Carbohydrate Polymers 215 (2019) 377–387

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

Potato starch-based biocomposites with enhanced thermal, mechanical and T

barrier properties comprising water-resistant electrospun poly (vinyl
alcohol) fibers and yerba mate extract
⁎ ⁎
Alex López-Córdobaa, , Santiago Estevez-Arecob, Silvia Goyanesb,
a
Universidad Pedagógica y Tecnológica de Colombia, Facultad Seccional Duitama, Escuela de Administración de Empresas Agropecuarias, Carrera18 con Calle 22
Duitama, Boyacá, Colombia
b
Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Departamento de Física, Laboratorio de Polímeros y Materiales Compuestos (LP&MC), Instituto
de Física de Buenos Aires (IFIBA-CONICET), Buenos Aires, Argentina

A R T I C LE I N FO A B S T R A C T

Keywords: Water-resistant electrospun poly(vinyl alcohol) (PVA) mats and a yerba mate extract (YM) were incorporated
Composites together within potato starch (PS) matrices to prepare biocomposites (PS-YM/PVA/PS-YM). The thermal, me-
Starch chanical and barrier properties of the PS-YM/PVA/PS-YM systems were compared with biocomposites without
Poly (vinyl alcohol) YM (PS/PVA/PS) and, with potato starch films without (PS) and with (PS-YM) the YM extract. Scanning electron
Electrospinning
microscopy analysis showed that the electrospun mats were fully incorporated into the biocomposites and that
Fibers
the PS/PVA interlayer adhesion was only slightly affected by the addition of the extract. Infrared spectra analysis
confirmed that this behavior was due to the lower amount of hydroxyl groups available in the biocomposites. As
compared with the other systems, the PS-YM/PVA/PS-YM biocomposites exhibited better light- and water vapor
barrier properties. Moreover, the presence of the electrospun PVA core layer and the YM extract caused an
increase of around 60% in the elastic modulus of these materials.

1. Introduction Bioplastics industry is a fast-growing and attractive trend worldwide

Achieving sustainable patterns of consumption and production is an
important issue within the global suitable development goals (PNUD,
2012). In this context, bioplastics are a promising option for reducing
plastic waste and energy use (European Bioplastics, 2017).
Plastics are very versatile materials which are widely used in nu-
merous applications including packaging, agriculture, building and
construction, and energy. In 2016, world production of plastic materials
was around 335 million tons, being the polyolefins (e.g., polyethylene
and polypropylene) the most demanded plastic materials (Plastics
Europe, 2017). Packaging sector is one of the most important markets
for the plastic industry, being the food and beverage industry one of the
largest consumers of packaging products (Plastics Europe, 2017). Cur-
rently, more than 95% of the world’s plastic is derived from fossil
feedstocks. This fact has been associated with critical environmental
concerns (Plastics Europe, 2018). Therefore, several initiatives are
carried out to reduce the dependency on limited fossil resources and
reduces greenhouse gas emissions.
aimed toward the sustainable production and use of renewable re-
source-based plastics (European Bioplastics, 2017). Currently, the bio-
plastic market represents about one percent of the amount of plastic
produced annually (European Bioplastics, 2017). Starch blends, poly-
lactic acid, and polyhydroxyalkanoate are some of the most widely used
polymers for the industrial production of bio-based and biodegradable
plastics (Odegard, Nusselder, Roos Lindgreen, Bergsma, & de Graaff,
2017).
Thermoplastic starch (TPS) is a very appealing bio-based material
because starch is cheap, edible, abundant and processable with
common industrial equipment like extruder (González-Seligra, Guz,
Ochoa-Yepes, Goyanes, & Famá, 2017). Furthermore, TPS fulfill the
requirements for biodegradability in soil (Medina Jaramillo, Gutiérrez,
Goyanes, Bernal, & Famá, 2016; Piñeros-Hernandez, Medina-Jaramillo,
López-Córdoba, & Goyanes, 2017). However, TPS has limited uses due
to its low thermal, mechanical and barrier properties (Ribba, Garcia,
D’Accorso, & Goyanes, 2017).
Several starch botanical sources have been used for the production

⁎
Corresponding authors.
E-mail addresses: alexlcordoba@gmail.com, alex.lopez01@uptc.edu.co (A. López-Córdoba), sestevezareco@df.uba.ar (S. Estevez-Areco),
goyanes@df.uba.ar (S. Goyanes).

https://doi.org/10.1016/j.carbpol.2019.03.105
Received 30 November 2018; Received in revised form 25 March 2019; Accepted 30 March 2019
Available online 01 April 2019
0144-8617/ © 2019 Elsevier Ltd. All rights reserved.
A. López-Córdoba, et al.
of TPS including cassava, potato, corn, wheat, rice and yam (García,
Famá, Dufresne, Aranguren, & Goyanes, 2009; Chang-Bravo, López-
Córdoba, & Martino, 2014; Moreno, Atarés, & Chiralt, 2015; Piñeros-
Hernandez et al., 2017). The physicochemical properties of TPS have
been found very dependent on the starch origin, the plasticizer type and
the fabrication method and conditions, among others (Talja, Helén,
Roos, & Jouppila, 2007). Basiak, Lenart, & Debeaufort, 2017 studied the
effect of starch type (wheat (25% amylose), corn (27% amylose) or
potato (20% amylose)) on the physicochemical properties of edible
films. The films made from potato starch showed a more significant
barrier for oxygen and water vapor though they were weaker me-
chanical properties than wheat and corn starch films.
Different approaches have been proposed in order to improve the
properties of TPS, including the blending of starch with other polymers
(e.g. PVA, chitosan, poly(ε-caprolactone), polylactic acid, carrageenan
and guar gum) (Chang-Bravo et al., 2014; González Seligra, Eloy
Moura, Famá, Druzian, & Goyanes, 2016; Nuona, Li, Zhu, Xiao, & Che,
2015; Saberi et al., 2017), the incorporation of micro- or nanofillers
(López-Córdoba, Medina-Jaramillo, Piñeros-Hernandez, & Goyanes,
2017; Ortega, Giannuzzi, Arce, & García, 2017; Teodoro, Mali, Romero,
& de Carvalho, 2015; Valdés & Garrigós, 2017) and the addition of
hydrophobic components (Garcia, Martino, & Zaritzky, 2000). Also,
TPS-based active films have been obtained through the incorporation of
antioxidants, antimicrobial agents, oxygen scavengers, moisture ab-
sorbing, among others (López-Córdoba, 2018; Medina-Jaramillo,
Ochoa-Yepes, Bernal, & Famá, 2017; Valdés & Garrigós, 2017). For
instance, the addition of natural extracts into TPS films have proved to
be a useful strategy to the production of antioxidant films with en-
hanced physicochemical properties (Chang-Bravo et al., 2014; López-
Córdoba, Duca, Cimadoro, & Goyanes, 2017; Medina Jaramillo,
González Seligra, Goyanes, Bernal, & Famá, 2015; Medina-Jaramillo
et al., 2017; Piñeros-Hernandez et al., 2017). Moreover, phenolic
compounds from natural extracts are available to act as an excellent UV
barrier rendering active films which can be used to package light-sen-
sitive products such as fatty foods (Balasubramanian, Kim, & Lee, 2018;
Piñeros-Hernandez et al., 2017; Stoll, Rech, Flôres, Nachtigall, & de
Oliveira Rios, 2018).
Yerba mate (Ilex paraguariensis) tea is a traditional South American
beverage which is gaining rapid introduction into the world market,
either as tea itself or an ingredient in formulated foods or dietary
supplements (Heck & De Mejia, 2007). The polyphenols are abundant
compounds in yerba mate extract and some of its pharmacological
properties (antioxidant activities, and hepatoprotective, choleretic,
diuretic, hypocholesterolemic, antirheumatic, antithrombotic, anti-in-
flammatory, antiobesity or antiageing properties) have been related
mainly to the high content of chlorogenic acid and its derivatives
(Bracesco, Sanchez, Contreras, Menini, & Gugliucci, 2011; López-
Córdoba, Deladino, & Martino, 2014). The research literature provides
examples of yerba mate extracts used as ingredients to prevent dete-
rioration of meats and meat products and as a natural source of caffeine
in energy drinks (López Córdoba, Deladino, & Martino, 2013; López-
Córdoba, Deladino, Martino et al., 2014). In packaging applications, the
yerba mate extract has proved to be a good TPS plasticizer, a biode-
gradability enhancer and a robust antioxidant additive (Chang-Bravo
et al., 2014; Medina Jaramillo et al., 2015, 2016, 2017).
Electrospinning is a process employed for the fabrication of mats of
continuous micro- or nano-fibers by an electrostatically driven jet of
polymer solution (or polymer melt) (López-Córdoba, Lagarón, &
Goyanes, 2018; López-Córdoba, Duca et al., 2017). This electro-
hydrodynamic technology has gained high impact on polymer proces-
sing, mainly because it allows the control of fiber morphology, dia-
meter, and even porosity. Electrospun nanofibers have found numerous
applications mainly in the biomedical field (e.g., wound dressing or
tissue substitutes) and in drug delivery. In the food industry, electro-
spinning has been mainly used for the encapsulation of bioactive
compounds such as antioxidants, probiotic bacteria, polyunsaturated
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Carbohydrate Polymers 215 (2019) 377–387
fatty acids, among others (López-Córdoba et al., 2018; López-Córdoba,
Duca et al., 2017). However, the use of electrospinning for food
packaging applications is a start point.
Electrospun mats have a considerable potential in the design of
innovative food packaging’s because they can be used for instance as an
active coating or core layer, hydrophobic or superhydrophobic coatings
or as a compatibilizer within multilayered systems (Cherpinski, Torres-
Giner, Cabedo, Méndez Jose, & Lagaron, 2017; Cherpinski, Gozutok,
Sasmazel, Torres-Giner, & Lagaron, 2018; López-Córdoba, Duca et al.,
2017; Pardo-Figuerez, López-Córdoba, Torres-Giner, & Lagaron, 2018).
Poly(vinyl alcohol) (PVA) is considered a promising polymer for the
fabrication of biodegradable materials for several industrial applica-
tions through electrospinning. This polymer has the advantage of being
abundant, water-soluble and non-toxic (DeMerlis & Schoneker, 2003;
Kadajji & Betageri, 2011). However, PVA is very sensitive to moisture
and, therefore, are not an effective barrier against water vapor (Nyflött
et al., 2017). Cross-linking is one of the routes commonly used to ensure
prolonged structural integrity and to enhance its performance (López-
Córdoba, Castro, & Goyanes, 2016; Peresin et al., 2014; Stone, Gosavi,
Athauda, & Ozer, 2013).
In the current work, an innovate approach for the fabrication of
potato starch- based biocomposites with enhanced physicochemical
properties is presented. Water-resistant electrospun poly(vinyl alcohol)
fibers were obtained through a heat-induced in situ cross-linkage with
citric acid, and they and a yerba mate extract were incorporated to-
gether within potato starch films to produce biocomposites. The new
materials were characterized in terms of their morphology, thermal
stability, barrier, and tensile properties. The results suggested that the
current approach constitute a useful way for the fabrication of starch-
based materials for potential use as active food packaging. As far as the
authors are aware, there are no works carried out on the fabrication of
starch-based biocomposites comprising electrospun PVA mats as core
layer and yerba mate extract as an additive.
2. Materials and methods
2.1. Materials
Fully hydrolyzed poly(vinyl alcohol) (PVA) ELVANOL® T25 was
supplied by Diatex (Buenos Aires, Argentina). The molecular weight
(Mw) of ELVANOL® T25 is between 50,000 and 55,000 Da, as informed
by the manufacturer (E. I. DuPont Co., USA). Citric acid (CA) was
supplied by Sigma-Aldrich (USA). Potato starch was isolated from fresh
potato tubers variety Diacol Capiro (Boyacá, Colombia) according to
Doporto, Dini, Mugridge, Viña, & García, 2012. Amylose content of
starch determined by the iodine binding method was 18.55 ± 1.3%
(w/w of solids) (McCready & Hassid, 1943). The granule size of starch
was measured using a Laser Diffraction Particle Size Analyzer SALD-
3101 (Shimadzu, Japan) as reported López-Córdoba, Duca et al., 2017.
The average size of potato starch granules was 17.9 ± 0.7 μm.
Analytical grade glycerol (Aldrich, USA) was used as a plasticizer.
Yerba mate (Ilex paraguariensis) extract was prepared as reported in
previous work (López Córdoba et al., 2013). Briefly, 3 g of commercial
yerba mate (Rosamonte®, Misiones, Argentina) with 100 mL of distilled
water were placed in a thermostatic bath (Viking, Argentina) at 100 °C
for 40 min. Once obtained, the extracts were filtered, cooled and kept in
the dark flasks until used.
2.2. Preparation of PVA fibers by electrospinning
Electrospun PVA fibers were fabricated as reported in previous work
(López-Córdoba et al., 2016). The electrospinning solutions were fab-
ricated mixing 12.0 g of PVA with 100 mL of distilled water, under
heating at 75 °C until complete dissolution. Then, citric acid was added
to the PVA solution (5.0 g/100 g of PVA). After total dissolution, the
blends were sonicated for 5 min to remove bubbles. The electrospinning
A. López-Córdoba, et al.
Fig. 1. Schematic representation of the process of fabrication of starch-based biocomposites.
process was carried out using a horizontal setup. The solutions con-
tained in 10-mL syringes were pushed employing a syringe pump
(Apema PC11U, Argentina) with controlled feed rate (2 mL.h−1)
through a 21 G needle (0.8 mm). An electrical voltage of 30 kV was
applied to the needle using a high-voltage supply unit (50 kV, 20 mA).
The polymer ejected from the needle tip was collected on a rotating
drum of 6-cm diameter covered by aluminum foil, located at 20 cm
from the tip. The collector was connected to the negative electrode of
the power supply (ground), while the spinneret filled with the polymer
solution was connected to the positive terminal. These electrospinning
conditions and solution characteristics were found adequate for the
optimal electrospinning of PVA in previous work (López-Córdoba et al.,
2016). In order to obtain water-resistant PVA electrospun mats, they
were heat-treated at 190 °C for 3 min (López-Córdoba et al., 2016). Neat
PVA mats without citric acid nor heat-treated were also prepared under
similar conditions for comparison.
2.3. Preparation of starch-based biocomposites
The preparation process of the starch-based biocomposites is sche-
matized in Fig. 1.
Potato starch (PS) filmogenic solutions were produced as reported
in previous works (López-Córdoba, Duca et al., 2017; Piñeros-
Hernandez et al., 2017). Briefly, blends containing potato starch (2 g),
glycerol (0.6 g) and distilled water (97.4 g) were prepared. For the
preparation of the yerba mate extract-containing filmogenic solutions
(PS-YM), a water mass (20 g) from the formulations was replaced with
the same amount of aqueous yerba mate extract. Each blend was
homogenized for 40 min and then heated until 96 °C (heating rate
3 °C min−1), under constant stirring. The formulations (PS and PS-YM)
were degassed for 7 min with a mechanical vacuum pump, dispensed
into polypropylene plates and a water-insoluble electrospun PVA mat
was placed flatly in each one. The systems were dried at 50 °C for 24 h
and removed from the mold. PS and PS-YM films without electrospun
PVA mat were also prepared for comparison. All films were conditioned
at room temperature into desiccators containing a supersaturated so-
lution of sodium bromide (RH 57%) for 48 h, prior to characterization
studies.
The potato starch films without and with yerba mate extract will be
referred as “PS” and “PS-YM”, respectively while the biocomposites
with and without yerba mate extract will be referred as “PS/PVA/PS”
and “PS-YM/PVA/PS-YM”, respectively.
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Carbohydrate Polymers 215 (2019) 377–387
2.4. Moisture content and water solubility
Moisture content (%) was determined gravimetrically according to
AOAC methods in an oven at 105 °C (AOAC, 1998).
The water solubility of the samples was assayed as reported in
previous work (López-Córdoba et al., 2016). Samples were weighed and
submerged into a volume of distilled water (pH = 6.0) at room tem-
perature (22–25 °C) for 24 h. Later, the water was removed, and the
samples were dried at 50 °C until constant weight. The mass loss during
dissolving in water was calculated with the following equation:
W − W1 ⎞
S (%) = ⎛ 0
⎜ × 100
⎟
⎝ W0 ⎠ (1)
where W0 is the initial dry weight of the sample and W1 is the dry
weight after dissolving in water.
2.5. Barrier properties
Water vapor permeability (WVP) tests were carried out at room
temperature following the ASTM E96/ASTM E96M-16 method
(Piñeros-Hernandez et al., 2017). Film samples were sealed over a
circular opening of 4 × 10 −4 m2 in a permeation cell containing cal-
cium chloride. Then, the cells were placed in desiccators conditioned
with a sodium chloride saturated solution (75% RH). Changes in the
weight of the cell were recorded to the nearest 0.0001 g and plotted as a
function of time, and the slope of each line was calculated by linear
regression. WVP (g Pa−1 s−1 m−1) was calculated as follows:
WVTR ⎤
WVP = ⎡ × d
⎣ P × RH ⎦ (2)
where WVTR is the water vapor transmission rate calculated as the ratio
between the slope of the straight line (g/s) and the cell area (m2); P is
the saturation vapor pressure of water (Pa); RH is the relative humidity
in the desiccator, and d is the film thickness (m).
The light transmittance of the materials was measured in the visible
light wavelength range (400–800 nm). The films were cut into rectan-
gular shapes (50 mm × 10 mm) and placed inside the spectro-
photometer cell. The light transmittance (%) was measured using the
UV–Vis spectrometer (Shimadzu UV-1800, Japan).
2.6. Scanning electron microscopy (SEM)
Cross-cuts were obtained by cryo-fracture, immersing the films in
A. López-Córdoba, et al.
liquid nitrogen. The samples were attached to stubs using a two-sided
adhesive tape and sputtered with a thin layer of gold. SEM analysis was
performed using a field emission gun (FE-SEM) (SUPRA 40, Carl Zeiss
NTS, Germany).
2.7. Fourier transform infrared spectroscopy (FTIR)
FTIR analysis was performed in a Jasco FT-IR 4100 spectrometer
(USA) equipped with attenuated total reflectance (ATR) module. The
samples were placed on the ATR accessory and then were analyzed
under transmission mode, taking 64 scans per experiment with a re-
solution of 4 cm−1. Taking into account that the crosslinking reaction
occurs by interaction of PVA hydroxyl groups and carboxylic ones of
citric acid; FTIR data of electrospun PVA mats were normalized with
respect to the CH2 bending signal located around 1426 cm−1, which
was not expected to change after such interactions (López-Córdoba
et al., 2016). In the case of the starch films, IR spectra were normalized
with respect to the CeO stretching signal from glucosidic ring located
around 1140 cm−1. This signal was chosen as the reference peak as-
suming that the total number of ‘C–O’ bonds in ‘C–O–H’ groups re-
mained the same in the samples with and without extract nor PVA
(González-Seligra, Medina Jaramillo, Famá, & Goyanes, 2016; Piñeros-
Hernandez et al., 2017)
2.8. Thermogravimetric analysis (TGA)
Thermogravimetric analysis (TGA) was performed in a SHIMADZU
DTG-60 (Japan). Samples (3.0–5.0 mg) were placed in aluminum pans
inside the thermogravimetric balance and then heated under a dry ni-
trogen atmosphere (20 mL/min) in the range of 30–450 °C at a heating
rate of 10 °C min− 1. TGA data of starch films were normalized at 100 °C
in order to disregard the differences in water loss.
2.9. Mechanical properties
Uniaxial tensile tests were carried out using a Brookfield Texture
Analyzer CT3-100 following the ASTM-D882-20 method. Strain rate
was fixed to 10−3 s-1, and the sample dimensions were 35 × 5 ×
0.1 mm (length, width, and thickness, respectively). Elastic modulus,
tensile strength, and strain at break were obtained from the stress-strain
curves.
2.10. Differential scanning calorimetry and X-ray diffraction
Differential scanning calorimetry (DSC) and X-ray diffraction (XRD)
studies from selected film samples were carried out to provide more
information on the plasticizing effect of yerba mate extract.
DSC assays were performed using a DSC-60 unit (Shimadzu, Japan).
The samples (3–5 mg) were placed in aluminum pans, and a first
scanning was performed from -80 to 160 °C at a rate of 20 °C/ min.
Then, a second scanning was performed re-cooled and re-heated the
sample under the same conditions. Glass transition temperature was
analyzed from the second scanning.
X-ray diffractograms were recorded at 2θ between 10° and 35° with
a step size of 0.026 in a Malvern PANalytical Empyrean diffractometer
(UK) using Cu (K-α) radiation (λ = 1.54056 Å).
2.11. Polyphenol content and antioxidant activity of the yerba mate extract
and the films
Film extract solutions were prepared by mixing 50 mg of films with
10 mL of distilled water. Aliquots of the supernatant were removed
after 24 h. Polyphenols content of yerba mate extract and resulting
films was measured by the Folin-Ciocalteu method. Briefly, 400 μL of
sample (yerba mate extract or film extract solution) was mixed with
2 mL of Folin-Ciocalteu reagent (1:10 diluted) and 1.6 mL of sodium
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Carbohydrate Polymers 215 (2019) 377–387
carbonate (7% w/v). After 30 min, absorbance was measured at 760 nm
using the spectrophotometer. Results were expressed as gallic acid
equivalent per unit of volume for the yerba mate extract (mg GAE/mL)
or gallic acid equivalent per unit of mass for the films (mg GAE/g).
Antioxidant activity of yerba mate extract and the film extract so-
lutions was measured using 1,1-diphenyl-2-picrylhydrazyl (DPPH%) free
radical. A volume of 100 μL of each sample was mixed 3.9 mL of DPPH%
solution (methanol 25 mg/L). Absorbance was measured at 516 nm
after 60 min of dark reaction. The DPPH• scavenging activity of each
sample was expressed as the inhibition percentage calculated with the
following equation:
A − As ⎞
DPPH inhibition (%) = ⎛ b
⎜ × 100
⎟
⎝ Ab ⎠ (3)
where Ab is the absorbance of the blank and A s is the absorbance of the
sample.
2.12. Statistical analysis
The statistical analysis was performed using the Systat Inc. software
(Evanston, USA). The experiments were performed at least in triplicate,
and the data were reported as mean ± standard deviation. Analysis of
variance (ANOVA) and Tukey pairwise comparisons were carried out
using a level of 95% confidence (α = 0.05).
3. Results and discussion
3.1. Water-resistant electrospun PVA mats
PVA electrospun mats showed typical morphology of 3D ultrathin
randomly oriented fibers with a mean diameter around 370 ± 80 nm
(Fig. 2a). After thermal treatment, fibers morphology was well pre-
served despite that coalescence of some fibers was also observed
(Fig. 2b).
Electrospun PVA materials were successfully turned into water-re-
sistant mats by a heat-induced in situ cross-linkage with citric acid.
Untreated PVA mats were almost completely dissolved in water in
short-time (Data not shown). In contrast, the heat-treated PVA mats
were maintained almost completely insoluble after 24 h of soaking in
distilled water (Fig. 2c and d). They showed a solubility percentage of
around 2% maintaining their fibrous structure (Fig. 2d). It has been
reported early that the crosslinking of PVA electrospun mats with or-
ganic acids improve the mats resistance not only in water but also in
low polarity solvents such as DMF, acetonitrile, methanol, and
chloroform. Besides, crosslinked PVA mats exhibit higher thermal sta-
bility (Peresin et al., 2014; Stone et al., 2013).
Concerning the light barrier properties, untreated and heat-treated
PVA electrospun mats show an expected very low visible light trans-
mittance (ca. 0.3%) (Fig. 3). It has been well documented that elec-
trospun nanofibers are loosely packed porous films comprising a large
amount of air/fiber interfaces and therefore the incident light not only
is reflected and refracted many times at these interfaces but is absorbed
within the mat, resulting in little light being transmitted through the
one (Cherpinski et al., 2018; Tang & Liu, 2008).
Fig. 4 shows the FTIR spectra for untreated and heat-treated PVA
mats. Untreated PVA mats showed characteristic bands associated to
functional groups of the PVA polymer at 3300 cm−1 (OeH stretching),
2854 cm−1 and 2940 cm−1 (CeH stretching from alkyl groups),
1745 cm−1 (CeO stretching from remaining acetate groups), 1426 cm-1
(CH2 bending) and 1093 cm−1 (CeO stretching) (Fig. 4) (Holland &
Hay, 2001; López-Córdoba et al., 2016; Mansur, Sadahira, Souza, &
Mansur, 2008). In the case of the heat-treated PVA mats, the absorption
band located at 1745 cm−1 became stronger and shift to lower wave-
number (1721 cm−1), which could be associated to the C]O stretching
from ester groups formed from hydroxyl and carboxylic groups of PVA
A. López-Córdoba, et al.
Fig. 2. SEM micrographs of (a) untreated and (b) heat-treated electrospun PVA mats; (c) Imagen of heat-treated PVA mat soaked in water and (d) SEM micrograph of
the heat-treated PVA mat after 24 h of soaking in distilled water.
and citric acid, respectively (López-Córdoba et al., 2016). Intensities of
bands centered at 2854 cm−1 and 2940 cm−1 bands became almost
equal in heat-treated samples, indicating that a CeH stretching mode is
being avoided. Another band could be observed at 1144 cm−1 in heat-
treated samples, associated with CeO bending in the crystalline frac-
tion. Also, the heat-treated mats exhibited a substantial reduction of the
bands located around 3300 cm−1, typically assigned to the hydroxyl
groups, when compared to untreated mats (Fig. 4). A decrease in the
hydroxyl groups results in a loss in the polar nature of the compound
and as a result the solubility of the polymer in water decreases (Gohil,
Bhattacharya, & Ray, 2006; López-Córdoba et al., 2016; Peresin et al.,
2014; Shi et al., 2008).
TGA curves of untreated and heat treated PVA electrospun mats are
shown in Fig. 5. The weight loss up to 200 °C was attributed to the
water evaporation; while, the thermal event occurred between 200 °C
and 400 °C was associated with the decomposition of the PVA chain.
Above 400 °C, the remaining mass corresponds to polymer degradation
subproducts (López-Córdoba et al., 2016; Van Etten et al., 2014).
However, in the water-insoluble PVA electrospun mats, the chain de-
composition of the PVA matrix was significantly delayed (Fig. 5). This
behavior could be attributed to both the citric acid crosslinking effect
and the dehydration of PVA due to the thermal treatment applied that
caused changes in the molecular packing of polymers molecules (Gohil
et al., 2006; López-Córdoba et al., 2016). These results agree with FTIR
studies suggesting the heat-induced interaction between PVA and citric
acid.
3.2. Potato starch-based biocomposites comprising water-resistant
electrospun PVA fibers and yerba mate extract
Potato starch-based biocomposites containing water-resistant elec-
trospun PVA fibers and yerba mate extract were successfully prepared.
In order to analyze the individual and combined effect of the different
381
Carbohydrate Polymers 215 (2019) 377–387
components of the biocomposites (electrospun PVA mats, yerba mate
extract and both), the properties of PS-YM/PVA/PS-YM composites will
be presented in comparison with the PS films, PS-YM films, PS/PVA/PS
composites.
3.2.1. Morphological studies
Cross-sections images of the potato starch films without and with
yerba mate extract are shown in Fig. 6a and b, respectively. It can be
seen that both films showed a homogeneous structure typical of gly-
cerol-plasticized starch films, without pores and cracks (Piñeros-
Hernandez et al., 2017). However, the cross-section surface of the PS
films was smoother compared with the PS-YM films (Fig. 6a and b).
Cross-sectional SEM images of PS/PVA/PS and PS-YM/PVA/PS-YM
composites revealed a sandwich-type structure with regions of neat
polymer on both sides of the electrospun mat, indicating that the
electrospun mat was fully incorporated into the composites (Fig. 6).
However, PS/PVA/PS composites showed a better-compacted structure
(Fig. 6c and d) in comparison with the PS-YM/PVA/PS-YM ones (Fig. 6e
and f). In the last materials, some cracks were observed around the
sandwiched structure indicating slight delamination (Fig. 6e and f).
This behavior could be due to that the addition of yerba mate extract
increased the surface hydrophobicity of the films decreasing their in-
terfacial interaction with the PVA matrix. Medina Jaramillo et al., 2015
reported an increase in the roughness and the surface hydrophobicity of
cassava starch films due to the addition of yerba mate extract.
3.2.2. Moisture content and water solubility
The moisture content (MC) and the water solubility (WS) of the
films are shown in Table 1. All samples showed moisture contents of
around 12% (p > 0.05). In the case of the water solubility (%), the
films without yerba mate extract (PS and PS/PVA/PS) showed higher
water resistant than the films containing the antioxidant additive (PS-
YM and PS-YM/PVA/PS-YM).
A. López-Córdoba, et al. Carbohydrate Polymers 215 (2019) 377–387

Fig. 3. Light transmittance (%) (3a) and contact transparency pictures (3b) of PS films (a); PS/PVA/PS composites (b); PS-YM films (c); PS-YM/PVA/PS-YM
composites (d); untreated PVA mats (e); and heat-treated PVA mats (f).

Fig. 4. FTIR spectra of untreated and heat-treated PVA mats. Fig. 5. TGA curves of untreated and heat-treated PVA mats.

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Fig. 6. Cross-section images of potato starch films without (a) and with (b) yerba mate extract. (c) and (d) cross-section images of PS/PVA/PS composites. (e) and (f)
cross-section images of PS-YM/PVA/PS-YM composites. Arrows show the PVA electrospun mats filler sandwiched between the PS layers. Images 5c and 5e are shown
intentionally at lower magnification to better visualization of the sandwich-type structure.

3.2.3. Barrier properties
The presence of the electrospun PVA mats provoked a statistically
significant reduction in the water vapor permeability of the films
(Table 1). PS and PS-YM samples showed values of water vapor per-
meability about 1.5-fold greater compared with the PS/PVA/PS and PS-
YM/PVA/PS-YM ones (Table 1). This behavior was attributed to both
the excellent PVA/starch interfacial adhesion and the changes in the
tortuosity of the system due to the PVA filler presence (Fig. 6).
All films were clear enough to be used as see-through packaging.
However, significant differences between their light transmittance (%)
were found (Fig. 3). PS films show a high light transmittance (c.a. 80%)
in the visible light wavelength range (Fig. 3a). Similar results have been
reported for glycerol-plasticized films based on other botanical starch
sources such as cassava tubers (López-Córdoba, Duca et al., 2017;
Piñeros-Hernandez et al., 2017). Unlike the electrospun PVA mats, PS/
PVA/PS composites showed a high light transmittance (c.a. 69%), in-
dicating a strong matrix-filler interaction (Fig. 3a). Similar observations
were reported by Stone et al. (2012) when developed composite films
comprised of ethylene oxide/ epichlorohydrin copolymer (EO-EPI) as
the matrix and electrospun poly(vinyl alcohol) mats as a filler. Besides,
it can be hypothesized that the pores within the PVA electrospun mats
were filled with thermoplastic potato starch increasing their reflective

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Table 1
Moisture content (MC), water solubility (WS), and water vapor permeability
(WVP) of the films.
Sample MC (%) WS (%) WVP
(g m−1 s−1 Pa−1 x 10-10)

PS 15.2 ± 2.3a 21.2 ± 3.4a 6.94 ± 0.67a

PS-YM 16.2 ± 2.2a 30.8 ± 1.7b 5.48 ± 0.60a
PS/PVA/PS 17.4 ± 0.2a 18.4 ± 2.3a 4.32 ± 0.40b
PS-YM/PVA/PS-YM 12.4 ± 2.4a 27.9 ± 1.4b 4.04 ± 0.18b

Different letters within the same column indicate statistically significant dif-
ferences (p < 0.05).

coefficient. It is well-known that the amount of light reflection at the

interface is highly related to the refractive index of the two materials
forming the interface (Tang & Liu, 2008). From another point of view,
the presence of PVA fibers within the potato starch-based composites
enhanced their light barrier properties, decreasing the light transmit-
tance (%) (Fig. 3a). According to Tang & Liu, 2008 light scattering
occurs when it encounters nanofibers with diameters larger than
400 nm provoking the formation of an opaque composite film.
The films PS-YM and PS-YM/PVA/PS-YM developed a green color
similar to that the extract used in the formulations (Fig. 3b). In all cases,
the addition of yerba mate extract enhanced the light barrier properties
of the materials, provoking an important reduction in their light
transmittance (%) (Fig. 3a and b). This behavior was attributed to the
presence of phenolic compounds of the extract which were available to
act as excellent light scavengers (Piñeros-Hernandez et al., 2017).
3.2.4. Infrared spectra analysis
All films (PS, PS-YM, PS/PVA/PS and PS-YM/PVA/PS-YM) showed
characteristic bands associated with functional groups of the starch
polymer at 3300 cm−1 (OeH stretching), 2947 cm−1 (CeH from alkyl
groups) and 1149 cm−1 (CeO stretching) (Fig. 7) (López-Córdoba,
Duca et al., 2017; Piñeros-Hernandez et al., 2017). Besides, PS-YM films
showed a signal at 1609 cm-1 attributed to the stretching of the aro-
matic rings due to the presence of yerba mate phenolic compounds
(Fig. 7b). Other signals around 1367 cm−1 and 1262 cm−1 were also
detected and attributed to CeOH bending from phenolic groups
(Fig. 7b). On the other hand, the FTIR spectra of the films with yerba
mate extract added (PS-YM and PS-YM/PVA/PS-YM) showed a di-
minution of the intensity of the band located around 3300 cm−1, in-
dicating a lower amount of hydroxyl groups available, when compared
to the films without extract (PS and PS/PVA/PS) (Fig. 7c). Such di-
minution of OeH groups was higher in the biocomposites comprising
both electrospun PVA fibers and the natural extract. These observations
agree with the fact that the addition of yerba mate extract could have
increased the hydrophobicity of the films and therefore their interfacial
adhesion with the electrospun PVA fibers decreased provoking slight
delamination (Fig. 6f).
Fig. 8. TGA curves of PS, PS-YM, PS/PVA/PS, and PS-YM/PVA/PS-YM films.
Also, PS/PVA/PS and PS-YM/PVA/PS-YM composite films showed a
signal around 1744 cm−1 attributed to the presence of the electrospun
PVA mat. In these materials, the characteristic CeH stretching band
appeared broadened and increased in intensity, suggesting a higher
number of vibration modes of the starch-PVA interactions.
3.2.5. Thermal properties
Fig. 8 shows the TGA curves of PS, PS-YM, PS/PVA/PS, and PS-YM/
PVA/PS-YM films. The thermal degradation of potato starch films (PS)
followed the pattern described in the literature typical of glycerol-
plasticized starch-films (García et al., 2009; Piñeros-Hernandez et al.,
2017). The weight loss up to 150 °C was attributed to the water eva-
poration. The thermal event occurred between 180 °C and 250 °C was
attributed to the decomposition of the glycerol-rich phase. Above
250 °C, the main weight loss occurred, and it was attributed to the
oxidation of the partially decomposed starch-rich phase. In the PS/
PVA/PS composites, the thermal event occurred between 180 °C and
250 °C was significantly delayed in comparison with the PS films
(Fig. 8). At 250 °C, the remaining mass was around 80% for PS and 88%
for PS/PVA/PS. This behavior was attributed to the presence of the
cross-linked electrospun PVA core layer that was able to increase the
thermal stability of the composites.
The presence of yerba mate extract in PS-YM and PS-YM/PVA/PS-
YM samples decreased the glycerol-rich phase decomposition (Fig. 8).
This behavior agrees with FTIR results suggesting that the yerba mate
extract affected the starch-glycerol interactions decreasing the number
of free glycerol chains. Similar observations have been reported for corn
and pea starch films loaded with donut-shaped starch-quercetin mi-
croparticles (Farrag et al., 2018), while the opposite behavior has been
observed in cassava starch films containing yerba mate extract (Medina

Fig. 7. FTIR spectra of PS and PS-YM films and PS/PVA/PS and PS-YM/PVA/PS-YM composites. IR spectrum of the electrospun PVA mat is shown in Fig. 7a for
comparison purposes.

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Table 2
Tensile properties of the films.
Sample Elastic modulus Tensile strength Strain at break
(MPa) (MPa) (%)

a,b
PS 22.3 ± 4.5 ª 2.1 ± 0.3 ª 41 ± 2
PS-YM 24.2 ± 3.6 ª 2.3 ± 0.8 ª,b 36 ± 7 b

PS / PVA / PS 24.7 ± 4.2 ª 2.7 ± 0.1 b 44 ± 7 a

PS-YM / PVA / PS- 37.6 ± 5.4 b 2.4 ± 0.2 a,b 38 ± 5 a,b

YM

Means that do no share a letter within the same columns are significantly dif-
ferent.

3.2.6. X-ray diffraction

Fig. 9. DSC thermographs of potato starch films without (PS) and (PS-YM)
yerba mate extract and PS-YM/PVA/PS-YM biocomposites.
Jaramillo et al., 2016). Therefore, it can be suggested that starch source
determines the packing mode of polymer chains, which seems to de-
termine possible linkages between the matrix, the plasticizer, and the
additives. On the other hand, the starch-rich phase degradation in the
PS-YM film was shifted towards lower temperatures respect to the PS
samples, while in the PS/PVA/PS and the PS-YM/PVA/PS-YM compo-
sites these thermal events were shifted towards greater temperature
values indicating higher thermal stability. At 450 °C, the remaining
mass was higher for PS-YM and PS-YM/PVA/PS-YM films (c.a. 22%)
than for PS and PS/PVA/PS ones (c.a. 15%). This behavior was prob-
ably due to that some yerba mate extract components cannot be de-
graded up to 450 °C, as reported in previous work (Medina Jaramillo
et al., 2016).
In complementary studies by DSC, similar glass transition tem-
peratures were found for PS (Tg ≈ 10.5 °C) and PS-YM (Tg ≈ 10.9 °C)
films (Fig. 9). In the case of the PS-YM/PVA/PS-YM biocomposites, the
glass transition temperature was shifted toward lower temperatures (Tg
≈ 8.7 °C) due to the synergistic effect caused by the presence of yerba
mate extract and electrospun PVA mats (Fig. 9). Mitrus, 2005 reported
glass transition temperatures about 18 °C for thermoplastic starch films
(30% glycerol) produced by extrusion.
Fig. 10 shows the X-ray diffraction patterns of the glycerol-plasti-
cized potato starch films with (PS-YM) and without (PS) yerba mate
extract. The diffractograms of PS and PS-YM films were matched with
the X-ray pattern of potato starch, showing signals at 2θ (º) = 17.0,
19.7, and 22.4°, corresponding to a B-type crystallinity pattern (Fonseca
et al., 2018; van Soest, Hulleman, de Wit, & Vliegenthart, 1996).
However, in the films containing yerba mate extract (PS-YM), the signal
detected about 19.3° was noted widened and with stronger intensity
compared with the PS film. This behavior was probably due to the
complex formation between amylose and low molecular weight mole-
cules such as yerba mate polyphenols (Putseys, Lamberts, & Delcour,
2010).
3.2.7. Mechanical properties
Tensile properties of all films (PS, PS-YM, PS/PVA/PS, and PS-YM/
PVA/PS-YM) are summarized in Table 2. All materials showed a vis-
coelastic behavior characteristic of thermoplastic starch. Initially, the
stress increases linearly with the strain, followed by a non-linear be-
havior until failure (Data not shown).
PS, PS-YM and PS/VA/PS films showed similar elastic modulus
values (c.a.24 MPa) (p > 0.05). In the case of the PS-YM/PVA/PS-YM
biocomposites, the presence of the electrospun PVA mat and the yerba
mate extract produced a synergistic effect increasing their elastic
module in a 60% (c.a.38 MPa) (p < 0.05).
Statically significant differences were found between the tensile
strength of PS (c.a. 2.0 MPa) and PVA/PS/PVA (c.a.2.7 MPa) samples
(p < 0.05). Therefore, it can be stated that the electrospun PVA mat
was able to act as a reinforcement of the potato starch matrix increasing
its tensile strength at break. This effect of PVA was also recently ob-
served in composite films from regenerated cellulose-glycerol-polyvinyl
alcohol (Cazón, Velazquez, & Vázquez, 2019). In those systems, the
incorporation of PVA improved the plasticizing efficiency, promoting
the interaction between components resulting in better mechanical
properties (Cazón et al., 2019). On the other hand, PS-YM and PS-YM/
PVA/PS-YM films showed a slightly increasing trend in the tensile
strength in comparison with PS samples, but the differences were found
to be statistically insignificant (p > 0.05). Concerning the strain at
break, the yerba mate extract produced a slight decrease in the strain at
break (%) of the PS films, while, the presence of the electrospun PVA
mats caused an increase in this tensile parameter (i.e., PVA/PS/PVA
biocomposites showed higher strain at break than the PS-YM films).
This behavior could be due to the well-compacted structure of the PVA/
PS/PVA composites (Fig. 6d) and also to the effect of the yerba mate
extract on the starch-glycerol interactions (Figs. 7 and 8). It has been
reported that when a low amount of the plasticizer is available, a robust
contact might be taking place between the polymer and the plasticizer
reducing the free volume and the mobility of molecules in the polymer
matrix and also the film strain (Cazón et al., 2019).

3.2.8. Antioxidant properties

Fig. 10. X-ray diffraction patterns of glycerol-plasticized potato starch films The extract of yerba mate showed an average polyphenol content of
with (PS-YM) and without (PS) yerba mate extract. 1.78 ± 0.01 mg GAE/mL and an efficient concentration (EC50) about

385
A. López-Córdoba, et al.
0.09 ± 0.01 mg GAE/mL (EC50 is the polyphenols concentration ne-
cessary to reduce the initial amount of DPPH radical to 50%). Several
authors have tested the composition of the aqueous extract of yerba
mate by high performance liquid chromatography (HPLC), finding that
chlorogenic acid, caffeic acid, and rutin are the main antioxidant
compounds present in this extract (Jaiswal, Sovdat, Vivan, & Kuhnert,
2010; López-Córdoba, Deladino, Agudelo-Mesa, & Martino, 2014). PS-
YM and PS-YM/PVA/PS-YM films showed an average polyphenol con-
tent of 18.0 ± 0.3 mg GAE/g and 15.1 ± 0.3 mg GAE/g, respectively.
Besides, the films showed a time- and dose-dependent DPPH radical
scavenging activity. On the one hand, the DPPH-radical scavenging
activities of the films increased when increased the time of assay (Data
not shown). On the other hand, the DPPH-radical scavenging activities
of the films increased when increased the polyphenols content. There-
fore, PS-YM films exhibited a higher DPPH- scavenging activity
(41.3 ± 1.2%) than PS-YM/PVA/PS-YM ones (34.1 ± 5.9%). Similar
behavior was observed by Yong et al. (2019) and Chang-Bravo et al.
(2014) in antioxidant starch films containing anthocyanin- and poly-
phenol-rich extracts (propolis and yerba mate), respectively. It is well-
known that free radicals can cause oxidative deterioration of foods and
also nutritional quality loss. Thus, these antioxidant films with suitable
free radical scavenging activity can be potentially used in active
packaging applications of foods such as meats, fish, and oils.
4. Conclusions
An innovative process for the production of starch-based bio-
composites with enhanced properties was successfully carried out
through the combination of electrospinning and solvent casting pro-
cesses. The presence of both the water-resistant electrospun PVA mat
and the yerba mate extract caused a synergistic effect that significantly
increased the elastic module of the biocomposites while their tensile
strength and strain at break were maintained almost unaltered, respect
to the neat potato starch film. Moreover, the presence of both additives
was useful to bestow a protective barrier against light to the bio-
composites. Microscopical observations confirmed that the layered
systems exhibited a well-compacted structure (i.e., an excellent inter-
facial adhesion) although compatibilizers agents were not used.
Overall, the electrospun PVA mats proved to be a useful filler to re-
inforce potato starch matrices which can help to overcome their lim-
itations in industrial applications. The approach used here could be
tailored to the fabrication of other new biobased materials for food
packaging applications.
Acknowledgments
The authors would like to thank the Agencia Nacional de Promoción
Científica y Tecnológica (ANPCyT PICT 2017-2362) for their financial
support. A.L.-C. would like to thank the Universidad Pedagógica y
Tecnológica de Colombia (UPTC) for their support through the SGI
2461 project and to Dario Diaz for assistance with Fig. 1.
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