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Quality assessment of recycled and modified LDPE/PP blends

Article  in  Journal of Elastomers and Plastics · November 2012

DOI: 10.1177/0095244312441731

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Article
Journal of Elastomers & Plastics
44(6) 479–497
Quality assessment of ª The Author(s) 2012
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DOI: 10.1177/0095244312441731

LDPE/PP blends jep.sagepub.com

Irena Borovanska1, Tatyana Dobreva1,

Rosario Benavente2, Strashimir Djoumaliisky1 and
George Kotzev1

Abstract
An experimental study was conducted to investigate the morphology, thermal and
mechanical properties of recycled polyolefin blends with different prehistory modified
with ethylene propylene rubber (ethylene-propylene diene monomer (EPDM)) using the
differential scanning calorimetry (DSC), wide angle X-ray scattering, Fourier transform
infrared spectroscopy (FTIR), scanning electron microscope and mechanical methods.
The efficiency of the modification was investigated as a function of the modifier content
in the range from 7 wt% to 15 wt%. DSC results show that the single polymers are not
clean material and contain some quantity of another polyolefins. In the processing and
exploitation conditions, there is an increase in imperfect crystals in the postconsumer
waste polypropylene. FTIR provides clear evidence about the oxidative processes and
mechanical destruction during exploitation and blending. The obtained results proved
that the technological and postconsumer wastes could be successfully reused as blends
by the addition of EPDM.

Keywords
Plastic, recycling, blends, modification, LDPE, PP, EPDM

Introduction
In our modern consumer society, large quantities of plastic wastes are produced annu-
ally. Many of the utilized plastics are reusable and arises the necessity for decreasing the

1
Institute of Mechanics, Bulgarian Academy of Sciences, Sofia, Bulgaria
2
Instituto de Ciencia y Tecnologı́a de Polı́meros, ICTP-CSIC, Madrid, Spain

Corresponding author:
Irena Borovanska, Institute of Mechanics, Bulgarian Academy of Sciences, Acad. G. Bonchev St., Block 1, 1113
Sofia, Bulgaria
Email: reniboro@abv.bg
480 Journal of Elastomers & Plastics 44(6)

volume of dumped solid plastic waste. Recycling represents a process of recovering

scrap or waste plastics and reprocessing the material into useful products, sometimes
completely different in form from their original state.
The statistics data show that the largest portions of plastic wastes are of polyethylene
(PE) and polypropylene (PP).1 Their separation gravimetrically is difficult. Since they
have similar properties and are usually mixed in the plastic waste, they should be utilized
as a blend. When a polymer blend consists of two or more polymers, they tend to separate
from each other in the melt because of their mutual incompatibility.2–5 The obtained phase
boundaries cause structural weakness in the resulting material and deteriorate the
mechanical properties of the blends. Compatibilization is a process of modification of the
interfacial properties in immiscible polymer blends resulting in reduction of the interfacial
tension, formation and stabilization of the desired morphology. Thus, the compatibiliza-
tion is an essential process that converts a mixture of polymers into an alloy with desired
set of performance characteristics.6 In practice, a variety of methods for PE/PP compati-
bilization are used. One of them is the addition of low molecular substances,7 another way
is inclusion of reactive polymers capable of interchange reactions8 or addition of mod-
ifying copolymers.9 From technological point of view, the latter method is easiest to apply.
Moreover, modification with a third polymer, which has affinity to each of the polymers in
the blend at specific processing conditions, is a preferable way for increasing the mutual
affinity of both polymers. The use of an elastomer as a third polymer for improving some
of the properties is widely described in the literature.10–13
Quality assessments of recycled polymeric materials are important for evaluating the
possibility of their reuse. Some of the important properties for secondary use of the
polymer wastes are degree of degradation, degree of crystallinity, structural and
chemical changes. They can be evaluated by the following widely used methods: Fourier
transform infrared spectroscopy (FTIR), wide angle X-ray scattering (WAXS) and dif-
ferential scanning calorimetry (DSC).14,15 The objective of this article is to prepare mod-
ified blends from two types of recycled low-density polyethylene (LDPE) and PP waste
with different amounts of impact modifier and to characterize the resulting blends using
the above-mentioned methods. The influence of the impact modifier on the mechanical
properties of these blends is also discussed.

Materials and methods

Experimental
Materials. The materials used were two types of plastic waste each with a different
prehistory. One of them was technological industrial waste, low-density polyethylene
marked as LDPEtw and polypropylene marked as PPtw. Both were obtained from ‘‘Ase-
nova Krepost’’ Ltd (Asenovgrad – Bulgaria) in the form of pellets. The other was postcon-
sumer waste, low-density polyethylene marked as LDPEpw and polypropylene marked as
PPpw. They were kindly obtained from ‘‘Unitrade 2002’’ Ltd in the form of flakes. Melt
flow indices determined at the same condition (230 C/2.16 kg) were as follows: LDPEtw
– 1.37 g/10 min, PPtw – 4.33 g/10 min, LDPEpw – 1.97 g/10 min and PPpw – 6.60 g/10 min.
Borovanska et al. 481

The used impact modifier was the nonpolar terpolymer ethylene–propylene diene
monomer (EPDM) ‘‘Keltan 512’’ (DSM Elastomers, the Netherlands) with content of
ethylnorbornene and ethylene 4.3 and 55%, respectively, and Mooney viscosity ML
(1 þ 4)125 C ¼ 46 UM.

Sample preparation by compression molding. The binary LDPE/PP and ternary LDPE/
PP/EPDM blends from technological industrial waste (labeled as TWB) and from
postconsumer waste (labeled as PWB) were prepared by extrusion using a corotating
twin screw extruder DSE35/17D (Brabender Co., Germany) at melt temperature of
200 C and screw speed of 20 r/min. The ratio between different LDPE and PP was kept
at a constant of 1:1, because the statistic data from plastic waste stream in Bulgaria show
that both polymers are approximately in equal quantities.16 The modified polymer blends
from technological industrial waste were labeled as 7TWB, 10TWB, 15TWB and
20TWB where the EPDM concentration ranged from 7 wt% to 20 wt%, respectively. The
blend from postconsumer waste containing 15% EPDM was labeled as 15PWB. The
extrudates were cooled between tempered rollers and pelletized by cutting machine
(Vespa 16/22, Bulgaria).
The plates with dimensions 1501500.4 mm were prepared by compression
molding in Collin press at 190 C and a pressure of 30 bar and fast quenched with cold
water between aluminum plates at an approximate rate of 60 C/min.
The cuttings from these plates were used for DSC, WAXS and FTIR experiments.

Sample preparation by injection molding. Plates with dimensions of 801004 mm were

prepared by means of injection molding machine KuASY 25/35L under the following
processing conditions: temperature of the cylinder 170–240 C, injection pressure of
15 MPa, packing time of 1 s and cooling time of 90 s. Specimens for mechanical tests
were punched out from these plates.

Methods
DSC measurements. DSC was carried out in a temperature range from 50 C
to 200 C with a TA Q 100 (TA Instruments, USA) at a scanning rate of 10 C/min,
connected to a liquid nitrogen cooling system and calibrated with indium. The sample
weights were about 7 mg. The degree of crystallinity fcDSC for each component was
calculated by equation (1)
DHm
fcDSC ¼ ð1Þ
DHmo 
where DHm is the heat of fusion of the corresponding component; DHm0 is the heat of
fusion of 100% crystalline polymer, and  is the portion of the defined component in the
blend. DHm0 is 182.6 J/g and 288 J/g for iPP and PE, respectively.17

Wide-angle X-ray diffraction measurements. Wide-angle X-ray diffraction (WAXD) pat-

terns were recorded in the reflection mode by means of D8 Advance diffractometer
482 Journal of Elastomers & Plastics 44(6)

containing a PSD Vantec detector (from Bruker, Germany). The experiments were
carried out using Cu K radiation (l ¼ 0.1542 nm) operating at 40 kV and
40 mA. The intensity of WAXD was registered as a function of the scattering angle
2Y from 5 to 40 at a scanning rate of 4 /min. The degree of crystallinity was
calculated by equation (2)
Icr
fcWAXS ¼ ð2Þ
ðIcr þ Iam Þ
where Icr is the area of the crystalline phase and Iam is the area of the amorphous phase.
The relative portion of  form K in the PP specimen was determined by X-ray dif-
fraction and calculated according to the equation of Turner-Jones et al.18
Ið3 0 0Þ
K ¼ ð3Þ
Ið3 0 0Þ þ Ið1 1 0Þ þ Ið0 4 0Þ þ Ið1 3 0Þ
where I(110), I(040) and I(130) are the intensities of the peaks for (1 1 0), (0 4 0) and
(1 3 0) diffracting planes of monoclinic  form and I(300) is the intensity of the peak for
(3 0 0) diffraction plane of the hexagonal  form.

FTIR measurement. FTIR was carried out on a Spectrum One FT-IR (Perkin Elmer,
USA) using the attenuated total reflection technique in the region between 400 and
4000 cm1 at room temperature.

Scanning electron microscope measurements. The phase morphologies of the blends

were characterized from cryogenically fractured samples using a JSM 5510 (JEOL Ltd,
Japan) scanning electron microscope (SEM) in a regime of secondary electrons and
10 kV accelerating voltage. The examined fracture surfaces were coated with thin layer
of gold (2 nm) in argon atmosphere.

Mechanical testing. The mechanical properties (tensile strength and elongation at

break) were determined according to the EN ISO 527 standard by means of TIRATEST
2300 testing machine at a crosshead speed of 50 mm/min. Five dumbbell-shaped speci-
mens with gauge dimensions of 30 mm in length and 6 mm in width for each composi-
tion were tested.
The impact strength was determined according to the EN ISO 179 standard by means
of M 1488-4 Charpy impact tester. Six notched test specimens with dimensions of
80  10  4 mm for each sample were tested. The U-shaped notch was cut at the center
of each specimen with a depth of 2 mm.

Results and discussion

DSC – first melting
DSC is a widely used technique for thermal characterization. The changes in the shape of
the first melting endotherms give some qualitative information about the content of
Borovanska et al. 483

Figure 1. Differential scanning calorimetry (DSC) first melting curves of technological wastes of
low-density polyethylene (LDPEtw), polypropylene (PPtw) and their blends.

different phases as well as the perfection of the crystal structure which depends on the
prehistory of the material.
Typical melting curves for the initial single polymers LDPEtw and PPtw and their
blends modified with EPDM of technological wastes can be observed in Figure 1. The
melting temperature of LDPEtw is about 109 C. Also a small broad peak at around 60 C
is observed which is due to ageing effect. The PPtw shows a melting peak at about 163 C
and a small peak at 109 C, which indicates the presence of certain amount of PE.
Both components within the blends exhibit their own melting behavior at the same
temperatures, indicating that the two crystalline phases are not cocrystallizable; and
both types of crystallites remained in the blends as can be seen in the next section from
the WAXS results. It could be said that the technological waste binary blends (referred
to in brief as TWB) melt at the same temperature as their components due to their
immiscibility (Figure 1). The melting peaks of LDPEtw and PPtw are lower than the
melting peaks of the initial single polymers, which indicates the presumable imper-
fection of the obtained crystals.
DSC curves of the ternary TWBs present the same characteristic peaks as the initial
single polymers. It is clearly observed that the addition of EPDM has more influence
on the PPtw than the PEtw. It could be said that the increase in modifier content leads to
the decrease in melting temperatures for both thermoplastics. The melting temperature
sharply decreases in the ternary blends with the highest content of EPDM (20TWB).
This result could be due to the partial miscibility of EPDM and PP described in the
literature.19
484 Journal of Elastomers & Plastics 44(6)

Figure 2. Differential scanning calorimetry (DSC) first melting curves of postconsumer wastes of
low-density polyethylene (LDPEpw), polypropylene (PPpw) and their blends.

The DSC results for the postconsumer waste are presented in Figure 2. The complex
triple peak at 105 C, 114 C and 121 C obtained during the melting of LDPEpw is in a good
agreement with literature data.14 The existence of multiple peaks can appear in (a) a sample
that consists of more than one plastic; (b) a sample that consists of only one plastic but with
different molecular weight; (c) a sample that consists of different size and/or type of
crystals; (d) a degraded sample. This material should consist only of LDPE; but depending
on how successful the sorting process has been, the material may consist of other plastics or
mechanical contaminants. Perhaps, the triple peak of initial single polymer LDPEpw is due
to the different recrystallization processes as well as to the possibility of simultaneous
sample degradation, which results in the formation of different imperfect crystals.
The first melting curve of PPpw shows three peaks. The main characteristic peak
at about 162 C is in the region of the melt temperature of virgin iPP which is about
160–171 C.20 The peak at 123.5 C may be due to the existence of small quantity of PE or
PE/PP block copolymer.21 The peak at 144 C and the shoulders at about 151 C and
158 C of PPpw could be explained with the specificity of PP crystal melting process,
namely melting recrystallization of the forming crystals or the presence of  phase.
Generally, the isotactic PP under usual industrial thermal conditions crystallizes into the
monoclinic  form. The processing conditions that assist with the formation of imperfect
 crystals of iPP are (a) the presence of additives resulting in the retardation of chain
mobility; (b) the presence of shear stress, changing the chain structures22; (c) fast cooling
conditions at foil production when the  phase has not enough time to be transformed
into the more stable  form.23 It could be supposed the presence of  phase have been
formed mainly in the result of the blend processing conditions.
Borovanska et al. 485

Figure 3. Differential scanning calorimetry (DSC) second melting curves of technological wastes
of low-density polyethylene (LDPEtw), polypropylene (PPtw), and their blends.

Analyzing the melting behavior of binary and ternary postconsumer blends (PWB and
15PWB), it could be inferred that their DSC curves are very different from the analogical
curves of the technological blends (Figure 2). The main endotherms for LDPE and PP
appear separately as well as many other small peaks. In contrast, the technological
wastes have only two peaks. The degradation processes or the influence of other addi-
tives result in multiple peak appearances in the postconsumer blends. Moreover, the peak
at 144 C of PPpw becomes higher in the PWB blend than in the initial single PPpw; the
shoulder at 151 C transforms into a peak in PWB (Figure 2). Unlike PWB, only a
shoulder at about 160 C is observed on the melting curve of TWBs (Figure 1). Hence,
the processes of blending, and the use at different conditions and additives enhances the
polymorphism of iPP.24
After cooling, we could conclude that the single polymer PEpw is performed as a
mixture of low- and high-density PE because of the splitting of crystallization peak. Also
the binary crystallization curves of single polymer PPpw prove the presence of  phase.
Generally, the degradation process facilitates the polymorphism of PP.

DSC – second melting

The second melting curves of TWBs recorded immediately after the crystallization do
not differ so much from the first melting ones (Figure 3). LDPEtw is similar to the first
melting endotherm but without the small peak at 60 C and PPtw performs at the principal
peak at about 160 C and the smaller one at about 109 C. No evidence for PP poly-
morphism on the second melting scan is observed. It can be seen that the peak at 109 C
486 Journal of Elastomers & Plastics 44(6)

Figure 4. Differential scanning calorimetry (DSC) second melting curves of postconsumer wastes
of low-density polyethylene (LDPEpw), polypropylene (PPpw) and their blends.

of PPtw is sharper than the one in the first melting, which confirms again our suggestion
for the presence of some amount of unit of PE.
The melting peak of the blends around 160 C changes its shape by increasing the
EPDM content; and at 20% EPDM it turns into a binary one probably due to the phase
transformation and the presence of imperfect crystallites.
DSC second melting curves of postconsumer wastes and their blends (PWB) reveal that
some structural changes occur in the examined samples during crystallization (Figure 4).
Regardless of the shape and number of the peaks, they are clearly distinguished.
First, the LDPEpw shows bimodal behavior typical for a copolymer or blend of dif-
ferent types of PEs or broadness distribution of molecular weight.25 Also the double
endotherms could be associated probably with melting recrystallization or melting of the
preliminarily quickly cooled sample.26–28 The single LDPEpw proves the binary blend of
LDPE and HDPE. Also the broad peak at 46 C corresponding to physical aging process
disappeared. The PPpw shows small endotherm (123 C) corresponding to the unit of PE
and double peak in the principal endotherm corresponding to the different types of
crystals obtained during the cooling at 10 C/min, and additionally a small peak that
appears at around 146 C which may correspond to the typical polymorphism of PP. It is
proved by X-ray diffraction further in the next section.
The PWB melting curves present the results in the formation of significant amount of
the  polymorph: the peak at about 146 C is clearly seen and it is higher than the same
peak for PPpw. This tendency is found in the blends containing EPDM. The ternary peak
of the first melting LDPEpw is transformed into two separate peaks – one for LDPE and
another for HDPE. Both peaks have their location in the second melting curves of the
blends, showing the stability of the PE phase during blending.
Borovanska et al. 487

Table 1. The melting temperatures (Tm) and the degree of crystallinities estimated from DSC –
second melting (fcDSC) and WAXS (XcWAXS)

Concentration of the EPDM

compatibilizer (weight %) TmLDPE ( C) TmPP ( C) LDPE
fcDSC PP
fcDSC XcWAXS

Technological waste
100%LDPEtw 109.4 0.35 0.44
100%PPtw 160.7 0.38 0.47
TWB 108.9 159.8 0.40 0.34 0.43
7TWB 108.2 159.4 0.38 0.34 0.41
10TWB 108.1 159.4 0.37 0.34 0.40
15TWB 108.1 159.7 0.36 0.36 0.40
20TWB 106.9 156.7 0.32 0.35 0.39
Postconsumer waste
100%LDPEpw 107.2 0.36 0.42
100%PPpw 163.5 0.42 0.46
PWB 107.2 149.1 0.36 0.39 0.45
15PWB 106.1 148.8 0.37 0.39 0.42

DSC: differential scanning calorimetry; EPDM: ethylene-propylene diene monomer; LDPEpw: postconsumer
waste of low density polyethylene; LDPEtw: technological waste of low density polyethylene; PPpw: postcon-
sumer waste of polypropylene; PPtw: technological waste of polypropylene; PWB: postconsumer waste blend;
TWB: technological waste blend; WAXS: wide angle X-ray scattering.

The melting temperatures of LDPE, PP and LDPE/PP blends with and without EPDM
are summarized in Table 1. When the quantity of rubber is in the range 7–15%, the
melting temperatures do not change significantly. However, the addition of 20%
modifier leads to the decrease in melting temperatures and in degree of crystallinity for
both PE and PP.

Wide angle X-ray scattering

In order to obtain additional information about the structural characterization of these
blends, different X-ray diffraction experiments have been performed. The X-ray diffrac-
tograms for the technological and postconsumer wastes (LDPEtw/pw and PPtw/pw) are
shown in Figures 5 and 6.
The initial PPtw exhibits the characteristic diffraction peaks of the monoclinic  phase
at scattering angles 2 of 14.2 (110), 17.1 (040), 18.6 (130) and complex peak 21.9
(111þ131þ041),29 as well as characteristic peaks for LDPE – (110) (200)30 located in
the figure from left to right, respectively.
In the TWB blend, most of the characteristic peaks retain their shape and position;
while in the PWB blend, only one peak for PP and another for LDPE can be seen. With
the addition of EPDM, the intensity of the characteristic peaks slightly decreases. The
complex peak (111þ131þ041) for technological binary and ternary blends is trans-
formed into a sharper and higher one than the same peak of the initial PPtw, since it
overlaps with the (110) reflection PE characteristic peak and corresponds to the higher
488 Journal of Elastomers & Plastics 44(6)

Figure 5. X-ray diffractograms of technological wastes of low-density polyethylene (LDPEtw), polypro-

pylene (PPtw) and their blends with different amounts of ethylene–propylene diene monomer (EPDM).

Figure 6. X-ray diffractograms of postconsumer wastes of low-density polyethylene (LDPEpw),

polypropylene (PPpw) and their blends without ethylene–propylene diene monomer (EPDM) and
with 15% EPDM.
Borovanska et al. 489

imperfection of the growing crystals. The EPDM incorporation does not significantly
change the crystal structure of the binary LDPE/PP blend, but it obviously leads to the
growth of the amorphous phase and occurrence of two small peaks at 2 ¼ 10 and 28.5
on the X-ray diffractograms.
Figure 6 presents WAXS patterns of postconsumer waste LDPEpw, PPpw and their
blends. Besides the characteristic peaks for the  phase in the PPpw and the  phase are
also clearly observed. The relative portion of  form (K ¼ 0.45) in PPpw calculated by
equation (3) confirms our assumption that as a result of the exploitation period, the
presented  polymorph transforms into the  polymorph, while PPtw indicates only the 
phase. Moreover, the X-diffractograms also confirm that the  phase content increases in
the binary and ternary postconsumer blends and the relative portion of the  form for
both blends calculated by equation (3) is K ¼ 0.576 and K ¼ 0.497, respectively. In
both the blends, two peaks can be clearly seen: one for the  phase at 2 ¼ 16.2
(3 0 0) and another at 2 ¼ 21.6 , where the complex peak of PPpw overlaps with the
peak of LDPEpw. These peaks are sharper and higher than the same peaks for initial
PPpw. The peaks at 2 ¼ 10 and 2 ¼ 28.5 , observed for the technological blend with
15% EPDM, also appear in the postconsumer blend as a result of EPDM addition.
Comparing the binary blends of technological and postconsumer waste, it may be
inferred that there is a large difference between them. Obviously PPpw has crystallization
ability for  phase, which is intensified during the exploitation period. The addition of
15% EPDM does not change the  formation significantly.

Fourier transform infrared spectroscopy

Infrared (IR) spectroscopy is another popular technique for studying the chemical
changes in polymers. Some new chemical bonds form during ageing. Their formation
rate strongly depends on the chemical structure of the polymers. The main chemical
bonds detected by IR spectroscopy of the investigated blends are hydroxyl and carbonyl
groups. The formation of carbonyl, hydroxy and hydroperoxy groups leads to the
occurrence of typical bands in the regions of 1800–1650 cm1 and 3650–3300 cm1.31,32
PP wastes show typical characteristic peaks for the specific C–H stretching
(2918 cm1 and 2839 cm1) and deformation (CH2– 1457 cm1 and CH3– 1376 cm1)
vibration. LDPE wastes also show typical characteristic peaks for the C–H stretching
bands (2918 cm1 and 2839 cm1) and a single peak for the CH band – 1463 cm1
(Figures 7 and 8). Also the typical peak at 720–730 cm1 associated with the amorphous/
crystal form of PE appears in the PP, which proves the appearance of small peak of
LDPE in the DSC experiments for both polymers PPtw/pw.
Generally, the polyolefins are very accessible to the oxidative processes. Observing
Figures 7 and 8 for the technological and postconsumer single polymer, it may be
concluded that the weak and broad absorption peak at 1598 cm1 for postconsumer
polymers and at 1646 cm1 for technological polymers corresponds to the stretching
vibration of the (C¼O) group. The intensity of the carbonyl group band strongly
increases for coupling with other multiple bonds and the frequency may be decreased
even to 1580 cm1, as is the current case with the postconsumer waste. LDPE is known
490 Journal of Elastomers & Plastics 44(6)

Figure 7. Fourier transform infrared spectroscopy (FTIR) diffractograms of technological wastes

of low-density polyethylene (LDPEtw), polypropylene (PPtw) and their blends with different quan-
tity of ethylene–propylene diene monomer (EPDM).

Figure 8. Fourier transform infrared spectroscopy (FTIR) diffractograms of postconsumer wastes

of low-density polyethylene (LDPEpw), polypropylene (PPpw) and their blends without ethylene–
propylene diene monomer (EPDM) and with 15% EPDM.
Borovanska et al. 491

Figure 9. Scanning electron microscope (SEM) images of technological waste blend TWB (a) and
postconsumer waste blend PWB (b) at magnification 1000.

as a polymeric material which is more stable to oxidation than PP because of the lack of a
tertiary carbon atom in its chemical structure. However, it can be seen in the figure that
these bands are significantly lower in the recycled PPs than in both PEs. These peaks
could be the result of mechanical destruction due to the shear stresses that are higher
during the numerous cycles of the extrusion process, as a result of which the post-
consumer wastes show bigger peaks. The absorption at 1167 cm1 in the spectrum of
PPtw was attributed to anhydride groups.
The broad peak at 1596 cm1 in the binary blend without EPDM in Figure 7 could be
due to the mechanical destruction mainly in PP and formation of C¼O bonds. On the
contrary, upon addition of EPDM modifier, the polymer melt undergoes less shear
stresses, and the peak at 1596 cm1 is smaller.

Scanning electron microscope

The observation of the blend morphology is essential for understanding the mechanical
performance of polymer blends. There are three main factors that govern the impact
modification as a whole: the elastomeric nature of the impact modifier; the interfacial
adhesion between the impact modifier and the other components, the particle size and
distribution of the impact modifier.33 The presence of large particles can initiate cracks
leading to brittle failure.34 The formation of a co-continuous structure helps to improve
the poor impact performance even with exhibited dispersed morphologies in PE/PP
blends since the cocontinuity does not require a very good adhesion between phases
to achieve a good stiffness–toughness balance.35 On the other hand, the tensile properties
of incompatible and partly compatible blends depend on two interrelated factors: the
adhesion between the two phases and the domain size of the dispersed component, both
controlled mainly by the interfacial tension.36
The comparative SEM observations of both TWB and PWB binary blends (Figure 9)
reveal good compatibilization in the technological and the postconsumer wastes. The
phases are undistinguishable from one another. Amphitheatrical morphology is
492 Journal of Elastomers & Plastics 44(6)

Figure 10. Scanning electron microscope (SEM) images of 15TWB (a) and 15PWB ternary blends
(b) at magnification 1000. PWB: blend from postconsumer waste; TWB: blend from technological
waste.

observed. As a result, the interfacial tension generates some propagations and cracks
in the technological blend and the phase recession and shrinkage of the components
are obvious.
Comparing the binary (Figure 9) and ternary (Figure 10) blends, it could be noticed
that the ternary blends have better compatibility than the binary ones. Much more uni-
form and smooth surface is observed in the fracture surface of the composites modified
with EPDM – 15TWB and 15PWB (Figure 10), which could be indicative of a com-
patibilization effect of the modifier for these blends and formation of a co-continuous
structure. The addition of EPDM increases the interfacial adhesion in both kinds of
blends – technological and postconsumer and prevents the formation of cracks and
phase separations.

Mechanical properties
The effects usually associated with impact modification are reduced elastic modulus and
tensile strength and increased impact strength and elongation at break.37 Copolymers are
compatible with thermoplastics and thus are frequently used for impact modification and
improvement in stress–crack resistance.38
The impact strength values of binary and ternary recycled blends with different
quantities of EPDM are shown in Figure 11. The mechanical properties of the binary
technological blend (TWB) are reasonably poor. It is possible for the weak PE/PP
interspherulitic boundaries to cause poor impact resistance of PE/PP blend as a result of
their crystallizabilities. The impact strength of the ternary 15TWB as well as 15PWB
blends increases with the EPDM addition. This is due to the fact that the compatibilizer is
localized at the interphase boundaries39 and enhances the stress transfer, contributing to
particle size reduction.40 Moreover, it is clearly seen that EPDM exhibits more signif-
icant impact modification effect on the technological blends. The good impact resistance
shown by the 15TWB and 15PWB ternary blends is attributed in part to the fine
Borovanska et al. 493

Figure 11. Impact strength of technological waste (TWB) and postconsumer waste (PWB)
polymer blends versus ethylene–propylene diene monomer (EPDM) content.

dispersion of modifier and to possible involvement of a portion of the polymers in the co-
continuous structure observed by SEM.
The tensile strength of the blends is presented in Figure 12. The tensile strength does
not exhibit significant change in the addition of the compatibilizing agent to TWB where
a more essential decreasing can be noticed when EPDM is added to binary blends of
postconsumer waste. This behavior indicates that the elastic limits are not altered by the
compatibilization. The addition of EPDM to the TWB and PWB recycled blends in our
study significantly improves the elongation at break (Figure 13). Since the tensile
strength of the blends depends mostly on the adhesion between the two phases, the
elongation at break depends mostly on the domain size of the dispersed component,36
and it may be concluded that the adhesion between the components in the TWBs is better
than that in the postconsumer ones. The lower growth of impact strength and the bigger
decrease of tensile strength of the ternary 15PWB blend may be due to the presence of 
phase or imperfect crystals in this blend.

Conclusion
The technological and postconsumer wastes of LDPE, PP and their blends were studied
by the DSC, FTIR, WAXS and SEM techniques. DSC results reveal that the single
polymers do not consist of clean material but consist of some quantity of another
polyolefins. In the results of processing and exploitation conditions, the imperfect
crystals in the PPpw are increased. The addition of modifier decreases the melting
494 Journal of Elastomers & Plastics 44(6)

Figure 12. Tensile strength of technological waste (TWB) and postconsumer waste (PWB)
polymer blends versus ethylene–propylene diene monomer (EPDM) content.

Figure 13. Elongation at break of technological waste (TWB) and postconsumer waste (PWB)
polymer blends versus ethylene–propylene diene monomer (EPDM) content.
Borovanska et al. 495

temperatures for both thermoplastics. In spite of that, the obtained blends keep their
crystal ability and present almost the same crystallization ability as that of single polymers.
FTIR provides clear evidence about oxidative processes and mechanical destruction
running during exploitation and blending, respectively. Using rubber as a compatibilizer
minimizes significantly these undesired effects. The FTIR spectra reveal the expected
chemical changes due to the oxidation during exploitation or due to some additives.
The different quantity of EPDM rubber successfully serves as a modifier up to 15%.
The crystallization ability of PE and PP sharply decreases, resulting in low melting
temperatures and low degree of crystallites.
The ternary blends PE/PP/EPDM from technological and postconsumer wastes
present better mechanical properties than the double blend PE/PP.
The obtained results proved that the technological and postconsumer wastes could be
successfully reused by the addition of EPDM. This compatibilization substantially
enhances the impact strength and elongation at break.

Acknowledgement
The authors wish to express their gratitude to the Ministry of Education and Science of Bulgaria for
the financial support it provided for the experiments through contracts No BG051PO01/07/3.3-02/
51 and No DTC 02/07/2010.

Funding
This research received no specific grant from any funding agency in the public, commercial, or
not-for-profit sectors.

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