POLYMERS FOR ADVANCED TECHNOLOGIES

Polym. Adv. Technol. 2005; 16: 310317

Published online 15 February 2005 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/pat.581

Effects of the compatibilizer PE-g-GMA on the

mechanical, thermal and morphological properties
of virgin and reprocessed LDPE/corn starch blends
A. G. Pedroso and D. S. Rosa*
Laboratorio de Polmeros Biodegradaveis e Solucoes Ambientais, Programa de Pos-Graduacao Stricto Sensu em Engenharia e Ciencia dos
Materiais, Universidade Sao Francisco, Rua Alexandre Rodrigues Barbosa, no. 45, Centro, CEP 13251-900, Itatiba, SP, Brazil
Received 24 June 2004; Revised 17 September 2004; Accepted 6 October 2004

The effects of the compatibilizer polyethylene grafted with glycidyl methacrylate (PE-g-GMA) on
the properties of low-density polyethylene (LDPE) (virgin and reprocessed)/corn starch blends
were studied. LDPE (virgin and reprocessed)/corn starch blends containing 30, 40 and 50 wt%
starch, with or without compatibilizer, were prepared by extrusion and characterized by the melt
flow index (MFI), tensile test, dynamic mechanical analysis (DMTA) and light microscopy. The
addition of starch to LDPE reduced the MFI values, the tensile strength and the elongation at break,
whereas the modulus increased. The decreases in the MFI and tensile properties were most evident
when 40 and 50 wt% starch were added. Blends containing 3 wt% PE-g-GMA had higher
tensile strength values and lower MFI values than blends without compatibilizer. Light
microscopy showed that increasing the starch content resulted in a continuous phase of starch.
Copyright # 2005 John Wiley & Sons, Ltd.
KEYWORDS: biodegradable; polyethylene (PE); blends; reactive processing; starch

INTRODUCTION
Low density polyethylene (LDPE), which is hard to degrade
in landfills, is currently one of the most commonly used thermoplastics for packaging material. For some short lifetime
applications such as bags, agricultural mulch films and
food packaging, it would be advantageous if plastics
degraded into safe by-products under normal composting
conditions.1 The resistance of polyethylene (PE) to biological
attack is related to its hydrophobicity, high molecular weight,
and lack of functional groups recognizable by microbial
enzymatic systems. All of these properties limit applications
in which biodegradability is a desirable attribute.2 The blending of biodegradable polymers, such as starch, with inert
polymers, such as PE, has received considerable attention
because of its possible applications in the waste disposal of
plastics. The reasoning behind this approach is that if the biodegradable component is present in sufficient amounts, and
if it is removed by microorganisms in the waste disposal
environment, then the plastic or film containing the remaining inert components should disintegrate and disappear.3
Peanasky et al.4 investigated the accessibility of starch in PE
starch blends by computer simulation, percolation theory,
*Correspondence to: D. S. Rosa, Laboratorio de Polmeros
Biodegradaveis e Solucoes Ambientais, Universidade Sao
Francisco, Rua Alexandre Rodrigues Barbosa, no. 45, Centro,
CEP 13251-900, Itatiba, SP, Brazil.
E-mail: derval.rosa@saofrancisco.edu.br

and acid hydrolysis experiments and concluded that the

accessibility of starch is highly dependent on an apparent
percolation threshold near 30% by volume or approximately
40% by weight of starch.
Starch is a natural polymer found in granular form in a
variety of plants, such as corn and cassava.5 Starch is a blend
of amylose and amylopectin, both of which are polysaccharides composed of a-D-glucopyranosyl units, (C6H10O5)x.
Native starch granules swell after absorbing water through
hydrogen bonding with their free hydroxyl groups, but they
still retain their order and crystallinity. However, when
these swollen granules are heated, the hydrogen bonding
between adjacent glucose units is disrupted and the crystallinity is progressively destroyed. This process is called
gelatinization.6
Most synthetic polymers are immiscible with starch at the
molecular level. This thermodynamic incompatibility often
leads to poor performance of these blends.7 One way to
increase compatibility in starch blends is to use a compatibilizer containing groups capable of hydrogen bonding with
starch hydroxyls. An alternative approach is to form graft or
block copolymers in situ during the blend preparation by
using polymers containing reactive functional groups. This
method is commonly known as reactive blending,7 in
which small amounts of block or graft copolymers formed
during the blending process, through reaction between the
two components, are generally enough to stabilize the
morphology and improve the properties of the blend.
Copyright # 2005 John Wiley & Sons, Ltd.

LDPE/corn starch blends

Synthetic polymers with functional groups such as

carboxylic acid, anhydride, epoxy, urethane, or oxazoline,
can react with the hydroxyl or carboxyl group (in modified
starch) to form a blend with a stable morphology.7 Sailaja
et al.8 observed that the mechanical properties of LDPE/
tapioca starch blends improved significantly with the
addition of poly(ethylene-co-glycidyl methacrylate), approaching values close to those of virgin LDPE. Jang et al.9
showed that high-density polyethylene (HDPE) modified
with glycidyl methacrylate (GMA) enhanced the miscibility
of HDPE/starch blends. In addition, according to Jane et al.,10
the carboxylic groups and the ketone groups of oxidized PE
react with the hydroxyl groups of starch to form bonds
among the components of the LDPE/starch blend.
In this study, the mechanical and thermal dynamic
mechanical properties, melt flow index (MFI) and morphology of LDPE/starch blends containing high starch contents
(30, 40 and 50 wt%), with or without the compatibilizer PE
grafted with GMA (PE-g-GMA).

EXPERIMENTAL
Materials
Virgin LDPE, PB 526, MFI 0.25 g/10 min (1908C, 2.16 kg), was
supplied by Braskem (Triunfo, RS, Brazil). Pre-gelatinized
corn starch (RD 337) was supplied in powder form by Corn
Products Brazil-Ingredientes Industriais Ltda. (Jundia, SP,
Brazil), and contained 27 wt% amylose and 73 wt% amylopectin. Ethylene-co-glycidyl methacrylate copolymer containing 8 wt% GMA (PE-g-GMA), Lotader AX8840-Elf
Atochem, MFI 5.0 g/10 min (1908C, 2.16 kg), was supplied
by Atofina (Sao Paulo, SP, Brazil).

LDPE reprocessing
Virgin PB 526 LDPE, in pellet form, was extruded with
extruder CARNEVALLI CHD to obtain films 40 mm thick.
The thermal profile was 1751911981981902012008C
(zones 17). The film obtained was ground and subsequently
agglutinated using equipment with a rotating cylinder that
heated the ground plastic through friction transforming it
into a paste and then, a small quantity of water was added
to cause a sudden cooling.

Blend preparation
Pure virgin and reprocessed LDPE and their blends containing 30, 40 and 50 wt% starch were prepared with a co-rotating
twin-screw extruder (Werner & Pfleiderer, model ZSK 30).
The LDPE and starch were dried in an air-circulating oven
at 708C for 1 hr before extrusion. For the blends containing
compatibilizer, PE-g-GMA content was fixed at 3 wt% relative to the LDPE content and the compatibilizer was mixed
to the LDPE before extrusion. The LDPE was fed in the first
zone and the starch was fed in the third zone. The thermal
profile was 1401601601601601508C (zones 16,
respectively) and the screw speed was 200 rpm. The extruded
materials were granulated.

Molding
Virgin and reprocessed LDPE and the blends were compression molded into sheets (180 mm
180 mm
2 mm) using a
Copyright # 2005 John Wiley & Sons, Ltd.

311

model MA 098 Marconi Press (Marconi-Equipamentos e

Calibracao para Laboratorios, Piracicaba, SP, Brazil). The
mold containing the desired material was initially placed in
the press and heated for 3 min without applying any pressure, in order to ensure uniform heat flow throughout the
material. For all of the blends, the temperature was kept at
170  58C for 3 min at 10 t. The resulting sheets were cooled
to room temperature.

Melt flow index (MFI)

MFI measurements of the LDPE and blends were obtained
using a model MI-1 plastometer (DSM Instrumentacao Cientfica Ltda., Sao Paulo, SP, Brazil), according to ASTM D 1238
(procedure A, 1908C/5 kg).

Tensile properties
The tensile properties were determined with an EMIC model
DL 2000 universal testing machine (EMIC Equipamentos e
Sistemas de Ensaio Ltda., Sao Jose dos Pinhais, PR, Brazil)
using specimens (type IV) cut from compression molded
sheets, according to the ASTM D-638 standard. The control
program used was Mtest LBP version 3.00 and the load cell
had a capacity of 200 kgf, at a rate of 20 mm/min. The average
and standard deviations of the tensile strength, elongation at
break and Youngs modulus were determined for each formulation.

Dynamic mechanical thermal analysis (DMTA)

Dynamic mechanical thermal analysis (DMTA) was done
using a dynamic mechanical analyzer, model MK III
(Rheometric Scientific, Inc., Piscataway, NJ, USA) over
the temperature range of 408C to 1108C at a frequency
of 1 Hz. The heating rate was 58C/min. The analyses were
done in duplicate using specimens 30 mm
10 mm

1.5 mm.

Light microscopy
Specimens were fractured after freezing in liquid nitrogen
and micrographs of the fractured surfaces were obtained
using a light microscope, model XP-500 (LABORANA, Sao
Paulo, SP, Brazil).

RESULTS AND DISCUSSION

Melt flow index (MFI)
Figure 1 shows the MFI values for virgin and reprocessed
LDPE and their blends with starch, and Fig. 2 shows the effect
of compatibilizer on the MFI values for these blends.
The MFI Values for virgin and reprocessed pure LDPE
(1908C/5 kg) did not differ significantly. When starch was
added to the LDPE, the MFI values decreased with increasing
starch content, independently of the LDPE used in the blends.
Since the MFI is an indirect measurement of viscosity, it
follows that the starch must act as a rigid filler, because the
main effect of rigid fillers is to increase the elastic modulus of
a composite or the viscosity of a fluid suspension.11 For
blends containing 30 wt% starch, the decrease in the MFI was
more significant for virgin LDPE. For the blends containing
40 and 50 wt% starch, the MFI values decreased more
significantly when reprocessed LDPE was used, perhaps
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312

A. G. Pedroso and D. S. Rosa

Figure 1. MFI for virgin and reprocessed LDPE and LDPE/

starch blends.

Figure 3. Tensile strength for virgin and reprocessed LDPE

and LDPE/starch blends.
content of grafted GMA, which implies that the degree of
crosslinking increased with the GMA content.

Tensile tests

Figure 2. MFI for LDPE and LDPE/starch blends, with and

without compatibilizer. (a) Virgin and (b) reprocessed.

because of the higher interfacial interaction between reprocessed LDPE and starch. Since reprocessed LDPE underwent
previous processing, it was more susceptible to degradation
during processing. As a result, there was a greater tendency
to form carboxylic groups and ketone groups which could
react with the hydroxyl groups of starch, thereby promoting
bonds among the components of the LDPE/starch blend.10
The MFI values decreased as PE-g-GMA was added, which
implies that PE-g-GMA increased the extent of crosslinking
between the blend components. Jang et al.9 showed that the
modification of HDPE by the grafting of GMA was an
effective method for enhancing the compatibility of the
blend, and that the MFI of the blend decreased with the
Copyright # 2005 John Wiley & Sons, Ltd.

Figure 3 shows also evidence of possible degradation of

reprocessed LDPE since pure reprocessed LDPE and blends
with reprocessed LDPE had lower tensile strengths. For all
LDPE/starch formulations, the tensile strength decreased
with increasing starch content, indicating that corn starch
behaved as a non-reinforcing filler. For blends containing virgin LDPE, the tensile strength decreased by 57, 60 and 74% for
the blends containing 30, 40 and 50 wt% starch, respectively,
in relation to pure LDPE. For blends containing reprocessed
LDPE, tensile strength decreased by 50, 59 and 76%, for the
blends containing 30, 40 and 50 wt%, respectively, compared
to pure reprocessed LDPE. A possible explanation for the
decrease in tensile strength after the addition of starch could
be the heterogeneous distribution of starch in LDPE and the
low interfacial interaction between components of the blend,
which resulted in mechanical rupture at the blend interface.
Figure 4 shows that the addition of PE-g-GMA increased
the tensile strength of all the blends, indicating that there was
a better interaction between the phases of the blend.
According to Jang et al.,9 the compatibilizer induces the
formation of a network, causing crosslinking that increases
the tensile strength of the blend. These results corroborate
with findings for the MFI, in which blends containing
compatibilizer showed lower MFI values (another indicator
of increased compatibility between the phases of the blend).
The increase in tensile strength was highly significant for
blends containing reprocessed LDPE, suggesting that the
carboxylic and ketone groups, that possibly formed during
the reprocessing and preparation of these blends, also
contributed to the greater compatibility of the blends.
Figure 5 shows Youngs modulus (E0 ) values for virgin and
reprocessed LDPE and their blends with starch LDPE. There
was no significant difference between the values for virgin
and reprocessed LDPE. When starch was added to LDPE, the
modulus showed high standard deviations and increased
when 30 wt% starch was added to virgin LDPE and when 30
and 40 wt% starch was added to reprocessed LDPE. In
general, the modulus is closely related to the hard domain of
the material.9 For starch contents higher than 30 wt% added
to virgin LDPE and for starch contents higher than 40 wt%
added to reprocessed LDPE, the modulus showed a tendency
Polym. Adv. Technol. 2005; 16: 310317

LDPE/corn starch blends

Figure 4. Tensile strength for LDPE and LDPE/starch

blends, with and without compatibilizer. (a) Virgin and (b)
reprocessed.

Figure 5. Youngs modulus for virgin and reprocessed

LDPE and LDPE/starch blends.
to decrease, which could be attributed to a higher starch
agglomeration, where the lower rigidity of these agglomerates prevailed.
Figure 6 shows that the addition of PE-g-GMA to blends
containing virgin LDPE, increased Youngs modulus only
when 50 wt% starch was added, while for blends containing
reprocessed LDPE, the addition of PE-g-GMA was very
effective at all starch contents. Again, this effect may reflect
the interaction of carboxylic and ketone groups that possibly
formed during reprocessing and preparation of the blends
with the starch, also increasing this compatibility.
Figure 7 shows the values of elongation at break for virgin
and reprocessed LDPE and their blends with starch. The
elongation at break was lower for pure reprocessed LDPE,
Copyright # 2005 John Wiley & Sons, Ltd.

313

Figure 6. Youngs modulus for LDPE and LDPE/starch

blends, with and without compatibilizer. (a) Virgin and (b)
reprocessed.
compared to pure virgin LDPE (Fig. 7a), since the degradation
induced by radical chain reactions caused crosslinking and
branching along polymer chains during reprocessing, which
led to a decrease in this property.12,13 Figure 7(b) shows that
the elongation at break decreased as the starch content
increased, and that blends containing reprocessed LDPE
had lower elongation at break values than those containing
virgin LDPE. The addition of starch granules to LDPE
produced the general trend for filler effects on polymer
properties, i.e. the modulus increased through stiffening of the
granules and elongation decreased as the starch content
increased.6 In synthetic polymer blends, the addition of a
second immiscible phase to a ductile matrix material usually
significantly diminishes the elongation properties at break. In
many cases when 20 wt% of the dispersed minor phase has
been added, highly deformable matrix materials are transformed into fragile materials. In synthetic polymer blends
with a ductile matrix, the elongation at break is therefore
considered to be highly sensitive to the interfacial interaction
between the phases of the blend.6 In this work, starch contents
higher than 20 wt% were used which led to catastrophic
decrease in the elongation when the starch was added.
Figure 8 shows that the addition of PE-g-GMA increased the
elongation at break only for virgin LDPE/30 wt% starch and for
reprocessed LDPE/40 wt% starch blends. However, for all
starch blends, the values of elongation at break fell markedly
when compared to those of pure PE (Fig. 7a), and the small
differences among blends with different starch contents, with
and without compatibilizer, were insignificant.
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A. G. Pedroso and D. S. Rosa

Dynamic mechanical thermal analysis (DMTA)

Based on the DMTA, the glass transition values (Tg) can be
defined as the temperature at which: (1) the loss tangent
(tan d) is maximum, (2) the loss modulus (E00 ) is maximum,
and (3) the inflexion point at which a significant drop in the
storage modulus (E0 ) occurs.14 The viscoelastic behavior of
the PEs and their blends was studied by DMTA.
Figure 9(a)9(c) shows the E0 versus T, E00 versus T and tan
d versus T, respectively, for virgin and reprocessed PEs.

Figure 7. Elongation at break for virgin and reprocessed

LDPE and LDPE/starch blends.

Figure 8. Elongation at break for LDPE and LDPE/starch

blends, with and without compatibilizer. (a) Virgin and (b)
reprocessed.
Copyright # 2005 John Wiley & Sons, Ltd.

Figure 9. DMTA curves for virgin and reprocessed LDPE.

(a) E 0 versus T, (b) E 00 versus T, (c) tan d versus T.
Polym. Adv. Technol. 2005; 16: 310317

LDPE/corn starch blends

Figure 9(a) shows that the E0 values for virgin and

reprocessed LDPE were practically the same, indicating that
reprocessing did not significantly change the material
rigidity, as also observed for Youngs modulus.
Figure 9(b) shows that virgin LDPE had a higher E00 maximum
value compared to reprocessed LDPE, in contrast to the E0
versus T curves which showed no difference between virgin
and reprocessed LDPE. The E00 value is related to loss of energy
as heat, i.e. to viscous behavior (irreversible deformation).
Therefore, the lower E00 maximum value for reprocessed LDPE

315

implied a higher elastic recovery, which could be attributed to

the greater polymer rigidity probably caused by the crosslinking that resulted from the degradation processes.
Considering Tg values as the temperature where E00 was
maximum, the PEs had a transition in the range of 13 to 08C,
which was attributed to b relaxation (relaxation of
branches).15 Although the PEs showed similar relaxation
ranges, the b relaxation of reprocessed LDPE tended to have a
lower temperature which was attributed to a decrease in
molecular weight caused by reprocessing.

Figure 10. DMTA curves for virgin and reprocessed LDPE and LDPE/starch blends. (a) E 0
versus T for virgin LDPE and virgin LDPE/starch blends, (b) E0 versus T for reprocessed LDPE
and reprocessed LDPE/starch blends, (c) E00 versus T for virgin LDPE and virgin LDPE/starch
blends, (d) E 00 versus T for reprocessed LDPE and reprocessed LDPE/starch blends, (e) tan d
versus T for virgin LDPE virgin LDPE/starch blends, (f) tan d versus T for reprocessed LDPE and
reprocessed LDPE/starch blends.
Copyright # 2005 John Wiley & Sons, Ltd.

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A. G. Pedroso and D. S. Rosa

Figure 11. E 0 versus T curves for virgin and reprocessed LDPE and LDPE/starch blends, with
and without compatibilizer. (a) Virgin LDPE and virgin LDPE/30 wt% starch blends, (b)
reprocessed LDPE and reprocessed LDPE/30 wt% starch blends, (c) virgin LDPE and virgin
LDPE/40 wt% starch blends, (d) reprocessed LDPE and reprocessed LDPE/40 wt% starch
blends, (e) virgin LDPE and virgin LDPE/50 wt% starch blends, (f) reprocessed LDPE and
reprocessed LDPE/50 wt% starch blends.
Figure 9(c) shows the tan d versus T curves. The
temperature at which tan d was maximum was approximately 908C for both virgin and reprocessed LDPE. This
temperature is related to a relaxation, which has been
interpreted as relaxation of the constrained molecules with
reduced mobility located near crystallites.15
Figure 10(a) and 10(b) show that, in general, the addition of
starch to virgin and reprocessed LDPE resulted in a shift in
the E0 curves to higher temperatures, indicating that the
starch caused a decrease in polymer chain mobility. The E0
Copyright # 2005 John Wiley & Sons, Ltd.

values increased with starch contents up to 40 wt%, whereas

at 50 wt%, the E0 values decreased. These results corroborated
the Youngs modulus results obtained in the tensile tests.
The E00 value decreased slowly up to 258C, after which, a
peak appeared (Fig. 10c and 10d). This peak was attributed to
b relaxation, which has properties of the glassrubber
transition.15 In general, the addition of starch shifted the
E00 maximum value to a higher temperature, indicating that
there was an increase in the relaxation temperature and that
this was caused by a decrease in chain mobility.
Polym. Adv. Technol. 2005; 16: 310317

LDPE/corn starch blends

317

when producing biodegradable blends since, according to

Zuchowska et al.,16 an increase in the content of the continuous starch phase improves the accessibility of the polymer
matrix to different degrading factors. It was not possible to
observe any difference among blends wthout compatibilizer
and blends with compatibilzer by light microscopy analysis
(Fig. 12).

CONCLUSION
Blends of virgin or reprocessed LDPE containing 30, 40 and
50 wt% starch were prepared. The addition of starch to
LDPE reduced the MFI values, the tensile strength and the
elongation at break, whereas the modulus increased. The
decreases in the MFI and tensile properties were most evident
when 40 and 50 wt% starch was added. The addition of the
compatibilizer PE-g-GMA decreased the MFI values and
increased the tensile strength in all blends, indicating an
improved interfacial interaction between the phases of
the blends. However, the effect of the compatibilizer on the
tensile strength was more efficient for blends containing
reprocessed LDPE.

Acknowledgements
The authors thank Brasken, EcoQuali and Corn Products
Brazil-Ingredientes Industriais Ltda. for supplying the virgin
LDPE, recycled LDPE and starch, respectively. This work
was supported by FAPESP (grants 99/10716-4 and 02/
06803-3), CNPq (grant 303500/2002-6) and Universidade
Sao Francisco.

REFERENCES

Figure 12. Light micrographs for virgin LDPE/starch blends:

(a) 70/30; (b) 60/40; (c) 50/50 (30
).
The peaks where tan d was maximum showed broadening
and a small shift to the right when starch was added to LDPE
(Fig. 10c and 10f).
Figure 11(a) and 11(b) show the E0 versus T curves for virgin
and reprocessed LDPE and their blends with starch, with and
without PE-g-GMA. For blends containing virgin LDPE, the
addition of PE-g-GMA increased the E0 value only in the
presence of 30 wt% starch, indicating that there was an
improvement in the interfacial interaction between the phases
of the blend. For blends containing reprocessed LDPE, the
addition of PE-g-GMA was efficient for all starch contents,
indicating an improvement in the interfacial interaction
between the LDPE and starch.

Light microscopy
Light microscopy showed that increasing the starch content
resulted in a continuous phase of starch. This is important
Copyright # 2005 John Wiley & Sons, Ltd.

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