Polymer Testing 21 (2002) 163–170

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Material Properties
The effect of various compatibilizers on mechanical
properties of polystyrene/polypropylene blend
Halimatudahliana, H. Ismail *, M. Nasir
Polymer Division, School of Industrial Technology, Universiti Sains Malaysia, 11800 Minden, Penang, Malaysia

Received 2 April 2001; accepted 7 June 2001

Abstract

The effect of various compatibilizers on the mechanical properties of polystyrene/polypropylene (PS/PP) blends was
investigated. Blends of 20/80, 50/50 and 80/20 (wt%) were prepared through melt blending in a single screw extruder
at a blend temperature of 200°C and a screw speed of 40 rpm. Four compatibilizers, viz. polystyrene-block–poly
(ethylene–butylene)-block–polystyrene (SEBS), Surlyn, ethylene vinyl acetate (EVA) and sodium salt hydrate of 4
styrenesulfonic acid (4ssa,ssh) with concentration of 7.5% w/w were used. The tensile strength, elongation at break,
Young’s modulus and impact strength of binary and ternary blends were compared. The blends containing SEBS and
EVA showed a positive effect on the ductility of the blend. In the presence of Surlyn the strength of the blend increased,
whereas 4 ssa,ssh showed a negative effect.  2001 Elsevier Science Ltd. All rights reserved.

1. Introduction low, giving poor stress transfer across the interface. In

Combination of different polymers into multiphase
systems represents a very attractive route towards new
materials. It is also an efficient way to improve some
deficient properties of common plastics [1,2]. Despite the
high performance, the cost of block and graft copolymers
generally prevents them from being used on a large
scale. Melt blending of immiscible polymers is a more
direct and less expensive way to producing multiphase
systems. The advantage is however counterbalanced by
weak interfacial adhesion and poor stability of the phase
dispersion. The incompatibility between polymeric
components is responsible for the very poor mechanical
properties of most polymer blends [3]. When two poly-
mers separate into a two-phase system, the domain size
is coarse, irregular, and unstable, moreover the interface
is sharp and weak, giving poor properties and practical
incompatibility problems. In such a case, the interfacial
tension is high and adhesion between the two phases is
* Corresponding author. Tel.: +60-4-657-7888x2214; fax:
+60-4-657-3678.
E-mail address: ihanafi@usm.my (H. Ismail).
other words, a fracture path may preferentially follow
the weak interface between the polymer phases, or the
fracture initiate at the interface when tension is applied
to the specimen [4].
The process of modification of interfacial properties
of an immiscible polymer blend leading to the creation
of a new blend, which is called compatibilization, has
played an important role in the development of polymer
blends. Compatibilization by addition of a third compo-
nent can significantly improve the mechanical properties
of the blend by reducing the dispersed phase domain size
and by enhancing phase adhesion [5,6]. Blends of PS/PP
exhibit poor mechanical properties owing to the incom-
patibility of these two polymers. The mechanical proper-
ties for such a blend normally improved with the addition
of compatibilizers [7–12]. In this work, there are four
types of compatibilizers used. Surlyn, ethylene vinyl
acetate (EVA), sodium salt hydrate of 4 styrenesulfonic
acid (4ssa,ssh) were chosen for this study with the hope
of achieving improvements in properties through an
affinity and polarity concept. Polystyrene-block–
poly(ethylene–butylene)-block–polystyrene (SEBS), on
the other hand, was chosen owing to the possible affinity
with both components of a PS/PP blend: PS with PS

0142-9418/01/$ - see front matter  2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 4 2 - 9 4 1 8 ( 0 1 ) 0 0 0 6 4 - 2
164 Halimatudahliana et al. / Polymer Testing 21 (2002) 163–170

blocks of SEBS and PP with polyolefinic block EB of 5101. A specimen size of 7×1.5 cm was prepared for
SEBS. The effects of these compatibilizers on mechan- this test. Five samples were again tested in each case.
ical properties of PS/PP blends are reported.

3. Results and discussion

2. Experimental
3.1. Stress–strain curves
2.1. Materials
Figures 1, 2 and 3 show the stress–strain curves that
The PP grade TITANRO 6431 (MFI=7.5 gm/10 min) were observed at blend compositions of 20/80, 50/50 and
obtained from Titan PP Polymers (M) Sdn. Bhd. Malay- 80/20, respectively, with and without compatibilizers.
sia and the PS grade Poly-Star HH-30G (MFI=8 gm/10 The effect of adding compatibilizers on the yield peak
min) supplied by Petrochemicals (M) Sdn Bhd. Malaysia of 20/80 PS/PP blend results in variations of yield stress,
were used in the study. Four compatibilizers were used: yield strain, and width of the yield peak as shown in Fig.
Ethylene vinyl acetate (EVA) was supplied from Indus- 1. It can be seen that the yield peak of the binary blend
trial Resin (M) Sdn. Bhd. Malaysia, Surlyn was obtained of PS/PP does not differ much from that of the compatib-
from Du Pont Company, while both polystyrene-block– ilized blend with Surlyn. A considerable broadening for
poly(ethylene–butylene)-block–polystyrene (SEBS) and both compatibilized blends with SEBS and EVA and
sodium salt hydrate of 4 styrenesulfonic acid (4ssa,ssh) narrowing in the case of the blend with 4ssa,ssh are
were purchased from Aldrich Chem. Co. Inc. clearly apparent. SEBS has a tendency to increase the
width of the yield peak and produces a slight decrease
in the height of yield stress. According to Gupta and
2.2. Preparation of blends
Purwar [13], the decrease of yield stress accompanied
by the observed peak broadening implies the increase of
Three different blends were prepared viz. 20/80, 50/50 ductility. Welander and Rigdahl [14] have observed
and 80/20 (wt%) which covers the cases of PP dominant similar findings. They reported that the elastomeric nat-
(20/80), PS dominant (80/20) and intermediate (50/50). ure of SEBS has a profound influence on the deformation
They were dry-mixed in small cups before being fed into
the extruder. The blends were prepared by mixing the
appropriate amounts of binary (PP/PS) or ternary
(PP/PS/compatibilizer) mixtures through melt blending
in a single screw extruder (Betol BM-116) at a blend
temperature of 200°C and a screw speed of 40 rpm. The
thick strand extrudates were quenched immediately in
water, and then pelletized or granulated. These pellets
were compression molded using a Fontune type SRC
into sheets of about 2 mm and 5 mm thickness for tensile
and impact tests, respectively. A molding temperature of
200°C was used to compress all the blends The preheat-
ing time used was 9 and 12 min for tensile and impact
test pieces, respectively. Pressure of 1500 psi and mold-
ing time of 3 min were applied for all samples.

2.3. Tensile test

A specimen size of 12×2 cm (length×width) was used

for tensile tests (ASTM D 638) using a Testometrix Ax
(M-500-25 kN). The machine was set at a crosshead
speed of 50-mm/min and 70 mm gage length while tem-
perature was 25°C. Five samples were tested in each
case.

2.4. Impact test

Fig. 1. Stress–strain curves of 20/80 PS/PP blend (wt%) with
Izod impact strength of unnotched samples was meas- and without the addition of various compatibilizers (7.5% w/w)
ured using a Pendulum Impact Tester, model Zwick at a blend temperature of 200°C.
 Halimatudahliana et al. / Polymer Testing 21 (2002) 163–170
Fig. 2. Stress–strain curves of 50/50 PS/PP blend (wt%) with
and without the addition of various compatibilizers (7.5% w/w)
at a blend temperature of 200°C.
Fig. 3. Stress–strain curves of 80/20 PS/PP blend (wt%) with
and without the addition of various compatibilizers (7.5% w/w)
at a blend temperature of 200°C.
165
behavior of 20/80 PS/PP blend. Hence, the ductility of
such a blend increases.
In Fig. 2, the 50/50 PS/PP blends, the uncompatibil-
ized blend shows brittle behavior. In the presence of Sur-
lyn and 4 ssa,ssh, the stress–strain curve exhibits an
approximately linear relationship. The addition of Surlyn
into this blend gives a slight improvement in tensile
strength (21.70 MPa), whereas the elongation remains
low (1.97%). This result is also found by previous work-
ers. Mekhilef et al. [15] reported that addition of Surlyn
as a compatibilizer in polycarbonate/HDPE blend
increased yield stress. However the addition of 4ssa,ssh
to 50/50 PS/PP blend shows a negative effect, where
both strength and fracture strain are lowered but the stiff-
ness of the blend increases slightly. The use of SEBS
has changed deformation behavior from brittle to ductile.
It can be seen that the uncompatibilized blend elongated
approximately 2.2% and failed, but the similar blend
containing SEBS failed at 3.6% strain. In the case of
using EVA as compatibilizer the fracture strain (2.92%)
was enhanced slightly.
For 80/20 PS/PP blends, as shown in Fig. 3, the stress–
strain curve of the uncompatibilized blend has a high
initial slope (high elastic modulus) and fractured at about
1.9% strain. When EVA is used, there is a slight increase
in fracture strain (2.2%) but a dramatic reduction in stiff-
ness and stress at failure. The addition of either Surlyn
or 4ssa,ssh to the 80/20 PS/PP blend results in the stress
strain curve being almost linear right up to failure. How-
ever, the addition of SEBS as a compatibilizer to such
a blend has changed the stress–strain behavior from
brittle to ductile and a fracture strain of about 2.6% was
attained. Schwarz et al. [16], who worked on HDPE/PS
blends, reported that the brittleness of 75/25 PS/HDPE
changed with the addition of 5% SEBS.
3.2. Tensile strength
The properties at high deformation are illustrated in
Fig. 4 as indicated by the ultimate stress at rupture. Here,
the effect of addition of various compatibilizers on the
tensile strength is shown for different blend ratios. It can
be seen that the tensile strength bar charts fall below the
additivity rule line for the whole range of compositions.
The addition of SEBS to PS/PP blends reduced the
tensile strength for all blend compositions. The reduction
agrees with an observation made by Bartlett et al. [17].
Since the SEBS is a thermoplastic elastomer, the pres-
ence of such a copolymer will reduce the tensile strength
of the blend. The addition of Surlyn to PS/PP blends
gave slightly higher tensile strength than the uncompati-
bilized one for all blend compositions due to the
improvement of adhesion and better stress transfer within
the blend. With SEBS and Surlyn, no minimum in tensile
strength appears between 20/80 and 80/20 blends.
The addition of 4 ssa, ssh, as well as EVA in PS/PP
166 Halimatudahliana et al. / Polymer Testing 21 (2002) 163–170
Fig. 4. Effect of adding compatibilizers (7.5% w/w) on the tensile strength at various PS/PP blend compositions.
blend exhibits the same trend as with the uncompatibil-
ized blend, which shows a minimum value of tensile
strength at the blend composition of 50/50 (% w/w)
PS/PP. The drop in tensile strength of the PS/PP blend
by the presence of EVA may be due to a reduction of
the crystallinity of the blend as a result of the presence
of vinyl acetate in EVA [18].
3.3. Elongation at break
Figure 5 shows the effect of PS/PP blend composition
on the elongation at break with various compatibilizers.
Similarly to the case of tensile strength, the elongation
at break of the blends falls well below the additivity line.
It can be seen that for all blend compositions, the elong-
ation at break of the PS/PP blend system with the
addition of SEBS is much greater than others, viz Surlyn,
EVA and 4 ssa,ssh. According to Gupta and Purwar [13],
when SEBS is added to PS/PP blend, adhesion between
two incompatible polymers is promoted and mechan-
ically induced slippage between the PS and PP phase
inhibited. A much stronger effect can be seen with the
presence of SEBS in the PP-rich blend. The SEBS might
be expected to adhere to both components of the present
system owing to the identity of the end blocks with the
polystyrene component and the expected affinity of the
EB (ethylene–butylene) midblock with polypropylene.
For EVA, its addition has improved the ductility of
the blend. This result is in agreement with the findings
of previous work by Feldman and Rusu [19]. They
reported that the elongation at break of PVC/EVA blend
increased with increases in EVA content. Here, the lack
of tensile strength with the presence of EVA was
accompanied by improvement in elongation at break, and
again the highest was shown by the PP-rich blend. How-
ever, the improvement was lower than that of SEBS. On
 Halimatudahliana et al. / Polymer Testing 21 (2002) 163–170
Fig. 5. Effect of adding compatibilizers (7.5% w/w) on the elongation at break at various PS/PP blend compositions.
the other hand, addition of Surlyn and 4ssa,ssh has nega-
tive effect on the elongation at break for all PS/PP blend
compositions. Here, the elongation at break of either
PS/PP/surlyn or PS/PP/4ssa,ssh blends for both the inter-
mediate (50/50 PS/PP) and PS-rich (80/20) blends was
lower than that of PS homopolymer. In other words,
PS/PP blends containing either Surlyn or 4ssa,ssh main-
tained the brittle behavior of the blend at 50 and 80%
of PS. This observation might be due to the presence of
the ionic group in Surlyn and sulfonate group in 4ssa,ssh
making both PS/PP/surlyn and PS/PP/4ssa,ssh more
brittle.
3.4. Young’s modulus
Figure 6 shows the effect of the various compatibiliz-
ers on Young’s modulus of PS/PP blends and displays
some negative and positive deviations from the additivity
167
rule represented by the line. The decrease of modulus
with increase in PP content is due to the contribution of
the same compatibilizers and the reduction of hard PS
content. Improvements in ductility and impact resistance
are often accompanied by sacrifices in stiffness [16–20].
As seen in Fig. 6, the Young’s modulus of compatibil-
ized blends containing SEBS, EVA or 4ssa,ssh fell just
below that of the uncompatibilized ones. Blends contain-
ing Surlyn exhibited Young’s modulus higher than that
of uncompatibilized blends. As an ionomer, Surlyn con-
sists of an ethylene backbone and pendant methacrylic
acid groups, which are neutralized with metal. Although
incorporation of low concentration of methacrylic acid
into the ethylene backbone has little effect on properties,
the neutralization of these groups can have more dra-
matic influence, especially on improving the stiffness.
The Young’s modulus of the blends with compatibilizer
has the same trend as with the uncompatibilized blends
168 Halimatudahliana et al. / Polymer Testing 21 (2002) 163–170
Fig. 6. Effect of adding compatibilizers (7.5% w/w) on the Young’s modulus at various PS/PP blend compositions.
with the highest Young’s modulus being found in PS-
rich blends the modulus decreasing as the amount of PS
in the blend reduces. For instance, the modulus for 20%
of PS blended with 80% of PP containing Surlyn (about
1287 MPa) is considerably lower than the 1458 MPa for
50/50 PS/PP with Surlyn
3.5. Impact strength
The unnotched impact strength of the blend systems
investigated was plotted against the blend composition
in Fig. 7. Here, the effect of compatibilizers on impact
strength is shown at various compositions. In comparison
with the uncompatibilized blends, it can be seen that the
impact strength of the PS/PP blends increases with the
addition of SEBS, Surlyn or EVA as compatibilizer. Due
to the presence of SEBS as a thermoplastic elastomer in
PS/PP blends the impact strength of such blends
improved over the linear additivity line. The positive
deviation of impact strength in all blend compositions
was exhibited by the presence of SEBS, but the values
did not exceed that of pure PP. The increase in toughness
is accompanied by an increase in elongation at break,
and this effect occurs mainly in the blends containing
SEBS. The addition of such a compatibilizer to the PP-
rich blend has a pronounced effect with the area under
the stress–strain curve, i.e. the work to fracture is larger
than that found for intermediate or PS-rich blends. This
effect was observed for several blends consisting of a
ductile matrix and brittle particle reported by Angola et
al. [9].
The compatibilizers Surlyn and EVA seem to behave
in a similar manner to SEBS and produce best impact
strength in the PP-rich blend. As mentioned before, Sur-
lyn was chosen for this study with the hope of achieving
improvements in properties through both affinity and
polarity concepts. The affinity was implied by the
adhesion of PP with polyolefin of Surlyn. Basically, the
free radicals have certain tendencies to gain or loss elec-
trons, and hence they have the character of being electro-
 Halimatudahliana et al. / Polymer Testing 21 (2002) 163–170 169

Fig. 7. Effect of adding compatibilizers (7.5% w/w) on the impact strength at various PS/PP blend compositions.

philic or nucleophilic. A free radical electrophilic reac- In the case of using EVA copolymer as compatibilizer,
tion is produced by electron withdrawal, whereas a free the mechanisms involved are similar to those explained
radical nucleophilic reaction is produced by electron- for Surlyn. The reaction can be depicted as [21]:
releasing. An electrophilic radical will then prefentially
add to a monomer containing an electron-releasing
group, while a nucleophilic radical acts vice versa. Styr-
ene and methacrylate tend to alternate because their sub-
stituents are of opposite polarity. In methacrylate Na,
the -COONa group tends to withdraw electrons; in poly-
styrene the phenyl group tends to release electrons. The
transition states for addition to the opposite monomers
are thus stabilized [21]. Here, the methacrylate group was changed with the vinyl
acetate group.
Almost all of the compatibilizers showed the same
trend, i.e., impact strength reduced with increasing PS
content and it is clearly shown that PS’s brittleness plays
a role in the blends toughness. However, the blend con-
taining SEBS, Surlyn or EVA exhibit much higher
impact strength than pure PS. On the other hand, adding
170 Halimatudahliana et al. / Polymer Testing 21 (2002) 163–170
4ssa,ssh as a compatibilizer produces totally different
behaviour and appears to reduce the toughness at all
blend compositions.
4. Conclusion
In conclusion, it can be stated that those blends with
7.5% SEBS produce an improvement in toughness of
PS/PP blends for all blend compositions. Moreover, the
brittle behavior can be converted into a quite ductile
material in 50/50 and 80/20 PS/PP blend with the
addition of SEBS. The addition of 7.5% Surlyn increased
the tensile strength and Young’s modulus of the blend.
In the case of adding 7.5% of EVA in PS/PP blend, the
results indicate that a slight improvement in elongation
at break was obtained, whereas incorporation of 7.5%
4ssa,ssh has reduced the properties in all blend compo-
sitions.
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