Article

pubs.acs.org/IECR

Investigation on the Influence of Different Compatibilizers on

Polycarbonate and High Density Polyethylene Blends: Mechanical
Properties, Thermal Properties, Morphology, and Chemical
Resistance
Lohith Manjunatha Nanjegowda,† Ramaraj Bommulu,‡ Vishvajit Juikar,† and Siddaramaiah Hatna*,§
†
SABIC Innovative Plastics Program, GE Global Research Center, Whitefield Road, Bangalore 560 066, India
‡
Central Institute of Plastics Engineering and Technology, Ahmedabad 382 445, India
§
Department of Polymer Science and Technology, Sri Jayachamarajendra College of Engineering, Mysore 570 006, India
*
S Supporting Information

ABSTRACT: This investigation focused on a systematic approach of selecting the best possible polycarbonate/high density
polyethylene (PC/HDPE) blend ratio and a suitable compatibilizer to improve the notch sensitivity, craze, and cracking
tendency of PC. Among five different compatibilizers, polyethylene glycol (PEG) was found to be more effective based on
mechanical performance and changes in phase morphology. The phase morphology of dispersed HDPE phase changed from
elongated domain to fine spherical domain, and the tensile modulus and heat distortion temperature of PC/HDPE blend
increased with increase in PEG content. DSC analysis showed an inward shift in the glass transition temperature (Tg), indicating
enhanced compatibility between the PC and HDPE phases. Furthermore, PEG compatibilized PC/HDPE (80/20) blend was
found to have very good notch performance and chemical resistance compared to PC. Hence, this blend can be used to design
products with intricate shapes with less notch sensitivity and high chemical resistance with the superior mechanical performance
of PC.

1. INTRODUCTION The role of the compatibilizer is to act at the interface to

Polycarbonate (PC) is one of the most widely used engineering
thermoplastics with many excellent properties such as high
transparency, dimensional stability, impact strength, high heat
distortion temperature, and flame retardance, and very wide
service temperatures. However, some characteristics of PC such
as notch sensitivity, tendency to craze, and tendency to crack
limit its use in many applications. Apart from these, PC has a
high melt viscosity and is difficult to fabricate. These
disadvantages can be overcome by blending PC with
polyethylene (PE). Blending of PC with PE increases
toughness and reduces the melt viscosity, thus improving the
processing difficulties and reducing notch sensitivity. Even
though this blend contains all the advantages cited above, phase
separation between PC and PE phases cannot be avoided,
because of the immiscibility of PC with PE. PC/PE blends have
a coarse phase morphology with poor interfacial adhesion with
sharp phase boundaries. Immiscibility is due to the wide
chemical and structural differences between PE and PC. The
immiscibility of PC with PE is well-known from literature
reports and is predictable from basic thermodynamic
considerations.1−7
Improvement in the interfacial adhesion between the blend
components would refine, stabilize the phase morphology, and
upgrade the blend material with beneficial properties of both
components. Immiscible blends have become commercially
successful after being efficiently compatibilized with suitable
compatibilizers. Compatibilizers are macromolecular species
exhibiting interfacial activities in immiscible polymer blends.
increase adhesion between two different polymer components
through the reduction of the interfacial tension. The
compatibilizers can be reactive or nonreactive. Reactive
compatibilizers will reduce or entirely eliminate the repulsion
effect between the blend components by formation of covalent
bonds, whereas the nonreactive compatibilizers increase the
interfacial adhesion by creating specific polar interactions
through hydrogen bonding or van der Waals forces. Generally,
compatibilizers are block copolymers and belong to either
diblock, triblock, or multigraft with one constitutive block
miscible with one blend component and the second block
miscible with the other component. These preformed block
and graft copolymers allow the interfacial tension to be largely
decreased, and impart a strong mutual anchoring to the phases.
Kunori and Geil8,9 have investigated the mechanical
properties of PC/high density polyethylene (HDPE) blends.
In their investigation, they reported that there is no adhesion
between the PC and the HDPE phases, and the dispersed
HDPE domains were loosely sitting (without strong
interaction) in the holes in the PC matrix. Mascia and Valenza
have reported10 on the concept of ionomeric mixtures as dual-
component compatibilizers; however, at higher levels of
compatibilizer loading, the PC phase undergoes cross-linking
Received: December 11, 2012
Revised: March 5, 2013
Accepted: March 29, 2013
Published: March 29, 2013

© 2013 American Chemical Society 5672 dx.doi.org/10.1021/ie303382g | Ind. Eng. Chem. Res. 2013, 52, 5672−5682
Industrial & Engineering Chemistry Research Article

reactions, causing severe embrittlement. Fan et al.11 developed

a method to compatibilize PC with ultrahigh molecular weight
high density polyethylene (UHMWPE). The experimental
results showed that γ-ray irradiation partly causes oxidative
degradation of UHMWPE and the content of oxygen-
containing groups increases with irradiation dose. Yang et
al.12 studied HDPE/PC blends with PC as a minor phase
through blend morphology, heat resistance, mechanical proper-
ties, crystallizing behavior, and rheological measurement using
low density polyethylene grafted diallyl bispheno1 A ether
(LDPE-g-DBAE) as compatibilizer. The compatibilized blends
were found to possess a high apparent viscosity compared with
the uncompatibilized ones. However, the apparent viscosity of
the blends, with or without compatibilizer, was lower than that
of the neat HDPE and PC. Sue et al.13 studied interfacial
adhesion and toughening mechanisms of PC/PE blends
through transmission electron microscopy (TEM). Yin et
al.14 studied the morphological development of PC/PE blends
in a twin-screw extruder using scanning electron microscopic
(SEM) images. The effects of extrusion temperature, viscosity
ratio, and the screw configuration on the morphology of the
PC/PE blends during the extrusion were discussed in detail. It
was found that the morphology of the dispersed particles and
the interfacial adhesion between the dispersed phase and matrix
were both influenced by the extrusion temperature. The
dispersed phase had a spheroidal shape during the high
temperature processing, and an irregular shape when it was
processed at low temperature. Yin et al.15 analyzed reactive Figure 1. Representative molecular structures of polymers and
compatibilization of PC/HDPE blends using PC-graf t-ethyl- compatibilizers.
ene-co-acrylic acid (PC-g-EAA) as a compatibilizer generated in
situ during a processing operation. Yee et al.16 have reported
impact modification mechanism through a volume dilation Supporting Information. HDPE (M00675) was procured from
technique. Shigeru et al.17 used styrene−(ethylene/butene) M/s Reliance Industries Ltd., Mumbai. The physical and
block copolymer to control the phase morphology, and the mechanical properties of HDPE are given in Table S3 in the
phase growth of PE/PC blends. Supporting Information. Five different compatibilizers were
Overall, from the literature review, it was found that attempts used in this study. They are ethylene−methyl acrylate−glycidyl
were made to compatibilize the PC/HDPE blends either by methacrylate (LOTADER AX8900), ethylene−n-butyl acryl-
chemical modification of the interfacial region or by the ate−glycidyl methacrylate (ELVALOY PTW), styrene−ethyl-
addition of modifiers as the third component.8−17 In the ene−butylene−styrene (SEBS, SEBS G1650E), polyethylene
ongoing efforts to find a suitable compatibilizer for PC/HDPE grafted maleic anhydride (PE-g-MA, OPTIM E-156), and
blends, the present investigation employed a three-pronged polyethylene glycol (PEG2000); they were selected on the
strategy involving the following: selection of a particular PC/ basis of literature knowledge. LOTADER AX8900 is a
HDPE blend ratio, based on its mechanical and thermal terepolymer, ELVALOY PTW is a copolymer, and SEBS
performance; screening of five different kinds of compatibilizers G1650 E is a clear linear triblock copolymer based on styrene−
to select the best of them based on tensile and impact ethylene/butylene−styrene block, with 29.2% styrene. OPTIM
performances; and, finally, characterization of the selected E-156 is a grafted polyethylene with anhydride and acid
blend ratio compatibilized with the selected compatibilizer for functionality.
notch sensitivity and chemical resistance. The representative 2.2. Compounding and Specimen Preparation. Poly-
molecular structures of the polymers and compatibilizers used carbonate and HDPE materials were mixed in various
are shown in Figure 1. PC is a notch sensitive material, and proportions and extruded. Before extrusion, the PC powder
performs very badly under certain chemical environments. was dried at 120 °C for more than 8 h in a vacuum oven.
Although HDPE gives very good chemical resistance compared HDPE and compatibilizers were dried at 80 °C for at least 12 h
with PCs, there is a lack of literature on the chemical properties in the same oven, and then dried PC, HDPE, and
of these blends; hence, this research work also focused on the compatibilizers were mixed together. All the formulations
notch sensitivity and chemical resistance of PC/HDPE blends. were, then, extruded at 300 rpm. The extrusion was carried out
in a corotating (W&P ZSK25) twin-screw extruder with a 25
2. EXPERIMENTAL SECTION mm screw diameter having an L/D ratio of 40 at temperatures
2.1. Materials. Trade names and suppliers of PC, HDPE, of 180−250 °C. The pellets collected from the pelletizer were
and the compatibilizers used in this study are listed in Table S1 dried at 80 °C for 3−4 h prior to molding. The molding
in the Supporting Information. Polycarbonate (Lexan 105) is a process was carried out in an ENGEL 80 ton automatic
general-purpose, low flow powder grade material procured from injection molding machine at 190−240 °C with an injection
M/s SABIC India Ltd. The key properties of this material as speed of 30−50 mm/min and an injection pressure of 30−40
given by the manufacturer are shown in Table S2 in the bar.
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2.3. Techniques and Instrumentation. The tensile test
was carried out on injection-molded dumbbell specimens in a
Universal testing machine (Zwick Z010) as per the ISO 527
standard. The impact test was performed using a Zwick HIT
25P impact testing machine as per the ISO 180 standard. The
heat distortion temperature (HDT) test as per ISO 75A was
carried out with an applied load of 1.8 MPa with 120 °C/h
heating rate. For TEM images, the sample was kept at cryo
conditions and final microtomy was carried out at −60 °C.
Sections were stained with RuO4 for 2 min, and analysis was
carried out by using a Tecnai G2 microscopy instrument.
Differential scanning calorimetric (DSC) analysis was carried
out in a Thermal Analyzer 2000 system at a heating rate of 10
°C/min from −150 to 250 °C in an inert atmosphere.
Measurement of the melt volume rate was carried out as per
ASTM D1238. The environmental stress cracking resistance
test was carried out as per ISO-22088-3. Samples were exposed
to chemicals such as acetone and methyl pentyl ketone (MPK)
at a constant strain rate of 1% for 24 h at room temperature.
Then, the samples were removed from the test fixture and
analyzed for their tensile strength property with the controlled
samples.
3. RESULTS AND DISCUSSION
3.1. Effect of PC Content on Mechanical and Thermal
Properties of the Blends. Polycarbonate attracts much
attention in materials research, because of its outstanding
mechanical and thermal performances. The mechanical and
thermal performances of PE/PC blends increase with increase
in PC content despite the absence of interfacial adhesion. So
far, structure−property relationships of many binary blends of
PC have been investigated extensively. In this work, with an
objective to select a particular PC/HDPE ratio with the best
possible mechanical and thermal performances, PC was
blended with HDPE in different ratios and evaluated for its
mechanical and thermal performances. The tensile strength,
tensile modulus, notched Izod impact strength, and HDT of
PC/HDPE as a function of PC content are shown in parts a, b,
c, and d, respectively, of Figure 2. The very low mechanical and
thermal performances of HDPE improve with an increase in the
volume fraction of PC, especially when the PC content is more
Figure 2. Effect of polycarbonate content on tensile strength, tensile
modulus, impact strength, and heat distortion temperature of PC/
HDPE blends.
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than 50% and forms a continuous matrix. However, it does not
follow a simple linear relationship. That is from 0 to 30% PC,
where amorphous/rigid PC is a minor phase, which can be
called the first zone, follows a particular pattern. From 40 to
60% PC, where both amorphous PC and elastic HDPE phase
form a cocontinuous phase, which can be called the second
zone, follows a little different trend. Finally, from 70 to 100%
PC, the amorphous/rigid PC forms the continuous phase and
where the elastic HDPE phase was dispersed as a minor phase,
which can be called the third zone, forms a positive trend. In
the first zone, the tensile strength and impact strength decrease,
whereas the tensile modulus and HDT increase. This effect is
due to the mismatch of the thermal expansion coefficient of the
individual components in the blend. The crystalline HDPE
matrix shrinks more than the minor dispersed amorphous PC,
since the coefficient of thermal expansion of HDPE was much
higher than that of PC. As it cooled from processing
temperature to room temperature, the HDPE matrix strongly
shrank around the PC dispersed phase and caused macro-
molecular chains to orient particularly around the PC phase.12
This contraction apparently promotes stress transfer at the
interface and thus increases stiffness and heat resistance around
the PC phase and blends.
The second zone (40−60% PC) represents the region of
phase inversion and cocontinuity, showing a major departure
from the first zone. Tensile and impact strengths (Figure 2a,c)
of the PC/HDPE blends increased with increase of PC content
due to the mechanical superiority of the PC. The modulus and
HDT also increased with increase in PC content in the blends
(Figure 2b,d). In the third zone, with PC content from 70 to
90%, the PC is the major continuous phase in which HDPE is
dispersed as the minor phase. All the mechanical properties are
superior to those of neat HDPE material. Notched impact
strength of the blends shows a drastic improvement above 80%
PC content, since HDPE has a very low notched impact
strength (Figure 2c) which is modified by the addition of PC.
The transition from one behavior to the other is closely related
to the estimated region of phase inversion. The PC80/
HDPE20 blend is the optmized composition, and it exhibits
the best performance compared to the other formulations
studied. Generally, mechanical properties of PCs are usually
superior to those of other polymers blended with it such as
poly(methyl methacrylate) (PMMA),18,19 polystyrene (PS),8,20
and styrene−acrylonitrile (SAN).21−23 It is generally known
that the mechanical properties of PC blends are sharply
enhanced when the volume fraction of the PC phase becomes
sufficient to bring a continuity. Therefore, it is desirable to
control the PC matrix continuity in blends to suppress their
phase structure coarsening. On the basis of the mechanical
performance, thermal performance, and cost considerations, the
PC/HDPE (80/20) ratio has been selected for further study.
3.2. Role of Interfacial Adhesion on Mechanical
Performance. Interfacial adhesion is a critical factor in
improving the mechanical performance of immiscible blends,
and it has to be strong enough to ensure stress transmission
between the phases. Interfacial adhesion is generally improved
either by chemical modification of the interfacial region or
through the addition of interface agents as a third component.
In this investigation, we approached improving the interfacial
adhesion of the selected PC/HDPE (80/20) blend with five
different interfacial agents: SEBS G1650E, OPTIM E-156,
ELVALOY PTW, LOTADER AX8900, and PEG2000 (see
Figure 1 for their chemical structures). These interfacial agents/
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Figure 3. Influence of different compatiblizers on the tensile strength of PC/HDPE blends.
compatibilizers were selected based on the literature survey and
on the theoretical understanding of their polarities and
functionalities. A hydrophobic terpolymer (SEBS G1650E),
two terpolymers with ester and epoxy groups (ELVALOY
PTW, LOTADER AX8900), a graft copylymer (OPTIM E-
156), and a low molecular weight polar polymer (PEG2000)
were used as compatibilizers. The performance of these
compatibilizers was evaluated on the basis of tensile and
notched Izod impact strengths, and test results are presented in
Figures 3 and 4. Figure 3 shows that the tensile strength of the
PC80/HDPE20 (40 MPa) blend was unaffected by the
addition of 2.5 and 5.0% SEBS G1650E in the blend. This
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response may be because SEBS G1650E is a hydrophobic block
copolymer and does not have polar groups or reaction sites to
interact with PC’s amorphous phase. At the same time, it does
not reduce the tensile strength of the PC, because the
polystyrene blocks present in the compatibilizer support the
stiffness, hardness, and strength of the PC. OPTIM 156E is a
grafted polyethylene with anhydride and acid functionality; it
has been introduced with the assumption that it will provide a
polarity match with PC as well as reaction sites. However, it
does not show any influence on tensile strengths of blends, may
be because of its flexibility compared to the greater rigidity and
stiffness of the PC, but at the same time it retains the tensile
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Figure 4. Influence of different compatiblizers on the impact strength of PC/HDPE blends.
strength, which may be due to its anhydride and acid
functionality. ELVALOY PTW is a terpolymer containing
ethylene−n-butyl acrylate−glycidyl methacrylate, and it shows a
reduction in tensile strength from 40 to 37 MPa for the
addition of 4 wt % compatibilizer. Reduction in the tensile
strength has happened despite the presence of ester and epoxy
functional groups that can interact and react with ester and
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hydroxyl groups of PC. This kind of response can be explained
only on the basis of the flexibility associated with this aliphatic
compatibilizer. The fourth compatibilizer tried with PC/HDPE
(80/20) blend was LOTADER AX8900; it is a random
terpolymer of ethylene/methyl acrylate (24%)/glycidyl meth-
acrylate (8%) (Figure 1). There is not much difference between
LOTADER AX8900 and ELVALOY PTW, except the
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difference in the structure between the methyl acrylate and n-

butyl acrylate. The introduction of LOTADER AX8900 varies
the tensile strength of the PC/HDPE blend, but the overall
value remains less than that of the PC/HDPE (80/20) blend.
Again the flexibility associated with the compatibilizer does not
support or enhance the outstanding tensile strength associated
with the PC. Finally, the fifth compatibilizer used was
polyethylene glycol (PEG); it is a very simple and linear
polymer. PEG having a molecular weight of 2000 has been used
for this study; the theoretical understanding of PEG miscibility
with blends of PC/HDPE has been interpreted. The methylene
groups of PEG are miscible with HDPE of the blend, and the
presence of terminal hydroxyl groups in the glycol may react
with a carbonate group of PC, by which it will get linked with
HDPE. The influence of the compatibilizer addition on the
impact strength of PC/HDPE (80/20) blend is shown in
Figure 4. PC is an amorphous material and has a notched
impact strength of 74 kJ/m2. The addition of 20 wt % HDPE
has reduced the impact strength of PC from 74 to 40 kJ/m2.
The addition of compatibilizers to the PC/HDPE blend does
not bring significant enhancement in the impact strength;
however, the performance of ELVALOY and PEG2000 was
better. Overall, it was found that PEG shows better tensile and
impact strength performance than those of the rest of the
compatibilizers. Hence, PEG compatibilized PC/HDPE (80/
20) blend was selected for further study.
3.3. Effect of Compatibilizer on Phase Morphology of
PC/HDPE Blends. Generally, immiscible blends have coarse
morphology, the interface is sharp, and the adhesion between
the individual components is poor. The shape, size, and spatial
distribution of the phases result from a complex interplay
between viscosities of the phases, interfacial properties, blend
Figure 5. TEM images of PC/HDPE (80/20) blend alone, with 2.5%
composition, and processing conditions. An elementary step is
MA-g-PE, and with 4.0% ELVALOY.
the deformation of dispersed droplets in the flow field. The
interfacial area is accordingly increased and the local
dimensions are decreased perpendicular to the flow direction. PEG at two different magnifications. TEM images of PC/
The morphological development of the dispersed HDPE phase HDPE blend containing 2.5% SEBS show biphasic structures
in the PC/HDPE (80/20) with different well-known polymeric with slightly elongated dispersed phases. However, TEM
compatibilizers has been examined. TEM photomicrographs of images of PC/HDPE blends containing PEG show changes
the PC/HDPE (80/20) blends are shown in Figure 5. It in the elongated shape of the minor phase toward a spherical
exhibits a darker PC phase while the HDPE phase remains shape. On increasing the PEG content to 1.5%, the change in
much lighter. It is relatively easy to visualize the phase structure blend morphology is tremendous. The elongated phase of
of PC/HDPE blends, in which the majority phase is continuous HDPE has been vanished almost to form fine spherical domains
and the minority phase is discontinuous, where the dispersed which are uniformly distributed in the continuous PC phase
HDPE domains are not spherical, but elongated in the direction (Figure 6). The change in morphological behavior supports the
of the flow field acted on during the injection molding.24,25 compatibilizing effect of PC/HDPE blend at 1.5% PEG
Similar phase morphology is observed for the PC/HDPE blend content.
compatibilized with 2.5% PE-g-MA as well as 4% ELVALOY 3.4. Effect of PEG Content on Thermal Properties of
with minor variations. It is important to note that no voids can PC/HDPE Blends. In recent years, the study of structure−
be observed, which would be necessarily produced at extensive property relationships of multicomponent polymer systems has
interfacial debonding because of large differences in plastic gained a great deal of attention as a consequence of their wide
deformation of the components in a three-dimensional technological applications. Most of these systems are
structure. Injection molding is a commonly used processing constituted by scarcely miscible polymers, forming multiphase
operation in the plastic industry that imparts high stress and materials, whose properties can be greatly affected by interfacial
rapid cooling. Especially for immiscible blends, under both adhesion and phase behavior. The thermal transition of PC80/
strong stress field and nonisothermal field during injection HDPE20 blends with 0.5, 1.0, and 1.5% PEG2000 along with
molding, the deformable minor phase can be deformed in situ HDPE100 have been examined by differential scanning
into a variety of morphological structures such as spheres, calorimetry (DSC). DSC thermograms show the thermal
ellipsoids, fibers, and plates.26−33 Additionally, the micro- transitions of two polymeric components in the blend along
structure is unevenly distributed in the injection molded parts, with PEG2000. The DSC melting endotherms and crystal-
displaying an anisotropic morphology, termed skin−core lization exotherms of (a) pure HPDE, (b) PC/HDPE (80/20)
structure.33−35 Figure 6 shows the TEM photomicrographs of blend, and the blend with (c) 0.5, (d) 1.0, and (e) 1.5%
PC/HDPE blend containing 2.5% SEBS, 1% PEG, and 1.5% PEG2000 along with the Tg of PC are shown in Figure 7, and
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Figure 6. TEM images of PC/HDPE (80/20) blend with 2.5% SEBS,
1.0% PEG2000, and 1.5% PEG2000.
Figure 7. Heating and cooling DSC thermograms of PC/HPDE
blends with PEG2000.
results are summarized in Table 1. In the DSC heating scan, the
melting endotherm of pure HDPE appears at 135 °C (see
Figure 7a), whereas for neat PC80/HDPE20 blend, see Figure
7b), and the blend with (c) 0.5, (d) 1.0, and (e) 1.5% PEG2000
shows melting region characteristics of HDPE, with a peak
maximum around 131−134 °C along with Tg deflection of PC.
In the thermogram of PC/HDPE blend, the Tg of PC is not
visible, even though the PC content is around 80%, This is
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because, the PC being a amorphous material, it has only a weak
transition peak at 152 °C and it can be seen only in the
magnified view shown in the inset of Figure 7. The peak
position of the Tg varied from 154 to 145 °C. The data listed in
Table 1 show decreases in both melting point and crystallinity
of HDPE in the blends, and further decreases in the presence of
PEG2000 compatibilizer, which indicates a positive effect of
PEG2000 as compatibilizer. The DSC cooling curves were used
to determine the crystallization behavior of components in the
blends. As shown in Figure 7b, on cooling from isothermal
stabilization at 250 °C for 10 min, multiple crystallization
exotherms have been recorded for PC/HDPE (80/20) (b),
with (c) 0.5, (d) 1.0, and (e) 1.5% PEG2000 in the temperature
range from 78 to 113 °C. The HDPE melting endotherm
appeared at 135 °C in the heating cycle and reappeared as the
crystallization temperature at 111 °C. The changes recorded in
the position of crystallization peaks, melting peaks, and Tg of
HDPE and PC indicate at least partial compatibility between
PC and HDPE, due to the compatibilization effect of PEG2000,
which further indicates a development of chemical and physical
interactions between PC and HDPE phases through PEG2000.
On comparing the thermal parameters of HDPE in the blends,
with and without compatibilizer PEG2000, with that of pure
HDPE, it was found that the melting and crystallization peak
shows appreciable reduction in peak width and height. This
implies that the PEG2000 reduces the width and height of the
crystallization peak. This also implies that the PC-g-PEG2000
copolymer formed during the compounding process by in situ
reaction improves the interaction between PC and HDPE
phases. Two separate transitions have been observed for the
control blend where no compatibilizer has been used, and the
transition temperatures were the same for their respective
polymers (Figure 7a), which proves the existence of a two-
phase structure for blends. However, after compatibilizing with
PEG, the Tg’s of the components have come closer. The Tg of
PC domain decreased, which is attributed to the presence of
flexible PEG and HDPE domains. This effect is a direct
inference of compatibilization. Also, the percentage crystallinity
of HDPE was found to be reduced from 67 to 51 by blending
with PC (Table 1). It was further reduced to 43% after
compatibilizing with PEG. This effect may be due to the
inclusion of amorphous PC and PEG domains on the
crystalline HDPE. The reduction in crystallization temperature
is also observed with compatibilization, which implies that the
compatible blend is easily crystallizable. These results reveal the
efficiency of PEG as a good compatibilizer for the HDPE and
PC blend system. This implies that the in situ reaction products
of PEG2000 with PC improve the interaction between PC and
HDPE phases.
3.5. Effect of PEG Content on Tensile Modulus and
HDT of PC/HDPE Blends. The tensile modulus and heat
distortion temperature (HDT) are much different from the
properties such as tensile strength and impact strength: they are
not so sensitive to the interfacial adhesion. The effect of
PEG2000 addition on the tensile modulus and HDT of PC/
HDPE (80/20) blend is shown in Figure 8. It reveals that both
tensile modulus and HDT increase with increase in PEG
content, even though there was a sudden drop initially. A
possible explanation for the increase in modulus with an
increase in PEG content is that the addition of PEG goes into
the HDPE domain, which reduces the crystallinity of HDPE
domain; in turn the reduction in the percentage crystallization
increases the volume occupied by the elastic domain.
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Table 1. DSC Analysis Results of PC/HDPE Blends with PEG2000

composition (%)
sample codea PC HDPE PEG2000 Tg1 (°C) Tm (°C) Tg2 (°C) ΔH (J/g) Xc (%)
a 0 100 0 −115 135 − 197.7 67
b 80 20 0 −110 132 150 30 51
c 78.8 19.7 0.5 −100 132 147 28 48
d 78.6 19.4 1.0 −90 131 144 26 46
e 78.4 19.1 1.5 −84 130 141 25 43
a
See Figure 7.

hydrolytic degradation of PC at higher temperatures as

Figure 8. Effect of PEG2000 addition on tensile modulus and HDT of
PC/HDPE blends.
Therefore, with increases in the PEG2000 content in PC/
HDPE (80/20) blend, the volume occupied by the HDPE
domains increases. This expansion apparently promotes the
stress transfer at the interface and thus increases the tensile
modulus and HDT. ̀
3.6. Compatibilization Mechanism of PEG in PC/HDPE
Blend. Polycarbonate is very sensitive to moisture, and it is
reported to undergo hydrolytic degradation in the presence of
0.02% moisture or water molecules especially at higher
temperature. During the compounding process, It was observed
that there was a sudden drop in viscosity and increase in the
flow rate of batches containing PEG2000. In order to analyze
these observations, the melt volume rate (MVR) was measured
and it was found that (Table 2) the MVR increased with
increase in PEG2000 content. It is likely that the residual
moisture present in the PEG2000 might have initiated
Table 2. Melt Volume Rate of PC/HDPE (80/20) Blends
with Different Weight Fractions of PEG2000
PEG2000 content (wt %) MVR (g/cm3)
1.5 1.355
2.0 1.502
2.5 3.516
5.0 113.16
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shown in Figure 9. The initial degradation begins at the end
groups which react with water or free hydroxyl groups. The two
terminal hydroxyl groups present in PEG2000 result in
hygroscopicity and provide reaction sites. The next step is
depolymerization consisting of hydrolysis and alcoholysis,
which is a form of ester exchange when the chain breaks
somewhat near the middle. The chain scission in the middle of
the chain leads to a sudden drop in molecular weight and MVR
(Table 2). The hydrolysis produces carbon dioxide and either
bisphenol A or two other chains. Further, the PC can undergo
decarboxylation, hydrogen abstraction, chain scission, and ether
cleavage. As a result, a graft copolymer of PC-g-PEG2000 was
generated during the compounding operation in the presence
of moisture or water molecules (see Figure 9). PEG2000
exhibits some of the properties of ethers, because of the ether
linkage in their molecular structures. The nature of the reaction
of PEG2000 is similar to that of monohydric alcohols. Organic
acids react with PEG to produce mono- and diesters. PEG can
also form mono- and diethers, because of its two hydroxyl
groups. Additional evidence for the generation of the graft
copolymer was also obtained from DSC data. Compared to the
shape and size of the neat HDPE melting peak, the melting
peak width and shape of the blend compatibilized with
PEG2000 show significant changes. It is suggested that the
formation of graft copolymer leads to a big change in the crystal
structure and thus reduces the heat of fusion and percentage of
crystallinity.
3.7. Effect of PEG and HDPE on Notch Sensitivity of
the PC Material. Notch sensitivities of PC, PC80/HDPE20,
and PC80/HDPE20 with 1.5% PEG have been analyzed using
the notched Izod impact strength at various notch radii, and the
results are shown in Figure 10. Notched impact strength is the
impact energy absorbed in breaking a notched specimen,
referred to the original cross-sectional area of the specimen at
the notch, with the pendulum striking the face containing the
notch, and it is expressed in kilojoules per square meter. One of
the major drawbacks of PC is its notch sensitivity,36−39 which
shows a drastic reduction in the impact strength as the notch
radius become sharper and sharper. PC’s notch sensitivity is
strongest and shows its highest value around 0.25 mm.
However, as the notch radius decreases, it shows a drastic
reduction in the impact strength, whereas the PC/HDPE (80/
20) blend and the PC/HDPE (80/20) blend with 1.5% PEG as
compatibilizer retain the notched impact strength at all notch
radii (Figure 10). Therefore, PC’s notch sensitivity can be
neutralized by the addition of HDPE and PEG. This is because
the addition of elastomer can change the stress ahead of a
notch. This results in a brittle to ductile transition in the blend.
3.8. Influence of PEG and HDPE on Stress and
Chemical Resistance of the PC Material. Basically, HDPE
has very good chemical resistance to ketonic solvents, whereas
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Industrial & Engineering Chemistry Research
Figure 9. Hydrolytic degradation products of polycarbonate and its possible reaction with PEG2000.
Figure 10. Effect of HDPE and PEG2000 addition on notch sensitivity
of polycarbonate.
PC shows very poor resistance. Blending HDPE with PC can
improve the chemical resistance of PC toward acetone and
MPK solvents. On strained tensile samples, acetone and MPK
solvents were applied separately and kept for 24 h. After 24 h,
these specimens were subjected to tensile testing to evaluate
the tensile property retention. The tensile strength results of
acetone exposed (Figure 11a) and MPK exposed (Figure 11b)
samples along with control specimens are shown in Figure 11.
The control specimens were kept at 1% strained for 24 h
without chemical exposure. Neat PC tensile specimens exposed
to acetone were broken inside the jigs even before the testing.
However, neat PC80/HDPE20 blend and the blend with 1.5%
PEG2000 were intact visibly and retained their tensile
properties (Figure 11). Neat PC has better retention of tensile
property gainst MPK exposure compared to acetone exposure,
but not better than its blends. Among the blends, the PC/
HDPE (80/20) with 1.5% PEG2000 shows better retention of
tensile property than that of neat PC/HDPE (80/20) blend
(Figure 11). Stress cracking is a common cause of failure in
amorphous plastics, accounting for 15−30% of all plastic
product failures in service. Exposure of plastic products to
corrosive chemicals tends to accelerate the crazing process.
However, in environmental stress cracking (ESC), the initiation
and growth of a crack are caused by the combined action of the
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Figure 11. Effect of chemical exposure on tensile strength of PC/
HDPE blends.
stress and a corrosive environmental liquid. This environmental
stress cracking is different from the polymer degradation: it
does not break the covalent bonds, but only breaks the
secondary attractions. Environmental stress cracking happens
when mechanical stress causes hair cracks in the polymer, and
they propagate rapidly under harsh environmental conditions.
ESC happens mostly in amorphous polymers rather than in
semicrystalline polymers. Once a craze is formed in a polymer,
this creates an easy diffusion path so that the environmental
attack can continue and the crazing process can accelerate.
4. CONCLUSIONS
The performance of five different compatibilizers was evaluated
with PC80/HDPE20 blends. Among the five different
compatibilizers, PEG was found to exhibit better tensile and
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Industrial & Engineering Chemistry Research
impact strengths. TEM analysis shows the phase structure of
the PC/HDPE blend, in which the major phase is continuous
and the minor phase is in the form of a discontinuous and
elongated shape. The addition of PEG content shows a change
in the phase morphology of an elongated HDPE domain to a
fine spherical domain. Further, the tensile modulus and heat
distortion temperature performance of PC/HDPE (80/20)
blend increased with increase in PEG content. Differential
scanning calorimetric analysis of the PC/HDPE blend shows
two widely distant glass transition temperatures (Tg’s): one for
the PC matrix and another one for the HDPE minor phase.
The two Tg’s show inward shift on incorporation of PEG. The
inward shift of Tg, reduction in heat of fusion, and percentage
of crystallinity of HDPE phase indicate enhanced compatibility
between PC and HDPE phases. The PEG compatibilized PC/
HDPE (80/20) blend was also evaluated for notch sensitivity
and environmental stress cracking resistance (ESCR), and it
was found to have very good notch and chemical resistance
performance compared to PC. Hence, PC/HDPE (80/20)
blend compatibilized with PEG can be used in the design of
intricate shapes with less notch sensitivity, and where high
chemical resistance along with the superior mechanical
performance of PC is required.
■
ASSOCIATED CONTENT
*
S Supporting Information
Tables listing the important physical and mechanical properties
of polycarbonate and high density polyethylene provided by the
manufacturer. This material is available free of charge via the
Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*Tel.: 091-821-2548285. Fax: 091-821-2548290. E-mail:
siddaramaiah@yahoo.com.
Notes
The authors declare no competing financial interest.
■
REFERENCES
(1) Yin, B.; Lan, J.; Li, L.-P.; Yang, M.-B. Morphology evolution in
PC/PE blends with and without compatibilization during twin-screw
extrusion. Polym.-Plast. Technol. Eng. 2010, 49, 503−509.
(2) Mielke, W. Thermal analysis of polycarbonate/linear low-density
polyethylene blends. Polym. Eng. Sci. 2004, 28, 1077−1084.
(3) Utracki, L. A.; Sammut, X. Rheology of polycarbonate/linear low
density polyethylene blends. Polym. Eng. Sci. 2004, 30, 1027−1040.
(4) Romano, V.; Valenza, A. Rheological properties and morphology
in LLDPE and PC based blends. Eur. Polym. J. 1990, 26, 1049−1054.
(5) Wippler, C. Dynamic mechanical properties of VAMAS
polycarbonate/polyethylene blends. Polym. Eng. Sci. 1990, 30, 1106−
1113.
(6) Acierno, A.; Demma, G.; La Mantia, F. P.; Martuscelli, E.;
Romano, V.; Valenza, A. Rheological properties and morphology in
LLDPE and PC based blends. Eur. Polym. J. 1990, 26, 1049−1054.
(7) Paul, D. R.; Barlow, J. W. A binary interaction model for
miscibility of copolymer blends. Polymer 1984, 25, 487−494.
(8) Kunori, T.; Geil, P. H. Morphology-property relationships in
polycarbonate based blends. I. Modulus. J. Macromol. Sci., Part B: Phys.
1980, 18, 93−134.
(9) Kunori, T.; Geil, P. H. Morphology-property relationships in
polycarbonate based blends. II. Tensile and impact strength. J.
Macromol. Sci., Part B: Phys. 1980, 18, 135−175.
(10) Mascia, L.; Valenza, A. Reactive dual-component compatibilizer
for polycarbonate/high-density polyethylene blends. Adv. Polym.
Technol. 1995, 14, 327−335.
5681
Article
(11) Fan, P.; Xu, W.; Lu, C.; Zou, H.; Wang, B. Improving the
compatibility of polycarbonate/UHMWPE blends through gamma-ray
irradiation. Int. J. Polym. Anal. Charact. 2006, 11, 429−440.
(12) Yang, M.; Li, Z.; Feng, J. Studies on High density polyethylene
polycarbonate blend system compatibilized with low density poly-
ethylene grafted diallyl bisphenol A ether. Polym. Eng. Sci. 1998, 38,
879−883.
(13) Sue, H.-J.; Huang, J.; Yee, A. F. Interfacial adhesion and
toughening mechanisms in an alloy of polycarbonate/polyethylene.
Polymer 1992, 33, 4868−4871.
(14) Yin, B.; Zhao, Y.; Yu, R.-Z.; An, H.-N.; Yang, M.-B. Morphology
development of PC/PE blends during compounding in a twin-screw
extruder. Polym. Eng. Sci. 2007, 47, 14−15.
(15) Yin, B.; Zhao, Y.; Pa, M.-M.; Yang, M.-B. Morphology and
thermal properties of a PC/PE blend with reactive compatibilization.
Polym. Adv. Technol. 2007, 18, 439−445.
(16) Yee, A. F. Effect of strain rate on the toughing mechanisms of
rubber-modified plastics. Polym. Eng. Sci. 1981, 21, 205−211.
(17) Shigeru, E.; Kyonsuku, M.; White, J. L.; Thein, K. Polyethylene-
polycarbonate blends: interface modification, phase morphology and
measurement of orientation development during cast film and tubular
extrusion by infrared dichroism. Polym. Eng. Sci. 1986, 26, 45−53.
(18) Chiou, J. S.; Barlow, J. W.; Paul, D. R. Miscibility of bisphenol-A
polycarbonate with poly(methyl methacrylate). J. Polym. Sci.: Polym.
Phys. 1987, 25, 1459−1471.
(19) Kolarik, J.; Pukanszky, B.; Lednicky, F.; Pegoraro, M. Blends of
polycarbonate with poly(methylmethacrylate): miscibility, phase
continuity, and interfacial adhesion. Polym. Eng. Sci. 1992, 32, 886−
893.
(20) Kim, W. N.; Bums, C. M. Thermal behavior, morphology, and
the determination of the Flory-Huggins interaction parameter of
polycarbonate-polystyrene blends. J. Appl. Polym. Sci. 1987, 34, 945−
967.
(21) Keitz, J. D.; Barlow, J. W.; Paul, D. R. Polycarbonate blends with
styrene-acrylonitrile copolymers. J. Appl. Polym. Sci. 1984, 29, 3131−
3145.
(22) Koo, K.; Inoue, T.; Miyasaka, K. Toughened plastics consisting
of brittle particles and ductile matrix. Polym. Eng. Sci. 1985, 25, 741−
746.
(23) Skochdopole, R. E.; Finch, C. R.; Marshall, J. Properties and
morphology of some injection moulded polycarbonate-styrene-
acrylonitrile copolymer blends. Polym. Eng. Sci. 1987, 27, 627−631.
(24) Hromadkova, J.; Lednicky, F.; Kolarik, J. Visualisation of the
phase structure of selected polycarbonate blends using various
preparation techniques. Polym. Test. 1994, 13, 461−478.
(25) Lee, M. P.; Hiltner, A.; Baer, E. Phase morphology of injection
moulded polycarbonate/acrylonitrile-butadiene-styrene blends. Poly-
mer 1992, 33, 685−697.
(26) Favis, B. D.; Chalifoux, P. Influence of composition on the
morphology of polypropylene/polycarbonate blends. Polymer 1988,
29, 1761−1767.
(27) Hsiung, C. M.; Cakmak, M.; Ulcer, Y. A structure oriented
model to simulate the shear induced crystallization in injection molded
polymers: a Lagrangian approach. Polymer 1996, 37, 4555−4571.
(28) Bureau, M. N.; Francesco, E. D.; Denault, J.; Dickson, J. I.
Mechanical behaviour of injection molded polystyrene/polyethylene
blends: fracture toughness vs. fatique crack propoagation. Polym. Eng.
Sci. 1999, 39, 1119−1129.
(29) Karger-Kocsis, J.; Mouzakis, D. E. Effects of injection moulding
induced morphology on the work of fracture parameter in rubber
toughened polypropylene. Polym. Eng. Sci. 1999, 39, 1365−1374.
(30) Guerrica-Echevarria, G.; Eguiazabal, J. I.; Nazabal, J. Phase
behaviour and physical properties of injection molded polyamide 6/
phenoxy blends. J. Appl. Polym. Sci. 1999, 72, 1113−1124.
(31) Bureau, M. N.; Ei Kadi, H.; Denault, J.; Dickson, J. I. Injection
and compression moulding of polystyrene/high density polyethylene
blendsphase morphology and tensile behavior. Polym. Eng. Sci.
1997, 37, 377−390.
dx.doi.org/10.1021/ie303382g | Ind. Eng. Chem. Res. 2013, 52, 5672−5682
Industrial & Engineering Chemistry Research Article

(32) Ohlsson, B.; Tonell, B. Blends and interpenetrating polymer

networks of polypropylene and polystyrene-block-poly(ethylene-stat-
butylene)-block-polystyrene 2: Melt flow and injection molding
properties. Polym. Eng. Sci. 1999, 38, 108−118.
(33) Mclaughlin, K. W. The influence of microstructure on the
dynamic mechanical behaviour of polycarbonate/poly(styrene-acryl-
onitrile) blends. Polym. Eng. Sci. 1989, 29, 1560−1568.
(34) D’orazio, L.; Mancarella, C.; Martuscelli, E.; Cecchin, G.;
Corrieri, R. Isotactic polypropylene ethylene-co-propylene blends:
effects of the copolymer microstructure and content on rheology,
morphology and properties of injection moulded samples. Polymer
1999, 40, 2745−2757.
(35) Guerrica-Echevarria, G.; Eguiazabal, J. I.; Nazabal, J.
Morphology and mechanical properties of direct injection molded
polypropylene/thermoplastic copolyester blends. Polym Compos. 2000,
21, 864−871.
(36) Kayano, Y.; Keskkula, H.; Paul, D. R. Effect of polycarbonate
molecular weight and processing conditions on mechanical behaviour
of blends with a core-shell impact modifier. Polymer 1996, 37, 4505−
4518.
(37) Kayano, Y.; Keskkula, H.; Paul, D. R. Fracture behavior of
polycarbonate blends with a core-shell impact modifier. Polymer 1998,
39, 821−834.
(38) Li, C.; Zhang, Y.; Zhang, Y.; Zhang, C. Blends of polycarbonate
and ethylene-1-octylene copolymer. Eur. Polym. J. 2003, 39, 305−311.
(39) Zhang, J.; Li, J.; Liu, X.; Cong, P. Tribological properties of
polycarbonate blended with high-density polyethylene and high-
density polyethylene grafted with maleic anhydride. J. Macromol. Sci.,
Part B: Phys. 2007, 46, 373−385.

5682 dx.doi.org/10.1021/ie303382g | Ind. Eng. Chem. Res. 2013, 52, 5672−5682