Polymer-Plastics Technology and Engineering, 53: 312–318, 2014
Copyright # Taylor & Francis Group, LLC
ISSN: 0360-2559 print=1525-6111 online
DOI: 10.1080/03602559.2013.866246
Modification of Physico-Mechanical Properties of
Chitosan-Tapioca Starch Blend Films Using Nano Graphene
Alireza Ashori and Reza Bahrami
Department of Chemical Technologies, Iranian Research Organization for Science and Technology
(IROST), Tehran, Iran
Biodegradable blend films from chitosan-tapioca starch were
prepared by the casting method. To improve the properties of chit-
osan–starch blend films, nano graphene was used. The influences of
the loading of graphene on the physico-mechanical properties in
terms of water vapor transmission rate (WVTR), thermal stability,
and tensile strength of the blend films were investigated. Scanning
electron microscopy (SEM) and FTIR were used to investigate
the surface morphology and molecular interaction of the blend films,
respectively. After the incorporation of nano graphene, the blend
film from chitosan-starch showed an increase in tensile strength
and thermal stability, and a decrease in WVTR and elongation at
the break. These results showed that the combination of a tiny
amount of graphene presents a promising method for improving
the mechanical and barrier properties of chitosan-starch biocompo-
site films. The SEM observations indicated that a high amount
(3 wt.%) of graphene was easily agglomerated. This caused the
mechanical properties of the composite films to be reduced. Among
the various compositions studied, chitosan-starch film filled with
0.8 wt.% graphene showed superior properties. The structural
properties investigated by FTIR showed a clear interaction between
chitosan and starch, forming a new material with enhanced mechan-
ical properties.
Keywords Blend film; Chitosan; Graphene; Tapioca starch;
Tensile strength
INTRODUCTION
The interest in biodegradable films and films made from
renewable and bio-based polymers has increased over the
last few years[1,2]. Biopolymer materials present the possibil-
ity of obtaining thin films and coatings for covering fresh or
further processed foods to extend their shelf life[3]. Not only
can edible films made from natural biopolymers improve
handling properties and extend shelf life of food products,
but they can also relieve the pressure on environment caused
by plastic packaging wastes[4]. Edible films and coatings
offer some advantages such as edibility, biocompatibility,
Address correspondence to A. Ashori, Department of Chemi-
cal Technologies, Iranian Research Organization for Science and
Technology (IROST), P. O. Box 15815-3538, Tehran, Iran.
E-mail: ashori@irost.org
Color versions of one or more of the figures in the article can
be found online at www.tandfonline.com/lpte.
312
aesthetic appearance, barrier properties, nontoxicity,
nonpolluting and low cost[5].
Many bio-based materials may be utilized for making
green packaging films including proteins, polysaccharides,
and lipids[6]. Among these natural biopolymers, chitosan, an
important derivative produced by deacetylation of chitin, is
one of the most attractive materials because of its many
unique properties. It has been proved to be nontoxic,
biodegradable, biofunctional, and biocompatible and has
antimicrobial characteristics[7–9]. Furthermore, chitosan films
are tough, long-lasting, flexible, and very difficult to tear[10].
Chitosan has been used in various applications, such as
medical, pharmaceutical, textile, water treatment, food, cos-
metics, packaging, etc.[11–13].
However, pure chitosan film has relatively poor water
barrier and mechanical properties. To improve the physical
and functional properties of chitosan films, blending with
other natural biopolymers has been proposed[2,14]. There are
some reports about chitosan-blended films in open access
literature such as chitosan-whey protein films[15], chitosan
methylcellulose films[16], chitosan-gelatinfilms[17], and
chitosan-pea starch films[18].
Starch-based films have been considered particularly
because they exhibit physical characteristics similar to syn-
thetic polymers: transparent, odorless, tasteless, semiperme-
able to CO2 and resistant to O2 passage[19,20]. According to
the Food and Agriculture Organization[21], one important
source of starch in South America is tapioca. Therefore,
the use of tapioca starch to develop edible films and coatings
has been considered[22]. However, wide applications of
starch film are limited by its water solubility and brittle-
ness[23]. To overcome these shortcomings, starch is blended
with different proteins to decrease the water vapor permea-
bility of the films and to increase their tensile strength[24].
The blending of starch and chitosan is an alternative way,
which not only improves the mechanical and water vapor
barrier properties, as well as the antimicrobial attributes of
starch film, but also reduces the cost and enhances the bio-
degradability of chitosan film[14].
The aim of this work is to prepare and characterize
the performance of chitosan–tapioca starch based films.
 CHITOSAN-TAPIOCA STARCH BLEND FILMS
In addition, the influences of nano graphene loading on the
morphologic, thermal stability, mechanical properties and
water vapor transmission rate of chitosan–starch films were
studied.
EXPERIMENTAL
Materials
Unmodified starch used in this study was made from
tapioca obtained from National Starch and Chemical Co.,
Malaysia. It was composed of 17% amylose and 83% amy-
lopectin and had a degree of substitution (DS) of 0.036. Its
viscosity and ash content were 22.6 cP and 0.47%,
respectively.
Chitosan was a Vanson product (USA), natural
biopolymer 02-CIS-0117, and a material with 85.4% deace-
tylation. Its molecular weight and viscosity were 9
105
gmol1 and 230 cP, respectively.
Glycerin (purchased from Sinopharm Chemical Reagent
Co. Ltd., Shanghai, China) was diluted into 25% solution
for use as the plasticizer. It is one of the most popular plas-
ticizers used in film-making techniques, due to stability and
compatibility with hydrophilic bio-polymeric packaging
chains[25].
The graphene powder (grade AO-4) was obtained from
the Graphene Supermarket Co., USA. The specific surface
area and purity were <15 m2 g1 and 99.2%, and the average
thickness and lateral size of graphene nanosheets were about
12 nm and 4.5 mm, respectively. All other reagents and
solvents were of analytical grade and were used without
further purification.
Film Preparation
The films were prepared according to the so-called
casting technique described by Gómez-Estaca et al.[17].
A stock solution of chitosan (2%, w=v) was prepared by dis-
persing 10 g of chitosan in 500 mL of acetic acid solution
(1%, v=v). To achieve complete dispersion of chitosan, the
solution was heated at 45 C on a hot plate for 6 h under
gentle magnetic stirring, followed by filtering through sin-
tered glass filter (grade 1) to remove undissolved impurities.
Starch solution with concentration of 3% (w=v) was pre-
pared by dispersing starch in distilled water and heating the
mixture in a temperature-controlled water bath with stirring
until they gelatinized, and then cooling down to 25 C.
Chitosan-starch composite films were prepared by
mixing 100 mL of 2% chitosan solution with 100 mL of 3%
starch solution. Glycerin was added as 25% (w=w) of the
total solid weight in solution. All the solutions prepared
were adjusted to pH 4.0 with acetic acid 50% (w=w). A series
of films were prepared by the addition of 0%, 0.2%, 0.5%,
0.8%, 1.5%, 2.5%, and 3% (by weight) graphene platelets.
All mixtures were stirred at 80 C for 10 min and, after cool-
ing to room temperature, were left standing for 2 days for
313
degassing. Then, the mixtures were cast onto flat, level
Teflon-coated glass plates (thickness 0.2 mm). After drying
the films at room temperature for at least 72 h, they were
peeled from the plates. Dried films were conditioned inside
desiccators at 50% RH and 25 C for 48 h prior to testing.
Tensile Testing
Mechanical properties, namely tensile strength and
elongation at break, were measured with a Universal
Testing Machine (Santam model STM-150) following the
guidelines of ASTM Standard Method D 882. The vari-
ables of loading-cell of 50 N, gauge length 40 mm, and
crosshead speed of 5 mm min1 were used throughout the
experiment. Each type of film was tested by at least three
replicates.
Morphological Study
Studies on the surface morphology of the composite
films were carried out using a scanning electron microscope
(SEM). SEM micrographs of the surfaces of specimens were
taken using SEM Model WEGA-II TESCAN. The speci-
mens were coated with a thin film (20 nm) of gold to avoid
electrical charge accumulation during the examination, and
then analyzed at an accelerating voltage of 7–15 kV.
Water Vapor Transmission Rate
Water vapor transmission rate (WVTR) was determined
gravimetrically using a modification of ASTM Method E
96. Film specimens were mounted on poly(methyl methac-
rylate) cups containing 16 mL of distilled water. The cups
were placed in an environmental chamber at 25 C and 50%
RH. A fan in the chamber was used to move the air at
a speed of approximately 200 m min1 over the surface of
the films to remove the permeating water vapor. The weights
of the cups were recorded every hour for a total of 6 h.
Linear regression was used to estimate the slope of this
line given in g h1. Three film specimens were tested for each
type of film.
Thermogravimetric Analysis
Thermogravimetric analysis (TGA) was conducted using
a Polymer Laboratories Thermogravimetric Analyzer, over
the heating range from 40 C to 800 C in nitrogen atmos-
phere with a flow rate of 20 mL min1. The heating rate was
10 C=min.
Fourier Transform Infrared Spectra
Fourier transform infrared (FT-IR) spectra of the films
were measured with a spectrophotometer (Bruker, Tensor
27) in total reflection mode. The spectra were obtained at
resolution 4 cm1, averaging over 32 scans in the range of
4000–400 cm1. The FTIR spectrum was taken in a trans-
mittance mode.
314 A. ASHORI AND R. BAHRAMI

RESULTS AND DISCUSSION
Tensile Strength and Elongation at Break
The tensile strengths of blend films from chitosan-starch
with and without graphene are shown in Figure 1. As
clearly seen, the tensile strengths of films were considerably
affected by the addition of grapheme content. The results
demonstrated that the tensile strength values increased
with the addition of graphene, and the maximum occurred
at 0.8 wt.%. The tensile strength then decreased with fur-
ther increase in graphene content. This could be explained
by the agglomeration of nanoparticles. The SEM study
also supported the agglomeration of nanoparticles at
higher graphene contents. This phenomenon indicated the
critical loading content of graphene in the chitosan-starch
blends.
Elongation at break for chitosan-starch blend films was
studied as a function of graphene dose in Figure 1. It was
FIG. 1. Tensile strength and elongation a break of the blend films as a
function of graphene content.
observed that the values of elongation were significantly
affected by increasing graphene contents. The average elon-
gation values of the blend film behaved conversely to the
tensile strength values, decreasing from 65% to a minimum
40%. Elongation at the break was reduced in the presence
of graphene, probably due to the decreased flexibility of
the blend film. It may be due to the high stiffness of graphene
with high aspect ratio compared with chitosan and starch.
This is a common tendency that has been reported with
graphene[26–28].
Table 1 shows the tensile strength and elongation at break
of chitosan-starch blend films and of various films. The
increase in tensile strength values of the blend chitosan-
starch films, compared with chitosan and starch films (indi-
vidually), is attributable to a high formation of intermolecular
hydrogen bonding between NH3 of the chitosan backbone
and OH of the starch. The amino groups (NH2) of chito-
san were protonated to NH3 in the acetic acid solution,
whereas the ordered crystalline structures of starch mole-
cules were destroyed bythe gelatinization process, resulting
in the OH groups being exposed to readily form hydrogen
bonds with NH3 of the chitosan (Fig. 2).
As can be seen from Table 1, chitosan-starch film filled
with graphene had the highest tensile strength among the
compared films. However, elongation at break was slightly
lower (films were less deformable) than chitosan-waxy
corn starch film reported by Xu et al.[23]. Chitosan-starch
blend film had substantially higher tensile strength but
lower elongation at break than some synthetic polymers
(such as low density polyethylene and high density
polyethylene)[14].

TABLE 1
Tensile strength and elongation at break of various films
Tensile strength Elongation
Film type (MPa) at break (%) Test condition Reference
 
Chitosan-starch 35–44 40–63 25 C, 60% RH Current study
Chitosan-starch 32 65 25 C, 60% RH Current study
Chitosan-rice starch 27.5–38.1 8.1–13 25 C, 60% RH [14]
Chitosan-native corn starch 40.3 28–61.1 25 C, 60% RH [23]
Chitosan-waxy corn starch 33.7 45–61.1 25 C, 60% RH [23]
Cassava starch 9–17 9–28 25 C, 60% RH [29]
Corn starch 3.8–4.3 4–10 25 C, 60% RH [29]
Chitosan 27 33.3 25 C, 60% RH [23]
Chitosan 39.1 10.8 25 C, 60% RH [30]
Low density polyethylene 7.6–17.3 500 38 C, 90% RH [31]
High density polyethylene 17.3–34.6 300 38 C, 90% RH [31]
Cellulose acetate 48.5–82.7 15–45 38 C, 90% RH [31]
Polyester 178 70–100 38 C, 90% RH [31]

Composite films filled with 0.2–3 wt.% graphene.
 CHITOSAN-TAPIOCA STARCH BLEND FILMS 315

FIG. 2. Scheme of formation of chitosan-starch blend films.

Among various chitosan-starch films prepared, the sam-

ple filled with 0.8 wt.% graphene gave better mechanical
properties. Hence, it was used for further characterization
studies such as SEM, WVTR, FTIR, and TGA.

Surface Microstructure
To observe the dispersion of graphene sheets microscopi- FIG. 3. SEM images of the surface of chitosan-starch films with (a) 0
cally for more information concerning the interfacial inter- wt.% graphene, (b) 0.8 wt.% graphene, and (c, d) 3 wt.% graphene
30,000
(the red arrows point at the agglomerated graphene).
action between the chitosan-starch matrix and graphene
sheets, the surfaces of composite films were further investi-
gated by SEM. The micrograph of pure chitosan-starch film
The WVTR of blend films decreased from 44.3 to
(without graphene) shows relatively a smooth and homoge-
38.7 gm2 h1, when the graphene content increased from 0 to
neous surface with very sparsely distributed small particles
3 wt.%, and the minimum WVP occurred at the graphene
without any phase separation (Fig. 3a). The regular dots
content of 2.5 wt.%. It was reported that the WVTR process
might be due to starch as it was reported that the intensity
depended on the simultaneous actions of water diffusivity
of dots decreased with decreasing starch concentration[32].
and solubility in a polymeric matrix[34]. Then, the lower
However, the specimen films filled with 0.8 and 3 wt.% gra-
WVTR for chitosan-starch film can be explained by its
phene exhibited are latively rough surface and a certain
lower water absorbing ability. The different compositions of
degree of phase separation, respectively (Figs. 3b, c, and
d). Apparently, it is observed in Figure 3(b) that grapheme
sheets were uniformly dispersed and embedded into the
bio-polymer matrix. A homogeneous dispersion of gra-
phene and efficient interfacial load transfer should result
in a uniform stress distribution and be able to minimize
the occurrence of stress concentration, leading to a signifi-
cant increase in mechanical properties of composite films.
Figures 3 (c and d), at a high magnification, show the
graphene sheets were unidirectionally distributed and stacked
together, which might have a negative effect on mechanical
reinforcement.

WVTR
Because a main function of food packaging is often to
avoid, or at least to decrease, moisture transfer between the
food and the surrounding atmosphere, WVTR should be as
low as possible[33]. WVTR results are shown in Figure 4, and FIG. 4. The effect of graphene loading on the water vapor transmission
they display moderate reduction after addition of graphene. rate (WVTR) of chitosan-starch films.
316 A. ASHORI AND R. BAHRAMI
these two biopolymers, along with the various contents of
graphene, were responsible for the differences. A tough film,
resulting from the interactions between chitosan and starch
molecules, prevented water molecules from diffusing
through the films, thus reducing the WVTR values[14]. A
similar result was previously observed in the chitosan and
starch films filled with graphene[27].
FT-IR Spectroscopy
FT-IR spectroscopy was used to determine the interac-
tions between chitosan and tapioca starch. The infrared
spectra of chitosan, tapioca starch and their blend are
shown in Figure 5. The chitosan spectrum was similar to
previous reports[14,23,35]. The broad band at 2881–3453 cm1
was assigned to the O–H vibration stretching, which over-
laps the N–H in the same region. Also, the peak at about
2900 cm1 corresponded to the C–H stretching vibration.
The bands at 1650 and 1599 cm1 were assigned to the C¼O
stretching and N–H bending vibrations, respectively. The
band at 1085 cm1 in the fingerprint region resulted from the
C–O bond stretching.
The main chain elements of starch and chitosan were
similar except for the amino group, which only existed in
chitosan, so the chief differences of FT-IR spectra between
chitosan and starch came down to the bands related to
amino groups[36]. The band at 1645 cm1 was assigned to the
O–H bending[37]. When two or more substances are mixed,
physical blends versus chemical interactions are reflected by
changes in characteristic spectra peaks[38]. In the typical
spectrum of chitosan-starch composite film, the amino
peak of chitosan shifted from 1599 to 1559 cm1 with the
addition of starch. This result indicated that interactions
were present between the hydroxyl groups of starch and the
FIG. 5. Attenuated total reflection (ATR) spectra of chitosan film,
starch film, and typical chitosan-starch composite film.
FIG. 6. Thermogravimetric analysis of chitosan-starch film: effect of
graphene on the thermal stability.
amino groups of chitosan[32]. This is consistent with our
other results (Fig. 2).
Thermal Degradation
Thermogravimetric analysis (TGA) was performed on
the pure chitosan-starch film (control) and chitosan-starch
film with 0.8 wt.% graphene (Fig. 6). The mass loss before
the onset temperature was related to the volatilization of
glycerol and water[39]. The introduction of graphene may
decrease mass loss at onset temperature. The degradation
of film reinforced with graphene took place at temperatures
higher than that for the control sample, namely, 300 and
330 C, respectively. The introduction of graphene may
increase thermal stability, which has been attributed to the
better thermal stability of graphene, and the better interfa-
cial interaction between graphene filler and biopolymer
matrix. The TGA results clearly indicate that thermal degra-
dation of the chitosan-starch film reduced after modification,
which is important for different packaging applications.
This result was consistent with the research on the improve-
ment of thermal stability for composites loaded with
graphene[28].
CONCLUSIONS
This is the first report on the feasibility of chitosan-
tapioca starch biocomposite films reinforced with graphene
nanosheets. The blend films were prepared successfully by
the casting method. The effects of nano graphene, as rein-
forcing agent, on the mechanical and physical properties
were investigated. Some conclusions follow:
1. The mechanical properties were enhanced considerably
by incorporating graphene into the chitosan-starch blend
films. The highest improvement in the tensile strength of
 CHITOSAN-TAPIOCA STARCH BLEND FILMS
the composite films was achieved when 0.8 wt.% of
graphene was used.
2. The modified chitosan-starch films showed tensile
strength values much higher than those of other
chitosan-starch films in the literature.
3. The surface of the control film appeared smooth.
However, reinforced blend films showed remarkable
differences in terms of surface microstructure compared
to the control film.
4. SEM micrographs showed that high content (3 wt.%) of
graphene was easily agglomerated. This caused the
mechanical properties of the composite films to be reduced.
5. The results showed that the WVTR of blend films
decreased with an increase in the content of graphene.
The mean WVTR values of reinforced chitosan-starch
films varied from 38 to 43 g=m2 h.
6. Theamino group band of the chitosan molecule in the
FTIR spectrum shifted from 1599 cm1 in the chitosan
film to 1559 cm1 in chitosan-starch blend films. These
results indicated that there was a molecular miscibility
between these two components.
7. It was observed that the thermal stability of the chitosan-
starch films was improved by the addition of graphene.
FUNDING
This study was financially supported as a research
project by Grant No. 91041751 from the Iran National
Science Foundation (INSF).
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