Compatibilization of StarchPolyester Blends Using

Reactive Extrusion

R.B. Maliger, S.A. McGlashan, P.J. Halley, L.G. Matthew

Centre for High Performance Polymers (CHPP), Division of Chemical Engineering, University of Queensland,
St. Lucia, Brisbane, Queensland-4072, Australia

Maleic anhydride (MA) and dicumyl peroxide (DCP) were

used as crosslinking agent and initiator respectively for
blending starch and a biodegradable synthetic aliphatic
polyester using reactive extrusion. Blends were characterized using dynamic mechanical and thermal analysis
(DMTA). Optical micrographs of the blends revealed that
in the optimized blend, starch was evenly dispersed in
the polymer matrix. Optimized blends exhibited better
tensile properties than the uncompatibilized blends. Xray photoelectron spectroscopy supported the proposed structure for the starchpolyester complex. Variation in the compositions of crosslinking agent and
initiator had an impact on the properties and color of the
blends. POLYM. ENG. SCI., 46:248 263, 2006. 2006 Society
of Plastics Engineers

INTRODUCTION
Plastics obtained from petrochemical sources generally
have lifetimes of hundreds of years when buried in typical
solid waste sites, and thus have posed signicant environmental threats [1]. These plastics have contributed 1725%
of the volume of waste being land lled [2]. Hence, recently, much research has concentrated on the development
of environmental-friendly biodegradable plastics obtained
from various natural renewable resources including starch,
cellulose, poly(hydroxyalkanoates), and poly(lactic acid).
Three main classes of biodegradable polymers have been
recognized. The rst class consists of synthetic polymers
sourced from nonrenewable resources with vulnerable
groups susceptible to hydrolysis attack by microbes. The
second class of materials is composed of naturally-occurring bacterial polymers such as polyhydroxybuterates
(PHB), polyhydroxyvalerates (PHV), and polyhydroxybuterates-co-valerates (PHB/V). Although polyhydroxyalkanoates are truly renewable and biodegradable, the determination of processing parameters and high production

Correspondence to: Peter J. Halley; e-mail: p.halley@uq.edu.au

Contract grant sponsor: Plantic Technologies, Melbourne.
DOI 10.1002/pen.20479
Published online
in Wiley InterScience (www.interscience.wiley.
com).
2006 Society of Plastics Engineers

POLYMER ENGINEERING AND SCIENCE2006

costs are the concerning factors [1]. The third class of

materials is biodegradable polymers from renewable resources such as starch, cellulose, and polylactic acid.
Starch-based thermoplastics are inexpensive, but generally
possess high viscosities and poor melt properties that make
them difcult to process. As a result, products made from
starch are often brittle and water-sensitive [3]. To alleviate
these problems, starch polymers are often blended with
more high performance synthetic polymers. Of course, in
the case of starch-polyester blend systems one must also
factor in the higher cost of the polyester, and aim to increase
the percentage of the lower cost starch in the blend while
maintaining the desired mechanical properties and performance of the polymer product. Thus to achieve this costperformance optimization, much must be understood and
optimized about the individual polymers and the blending
process.

STRUCTURE, MORPHOLOGY, COMPOSITION,

AND PROPERTIES OF STARCH
Recent NMR studies suggest that there are at least three
distinct components in wheat starch granules [4]. They are
as follows: (i) highly crystalline regions formed from double-helical starch chains, (ii) solid-like regions formed from
amylose-lipid inclusions complexes, and (iii) completely
amorphous regions associated with branching regions of the
amylopectin components of starch and possibly the lipidfree amylose. Starch granules essentially consists of linear
poly-(1 3 4)--D-glucose, amylose, and the branched molecule, amylopectin, where the linear chains are connected
through (1 3 6)- linkages. When starch granules are
observed under polarized light, a characteristic dark cross is
seen, which has led to regard the granules as distorted
sphaerocrystals [5]. The proportion of amylopectin ranges
from 95% in the low amylose or waxy starches through
70 75% in normal starches to 30% in some high amylose
starches [6, 7].
Hydroxyl groups cause starch to generally behave as an
alcohol during chemical reactions. This property of starch is
important when considering reactive blending of starch with

synthetic polymers. The presence of such large number of

OOH groups affords starch hydrophilic properties and
therefore adds afnity for moisture and dispersability in
water [8]. However, hydrophilicity is undesirable in many
plastic packaging applications and hence it is a major limitation in using starch as a homopolymer.
STARCHPOLYMER BLENDS
Most synthetic polymers are incompatible with starch
and it is difcult to add starch to synthetic polymer systems
in large quantities without dramatically reducing performance properties [9]. To enhance the compatibility of starch
and synthetic polymers, a reactive functional group such as
maleic anhydride (MA) can be added to the synthetic polymer [10]. In these blends, the interfacial tension is lowered
to generate a small phase size and strong interfacial adhesion to transmit applied force effectively between the component phases [11]. Thus, compatibilization through in situ
formation of compatibilizer in polymer blends has become
increasingly important and an alternative to replace the
method of adding block or graft copolymers separately [12].
Synthetic polymers having functional groups such as carboxylic acid, anhydride, epoxy, urethane, or oxazoline can
react with the OOH group in starch to form a blend with
stable morphology. These reactive groups form a chemical
or physical bond with hydroxyl or carboxyl groups in natural polymers such as starch [13].
The role of a compatibilizer is to control the properties of
multiphase blends not simply by converting immiscible
blends into fully miscible blends, but by controlling the size
of the phase domains of immiscible blends. Effective compatibilizers must be located at the interface between the
phase domains of the immiscible blend. Most importantly,
the degree of compatibilization in a particular system depends on the reactivity of the compatibilizer used. It has
been found that a compatibilizer is most effective when its
sections are of higher molecular weight than the corresponding blend components [14]. Several theories have
been proposed to explain the role of compatibilizers, of
which two mechanisms are considered plausible. The rst
mechanism is thermodynamic in nature in that the compatibilizer reduces the interfacial tension between the phases.
The second mechanism is kinetic in nature in that the
presence of the compatibilizer at the interface reduces the
agglomeration of domains by steric stabilization. However
it is often unclear which of these mechanisms dominates the
reduction in the particle size [14], and hence, the mechanism of compatibilization is still a debatable issue.
Several researchers have showed that dissimilar blends
could be compatibilized using different techniques. Bacon
and Farmer [15] showed that MA reacts with natural rubber
in presence of benzoyl peroxide and results in the addition
of MA to the double bonds and to the -methylene groups
of the polymer. Alder et al. [16] have conrmed the addition
reaction of MA with rubber in solid phase and in solution.
Mani, Bhattacharya, and Tang [12] have used initiators such
DOI 10.1002/pen

as dicumyl peroxide (DCP), benzoyl peroxide, and di-tertbutyl peroxide (DBP) for grafting biodegradable polybutylene succinate (PBS) with starch in presence of MA as a
crosslinking agent. Sailaja and Chanda [17] have used MAgrafted polyethylene (PE) for preparing PE-starch blends in
presence of benzoyl peroxide as initiator. Ceric ammonium
nitrate (CAN) is another initiator commonly used during
reactive grafting. Luftor et al. [18] studied the kinetics of
graft polymerization of acrylonitrile onto sago starch using
CAN as initiator. These works suggested the use of other
crosslinking agents such as phthalic anhydride and dodecyl
succinic anhydride in the presence of initiators to facilitate
grafting reactions.
Of all the methods used to achieve compatibilization in
starchpolyester blends, reactive extrusion (REX) is a wellutilized technique as it combines the traditionally separated
chemical processes (polymer synthesis and/or modication)
and extrusion (melting, blending, structuring, devolatilization, and shaping) into a single process carried out in the
extruder [19]. Using REX, modied polymer can be obtained in a ready-to-use form at the die.
Unmodied starch-based thermoplastics generally have
higher viscosities and poor melt properties than traditional
synthetic polymers that make them difcult to process.
Also, starch and synthetic polymers are generally thermodynamically dissimilar in nature, and hence are incompatible unless a compatibilizer is used. In REX of crosslinking
dissimilar polymers, free-radical initiation plays a predominant role. However in the extruder, mechanochemistry, by
itself, is not powerful enough for free-radical generation in
such grafting reactions. Hence, in this study, we have attempted to graft MA to a biodegradable polyester in presence of a free-radical initiator during stage-one of extrusion,
and further crosslinked MA-grafted polyester to starch during a second extrusion stage. We used different temperature
proles during the REX process. Should the compatibilized
blends exhibit improved mechanical properties, determination of interfacial tension and controlling the interfacial
properties of such blends will lead us on the path to developing well-controlled biodegradable blends with tailorable
mechanical properties.
MATERIALS
EnPol, a biodegradable thermoplastic polyester, was
obtained from IRe Chemical, Korea. Two types of starch
with different levels of amylopectin-to-amylose ratios were
used in a preset blend ratio in all formulations. The rst was
a low-amylose common waxy wheat starch and the other a
high-amylose, chemically-modied maize starch (hydroxypropylated starch). The second has a lower gelatinization temperature than the rst and is able to withstand
higher processing temperatures. Both starches were sourced
from Penford (Australia). These starches were blended together with plasticizers in accordance with the patents [20,
21] held by the Cooperative Research Centre for International Food Manufacture and Packaging Science and a
POLYMER ENGINEERING AND SCIENCE2006

249

TABLE 1.

Blends prepared using twin-screw extruder.

TABLE 2.
extrusion.

S (wt%)

PEst (wt%)

MA (wt%)

DCP (wt%)

40
40
40
40
40
40
40
40
40
40
40
40
40
40
40

60
60
60
60
60
60
60
60
60
60
60
60
60
60
60

0.0
0.5
0.5
0.5
0.5
1.0
1.0
1.0
1.0
1.0
1.5
1.5
1.5
1.5
1.5

0.0
0.3
0.5
0.8
1.2
0.0
0.3
0.5
0.8
1.2
0.0
0.3
0.5
0.8
1.2

spin-off company, Plantic Technologies, Melbourne,

Australia. Maleic anhydride (MA) (98.06%), obtained from
ICN Biomedicals, USA, was used as a crosslinking agent,
and Dicumyl peroxide (DCP, 99%), obtained from Sigma
Aldrich, was used as a free-radical initiator. Inert nitrogen
gas was used to prevent the effect of moisture on grafting
during the rst stage of extrusion.
Blend Preparation
A batch of Starch Patent Formulation (SPF) was prepared using a granulator. The composition of SPF to EnPol
was maintained at 40:60 (wt%) in all the blends. The
different blends prepared using a laboratory scale PRISM
corotating twin-screw extruder (length to diameter ratio of
40:1 and screw diameter of 16 mm) are shown in Table 1.

Temperature (C) proles for stage-1 and stage-2 of

Die
Zone9
Zone8
Zone7
Zone6
Zone5
Zone6
Zone5
Zone4
Zone3
Zone2
Zone1

Stage-1

Stage-2

100
120
160
180
180
180
180
180
180
180
150
120

100
120
160
180
180
180
180
180
180
180
150
120

speed of 45 rpm was used here. A continuous ow of

nitrogen was maintained with the help of an inlet device
during the rst stage of extrusion. The torque and die
pressure were monitored using a torque-meter and pressuretransducer, respectively. The temperature between mixing
and transportation zones was maintained at 180C to facilitate peroxide-initiated free-radical generation. The extrudate obtained from the rst stage of extrusion was pelletized
using a pelletizer and stored in a humidier at 60% RH until
further use.
The second step was compounding of the pelletized
MA-grafted polyester with SPF. Here, a screw speed of 70
rpm and a feed rate of 0.45 kg/h were used. The temperature
between mixing and transportation zones was maintained at
145C. The extruded strands were stored in a humidier at
60% RH.
ANALYSIS

Grafting Procedure
The grafting reactions were carried out in a laboratory
scale PRISM co-rotating twin-screw extruder with a barrel
length to diameter ratio of 40:1, a screw diameter of 16 mm
and eight heating zones. The composition of SPF and the
polyester was maintained at 40:60 (wt%) in all the blends.
The rst step was the preparation of maleated polyester.
From initial trials we found that the color of the extrudate
varied as the composition of MA was increased (0.5% MA,
white; 1% MA, light-pink; 1.5% MA, dark-pink; 2% MA,
brown; 3% MA, brownish-black; 5% MA, black). Maleated
polyesters with MA concentration of more than 2% were
found to be unsuitable for compounding with starch. Therefore, after optimizing the process, three different compositions of MA (0.5, 1, 1.5%) and four different compositions
of DCP (0.3, 0.5, 0.8, 1.2%) were selected. The temperature
proles for stage-1 and stage-2 of extrusion are shown in
Table 2. EnPol was dried under vacuum for 24 h prior to the
day of extrusion. MA and DCP were used in their powder
form. A mixture of polyester, MA, and DCP was introduced
using a mechanical feeder at a feed rate of 0.38 kg/h. Screw
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POLYMER ENGINEERING AND SCIENCE2006

Tensile Testing
The strands of different blends were subjected to tensile
testing using an Instron Universal tensile testing machine
(model 5584). A 5 KN load cell was used for determining
important properties such as stress at break, strain at break,
Youngs modulus, and stress and strain at maximum load. A
grip separation of 50 mm, crosshead speed of 5 mm/min,
and a sensitivity factor of 20% were adopted. All testings
were done according to the procedure outlined in ASTM
test method D-638.
Dynamic Mechanical and Thermal Analysis
A Dynamic Mechanical and Thermal Analysis (DMTA)
instrument (model IV) from Rheometric Scientic, Piscataway, NJ was used to study the effect of crosslinking and
phase separation on the thermal properties of starchEnPol
blends. A temperature sweep test was conducted with a
temperature range of 30 85C, a frequency of 1 Hz, soak
time of 10 sec, and a xed strain of 0.1%. The extruded
DOI 10.1002/pen

samples were sample-pressed to a size of 100 10 1

mm3 and subjected to DMTA.
X-ray Photoelectron Spectroscopy
Compression-molded lms (thickness 1 mm) of six different blends were subjected to X-ray photoelectron spectroscopy (XPS) using a PHI model 560 XPS/SAM/SIMS I
multitechnique surface analysis system incorporating a
model 25270 AR electron energy analyzer. Mg K X-rays
(1253.6 eV) generated using 400 W (15 kV, 27 mA) was
used to produce photoelectrons from the sample surface.
Survey (wide) scans, at analyzer pass energy of 100 eV,
over 1000 eV were taken, followed by multiplex (narrow)
scans of C 1s, O 1s, and Si 2p energy levels at high
resolution using a pass energy of 25 eV. Curve ttings of C
(1s) and O (1s) were carved out using Resident PHI V6.0
curve-tting software to establish the relative percentage of
different functional groups.

pus BH-2 model and a lens of the type Splan 10PL were
used. A scale of 10 m was adopted for all the samples. The
blends were pressed into lms of thickness of 10 m using
a sample press device. The thin sections were stained with
iodine/KI solution before obtaining images under the microscope at a magnication of 10. This method was used
to differentiate starch from EnPol in the optical micrographs.
CROSSLINKING MECHANISM
Before examining the studys main results, it is instructive to discuss hypothesized reaction mechanism. The proposed crosslinking mechanism for our starch-polyester system is described by the scheme below.
Consider the structure of EnPol.

Differential Scanning Calorimetry

(1)

A TA Instrument modulated DSC (TA2920) was used to

determine the thermal transitions of starchpolyester
blends. The sample size was 10 15 mg, with heating and
cooling rates of 10 and 20C min1, respectively.

Consider b 4. There are three steps involved in the

crosslinking of starch to the polyester. They are initiation,
propagation, and termination.

Optical Microscopy (OM)

Initiation

Analysis of the morphology of the blends was performed

using an optical microscope. An optical microscope Olym-

Step 1.
Formation of EnPol microradical

(2)
Step 3.
The EnPol microradical undergoes -scission under high temperature conditions (150C).

(3)
DOI 10.1002/pen

POLYMER ENGINEERING AND SCIENCE2006

251

Step 4.
ROO could further react with {2} to form another microradical.

(4)

Propagation
Step 5.
The free radical associated chain attaches itself to MA (double-bond cleavage)

(5)

Step 6.
Microradical {3} formed in step 4 could participate in the grafting process, resulting in the formation of a stable complex
shown below.

(6)

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POLYMER ENGINEERING AND SCIENCE2006

DOI 10.1002/pen

Step 7.
During stage 2 of extrusion where starch is compounded with MA-grafted EnPol, C-6 atom of starch [12] reacts with the
anhydride group of MA to form starchMApolyester complex.

(7)

The following starchMApolyester complex can also be expected.

DOI 10.1002/pen

POLYMER ENGINEERING AND SCIENCE2006

253

(8)

Termination
Step 8.
The reaction could be terminated in two ways; combination (coupling) or disproportionation. The possible termination
steps are given below.
Scheme 1(a) of Coupling

(9)
Scheme 1(b) of Coupling:

(10)

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POLYMER ENGINEERING AND SCIENCE2006

DOI 10.1002/pen

Scheme 2(a) of Disproportionation:

(11)
Scheme 2(b) of Disproportionation:

(12)
It has been found that polystyrene terminates predominantly by combination, whereas poly(methyl methacrylate)
terminates by disproportionation at polymerization temperatures higher than 60C, and partly by each mechanism at
lower temperatures [22]. Major studies on termination reaction schemes have been completed with linear-chain polymers, but no published research is available on the termination mechanism of starchpolyester crosslinking.
RESULTS AND DISCUSSION
Twin Screw Extrusion
The twin-screw extruder here was used as a reactive
extruder to combine peroxide-initiated grafting reaction and
conventional extrusion into a single process. The screw
conguration, torque, rotational speed, and mass ow rate
are the important terms in determining Specic Mechanical
Energy (SME), which is given as
SME Md/m.

(13)

Where, SME Specic mechanical energy (J/kg),

Md Torque (Nm)
Rotational speed of screw (s1),
m Mass ow rate (kg/s).
The greater the torque in the extruder the higher the bulk
viscosity of the system. Thus, for crosslinked systems, the
SME required should be more. The calculated SMEs for
different blends are given in Table 3.
During blending of starch with polyesters in presence of a
crosslinking agent and initiator, the anhydride functional group
DOI 10.1002/pen

could react with OOH group of starch to form ester linkages

[23]. Hence, in this reactive extrusion (REX), inter-crosslinked
polymer chains are expected, and as a result, the torque generated and hence the SME of a compatibilized blend should be
higher than the SME of uncompatibilized blends. It is evident
from Table 3 that the SME of each compatibilized blend is
higher than the SME of the uncompatibilized blend (40S,
60PEst). It can be observed that the SME variation in blends
containing 1% MA is greater than in other blends. In case of
blends containing 0.5% and 1.5% MA, the variation in SME
was negligible. This indicates that blends containing 1% MA
had higher microradical generation and better crosslinking than
in other blends. This could have increased the bulk viscosity
and SME of system.

TABLE 3.

Specic mechanical energy of different blends.

BLEND
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,

SME (kJ/kg)

60PEst
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,

0.5MA
0.5MA, 0.3DCP
0.5MA, 0.5DCP
0.5MA, 0.8DCP
0.5MA, 1.2DCP
1MA
1MA, 0.3DCP
1MA, 0.5DCP
1MA, 0.8DCP
1MA, 1.2DCP
1.5MA
1.5MA, 0.3DCP
1.5MA, 0.5DCP
1.5MA, 0.8DCP
1.5MA, 1.2DCP

152.98
198.53
535.23
560.42
579.31
540.81
214.35
271.66
353.23
413.23
598.97
348.94
453.37
454.46
452.53
458.9

POLYMER ENGINEERING AND SCIENCE2006

255

TABLE 4.

Blend
40S, 60PEst
40S, 60PEst, 0.5MA, 0DCP
40S, 60PEst, 0.5MA, 0.3DCP
40S, 60PEst, 0.5MA, 0.5DCP
40S, 60PEst, 0.5MA, 0.8DCP
40S, 60PEst, 0.5MA, 1.2DCP
40S, 60PEst, 1MA
40S, 60PEst, 1MA, 0.3DCP
40S, 60PEst, 1MA, 0.5DCP
40S, 60PEst, 1MA, 0.8DCP
40S, 60PEst, 1MA, 1.2DCP
40S, 60PEst, 1.5MA
40S,60PEst, 1.5MA, 0.3DCP
40S, 60PEst, 1.5MA, 0.5DCP
40S, 60PEst, 1.5MA, 0.8DCP
40S, 60PEst, 1.5MA, 1.2DCP

Tensile properties of different blends.

Tensile stress at maximum

load (Mpa)

Strain at break (%)

Youngs modulus (5% Tangent) (MPa)

14.68 0.95
15.70 1.22
20.11 0.9
19.89 1.78
18.63 1.75
17.55 1.55
12.54 4.42
10.5 3.33
15.71 0.96
18.92 1.04
16.05 1.71
17.61 0.54
19.8 2.78
18.27 1.56
19.35 1.61
18.98 1.58

78.68 9.58
80.82 4.38
75.18 8.74
78.68 11.52
92.38 8.65
50.24 10.19
31.06 2.42
150.12 15.15
111.24 12.98
257.35 37.69
165.73 38.61
35.34 3.62
40.86 4.81
36.06 5.51
44.08 7.85
43.02 4.96

36.77 6.02
38.57 12.48
86.87 13.22
79.87 1.10
62.87 15.55
48.38 19.83
51.74 21.79
30.88 9.94
43.07 9.09
51.59 6.89
44.07 5.88
82.64 20.33
88.31 11.63
80.86 5.18
74.78 27.36
79.99 20.28

Tensile Testing Analysis

Three important parameters were considered for tensile
testing analysis, namely tensile stress at maximum load,
stress at break, and Youngs modulus (tangent 5%). The
effect of the concentration of MA and DCP on these parameters was determined and is shown in Table 4.
The blends at 0.5% MA exhibited better tensile properties in terms of Youngs modulus and stress at break, than
the unmodied blend, but showed little or no improvement
in elongation at break. The blends with 1% MA had moderately higher Youngs modulus and stress at break values
than the unmodied blend. They also showed much higher
elongation at break than the uncompatibilized blend and
indeed the other reactively extruded blends. All blends
containing 1.5% MA had lower elongation at break than the
uncompatibilized blend. The Youngs modulus and stress at
break were increased over the uncompatibilized system. In
comparing between the compatibilized blends, blends containing 0.5% MA and 1.5% MA had higher Youngs modulus than the blends containing 1% MA. However the
blends at 1% MA had greatly improved elongation at break
values than 0.5% and 1.5% MA blends.
Mani et al. [23] observed that starch blends that encountered higher specic mechanical energy had high tensile
strength. Our results indicated that only few starch blends
with higher specic mechanical energy had better tensile
strength. It is hence important to consider the effects of
interfacial properties and maleation on the tensile properties
of starchpolyester blends.
Bhattacharya et al. [24] noticed that the addition of
compatibilizers (styrene MA copolymer and ethylenepropylenegmaleic anhydride copolymer) had a profound effect on the tensile properties of the starch blend (60% starch,
40% compatibilizer). However, those blends exhibited poor
elongation at break. Avella et al. [25] have shown that an
increase in the composition of starch and precompatibilizer
decreases both tensile strength and elongation at break, but
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POLYMER ENGINEERING AND SCIENCE2006

increases Youngs modulus. In synthetic polymer blends,

the addition of a second phase to the polymer matrix usually
diminishes the elongation properties at break [26] and in
many cases, when 20% of the dispersed minor phase has
been added highly deformable matrix materials are transformed into brittle materials [27]. The elongation at break in
synthetic polymer blends is therefore considered to be
highly sensitive to the state of the interface. However, we
observed a notable increase in elongation at break and
overall decrease in Youngs modulus in blends containing
1% MA. Krishnan and Narayan [28] have described in their
patent that the hydroxyl groups of plasticizers and starch
molecules could interact with compatibilizers, promoting
interfacial adhesion. They also indicate an acute possibility
of plasticizers acting as stretching agents. If it is assumed
that maleation did not occur, then starch plasticizers should
have increased elongation at break and interfacial adhesion
in all blends, irrespective of the composition of the
crosslinking agent and the initiator. The observation that
only few maleated starch blends showed improved mechanical properties indicates the importance of optimizing the
composition of the crosslinking agent and the initiator. In
particular, the blend (40S, 60PEst, 1MA, 0.8DCP) showed
the highest elongation at break (257%). This could have
resulted from the strong interfacial adhesion due to
crosslinking of the two phases, and the greater ability of this
interface to withstand higher extension to break. However,
blends containing 1.5% MA had relatively higher Youngs
modulus and lower elongation at break. Ideally an optimized compatibilized blend here is a compromise between
desired mechanical properties and starch composition.

Dynamic Mechanical and Thermal Analysis

Dynamic Mechanical and Thermal Analysis (DMTA)
experiments are used to investigate the mechanical behavior
of materials, and to obtain information about the relaxation
DOI 10.1002/pen

FIG. 1.

Graph of E and E Vs temperature for uncompatibilized blend.

mechanisms that may be correlated with the dynamics and

the microstructure of the material [29]. The effect of temperature on storage modulus (E), loss modulus (E), and
loss factor (tan ) at a xed strain rate (0.1%) was studied
here. The storage modulus E is related with the mechanical
energy stored during each load cycle and per unit volume.
Loss modulus E signies the dissipation of energy as heat
during the deformation. The loss factor tan is equal to
E/E and is thus sensitive to balance of the dissipated and
stored energy of the system and is useful to detect thermomechanical relaxations [30].
E for the uncompatibilized blend (40S, 60PEst) was
found to decrease gradually with increase in temperature,
indicating a stiffness loss. Here, a denite glass transition
was observed for E and tan curves between 35 and 50C,
which should be due to starch. The graphs for E and tan
are shown in Figure 1.
Analysis of compatibilized blends
Graphs of storage modulus versus temperature of different blends containing 0.5, 1, 1.5% MA, and various compositions of DCP are shown in Figures 2 4.
Although there appears to be no specic trend, the blend
(40S, 60PEst, 0.5MA, 0.8DCP) exhibited the highest storage modulus (4.64 108Pa) at 30C, followed by blends
containing 0.5, 0.3, and 1.2% DCP (Fig. 2). It was also
DOI 10.1002/pen

FIG. 2. Graph of E and tan Vs temperature for blends containing 0.5%

MA { (40S, 60PEst, 0.5MA, 0.3DCP); (40S, 60PEst, 0.5MA,
0.5DCP); (40S, 60PEst, 0.5MA, 0.8DCP); (40S, 60PEst, 0.5MA,
1.2DCP)}.

observed that at higher temperatures (80C), blends containing higher compositions of DCP lost their stiffness more
quickly than the blends containing lower compositions of
DCP. For the blend (40S, 60PEst, 0.5MA, 0.3DCP), two
distinct peaks were observed at 55 and 68C. The rst peak
at 55C is due to the addition of the interface modier
(compatibilizer). The other peak at 68C could be due to the
molecular motions within the starch phase. At higher concentrations of DCP, these peaks were found to disappear.
When compared with the transition peak in the uncompatibilized blend, it is found that with the addition of compatibilizer the transition peak in compatibilized blends shifted
towards higher temperatures. It can be observed from Figure
3 that in all the blends containing 1% MA, a drastic decrease
in storage modulus (E) is observed. This indicates that as
the concentration of MA in the blend is increased from 0.5
to 1%, there is a sharp decrease in stiffness. This is in
agreement with the tensile testing results. In all the blends
containing 1% MA, a transition peak is observed between
70C and 85C, which is a shift by about 10C when
compared with the transition peak in the blend (40S,
60PEst, 0.5MA, 0.3DCP). This indicates that the
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FIG. 3. Graph of E and tan Vs temperature for blends containing 1%

MA. { (40S, 60PEst, 1MA); (40S, 60PEst, 1MA, 0.3DCP); (40S,
60PEst, 1MA, 0.5DCP); (40S, 60PEst, 1MA, 0.8DCP); (40S, 60PEst,
1MA, 1.2DCP)}.

crosslinked points could have been obstructing the conformational mobility of the segments of EnPol, resulting in
further shift of the transition peak. A series of transitions
observed in the blends containing 0.3, 0.5, and 0.8% DCP
could be due to the side groups and segmental motions of
the crosslinked chains.
It is noticeable that all the blends containing 1.5% MA
have storage modulus between that of blends containing 1
and 0.5% MA. These blends are found to exhibit similar
tensile properties to the blends containing 0.5% MA. Most
of these blends exhibit a transition between 50 and 60C,
which could again be due to the presence of interface
modier. These blends also showed transition peak between
60 and 70C, signifying the molecular motion within starch.
X-ray Photoelectron Spectroscopy
Although X-ray Photoelectron Spectroscopy (XPS) is a
surface analysis technique, it still gives information about
the structure of crosslinked polymers. Compression molded
lms of six blends [(40S, 60PEst), (40S, 60PEst, 0.5MA,
0.5DCP), (40S, 60PEst, 1MA), (40S, 60PEst, 1MA,
0.8DCP), (40S, 60PEst, 1.5MA), (40S, 60PEst, 1.5MA,
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FIG. 4. Graph of E and tan Vs temperature for blends containing 1.5%

MA. { (40S, 60PEst, 1.5MA); 224 (40S, 60PEst, 1.5MA, 0.3DCP);
(40S, 60PEst, 1.5MA, 0.5DCP); (40S, 60PEst, 1.5MA, 0.8DCP); (40S,
60PEst, 1.5MA, 1.2DCP)}.

0.5DCP)] were washed using hexane to remove the surface

impurities and then examined with XPS. In the survey
scans of all the graphs, Si (2p) and Si (2s) peaks were
observed in the range of 102 and 106 eV. Peaks at binding
energies of 102 and 103.4 eV correspond to Si and methyl
(CH3) group, respectively. Hence, it is assumed that the
active peaks between 102 and 106 eV were the presence of
poly(dimethylsiloxane) [PDMS], which could have been
present in the polyester in the form of crystal impurity. In
the survey scan, a graph of electron count Vs binding energy
(eV) was plotted. In all the graphs, distinct peaks corresponding to C (1s) and O (1s) were observed in the range
250 300 eV and 500 550 eV, respectively.
Then a high resolution scan (called multiplex) of the C
(1s) and O (1s) energy levels of the mentioned blends was
carried out at a pass energy of 25 eV. It was observed that
the ratio of C/O of the blends was approximately 3. According to the proposed structure, the OOH group of C-6 of
starch attaches itself to the CAO group of MA, resulting in
the formation of a carboxylic group (OCOOH). We determined the compositions of OCO and OCOO groups in
different blends using curve-tting software Resident PHI
DOI 10.1002/pen

FIG. 5. High resolution scans of (a) uncompatibilized blend; (b) 40S, 60PEst, 0.5MA, 0.5DCP; (c) 40S,
60PEst, 1MA; (d) 40S, 60PEst, 1MA, 0.8DCP; (e) 40S, 60PEst, 1.5MA; (f) 40S, 60PEst, 1.5MA, 0.5DCP.

V6.0. All the data was charge-corrected at 101.8 eV using

Si (2p) as reference for PDMS. The results of the curvetting are shown in Figure 5.
The curve tting results of C (1s) energy levels of
different blends are shown in Table 5.
For six different blends, the factor A1/A2 (Area of
OCOO/Area of OCO) was determined based on the area of
respective peaks in the curve-tted graphs. It is to be noted

TABLE 5.
Blend
40S,
40S,
40S,
40S,
40S,
40S,

60PEst
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,

0.5MA, 0.5DCP
1MA
1MA, 0.8DCP
1.5MA
1.5MA, 0.8DCP

DOI 10.1002/pen

here that XPS does not detect H. It was observed that the
composition of OCOO groups in the blend (40S, 60PEst,
1MA, 0.8DCP) was higher than the composition of OCOO
groups in other blends. The OCOO peak in the curve-tted
graph is due to the presence of OCOO groups of EnPol and
OCOOH groups, which are formed due to crosslinking
(refer to mechanism). As crosslinking increases, the percentage of OCOOH groups in the compatibilized blends

Curve-tting results of C (1s) energy levels of different blends.

Area of OCOO groups (A1)

Area of OCO groups (A2)

A1/A2

983
880
1246
1362
872
789

1372
1074
1508
1125
1354
977

0.72
0.82
0.83
1.21
0.64
0.81

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TABLE 6. Thermal transitions for starch/polyester uncompatibilized

and compatibilized blends.
Blends
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,

60PEst
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,

0.5MA, 0.3DCP
0.5MA, 0.5DCP
0.5MA, 0.8DCP
0.5MA, 1.2DCP
1MA
1MA, 0.3DCP
1MA, 0.5DCP
1MA, 0.8DCP
1MA, 1.2DCP
1.5MA
1.5MA, 0.3DCP
1.5MA, 0.5DCP
1.5MA, 0.8DCP
1.5MA, 1.2DCP

Endotherm T (C)

Exotherm T (C)

98.8
99.1
98.4
98.4
97.1
99.9
98.5
98.2
97.5
97.5
99.0
98.9
98.1
98.1
98.2

63.8
49.6
45.9
51.6
52.6
48.4
50.7
48.4
59.2
64.8
50.2
55.9
45.3
44.8
45.1

also increases, which is due to the transfer of OOH group

of C-6 of starch to the CAO group of MA to form OCOOH
group. The number of CAO groups in the compatibilized
blends varies with the degree of crosslinking. For example,
even in compatibilized blends, the presence of unreacted
MA increases the number of CAO groups. Also, in the
blends that did not contain DCP, XPS detected more CAO
groups, indicating that there is a possibility of MA remaining in unreacted state or partially reacted state.
Differential Scanning Calorimetry
Differential scanning calorimetry was used to evaluate
the thermal transition of the blends. To eliminate thermal
history, the samples were equilibrated at 30C, heated to
220C at 10C min1, cooled to 70C at 20C min1,
maintained under isothermal conditions for 5 min, and
heated to 220C min1 at 10C min1.
Thermal transitions such as melting and crystallization
are of high importance in polymer processing techniques.
For the base blend containing 60% polyester and 40% starch
based plastic, the melting endotherm occurred at 98.8C,
while the crystallization exotherm occurred at 63.8C (Ta-

ble 6). For compatibilized starchpolyester blends, no signicant change in the endotherm (melting) temperature was
observed, but the exotherm (crystallization) temperatures of
all the compatibilized blends were lower than the crystallization temperature of the base blend (refer to Table 6).
Hence, crosslinking agents do have signicant effect on the
crystallization temperature of starchpolyester blends. Because of -scission of the polyester the chains could form
crosslinked regions, resulting in the restriction of polymer
chain mobility, which could signicantly reduce the degree
of crystallinity. However, it is interesting to note that the
crystallization temperatures of the two blends at 1.0% MA
addition {(40S, 60PEst, 1MA, 0.8DCP) and (40S, 60PEst,
1MA, 1.2DCP)} were higher than the crystallization temperatures of other compatibilized blends. In fact, the greatest increase in exotherm temperature was found in (40S,
60PEst, 1MA, 1.2DCP). The presence of optimum concentration of the compatibilizer could have prevented appreciable micelle formation and hence reduced the interfacial
energy of the blend. As a result, the degree of crystallization
could have increased in both phases and at the interface,
further leading to an increase in the number of nucleation
sites. In the two blends mentioned earlier, the compositions
of MA and DCP could hence be in the proximity of their
respective optimum concentrations. The crystallization temperatures of other compatibilized blends were low, indicating that the compositions of the crosslinking agent and the
initiator in these blends are not optimized. It could also be
observed that the crystallization temperature for the uncompatibilized blend (40S, 60PEst) is quite high (63.8C), and
yet the blend exhibited poor mechanical properties. The
absence of crosslinking agent could promote micelle formation at the interface of the hydrophobic polyester and the
hydrophilic starch, thus contributing towards poor mechanical properties. At the same time, the two phases could
crystallize in their domains, resulting in an increase in the
crystallization temperature of the blend.
Optical Microscopy
The optical micrographs of the uncompatibilized blend
and blends that did not contain DCP are shown in Figure 6.

FIG. 6. Optical micrographs of (a) uncompatibilized blend; (b) 40S, 60PEst, 1MA ; and (c) 40S, 60PEst,
1.5MA.

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FIG. 7. Optical micrographs of (a) 40S, 60PEst, 0.5MA, 0.3DCP; (b)

40S, 60PEst, 0.5MA, 0.5DCP; (c) 40S, 60PEst, 0.5MA, 0.8DCP; and (d)
40S, 60PEst, 0.5MA, 1.2DCP.

In the uncompatibilized blend (Fig. 6a), due to interfacial

tension between the starch and the polyester phases, the
starch phase is not homogeneously distributed in the polymer matrix. In the blend {40S, 60PEst, 1MA}, the starch
phase could have remained as a separate phase (Fig. 6b),
whereas in the other blend {40S, 60PEst, 1.5MA}, the
starch phases are ner than the phases of the former blend.
This could be due to hydrolysis of starch by MA that is
present in excess concentration, leading to the break down
of the starch phase (Fig. 6c).

FIG. 8. Optical micrographs of (a) 40S, 60PEst, 1MA, 0.3DCP; (b) 40S,
60PEst, 1MA, 0.5DCP; (c) 40S, 60PEst, 1MA, 0.8DCP; and (d) 40S,
60PEst, 1MA, 1.2DCP.

Analysis of Blends Containing 1.5% MA.

The micrographs of the blends containing 1.5% MA and
different compositions of DCP are shown in Figure 9.
It can be observed from micrographs of blends containing 1.5% MA and different compositions of DCP that starch
phases are concentrated in certain regions of the polymer
matrix, and that the cocontinuous phases exhibited at 1%
MA, have now been lost. In these blends with higher com-

Analysis of Blends Containing 0.5% MA.

The optical micrographs of the blends containing 0.5%
MA and different compositions of DCP are shown in Figure
7.
It could be observed in the micrographs (Fig. 7) that the
starch phase is homogeneously distributed and has formed a
cocontinuous phase with the polyester phase. These blends
exhibited better mechanical properties than the uncompatibilized blend.
Analysis of Blends Containing 1% MA.
The optical micrographs of blends containing 1% MA
and different compositions of DCP are shown in Figure 8.
It can be observed that in the blends with higher DCP
content ((40S, 60PEst, 1MA, 0.8DCP) and (40S, 60PEst,
1MA, 1.2DCP)) (Figure 8c and d), starch is evenly dispersed throughout the polymer matrix. This suggests optimum compositions of MA and DCP helps generate polyester microradicals, promoting efcient crosslinking
whereupon more and more starch reacts with the compatibilizer. This reduces the interfacial tension between the two
dissimilar phases and promotes adhesion.
DOI 10.1002/pen

FIG. 9. Optical micrographs of (a) 40S, 60PEst, 1.5MA, 0.3DCP; 40S,

60PEst, 1.5MA, 0.5DCP; (c) 40S, 60PEst, 1.5MA, 0.8DCP; and (d) 40S,
60PEst, 1.5MA, 1.2DCP.

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position of DCP (Fig. 9b, c, and d), numerous microradicals

generated could react among themselves (disproportionation or coupling) and terminate the reaction. By this, the
crosslinking of the two phases is hindered forcing some
starch phase to remain in unreacted state.
DISCUSSION
It is apparent that the mechanical and thermal properties
of the compatibilized starch based polymerpolyester polymers are affected by the addition of the compatibilization
system. In summary it appears that

All blends (0.5, 1.0, and 1.5 wt% MA) showed an improvement in Youngs modulus and stress at break.
Blends with 1.0% MA showed larger improvements in
elongation at break.
DMTA studies revealed that the blends containing 1%
MA had lower stiffness (E) than blends containing 0.5%
MA and 1.5% MA.
XPS analysis indicated the presence of more OCOO
groups in the blend with 1% MA, thus supporting the
proposed compatibilized structure for the blend.
The DSC results indicated that the crystallization temperatures were reduced with increasing compatibilizers because of an increased hindrance to crystallization. Crystallization temperatures of the two blends at 1.0% MA
addition {(40S, 60PEst, 1MA, 0.8DCP) and (40S, 60PEst,
1MA, 1.2DCP)} had higher than the crystallization temperatures than that of other compatibilized blends.
Optical micrographs of compatibilized blends with 1%
MA revealed uniform distribution of starch in the polymer matrix, indicating compatibilization between starch
and polyester phases

Thus optical, DSC, and XPS tests indicates that a reactively compatibilized structure is optimized for the 1.0%
MA samples. Interestingly the 1.0% MA samples showed
lower elastic modulus or stiffness during DMTA tests, yet
showed high youngs modulus, stress at break and elongation at break during tensile testing. This is possibly due to
the fact the DMTA tests are linear deformation tests and the
tensile tests induce nonlinear deformation. That is, the linear
DMTA tests determine a lower linear elastic modulus under
small deformations, possibly due to the plasticizing addition
of the MA to the system as previously noted [30], and the
MA induced crosslinks have little effect. However, under
nonlinear tensile testing the deformation is larger and more
destructive, and the compatibilized network structure is able
to reduce the breaking of tie layers commonly described in
basic polymer fracture studies. It is also interesting that the
Youngs modulus, stress at break and elongation at break all
increase, unlike normal composite systems, which sacrice
elongation [extensibility] for increases in strength.

an improvement in Youngs modulus and stress at break.

Blends with 1.0% MA showed larger improvements in
elongation at break. DMTA studies revealed that the blends
containing 1% MA had lower stiffness than blends containing 0.5% MA and 1.5% MA. The compatibilized blends
exhibited several transition peaks due to the presence of
interface modier, molecular motions within starch phase,
and side groups and segmental motions of the crosslinked
chains. XPS analysis indicated the presence of more OCOO
groups in the compatibilized blend with 1% MA, thus
supporting the proposed structure for the blend. The DSC
results indicated that the crystallization temperatures were
reduced with increasing compatibilizers because of an increased hindrance to crystallization. Crystallization temperatures of the two blends at 1.0% MA addition {(40S,
60PEst, 1MA, 0.8DCP) and (40S, 60PEst, 1MA, 1.2DCP)}
had higher crystallization temperatures than that of other
compatibilized blends. We believe that the presence of
optimum concentrations of MA and DCP in these blends
reduces appreciable micelle formation and increases the
number of nucleation sites resulting in an increase in crystallization temperature and interfacial adhesion. Optical micrographs of compatibilized blends with 1% MA revealed
uniform distribution of starch in the polymer matrix, indicating compatibilization between starch and polyester
phases.
In this study, compatibilization of starch and biodegradable polyester has been achieved using REX, and thus it
offers a new direction for enhancing the properties of low
cost-base renewable biodegradable polymers. Also, for
compatibilized blends the study of interfacial tension (subject of future work) is a vital aspect with regards to improving the properties of biopolymers. This ability to tailor
biodegradable polymer morphology and properties is crucial if low cost biodegradable polymers are ever to be fully
optimized for appropriate performance properties.

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