Radiation Physics and Chemistry 81 (2012) 1659–1668

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Radiation Physics and Chemistry

journal homepage: www.elsevier.com/locate/radphyschem

Modification of mechanical and thermal property of chitosan–starch

blend films
Mohammad O. Tuhin a,b, Nazia Rahman a,n, M.E. Haque a, Ruhul A. Khan a, N.C. Dafader a, Rafiqul Islam b,
Mohammad Nurnabi b, Wafa Tonny a,b
a
Nuclear and Radiation Chemistry Division, Institute of Nuclear Science and Technology, Bangladesh Atomic Energy Commission, Dhaka, Bangladesh
b
Department of Applied Chemistry and Chemical Engineering, University of Dhaka, Dhaka-1000, Bangladesh

H I G H L I G H T S

c Chitosan–starch blend films (thickness 0.2 mm) were prepared by casting.

c To improve the properties of chitosan–starch films, glycerol and mustard oil of different composition were used.
c Chitosan–starch films, incorporated with glycerol and mustard oil, were further modified with monomer 2-hydroxyethyl methacrylate (HEMA)
using gamma radiation.
c Properties of the modified films such as tensile strength, elongation at break, water uptake, TGA, DMA, SEM, FTIR were studied.
c Results indicate that modification of chitosan–starch film with mustard oil improved the properties of the blend films which could be further
modified by HEMA using gamma radiation.

a r t i c l e i n f o abstract

Article history: Chitosan–starch blend films (thickness 0.2 mm) of different composition were prepared by casting and
Received 22 September 2011 their mechanical properties were studied. To improve the properties of chitosan–starch films, glycerol
Accepted 29 April 2012 and mustard oil of different composition were used. Chitosan–starch films, incorporated with glycerol
Available online 23 May 2012
and mustard oil, were further modified with monomer 2-hydroxyethyl methacrylate (HEMA) using
Keywords: gamma radiation. The modified films showed improvement in both tensile strength and elongation at
Biodegradable film break than the pure chitosan–starch films. Water uptake of the films reduced significantly than the
Chitosan pure chitosan–starch film. Thermo gravimetric analysis (TGA) and dynamic mechanical analysis (DMA)
Starch showed that the modified films experience less thermal degradation than the pure films. Scanning
Mustard oil
electron microscopy (SEM) and FTIR were used to investigate the morphology and molecular
g radiation
interaction of the blend film, respectively.
2-Hydroxyethyl methacrylate
& 2012 Elsevier Ltd. All rights reserved.

1. Introduction good mechanical and thermal properties, and provide a good

Current worldwide environmental awareness strongly stimu-
lates the introduction of biodegradable materials instead of the
prevalent trend of petroleum based synthetic polymers used for
packaging purpose. The widespread practice of the latter one is
due to their excellent mechanical and thermal properties as well
as their cost effectiveness. However, being non-biodegradable,
these are inappropriate to cope with the steps towards achieving
environmentally friendly sustainable development. Hence, versa-
tile efforts are in progress to develop biodegradable alternative
packaging materials that, simultaneously, will be cheap, possess
n
Corresponding author.
E-mail address: nazia1982_du@yahoo.com (N. Rahman).
resistance to moisture. Such attempted films are usually fabri-
cated from elements collected from natural sources. However, the
major drawbacks of these films include poor mechanical proper-
ties and a strongly hydrophilic nature. That is why, multitude of
studies are in progress to overcome these limitations to approach
physiochemical attributes analogous to those of petrochemical
properties (Salmieri and Lacroix, 2006; Rooney, 1995; Suppakul
et al., 2003; Tien et al., 2000; Ciesla et al., 2006).
Chitosan is a high molecular weight polysaccharide composed
of primarily of b-(1,4)-linked 2-deoxy-2-amino-D-glucopyranose
units and partially of b-(1,4)-linked 2-deoxy-2-acetamido-D-glu-
copyranose. It is prepared by the N-deacetylation of chitin, the
most abundant natural polymer next to cellulose, with 40–50%
aqueous alkali at 120–160 1C (Muzzarelli, 1977; Roberts, 1992).
Chitin is not easily soluble in any solvent. Nevertheless, unlike

0969-806X/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.radphyschem.2012.04.015
1660 M.O. Tuhin et al. / Radiation Physics and Chemistry 81 (2012) 1659–1668
chitin, chitosan is dissolved in aqueous solutions of some organic
and inorganic acids and becomes cationic polymer because of
protonation of amino groups on the C-2 position of the pyranose
ring. Chitosan consists of a large number of amino groups and
hydroxyl groups. These two functional groups provide several
possibilities for grafting of desirable bioactive groups (Roberts,
1992; Sugimoto et al., 1998; Crescenzi, 1994). Since chitosan is
non-toxic and biocompatible with the human physiological
system, it has been investigated as biomaterials (Luyen and
Huong, 1996; Burke et al., 2002) in the fields such as biomedicine,
pharmacology and biotechnology. Chitin and chitosan have
already been used in agricultural, food, industrial and medical
fields (Miskiel and Pazur, 1991). It also acts as flocculent for the
treatment of wastewater (Sinha et al., 2004). Again, starch-based
plastics due to its renewable natural origin became a major
attraction in recent years (Graaf and Janssen, 2000, 2001).
In the present research, our aim was to prepare biodegradable
and biocompatible films for different packaging applications
either in food or medical fields. So chitosan and starch are
chosen, as the base material to prepare polymeric films as the
biopolymers derived from chitosan and starch are renewable,
biodegradable and biocompatible. Starch and chitosan are hydro-
colloids with well-known good film forming capacities. Both have
been reported as potential materials for food packaging, espe-
cially as edible films and coatings (Garcia et al., 2000, 2001; El
Gaouth et al., 1991). However, a major drawback of chitosan–
starch film is its brittleness and sensitivity to water. With the
addition of plasticizers brittleness of the films can be reduced and
flexibility, extensibility can be improved. In this study, glycerol is
used as the plasticizer to formulate the chitosan/starch film.
Mustard oil, being lipid, acts as a hydrophobic agent. In the
present research, mustard oil is used to prevent the hygroscopic
nature of the film (Khan et al., 2010). Mustard oil was chosen
because it is indigenous Bangladeshi oil which is also economic-
ally feasible.
To improve the mechanical properties of natural polymer films
various routes are followed. Such a route to accomplish the
objective is graft copolymerization using electromagnetic radia-
tion such as gamma ray, ultraviolet light and free radical initia-
tors. Some approaches for the graft copolymerization of
hydrophilic polymer onto chitin and chitosan were reported as
a technique to improve the affinity to water or organic solvents
(Sugimoto et al., 1998; Crescenzi, 1994; Miskiel and Pazur, 1991;
Sinha et al., 2004; Zhao et al., 2003; Tangpasuthadol et al., 2003;
Jaykumar et al., 2005). Grafting of polyethylene glycol onto
chitosan is a convenient approach to water-soluble chitosan
derivatives (Dal Pozzo et al., 2000). Chitosan was photo grafted
using acrylic monomers, ethylene glycol and ethylene glycol
dimethacrylate and reported higher mechanical properties keep-
ing its inherent biodegradable properties (Khan et al., 2005;
Ferdous et al., 2003; Haque et al., 2007). In the present study,
modification with acrylic monomer is carried out using g radia-
tion to improve the properties of chitosan/starch based film. Over
the previous decades, the application of g radiation has been
widespread in the development and application of radiation
techniques. The use of g radiation offers many advantages
over the use of UV radiation-like continuous operation, minimum
time requirement, design flexibility through process control
and less atmospheric pollution than chemical methods (Ghoshal
et al., 2009). In the present work to improve the properties of
the films acrylic monomer 2-hydroxyethyl methacrylate (HEMA)
was grafted onto the film. HEMA was selected for the work because
poly(2-hydroxyethyl methacrylate), PHEMA is a well known
amphiphilic, biocompatible material (Fares et al., 2011). Some of
previous study showed that the presence of 2-hydroxyethyl metha-
crylate (HEMA) in copolymers improve the biocompatibility of the
materials (Carenza, 1992; Montheard et al., 1992; Ferreira et al.,
1998). Moreover, the use of chitosan-based copolymers and the use
of HEMA as a grafting monomer onto a range of polymeric
substrates was reported as successful for biomaterials (Ahn et al.,
2002; Zhang et al., 2002).
In the present research work, chitosan–starch blend-films of
different composition were prepared and their mechanical prop-
erties were studied. To improve the properties of chitosan-starch
films, glycerol and mustard oil of different compositions were
used. Chitosan–starch films incorporated with glycerol and mus-
tard oil were further modified with monomer HEMA using
gamma radiation. Soaking time was varied from 3 to 20 min
and radiation dose were varied from 1 to 8 kGy. Mechanical
properties of the modified films such as tensile strength and
elongation at break were studied. Thermal properties of the films
were characterized by thermo gravimetric analysis (TGA) and
dynamic mechanical analysis (DMA). SEM and FTIR were used to
investigate the morphology and molecular interaction of the
blend film, respectively. Water uptake of the films was also
studied.
2. Experimental
2.1. Materials
Chitosan (molecular wt. 190–310 kDa; degree of deacetylation
75–85%) and potato starch (molecular wt. 296 kDa) was pur-
chased from Sigma Aldrich (Iceland), glycerol and acetic acid was
supplied by Merck (Germany). HEMA was procured from Fluka
Chemika (Switzerland). Mustard oil (Radhoni) was collected from
local market.
2.2. Preparation of chitosan–starch films
A 2% w/v solution of chitosan was prepared in 2% aqueous
acetic acid. 10% w/v starch solution was prepared in water. Then
chitosan–starch blend, were prepared by mixing chitosan and
starch solution in different composition. Chitosan-starch films
(thickness 0.2 mm) were prepared from chitosan–starch solution
by casting. Good mechanical properties were obtained for chitosan:
starch¼4: 6 (w/w) film. To improve the properties of chitosan–
starch films, glycerol and mustard oil was added to chitosan–starch
solution in different composition.
2.3. Modification of chitosan–starch film with HEMA
Chitosan–starch films incorporated with glycerol and mustard
oil were further modified with HEMA using gamma radiation
from 60Co at the dose rate of 2.35 kGy/h in presence of oxygen.
The dose rate was determined with the help of the Fricke
dosimeter. The blend films were soaked in four different formula-
tions of HEMA in methanol as shown in Table 1 and then
irradiated by gamma radiation. Soaking time was varied from
3 to 20 min and radiation dose were varied from 1 to 8 kGy.
Table 1
Composition of different monomer formulation (w/w).
Formulations Methanol (%) HEMA (%)
M-1 97 3
M-2 95 5
M-3 93 7
M-4 90 10
 M.O. Tuhin et al. / Radiation Physics and Chemistry 81 (2012) 1659–1668 1661

2.3.1. Tensile properties
Tensile properties of the films were measured by Hounsfield
Series S H testing machine (UK) with a crosshead speed of 10 mm/
min. The load range of 500 N and the gauze length 40 mm were
used throughout the experiment.
2.3.2. Polymer loading
The polymer loading (PL) of the films was determined on the
basis of weight gain by the film after the entire treatment process.
The PL was determined by the following equation
PL ð%Þ ¼ ½ðW t 2W o Þ=W o   100
where, Wt is the weight of the treated film and Wo is the weight of
the film after treatment with glycerol and oil before grafting. The
weight was calculated on dry basis.
25% to 40% of total polymer (chitosanþstarch) weight. For the
packaging application, the films should have both sufficient
tensile strength and elongation property. After addition of gly-
cerol elongation property of the films improved significantly.
Therefore, in the rest of the work we preferred the film with
higher tensile strength. Best performance was obtained for 25%
glycerol. For 25% glycerol weight of mustard oil was varied from
10% to 75% of total polymer (chitosanþstarch) weight. Optimum
mechanical properties were obtained for 25% glycerol and 25%
mustard oil. The tensile strength and elongation at break of the
chitosan–starch films with different composition of glycerol and
mustard oil is shown in Table 2.
3.2. Modification of chitosan–starch film with HEMA using gamma
radiation

2.3.3. Water uptake The TS and Eb of chitosan–starch films incorporated with

Water uptake was measured by soaking the films in distilled
water contained in a static beaker at 25 1C up to 360 h. The water
uptake was calculated by the following equation
water uptake ð%Þ ¼ ½W w W d =W d   100
where Ww is the weight of the wet film and Wd is the weight of
the dry film.
2.4. Thermogravimertic analysis
The thermal gravimetric analysis (TGA) was conducted on a
Perkin-Elmer TGA 7-thermal analyzer from 30 to 500 1C with a
heating rate of 10 1C/min – under nitrogen atmosphere with a
flow rate of 20 ml/min.
2.5. Dynamic mechanical analysis
The thermal properties of films were studied from 27 to 160 1C
at a rate of 4 1C/min and an oscillating frequency of 1 Hz using
dynamic mechanical analyzer (DMA), Triton technology
TTDMA, UK.
2.6. Scanning electron microscopy
The morphological study of the chitosan–starch blend film
was done using a JEOL 6400 SEM at an accelerating voltage of
15–20 kV. The SEM specimens were sputter-coated with platinum.
2.7. FTIR spectroscopy
The FTIR spectroscopy of chitosan/starch blend films was
performed by FTIR spectrophotometer, Imprestige-21 model,
Shimadzu corporation, Japan, equipped with an attenuated total
reflectance (ATR) device in the wave number range 700–4000 cm-1
with 20 scanning rate with resolution of 4 cm  1. The FTIR spectrum
was taken in a transmittance mode.
3. Results and discussion
glycerol and mustard oil was found as 8.3 MPa and 33%, respec-
tively. Chitosan–starch films incorporated with glycerol and
mustard oil were further modified with monomer 2-hydroxyethyl
methacrylate (HEMA) using gamma radiation. The blend films
were soaked in different formulations of HEMA (3–10%) in
methanol and then irradiated by gamma radiation. Soaking
time was varied from 3 to 20 min and radiation dose were varied
from 1 to 8 kGy. Monomer concentration, soaking time and
gamma radiation dose was optimized on the basis of mechanical
properties.
3.2.1. Effect of monomer concentration on mechanical properties of
chitosan/starch blend films
The chitosan–starch films were soaked in different formula-
tions (M1–M4) for 10 min soaking time. The films were then
irradiated by gamma radiation at 5 kGy. After 24 h of radiation,
various mechanical properties were determined. The TS values of
the irradiated films as a function of monomer concentration are
presented in Fig. 1. For 3% HEMA TS was found 12 MPa. TS
increased with increase in the percentage of HEMA and reached
the maximum of 15.7 MPa for 7% HEMA (M3 formulation) which
is 80% higher than the TS of the film before radiation treatment.
After 7% HEMA the TS values of the chitosan film decreased with
increasing HEMA concentration and reached to 11 MPa for 10%
HEMA. At low monomer concentration, monomer–polymer back
bone reaction has occurred (as shown in Scheme 1). As monomer
concentration increases, more HEMA may undergo reaction with
chitosan to give an extended carbon chain attached to the side
group of the chitosan molecules and the TS increased. But the
high concentration of HEMA not only increases co-polymerization
Table 2
The tensile strength and elongation at break of the chitosan–starch films with
different composition of glycerol and mustard oil.
Composition of film (w/w) Tensile Elongation at
strength (MPa) break (%) of
Chitosan Starch Glycerol Mustard of film film
(php)* (php)* (php)* oil
(php)*

3.1. Preparation of chitosan–starch biodegradable films 40 60 0 0 13 3

20 0 5 49
25 0 8.88 27
Chitosan–starch films (thickness 0.2 mm) were prepared by 30 0 2.4 97
casting. Good mechanical properties were obtained for chitosan: 40 0 1.7 90
starch ¼4: 6 (w/w) films. The tensile strength and elongation at 25 10 6.34 28
break of the chitosan: starch ¼4: 6 (w/w) film was 13 MPa and 3%, 25 25 8.3 33
25 50 4 16
respectively. To improve the properties of chitosan–starch films, 25 75 2 23
glycerol and mustard oil was added to chitosan–starch solution in
different composition. Weight of glycerol added was varied from n
Per hundred part of polymer (chitosan þstarch).
1662 M.O. Tuhin et al. / Radiation Physics and Chemistry 81 (2012) 1659–1668
Fig. 1. Tensile properties of the irradiated films against monomer concentration
for 10 min soaking time and 5 kGy radiation dose.
Scheme 1. Mechanism of grafting of HEMA onto chitosan by gamma radiation
induced grafting.
Table 3
Tensile modulus of the irradiated films against monomer concentration for 10 min
soaking time and 5 kGy radiation dose.
Concentration of HEMA in soaking formulation 3% 5%
Tensile modulus 363 380
but it also increases homopolymerization. Thus, at higher HEMA
concentration TS decreased due to the dominated recombination
process, creating homo-polymer rather than monomer–polymer
back bone reaction (Alam et al., 2008; Nunthanid et al., 2001).
Tensile modulus (TM) of films also increased with increasing
monomer concentration and reached maximum for 7% HEMA.
With further increase of monomer concentration after 7% HEMA
TM decreased as shown in Table 3.
Elongation at break of the irradiated films was studied as a
function of monomer concentrations and the results are pre-
sented in Fig. 1. It was observed that for all HEMA concentration
Eb found after radiation treatment was lower than the Eb of the
film before irradiation. For 3% HEMA, Eb was found to be 11%. Eb
increased with increase in the percentage of HEMA and reached
the maximum of 16% for 7% HEMA. After 7% HEMA the Eb values
of the chitosan film decreased with increasing HEMA concentra-
tion and reached to 13.8% for 10% HEMA. After HEMA treatment
using gamma radiation the rigidity of the film increased causing
decrease of Eb. At optimum monomer concentration (7% HEMA)
the film became slightly flexible and gained maximum Eb may be
due to the maximum interaction between HEMA and chitosan at
that HEMA concentration.
3.2.2. Effect of radiation dose on mechanical properties of chitosan/
starch blend films
On having the highest TS and Eb for 7% HEMA (M3 formula-
tion) the TS and Eb values of the irradiated films were studied as a
function of radiation dose for 7% HEMA at 10 min soaking time.
The TS values of the irradiated films as a function of radiation
dose are presented in Fig. 2. For 1 kGy TS was found 11 MPa. TS
increased with increase in the radiation dose and reached the
maximum of 15.7 MPa for 5 kGy radiation dose. After the 5 kGy
radiation dose TS values of the chitosan film decreased with
increasing radiation dose and reached to 10 MPa for 8 kGy
radiation dose. It is expected that with the increase of radiation
dose some radicals were generated in chitosan. These radicals
may react with HEMA and can form copolymer of chitosan and
HEMA. As a result, the TS increased. But radicals can also form
from HEMA which promotes homopolymerization. At higher
radiation dose, homopolymer formation dominates that sup-
presses reaction between chitosan and HEMA. High dose of
radiation also cause degradation of chitosan (Zelinska et al.,
2009). Thus, at high radiation dose, the film became brittle and
the TS decreased.
The grafting was done in presence of oxygen because this
process is convenient and can serve our purpose of improving the
mechanical properties of the films to desirable extend. On the
other hand, deoxygenation of the films before irradiation might
increase the cost. Oxygen delays the grafting reaction (higher
radiation dose requires) but does not inhibit it completely. In the
case of direct grafting copolymerization, the main active species
are the free radicals produced by irradiation, in the presence of
oxygen; oxygen reacts with radicals to form peroxides and
consumes radicals (Pengfei et al., 2001). Thus although oxygen
7% 10%
400 286
Fig. 2. Tensile properties of the irradiated films against radiation dose for 10 min
soaking time and 7% HEMA concentration.
 M.O. Tuhin et al. / Radiation Physics and Chemistry 81 (2012) 1659–1668
delays the grafting reaction, the main reaction mechanism will
not change.
Tensile modulus (TM) of films also increased with increasing
radiation dose and reached maximum for 5 kGy. With further
increase of radiation dose TM decreased as shown in Table 4.
Elongation at break of the irradiated films was studied as a
function of radiation dose and the results are presented in Fig. 2. It
was observed that for all radiation doses Eb found after radiation
treatment was lower than the Eb of the film before irradiation. For
1 kGy Eb was found be 5%. Eb increased with increase in the
radiation dose and reached the maximum of 16% for 5 kGy. After
5 kGy, Eb values of the chitosan film decreased with increasing
radiation dose and reached to 15% for 8 kGy. After gamma radiation
treatment the rigidity of the film increased causing decrease of Eb.
At optimum radiation dose (5 kGy) the film became slightly flexible
and gained maximum Eb may be due to the maximum interaction
between HEMA and chitosan at that radiation dose.
3.2.3. Effect of soaking time on mechanical properties of chitosan/
starch blend films
On having the highest TS and Eb for M3 formulation and 5 kGy
gamma radiation dose, the blended films were soaked in M3 for
different soaking times (3, 5, 10, 15 and 20 min) and then
irradiated at 5 kGy radiation. After 24 h of radiation, TS and Eb
were investigated.
The change of TS of chitosan–starch films as a function of
soaking time are shown in Fig. 3. It was observed from Fig. 3 that
for 1 min soaking time TS was found 9.1 MPa. TS increased with
increase in soaking time and reached the maximum of 15.7 MPa
for 10 min soaking time. Increase of soaking time cause more
diffusion of monomer into the sites of reaction and thus increase
the possibility of formation of copolymer by reaction between
monomer and polymer (Rahman et al., 2011). Thus, with increase
of soaking time, more HEMA came in contact with chitosan to
form cross linked network polymer and the TS of the films
increased. However, with further increase in soaking time
homo-polymerization might have predominated. Again soaking
in the monomer solution for longer time might have caused
Table 4
Tensile modulus of the irradiated films against radiation dose for 10 min soaking
time and 7% HEMA.
Radiation dose (kGy) 1 2.5 5 8
Tensile modulus 131 339 400 335
Fig. 3. Tensile properties of the irradiated films against soaking time for 5 kGy
radiation dose and 7% HEMA concentration.
1663
degradation of the film. Therefore, the film became twisted,
shrank and TS decreased.
Tensile modulus (TM) of films also increased with increasing
soaking time and reached maximum for 10 min. With further
increase of soaking time, TM decreased as shown in Table 5.
Elongation at break of the irradiated films was studied as a
function of soaking time and the results are presented in Fig. 3. It
was observed that for all soaking time Eb found after radiation
treatment was lower than the Eb of the film before irradiation. For
3 min soaking time Eb was found to be 8%. Eb increased with the
increase in the radiation dose and reached the maximum of 16%
for 10 min soaking time. After 10 min, Eb values of the chitosan
film decreased with increasing soaking time and reached to 9% for
20 min. After HEMA treatment using gamma radiation the rigidity
of the film increased causing decrease of Eb. At optimum soaking
time (10 min) the film became slightly flexible and gained
maximum Eb may be due to the maximum interaction between
HEMA and chitosan at that soaking time.
Thus the best performance was observed for the chitosan–
starch films soaked in 7% monomer solution for 10 min soaking
time and irradiated by 5 kGy radiation dose. The TS and Eb found
under this condition was 15 MPa and 16%, respectively.
3.3. Polymer loading
Polymer loading (PL) values of the radiated films were studied
and presented as a function of radiation dose for 7% HEMA at
10 min soaking time in Fig. 4. For 1 kGy, PL was found 0.5%. PL
increased with increase in the radiation dose and reached the
maximum of 1% for 5 kGy radiation dose. After the 5 kGy radiation
dose PL values of the chitosan film decreased with increasing
radiation dose and reached to 0.8% for 8 kGy radiation dose. The PL
values obtained are in agreement with the mechanical properties.
3.4. Water uptake
Water uptake of chitosan–starch film (STþCH), chitosan–
starch–glycerol–mustard oil film (STþCHþGþMO) and irradiated
Table 5
Tensile modulus of the irradiated films against soaking time for 7% HEMA and
5 kGy radiation dose.
Soaking time (min) 3 5 10 15 20
Tensile modulus 219 263 400 292 156
Fig. 4. Polymer loading of the irradiated films against radiation dose for 10 min
soaking time and 7% HEMA concentration.
1664 M.O. Tuhin et al. / Radiation Physics and Chemistry 81 (2012) 1659–1668
chitosan–starch–glycerol–mustard oil film were studied for 360 h
and the results are shown in Fig. 5. It was observed that chitosan–
starch–glycerol–mustard oil films showed much lower water
uptake than the chitosan–starch film. Addition of mustard oil
reduced the hydrophilicity of the films. Water uptake values of
irradiated chitosan–starch–glycerol–mustard oil films are slightly
higher than that of chitosan–starch–glycerol–mustard oil films but
still much lower than the chitosan–starch film. It was also observed
that after certain immersion time water uptake values of the films
started to decrease with increasing immersion time, which may be
due to the degradation of the swollen film. The rate of degradation
was also lower for the irradiated chitosan–starch–glycerol–mustard
oil films than the chitosan–starch films. Thus, modified films
showed improved water stability.
3.5. Thermogravimertic analysis of chitosan–starch film
The TGA thermograms for pure chitosan film, chitosan–starch
film (STþCH), chitosan–starch–glycerol–mustard oil film
(STþCHþGþMO) and irradiated chitosan–starch–glycerol–mus-
tard oil film are shown in Fig. 6. It was observed that the thermal
stability of the chitosan film improved by addition of starch.
Incorporation of glycerol and mustard oil also decreased weight
loss. Radiation modification of the chitosan–starch film incorpo-
rated with glycerol and mustard oil caused further improvement
Fig. 5. Water uptake of chitosan–starch films against immersion time.
Fig. 6. The TGA thermograms of chitosan films.
of the thermal stability of the film. The total weight loss of
pure chitosan film at 250 1C was found to be 23 wt%, while the
weight losses of chitosan–starch film (ST þ CH), chitosan–starch–
glycerol–mustard oil film (STþCHþGþMO) and irradiated
chitosan–starch–glycerol–mustard oil film at 250 1C were found
to be 18 wt%, 16 wt% and 10 wt%, respectively. The weight loss of
chitosan films at different temperature in thermogravimertic
analysis are given in Table 6. The TGA data for chitosan films
showed two steps in weight loss: below 100 1C, ranges of 250–
280 1C. The TGA data for chitosan–starch–glycerol–mustard oil
film (STþCHþGþMO) showed one additional step of weight loss
in the ranges of 420–440 1C. As temperature increased from 30 to
100 1C, the TGA curve of chitosan films indicates 5–12% weight
loss due to the adsorbed water (Kumar et al., 2003). The major
weight loss started above 280 1C is related to the char formation
of chitosan. (Rana et al., 2010).
The TGA results clearly indicate that thermal degradation of
the chitosan films reduced after modification of the films, which
is important for different packaging application.
3.6. Dynamic mechanical properties
For the determination of the dynamic mechanical properties of
polymeric materials, the glass transition phenomena and time–
temperature superposition principles of viscoelasticity are impor-
tant factors. The Tg is often measured by differential scanning
calorimetry but the DMA technique is more sensitive and yields
more precise data. DMA can also be used to investigate the
frequency (and therefore time) dependent nature of the transi-
tion. Thus, we have used DMA to investigate the phase relaxation
behavior of chitosan films in this work.
Fig. 7 illustrates the loss factors vs. temperature, often called as
relaxation or inelastic spectra. In the transition region, damping
was high owing to the initiation of micro-Brownian motion in
molecular chains. Some of the molecular chain segments are free
to move, while others are not. A frozen-in segment can store
much more energy for a given deformation than a free rubbery
segment. Thus, every time a stressed, frozen-segment becomes
free to move and its excess energy is dissipated as heat. Micro-
Brownian motion is concerned with the corporative diffusional
motion of main chain segments. This transition is so conspicuous
that it is called the primary relaxation (the a-peak) (Um et al.,
2009).
The primary relaxation (the a-peak) corresponding to the
Tg results from the initiation of micro-Brownian motion of the
amorphous chain. In this glass transition region, the dynamic
modulus (Fig. 8) of the glassy state decreases to the lathery state
modulus. The appearance of the leathery state is caused by the
micro-Brownian motion of the nanocrystalline region under
structural restraint of the neighboring molecular chain in the
crystalline region (Rana et al., 2010).
Three relaxations may be measured by DMA but in this study
only a-relaxation is discussed i.e., 40 1C. Relaxation in the region
Table 6
Weight loss of chitosan films at different temperatures.
Sample Weight loss (%)
At At At
200 1C 250 1C 280 1C
Chitosan film 17 23 35
Chitosan–starch film 15 18 28
Chitosan–starch–glycerol–mustard oil film 10 16 24
Radiation modified chitosan–starch–glycerol– 8 10 22
mustard oil film
 M.O. Tuhin et al. / Radiation Physics and Chemistry 81 (2012) 1659–1668
Fig. 7. Ten delta (tand) vs. temperature of dynamic mechanical analysis of
different chitosan films.
Fig. 8. Dynamic modulus as a function of temperature for different chitosan films.
of glass transition temperature of chitosan depends on water,
which is acting as a plasticizer. A broad water evaporation peak in
the vicinity of 80 to 96 1C covers first transition of water-
plasticized chitosan. The free and weak bonded water molecules
are removed easily from the system by heating up to 120 1C
(Bradley and Carr, 1976; Pizzoli et al., 1991; Ratto et al., 1996).
Pure chitosan film showed two peaks at 85 1C and 134 1C. The
first a-relaxation peak might be formed by intramolecular moist-
ure; second one indicates the reported Tg of chitosan. Chitosan–
starch film, chitosan–starch–glycerol–mustard oil film and HEMA
treated chitosan–starch–glycerol–mustard oil films also showed
two peaks. The two relaxation peaks for chitosan-starch film
became weaker and wider. The interactions between chitosan and
starch might have restrained and hindered the movement of
chitosan molecules and destroyed orderliness of molecular
chains, so that chitosan crystallinity was suppressed. This type
of effect was also observed for chitosan–poly ethylene glycol
blend film (Rana et al., 2010). Again it was observed that the
temperature of first a-relaxation peak for chitosan–starch–
glycerol–mustard oil film and HEMA treated chitosan–starch–
glycerol–mustard oil films was increased to 88 1C and 95 1C,
1665
respectively. This might be due to the reduced hydrophilicity of
the films. But the temperature of second a-relaxation peak for
chitosan–starch–glycerol–mustard oil film and HEMA treated
chitosan–starch–glycerol–mustard oil films was decreased to
126 1C and 125 1C, respectively. This might have caused due to
the glycerol and mustard oil incorporated in the blend films.
Fig. 8 shows the change in the dynamic modulus of chitosan
films. Although the drop in the modulus was observed in all cases,
the initial modulus was not the same. It was observed that the
initial modulus of the chitosan film increased by addition of
starch. Incorporation of glycerol and mustard oil also increased
the initial modulus. Radiation modification of the chitosan–starch
film incorporated with glycerol and mustard oil caused further
increase of initial modulus of the film. A higher storage modulus
was maintained for the blend films than pure chitosan film with
increase in temperature. The storage modulus was increased up
to 80 1C and then storage modulus started to decrease. This
transition, called the a-transition (T a) around 70 to 90 1C in this
case, was defined as glassy region. After the sharp drop of the
storage modulus in the glass transition region, the behavior of
chitosan films moves to the leathery state plateau region caused
by the micro-Brownian motion of non-crystalline region between
90 to 130 1C. At high temperature, chitosan films moved to
rubbery region providing the higher dynamic modulus.
Chitosan showed two transitions. First transition of chitosan at
lower temperature is related to its behavior changes due to water
evaporation. The second transition temperature (the higher tempera-
ture) is called the Tg at which chitosan changes its behavior from
being ’glassy’ to being ’rubbery’. The most important outcome of DMA
studies is that the first transition temperature of chitosan increased
after modification which might be useful for some applications.
3.7. Scanning electron microscopy (SEM)
The scanning electron micrographs of pure chitosan film,
chitosan–starch film (STþCH), chitosan–starch–glycerol–mustard
oil film (STþCHþGþMO) and irradiated chitosan–starch–gly-
cerol–mustard oil film (STþCHþGþMOþHEMA) are shown in
Fig. 9. The SEM micrographs of pure chitosan shows relatively
smooth and homogeneous surface with very sparsely distributed
small particles without any phase separation. The chitosan–starch
blend films also exhibit such patterns. The regular dots might be
due to starch as it was reported that the intensity of dots
decreased with decreasing starch concentration (Salleh et al.,
2009). The chitosan microdomains were dispersed within the
starch matrix in the chitosan–starch blend film with relatively
good interfacial adhesion between the two components and were
similar to the surface of cellulose/carboxymethylated–chitosan
blend films (Li et al., 2002). The micrographs for chitosan–
starch–glycerol–mustard oil film (STþCHþGþMO) showed the
presence of oil droplets in the matrix. The regular dots might have
disappeared due to the dispersion of oil droplets on the surface of
the films. The micrographs of irradiated film showed the presence
regular dots again. Treatment of the chitosan–starch–glycerol–
mustard oil film (STþCHþGþMO) with monomer mixture might
have removed the excess oil droplets from the surface of the film.
It is in agreement with the fact that the water uptake value of the
chitosan–starch–glycerol–mustard oil (STþCHþGþMO) films
increased slightly after radiation modification. The irradiated film
showed uniform distribution of components in the matrix, which
is an indicator of the structural integrity of the film.
3.8. FTIR spectroscopy
The FTIR spectroscopy of chitosan/starch blend films was per-
formed by FTIR spectrophotometer to study interaction between
1666 M.O. Tuhin et al. / Radiation Physics and Chemistry 81 (2012) 1659–1668

Fig. 9. (a) Scanning electron micrograph of pure chitosan film. (b) Scanning electron micrograph of chitosan–starch film. (c) Scanning electron micrograph of chitosan–
starch–glycerol–mustard oil film9 (d). Scanning electron micrographs of irradiated chitosan–starch–glycerol–mustard oil–HEMA film.

Fig. 10. The FTIR spectra for irradiated chitosan–starch–glycerol–mustard oil film.

chitosan and HEMA. The FTIR spectrum of chitosan–starch-glycerol– spectrum of the chitosan films showed peaks at 1030, 1076, and
mustard oil film before and after irradiation is shown in Figs. 10 and 1250 cm  1, characteristic peaks of a saccharide structure (due to C–O
11, respectively. The typical adsorption peaks of the functional groups stretching, O–H bending, and C–N stretching). The band near 1520–
of chitosan were also observed in the spectra of the blend films. The IR 1550 cm  1 was the N–H bending (amide II). A peak near 1745 cm  1
 M.O. Tuhin et al. / Radiation Physics and Chemistry 81 (2012) 1659–1668
Fig. 11. The FTIR spectra for irradiated chitosan–starch–glycerol–mustard
oil–HEMA film.
suggested the presence of a carbonyl group in the film. The peak near
2920 cm  1 corresponded to the C–H stretching, while the bands near
1456 cm  1 was assigned to the CH2 group. Peak near 1369 cm  1 and
1240–1260 cm  1 is characteristic of the CH3 group. Again, peak near
1150–1160 cm  1 is due to C–O bond stretching. The broad band at
3305 cm  1 was the O–H stretching, which overlaps the N–H stretch-
ing in the same region which is prominent in Fig. 10 but not
significant in Fig. 11. The peak at 935 cm  1 is due to O–H bending
which is also absent in Fig. 11. Peaks at 1030 and 1076 cm  1 due to
C–O and O–H bond, respectively, are reduced in intensity for the
irradiated film with respect to the film before irradiation. The
significant reduction of the intensity of peak due to primary alcohol
group (C–O stretch at 1030 cm  1) indicates that substitution might
have occurred at C-6 position.
4. Conclusion
Mechanical properties of the modified chitosan–starch were
studied. The TS and Eb found was 15.7 MPa and 16%, respectively.
Water uptake of the films was also studied. It was found that
modified films possess improved water stability than chitosan–
starch film. Thermal properties of the films were characterized by
thermo gravimetric analysis (TGA) and dynamic mechanical
analysis (DMA). It was observed that the thermal stability of the
chitosan film improved after modification. TGA showed that
the total weight loss of pure chitosan film at 250 1C was 23 wt%,
while the weight losses of chitosan–starch film (ST þCH),
chitosan–starch–glycerol–mustard oil film (ST þCHþG þMO) and
irradiated chitosan–starch–glycerol–mustard oil film at 250 1C
were 18, 16 and 10 wt%, respectively. In DMA a higher storage
modulus was observed for the modified chitosan films than pure
chitosan film with increase in temperature. Scanning electron
microscopy (SEM) showed uniform distribution of components in
the matrix for modified film which is an indicator of the structural
integrity of the film. FTIR indicates grafting of HEMA onto the
modified chitosan–starch film. The results suggest that the
modified films might be suitable for packaging application in
food or biomedical field.
1667
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