8
Philips) placed annular. The UV-B fluorescent lamp emits up to 365 nm. In these
conditions, TiO2 has a photocatalytic activity making possible the degradation of
the organic/polymeric components (rubber, PET, HDPE) in systems containing
traces of water. This water can result from simple humidity condensation, in
regular storage conditions.
Previous studies have suggested that photo-degradation produces carbonyl and
hydroxyl groups by cleavage of the polymer chain and it can be synthesized by the
mechanism given in Scheme 1 by Rabek. A number of authors [79, 80] have
reported that final carboxyl groups are formed during the photodegradation of
PET, and they act as a catalyst to further promote degradation [81].
During photodegradation, PET molecules are subject to division on both ends
of the chain, forming the final carboxyl groups. Possible reactions are shown in
Scheme 2. PET strongly absorbs radiations up to 310 nm, while higher wave-
lengths support the generation of carboxyl marginal groups also inside the com-
posite not only in the surface layers. However, the results indicate that degradation
is more intense near the samples surface, [82].
A certain protection is given by the carbon black, existent in recycled rubber,
[83], which strongly absorbs into the ultraviolet energy domain. Thus, the carbon
black from rubber could protect the sample’s components from UV degradation.
The same role can be played by the metal oxides, including TiO2 [84], the pro-
tective actions of this compound depending on the polymorph, rutile or anatase. In
rutile form, the hydroxyl groups (OH) on the filler surface are relatively stable,
while in the anatase form they are highly reactive and can initiate the polymers
degradation. TiO2 used in this work was a mixture of 75 and 25 % rutile anatase
(Degussa P25), thus explaining the relatively poor performance of the samples.
218 C. Cazan and A. Duta

Scheme 2 Possible reactions during UV degradation of PET

FTIR Analysis

Interface characterization and photochemical behavior under UV irradiation of the

samples were investigated by FTIR analysis, to monitor chemical changes and to
identify the degradation products.
The IR spectra of the composite containing TiO2 showed a band shift, from 1,473
to 1,486 cm-1 and the formation of new bands at 3,387 and 3,207 cm-1. The change
in the distribution of the molecular conformation is also observed in the interface
TiO2/PET, and is confirmed in these experiments by the newly formed bands.
For samples with CaO, bands shift were recorded from 2,116 to 2,113 cm-1,
from 1,714 to 1,718 cm-1 (band corresponding to C=O group and resulting from
the oxidation of polymers; it is a measure of UV degradation) and from 1,060 to
1,041 cm-1 (C–C valence vibration); the disappearance of the band at 1,537 cm-1
and the development of a low-intensity band at 1,409 cm-1 corresponding to the
planar deformation of the alcohol group –OH support the assumptions of oxidative
degradations in the composite.
For samples containing ZnO the following changes have been noted: the for-
mation of low-intensity bands at the wave numbers 1,559 cm-1 (assigned to
stretching vibrations of C=C from aromatic nuclei), 1,406, 1,203, 793 cm-1, the
band from 1,990 cm-1 is no longer shown and bands shift, from 1,714 to
1,701 cm-1, 1,494 to 1,489 cm-1, 1,098 to 1,091 cm-1. It is to remember that
ZnO also can act as photocatalyst in moisture conditions and (almost) neutral pH.
Also, we note that bands disappeared (1,302, 1,340, 1,141 cm-1 –CH plane
deformation, C–C valence vibration) in ash containing samples and the formation
of a band at 1,720 cm-1. Band shifts were shown from 1,793 to 1,900 cm-1, 932
to 958 cm-1 (corresponding to the deformation vibration of carbon-hydrogen bond
at aromatic ring). This can be linked with the rather high iron oxide content in fly
ash, likely to support a photo-Fenton degradation mechanism.
Rubber/Thermoplastic Blends 219

Table 7 Thermophysical properties of samples containing TiO2 kept UV

Thermophysical properties Tm (8C) DHm (J/g) Tg (8C) DCp (J/g*8C) vc
Composite with TiO2 124.01 12,08 -50.7 0.586 0.08
237.33 10.85

DSC Thermal Analysis

The DSC diagram of the sample containing TiO2 demonstrates that the UV
exposure led to an increased crystallinity, that is confirmed by the lower glass and
melting transition temperatures Tg and Tm, Table 7.

X-ray Diffraction

The XRD pattern of the sample containing TiO2 kept for 500 h under UV radiation
is presented in Fig. 14. Broad diffraction peaks are observed corresponding to very
small particles and/or to a significant amount of amorphous phase. The remained
crystalline phase may be the result of (re)arrangement of the polymer and/or phase
transitions (amorphous-crystalline). Crystallite sizes are about 280 nm, larger than
in the standard sample (157 nm).
The specific peaks of rubber and polyethylene are easily displaced. In addition
there are present specific HDPE peaks at 21.438 and those of TiO2. These findings
confirm the results of FT-IR and DSC analysis.

Fig. 14 Diffractometry for

samples containing TiO2 kept
in UV radiation
220 C. Cazan and A. Duta

Fig. 15 Images of atomic

force microscopy for samples
kept in UV radiation

AFM Analysis

The average roughness (RMS) was calculated based on the AFM images, Fig. 15,
for a scanned area of 25 9 25 lm2, being 89.27 nm. There is a sharp decrease of
roughness compared with the standard sample and these values can be corrobo-
rated with the expansion of the crystallites’ size. One can distinguish two majority
phases: rubber and PET, as well as spherical nanometric TiO2 particles, clustered
in the interface area.

Contact Angle Measurements

Following UV irradiation at the polymer surface, oxidation compounds result which

contain C=O groups, –OH and –COOH leading to changes in surface polarity. In
order to understand these mechanisms, contact angle (h) measurements were made
and calculation for the surface energy, [85] were developed, using as test liquids
water and 3.5 % NaCl solution; the results are presented in Figs. 16 and 17.
The contact angle measurements show higher values when 3.5 % NaCl solution
is used, as an ionic solution forms large contact angles on predominantly hydro-
phobic surfaces. Also, the use of water as test fluid produced high values of angles,
the adsorption/absorption rate in this case being smaller, which means that the
samples have a more compact structure and form stronger interfaces with low
wetting capacity.
The fitting parameters, specific to a linear dependence of the hwater angle variation
with time, for the samples UV irradiated are presented in Table 8. Adsorption/
absorption mechanisms are carried out predominantly as a pseudo-second order
kinetics, and the highest rate corresponds to the samples containing fly ashes.
In both types of tests, the samples which formed large angles were those
containing ZnO (1028 for the angle formed by water and NaCl solution and 978)
Rubber/Thermoplastic Blends 221

Fig. 16 Hwater angle variation with time for samples kept in UV radiations

Fig. 17 Hsalt angle variation with time for samples kept in UV radiations

Table 8 Linear dependence of specific fitting parameters hwater for the specimens kept at UV
radiations
Composites with First-order pseudo-kinetics Second-order pseudo-kinetics
k R2 k2 he R2
TiO2 0.0121 0.9985 0.0713 71 0.9994
CaO (0…0,8 min) 0.0155 0.9843 0.0658 69 0.9991
CaO (0,8…10 min) 0.0231 0.9878 0.0756 64 0.9996
ZnO 0.0080 0.9974 0.0828 93 0.9997
Fly ash (0…1,5 min) 0.0001 0.9761 0.0872 86 0.9997
Fly ash (1,5…10 min) 0.0023 0.9854 0.0854 79 0.9993
222 C. Cazan and A. Duta

Table 9 Surface energy values for samples kept UV radiation

Composites with Surface tension Dispersive component Polar component
(mN/m) (mN/m) (mN/m)
TiO2 24.90 8.09 16.81
CaO 28.07 2.44 25.63
ZnO 14.15 10.25 3.90
Fly ash 21.85 3.23 18.61

and ash (858 for the angle formed by water and 958 for solution NaCl). The
photochemical degradation is possible to form surfaces more or less porous, or
rough, so the samples on which the UV effect was the strongest exhibit the lower
contact angles (surface rich in polar/ionic groups). For example, there is a decrease
of the hsalt angle by 34.7 % for the samples with fly ash, due to the large pores on
the composite surface, emerged from the UV degradation.
The surface energy values are presented in Table 9. Except the samples con-
taining ZnO, all the other samples show a predominant polar surface, confirming
oxidation/degradation. The overall surface energy corresponding to the sample
with ZnO is low, the surface is thus predominant hydrophobic, supporting the idea
that, the photocatalytic effect of ZnO is not very strong and/or the oxides particles
are not predominantly stacked at the surface.
As a result of oxidation processes, on the surface of the samples new volatile
chemical species may occur, which cause cracks and holes that lead to a brittle
material, mechanically weaker. As degradation occurs, the composite matrix is
damaged, so it reduces the quality of the filler—additive—matrix interfaces. Sup-
plementary, inorganic nano- and micro-particles can agglomerate at the surface and/
or in the bulk. In these cases the contact angle values can be modified, due to the
roughness values that changes the droplet disposition on the sample surface, [86]. So,
although the contact angle measurements provide an overall view of the hydro-
phobic/hydrophilic surface behavior, they cannot uniquely assign the cause.
Based on the values of the polar and dispersive components of the surface
energy, the work of adhesion chart can be developed, allowing to estimate the
sample’s wettable behavior, Fig. 18. It is noted that the two characteristic points
corresponding to the test liquids are not under red lines, indicating the phenom-
enon of wetting. The work of adhesion for water is 84.44 mN/m and for the NaCl
solution it is 78.88 mN/m.
UV radiation mainly affects the rubber structure in the surface layer, releasing
volatile products, [87] and forming pores. The PET is also susceptible to degra-
dation under the UV irradiation, leading to molecular weight reduction [88]. These
changes could be limited or expanded by adding the inorganic fillers.
Samples containing ZnO are more resistant to UV irradiation, comparing to the
samples without any inorganic additive. The results prove that ZnO acts as a
photo-stabilizer in small amounts and can effectively improve the photo-stability
of the composite polymers [89–91]. A similar effect is registered for samples
Rubber/Thermoplastic Blends 223

Fig. 18 Adhesion work diagram for the sample containing TiO2 kept in UV radiation

containing CaO, which showed the best UV stability (having, for example, the
tensile strength diminished only by 5 % comparing to the non-irradiated samples).
On the other hand, titanium dioxide promotes UV photodegradation, forming
active hydroxyl radicals, [92, 93], and accelerate the samples’ degradation.
Choosing the inorganic filler must be done according to the applications. Indoor
products, seldom subjected to UV irradiation, can benefit on the enhanced
mechanical properties of the composites containing TiO2 or fly ash, while outdoor
goods are recommended to be developed using fillers that never promote photo-
degradation, as CaO.

12 Conclusion

Composite materials can be considered advanced materials with controlled prop-

erties, being a particular priority area supported worldwide. Their design, the
structural and functional optimization, the development of specific products, of
manufacturing and processing technologies is mostly characterized by extended
interdisciplinary.
The properties of composite materials can be modified under the action of
certain physical, chemical, environmental or mechanical factors, both at micro-
and macroscopic level.
Tailoring a composite must target a set of properties, directly related to the
applications. It is also important to remember that this set of properties must be
preserved during their lifetime, under the working conditions. Being the result of a
synergic mix of components, the composites may act as a new material or as an
224 C. Cazan and A. Duta

assembly of components, depending especially on the newly developed interfaces.

Strong interfaces can result by new chemical bonds or by cumulative (but large)
physical interactions. The PET-rubber composites, using HDPE as compatibility
agent represent a good example, detailed in this chapter.
Second raw materials used for composite development raise supplementary
problems, derived from the various degrees of degradation, existent in each
component. Still, as the results proved, rubber—PET—HDPE composites, with
good mechanical properties can be obtained. Adding low amounts of inorganic
fillers represents a supplementary path to tailor the functional properties.
Not any inorganic filler is suitable for any application. The studies on the
influence of environmental factors (temperature, UV radiation), [39, 40] on rubber-
PET-HDPE composites with inorganic fillers (TiO2, ZnO, CaO, ash) found that:
• The fillers in the polymer nanocomposites structure increase the thermal sta-
bility of the material;
• Interactions between polymer and inorganic filler materials are strong and
increase molecular cohesion, thus increasing the heat required for thermal
degradation;
• Low temperatures have a much stronger influence on composites degradation
(aging) comparing to average and high temperatures;
• Photocatalytic materials are to be avoided for outdoor products and have no or
little effect in indoor applications;
• The use of an inorganic waste, fly ash, results in composites with very good
mechanical properties, and these composites are recommended especially for
indoor applications.
‘‘The results prove that the use of waste-polymers as second raw materials
represent a topic where research is still expected, for increasing the quality of the
resulted materials and for extending the applications, towards high-tech products.
Following the increasing demands of the recycling legal framework, it is expected
that the interfaces control, particularly in organic-inorganic composites will be
able to provide new paths, readily up-scalable for a truly sustainable industrial
development.’’

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