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LWT - Food Science and Technology 41 (2008) 1633e1641

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Preparation and properties of rice starchechitosan blend

biodegradable film
Thawien Bourtoom a, Manjeet S. Chinnan b,*
a
Department of Material Product Technology, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand
b
Department of Food Science and Technology, University of Georgia, 1109 Experiment Street, Griffin, GA 30223-1797, USA
Received 25 May 2007; received in revised form 15 October 2007; accepted 23 October 2007

Abstract

Biodegradable blend films from rice starchechitosan were developed by casting film-solution on leveled trays. The influence of the ratio of
starch and chitosan (2:1, 1.5:1, 1:1, and 0.5:1) on the mechanical properties, water barrier properties, and miscibility of biodegradable blend
films was investigated. The biodegradable blend film from rice starchechitosan showed an increase in tensile strength (TS), water vapor
permeability (WVP), lighter color and yellowness and a decreasing elongation at the break (E ), and film solubility (FS) after incorporation
of chitosan. The introduction of chitosan increased the crystalline peak structure of starch film; however, too high chitosan concentration yielded
phase separation between starch and chitosan. The amino group band of the chitosan molecule in the FTIR spectrum shifted from 1541.15 cm1
in the chitosan film to 1621.96 cm1 in the biodegradable blend films. These results pointed out that there was a molecular miscibility between
these two components. The properties of rice starchechitosan biodegradable blend film and selected biopolymer and synthetic polymer films
were compared; the results demonstrated that rice starchechitosan biodegradable blend film had mechanical properties similar to the other
chitosan films. However, the water vapor permeability of rice starchechitosan biodegradable blend film was characterized by relatively lower
water vapor permeability than chitosan films but higher than polyolefin.
2007 Swiss Society of Food Science and Technology. Published by Elsevier Ltd. All rights reserved.

Keywords: Rice starch; Chitosan; Biodegradable film; Miscibility

1. Introduction absorption of oxygen, to lessen migration of lipids, to improve

mechanical handling properties, to provide physical protec-
There is a considerable interest in biodegradable films tion, or to offer an alternative to the commercial packaging
made from renewable and natural polymers, such as starch materials (Kester & Fennema, 1986; Murray & Luft, 1973;
(Lawton, 1996). Several studies have been performed to Nelson & Fennema, 1991). The use of a biopolymer such as
analyze the properties of starch-based biodegradable films starch can be an interesting solution because this polymer is
(Arvanitoyannis & Biliaderis, 1998; Garcia, Martino, & relatively inexpensive, abundant, biodegradable, and edible
Zaritzky, 1999; Lourdin, Valle, & Colonna, 1995; Mali & (Mali & Grossmann, 2003).
Grossmann, 2003). Biodegradable polymer films are not Rice is the most widely consumed basic food in the world.
meant to totally replace synthetic packaging films, but to limit Each year over 500 million tons of rice is harvested, providing
moisture, aroma, and lipid migration between food compo- sustenance to many countries and people throughout the world.
nents where traditional packaging cannot function. For The unique properties of rice starches are found in its many
instance, biodegradable and edible films can be used for versa- varieties. Due to different climates, soil characteristics and
tile food products to reduce loss of moisture, to restrict cultures, over 240,000 registered varieties of rice exist in the
world. These varieties lead to a wide range of rice starches
* Corresponding author. Tel.: 1 770 412 4741; fax: 1 770 412 4748. with many different characteristics including: different starting
E-mail address: [email protected] (M.S. Chinnan). gelatinization temperatures, textures, processing stabilities and

0023-6438/$34.00 2007 Swiss Society of Food Science and Technology. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.lwt.2007.10.014
1634 T. Bourtoom, M.S. Chinnan / LWT - Food Science and Technology 41 (2008) 1633e1641

viscosities. Rice starch and its major components, amylose and content of about 14 g/100 g sample (determined in triplicate
amylopectin, are biopolymers, which are attractive raw mate- by vacuum drying at 70  C and <1 mmHg pressure for 24 h,
rials for use as barriers in packaging materials. They have EYELA, Model VOS-300VD, Japan) and peak viscosity
been used to produce biodegradable films to partially or entirely (8 g/100 g sample solid) of 500 BU (Brabender unit, Model
replace plastic polymers because of its low cost and renewabil- VISKOGRAPH, Germany). Commercial grade chitosan flake
ity, as well as possessing good mechanical properties (Xu, Kim, (approximately 85% degree of deacetylation) with average
Hanna, & Nag, 2005). However, wide application of starch film molecular weight of about 75 kDa was purchased from Bona
is limited by its mechanical properties and efficient barrier Fides Marketing Co. Ltd. (Thailand).
against low polarity compounds (Azeredo, Faria, & Azeredo,
2000; Kester & Fennema, 1986). This constraint has led to 2.2. Film preparation
the development of the improved properties of rice-based films
by modifying its starch properties and/or incorporating other Rice starch was dissolved in distilled water at concentra-
materials. Jagannath, Nanjappa, Das Gupta, and Bawa (2003) tions of 1, 2, 3, and 4 g/100 ml by heating the mixtures on
blended starch with different proteins to decrease the water hot plates and stirring until it gelatinized (85  C for 5 min).
vapor permeability of the films and to increase their tensile The mixtures were then cooled to 27  2  C. The chitosan
strength. However, these films still did not perform well solution (2 g/100 ml) was prepared by dispersing 20 g of
compared to synthetic polymer based films. chitosan in 1000 ml of acetic acid (1%, v/v; SigmaeAldrich
In the present article, we reinforced the mechanical strength Chemie, Darmstadt, Germany). After the chitosan dissolved
of rice starch film by mixing with chitosan, a 1,4 linked-2- completely, the solutions were filtered through a polyester
deoxy-2-aminoglucose, prepared by N-deacetylation of chitin screen (mesh no. 140 with mesh opening of 106 mm) by
(Xu et al., 2005). Chitosan provides unique functional, nutri- vacuum aspiration to remove any small lumps in the solution.
tional, and biomedical properties, and its present and potential While pulling a vacuum with an aspirator, the vacuum flask
uses range from dietary fiber to a functional ingredient and pro- containing the chitosan solutions was sealed with a rubber
cessing aid. Some of the well known applications of chitosan in- stopper and held for a few hours to de-gas the solution, which
clude its use for prevention of water pollution, medicine against prevented the formation of air bubbles in the films when the
hypertension, antimicrobial and hypocholesterolemic activity, casting solvent evaporated. A series of starchechitosan blend
flavor encapsulation, seed coating, film-forming, and controlled films was prepared by mixing 100 ml of the starch solutions
release of food ingredients and drugs (Dunn, Grandmaison, & (1, 2, 3 and 4 g/100 ml) with 100 ml of the chitosan solution
Goosen, 1997; Muzzarelli, 1985, 1996; Muzzarelli & De (2 g/100 ml). Sorbitol was added as 40% (w/w) of the total
Vincenzi, 1997; Onishi, Nagai, & Machida, 1997; Struszczyk solid weight in solution. The mixtures were cast onto flat,
& Pospieszny, 1997). Relatively low cost, widespread availabil- leveled, non-stick trays to set. Once set, the trays were held
ity from a stable renewable source, that is, shellfish waste of the overnight at 55  C for 10 h undisturbed, and then cooled to
sea food industry, along with chitosans ability to form a good ambient temperature before peeling the films off the plates.
film, are primary reasons to seek new applications of this Film samples were stored in plastic bags and held in desicca-
polymer (Bangyekan, Aht-Ong, & Srikulkit, 2005). Numerous tors at 60% RH for further testing. All treatments were made
investigations have been reported on the studies of films made in triplicate.
from chitosan (Butler, Vergano, Testin, Bunn, & Wiles, 1996;
Caner, Vergano, & Wiles, 1998; Park, Marsh, & Rhim, 2002; 2.3. Film testing
Singh & Ray, 1998; Wiles, Vergano, Barron, Bunn, & Testin,
2000) and chitosan blends with natural polymers 2.3.1. Conditioning
(Arvanitoyannis & Biliaderis, 1998; Hasegawa, Isogai, Onabe, All films were conditioned prior to subjecting them to
Usuda, & Atalla, 1992; Hosokawa, Nishiyama, Yoshihara, & permeability and mechanical tests according to the Standard
Kubo, 1990; Lazaridou & Biliaderis, 2002; Xu et al., 2005) method, D618-61 (ASTM, 1993a). Films used for testing
or synthetic polymers (Arvanitoyannis, Psomiadou, Nakayama, water vapor permeability (WVP), tensile strength (TS), and
Aiba, & Yamamoto, 1997; Guan, Liu, Zhang, & Yao, 1998). elongation (E ) were conditioned at 60% RH and 27  2  C
This study shows the preparation and characterization of by placing them in desiccators over a saturated solution of
biodegradable blend films from rice starchechitosan as well Mg(NO3)2$6H2O for 72 h or more. For other tests, film
as their mechanical and water barrier properties. The possible samples were transferred to plastic bags after peeling and
molecular miscibility between rice starchechitosan has also placed in desiccators.
been investigated.
2.3.2. Film thickness
2. Materials and methods Thickness of the films was measured with a precision dig-
ital micrometer (Digimatic Indicator, Mitutoyo Corporation,
2.1. Materials Japan) to the nearest 0.0001 (5%) at five random locations
on the film. Mean thickness values for each sample were
Native rice starch (Thai Flower brand) used was obtained calculated and used in water vapor permeability (WVP) and
from Bangkok Starch Industrial Co. Ltd. and had a moisture tensile strength (TS) calculations.
 T. Bourtoom, M.S. Chinnan / LWT - Food Science and Technology 41 (2008) 1633e1641 1635

2.3.3. Film solubility calculated by dividing the maximum force by the initial spec-
A modified method from Jangchud and Chinnan (1999) was imen cross-sectional area, and the percent elongation at the
used to measure film solubility. Film pieces, 20 mm  20 mm, break was calculated as follows:
were dried at 70  C in a vacuum oven for 24 h and then weighed

to the nearest 0.0001 g for the initial dry mass. Films were im- E 100  dafter  dbefore dbefore
mersed into 20 ml of distilled water in 50 ml screw cap tubes
containing 0.01 g/100 g sodium benzoate. The tubes were cap- where, d was the distance between grips holding the specimen
ped and placed in a shaking water bath for 24 h at 25  2  C. A before or after the break of the specimen.
portion of the solution was removed and set aside for later use in
protein solubility tests as described later. The remaining solu- 2.3.6. Color
tion and film piece were poured onto (Whatman #1) qualitative A CIE colorimeter (Hunter Associates Laboratory, Inc., VA,
filter paper, rinsed with 10 ml distilled water, and dried at 70  C USA) was used to determine the film L*, a*, and b* color
in a vacuum oven for 24 h to determine the dry mass of the film. values [L* 0 (black) to 100 (white); a* 60 (green) to
Five measurements were taken for each treatment. Total soluble 60 (red); and b* 60 (blue) to 60 (yellow)]. The
matter was calculated from the initial gross mass and the final standard plate (calibration plate CX0384, L* 92.82,
dry mass using the following equation: a* 1.24, and b* 0.5) was used as a standard. Color
(means of five measurements at different locations on each
film mass before test  film mass after test specimen) was measured on 10 cm  10 cm segment of film.
%FSdb
film mass before test Total color difference DEab , hue angle (H ), and chroma
 100% (C ) were calculated using the following equation:

DL Lsample  Lstandard ; Da asample  astandard ;

2.3.4. Water vapor permeability (WVP) Db bsample  bstandard
The gravimetric Modified Cup Method based on ASTM E96-
92 (McHugh, Avena-Bustillos, & Krochta, 1993) was used to  2 2 2 0:5
DEab DL Da Db
determine the WVP of films. The test cups were filled with
20 g of Silica gel (desiccant) to produce a 0% RH below the  0:5
film. A sample was placed in between the cup and the ring cover C a 2 b 2
of each cup coated with silicone sealant (high vacuum grease,
Lithelin, Hanau, Germany) and held with four screws around H tan1 b =a when a > 0 and b > 0
the cups circumference. The air gap was at approximately
1.5 cm between the film surface and desiccant. The water vapor H 180 tan1 b =a when a < 0
transmission rates (WVTR) of each film were measured at
60  2% RH and 25  2  C. After taking the initial weight of H 360 tan1 b =a when a > 0 and b < 0
the test cup, it was placed into a growth chamber with an air ve-
locity rate of 135 m/min (Model KBF115, Contherm Scientific, Prior to taking color measurements, film specimens were
Lower Hutt, New Zealand). Weight gain measurements were pre-conditioned at 60% RH and 27  2  C for 72 h.
taken by weighing the test cup to the nearest 0.0001 g with an
electronic scale (Sartorious Corp.) every 3 h for 18 h. A plot 2.3.7. X-ray diffraction
of weight gained versus time was used to determine the X-ray patterns of chitosan, starch powders, and starche
WVTR. The slope of the linear portion of this plot represented chitosan blend films were analyzed using an X-ray diffractom-
the steady state amount of water vapor diffusing through the eter (Phillips X, Pert MPD, Japan) with Cu Ka radiation at
film per unit time (g/h). The WVTR was expressed in gram units, a voltage of 40 kV and 30 mA. The samples were scanned
per square meter, per day. Steady state over time (slope) yielded between 2q 3e40 with a canning speed of 2 /min. Prior
a regression coefficient of 0.99 or greater. Six samples per treat- to testing, the samples were dried and stored in a desiccator.
ment were tested. The WVP of film was calculated by multiply-
ing the steady WVTR by the film thickness and dividing that by 2.3.8. Fourier transform infrared (FTIR)
the water vapor pressure difference across the film. FTIR spectra of the films were recorded using an attenuated
total refraction (ATR) method in an IR spectrometer (Bruker,
2.3.5. Tensile strength and elongation at the break Equinox 55, Japan). The films were applied directly onto the
(TS and E ) ZnSe ATR cell. For each spectrum, 128 consecutive scans at
Tensile strength was measured with a LLOYD Instrument 4 cm1 resolution were averaged.
(Model LR30K, LLOYD Instruments Ltd., Hampshire,
England) as per ASTM D882-91 Standard method (ASTM, 2.4. Statistical analysis
1993b). Ten samples, 2.54 cm  12 cm, were cut from each
film. Initial grip separation and crosshead speed were set at A completely randomized experimental design was used to
50 mm and 50 mm/min, respectively. Tensile strength was characterize the blend films. Analysis of variance (ANOVA)
1636 T. Bourtoom, M.S. Chinnan / LWT - Food Science and Technology 41 (2008) 1633e1641

was used to compare mean differences of the samples. If the chitosan ratio of 1:1 and 0.5:1.0. The increasing TS values
differences in mean existed, multiple comparisons were of the biodegradable blend films, with the increase of rice
performed using Duncans Multiple Range Test (DMRT). starch and chitosan ratios from 2:1 to 0.5:1, are attributable
to a high formation of intermolecular hydrogen bonding
3. Results and discussion between NH 
3 of the chitosan backbone and OH of the rice
starch. The amino groups (NH2) of chitosan were protonated
3.1. Tensile strength (TS) and elongation at the break (E ) to NH 3 in the acetic acid solution, whereas the ordered
crystalline structures of starch molecules were destroyed
A biodegradable or edible film must withstand the normal with the gelatinization process, resulting in the OH groups
stress encountered during its application and subsequent being exposed to readily form hydrogen bonds with NH 3 of
shipping and handling of the food to maintain its integrity the chitosan. The number of NH 3 groups increased with in-
and barrier properties. Tensile strength is the maximum tensile creased chitosan ratios in the film-forming solution. However,
stress sustained by the sample during the tension test. If the TS of biodegradable blend film prepared at the starch to
maximum tensile stress occurs at either the yield point or chitosan ratio of 1:1 and 0.5:1 was not significantly different.
the breaking point, it is designated tensile strength at yield This phenomenon indicated the critical ratios of the greatest
or at break, respectively (ASTM, 1991). High tensile strength miscibility of the two main film-forming components.
is generally required, but deformation values must be adjusted Elongation at the break (E ) is an indication of the films
according to the intended application of the films. That is, flexibility and stretchability (extensibility), which is deter-
whether it is undeformable material to provide structural mined at the point when the film breaks under tensile testing
integrity or reinforce structure of the food (Gontard, Guilbert, and is expressed as the percentage of change of the original
& Cuq, 1992). The TS of biodegradable blend films from rice length of the specimen between the grips of a film to stretch
starchechitosan with different chitosan ratios is shown in (extend). The value of E was affected by the chitosan ratios
Fig. 1A. The TS of biodegradable blend films was affected (Fig. 1B). The average E values of the biodegradable blend
by the chitosan ratios. The results demonstrated that the TS film behaved inversely to the TS value, decreasing from
of biodegradable blend films increased with the addition of
chitosan, and the maximum occurred at the rice starch and
A 9.0
a
A 45.0 8.0 a
Water vapor permeability

a a 7.0
(g.mm/m2.day.kPa)

40.0
Tensile strength (MPa)

6.0 b
35.0 b
b
5.0 c
30.0
25.0 4.0

20.0 3.0

15.0 2.0

10.0 1.0
5.0 0.0
2:1 1.5:1 1:1 0.5:1
0.0
2:1 1.5:1 1:1 0.5:1 Ratio g starch : chitosan
Ratio g starch : chitosan
B 45.0 a
B 40.0 ab
15.0 a
bc
Elongation at break (%)

35.0
Film solubility (%)

c
b 30.0
10.0 c c 25.0
20.0
15.0
5.0
10.0
5.0
0.0 0.0
2:1 1.5:1 1:1 0.5:1 2:1 1.5:1 1:1 0.5:1
Ratio g starch : chitosan Ratio g starch : chitosan

Fig. 1. Effects of chitosan ratios on (A) tensile strength (TS) and (B) elonga- Fig. 2. Effects of chitosan ratios on (A) water vapor permeability (WVP) and
tion at break (E ) of the biodegradable blend films. aec Means with the differ- (B) film solubility (FS) of the biodegradable blend films. aec Means with the
ent letters represent significantly different value at p  0.05 using Duncans different letters represent significantly different value at p  0.05 using Dun-
Multiple Range Test. cans Multiple Range Test.
 T. Bourtoom, M.S. Chinnan / LWT - Food Science and Technology 41 (2008) 1633e1641 1637

A 90.0 a
A 25.0 a
89.5 ab b
20.0
89.0 bc c
88.5 15.0

E*
d
88.0 c 10.0
L*

87.5
5.0
87.0
86.5 0.0
86.0 2:1 1.5:1 1:1 0.5:1
85.5 Ratio g starch: chitosan
85.0
2:1 1.5:1 1:1 0.5:1 B 185.0 a a a a
Ratio g starch : chitosan 180.0

Hue angle
175.0
B 0.0 170.0
2:1 1.5:1 1:1 0.5:1 165.0
160.0
-1.0
155.0
150.0
-2.0 2:1 1.5:1 1:1 0.5:1
a*

Ratio g starch: chitosan

-3.0 a
C 5.00 a
-4.0 b a
4.00 b
c
Chroma

c
-5.0 c 3.00
Ratio g starch : chitosan 2.00

1.00
C 25.0
a 0.00
2:1 1.5:1 1:1 0.5:1
20.0 a Ratio g starch: chitosan

Fig. 4. Effects of chitosan ratios on (A) DE*, (B) hue angle and (C) chroma
15.0 b values of the biodegradable blend films. aed Means with the different letters
b*

c represent significantly different value at p  0.05 using Duncans Multiple

10.0
Range Test.

5.0

in the films structure (Hagenmaier & Shaw, 1990). Deviation

0.0
2:1 1.5:1 1:1 0.5:1
from the ideal behavior can also be induced by structure
Ratio g starch : chitosan effects on materials (Myers, Meyer, Rogers, Stannett, &
Szwarc, 1962). Since a main function of a biodegradable or
Fig. 3. Effects of chitosan ratios on (A) L*, (B) a*, and (C) b* values of the edible film is often to impede moisture transfer between
biodegradable blend films. aec Means with the different letters represent sig-
nificantly different value at p  0.05 using Duncans Multiple Range Test.
food and the surrounding atmosphere, or between two
components of a heterogeneous food product, water vapor
permeability should be as low as possible. The WVPs of bio-
12.99% to a minimum 8.06% when the rice starch and chito- degradable blend films with different ratios of rice to chitosan
san ratio was 0.5:1 (Fig. 1B). E was reduced in the presence of were examined at a vapor pressure difference of 0/60% across
chitosan, probably due to the increased crystallinity of starch films. The results showed that the biodegradable blend film
in the blend film. Xu et al. (2005) observed that the crystalline WVP increased with an increase in the content of chitosan.
structure of waxy starch in the composite film was apparent by The WVP of biodegradable blend film increased from 4.11
the addition of chitosan. to 7.80 g mm/m2 day kPa, when the chitosan ratios increased
from 2:1 to 0.5:1, and the maximum WVP occurred at the
3.2. Water vapor permeability (WVP) rice starch and chitosan ratio of 0.5:1 (Fig. 2A). This tendency
could be explained by a higher hydrophilicity (NH 3 groups) of
Water vapor permeability is a proportionality constant the biodegradable blend films when increasing the chitosan
assumed to be independent of the water vapor pressure gradi- ratio. Butler et al. (1996) reported that the chitosan films are
ent applied across the films. However, hydrophilic materials, highly impermeable to oxygen; however, they have relatively
such as protein films, deviate from this ideal behavior due to poor water vapor barrier characteristics, which result from
interactions of permeating water molecules with polar groups their hydrophilicity.
1638 T. Bourtoom, M.S. Chinnan / LWT - Food Science and Technology 41 (2008) 1633e1641

Fig. 5. Attenuated total reflection (ATR) spectra of rice starch film, chitosan film and typical rice starchechitosan biodegradable film with the ratio of rice starch to
chitosan of 1:1.

3.3. Film solubility (FS) of biodegradable blend films decreased with the addition of
chitosan. The decreasing FS values of the biodegradable blend
Water resistance is an important property of biodegradable films had a rice starch and chitosan ratio decreasing from 2:1
or edible films for applications as food protection where water to 0.5:1 (Fig. 2B). These results could arise from the fact that
activity is high, or when the film must be in contact with water higher chitosan content induced a rice starch and chitosan
during processing of the coated food (e.g. to avoid exudation interaction and resulted in a decrease in the FS.
of fresh or frozen products) (Gontard et al., 1992). Generally,
higher solubility would indicate lower water resistance. 3.4. Film color
However, a high solubility may be an advantage for some
applications. Film solubility is advantageous in situations Color of the packaging is an important factor in terms of
when the films will be consumed with a product that is heated general appearance and consumer acceptance (Srinivasa,
prior to consumption and may also be an important factor that Ramesh, Kumar, & Tharanathan, 2003). The results of the
determines biodegradability of films when used as packaging measurements performed on the blend films color were
wrap. Biodegradable blend film pieces produced from rice expressed in accordance with CIELAB system and the rectan-
and chitosan maintain their integrity (i.e., did not dissolve or gular coordinates (L*, a*, and b*) and the total color
break apart) even after 24 h of incubation with gentle motion. difference DEab , hue angle, and chroma were calculated.
This indicates that the rice starch and chitosan intra and/or The main difference observed was that biodegradable blend
intermolecular network remained intact and only the mono- films with higher content of chitosan had lighter color as indi-
mers, small peptides, and non-protein material were soluble cated by the L* value (Fig. 3A) and DEab (Fig. 4A). Similar
(Stuchell & Krochta, 1994). The FS of the biodegradable changes were also observed in a* (Fig. 3B). The measure of
blend films as a function of chitosan in the film-forming solu- b* and chroma (yellowness) values increased when the rice
tions is shown in Fig. 2B. The results demonstrated that the FS starch and chitosan ratio of 2:1 to 0.5:1 (Figs. 3C and 4C).
 T. Bourtoom, M.S. Chinnan / LWT - Food Science and Technology 41 (2008) 1633e1641 1639

This was somewhat expected since color change is attributed

to the content of chitosan. However, the hue angle of the blend
Starch powder
film was not significantly different ( p < 0.05, Fig. 4B).
Starch film
3.5. FTIR spectroscopy 2:1

Intensity
1.5:1
ratio g
FTIR spectroscopy was used to determine the interactions Starch: chitosan
1:1
between rice starch and chitosan. The infrared spectra of
rice starch, chitosan, and their blends are shown in Fig. 5. 0.5:1
The broad band of rice starch film at 3233.41 cm1 was the Chitosan powder
OeH stretching. The peak at 2908.04 cm1 corresponded to
the CeH stretching, while the band at 1335.74 cm1 was Chitosan film

the OeH of water. The chitosan film spectrum was very 0 20 40

similar to that in the study of Nunthanid, Puttipipatkhachorn,
2 (degree)
Yamamoto, and Peck (2001). The broad band at 3268.23
cm1 was the OeH stretching, while the band at 1541.15 Fig. 6. X-ray diffractograms of rice starch, chitosan, and rice starchechitosan
cm1 was the NeH bending (amide II). A small peak at biodegradable blend film.
1631.77 cm1 was due to the C]O stretching (amide I),
and a peak at 993.33 cm1 suggested the presence of an ether because two main diffraction peaks (2q 11 and 20 ) were
group in the film. When two components are mixed, the observed in its X-ray diffraction pattern. This agrees with
physical blends versus chemical interactions are affected by the finding of Nunthanid et al. (2001) and Xu et al. (2005). Af-
changes in the characteristic spectra peaks (Guan et al., ter making the films, two crystalline structures still existed, but
1998; Yin, Yao, Cheng, & Ma, 1999). In the spectrum of the intensity was less. When these two film-forming compo-
rice starchechitosan biodegradable blend film, the amino nents were mixed, increase of the amorphous peaks of rice
group peak of chitosan shifted from 1541.15 to starch was suppressed, concomitantly with the presence of
1621.96 cm1. This phenomenon pointed out that interactions the crystalline structure of rice starch film when the chitosan
were present between the hydroxyl group of rice starch and the content was increased. The increase in crystalline peaks
amino group of chitosan (Meenakshi et al., 2002; Xu et al., with increase in chitosan content might be explained by
2005). the incidence of a molecular miscibility between these two
components.
3.6. X-ray diffraction

The X-ray diffractograms of rice starch powder, chitosan 3.7. Comparison of rice starchechitosan biodegradable
powder, and rice starchechitosan biodegradable blend films blend film with selected biopolymer and synthetic
are shown in Fig. 6. As observed, the rice starch powder polymer films
showed a typical A-type diffraction pattern with strong
reflection at 17 and 17.5 . The dried regular rice starch films, The mechanical properties (tensile strength and elongation
after gelatinization, had different structures. The amorphous at break) of rice starchechitosan biodegradable blend film and
structure was observed in the rice starch film. The results dem- of various films were compared (Table 1). Rice starche
onstrated that the chitosan powder was in a crystalline state chitosan biodegradable blend film had mechanical properties

Table 1
Tensile strength (TS), elongation at break (E ) and water vapor permeability (WVP) of various films
Film type Test condition Tensile strength (MPa) Elongation at break (%) Water vapor permeability Reference
(g mm/m2 day kPa)
Rice starchechitosan 25  C, 60% RH 27.5e38.1 8.1e13.0 4.11e7.08 Current study
Cassava starch 25  C, 75% RH 9.0e17.0 9.0e28.0 Mali et al. (2006)
Corn starch 25  C, 75% RH 3.8e4.3 4.0e10.0 Mali et al. (2006)
Chitosan 25  C, 50% RH 27.0 33.3 52.73 Xu et al. (2005)
Chitosan 25  C, 50% RH 39.1 10.8 13.22 Srinivasa, Ramesh, and
Tharanathan (2007)
Chitosan-native corn starch 25  C, 50% RH 40.3 28.0e61.1 Xu et al. (2005)
Chitosan-waxy corn starch 25  C, 50% RH 33.7 45.0e61.1 Xu et al. (2005)
Low density polyethylene 38  C, 90% RH 7.6e17.3 500.0 0.08 Briston (1988)
High density polyethylene 38  C, 90% RH 17.3e34.6 300.0 0.02 Briston (1988)
Cellulose acetate 38  C, 90% RH 48.5e82.7 15.0e45.0 e Briston (1988)
Polyester 38  C, 90% RH 178.0 70.0e100.0 Briston (1988)
Cellophane 38  C, 90/0% RH e e 7.27 Taylor (1986)
1640 T. Bourtoom, M.S. Chinnan / LWT - Food Science and Technology 41 (2008) 1633e1641

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