THERMAL AND MECHANICAL PROPERTIES OF POLY(LACTIC

ACID) AND STARCH BLENDS WITH VARIOUS PLASTICIZERS

T. Ke, X. Sun

ABSTRACT. Poly(lactic acid) (PLA) has potential for use in disposable and biodegradable plastics. Blending starch with PLA
would increase biodegradability and reduce costs. However, the brittleness of the starch/PLA blend is a major drawback for
many applications. The objective of this study was to characterize thermal and mechanical properties of PLA/starch blends
with addition of six plasticizers at various levels. Three groups of plasticizers were used: (1) acetyl triethyl citrate (AC) and
triethyl citrate (TC); (2) poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG) of low molecular weight and
containing an ether group that might interact with PLA; and (3) glycerol and sorbitol, which are miscible with starch. The
PLA and cornstarch were blended at a 60:40 weight ratio by using a lab–scale twin–screw extruder with addition of these
plasticizers ranging from 5% to 25%. The thermal transition temperatures (glass transition, crystallization, and melting) of
the extruded PLA/starch blends decreased as AC, TC, and PEG contents increased. The PPG almost had no effect on the
transition temperatures of the blends. Cold crystallization and melting temperatures of PLA increased slightly with increasing
sorbitol content. Glycerol reduced the cold crystallization and melting temperatures but had no effect on the glass transition
temperature. Starch formed a continuous phase in the presence of 25% sorbitol or 15%, 20%, or 25% glycerol. The TC and
PEG enhanced the crystallization of PLA. The annealed samples containing glycerol had the highest crystallinity. As
concentration of AC, TC, PEG, PPG, and glycerol increased, tensile strength and Young’s Modulus of the extruded and
molded blends decreased, and elongation increased in comparison to the blend without plasticizers.
Keywords. Poly(lactic acid), Plasticizer, Acetyl triethyl citrate, Triethyl citrate, Poly(ethylene glycol), Poly(propylene
glycol), Glycerol, Sorbitol.

E
nvironmental concern over the use of conventional
nondegradable polymers has stimulated research in
biodegradable materials as alternatives. Starch has
been considered as an alternative because it is a
naturally occurring biopolymer with abundant resources and
is low in price. It has been broadly blended with
petroleum–based plastics to increase biodegradability or
with biodegradable resin to decrease cost. Poly(lactic acid)
(PLA) is a promising synthetic biodegradable polymer
because of its good mechanical properties (Engelberg and
Kohn, 1991). Blending starch with PLA will increase
biodegradability and reduce costs for raw materials.
However, starch and PLA are both brittle, which is a major
drawback for many applications. Processibility of the blend
is also a problem because the addition of starch reduces
flowability.
A plasticizer is commonly used to improve the
processibility, flexibility, and stretchability of a polymer
Article was submitted for review in January 2001; approved for
publication by the Food & Process Engineering Institute of ASAE in May
2001.
Contribution no. 00–488–J from the Kansas Agricultural Experiment
Station.
The authors are Tianyi Ke, Post–Doctoral Research Associate, and
Xiuzhi Sun, ASAE Member Engineer, Associate Professor, Department of
Grain Science and Industry, Kansas State University, Manhattan, Kansas.
Corresponding author: Xiuzhi Sun, Dept. of Grain Science and Industry,
Kansas State University, Manhattan, KS 66506–2201; phone:
785–532–4077; fax: 785–532–7010; e–mail: xss@wheat.ksu.edu.
because it can reduce the intermolecular force and increase
the intermolecular mobility. A good plasticizer should be
chemically compatible with the polymer to yield a stable,
homogeneous mixture. Starch is a polyol and PLA is a
polyester, so they are immiscible. Native starch is usually in
a granular form in which the polymer molecules are hydrogen
bonded and aligned radially. Starch alone in a dry state is not
considered a true thermoplastic in the sense that it would be
degraded upon heating rather than melt on its own. However,
in the presence of a plasticizer, starch would behave as a
thermoplastic (Simmons and Thomas, 1995).
In this study, the following plasticizers were included:
acetyl triethyl citrate (AC), triethyl citrate (TC), poly(ethyl-
ene glycol) (PEG), poly(proplylene glycol) (PPG), glycerol,
and sorbitol. These plasticizers can be classified into three
groups according to their structure. AC and TC are small
molecular citrate esters; they are synthesized from naturally
occurring citric acid and are commonly used as plasticizers
for many polymers. They are often recommended for
materials that come into contact with food because of their
favorable physiological properties (i.e., nontoxicity, nonir-
ritation, etc.) (Gachter and Muller, 1990). A previous study
reported that citrate esters were miscible with PLA and
effectively improved its elongation (Labrecque et al., 1997).
Glycerol and sorbitol are polyhydric alcohols that are
miscible with starch and are good plasticizers to starch (Yu et
al., 1998; Lawton and Fanta, 1994; Arvanitoyannis et al.,
1998). Some hydroxyl groups of glycerol and sorbitol were
expected to interact with the ester group from PLA in some
degree, such as hydrogen bonding. PEG and PPG are
polyethers with low molecular weight and are used widely as

Transactions of the ASAE

Vol. 44(4): 945–953 E 2001 American Society of Agricultural Engineers ISSN 0001–2351 945
plasticizers. Younes and Daniel (1998) studied the
miscibility of PEG with PLA from L–lactic acid by a solution
casting method. Sheth et al. (1997) studied the miscibility of
PEG and PLA from L–lactic acid and the effect of PEG
concentration on the mechanical properties, enzymatic
degradation, and hydrolytic degradation of the PEG/PLA
blend. Both studies showed that PEG has good miscibility
with PLA and enhances the flexibility of PLA. PPG was used
in this work to determine the effects of the side group (methyl
group) on plasticization.
A polymer has a number of phase changes upon heating,
from glassy to rubbery to melt. The temperature at which a
phase transition occurs is considered a phase transition
temperature, which includes glass transition temperature,
crystallization temperature, and melting temperature. These
thermal transition temperatures are important properties for
determining processing parameters of a polymer, and they
significantly affect the properties of the final product. Little
information is available about how these plasticizers
influence the thermal and mechanical properties, as well as
the morphology, of PLA and starch blends. The objective of
this research was to characterize the thermal and mechanical
properties of starch/PLA blends with addition of these
plasticizers at various levels.
MATERIALS
Industrial cornstarch (Silver Medal Pearl–1100), contain-
ing approximately 75% amylopectin and 25% amylose, was
purchased from Cargill, Inc. (Minneapolis, Minn.). PLA was
obtained from Shimadzu, Inc. (Japan); it had a molecular
weight of about 120,000 Dalton and was polymerized mainly
from L–lactic acid. AC (Citroflex A2) and TC (Citroflex C2)
were obtained from Morflex, Inc. (Greensboro, N.C.). PEG
(Mn Ca. 2,000) and PPG (Mn Ca. 2,000) were purchased
from the Aldrich Company (Milwaukee, Wisc.). Glycerol
and sorbitol were purchased from Sigma Company
(St. Louis, Mo.).
PREPARATION OF BLENDS AND TENSILE BARS
Cornstarch was dried in an air oven at 130³C for 2 hrs.
PLA beads were ground into small particles in the range of
about 2 mm using a mill (Model 4 Laboratory Mill,
Thomas–Wiley Company, Philadelphia, Penn.). The dried
cornstarch, plasticizer, and the ground PLA were premixed
using a stand mixer (Ultra Power, KitchenAid, St. Joseph,
Mich.) at room conditions. The ratio (40:60, by weight) of
starch and PLA was used because our previous work
indicated that the PLA phase would became partially
discontinuous when the starch content was up to 60% (Ke and
Sun, 2000). A plasticizer was added into the mixture of starch
and PLA at five concentrations: 5%, 10%, 15%, 20%, and
25%. The percentage of plasticizer used was calculated based
on the total amount of PLA and starch. A PLA and starch
mixture without a plasticizer was used as the control. Each
mixture was stored in a polyethylene ziplock plastic bag for
about 1 h and then blended in a lab–scale, co–rotating,
conical twin–screw extruder (TW–100, Haake, Paramus,
N.J.) with a screw diameter of 19.1 mm and a length to
diameter ratio of 25:1.
Each mixture was loaded into a feeding funnel. It was
extruded through a rod die with an 8 mm diameter at a
946
temperature profile of 120³C (near the feed inlet, zone 1),
185³C (zone 2), 185³C (zone 3), and 185³C (at the die). The
screw speed was fixed at 100 rpm. The extruded rods were cut
into short cylinders about 10 mm in length and were then
ground into small particles of about 2 mm using the mill. The
ground extrudates were dried in an oven at 110³C for 24 h to
remove moisture before molding to avoid degradation of
PLA.
Samples of dried ground extrudates were molded into type
IV tensile bars (ASTM, D686–92) using an injection–mold-
ing machine (Boy 22S, Boy Machines, Postfach, Germany).
The temperature profile was 150³C for the feeding zone,
175³C for the barrel adapter, and 139³C for the injection
nozzle. The molding injection pressure was 150 psi, and
injection and cooling times were 5 and 10 s, respectively.
SCANNING ELECTRON MICROSCOPY
Microstructures of the fractured samples obtained after
tensile testing were observed by using a scanning electron
microscope (SEM) (AutoScan, ETEC Corporation, High-
lands, Texas) at an accelerated voltage of 20 kV.
To observe starch phase only, the narrow part cut from the
tensile bar was soaked in a chloroform solvent to remove
PLA phase. The starch “skeleton” left was dried in an air oven
at 50³C for a day and was then observed using the SEM.
THERMAL ANALYSIS
A differential scanning calorimeter (DSC) (DSC7,
Perkin–Elmer, Shelton, Conn.) was used to determine
thermal transition. The DSC was calibrated using the melting
temperature and enthalpy of a standard material, indium.
Samples of dried, ground extrudates were weighed
accurately into aluminum pans and sealed hermetically. The
sample size was about 15 mg. An empty pan was used as a
reference. The DSC temperature increased from –30³C or
25³C to 200³C at a rate of 10³C/min, depending on the
thermal properties of each plasticizer. To assure the same
thermal history of each sample, data from the second DSC
scan were used. To observe the effects of annealing treatment
on thermal properties of the blends in the presence of
plasticizers, the extrudate samples were annealed in an air
oven at 100³C for 1 h, DSC was then performed, and data
from the first DSC scan were used. Crystallinity of each
extruded blend was estimated by using the DSC data and the
following equation:
Xc (%) = (DHm + SDHci) Ü 100/(93 Ü XPLA) (1)
where
DHm = enthalpy of fusion of the blend (J/g)
SDHci = enthalpy of crystallization of the blend (J/g)
93 = enthalpy of fusion (J/g) of a PLA crystal of
infinite size (Fisher et al., 1973)
XPLA = PLA content.
MECHANICAL ANALYSIS
Tensile tests were performed on the bars with an Instron
testing machine (Model 4466, Canton, Mass.) according to
ASTM test method D638–92 with a crosshead speed of
5 mm/min and a gauge length of 30 mm. All samples were
preconditioned at an ambient temperature (23³C) and 50%
RH for 48 h, and tests were performed at the same conditions.
Data reported in this study are the averages of five samples.
TRANSACTIONS OF THE ASAE
RESULTS AND DISCUSSION
SCANNING ELECTRONIC MICROSCOPY
The morphology of extruded and molded samples
containing various plasticizers at 25% concentration is
shown in figure 1. Starch granules were observed for the
blends with AC, TC, PEG, and PPG, indicating that the starch
was mostly blended without “melting” (gelatinization). The
presence of a few smaller particles indicated that some starch
granules were crushed during blending. In addition, many
voids were observed. The blends containing glycerol and
sorbitol had a uniform and smooth morphology, indicating
that the starch became destructurized (or plasticized).
Therefore, the phase behavior of the starch and PLA of the
blends could not be clearly observed by the SEM.
By dissolving the blends in chloroform, a starch
“skeleton” was found for the blends containing 15%, 20%,
and 25% glycerol. A continuous starch phase was observed.
The continuous phase of the plasticized starch became
aggregated as glycerol contents increased, as shown in
figures 2A, 2C, and 2E (or figs. 2B, 2D, and 2F for an
enlarged view). A similar continuous starch phase of the
blend with 25% sorbitol was also observed (fig. 2G, or fig. 2H
for enlarged view) but less aggregated than that with 25%
glycerol (fig. 2E, or fig. 2F for enlarged view). The results
Figure 1. Scanning electron micrographs of fractured samples of extruded and molded poly(lactic acid)/starch (60:40) blends containing 25% of
various plasticizers (1000X).
Vol. 44(4): 945–953
indicated that glycerol has better plasticization on starch than
sorbitol. Besides the starch “skeleton,” some solid material
in flocculus form was also observed in the chloroform for the
blend containing 25% sorbitol. However, powder–like
starches were found in the chloroform solutions for the rest
of blends containing AC, TC, PEG, PPG, the control sample
(without plasticizer), 5% to 10% glycerol, and 5% to 20%
sorbitol.
TRANSITION TEMPERATURES
The DSC graphs of the extruded blends containing various
plasticizers indicate the thermal changes of PLA (fig. 3). For
comparison purposes, the thermal properties of the extruded
blend (control sample) without plasticizer were as follows:
Tg (glass transition temperature) = 58.2³C
Tc1 (first crystallization temperature) = 103³C
DHc1 (enthalpy of crystallization at Tc1) = –18.28J/g
Tc2 (second crystallization temperature) = 158³C
DHc2 (enthalpy of crystallization at Tc2) = –0.98J/g
Tm (melting temperature) = 174³C
DHm (enthalpy of fusion) = 22.635J/g.
The Tg values were consistent with the characteristics of
each class of plasticizers except for PPG. Tg decreased
linearly with increasing content of AC (r2 = 0.99) and TC
947
 A B 10µm
40µm

C D

E F

G H

Figure 2. Scanning electron micrographs of starch “skeleton” after PLA leached out in the chloroform: containing 15% glycerol (A = 200X, B = 1000X);
containing 20% glycerol (C = 200X, D = 1000X); containing 25% glycerol (E = 200X, F = 1000X); containing 25% sorbitol (G = 200X, H = 1000X).

(r2 = 0.99) in the blends (fig. 4A). AC and TC have similar
chemical structures, contain ester groups as the repeating unit
of PLA, and their compatibility was enhanced greatly,
resulting in the decrease in Tg. The Tg values of the extruded
blends containing TC were smaller than those of the blends
containing AC at the same concentration level, indicating
that the effect of TC on Tg was slightly greater (fig. 4A). The
Tg of the extruded blends decreased rapidly as PEG content
increased. PEG contains a repeating unit of an ether group,
which is compatible in some degree with the repeating unit
of the ester group in PLA. Sheth et al. (1997) reported that
PLA and PEG had good miscibility, and the results obtained
from this study showed that PEG was a good plasticizer for
PLA.

948 TRANSACTIONS OF THE ASAE

 Although the PEG used in this experiment had a melting
AC temperature of 48³C, which was close to the Tg of the blend,
the melting peaks at lower PEG concentrations of 5%, 10%,
TC
PEG
and 15% were smaller, making Tg easy to identify. However,
as PEG contents increased beyond 20%, the Tg values could
Endo Heat Flow (mv)

PPG not be estimated because the large melting peaks of PEG

Glycerol overwhelmed the Tg. Glycerol, sorbitol, and PPG had few
Sorbitol effects on Tg of the blends. Evidently, glycerol and sorbitol,
CONTROL which are polyol compounds and are immiscible with PLA,
did not influence its mobility. However, they are good
PLA plasticizers for starch. In structure, PPG contains a repeating
unit of ether–like PEG but also contains a side methyl group.
This group may hide the “ether bond” in the PPG main chain,
decreasing PPG’s miscibility with PLA.
0 50 100 150 200 Two cold crystallization peaks were observed in the DSC
o
Temperature( C)
measurements at most conditions (fig. 4), which occurred in
heating from the glassy state and began somewhat above the
Figure 3. Differential scanning calorimetry of pure poly(lactic acid) glass transition. This crystallization was defined as cold
(PLA), extruded PLA/starch (60:40) blend without plasticizer, and crystallization. A main peak (Tc1) occurred at about
extruded PLA/starch (60:40) blends with 15% of various plasticizers. 80³–100³C, and a minor peak (Tc2) occurred at about

60 120
(A)
110 (B)
50

40 100

30 90
C)
Tg(oC)

80
o

20
Tc1(

70
10
60
0
50
–10
0 5 10 15 20 25 30 40
Plasticizer contents (%) 0 5 10 15 20 25 30

AC TC PEG Plasticizer contents (%)

PPG Glycerol Sorbitol AC TC PEG
PPG Glycerol Sorbitol

176
160
(C) 174 (D)
158
172
156
170
154 168
152 166
Tm(oC)
Tc2(oC)

150 164
148 162
160
146
158
144
156
142
154
0 5 10 15 20 25 30
0 5 10 15 20 25 30
Plasticizer contents (%)
Plasticizer contents (%)
AC TC PEG
AC TC PEG
PPG Glycerol Sobitolr
PPG Glycerol Sorbitol

Figure 4. Thermal transition temperatures of extruded poly(lactic acid)/starch blends (60:40) as affected by plasticizer concentrations: (A) glass transition
temperature (Tg); (B) first crystallization temperature (Tc1); (C) second crystallization temperature (Tc2); and (D) melting temperature (Tm).

Vol. 44(4): 945–953 949

150³–160³C. The effects of the plasticizers on Tc1 (fig. 4B) 30 51.7
(A)
were similar to those on Tg. The Tc1 of the blends decreased
linearly as AC and TC contents increased. Similarly, AC and
25 43.1
TC increased the mobility of the PLA chain, and a higher
mobility would allow PLA to reorder its chain easily and

Hm (J/g)
crystallize at a lower temperature. The effects of TC on Tc1

Xc(%)
20 34.5
were more significant than those of AC because TC’s
hydroxyl group interacted with PLA to induce crystalliza-
tion. The effects of PEG on Tc1 were interesting; the Tc1 15 25.9
decreased at first, then increased, and then leveled off
(fig. 4B). This phenomenon may have been associated with
the initial crystallinity of the blends with PEG. 10 17.3
The SDHi in fig. 5A is the sum of all enthalpies in the DSC 0 5 10 15 20 25 30
heating and was used to estimate the initial crystallinity of the Plasticizer contents (%)
extruded blends, according to equation 1. The corresponding
AC TC PEG
crystallinity is plotted in figure 5A on the right Y–axis. The PPG Glycerol Sorbitol
initial crystallinity was small at low PEG contents (i.e., 5%
and 10%), although it was slightly greater than that of blends
25 43.2
with other plasticizers. However, it increased significantly at
(B)
15% and 20% PEG contents, much more than in blends with
other plasticizers, and then leveled off as PEG content 20
32.4
increased to 25%. PLA is a semi–crystalline polymer, so its

Hi (J/g)
crystallinity is limited. Therefore, at lower concentrations of 15
PEG, there is more space for PLA to crystallize further. As 21.6
the PEG content increased, the initial crystallinity of the

Xc(%)
10
blend increased significantly (fig. 5A), which would make
further crystallization more difficult because of the limitation 10.8
5
of PLA crystallinity. Although PEG involved enhancing the
mobility of PLA molecular chains, at the same time, a greater
initial crystallinity would decrease the mobility of the PLA 0 0
molecular chains. Therefore, a higher temperature (Tc1) was 0 5 10 15 20 25 30
required for PLA crystallization of the blends with higher Plasticizer contents (%)
PEG contents. AC TC PEG
The Tc1 of the extruded blends remained almost PPG Gylcerol Sorbitol
unchanged as glycerol and PPG contents increased (fig. 4B).
The Tc1 was about 100³C, close to the Tc1 (103³C) of the
30
control sample, at all PPG concentrations but was 90³C at all (C)
glycerol contents except for 5%. As mentioned before, PPG
contains a side methyl group whose steric bulk decreases its 25 43.4
interaction with PLA, resulting in less effect on PLA’s
Hai (J/g)

thermal behavior. However, a Tc1 lower than that of the

control indicated that PPG could still increase the mobility of 20 34.7
PLA to some degree.

Xc(%)
For glycerol, as mentioned before, Tg remained
unchanged, indicating that glycerol did not influence the 15 26
mobility of PLA molecules. The molecules of starch are held
together by inter– or intramolecular hydrogen bonds, and a
10 17.3
few free hydroxyl groups occur on the surface of starch
0 5 10 15 20 25 30
granules. However, the starch was destructurized by glycerol
under heat and shear force during extrusion, so more Plasticizer contents (%)
hydroxyl groups would exist at the interface and could AC TC PEG
PPG Glycerol Sorbitol
interact with ester groups of PLA molecules. In addition,
some glycerol molecules would be distributed at the interface Figure 5. Thermal enthalpies and percent crystallinity (Xc) of extruded
between PLA and starch because of the glycerol’s poly(lactic acid)/starch (60:40) blends as affected by plasticizer
flowability. It is possible that these two factors enhanced the concentrations: (A) enthalpy sum (SDHi); (B) crystallization enthalpy
crystallization of PLA. At 5% glycerol content, these effects (DHc1) at about 100³C; (C) fusion enthalpy (DHm); and (D) enthalpy sum
were weak, resulting in no effect on Tc1 of the blends. At high (DHi) after annealing 1 h at 100³C.
glycerol content, these two factors somewhat enhanced the
crystallization of PLA, resulting in a reduction in Tc1 value. resulting in an increase in Tc1. At high sorbitol content, the
The Tc1 of PLA increased slightly when sorbitol content starch became more continuous due to the plasticization,
increased from 5% to 15%, and then leveled off. At low resulting in less scattered PLA, which would balance the
sorbitol content, sorbitol acted as filler, which would make filler effects. Therefore, the Tc1 remained unchanged.
the PLA phase more scattered as sorbitol content increased,

950 TRANSACTIONS OF THE ASAE

 The effects of these plasticizers on the second
crystallization temperature (Tc2) were similar to those on
Tc1 (fig. 4C). However, no Tc2 data were available at higher
concentrations of AC or TC because the melting temperature
of the blends decreased significantly (fig. 4D), and their
melting peaks overwhelmed the second crystallization
peaks.
The melting temperatures of the extruded blends in the
presence of plasticizers showed behavior similar to that of
Tc1. AC and TC were good plasticizers for PLA, and the
melting temperatures of the blends decreased rapidly as their
contents increased. PPG did not have any influence on the
melting temperatures of the blends because it was not
miscible with PLA. The melting temperatures of the extruded
blends in the presence of sorbitol increased slightly with
increasing sorbitol content. This was consistent with the
corresponding Tc1. For glycerol, the melting temperature of
the blends decreased as contents increased (fig. 4D). As
mentioned, destructurized starch and glycerol might induce
PLA crystallization to some degree, but the crystals formed
at interaction or at lower crystallization temperature would
be smaller, less perfect, and would melt at a lower
temperature. PEG had little effect on the melting temperature
of the blends, which was in agreement with the results
observed by Sheth et al. (1997).
TRANSITION AND CRYSTALLINITY ENTHALPIES
The total crystallinity enthalpy (DHm) presented in figure
5A is the sum of the initial crystallinity and the crystallinity
gained during DSC heating. The initial crystallinity, as
estimated by using the sum of enthalpies (SDHi), was the
degree of crystallization formed during cooling after the first
DSC heating (fig. 5B). The initial crystallinity of the
extruded blends containing AC was different from that of
blends containing TC. It increased at first and then decreased
as AC content increased. At a low concentration, AC
increased the mobility of the PLA molecular chain, which
allowed reordering and resulted in an increase in
crystallinity. At a high concentration, a solvating effect of AC
decreased the concentration of crystal molecules of PLA,
resulting in a decrease in crystallinity. Maximum crystallin-
ity of the blend occurred at 15% AC content. The PLA
crystallinity generally increased as TC content increased. As
mentioned, both AC and TC are good plasticizers for PLA,
and the only difference between them is that TC has a
hydroxyl group that is not esterified. We naturally assumed
that the hydroxyl group has a positive effect on the
crystallization of PLA because it may form a hydrogen bond
with the carboxyl group in PLA. Therefore, TC would have
had some positive effect on the crystallinization of PLA.
The extruded blends with PEG had the highest initial
crystallinity among the blends, and the initial crystallinity
increased as PEG contents increased, which meant that PEG
could enhance the crystallization of PLA. The degree of
enhancing PLA’s crystallization is: PEG > TC > AC (fig. 3B).
PPG behaved as an inert dilute agent because of its
immiscibility with PLA, and the initial crystallinity
decreased as PPG concentration increased. For sorbitol, the
initial crystallinities of the blends at 5% and 10% were almost
the same as that of the control sample because sorbitol is
immiscible with PLA. The initial crystallinity decreased
slightly as sorbitol contents increased beyond 15% because
the starch became more destructurized and dispersed
Vol. 44(4): 945–953
uniformly. Hence, thePLAphase domain became small,
inhibiting large crystal formation. For glycerol, the initial
crystallinity of the blends increased slightly at contents of 5%
to 10%, then leveled off after about 15% content, but was
larger than that of the control. The reasons are similar to those
given above for the effect of glycerol on TC1.
The curves in figure 5C present the crystallinity of
annealed samples that had undergone the crystallization
thermodynamic process. In this case, the solvating effect
would become predominant. For AC, TC, and PEG, the
crystallinity of the blends gained in this procedure decreased
as plasticizer contents increased because they were good
plasticizers for PLA and had strong solvating effects. The
crystallinity of the annealed samples at 25% PEG content was
even less than the initial crystallinity. This is because PEG
melted, its “solvating” effect became strong at the annealing
temperature, and the crystal of PLA melted partially. The
annealed blends containing glycerol had the highest
crystallinity. Destructurized starch (i.e., gelatinized starch,
damaged starch granules, etc.) and glycerol at the interface
induced a crystallization effect in PLA and would form many
crystal nuclei, including both starch and PLA, that would
result in formation of a large amount of crystals. The high
viscosity of sorbitol restricted its effect of enhancing
crystallization of PLA. As an inert dilute agent, PEG slightly
decreased the crystallinity of the annealed blends.
MECHANICAL PROPERTIES
For comparison, the mechanical properties of the control
were as follows: tensile strength = 35.8 (µ1.5) MPa,
elongation at break = 4.39% (µ0.09), and Young’s
Modulus = 1.06 (µ0.03) GPa. The mechanical properties of
the blends containing various plasticizers are presented in
figure 6. The tensile strength of the extruded and molded
blends decreased as the concentrations of AC, TC, PEG, and
PPG increased (fig. 6A). This is because a plasticizer can
reduce intermolecular force and increase intermolecular
mobility. Glycerol also significantly reduced the tensile
strength of the blends, although the plasticized starch of the
blend with glycerol above 15% was in continuous phase.
Voids were produced due to the flowability of glycerol and
resulted in low tensile strength. However, tensile strength of
the blends containing sorbitol increased slightly as sorbitol
contents increased. Sorbitol had less effect on the mobility of
starch than glycerol did because sorbitol is in solid form at
room temperature. The morphology of the blend containing
sorbitol was more solid than that of the blends containing
other plasticizers (fig. 1).
Elongation of the extruded and molded blends increased
as the concentrations of AC, TC, PEG, PPG, and glycerol
increased, but decreased slightly or remained constant at all
sorbitol levels (fig. 6B). AC and TC were small molecular
plasticizers and effectively increased the mobility of PLA,
yielding a large increase in elongation. Elongation increased
less in the blends with PEG and PPG. For the blend with
glycerol, the elongation of the blend was not improved,
although the starch was plasticized into a continuous phase.
However, at 25% glycerol, the elongation of the blend was
improved to some degree. Sorbitol had no significant effect
on elongation, but it decreased slightly because of the
increasing of filler volume as sorbitol content increased.
The modulus indicates the stiffness of a material. Because
the plasticizers AC, TC, PEG, and PPG (considered to
951
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+
20

Stress(MPa)
20 Glycerol

ÓÚÚ
Ÿ
&&ÔŽ
!
ÛÛ
’’ÜÜ
Ö

" ÒÙ

#ÕÕ
$$
ÚŠŠ
* Û

%%
+
15 AC
TC

Ó&&
ŸÛÛ
Ô’’
ŽÜÜ
! Ö((


" Ò#
Ù)
ÕÕ ŠŠ
Ú*

$$ Û+

%%
10 15

ÚÚ
Ó&&
ŸÛÛ
Ô’’
ŽÜÜ
! Ö((

Ò#
" Ù)
ÕÕ ŠŠ
Ú*

$$ Û+

%%
5 PEG
10
0
AC TC PEG PPG Glycerol Sorbitol 5 PPG
PPG
0

ÖÖ
0 5 10 15
25

00
(B) 5% Strain (%)

++ ,,


20 10%
Figure 7. Typical tensile curves of extruded and molded poly(lactic
15%

++ ,, ++
acid)/starch (60:40) blends containing 15% of various plasticizers as
15 20% representatives.
Elongation(%)

++
++ ,,
3 +
25%

 -,,
00
3  *+ )
10

Ó//
//++
 -,,
00
3 11
 *+ ÕÕ
) /
*
CONCLUSIONS
5 AC, TC, and PEG reduced the thermal transition

0 Ó++
00
AC
,,
-3 .*
11 ŠŠ--
2+
 0)
ÕÕ
TC
/*
 PEG PPG Glycerol Sorbitol
temperatures (Tg, Tc, Tm) of extruded PLA/starch blends.
Glycerol reduced the Tc and Tm but had no effect on Tg. PPG
had no effect on any of these transition temperatures. The Tc1
of PLA increased slightly when sorbitol content increased
from 5% to 15%, and then leveled off. PEG, TC, and AC can

Õ 00
44 Š 33
1600 enhance the PLA crystallization, and the degree of
5% 10% 15%
enhancement was: PEG > TC > AC. Glycerol also enhanced

ÔÔ
1400 (C) 20% 25%
the crystallization of PLA to some degree by plasticizing the

ÔÔ Ò Õ
0 Š
1 33
,
1200 starch. However, PPG and sorbitol had no effect on

ÔÔ 1 Ò Õ
0 Š
1
 33
/,
1000 crystallization. SEM showed that the granular state of the
Modulus (MPa)

starch in the extruded and molded blends was not affected by

ÔÔ Ž
1 Ö 2
Ò 
Õ
0 Š
1
 33
-
/,
800
AC, TC, PEG, and PPG, but it was destructurized by glycerol

ÔÔŽ1

Ö 2
/ Ò 
Õ*
0 Š+33
1 -,
/
600 and sorbitol. Starch was plasticized and became continuous
phase at 15% to 25% glycerol or 25% sorbitol content.

ÔÔ
ÔÔŽ1Ž1’ Ö(
Ö
’


/ (
Ò
2
Ò)
)0
Õ
Õ*
Š
1

Š+
33
-
/
-,
400
Tensile strength and Young’s Modulus of the extruded and

/


2
 
0*
1+33
/,
200
0 elongation of the blends increased as concentrations of AC,
AC TC PEG PPG
Figure 6. Tensile strength (A), elongation (B), modulus (C) of extruded
and molded poly(lactic acid)/starch (60:40) blends as affected by
plasticizers at various concentrations.
interact mainly with PLA) increased the mobility of PLA
molecules, the modulus of the extruded and molded blends
decreased as their contents increased (fig. 6C). This was
related to the reduction in tensile strength and increase in
elongation. Similarly, the modulus of the blends decreased as
glycerol contents increased, but it increased as the sorbitol
content increased. Figure 7 shows typical tensile curves of
selected samples of the extruded and molded blends
containing different plasticizers at 15%. The curves indicate
that the blends containing sorbitol and glycerol at 15% were
brittle, while those containing AC, TC, and PEG were
ductile. The curve for the blend containing PPG indicates that
it was also ductile, but a yield point is evident.
molded PLA/starch blends were reduced greatly, and
Glycerol Sorbitol TC, PEG, and PPG increased. A similar effect was observed
for the blends containing glycerol, although it was
immiscible with PLA. However, the blend containing
sorbitol showed increases in tensile strength and Young’s
Modulus and a decrease in elongation as the concentration
increased.
REFERENCES
Arvanitoyannis, I., A. Nakayama, and S. Aiba. 1998. Edible films
made from hydroxypropyl starch and gelatin and plasticized by
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Engelberg, I., and J. Kohn. 1991. Physico–mechanical properties of
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Gachter, R., and H. Muller. 1990. Plastics Additives Handbook. 3rd
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Fisher, E. W., H. J. Sterzel, and G. Wegner. 1973. Investigation of
the structure of solution grown crystals of lactide copolymers by
means of chemical reactions. Kolloid–Z. U. Z. Polymer 251:
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Ke, T., and X. S. Sun. 2000. Properties of poly(lactic acid)/starch
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Labrecque, L. V., R. A. Kumar, V. Dave, R. A. Gross, and S. P.
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953
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