pubs.acs.

org/acsapm Article

Biodegradable Films Derived from Corn and Potato Starch and

Study of the Effect of Silicate Extracted from Sugarcane Waste Ash
Luciana C. de Azevedo,* Suzimara Rovani,* Jonnatan J. Santos, Djalma B. Dias, Sandi S. Nascimento,
Fab́ io F. Oliveira, Leonardo G. A. Silva, and Denise A. Fungaro
Cite This: ACS Appl. Polym. Mater. 2020, 2, 2160−2169 Read Online

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ABSTRACT: The growing concern with the amount of plastic materials found in
the oceans makes it necessary to develop biodegradable materials that have low
toxicity to marine animals and humans, but at the same time are resistant to the
actions of microorganisms such as fungi or bacteria. On the other hand, agricultural
waste rich in inorganic materials (such as silica) is often discarded, while it could
be reused as a source of raw material. Considering these points, sodium silicate
solution extracted from sugarcane waste ash was utilized to prepare biodegradable
bioplastics based on corn starch and potato starch. The starch-based bioplastics
were produced by casting and characterized by several physical-chemical
techniques evaluating tensile strength, elongation at break, color analyses,
transparency, opacity, moisture, and biodegradation assay. Bioplastics prepared
with corn starch presented better physical, mechanical, and thermal properties and
optical quality than bioplastics based on potato starch. The samples called CS3 and
PS3, with 5.0% glycerol, were the most resistant to tensile strengths of 0.73 and
0.36 MPa, respectively. On the other hand, the highest elongation at break values were found for the samples with 7.5% glycerol
(CS9, 52.90% and PS9, 49.33%). Corn starch-based bioplastics were more thermally resistant (CS3, 152.86 °C and CS9, 135.20 °C)
when compared to potato starch-based bioplastics (PS3, 140.39 °C and PS9, 127.57 °C). In general, the addition of sodium silicate
solution improved the mechanical and thermal properties of both types of bioplastics. The potato starch-based bioplastics were
biodegraded in 5 days, while those made from corn starch took almost 40 days. The inclusion of sodium silicate inhibited fungal
growth for both corn starch and potato starch bioplastics. The results suggest that sodium silicate solution obtained from renewable
sources can be incorporated into starch-based bioplastics for production of biodegradable packaging with antifungal activity.
KEYWORDS: starch-based bioplastics, sugarcane waste ash, corn starch, potato starch, sodium silicate

1. INTRODUCTION obtained from starch show broad utility in food packaging,

Growing concern for the environment has stimulated the
development of biodegradable bioplastics produced from
renewable sources.1,2 Natural polymers such as starch, chitin,
cellulose, gelatin, and lignin are excellent alternatives to
decrease the use of non-biodegradable substances,3 and
many studies have been reported on starch-based bioplastics
since 1950. 4,5 Recent research has demonstrated the
importance of starch-based bioplastics as substitutes for
conventional plastics;6−10 however, the technology for
obtaining these materials still requires further adjustments to
provide mechanical and barrier properties compatible with
those of petroleum-derived polymers.
Starch, in particular, has been considered one of the most
promising materials due to its availability from a variety of
renewable sources (including wheat, rice, corn, potato, and
cassava), low cost, and good performance; further, it has
excellent biocompatibility and is utterly biodegradable in soil
and water.10−12 According to the literature, bioplastics
drug transport, and bioengineering.
The gelation of starch is one of its most vital properties,
involving the irreversible transformation of the granular starch
into a viscoelastic paste. When granular starch is subjected to
heating in an aqueous medium, some internal hydrogen
bondsresponsible for the stabilization of the crystalline
structure of the granuleare broken, and water enters its
molecular structure, causing grain rupture and loss of
birefringence. At this time, the gelatinization of the starch
occurs.13
The plasticizers most commonly used in starch-based
bioplastics are polyols, such as glycerol and sorbitol. Glycerol
Received: February 4, 2020
Accepted: May 14, 2020
Published: May 14, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsapm.0c00124

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is a very useful plasticizer because it presents a smaller capacity
for interaction with the starch molecules, giving greater
wettability to the chains of the polymeric matrix, destroying
the crystalline structure of starch; it also improves the thermal
stability and thermoplasticity of the starch bioplastics.14,15 The
simplest and most straightforward method for preparing
starch-based bioplastics is casting, which involves the
preparation of a film-forming solution, its deposition in a
suitable support, and subsequent drying of the solvent at room
temperature.16−19
Some of the technological applications of starch-based
bioplastics,20 for example, bioplastics for food packaging,
require specific functions that cannot be satisfied by the starch
alone. Sodium silicate solution can be added to the film-
forming solution because, according to many studies reported
in the literature,21−23 the silicate has good antifungal
properties, which is considered very important for the
development of food packaging. Silicate is a very inexpensive
reagent of great abundance that is usually extracted from
sand,24 but its extraction from renewable sources, in particular
plant waste, such as that from rice,25 bamboo,26 wheat,27 and
sugarcane,28 has gained significant importance as the
generation of waste from the agriculture industry grows
every year.
Therefore, the objectives of this study based, on a literature
review, were to develop a process for the preparation of starch-
based bioplastics, evaluate the ability to form bioplastics with
two different sources of starch, and investigate the addition of
sodium silicate solution extracted from sugarcane waste ash.
Other objectives were to evaluate some physical and
mechanical properties of the products obtained and also
perform a biodegradability assay of starch-based bioplastics.
2. EXPERIMENTAL SECTION
2.1. Materials. All aqueous solutions were prepared using
deionized water (resistivity >18.2 MΩ·cm) obtained from a Milli-Q
deionizer (Elix Millipore). Sugarcane waste ash (SWA) was donated
by COSAN S.A. Sodium hydroxide micropearls (>99%) and
hydrochloric acid (35−37%) were purchased from Synth, Brazil.
Glycerol (≥99.5%) was obtained from Sigma-Aldrich, Brazil. Corn
starch was purchased from Unilever Brazil Industrial, and potato
starch was purchased from Dinâmica Quimica ́ Contemporânea Ltd.,
Brazil.
2.2. Procedures. 2.2.1. Extraction of Sodium Silicate Solution
from Sugarcane Waste Ash. Sodium silicate (Na2SiO3) solution was
obtained as previously published,29,30 wherein SWA was mixed with
NaOH solid (1:1.5, w/w) and heated to 550 °C over 1 h in a muffle
oven. After 1 h, the mixture was cooled, and deionized water was
added to the molten mixture, which was then refluxed for 4 h. Finally,
the mixture was filtered to remove the solid residue from the sodium
silicate solution.
2.2.2. Casting of Bioplastics. The filmogenic solution was prepared
by dissolving corn starch or potato starch in 0.10 mol L−1 HCl
aqueous solution under stirring and heating for 30 min. Glycerol and
sodium silicate solution were added to the mixture when the
temperature reached at 55 and 65 °C, respectively (Table S1).31,32
According to the casting technique, for each formulation, a specific
content of the filmogenic solution was poured onto rectangular plates,
followed by drying at ambient temperature for approximately 96
h.1,6,33 A flow diagram of the procedure used to obtain the
biodegradable films is shown in Figure S1.
2.3. Characterization. Scanning electron microscopy (SEM)
images were recorded using a Quanta FEG 650 tabletop microscope
from Thermo Fischer Scientific (Oregon, USA) and a model TM
3000 tabletop microscope from Hitachi (Tokyo, Japan). Before the
SEM analysis, the sample was fixed in the sample holder with carbon
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tape and covered with gold in the BAL-TEC sample coater/sputterer,
model SCD 050.
X-ray diffraction (XRD) analyses were performed using a Rigaku
Multiflex diffractometer with a Cu anode using Co Kα radiation at
40.0 kV and 20.0 mA over the 2θ range of 5−80° with a scan rate of
0.5° min−1.
Fourier transform infrared (FTIR) spectroscopy was performed
using an Alpha spectrometer from Bruker, operating in attenuated
total reflectance (ATR) mode. The spectra were obtained using 200
cumulative scans in the range 375−4000 cm−1.
Thermogravimetric analysis (TGA) was recorded on a TGA/
SDTA thermogravimetric analyzer from Mettler Toledo. The sample
weighed ∼10.0 mg and was analyzed under a nitrogen atmosphere
with a flow of 65.0 mL min−1, using an alumina-port sample heated to
600 °C with a heating rate of 20 °C min−1.
Differential scanning calorimetry (DSC) was performed on a DSC
822e instrument from Mettler Toledo. Dry samples (∼40.0 mg) were
analyzed under a nitrogen atmosphere with a flow of 30.0 mL min−1,
using an aluminum-port sample heated 250 °C with a heating rate of
10 °C min−1.
2.4. Mechanical Properties. The thickness of the samples
(conditioned at 25 °C and 46% relative humidity (RH) for 72 h) was
measured with an INSIZE 3109-25 micrometer (São Paulo, Brazil)
before the tests. The measurements were taken at five different
positions for each sample, and the average value of these
determinations was calculated. This average value was used to
calculate the cross-sectional area of the samples (the area is equal to
the thickness multiplied by the width of each sample).
The mechanical properties, tensile strength, and percent elongation
at break were performed with three or more specimens (size of 73 ×
12 mm) cut from each bioplastic. The tensile strength and percent
elongation at break were measured using an Instron 5567 electro-
mechanical universal testing machine (São José dos Pinhais, Paraná,
Brazil), using a calibrated 1 kN (100 kg) load cell, according to
ASTM Standard Methods ASTM D882-12 and ASTM D638-14, with
some adaptations. The initial grip separation was 45 mm, and the
cross-head speed was 50 mm/min. The tensile strength was calculated
by dividing the maximum force exerted on the bioplastic during
fracture by the cross-sectional areas. Percent elongation at break was
expressed as the percentage of change of the original length of a
specimen between grips at the break.34,35
2.5. Transparency and Opacity. Color analyses of bioplastics
were determined using a Miniscan EZ colorimeter from Hunterlab
(Murnau, Germany), adopting L* (luminosity), a* (red-green), and
b* (yellow-blue), which were analyzed by using the CIELab scale.1 In
the case of bioplastics, the attributes a* and b* represent redness and
yellowing, respectively.
Transparency and opacity were determined by cutting rectangular
strips of the bioplastic, with size of 0.8 × 30 mm, which were then
adhered to the inner wall of a quartz cuvette, to remain perpendicular
to the light beam to read the transmittance in the range from 200 to
800 nm (model Cary 1E UV−vis spectrophotometer from Varian,
California, USA), using the empty cuvette as a control.7,36 The
transparency was calculated according to eq 1:
transparency = 1/(A500 /t ) (1)
where A500 is the absorption at 500 nm and t is the bioplastic
thickness in mm.
Apparent opacity was determined on the same spectrophotometer,
according to the methodology described in ref 37. The absorbance at
500 nm was read for each bioplastic, and the opacity was calculated
according to eq 2:
opacity = A500 /t (2)
where A500 is the absorption at 500 nm and t is the bioplastic
thickness in mm.
The moisture was determined in an oven at 105 °C (∼4 h),
according to the methodology suggested by Rocha et al. (2014).37
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2.6. Biodegradation Assay. A biodegradation assay of the
starch-based bioplastics was performed as follows. The bioplastics
were cut into 4 × 10 cm pieces (40 cm2 area) and packed into foil
bags with four pieces of each sample per bag (n = 4), as shown in
Figure S2. They were then buried in a garden area in the IF SERTÃ O-
PE, Petrolina-PE campus, at a depth of 20 cm under soil (Figure S3).
Samples were dug up and observed periodically, every 48 h, for 2
weeks. From the third week, the frequency of observations was
reduced to weekly. The total period of observation was 40 days, and
the term was defined according to the degradation state of the
bioplastics. The observations were made based on the bioplastic
sample’s area and completed when the samples decreased their area
and degraded. Evaluation of the decomposition of the residues
followed the simple exponential model used by Thomas and Asakawa
(1993),38 using eq 3:
X t = X 0 e−kt
where Xt is the amount of dry matter remaining after a period of time
t, X0 is the initial amount of dry matter, k is the decomposition
constant, and t is the time in days. By rearranging the terms of this
equation, it is possible to calculate the value of the decomposition
constant k, using eq 4:
k = ln(X t /X 0)/t
Half-life is another important parameter in the evaluation of the
decomposition of plant residues, expressing the time, in days,
necessary for half of the material to decompose, or for half of the
nutrients contained in the residues to be released. According to
Rezende et al. (1999),39 it is possible to calculate the half-life through
eq 5:
t 1/2 = ln(2)/k
3. RESULTS
3.1. Description of Samples. In the present study, we
evaluated various conditions for the formation of biodegrad-
able bioplastics with fungicidal properties from corn starch and
potato starch prepared with sodium silicate solution extracted
from sugarcane waste ash. A total of 16 samples were prepared,
and the four best results are presented, as well as a bioplastics
control. All conditions investigated are described in Table S1.
These results were obtained after optimization of the process
for preparation of the bioplastics, in which the quantities of
starch, hydrochloric acid, glycerol, and sodium silicate solution
were varied. The percentage values of the components were
calculated in relation to the volume of the filmogenic solution.
The samples prepared with corn starch and potato starch were
named as CS and PS, respectively, where the samples CS1 and
PS1 do not contain silicate, but to each was added 0.10 mol
L−1 NaOH solution (control bioplastics). The complete
characterization of these samples is given below.
3.2. Structural Characterization and Mechanical
Properties. The formation of bioplastics occurs through a
process of starch organization during drying. The chemical
influence of sodium silicate and glycerol concentration was
evaluated by infrared (IR) spectroscopy and XRD.
The possible bond formation or modification was assessed
by IR spectroscopy. The spectra obtained for the starch-based
bioplastic samples before the addition of sodium silicate
solution (CS1 and PS1) and with sodium silicate and two
different contents of glycerol (CS3, CS9 and PS3, PS9) are
shown in Figure 1.
In general, no changes are observed in the bioplastics spectra
after addition of the sodium silicate solution. All IR spectra of
the starch-based bioplastics present an intense band at 3285
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Figure 1. Infrared spectra of starch-based bioplastics: (a) CS samples
and (b) PS samples.
cm−1, associated with OH stretching, attributed to the
(3) hydrogen bonds (H−O···H) between the plasticizer molecules
and the starch molecules and also to the presence of water in
the starch-based bioplastics.40 Two bands of low intensity
located at 2930 and 2885 cm−1, attributed to the C−H
stretching, and a band at 1650 cm−1, corresponding to the
δ(O−H) flexion due to the tightly bound water, were observed
in the spectra.41 A medium-intensity band was observed at
(4)
1370 cm−1, attributed to bending of the CH2 and C−OH
groups. The 1150 and 1079 cm−1 bands observed correspond
to the C−O stretch vibration in C−O−H groups, and the 1110
cm−1 band observed only for starch-based bioplastic samples is
attributed to the C−O stretch vibration in C−O−C groups.41
These results corroborate with those reported by Dang and
Yoksan (2015).1 According to Shi et al. (2007),42 the bands at
(5) 1040 and 1025 cm−1 are sensitive to the amount of ordered or
crystalline starch and related to amorphous starch, respectively.
The two low-intensity bands at 925 and 850 cm−1 observed
in the IR spectra are characteristic absorption bands of
anhydroglucose ring stretching vibrations of the starch
structure.41 The band at 925 cm−1 is attributed to a skeletal
mode involving an α-1,4-glycosidic linkage (C−O−C), and the
band at 570 cm−1 is attributed to skeletal modes of the
pyranose ring.43
These results demonstrate that the implicit chemical
properties of starch are not altered, and the presence of
glycerolresponsible for maintaining the adhesion between
the polymeric starch chains and for the plastic flexibilityat
different concentrations (5% for CS3 and PS3 and 7.5% for
CS9 and PS9) does not change the chemical bonds/groups.
The silicate peaks in turn are not observed, since they are in
low concentration.
The XRD patterns of native corn starch (CS), native potato
starch (PS), and starch bioplastics modified with silicate show
similar results, as can be seen in Figure 2.
As can be seen from Figure 2, CS and PS present very
similar spectra, with main diffraction peaks at 15.2°, 17.5°,
23.0° and 14.9°, 17.4°, 23.0°, respectively. Generally, the
native starch crystallinity is of types A, B, and C, as an
intermediate form crystalline.44−46 The peaks exhibited by CS
and PS are the A-type diffraction patterns typical of corn and
potato starch.47 The peak at 2θ = 17.1° and 17.5° of some
starch-based bioplastics, including the control bioplastics CS1
and PS1, is attributed to typical peaks of amylose complexed
with glycerol.48
3.3. Morphological Characteristics and Thermal
Stability. IR spectroscopy and XRD do not show significant
alterations in the chemical characteristics of the bioplastics. On
the other hand, SEM images present real changes in the
physical characteristics, as can be seen in Figure 3.
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Figure 2. X-ray diffraction patterns of starch-based bioplastics: (a) CS
samples and (b) PS samples.
The SEM images confirm that plastification and processing
completely modified the structure of the starches, as the
resulting bioplastics differ completely from the native starches
(Figure S4A,B). The morphology of the bioplastics CS1 and
PS1 (Figure 3A1,B1) was similar to those of a corn starch/
chitosan film obtained by Ren et al. (2017)49 and sweet potato
starch film obtained by Li et al. (2015).50 In the samples with
the addition of sodium silicate (CS3, CS9, PS3, and PS9) the
formation of fibrous silicate was observed, which indicates a
higher inorganic character for silicate-doped bioplastics.
The results from the measurements of the tensile strength
and percent elongation at break of the starch-based bioplastics,
obtained for the samples CS/PS1, CS/PS3, and CS/PS9, are
shown in Figure 4, corroborating the SEM observations. It can
be seen that the CS3 sample (0.73 MPa) was the most
Figure 3. SEM images of starch-based bioplastics: (A1) CS1, (A2) CS3, and (A3) CS9, and (B1) PS1, (B2) PS3, and (B3) PS9.
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resistant to the tensile strength when compared to samples
CS9, PS3, and PS9. This is probably due to the higher amylose
content in corn starch than in potato starch,6 corroborating the
results obtained by Luchese et al. (2018),3 where the corn
starch-based films also presented higher tensile strength than
potato, cassava, and wheat starch-based films.
Comparing the different contents of glycerol for the starch-
based bioplastics, the highest E values (Table S2) were
obtained for the samples with 7.5% glycerol (CS9 and PS9).
The addition of sodium silicate in the starch-based bioplastics
decreased the elongation at break and the tensile strength; on
the other hand, the E values found in this study for corn and
potato starch-based bioplastics were about 3 and 10 times
higher, respectively, than those found by Basiak et al. (2017)51
for films obtained with the same starches.
Thermogravimetric analysis was used to evaluate the thermal
stability of the starch-based bioplastics, in order to know the
maximum temperature at which these materials could be used
without degradation or loss of their characteristics, as well as to
compare the thermal resistance between the two types of
starch used in the study. Thermogravimetric (TG) and
differential thermogravimetric (DTG) curves of some plasti-
cized samples are shown in Figure 5.
From the TG and DTG curves, five and four weight loss
stages can be seen for corn and potato starch-based bioplastics,
respectively (Figure 5 and Table S3). The first mass loss,
between 25 and ∼110 °C for all starch-based bioplastics,
ranged from ∼5 to ∼10%, except for the PS1 sample (∼16%);
this is related to evaporation of free water.3,36 The PS1 sample
presented higher free water loss compared to the other samples
since PS1 had the lowest thickness (Table S3).
The second weight loss, between ∼110 and ∼200 °C for all
starch-based bioplastics, ranged from ∼14 to ∼22%, except for
PS1 (∼11%) and PS3 (∼40%); this is related to loss of
moisture and/or evaporation of water.48 Corroborating the
results of moisture analysis (Table S2), PS1 and PS3 have the
lowest and highest moisture percent, respectively, among the
studied samples.
The third stage of mass loss, between ∼200 and ∼300 °C for
all starch-based bioplastics, ranged from ∼26 to ∼33%, except
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Figure 4. Mechanical properties of starch-based bioplastics: (a) tensile strength (MPa) of CS samples, (b) elongation at break (%) of CS samples,
(c) tensile strength (MPa) of PS samples, and (d) elongation at break (%) of PS samples.
for PS1 (∼54%) and PS3 (∼22%), which demonstrates
thermal expansion of the material and degradation of glycerol
(boiling point 290 °C). These results were similar to those
reported by Shi et al. (2007)42 and by Luchese et al. (2018).3
The fourth weight loss, between ∼300 and ∼360 °C for
samples with sodium silicate (CS3 and CS9), ranged from ∼4
to ∼10%. This was associated with low-molecular-weight
reaction products.3 The fifth and final weight loss, between
∼360 and ∼500 °C for corn starch-based bioplastics with
sodium silicate (CS3 and CS9), ranged from ∼8 to ∼12%,
corresponding to the degradation of starch and loss of the
chemically adsorbed water bonded to Si−OH through the
hydrogen bond.51,52 For CS1 (without sodium silicate) the
fourth and fifth weight losses (∼15%) occurred until ∼465 and
∼500 °C, respectively, and for potato starch-based bioplastics
the fourth and fifth weight losses occurred until ∼465 °C (PS1,
∼4% and PS3, ∼10%) and until ∼500 °C for the other samples
and ranged from ∼12 to ∼15%. These samples showed only
four weight losses, and this fourth corresponds to the
degradation of starch and loss of the chemically adsorbed
water bonded to Si−OH (from sodium silicate) through the
hydrogen bond.51,52 Above these temperatures no further
weight loss occurred; only inorganic components remained.
Thermal analyses performed by DSC are shown in Figure 6.
The thermograms exhibited a single endothermic peak, which
indicated homogeneity of the bioplastics.3,53 The Tpeak values
of most of the crystals obtained in this work ranged from
135.20 to 157.61 °C for CS samples and from 125.12 to
140.39 °C for PS samples (Table S4). These results
demonstrate that the starch-based bioplastics have good
resistance at high temperatures. Similar results were found by
Tongdeesoontorn et al. (2011),54 who reported crystallization
temperatures of 96−165 °C for cassava starch films.
The values found in this study were higher than those
reported by Woggum et al. (2014)6 and Podshivalov et al.
(2017),36 who reported crystallization temperatures of 70.7−
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76.1 °C and ∼80 °C for rice starch-based biodegradable films
and gelatin/potato starch edible biocomposite films, respec-
tively.
Comparing bioplastics with 5% of glycerol without the
addition of sodium silicate (CS1 and PS1) to bioplastics with
the addition of 25% sodium silicate solution (obtained from
sugarcane waste ash), it was possible to observe an increase of
15 °C and a decrease of 5 °C (see Table S4) in the melting
temperature of most of the crystals of PS3 and CS3,
respectively.
3.4. Biodegradability Assay. The biodegradability assay
of the bioplastics included observation of the visual aspects
during the period in which the samples remained buried as well
as measurement of the area of the material. The initial proposal
was that the visual analysis would be accompanied by the loss
of mass of the bioplastics; however, this variable was affected
by soil moisture and aggregation of sand grains and other
residues, and thus it was discarded. Figure 7 shows the CS and
PS bioplastics at the beginning and end of the biodegradability
test.
Degradation curves for corn and potato starch-based
bioplastics shown in Figure S6 represent the bioplastic area
reduction curve in the test period. It is possible to perceive the
fragility of the potato starch-based bioplastics (PS), which
degraded in only 5 days, which implies that its use for
commercial purposes is unviable, although it is very good from
an environmental point of view. For corn starch-based
bioplastics (CS), however, a higher resistance to soil
conditions is observed relative to PS bioplastics. The time
required for degradation of CS was approximately 40 days,
which can be considered an excellent degradation time when
compared to synthetic commercial polymers, like PVC films.
Luchese et al. (2018) evaluated the biodegradability of cassava,
wheat, and corn-based films and commercial PVC films and
observed that after 56 days the starch-based films were
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Figure 5. TG curves of starch-based bioplastics: (a) CS samples and (e) PS samples. TG/DTG curves of starch-based bioplastics: (b) CS1, (c)
CS3, (d) CS9, (f) PS1, (g) PS3, and (h) PS9. Samples were analyzed under a nitrogen flow of 65 mL min−1 with a heating rate of 20 °C min−1.

Figure 6. DSC curves of starch-based bioplastics: (a) CS samples and (b) PS samples.

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Figure 7. Biodegradability assay images of corn starch-based
bioplastics, (a) day 0 and (b) at the end of the degradation period
(day 39), and potato starch-based bioplastics, (c) day 0 and (d) at the
end of the degradation period (day 5).
practically all bio-disintegrated, while the commercial PVC-
based film remained intact.3
Table 1 shows the half-life times of the starch-based
bioplastics (CS and PS) submitted to the biodegradability
Table 1. Half-Life Values of Corn and Potato Starch-Based
Bioplastics
bioplastics t1/2 (days)
CS1 22.52
CS3 22.34
CS9 17.64
PS1 3.05
PS3 2.59
PS9 2.59
test. These values corroborate with the results presented in
Figure 7. The half-life time of the CS3 sample (t1/2 = 22.34
days) approached that of the CS1 sample, whereas for the CS9
sample, containing higher glycerin content, it was lower (t1/2 =
17.64 days). For the potato starch-based bioplastics, the half-
life time was short for all samples, ranging from 2.59 to 3.05
days. These results corroborate with the DSC thermal analyses
(Figure 6), which showed that the corn starch-based
bioplastics were more thermally resistant when compared to
potato starch-based bioplasticsthis is an indication that CS
bioplastics are less biodegradable than PS bioplastics.
These results of half-life time obtained for CS samples were
equivalent to that of some organic materials found naturally in
the soil, such as some plant species studied by de Paula et al.
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2015,55 Gliricidia sepium (t1/2 = 14 days), Pueraria phaseoloides
(t1/2 = 23 days), and Panicum maximum (t1/2 = 20 days).
3.5. Antifungal Activity. Silicate has antifungal activity, as
shown by Capeletti et al. (2014)56 and Derbalah et al.
(2018).57 In this study, it was also observed that the addition
of sodium silicate in the starch-based bioplastics inhibited the
growth of fungi. All starch-based bioplastics produced have
starch, glycerol, NaOH, and acid solution. However, in
bioplastics made without sodium silicate, fungal growth was
observed (Figure 8).
Figure 8. Photographs of starch-based bioplastics: (a) CS samples
and (b) PS samples. Fungal growth in control films (CS1 and PS1).
In the control bioplastics (CS1 and PS1), black dots related
to fungal growth were observed, and Figure S7 shows different
colors in starch-based bioplastics also associated with fungal
growth. This result agrees with those found in the literature:
Ge et al. (2017)21 observed in their study that sodium silicate
expressively inhibited mycelial growth and spore germination
of Trichothecium roseum (fungus); Li et al. (2009)22 observed
that sodium silicate had direct fungitoxic activity against
Fusarium sulphureum (fungal plant pathogen) in potato tubers;
Bi et al. (2006)58 observed that sodium silicate inhibited
pathogen growth and thus induced disease resistance in Hami
melons; Ellepola et al. (2011)59 observed that toothpaste with
sodium silicate as one of the ingredients presented anti-
candidal activity against Candida albicans and Candida
dubliniensis.
4. CONCLUSION
The results obtained in this study show that corn starch-based
bioplastics are more colorless, more transparent, and less
opaque and present lower moisture content than potato starch-
based bioplastics. However, the thickness of the corn starch
bioplastics was higher than that of the potato starch bioplastics,
but the mechanical and thermal properties remained higher for
the corn starch-based bioplastics.
In general, the addition of sodium silicate solution, obtained
from a renewable source, improved the mechanical and
thermal properties of both types of bioplastics.
The corn starch-based bioplastic obtained with 5% glycerol
and 25% sodium silicate solution (CS3) showed the highest
tensile strength.
In the biodegradability assay, although the potato starch-
based bioplastics had worse physical, mechanical, and thermal
properties, they presented higher biodegradability than corn
starch-based bioplastics. The potato starch bioplastics were
https://dx.doi.org/10.1021/acsapm.0c00124
ACS Appl. Polym. Mater. 2020, 2, 2160−2169
ACS Applied Polymer Materials
biodegraded in 5 days, whereas those of corn starch took
almost 40 days.
Finally, the addition of sodium silicate solution from a
renewable source inhibited fungal growth for both corn starch
and potato starch bioplastics. These starch-based bioplastics
can be considered for use in biodegradable packaging with
antifungal activity. However, further research is recommended
to improve the main properties of these bioplastics in order for
them to withstand external stress and maintain integrity.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsapm.0c00124.
Photographs of bioplastics packed in foil bags for
biodegradability analysis; flow diagram of the procedure
used to produce of the biodegradable films; preliminary
test formulations for obtaining starch-based bioplastics
(bioplastics preparation: selection of samples); SEM
images of native corn and potato starch; physicochem-
ical characterization and mechanical and thermal
properties of the starch-based bioplastics; and degrada-
tion curves for starch-based bioplastics (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Luciana C. de Azevedo − Department of Food Technology,
Federal Institute - IF SERTAO-PE, CEP: 56314-520 Petrolina,
Pernambuco, Brazil; Instituto de Pesquisas Energéticas e
Nucleares (IPEN-CNEN/SP), CEP: 05508-000 São Paulo,
SP, Brazil; Email: luciana.cavalcanti@ifsertao-pe.edu.br
Suzimara Rovani − Instituto de Pesquisas Energéticas e
Nucleares (IPEN-CNEN/SP), CEP: 05508-000 São Paulo,
SP, Brazil; orcid.org/0000-0002-7802-1050;
Email: suzimara.rovani@ipen.br, suzirovani@gmail.com
Authors
́ Biomaterials. Carbohydr. Polym. 2018, 179, 93−99.
Jonnatan J. Santos − Instituto de Quimica, Universidade de São
Paulo, CEP: 05508-000 São Paulo, SP, Brazil; orcid.org/
0000-0003-3789-6229
Djalma B. Dias − Instituto de Pesquisas Energéticas e Nucleares
(IPEN-CNEN/SP), CEP: 05508-000 São Paulo, SP, Brazil
Sandi S. Nascimento − Department of Food Technology,
Federal Institute - IF SERTAO-PE, CEP: 56314-520 Petrolina,
Pernambuco, Brazil
Fábio F. Oliveira − Departamento de Ciências Agrárias/Solos,
Federal Institute - IF SERTAO-PE, CEP: 56302-970 Petrolina,
Pernambuco, Brazil
Leonardo G. A. Silva − Instituto de Pesquisas Energéticas e
Nucleares (IPEN-CNEN/SP), CEP: 05508-000 São Paulo,
SP, Brazil
Denise A. Fungaro − Instituto de Pesquisas Energéticas e
Nucleares (IPEN-CNEN/SP), CEP: 05508-000 São Paulo,
SP, Brazil
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsapm.0c00124
Notes
The authors declare no competing financial interest.
2167
■
pubs.acs.org/acsapm Article
ACKNOWLEDGMENTS
This study was financed in part by the Coordenaçaõ de
Aperfeiçoamento de Pessoal de Nivel ́ Superior - Brazil
(CAPES) - Finance Code 001, in part by the Conselho
́ e Tecnológico - Brazil
Nacional de Desenvolvimento Cientifico
(CNPq), and in part by the Fundaçaõ de Amparo à Pesquisa
do Estado de São Paulo - Brazil (FAPESP). The authors also
are grateful to COSAN S.A. (São Paulo, Brazil) for supplying
the sugarcane waste ash.
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