Radiation Physics and Chemistry 81 (2012) 995998

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Radiation Physics and Chemistry

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

Fabrication and mechanical characterization of biodegradable and synthetic

polymeric lms: Effect of gamma radiation
Nousin Akter b, Ruhul A. Khan a, Stephane Salmieri a, Nusrat Sharmin a, Dominic Dussault a,
Monique Lacroix a,n
a
Research Laboratories in Sciences Applied to Food, Canadian Irradiation Center (CIC), INRSInstitute Armand-Frappier, University of Quebec, 531 Boulevard des Prairies, Laval,
Quebec H7V 1B7, Canada
b
Department of Applied Chemistry and Chemical Engineering, University of Dhaka, Dhaka 1000, Bangladesh

a r t i c l e i n f o

abstract

Article history:
Received 24 June 2011
Accepted 30 October 2011
Available online 7 November 2011

Chitosan (1 wt%, in 2% aqueous acetic acid solution) and starch (1 wt%, in deionised water) were
dissolved and mixed in different proportions (2080 wt% chitosan) then lms were prepared by casting.
Tensile strength and elongation at break of the 50% chitosan containing starch-based lms were found
to be 47 MPa and 16%, respectively. It was revealed that with the increase of chitosan in starch, the
values of TS improved signicantly. Monomer, 2-butane diol-diacrylate (BDDA) was added into the lm
forming solutions (50% starch-based), then casted lms. The BDDA containing lms were irradiated
under gamma radiation (525 kGy) and it was found that strength of the lms improved signicantly.
On the other hand, synthetic petroleum-based polymeric lms (polycaprolactone, polyethylene and
polypropylene) were prepared by compression moulding. Mechanical and barrier properties of the
lms were evaluated. The gamma irradiated (25 kGy) lms showed higher strength and better barrier
properties.
& 2011 Elsevier Ltd. All rights reserved.

Keywords:
Chitosan
Starch
Biodegradable lms
Synthetic polymers
Packaging materials

1. Introduction
In recent years, there has been a marked increase in interest in
the use of biodegradable materials for packaging, agriculture,
medicine and other areas. In particular, biodegradable polymeric
lms for packaging are of main interest. A number of blends using
bio-polymers can be the alternative of currently used synthetic
polymeric materials. The most common and potential bio-polymers are starch, chitosan, alginate, gelatin etc. It is expected that
these biodegradable polymeric materials will reduce the use of
synthetic non-biodegradable polymeric materials and thus reduce
the environmental pollution. Non-degradable polymers, mainly
from petrochemical origin, used in many packaging applications,
pose a threat to waste disposal. Thus, the use of biodegradable
polymers for packaging offers a solution to the problem of
accumulation of non-degradable waste materials (Yang et al.,
2008; Tang et al., 2009; Khan et al., 2010).
Starch is a potentially interesting biodegradable material due
to its availability, low cost and renewability. Moreover, the use of
starch in the plastics industry can reduce dependence on synthetic polymers. In fact, starch is not truly a thermoplastic like

Corresponding author. Tel.: 1 450 687 5010; fax: 1 450 686 5501.
E-mail address: monique.lacroix@iaf.inrs.ca (M. Lacroix).

0969-806X/$ - see front matter & 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.radphyschem.2011.10.029

most of the synthetic polymers. Starch is a carbohydrate consisting of a large number of glucose units joined together by
glycosidic bonds. It occurs as partially crystalline, water-insoluble
granules that may be destructurized at high temperatures under
pressure and shear in the presence water. When dried, the
resulting product is glassy at room temperature and its glass
transition temperature is higher than its degradation temperature. Starch is a widely useful material for making biodegradable
plastics, but pure starch based lms possesses low mechanical
properties. To improve the drawbacks, blending of starch or its
derivatives with various thermoplastic polymers have been
investigated enormously (Siddaramaiah and Somashekar, 2004;
Chen et al., 2010; Bao et al., 2008).
Among biodegradable lms, a considerable attention has been
given to chitosan because of its unique properties. Chitosan
[b-(1,4)-2-amino-2-deoxy-d-glucopyranose] is a biopolymer
derived by deacetylation of chitin, which is the second most
abundant biopolymer in nature after cellulose. Chitin is present in
the exoskeleton of arthropods such as insects, crabs, shrimps,
lobsters and certain fungal cell walls. The production of chitosan
from crustacean shells, wastes of the seafood industry, is economically feasible. A signicant research works has been done
using chitosan in different elds (Shahidi et al., 1999; Majeti and
Kumar, 2000; Chen et al., 1996). The presence of active groups in
chitosan molecules favored it to use chitosan in many elds.

N. Akter et al. / Radiation Physics and Chemistry 81 (2012) 995998

Chitosan has been reported as a potential material of food

packaging, especially as edible lms and coatings due to its lm
forming properties. Because of reactive amino and hydroxyl
functional groups, chitosan is frequently blended with other
polymers or cross-link to improve their functional properties by
inducing inter- or intra-molecular cross-linking in the polymer
matrix (Alam et al., 2008; Helander et al., 2001; Coma et al.,
2002).
The objective of the present research was to evaluate the effect
of chitosan addition in starch for the development of biodegradable lms for packaging. The mechanical properties of the
prepared lms were measured. Monomer, 2-butane diol-diacrylate (BDDA) was added into the lm forming solutions then
casted the lms. The BDDA containing lms were irradiated for
grafting and cross-linking to improve its mechanical properties.
Synthetic polymeric lms were also exposed to gamma radiation
and the mechanical properties were measured to investigate its
irradiation effect.

2. Materials and methods

2.1. Materials
Chitosan from crab shell (powder form; viscosity of 200 cP)
and starch (from potato) were purchased from Sigma-Aldrich
Chemie GmbH, Germany. Monomer, 2-butane diol-diacrylate
(BDDA) was procured from Sigma-Aldrich, Canada. Synthetic
polymers (polycaprolactone, high density polyethylene and polypropylene) were procured from Sigma-Aldrich, Chemie GmbH,
Germany.
2.2. Preparation of biopolymeric lms by casting
Starch (1% w/w) was dissolved in de-ionized hot (70 1C) water
with constant stirring and chitosan was dissolved in 2% aqueous
acetic acid solution. Then starch and chitosan solutions were
mixed together at different proportions. Films were prepared by
solution casting at 35% relative humidity and then allowed to dry
at room temperature for 96 h. The dried lms were then peeled
off. The lms were then kept in a desiccator at room temperature
and constant relative humidity (65%) prior to testing.
2.3. Preparation of synthetic polymeric lms by compression
molding
Synthetic polymeric (PCL, PE and PP) lms were prepared from
its granules by compression molding machine (Carvar, Inc.,
Indiana, USA, Model 3912) operated above their melting temperatures under a consolidation pressure of 2 t for 1 min. The
mould containing lms was rapidly cooled using a cold press
(Carvar, Inc.,) for 2 min. The polymeric lm was taken out from
the mould and kept in the desiccator prior to testing.
2.4. Mechanical properties of the lms
The mechanical properties (TS and Eb) of the lms were
investigated by the Universal Testing Machine (Hounseld series
S testing machine, UK, H50 KS-0404) with a crosshead speed of
1 mm s  1 at a span distance of 25 mm. The dimensions of the test
specimen were (ISO 14125): 60 mm  15 mm  0.05 mm.
2.5. Water vapor permeability (WVP)
The WVP tests were conducted gravimetrically using an ASTM
procedure (Khan et al., 2010). Films were mechanically sealed

onto Vapometer cells (No. 68-1, Twhing-Albert Instrument Company, West Berlin, NJ, USA) containing 30 g of anhydrous calcium
chloride (0% RH). The cells were initially weighed and placed in a
Shellab 9010 L controlled humidity chamber (Sheldon Manufacturing Inc., Cornelius, OR) maintained at 25 1C and 60% RH for
24 h. The amount of water vapor transferred through the lm and
absorbed by the desiccant was determined from the weight gain
of the cell. The assemblies were weighed initially and after 24 h
for all samples and up to a maximum of 10% gain. Changes in
weight of the cell were recorded to the nearest 10  4 g. WVP was
calculated according to the combined Fick and Henry laws for gas
diffusion through coatings and lms, according to the equation
WVPg mm=m2 day kPa Dwx=ADP
where Dw is the weight gain of the cell (g) after 24 h, x is the lm
thickness (mm), A is the area of exposed lm (31.67  10  4 m2),
and DP is the differential vapor pressure of water through the lm
(DP 3.282 kPa at 25 1C).
2.6. Statistical analysis
For each measurement, ve samples in each replicate were
tested. Analysis of variance and Duncans multiple-range tests
were used to perform statistical analysis of all results, using
PASW Statistics Base 18 software (SPSS Inc., Chicago, IL, USA).
Differences between means were considered to be signicant
when p r0.05.

3. Results and discussion

3.1. Effect of chitosan addition on the mechanical properties of
starch-based lms
The tensile strength (TS) and elongation at break (Eb%) of
chitosan lms were found to be 56 MPa and 11%, respectively.
Chitosan was added into the starch-based solution. The TS values
of starch-based lms improved signicantly (p r0.05) with the
addition of chitosan. Fig. 1 shows the effect of chitosan on TS and
Eb (%) values of starch-based lms. For 20%, 50% and 80% addition
of chitosan, the TS values were observed to be 27, 47 and 53 MPa,
respectively. With the rise of strength, the Eb values of the starchbased lms decreased signicantly (p r0.05) due to chitosan
addition. The Eb values of 20, 50 and 80% chitosan content lms
were 23%, 16% and 12%, respectively. The starch-based lms

70
TS

Eb (%)

60
Tensile Strength (MPa)

996

50
40
30
20
10
0
0

20

40
60
80
Chitosan Content (%)

100

120

Fig. 1. Effect of chitosan on tensile strength (TS) and elongation at break (Eb%) of
starch-based lm.

N. Akter et al. / Radiation Physics and Chemistry 81 (2012) 995998

became brittle below 20% chitosan. So, in this investigation, the

minimum amount of chitosan was maintained to 20% (by wt). It
may be mentioned here that starch could not form lms by
solution casting. But chitosan has excellent lm forming capability (Alam et al., 2008). So, chitosan containing starch-based lms
were prepared easily by solution casting. Starch is comparatively
much cheaper than chitosan. So, biodegradable lms were made
of starch and chitosan. In the following investigation, 50% chitosan containing starch-based lms were taken into considerations because the lms had good strength and optimum Eb
values.
3.2. Effect of gamma radiation on chitosan, starch chitosan and
monomer BDDA grafted starch chitosan lms
Chitosan lms were exposed to gamma radiation (525 kGy).
The strength of the lms improved upto 5 kGy dose due to crosslinking then decreased because of radiation degradation of
chitosan chain (Alam et al., 2008). At 25 kGy, the TS of the lms
decreased to 30%. Fig. 2 represents the effect of gamma radiation
on chitosan, starchchitosan and monomer BDDA grafted
starch chitosan lms. The 50% chitosan containing starch-based
lms showed a linear degradation of TS values during the
exposure of gamma radiation from 5 to 25 kGy. It indicated that
starch is more susceptible to gamma radiation compared to
chitosan. A 51% reduction of TS values was observed for 25 kGy
dose. To improve the strength of starch chitosan-based lms,
monomer (BDDA) was added in the lm forming solution then
lms were casted. The monomer content in the dry lms was
33.34% (wt). A dramatic result was observed when monomer
containing starch chitosan lms were exposed to gamma radiation (525 kGy). A signicant rise of TS values was observed. This
is because of radiation grafting of monomers with starch and
chitosan. The acrylate group of BDDA reacted with hydroxyl
group of starch and amino group of chitosan (Alam et al., 2008;
Khan et al., 2009), thus improved the strength of the lms. The TS
value of starch chitosan lm was found 47 MPa, but addition of
BDDA, the TS value reached to 70 MPa. It is indicated that BDDA
successfully grafted to starch chitosan-based lms.
It is to be noted here that starch/chitosan lms were readily
soluble in water but the monomer BDDA grafted lms was quite
stable for few hours in aqueous medium. The monomer BDDA is a
water insoluble bi-functional acrylic monomer but have biocompatibility. In the prepared lms, the monomer content was

around 33% (weight percent in dry lms). So, the remaining

portion (around 67%) of the prepared lm is totally biodegradable. So, the lm did not lose its total inherent biodegradable
character but withstand its stability for longer period. It is
reported that BDDA was grafted with natural resin shellac via
gamma radiation and demonstrated that mechanical properties of
the shellac lms improved and kept its inherent biodegradable
character (Ghoshal et al., 2010). One researcher (Rahman et al.,
2009) used BDDA grafting for the reduction of hydrophilic nature
of nature ber (jute) and reported better hydrophobic nature with
prolonged degradation behavior. Very recently Mollah and Khan
(2011), successfully grafted BDDA with biodegradable alginate
lms using UV radiation and found higher mechanical properties.
Dong et al. (2007) reported BDDA cross-linked polyethylenimine
have good biocompatibility. It is also reported that BDDA could be
biodegradable with the reaction by piperazine (Kim et al., 2005).
The purpose of these discussions is to conrm that the BDDA
grafted lms did not lose its biodegradability. The starch/chitosan
lms gained better stability in aqueous medium with the grafting
of BDDA by gamma radiation. The two third portions of the
prepared lms are fully biodegradable. It is already mentioned
that BDDA have good biocompatibility, so the prepared lms have
the potential to be the alternative of totally synthetic nonbiodegradable polymeric lms for packaging.
3.3. Effect of gamma radiation on tensile strength (TS) of synthetic
polymers
Synthetic petroleum-based polymeric lm such as PCL, PE and
PP were exposed to gamma radiation (525 kGy), the results are
presented in Fig. 3. It was found that with the rise of radiation
dose, the strength of the polymers improved signicantly
(p r0.05). The TS values of PCL, PE and PP were found to be 16,
20 and 32 MPa, respectively. For 25 kGy irradiated lms, the TS
values reached to 24, 35 and 52 MPa, respectively. This is clear
that a linear rise of strength was observed for synthetic polymers.
When synthetic polymers are subjected to high-energy radiation
(gamma), radicals are produced on the polymeric chain by
hydrogen and hydroxyl abstraction. Gamma radiation also ruptures some carboncarbon bonds and produces radicals. Chain
scission may also take place to form some other radicals. The
ionizing radiation produces three types of reactive species in
polymer. These are ionic, radical and peroxide. The peroxides
species are produced when polymers are irradiated in the

100

60
Chitosan

Chitosan+Starch

Chitosan+Starch+BDDA

80

50

Tensile Strength (MPa)

Tensile Strength (MPa)

997

60

40

20

40
30
20
10
PCL

0
0

10

15
20
Total Dose (kGy)

25

30

Fig. 2. Effect of gamma radiation on tensile strength of chitosan, chitosan starch

and chitosan starch BDDA-grafted lms.

PE

PP

0
0

10

15
20
Total Dose (kGy)

25

30

Fig. 3. Effect of gamma radiation on tensile strength of synthetic polymers.

998

N. Akter et al. / Radiation Physics and Chemistry 81 (2012) 995998

4. Conclusion

2
PCL

PE

PP

Starch chitosan-based biodegradable lms were successfully

prepared by solution casting. Incorporation of chitosan into starch
increased the strength of the lm signicantly. Chitosan was
found to be a very satisfactory lling agent in biodegradable
starch-based packaging. Monomer, BDDA was grafted with
starchchitosan-based lms using gamma radiation. The monomer grafted lms showed excellent mechanical properties. Synthetic polymeric lms were also exposed to gamma radiation. The
mechanical and barrier properties of the irradiated lms indicated
that synthetic polymers cross-linked during the exposure of
radiation. In conclusion, gamma radiation was found to be an
excellent method for grafting and cross-linking of synthetic and
biodegradable lms for packaging.

WVP (g.mm/m2.day.kPa)

1.6

1.2

0.8

0.4

0
0

10

15
20
Total Dose (kGy)

25

30

Fig. 4. Effect of gamma radiation on water vapor permeability (WVP) of synthetic

polymers.

presence of oxygen. In the present study, samples were irradiated

in presence of oxygen. Peroxide reacts with polymers and produces polymer diperoxides and hydroperoxides by a radical chain
reaction process. The effect of high-energy radiation on synthetic
polymers produced ionization and excitation, as a result some
free radical produced. Polymers may undergo cleavage or scission
(i.e., the polymer molecules may be broken into smaller fragment). Subsequent rupture of chemical bonds yields fragments of
the large polymer molecules. The free radicals thus produced may
react to change structure of the polymer and after the physical
properties of the materials. It also may undergo cross-linking (i.e.,
the molecules may be linked together into large molecules).
Gamma irradiation also affects the polymeric structure and
produces active site. Gamma irradiation of synthetic polymers
may result in cross-linking, which produces higher mechanical
properties. Active sites inside the PP matrix might be produced by
the application of gamma radiation. This may be the reason
behind the increased mechanical properties of irradiated synthetic polymers (Zaman et al., 2009; Charlesby, 1958).

3.4. Effect of gamma radiation on water vapor permeability (WVP)

of synthetic polymers
The WVP of PCL, PE and PP were found to be 1.51, 0.16 and
0.24 g mm/m2 day kPa, respectively. Effect of gamma radiation on
the WVP of synthetic polymers is presented in Fig. 4. The values of
WVP decreased signicantly (p r0.05) as the radiation doses
increased. It indicated better barrier properties of the irradiated
lms. Therefore, 24, 50 and 33% reduction of WVP values were
obtained for irradiated (25 kGy) PCL, PE and PP, respectively.
During irradiation of synthetic polymers, some cross-linking can
happen and thus improve the barrier properties. It was also
observed that irradiated lms possess higher strength. Active
sites inside the polymeric matrix might be produced by the
application of gamma radiation and as a result more cross-linked
structure might form (Zaman et al., 2009; Charlesby, 1958).

References
Alam, R., Khan, M.A., Khan, R.A., 2008. Study on the physicomechanical properties
of photocured chitosan lms with oligomer and acrylic monomer. J. Polym.
Environ. 16 (3), 213219.
Bao, J., Jin, L., Xiao, P., Shen, S., Sun, M., Corke, H., 2008. Starch physicochemical
properties and their associations with microsatellite alleles of starch-synthesizing genes in a rice RIL population. J. Agric. Food Chem. 56, 15891594.
Charlesby, A., 1958. Effects of Radiation on Materials. Reinhold Publishing
Corporation, New York 261265.
Chen, C.J., Shen, Y.C., Yeh, A.I., 2010. Physicochemical characteristics of mediamilled corn starch. J. Agric. Food Chem. 58, 90839091.
Chen, M.C., Yeh, G.H.C., Chiang, B.H., 1996. Antimicrobial and physicochemical
properties of methylcellulose and chitosan lms containing a preservative. J.
Food Process. Preserv. 20, 379390.
Coma, V., MartiaL-Gros, A., Garreau, S., Copinet, A., Salin, F., Deschamps, A., 2002.
Edible antimicrobial lms based on Chitosan matrix. J. Food Sci. 67,
11621169.
Dong, W., Li, S., Jin, G., Sun, Q., Ma, D., Hua, Z., 2007. Efcient gene transfection into
mammalian cells mediated by cross-linked polyethylenimine. Int. J. Mol. Sci. 8,
81102.
Ghoshal, S., Khan, M.A., Khan, R.A., Gul-E-Noor, F., Chowdhury, A.M.S., 2010. Study
on the thermo-mechanical and biodegradable properties of shellac lms
grafted with acrylic monomers by gamma radiation. J. Polym. Environ. 18,
216223.
Helander, I.M., Nurmiaho-Lasilla, E.L., Ahvenainen, R., Rhoade, S.J., Roller, S., 2001.
Chitosan disrupts the barrier properties of the outer membrane of Gramnegative bacteria. Int. J. Food Microbiol. 71, 235244.
Khan, R.A., Salmieri, S., Dussault, D., Calderon, J.U., Kamal, M.R., Safrany, A., Lacroix, M.,
2010. Production and properties of nanocellulose reinforced methylcellulosebased biodegradable lms. J. Agric. Food Chem. 58, 78787885.
Khan, M.A., Alam, Rashidul, Noor, Farhana G., Rahman, M.A., Khan, Ruhul A., 2009.
Modication and characterization of chitosan lms using 3-trimethoxyl silyl
propylmethacrylate. J. Macromol. Sci.: Part A, Pure Appl. Chem. 46, 751758.
Kim, M.S., Lee, D.S., Choi, E.K., Kim, J.S., 2005. Modulation of poly(b-amino ester)
pH-sensitive polymers by molecular weight control. J. Macromol. Res. 13 (2),
147151.
Majeti, N.V., Kumar, R.A., 2000. Review of chitin and chitosan applications. React.
Funct. Polym. 46, 127.
Mollah, M.Z.I., Khan, M.A., 2011. Mechanical properties development of sodium
alginate lms with additives by UV-radiation processing. J. Appl. Polym. Sci.
Published online.
Rahman, S.M.A., Mustafa, A.I., Khan, M.A., 2009. Jute reinforced polypropylene
composite: effect of surface pretreatment by photocuring with acrylic monomers. J. Reinf. Plast. Compos. 28 (14), 17331745.
Siddaramaiah, R., Somashekar, R., 2004. The effect of citric acid on the structural
properties and cytotoxicity of the polyvinyl alcohol/starch lms when molding
at high temperature. J. Appl. Polym. Sci. 91, 630.
Shahidi, F., Arachchi, J.K.V., Jeon, Y., 1999. Food applications of chitin and chitosan.
Trend Food Sci. Technol. 10, 3751.
Tang, H., Xiong, H., Tang, S., Zou, P., 2009. A starch-based biodegradable lm
modied by nano silicon dioxide. J. Appl. Polym. Sci. 2009 (113), 3440.
Yang, S.Y., Liu, C.I., Wu, J.Y., Kuo, J.C., Huang, C.Y., 2008. Improving the processing
ability and mechanical strength of starch/poly(vinyl alcohol) blends through
plasma and acid modication. Macromol. Symp. 272, 150155.
Zaman, Haydar U., Khan, Ruhul A., Khan, Mubarak A., Khan, A.H., Hossain, M.A.,
2009. Effect of gamma radiation on the performance of jute fabrics reinforced
polypropylene composites. Radiat. Phys. Chem. 78, 986993.