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Article history: The characteristics of engineering plastics used in the preparation of electrical and electronic equipment
Available online 23 November 2009 were studied. More specifically, their thermal response was recorded by DSC experiments, the rheo-
logical properties were investigated via MFI tests and the mechanical properties were evaluated with
Keywords: tensile tests. The aim was to establish a procedure for recycling the same engineering plastics deriving
Acrylonitrile-butadiene-styrene (ABS) from waste of electrical and electronic equipment (WEEE), which offers the additional advantage of using
copolymer
the as-received waste stream as a recyclable mixture, i.e. without sorting and classification of its
Polycarbonates (PC)
components.
High impact polystyrene (HIPS)
Blends, recycling
The experimental results showed that blends of PC with ABS or ABS/HIPS can be prepared by direct
Waste of electrical and electronic mixing and this, would allow easy handling of the engineering plastics coming from WEEE, i.e. blending
equipment (WEEE) without the need of sorting. These mixtures can be easily processed and display acceptable mechanical
properties with reasonable cost. Therefore, the processing characteristics and properties of the systems
studied in this work could be the key for the design of an interesting approach for handling solid plastic
waste from electrical and electronic devices.
Ó 2009 Elsevier Ltd. All rights reserved.
0141-3910/$ e see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2009.11.029
406 P.A. Tarantili et al. / Polymer Degradation and Stability 95 (2010) 405e410
frequently selected as modifier [8]. The relatively low cost of these Table 1
two polymers makes it especially interesting for blending with the Temperature profile for extrusion of ABS/PC and ABS/HIPS blends.
more expensive high performance engineering plastics. Both Polymer blends Extruder zones Die
materials can be found either individually or mixed in many 1st 2nd 3rd 4th 5th 6th
commercial blends used in electric and electronic equipment [9].
ABS/PC (w/w) Temperature ( C)
Another approach to modify PC and overcome the above 0/100 290 280 280 275 275 265
mentioned weaknesses was reported by Elmaghor et al. [8], who 20/80 260 255 255 255 250 250
studied the effect of maleic anhydride grafted ABS (ABS-g-MA) as 50/50 245 240 240 240 235 235
80/20 240 235 235 235 230 230
an additive. The above authors observed improved dispersion of
100/0 220 220 215 215 220 220
ABS-g-MA in PC, resulting in excellent toughening of the mixture.
However, it was shown that the effect of grafting of maleic anhy- ABS/HIPS (w/w)
0/100, 20/80, 50/50, 80/20 200 200 190 190 190 190
dride onto ABS was not the promotion of compatibilisation, but the
generation of special morphology of ABS domains dispersed in the
PC matrix. At a certain PC/ABS-g-MA weight ratio, the ABS domains mechanical response of the obtained mixtures was recorded and
connected together to form a network and gave rise to a maximum the observed interactions were interpreted, in terms of the influ-
of the notched impact strength [8]. ence of each component on functional properties of the final
Some interesting results have been published by Paul [10], who mixture, considering the structure complexity of the basic poly-
suggested that virgin ABS can be well dispersed in PC without the mers, such as ABS and HIPS. This would be a significant contribu-
aid of a compatibiliser. On the other hand, Lee et al. [11] studied tion to the existing know-how of the recycling of engineering
extensively the morphology of PC/ABS blend throughout the entire plastics deriving from WEEE, with the additional aspect of using the
composition range. The PC-rich blends showed that dispersed ABS as received waste stream as a recyclable mixture, i.e. without
obtained a bead-and-string structure. With increasing ABS content sorting and classification of its components.
the bead-and-string structures became more densely arrayed and
more interconnected. A transition was observed between the 70/30 2. Experimental
and 60/40 compositions, from the bead-and-string structure to
a coalesced configuration. For the 40/60 compositions, PC formed 2.1. Materials
a dispersed phase with SAN inclusions. ABS-rich blends showed PC
domains dispersed in the continuous ABS phase. The following commercial grades of engineering thermoplastics
Another very interesting material, also found in WEEE, is high used in electrical and electronic application were studied. An easy
impact polystyrene (HIPS). This polymer is widely used, especially flowing ABS grade, suitable for injection moulding, with trade
in those products where the brittle polystyrene (PS) cannot meet name Terluran GP-22 (BASF, Germany), exhibiting high resistance
the required standards of impact resistance. HIPS can be structur- to impact and heat deflection; a medium viscosity PC grade
ally defined as a multiphase system that exhibits a continuous rigid (Makrolon, Bayer, Germany), with melt volume rate 9.5 cm3/
phase together with dispersed rubber particles, with diameters 10 min, containing flame retardant and UV stabilizers; Styron
varying from 0.5 to 10 mm. A-TECH 1200 (Dow Hellas, Greece), a HIPS grade with good
Recyclability of HIPS is not only important in the context of combination of toughness and stiffness, good processability and
WEEE management, but also in thermoforming, where HIPS sheets specially designed for packaging applications.
can give 25e30% scrap, which is to be recycled [12]. It should be
noted that, currently, only 1% is recovered from the total 19%
2.2. Methods
market share of HIPS [13,14]. In order to overcome some of the
barriers that restrict the process of recycling activities, such as
2.2.1. Preparation of blends
dismantling, removal of impurities, classification and sorting,
PC/ABS and HIPS/ABS blends were prepared using a co-rotating
attempts to recycle mixtures of HIPS and ABS have been made [15].
twin screw extruder with L/D-25 and 16 mm diameter (Haake PTW
In fact, it was reported that most thermoplastics may be reproc-
16). The extruder was heated at five zones along the cylinder and
essed with small amounts of other polymers without substantial
the die, according to the temperature profile presented in Table 1
decrease in mechanical properties [16]. More specifically, previous
and the rotational velocity of the screw was kept at 36 rpm, for all
work has shown that multiple recycling passes had negligible
the runs. A circular die with an opening of 2 mm diameter was
effect on the tensile properties of the above polymers, although
mounted to the extruder. The obtained polymer blend, in the form
more apparent effects were observed in elongational and impact
of continuous strand was granulated using a Brabender pelletizer.
properties [17e19].
It seemed therefore interesting to launch a parallel study on
2.2.2. Injection moulding
ABS/HIPS systems deriving from melt mixing of the above poly-
Injection moulding was performed with an ARBURG 221K
mers. The investigation of rheological characteristics along with
ALLROUNDER machine, equipped with a screw of 25 mm diameter
some structure parameters and final properties of the mixture
and clamping unit force of 350 kN. The mould was a two-cavity
might be an interesting data source for their recycling process. In
system capable of producing dumbbell specimens for subsequent
addition, ABS/HIPS mixtures could be suitable for use as additives
measurement of tensile properties (ASTM D-638, specimens type IV).
in PC recycling, instead of ABS alone, contributing to the low cost of
final products. This is reasonable taking into account that the Table 2
dispersed rubber phase in HIPS could act in a similar mode as the Melt flow index test parameters.
butadiene phase present in ABS, i.e. as shock absorber that greatly Sample Weight of the ram load (kg) Temperature ( C)
contributes to impact resistance of the recycled mixture of plastics. ABS 5 220
Based on the above, the main goal of the present work was the PC 1.2 250
preparation of blends of ABS with PC and HIPS and the investigation HIPS 5 200
of their rheological properties via MFI tests, as a measure of their ABS/PC blends 1.2 250
ABS/HIPS blends 5 200
processability during melt mixing. Furthermore, the thermal and
P.A. Tarantili et al. / Polymer Degradation and Stability 95 (2010) 405e410 407
Table 3 Table 4
DSC analysis of ABS/PC blends (2nd heating cycle). DSC analysis of ABS/HIPS blends (2nd heating cycle).
27
26
Tg 94oC
25
24
Heat flow (mW)
23
22 Tg 135oC
21
Tg1 124oC
Tg1 98oC
20
ABS/PC 100/0
19 ABS/PC 50/50
ABS/PC 0/100
18
30 50 70 90 110 130 150 170 190 210 230 250
ο
Temperature ( C)
Table 5 Table 6
MFI measurements of ABS/PC and ABS/HIPS blends. Tensile test results for ABS/PC blends.
Blend MFI MFI accord. MFI MFI accord. ABS/PC Tensile strength Modulus of elasticity Strain at break
composition (g/10 min) to rule of (g/10 min) to rule (w/w) (MPa) (MPa) (%)
(w/w) mixtures of mixtures 0/100 69 0.2 1960 24 57 5
ABS/PC ABS/HIPS 20/80 64 0.7 2075 111 37 5
50/50 62 1 2040 140 28 3
0/100 2.6 0.14 e 5.7 0.30 e
80/20 58 1 2180 84 10 4
20/80 4.6 0.27 2.1 6.0 0.19 5.26
100/0 51 5 1920 82 4.4 2
50/50 2.0 0.28 1.3 4.2 0.23 3.96
80/20 2.0 0.09 0.68 2.3 0.09 2.69
100/0 0.23 0.01 e 1.8 0.13 e
From the results of Table 5 it can be observed that the MFI values
of PC and ABS differ significantly, and therefore, most of the
Balart et al. [20], used the Fox equation for calculation of the mixtures show rheological behaviour similar to that of PC. Also, it
weight and volume fractions of the miscible segments (PC and seems that the law of mixtures cannot be applied for calculation of
SAN), assuming that butadiene phase does not take part in misci- the MFI of ABS/PC systems, since the behaviour of the examined
bility interactions, because of its net structure. The above authors blends is mainly controlled by the concentration of PC, at least in
concluded that PC is able to incorporate higher amounts of SAN, terms of melt flow rate. Very interestingly, the blend containing
due to the formation of low molecular weight species on SAN, as 20% ABS shows an impressive increase of MFI, which suggests that
derived from degradation during pre-processing and service life. this blend can be easily processed in comparison with PC alone.
The results obtained from the DSC thermograms of ABS/HIPS This effect can probably be interpreted by the fact that ABS plays
blends are shown in Table 4 and display a single Tg peak, within the the role of plasticizer at that concentration, due to the elastomeric
temperature range 85e95 C. According to the above reference, this phase interactions, as already described. Similar results have been
would suggest that the tested compositions give fully miscible reported by Khan et al. [22], who studied the rheological properties
mixtures of the HIPS and SAN phases, whereas the rubber phase is of ABS/PC blends and observed that the shear thinning behaviour of
expected to present an additional Tg far below the above temper- ABS improves the processability of PC. This effect provides signifi-
atures. The results of Table 4, shows that Tg of ABS decreased with cant power saving and facilitates melt processing of these blends
increasing proportion of HIPS. The Fox equation gave a good for mixing or moulding purposes. Moreover, plasticization of PC by
approximation in the obtained experimental results. Finally, it the addition of ABS is of great importance to the recycling proce-
should be noted that Brennan et al. [15] studied the Tg of ABS/HIPS dures of plastics from WEEE. In fact, recycling of these plastics
blends using dynamic mechanical thermal analysis (DMTA) and requires a minimal exposure to high temperatures and shear in
concluded that recycling and blending had no serious detrimental order to avoid extensive decomposition of the polymers due to
effects on the Tg values. thermo-oxidative and thermo-mechanical degradation.
As far as ABS/HIPS blends are concerned, from Table 5 it can be
seen that the MFI values increase by increasing HIPS concentration
3.2. MFI
in the polymer blend, as it was expected by the application of the
“rule of mixtures”. In that case, we cannot see any plasticizing effect
For the assessment of the data obtained from MFI measurements,
because both components of the mixture, i.e. ABS and HIPS, contain
it should be kept in mind that PC is homogeneous, single phase
a rubbery phase, probably acting already as a plasticizer.
polymer, while ABS is a heterogeneous terpolymer consisting of
a rubbery polybutadiene phase dispersed into the continuous plastic
phase of SAN. The incorporation of PC into ABS results in an increase 3.3. Tensile testing
of the ratio of plastic/rubbery phase, which modifies the interactions
between these phases and further alters the structural morphology Fig. 2 shows typical stressestrain curves for PC, ABS and their
of the system, resulting in different rheological properties. blends. PC exhibits the highest yield strength and ductile
0.8
0.7
0.6
0.5
Load (kN)
0.4
0.3
0.2
ABS/PC 100/0
0.1 ABS/PC 50/50
ABS/PC 0/100
0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34
Elongation (mm)
Table 7 effect, when incorporated to PC. Elmaghor et al. [8] using maleic
Tensile test results for ABS/HIPS blends. anhydride grafted ABS in order to improve compatibility with PC
ABS/HIPS Tensile Modulus of Strain at explained the enhancement of the impact strength taking into
(w/w) strength (MPa) elasticity (MPa) break (%) consideration the morphology of the blends.
0/100 32 1.3 1320 42 40 3 ABS was found to have tensile strength greater than that of HIPS.
20/80 35 0.65 1410 14 40 5 The tensile strength results for the blends ABS/HIPS follow the “rule
50/50 41 0.5 1975 57 23 6
of mixtures” showing a decreasing trend with the increase of HIPS
80/20 47 0.4 2045 60 21 6
100/0 51 5 1920 80 4.4 2 content. However, a synergistic effect in the modulus of elasticity
was observed for all the examined ABS/HIPS blends, in comparison
with their pure components.
behaviour, whereas ABS breaks at lower load essentially showing From Fig. 3, it is obvious that the addition of HIPS in ABS
elastic deformation, i.e. without significant yield. increases the ductility of the obtained material, in comparison with
From the data of Table 6 it can be observed that the incorpo- pure ABS. These results are in agreement with the research work of
ration of ABS into PC is accompanied by a decrease in both, tensile Brennan et al. [15] on the effect of mixing ABS with HIPS on their
strength and ductility of the blend in comparison with pure PC. In mechanical properties. They came to the conclusion that blending
fact, the tensile strength decreases as the concentration of ABS ABS and HIPS does not produce any further deterioration of prop-
increases in the polymer blend, as expected by the law of mixtures. erties compared to that deriving from the recycling process, and the
The same trend can be seen for ABS/HIPS systems but a synergistic presence of small amounts of the one material into the other
effect can also be observed in the modulus of elasticity of ABS/HIPS restored significant ductility.
blends, which is more significant at the composition of ABS/HIPS:
80/20 (Table 7).
A decrease of mechanical properties of ABS/PC blends deriving 4. Conclusions
from recycled WEEE was also reported by Balart et al. [9]. The above
authors interpreted this behaviour by the thermo-oxidative The blends of engineering plastics studied in this work show
degradation process, taking place in the sensitive elastomeric phase interesting properties and more specifically: PC/ABS mixtures
(polybutadiene rubber dispersed in SAN). The partial miscibility of display partial miscibility as shown by the results of differential
the ABS/PC system is an additional reason for this effect. In fact, it scanning calorimetry. Regarding their microstructure, the above
was found that SAN domains are not completely miscible with mixtures contain PC rich zones that include part of the ABS
those rich in PC and the lack of adherence between the above configuration, as well as ABS-rich zones where some PC chains are
conjugated phases can influence negatively the mechanical also present in the SAN matrix. Very interestingly, ABS seems to act
performance. In agreement with our results, they indicated as as plasticizer when incorporated into PC at concentrations of about
optimum blend composition, in terms of mechanical performance, 20%, probably due to the dispersion of the polybutadiene phase
the range of PC concentration from 10 to 20%. within the thermoplastic matrix of the blend. This effect was also
The rule of mixture for tensile yield strength of ABS/PC blends clear during the determination of rheological characteristics of the
was confirmed by Khan et al. [22], but it was also found that the PC/ABS blend via MFI measurements. Here again, the sample with
changes of elongation at break and impact strength do not follow composition 80/20 shows increased flow rate which suggests easier
this relationship. The above researchers concluded that the blend processing. On the other hand, the mixtures of HIPS and ABS seem
morphology plays a significant role on the determination of to consist in fully miscible blends and, furthermore, the determined
mechanical characteristics of the samples. In another work, Wong changes of blend properties are mostly in good agreement with
[23], reports that the magnitude of tensile modulus of the system values calculated from the law of mixtures.
ABS/PC, as well as its increasing or decreasing tendency, depend on A decrease in mechanical properties, in terms of tensile strength
the viscosity of ABS. This concluding remark could be correlated to and elongation, was recorded for both types of mixtures i.e. PC/ABS
the above mentioned hypothesis that ABS produces a plasticizing and ABS/HIPS, with respect to the properties of pure polymers.
0.8
0.7
0.6
0.5
Load (kN)
0.4
0.3
0.2
ABS/HIPS 100/0
0.1 ABS/HIPS 50/50
ABS/HIPS 0/100
0.0
0 2 4 6 8 10 12 14 16 18 20 22 24 26
Elongation (mm)
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