Journal of Wuhan University of Technology-Mater. Sci. Ed. www.jwutms.net Apr.

2015 423

DOI 10.1007/s11595-015-1164-z

Thermoplastic Starch Prepared with Different Plasticizers:

Relation between Degree of Plasticization and Properties

ZUO Yingfeng, GU Jiyou, TAN Haiyan, ZHANG Yanhua*

(Key Laboratory of Bio-based Material Science and Technology (Ministry of Education),
Northeast Forestry University, Harbin 150040, China)

Abstract: Ethylene glycol, glycerol, sorbitol, formamide, and urea were used as plasticizers for the
preparation of thermoplastic starch (TPS) from corn starch. The properties of TPS were tested by analysis
method. The results showed that TPSs were more highly plasticized with amines than alcohols. For the same
type of plasticizer, the degree of plasticization decreased as the molecular weight of plasticizer increased. The
relationship between plasticization degree and TPS properties was characterized and described by mechanical
properties and water absorption. The experimental results showed that when the degree of plasticization
increased, the tensile strength decreased and the elongation at breakage and water absorption increased.
Key words: corn starch; plasticizer; thermoplastics; degree of plasticization; properties

1 Introduction of handling[2]. However, starch itself is unfavorable

The continued success of the traditional plastics
industry is facing two major challenges. One is the
petroleum resources shortage, which will directly
affect the supply of raw materials, cost, and production
capacity of plastic products. The second challenge is a
lack of biodegradability of plastics, which, due to the
large size of polymer molecules and the stability of
the carbon-hydrogen bond, are difficult to decompose
by organisms[1]. In light of the increased awareness of
the need to preserve the natural environment, efforts
have been made to develop biodegradable plastics
that are made from renewable resources. Among the
biopolymers investigated as potential alternative raw
materials for plastics, starch has drawn a great deal
of attention. The appeal of starch comes from its
biodegradability, renewable sources, low cost, and ease
©Wuhan University of Technology and SpringerVerlag Berlin Heidelberg 2015
(Received: Feb. 4, 2014; Accepted: Apr. 27, 2014)
ZUO Yingfeng (左迎峰): Ph D Candidate; E-mail: zuoyf1986@163.com
*Corresponding author: ZHANG Yanhua (张彦华): Assoc.
Prof.; Ph D; E-mail: zyhnefu@163.com
Funded by the Fundamental Research Funds for the Central
Universities (DL13CB13), the China Postdoctoral Science
Foundation Funded Project (No.2014M550178), and the National
Natural Science Foundation of China (No. 31200442)
in terms of process ability, dimensional stability, and
mechanical properties for its end products. Therefore,
native starch cannot be used directly as a plastics
material[3].
Starch plastics processing technology is one
of the most important issues in starch processing
production. In order to plasticize starch, adding an
appropriate amount of plasticizer is a commonly
used method. Plasticizers are commonly used to
increase film flexibility by reduction of intramolecular
hydrogen bonding along polymer chains thereby
increasing the intermolecular spacing[4]. This results
in increased molecular mobility, lowers the glass
transition temperature, and decreases the degree
of crystallinity [5]. Commonly used plasticizers are
hydrophilic low molecular weight compounds, such
as polyols[6,7] and amines[8,9]. Thermoplastic starches
(TPSs) plasticized by polyols are thought to show
some recrystallization of starch after being stored for
a period of time, which tends to embrittle the TPSs[10].
In contrast, amine plasticizers can inhibit starch
recrystallization because of the stronger hydrogen
bond interaction between amide groups and starch[11].
Ogawa[12] found that guanidine hydrochloride, urea,
and thiourea can promote starch gelling, and inhibit
starch retrogradation. However, such solids often have
424 Vol.30 No.2 ZUO Yingfeng et al: Thermoplastic Starch Prepared with Different Plastici...
little internal flexibility; urea-plasticized TPSs tend to
become rigid and brittle[13].
In this study, several polyols such as ethylene
glycol, glycerol, and sorbitol, and amines such as
formamide and urea were used as plasticizers to
plasticize corn starch, and the effects of the different
plasticizers on the degree of plasticization of corn
starch were examined. The mechanical properties and
water absorption of the TPSs were tested to study the
relationship between the degree of plasticization and
properties of the TPS. The findings will provide some
significant guidance for the preparation and use of
TPSs.
2 Experimental
2.1 Materials
Corn starch was obtained from Dacheng Corn
Development (Changchun, Jilin, China). Ethylene
glycol, glycerol, sorbitol, formamide, and urea
(analytical grade) were purchased from Tianjin
Hengxing Chemical Preparation (Tianjin, China).
2.2 Preparation of thermoplastic starch
Different TPSs were prepared by a melt extrusion
process with different plasticizers: ethylene glycol,
glycerol, sorbitol, formamide, or urea. The ratio of
plasticizer to corn starch was 30:100 (w/w). Plasticizer
and corn starch were blended uniformly and then stored
for 18 h. The plasticized starch was manually fed into a
single-screw plastic extruder [SJ-25(s), Harbin Special
Plastic Products, Harbin, China; screw ratio l/d = 25:1]
with a screw speed of 15 r/min. The temperature profile
of the extruder barrel from the feed zone to the die was
100, 110, 120, and 90 ℃. The die was a rectangular
sheet with one hole of 2 mm× 3 mm. The extruded
samples were conditioned in sealed polyethylene bags
to maintain stable moisture content.
Starch powders plasticized with ethylene glycol;
glycerol, sorbitol, formamide, and urea were labeled
as EPS, GPS, SPS, FPS, and UPS, respectively. The
corresponding TPS samples were labeled as EPTPS,
GPTPS, SPTPS, FPTPS, and UPTPS, respectively.
2.3 Testing and analyses
2.3.1 Differential scanning calorimetry (DSC)
The gelatinization properties of plasticized starch
powder and the degree of plasticization of TPS were
determined by differential scanning calorimetry (DSC;
D204, NETZSCH). The instrument was calibrated using
pure indium (melting point 156.4 ℃). The samples
(about 5 mg) were hermetically sealed in aluminum
sample pans using an inverted lid configuration. The
samples were heated from 30 to 170 ℃ at a rate of 5
℃/min. An empty sample pan was used as a reference.
The DSC cell was flushed with nitrogen at a flow rate
of 30 mL/min to maintain an inert atmosphere.
2.3.2 Scanning electron microscopy (SEM)
The native starch and the fracture surfaces of
extruded thermoplastic starch strips were observed by
scanning electron microscopy (SEM; Quanta 200, FEI),
operating at an acceleration voltage of 20 kV. Native
starch powder was compacted and sputter-coated with
gold for observation. The TPS strip samples were
cooled in liquid nitrogen, and then broken into pieces.
The fracture faces were sputter-coated with gold for
SEM observation.
2.3.3 X-ray diffraction (XRD)
X-ray diffraction (XRD) patterns were obtained
with the plasticized starch powders and TPSs using an
X-ray diffractometer (D/Max-220, Rigaku, Japan) at 40
kV and 30 mA with 0.154 nm CuKα radiation (Ni filter).
The 2θ scan range was 10-40 ° in 0.02 ° increments
with a scan speed of 4 s/step. The corn starch powder
was compacted in the sample groove for testing, while
TPSs were tested directly.
2.3.4 Mechanical properties
The mechanical properties of TPSs, such
as tensile strength and elongation at break, were
evaluated. The mechanical testing (ISO 6239-1986
standard) of specimens was determined in a CMT-5504
Materials Testing Machine (Sans, Shenzhen, China)
at a crosshead speed of 25 mm/min. To promote the
failure of specimens toward the center of the film, they
were cut in a dumbbell shape. The data were averages
of five specimens. The tensile strength (TS, unit: MPa)
was calculated by dividing the peak force with the
cross-sectional area of the sample. The elongation was
obtained by dividing the change in length achieved at
breakage by the original specimen length (0.025 m).
2.3.5 Water absorption
According to National Standard of China
GB1034-98, the bars of samples were cut into small
pieces measuring 10 mm × 10 mm, and the pieces were
vacuum-dried at 50 ℃ for 48 h. The dried pieces were
weighed immediately and then the specimens were
soaked in distilled water at room temperature. After 24
h, the specimens were removed from distilled water,
blotted dry with filter paper, and then weighed again.
Data were recorded as averages of three specimens.
Water absorption of the starch plastic was calculated as
follows:
Journal of Wuhan University of Technology-Mater. Sci. Ed. www.jwutms.net Apr.2015
where, W 2 is the mass of the sample after water
absorption and W1 is the mass of the dry sample.
3 Results and discussion
3.1 DSC analysis
Plasticization of starch can be seen as
gelatinization under the condition of a shearing
action in the presence of a plasticizing agent. DSC
is a common method for determining gelatinization
properties, and when used on starch gelatinization can
also be used to characterize the degree of plasticization
of starch. By comparing the DSC endothermic peak
area, one can study the effect of different plasticizers on
the corn starch gelatinization enthalpy, and the relative
effectiveness of plasticizers during gelatinization of
corn starch powder.
The DSC curves of plasticized starch powder
are shown in Fig.1(a). As is well known, plasticizers
can make starch powders easier to gelatinize, and the
gelatinizing effects of different plasticizers were not
identical. For alcohol plasticizers, the endothermic
peak area was the smallest for EPS and largest for SPS.
This is because ethylene glycol is the smallest of the
alcohols used, has the least number of hydroxyl groups,
and penetrates more effectively into the starch structure
where it can disrupt intermolecular hydrogen bonds,
425
thereby allowing the starch to gelatinize more readily.
Sorbitol has the highest molecular weight of the alcohol
plasticizers, so its capacity to penetrate the starch
structure was the lowest. As a result, plasticization of
SPS was incomplete, leading to a higher gelatinization
enthalpy. In summary, with carbon chain growth,
the gelatinization effect of alcohol plasticizers was
decreased.
For the amine plasticizers, the DSC endothermic
peak area of UPS was much larger than that of FPS,
indicating that formamide was more effective for starch
gelatinization. As for the alcohols, the larger molecular
weight of urea meant that it was less effective than
formamide in penetrating the starch structure, and was
less able to form hydrogen bonds with starch.
After extrusion molding, TPS was submitted
for DSC testing. Comparisons were made of the
endothermic peak area before and after extrusion
for the same plasticizer, and for TPSs prepared with
different plasticizers. The DSC curves of TPSs are
shown in Fig.1(b).
The DSC endothermic peak area of each TPS
decreases more than the corresponding plasticized
starch powder (Table 1). It was because starch obtained
good plasticization after extrusion. For TPSs prepared
with alcohol plasticizers, it still follows that the
endothermic peak area of the TPS increases as the
number of carbon atoms increases. It was also observed
that the degree of plasticization gradually reduced with
increasing number of carbon atoms in the plasticizer.
The trend for amine plasticizers was the same; the
degree of plasticization of FPTPS was greater than that
of UPTPS.
From Fig. 1 and Table 1, it can be observed
that the endothermic peak areas of FPS and FPTPS
were less than that of plasticized starches that used
alcohol plasticizers. This was attributed to the stronger
hydrogen bonding capacity of amine plasticizers over
the alcohols[14], which allowed better plasticization of
the starch. However, urea itself may crystallize in the
starch [15], thus affecting the plasticizing effect.
3.2 SEM analysis
Native starch granules were destroyed and
426 Vol.30 No.2 ZUO Yingfeng et al: Thermoplastic Starch Prepared with Different Plastici...
became a uniform continuous phase after plasticization.
This is a result of the plasticizer penetrating into the
starch granules and forming hydrogen bonds with
starch molecules, thereby weakening the intermolecular
and intramolecular hydrogen bonding within the starch.
Furthermore, with the high shearing and temperature
conditions and the action of the plasticizer, the native
starch granules melted or were physically broken up
into small fragments to form a continuous phase. The
effects of the plasticizer behavior were reflected by the
SEM images.
It was clearly observed in SEM micrographs of
TPSs that the fracture surfaces of alcohol-plasticized
starches were rougher than those plasticized with
amines. This phenomenon showed that the plasticizing
ability of alcohols was lower than that of amines[16].
Once again, this difference was attributed to greater
ability of the amines to form hydrogen bonding within
the starch. In addition, alcohol-plasticized starch tended
to degrade somewhat, resulting in brittle TPSs[17].
Fig.2 SEM images of TPS with different plasticizers
From Figs.2 (a, b, c), it is observed that for
the alcohol-plasticized TPSs, the fracturesurface of
EPTPS was the smoothest and that of SPTPS was the
roughest. This result is a reflection of the high degree
of plasticization of EPTPS and the low plasticization
of SPTPS. When the degree of plasticization was low,
starch microcrystalline was more; TPS showed brittle
facture, so facture surface was coarser. The better the
plasticizing effect, the less the starch crystallite, and
therefore, the more smooth of the surface[18]. Similarly,
Figs.2 (d, e) show that the surface of FPTPS was
smoother than that of UPTPS. This also follows the
higher plasticization of FPTPS than that in UPTPS,
which was attributed to the smaller molecular weight
of formamide allowing better plasticization than urea.
3.3 XRD analysis
XRD was used to examine corn starch plasticized
with different plasticizers, by examining the changes
in crystallinity from native starch to TPS. The XRD
patterns of native starch and TPS are shown in Fig.3.
As can be seen in Fig.3, the XRD peak type and
intensity for native starch change after plasticizing
treatment. The native corn starch granule exhibited the
typical α-type X-ray diffractogram with peaks at 2θ
values near 15°, 18°, and 23°[19]. The crystal type and
degree of crystallinity of corn starch changed according
to the different plasticizers used.
XRD lines of EPTPS and GPTPS showed ν-type
crystallization diffraction peaks produced by amylose,
which was free from broken starch particles during
processing; the most obvious peaks are at 2θ = 13.5°
and 20.8°. At the same time, XRD lines of EPTPS and
GPTPS also showed β-type crystallization diffraction
peaks at 2θ = 17.2°, which was attributed to a double
helix structure looser than α-type crystallization[20]. The
crystallization peaks of SPTPS were similar to those of
native corn starch; only the crystallization peak height
was lower than that of native starch. The crystallite type
of starch was changed by ethylene glycol and glycerol,
but not by sorbitol. This suggested that SPTPS had the
lowest degree of plasticization. Furthermore, the ν-type
and β-type diffraction peak intensities of EPTPS were
lower than those of GPTPS, which suggests that the
degree of plasticization of EPTPS was higher than that
of GPTPS.
The XRD peaks of FPTPS and UPTPS were very
small and the diffraction peak heights were much lower
than for the alcohol-plasticized TPSs. This showed
Journal of Wuhan University of Technology-Mater. Sci. Ed. www.jwutms.net Apr.2015 427

that the degree of crystallinity of the amine-plasticized

corn starch was much lower than that of the alcohol-
plasticized corn starch, which is another reflection
of the higher plasticizing ability of the amines over
the alcohols. The crystallization peak of UPTPS did
not disappear completely, which also suggested the
superior plasticization effect of formamide over urea.
3.4 Mechanical properties analysis
Different plasticizers can change the brittleness
of a native starch film and impart certain degrees
of toughness and strength. The tensile strength and
elongation at breakage of TPSs are shown in Fig.4.
related with the degree of plasticization; the results of
water absorption are shown in Fig.5. As the molecular
chain length increased for the alcohol plasticizers, the
water absorption of the TPSs gradually decreased.
Meanwhile, the water absorption of FPTPS was
higher than that of TPSs prepared with alcohols as the
plasticizer. The relative plasticization effects of the
amine and alcohol plasticizers, and the effect of carbon
chain length had been discussed; water absorption
of the TPSs was found to gradually increase with
the degree of plasticization. This phenomenon was
attributed to the more extensive network of hydrogen
bonding between starch molecules and the plasticizer
at higher degrees of plasticization. After immersion
in water, the hydrogen bonds formed between the
plasticizer and starch were easily disrupted and allowed
the TPS to absorb more water. However, the water
resistance of urea was superior to ethylene glycol and
glycerol, so that the water absorption of UPTPS was
lower than that of EPTPS and GPTPS.

Fig.4 shows that SPTPS had the highest tensile 4 Conclusions

strength, but the lowest elongation at breakage.
The molecular weight and hydrogen-bonding
In contrast, FPTPS had the highest elongation at
ability of plasticizers play important roles in the
breakage and the lowest tensile strength. These results
plasticization of starch in the preparation of TPSs. The
are closely related to the degree of plasticization;
degrees of plasticization of TPSs prepared with amine
amine plasticizers showed better plasticization
plasticizers were greater than those of TPSs plasticized
than the alcohols. With higher plasticization, more
with alcohols. For the same type of plasticizer, the
intramolecular and intermolecular hydrogen bonds
degree of plasticization decreased as the molecular
in the starch structure were destroyed, which results
weight increased. The mechanical properties and water
in low tensile strength and increased elongation at
absorption of TPSs were closely related to the degree
breakage for the TPS. However, urea itself was found
of plasticization. When the degree of plasticization of
to recrystallize in the TPS so that UPTPS became hard
the TPS was increased, tensile strength was decreased,
and brittle. As a result, the tensile strength of UPTPS
but elongation at breakage and water absorption was
was greater than that of EPTPS, but the elongation at
increased. Our results demonstrate that with careful
breakage was smaller than that of EPTPS and GPTPS.
consideration of the relative plasticizing effects of
3.5 Water absorption analysis
different plasticizers in the preparation of TPSs, the
The water absorption of TPS is also closely
overall properties of the product can be finely tuned
428 Vol.30 No.2 ZUO Yingfeng et al: Thermoplastic Starch Prepared with Different Plastici...
toward its intended application.
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