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

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

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
Fig.2 SEM images of TPS with different plasticizers was lower than that of native starch. The crystallite type
of starch was changed by ethylene glycol and glycerol,
From Figs.2 (a, b, c), it is observed that for but not by sorbitol. This suggested that SPTPS had the
the alcohol-plasticized TPSs, the fracturesurface of lowest degree of plasticization. Furthermore, the ν-type
EPTPS was the smoothest and that of SPTPS was the and β-type diffraction peak intensities of EPTPS were
roughest. This result is a reflection of the high degree lower than those of GPTPS, which suggests that the
of plasticization of EPTPS and the low plasticization degree of plasticization of EPTPS was higher than that
of SPTPS. When the degree of plasticization was low, of GPTPS.
starch microcrystalline was more; TPS showed brittle The XRD peaks of FPTPS and UPTPS were very
facture, so facture surface was coarser. The better the small and the diffraction peak heights were much lower
plasticizing effect, the less the starch crystallite, and 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. [10] Van Soest JJG, Knooren N. Influence of Glycerol and Water Content on
the Structure and Properties of Extruded Starch Plastic Sheets during
Aging[J]. J. Appl. Polym. Sci., 1996, 64(7): 1 411-1 422
References
[1] Muscat D, Adhikari B, Adhikari R, et al. Comparative Study of Film [11] Ma XF, Yu JG. Thermoplastic Starch Plasticized by the Mixture of Urea
Forming Behavior of Low and High Amylose Starches Using Glycerol and Formamide[J]. Acta. Polym. Sin., 2004, 4: 483-489
and Xylitol as Plasticizers[J]. J. Food. Eng., 2012, 109(2): 189-201 [12] Ogawa KZ, Aso KJ, Ono S, et al. Effects of the Noncyclic Cyanamides
[2] Zhang Y, Han JH. Plasticization of Pea Starch Films with on the Retrogradation of Waxy Corn Starch[J]. B. Chem. Soc. Jpn.,
Monosaccharides and Polyols[J]. J. Food. Sci., 2006, 71(6): 253-261 2000, 73: 1 283-1 284
[3] Lu DR, Xiao CM, Xu SJ. Starch-based Completely Biodegradable [13] Thomas MS, Richard VG. Amino Acids as Plasticizers for Starch-based
Polymer Materials [J]. J. Polym. Sci. Polym. Lett., 2009, 3(6): 366-375 Plastics[J]. Starch/starke, 1997, 49: 245-249
[4] Janjarasskul T, Krochta JM. Edible Packaging Materials [J]. Annu. Rev. [14] Ma XF. Yu JG. Formamide as the Plasticizer for Thermoplastic
Food. Sci. T., 2010, 1: 415-448 Starch[J]. J. Appl. Polym. Sci., 2004, 93: 1 769-1 773
[5] Guilbert S, Cuq B, Contard N. Recent Innovations in Edible and/or [15] Ma XF, Yu JG, Wan JJ. Urea and Ethanolamine as a Mixed Plasticizer
Biodegradable Packaging Materials [J]. Food. Addit. Contam., 1997, for Thermoplastic Starch [J]. Carbohyd. Polym., 2006, 64: 267-273
14(6-7): 741-751 [16] Van Soest JJG, Vliegenthart JFG. Crystallinity in Starch Plastics:
[6] Laohakunjit N, Noomhorm A. Effect of Plasticizers on Mechanical and Consequences for Material Properties [J]. Trends. Biotechnol., 1997,
Barrier Properties of Rice Starch Film [J]. Starch/Starke, 2004, 56(8): 15: 208-213
348-356 [17] Ma XF, Yu JG. Studies on the Properties of Formamide Plasticized-
[7] Pareta R, Edirisinghe MJ. A Novel Method for the Preparation of Starch Thermoplastic Starch [J]. Acta. Polym. Sin., 2004, 2: 240-245
Films and Coatings[J]. Carbohyd. Polym., 2005, 63(3): 425-431 [18] Yao DM, He HZ. Thermoplastic Starch Plasticized by Mix of Urea and
[8] Shogren RL, Swanson CL, Thompson AR. Extrudates of Cornstarch Glycerol[J]. Chem. Ind. Eng. Prog., 2011, 30(9): 2 018-2 020
with Urea and Glycols: Structure/Mechanical Property Relations[J]. [19] Tung CC, Ku TH, Lin CA. Study of the Plasticizer Effect and
Starch/Starke, 1992, 44(9): 335-338 Characterization on Diverse Pseudo- Thermoplastic Starch
[9] Zheng PW, Chang PR, Yu JG, et al. Formamide and 2-Hydroxy-N- Biodegradable Films[J]. Polym.-Plast. Technol., 2011, 50(3): 320-327
[2-(2-Hydroxy-Propionylamino)-Ethyl] Propionamide (HPEP) as a [20] Thomas AW, Donald AM, Heidelbach F. Analysis of the Native
Mixed Plasticizer for Thermoplastic Starch[J]. Carbohyd. Polym., Structure of Starch Granules with Small Angle X-ray Microfocus
2009, 78(2): 296-301 Scattering[J]. Biopolymers, 1999, 49(1): 91-105