International Journal of Biological Macromolecules 128 (2019) 290–296

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International Journal of Biological Macromolecules

journal homepage: http://www.elsevier.com/locate/ijbiomac

Synthesis and characterization of a low solubility edible film based on

native cassava starch
Otavio A. Silva a,d, Michelly G. Pellá a, Matheus G. Pellá b, Josiane Caetano d, Márcia R. Simões d,
Paulo R.S. Bittencourt c, Douglas C. Dragunski d,⁎
a
Department of Chemistry, State University of Maringa, Av. Colombo, 5790, CEP 87020-900, Maringá, Paraná, Brazil
b
Federal University of Parana (UFPR), Sector of Palotina, R. Pioneiro, 2153 - Dallas, Palotina, PR CEP 85950-000, Brazil
c
Technological Department Environmental Management, Federal Technological University of Paraná, Campus Medianeira, Av. Brasil, Parque Independência, 85884-000 Medianeira, PR, Brazil
d
GIPeFEA, Department of Chemistry, State University of West Paraná, 85903-000, Toledo, Paraná, Brazil

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

Article history: Films based on cassava starch have been widely used for fruit coating; however, it is necessary to incorporate
Received 27 October 2018 other polymers in order to improve mechanical properties, once starch only leads to highly hydrophilic films,
Received in revised form 28 December 2018 compromising their application. In this way, a polymeric blend based on cassava starch, chitosan and gelatin
Accepted 24 January 2019
was combined with a plasticizer to produce biodegradable films with satisfactory mechanical and barrier prop-
Available online 25 January 2019
erties, in order to be used as fruit coating. The films were prepared by casting method and a statistical design
Keywords:
of 23 was used to evaluate the effect of each polymer and what their combinations would influence over the
Polymeric blend final product. The formation of a physical blend was confirmed by FTIR. It showed low solubility, varying (10
Carbohydrate ± 2) % a (23 ± 4) %, Opacity ranging from (1.06 ± 0.04) to (1.55 ± 0.13) AU x nm/mm, thickness from (0.20
Protein ± 0.01) mm to (0.44 ± 0.03) mm and water vapor transmission rate ranging from 25 ± 0.2 to 30 ±
Gelatin 1.4 g s−1 m−2. Lower amounts of starch led to more flexible, less opaque and soluble films, while the combination
Chitosan of higher levels of starch and chitosan was responsible for lowering films water vapor transmission rate. Thus, the
films showed interesting properties for fruit surface coating.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction
One of the main ways to preserve products is by utilizing synthetic
packages obtained from, among others, petroleum derivate polymers
[1]. Although, the accelerated waste production occurs, in parts, due to
these particular sorts of materials, which are non-biodegradable. Thus,
it becomes a serious environmental threat, turning into a non-viable op-
tion when we think about environmental preservation and technologi-
cal advances. In this way, a possible solution is the utilization of smart
and/or biodegradable packages [2]. Thus, to be considered a biodegrad-
able and smart package, it must provide an active food protection, in-
creasing its shelf life by, e. g., decreasing mass loss and microbial
activity [3].
Among biodegradable products, starch biodegradable films have
been gaining space due to their several advantages [2,4–6], like, for ex-
ample, low cost, odorless, colorless, non-toxic, biocompatible and
environmentally-friendly [2,7].
Starch can be obtained from several sources like rice, corn and cas-
sava, which is a Brazilian plant scientifically known as Manihot esculenta
⁎ Corresponding author.
E-mail address: dcdragunski@gmail.com (D.C. Dragunski).
Crantz [8] and, among its use advantages, high yield of starch per ton of
cassava, low cost of production and resistance to long dry periods can be
highlighted when compared to other starch sources [9,10]. However,
starch is highly hygroscopic and shows low flexibility, so films based
on starch only do not show satisfactory mechanical properties, hinder-
ing the production of these kinds of packages [6,11,12].
Blending formation and/or plasticizer addition are interesting alter-
natives to improve starch films mechanical properties, once both tends
to lower the interaction between starch chains, increasing, thus, their
mobility. Among the most commonly used plasticizer, glycerol is con-
sidered by some authors as the best one for water soluble polymers
due to its natural glycosidic form, found in animals and vegetables
[2,13]. However, sorbitol, a nontoxic plasticizer, shows higher interac-
tion with starch chains, becoming a more interesting and advantageous
alternative [14–16]. Blending formation, on the other hand, consists in a
macroscopic homogeneous mixture of two or more polymers, natural or
synthetic, and it is also efficient to improve mechanical properties of
biopolymer-based films [17].
When we combine starch with gelatin and chitosan in a polymer
blend, more flexible films are obtained when compared to films based
in starch only. Gelatin is an animal protein able to improve mechanical
properties due to its ability of films formation [18]. Its main source is by

https://doi.org/10.1016/j.ijbiomac.2019.01.132
0141-8130/© 2019 Elsevier B.V. All rights reserved.
 O.A. Silva et al. / International Journal of Biological Macromolecules 128 (2019) 290–296
collagen thermal or physical-chemical denaturation, causing the de-
struction of the triple helix into random parts [19,20]. But, besides the
ability of films formation, gelatin and starch end up in a highly hydro-
philic film, what may compromise its application depending on the
kind of surface it will be coating. It can be minimized by chitosan
(CTS) addition, which is a biopolymer with low water solubility [21,22].
Chitosan is also a nontoxic, biodegradable and renewable polymer
with the ability of films formation, obtained by chitin partial
deacetylation [23]. It has been used to fruit coating, once its protector
barrier is able to avoid mass loss shelf-life [24–26], besides controlling
microorganism proliferation due to its antimicrobial activity [27,28].
Thus, this work aimed to develop a polymeric blend by the combina-
tion of three biopolymers (starch, gelatin and chitosan) in order to ob-
tain an odorless, nontoxic and biodegradable film with good
mechanical properties, able to increase post-harvest fruit's lifetime.
2. Materials and methods
2.1. Materials
Native cassava starch (S) was donated by Avebe – Guaíra (15% of
moisture and 72% of amylose). Pure gelatin (Gel; BIOTEC), citric acid
and sorbitol (Sor; BIOTEC). Chitosan (C) was purchased from
POLIMAR (85% degree of deacetylation).
2.2. Biodegradable films preparation
The films were prepared by casting method, by using a 23 factorial
design with 3 central points. The evaluated variables were the amount,
in mass, of starch, gelatin and chitosan, as showed on Table 1.
Four mixtures were, separately, prepared: 1) Starch in 40 mL of dis-
tilled water; 2) Chitosan in a solution of 80 mL of citric acid 1,7% (v/v);
3) Gelatin in 20 mL of distilled water; 4) Sorbitol in 10 mL of distilled
water. Mixtures 1 and 3, were heated in a water bath, at 85 °C, being
manually stirred until complete gelatinization. Mixture 2, was prepared
by adding chitosan to the citric acid solution, under stirring, for 24 h,
while mixture 4 was prepared just by adding sorbitol to distilled
water. Then, the mixtures were put together and manually stirred
until complete miscibility. Samples of 50 mL were transferred to Teflon
plates and dried, into an oven, by 48 h at 40 °C, and stored into a
desiccator.
The samples were named SxCyGz, being the starch represented by
“S”, chitosan, by “C” and gelatin, by “G”. The sub-indexes “x”, “y” and
“z” refers to the amount of starch, chitosan and gelatin, respectively.
The letters a, b and c were used to differ the replicates on central point.
2.3. Characterization
2.3.1. Fourier transform infrared (FTIR) analysis
Films were characterized by Fourier transform infrared (FTIR) - at-
tenuated total reflection (ATR) using a PERKIN ELMER spectrometer.
The spectra were recorded at a wavenumber range from 4000 cm−1
to 400 cm−1, at room temperature, using 32 accumulated scans and res-
olution of 4 cm−1.
Table 1
Factorial design of 23 experiments with three central points.
Level Starch (g) Gelatin (g)
-1 1.0 1.0
0 2.0 2.0
+1 3.0 3.0
291
2.3.2. Thickness
A micrometer (DIGIMESS) with precision of 5 μm, was used to mea-
sure the films thickness by performing, randomly, five replicates for
each film. Then, the average value was calculated.
2.3.3. Opacity
This analyze was performed measuring the light absorption of the
films at wavelength ranges from 400 nm to 700 nm, using a spectropho-
tometer (SHIMADZU). The opacity was, then, calculated, accordingly to
Eq. (1) [29], where Aλ is the selected wavelength (Aλ = 450 nm) and x is
the film thickness:
Aλ
Opacity ¼ ð1Þ
x
2.3.4. Water solubility (WS)
Films WS were measured as described by Gontard et al. (1994).
Samples were cut into square shapes (2 cm2) and dried at 105 °C for
24 h, before and after the solubilization period. After each drying period,
samples mass was measured using an analytical balance.
The WS was calculated using Eq. (2) [30], where DM0 refers to the
first dried material (before the solubilization) and DM24 refers to the
dried material after 24 h of solubilization.
 
DM0 −DM 24
WS ¼ :100% ð2Þ
DM 0
2.3.5. Water vapor transmission rate (WVTR)
For this analysis, samples were cut into round shape (~6 cm2) and lo-
cated in a test cup, filled with 10 mL of distilled water, without getting in
touch with the water. The mass of the system (test cup + water + film)
were measured in time intervals of 24 h, from 0 to 144 h, being stored in
a desiccator. To maintain 100% of relative humidity (RH) gradient across
de film, silica gel was placed inside the desiccator.
The WVTR was calculated using the Eq. (3) [31], where ΔW is the
amount of water absorbed by silica as a function of the time, A is the
area of the film (m2), being the slope (ΔW/Δt) of each line determined
by linear regression (R2 N 0.99).
ΔW
WVTR ¼ ð3Þ
Δt:A
2.3.6. Mechanical properties
The standard method D882–02 (ASTM, 2002) was used to deter-
mine tensile strength (ES), Young's modulus and percentage of elonga-
tion (% E) of the films. The samples were cut into rectangular shapes
with a dimension of 25 mm × 10 mm, placed in a TA.HD - plus - Stable
Micro Systems with 5 kg loaded cell and stretched at a constant rate of
2 mm.s−1. Grip separation was 15 mm and the analysis were performed
in quintuplicate to the films formulations, synthesized in triplicate.
2.3.7. X-ray diffraction analysis (XRD)
The pattern of XRD of the samples were analyzed by a Bruker® X-ray
diffractometer, with diffraction angles (2θ) from 4° to 80°, using radia-
tion CuKα of λ = 15,406 Å.
2.3.8. Termogravimetric analysis (TGA)
Chitosan (g)
Thermogravimetric analyses were carried in a Perkin Elmer STA
0.50 6000 thermal analyzer. Samples (~ 7 mg) were placed into ceramic cru-
0.75 cibles and heated from 30 °C to 800 °C at a heating rate of 10 °C·min−1,
1.0
under a nitrogen atmosphere with a N2 flow rate of 50 mL·min−1.
292 O.A. Silva et al. / International Journal of Biological Macromolecules 128 (2019) 290–296

2.3.9. Statistical analysis Table 2

To evaluate the interaction between the factors and its effect on the Mean values ± standard deviation of thickness (mm), opacity (at 450 nm, Abs.nm), solu-
bility (%) and water vapor transmission rate (WVTR) g s−1 m−2.
final film, analysis of Variance (ANOVA) and Tukey mean comparison
test (p ≤ 0.05) and non-linear regression procedure were performed Film Thickness Opacity (Abs. Solubility WVTR (g s−1
employing the software Minitab 14 (OSB Software) and Statistica 7 (mm) nm) (%) m−2)

(Statsoft).
S1C0.5G1 0.20 ± 0.01 1.38 ± 0.21 10 ± 2 30 ± 1.2
S3C0.5G1 0.27 ± 0.02 1.53 ± 0.18 17 ± 2 29 ± 0.9
3. Results and discussions S1C1G1 0.22 ± 0.01 1.34 ± 0.07 12 ± 4 30 ± 1.4
S3C1G1 0.35 ± 0.02 1.46 ± 0.11 22 ± 4 30 ± 0.9
S1C0.5G3 0.33 ± 0.01 1.32 ± 0.04 18 ± 3 29 ± 0.4
3.1. FTIR
S3C0.5G3 0.39 ± 0.02 1.06 ± 0.04 22 ± 4 28 ± 0.4
S1C1G3 0.38 ± 0.03 1.39 ± 0.13 19 ± 3 26 ± 0.2
FTIR analyses were used to confirm the formation of physical inter- S3C1G3 0.44 ± 0.03 1.20 ± 0.08 23 ± 4 25 ± 0.2
actions from the biopolymers combination. It is possible to notice that aS2C0.75G2 0.32 ± 0.01 1.48 ± 0.20 19 ± 3 29 ± 0.4
the films showed the same bands, varying just their intensity, as seen bS2C0.75G2 0.32 ± 0.01 1.33 ± 0.07 19 ± 3 29 ± 0.3
cS2C0.75G2 0.32 ± 0.01 1.55 ± 0.13 19 ± 4 29 ± 0.3
on Fig. 1. Carbohydrates and proteins characteristic bands are observed
in the spectra, like the bands at the range of 3700 cm−1 to 3000 cm−1, The biodegradable films were named as SxCyGz, being the starch represented by “S”, chi-
tosan, by “C” and gelatin, by “G”. The sub-indexes “x”, “y” and “z” refers to the amount, in
for example, which can be assigned to the OH and/or NH2 stretching
mass, of starch, chitosan and gelatin, respectively.
[32].
Once gelatin is protein, it has carbonylic (C=O) and amine (NH2)
3.2.1. Thickness
groups in its structure [33], as confirmed by the band at 1630 cm−1
Thickness control allows the obtainment of more uniform films, be-
[33]. For both functional groups, there are possibilities of intra and inter-
sides providing important information to mechanical resistance analy-
chain hydrogen bonding formation [33], and the combination of carbo-
sis [35]. Thicker films are the ones able to ensure higher protection to
hydrates and proteins affects the length of these hydrogen bonds,
coated fruit once it will show higher resistance against external stresses
changing the band position on the spectra, as observed for the band at
[36], as confirmed by mechanical analysis (Table 3).
~ 1540 cm−1, which belongs to NH2 angular deformation [34]. Such
In this work, films thickness varied from (0.20 ± 0.01) mm to (0.44
band varied from 1532 cm−1 to 1546 cm−1 to, respectively, S1C0.5G1
± 0.03) mm. Statistical analyses indicated significant interaction (p b
and S1C0.5G3, characterizing the enhancing of hydrogen bonding be-
0.05) between starch/gelatin, as shown on Fig. 3a, but no significant in-
tween the polymers, confirming the formation of a physical blend [33].
teraction between casein/gelatin and gelatin/casein were observed. It is
When the blend constituents were mixed, polymers characteristic
possible to verify that thicker films were obtained by the combination of
bands were displaced from their regular observed wavelength. Taking
higher amounts of starch and gelatin, but individual factors were also
pure chitosan films for example, a displacement from 1700 cm−1 to
responsible for increases on films thickness: casein, starch and gelatin
1630 cm−1 was observed, confirming physical interaction between hy-
promoted increases of 0.05 mm, 0.08 mm and 0.13 mm on thickness,
droxyl groups present on both carbohydrates, starch and chitosan [33].
respectively.
It could be associated to the amount of each biopolymer used to form
3.2. Physical-chemistry analysis the blend, once it changes the space between chains, favoring the inter-
action between hydrophilic groups from different polymers, decreasing
The obtained results for thickness, opacity, solubility and WVTR are interactions between chains of the same polymer [37], besides increas-
shown on Table 2. Statistical analyses were performed to determine ing solution viscosity, changing the space between chains [38].
the effect of each evaluated factor on the variables (thickness, opacity,
solubility and WVRT), being reported, on support information
(Table S1), the obtained results. The interaction between the three fac- 3.2.2. Opacity
tors (starch, chitosan and gelatin) has, generally, insignificant values (p The opacity is represented by coloration changes occurred during
N 0.05) when compared to the interaction between two polymers. carbohydrate gelatinization process, due to the disruption of crystalline
Therefore, the present work only shows interaction plots to significant starch granule, leading to the obtainment of an opaque gel, [39,40].
interactions (p b 0.05) (Fig. 2). Varying from (1.06 ± 0.04) e (1.55 ± 0.13) AU x nm/mm, referring to

Fig. 1. Infrared spectra, at a wavenumber range from 4000 cm−1 to 400 cm−1, for the films (A) based on pure starch, chitosan and gelatin, and (B) based on the polymeric blend, which are
identified as SxCyGz, being the starch represented by “S”, chitosan, by “C” and gelatin, by “G”. The sub-indexes “x”, “y” and “z” refers to the amount of starch, chitosan and gelatin,
respectively.
 O.A. Silva et al. / International Journal of Biological Macromolecules 128 (2019) 290–296 293

Fig. 2. Significant interactions (p b 0.05) to (a) thickness, (b) solubility and WVTR between (c) starch/chitosan, (d) starch/gelatin.

the solid film, and not showing significant statistical differences, it was
expected that higher amounts of gelatin would decrease the opacity,
once it cannot crystallize, keeping its amorphous form, making easier
to the light to go through the film, but it was not observed. However,
such effect was not observed due to chitosan addition, since polysaccha-
rides incorporation decreases transparency of protein films due to a
possible interaction between the polysaccharides and the protein [18].
Furthermore, higher amounts of starch would also be responsible for
the increase on opacity due to its gelatinization process [4].
3.2.3. Solubility
Solubility is an important factor for films destined to fruit coating
once it will act as a barrier to water vapor transferences from fruit to
the environment. In this way, films with high solubility might have its
structure compromised as water is transferred [5]. As shown on
Table 2, this parameter varied from (10 ± 2) % to (23 ± 4) % and statis-
tical analysis indicated lower solubility on films with lower levels of
starch and gelatin. It could be attributed to the introduction of gelatin
molecules between amylose and amylopectin chains, so, higher
amounts of starch and gelatin leads to an increase on free volume, in-
creasing, consequently, water diffusion through the chains and ending
in a more hydrophilic product [4]. The amount of chitosan, however,
was not statistically significant.
The solubility values observed in this present work were lower or
similar when compared to reports from literature like, e.g., the films
based on cassava starch with Mentha x piperita L. essence, obtained by
MOOSAVIAN et al. [41].They observed solubility values varying from
22% to 32%, while the films based on chitosan and xanthan gum, ob-
tained by De MORAIS LIMA et al. [26], varied from 19.50% to 22.44%.
On the other hand, LUCHESE et al. [42], observed solubility values simi-
lar to the ones shown on the present work. They developed biodegrad-
able films from several amounts and sources of starch, using glycerol as
plasticizer. The observed solubility ranged from 13.7 to 26.5%, being the
lower value (13.7%) observed for the cassava starch biodegradable film.

Table 3
Young's Modulus (MPa), Tensile strength (MPa) and Elongation at break (%) of the biode-
gradable films based on starch, cassava and gelatin.b

Film Young's Modulus Tensile strength Elongation at break

(MPa) (MPa) (%)

S1C0.5G1 0.31 ± 0.08 2.09 ± 0.50 76.63 ± 10.44

S3C0.5G1 0.68 ± 0.04 5.16 ± 0.03 19.88 ± 2.22
S1C1G1 0.87 ± 0.30 7.13 ± 2.23 18.86 ± 0.58
S3C1G1 1.90 ± 0.01 5.40 ± 0.00 4.75 ± 0.00
S1C0.5G3 INa INa INa
S3C0.5G3 0.48 ± 0.02 2.73 ± 0.92 18.16 ± 13.11
S1C1G3 0.79 ± 0.10 8.76 ± 0.16 16.14 ± 0.53
S3C1G3 0.86 ± 0.14 4.88 ± 0.67 10.80 ± 4.01
aS2C0.75G2 0.62 ± 0.26 5.84 ± 1.38 11.47 ± 3.83
bS2C0.75G2 0.79 ± 0.04 8.38 ± 0.49 13.57 ± 0.27
cS2C0.75G2 0.84 ± 0.25 7.04 ± 2.60 13.96 ± 0.56
a
IN means that was not possible to determine the values of the respective property. Fig. 3. DRX analysis for the films obtained from the polymeric blend, which are identified
b
At the samples name (SxCyGz), starch is represented by “S”, chitosan, by “C” and as SxCyGz, being the starch represented by “S”, chitosan, by “C” and gelatin, by “G”. The
gelatin, by “G”. The sub-indexes “x”, “y” and “z” refers to the amount of starch, chitosan sub-indexes “x”, “y” and “z” refers to the amount of starch, chitosan and gelatin,
and gelatin, respectively. respectively.
294 O.A. Silva et al. / International Journal of Biological Macromolecules 128 (2019) 290–296
It ensures that cassava starch utilization, in lower amounts, decrease
biodegradable films solubility.
Thus, it is possible to conclude that the higher values of solubility
from the present work (~20%) are lower than the ones observed on lit-
erature (~22%) [26,41], ensuring that the films will not be compromised
as water goes through it, especially considering fruit surface coating as a
possible application for them.
3.2.4. Water vapor transmission rate (WVTR)
The WVTR indicates the amount of water vapor that can permeate
per one unit of material area for certain time [43], therefore, it indicates
the barrier capacity of the film [44]. Results shown on Table 1 indicates
that this parameter varied from 25.36 to 30.35 g s−1 m−2, being the
combination of starch/chitosan and starch/gelatin statistically
significant.
For starch/chitosan interaction, higher amounts of these polymers
led to lower values of WVTR, occurring due to hydrogen-bonding be-
tween polymers chains [33], disfavoring the interaction between
water and the chains, lowering water permeation [33,45]. Similarly,
the interaction between chitosan/gelatin also decreased WVTR. This
also occurs by hydrogen bonding, considering the several polar groups
present on the chains like, e.g., hydroxyl and amino [46], decreasing
the free volume between the chains.
3.3. Mechanical properties
A biodegradable film is considered efficient when it is resistant to
stresses that the product is put into during application, transportation
and handling process [47]. In this way, mechanical properties were
evaluated and the results are shown on Table 3 and statistical analysis
are reported on support information (Table S1). It is possible to notice
that all the films, but S1C0.5G1, were considerably hard and fragile [48],
once they disrupted before plastic deformation was reached [49].
Young's modulus (E) is determined by energy needed to deform the
angles and bonding length between the atoms of polymeric chains
[44,47,49] In the present work, E ranged from (0.31 ± 0.08) MPa to
(1.90 ± 0.01) MPa. Tensile strength (TS), which measures the deforma-
tion while a force is applied at a constant rate [48], it varies along with
thickness, so TS for films with lower thickness were (2.09 ± 0.50)
MPa, while for thicker films, it was (8.76 ± 0.16) MPa. For both analyses,
E and TS, no significant interactions among polymers combination were
observed.
Higher amounts of chitosan led to harder films with higher TS, but
films with higher amounts of starch and chitosan showed a decrease
on % E values [33]. It can be verified if extreme levels are compared
(the films S1C1G1 and S3C1G1), being observed that higher starch con-
centration led to non-satisfactory mechanical properties, as related on
literature [6,11,12].
Fig. 4. (a) Thermal behavior and (b) thermal degradation of the films obtained from the polymeric blend, which are identified as SxCyGz, being the starch represented by “S”, chitosan, by
“C” and gelatin, by “G”. The sub-indexes “x”, “y” and “z” refers to the amount of starch, chitosan and gelatin, respectively.
Chitosan, on the other hand, acts almost as a plasticizer, decreasing
hydrogen bonding length between starch chains and favoring the inter-
action with chitosan chains, increasing film flexibility. However, it was
not observed probably because of the higher starch content [33], in-
creasing significantly the amount of –OH groups exposed after the dis-
ruption of starch granules, favoring intrachains interactions. Another
factor to be considered is the lower number of polar groups (NH3 or
NH2) available for each chitosan monomer, restricting the possibility
of hydrogen bonding with starch chains [33].
Unlikely the expected behavior, the film S1C0.5G3 disrupted during
the tests. Low amounts of starch and chitosan led to obtainment of a
brittle film. According to FAKHOURI et al. [20], the increase of gelatin
leads to a decrease on films elasticity (Elongation to Break) [50].
3.4. X-ray analysis
DRX analyses give information about material crystallinity, where
well defined peaks and broadband are seen on crystalline and amor-
phous regions, respectively. The results on Fig. 3 shows a broadband
for the film S1C0.5G1, from 2θ = 16 to 2θ = 50, while the other films
were less amorphous, showing bands among 2θ = 12 to 2θ = 26.
During starch gelatinization, the granules absorb considerable
amounts of water, what starts the swelling process, leading to their irre-
versible disruption and causing birefringence losses [51,52]. It is known
that gelatinization process starts in the amorphous regions of the gran-
ule because it is easy for water to reach them, once their intermolecular
bonding is not as strong as it is on crystalline parts [51,52]. After the dis-
ruption, occurs the interlacing of the exposed amylose (linear) and am-
ylopectin (branched) chains, leading to a more crystalline region [53].
Thus, higher polymers amounts will lead to more crystalline films and,
consequently, harder, while lower amounts will decrease the ordination
degree, leading to more flexible films.
Such results corroborate with mechanical analysis results, being
possible to notice that the film S1C0.5G1 were more flexible than the
others because of its higher free space in what, as the tension was in-
creased, polymeric chains started being oriented in the direction of
the applied force, increasing the orientation degree. From this point
on, the fracture process gets started [49]. This film was, also, the less
thick and soluble among all the films.
3.5. Thermogravimetric analysis
Thermogravimetric analysis (TG) determines the material thermal
stability from its mass variation over temperature [54]. The first derivate
(DTG) gives information about the degradation behavior, as well as the
temperatures which the degradation rate is maximum [55].
Thermal stability and degradation behavior (Fig. 4a and b, respec-
tively) were similar for all the films. Three regions can be highlighted
 O.A. Silva et al. / International Journal of Biological Macromolecules 128 (2019) 290–296
on Fig. 4b: the first one (~ 30 °C to 160 °C), corresponding to 40% of mass
loss, can be attributed to physically adsorbed water molecules loss [56].
The second one (~ 170 °C to 450 °C), corresponding to 50% of mass loss,
occurred due to polymer degradation [54–56]. It occurred in two con-
secutive steps (the slower step is observed from 170 °C to 250 °C and
the faster, from 250 °C to 450 °C). Similar values were found by Caetano
et al. e Pelissari et al., where the degradation started at 250 °C [57].
The observed mass loss differences between the films could have
happened due to possible different percentages of individual polymers
constituents like, for example, higher amounts of amylose in starch
and higher acetylated chitosan, since they are consisted of a non-
homogeneous mixture of individual components [58]. Once mass varia-
tion is not significantly different among the films, it can be concluded
that the amount of polymer does not affects films thermal stability. So,
the best film to be used as coating is the S1C0.5G1, because of its lower
solubility (9.79 ± 2.04%) among the others and low WVTR
(30.25 g s−1 m−2). It was, still, the most flexible film (about 50% more
flexible).
Economic viability is another important factor to be considered. Gel-
atin and starch are relatively cheap and abundant [44,59] while chitosan
is not so cheap. However, for the film with the best performance
(S1C0.5G1), the amount of chitosan is only 20% of its total mass. Thus,
its utilization is still economically viable.
4. Conclusions
The polymeric blend based on chitosan and gelatin, added to starch
biodegradable films, was able to improve films' mechanical properties.
It was observed that the polymeric blend formation had an important
role in the obtainment of low soluble and, mostly, hard films, with po-
tential application on fruit coating, ensuring the protection of fruit sur-
face. The films also showed low values of WVTR, what is interesting for
increasing the shelf life of fruit post-harvest.
Acknowledgments
This study was supported by UNIOESTE and CAPES. The authors
would like to thank CNPq (National Council for Scientific and Techno-
logical Development) and Araucária Foundation for the financial sup-
port and fellowships.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ijbiomac.2019.01.132.
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