Carbohydrate Polymers 251 (2021) 117009

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Preparation of a novel biodegradable packaging film based on corn

starch-chitosan and poloxamers
Abril Fonseca-García a, Enrique Javier Jiménez-Regalado b, Rocio Yaneli Aguirre-Loredo a, *
a
CONACYT-CIQA, Blvd. Enrique Reyna Hermosillo 140, Saltillo, Coahuila 25294, Mexico
b
Centro de Investigación en Química Aplicada (CIQA), Blvd. Enrique Reyna Hermosillo 140, Saltillo, Coahuila 25294, Mexico

A R T I C L E I N F O A B S T R A C T

Keywords: Starch is an excellent alternative to produce packaging materials, however, due to its high hydrophilicity, it is
Biodegradable film necessary to mix it with other polymers. Chitosan (CTS) is a polymer extracted from shrimp shells and crabs,
Composite film which can be used to make biodegradable materials. The principal component of biodegradable was corn starch
Starch
and chitosan, the copolymer pluronic F127 was incorporated in several concentrations and its effect on the water
Chitosan
Water vapor permeability
vapor barrier, morphological, thermal, and mechanical properties of the films was evaluated, because its
Water solubility incorporation in the formulation of biodegradable materials could increase its hydrophobicity. The surface of
starch-chitosan composite films obtained was more homogeneous and smoother with the increase in the content
of pluronic F127. The %S and WVP of the starch-chitosan films decreased from 42 to 3%, and 21 × 10− 11 to 3 ×
10-14 g. m-1s-1 Pa-1, respectively, with the incorporation of pluronic from 3%, which makes these materials a good
alternative for product packaging.

1. Introduction kingdom, is abundant in nature and readily available as a commercial

World plastic consumption is currently estimated to exceed 700
million tons per year and will reach one billion by 2021. According to
estimates by the United Nations Joint Group of Experts on the Scientific
Aspects of Marine Pollution (GESAMP), between the 70 and 95% of this
waste will join millions of tons already present in seas, lakes, air, rivers,
groundwater, crop fields, landfills, and cities. Packaging materials are an
essential part of product processing, so the number of investigations on
the development and use of new alternatives has increased, mainly due
to the interest in minimizing the environmental impact caused by the
use of synthetic packaging materials. Biodegradable packaging is one
that is capable of decomposing into carbon dioxide, methane, water,
inorganic compounds, or biomass, the dominant mechanism of decom­
position being the enzymatic action of microorganisms and that the
resulting products can be obtained and measured in a period of a certain
time (Tian & Bilal, 2020). The materials used to make biodegradable
packaging can be polymers of natural origin (starch, gelatin, collagen,
zein, chitosan, cellulose, pectin, waxes) or of synthetic origins such as
polylactic acid, polycaprolactone and polyvinyl alcohol (Pavlath & Orts,
2009; Skurtys et al., 2014; Tian & Bilal, 2020).
Starch, the main polysaccharide used to store energy in the plant
product, it is widely used in food packaging due to its low cost and good
film-forming properties. Commercial starches are obtained mainly from
corn, potato, rice, wheat, and cassava. The starch, due to its hydrophilic
properties and its easy degradation, allows it to be modified to form
thermoplastics that are then mixed with degradable synthetic polymers,
such as poly(-caprolactone), poly(lactic acid) or polyvinyl alcohols or
other polyesters, as well as with various natural polymers such as
gelatin, chitosan (Bergel, da Luz, & Santana, 2018; Datta & Halder,
2019; Gómez-Aldapa, Velazquez, Gutierrez, Rangel-Vargas et al., 2020;
Laycock et al., 2017). Due to this, in recent years it has been used in an
important way for its application in films. However, starch-based films
have poor mechanical properties and high rigidity, which limits the
applications in material engineering.
A proposal for the development of packaging materials has been the
combination of two or more polymers to improve gas exchange,
adherence to surfaces or moisture barrier properties, as well as
compatibility between polymers.
Chitosan is a natural linear amino polysaccharide derived from
chitin, the second most abundant polysaccharide in nature after cellu­
lose and it is the main component of the exoskeleton of crustaceans, it is
obtained from the by-product of the fishing industry, it has some

* Corresponding author.
E-mail address: yaneli.aguirre@ciqa.edu.mx (R.Y. Aguirre-Loredo).

https://doi.org/10.1016/j.carbpol.2020.117009
Received 18 June 2020; Received in revised form 22 August 2020; Accepted 24 August 2020
Available online 30 August 2020
0144-8617/© 2020 Elsevier Ltd. All rights reserved.
A. Fonseca-García et al.
biological properties that include activities biocompatibility, antimi­
crobial, antioxidant and acceleration in the wound healing process, it is
non-toxic and the materials obtained from it have a low oxygen
permeability (Rocio Yaneli Aguirre-Loredo et al., 2018; Liu et al., 2018).
Pluronic is a triblock copolymer of poly(ethylene oxide)x -poly
(propylene oxide)y and -poly(ethylene oxide)x (PEOx - PPOy - PEOx),
commercially available under the Pluronic® or Poloxamer® brand
names. This arrangement in the poloxamers endows them with amphi­
philicity and the variation in the proportions of the PPO/PEO compo­
sition allows them to be classified and characterized by their distinctive
hydrophilic-lipophilic balance (HLB) (Khaliq et al., 2019).
Pluronic is a nonionic surfactant or surface-active agent, it can
generate thermoreversible aqueous gels. Poloxamers are non-
biodegradable materials, however, they are approved by the FDA and
are included in the European and US pharmacopeia. As they are not
toxic or irritant, they can be used as solubilizers, stabilizers, and emul­
sifiers (Russo & Villa, 2019). It is commonly used in various industrial
applications, such as foams, detergents, cosmetics, and in particular in
the pharmaceutical industry for the controlled release of active sub­
stances and drugs due to its biocompatibility and environmental sensi­
tivity (Serrano Castañeda et al., 2015). In aqueous solutions, at
concentrations above the concentration of critical micelles, these co­
polymers self-assemble into micelles with a hydrophobic PPO core sur­
rounded by a hydrophilic PEO crown, providing interesting
self-assembling and thermo-gelling properties (Branca, Khouzami,
Wanderlingh, & D’Angelo, 2018). Among poloxamers, F127 with a
PEO/PPO at 2:1 wt ratio, is one of the most widely used triblock co­
polymers in pharmaceutical formulations due to low body toxicity and
the ability to encapsulate any hydrophobic agent (Branca et al., 2018).
The use of Pluronic F127 has been found to achieve a significant
improvement in the rate of wound healing and skin burns, which is why
it has been included in the formulation of creams and skin substitutes for
the treatment of burns and other applications like tissue engineering
(Guo et al., 2013) as well as for the formulation of nanoparticles that
transport drugs for the treatment of diseases such as cancer (Khaliq
et al., 2019). Previous studies showed that the addition of poly­
saccharides like chitosan to an aqueous solution of pluronic F127 does
not affect micelle formation or stability creating nanocapsules with
improved bioavailability (Fullagar et al., 2017; Manaspon,
Viravaidya-Pasuwat, & Pimpha, 2012; Rao et al., 2014; Zhang et al.,
2010).
The hypothesis was that the incorporation of a poloxamer like
pluronic F127 in starch and chitosan-based films would help to obtain a
more hydrophobic material with a good moisture barrier. The objective
of this study was to obtain a new biodegradable material made from the
mixture of corn starch, chitosan and pluronic F127 polyester. To
determine its structural, mechanical, and water vapor barrier properties,
to determine its viability as a new biodegradable packaging material.
2. Materials and methods
2.1. Materials
Normal corn starch with 30 % amylose was obtained from KMC
(Denmark). Practical grade shrimp shell chitosan (417963, deacetyla­
tion degree ≥ 75 %, 190-375 KDa) and pluronic F127 (P2443, with a
content of 70 % of ethylene oxide) were purchased from Sigma-Aldrich,
USA. The glacial acetic acid acquired from Productos Quimicos Mon­
terrey S.A. (Mexico). Reagent grade glycerol (Meyer, Mexico) was used
as a plasticizer and NaBr (Jalmek Cientifica, Mexico) to prepare a su­
persaturated saline solution in order to obtain an equilibrium relative
humidity of 54 %.
2.2. Film preparation
The starch solution was prepared at 5% (w/v), the chitosan was
2
Carbohydrate Polymers 251 (2021) 117009
prepared at 1% (w/v) in a 1% (v/v) aqueous solution of acetic acid,
while the pluronic F127 was prepared in distilled water at concentra­
tions of 1, 3 and 5% (w/v). 25 % (w glycerol/w total polymers) of
glycerol was added as a plasticizing agent. The mixtures of the bio­
polymers with the poloxamer were prepared at a ratio of 60:20:20,
corresponding to starch:chitosan:pluronic F127. For the preparation of
filmogenic solutions, first the corn starch solution was kept under stir­
ring gradually increasing the temperature when it reached 50 ◦ C the
chitosan and pluronic F127 solutions were added under constant stirring
until reaching 85 ◦ C and it was kept at that temperature for 5 min to
obtain adequate gelatinization of the starch. Subsequently, the air
bubbles present in the filmogenic solution were removed with the help
of a vacuum pump. 50 mL of the filmogenic solution was poured into 15
× 15 cm acrylic molds. They were dried in a convection oven (Duo-Vac
Oven, Lab-Line Instruments, Inc.) at 60 ◦ C for 4 h. Finally, the films were
removed from the mold and cut to the corresponding measurements for
each characterization analysis.
2.3. Physicochemical characterization of the films
2.3.1. Scanning electron microscopy (SEM)
To know the surface morphology, the scanning electron microscopy
(SEM) technique was used using a JEOL model JCM-6000 Neoscope
using a voltage of 10 kV. The samples were placed on electrically
conductive double-sided carbon tape, which was previously attached to
aluminum stubs. The samples were coated with a thin layer of gold using
a Denton Vacuum model DESK II sputter.
2.3.2. X-ray diffraction (XRD) analysis
The atomic arrangement of films was done by X-ray diffraction using
a Siemens D500 powder diffractometer with a voltage of 35 kV and a
current of 25 mA with Cu Kα = 1.5406 Å. The diffractograms were
obtained in the range of Bragg angle (2θ) of 5◦ and 35◦ with the
configuration of powder diffraction in Bragg–Brentano geometry.
2.3.3. Differential scanning calorimetry (DSC)
Thermal properties were determined on a DSC 2 STAR System
thermogravimetric analyzer, Mettler Toledo. The samples were placed
in aluminum crucibles in a temperature range between 25 ◦ C to 300 ◦ C
under a nitrogen atmosphere (50 cm3 min− 1), following the standard
ASTM D3418-15 (ASTM, 2015).
2.3.4. Thickness
The film thickness was measured with a high accuracy digital
micrometer (Mitutoyo, model C112EXB, USA, precision 0.001 mm). Ten
measurements were made randomly over the entire surface of the film.
2.3.5. Water solubility
Samples of 15 × 15 mm film were dried at room temperature (~25
◦
C) for 14 days on silica gel, to extract the higher amount of moisture,
and then weighed. The samples were individually placed in 30 mL glass
jars with lids and 20 mL of distilled water were added. The vials were
closed and kept under constant stirring for 20 h at room temperature.
The contents of the tube were filtered on dry filter paper and dried at
110 ◦ C for 20 h, to determine the weight of the final dry matter. The
percentage of the solubilized matter was calculated with Eq. 1. At least 3
replications were made.
initial dry weight − final dry weight
Water solubility (%) = ∗ 100 (1)
initial dry weight
2.3.6. Mechanical properties
The films were conditioned prior to characterization of mechanical
properties and water vapor permeability for 48 h at room temperature
(~25 ◦ C) and at a relative humidity (RH) of 58 %, which was generated
by a supersaturated saline solution of NaBr. Mechanical performance
A. Fonseca-García et al.
was obtained using a TA.XT Express Enhanced texture analyzer (Stable
Micro Systems, England), with an A/TG tension clamping system at
room temperature (~25 ◦ C), operating at a speed of 1 mm.s− 1, with an
initial separation of 25 mm, according to standard D882-12 (ASTM,
2012). The tensile strength (TS) and the percentage of elongation at
break (%E) of rectangular samples of 10 × 50 mm conditioned at 58 %
RH for 48 h were calculated. Ten replicates were made and the values of
the samples that were fractured at the center of the film were taken,
from which the average and standard deviation were obtained.
2.3.7. Water vapor permeability (WVP)
The water vapor permeability (WVP) was determined according to
the methodology proposed by Aguirre-Loredo, Rodríguez-Hernández,
Morales-Sánchez, Gómez-Aldapa, and Velazquez, (2016) and following
ASTM E96-00 standard (ASTM, 2002). The permeability cell consisted of
a glass container with an internal diameter of 41.1 mm, distilled water
(~100 % RH) was placed inside, the cell with the sample was placed in a
permeability chamber with the controlled temperature at 30 ◦ C, in the
presence of silica gel (~0% RH), generating a differential pressure of
4244.73 Pa. The change in cell weight was recorded every 60 s for 6 h.
The determinations were made in triplicate and the average and stan­
dard deviation were calculated.
2.4. Statistical analysis
The OriginPro 8.5.0 SR1 software (OriginLab Corporation, North­
ampton, Massachusetts, USA) was used to analyze the experimental
results by analysis of variance (ANOVA) and Tukey’s test with a p < 0.05
significance level.
3. Results and discussions
3.1. SEM
The surface morphology of the biodegradable films obtained in this
study is presented in Fig. 1. The films made from the polymers alone,
both, corn starch and chitosan, presented a smooth and homogeneous
appearance without the presence of pores or superficial cracks. While
Fig. 1. Micrographs of the surface (500x) of biodegradable films made from corn starch (a), chitosan (b), and from starch-chitosan-pluronic F127 mixtures in
concentrations of 0, 1, 3 and 5% (c, d, e, and f).
3
Carbohydrate Polymers 251 (2021) 117009
the film made from the mixture of both polymers without the presence of
pluronic F127 (F127 0 %), presented a surface with circular shapes over
the entire sample, an effect that decreased as the content of polyester
pluronic F127 increased from 1 to 5% in the formulation of materials,
giving rise to more homogeneous surfaces.
3.2. XRD analysis
X-ray diffraction analysis (XRD) was performed to study the struc­
tural organization (amorphous and crystalline) of films composed of
starch, chitosan, and pluronic F127 due to has been reported that by
solvent casting method these polymers can be affected in their structural
organization. The level of crystallinity is important when storing ma­
terials or products prepared with starch since during storage there is a
retrogradation of the starch, which has been reported to significantly
modify the absorption of water and the barrier properties and me­
chanical behavior of the materials. Corn starches with higher crystal­
linity can retrograde more quickly (Yuan, Thompson, & Boyer, 1993).
The X-ray diffraction patterns of the materials studied in this investi­
gation are shown in Fig. 2a, where the corn starch-based films only
showed X-ray diffraction patterns typical of type A starches, this pattern
is mainly associated with starches obtained from cereals, such as corn,
presenting peaks at 20.4◦ and 22◦ at 2θ. In this compact type of crys­
talline package of the double helices, there is a low content of water
molecules and they form a single cell of the monoclinic type (Casarru­
bias-Castillo, Méndez-Montealvo, Rodríguez-Ambriz, Sánchez-Rivera, &
Bello-Pérez, 2012). The chitosan film presented two characteristic
peaks, at 9.4◦ and 20◦ at 2θ, corresponding to crystalline forms I and II,
respectively (Leceta, Guerrero, Ibarburu, Dueñas, & de la Caba, 2013;
Mishra & Kannan, 2014). While the pluronic F127 powder presented
peaks at 12.9◦ , 18.3◦ , 22.6◦ , and 27.7◦ at 2θ characteristics of pluronic
F127 (R. Zhang et al., 2004).
The diffraction patterns of the films of mixtures of starch and chi­
tosan with different concentrations of pluronic F127 (0, 1, 3, and 5 %)
are shown in Fig. 2b. In the diffractograms, it is observed that all the
materials formed by the mixture of the polymers with the polyester
showed similar X-ray diffraction patterns. However, for the material
with 1% of pluronic F127 peaks are shown at 19.83◦ and 22.27◦ at 2θ,
A. Fonseca-García et al.
Fig. 2. Diffractograms of a) pure starch film, pure chitosan films, starch-chitosan mixture film, and pluronic F127 powder; b) composite films of starch-chitosan
mixtures with different concentrations of pluronic F127 (0, 1, 3 and 5%).
these peaks being similar to those observed in the film with 0% of
pluronic F127. The characteristic peaks of corn starch are observed at
20.4◦ and 22◦ at 2θ, while for the material with 3 % of pluronic F127 a
transition between the pattern of pluronic F127 powder and that of
pluronic F127 0% is shown because peaks are shown at 19.4◦ , 20◦ ,
22.23◦ and 23.35◦ to 2θ, of which peaks at 20◦ and 22.23◦ are identified
as typical peaks of cereal starches. The peaks presented at 19.4◦ and
23.35◦ correspond to the diffraction of the pluronic F127, it was
observed that these peaks are run at higher angles, which indicates that
the poloxamer is contracted by being retained in the polymeric matrix of
the starch-chitosan film. Finally, the material with 5 % pluronic F127
shows in its diffractogram peaks at 19.4◦ , 22.03◦ , 23.47◦ , 26.46◦ to 2θ, is
similarly associated with the peaks found in starch and in pluronic F127.
However, in this material, the peaks related to the poloxamer are also
found at higher angles, and in addition, they are more intense than in the
material with 3% poloxamer, this is not surprising because the con­
centration of the pluronic F127 is higher.
3.3. FT-IR
The infrared spectroscopy analysis of the films obtained from the
mixture of the corn starch, chitosan, and pluronic F127 polymers
allowed to identify electrostatic interactions such as hydrogen bonds
Fig. 3. FT-IR spectra of (a) corn starch film, chitosan film, pluronic F127, and mix of starch-chitosan with pluronic F127 at 0%, (b) mixtures of starch-chitosan films
with different concentrations of pluronic F127 (0, 1, 3, and 5%).
4
Carbohydrate Polymers 251 (2021) 117009
among, the starch, chitosan, and pluronic F127. The Fig. 3 shows the
characteristic absorption bands of the polymers used in the formulation
of the films and Table 1 are shown the specific vibrations modes cor­
responding to every film. The characteristic starch groups are observed
at 3450− 3100 cm− 1 (assigned to the stretch of − OH bonds), the C–H
groups of − CH2– in the C6 of the glucose unit of the starch at 2925 cm− 1
and 1450 cm− 1. Meanwhile, the absorption band around 1650 cm− 1
belongs to the flexing vibration of H2O which is attributed to the ab­
sorption of water by hydroxyl groups present in both starch and chitosan
(Caicedo et al., 2019; Maréchal, 2007). Characteristic chitosan bands
were observed at 1650 cm− 1 corresponding to the amide I group (C– –O
stretch, NH– flexion in -NH2 mode), 1560 cm− 1 (amide II, NH), 1410
cm− 1 (assigned to flexion of the carboxyl C–H group) and 1375 cm− 1
(corresponding to the amide III bond), most of which remained visible in
the composite films of the mixture of the three polymers used (Hosseini,
Rezaei, Zandi, & Ghavi, 2013; Leceta et al., 2013; Huihua Liu, Adhikari,
Guo, & Adhikari, 2013). While the typical peaks of the pluronic F127 are
3665− 3320 cm− 1 (assigned to the stretch of − OH bonds), 2985 cm− 1
and 2898 cm− 1 (assigned to the stretch of C–H bonds); 1470 cm− 1, 1350
cm− 1 and 971 cm− 1 (assigned to C–H bond bending); 1275 cm− 1 and
1249 cm− 1 (assigned to stretch C–OC bonds), 1119 cm− –1 (assigned to
stretch C–O bonds) and 846 cm− 1 (assigned to stretch C–C bonds)
(Shaker, Elbadawy, & Shaker, 2020).
A. Fonseca-García et al. Carbohydrate Polymers 251 (2021) 117009

Table 1
Specific vibrations modes corresponding to the films by FT-IR.
1
Film Band centered at cm−

Corn starch 3308 2928 1635 1149 1077 1016 998 849 748 570
Chitosan (CTS) 3308 2881 1635
F127 (powder) 2881 1343 849
Starch-CTS-F127 0% 3308 2928 1635 1149 1077 1016 998 849 748 570
Starch-CTS-F127 1% 3308 2928 1635 1343 1149 1077 1016 998 849 748 570
Starch-CTS-F127 2% 3308 2928 2881 1635 1343 1149 1077 1016 998 849 570
Starch-CTS-F127 5% 3308 2928 2881 1635 1343 1149 1077 1016 998 849 570
Assignment OH C–H CH OH CH C–O C–O–H OH CH C–C C–O C–O–C

3.4. DSC
Table 2
Thermodynamic results obtained from the thermograms of the films, such as the
The thermal behavior of biodegradable films was analyzed by DSC,
glass transition temperature, melting temperature, and enthalpies obtained.
in Fig. 4 are shown the DCS thermograms. The results indicate that is
produced an important thermodynamic interaction due to the increase Film Tg (◦ C) Tm (◦ C) Hm (J/g)

of pluronic F127 in biodegradable films. In case of films with stach- Corn starch 56 142 6
chitosan-F127 0% and starch-chitosan-F127 1% the thermal behavior Chitosan (CTS) § 105 28
Pluronic F127 powder 56 − 21.8
was similar, according to their values of the glass transition temperature,
§
Starch-CTS-F127 0% 55 139 6.4
melting point temperature and enthalpy were similar, this phenomenon Starch-CTS-F127 1% 44 138 8.4
is related to the low concentration of pluronic F127, and the films had a Starch-CTS-F127 3% § 52 1.5
behavior similar to pure starch. However, in case of films with starch- Starch-CTS-F127 5% § 48 3.3
chitosan-F127 3% and starch-chitosan-F127 5%, the pluronic F127 §
The polymer did not show the glass transition temperature.
showed an important thermodynamic interaction with starch and chi­
tosan. The melting temperature in both films was close but, lower than
this study was between 31 and 97 μm (Table 3), values corresponding to
the pure pluronic F127, these results suggest how the pluronic govern­
the films of the pure polymers chitosan and corn starch, respectively. It
ments the thermal behavior in both films. Another condition to consider
was observed that when increasing the content of pluronic F127 in the
is the fact that in both films the melting temperature was lower
preparation of filmogenic solutions from 0 to 3%, the thickness of the
comparing with pure pluronic F127, being the lowest melting temper­
resulting film increased significantly, while when adding 5%, a reduc­
ature to the film with 5% of pluronic, these results suggest how in both
tion in thickness was observed when compared to the film containing
films there was nucleation of pluronic inside the matrix of films. Table 2
3% pluronic.
shows the results of the glass transition temperature, melting tempera­
ture and enthalpies obtained in the thermograms of the films.
3.6. Solubility

3.5. Thickness and appearance
Homogeneous, thin, flexible, and opaque (non-translucent) corn
starch films were obtained, while those of pure chitosan had a yellowish
and translucent appearance (Fig. 5). All films were easily removed from
the pour mold. The biodegradable films of corn starch and chitosan with
different concentrations of pluronic F127 (0, 1, 3, and 5%) presented a
homogeneous appearance and appearance similar to those obtained
with pure starch. The thickness of the biodegradable films obtained in
Water-resistance is an important property of biodegradable films for
applications as a food packaging material where water activity is high,
or when the film will be in contact with water during the storage of
foods, such as avoiding exudation of fresh or processed products. Higher
values of solubility in water at room temperature were observed in the
films made from the polymers alone, with a solubility of 21 and 76 % for
the starch and chitosan, respectively, while mixing both polymers
without the incorporation of the pluronic (F127 0%), the resulting film
had a solubility of 42 % (Table 3), which is an intermediate value

Fig. 4. Thermograms of (a) the pure polymers as corn starch film, chitosan film, pluronic F127, and mix of starch-chitosan with pluronic F127 at 0%, (b) mixtures of
starch-chitosan films with different concentrations of pluronic F127 (0, 1, 3, and 5%).

5
A. Fonseca-García et al. Carbohydrate Polymers 251 (2021) 117009

Fig. 5. Biodegradable films based on corn starch, chitosan, and starch-chitosan mixtures with different concentrations of pluronic F127 (0 and 3%).

3.7. WVP
Table 3
Thickness, solubility, WVP, tensile strength, and percentage of elongation at
Water vapor permeability (WVP) is an important parameter because
break of corn starch films, chitosan, and of starch-chitosan mixtures with
different concentrations of pluronic F127 (0, 1, 3 and 5%). most biopolymers are prone to plasticize with water, which can modify
the characteristics of the polymer matrix. The water vapor permeability
Film Thickness Water WVP (g Tensile Elongation
of the films based on the polymers alone was 32 and 7 × 10− 11 g. m-1s-1
(μm) solubility m− 1s− 1 strength at break (%)
(%S) Pa− 1) (MPa) Pa-1 for those of starch and chitosan, respectively (Table 3), while for the
films made from the mixture of both polymers (F127 0%), the WVP
Starch 97.21 ± 21.40 ± 32.38 ± 5.31 ± 121.95 ±
8.04e 3.43d 4.00 × 0.26a 10.20d
presented an intermediate value of 21 × 10− 11 g m-1 s-1 Pa-1. The
10− 11 f incorporation of the polyester pluronic F127 in concentrations from 1%,
Chitosan 31.21 ± 75.93 ± 7.02 ± 38.10 ± 29.65 ± significantly improved the barrier capacity of the films made in this
3.77a 4.59f 0.74 × 3.53c 5.67a investigation, with values of the order of magnitude of 10-14 g m-1 s-1 Pa-
10− 11 d 1
, decreasing the amount of water vapor that passes through the mate­
F127 0% 44.68 ± 42.58 ± 21.33 ± 4.24 ± 149.05 ±
2.84b 1.37e 2.22 × 0.61a 11.68e rial. The amount of water vapor permeating through the material was
10− 11 e reduced with the increase in the concentration of pluronic F127. Ac­
F127 1% 51.01 ± 7.81 ± 6.66 ± 6.49 ± 53.30 ± cording to the WVP results observed in the films made with pluronic
4.40c 1.40bc 0.07 × 0.55ab 5.51b
F127, it was observed that, with the addition of this polyester in low
10− 14 bc
F127 3% 77.55 ± 4.02 ± 3.47 ± 4.96 ± 95.20 ±
concentrations, its capacity as a barrier to water vapor is significantly
6.54d 1.27ab 0.13 × 0.67a 7.70c improved, turning this material into a good alternative for food pres­
10− 14 ab ervation that needs to maintain a good moisture barrier. The water
F127 5% 71.30 ± 3.34 ± 2.76 ± 3.68 ± 84.96 ± vapor permeability of the films obtained in the present study was
6.64d 0.70a 0.06 × 0.25a 5.43c
significantly lower than that obtained for composite materials based on
10− 14 a
biopolymers and fatty agents such as potato starch-lauric acid (Wang,
Values with different letter in a same column denote significant difference Liu, Cui, Kang, & Yu, 2019), starch-chitosan-peanut extracts (Meng
(Tukey test; p < 0.05). et al., 2020).
Values are given as mean ± standard deviation (n = 10 for thickness and n = 3
for solubility and WVP).
3.8. Mechanical properties
between those obtained for pure films. With the incorporation of plur­
onic F127 into the formulation of the starch-chitosan films, a significant The behavior of the mechanical properties of the tensile strength (TS)
decrease in the water solubility of the films was observed, which was and percentage of elongation at break (%E) of corn starch films, chito­
reduced to the solubility of only 3% when the concentration of pluronic san, and their mixtures with the incorporation of pluronic F127 in
F127 increased to 5%. In this study, 25 % glycerol was added (depending concentrations of 1, 3 and 5% are presented in Table 3. The TS of the
on the total weight of polymers), which evidenced the importance of the chitosan film was only 38 MPa, much higher than that presented by the
glycerol content in the solubility of the material, which was lower in corn starch sample, which was 5 MPa. The films made from the starch,
starch films only compared to the results obtained in a previous inves­ chitosan, and pluronic F127 mixtures showed a tensile behavior similar
tigation, wherewith the addition of 30 % glycerol, a material with a to that of the pure starch film (Table 3). While the performance of the %
water solubility of up to 32 % was obtained (Rocio Yaneli Aguirre-­ E of the film composed of the mixture of starch-chitosan (F127 0%) was
Loredo et al., 2018). Due to their hydrophilic nature, plasticizers improved by the combination of both polymers, with an elongation of
(particularly polyols such as glycerol) play an essential role in weak­ 149 %, higher than that of the films obtained with the pure polymers.
ening the interactions between the molecular chains of the polymers, While the addition of pluronic F127 decreases the %E of the films
increasing the free volume between the chains (Sanyang, Sapuan, compared to the film it does not have, however, by increasing its con­
Jawaid, Ishak, & Sahari, 2016). This promotes the diffusion of water centration from 1 to 5%, it significantly increases the elongation of these
molecules into the film matrix and, consequently, increases their solu­ materials. The mechanical behavior of starch-based materials is very
bility. The solubility of composite films was much lower than that ob­ poor (Gómez-Aldapa, Velazquez, Gutierrez, Castro-Rosas et al., 2020),
tained by various authors in biodegradable starch-chitosan films (Meng so it is sought to improve it by mixing it with other polymers such as
et al., 2020), konjac glucomannan-mung bean starch (Fang et al., 2020), chitosan (Hasan et al., 2020; Meng et al., 2020) or fatty acids such as
and starch-cellulose-rye flour (Beigmohammadi, Barzoki, & Shabanian, lauric (Wang et al., 2019) however, the mechanical behavior obtained in
2020). those researches is less than that found in the present study. However,
these mechanical properties could still be improved with the addition of
the biodegradable synthetic polymer, PVOH, in ratios higher than 10 %,
according to a previous study carried out by our working group on

6
A. Fonseca-García et al.
starch-PVOH mixtures (Gómez-Aldapa, Velazquez,
Rangel-Vargas et al., 2020).
4. Conclusions
The preparation of a new biodegradable packaging film based on
starch, chitosan, and the poloxamer pluronic F127 was possible. The
physicochemical properties such as the water vapor barrier and resis­
tance to liquid water, the morphological, thermal, and mechanical
properties were studied. The surfaces of the corn starch-chitosan com­
posite films obtained were more homogeneous with the increase in the
content of pluronic F127. The water solubility (%S) and the water vapor
barrier capacity (WVP), as well as the mechanical behavior of the films,
were improved with the incorporation of the poloxamer at concentra­
tions from 3%. Based on the behavior and characteristics of these ma­
terials, it was concluded that the most relevant formulation was starch-
chitosan-F127 3%, being the most suitable composite material for
application as biodegradable packaging for the food or medical areas.
Funding
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Declaration of Competing interest
The authors declare no conflict of interest.
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time due to technical or time limitations.
CRediT authorship contribution statement
Abril Fonseca-García: Methodology, Investigation, Formal analysis,
Writing - original draft. Enrique Javier Jiménez-Regalado: Supervi­
sion, Visualization, Writing - original draft. Rocio Yaneli Aguirre-
Loredo: Project administration, Conceptualization, Methodology,
Investigation, Formal analysis, Supervision, Visualization, Writing - re­
view & editing.
Acknowledgments
The authors are grateful to CIQA for the support with the research
project 6521. Thanks to M.C. Maria Guadalupe Mendez-Padilla, M.C.
Blanca Huerta Martinez and LNMG-CIQA for DSC, DRX and SEM char­
acterizations, respectively. The doctors Fonseca-García and Aguirre-
Loredo thanks CONACYT for his nomination as a researcher’s fellow
assigned to CIQA.
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