Effects of Hydrophilic Plasticizers on Mechanical, Thermal, and

Surface Properties of Chitosan Films

NUGRAHA E. SUYATMA, LAN TIGHZERT,* AND ALAIN COPINET
Centre dEtudes et de Recherche en Materiaux et Emballage (CERME), Ecole Superieure dIngenieurs
en Emballage et Conditionnement (ESIEC), Universite de Reims Champagne Ardenne, Esplanade
Roland Garros, BP 1029, 51686 Reims Cedex 2, France
VE RONIQUE COMA
Laboratoire de Chimie des Substances Vegetales, Centre de Recherche en Chimie Moleculaire,
Universite Bordeaux 1, 351 Cours de la Liberation, 33405 Talence, France
Chitosan films were plasticized with four hydrophilic compounds, namely, glycerol (GLY), ethylene
glycol (EG), poly(ethylene glycol) (PEG), and propylene glycol (PG). Our objective was to investigate
the effect of plasticizers on mechanical and surface properties of chitosan films. The stability of
plasticized films was observed by storage for 3 and 20 weeks in an environmental chamber at
50 ( 5% RH and 23 ( 2 C. Plasticization improves the chitosan ductility, and typical stress-strain
curves of plasticized films have the features of ductile materials, except the film made with 5% PG
that exhibits as a brittle polymer and shows an antiplasticization effect. In most cases, the elongation
of plasticized films decreases with the storage time, which might be due to the recrystallization of
chitosan and the loss of moisture and plasticizer from the film matrix. Although at the beginning the
mechanical properties of films made with PG, at high plasticizer concentration, are comparable to
those of films made with EG, GLY, and PEG, their stability is poor and they tend to become brittle
materials. The surface properties, analyzed by contact angle measurement, reveal that plasticization
increases film hydrophilicity. It is found that GLY and PEG are more suitable as chitosan plasticizers
than EG and PG by taking into account their plasticization efficiency and storage stability. Furthermore,
a plasticizer concentration of 20% (w/w) with GLY or PEG seemingly is sufficient to obtain flexible
chitosan film with a good stability for 5 months of storage.
KEYWORDS: Chitosan; plasticizers; edible film; mechanical properties; surface properties
INTRODUCTION
The concept of employing edible films as protective coatings
for food is not novel. Patents on edible films to extend the shelf
life of foods date back to the 1950s (1). However, there has
been a resurgence of interest in recent years in the development
of edible films and coatings for food due to the increased
consumer demand for food quality, long shelf life, convenience,
and reducing the environmental impact of packaging wastes (2).
Edible films and coatings are thin films prepared from edible
material that act as a barrier to the external elements (factors
such as moisture, oil, and vapor) and thus protect the product
and extend its shelf life. The major benefit of the edible films
and coatings is that they can be consumed along with the food,
can provide additional nutritients, may enhance sensory char-
acteristics, and may include quality-enhancing antimicrobials.
Biopolymer films and coatings are generally designed using
biological materials such as polysaccharides, proteins, lipids,
and derivatives (1).
Chitosan [-(1,4)-2-amino-2-deoxy-D-GLUCOPYRANOSE] is a
natural polymer derived by deacetylation of chitin, which is the
second most abundant biopolymer in nature after cellulose (3).
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 (4). Compared with
other polysaccharides, chitosan has several important advan-
tages, including biocompatibility, biodegradability, and no
toxicity. Moreover, several studies have indicated the bacterio-
static (5-10) and fongistatic (11) activities of chitosan.
Thanks to its film-forming properties, chitosan has been
reported as a potential material of food packaging, especially
as edible films and coatings (12). Furthermore, the potential of
chitosan as antimicrobial films and coatings for extending shelf
life of foodstuffs has been reported in several publications, e.g.,
in the storage of fruits and vegetables (13-15), meat products
* Corresponding author. Telephone/Fax: +33-326-913764. E-mail:
lan.tighzert@univ-reims.fr.
3950 J. Agric. Food Chem. 2005, 53, 39503957
10.1021/jf048790+ CCC: $30.25 2005 American Chemical Society
Published on Web 04/20/2005
(16, 17), and seafood products (18, 19). Unfortunately, chitosan
film is brittle (20, 21); thus it needs a plasticizer to increase
film flexibility.
Plasticizers are additives used to increase the flexibility or
plasticity of polymers, and occasionally they are used only to
facilitate the polymer processing (22). Several theories have been
proposed to explain the mechanisms of plasticization action (23).
The lubrication theory postulates that plasticizers, by interspers-
ing themselves, act as internal lubricants by reducing frictional
forces between polymer chains. The gel theory postulates that
the rigidity of polymer comes from three-dimensional structures,
and plasticizers take effect by breaking polymer-polymer
interactions (e.g., hydrogen bonds and van der Waals or ionic
forces). The free volume theory states a plasticization as a study
of ways to increase free volume and is useful in explaining the
lowering of the glass transition temperature (T
g
) by a plasticizer.
Ideal plasticizers are miscible and compatible in all proportions
with plastic components, and they may be added to polymers
in solution (dispersion technique) or after solvents have been
removed (absorption technique) (24). Water, oligosaccharides,
polyols, and lipids are different types of plasticizers widely used
in hydrocolloid-based films.
Several studies on plasticization of chitosan films revealed
that poly(ethylene glycol) (PEG) could improve the elastic
properties of chitosan (25-27). Caner et al. (28) observed that
chitosan plasticization using PEG was stable until 9 weeks of
storage. On the contrary, Butler et al. (29) found the water
barrier and mechanical properties of plasticized chitosan films
with glycerol changed during storage. Other authors used
plasticizers in chitosan blends. Hosokawa et al. (30) used
glycerol to plasticize chitosan/cellulose composites, whereas
Arvanitoyannis et al. (31) used sorbitol and sucrose to plasticize
chitosan/poly(vinyl alcohol) blends. They stated that the elonga-
tion of blended films increased with increasing plasticizer
contents, but at high plasticizer contents there were decreases
in both tensile strength and modulus. From these studies, the
film aging and the amount and type of plasticizer would be
important issues in the application of chitosan as edible films
and coatings. However, the comparisons among plasticizer
efficiencies have not been studied for chitosan films.
The aim of this study is to investigate the influence of four
hydrophilic plasticizers, namely, glycerol (GLY), ethylene glycol
(EG), poly(ethylene glycol) (PEG), and propylene glycol (PG),
on chitosan films. The plasticizer efficiencies of four hydrophilic
compounds and their stability during storage were compared
using the same conditions.
MATERIALS AND METHODS
Materials. Chitosan powder (No. 234), food grade with a degree of
deacetylation of 98%, was kindly provided by France Chitine
(Marseille, France). Ethylene glycol (MW) 62), poly(ethylene glycol)
(MW) 200), propylene glycol (MW) 76), and glycerol (MW) 92)
were purchased from Sigma-Aldrich Co. (St. Louis, MO).
Preparation of Plasticized Chitosan Films. Plasticized chitosan
films were prepared with some modifications of the method of Kolhe
and Kannan (27). A 2% chitosan or chitosan/plasticizer solution was
prepared by adding 10 g of chitosan powder or chitosan/plasticizer in
500 mL of 1% acetic acid aqueous solution by vigorously stirring the
chitosan suspension. The chitosan and chitosan/plasticizer solutions
were filtered through a coarse sintered glass filter to remove undissolved
impurities. The compositions of chitosan/plasticizer blends were
100/0; 95/5; 80/20, and 60/40 by weight. Films were cast on a poly-
(methyl methacrylate) plate and dried at ambient conditions. The
obtained films were conditioned in humidity chamber (CIAT, France)
at 50 ( 5% relative humidity (RH) and 23 ( 2 C.
Film Characterization. Thickness Measurements. Film thickness
was measured with a thickness tester (Thwing-Albert Instrument Co.,
Philadelphia, PA). Five values were randomly taken at different
locations for each specimen of tensile tests, and the mean value was
used in the determination of mechanical properties.
Moisture Content. To determine the moisture content of films stored
for 3 and 20 weeks (23 ( 2 C and 50 ( 5% RH), about 100 mg of
film samples was dried in a vacuum oven at 60 C until an equilibrium
weight was reached. This method was adopted from Hulleman et al.
(32). At these conditions, evaporation of plasticizers from matrix film
was negligible. The weight loss of the sample was determined, from
which the moisture content was calculated using the equation
WC ) (Mi - Md)/Md 100, where Mi and Md are the masses of initial
and dried samples, respectively.
Mechanical Properties. Tensile tests were performed on a tensile
testing machine (model TEST 108 from GTTest, France, equipped with
the software Test Winner 920), with a crosshead speed of 10 mm/min
and a 2 kN static load cell. The films were cut into standard tensile
samples from a dumbbell-shaped knife (H3 type) with a dimension
17 mm 4 mm 0.08 mm (length width thickness). At least
five samples of each type of film were tested after a suitable storage
period (3 and 20 weeks) at 50 ( 3% RH and 23 ( 2 C in a humidity
chamber (CIAT, France). We started the film characterizations after
3 weeks because in our experiments the materials did not achieve the
moisture equilibrium before this time. The maximal tensile stress (TS)
was calculated by dividing the maximum load for breaking film by
cross-sectional area and elongation at break (Eb) by dividing film
elongation at rupture by the initial gauge length.
Surface Hydrophobicity. Contact angle measurements were per-
formed with a goniometer (Kruss G23, Germany). A drop of distilled
water (5 L) was placed on the film surface. The evolution of the droplet
shape was recorded. A CCD video camera and image analysis software
were used to determine the contact angle evolution, which may be used
to determine the initial contact angle and the kinetics of the water
sorption (slope of the curve contact angle ) f(time)). A minimum of
seven measurements, taken at different positions on the film, was carried
out. The contact angles were measured on both sides of the drop and
averaged.
Moisture Uptake. Moisture uptake were measured by following the
method of Angle`s and Dufresne (33) instead of the classical technique
(immersion in water), because chitosan is very sensitive to liquid water
and can partially dissolve after long time exposure to water. The dried
sheets of 20 mm 20 mm were first conditioned at 0% RH (P2O5) for
1 week. After weighing, they were conditioned at 20-25 C in a
desiccator containing CuSO45H2O saturated solution to ensure a
relative humidity of 98%. The samples were removed at desired
intervals and weighed until the equilibrium state was reached. The
moisture uptake of the samples was calculated as follows:
where W
t and W0 are the weights of the sample after t time in 98% RH
and the initial weight of the sample, respectively.
Thermal Analysis. The thermal characteristics of the films were
determined using a differential scanning calorimeter (TA instrument)
cooled with liquid nitrogen circulation. Samples (10 mg) were cut
from a sample specimen after conditioning and placed in sealed
aluminum pans. For each sample, the following thermal cycle was
applied: a first scan was made from -30 to +190 C, conditions were
isothermal for 1 min at 190 C, then the sample was cooled rapidly to
0 C and kept isothermal for 5 min at 0 C, and then there was a second
heating to 300 C. The heating rate used was 5 C/min, and an empty
pan was used as the reference. With two cycles of heating and cooling
runs, the effect of moisture is eliminated, and we observed the thermal
properties of films just once in the middle of the storage time.
Statistical Analysis. All experiments were measured in triplicate, with
individually prepared and cast films as replicated experimental units.
STATGRAPHICS Plus for Windows (Statistical Graphic Corp, Rock-
ville, MD) was used for multifactor analysis of variance. Differences
in the properties of the film samples were determined by Fishers least
moisture uptake (%) )
W
t
- W
0
W
0
100
Effects of Hydrophilic Plasticizers on Chitosan Films J. Agric. Food Chem., Vol. 53, No. 10, 2005 3951