Properties of Biodegradable Thermoplastic Cassava
Starch/Sodium Alginate Composites Prepared From
Injection Molding
Chayapa Weerapoprasit,1 Jutarat Prachayawarakorn1,2
1
Department of Chemistry, Faculty of Science, King Mongkut’s Institute of Technology Ladkrabang,
Ladkrabang, Bangkok 10520, Thailand
2
Advanced Materials Research Unit, Faculty of Science, King Mongkut’s Institute of Technology Ladkrabang,
Ladkrabang, Bangkok 10520, Thailand
Due to poor mechanical properties and high water
uptake of biodegradable thermoplastic starch (TPS), in
this study, the influence of sodium alginate on properties
of biopolymer based on thermoplastic cassava starch
(TPCS) was investigated. The TPCS polymer was com-
pounded and shaped using an internal mixer and injec-
tion molding machine, respectively. In addition, the TPCS
polymer was, then, modified by different contents of
sodium alginate, i.e., 0, 10, 20, and 30 wt%. It was found
that the TPCS composites showed good phase compati-
bility between the starch and sodium alginate. In addi-
tion, maximum stress, Young’s modulus, and hardness
of the TPCS composites significantly increased by the
addition of sodium alginate. Furthermore, the TPCS
composites modified by sodium alginate degraded faster
than the neat polymer. Moreover, Fourier transform infra-
red spectroscopy and thermogravimetric analysis (TGA)
were used to characterize the TPCS composites. POLYM.
COMPOS., 37:3365–3372, 2016. V
C 2015 Society of Plastics
Engineers
INTRODUCTION
In recent years, the research and development on bio-
degradable polymers has been accelerated. Biodegradable
polymers are capable of biodegradation in certain envi-
ronments. Among the biopolymers investigated as poten-
tial alternative raw material for plastics, starch is one of
the interesting materials due to its availability from
renewable resources, low price, and total biodegradability.
Starch can be mixed with plasticizers—such as, glycerol,
water, sorbitol and others—under the action of high tem-
perature, pressure, and shear force. With this process, a
Correspondence to: J. Prachayawarakorn; e-mail: ksjutara@kmitl.ac.th
Contract grant sponsor: KMITL Research Fund.
DOI 10.1002/pc.23534
Published online in Wiley Online Library (wileyonlinelibrary.com).
C 2015 Society of Plastics Engineers
V chemical compound of sodium alginate is the sodium salt
POLYMER COMPOSITES—2016
conversion of the molecular structure to thermoplastic
starch (TPS) is obtained [1–16]. Several types of starch
have been used to produce TPS polymer such as wheat
starch [2], corn starch [3, 5, 7], maize starch [4, 6], cas-
sava starch [8], rice starch [13], and so on. However, TPS
still has disadvantages when compared to most plastics
currently in use, i.e., poor mechanical properties, high
water absorption, and limited processability [10–14].
Previous studies have reported that thermoplastic waxy
rice starch (TPWRS) polymer modified by agar and cotton
fibers using compression molding technique showed the
increase of tensile property, water uptake value, and ther-
mal stability [14]. There was another report on thermoplas-
tic cassava starch (TPCS)/low-density polyethylene (LDPE)
polymer blends modified by small content of carrageenan
and cellulose fibers using injection molding technique [15].
It was shown that Young’s modulus of the TPCS/LDPE
blends modified by carrageenan increased significantly and
percentage crystallinity of all the blends appeared to be
similar [15]. Sodium alginate/potato starch casted films
were reported to be compatible but thermal stability of the
films was found to be reduced with the increase of the
starch content [16]. Furthermore, a decrease in the elastic
properties and an increase in impact resistance of the
extruded thermoplastic corn starch were found when low
amount (1–10 wt%) of alginate was incorporated [17].
Therefore, one interesting approach to improve
mechanical properties of TPS polymer is achieved by the
addition of sodium alginate. Sodium alginate is one of
natural gelling agents based on polysaccharides widely
used in food industries [18]. Sodium alginate is a gum,
extracted from the cell walls of brown algae. This natural
polymer contains random or alternating unit of 1,4-
linked-b-d-mannuronic acid (M) and a-l-guluronic acid
(G) residues arranged in the polymer chains in blocks
[18]. Sodium alginate is a water-soluble polymer and the
 FIG. 1. IR spectra of the TPCS composites modified by different contents of sodium alginate: (a) 0%, (b)
10%, (c) 20%, and (d) 30%.
of alginic acid. Alginic acid represents the structural com-
ponent of intercellular walls, providing both strength and
flexible to the algal tissue [18].
Consequently, the purpose of this article was to study
on the properties of biodegradable polymer based on
TPCS using injection molding technique, typical process
for synthetic thermoplastic polymers. The TPCS polymer
was, then, modified by different contents of sodium algi-
nate, i.e., 0, 10, 20, and 30 wt%. It was expected that
properties of the TPCS polymer would be improved by
good phase compatibility due to the chemical structural
similarity of polysaccharides of the starch and the sodium
alginate. The effect of sodium alginate contents on
mechanical properties determined from tensile testing was
studied. In addition, different TPCS polymers were exam-
ined for water absorption, melt flow index (MFI), mor-
phology by Scanning Electron Microscopy (SEM)
techniques, functional group analysis by Fourier transform
infrared spectroscopy (FT-IR), and also biodegradable
properties by soil buried test.
EXPERIMENTAL
Materials
Cassava starch (11.5–13.0% moisture) was obtained
from Chaopraya Phuchrai 2999 Co., Ltd. (Kamphaeng-
phet, Thailand). The starch contained approximately
20 6 1 wt% amylose and 75 6 1 wt% amylopectin. Glyc-
erol (plasticizer) was obtained from Lab System Co., Ltd.
(Bangkok, Thailand). Sodium alginate (Food grade) was
obtained from Ruam Chemie 1986, Co. Ltd. (Bangkok,
Thailand). LDPE (DNDV-0405 R) with MFI of 28 g/10
3366 POLYMER COMPOSITES—2016
min. was obtained from Global Connections Public Co.,
Ltd. (Samuthprakarn, Thailand) and maleic anhydride-
grafted-polyethylene (MAPE, MB100D) compatibilizer
with the MFI of 2.0 g/10 min were purchased from
Chemical Innovation, Co., Ltd. (Bangkok, Thailand).
Sample Preparation
Cassava starch and glycerol were premixed in a closed
container and kept overnight. The weight ratio of cassava
starch and glycerol was maintained at 70:30. The TPCS
polymer was first compounded with LDPE, assisting for
flowability in the injection molding machine, and the
weight ratio of the TPCS and LDPE was kept at 70:30.
The MAPE compatibilizer content was maintained at 5%
by weight of the LDPE in order to promote phase com-
patibility. The TPCS polymer was compounded using an
internal mixer at the temperature of 1408C at the rotor
speed of 40 rpm for 12 min, in order to obtain a homoge-
neous material and the specimens were shaped by injec-
tion molding technique using the injection pressure,
injection flow speed, and injection temperature of approx-
imately 30 bar, 50 rpm, and 150–1708C, respectively. The
property modification of the TPCS polymer was carried
using different contents of sodium alginate, i.e., 0, 10, 20,
and 30% by weight of the TPCS polymer.
FTIR Spectroscopic Study
FTIR spectrum in transmission mode of a sample was
recorded on a Spectrum 2000 GX spectrometer (Perkin
Elmer, USA) using KBr disk technique with a resolution
DOI 10.1002/pc
 FIG. 2. SEM micrographs of fracture surfaces of different the TPCS composites modified by different
contents of sodium alginate (a) 0%, (b) 10%, (c) 20%, and (d) 30%. [Color figure can be viewed at
wileyonlinelibrary.com]

of 4 cm21 in a spectral range of 4,000–400 cm21 using
16 scans per sample.
Morphology Evaluation
A JEOL-6400 scanning electron microscope (Tokyo,
Japan) was employed to study the morphology of a sam-
ple. Each tested sample was sputter-coated with a thin
layer of gold to prevent electrical charge during observa-
tion and a sample was immersed into liquid nitrogen
before being fractured.
weight of 21.6 N. The extruded molten polymer was
weighted after 10 min of testing. The MFI value was
reported as grams in 10 min. Three measurements were
made for each sample.
Mechanical Property Evaluation
Mechanical tests were conducted according to ASTM
D-638 at the temperature of 23 6 18C and relative humid-
ity of 60 6 5%. A mechanical measurement of each

Melt Flow Index

MFI measurement of a sample was obtained using a
Ceast 6814 melt flow indexer (Turin, Italy), according to
ASTM D-1238. A sample was molten in the melt flow
indexer using the temperature of 1908C and the constant

TABLE 1. Melt-flow index values of different TPCS composites.

Samples MFI (g/10 min)

TPCS 6.3 6 0.3

TPCS 1 10% sodium alginate 5.2 6 0.2
TPCS 1 20% sodium alginate 4.9 6 0.2
TPCS 1 30% sodium alginate 4.0 6 0.3
FIG. 3. The stress–strain curves of different TPCS composites.

DOI 10.1002/pc POLYMER COMPOSITES—2016 3367

 FIG. 4. Mechanical properties of the TPCS composites modified by different contents of sodium alginate:
(a) stress at max load and Young’s modulus and (b) strain at max load and hardness.
dumbbell-shaped specimen was carried out using a Uni-
versal Testing Machine (Lloyd Instrument, LR 5K, West
Sussex, UK) with a 100 N load cell and the crosshead
speed was maintained at 40 mm/min. It should be noted
that the mechanical property results were obtained by
averaging the measurement results of 10 independent
specimens. In addition, hardness test was conducted
according to ASTM D-2240 using Shore D hardness
durometer. The hardness values were recorded from 10
different measurements for each sample.
Water Absorption
Water absorption test was carried out according to
ASTM D-570. A sample was first dried at 1058C for 2 h
and then immersed in distilled water. The amount of
water absorbed by a sample was determined for 30 days.
The percentage of water absorption was calculated as
followed:
FIG. 5. The relationship between water absorption and immersion time
of different TPCS composites.
3368 POLYMER COMPOSITES—2016
Water absorption ¼ ðW2 2W1 Þ=W1 3 100 (1)
where W2 and W1 are the wet weight and dried weights
of a sample, respectively.
Thermal Properties
Thermogravimetric (TG) and derivative thermogravi-
metric (DTG) thermograms of samples were recorded by
a TG analyzer (Perkin Elmer, Pyris 1, Massachusetts,
USA). A sample was tested under nitrogen atmosphere
within a temperature range of 50–6008C at a heating rate
of 108C/min. Thermal degradation temperature (Td) was
reported by the maximum degradation temperature where
the weight loss occur at the maximum rate.
Mechanical Properties Changes After Biodegradation in
Soil
A dumbbell sample was buried at approximately 10 cm
under the soil surface. The water content of the soil was main-
tained in the range of 30–40%. The test was conducted for 3
months and the samples were taken at 1, 2, and 3 months to be
analyzed. After that, the tensile test of a soil-buried sample
was conducted in comparison with an original sample.
RESULTS AND DISCUSSION
IR Spectroscopic Study
An FTIR spectrum of the TPCS polymer is shown in
Fig. 1a. The polymer showed the main peak at 3,500–
3,300 cm21, attributed to OAH stretching from the TPCS
polymer and sodium alginate. The peaks at 3,000–
2,800 cm21 were assigned to CAH asymmetric stretching
of ACH2A from TPCS, LDPE, and MAPE. The wave-
number in the range of 1,636–1,641 cm21 was attributed
to bounded water presented in starch and also to COO2
asymmetric stretching of sodium alginate. The band at
DOI 10.1002/pc
 FIG. 6. (a) TG and (b) DTG thermograms of different TPCS composites with the addition of different con-
tents of sodium alginate.
1,465 cm21 was the characteristic of ACAH bending of
ACH2A of LDPE. The absorption bands in the range of
1,300–1,000 cm21 and 1,200–1,000 cm21 were assigned
to CAOAC stretching and CAOAH bending of TPCS,
respectively [19].
Figure 1 shows the FTIR spectra of the different TPCS
composites incorporated by sodium alginate. It was found
that most IR peak positions were similar to the nonmodi-
fied TPCS polymer (Fig. 1a) and no distinct new peak
position was noticed. This was due to the similar chemi-
cal structures of the sodium alginate which was also
based on polysaccharide and the main functional group of
sodium alginate is also hydroxyl groups, leading to the
overlapped peak positions.
It should be noted that the peaks at 3,500–3,300 cm21
which was assigned due to OAH stretching region shifted
to lower wavenumber. The change demonstrated a strong
evidence of the new intermolecular interaction of hydro-
gen bonds between the hydroxyl group of the TPCS poly-
mer and sodium alginate. Similar observation was also
reported for the shift of the IR peak position and claimed
to be due to hydrogen bonding existed between two com-
patibility polymers [13–15, 20–22].
Morphology
SEM micrographs of different TPCS composites were
presented in Fig. 2. The TPCS polymer (Fig. 2a) showed
TABLE 2. Degradation temperatures of different TPCS composites
obtained from TG and DTG thermograms.
Degradation temperatures (8C)
Sodium alginate
contents (%) Step 1 Step 2
0 203.2 308.8
10 212.4 269.3
20 206.1 262.0
30 201.1 259.4
DOI 10.1002/pc
rough surface due to the different morphologies between
the hydrophilic TPCS matrix phase and the hydrophobic
LDPE dispersed phase and small voids between interfa-
cial boundaries were also noticed. However, when sodium
alginate content increased (Figs. 2b–d), smoother surface,
better phase compatibility, and the reduction of voids
were obtained due to the similarity of the chemical struc-
tures between the TPCS polymer and sodium alginate.
Melt Flow Index
MFI value was an indirect measurement of polymer vis-
cosity. The MFI values of TPCS composites modified by
different contents of sodium alginate were shown in Table
1. It was found that the increase in sodium alginate content
led to the slight decrease of MFI, possibly due to the thick-
ening characteristic of the sodium alginate [18]. The results
indicated that the incorporation of sodium alginate into the
TPCS composites caused the small increase in the viscosity
of the blends; or in other words, the slight decrease in
flowability. The results were consistent with the previous
report for the acid hydrolyzed hydroxypropylated pea
starch (HPPS)/j-carrageenan (jC) cast films [23].
Mechanical Properties
Figure 3 showed the typical stress–strain curves
obtained for different TPCS composites. A significant
increase in the maximum stress together with decrease in
the strain was observed when sodium alginate content
increased from 0 to 30 wt%. The effect of sodium algi-
nate contents on the mechanical properties of the TPCS
composites are shown in Fig. 4. It can be seen in Fig. 4a
Step 3 that the TPCS composites modified by sodium alginate
presented higher maximum stress, Young’s modulus, and
443.5 hardness than those of the neat TPCS polymer. On the
440.4
contrary, the strain at maximum load (Fig. 4b) was signif-
447.5
463.9 icantly dropped when sodium alginate was added into the
TPCS polymer. Furthermore, it should be noted that the
POLYMER COMPOSITES—2016 3369
 FIG. 7. Mechanical properties of the different sodium alginate-modified TPCS composites after buried in
soil for 0, 1, 2, and 3 months.
relationship between the maximum stress, Young’s modu-
lus, and hardness of the TPCS composites and sodium
alginate contents appeared to be linear.
The rise in the maximum stress, Young’s modulus,
and hardness could be due to the similar chemical struc-
tures of starch and sodium alginate, leading to good com-
patibility between the different phases (Fig. 2). Besides,
the mechanical property results were also consistent with
the shift of the IR peak position (Fig. 1) including the
MFI values (Table 1). The results indicate that the incor-
poration of sodium alginate into the TPCS composite pos-
sibly increased the difficulty of the mobility of the
polymer chains and leading to harder and more rigid
polymer. Similar mechanical property results were
reported for the extruded TPS modified with 1–10 wt%
sodium alginate [17], the compressed TPWRS modified
by agar [14], and the HPPS/jC casted films [23].
Water Absorption
The result of percentage water absorption of different
TPCS composites performed at the temperature of
3370 POLYMER COMPOSITES—2016
30 6 28C is shown in Fig. 5. It was found that percentage
water absorption of the neat TPCS polymer tended to
increase slowly when the water immersion time increased
and reached its maximum within 20 days. Moreover, the
percentage water absorption of different TPCS composites
rapidly increased with the addition of sodium alginate
during the 5 days of testing. After that, the percentage
water uptake tended to decrease.
When considered on the increasing of sodium alginate
contents, it is interesting to note that water absorption of
the TPCS composites decreased. It was found that the
maximum percentage water absorption was observed for
the TPCS composite with 10 wt% sodium alginate con-
tent. Additionally, the percentage water absorption of the
TPCS composite modified by 30 wt% sodium alginate
was the lowest and apparently lower than 10 and 20 wt%
sodium alginate. Nevertheless, the percentage water
absorption of the TPCS composite modified by 30 wt%
sodium alginate determined at days 5 and 10 was higher
than the neat TPCS polymer because, in general, sodium
alginate shows more the hydrophilic property than cas-
sava starch [18]. It should be noted that the percentage
DOI 10.1002/pc
water absorption of the TPCS composite modified by 30
wt% sodium alginate was lower than the neat TPCS poly-
mer determined at days 20 and 30. This could possibly be
due to the most homogeneous morphology, observed for
the 30 wt% sodium alginate-modified TPCS composite
(Fig. 2d). Similar results for the increase of water absorp-
tion were reported for TPS polymers modified by other
gelling agents such as agar [14] or carrageenan [15].
Thermal Properties
TG and DTG thermograms of different TPCS compo-
sites were examined using TG technique and are shown
in Fig. 6 and Table 2. Thermal transitions were scanned
from temperature 50 to 6008C. The first maximum degra-
dation temperature of different TPCS composites was
found from 201 to 2128C, arisen from the decomposition
temperature of glycerol [24]. The second step found from
260 to 3088C was due to the decomposition temperatures
of cassava starch [24] and also of the sodium alginate
[16]. The two components showed the same in second-
step thermal transitions due to the similar chemical struc-
tures of starch and sodium alginate, which represented the
compatible blends from the combination of two compo-
nents. Finally, the LDPE component also showed a ther-
mal transition at 443 to 4648C as the third step in the
thermograms.
When the sodium alginate contents in the TPCS com-
posites were increased from 0 to 30%, it was observed
that the maximum degradation temperatures in the second
step tended to decrease. This could be due to the lower
decomposition temperature of sodium alginate compared
to starch [16].
Mechanical Properties Changes After Biodegradation in
Soil
Mechanical properties of different TPCS composites
after biodegradation in soil for 0, 1, 2, and 3 months
were carried out in order to determine biodegradability
(Fig. 7). It was found from Fig. 7 that the maximum
stress, Young’s modulus, and strain at maximum load of
different TPCS composites clearly decreased after the
biodegradation test. This was because the TPCS compo-
sites could absorb water from the soil, leading to the deg-
radation by hydrolysis. After that, the TPCS composites
continued to degrade by microorganisms existed in soil
[25]. The decrease of the strength and elasticity of differ-
ent sodium alginate-modified TPCS composites was
related to the water absorption behavior (Fig. 5). More-
over, a significant drop of the maximum stress, Young’s
modulus, and strain at maximum load was more obvious
(Fig. 7) after 3 months of the soil burial test. The result
implies that the sodium alginate could accelerate the deg-
radation of different TPCS composites. The degradation
result was similar to the disintegration for the plasticized
PLA–PHB blends [26].
DOI 10.1002/pc
CONCLUSIONS
The biodegradable composites based on TPCS polymer
were prepared using internal mixing and shaped by injec-
tion molding technique. It was found that the IR peak in
the region of OAH stretching shifted to lower wavenum-
ber for different TPCS composites modified by sodium
alginate, presenting the new hydrogen bond formation.
Moreover, water absorption of the TPCS composites
slightly decreased by the increasing sodium alginate con-
tents. For morphology, the sodium alginate was well com-
patible with the TPCS matrix. In addition, the mechanical
properties of different TPCS composites modified by
sodium alginate were significantly greater than the neat
TPCS polymer. Besides, sodium alginate clearly acceler-
ated the biodegradation of the TPCS composites. From
this study, the highest overall mechanical properties and
lowest water absorption were obtained from the TPCS
composite modified by 30 wt% of sodium alginate.
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3372 POLYMER COMPOSITES—2016 DOI 10.1002/pc