Polymer Testing 23 (2004) 675683

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Material Properties

Blend of waste poly(vinylchloride) (PVCw)/acrylonitrile

butadiene-rubber (NBR): the eect of maleic anhydride
(MAH)
H. Ismail
, Supri, A.M.M. Yusof
Polymer Division, School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, Nibong Tebal,
14300 Penang, Malaysia
Received 13 October 2003; accepted 13 January 2004

Abstract

Waste poly(vinylchloride) (PVCw) was blended with acrylonitrile butadiene-rubber (NBR) in dierent proportions.
v
The blends were melt mixed using a Haake Rheomix Polydrive R 600/610 at 150 C and rotor speed of 50 rpm.
Maleic anhydride (MAH) was used to improve the compatibility of PVCw/NBR blends. Virgin PVC/NBR blends
were also prepared as comparison. It was found that PVCw=NBR MAH blends exhibit higher stabilization torque,
mechanical energy, stress at peak and stress at 100% elongation (M100) but lower elongation at break, Eb and
swelling index than PVCw/NBR and PVCv/NBR blends. The scanning electron microscopy (SEM) study of tensile
fracture surfaces of the blends indicates that the presence of MAH increased the interfacial interaction between
PVCw and NBR phases and, thus, improved compatibility between PVCw and NBR blends.
# 2004 Elsevier Ltd. All rights reserved.

Keywords: Waste poly(vinylchloride) (PVCw); Acrylonitrile butadiene-rubber (NBR); Mechanical properties; Swelling behaviour

1. Introduction cost reduction of the nal product. Some of these

In recent years, elastomeric rubberplastic blends
have become technologically important for use as
thermoplastic elastomers (TPEs) [1]. Acrylonitrile buta-
diene-rubber (NBR) has generally good resistance
towards oil and low gas permeability. Its use in auto-
motive applications is interesting but the ageing resist-
ance is limited because of the unsaturated backbone of
the butadiene. PVC improves ozone and mechanical
resistance in applications such as fuel hose, conveyor
belt covers and printing roll covers [2]. The objective of
the blending of plastic and rubber is the improvement
of physical, thermal, and mechanical properties as well
as the modication of processing characteristics and


Corresponding author. Tel.: +60-4-593-7788x6113; fax:
+60-4-594-1011.
E-mail address: hana@eng.usm.my (H. Ismail).
blends are, however, incompatible. To improve the
mechanical properties of these blends, it is important to
develop a proper control of phase morphology and
good interfacial adhesion by using compatibilizing
agents. Sooppy et al. [3] reported that for maleic
anhydride/poly(propylene) (MAH-PP) compatibilized
blends, the increase in tensile strength is due to the
increased dipolar interaction between the MAH-PP and
NBR phases, which cause an increase in interface
adhesion between PP and NBR phases. Recently, the
reactive compatibilization technique has been used for
poly(methylmethacrylate-co-acrylic acid)/poly(n-butyl-
methacrylate-co-4-vinylpyridine) (MMAA/BM4VP),
poly(vinylchloride)/styrene butadiene-rubber (PVC/SBR),
nylon 6/PP, and poly(propylene)/poly(carbonate) (PP/
PC) blends [47]. In our previous work [8], we have
reported the comparison of properties of virgin poly
(vinylchloride)/acrylonitrile butadiene-rubber (PVCv/

0142-9418/$ - see front matter # 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymertesting.2004.01.008
676 H. Ismail et al. / Polymer Testing 23 (2004) 675683

NBR) and waste poly(vinylchloride)/acrylonitrile buta- Table 2

diene-rubber(PVCw/NBR) blends. It was found that Formulations of PVCw/NBR blends with maleic anhydride
PVCw/NBR blends exhibit lower properties (i.e. mech- (MAH)a
anical properties and swelling resistance) than PVCv/ Materials Blend (phr)
NBR blends. Here, we report the eect of maleic anhy-
dride (MAH) on processability, mechanical properties, 1 2 3 4 5
swelling behaviour and morphology of PVCw/NBR PVCw 80 60 50 40 20
blends. NBR 20 40 50 60 80
Stabilizerb 3 3 3 3 3
Plasticizerc 20 20 20 20 20
2. Experimental
DCPd 0.2 0.2 0.2 0.2 0.2
Maleic anhydride 4 4 4 4 4
2.1. Materials
(MAH)e
PVC powder, a suspension polymer with a K value a
A similar series of PVCw/NBR and PVCv/NBR blends
of 65 and degree of polymerization of 9201060 were prepared but without maleic anhydride (MAH).
b
was supplied by Malayan Electro Chemical Industry, Ba/Cd stearate, at php of plastic.
c
Penang, Malaysia. PVC waste was supplied by Alfasya Diocthyl-phthalate (DOP), at php of plastic.
d
Jaya Sdn. Bhd. Penang, Malaysia and the inorganic Dicumyl-peroxide (DCP), at php of plastic.
e
content of the waste PVC is shown in Table 1. NBR at php of plastic.
was obtained from Kumpulan Guthrie, Seremban,
Malaysia. Diocthyl-phthalate (DOP), barium/cadmium allowed to equilibrate for 2 min and followed by the
stearate, maleic anhydride and dicumyl-peroxide (DCP) addition of NBR. Mixing was then continued until a
were obtained from Bayer (M) Penang, Malaysia. constant torque was obtained. The total mixing time
was 9 min. The compound was removed from the
2.2. Preparation of the blends mixer and sheeted on a cold two-roll mill.

The formulations of the blends are given in Table 2. 2.3. Compression molding and testing
Blends of plastics and rubber were prepared at ratios of
80/20, 60/40, 50/50, 40/60, and 20/80 (wt%). The The samples of PVCw/NBR, PVCw=NBR MAH,
MAH concentration was xed at 4 php of plastic. The and PVCv/NBR blends were compression molded
PVCw/NB blends were prepared by melt mixing in a in an electrically heated hydraulic press. Hot-press
v
Haake Rheomix Polydrive R 600/610 at 150 C and v
procedures involved preheating at 150 C for 4 min,
rotor speed of 50 rpm. The amounts of DOP and followed by compressing for 4 min at the same tem-
Cd/Ba stearate used for the mixing of the blends were perature. Tensile tests were carried out with a Testo-
20 and 3 php, respectively, based on total PVCw con- metric tensometer M 500. Tests were done according to
tent in all compositions. The PVCw was initially pre- ISO 37. Dumbbell specimens of 2 mm thickness were
mixed with stabilizer and plasticizer in a glass beaker cut from molded sheets with a Wallace die cutter S6/1/
for 5 min at room temperature. The PVCw with stabi- 4.A. Five specimens were used in each case and the
lizer and plasticizer were charged into the mixing median value was selected. Readings of peak stress
chamber together with dicumyl-peroxide and MAH, (which occurred before break), stress at 100% elonga-
tion (M100) and elongation at break (Eb) were recorded
Table 1
directly from the digital displays at the end of each test.
Inorganic compound of waste PVCa
2.4. Swelling test
Composition Weight %
Al2O3 1.7
Determination of the swelling percentage of the
MgO 0.39 blends was carried out in general accordance
SiO2 0.88 with ISO 1817. The test pieces with dimensions
Cl 20 30 mm  5 mm  1:5 mm were weighed using an elec-
CaO 13 trical balance and this was considered to be the original
TiO2 0.26 weight. The test pieces were immersed in toluene at
Sb2O3 0.21 room temperature for 46 h. After removal from the
PbO 1.2 toluene they were wiped with tissue paper to remove
Carbon 61 excess toluene from the surface, and weighed (swollen
Other materials 2.56
weight). A similar test procedure was used for swelling
a
X-ray Fluorescence Spectrometer Rigaku RIX 3000. in IRM 903 oil for 70 h at room temperature. The
 H. Ismail et al. / Polymer Testing 23 (2004) 675683
swelling index of the blends was calculated as follows:
swollen weight
Swelling index 1 the mixing chamber at 2 min. As the NBR melted,
original weight
2.5. Scanning electron microscopy study
Studies on morphology of the fracture surfaces of
PVCw/NBR, PVCw=NBR MAH and PVCv/NBR
blends were carried out using a Leica Cambridge S 360
scanning electron microscope (SEM). Surfaces of the
sample were coated with a thin gold layer of about
20 nm thickness.
2.6. Infra red spectroscopy study
The FTIR spectrum was obtained using a Perkin
Elmer 2000 series instrument. The spectrum resolution
was 4 cm1 and scanning range was from 600 to
4000 cm1. The samples for FTIR were prepared by
using the attenuated total reectance (ATR) technique
and were subjected to FTIR analysis immediately
afterwards.
3. Results and discussion
Fig. 1 shows the typical plastograms recorded for
PVCw/NBR blends with dierent blend composition.
For all blends (PVCw/NBR, PVCw=NBR MAH,
and PVCv/NBR blend), PVC was charged into the
mixing chamber together with stabilizer and plasticizer
(and MAH for PVCw=NBR MAH blends). The
rotors were immediately started and the torque rises
due to the resistance exerted on the rotor by the
unmolten PVC. As the PVC melted and was subjected
Fig. 1. Torque versus time of PVCw/NBR blends with dierent blend composition.
677
to mechanical shearing, the torque become stable. The
torque rises again sharply after NBR was charged into
viscosity again decreased until equilibrium torque was
achieved when the blend become homogenized.
The stabilization torque at 9 min versus blend com-
position of PVCw/NBR, PVCw=NBR MAH, and
PVCv/NBR blends is shown in Fig. 2. It can be seen
that for all blends the stabilization torque increases
with increasing NBR content. As the NBR content in
the blend increases, the blend viscosity is increased.
The increase in viscosity as a result of incorporation
of rubber has been reported by various researchers
[912]. However, at a similar blend composition,
PVCw=NBR MAH blends exhibit higher stabiliza-
tion torque than PVCw/NBR and PVCv/NBR blends.
Since stabilization torque is indicative of stable melt
viscosity, it is clear from the above results that
incorporation of MAH in the PVCw/NBR blends has
resulted in higher energy requirement. In our previous
work [13] we have reported that the work done to pro-
cess the blends, dE=dt, is energy consumed during
rotation and can be expressed as WM, where W is the
angular velocity and M is the torque. Thus, an
expression for the energy can be derived as
dE WM dt. By integration, the mechanical energy
for processing the blends at a given temperature and
rotor speed is obtained.
Fig. 3 shows the eect of blend composition on mech-
anical energy of PVCw/NBR, PVCw/NBR MAH,
and PVCv/NBR blends. It can be seen that the mechan-
ical energy of all blends increases with increasing NBR
content and at a similar blend composition PVCw/
NBR MAH blends show the highest mechanical
678 H. Ismail et al. / Polymer Testing 23 (2004) 675683

Fig. 2. Stabilization torque versus blend composition of PVCw/NBR, PVCw=NBR MAH and PVCv/NBR blends.

energy. Various researchers [1417] have reported the
increase in viscosity on compatibilization of immiscible
polymer blends. According to George et al. [18], upon
compatibilization of an immiscible blend, the compati-
bilizer will generally locate at the interface between the
dispersed phase and the matrix and this will lead to an
increase in interfacial thickness.
Figs. 4 and 5 exhibit the eect of blend composition
on peak stress and stress at 100% elongation (M100) of
PVCw/NBR, PVCw=NBR MAH and PVCv/NBR
blends. It can be seen that as the NBR composition
increases both properties decrease due to the decreasing
of blend rigidity. The increasing of NBR in the PVCw/
NBR, PVCw=NBR MAH and PVCv/NBR blends
also increases the elongation at break, Eb (Fig. 6). As
the NBR content increases, the stiness and brittleness
of the blends decreases gradually with an associated
increase in Eb. However, at a similar blend compo-
sition, PVCw=NBR MAH blends show higher peak
stress and stress at 100% elongation (but lower elonga-
tion at break, Eb) than PVCw/NBR and PVCv/NBR
blends. The better peak stress and stress at 100% elon-
gation of PVCw=NBR MAH blends over PVCw/
NBR and PVCv/NBR blends is due to the enhance-
ment in interfacial adhesion between PVCw and NBR
phases.
Figs. 7 and 8 show the comparison of FTIR spectra
of PVCw/NBR and PVCw=NBR MAH blends at
80/20 (wt%). Both gures exhibit the olenic CH
stretching frequency just above 3000 cm1, the CH2
bending vibration at above 1436 cm1, the COC
stretching, ester vibration at 1274 cm1, the vibration

Fig. 3. Mechanical energy versus blend composition of PVCw/NBR, PVCw=NBR MAH and PVCv/NBR blends.
 H. Ismail et al. / Polymer Testing 23 (2004) 675683 679

Fig. 4. Stress at peak versus blend composition of PVCw/NBR, PVCw=NBR MAH and PVCv/NBR blends.

Fig. 5. Stress at 100% elongation versus blend composition of PVCw/NBR, PVCw=NBR MAH and PVCv/NBR blends.

Fig. 6. Elongation at break versus blend composition of PVCw/NBR, PVCw=NBR MAH and PVCv/NBR blends.
680 H. Ismail et al. / Polymer Testing 23 (2004) 675683

Fig. 7. FTIR spectrum of PVCw=NBR MAH blends.

of CN at 2237 cm1 from NBR structure and the CH
out-of-plane bending frequency at 968 cm1. In both
gures the absorption of carbonyl (CAO) at 1724 and
1726 cm1 indicated the presence of ester groups from
DOP. However, in the spectrum of PVCw/
NBR MAH blends the absence of CC double bond
at 1600 cm1 of MAH structure might be due to CC
radical of MAH which grafted with PVCw. Fig. 9
shows the reaction mechanism of MAH grafted waste
PVC with NBR which occurred during melt mixing.
According to Bucknall [19], an increase of inter-
facial adhesion suppressed production of void or aws
in the blends, which might grow into cracks. The
increased interfacial adhesion enables the deformation
to occur easily in the cross-section and facilitates shear
yielding.
Figs. 10 and 11 show the eect of blend composition
on the swelling index of PVCw/NBR, PVCw/
NBR MAH and PVC/NBR blends in IRM 903 oil
for 70 h and in toluene for 46 h. It can be seen in both
gures that the swelling index increases with increasing
NBR content in all blends. However, at a similar blend
composition, the swelling index of PVCw/NBRMAH
blends is lower than PVCw/NBR and PVCv/NBR

Fig. 8. FTIR spectrum of PVCw/NBR blends.

 H. Ismail et al. / Polymer Testing 23 (2004) 675683 681

Fig. 9. Reaction mechanism of maleic anhydride grafted waste PVC with NBR.

blends. Again, this observation was perhaps due to the
enhancement in interfacial adhesion between PVCw
and NBR phases.
Figs. 1214(ac) show a comparison of tensile frac-
ture surfaces of PVCw/NBR, PVCv/NBR and
PVCw=NBR MAH at 80/20, 50/50, and 20/80. It
can be seen in all gures that as the NBR composition
increases, the nature of the failure surface changes from
rough to smooth. However, at a similar blend compo-
sition, the PVCw=NBR MAH blends show better
strength with many tear lines and more homogeneous
blends than PVCw/NBR and PVCv/NBR blends.
Fig. 12(a) shows a coarse and unstable particle struc-
ture and an uneven distribution of the dispersed NBR

Fig. 10. Swelling index versus blend composition of PVCw/NBR, PVCw=NBR MAH and PVCv/NBR blends which were
immersed in IRM 903 oil for 70 h.
682 H. Ismail et al. / Polymer Testing 23 (2004) 675683

Fig. 11. Swelling index versus blend composition of PVCw/NBR, PVCw=NBR MAH and PVCv/NBR blends which were
immersed in toluene for 46 h.

Fig. 12. SEM micrographs of tensile fracture surfaces of Fig. 13. SEM micrographs of tensile fracture surfaces of
PVCw/NBR blends; (a) 80/20, (b) 50/50, (c) 20/80. PVCv/NBR blends; (a) 80/20, (b) 50/50, (c) 20/80.
 H. Ismail et al. / Polymer Testing 23 (2004) 675683
Fig. 14. SEM micrographs of tensile fracture surfaces of
PVCw=NBR MAH blends; (a) 80/20, (b) 50/50, (c) 20/80.
phase. This indicates low adhesion between phases,
giving rise to poor stress transfer across the interface
[20]. However, with the presence of MAH (Fig. 14(a))
there is better dispersion of NBR and it is more evenly
distributed in the PVC matrix, indicating improvement
in compatibility between PVCw and NBR. The pres-
ence of many tear lines on the tensile fracture surfaces
of PVCw=NBR MAH blends (Fig. 14(ac) indicates
the eect of increased interaction between phases, thus
improving compatibility and consequently enhancing
the mechanical properties.
683
4. Conclusions
Blends of waste PVC and NBR are attractive. The
presence of MAH signicantly improved the mechan-
ical properties and swelling behaviour of PVCw/NBR
blends as evidenced by higher stabilization torque,
mixing energy, stress at peak, stress at 100% elongation
(M100) and reduced elongation at break, Eb and swell-
ing index than PVCw/NBR and PVCv/NBR blends.
Morphology study of tensile fracture surfaces of the
blends indicates the improvement of interfacial
adhesion between PVCw and NBR phases with the
presence of MAH.
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