Starch/Strke 2017, 69, 1500366 DOI 10.1002/star.

201500366 1500366 (1 of 11)

RESEARCH ARTICLE

Effect of various plasticizers and concentration on the physical,

thermal, mechanical, and structural properties of
cassava-starch-based films
Ahmed Edhirej 1,2, Salit Mohd Sapuan 1,3, Mohammad Jawaid 3,4 and Nur Ismarrubie Zahari 1

1
Department of Mechanical and Manufacturing Engineering, University Putra Malaysia, Serdang, Selangor, Malaysia
2
Department of Chemical and Material Engineering, Sabha University, Libya
3
Laboratory of Biocomposites Technology, Institute of Tropical Forestry and Forest Products, University Putra Malaysia,
Serdang, Selangor, Malaysia
4
Department of Chemical Engineering, College of Engineering, King Saud University, Riyadh, Saudi Arabia

The present study investigated the effects of plasticizers (fructose, urea, tri-ethylene glycol, and Received: December 17, 2015
triethanolamine) with different concentrations on the physical, thermal, and mechanical Revised: April 14, 2016
properties of cassava-starch-based lms. The lm samples were prepared using casting methods. Accepted: April 14, 2016
The moisture content, water solubility, and water absorption of the lms increased with
increasing plasticizer content. Fructose-plasticized lms show excellent water resistance
compared to other plasticizers. Film plasticized with 30% fructose showed the highest density
(1.74 g/cm3), but the lowest water content (10.96%) and water absorption (110%). Films
containing fructose presented smooth surfaces without pores. The glass transition temperatures
of the plasticized lm also decreased with increased plasticizer content, irrespective of the
plasticizer type. The relative crystallinity decreased with increasing plasticizer content. The lm
plasticized by 30% fructose presented higher relative crystallinity (0.31). The increase of
plasticizer concentration resulted in a decrease of tensile strength, but increased elongation at
break of the lm samples. Film plasticized with 30% fructose showed the highest tensile strength
(4.7 MPa) and tensile modulus (69 MPa). Thus, fructose was the most efcient plasticizer agent
among the various plasticizers used in this study. High contents of plasticizer resulted in changes
in the properties of the lms. Overall, it can be concluded that the plasticizer type and
concentration signicantly inuence the properties of cassava-starch-based lm.

Keywords:
Cassava film / Mechanical properties / Physical properties / Plasticizers / Thermal
properties

1 Introduction biodegradable materials, which are suitable for packaging. In

The increase in non-biodegradable waste material and the
difculty in recycling most of the available synthetic packaging
have been pushing researchers toward the development of new
Correspondence: Prof. S. M. Sapuan, Department of Mechanical
and Manufacturing Engineering, University Putra Malaysia, 43400
UPM Serdang, Selangor, Malaysia
E-mail: sapuan@upm.edu.my
Fax: 603-86567122
Abbreviations: F, fructose; RH, relative humidity; TEA,
triethanolamine; TEG, tri-ethylene glycol; U, urea; WC, water
content; WS, water solubility.
this regard, the production of edible lms plays an important
role in food preservation [13].
Among the natural polymers, starch has been considered
as one of the most promising environmentally friendly
materials due to its low cost, easy availability, and
biodegradability. However, starch-based materials are known
to be brittle with poor mechanical properties. Thus, the
incorporation of a plasticizer is required to overcome the
brittleness of these materials. The principle function of
plasticizers is to reduce intermolecular forces and increase
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1500366 (2 of 11) A. Edhirej et al.
the mobility of polymer chains, which help to decrease the
glass transition temperature (Tg) of plasticized starch
materials as well as improve their exibility [4, 5].
Recently, many studies have focused on the use of
glycerol [69], urea [10, 11], sorbitol [12, 13], fructose,
glucose and sucrose [14, 15], xylitol [16] as well as tri-
ethylene glycol, and tri-ethanolamine [11, 17] as plasticizers
of edible and/or biodegradable lms. The role of plasti-
cizers is to enhance the exibility of starch by reducing the
strong intermolecular interactions between the starch
molecules. As a result, the mobility of polymeric chains
increases, which improves the exibility, extensibility, and
ductility of plasticized lms [18, 19]. The addition of
plasticizers to starch lms helps to decrease their inherent
brittleness by reducing intermolecular forces, increasing
the mobility of polymer chains, decreasing the glass
transition temperature of these materials and improving
their exibility. The plasticizers must be compatible with
the lm-forming polymers. Hydrophilic compounds, such
as polyols (glycerol and sorbitol), are commonly used in
starch lm, but sugars, amino acids, and fatty acids could
also be employed [15, 20].
The aim of this study was to study the effect of various
plasticizers and their concentration on the physical, thermal,
tensile, and structural properties of thermoplastic cassava
starch lm. The lms were prepared using cassava starch
and Fructose (F), Urea (U), Tri-ethylene glycol (TEG) and
Triethanolamine (TEA) as plasticizers with different concen-
tration. The aim was also to optimize the most efcient
plasticizer type and concentration among these plasticizers.
2 Materials and methods
2.1 Materials
Native cassava starch was extracted from cassava tubers
following the method used by Akpa et al. [21]. The chemical
composition of dry matter starch was studied according to
the methods described by Versino and Garca [8]. The cassava
starch contains 0.31 g/100 g ash, 0.555 g/100 g crude protein,
86.47 g/100 g carbohydrate, and 0.24% lipid. The amylose
content of total starch was determined from the native starch
by using enzymatic method. The amylose content of cassava
starch was determined by standard methods as described in
previous work [22]. The amylose content was 16.6% and the
rest of the starch sample was amylopectin with 83.4%. The
cassava starch granules were rounded and oval-shaped and
the majority were between 5 and 30 mm with 93%. The
moisture content of starch was 14.25% and the density was
1.48 g/cm3. Fructose (345700), urea (184600), tri-ethylene
glycol (934720), and tri-ethanolamine (660400) were
supplied by LGC Scientic SDN-BHD, Malaysia, and were
used as plasticizers.
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Starch/Strke 2017, 69, 1500366
2.2 Film preparation and characterization
Films were prepared by the casting technique using a lm-
forming solution containing 5 g of cassava starch/100 mL
distilled water. F, U, TEG, and TEA were used as plasticizers,
at concentrations of 0.30, 0.45, and 0.60 g/g dry starch. The
mixture was heated to 80C in a thermal bath and kept at this
temperature for 20 min under constant stirring. Thereafter,
the mixture was poured homogeneously onto a circular plate
of 10 cm diameter. The plates were then dried at 45C in an
oven with air circulation. The dry lms were removed from
the plates and stored at ambient conditions (around 25C and
60% of relative humidity) in a plastic bag for a week before
characterization.
2.3 Physical properties
2.3.1 Film thickness
The lm thicknesses were determined according to the
method of Lu et al. [23], using a digital micrometer
(Mitutoyo-Co, Japan); ve random measurements were
performed for each lm and an average value was calculated.
2.3.2 Film density
For the square samples of the lms (20 mm  20 mm), the
lm density was determined directly from the lm weight
and dimensions (volume) and the values considered were the
average of ten determinations. The lm density was
calculated by dividing the lm weight by the lm volume
following Eq. (1), where the lm volume was calculated by
multiplying the lm area by the thickness [24].
m
r g=cm3 1
v
where r density; m mass; and v volume.
2.3.3 Water content (WC)
WC was determined through the weight loss. Film samples
were weighed (w1), dried at 90C for 24 h, and weighed (w2)
again. WC was determined as the percentage of the initial
lm weight lost during drying and reported on a wet basis
according to Eq. (2). The temperature was chosen to avoid
loss of plasticizer.
w1  w2
WC%  100 2
w1
where WC water content; w1 initial weight; and w2
nal weight.
2.3.4 Water solubility (WS)
The WS of the lms was performed in triplicate and
measured following the method of Shojaee et al. The lm
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Starch/Strke 2017, 69, 1500366
samples were dried at 90C for 24 h in a laboratory oven and
then weighed to determine the initial solid content. The
temperature was chosen to avoid loss of plasticizer [6]. Pre-
weighed lm samples (1  3 cm2) were immersed under
constant agitation in 50 mL of distilled water for 6 h at 25C.
After that period, the remaining pieces of the lms were
ltered and dried at 90C to constant weight (nal dry
weight). The WS (%) of the lm was calculated according to
Eq. (3) [25]
wi  wf
WS%  100 3 operated at a generator voltage of 40 kV, a current of
wi
where WS water solubility: wi initial dry weight and
wf nal dry weight.
2.3.5 Water absorption (WA)
The WA test was performed in accordance with ASTM
D-57098, where the lm samples were rst dried for 24 h at
50C, cooled in a desiccator and immediately weighed, and
then soaked in distilled water at room temperature. After a
specic immersion period, the samples were removed from
the water, gently wiped with a dry cloth to remove all surface
water and then weighed. The differences in the initial and
nal masses of the samples were calculated using Eq. (4).
Water absorption % Mfinal  Minitial =Minitial   100 4
2.4 Thermal properties
2.4.1 Differential scanning calorimetry (DSC)
A DSC test was conducted in a differential scanning
calorimeter after heating the sample from room temperature
to 280C at 10C/min. About 10 mm2 of lm was conditioned
at 25C and 60% RH. The following factors were obtained
through these thermo-grams: the onset temperature (To) and
the peak temperature (Tp).
2.4.2 Thermal gravimetric analyzer (TGA)
TGA was conducted using 10 mm2 of the lm. The following
conditions were provided for the analysis: heating rate of
10C/min, temperature range from room temperature to
500C and a ow rate of 25 mL/min in a nitrogen atmosphere.
2.5 Structural properties
2.5.1 Scanning electron microscopy (SEM)
A SEM S-3400N (Hitachi, Japan), operating at an acceleration
voltage of 20 kv was used to study the fracture surface
morphology of the samples. The lm samples were mounted
on bronze stubs using a double-sided tape and coated with a
gold layer (4050 nm), under high vacuum mode.
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2.5.2 Fourier transform infrared spectroscopy (FTIR)
An IR spectrometer (Bruker Vector 22) was used to determine
the FTIR spectra using the frequency range of 4004000 cm1.
The samples were prepared by the KBr-disk method.
2.5.3 X-ray diffraction (XRD)
XRD measurements were performed, using reection
geometry, on a Rigaku, Tokyo, Japan, diffractometer,
40 mA and a goniometer speed of 0.02 (2u)/s, and the XRD
patterns were recorded in the reection mode in the angular
range 550 (2u) at the ambient temperature. The relative
crystallinity index was calculated according to Eq. (5),
proposed in a previous work [26], based on the calculus of
amorphous area (Aa) and crystalline areas (Ac).
Ac
Rc 5
Ac Aa
where (Rc) relative crystallinity; (Ac) crystalline area; and
(Aa) amorphous area in the XRD pattern.
2.6 Tensile test
The mechanical properties of the lms were determined
using the ASTM-D882 standard, with a slight modication.
Film strips were cut into 70  10 mm2 sections and then
characterized using a 5KN INSTRON tensile machine with
an initial grip separation and crosshead speeds of 30 mm and
2 mm/min, respectively. At least ve replicates were carried
out for each sample.
3 Results and discussion
3.1 Physical properties
3.1.1 Film formulation
Preliminary experiments were carried out to determine the
plasticizer concentration range for lm formulation. The
maximum compatible concentration of plasticizer used in
the formulations was 60% w/w. When this limit was exceeded
the lm became sticky and difcult to handle from the plate.
Therefore, it was not possible to evaluate their properties. The
lms formulated with 15% w/w plasticizer were found to be
weak, brittle, and difcult to handle and peel from the plates
and thus, it was not possible to evaluate their properties, these
results are in agreement with Jouki et al. [6].
3.1.2 Thickness and density
There was no signicant difference in the lm thicknesses
and density among the different lms. The lm thickness
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Table 1. Physical properties of cassava films incorporated with various plasticizer types and concentrations

Plasticizer type and content Thickness (mm) Density (g/cm3) Water content (%) Solubility in water (%)

F, this study 30% 0.1675  0.11 1.74  0.08 10.96  0.11 33.90  0.43
45% 0.272  0.09 1.73  0.07 12.00  0.12 42.70  0.52
60% 0.291  0.10 1.62  0.05 13.17  0.10 43.39  0.41
TEG, this study 30% 0.262  0.18 1.72  0.06 20.94  0.19 24.10  0.34
45% 0.317  0.15 1.66  0.11 29.11  0.13 27.10  0.51
60% 0.350  0.20 1.45  0.03 30.70  0.21 29.32  0.27
TEA, this study 30% 0.173  0.09 2.44  0.07 11.14  0.09 39.00  0.34
45% 0.193  0.13 2.23  0.09 11.48  0.12 41.90  0.28
60% 0.349  0.12 1.46  0.02 15.48  0.17 42.11  0.52
U, this study 30% 0.311  0.21 1.63  0.04 15.34  0.20 22.50  0.09
45% 0.250  0.19 1.56  0.06 21.97  0.23 22.59  0.15
60% 0.232  0.14 1.44  0.09 25.30  0.19 22.74  0.17
GLY (ref. [27]) 30% 0.193  0.10 11.80  0.10 23.00  0.10
45% 0.210  0.10 41.1  0.10 32.10  0.10

F, fructose; TEG, tri-ethylene glycol; TEA, tri-ethanolamine glycol; U, urea; and GLY, glycerol.

increased upon plasticizer addition and showed very small
variations (as shown in Table 1). The higher the plasticizer
concentrations in the cassava lm, the thicker the lm. Thus,
plasticized lms with 45 and 60% of plasticizers were thicker
compared to lms containing 30% plasticizers. Fructose-
plasticized lms were thinner than other-plasticized lms,
and the 30% was the thinnest with 0.167 mm. On the other
hand, 60% TEG- and TEA-plasticized lms were the thickest
with 0.35 mm. Plasticizers can penetrate the network of
starch quickly and easily to form a thicker lm [15]. Films
with a higher concentration of plasticizer showed lower
densities and the type of plasticizers also inuenced the
lm densities. The lowest density (1.44 g/cm3) was recorded
for lm plasticized with 60% U and the highest density
(2.44 g/cm3) was recorded for lm plasticized with 30% TEA.
3.1.3 Moisture content and water solubility
When the plasticizer concentration increased from 30 to 45
and then to 60% w/w, the moisture content of the cassava lms
increased signicantly due to the water holding capacity of the
plasticizers. Similar results were reported by Cerqueira
et al. [28]. Water solubility is an important property of
starch-based lms. Potential applications may require water
insolubility to improve product integrity and water resis-
tance [29]. Film solubility in water increases with increasing
plasticizer concentration. In plasticized lms, plasticizers can
reduce the interactions between biopolymer molecules and
increase the solubility due to its hydrophilic nature, giving the
polymer molecules a higher afnity to bind water. Similar
results were reported by Ghasemlou et al. [30]. The highest
solubility was achieved when the highest concentration of
plasticizers was used [6]. Films were found to be unable to
maintain their integrity when dispersed in water. This effect
was dependent on the type and concentration of plasticizer. For
each plasticizer, the solubility of the lm was found to have
increased with the increase in concentration. The addition of
the plasticizer increases the hydrophilic content; thus, it
increases the solubility of lms. In addition, it also alters the
interaction between the polymer chains which may increase
the dissolution of the polymer [31].
3.1.4 Water absorption
WA is important for starch lms because water acts as a
plasticizer. Plasticized lms at higher plasticizer content and
higher water content had greater exibility [32]. Films
plasticized with higher plasticizer content possessed higher
hydrophilicity [33]. The presence of hydroxyl groups in the
plasticizer molecule is responsible for the highest tendency
for water absorption in the plasticized-polymer because the
plasticizers could form hydrogen bonds with the starch [3].
OH groups in plasticizers could form hydrogen bonds with
the starch. This result was in agreement with water solubility
and water content result.
Figure 1 shows the water absorption percentage as a
function of time for the cassava lms with different plasticizer
type and content. It is interesting to note that all lms absorbed
a high amount of water after 30 min of water immersion at
room temperature. The water absorption of the lms increased
with the higher content of plasticizers due to the properties of
the actual plasticizers, since they are soluble in water and
naturally hygroscopic [34]. The control lm absorbs about
560% in 90 min, whereas the lms with 30% absorb about 110,
630, 530, and 495% for F, TEG, U, and TEA, respectively. When
200 min was reached, the control lm and all the lms with a
different plasticizer type and content started to dissolve in
water except for the lms plasticized by fructose. Fructose-
plasticized lms absorb less water compared to other lms; the
maximum water absorbed by fructose plasticized lms are 110,

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Starch/Strke 2017, 69, 1500366 Effect of various plasticizers . . . 1500366 (5 of 11)

Figure 1. Water absorption of cassava films with different plasticizers type and content.

180, and 195% for the lms with 30, 45, and 60% fructose, It is evident that plasticizers could increase the onset
respectively. Fructose-plasticized lms have excellent water temperature and the peak temperature of starch lms
resistance compared to the other plasticizers which are used in compared to the control lm. Table 2 shows the peak and
this study. Therefore, fructose can contribute a more palatable onset temperature for all lms. This data shows that lms
texture and longer shelf life to the products which contain it. plasticized with TEA or F had a signicant difference
between To and Tp and consequently they were expected to
3.2 Thermal properties have the highest seal strength. This discrepancy might be
due to the differences between the polysaccharides and the
3.2.1 Differential scanning calorimetry (DSC) starch lms and their interaction with lipids, water, and
plasticizers [36].
DSC is a common method for the determination of
transition temperatures (onset temperature To and peak Table 2. DSC of cassava film with different plasticizers type
and content
temperature Tp). A signicant difference between To and Tp
is important to achieve good sealing [35]. If the To and Tp
Sample To (C) Tp (C)
values were very close, the lm would nearly completely melt
during sealing. At this temperature, the lm loses its Cassava starch 142.9 172.8
structure [35]. Table 2 shows the To and Tp from the DSC of Control film 148 185.5
the individual plasticizer used in the preparation of the F 30 155.3 191.6
cassava starch lms. Cassava starch (dry powder) exhibits F 45 159.9 191.4
F 60 152.8 188.6
lower To and Tp with values of 142.96 and 172.87C,
TEA 30 153 202.8
respectively. The To and Tp of the control lm are 148 and
TEA 45 153.1 201.8
185.5C, respectively. The addition of plasticizers increases TEA 60 153.2 193.6
the To and Tp of all lms due to the strong hydrogen bonds, TEG 30 157.3 198.4
which are formed between the plasticizers and the starch. TEG 45 156.3 161.5
This decreased the starch chain mobility and consequently TEG 60 151.6 193.3
increased the matrix glass transition. These ndings are in U 30 160.9 194.3
U 45 162.1 194.9
favor of previous studies [3, 36]. All lms exhibited
U 60 161 192.3
endothermic peaks in the range between 150 and 210C.

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1500366 (6 of 11) A. Edhirej et al.
3.2.2 Thermal gravimetric analyzer (TGA)
Figure 2 shows the TGA experimental results of cassava
lms with different plasticizer types and content. As can be
observed, all the curves show a similar behavior for the
mass loss in all lms with different plasticizer types and
concentration. The mass loss below 100C was mainly
ascribed to water loss, whereas, the mass loss from 100C to
the onset temperature was related to the volatilization of
both water and plasticizers. So the difference in the
decomposition onset and the mass residue was mainly
due to the different volatility of the plasticizers in the TPS
lm. The onset of the decomposition temperature of all the
plasticized lms decreased compared to the control lm. The
onset of the decomposition temperature (To) and the peak
temperature (Tp) of all the plasticized lms decreased with
increasing plasticizer concentration. The mass residue at
500C increased with the addition of F and U, while it
decreased with the addition of TEG and TEA. The highest
was observed in fructose plasticized lm which reached
28.25%, and the lowest was observed in TGE plasticized
lm with 8.34%, as compared to the control lm with
18.41%. It can be observed from Fig. 2 that the increase of
plasticizer concentration signicantly increased the thermal
Figure 2. TGA curves of cassava film with different plasticizers type and content.
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Starch/Strke 2017, 69, 1500366
degradation rate of the plasticized lm as compared to the
control lm at constant temperature. For example, the
percentage weight loss at 300C was 28% for F30, 33% for
F45, and 34% for F60; while that of the control lms was
26%. In other words, the increase of plasticizer concentra-
tion from 30 to 60% reduces the thermal resistance of the
TPS lms.
3.3 Structural properties
3.3.1 Scanning electron microscopy (SEM)
SEM images did not show a great difference among samples
containing the same concentration of different plasticizers.
Films with 45% plasticizer presented smooth surfaces
without pores as shown in Fig. 3B, H, E, and K. The sample
plasticized by 30% plasticizer showed a less compact
structure with large pores, except for the case of fructose
which presented a better surface structure compared to the
other plasticizers with the same concentration as presented
in Fig. 3A, D, G, and J. The homogeneity of the matrix in the
lms is a good indicator of their structural integrity. For this
reason, it can be expected that the lms plasticized by
fructose will show better mechanical properties [15]. SEM
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Starch/Strke 2017, 69, 1500366
Figure 3. SEM micrographs of cassava film with different plasticizers type and content.
images show that the lm plasticized with 30% fructose
presented smooth surfaces without pores, and with a
compact structure. On the contrary, lms plasticized with
30% urea, TEA, and TEG displayed some small pores on
their surface. The lms plasticized with 60% TEA and TEG
show a less compact structure with large pores, while the
lms with 60% F and U show a better surface structure as
illustrated in Fig. 3C, F, I, and L.
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3.3.2 Fourier transform infrared (FT-IR) spectroscopy
FT-IR spectroscopy was used for investigating the changes in
the TPS structure on a short-range molecular level and to
identify the potential interactions between the starch and the
plasticizers. Yin et al. stressed that when two or more
substances are mixed, physical blends versus chemical
interactions are reected by changes in the characteristic
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1500366 (8 of 11) A. Edhirej et al.
Figure 4. FTIR spectra of cassava film with different plasticizers type and content.
spectral bands [37]. Figure 4 shows the FT-IR spectra
corresponding to the cassava lms with different plasticizer
types and concentration. The control lm shows peaks at
705.49, 764.03, 862.8, 932.44, 1042.81, 1079.82, 1150.97,
1368.57, 1644.25, 2934.99, and 3369 cm1. The peak observed
around 3369 cm1, is associated with the stretching of the
OH groups, whereas the bands identied at 2934 cm1 are
attributed to CH stretching. The peak at 1644.25 cm1 was
assigned to the bending mode of the absorbed water and the
peaks around 1368.57 cm1 are assigned to CH bonding.
The peaks at 1150.97 and 1079.82 cm1 were attributed to the
CO bond stretching of the COH group in the cassava
starch [38]. The main differences between the control lm
and the lms plasticized by fructose are the presence of a
peak at 3757.01, 3853.12, and 3879.41 cm1, which are
attributed to the OH stretch, free hydroxyl. For example, the
intense peaks at 32003500 cm1 indicated the presence of
OH groups in starch, which evidenced that starches are
sensitive to water molecule due to the presence of hydroxyl
groups. This was also supported by Sakina et al. [39] and
Sahari et al. [40], as these peak ranges were attributed to the
2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Starch/Strke 2017, 69, 1500366
stretching of the hydroxyl groups due to the hydrogen
bonding between the molecules. Meanwhile, the strong
bands at 28503000 cm1 were assigned to CH stretching
and the peaks at 9901030 cm1 were characteristic of the
anhydro-fructose ring OC stretch [41]. The peaks at 1500
1600 cm1 were attributed to the bending of the water in the
starch [42]. The intensity of the water bond peak at 1644 cm1
was found to be increased by the increase in fructose content.
This peak was shifted to 1655 cm1 in 30% F containing lm,
indicating the interaction of bound water with fructose [31].
The absorbance in the region 36872988 cm1 was found to
be increased with the increase in urea concentration. This
shows that more water was attracted in these lms. Within
this region, the wave number of highest intensity was also
shifted from 3326 to 3271 cm1 by the increase in the glycerol
content, showing a change in the nature of the hydrogen
bonding in the lm. As shown in Fig. 4B, lms plasticized
with urea show a double-peak at the higher wave number
3369 cm1 instead of the single peak of the control lm. This
is because urea could form stable hydrogen bonds with
both the O of COH and the O of the anhydroglucose ring
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OC in starch molecules [3]. Films plasticized with TEG and plasticizer content. According to Kar et al., this effect was
TEA are similar to the control lm except for the decrease in attributed to a change in melt viscosity [46]. The comparison of
intensity in the CH stretching region (29343369 cm1). the plasticizers shows that the U and TEG lms had a lower
No signicant increase of TEA lms in the free water region relative crystallinity than the Fand TEA lms. According to Ma
(16443369 cm1) was observed, which is consistent with the et al. [3], the capacity of urea to form more stable bonds
low moisture content of these lms [31]. Therefore, as prevents the interaction and the crystallization of the starch
revealed by FT-IR, the F and U could form a stronger molecules. There were no great differences between the F and
interaction with the starch than TEA and TEG. TEA lms, although the values for F were slightly superior to
those for TEA.
3.3.3 X-ray diffraction (XRD)
3.4 Mechanical properties
XRD measurements were performed to determine the effect of
plasticizer type and concentration on the crystallinity of the The mechanical parameters recorded from the tensile test
lms. The XRD spectra of native starch and plasticizer starches were: tensile stress (MPa), extension at break (mm), and
are presented in Fig. 5. XRD results indicated that the Youngs modulus (MPa). The tensile strength of the cassava-
crystalline structure of the native starch was destroyed. starch-based lm decreased signicantly with increasing
The intra-molecular hydrogen bonds were responsible for plasticizer content. The highest tensile stress was recorded
the highly ordered crystalline structure [43]. The control lm for lms with 30% fructose (4.7 MPa), which is higher than
had sharp diffraction peaks at 17.3 and a few small peaks at the 2.68 MPa reported for cassava starch plasticized with 30%
around 16.7 and 16.1, which indicated a typical A-type
pattern [44]. As can be seen in Fig. 5, the lms with a higher
concentration of plasticizer have a highly crystalline structure.
Films plasticized with F, TEA, and TEG showed a similar
prole to the control lm, as illustrated in Fig. 5A, C, and D.
However, the lm plasticized with urea (Fig. 5B) shows a sharp
peak at 23.3 and other peaks at 25.1 and 29.3 indicating a
typical C-type pattern. Similar peaks were reported for urea by
Debiagi et al. [45]. The relative crystallinity of cassava lm
plasticizers with various plasticizer types and concentration
are illustrated in Fig. 5. The amount and type of plasticizer did
not signicantly affect the crystallinity of the lms. However,
all lms showed decreasing crystallinity as a function of

Figure 5. XRD of cassava film with different plasticizers type and Figure 6. Mechanical properties of cassava film with different
content. RC is relative crystallinity. plasticizers type and content.

2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.starch-journal.com

1500366 (10 of 11) A. Edhirej et al.
glycerol [47] and the 2.03 MPa for cassava starch plasticized
with 25% glycerol [8], and similar to the result reported for
30% fructose with edible lm [48]. Films containing 60%
TEA showed the lowest values for tensile stress (Fig. 6A), due
to its hygroscopic character which tends to provide additional
water into the lm matrix.
The Youngs modulus or elastic modulus is the
fundamental measure of lm stiffness, as the higher the
Youngs modulus, the higher the stiffness of the material.
Increasing plasticizer content results in lms with a lower
Youngs modulus and then they are less rigid. The decrease
of stiffness with increasing plasticizer content in hydrophilic
lms has been reported previously [49]. This behavior could
be related to the structural modications of the starch
network when plasticizers are incorporated and the matrix of
the lms becomes less dense. This explains the decrease of
tensile strength and modulus as the plasticizer concentration
increases from 30 to 45 and 60% in all lms.
Among the plasticizers used in this study, TEA showed
the greatest ability to decrease tensile strength and increase
elongation at break when the same plasticizer concentration
was used, especially at higher concentration. This may be
due to its having the smallest molecular size, which allows
TEA to t easily into the polymer chains. Similar results were
reported for glycerol as a low molecular weight plasti-
cizer [48]. According to the results, tensile strength and
elongation at break were inversely correlated. Similar
changes in mechanical properties as affected by hydrophilic
plasticizers were previously observed for various hydrocol-
loid-based lms [11, 48].
4 Conclusions
The effects of plasticizer type and content on the physical,
mechanical, and morphological properties of cassava lm
have been studied. Fructose-plasticized lm absorbed less
water (110 for 30% F at 90 min) as compared to the other
lms. A study of the morphological surface indicated that
the lm with fructose presented smooth and homogeneous
surfaces without pores, which is a good indicator of their
structural integrity. Therefore, the lms plasticized by
fructose show better tensile stress and tensile modulus,
recorded as 4.7 and 69 MPa, respectively, for the lm with
30% fructose. The plasticized lms exhibited a decreased
relative crystallinity from 0.32 to 0.21, irrespective of the
plasticizer types. The lm plasticized by fructose presented
higher relative crystallinity values of 0.31, 0.3, and 0.29 for
lms with 30, 45, and 60 %, respectively, as compared with
the other plasticized lms. The To and Tp of all plasticized
lms decreased with increasing plasticizer content. The
mass residue at 500C increased with the addition of F and
U from 18.41 to 28.25%, while it decreased with the addition of
TEG and TEA from 18.41 to 8.34%. The lm plasticized
2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Starch/Strke 2017, 69, 1500366
by fructose could obviously improve the thermal stability of the
lms. These phenomena could be explained by the FT-IR
results, which indicated that fructose could form more stable
and strong hydrogen bonds with the hydroxyl group of the
starch molecules than other plasticizers.
The authors are grateful for the nancial support from
University Putra Malaysia and for funding this project through
the Exploratory Research Grant Scheme (vote number 9389900).
The authors declare that there is no conict of interest.
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