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International Journal of Polymeric


Materials
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Mechanical and Physical Properties of


Cassava Starch-Gelatin Composite Films
a b
Wirongrong Tongdeesoontorn , Lisa J. Mauer , Sasitorn Wongruong
c d e f
, Pensiri Sriburi & Pornchai Rachtanapun
a
Division of Biotechnology, Graduate School, Chiang Mai University,
Chiang Mai, Thailand
b
Department of Food Science, Whistler Center for Carbohydrate
Research, Purdue University, West Lafayette, IN, USA
c
Division of Biotechnology, Faculty of Agro-Industry, Chiang Mai
University, Chiang Mai, Thailand
d
Department of Chemistry, Faculty of Science, Chiang Mai
University, Chiang Mai, Thailand
e
Division of Packaging Technology, Faculty of Agro-Industry, Chiang
Mai University, Chiang Mai, Thailand
f
Materials Science Research Center, Faculty of Science, Chiang Mai
University, Chiang Mai, Thailand

Available online: 27 Mar 2012

To cite this article: Wirongrong Tongdeesoontorn, Lisa J. Mauer, Sasitorn Wongruong, Pensiri Sriburi &
Pornchai Rachtanapun (2012): Mechanical and Physical Properties of Cassava Starch-Gelatin Composite
Films, International Journal of Polymeric Materials, 61:10, 778-792
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International Journal of Polymeric Materials, 61:778792, 2012
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ISSN: 0091-4037 print=1563-535X online
DOI: 10.1080/00914037.2011.610049
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Mechanical and Physical


Properties of Cassava
Starch-Gelatin Composite
Films
Wirongrong Tongdeesoontorn,1 Lisa J. Mauer,2
Sasitorn Wongruong,3 Pensiri Sriburi,4 and
Pornchai Rachtanapun5,6
1
Division of Biotechnology, Graduate School, Chiang Mai University,
Chiang Mai, Thailand
2
Department of Food Science, Whistler Center for Carbohydrate Research,
Purdue University, West Lafayette, IN, USA
3
Division of Biotechnology, Faculty of Agro-Industry, Chiang Mai University,
Chiang Mai, Thailand
4
Department of Chemistry, Faculty of Science, Chiang Mai University,
Chiang Mai, Thailand
5
Division of Packaging Technology, Faculty of Agro-Industry,
Chiang Mai University, Chiang Mai, Thailand
6
Materials Science Research Center, Faculty of Science, Chiang Mai University,
Chiang Mai, Thailand
The effect of gelatin concentrations on the mechanical properties and solubility of cas-
sava starch-based films containing glycerol was studied. Increasing concentration of
gelatin increased tensile strength but reduced elongation at break and water solubility
of the composite films. Films containing 30% gelatin showed the highest tensile
strength. Fourier transform infrared spectroscopy (FT-IR) spectra indicated intermole-
cular interactions between cassava starch and gelatin in composite films. The X-ray
diffraction (XRD) technique demonstrated pseudo-crystalline regions in the cassava
starch-gelatin composite films, and it is supposed that the interactions between cassava
starch and gelatin were shown in the diffractograms by shifts in scattering angles.

Received 21 December 2010; accepted 31 July 2011.


The authors gratefully acknowledge the National Research University Project under
Thailands Office of the Higher Education Commission (CHE), Thailand, for financial
support.
Address correspondence to Pornchai Rachtanapun, Division of Packaging Technology,
Faculty of Agro-Industry, Chiang Mai University, Chiang Mai 50100, Thailand. E-mail:
p.rachta@chiangmai.ac.th
Cassava Starch-Gelatin Composite Films 779
The differential scanning calorimetry (DSC) thermograms and scanning electron
microscopy (SEM) micrographs confirmed homogeneity of cassava starch-gelatin films.
Cassava starch-gelatin composite films have the potential to replace conventional
packaging, and the films developed in this work are suggested to be suitable for
low-moisture food and pharmaceutical products.
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Keywords biopolymer, cassava starch, composite film, gelatin, mechanical


properties

INTRODUCTION
The use of biopolymers for development of edible and=or biodegradable films
could be an alternative to increase their applications and reduce or replace
conventional non-biodegradable plastics [1,2]. Polysaccharides, proteins, and
lipids or a combination of these have been used for preparing edible films [1].
Cassava (Manihot esculenta Crantz) or tapioca is one of the economically
important crops in Thailand and the cheapest raw material of starch pro-
duction. Structurally, cassava starch consists of 17% of amylose content that
is responsible for strong film-forming characteristics [3]. Cassava starch can
readily be cast into films [4]. However, the cassava starch film is brittle and
weak, leading to inadequate mechanical properties. Overcoming the brittle-
ness of the film can be accomplished by adding plasticizers. The most widely
used plasticizers include glycerol [57], sorbitol [810], propylene glycol and
polyethylene glycol [7,11]. Glycerol and sorbitol are widely used as plasticizers
because of their stability and edibility [5,6,12]. Addition of plasticizers makes
the brittle films more flexible, but also less strong [5].
This problem has led to the development of alternative approaches for
improving the mechanical properties of cassava starch films. Blending [13]
or laminating [14] with other biopolymeric materials could improve film per-
formance. However, these approaches may not offer good barriers against
humidity [15]. Park [16] and Cuq et al. [17] indicated that proteins, such as
zein, wheat gluten, keratin, and gelatin, are better gas barriers than polysac-
charides because of their unique structures and high intermolecular binding
potential. The interest in blending polysaccharides, proteins, and lipids is
due to the complementary advantages and disadvantages of these components
[18]. Polysaccharide-based films generally have good mechanical properties
and are also effective barriers against low polarity compounds, but they do
not offer a good barrier against moisture [12]. On the other hand, protein-
based films are generally excellent barriers to oxygen, carbon dioxide, and
some aromatic compounds, but their mechanical properties are not satisfac-
tory, which limits their applications [19]. Some edible films based on the
blends of polysaccharides and proteins, such as methylcellulosewheat gluten
[20], soluble starchgelatin [21], hydroxypropyl starchgelatin [22], soluble
780 W. Tongdeesoontorn et al.

starchcaseinate [23], and glucomannan-gelatin [24], were investigated with


formulation having varying results on the physicochemical properties of the
films.
Gelatin has a considerable number of food applications [25]. Overall, its
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functional uses include in stabilizer, thickener, and texturizer applications.


Schrieber and Gareis [26] have discussed in detail various food and nonfood
applications of gelatin. Occasionally, gelatin has been used in conjunction with
other hydrocolloids such as hydroxy propyl starches [21], pectin [27], acacia
(gum arabic), alginate and pectate esters [28]. The properties of composite
films based on gelatin and different kind of starches such as soluble starch
[21], corn starch [29], and cassava starch [30,31] have been investigated. How-
ever, there are limited studies about cassava starch films with added gelatin
[30,31]. Veiga-Santos et al. [30] found that gelatin addition did not influence
the mechanical characteristics of cassava starch films plasticized with sucrose
or inverted sugar. However, gelatin addition increased the water vapor per-
meability of cassava starch film plasticized with glycerol [31]. To determine
the effects of gelatin concentration on mechanical and physical properties of
cassava starch composite films plasticized with glycerol, this study applied
FT-IR, SEM, XRD, and DSC techniques to investigate morphology and inter-
molecular interactions along with traditional mechanical and water solubility
analyses. Understanding how cassava starch and gelatin behave in composite
films will provide greater insight into starch-biopolymer interactions, with the
added benefit of creating opportunities to produce new biocomposite materials,
at potentially lower costs than conventional non-biodegradable plastics.

MATERIALS AND METHODS


Materials
Cassava starch (Bangkok Inter Food Co., Ltd., Thailand), gelatin (from
bovine type B, 750 Bloom, Sigma-Aldrich, Germany), and glycerol (EM
Science, Germany) were used to form the films. MgCl2 and Mg(NO3)2 (analyti-
cal reagent grade) were obtained from Ajax Finechem (Australia).

Cassava Starch Composite Films Preparation


Cassava starch films were prepared using the methodology proposed by
Tongdeesoontorn et al. [31]. Solutions used to prepare films (5% w=v) were
made by dispersing cassava starch and gelatin at different concentrations in
distilled water (Table 1). Glycerol (30% w=w solid) was added as the plasticizer.
The film solutions were heated to 80 C with constant stirring to obtain starch
gelatinization. Then the film-forming solutions (200 ml) were cast on flat
Cassava Starch-Gelatin Composite Films 781
Table 1: Composition of gelatin-cassava starch in 100 ml film solution

Composition (g/100 ml water)

Film Starch Gelatin Glycerol


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Control 5.0 0 1.5


Gelatin 10% 4.5 0.5 1.5
Gelatin 20% 4.0 1.0 1.5
Gelatin 30% 3.5 1.5 1.5
Gelatin 40% 3.0 2.0 1.5

30  30 cm Teflon plates. The films were dried at room temperature (25 C) for
24 h.

Fourier Transform Infrared Spectroscopy (FT-IR)


Transmission infrared spectra of the films were recorded at room tempera-
ture using a Nicolet 6700 FT-IR spectrometer (Thermo Electron Corporation,
USA) in the range of 4000400 cm1 with 64 scans, 4 cm1 resolution, using
a DTGS KBr detector and KBr beam splitter. The films were mounted directly
in the sample holder.

Mechanical Characterization
Films were cut into 25  100 mm strips and then equilibrated in desiccators
over saturated salt solutions having the desired relative humidity conditions
[34% (MgCl2) and 54% RH (Mg(NO3)2)] at 25 C for 48 h before testing. The
tensile strength and elongation at break of the films were measured using a
universal testing machine (Hounsfield, England) according to the ASTM
D882-91 method [32]. The initial gauge length was 50 mm and crosshead speed
was 50 mm=min. Fifteen specimens were tested for each sample.

Water Solubility of Cassava Starch Compositefilms


Film solubility in water was measured as percentage of dry matter of the
film solubilized in water during a 24 h period. This method was adapted from
Phan et al. [33]. The initial dry matter of each film was obtained after drying
film specimens at 65 C for 24 h followed by placement in 0% RH silica gel
desiccators for 2d. Dried films (about 0.3 g) were weighed (initial dry weight)
and immersed in beakers containing 50 ml distilled water at 23 C that were
then sealed and periodically agitated for 24 h. The solutions containing film
residues were filtered through Whatman filter paper No. 1 (previously dried
at 105 C for 24 h and weighed before using), the filters were then dried at
782 W. Tongdeesoontorn et al.

80 C for 24 h, and the dried filters with film residues were weighed to
determine the weight of dry matter (final dry weight). Tests were performed
in triplicate, and the solubility was calculated using Equation (1):
 
initial dried weight  final dried weight
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solubility %  100 1
initial dried weight

Film Morphology
Film samples were conditioned at 25 C in 54% RH desiccators for 7d prior
to analysis. The cassava starch film, gelatin film, and composite films were
mounted on the specimen holder and then sputtered with gold inanSPI-
moduleTM sputter-coater (SPI Supplies, USA). The surface and cross-section
microstructures of films were observed by a Field-Emission Scanning Electron
Microscope (FESEM, JOEL JSM-6700F, Japan).

X-Ray Diffraction (XRD)


The X-ray diffraction patterns of cassava starch film, gelatin film, and cas-
sava starch-gelatin films were carried on an XPert MPD X-ray diffractometer
(Philips, the Netherlands), using nickel-filtered Cu Ka radiation at 40 kV and
35 mA in the 2h range of 5 50 C.

Differential Scanning Calorimetry (DSC)


Differential scanning calorimetry was carried out using a Mettler Toledo
Schwerzenbach instrument (Mettler, USA). Samples were previously condi-
tioned at 54% RH and 25 C. Three replicates of film samples (10 milligrams)
contained in aluminum pans were heated in the temperature range 20 to
220 C at a heating rate of 5 C=min in nitrogen atmosphere (50 ml=min).

Statistical Analysis
ANOVA analysis and Duncans multiple range test were performed on all
results using a statistical program SPSS v. 10.0 at a confidence interval of 95%
to determine the significant differences between group samples.

RESULTS AND DISCUSSION


All cassava starch films with and without gelatin appeared smooth, clear, and
transparent. Film thickness ranged from 120160 mm. The influence of gelatin
concentrations on properties of cassava starch composite films was analyzed
Cassava Starch-Gelatin Composite Films 783
in terms of water solubility, mechanical and thermal properties of the films, as
well as film microstructures as reported below.

FT-IR
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FT-IR spectra of cassava starch film and a gelatin film are shown in
Figure 1a and 1f, respectively. In the cassava starch FT-IR spectrum, there
is a broad absorption band at 3268 cm1, due to the stretching frequency of
the -OH groups [34], and a band at 2920 cm1 attributable to C-H stretching
vibrations [35,36]. The presence of a strong absorption band at 1630 cm1 con-
firms the presence of water. The bands around 1413 and 1337 cm1 are
assigned to -CH2 bending in plane and C-OH bending vibrations, respectively.
The band at 1149 cm1 is due to C-O-C antisymmetric bridge stretching [37].
For gelatin films, absorbance bands related to C O stretching at 1631 cm1
(amide I), angular deformation of N-H at 1538 cm1 (amide II), and C-H
deformation at 1448 cm1 are shown. The absorption band at 1236 cm1 is
attributed to C-N stretching and the vibrational band of N-H (amide III).
The broad band from 36003100 cm1 was the O-H and=or N-H stretching
[27]. The band at 2930 cm1 was C-H stretching [38].
All cassava starch-gelatin composite films gave the same characteristic
FT-IR spectra (Figure 1b, 1c, 1d, and 1e). These spectra of composite films

Figure 1: FTIR spectra of (a) cassava starch film, cassava starch films with (b) 10% gelatin,
(c) 20% gelatin, (d) 30% gelatin, (e) 10% gelatin, and (f) gelatin film.
784 W. Tongdeesoontorn et al.

have traits characteristic of bothstarch and gelatin films, but the amide (I)
band (C=O) of gelatin shifted from 1631 to 16401652 cm1, the amide (II) band
(N-H) of gelatin shifted from 1538 to 15481550 cm1, and the N-H and=or O-H
peaks of gelatin and cassava starch shifted from 3267 and 3260, respectively, to
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3272 cm1 in the composite films [39]. The presence of O-H and N-H groups
(36003000 cm1) in gelatin film and absorbed water leads to inter and intra
hydrogen bonds [34]. Thus there is an indication that there was an interaction
and molecular miscibility between cassava starch and gelatin in the composite
film matrix. Thisis consistent with observations of FT-IR spectra of cassava
starch-chitosan-gelatin films [38] and pectin-gelatin films [27].

Mechanical Properties
The effects of gelatin concentration and percentage of relative humidity
(RH) on tensile strength and elongation at break of cassava starch composite
films are shown in Figure 2. It was obvious that the tensile strength and elonga-
tion at break were influenced by concentration of gelatin in both 34 and 54% RH
conditions. Additionally, the tensile strength and elongation at break of cassava
starch composite films were inversely related. At 34%RH, composite films con-
taining 30 and 40% gelatin gave higher tensile strength but lower elongation at
break than cassava starch film.Increasing the concentration of gelatin,
increased the tensile strengths of films but decreased the elongation at break.
Films with 30% gelatin had the highest (P < 0.05) tensile strength. These results
were similar to the increasing tensile strength and percent elongation of whey
protein films when polysaccharides (pectin, carrageenan, and konjac flour) were
added [40]. Parris et al. [41] reported that films formed from combinations of
proteins and polysaccharides had greater tensile properties than films formed
from proteins or polysaccharides in isolation. The increasing tensile strength
of the composite cassava starch films with increasing gelatin concentrations is
attributable to the formation of intermolecular hydrogen bonds between OH-
of starch and NH 3 of gelatin [21], which is supported by the FT-IR results. These
interactions were a cause of higher tensile strength. These results are similar to
the results of tensile strength of gelatin-soluble starch film [21] and
chitosan-cassava starch-gelatin film [38,42]. Based on the data set, the 30%
gelatin concentration was the critical value for the tensile strength of composite
cassava starch films and indicated the greatest integrity of the film-forming
components. At the 40% concentration, the tensile strength of the films slightly
decreased. This phenomenon may occur because starch intramolecular
hydrogen bonds rather than intermolecular hydrogen bonds were formed [43].
Different results were obtained at 54% RH. At 54% RH the tensile
strength of all films decreased, but the elongation at break increased when
compared with those at 34% RH. These results could be related to structural
modifications of the starch network produced by water, which causes a greater
Cassava Starch-Gelatin Composite Films 785
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Figure 2: Effect of gelatin concentration and relative humidity (% RH) on tensile strength
(a) and elongation at break (b) of cassava starch-based films.

flexibility in polymer structure [21]. In general, water has a plasticizing effect


through molecular movement [44]; it enhanced molecular mobility by acting
as a plasticizer between the polymer chains. At 54% RH, gelatin concentration
had less of an effect on the tensile strength of the films. Increasing gelatin con-
centration slightly reduced elongation at break of films at 54% RH. This result
agreed with the effects of humidity on tensile strength and elongation at break
of composite chitosan-methylcellulose films [45].

Water Solubility of Films


Solubility in water is an important property of starch composite films.
Potential applications may require water insolubility to enhance product
786 W. Tongdeesoontorn et al.

integrity and water resistance. However, in other cases, the water solubility of
films might be useful for applications in the encapsulation of food or
additives [46].
The water solubility of cassava starch-gelatin composite films depended on
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gelatin concentration (Figure 3). The water solubility of control films was
about 73%, and film solubility decreased with increasing gelatin concen-
tration. This result was consistent with the water solubility of cross-linked
fish gelatin-chitosan films [47]. Moreover, the solubility of cassava starch-
gelatin films is also related to the observations of the FT-IR spectra and mech-
anical properties of the films as discussed previously. This indicated that
cross-linkage [21,42] likely occurred between the starch and gelatin in cassava
starch-gelatin composite films. The gelatin molecules have both positively and
negatively charged segments. The two charged segments can join through
inter- and intramolecular interactions [48]. The hydroxyl (O-H) group and
amide group (N-H) of gelatin can form strong hydrogen bonds with the
hydroxyl groups on starch [34], thus improving the interactions between mole-
cules, improving the cohesiveness of the biopolymer matrix, and decreasing
the water solubility [49].

Film Microstructures
Sample surfaces and cross-sections of SEM micrographs were recorded
after films were stored at 54% RH for 7 days. All films showed visibly smooth
and compact surface structures, similar to the microstructure of cassava

Figure 3: Effect of gelatin concentrations on films solubility at 25 C.


Cassava Starch-Gelatin Composite Films 787
starch-gum bio-based films [50]. Based on the mechanical property results, a
cassava starch composite film with 30% concentration of gelatin was chosen
for cross-section analysis. The films were cryogenically cut in liquid nitrogen
to obtain the cross-section. The scanning electron micrographs of the cross-
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sections of cassava starch films with and without 30% gelatin are shown in
Figure 4.
The micrographs of cassava starch film, cassava starch-gelatin composite
film, and gelatin film are shown in Figure 4a, 4b, and 4c, respectively. The
SEM image of cassava starch film (Figure 4a) showed a relatively smooth
and continuous cross-section without pores and cracks, which confirmed a
dense and homogeneous structure. The micrographs of gelatin film exhibited
a patchy and rough cross-section (Figure 4c), which may occur because of
the flexibility of gelatin films[2]. Blending with cassava starch was noted to
improve the internal structure of gelatin films, in which cassava starch-
gelatin composite films showed less roughness and more compact and dense
appearance. This result agreed with SEM micrographs of gelatin-gellan
composite films, which indicated that interaction between gelatin and gellan
might occur [51]. The observed microstructures also confirmed the tensile
strength improvements imparted by adding gelatin to cassava starch films.

Figure 4: SEM observations of cross sections of cassava starch films; (a) cassava starch
film, (b) the film with 30% gelatin, and (c) gelatin film.
788 W. Tongdeesoontorn et al.

X-Ray Diffraction Patterns


The X-ray diffraction patterns of cassava starch film, cassava starch-
gelatin composite films, and gelatin filmare shownin Figure 5. The diffracto-
gram obtained for cassava starch (Figure 5a) showed a characteristic pattern
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reported in the literature [29]; the peaks correspond to amylopectin (pseudo-


crystalline) located at 2h 16 and 2h 19 , which presents some granular
structure in cassava starch.
Gelatin type B film (used in this work) presented an X-ray diffraction
pattern characteristic of a partially crystalline material, with a broad peak
located at 2h 20 , a sharp peak located at 2h 28 , and a peak located in
the region of 2h 7 to 8 (Figure 5f) [29]. According to Tanioka et al. [52],
these peaks indicated the reconstitution of the collagen-like triple-helix
structure.
Diffractograms of cassava starch-gelatin composite films are shown in
Figure 5b, 5c, 5d, and 5e. A peak appeared more clearly defined at 2h 16 ,
19 , 22 , and 28 . Due to the formation of hydrogen bonds between gelatin
and starch, the peak shifts to larger scattering angles [29]. However, the crys-
talline peaks (at 2h 16 , 19 , 22 ) of cassava starch film were suppressed
when the gelatin concentration in the composite film increased. The crystal-
line peaks of the composite films decreased because the added gelatin blocked
the rearrangement of starch crystallization in composite films [53]. A new
broad amorphous peak was observed, demonstrating an interaction between
these two components [43]. Therefore, it is possible to suppose that there

Figure 5: XRD patterns of (a) cassava starch film, (b) cassava starch film 10% gelatin,
(c) cassava starch film 20% gelatin, (d) cassava starch film 30% gelatin, (e) cassava
starch film 40% gelatin, and (f) gelatin film.
Cassava Starch-Gelatin Composite Films 789
Table 2: Melting temperature (Tm) and heat of fusion (DH) of
cassava starch film without and with gelatin

Films Tm ( C) DH (J/g)
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100% cassava starch 157.81  0.56a 167.50  34.56c


b
10% gelatin 111.29  8.57 86.63  19.09d
20% gelatin 112.31  3.54b 64.88  15.56d
30% gelatin 111.42  3.13b 64.55  11.74d
40% gelatin 145.48  11.14a 74.70  17.72d
100% gelatin 149.28  17.13a 40.24  13.36e

Different letters in the same column indicate significant differences


between the means obtained in Duncans test (p < 0.05).

are pseudo-crystalline regions in the films due to the cassava starch-gelatin


interactions [29]. These results were corroborated with the results of FT-IR
and microstructure investigations.

DSC
The melting temperature (Tm) and heat of fusion (DH) of cassava starch
films with and without gelatin are presented in Table 2. Thermograms of
the films blended with gelatin exhibited a single sharp endothermic peak
(Figure 6), which indicated homogeneity of the films. This endothermic peak

Figure 6: Thermograms of (a) cassava starch film, (b) cassava starch film 30% gelatin,
and (c) gelatin film.
790 W. Tongdeesoontorn et al.

has been associated with the melting of crystalline starch domains reorganized
during retrogradation [49]. This result agreed with DSC thermograms of corn
starch-gelatin films [29] and soluble starch-gelatin films [21].
The melting temperatures (Tm) of cassava starch-gelatin composite films
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were lower than the Tm of cassava starch films and gelatin films. The Tm of
composite films shifted to lower temperatures with an increasing gelatin con-
centration due to the interaction of the two biopolymers [30]. The area under
the endothermic peak expressed the heat of fusion of the films [54,55], which
also decreased with increasing gelatin concentrations in cassava starch com-
posite films. This is because the incorporation of gelatin into the starch matrix
decreases the inter-molecular force between starch chains, and partly decrea-
ses the crystallinity of cassava starch, resulting in a decrease in the degree of
crystallinity in composite films [56] as the gelatin content increased (as shown
in the results from XRD). The heat of fusion of the composite films decreased
because of the low degree of crystallinity of gelatin films [55]. According to
Arvanitoyannis et al. [21], polyols, such as glycerol, interact with starch and
gelatin polymers favoring hydrogen bonding formation and decreasing the
interactions between polymer chains. This behavior leads to lower interaction
energies between polymer chains. These results were similar to DSC thermo-
grams of HDPE=PP blends [54], chitosan-MC films with vanillin [55], and pea
starch-konjac glucomannan blend films [56].

CONCLUSION
Increasing concentrations of gelatin in cassava starch composite films
increased tensile strength and reduced elongation at break. Films containing
30% gelatin showed the highest tensile strength. The effects of relative
humidity (34% and 54% RH) on mechanical properties of the composite film
were also investigated. All films stored at 54% RH gave higher elongation
but lower tensile strength than films at the 34% RH condition. FT-IR spectra
indicated intermolecular interactions between cassava starch-gelatin com-
posite films with shifting in the signalsfrom amide (N-H) and hydroxyl
(O-H) groups. The XRD results demonstrated pseudo-crystalline regions in
the cassava starch-gelatin films and also confirmed the interactions between
cassava starch and gelatin. The DH decreases in the thermograms of the com-
posite films also confirmed chemical interactions between cassava starch and
gelatin. The melting temperature of cassava starch films decreased with the
addition of gelatin. The homogeneity of cassava starch-gelatin films was repre-
sented as a single melting peak, and SEM micrographs visibly confirmed the
homogeneous structure of cassava starch-gelatin composite films. The appro-
aches used in this study enabled a mechanistic understanding of the effects of
gelatin on the structure and function of cassava starch composite films.
Cassava Starch-Gelatin Composite Films 791

REFERENCES
[1] Tapia-Blacido, D.; Mauri, A. N.; Menegalli, F. C.; Sobral, P. J.; Anon, M. C. J. Food
Sci. 2007, 72, 293.
[2] Wang, L. Z.; Liu, L.; Holmes, J.; Kerry, J. F.; Kerry, J. P. Int. J. Food Sci. Technol.
Downloaded by [Mae Fah Luang University], [Wirongrong Tongdeesoontorn] at 20:31 25 June 2012

2007, 42, 1128.


[3] Bangyekan, C.; Aht-Ong, D.; Srikulkit, K. Carbohydr. Polym. 2006, 63, 61.
[4] Vicentini, N. M.; Dupuy, N.; Leitzelman, M.; Cereda, M. P.; Sobral, P. J. A. Spec-
trosc. Lett. 2005, 38, 749.
[5] Chang, Y. P.; Abd Karim, A.; Seow, C. C. Food Hydrocolloid. 2006, 20, 1.
[6] Rachtanapun, P.; Tongdeesoontorn, W. As. J. Food Ag-Ind. 2009, 2, 478.
[7] Gomez, C.; Torres, F. G.; Nakamatsu, J.; Arroyo, O. H. Int. J. Polym. Mater. 2006,
55, 893.
[8] Thomazine, M.; Carvalho, R. A.; Sobral, P. J. J. Food Sci. 2005, 70, E172.
[9] Kristo, E.; Biliaderis, C. G. Food Hydrocolloid. 2006, 20, 1057.
[10] Carvalho, R. A.; Sobral, P. J. A.; Thomazine, M.; Habitante, A. M. Q. B.; Gimenez,
B.; Gomez-Guillen, M. C.; Montero, P. Food Hydrocolloid. 2008, 22, 1117.
[11] Vanin, F. M.; Sobral, P. J. A.; Menegalli, F. C.; Carvalho, R. A.; Habitante, A. M. Q.
B. Food Hydrocolloid. 2005, 19, 899.
[12] Parra, D. F.; Tadini, C. C.; Ponce, P.; Lugao, A. B. Carbohydr. Polym. 2004, 58,
475.
[13] Chandra, R.; Rustgi, R. Rev. Macromol. Chem. Phys. 1998, 23, 1273.
[14] Coffin, D. R.; Fishman, M. L. J. Agr. Food Chem. 1993, 41, 1192.
[15] Kester, J. J.; Fennema, O. Food Technol. 1986, 40, 47.
[16] Park, H. J. Trends Food Sci. Tech. 1999, 10, 254.
[17] Cuq, B.; Aymard, C.; Cuq, J. L.; Guilbert, S. J. Food Sci. 1995, 60, 1369.
[18] Dias, A. B.; Muller, C. M. O.; Larotonda, F. D. S.; Laurindo, J. B. J. Cereal Sci.
2010, 51, 213.
[19] Gennadios, A.; Weller, C. L.; Testin, R. F. J. Food Sci. 2006, 58, 212.
[20] Debeaufort, F.; Voilley, A.; Meares, P. J. Mem. Sci. 1994, 91, 125.
[21] Arvanitoyannis, I.; Psomiadou, E.; Nakayama, A.; Aiba, S.; Yamamoto, N. Food
Chem. 1997, 60, 593.
[22] Arvanitoyannis, I.; Nakayama, A.; Aiba, S. Carbohydr. Polym. 1998, 36, 105.
[23] Arvanitoyannis, I.; Biliaderis, C. G. Food Chem. 1998, 62, 333.
[24] Li, B.; Kennedy, J. F.; Jiang, Q. G.; Xie, B. J. Food Res. Int. 2006, 39, 544.
[25] Hudson, C. B. Gelatine: Relating Structure and Chemistry to Functionality,
Springer: New York, 1994, pp. 347354.
[26] Schrieber, R.; Gareis, H. Gelatine Handbook: Theory and Industrial Practice,
Wiley-VCH: Weinhem, 2007, pp. 163301.
[27] Zaher, K.; El Kolli, M.; Riahi, F.; Doufnoune, R. Int. J. Polym. Mater. 2009, 58,
665.
[28] McKay, J. E.; Stainsby, G.; Wilson, E. L. Carbohydr. Polym. 1985, 5, 223.
792 W. Tongdeesoontorn et al.

[29] Aguilar-Mendez, M.; Martin-Martnez, E.; Ortega-Arroyo, L.; Cruz-Orea, A. Int. J.


Thermophys. 2010, 31, 595.
[30] Veiga-Santos, P.; Oliveira, L. M.; Cereda, M. P.; Scamparini, A. R. P. Food Chem.
2007, 103, 255.
Downloaded by [Mae Fah Luang University], [Wirongrong Tongdeesoontorn] at 20:31 25 June 2012

[31] Tongdeesoontorn, W.; Mauer, L. J.; Wongruong, S.; Rachtanapun, P. As. J. Food
Ag-Ind. 2009, 2, 501.
[32] ASTM. Standard Test Methods for Tensile Properties of Thin Plastic Sheeting,
American Society for Testing and Materials: Philadelphia, 1991, pp. D88291.
[33] Phan, T. D.; Debeaufort, F.; Luu, D.; Voilley, A. J. Agr. Food Chem. 2005, 53, 973.
[34] Soares, R. M. D.; Scremin, F. F.; Soldi, V. Macromol. Symp. 2005, 229, 258.
[35] Biswal, D. R.; Singh, R. P. Carbohydr. Polym. 2004, 57, 379.
[36] Sun, R. C.; Tomkinsona, J. Int. J. Polym. Anal. Ch. 2003, 8, 29.
[37] Gennadios, A.; Weller, C. L.; Testin, R. F. T. ASAE 1993, 36, 465.
[38] Zhong, Q.-P.; Xia, W.-S. Food Technol. Biotechnol. 2008, 46, 262.
[39] Andreuccetti, C.; Carvalho, R. A.; Grosso, C. R. F. Food Res. Int. 2009, 42, 1113.
[40] Coughlan, K.; Shaw, N. B.; Kerry, J. F.; Kerry, J. P. J. Food Sci. 2004, 69, E271.
[41] Parris, N.; Coffin, D. R.; Joubran, R. F.; Pessen, H. J. Agr. Food Chem. 1995, 43,
1432.
[42] Li, Y.; Shoemaker, C. F.; Ma, J.; Shen, X.; Zhong, F. Food Chem. 2008, 109, 616.
[43] Xu, Y. X.; Kim, K. M.; Hanna, M. A.; Nag, D. Ind. Crop. Prod. 2005, 21, 185.
[44] Hatakeyama, H.; Hatakeyama, T. Thermochim. Acta 1998, 308, 3.
[45] Rachtanapun, P.; Wongchaiya, P. CM. J. Sci., 2012, 39, 133.
[46] Bertuzzi, M. A.; Armada, M.; Gottifredi, J. C. J. Food Eng. 2007, 82, 17.
[47] Kolodziejska, I.; Piotrowska, B. Food Chem. 2007, 103, 295.
[48] Yang, H.; Wang, Y. Food Hydrocolloid. 2009, 23, 577.
[49] Almasi, H.; Ghanbarzadeh, B.; Entezami, A. A. Int. J. Biol. Macromol. 2010, 46, 1.
[50] Veiga-Santos, P.; Suzuki, C. K.; Cereda, M. P.; Scamparini, A. R. P. Food Hydro-
colloid. 2005, 19, 1064.
[51] Pranoto, Y.; Lee, C. M.; Park, H. J. LWT Food Sci. Technol. 2007, 40, 766.
[52] Tanioka, A.; Miyasaka, K.; Ishikawa, K. Biopolymers 1996, 15, 1505.
[53] Hu, G.; Chen, J.; Gao, J. Carbohydr. Polym. 2009, 76, 291.
[54] Rachtanapun, P.; Selke, S. E. M.; Matuana, L. M. J. Appl. Polym. Sci. 2004, 93,
364.
[55] Sangsuwan, J.; Rattanapanone, N.; Rachtanapun, P. J. Appl. Polym. Sci. 2008,
109, 3540.
[56] Chen, J.; Liu, C.; Chen, Y.; Chen, Y.; Chang, P. R. Carbohydr. Polym. 2008, 74,
946.