Polymer International Polym Int 56:1440–1447 (2007)

Preparation and characterization

of thermoplastic starch/PLA blends by
one-step reactive extrusion
Ning Wang, Jiugao Yu∗ and Xiaofei Ma
School of Science, Tianjin University, Tianjin 300072, China

Abstract: In the presence of dicumyl peroxide, the compatibility of thermoplastic dry starch (DTPS)/poly(lactic
acid) (PLA) blends, using maleic anhydride (MA) as compatibilizer, was investigated. The plasticization of starch
and its compatibilizing modification with PLA was accomplished in a single-screw extruder by one-step reactive
extrusion. In the presence of MA, the plasticization of starch in DTPS/PLA blends could be improved and
homogeneous DTPS/PLA blends could be achieved as observed using scanning electron microscopy. Tensile tests
showed that the tensile strength of compatibilized DTPS/PLA blends was about 40.5 MPa higher than that of the
original composites. Differential thermal analysis indicated that the glass transition temperature of DTPS and
PLA became closer in the presence of MA than the blend without any additions, which suggested the compatibility
between DTPS and PLA was improved. In addition, Fourier transform infrared spectroscopy proved that MA
improved the interaction between DTPS and PLA. At the same time, the blend became more thermally stable
as shown by thermogravimetric analysis results. A novel decomposition peak at about 450 ◦ C was detected in the
compatibilized blend, which was higher than those observed for DTPS and PLA. Finally, a rheological study
suggested that MA could improve the fluidity of DTPS/PLA blends.
 2007 Society of Chemical Industry

Keywords: thermoplastic; starch; poly(lactic acid); one-step extrusion; compatibilizer

INTRODUCTION groups, are widely used as effective compatibilizers

The improper disposition of petroleum-derived plas-
tics leads to environmental pollution and has aroused
much interest recently in preparing substitutes.1
Poly(lactic acid) (PLA) is a promising thermoplastic
polymer derived from agricultural resources through
bioconversion and polymerization. Its stiffness, tensile
strength and gas permeability are comparable to those
of synthetic polymers from fossil fuels.2,3 However,
PLA is more expensive than conventional petroleum
polymers for disposable or short-term applications and
it degrades slowly in the environment over a period of
several months to 2 years.2 Starch of low price derives
from abundant and readily available sources. What
is more, the biodegradation rate of starch is rapid.4
Also, its small granule structure makes it good as a
particulate filler in polymer blend systems.4,5 Efforts
have been made to develop a biodegradable product
from a fully renewable resource by blending starch
with PLA.6 – 12
The major problem with this blend system is the
poor interfacial interaction between the hydrophilic
starch granules and the hydrophobic PLA. So
poly(hydroxyester ether)6 and poly(vinyl alcohol)7
have been used as the third component to enhance
the compatibility between PLA and starch. Also,
methylenediphenyl diisocyanate (MDI),8 PLA-graft-
(maleic anhydride),9 PLA-graft-(acrylic acid)10 and
PLA-graft-starch,11 which include reactive functional
to enhance the interfacial interaction of PLA/starch
blends. Recently reactive extrusion has been studied
widely to prepare starch/polymer blends.13 – 15 Com-
pared to the chemical blending process, the important
advantages of reactive extrusion are that it combines
several chemical process operations into an extruder
and no solvent is needed. In addition, gelatinization of
starch is also a good method to enhance the interfacial
affinity.12,16 Starch is gelatinized in order to disinte-
grate the granules and overcome the strong crystalline
intramolecular forces prior mixing with other poly-
mers.
In the work reported in this paper, glycerol was
used as the plasticizer for dry starch to avoid the
depolymerization of hydrophobic PLA during melt
processing. In order to enhance the properties of
thermoplastic dry starch (DTPS)/PLA blends, low-
toxicity maleic anhydride (MA) with dicumyl peroxide
(DCP) initiator was used as a compatibilizer to
enhance the compatibility between DTPS and PLA.
In addition, one-step reactive extrusion14,15 was used
to prepare compatible DTPS/PLA blends.
MATERIALS AND METHODS
Materials
PLA was purchased from Natureworks LLC
(USA). The general molecular weight was about

∗
Correspondence to: Jiugao Yu, School of Science, Tianjin University, Tianjin 300072, China
E-mail: gaojiuy@tju.edu.cn
(Received 12 December 2006; revised version received 7 February 2007; accepted 28 February 2007)
Published online 22 May 2007; DOI: 10.1002/pi.2302

 2007 Society of Chemical Industry. Polym Int 0959–8103/2007/$30.00


160 000–220 000. The concentration of the D-isomer
was 12.0 ± 1.0%. Cornstarch (12% moisture) was
obtained from Langfang Starch Company (Lang-
fang, Heibei, China). Glycerol (analytical reagent)
was purchased from Tianjin Chemical Reagent Fac-
tory (Tianjin, China). MA, purchased from Tianjin
Chemical Reagent Factory, was recrystallized twice
with CHCl3 before use. DCP, obtained from Shang-
hai Chemical Reagent Co., China Pharmacy Group
(Shanghai, China), was recrystallized from absolute
alcohol before use.
Sample plasticization
Starch was dried in an oven at 135 ◦ C for 2 h.
Glycerol was used as plasticizer which was mixed
(3000 rpm, 2 min) with dry starch using a GH-100Y
high-speed mixer (Beijing, China). The mixtures were
stored under airtight conditions until homogeneous
systems were obtained. These systems were blended
with PLA, MA and DCP using the high-speed mixer.
Sample designations and components are listed in
Table 1. DTPS/PLA blends were prepared as follows.
The mixtures were fed into an SJ-25(s) single-
screw plastic extruder (Beijing, China; screw diameter
(d) = 30 mm, screw ratio L/D = 25:1, 15 g min−1 ).
The screw speed was 10 rpm. The temperature profile
along the extruder barrel was 130, 140, 150 and
130 ◦ C (from feed zone to die). The die had three
round holes of 3 mm in diameter. The samples were
stored under airtight conditions immediately. When
the samples reached room temperature (about 20 ◦ C),
the extruded strips were pressed into sheets with a
flat sulfuration machine (Tianjin, China) and cut into
tensile bars with certain size and stored in desiccator
at room temperature immediately. Properties testing
was undertaken after one week.
SEM analysis
The microstructure of fracture surfaces of extruded
DTPS/PLA strips were examined using s Philips XL-
3 SEM instrument (FEI Company, Hillsboro, OR,
USA), operating at an acceleration voltage of 20 kV.
The samples were cooled in liquid nitrogen, and then
broken. The fracture surfaces were vacuum coated
with gold for SEM analysis.
Table 1. Sample designations and relevant sample components
PLA Dried Glycerol MAa
Sample (wt%) starch (wt%) (wt%) (wt%)
1 – 100 40 – –
2 50 35.7 14.3 – –
3 40 42.9 17.1 – –
4 30 50.0 20.0 – –
5 50 35.7 14.3 0.5
6 40 42.9 17.1 0.4
7 30 50.0 20.0 0.3
a The weight of MA and DCP was based on PLA.
Polym Int 56:1440–1447 (2007)
DOI: 10.1002/pi
Thermoplastic starch/PLA blends
Mechanical testing
Samples were pressured with the flat sulfuration
machine. A Testometric AX M350-10KN mate-
rials testing machine (Testometric Company Ltd,
Rochdale, UK) was used and a crosshead speed
of 10 mm min−1 was used for tensile testing (ISO
1184–1983). The data were averages of 5–8 speci-
mens.
Differential thermal analysis (DMA)
DMA using a Mark Netzsch DMA242 analyzer
(Bavaria, Germany) was performed on hot-pressed
thick specimens (40 × 7 × 2 mm, prepared using the
flat sulfuration machine, 5 MPa, 100 ◦ C), in a single
cantilever bending mode at a frequency of 3.33 Hz
and a strain of 2 N, corresponding to a maximum
displacement amplitude of 30 µm. DMA compared
the stress and strain signals and resolved the strain
into the in-phase (storage) and out-of-phase (loss)
components, from which storage or elastic (E  ) and
loss (E  ) moduli as well as tan δ = E  /E  were obtained
as a function of temperature. The range of temperature
was from −120 to 120 ◦ C. The standard heating rate
used was 3.0 ◦ C min−1 . A drop in storage modulus
and a peak in tan δ were used as indicators of a glass
transition.
Fourier transform infrared (FTIR) spectroscopy
FTIR spectra were measured using a BIO-RAD
FTS3000 IR spectrum scanner (Hercules, USA).
Extruded blend strips were pressured to transparent
slices with a thickness of around 0.2 mm using the flat
sulfuration machine.
Thermogravimetric analysis
The thermal properties of the blends were measured
with a ZTY-ZP type thermal analyzer (Beijing
University Instrument Factory, Beijing, China). The
sample weight varied from 10 to 15 mg. Samples
were heated from room temperature to 500 ◦ C at
a heating rate of 15 ◦ C min−1 . Derivatives of TGA
thermograms were obtained using Origin 7.0 analysis
software (RockWare Inc., Golden, USA).
Rheology
An XYL-II capillary rheometer (Jilin University
Instrument Factory, Jilin, China) was used to
determine the viscosity of the blends. The capillary
viscometer consists of a barrel into which material
DCPa
was loaded before being pushed by a plunger through
(wt%)
a capillary controlled by a surrounding heating unit.
The radius of the capillary was 1 mm and L/D = 40.
The small pieces were placed into the barrel through
a funnel and then packed down with the plunger
until the first extrudate appeared at the capillary exit.
0.05
The sample was allowed to come to temperature
0.04
0.03
(10–15 min), and was then forced through the
capillary by the plunger at pre-selected velocities. The
load on the plunger and plunger speed provide the
1441
N Wang, JG Yu, XF Ma

total pressure drop through the barrel and capillary
and the volume flow rate.
RESULTS AND DISCUSSION
Blend morphology
It is necessary to study the morphology of polymer
blends since many properties depend on it, espe-
cially the mechanical properties of immiscible blend
systems.17 As shown in Fig. 1, the fracture surface of
sample 2 (Fig. 1(B)) was rugged compared to that of
pure PLA (Fig. 1(A)). In addition, the average size of
starch particles was about 10 µm in Fig. 1(B), whereas
the native cornstarch particle was about 15 µm in
diameter.18 So most of the starch was obviously not
plasticized and some of it was removed from the
fracture surface leaving behind cavities (Fig. 1(B)).
Nevertheless, the interface between DTPS and PLA
was very clear. At the same time, by increasing the
content of DTPS, the diameter of the starch phase
increased (Fig. 1(C)). All of these are ascribed to the
poor interfacial adhesion between DTPS and PLA.
In the presence of MA and DCP, the dispersion
between DTPS and PLA improved and the granules
size of DTPS decreased dramatically (Figs 1(D) and
(E)). Especially, in Fig. 1(D) the fracture surface of
of the two copolymers. The maleation reaction
mechanism has been reported in previous work.19
This resulted in a reduction in interfacial tension
during molten blending and a finer dispersion in the
compatibilized blends. It had been reported that one-
step reactive extrusion could dramatically improve the
properties of LDPE/thermoplastic starch blends with
MA and DCP as the initiator.20 The maleation of
LDPE, the plasticization of starch and blending could
be simplified by one-step reactive extrusion.
Mechanical testing
The mechanical properties of pure components
showed typical brittle characteristics. The tensile
strength and elongation at break of PLA and DTPS
were 36.2 MPa and 3.0% and 38.3 MPa and 1.8%,
respectively. The mechanical properties of DTPS/PLA
blends, as well as these of the pure components were
of rigid and fragile materials as shown in Fig. 2.
After one-step extrusion of glycerol, dry starch
and PLA together, the mechanical properties of
DTPS/PLA blends were very poor, especially the
4.0 40
3.8
Elongation at break/% 35
3.6 Sample 2-4
Elongation at break / %

Tensile strength / MPa

3.4 Sample 5-7 Tensile strength/MPa
sample 5 turned into an evenly continuous phase. 3.2
30
Even at a high content of DTPS, homogeneous 3.0 25
DTPS/PLA blends still could be achieved. In addition, 2.8
2.6 20
the fracture surface of the blends became smoother 2.4
(Fig. 1(E)). The same phenomena had been found in 2.2 15
linear low-density polyethylene (LDPE)/starch blends 2.0
10
1.8
compatibilized with LDPE-graft-MA.5 The better 1.6 5
dispersion and compatibility between PLA and DTPS 1.4
arise from the formation of branched and crosslinked 1.2 0
30 35 40 45 50
macromolecules caused by reaction of the carboxyl
The content of PLA / wt%
groups of PLA-graft-MA with the hydroxyl groups
of starch. Branched and crosslinked macromolecules Figure 2. Mechanical properties of DTPS/PLA blends for different
contained different parts, each compatible with one ratios.

Figure 1. SEM images of pure PLA and DTPS/PLA blends: (A) PLA (×2000); (B) sample 2 (×2000); (C) sample 3 (×2000); (D) sample 5 (×2000);
(E) sample 6 (×2000).

1442 Polym Int 56:1440–1447 (2007)

DOI: 10.1002/pi
 Thermoplastic starch/PLA blends

tensile strength for samples 2–4. On increasing 5.0

the content of DPTS, the mechanical properties 4.8 PLA
worsened dramatically. This is ascribed to the poor Sample 1
4.6 Sample 2
interfacial adhesion between the two phases (as shown
4.4 Sample 5
in Figs 1(B) and (C)). In addition, on increasing

log(tan delta)
the content of DTPS, the increasing diameter of 4.2
DTPS phase in DTPS/PLA blend deteriorated the 4.0
continuous phase of the blends. 3.8
In the presence of MA and DCP, the mechanical 3.6
properties of DTPS/PLA blends improved markedly.
3.4
The maximum tensile strength and elongation at break
of sample 5 were 40.5 MPa and 3.5%, respectively. 3.2
Even on increasing the content of DTPS, the 3.0
mechanical properties of the blends did not worsen -150 -100 -50 0 50 100 150
dramatically. It was evident that the mechanical Temperature (°C)
properties of immiscible DTPS/PLA blends depended
strongly on the compatibility and the diameter of the Figure 4. Tan δ versus temperature of PLA, sample 1 and DTPS/PLA
starch phase. blends.

DMA study to primary α-relaxation process associated with the

The DMA data, i.e. the storage modulus (E  ) and
the loss factor (tan δ), for pure PLA, sample 1,
sample 2 and sample 5 are shown in Figs 3 and 4,
respectively. E  is an important parameter for rigid
materials. The values of E  of PLA, sample 1, sample 2
and sample 5 could be ranged in the order sample 1 >
sample 2 > sample 5 > PLA. This might be ascribed
to the plasticization of dry starch. It is known that after
excluding water, the polysaccharide chain mobility
and orientation were limited,21 which deteriorated
the plasticization of starch. So most residual starch
granules embedded in an entangled matrix consisting
of amylose and amylopectin might increase the
stiffness of the DTPS by physical crosslinks. After
blending with PLA, the disintegration of rigid starch
granules could be accelerated in DTPS/PLA blends
(as shown in Figs 1(B) and (C)). In the presence of
MA the plasticization of dry starch could be improved
as shown in Fig. 1(D).
In mechanical and dielectric relaxation studies of
amorphous polymers, the observation of two thermal
transitions in a single-phase material is usually assigned
8.8
log Storage Modulous (MPa)
upper transition temperature (Tg u ) and a lower
transition temperature (Tg l ) associated with relatively
localized molecular motions. Compared with Tg u of
PLA, the correlated Tg l at about 45.6 ◦ C was very
small (as shown in Fig. 4) which could be ascribed
to the poor mobility of relatively localized molecular
of PLA. Two glass transitions were detected in
thermoplastic starch materials which were recognized
to be phase-separated.22 Tg u is related to the glass
transition temperature in starch/water mixtures, and
Tg l is due to glycerol mixed with a small quantity
of polymeric material. So, only Tg l of sample 1 can
be seen in Fig. 4 after excluding water from the
thermoplastic starch system. In the presence of PLA,
Tg u of DTPS also could not be detected in samples
2 and 5 (Fig. 4). These transition temperatures are
summarized in Table 2; Tg l of DTPS shifted to high
temperature accompanying the Tg u of PLA shifting
to low temperature in the presence of MA and DCP.
This suggests that MA could enhance the compatibility
between DTPS and PLA.
FTIR spectroscopy
The interaction of polymer blends can be investigated
using FTIR spectra. If two polymers form completely

8.6 immiscible blends, there are no appreciable changes

8.4 in the FTIR spectra of the blends with respect to the
co-addition of each component.23 However, if two
8.2
polymers are compatible, a distinct chemical inter-
8.0 action (a hydrogen bonding or dipolar interaction)
7.8 exists between the chains of one polymer and those of
7.6 PLA the other, causing the FTIR spectra of the blends to
Sample 1
7.4 Sample 2 Table 2. The glass transition temperatures of PLA and DTPS
Sample 5
7.2
Sample Tg u (PLA) (◦ C) Tg l (DTPS) (◦ C)
7.0
-150 -100 -50 0 50 100 150 PLA 65.5 –
Temperature (°C) Sample 2 65.5 −43.9
Sample 5 57.8 −40.2
Figure 3. Storage modulus versus temperature of PLA, sample 1 and Sample 1 – −49.6
DTPS/PLA blends.

Polym Int 56:1440–1447 (2007) 1443

DOI: 10.1002/pi
N Wang, JG Yu, XF Ma

change (e.g. band shifts and broadening).24 As a result,
FTIR spectra can be used identify segment interac-
tions and to provide information about the phase
behavior of polymer blends.
Figure 5 shows the FTIR spectra of pure PLA, dry
starch, sample 1, sample 2 and sample 5 in specific
stretching regions. The peak band wavenumbers
related to hydrogen bonding of PLA, DTPS/PLA
blends and starch are listed in Table 3. When dry
starch was plasticized by glycerol, the characteristic
peaks of starch (the –C–O–bond stretching of
–C–O–H group at about 1156 and 1081 cm−1 and
the –C–O–bond stretching of –C–O–C–group in the
anhydroglucode ring at about 1020 cm−1 )25 shifted to
low wavenumber and split up into two peaks. This
is ascribed to both C–O–H and C–O–C groups
in starch forming hydrogen bond interactions with
glycerol, which decreased the stretching vibration
wavenumbers.
It is well known that PLA has a strong car-
bonyl stretching absorption at about 1749 cm−1 .
With the addition of DTPS, this peak shifted to
a lower wavenumber. When this blend was com-
patibilized with MA, this peak was shifted to
1745 cm−1 . This means that carbonyl groups also
take part in the interaction between PLA and DTPS,
resulting in the blue shift of the –C=O vibra-
tion of PLA. The same phenomenon was found
for –C–O–in –CH–O–(1182 cm−1 ) and –C–O–in
–O–C=O (1127, 1082, 1044 cm−1 ) of PLA in
DTPS/PLA blends on increasing the dispersion and
compatibility between DTPS and PLA.
TGA study
TGA was performed for pure PLA, starch, sample 1
and DTPS/PLA blends. The weight loss due to the
volatilization of the plasticizers and the degradation
products was monitored as a function of temperature,
as shown in Fig. 6. T5% , which is the temperature
corresponding to 5% weight loss determined from
Fig. 6 is summarized in Table 4. After plasticization
with glycerol, T5% of starch increased dramatically due
to the strong interaction between polysaccharide and
glycerol. Compared with sample 1, PLA is a thermally
stable polymer. T5% of DTPS/PLA increased by about
31 ◦ C compared with DTPS; hence the addition of
MA had little influence on the T5% of DTPS/PLA
blends.
From Fig. 7, the Tmax values of pure PLA, starch,
sample 1 and DTPS/PLA blends were determined
(derivative thermogravimetry, DTG), which are also
summarized in Table 4. Here Tmax is the temperature
at the maximum rate of weight loss, that is,
the decomposition temperature. Tmax of DTPS
decreased by about 20 ◦ C compared with starch,
which is ascribed to the disintegration of starch
molecules during plasticization at high temperature
and shear. After blending with PLA, Tmax of DTPS
in sample 2 decreased compared with sample 1.

C B A PLA
0.8 PLA
Sample 2 0.4
0.0
Sample 5 0.8
Sample 2
Weight Loss (%)

0.4
0.0
Sample 1 0.8
1182 Sample 5
1044 1749 0.4
1127 0.0
1082
0.8 Sample 1
Starch
0.4
0.0
0.8 Starch
1156
0.4
1020 1081 0.0
0 100 200 300 400 500 600
800 1000 1200 1400 1600 1800 2000 Temperature (°C)
Wavenumber (cm-1)
Figure 6. TGA curves for PLA, sample 1, starch and DTPS/PLA
Figure 5. FTIR spectra of PLA, DTPS and DTPS/PLA blends. blends.

Table 3. The wavenumber related to the hydrogen bonds in FTIR spectra and the change of the force constant f

Vibration wavenumber (cm−1 )

Sample –C–O of –C–O–H in starch –C–O of –C–O–C–in starch

Dried starch 1156 1081 1020

Sample 1 1150 1078 1017 994
Blends –C=O (carbonyl) –C–O–in –CH–O– –C–O–in –O–C=O
PLA 1749 1182 1127, 1082, 1044
Sample 2 1747 1180 1127, 1080, 1044
Sample 5 1745 1178 1125, 1078, 1042

1444 Polym Int 56:1440–1447 (2007)

DOI: 10.1002/pi
 Thermoplastic starch/PLA blends

Table 4. Thermogravimetric parameters of PLA, starch, sample1 and DTPS/PLA blends

DTPS PLA

Sample T5% (◦ C) DTPS, Tmax (◦ C) PLA, Tmax (◦ C) Slope Et (kJ mol−1 ) Slope Et (kJ mol−1 )

PLA 335 – 397 – – 0.0411 156.6

Sample 2 167 324 393 0.0104 38.8 0.0366 134.6
Sample 5 172 331 391 0.0195 59.2 0.0379 139.3
Sample 1 136 330 – 0.0109 33.0 – –
Cornstarch 68 349 – 0.0402 129.3 – –

-1.2 0.8 PLA

PLA 0.4
-1.8 y=0.2336+0.04111x
-2.4 0.0
-0.9 DTPS in Sample 2
-3.0
-1.2 -1.2 y=-1.1572+0.0104x
-1.8 Sample 2
0.6 PLA in Sample 2
-2.4 0.3 y=0.2059+0.03659x

ln[ln(1-α-1)]
-3.0 0.0
-1.4 Sample 5 -0.9 DTPS in Sample 5
DTG

-2.1 -1.2 y=-1.1346+0.0195x

-2.8 0.6 PLA in Sample 5
-0.7
-1.4 Starch 0.3 y=0.2564+0.0379x
0.0
-2.1
-2.8 -1.0 Sample 1
y=-1.1035+0.0109x
-0.7 -1.2
-1.4 Sample 1 -0.6 Starch
-2.1 -1.2
-1.8 y=-1.4988+0.0402
-2.8
0 100 200 300 400 500 600 -10 -5 0 5 10 15
Temperature (°C) theta (K)

Figure 7. DTG curves for PLA, sample 1, starch and DTPS/PLA Figure 8. Plots of ln[ln(1 − α)−1 )] versus θ for the determination of Et .
blends. The straight line is the linear fit of the data points.

But Tmax of DTPS in sample 5 remained nearly Rheology

the same compared with sample 1. At the same
time, Tmax of PLA in sample 5 shifted to lower
temperature. The closeness of these two Tmax values
might be ascribed to the increasing compatibilization
between DTPS and PLA. In addition, a new
decomposition temperature was detected in DTG at
about 459 ◦ C in sample 5, which was not found in
pure PLA, starch or DTPS/PLA blends without any
addition. This suggests that branched and crosslinked
macromolecules were formed during the one-step
reactive extrusion.
The activation energy of decomposition, Et , of the
polymer could be calculated from the TGA curves
by the integral method proposed by Horowitz and
Metzger26 using the following equation:
ln[ln(1 − α)−1 ] = Et θ/RTmax
2
(1)
where α is the decomposed fraction, T is the
temperature, θ is T − Tmax and R is the gas constant.
From the plots of ln[ln(1 − α)−1 ] versus θ , which
are shown in Fig. 8, Et could be determined (from
the slopes of the straight lines). As demonstrated in
Table 4, the Et values of starch decreased dramatically
after processing. The addition MA could increase the
thermal stability of DTPS in DTPS/PLA blends. Et of
DTPS in sample 5 was 59.2 kJ mol−1 , whereas Et of
DTPS in sample 2 was only 38.8 kJ mol−1 . However,
the influence of MA on Et of PLA was not evident.
In order to understand the DTPS/PLA processing
properties, rheology experiments were carried at
130, 140 and 150 ◦ C, which covered the processing
temperature range. Shear rate (γ ), shear stress (τ )
and apparent viscosity (η) were calculated by standard
methods, which are reported in our previous work.18
The η –γ curves were plotted using a double
logarithmic scale (Fig. 9). With increasing shear stress,
the viscosity of each blend decreased. Such flow
behavior is called shear thinning. At the same time,
according to the linear fit equations in Fig. 9, the
pure material and blends were more prone to flow
with increasing temperature. The flow index n, K and
viscous flow activation energy (Eη ) of PLA, sample
1 and DTPS/PLA blends at 130, 140 and 150 ◦ C are
listed in Table 5. According to our previous work,18
the linear fit equations are listed in Fig. 9. The slope
of the linear fit equation is −(1 − n) and the intercept
is log K .
As shown in Table 5, the flow index of PLA is larger
than that of sample 1. This is ascribed to the poor
fluidity of sample 1. So sample 1 hardly dispersed well
in more fluid PLA, which can be seen from Fig. 1(C).
When MA was used as the compatibilizer, the flow
index n of sample 5 increased which is similar to
pure PLA. It is suggested that MA could accelerate
the fluidity of sample 1 and increase the dispersion
between DTPS and PLA (Fig. 1(E)). In addition, it is
well known that the higher the Eη value, the more
sensitive are the blends to temperature. According

Polym Int 56:1440–1447 (2007) 1445

DOI: 10.1002/pi
N Wang, JG Yu, XF Ma

Table 5. The flow index n and vicious flow activation energy Eη (x = 0) of PLA, sample 1 and DTPS/PLA blends at 130, 140 and 150 ◦ C

Sample PLA Sample 1 Sample 2 Sample 5

130 ◦ C n 0.49 0.27 0.43 0.50

K 10 2329 3 754 049 56 872 52 735
140 ◦ C n 0.52 0.35 0.50 0.52
K 58 884 1 625 548 23 442 15 852
150 ◦ C n 0.55 0.36 0.52 0.55
K 34 673 838 687 13 375 13 807
Eη (x = 0) (kJ mol−1 ) 75.40 106.36 100.25 85.18

5.2 5.2
PLA 5.0 Sample 2
5.0 4.8

4.8 4.6
4.4
log η

log η
4.6 4.2

4.4 4.0
3.8
4.2 130°C Y = 5.0055-0.5072x
3.6 130°C Y = 4.7549-0.5667x
140°C Y = 4.7731-0.4771x
140°C Y = 4.3716-0.4978x
4.0 150°C Y = 4.5437-0.4520x 3.4
150°C Y = 4.1263-0.4813x
3.2
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
log γω log γω

5.0
6.6
4.8 Sample 5
Sample 1
6.4
4.6
6.2
4.4
6.0
log η

log η

4.2
5.8
4.0
5.6
150°C Y = 5.9236-0.63894x 3.8
5.4 130°C Y = 4.7221-0.4972x
140°C Y = 6.2110-0.6511x
3.6 140°C Y = 4.4758-0.4767x
130°C Y = 6.5745-0.7278x
5.2 150°C Y = 4.2001-0.4524x
3.4
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
log γω log γω

Figure 9. Rheology curves of PLA, sample 1 and DTPS/PLA blends Figure 9. Continued.
at 130, 140 and 150 ◦ C.

improved accompanied by homogeneous DTPS/PLA

to the values of Eη (x = 0) in Table 5, PLA and
sample 5 were less sensitive to processing temperature.
Therefore, during the thermoplastic processing, the
extruder screw speed could effectively adjust the flow
behavior of the blends.
blends being achieved. One-step reactive extrusion
is a novel and promising way to prepare starch-
based plastic materials. After blending with DTPS,
the flexibility of DTPS/PLA still was very poor in the
work reported here. This work is to be continued.

CONCLUSIONS
The physical properties and compatibility of DTPS/
PLA blends dramatically improved in the presence of
MA during one-step reactive extrusion processing.
At the same time, MA could also improve the
plasticization of dry starch and processing fluidity
of DTPS/PLA during one-step extrusion. Hence,
the tensile strength of DTPS/PLA blends could be
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