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Journal of Cereal Science 51 (2010) 213–219

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Journal of Cereal Science


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

Biodegradable films based on rice starch and rice flour


Amanda B. Dias, Carmen M.O. Müller, Fábio D.S. Larotonda, João B. Laurindo*
Federal University of Santa Catarina, Department of Chemical and Food Engineering, PO Box 476, Florianopolis-SC, Brazil, 88040-900

a r t i c l e i n f o a b s t r a c t

Article history: Rice flour is a starchy material with low-cost, because it can be produced from rice that is broken during
Received 31 July 2009 processing. The aim of this study was to develop biodegradable films based on rice starch and rice flour,
Received in revised form and to characterize their physicochemical, microscopic and mechanical properties. Films from rice starch
19 November 2009
and rice flour were prepared by casting, with glycerol or sorbitol as plasticizer. SEM analysis of starch and
Accepted 28 November 2009
flour films revealed compact structures. Rice flour films prepared in the present work have similar
mechanical properties to those of starch based films. However, their water vapor permeabilities are two
Keywords:
times higher than those of starch based films. Films with sorbitol were less permeable to water and more
Rice
Starch rigid, while films with glycerol are more plasticized and have poorer water vapor barrier properties.
Flour Therefore, preparing edible films from rice flour is a new alternative for using this raw material, which is
Films sometimes much cheaper than commercial starches.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction combining polysaccharides, proteins, and lipids is due to the


advantages and disadvantages of these components (Baldwin et al.,
One of the matters of great concern nowadays is the environ- 1995). The use of natural blends of protein, polysaccharides, and
mental impact caused by the excessive quantity of non-degradable lipids directly obtained from agricultural sources takes advantage
waste materials discarded every day. This reality has been stimu- of each component in the original system and appears to be a new
lating research to develop new biodegradable packaging materials opportunity for material in the area of edible films (Tapia-Blácido
that could be considered environmentally friendly raw materials et al., 2005). Rayas and Hernández (1997) prepared edible films
(Avérous et al., 2001). Among these materials, the ones derived from three types of wheat flours, and more recently, Mariniello
from renewable resources, which participate in the carbon cycle, et al. (2003) used whole soy flour and apple pectin, Tapia-Blácido
has received more attention since they combine environmental et al. (2005) and Colla et al. (2006) used amaranth flour as the raw
benefits and sustainability. materials for producing edible films.
The production of biodegradable and edible films from carbo- Rice flour can be considered such a natural mixture and
hydrates and proteins adds value to low-cost raw materials and can consequently a suitable raw material for preparing edible or
play an important role in food preservation (Avérous et al., 2001; biodegradable films. Rice (Oryza sativa L.) is the principal staple
Krochta and Miller, 1997; among others). Several studies reported food for half the world’s population (Hagenimana et al., 2006).
the use of starches from different sources to prepare films and Starch is the major chemical component of cereal grains,
coatings with different properties, and have indicated that these comprising around 90% of the dry weight of rice grain. Protein and
carbohydrates are promising materials in this regard (Avérous et al., lipid contents are also significant, being about 6.5% and 0.8%,
2001; Larotonda et al., 2005; Mali et al., 2005). respectively (Zhou et al., 2002). The aim of this work was to prepare
Few studies have reported in the last decade about the use of films based on rice starch and rice flour and compare their physi-
flour as raw materials suitable for preparing films. The interest in cochemical, microscopic and mechanical properties.

2. Materials and methods


Abbreviations: aw, water activity; b, solubility coefficient of water in the film (g
water/g dry solid.Pa); Dw, diffusion coefficient of water in the film (m2/s); 3, elon- 2.1. Materials
gation at break (%); GAB model, Guggenheim–Anderson–de Boer model; Kw, water
vapor permeability (g/h.m.Pa); rS, density (g/cm3); SEM, scanning electron
microscopy; T, tensile strength (MPa); Y, Young modulus (MPa).
Rice starch was extracted from grains of white rice O. sativa by the
* Corresponding author. Tel.: þ55 48 37215229; fax: þ55 48 37219687. alkaline method proposed by Yamamoto et al. (1973), customized by
E-mail address: joao@enq.ufsc.br (J.B. Laurindo). Lumdubwong and Seib (2000). Rice flour (Amitec A-100) was

0733-5210/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jcs.2009.11.014
214 A.B. Dias et al. / Journal of Cereal Science 51 (2010) 213–219

provided by the company Josapar S.A. (Pelotas, RS, Brazil). Glycerol where A is the film area (4 cm2), d the film thickness (cm), m the
and sorbitol were purchased from Nuclear (São Paulo, Brazil). film dry mass (g) and rS the dry matter density of the film (g/cm3)
Chemical analyses were performed to determine the chemical (Larotonda et al., 2005). The film density was expressed as the
composition of the starch extracted from rice and for the rice flour. average of ten determinations.
The methodologies used were: a) Kjeldahl method for determining
protein content, using the value 6.25 as the nitrogen-to-protein 2.3.3. Moisture sorption isotherms
conversion factor (AOAC, 1996); b) to determine the lipid content, Film moisture sorption isotherms were determined at 25  C by
Soxhlet extraction method was used for lipid content determina- the static method, using saturated saline solutions to obtain
tion, with petroleum ether as solvent (boiling point 40–60  C) and different relative humidities (Bell and Labuza, 2000). The Gug-
the minimum extraction time of 36 hours (AOAC, 1996); c) dry genheim–Anderson–de Boer (GAB) model (Eq. (2)) was used to
incineration method at 550  C to determine the ash content (AOAC, represent the experimental equilibrium data. In this equation, the
1996); d) oven desiccation at 105  2  C to determine the moisture parameter Xw is the equilibrium moisture (g water/g dry mass), m0
(AOAC, 1996); e) carbohydrates content was determined by differ- is the monolayer water content, C is the Guggenheim constant,
ence, from the contents of the others components. which represents the sorption heat of the first layer and k is the
sorption heat of the multilayers. GAB model parameters were
2.2. Film preparation determined by non-linear regression, using Statistica Software 6.0
(Statsoft, USA).
Rice starch and rice flour films were prepared by a casting
Ckm0 aw
technique. Glycerol and sorbitol were used as plasticizers at XW ¼ (2)
concentrations of 0.20 and 0.30 g/g dry raw material (starch or ð1  kaw Þð1  kaw þ Ckaw Þ
flour). Aqueous solutions containing 5% of raw material (starch or
flour) were prepared and stirred for 15 min at 4000 rpm. Plasticizer 2.3.4. Water vapor permeability (Kw)
was added to the aqueous solution and the mixture was heated to Film water vapor permeabilities (Kw) were determined in
85  C in a thermal bath under constant stirring during 1 h to appropriate diffusion cells (Sarantópoulos et al., 2002), using
promote the starch gelatinization, and poured homogeneously onto a relative humidity gradient of 2–75%. Water vapor permeability
plexiglass plates and dried at 30  C for 14 h in an oven with was determined using Eq. (3).
circulating air. For preparation of rice flour films, the pH of the
Wd
aqueous solution was adjusted to 10.0 with NaOH solution (0.1 N), Kw ¼ (3)
in order to promote protein solubilization. Films plasticized with Sps ðaw1  aw2 Þ
glycerol were codified as SG (starch based films) and FG (flour where d is the average film thickness, S is the film permeation area
based films), and the ones plasticized with sorbitol were codified as (0.005 m2), aw1 (75%) is the water activity in the chamber, aw2 (2%)
SS (starch based films) and FS (flour based films), followed by the is the water activity inside the cell, ps is the water vapor pressure at
corresponding amount of plasticizer. For example, SG20 and FS30 the experimental system temperature (25  C) and W ¼ G/t (g of
were the formulations with rice starch film with 0.20 g glycerol/g water/hour) was calculated using the linear regression of mass
starch and rice flour film with 0.30 g sorbitol/g flour, respectively. variation over time, under steady state permeation condition.

2.3. Film characterization 2.3.5. Solubility (b) and diffusion (Dw) coefficients of water in the
films
2.3.1. Scanning electron microscopy (SEM) The solubility coefficients of water in the films (b) were deter-
Scanning electron microscopy (SEM) of film samples was mined according to Larotonda et al. (2005), by the first derivative of
obtained using a Philips XL-30 scanning electron microscope. The the film’s moisture sorption isotherm (GAB model) in relation to
samples were coated with a fine gold layer before obtaining the the water activity (aw), divided by the water vapor pressure, ps, at
micrographs. All samples were examined using an accelerating the sorption isotherm temperature. Physically, the coefficient b is
voltage of 10 kV. Micrographs of drying exposed surface and frac- the partition coefficient of water between air and film, and is given
ture (cryofracture) of films plasticized with 0.3 g of plasticizer/g of by Eq. (4).
raw material were carried out.
2 3
1

Ckm0 6
6 ð1  kaw Þð1  kaw þ Ckaw Þ
7
7
b¼ aw (4)
ps 4 ½  kð1  kaw þ Ckaw Þ þ ð1  kaw Þðk þ CkÞ
5
2
ð1  kaw Þð1  kaw þ Ckaw Þ

2.3.2. Density where C, m0 and k are the adjust parameters of the GAB model and
Prior to film properties determination, samples were condi- b is given in g of water/g of dry solid  Pa.
tioned at 25  C and 58% relative humidity (RH) for 48 h. Films The water diffusion coefficients through the films (Dw) can be
thicknesses were measured (exactness of 0.001 mm) using determined from water vapor permeability (Kw), solubility coeffi-
a Digimatic digital external micrometer (Mitutoyo Co., Japan) at ten cient of water in the film (b) and density of the film (rS) (Eq. (5)).
different points of the film. For determining film density, samples of
2  2 cm were maintained in a desiccator with phosphorus pent-
K w ¼ rS bDw (5)
oxide (0% RH) for 20 days and weighed. Thus, dry matter densities
were calculated by Eq. (1).
Comparing Eq. (3) with Eq. (5), Dw can be given by Eq. (6). As
S m b varies with aw, the b values corresponding to aw2 ¼ 0.02 and to
r ¼ (1)
Ad aw1 ¼ 0.75 are calculated by Eq. (4).
A.B. Dias et al. / Journal of Cereal Science 51 (2010) 213–219 215

Fig. 1. SEM Micrographs of film surfaces and fractures: (a) and (b) rice starch film plasticized with glycerol (SG30) (0.3 g glycerol/g dry starch); (c) and (d) rice starch film plasticized
with sorbitol (SS30) (0.3 g sorbitol/g dry starch); (e) and (f) rice flour film plasticized with glycerol (FG30) (0.3 g glycerol/g dry flour); (g) and (h) rice flour film plasticized with
sorbitol (FS30) (0.3 g sorbitol/g dry flour).

extension at 0.8 mm/s, with an initial distance between the grips of


Wd 50 mm.
Dw ¼ (6)
rS Sps ðb1 aw1  b2 aw2 Þ
3. Results and discussion
2.3.6. Mechanical properties
Mechanical tests were carried out using a TA-XT2i texture analyzer 3.1. Chemical analysis
(Surrey – England). The dimensions of film samples used in tests were
25 mm  100 mm, cut with sharp scissors. Prior to mechanical tests, Chemical analysis showed that rice flour is a rich source of
samples were conditioned at 25  C and 58% RH for 72 h. carbohydrates and is composed of 7.74% of proteins, 0.87% of lipids,
Tensile strength (T), elongation at break (3) and Young modulus 0.72% of ash, 6.10% of moisture and 90.67% of carbohydrates. Rice
(Y) were determined from ten replicates for each film formulation starch extracted in this study was composed of 0.68% of proteins,
in accordance with ASTM-882-00 (2000). Samples were clamped 0.35% of ash, 5.60% of moisture and 98.97% of carbohydrates. Starch
between grips and force and deformation were recorded during extracted from rice reached a purity of 99%, with only 0.68% of
216 A.B. Dias et al. / Journal of Cereal Science 51 (2010) 213–219

Table 1
Density values determined for the film samples and GAB model parameters for moisture sorption isotherms for the rice starch films and rice flour films plasticized with
glycerol and sorbitol (r2 is the correlation coefficient).

Sample Density (g/cm3) m0 (g water/g dry solid) k C r2


a bc ab a
SG20 1.30  0.10 0.12  0.02 0.85  0.02 1.42  0.20 >0.99
SG30 1.36  0.11a 0.16  0.01c 0.87  0.01b 1.70  0.34a >0.99
SS20 1.17  0.06a 0.07  0.00a 0.87  0.01b 4.12  0.61a >0.99
SS30 1.40  0.17a 0.11  0.01ab 0.82  0.02a 1.31  0.22a >0.99
FG20 1.24  0.08a 0.10  0.01ab 0.89  0.01b 1.93  0.55a >0.99
FG30 1.25  0.06a 0.15  0.00ab 0.86  0.01b 2.50  0.66b >0.99
FS20 1.13  0.08a 0.08  0.01a 0.87  0.03ab 2.45  0.81a >0.99
FS30 1.24  0.07a 0.07  0.01a 0.92  0.01c 3.98  2.02a >0.99

Values with the same letter at the same column are not different statistically (p < 0.05) by the Tukey test.

protein content. It can be observed that rice flour is a product rich in 3.4. Moisture sorption isotherms
carbohydrates (90% dry basis), composed mostly by starch, and
with a significant presence of protein (around 7–8% in dry basis of Experimental data for moisture sorption isotherms of rice starch
rice flour). These proteins influenced the films’ properties, which films and rice flour films plasticized with glycerol and sorbitol are
are observed by comparing starch films and rice flour films, as presented in Fig. 2, together with the GAB model fitted for each
discussed in the following. sample. The GAB model parameters and correlation coefficients are
presented in Table 1. The values of k (<1) and the correlation
3.2. Scanning electron microscopy (SEM) coefficient (r2>0.98) showed that the GAB equation is an adequate
equation for fitting experimental data for starchy films, as previ-
Scanning electron microscopy surfaces and fractures of film ously reported by other authors (Mali et al., 2005; among others).
samples are presented in Fig. 1. Micrographs of the film surfaces, at Rice flour films and rice starch films plasticized with the same
a magnification of 200, did not show differences between the concentration of glycerol presented similar equilibrium moisture
films plasticized with glycerol and sorbitol. Both glycerol and (Fig. 2a). Films plasticized with sorbitol presented lower equilib-
sorbitol have the same plasticizing mechanism and are small rium moistures when compared with the films plasticized with
molecules if compared with amylose–amylopectin chains. Martelli glycerol. This behavior has been observed by other authors (Mali
et al. (2006) found important differences among the surfaces of et al., 2005; Müller et al., 2008; among others). According to these
keratin films plasticized with glycerol, sorbitol and PEG4000 using authors, glycerol and sorbitol have similar structures because they
a magnification of 2000 and 3000. These higher magnification are both straight-chain molecules. However, the glycerol molecule
levels cannot be used for starch films, because it can degrade them. presents higher water affinity, demonstrated by absorption
On the other hand, the surfaces of films prepared with rice flour isotherms reported in the literature (Leung, 1986). Moreover, since
were more irregular than those of films prepared with rice starch. sorbitol is more similar to the molecular structure of glucose units
For flour base films, the presence of insoluble particles was than glycerol, the chances of sorbitol to interact with polymeric
observed. The irregularities in the surface of rice flour films may be starch chains are higher, thus sorbitol-containing films present
related to the presence of more than one macromolecule in the higher intermolecular forces and show lower capacity to interact
polymeric matrix (starch, protein and lipid). with water. Films prepared with rice starch and rice flour presented
Fracture micrographs (Fig. 1b, d, f, h) showed homogeneity of similar water sorption isotherms, even for different sorbitol
rice starch films and of rice flour film sections. Considering that rice concentrations (0.20 or 0.30 g/g raw material). Data presented in
flour films are composed of starch, protein and lipid in different Table 1 showed that plasticizer content did not have a significant
amounts, starch being the major component, it can be concluded influence on the monolayer water content (m0) for each kind of
that the dense areas of the polymeric matrix are composed of film. Rice starch films plasticized with glycerol gave the highest
starch. The homogeneous matrix of these films is a good indicator values for monolayer moisture. The parameter k is the corrective
of their structural integrity, and consequently good mechanical constant taking into account properties of multilayer molecules.
properties would be expected (Mali et al., 2002). In this work, films gave values of k around 0.87, similar to the
values reported by Coupland et al. (2000) for whey protein films.
3.3. Density Müller et al. (2008) related a small variation in the parameter k
when using glycerol and sorbitol at different concentrations in
There were no significant differences among the densities of cassava starch films. The parameter C (Guggenheim constant) gave
film samples at the 5% significance level by the Tukey test important variations. This parameter is related to the first curvature
(p < 0.05). The presence of proteins and lipids in the rice flour films of the GAB model, with reduced values of water activity, where the
did not affect density when compared with the rice starch films. experimental equilibrium moistures showed higher deviations
The type of plasticizer did not influence film density (Table 1).
These results can be explained by the high concentration of starch 3.5. Influence of the solubility coefficient (b) and the diffusion
in the films, and also because the molecular packing is similar for all coefficient (Dw) of water in the films on the water vapor
films. permeabilities (Kw)
Density values obtained in this work were similar to the values
found by Moraes (2009) who reported density values around Since an important function of a food packaging is to avoid or at
1.35 g/cm3 for films composed of 3% of cassava starch. Famá et al. least to decrease moisture transfer between the food and the
(2009) obtained density values around 1.38 g/cm3 for cassava surrounding atmosphere, film water vapor permeability should be
starch films and cassava starch-wheat bran composites. Moore et al. as low as possible (Gontard et al., 1992). Water vapor permeabilities
(2006) reported density values ranging from 0.92 g/cm3 to 1.10 g/ (Kw) are presented in Table 2. Kw values ranged from 9.6  108 g
cm3 for keratin films, for different glycerol concentrations. water/h.m.Pa, for the rice starch films plasticized with 0.2 g
A.B. Dias et al. / Journal of Cereal Science 51 (2010) 213–219 217

a 1.0
SG20
SG30
FG20
0.8 FG30

(g water / g dry solid)


0.6

0.4

W
X
0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0
aw

b 1.0
SS20
SS30
FS20
(g water / g dry solid)

0.8 FS30

0.6

0.4
W
X

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0
aw

Fig. 2. Experimental data of moisture sorption isotherms of film samples fitted with the GAB model: (a) films of rice starch and rice flour plasticized with glycerol; (b) films of rice
starch and rice flour plasticized with sorbitol (symbols are the experimental data and lines are the GAB fitted curves).

sorbitol/g dry starch (SS20) to 63.6  108 g water/h.m.Pa, for the prepared with 20–30 g of glycerol/100 g of dry raw material. On the
rice flour films plasticized with 0.3 g glycerol/g dry flour (FG30). other hand, the higher water vapor permeabilities found for flour
The increase of glycerol content increases the water vapor perme- based films can be explained by their more open structure, repre-
ation through the films, as has been reported in the literature for sented by the higher diffusion coefficients.
other hydrophilic films (Cuq et al., 1997; Laohakunjit and Noom- Laohakunjit and Noomhorm (2004) determined the water vapor
horm, 2004; Mali et al., 2002; Müller et al., 2008). The behavior permeability of rice starch films prepared by casting, plasticized
found for starch films can be explained by the increase of film with 0.30 g glycerol/g dry starch. They reported values of Kw almost
hygroscopicity, represented by their higher solubility coefficients four times higher than those values found for similar films in the
(b). When the glycerol concentration was increased from 20 to 30 g present work. For films plasticized with sorbitol, the same authors
of glycerol/100 g of dry raw material, the b values increased by found a Kw of 90.9  108 g/h.m.Pa, eight times higher than the
about 40%. The results reported in Table 2 did not show important value of Kw obtained in this work (10.9  108 g/h.m.Pa). It is
differences between the diffusion coefficients of starch films important to note that Laohakunjit and Noomhorm used a higher

Table 2
Water vapor permeability (Kw), solubility coefficient (b) and diffusivity (Dw) of water in the films for rice starch and rice flour films.

Samples Kw  108 b2 (aw2 ¼ 0.02)  105 b2  aw2  ps b1 (aw1 ¼ 0.75)  105 b1  aw1  ps ps(b1  aw1–b2  aw2) Dw  1013
(g/h.m.Pa) (g water/g dry solid.Pa) (g water/g dry solid) (g water/g dry solid.Pa) (g water/g dry solid) (g water/g dry solid) (m2/s)
SG20 16.7  2.5a 4.8 0.0030 25.7 0.6067 0.6037 1.4
SG30 31.2  0.8b 7.6 0.0048 37.6 0.8877 0.8829 1.7
SS20 9.6  0.4a 7.3 0.0046 16.3 0.3848 0.3802 1.3
SS30 10.9  1.3a 3.9 0.0024 20.4 0.4816 0.4791 1.2
FG20 41.0  3.6c 5.6 0.0035 27.6 0.6516 0.6480 3.6
FG30 63.6  6.1d 10.4 0.0065 35.9 0.8475 0.8410 6.6
FS20 12.6  0.5a 5.2 0.0033 18.8 0.4438 0.4406 1.6
FS30 13.9  0.1a 7.0 0.0044 19.8 0.4674 0.4630 1.5

Values with the same letter at the same column are not different statistically (p < 0.05) by the Tukey test.
218 A.B. Dias et al. / Journal of Cereal Science 51 (2010) 213–219

280
260 SG20
SG30
240

β x 105 (g water / g dry solid . pa)


FG20
220 FG30
200 SS20
SS30
180
FS20
160 FS30
140
120
100
80
60
40
20
0
0.0 0.2 0.4 0.6 0.8 1.0
aw

Fig. 3. Solubility coefficient values (b) for rice starch films and rice flour films plasticized with glycerol and with sorbitol.

relative humidity gradient, 0–90% RH to determine Kw while, in this Kw values were not significantly affected by the plasticizer
work, the RH gradient was 2–75%. However, the much higher content in the films plasticized with sorbitol, neither for starch
values of permeability of these films seem to be associated with based films nor for flour based films.
their porous and irregular microstructure observed by the cited
authors from SEM micrographs.
3.6. Mechanical properties
Fig. 3 illustrates the behavior of the solubility coefficients (b) of
water in the films, showing that the values of this coefficient
The results for tensile strength (T), elongation at break (3) and
strongly depend on the range of the air relative humidity (water
Young modulus (Y) for all film samples are presented in Table 3. The
activity of the film). Although few works had investigated the
addition of higher contents of plasticizer increased the films’
influence of this coefficient in the water vapor permeability of
elongation capacity and decreased their tensile strength, as
starch and protein based films (Moore et al., 2006; Müller et al.,
expected. Film samples plasticized with glycerol showed lower
2008), the behavior of this coefficient is determinant in the water
tensile strength than films plasticized with sorbitol with the same
permeation processes, as discussed in the following.
plasticizer content, for both starch and flour based films. This
For films prepared with the same material (rice starch or rice
behavior can be associated with the molecular structure of glycerol,
flour), the values of Kw were increased by about 50–80% when the
which possesses a small chain, more able to enter into the poly-
glycerol changed from 0.20 to 0.30 g glycerol/g raw material. Values
meric net (Cuq et al., 1997). The smaller size of glycerol and its
of b1 (related to aw1 ¼ 0.75) and b2 (related to aw2 ¼ 0.02) for all the
greater amount of related water increase its effectiveness as
film samples are also presented in Table 2. The driving force that
a plasticizer, and contributed more plasticization effect than
causes water transfer in the film is given by the side-to-side
sorbitol at equivalent mass content. Ryu et al. (2002) observed the
moisture difference, i.e., ps(b1  aw1  b2  aw2), given in g water/g
same behavior for high amylose corn starch films.
dry solid. The comparison between the values of b1  aw1 and
Tensile strain values of rice starch films were higher than the
b2  aw2 shows that the higher RH determines the driving force that
values found for rice flour films. This result can be explained by
causes mass transfer through the film. Inside the diffusion cell,
both the existence of irregularities at the microstructure level, and
where RH ¼ 0.02, the films’ surface moistures ranged from about
the presence of lipids in the flour, because lipids are unable to form
0.025 to 0.065 g water/g dry solid, while outside the cell, where
a cohesive and continuous matrix, according Péroval et al. (2002).
RH ¼ 75%, the film’s surface moistures ranged from about 0.38 to
0.89 g water/g dry solid. The comparison of samples SG20 and SG30
data shows that the increase of Kw was caused partially by the Table 3
increase of the diffusion coefficient, Dw (that depends on the film Films’ mechanical properties.
structure), but mainly by the increase of the solubility coefficient b1 Samples Tensile strength Elongation at break Young Modulus
(that depends on the film hygroscopicity). The same reasoning can (MPa) (%) (MPa)
be used to explain the Kw increase for samples FG20 and FG30. SG20 10.9  1.2c 2.8  0.7a 532.8  115.6c
On the other hand, for the same glycerol concentration, rice SG30 1.6  0.2a 59.8  9.9b 21.3  5.0a
flour films gave values of Kw two times higher than the rice starch SS20 22.3  1.9e 2.8  0.7a 1052.6  146.0e
SS30 11.2  1.0c 3.9  1.9a 456.3  81.0c
films. The comparison of the values of Dw and b1 for samples SG20
FG20 10.3  1.0c 2.7  0.5a 560.7  64.3c
and FG20 and for samples SG30 and FG30 shows that the much FG30 1.3  0.1a 66.4  8.5b 22.2  6.0a
higher values of the diffusion coefficients can explain the increase FS20 15.0  2.9d 2.2  0.4a 816.0  116.7d
of Kw. The higher values of Dw can be explained by the more FS30 7.2  1.5b 4.3  0.3a 248.6  54.7b
irregular structure of flour based films, as reported by Martin-Polo Values with the same letter at the same column are not different statistically
et al. (1992). (p < 0.05) by the Tukey test.
A.B. Dias et al. / Journal of Cereal Science 51 (2010) 213–219 219

Films of starch and flour with 0.2 g plasticizer/g raw material Bell, L.N., Labuza, T.P., 2000. Moisture Sorption – Practical Aspects of Isotherm
Measurement and Use, second ed. AACC Egan Press, Egan, USA.
showed low values of strain at break (3 ¼ 2.2–2.8%), and presented
Colla, E., Sobral, P.J.A., Menegalli, F.C., 2006. Amaranthus cruentus flour edible films:
higher tensile strength values. Tensile strength was more influ- influence of stearic acid addition, plasticizer concentration, and emulsion stir-
enced by plasticizer content in films plasticized with glycerol than ring speed on water vapor permeability and mechanical properties. Journal of
in films plasticized with sorbitol. Agricultural and Food Chemistry 54, 6645–6653.
Coupland, J.N., Shaw, N.B., Monahan, F.J., ÓRiordan, E.D., ÓSullivan, M., 2000.
Higher values of Young modulus (Table 3) were found for films Modeling the effect of glycerol on the moisture sorption behavior of whey
with lower plasticizer content, which is in agreement with results protein edible films. Journal of Food Engineering 43, 25–30.
that have been reported in the literature (Lourdin et al., 1997; Mali Cuq, B., Gontard, N., Cuq, J.L., Guilbert, S., 1997. Selected functional properties of fish
myofibrillar protein-based films as affected by hydrophilic plasticizers. Journal
et al., 2005, among others). On the other hand, films plasticized of Agricultural and Food Chemistry 45, 622–626.
with sorbitol were more rigid than the films plasticized with Famá, L., Gerschenson, L., Goyanes, S., 2009. Starch-vegetable fibre composites to
glycerol at the same concentration, behavior that has been also protect food products. Carbohydrate Polymers 75, 230–235.
Gontard, N., Guilbert, S., Cuq, J.L., 1992. Edible wheat gluten films: influence of main
reported by other authors (Mali et al., 2005; Müller et al., 2008, process variables on films properties using response surface methodology.
among others). Journal of Food Science 57, 190–199.
It is important to note that all film samples were conditioned at Hagenimana, A., Ding, X., Fang, T., 2006. Evaluation of rice flour modified by
extrusion cooking. Journal of Cereal Science 43, 38–46.
58% RH before the mechanical tests. It was observed that the Krochta, J.M., Miller, K.S., 1997. Oxygen and aroma barrier properties of edible films:
equilibrium moisture of the film FG30 (0.20 g water/g dry solids) a review. Trends in Food Science and Technology 8, 228–237.
was higher than the moisture of the film FS30 (0.12 g water/g dry Laohakunjit, N., Noomhorm, A., 2004. Effect of plasticizers on mechanical and
barrier properties of rice starch film. Starch/Stärke 56, 348–356.
solid). As water is a powerful plasticizer in starchy and protein rich
Larotonda, F.D.S., Matsui, K.N., Sobral, P.J.A., Laurindo, J.B., 2005. Hygroscopicity and
materials, films with glycerol are also plasticized by water, due to water vapor permeability of Kraft paper impregnated with starch acetate.
their higher moisture, explaining their lower tensile strength and Journal of Food Engineering 71, 394–402.
lower Young modulus, and also their higher elongation capacities. Leung, H.K., 1986. Water activity and other colligative properties of foods. In:
Okos, M.R. (Ed.), Physical and Chemical Properties of Food. American Society of
Agriculture Engineers, Michigan, pp. 138–185.
4. Conclusions Lourdin, D., Bizot, H., Collona, P., 1997. Antiplasticization in starch-glycerol films?
Journal of Applied Polymer Science 63, 1047–1053.
Lumdubwong, N., Seib, P.A., 2000. Rice starch isolation by alkaline protease diges-
Rice flour films prepared in the present work have similar tion of wet-milled rice flour. Journal of Cereal Science 31, 63–74.
mechanical properties to those of starch based films. However, Mali, S., Grossmann, M.V.E., Garcı́a, M.A., Martino, M.N., Zaritzky, N.E., 2002.
their water vapor permeabilities are two times higher than those of Microstructural characterization of yam starch films. Carbohydrate Polymers
50, 379–386.
starch based films, when both are prepared with glycerol. Films Mali, S., Sakanaka, L.S., Yamashita, F., Grossmann, M.V.E., 2005. Water sorption and
with sorbitol are less permeable to water and more rigid, while mechanical properties of cassava starch films and their relation to plasticizing
films with glycerol are more plasticized and have poorer water effect. Carbohydrate Polymers 60, 283–289.
Mariniello, L., Pierro, P., Esposito, C., Sorrentino, A., Masi, P., Porta, R., 2003. Prepa-
vapor barrier properties. The selection of the plasticizer depends on ration and mechanical properties of edible pectin-soy flour films obtained in the
the specific application. The presence of lipids in the rice flour does absence or presence of transglutaminase. Journal of Biotechnology 102 (2),
not cause important changes in film hygroscopicity (similar water 191–198.
Martelli, S.M., Moore, G., Paes, S.S., Gandolfo, C., Laurindo, J.B., 2006. Influence of
sorption isotherms). From the results presented in this work, it is
plasticizers on the water sorption isotherms and water vapor permeability of
clear that the permeabilities are controlled mainly by plasticizer chicken feather keratin films. LWT – Food Science and Technology 39, 292–301.
concentration. In fact, both starch and flour films present poor Martin-Polo, M., Mauguin, C., Voilley, A., 1992. Hydrophobic films and their effi-
water vapor barrier and are not indicated for packaging low ciency against moisture transfer. 1. Influence of the film preparation technique.
Journal of Agricultural and Food Chemistry 40, 407–412.
moisture food, for example. In other words, the higher permeability Moore, G.R.P., Martelli, S.M., Gandolfo, C., Sobral, P.J.A., Laurindo, J.B., 2006. Influ-
of flour films is not a big problem, and flour is a good raw material ence of the glycerol concentration on some physical properties of feather
to prepare edible films. On the other hand, preparing edible films keratin films. Food Hydrocolloids 20, 975–982.
Moraes, J.O., 2009. Propriedades de filmes de amido incorporados de nanoargilas e
from rice flour is a new alternative for using this raw material, fibras de cellulose. MSc thesis, UFSC, Brazil. 123 p.
which is sometimes much cheaper than commercial starches. Müller, C.M.O., Yamashita, F., Laurindo, J.B., 2008. Evaluation of the effect of glycerol
New studies are necessary to better understand how proteins, and sorbitol concentration and water activity on the water barrier properties of
cassava starch films through a solubility approach. Carbohydrate Polymers 72
lipids and starch interact in the film polymeric matrix and to find (1), 82–87.
correct procedures to prepare more homogeneous films. The use of Péroval, C., Debeaufort, F., Despré, D., Voilley, A., 2002. Edible arabinoxylan-based films.
reinforcing fibers is a good alternative to improve film mechanical 1. Effects of lipid type on water vapor permeability, film structure, and other
physical characteristics. Journal of Agricultural and Food Chemistry 50, 3977–3983.
properties and water sensibility, but will be the subject of a further Rayas, L.M., Hernández, R.J., 1997. Development and characterization of biode-
paper. gradable/edible wheat protein films. Journal of Food Science 62 (1), 160–164.
Ryu, S.Y., Rhim, J.W., Roh, H.J., Kim, S.S., 2002. Preparation and physical properties of
zein coated high amylose corn starch film. Lebensmittel-Wissenschaft und-
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