Graziano 2018

Article
Journal of Elastomers & Plastics

1–46
Review on modification ª The Author(s) 2018
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DOI: 10.1177/0095244318783806
polypropylene immiscible journals.sagepub.com/home/jep
thermoplastic polymer
blends for enhancing their
mechanical behavior
Antimo Graziano1 , Shaffiq Jaffer2 and Mohini Sain1
Abstract
Blends of polyethylene (PE) and polypropylene (PP) have always been the subject of intense
reasearch for encouraging polymer waste recycling while producing new materials for
specific applications in a sustainable way. However, being thermodynamically immiscible,
these polyolefins form a binary system usually exhibiting lower performances compared
with those of the homopolymers. Many studies have been carried out to better under-
stand the PE/PP blend compatibilization for developing a high-performance and cost-
effective product. Both nonreactive and reactive compatibilization promote the brittle
to ductile transition for a PE/PP blend. However, the final product usually does not meet
the requirements for high demanding commercial applications. Therefore, further PE/PP
modification with a reinforcing filler, being either synthetic or natural, proved to be a good
method for manufacturing high-performance reinforcend polymer blend composites, with
superior and tailored properties. This review summarizes the recent progress in com-
patibilization techniques applied for enhancing the interfacial adhesion between PE and PP.
Moreover, future perspectives on better understanding the influence of themodynamics
on PE/PP synergy are discussed to introduce more effective compatibilization strategies,
which will allow this blend to be used for innovative industrial applications.
Keywords
Blends, compatibilization, mechanical properties, thermoplastic, polyolefins
1
Center for Biocomposites and Biomaterials Processing, Faculty of Forestry, University of Toronto, Toronto,
Canada
2
TOTAL American Services, Hopkinton, MA, USA
Corresponding author:
Antimo Graziano, Center for Biocomposites and Biomaterials Processing, Faculty of Forestry, University of
Toronto, Toronto, Ontario M5S 3BS, Canada.
Email: antimo.graziano@mail.utoronto.ca
2 Journal of Elastomers & Plastics XX(X)
Introduction
The study of polymers and polymer blends has had an enormous impact on both industry
and academia over the last decades. The potential of these materials in serving as a tool
for new applications is huge.1–3 Indeed, steel and aluminum are finding less use, espe-
cially in transportation industries, because polymers are able to reduce both cost and
mass, keeping the level of safety high. Thermoplastic polyolefins (POEs) are widely
exploited for automotive applications, offering additional sustainability and innova-
tiveness.4 A further way of developing a product with tailored properties and suitable for
high demanding applications is blending two polymers, which is also faster and cheaper
than synthesizing the final product from scratch. However, most of the times, polymers
are thermodynamically immiscible, as the Gibbs free energy of the system is positive.
This causes the creation of an interface and weakens the interfacial adhesion between the
two polymers. The extra energy present at the interface keeps them separated from each
other, leading to interfacial failure, thus lowering the mechanical properties.5,6 This is
definitely the case of polyethylene (PE) and polypropylene (PP), which are incompa-
tible, although they have similar structures. Much research has been done on blending PE
and PP and the overall properties of the resulting binary system.7–11 Another important
factor that has always been considered in the case of immiscible polymer blends is the
morphology development during melt blending.12 The creation of a matrix–droplet
morphology, where the minor phase is distributed in the major phase as droplets of
irregular and random shape, is often the case of incompatible polymer blends, and the
balance between shear forces and interfacial forces characterizes the breakup of the
minor phase during melt blending. Amount of shear, viscosity ratio, blend composition,
processing parameters, type of flow, and interfacial tension (IFT) are critical factors that
influence the blend morphology. Understanding how these parameters affect the final
morphology and how the coalescence of the minor phase can be hindered is vital for
having a final product with enhanced overall properties. The PE/PP binary system has
been gaining a great interest since decades ago, due to good availability, low cost, good
performance, and great processability.13 However, for this blend to be used in advanced
applications, there is the need for enhancing the synergy between PE and PP, leading to
superior physicochemical and mechanical properties. Different and effective methods of
PE/PP compatibilization have been widely explored in the past decades, giving a better
understanding of how specific coupling agents can act as emulsifiers at the blend
interface, reducing the energy gap that keeps the two polymers separated from each
other, hence increasing the interfacial adhesion. This ensures a more facilitated stress
transfer along a stronger and thicker blend interface, a finer morphology, and enhanced
overall properties. This review article is mainly focused on PE/PP polymer blends and
the methods of their compatibilization, along with PE/PP-reinforced composites with
both synthetic and natural reinforcing fillers. Finally, the introduction of graphene as a
precursor for bringing full synergy between PE and PP, leading to superior and unique
properties, is presented as a future perspective, which will allow the use of PE/PP blends
in advanced industrial applications.
Graziano et al. 3
Overview on PE
PE is a semicrystalline thermoplastic POE, with ethylene being the single monomer
constituent, and it is the most widely used commodity plastic in the world. The list of
commercial applications that PE is used for is quite large, going from packaging, pipes,
medical devices, coating, all the way to automotive applications.14 The particular type of
application that PE is used for depends on the nature and the characteristics of the PE
itself. Indeed, this polymer comes in several forms:
High-density PE (HDPE): It has the highest degree of crystallinity and is the most
versatile among all the PEs. It is also the most stable PE because it has less
number of short branches, meaning that the chains pack into the crystal structure
very well.
Low-density PE (LDPE): It is a ductile and flexible material, with unique flow
properties. This is because it has a high degree of chain branching, which causes
weak intermolecular interactions.
Linear low-density PE (LLDPE): It has a linear structure and very high number of
short branches, which makes it useful for film applications, given its transparency,
flexibility, and high toughness.
The structures of these types of PEs are depicted in Figure 1.15
Overview on PP
PP is the second most used thermoplastic polymer in the world, due to high
availability, moderate cost, ease of manufacturing, and good properties. It is
made from the combination of propylene monomers and used in many applica-
tions, such as household appliances, packaging, and electrical and equipment
manufacturing, as well as applications in the transportation sector. There are
three kinds of PP:
Atactic PP (aPP): These are completely amorphous with methyl groups randomly
placed on the main chain. It does not have a melting temperature, and it just
softens upon heating until it flows like a very viscous liquid.
Syndiotactic PP (sPP): These are semicrystalline polymers with methyl side
groups alternatively oriented and positioned along the main chain. It is more
homogeneous than aPP.
Isotactic PP (iPP): These are semicrystalline polymers with the highest
degree of crystallinity. The methyl groups are all oriented on one side of
the main chain, which makes this type of PP very homogeneous and
stable.16
The structure of iPP is illustrated in Figure 2.

Figure 1. Structures of HDPE (a), LLDPE (b), and LDPE (c). Source: Reprinted from the work of
Pasch and Eselem Bungu,15 copyright © with permission from the Royal Society of Chemistry.
HDPE: high-density polyethylene; LLDPE: linear low-density polyethylene; LDPE: low-density
polyethylene.
Figure 2. Structure of iPP. Source: Reprinted from the work of Maddah,16 copyright © with
permission from the Scientific and Academic Publishing. iPP: isotactic polypropylene.
POE catalysis technologies and industrial applications

Ziegler–Natta (ZN) catalysis is one of the oldest technologies employed to manufacture
POEs such as PEs and PPs. ZN catalysts have a titanium chloride as the main catalyst and
an aluminum alkyl as the co-catalyst. The combination of them gives the active site that
coordinates the ethylene molecules. ZN-derived POEs have high heterogeneity, due to a
high number of stereo defects and unwanted side reactions, and a broad molecular weight
distribution, leading to very different overall performances, also difficult to control.17
Consequently, this limits their potential of being used for a wide range of industrial
applications. Regarding durable long-term applications, they are used for plastic pipes,
wires, and cable coatings, while in terms of consumable short-term applications, they are
utilized for garbage bags, packaging, and paper coating. On the other hand, metallocene
(M) catalysis (developed in the 1990s) uses single-site catalysts, ensuring higher site
Graziano et al. 5
specificity, less stereo defects, and fewer unwanted side reactions. Furthermore, being
less heterogeneous in nature than ZN ones, M-based polymers have a narrower mole-
cular weight distribution.18 This gives M-based polymers more specific, better con-
trolled, and higher properties. M-based POEs are used as impact modifiers for
automotive parts to increase toughness, without scarifying stiffness and heat resistance.
An example is Dow’s ENGAGE ethylene–octene copolymer (EOC). They are also
employed in food packaging due to their high tensile strength (TS), toughness, and well-
controlled thermal stability for meeting the strict requirements of shrinkage, abuse
resistance, and seal performance. M-LLDPE ExxonMobil’s EXACT plastomer for
heavy-duty bags is an example. Recently, a new post-M catalysis technology was
developed (it consists of pyridyl amine catalysts), allowing manufacturers to come up
with unique POEs that exhibit superior physical and mechanical behavior, as well as
even narrower molecular weight distributions, compared to ZN- and M-based POEs.19
This will encourage mass production of cost-effective and high-performance POEs to be
used in high demanding and innovative industrial applications.
Immiscible PE/PP systems

Blending of PP and PE aims at combining the good properties of the two, developing a
final product that can be used for high demanding applications. Moreover, PE and PP
account for most of the worldwide plastic market, and, being nonbiodegradable, they
constitute a big issue when it comes to recycling them.20 Therefore, blending of PP and
PE is also seen as an effective way of reusing them and makes them useful for high
demanding applications and, while improving the recycling of commodity plastics,
favoring the development of a sustainable worldwide plastic market. However, despite
PP and PE are similar, they are immiscible, meaning that the blending of the two lowers
the properties of the final product. This is usually the case of one polymer that is neither
uniformly nor homogeneously dispersed into the other, in the form of spheres with
random dimensions. The IFT between the two polymers is high, and coalescence of the
dispersed phase is facilitated. Therefore, there is poor stress transfer along the interface
and the interfacial adhesion is low, leading to poor final properties. Nevertheless, it is
worth pointing out that there are some procedures to organize PE and PP in more
complex arrangements that combine favorably the properties of the components,
resulting in a new material that could actually be reused in industrial applications. This
also contributes in tackling the aforementioned PE and PP recycling problem. A good
example is the study carried out by Jordan et al.21 who analyzed how the interfacial
adhesion of PE/PP bilayer changes when employing different catalyzed PEs and PPs
(heterogeneous ZN vs. site-specific M), as well as different processing conditions, such
as cooling rate of the processed PE/PP bilayers. These factors affect the crystallization of
the polymers and the alignments of their chains at the PE/PP bilayer interface, having a
great impact on the interfacial adhesion. Four classes of interfaces were identified, as
illustrated in Figure 3.
The excess oligomer class is represented by ZN-based PE and PP, displaying a weak
interface, hence low interfacial adhesion. This happens because ZN polymers have a
Figure 3. Schematic representation of the four classes of POE interfaces. Source: Reprinted from
the work of Jordan et al.,21 copyright © with permission from the American Chemical Society.
POE: polyolefin.
large amorphous noncrystallizable character. Therefore, when blending ZN PE with ZN

PP, the excess of amorphous oligomer at the interface prevents cross-interfacial crys-
tallization (strong chain entanglements between the crystalline domains of the two
polymers), weakening the interface, which leads to low interfacial adhesion. On the
opposite end, there is the class of entangled crystals, represented by pairs of M-based PE
and PP, which have almost no amorphous character. Thus, interfacial interlocking is
favored in this case and the anchoring between the crystals of the two polymers is so
strong that the interfacial adhesion increases significantly, being 40 times higher than the
one displayed by the excess oligomer class. Another favorable aspect for the entangled
crystals class is that the applied cooling rate of the processed PE/PP bilayers was much
higher, compared to the case of excess oligomer class. The two intermediate classes of
easy chain pullout and kinetically trapped entanglements are connected to the employ-
ment of a lower cooling rate and the use of a PE with higher amorphous character,
compared to the excess oligomer case, respectively. This study suggests that, by
understanding and controlling processing conditions and polymer’s nature, a more
sustainable use of mixed recycled streams could be applied. Another interesting work on
this matter was done by Mauri et al.22 on the enhancing the properties of PE/PP binary
systems when arranging them in nanoscale multilayered films. By employing the layer
multiplying co-extrusion technique, they could come up with a PE/PP nanolayered
system, comprised of hundreds of layers, with each layer having a thickness of less than
100 nm. This way, a large amount of interfacial area between PE and PP is generated,
facilitating the surface nucleation effects. Indeed, during melt processing of a polymeric
binary system, the crystallization of one component is affected by the presence of the
other component. In their study, the presence of PE phase, in the case of high interfacial
area, favored the crystal rearrangement of PP phase, by offering a great number of
Graziano et al. 7
nucleating sites, leading to a significant increase of the mechanical properties of the

nanolayered PE/PP system, particularly the tensile modulus (TM). Moreover, no
annealing was needed since the nucleating effect of PE on the positive crystal
rearrangement of PP was effective immediately after production of the multilayered
system. More specifically, Young’s modulus, TS, and elongation at break (EB) of
the system with 257 layers (thickness of 50 nm each) increased by 87%, 21%, and
7%, respectively, compared to the system with 3 layers (thickness of 7.2 mm each).
These results could encourage large-scale manufacturing of high-performance
materials, where the high TS and heat resistance of PP is combined with high
flexibility and toughness of PE in an effective way, without the use of additives and
without the need of annealing, hence saving cost. An application that benefits from
this technique is packaging, as it is already well developed by The Compound
Company, for example, with their brand Yparex. However, applications like
packaging are short term in nature, posing an issue in recycling when there is the
need for fully recovering the pure components from these multilayered polymeric
systems, comprising petroleum-based thermoplastic POEs. Some techniques for
separation of PP and PE from mixed plastic waste streams exist, such as the
delamination process or the dissolution–reprecipitation technique for the recycling
of multilayer postindustrial waste.23 The first one consists of chemical decomposi-
tion of an interlayer, while the second one can be induced by dissolving the different
polymers of the mixture at a certain temperature, one after the other. However, these
two techniques are energy- and time consuming, very difficult and complex, and
they do not guarantee perfect separation of the components. Therefore, reprocessing
and blending of mixed plastic waste streams is usually preferred for developing a
sustainable worldwide plastics market. Compatibilization can enhance even more the
properties of both virgin and recycled immiscible binary blends. This technique,
along with other well-established modification strategies for increasing the synergy
between PE and PP, will be presented later in this review article.
Thermodynamics
A miscible polymer blend is homogeneous down to the molecular level, and it con-
stitutes a single phase, over the full range of blend compositions, under specific con-
ditions of pressure and temperature. Thermodynamically speaking, the Gibbs free energy
of mixing is given by the following equation
DGm ¼ DHm T DSm ð1Þ
where DHm is the enthalpy of mixing and DSm is the entropy of mixing. Full miscibility
is achieved when two conditions are satisfied:
1. The Gibbs free energy of the system is negative (spontaneous process).

2. The second derivative of the Gibbs free energy with respect to the volume
fraction of a component in the blend is positive (phase stability).
It must be considered that DHm refers to the interactions between the polymer
chains, and it is negative (exothermic) when attractive polar interactions (strong
covalent and ionic, in the case of bonding strong interactions, or dipole–dipole,
hydrogen, etc., in the case of nonbonding weak interactions) are present, whereas
it is positive (endothermic) when repulsive van der Waals interactions are present.
DSm is related to the degree of randomness, hence all the possible ways that the
chain units can be arranged in space. A polymer blend made up of PE and PP is a
completely immiscible system, meaning that the two polymers are incompatible.
This is because polymers with very high molecular weight create a blend with
limited possible arrangements, therefore DSm results to be very small. Moreover,
PE and PP have no attractive polar interactions, thus DHm is positive (endothermic).
This leads to a positive DGm. Flory and Huggins tried to derive an expression
(equation (2)) for DGm related to polymer blends24

DGm ja jb
¼ ln ja þ ln jb þ ja jb Xab ð2Þ
kB T ra rb
where r is the degree of polymerization, j is the volume fraction, T is the processing
temperature, kB is the Boltzmann constant, and Xab is the so-called “Flory–Huggins poly-
mer–polymer interaction parameter.” The first two terms represent the entropy of mixing,
while the last term indicates the enthalpy of mixing. Since DSm is always positive, the value
of Xab will determine the sign of DGm. Indeed, the introduction of attractive polar interac-
tions (e.g. using a coupling agent) will make Xab become negative, hence DGm will be
negative, leading to miscibility. Experimental analysis like Small Angle Neutron Scattering
(SANS), Small Angle X-Ray Scattering (SAXS), or solvent vapor sorption would give a
measurement of the value of Xab, leading to an appropriate experimental validation of the
prediction from the theory. However, Flory-Huggins Theory (FHT) assumes that Xab varies
only with temperature. Another assumption is that the monomers in the chain have the same
nature and occupy the same volume (DVm ¼ 0). Therefore, the use of the Born–Green–Yvon
theory would be more realistic, because it also considers the term DSm (exc), which could be
negative, related to free volume effect. Figure 4 illustrates the dependence of the Gibbs free
energy on the minor phase composition for a binary polymer system. As the enthalpy of
mixing is reduced by the introduction of polar strong interactions between the two polymers,
DGm becomes negative, leading to blend miscibility.
The unbalanced forces between bulk and surface create additional free energy. The
molecules at the surface have more energy than the ones in the bulk. The surface free
energy (SE) is therefore this cohesion energy U over the exposed area of a molecule,
according to equation (3)
U
g¼ ð3Þ
2a2
Each polymer has a dispersive (nonpolar) component of the SE and a polar compo-
nent (equation (4))
g ¼ gd þ g p ð4Þ
Graziano et al. 9
Figure 4. DGm dependence on the minor phase composition for different DHm. DGm: Gibbs free
energy of mixing; DHm: enthalpy of mixing.
Figure 5. SE gap between PE and PP. SE: surface free energy; PE: polyethylene; PP: polypropylene.
The gap in SEs between PP and PE is shown in Figure 5, and it is related to the
polymer binary system in the melt state (190 C).
The thermodynamic differences, in the case of a PE/PP binary polymer system, hinder
the overall properties of the final product, preventing it from being used for novel and
high demanding commercial applications. The unbalanced thermodynamics between
two immiscible polymers create an excess energy at the interface between these two
polymers, which is the IFT. Equation (5) is the Wu’s harmonic mean average equation,
and it gives the expression of IFT between two polymers25
d d
g1 g2 gp1 gp2
g12 ¼ g1 þ g2 4 d þ p p ð5Þ
g1 þ gd2 g1 þ g2
Table 1 depicts the polar and nonpolar components of the SEs of both PE and PP,
along with the IFT value for a PE/PP blend, according to equation (5), at 190 C.
Table 1. SEs, as well as polar and dispersive components, for both PE and PP.a,b
Surface free Polar component Dispersive Interfacial

T ¼ 190 C energy (mJ/m2) (mJ/m2) component (mJ/m2) tension (mJ/m2)
PE 25.9 0 25.9 —
PP 20.2 0.4 19.8 —
PE/PP — — — 1.2
SE: surface free energy; PE: polyethylene; PP: polypropylene; IFT: interfacial tension.
a
The IFT of PE/PP blend is also indicated. All the values are taken at 190 C.
b
Redrawn from the work of Sumita et al.11
Morphology
Blends with co-continuous morphologies are usually able to combine the properties of
both polymers in a favorable way. Co-continuity is, therefore, seen as the most favorable
morphological status for a polymeric binary system for displaying enhanced synergy and
superior performance. In co-continuous structures, both components form single con-
tinuous and interpenetrating structures, over the whole range of blend compositions. In
other words, each polymer is fully interconnected through a continuous pathway.
Nevertheless, co-continuity is an unstable and a nonequilibrium condition, achieved only
at the phase inversion point. Miles and Zurek26 considered a semiempirical equation
(equation (6), limited to low shear rates) for predicting co-continuity and simultaneous
interpenetrating network
Z1 j2
1 ð6Þ
Z2 j1
where Z is the viscosity of the components and j is the volume fraction.
However, phase morphology is not only influenced by viscosity ratio and composition
ratio but also by other main factors, such as IFT, amount of shear, and processing
conditions. Indeed, Taylor explained the influence of these factors by introducing a
parameter, the so-called “capillary number,” which is the ratio between hydrodynamic
stresses and interfacial stresses (equation (7))27
Zm gB
Ca ¼ ð7Þ
2G
where B is the diameter of the minor phase (spherical geometry), Zm is the matrix
viscosity, G is the IFT, and g is the shear rate. The morphology generation during melt
mixing of immiscible polymers involves processes such as fluid drop stretching into
threads, breakup of the threads into smaller droplets, and coalescence of the droplets into
larger ones. The balance of these competing processes determines the final particle size,
which results upon solidification of the blend. The analysis of Taylor considers how the
balance between applied shear forces and counteracting interfacial forces affects drop
dimensions and stability. When the two forces balance each other, equilibrium is
achieved and the critical capillary number is obtained. The surface area is minimized and
Graziano et al. 11
Figure 6. Relation between Cacrit and p for simple shear and extensional flow. Source: Reprinted
from the work of Janssen and Meijer,40 copyright © with permission from AIP Publishing.
the minor phase has a spherical shape. For Ca < Cacrit, the IFT is big and the minor phase
tends to retain its spherical shape. The IFT between two polymers provides a thermo-
dynamic driving force for resisting domain deformation and encouraging coalescence.
The shear force will never break the particle. For Ca > Cacrit, there is an irreversible
stretching and deformation, thus the drop becomes unstable and it eventually breaks.
Looking at the capillary number expression, one can understand the exact influence of
viscosity ratio, minor phase composition, shear rate, and IFT on blend morphology.28–38
The Taylor model is valid only for Newtonian fluids and simple shear flow. An
important aspect of morphology development for immiscible polymer blends is the type
of flow during melt blending. This is divided into two categories:
1. Simple shear flow: parts of the melting polymer slide over one other, in the same
direction, and go faster than one other (Taylor model).
2. Extensional flow: components flow away from one other or toward one other.
The relationship between Cacrit and viscosity ratio p, according to the type of
flow,39,40 is depicted in Figure 6.
According to simple shear flow, minimum capillary number is achieved when the
viscosities of the two polymers match, so the finest morphology is achieved. Above Zr ¼
4 it is impossible to breakup droplets. Simple shear is only for Newtonian fluids. On the
other hand, for extensional flow (2-D elongation), breakup can occur even at very high
Zr. A melting polymer acts like a viscoelastic fluid; therefore, the flow is in between
extensional and simple shear. The limiting drop size for viscoelastic systems is larger
than the one predicted by the Newtonian simple shear flow. There are two different
breakup mechanisms:
Figure 7. Schematic representation of stepwise (left) and transient (right). Source: Reprinted from
the work of Janssen and Meijer,40 copyright © with permission from AIP Publishing.
1. Stepwise equilibrium mechanism: at Ccrit, the drop breaks into two equal and
identical drops, then these break into four, and so on. In this case, the minor phase
has the shape of a droplet and it breaks only if D > Dcrit. Dcrit from Taylor limit,
which is valid only for Newtonian fluids in simple shear flow, and only for
viscosity ratios from 0.1 to 1, is given by equation (8)
4GðZr þ 1Þ
D¼ if Zr < 2:5 ð8Þ
gZm 19
4 Zr þ 4
where G is the IFT, g is the shear rate, Zm is the matrix viscosity, and Zr is the viscosity
ratio (droplet/matrix).
2. Transient mechanism: at Ca>>Cacrit, a single drop is stretched into a liquid thread

and then it breaks into multiple drops. The minor phase has a thread form and it
breaks only if D < Dcrit. Moreover, irreversible deformation occurs if Ca > 2
Cacrit (simple shear) and Ca > 5 Cacrit (extensional).
The schematic of breakup mechanism is shown in Figure 7.

By considering the Taylor theory, an equation for the final particle diameter in
immiscible polymer blends can be taken into account (equation (9))
4GZ+0:84
r
D¼ ð9Þ
gZm
where G is the IFT, g is the shear rate, Zm is the matrix viscosity, and Zr is the viscosity
ratio (droplet/matrix). The value 0.84 is considered positive if the viscosity ratio is higher
than 1, negative if Zr < 1. However, this is valid only for extruded polymer blends, low
Graziano et al. 13
Figure 8. Variation in average particle size as a function of blend composition. Source: Reprinted
from the work of Jose et al.,44 copyright © with permission from Elsevier.
concentrations of minor phase (coalescence neglected), stepwise equilibrium mechan-

ism, Newtonian fluids, and simple shear flow.
Coalescence is a phenomenon that brings particles of the minor phase to collide, then
recombination occurs, and eventually a bigger particle is created. Finer morphologies are
obtained only if coalescence is fully hindered. Collision and recombination are avoided if
the size of the minor phase is below a certain value and the viscosity of the matrix is above
a certain value.41–43 In addition, coalescence is not believed to happen if the concentration
of the minor phase is about 0.5 wt% or lower. Due to the viscoelasticity of polymers,
coalescence is a significant and common aspect of polymer melt blending. In the case of an
immiscible PE/PP binary system, the high IFT favors coalescence of the minor phase
particles, leading to a coarse morphology. The minor phase is neither homogeneously nor
uniformly dispersed into the major phase, the stress transfer is not facilitated, and the
overall properties of the final product are poor. Jose et al. studied the morphology
development of a thermoplastic polymer system made of HDPE and iPP, over the full
range of blend compositions.44 Viscosity ratio and volume fraction of the minor phase
have a big impact on coalescence of the dispersed phase in immiscible polymer blends.
Figure 8 shows the diameter of the minor phase as a function of blend composition.
Dn, Dw, and Dv are the number-average diameter, the weight-average diameter, and
the volume-average diameter, respectively. It can be noticed that as the composition of
the minor phase increases, the droplet diameter grows, because more particles are dis-
persed into the matrix, the probability of collision is higher, therefore the coalescence
effect is favored. This is valid in both cases of HDPE being the minor phase and iPP
being the minor phase. Moreover, when iPP represents the matrix, the HDPE particles
are smaller than the opposite situation of HDPE being the matrix, with the same
droplet/matrix composition ratio. For example, for iPP/HDPE (70/30) the droplet Dn is
about 3.1 mm, whereas for iPP/HDPE (30/70) the minor phase Dn is roughly 5.7 mm.
This is the proof that the viscosity ratio influences coalescence greatly. In fact, in this
research work, iPP is more viscous than HDPE. Thus, when iPP represents the matrix,
the HDPE particles are less free to flow and coalescence is more difficult to occur,
leading to a droplet size lower than the one obtained in the opposite case, with a less
viscous HDPE being the major phase. It is worth nothing that from blend composition
of 60/40 all the way to 40/60, a co-continuous morphology is seen, meaning that both
phases are dispersed and interconnected within each other. The phase morphologies of
the blends of iPP/HDPE at different compositions are represented in Figure 9. This is a
good way to graphically understand the effect of coalescence in increasing the size of
the minor phase, as the composition of the latter in the blend increases. Indeed, going
from Figure 9(a) to (c), which is the case of HDPE being the minor phase, the size of
the dispersed domains increases. The same thing happens in the cases of Figure 9(e)
to (g), where iPP is the minor phase. The insert (Figure 9(d)) indicates the case of
co-continuous morphology.
Mechanical performance
PP is known to have higher strength and stiffness than PE, while in the case of EB and
impact strength (IS), PE has better performances. When blending these two thermo-
plastics, immiscibility is seen and the resulting mechanical properties are poor, proving a
weak interface, a poor stress transfer between the two phases, and consequently a low
interfacial adhesion. Many scientific works have been done to analyze the mechanical
behavior of PE/PP binary systems.45–47 Of particular interest is the study by Shan et al.48
who investigated the tensile stress change over strain for a blend of LDPE and iPP, over
the full range of blend composition, as depicted in Figure 10.
Pure PP has the highest TS, while neat PE breaks at a very low stress point, showing
the lowest TS value. It is also worth noticing that, when iPP has a concentration of 40%
or higher, the binary system fails at very high elongations. This is related to the fact that
these materials undergo the so-called necking propagation, when being stretched in
tensile mode, showing a significant yield behavior. It can be related mainly to the
morphology and the nature of the interface of the two phases. Regarding the different
kinds of PEs and PPs, when blending LDPE with iPP, these two polymers have no
similarities in molecular structure, because the former has a high degree of short and long
side chain branching, which causes irregular packing, while the latter is very linear, has
no side branching, and its crystals are very well organized and homogeneously packed.
Therefore, no synergy occurs between LDPE and PP, with mechanical properties being
lower than the theoretical rule of mixture and the pure components, at all the blend
Graziano et al. 15
Figure 9. Phase morphologies of the blends of iPP/HDPE at different compositions. Source:

Reprinted from the work of Jose et al.,44 copyright © with permission from Elsevier. iPP: isotactic
polypropylene; HDPE: high-density polyethylene.
Figure 10. Stress–strain curves of LDPE/iPP binary system, at different blend compositions.
Source: Reprinted from the work of Shan et al.,48 copyright © with permission from Taylor and
Francis. iPP: isotactic polypropylene; LDPE: low-density polyethylene.
compositions.49 Conversely, a slightly higher synergy occurs between PP and LLDPE,

because the latter has very short and well-regulated side branches, facilitating the for-
mation of interpenetrating networks between the two phases, leading to a more densely
packed network. The highest synergy is seen in the case of blends comprising HDPE and
iPP, because a very linear PE (like HDPE) can closely approach other chains of similar
structure, thus creating a very densely packed network. Similarity in structure and
physical properties between HDPE and iPP makes them have some synergy, at some
blend compositions, under specific conditions.50 An interesting work done by Salih
et al.51 shows the difference in mechanical properties between HDPE/iPP blends and
LDPE/iPP blends. Table 2 combines their results, in the case of blends with symmetric
composition (50/50), with the results shown by Dumoulin and colleagues52 about
LLDPE/iPP blends (at the same composition). Only TS and Young’s modulus are rep-
resented in Table 2. It can be seen that HDPE/iPP has the highest properties, because of
the similar structures between the two polymers (very linear), hence more interfacial
entanglements are created at their interface. On the contrary, LDPE/iPP has the lowest
properties, due to the long side branching of LDPE, which lowers the degree of inter-
action with iPP drastically. LLDPE/iPP shows properties that are lower than the ones of
HDPE/iPP and higher than the ones of LDPE/iPP, because the side branches of LLDPE
are fewer and shorter, compared to LDPE, bringing some interactions with iPP.
Lovinger and Williams53 analyzed more closely the case of HDPE/iPP and, more
specifically, the fact that some good synergy can be seen only at some blend compositions
Graziano et al. 17
Table 2. Mechanical properties of LDPE/iPP, LLDPE/iPP, and HDPE/iPP blends.a
TS (MPa) TM (GPa)
LDPE (50)/iPP (50) 21 0.48

LLDPE (50)/iPP (50) 25 0.52
HDPE (50)/iPP (50) 32 0.61
HDPE: high-density polyethylene; iPP: isotactic polypropylene; LDPE: low-density polyethylene; LLDPE: linear
low-density polyethylene; TS: tensile strength; TM: tensile modulus.
a
Redrawn from the works of Salih et al.51 and Dumoulin et al.52
Figure 11. Variation of TS with composition for PE/PP blends, nominal stress on the primary
y-axis, true stress on the secondary y-axis. Source: Reprinted from the work of Lovinger and
Williams,53 copyright © with permission from John Wiley and Sons. TS: tensile strength;
PE: polyethylene; PP: polypropylene.
and under specific conditions. Regarding this, they investigated the ultimate TS at break,
over the whole range of blend compositions, as illustrated in Figure 11. The primary y-axis
refers to nominal stress, whereas the secondary y-axis refers to true stress. Looking at the
nominal stress, it can be observed that the TS of the blend iPP/HDPE (80/20) is higher than
the theoretical rule of mixture and even higher than pure PP. As expected, the stiffness of
iPP is higher than the one of HDPE. Interestingly, however, the modulus increases while
increasing the amount of PP in the blend, reaching a maximum in the case of iPP/HDPE
(80/20), with a value considerably higher than the one of pure iPP.
Figure 12. Variation of TM with composition for PE/PP blends. Source: Reprinted from the work
of Lovinger and Williams,53 copyright © with permission from John Wiley and Sons. TM: tensile
modulus; PE: polyethylene; PP: polypropylene.
Figure 12 represents the TM of the blend over the whole composition range. Simi-
larly, the stiffness of the blend reaches a maximum at a composition of iPP/HDPE (80/
20), higher than the rule of mixture and higher than neat PP. This phenomenon is
explained by considering that iPP crystallizes first (because it has a higher melting point)
and that, in the case of iPP/HDPE (80/20), iPP is also the major phase. Therefore, when
cooling down the blend after melt mixing, if the temperature is stopped at a point where
only iPP crystallizes, and HDPE is still in the molten state, thus flowing into the inter-
spherulite boundaries of iPP, and when the temperature is lowered below the HDPE
melting point, crystallites of the minor phase are formed, acting as a nucleating agent.
For this reason, the intercrystalline links are increased, the blend interface is thickened,
and the stress transfer is facilitated, enhancing both strength and stiffness.
Modification strategies
Combining two thermoplastic polymers to form a binary blend is a cheap procedure that
can bring a material with superior characteristics, without passing by the more expensive
synthesis of a new material. Moreover, a blend with tailored properties is suitable for
high demanding applications. However, especially in the case of immiscible thermo-
plastic binary systems, the final product is useless in applications if it is not compati-
bilized by the introduction of a precursor at the interface, making the blend more
Graziano et al. 19
Figure 13. Steric hindrance effect to suppress coalescence. Source: Reprinted from the work of
Sundararaj and Macosko,41 copyright © with permission from the American Chemical Society.
compatible, also called an alloy. For highly viscous thermoplastic polymers, breakup of
the minor phase occurs via transient mechanism under a flow that is a combination of
simple shear and longitudinal. Therefore, a long and thin thread breaks into small
spherical droplets upon increased shear.31,46,47,54–58 The compatibilizer helps with
decreasing the IFT, thus favoring a more pronounced breakup of the droplets, leading to
a finer morphology. Additionally, by placing it on the surface of the minor phase, the
compatibilizer hinders the mobility of the interface and prevent coalescence by creating
shells around the drops of the minor phase (steric hindrance or steric stabilization).41
This phenomenon is depicted in Figure 13. This way, the final morphology is stabilized,
even after long annealing time.59
Nonreactive compatibilization
Nonreactive coupling agents are often used for compatibilizing immiscible polymers,
because they bring strong interactions at the interface. The precursor is added physically
to the system, and it usually has one side miscible with one polymer, and the other side
miscible with the other polymer. There are different kinds of co-copolymers that can be
added to the blend,60 and their structures are depicted in Figure 14.
A significant amount of scientific work has been carried out on the nonreactive
compatibilization of PE/PP polymer blends.13,50–59 Among the non-in situ coupling
agents, ethylene–propylene rubber (EPR) has been one of the most used thermoplastic
elastomers in the case of PE/PP blends, because it is widely available, cheap, and easy to
Figure 14. Structures of compatibilizers. Source: Reprinted from the work of Muthuraj et al.60,
copyright © with permission from John Wiley and Sons.
process. When introducing EPR to the PE/PP binary system, the propylene repeating
units of EPR are inserted within the PP. The same thing happens between the ethylene
repeating units of EPR and PE. This brings compatibility between PE and PP. Its par-
ticular ability is to enhance both IS and EB while not affecting TS and stiffness.
Moreover, it acts as a nucleating agent, greatly affecting the crystallization of the two
polymers. Consequently, the morphology and, therefore, the mechanical properties of
the final product are better controlled. EPR can be divided into two different copolymers,
such as ethylene–propylene copolymer (or EPR) and ethylene–propylene–diene terpo-
lymer (or EPDM). Their functionalities as coupling agents are very similar. However,
EPDM has an additional monomer attached to the main chain. D’Orazio et al. analyzed
the mechanical performance of an iPP/HDPE binary system over the full range of blend
composition, with and without exploiting the functionality of an EPR.61 They found that
the TS of the blend is lower than the one of the pure polymers, due to immiscibility.
Nevertheless, the addition of a small amount of coupling agent stabilizes the interface,
creates additional entanglements between the two phases, and facilitates the stress at the
interface. Indeed, the strength of compatibilized blends is higher than the one of
uncompatibilized blends, as depicted in Figure 15.
Unmodified stands for pure blends with different iPP and HDPE compositions. Dutral
and Epcar refer to two types of EPR used in this case, both added at a 5 wt% composition.
Dutral has higher molecular weight than the Epcar but less ethylene content. An
important aspect to notice is that the final properties of an immiscible thermoplastic POE
binary system greatly increase with the addition of a small amount of rubbery copoly-
mer. The copolymer having more ethylene in it (Epcar) has a better impact on blend
modification. A similar outcome was obtained for IS, by the same group of researchers.62
A 15 wt% of Dutral leads to an 1175% increase compared to neat PP/HDPE (75/25)
binary system, whereas a 15 wt% of Epcar brings an improvement of 2100%. The
enhancement of IS given by the compatibilization of PP/HDPE blend rich in PP with an
elastomeric nonreactive copolymer has always been found to be very significant. In this
regard, a graph that combines all the positive outcomes from many different studies will
Graziano et al. 21
Figure 15. TS of unmodified iPP/HDPE blends, as well as Dutral and Epcar modified ones, at
different blend compositions. Source: Redrawn from the work of D’Orazio et al.62 TS: tensile
strength; iPP: isotactic polypropylene; HDPE: high-density polyethylene.
be presented later in this article. From the literature, it is also important to underline that
both the amount of coupling agent added and the blend ratio have an influence on
mechanical properties and therefore the final morphology. A good strategy would be
finding a way to control the modification procedure to maximize the blend properties
while keeping the amount of precursor low. Other factors that are to be taken into
account are processing conditions, viscosity, and molecular weight of the components.
Choudhary et al. studied the effect of an ethylene–propylene–diene terpolymer on the IS
of a PP-rich-based iPP/HDPE binary system.63 By adding 20% w/w of EPDM to a 90/10
iPP/HDPE blend, the IS increases by 620% compared to the neat (nonmodified) 90/10
iPP/HDPE blend. In this particular case, the EPDM used has an 80% w/w ethylene
content, and it was found to be very efficient in an iPP-rich system, if added at a con-
centration of 20% w/w. By adding less EDPM to the blend, there is not enough coupling
agent interacting with the two polymer phases. Saturation is reached with introducing
20% w/w to the system. Thus, adding more EPDM will create extra impurities that
weaken the interface, leading to a decreased interfacial adhesion. Conversely, Kim and
Chun investigated how a higher amount of a slightly different EPDM influences the
mechanical properties of a 70/30 wt% iPP/HDPE.64 In this case, the modification of this
binary system with 30 wt% EPDM leads to a 1800% increase in IS. The polymers used in
both studies are very similar in terms of nature and physical properties, while EPDM in
the Choudhary et al. work has more ethylene than the EPDM used by Kim and Chun.
Moreover, in the former work, the coupling agent was melt mixed with both polymers
simultaneously, whereas in the latter work, EPDM was first blended with the major
phase (iPP) and then the minor phase (HDPE) was added. This leads to a more efficient
stabilization of the precursor at the blend interface, stronger bonds between the polymers
and the compatibilizer, facilitating the transition from brittle to ductile behavior of the
iPP/HDPE blend. To sum up, the mixing order of polymers and interfacial agent affects
the final properties of the binary system, and more specifically, in Kim and Chun’s study,
the way EPDM is added makes it a much more efficient compatibilizer for the iPP/HDPE
blend, compared to the work done by Choudhary et al. The olefin block copolymers
(OBCs) class seems to work very well as coupling agents for a blend of two immiscible
thermoplastic polymers, such as PE and PP. The stabilization of these compatibilizers at
the PE/PP interface forms a tie-layer connecting the two constituents. Moreover, because
of a more organized and homogeneous structure, block copolymers are more efficient
than random copolymers, forming more interfacial bridges.65 Ethylene–octene block
copolymers have often been one of the most used OBCs for the compatibilization of PE/
PP binary systems. The ethylene/octane ratio, mechanical performance, morphology,
crystallinity, molecular weight, and physical properties are the main factors that
determine the effectiveness of an ethylene–octene block copolymer for PE/PP com-
patibilization. Lin et al. investigated the role of four different ethylene–octene block
copolymers as effective compatibilizers for an immiscible iPP/HDPE (70/30 wt%)
binary system.66 The four coupling agents have similar molecular weights, molecular
weight distributions and densities, but different crystalline/amorphous and octane/
ethylene contents. This affects the way the precursor acts at the blend interface,
interacting with both phases, facilitating the stress transfer, lowering the IFT, and
enhancing the interfacial adhesion. Particularly, it was found from this study that the
copolymer with the lowest amount of total octene block content and lowest crystal-
linity had the best impact on both toughness (GPa) and fracture strain (%) of iPP/HDPE
blend. Indeed, the former property increased by 5400% when modified the binary
system with 10 wt% of ethylene–octene block copolymer (going from 0.24 GPa for
unmodified blend to 13.2 GPa for modified one), while the latter property was
improved by 6600% upon compatibilization (EB 9% for unmodified blend, 605% for
modified one) although strength was not affected much (only 7% increase). The results
for EB, TS, and fracture toughness (GPa) are given in Table 3.
This outcome proves that when the ethylene–octene block copolymer stabilizes at the
PE/PP interface and creates strong chemical bonds with the two phases, the transition
from brittle to ductile behavior of the final PE/OBC/PP ternary system is seen, con-
siderably enhancing the capability of elongating before breaking and absorbing energy
before fracturing. Another well-known coupling agent, in the class of thermoplastic
elastomers, used for bringing compatibility between PE and PP is styrene–butadiene–
styrene (SBS) triblock copolymer. As the other aforementioned thermoplastic elastomers
(EPR and EPDM), SBS is able to create interactions with the two polymers through
electron clouds or p–p electrostatic interactions.67 The effectiveness of SBS as an
interfacial agent for a binary PE/PP system is related to its ability of greatly enhancing
Graziano et al. 23
Table 3. EB, TS, and FT for both unmodified and modified blends.a
EB (%) TS (MPa) FT (GPa)
Unmodified (PP70) 9 30 0.24

Modified (10% EOC) 605 32 13.2
Increase 6600% 7% 5400%
EB: elongation at break; TS: tensile strength; FT: fracture toughness; PP: polypropylene; EOC: ethylene-octene
copolymer.
a
Redrawn from the work of Lin et al.66
Table 4. IS for both unmodified and modified blends.a
D’Orazio et al. D’Orazio et al.

IS (J/m) Choudhary et al. Kim and Chun Chiu et al. (Dutral) (Epcar)
Unmodified 44 (90/10) 38 (70/30) 38 (70/30) 40 (75/25) 40 (75/25)

Modified 316 (20 EPDM) 722 (20 EPDM) 730 (10 SBS) 510 (15 EPR) 880 (15 EPR)
Increase 620% 1800% 1820% 1175% 2100%
EB: elongation at break; TS: tensile strength; FT: fracture toughness; IS: impact strength; SBS: styrene–buta-
diene–styrene; EPR: ethylene–propylene rubber.
a
Redrawn from the works of D’Orazio et al.,62 Choudhary et al.,63 Kim and Chun,64 and Chiu et al.68 The
values in boldface for both the unmodified and modified cases represent the IS in J/m. Furthermore, while the
values in parentheses for the unmodified specimens refer to the blend composition of neat iPP/HDPE binary
systems, the number and the acronym in parentheses for the modified samples are related to weight com-
position of the compatibilizer and its type, respectively.
the blend IS, while alleviating the reduction of both strength and stiffness. Chiu et al.
studied the potential of SBS to increase the ductility of an iPP/HDPE immiscible blend.68
First, they observed that for different blend ratios, the addition of SBS increases the IS of
the system slightly at the beginning, then sharply as the amount of SBS added to the blend
goes up. Sharp transition points in the graphs of IS of the system versus amount of SBS
added are observed, for all the different blend ratio cases. They refer to the so-called
“brittle to ductile transition points,” meaning that an optimized amount of SBS added to
an iPP/HDPE with a particular blend composition can lead to a sudden and significant
increase of IS. More specifically, Chiu et al. claimed that the IS of a 70/30 wt% iPP/HDPE
binary system goes up by 1820% when introducing 10 wt% of SBS in the blend, while the
flexural strength (FS) drops by 48% and the TS has a 31% decrease. To conclude, ther-
moplastic elastomers like EPR, EPDM, and SBS have a remarkable impact on the com-
patibility between PE and PP, serving specifically in bringing ductility in the binary
system, while not affecting strength and stiffness significantly. Table 4 summarizes the IS
enhancement for a PP-rich–based iPP/HDPE polymer blend, upon modification with a
nonreactive copolymer, when considering the four case studies mentioned above.62–64,68
Figure 16 shows these particular results in a more graphic way, underlining the trends
as well as the IS of both pure iPP and HDPE. The numbers in % are the IS increases for
modified systems compared to unmodified ones.
Figure 16. IS of both unmodified and modified iPP/HDPE blends, rich in iPP, according to different
nonreactive compatibilization studies. Source: Redrawn from the works of D’Orazio et al.,62
Choudhary et al.,63 Kim and Chun,64 and Chiu et al.68 IS: impact strength; iPP: isotactic poly-
propylene; HDPE: high-density polyethylene.
Reactive compatibilization
While nonreactive compatibilizers involve adding them to the blend physically, the
reactive ones lead to the creation of the compatibilizer in situ, by reaction of the func-
tional group of one polymer with the precursor, and the other polymer being miscible
with the precursor. Also, the reactive ones are better than the nonreactive ones because
they are less complex, less expensive, easier to control, and, in this case, it is much more
likely that the compatibilizer is placed at the interface. Moreover, they have lower
viscosities, thus the melting process for reactive compatibilizers is easier. For the
reactive compatibilization, chemical modification (introduction of reactive groups) can
be done either via melt blending or via solvent reaction. The latter is more effective than
the former, because the solvent acts on the medium viscosity so there is more chain
freedom, more intimate molecular contact, and faster molecular diffusion. Moreover,
reacting polymers are better in powder form as opposed to pellet form, because the
surface area is maximized and they have a higher initial state of dispersion. About the
content, the structure, and the form of the reactive agent, lower molecular weights lead to
better interfacial reactions, because the reactive agents have shorter chains and they
move faster and more freely along the interface. If the polymers of the blend have a high
reactive group content, the chemical reactions with the in situ compatibilizer will be
more effective. Lots of research has been carried out on the reactive compatibilization of
Graziano et al. 25
polymer blends.69–73 Among the several reactive compatibilizations of PE/PP binary

systems, of particular interest is the study carried out by Colbeaux et al. who focused on
forming in situ reactive coupling agents through the chemical reactions between two
maleated POEs (maleic anhydride-grafted polyethylene [MAPE] and maleic anhydride-
grafted polypropylene [MAPP]) and dodecane diamine (C12N2), for increasing the
compatibility between HDPE and iPP.74 It is well-known that the PE chains of MAPE
are miscible with the PE phase of the PE/PP binary system, while the PP chains of MAPP
are miscible with the PP. However, when blending PE/MAPE with PP/MAPP, there are
no specific chemical interactions between the anhydride groups of both MAPP and
MAPE. Thus, the PE/PP interface is weak and failure occurs easily. The introduction of
the C12N2 assured, in the work done by Colbeaux and coworkers, that strong covalent
bonds between the anhydride groups of MAPE and MAPP and the amino groups of
C12N2 were created, leading to a much stronger PE/PP interface. This facilitates the
stress transfer, reduces the IFT, and increases the interfacial adhesion. Interesting results
are obtained in the case of EB for a 70/30 wt% iPP/HDPE blend. Indeed, this property
goes up by 800% when compatibilizing the binary system with an in situ functionalized
25 wt% of MAPP-g-C12H28N2-g-MAPE. The blend made of iPP/HDPE/MAPP/MAPE
has an EB similar to the one of the pure iPP/HDPE blend, proving the ineffectiveness of
the maleated anhydride POEs in improving the binary system properties if no other
coupling agent is added to bring strong covalent bonds at the blend interface. However, if
the amount of compatibilizer is higher than 25 wt%, the cross-linking and anchors at the
blend interface are so strong that they start to affect the change in EB in a negative way,
as can be noticed in the work done by Colbeaux and coworkers. The basic requirements
for an effective reactive compatibilization method are not only strong reactions between
the interfacial agent and the polymers of the blend but also stable chemical bonds
throughout the whole processing and small reaction times, in particular smaller than the
residence time for the polymers during melt blending. Another interesting study, where
these requirements were met, is the one done by Tselios et al. who used the in situ
reactive blending technique to form, during melt blending of PE with PP, their com-
patibilizer from MAPP and polyethylene-co-vinyl alcohol (EVAL).75 The chemical
reaction occurring during the compatibilization process is the esterification reaction
between the hydroxyl (OH) group of EVAL and the anhydride of MAPP, leading to
strong chemical bonds that are expected to reduce the IFT of, in this particular study, a
blend made of iPP and LDPE. The production of branched or cross-linked macro-
molecules with high molecular weight at the interface makes the compatibilized blend
have a higher viscosity than the uncompatibilized one, proving that effective chemical
reactions have occurred at the blend interface. From the Tselios and coworkers study, it
is worth noticing that the mechanical properties of compatibilized blends are much
higher than the properties of uncompatibilized ones, as indicated in Table 5. The
unmodified specimen refers to a neat blend of iPP/LDPE (75/25), while for the modified
one, 10 wt% of EVAL-MAPP is added as a compatibilizer.
Compatibilization of immiscible polymer blends via reactive processes can also be
done with the use of low molecular weight reactive compounds promoting copolymer
formation and cross-linking reactions. A peroxide is often used in the case of PE/PP for
Table 5. EB, TS, and IS for both unmodified and modified PP/LDPE blends.a
EB (%) TS (MPa) IS (J/m)
Unmodified (PP75) 13 14.4 8

Modified (10% EVAL-MAPP) 21 17.5 11.5
Increase 47% 22% 44%
EB: elongation at break; TS: tensile strength; IS: impact strength; PP: polypropylene; EVAL: polyethylene-co-
vinyl alcohol; LDPE: low-density polyethylene; MAPP: maleic anhydride-grafted polypropylene.
a
Redrawn from the work of Tselios et al.75
increasing their synergy.76–80 These chemical reactions brought by the peroxide usually
increase the viscosity of HDPE by introducing branching cross-linking and decrease the
viscosity of PP by chain scission. This is done to reduce the viscosity mismatch between
the two polymers, enhancing their miscibility for a finer morphology and higher prop-
erties. However, the use of chemical reactions is neither environmentally friendly nor
economical, so this compatibilization procedure tends to be avoided.
Reinforced composites of PE/PP systems

Reactive compatibilization of immiscible thermoplastic POEs brings strong and irre-
versible ionic or covalent bonds at the blend interface, ensuring an increased interfacial
adhesion and a decreased IFT. As a result, the morphology of the binary system is of fine
particles of the minor phase, dispersed uniformly and homogeneously into the con-
tinuous phase. The mechanical properties of the blend are therefore enhanced, allowing
tailor-making materials that possess specific combinations of physical properties, pro-
cessing characteristics, and cost. The further step for manufacturing a product with even
more unique properties, suitable for high demanding applications, is polymer compo-
sites. A significant amount of research has been carried out on this matter.81–84 The use
of reactive and nonreactive block or graft copolymers for PE/PP binary system mostly
gives it a notable ductile behavior, increasing both EB and IS significantly. Further
introduction of a reinforcing cofactor, being stiff and strong, leads to the manufacturing
of a polymer composite that also has enhanced TS and TM. A considerable amount of
research is present in the literature about PE/PP-based reinforced composites with fillers
being in the form of fiber, nanotubes, particles, and so on. About its nature, the rein-
forcing agent can be green-based, coming from wood, flax, sisal, hemp, and so on, or
synthetic, such as carbon fiber or glass fiber (GF).
Synthetic reinforced PE/PP composites

Synthetic fillers are interesting compatibilizing agents for PE/PP blends, because they
bring some property enhancements to the binary system. Different studies have been
carried out on the effect of GF on the final properties of PE/PP, as well as how to
optimize its effectiveness while minimizing the overall cost.85–87 Following their work
(mentioned in the previous section) on compatibilizing a PP/LDPE binary system with
Graziano et al. 27
Figure 17. Esterification reaction between the OH groups of GF and MAPP (a) as well as
hydrogen bonding between the OH groups of GF and EVAL (b). Source: Reprinted from the work
of Tselios et al.,88 copyright © with permission from Springer Nature. GF: glass fiber; OH: hydroxyl
group; EVAL: polyethylene-co-vinyl alcohol; MAPP: maleic anhydride-grafted polypropylene.
both MAPP and EVAL, while increasing the EB, TS, and IS, Tselios et al. investigated
the potential of GF to enhance the TS of the composite even more.88 The hydrophilic
nature of GF relates to OH groups present on its main structure. These groups can create
chemical bonds with the anhydride of MAPP on one side, via esterification, and with the
OH groups of EVAL on the other side, via hydrogen bonding, as illustrated in Figure 17.
This unique MAPP-GF-EVAL compatibilizer can act as an emulsifier at the interface
of the two polymers, leading to effective stress transfer, reduction of IFT, and increase of
interfacial adhesion. More specifically, the TS is enhanced significantly. Indeed, the
introduction of a 10 wt% of MAPP-GF-EVAL coupling agent to a 75/25 wt% of PP/
LDPE increases the TS by 53% (the increase in the previous work without GF was 22%).
Furthermore, Tselios et al. exploited the functionality of a silane coupling agent to
surface modifying the GF. Extra functional groups are created on the GF surface, leading
to stronger and more numerous interactions with both MAPP and EVAL. This ensures
full exfoliation of the GF as well as its homogeneous and uniform dispersion at the
interface, avoiding the formation of clusters. This silane-functionalized coupling agent
stabilizes at the interface throughout melt blending and the reinforcement effect is even
more pronounced. As a consequence, the strength enhancement in this case is 67%
compared to the neat PP/LDPE binary system. Similarly, the IS increases gradually first
when adding a combination of EVAL and MAPP as a compatiblizer (44% increase), then
GF with EVAL-MAPP (106% increase), and eventually EVAL-MAPP bonded with
silane-coated GF (120% increase). This is because the GF is able to absorb mechanical
impact energy, even more when the interfacial adhesion between reinforcing agent and
polymer matrices is significant. Conversely, the EB of the composite is greatly
Table 6. TS, IS, and EB for both unmodified and modified PP/LDPE blends.a
TS (MPa) IS (J/m) EB (%)
75PP-25LDPE 14.4 8 13
10EVMA 17.5 (þ22%) 11.5 (þ44%) 21 (þ47%)
20SCGF 19.8 (þ38%) 14.8 (þ85%) 6 (54%)
20GF-10EVMA 22 (þ53%) 16.5 (þ106%) 5 (62%)
20SCGF-10EVMA 24 (þ67%) 17.5 (þ120%) 2 (85%)
TS: tensile strength; IS: impact strength; EB: elongation at break; PP: polypropylene; LDPE: low-density poly-
ethylene; GF: glass fiber; SCGF: silane-coated glass fiber; 10EVMA: 10 wt% of EVAL-MAPP; EVAL: polyethylene-
co-vinyl alcohol; MAPP: maleic anhydride-grafted polypropylene.
a
Redrawn from the work of Tselios et al.88 The values in parentheses are the percentage increases (with a þ
sign) and the percentage decreases (with a sign) compared to the unmodified neat PP/LPDE blend.
decreased, proving the transition from a ductile to a stiff nature, which is given by the
GF. Table 6 depicts the TS, IS, and EB values for the PP/LDPE (75/25) blend in the cases
where it is neat (75PP-25LDPE), modified with 10 wt% of EVAL-MAPP (10EVMA),
modified with 20 wt% of silane-coated GF, modified with 20 wt% of GF plus 10 wt% of
EVAL-MAPP (20GF-10EVMA), and modified with 20 wt% of silane-coated GF plus 10
wt% of EVAL-MAPP (20SCGF-10EVMA).
Figure 18 shows the trends of these properties from no PP/LDPE blend modification
to different compatiblization routes.
The enhancement of the synergy between PE and PP by the introduction of the
compatibilized GF-based reinforcing agent, leading to a significant boost of the
mechanical properties of the reinforced PE/PP blend composite, is strictly related to
homogeneous dispersion of the reinforcing agent in the PE/PP binary system, as well as
strong interactions between the two polymers and the cofactor itself. Tselios and cow-
orkers showed this important aspect very well in their morphological analysis. Indeed,
Figure 19 indicates the morphology of impact fracture surfaces of 75PP-25LDPE (left)
and 20SCGF-10EVMA (right). As can be seen, in the first case (left), the GFs do not
interact well with the polymers, leading to poor interfacial adhesion between PP and
LDPE, hence low mechanical properties. Conversely, for the second case (right), strong
interactions occur between the compatibilizer and the GF on one end, and the compa-
tibilizer and the two polymers on the other hand. The GFs are clearly covered by a
polymer layer, indicating great affinity brought by the amphiphilic coupling agent
EVMA and the silane modification.
Carbon-based reinforcements have the potential of boosting the electrical con-
ductivity of polymers, as well as thermal and mechanical properties. Among all the
synthetic additives for polymer composites, carbon-based fillers have the highest tensile
and electrical properties, making them the best candidates for designing and developing
conductive polymer composites (CPCs) for a wide range of applications, such as elec-
tronics, aerospace, energy sectors, and so on. Although carbon black and carbon fiber
have always had a great impact on CPCs,89–91 carbon nanotubes (CNTs) are preferred
Graziano et al. 29
Figure 18. Trends of TS, IS, and EB for both unmodified and modified blends. Source: Redrawn
from the work of Tselios et al.88 IS: impact strength; TS: tensile strength; EB: elongation at break.
Figure 19. Morphology of impact fracture surfaces of 75PP-25LDPE (left) and 20SCGF-
10EVMA (right). Source: Reprinted from the work of Tselios et al.,88 copyright © with per-
mission from Springer Nature. PP: polypropylene; LDPE: low-density polyethylene; SCGF:
silane-coated glass fiber.
over the other conductive fillers because of their excellent mechanical properties and
very high aspect ratio.92–98 Furthermore, their TM is in the range of 250–950 GPa and TS
in the range of 10–63 GPa. Since the CNT dimension is in the nanometer scale (diameter
5–50 nm), the surface area is significant; therefore, both the dispersion of the filler
into the polymer matrix and the degree of interaction between filler and matrix are
Table 7. TS and toughness of both unmodified and modified blends.a
TS (MPa) Toughness (MJ/m3)
Unmodified (PP90) 28 3
Modified (20% CNTs) 47 1.8
Outcome 68% increase 40% decrease
TS: tensile strength; CNT: carbon nanotube; PP: polypropylene.

a
Redrawn from the work of Al-Saleh.100
maximized. CNTs are divided into single-walled (SWCNTs), double-walled

(DWCNTs), and multiwalled ones (MWCNTs). They are utilized for the enhancement
of electrical, barrier, optical, mechanical, and thermal properties in polymer nano-
composites. MWCNTs are usually preferred to SWCNTs and DWCNTs, because they
can be produced in large quantities and relatively with high purity at low cost.99
Moreover, with the addition of MWCNTs into polymer matrices, manufacturers can
manipulate the material’s conductivity, strength, flexibility/flowability, thermal stabi-
lity/flame retardancy, static properties, weight, and need for other fillers. Al-Saleh
investigated the effect of MWCNTs on the mechanical properties of a PP/HDPE poly-
mer blend, with PP being the major phase.100 When reinforcing PP/HDPE (90/10 wt%)
with 20 wt% of MWCNTs, Al-Saleh found that the TS of the resulting nanocomposite
increases by 68%. CNTs are usually well dispersed into PE, due to good affinity with it.
In this case, HDPE is present in the blend with a very low concentration. Thus, the HDPE
minor phase is saturated with a rather strong reinforcing filler (MWCNT), leading to a
nanocomposite that exhibits a very high TS. On the other hand, toughness is registered to
be lower than the one of unreinforced blend (40% reduction) because the increase in
strength when adding MWCNTs to the blend is followed by a reduction in EB. A
summary of the results concerning both TS and toughness is given in Table 7.
More effort in functionalizing CNTs is needed to increase the chemical affinity
between the matrix and the filler, which will ensure good CNT dispersion and improved
polymer properties. In general, optimizing CNT chemistry and processing parameters to
maximize dispersion and interfacial bonding in the polymer matrix can yield nano-
composites showing substantial improvements in strength, toughness, modulus, and
electrical conductivity. Nevertheless, due to the very high manufacturing price of CNTs,
mass production of CNTs-based polymer nanocomposites for advanced industrial
applications tends not to be fully encouraged yet.
Natural reinforced PE/PP composites

Natural fibers represent a novel and unique route for eco-friendly reinforced polymer
composites. Compared to synthetic fibers, such as GFs, they are lighter, CO2 neutral,
renewable, recyclable, biodegradable, and they bring low energy consumption.101
Therefore, many industries have been trying to replace synthetic fibers with natural
fibers for a large variety of commercial applications, such as marine, automotive, and
Graziano et al. 31
construction. Furthermore, decking applications and consumer products have been

widely manufactured with natural fiber-reinforced polymer composites.102 However,
natural fibers often have high moisture uptake and thermal instability during processing.
In addition, when trying to blend a hydrophobic polymer matrix with a hydrophilic filler,
poor adhesion occurs, resulting in interfacial failure. The use of a coupling agent is
required in this case, because of its capability to create chemical bonds with the natural
fiber and entanglements with the polymer matrix at the same time. A coupling agent is a
compound that functions at the interface to create a chemical bridge between the filler
and the matrix. Various coupling agents are used, such as maleic anhydride-grafted
POEs, isocyanates, silanes, and so on. One end of the compatibilizer reacts chemi-
cally with the functional groups on the natural fiber (typically OH groups), while the
other end of the coupling agent is compatible with the polymer matrix, due to similar
polarities. A great deal of work has been done on natural reinforced composites of PE/PP
blends.103–110 A research work done by Kijeńska et al. underlines the advantage of using
rape straw over other natural fibers as a reinforcement for polymer composites, because
its structure does not have a lot of cellulose, hemicellulose, and lignin that would hinder
the mechanical properties of the final composite.111 Indeed, when reinforcing a PP/PE
(65/35 wt%) binary system, they registered a 157% increase in flexural modulus (going
from 0.7 GPa to 1.8 GPa) with a 50 wt% of filler added. However, all of the other
properties decreased or remained the same, proving that there is not enough interaction
between natural fiber and nonpolar matrix if no coupling agent is added. Clemons et al.,
who focused specifically on wood flour (WF) as a reinforcing filler, studied the
importance of using a coupling agent for introducing strong chemical bonds between
matrices and reinforcement.112 The use of wood as a bio-based reinforcement for
polymer composites is seen as an alternative way of recycling waste plastics and plant-
based residues, and at the same time a possibility of developing a strong and eco-friendly
composite material. Focusing on HDPE/PP blends rich in PE (75 wt%), Clemons et al.
found that, by introducing 30 wt% of WF to the blend, the TM increases significantly (by
183%), while not affecting the other properties. The stiffness greatly increases because
WF has a much higher modulus than PP and PE, whereas there is no increase in all the
other properties because the hydrophilic reinforcement is not chemically bonded with the
hydrophobic matrices. To overcome this hurdle, a silane chemical compound and a
benzoyl peroxide were introduced to functionalize the WF additive, which was therefore
better exfoliated and more homogeneously dispersed at the blend interface. Both silane
and peroxide also introduced additional and strong chemical bonds between WF (rein-
forcement) and polymer matrices. This resulted in a more pronounced increase in
stiffness, followed by an enhancement in TS. The amount of silane–peroxide modifier
added to the system was 2 wt%. The same group of researchers also worked on the
modification of the same HDPE/PP (75/25) blend with both MAPE and ethylene-pro-
pylene-diene terpolymer (EPDM) grafted on MAPE (MAPE-EPDM),113 as an alterna-
tive to the compatibilization procedure done with silane and peroxide in their other
study.112 Their intent was to optimize the efficiency of the reinforcing agent for
simultaneously increasing TS, Young’s modulus, and IS. The types of additives used for
Table 8. Types and weight compositions of the coupling agents for the HDPE/PP blend.a
WF (%) Silane–peroxide (%) MAPE (%) MAPE-EPDM (%)
30WF 30 0 0 0
30WF-2SP 30 2 0 0
30WF-3MAPE 30 0 3 0
30WF-10MA-EPDM 30 0 0 10
HDPE: High-density polyethylene; PP: polypropylene; WF: wood flour; MAPE: maleic anhydride-grafted
polyethylene; SP: silane-peroxide EPDM: ethylene-propylene diene terpolymer.
a
Redrawn from the works of Clemons et al.112,113
Figure 20. IS for both unfilled and filled HDPE/PP binary systems. Source: Redrawn from the work
of Clemons.113 IS: impact strength; PP: polypropylene; HDPE: high-density polyethylene.
compatibilizing a HDPE/PP (75/25) blend, along with their weight compositions, are
depicted in Table 8.
The results concerning the IS are illustrated in Figure 20. The effect of silane–per-
oxide on the IS is missing in the study by Clemons et al.112,113
The numbers in percentage are the IS increases, compared to neat blend. WF gave a
small increase in IS (25%), while adding MAPE along with WF did not enhance this
property as well (15%). On the other hand, the introduction of an elastomeric coupling
agent, such as MAPE-EPDM, contributed to a significant increase in IS for the HDPE-
rich-based blend (104%). Table 9 indicates the percentage increases and decreases of
both TS and TM upon the introduction of different coupling agents.
Graziano et al. 33
Table 9. TS and TM for both unfilled and filled HDPE/PP binary systems.a
TS (MPa) TM (GPa)
Pure PP 37.4 1.7

Pure HDPE 20.9 0.7
HDPE-PP (75-25) 25.7 0.82
30WF 23 (11%) 2.32 (þ183%)
30WF-2SP 29.7 (þ16%) 2.47 (þ200%)
30WF-3MAPE 26.1 (þ2%) 3.33 (þ306%)
30WF-10MA-EPDM 25 (3%) 2.26 (þ176%)
TS: tensile strength; TM: tensile modulus; HDPE: high-density polyethylene; PP: polypropylene; WF: wood
flour; MAPE: maleic anhydride-grafted polyethylene; SP: silane–peroxide.
a
Redrawn from the works of Clemons et al.112,113 The percentages in parentheses are the increases (þ) and
the decreases () of that particular property compared to neat HDPE/PP (75/25) blend.
First, having a very high stiffness as its intrinsic property, WF brings a significant
enhancement in TM, while the strength decreases because there is still poor compat-
ibility between the additive and polymer matrices. Second, the silane–peroxide func-
tionalizer leads to the strongest bonds at the interface between WF and the two polymers,
maximizing the interfacial adhesion, facilitating the stress transfer and ensuring failure
in one of the polymeric phases, instead of occurring at the interface. Indeed, both
strength and stiffness have good improvement. In the case of blend modified with WF
and MAPE, in fact, this maleic-grafted POE contributes to weaker bonds compared to
the ones given by silane–peroxide (indeed the strength almost remains unchanged).
However, it affects the mode of failure of the material. Indeed, the stress–strain curve has
a bigger slope, the material becomes stiffer and the TM increases even more than the
previous case with silane–peroxide. Finally, when introducing a maleic-grafted ethylene-
propylene-diene terpolymer to the blend, along with WF, the anhydride of MA-EPDM
reacts with the OH groups of WF, whereas the propylene and ethylene monomers of
MA-EPDM create entanglements with the PP and HDPE matrices. Good compatibility
between reinforcement and matrices is therefore developed, as well as strong interfacial
adhesion. Additionally, the presence of an elastomeric additive (EPDM) and a stiff filler
(WF) assures the enhancement of both IS and Young’s modulus, whereas the TS tends to
remain unchanged. Figure 21 represents the effect of these different compatibilizers on
both the TS and TM of HDPE/PP (75/25).
Another very interesting class of nanofillers employed for enhancing the synergy
between PE and PP is silicates, organic minerals that can serve in transferring some
unique properties to the polymer blend, as well as boosting the biodegradability char-
acter of the final material. Moreover, being in the form of nanoplatelets, silicates have a
higher aspect ratio than nanofillers that come in different shapes and dimensions, for
example, CNTs. This means that the reinforcing filler can be localized and dispersed
much more homogeneously at the blend interface, covering larger domains, hence
increasing even more the interfacial interactions between the two immiscible polymers.
Figure 21. Trends of TS and TM for both unfilled and filled HDPE/PP binary systems. Source:
Redrawn from the works of Clemons et al.112,113 PP: polypropylene; HDPE: high-density poly-
ethylene; TS: tensile strength; TM: tensile modulus.
Three of the most important factors that guarantee increased PE/PP interfacial adhesion,
when using nanoplatelets as reinforcing fillers, are full exfoliation of the nanofillers,
their selective localization at the blend interface, and strong interactions between the
polymers and the reinforcing agent. Silicates are hydrophilic, while PE and PP are
hydrophobic; therefore, surface modification of silicates (with surfactants or coupling
agents) is often needed to improve their affinity with the polymers. This also facilitates
the dispersion of the layered silicates at the blend interface and favors the formation of
single layer silicates (full exfoliation), instead of multilayers, covering an even larger
surface domain and increasing the compatibilizing and reinforcing effectiveness. The
sequence of mixing also plays an important role in selectively localizing the reinforcing
nanofillers at the blend interface. Some research has been carried out on the reinforce-
ment of immiscible PE/PP blends with silicates.105,110 Dhibar et al.114 studied the HDPE/
iPP (75/25 w/w) blend reinforcement with modified clay minerals, which belong to the
phyllosilicates class. These modified montmorillonite nanoclays (O-MMTs) ensure good
affinity with the two polymers. Furthermore, they first mix directly all three components
(HDPE, iPP, and O-MMT), then they try to selectively mix O-MMT with HDPE, before
adding the third component iPP. The second method leads to full localization of the
reinforcing filler at the blend interface; therefore, a finer morphology is achieved, as
indicated in Figure 22. The amount of O-MMT added was 0.5 phr.
Graziano et al. 35
Figure 22. Morphology of HDPE/iPP blend without clay ((a) and (b)) and with clay ((c) and (d)),
prepared by two methods: direct mixing ((a) and (c)) and selective mixing ((b) and (d)). Source:
Reprinted from the work of Dhibar et al.,114 copyright © with permission from John Wiley and
Sons. HDPE: high-density polyethylene; iPP: isotactic polypropylene.
When looking at the morphology of HDPE/iPP/O-MMT mixed all together all at once
(Figure 22(c)), compared to the one of HDPE/iPP mixed with the same method (Figure
22(a)), it can be seen that the introduction of O-MMT does not lead to a significant
reduction of minor phase domain size, meaning that the properties of the reinforced
blend will not be greatly enhanced. Conversely, when the reinforcing agent is added
using the selective mixing method (Figure 22(d)), the morphology of the ternary system
is much finer than the one of pure HDPE/iPP blend prepared with the same mixing
procedure (Figure 22(b)), showing smaller PP particles. In this case, a finer morphology
will lead to superior properties for the HDPE/iPP/O-MMT blend composite. This is an
evidence of the reinforcing effectiveness of the silicate nanofiller when their mod-
ification to increase their affinity with the two polymers and the processing conditions
(sequence of mixing in this case) are well controlled. A deeper look at the enhancement
Table 10. Thermal and mechanical properties of the materials under consideration.a
Td 10% ( C) TS (MPa) FS (MPa) IS (J/m)
Pure PP 377.2 34.5 49.7 4.6

Pure HDPE 452.3 24.1 23.6 18.7
HDPE/iPP 448.1 29.3 38.5 4.1
O-MMT 463.4 29.7 37.4 4.2
EPDM-MA/O-MMT 481.7 19.1 21.5 57.6
HDPE: high-density polyethylene; PP: polypropylene; iPP: isotactic polypropylene; O-MMT: montmorillonite
nanoclay; IS: impact strength; TS: tensile strength; FS: flexural strength; Td: degradation temperature; EPDM-
MA: maleic anhydride-grafted ethylene-propylene diene terpolymer.
a
Redrawn from the work of Chiu et al.109
of thermal and mechanical properties brought by a modified nanoclay is found in the

work done by Chiu and coworkers,109 who analyzed the impact of an O-MMT clay on
thermal stability, as well as TS, FS, and IS, of a HDPE/iPP blend with symmetric
composition (50/50 w/w). The concentration of the clay in the ternary system was 3 wt%.
Moreover, a maleated EPR (EPDM-MA) was added, with a concentration of 10 wt%, as
a coupling agent for bringing stronger interactions between the filler and the polymers.
The measured thermal and mechanical properties are represented in Table 10.
The properties depicted in Table 10 are Td 10% ( C), which is the degradation
temperature of the material when only 10% of its total weight is left, as well as the TS,
FS, and IS. The properties of pure HDPE/iPP are either in between the ones of their
parent homopolymers or lower than them (in the case of IS) because of immiscibility
between HDPE and iPP. The introduction of 3 wt% of O-MMT, as indicated in the
second last row of Table 10, increases the thermal stability of the blend and decreases its
IS, while TS and FS are slightly affected. On the other hand, when the reinforcing filler is
a combination of 10 wt% of EPDM-MA and 3 wt% of O-MMT, as shown in the last row
of Table 10, the thermal stability increases even more, due to the fact that the intro-
duction of EPDM-MA facilitates the dispersion and exfoliation of O-MMT, as well as
ensures more affinity between the latter and the two polymers. Therefore, this reinfor-
cement acts as an effective gas barrier to protect the HDPE/iPP system from thermal
degradation. Regarding the mechanical properties, IS rises greatly, while there is a
remarkable drop of both TS and FS. This is related to the rubbery nature of EPDM-MA,
which leads to a reduction of TS and FS, but gives a great toughening contribution. This
specific reinforcement of HDPE/iPP blend with the modified clay and EPDM-MA is
very efficient when the target application requires a material with very high thermal
stability and impact resistance. Indeed, although TS and FS decrease, the thermal sta-
bility of the HDPE/iPP binary system is enhanced by 75%, while its IS is raised by
14 times. More research on optimizing the modification of silicates to maximize their
homogeneous dispersion at blend interface and their interactions with the two polymers
is needed to expand the frontier of high-performance and cost-effective silicates-
reinforced blend nanocomposites for demanding industrial applications.
Graziano et al. 37
Figure 23. Structures of graphene and its derivatives, fullerene (left), CNT (center), and graphite
(right). Source: Reprinted from the work of Gao et al.,103 copyright © with permission from
Springer Nature. CNT: carbon nanotube.
Conclusion
An overview on structure and properties of both PE and PP was given. When
blending these two thermoplastic POEs, a thermodynamically immiscible system is
generated, resulting in poor interfacial adhesion and coarse morphology. Therefore,
the mechanical performance of the PE/PP binary system is lower than the one of the
homopolymers, over the whole range of blend composition, due to incompatibility
between PE and PP. The most used blend modification techniques to enhance
synergy and interfacial adhesion between the two polymers are nonreactive and
reactive (in situ) compatibilization. The first one consists of coupling agents added
physically to the system, promoting strong interactions between the polymers and
the compatibilizer. Elastomers such as ethylene–propylene block copolymers and
ethylene–propylene–diene terpolymer are the most typical precursors in the case of
nonreactive compatibilization. The second one is cheaper and faster, because it
relates to the formation of an effective coupling agent “in situ,” through chemical
reactions between additives and functional groups present on the polymers’ back-
bone. Maleic anhydride-grafted POEs and EVAL have been widely used for PE/PP
reactive compatibilization. The most interesting outcome for both the modification
methods are the enhancement of the IS and EB for the PE/PP blend, while TS and
TM are not greatly affected. Polymer blends-reinforced composites are seen as
advanced materials for superior engineering applications. The use of GF as a
reinforcement, along with functional coupling agent to maximize the dispersion of
the filler into the polymer matrix, leads the PE/PP blend to a ductile to brittle
transition, meaning that the strength is increased significantly, but the EB is
decreased. Similarly, natural fibers have a positive impact on both TM and flexural
modulus of a PE/PP blend, while EB is affected negatively. Finally, carbon-based
reinforcing materials are known to improve the strength of a PE/PP binary system,
but both toughness and IS are lower than the ones of neat blend. More research on
PE/PP compatibilization is needed to find an effective way of bringing full synergy
between the two polymers, maximizing the interfacial adhesion and optimizing the
overall properties of the blend for high demanding applications.
Future perspectives
Exploiting the functionality of a reinforcing filler to the fullest, while maximizing the
synergy between two immiscible hydrophobic polymers, such as PE and PP, gives
POE-reinforced nanocomposites a huge potential for advanced applications in the
automotive, aerospace, electronics, and packaging industries. Among all the possible
reinforcing additives for thermoplastic POE binary systems, graphene has recently
emerged as the most promising nanofiller, due to its extraordinary physical properties,
which has opened a new class of polymeric nanomaterials. Graphene is made of two-
dimensional layers composed of sp2 hybridized carbon atoms, and it is notorious for its
extraordinary properties, such as very high flexibility, impermeability, strength,
stiffness, and thermal stability. Additionally, graphene is inert and thermally stable. It
is also known as the thinnest material in the world with very high aspect ratio and
surface area.115 The structure of graphene is illustrated in Figure 23, along with the
different structures of graphitic materials that can be obtained from graphene, and vice
versa. Fullerene is on the bottom left, CNT is on the bottom center, and graphite is on
the bottom right.
Moreover, compared to other effective but expensive nanofillers, such as CNTs,
graphene can be made through alternative and cheap manufacturing methods, starting,
for example, from pure graphite and leading to the restoring of the original structure
and properties of pure graphene. It has been almost two decades now that manufac-
turers are trying to create graphene-based polymer nanocomposites, with the intent of
meeting the strict industrial requirements for high-performance and cost-effective
materials. Indeed, many reviews on graphene-based polymer composites are present
in the literature.116–120 Nevertheless, especially concerning nonpolar and hydrophobic
thermoplastics, such as PP and PE, it is difficult to disperse homogeneously and
Graziano et al. 39
uniformly graphene into the matrix. Moreover, for the same reason, creating strong
interactions between the two polymers and graphene is challenging. Thus, full exfo-
liation of graphene as well as introduction of extrafunctional groups on its structure is
needed, prior to combining it with the polymers. Indeed, superior mechanical prop-
erties can be obtained when graphene is fully dispersed in the matrices and strongly
bonded to the polymers. This is achieved by covalently attaching extrafunctional
groups to the graphene surface, resulting in enhanced compatibility with the poly-
mers.121–126 Furthermore, sonication (performed as the very first step, prior to intro-
ducing chemical bonds) leads to the complete graphene exfoliation, preventing the
creation of bundles and agglomerates and favoring the homogeneous dispersion of
graphene in the polymer matrix. This way, the surface area of graphene is exploited to
the fullest, and compatibility between the two polymers is expected to be max-
imized.127 However, the functionalization of the graphene affects its intrinsic prop-
erties. Thus, it is important to focus on different graphene functionalization techniques
and discover a route that can improve the dispersion and compatibility without
affecting the intrinsic properties. This will lead to a novel way of developing high-
performance and cost-effective PE/PP-reinforced composites, suitable for specific and
superior applications.
Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship,
and/or publication of this article.
Funding
The author(s) disclosed receipt of the following financial support for the research, authorship, and/
or publication of this article: This work was supported by the Ontario Research Fund (ORF)
program.
ORCID iD
Antimo Graziano http://orcid.org/0000-0001-9846-9488
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Journal of Elastomers & Plastics

strategies of polyethylene/ sagepub.co.uk/journalsPermissions.nav

polypropylene immiscible journals.sagepub.com/home/jep

The structures of these types of PEs are depicted in Figure 1.15

The structure of iPP is illustrated in Figure 2.

POE catalysis technologies and industrial applications

Immiscible PE/PP systems

large amorphous noncrystallizable character. Therefore, when blending ZN PE with ZN

nucleating sites, leading to a significant increase of the mechanical properties of the

1. The Gibbs free energy of the system is negative (spontaneous process).

Surface free Polar component Dispersive Interfacial

2. Transient mechanism: at Ca>>Cacrit, a single drop is stretched into a liquid thread

The schematic of breakup mechanism is shown in Figure 7.

concentrations of minor phase (coalescence neglected), stepwise equilibrium mechan-

Figure 9. Phase morphologies of the blends of iPP/HDPE at different compositions. Source:

compositions.49 Conversely, a slightly higher synergy occurs between PP and LLDPE,

Table 2. Mechanical properties of LDPE/iPP, LLDPE/iPP, and HDPE/iPP blends.a

LDPE (50)/iPP (50) 21 0.48

EB (%) TS (MPa) FT (GPa)

Unmodified (PP70) 9 30 0.24

Table 4. IS for both unmodified and modified blends.a

D’Orazio et al. D’Orazio et al.

Unmodified 44 (90/10) 38 (70/30) 38 (70/30) 40 (75/25) 40 (75/25)

polymer blends.69–73 Among the several reactive compatibilizations of PE/PP binary

EB (%) TS (MPa) IS (J/m)

Unmodified (PP75) 13 14.4 8

Reinforced composites of PE/PP systems

Synthetic reinforced PE/PP composites

TS (MPa) IS (J/m) EB (%)

Table 7. TS and toughness of both unmodified and modified blends.a

TS (MPa) Toughness (MJ/m3)

TS: tensile strength; CNT: carbon nanotube; PP: polypropylene.

maximized. CNTs are divided into single-walled (SWCNTs), double-walled

Natural reinforced PE/PP composites

construction. Furthermore, decking applications and consumer products have been

WF (%) Silane–peroxide (%) MAPE (%) MAPE-EPDM (%)

Pure PP 37.4 1.7

Td 10% ( C) TS (MPa) FS (MPa) IS (J/m)

Pure PP 377.2 34.5 49.7 4.6

of thermal and mechanical properties brought by a modified nanoclay is found in the

Declaration of conflicting interests

7. Alle N, Andersen FE, and Lyngaae-Jørgensen J. Polypropylene-polyethylene blend-

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