Industrial Crops and Products 21 (2005) 185192

Chitosanstarch composite film: preparation

and characterization
Y.X. Xu a , K.M. Kim b , M.A. Hanna a, , D. Nag c
a

Department of Food Science and Technology, Industrial Agricultural Products Center, University of Nebraska,
208 L.W. Chase Hall, Lincoln, NE 68583-0730, USA
Industrial Agricultural Products Center, University of Nebraska, 208 L.W. Chase Hall, Lincoln, NE 68583-0730, USA
c Department of Chemistry, University of Nebraska, 824 Hamilton Hall, Lincoln, NE 68588-0304, USA
Received 27 October 2003; accepted 17 March 2004

Abstract
Chitosan film has potential applications in agriculture, food, and pharmacy. However, films made only from chitosan lack
water resistance and have poor mechanical properties. Forming miscible, biodegradable composite film from chitosan with other
hydrophilic biopolymers is an alternative. The objective of this study was to prepare chitosan/starch composite films by combining
chitosan (deacetylated degree, 90%) solution and two thermally gelatinized cornstarches (waxy starch and regular starch with 25%
amylose). The films tensile strength (TS), elongation-at-break (E), and water vapor transmission rate (WVTR) were investigated.
The possible interactions between the two major components were evaluated by X-ray diffraction and Fourier-transform infrared
spectroscopy (FTIR). Regardless of starch type, both the TS and E of the composite films first increased and then decreased with
starch addition. Composite film made with regular starch showed higher TS and E than those with waxy starch. The addition
of starch decreased WVTRs of the composite films. The introduction of gelatinized starch suppressed the crystalline peaks of
chitosan film. The amino group band of chitosan molecule in the FTIR spectrum shifted from 1578 cm1 in the chitosan film to
1584 cm1 in composite films. These results indicated that there was a molecular miscibility between these two components.
2004 Elsevier B.V. All rights reserved.
Keywords: Chitosanstarch films; Mechanical properties; Water resistance; Miscibility

1. Introduction

Journal Series No. 13966, Agricultural Research Division,

Institute of Agriculture and Natural Resources, University of
Nebraska-Lincoln. This study was conducted at the Industrial Agricultural Products Center, University of Nebraska, Lincoln, NE,
USA.
Corresponding author. Tel.: +1-402-4721634;
fax: +1-402-4726338.
E-mail address: mhanna1@unl.edu (M.A. Hanna).

In recent years, increasing interest in edible films

has developed mainly due to concern over the disposal of conventional synthetic plastic materials
derived from petroleum. Degradation of plastics requires a long time and most of them end up overburdening on landfill. Conversely, edible films from
renewable agriculture products not only are degraded
readily after their disposal, but also can extend

0926-6690/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.indcrop.2004.03.002

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Y.X. Xu et al. / Industrial Crops and Products 21 (2005) 185192

the food shelf-life, thus improving the quality of

food.
Among various available edible film materials, considerable attention has been given to chitosan because
of its unique properties. First of all, abundant commercial supplies are available. Chitosan is derived from
chitin, which is the second most abundant polysaccharide on earth next to cellulose and is available from
waste products in the shellfish industry (Wong et al.,
1992). Chitosan possesses repeating units of 1,4 linked
2-deoxy-2-aminoglucose. The amino group NH2 can
be protonated to NH3 + and readily form electrostatic
interactions with anionic groups in an acid environment. This property has been applied on edible films.
Systematic investigations have been reported on the
effects of factors such as plasticizers concentrations,
storage time (Butler et al., 1996), acid types and concentrations (Caner et al., 1998), molecular weights of
chitosan (Park et al., 2002), and the degree of deacetylation of chitosan(Wiles et al., 2000) on the mehanical properties and barrier characteristics of chitosan
films. Although chitosan films are highly impermeable to oxygen, they have relatively poor water vapor
barrier characteristics (Butler et al., 1996). Plasticizers
have negative effects on barrier properties and positive effects on mechanical properties. The functional
properties of chitosan films are improved when chitosan is combined with other film-forming materials.
Hoagland and Parris (1996) prepared chitosan-pectin
laminated films by interacting the cationic groups on
chitosan with the anionic groups on pectin. Hosokawa
et al. (1990) reported that when biodegradable films
were made from chitosan and homogenized cellulose
oxidized with ozone the number of carbonyl and carboxyl groups on the cellulose interacting with the
amino groups on the chitosan increased. The water resistance of chitosan film was ameliorated by the incorporation of hydrophobic materials such as fatty acids
to enhance the films hydrophobicity (Wong et al.,
1992).
Starch has been used to produce biodegradable films
to partially or entirely replace plastic polymers because of its low cost and renewability. However, wide
application of starch film is limited by its water solubility and brittleness (Wu and Zhang, 2001). In order to overcome these shortcomings, Jagannath et al.
(2003) blended starch with different proteins to decrease the water vapor permeability of the films and

to increase their tensile strength (TS). The objective

of this study was to prepare composite films from chitosan and starch and to evaluate their mechanical properties, water resistance, and compatibility.

2. Materials and methods

2.1. Film preparation
Chitosan solutions (2%, w/v) were prepared by dispersing 10 g of chitosan (deacetylated degree of 90%;
Vanson, Redmond, WA) in 500 ml of lactic acid solution (1%, v/v). After the chitosan was dissolved completely, the solutions were filtered with cheesecloth by
vacuum aspiration. Starch solutions with concentrations of 1, 2, 3 and 4% (w/v) were prepared by dispersing 25% amylose cornstarch or waxy starch (American Maize Products Co., Hammond, IN) in distilled
water and heating the mixtures on hotplates with stirring until it gelatinized, and then cooling to 25 C.
A series of chitosan/starch composite films were prepared by mixing 100 ml of 2% chitosan solution with
100 ml of 1, 2, 3, 4% starch solutions. Glycerin was
added as 25% (w/w) of the total solid weight in solution. The blend compositions are given in Table 1. The
mixtures were cast onto flat, level Teflon-coated glass
plates. After drying the films at room temperature for
at least 72 h, they were peeled from the plates. Dried
films were conditioned at 50% RH and 25 C for 48 h
prior to testing.
2.2. Thickness
Film thickness was measured to the nearest 2.54 m
(0.1 ml) with a hand-held micrometer (B.C. Ames
Table 1
Compositions of chitosan/starch blends
Starch to
chitosan
ratio (g)

Compositions
Chitosan solution
(2%, w/v) (ml)

Starch solution
(w/v) (ml)

Glycerin
(g)

0
0.5:1
1:1
1.5:1
2:1

200
100
100
100
100

0
100
100
100
100

1.00
0.75
1.00
1.25
1.50

of
of
of
of

1%
2%
3%
4%

Y.X. Xu et al. / Industrial Crops and Products 21 (2005) 185192

Co., Waltham, MA). Five thickness measurements

were taken along the length of each specimen and
the mean was used in calculating the film tensile
strength.
2.3. Mechanical properties
Mechanical properties of TS and E were measured
with an Instron Universal Testing Machine (Model
5566, Instron Corp., Canton, MA) following the guidelines of ASTM Standard Method D 882-91 (1995a).
The initial grip separation was set at 50 mm and the
crosshead speed was set at 500 mm/min. TS was expressed in MPa and calculated by dividing the maximum load (N) by the initial cross-sectional area (m2 )
of the specimen. E was calculated as the ratio of the
final length at the point of sample rupture to the initial length of a specimen (50 mm) and expressed as a
percentage. TS and E tests were replicated five times
for each type of film.
2.4. Water vapor transmission rate (WVTR)
Five film specimens were tested for each type
of film. WVTR (g/m2 h) was determined gravimetrically using a modification of ASTM Method
E 96-95 (1995b) described by Gennadios et al. (1994,
1996). Film specimens were mounted on polymethylmethacrylate cups contaning 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 velocity of approximately
200 m/min 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
in g/h.
2.5. X-ray diffraction
X-ray patterns of chitosan, starch powders, and
chitosan/starch composite films were analyzed using
an X-ray diffractometer (Rigaku D/Max-B, Tokyo,
Japan) with Cu K radiation at a voltage of 40 kV
and 30 mA. The samples were scanned between
2 = 340 with a scanning speed of 2 min1 . Prior
to testing, the samples were dried and stored in a
desiccator.

187

2.6. Fourier transform infrared (FTIR)

FTIR spectra of the films were recorded using an
attenuated total reflection (ATR) method in IR spectometer (Nicolet Avatar 360, Madison, WI). The thin
films were applied directly onto the ZnSe ATR cell.
For each spectrum, 128 consecutive scans at 4 cm1
resolutions were averaged.

3. Results and discussions

3.1. Mechanical properties
3.1.1. Tensile strength (TS)
The TS values of the chitosan/starch composite
films with the different starch ratios are shown in
Fig. 1a. It was found that, no matter which type starch
was present, the TS values of the composite films first
increased with the addition of starch, passing through
a maximum at 40.25 MPa for those with regular starch
and 33.69 MPa for those with waxy starch. Both maximums occurred at the starch to chitsan ratio of 1:1.
The TS then decreased with further increase in the
starch to chitosan ratio up to 2:1. The increasing TS
values of the composite films, with the starch to chitosan ratio increasing from 0 to 1:1, are attributable
to the formation of inter-molecular hydrogen bonds
between NH3 + of the chitosan backbone and OH
of the starch. The amino groups (NH2 ) of the chitosan were protonated to NH3 + in the lactic acid
solvent, whereas the ordered crystalline structures
of the starch molecules were destroyed with gelatinization, resulting in the OH groups being exposed
to readily form hydrogen bonds with NH3 + of the
chitosan. The number of hydroxyl groups increased
with increasing starch ratio in the film-forming
solution.
Based on the data set, the starch to chitosan ratio
of 1:1 was the critical value for the TS value of the
composite films and indicated the greatest integrity of
the two main film-forming components. At the higher
starch to chitosan ratios, the TS of the composite films
decreased abruptly. The decrease in TS with increasing
starch ratio may occur because starch intra-molecular
hydrogen bonds rather than inter-molecular hydrogen
bonds are formed, resulting in a phase separation between the two main components.

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Y.X. Xu et al. / Industrial Crops and Products 21 (2005) 185192

45

(a)

Tensile strength (MPa)

40
35
30
25
20
15
10
5

(b)
70

Elongation (%)

60

50

40

30

20

10

Water vapor transmission rate (g/m

2.

h)

(c)
60

55

50

45

40
0.0

0.5

1.0

1.5

2.0

Ratio g starch : chitosan

Fig. 1. Effects of starch ratios on (a) tensile strengths (TS), (b) elongation-at-breaks (E), and (c) water vapor transmission rates (WVTR)
of the composite films (solid symbol denotes regular cornstarch (25% amylose) and open symbol denotes waxy cornstarch (100%
amylopectin)).

Y.X. Xu et al. / Industrial Crops and Products 21 (2005) 185192

Furthermore, the regular starch composite films

showed higher TS than the waxy starch films because
of differences in the compositions of the two starches.
Regular starch contains about 25% amylose, whereas
waxy starch contains almost 100% amylopectin. Amlyose consists of -1,4-glucopyranose, which is a
long linear polymer that can readily align closely or
associate with similar linear chitosan molecules to
form the inter-molecular hydrogen bonds. Conversely,
steric hindrance in the highly branched amylopectin,
comprised of both -1,4 and -1,6-glucopyranose,
decreases the possibility of forming hydrogen bonds
(FTNS, 1997).
3.1.2. Elongation-at-break (E)
The E values of the composite films were affected
by the starch to chitosan ratios (Fig. 1b). The average
E values of the composite films behaved similar to the
TS values, increasing from 33.3% for chitosan film to
a maximum of 61.1% for the regular starch film, and
58.9% for the waxy starch film. The maximum occurred at the starch to chitosan ratio of 1.5:1. However,
when the ratio was increased further to 2:1, the E values suddenly decreased to 27.9% for the regular starch
and 44.7% for the waxy starch film. Starch films are
typically very brittle. The addition of too much starch
lowered the flexibility of the film.
3.2. Water vapor transmission rate (WVTR)
The WVTR values of the composite films as a function of starch ratio in the film-forming solutions are
shown in Fig. 1c. The WVTR maximum occurred at
the starch to chitosan ratio of 0.5:1, and then decreased
with the addition of starch. When the ratio was 2:1,
the WVTR was 46.45 g/m2 h for the regular starch
composite film and 47.83 g/m2 h for the waxy starch
film. Pure chitosan film had a WVTR of 52.73 g/m2 h.
Low WVTR widens the application of the composite
packaging film, especially in a highly humid environment. 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.
The composite films with regular starch had a
lower WVTR than those with waxy starch. The different compositions of these two starches along with
the different interaction intensity between starch and

189

chitosan were responsible for the differences. In spite

of having an interaction between the two main components, the intensity of non-thermal mixing was
lower than that obtained by intensive thermal mixing
(Jagannath et al., 2003). The cross-linking caused
by thermal mixing transformed the hydrophilic
hydrophilic blend into a more hydrophobic one, thus
resulting in a five- to six-fold decrease in the WVTR
of the film.
The preceding discussions focused on the changes
in the mechanical properties and water resistance of
chitosan/starch composite films. The addition of starch
is assumed to cause hydrogen bond formation between
the two main components. In the following sections,
we identify whether interactions existed between chitosan and starch molecules by X-ray diffraction and
FTIR spectroscopy.
3.3. X-ray diffraction
X-ray diffractograms of chitosan/starch composite
films are shown in Fig. 2a and b. As observed, the chitosan powder was in a crystalline state because two
main diffraction peaks (2 = 11.6 and 20.25 ) were
observed in its X-ray diffraction pattern. This agrees
with the finding of Nunthanid et al. (2001). After making the films, two crystalline peaks still existed, but
the intensities were less. Moreover, native cornstarch
has a typical A-type crystalline structure (Kim et al.,
2003). The dried regular starch films and waxy starch
film, after gelatinization, had different structures. The
crystalline structure still existed in the regular starch
film, whereas an amorphous state was observed in the
waxy starch film.
When these two film-forming components were
mixed at a starch to chitosan ratio of 0.5:1, two chitosan peaks still were observed for the low ratio,
indicating that chitosan structure was not influenced
by the addition of a small amount of starch. However, the crystalline peaks of the chitosan were suppressed when the starch ratio in the composite film
was increased. In its place, a new broad amorphous
peak, with greater intensity was observed, demonstrating an interaction between these two components
(Yin et al., 1999). Interestingly, one chitosan peak
reappeared in the chitosan/regular starch composite
film when the ratio of starch to chitosan was 2:1.
Reappearance of this peak suggests that there was a

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Y.X. Xu et al. / Industrial Crops and Products 21 (2005) 185192

Fig. 2. X-ray patterns for (a) chitosan/regular starch composite films and (b) chitosan/waxy starch composite films.

phase separation between the two main components

of the composite films. This was consistent with the
results of the TS and E values as both decreased
noticeably at the highest starch ratio due to phase
separation.
3.4. FTIR spectroscopy
FTIR spectroscopy was used to examine the interactions between chitosan and starch. The infrared spectra of chitosan, starch, and chitosan/starch composite
film are presented in Fig. 3. The chitosan spectrum
was similar to previous reports (Nunthanid et al., 2001;
Ritthidej et al., 2002). The broad band at 3351 cm1
was the OH stretching, which overlaps the NH stretching in the same region. The band at 1578 cm1 was the
NH bending (amide II). A small peak near 1655 cm1
was due to the C=O stretching (amide I), and a peak at
1741 cm1 suggested the presence of a carbonyl group
in the film. In the spectrum for starch film, the broad

band at 3413 cm1 was the OH stretching. The peak at

2929 cm1 corresponded to the CH stretching, while
the bands at 1648 cm1 and 1458 cm1 were assigned
to the (OH) bendings of water and CH2 , respectively
(Mano et al., 2003). The bands from 763 to 1136 cm1
corresponded to the CO bond stretching.
When two or more substances are mixed, physical blends versus chemical interactions are reflected
by changes in characteristic spectra peaks (Guan
et al., 1998; Yin et al., 1999). In the typical spectrum of chitosan/starch composite film, the amino
peak of chitosan shifted from 1578 to 1584 cm1
with the addition of starch. This result indicated
that interactions were present between the hydroxyl
groups of starch and the amino groups of chitosan
(Meenakshi et al., 2002). This is consistent with our
other results. In our case, the peak of the hydroxyl
groups could not be used to evaluate the interactions
because of the effects of content of glycerin and
water.

Y.X. Xu et al. / Industrial Crops and Products 21 (2005) 185192

1741

chitosan

Transmittance (%)

191

3351

1655

2923

1578

starch
1648
2929

763
1458

1136

341 3
chi tosan- starch
2923
1584
3314

4500

4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumbers ( cm )
Fig. 3. Attenuated total reflection (ATR) spectra of chitosan film, starch film, and typical chitosan/regular starch composite film with the
ratio of starch to chitosan of 1:1.

4. Conclusion

References

Chitosan/starch composite films were made from

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water vapor transmission rates with increasing starch
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depressed with the addition of the gelatinized starch
and a broad amorphous peak appeared. The amino
group peak in IR spectrum of chitosan molecule
shifted from 1578 to 1584 cm1 with the incorporation of starch. These results suggested that these two
film-forming components were compatible and an
interaction existed between them.

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Acknowledgements
The authors thank Sara Basiaga, Chemistry Department, University of Nebraska for her assistance with
the FTIR measurements. We also thank Mr. Brian
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