A. de La Luz Ramos

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MRS Advances © The Author(s), 2020, published on behalf of Materials

Research Society by Cambridge University Press
DOI: 10.1557/adv.2020.377
Structural, thermal and morphological

studies of bio-based straws under aerobic
degradation process
A. De la Luz Ramos1, G. Pineda Flores1*, D. Palma-Ramírez1**, H. Dorantes-

Rosales2
1
Instituto Politécnico Nacional, Centro Mexicano para la Producción más Limpia
(CMPL), Av. Acueducto S/N, La Laguna Ticomán, C. P. 07340, Mexico City, Mexico.
2
Instituto Politécnico Nacional, ESIQIE, Departamento de Metalurgia, C.P 07300,
Ciudad de México, Mexico
ABSTRACT
https://www.cambridge.org/core/terms. https://doi.org/10.1557/adv.2020.377
The environmental problems caused by the persistence and improper disposal of single
use plastics, have led the worldwide authorities to migrate into a sustainable production
of bio-based materials, whose components need to be studied for proving their nature and
to confirm their degradability. For this reason, the identification and monitoring
degradation of five single use straws were assessed through FT-IR, TGA/DTA and SEM
techniques which demonstrate that the straws tagged as biodegradable contain polymers
of fossil origin in their formulation. Degradation of them was found to be influenced by
polar groups, such as ester and glycosidic bonds of the biodegradable phase. The thermal
stability decreased and the morphological characteristics as cracks and holes were
detected after biodegradation.
Corresponding authors: E-mail*gpineda@ipn.mx ** dpalmar@ipn.mx
1
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INTRODUCTION
The amount of plastic waste derived from long-lasting polymers has been
estimated to be c.a. 300 million Tons in the world provoking [1] serious environmental
problems caused by their improper disposal and persistence. For example, if they are
either burnt or dumped in landfills, can generate pollutants and to release toxic substances
in the ground and water reservoirs [2]. Similarly, it exists a great problem when plastics
are fragmented into microplastics in marine environments affecting the wildlife by
trapping, ingestion or habitat destruction and ecotoxicity [3]. This has led to the
worldwide authorities to implement several strategies such as either taxes and bans or
through of migration into a sustainable production to avoid those problems.
Mexico is reviewing its waste management laws and policies [4]. Now, it is
intending to implement the ban of single-use plastic for 2021, including bags, trays, coffee
capsules, balloons, cutlery, glasses and straws. As stated by O. H. Lara , it is necessary to
consider the plastics that are beneficial to a healthy society and those that are detrimental
as well as to consider the composition of polymers to be used to ensure the recyclability,
technical compatibility with closed loop systems [4]. In this context, it is of high
importance to have a state of the art of those products that are being commercialized in
the country.
Specifically, the fossil-based straws are considered as either single-use or
disposable and their improper disposal in conjunction with the slow degradation, which is
typically reported over 100 years, have made them a controversial product; they are
considered in the top 10 plastic items that are polluting the world´s seas and coasts. Then,
the industry has started to use and even to import several raw materials obtained
apparently from natural resources to produce ecofriendly products. The majority of straws
in the market are tagged as 100 % biodegradable and there are few studies confirming it.
For this reason, there is a need for carrying out the researcher to prove the nature of the
products, i.e. fossil, 100 % or partially biodegradable (bio-based), to confirm the
degradation time/percentage as well as to document under what conditions are
decomposed.
As known, two types of degradability can be considered in the plastic field.
The first is the ultimate degradability, which is associated to the degradation starting with
the action of the extracellular enzymes in the macromolecules obtaining oligomers
(known as primary) and then these molecules are taken into the microbial cell and
decomposed into carbon dioxide and water [5]. The second is the weight-loss
degradability that does not consider the ultimate decomposition but so the sum of the
primary and the ultimate [6]. To determinate the extent of biodegradation, the structural,
thermal and morphological performance related to the physical and chemical changes in
the polymer backbone is required [7].
The aim of this work is to determinate if the nature of selected-commercial
straws is of renewable resources, as they are labeled, and to analyze the degradability to
known their features before being composted. Here, the study of five common and tagged-
biodegradable straws used in the market are taken into account to evaluate their nature,
their identification and the biodegradability features through aerobic conditions by the
weight loss method. Fourier Transform Infrared (FT-IR) spectroscopy,
thermogravimetric/differential thermal analysis (TGA/DTA) and visualization under
Scanning Electron Microscopy (SEM) are discussed in structural, thermal and
morphological terms related to the type of plastic straws.
2
EXPERIMENTAL PROCEDURE
Five commercial straws were acquired from different suppliers dedicated to

either production or marketing of them. These products are tagged and identified as 1)
disposable straw based on biodegradable paper 2) polylactic acid green plastic 3)
biodegradable containing 15 to 60 wt.% of biopolymers from corn 4) biodegradable
containing 60 wt.% of biopolymers from avocado seed and 40 wt.% of synthetic organic
compounds and 5) polypropylene.
Samples of 4 cm in length were cut and dried at 60°C for 12 h in an oven
(Nade Scientific, model 9030). In order to identify the type of polymer used for the
fabrication of each straw, samples were structurally characterized in a Fourier Transform
Infrared (FT-IR) Spectrometer (Perkin Elmer, model Frontier) equipped with an
Attenuated Total Reflectance accessory (ATR) in the 4000-650 cm-1 interval using 4
scans. Also, simultaneous thermogravimetric/differential thermal (TGA/DTA) analysis
was performed in a thermal analyzer (PerkinElmer, model STA600) using alumina
crucibles under argon atmosphere. The amount used was ~ 10 mg. Samples were firstly
heated at 40 °C and hold for 2 min, then, analyzed from 30°C to 600°C with a heating rate
10°C/min. After, they were maintained at 600 °C for 2 min followed by cooling at the
same rate.
The morphological features were analyzed through Scanning Electron
Microscopy (SEM) in a JEOL microscope (model JSM 6701F) operating at 5 kV. Before
performing the measurements, samples were coated with an Au-Pd film. Weight loss
method was used to evaluate the biodegradation under aerobic conditions. Samples of 1
cm, in length and triplicate, were weighed and buried in a recipient with soil (15 g, sieved
at ~2380 µm and 18 wt.% of moisture) which were introduced in a natural convection
incubator (EQUIPAR, model IN450) at 20°C for 12 weeks with a period of irrigation
from 15 to 20 days, according to visual observations of soil conditions (2.805 ml). After
12 weeks, every sample was weighed and analyzed by its structural and thermal stability
as well as morphological and visual features through the same techniques, i.e. FT-IR,
TGA/DTA and SEM measurements.
RESULTS AND DISCUSSIONS

The nature of polymers of each straw was related through the association of its
functional groups detected in FT-IR spectra. The assignments are recorded in Table I and
the FT-IR spectra are shown in Figure 1a-e. The following assignments were identified in
the straws spectra: hydroxyl stretching groups between 3600 and 3100 cm -1, OH bending
(in plane) at 1335 cm-1, CH asymmetric stretching at 2894 cm-1, CO stretching at 1640
cm-1, CH2 symmetric bending at 1430 cm-1, CH2 wagging at 1316 cm-1, COC asymmetric
stretching at 1160 cm-1, CO antisymmetric stretching at 1104 cm-1 , β-(1,4) glycosidic at
897 cm-1 and CH2 rocking at 712 cm-1 (1st straw, Figure 1a) [8]. CH3 symmetric stretching
at 2919 cm-1, CH asymmetric stretching at 2996 cm-1, C=O symmetric stretching at 1750
cm-1, CO stretching at 1180 cm-1, CH3 symmetric bending at 1383 cm-1, COO stretching at
1267 cm-1, COC symmetric stretching at 1207 cm-1, COC stretching at 871 cm-1 and CH3
rocking as well as stretching CC at 956 cm-1 (2nd straw, Figure 1b) [9]. OH stretching at
3335 cm-1, CH stretching at 2912 cm-1, C=O stretching at 1754 cm-1, CH symmetric
bending at 1383 cm-1,CO stretching at 1079 cm-1 and α-1-4 glycosidic bond at 930 cm-1
(3rd straw, Figure 1c) . OH stretching at 3325 cm-1, CH stretching at 2916 cm-1, C=O
stretching at 1645 cm-1, CH2 bending at 1471 cm-1, CO bond stretching at 1017 cm-1 and
3
1-4 glycosidic at 930 cm-1 (4th straw, Figure 1d) [10]. CH3 asymmetric stretching at 2949
cm-1, CH2 symmetric bending at 1455 cm-1, CH3 symmetric bending at 1375 cm-1 and CH3
rocking at 1167 cm-1 (5th straw, Figure 1e) [11]. From these observations, straws were
recognized as 1) cellulose (biodegradable), 2) polylactic acid (PLA) (biodegradable), 3)
corn starch/polypropylene (PP) (partially biodegradable), starch/polyester (partially
biodegradable) and PP (fossil).
a)100 b)100 c)
100
Transmittance (%)
Transmittance (%)
Transmittance(%)
90
CH2
90
OH 90
OH
80 80 80
OH C=O
70 70 70
60
C=O 60 CH
60
50 50
50
Beginning
COC
40 Beginning 40 Beginning C=O
40 Week 12 COC Week 12
4000 3500 3000 2500 2000 1500 1000
30 Week 12 30 COC
4000 3500 3000 2500 2000 1500 1000 4000 3500 3000 2500 2000 1500 1000
Wavenumber (cm-1) Wavenumber (cm-1) Wavenumber (cm-1)
d)100 e)
100
Transmittance (%)
Transmittance (%)
90
C=O 90
80
70 OH CH2 80
60 70 CH3
50 CH 60
CH2
Beginning Beginning
40
CO 50 CH3 Week 12
30
Week 12
4000 3500 3000 2500 2000 1500 1000 4000 3500 3000 2500 2000 1500 1000
Wavenumber (cm-1) Wavenumber (cm-1)
Figure 1. FT-IR spectra of a-b) biodegradable, c-d) partially biodegradable and e) fossil straws before
and after being subjected to aerobic degradation by 12 weeks.
Table I. FT-IR assignments corresponding to the straw’s spectra

Straw 1 Straw 2 (cm-1) Straw 3 Straw 4 Straw 5
Functional (cm-1) (cm-1) (cm-1) (cm-1)
group
OH ν 3329 --- 3335 3325 ---
CH3 --- 2919 --- --- 2949
CH ν 2894 2996 2919 2916 ---
C=O ν --- 1750 1754 1645 ---

CO ν 1640 1180 1181 --- ---
CH2 δ 1430 --- --- 1471 1455
CH3 δ --- 1383 --- --- 1375
CHδ --- --- 1383 --- ---
OH ν 1335 --- --- --- ---
CH2ω 1316 --- --- --- ---
COO ν --- 1267 --- --- ---
COC ν 1160 1207 --- --- ---
871
CO ν 1104 --- --- --- ---
CH3 ρ --- 956 --- --- 1167
α- (1,4) --- --- 930 930 ---
glycosidic
β - (1,4) 897 --- --- --- ---
glycosidic
COC ν --- --- 871 --- ---
carbohydra
te ring
4
CH2 ρ 712 --- --- --- ---

Starch/
Identificati Poly(lactic Starch/ Poly(propylen
Cellulose Poly(propyl
on Acid) Polyester e)
ene)
Additionally, to the structural features, the thermal stability through the

decomposition temperatures and weight loss % of the straws were identified by
TGA/DTA results. Figure 2a-e show the curves of the weight loss % and DTA vs
temperature of straws. The straw identified as cellulose (Figure 2a) displays its first
weight loss (3.5 %) from 100 °C to 281 °C which is due to the evaporation of moisture
adsorbed (DTA peak at 105 °C) as well as to dehydration process involving the splitting
off of a hydroxyl group and of a hydrogen between two hydroxyl groups to form water
(DTA peak at 200 °C). The second stage (weight loss % of 73.5 %) and the most
significant weight loss starting at 300 °C while finishing at 400 °C (DTA peak at 350 °C)
has been related to the formation of aldehydes, aromatic compounds, ketones, alkanes and
alkenes. This step is followed to charring [12].
a) Cellulose b)120 Polylactic Acid

100 2.0 2.4
100
2.0
Weight loss (%)
Weight loss (%)
80 1.6
80 Beginning
Week 12 1.6
Delta T
1.2
60
60
0.8 1.2
40 40
0.4 0.8
20 20
Beginning 0.0 0.4
Week 12 0
0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Temperature (°C) Temperature (°C)
Starch/Polypropylene
c) 2.4 d)100 Starch/Polyester
100 2.4
Beginning 2.0
Weight loss (%)
80 2.0
Weight loss (%)
80
Week 12
1.6
1.6
Delta T
60 60
Delta T
1.2 1.2
40 40 Beginning
0.8 Week 12 0.8
20 20
0.4 0.4
0
0
0.0 0.0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Temperature (°C) Temperature (°C)
e) Polypropylene
2.8
100
2.4
Beginning
Weight loss (%)
80 2.0
Week 12
60 1.6
Delta T
1.2
40
0.8
20
0.4
0 0.0
0 100 200 300 400 500 600

Temperature (°C)
Figure 2. TGA/DTA curves spectra of straw before and after being subjected to aerobic degradation
by 12 weeks.
5
Similarly, the TGA/DTA curves of PLA straw in Figure 2b show two main
decomposition stages in the 260-350 °C (DTA peak at 335 °C) and 355-470 °C (DTA
peak at 390 °C) ranges with a weight loss of 86.7 % and 8.05 %, respectively; these
signals have been previously reported and associated to the lactide and methyl ketene
compounds releasing before obtaining the CO2 [13]. On the other hand, partially
biodegradable based on corn starch/PP (Figure 2c) showed a decomposition with two
main stages, one from 237°C to 400 °C losing 76.96 % (DTA peak at 365 °C) and the
second with a weight loss of 19.52 % from 400 °C to 475 °C (DTA peak at 450 °C); two
DTA peaks are also evident at 150 °C and 210 °C which could be of some plasticizers.
The starch/polyester (Figure 2d) is also decomposed through two stages in the 150 °C-300
°C (18.33 %, DTA peak at 230 °C), 300-326 °C (10.47 %, DTA peak at 310 °C), 330-500
°C (37.49 %, DTA peak at 470 °C) ranges corresponding to simple polysaccharides,
larger size protein fractions and complex polysaccharides, respectively. Finally, the fossil
straw in Figure 2e displays the typical degradation behavior of PP starting at 300 °C and
ending at 460 °C with a weight loss of 99.92 % (DTA peak at 425 °C).
Once the polymer type and the thermal transitions were identified, the straws
were subjected to degradation under aerobic conditions after twelve weeks, then, the
functional groups and the thermal decomposition were once again analyzed by obtaining
the FT-IR spectra and TGA/DTA thermograms. Results are included in Figure 1 and 2.
The main changes in cellulose straw (biodegradable) were the decrease of intensity of
OH, CO, COC, CC, CH2 and β-(1,4) glycosidic link bands and the appearance of a new
band corresponding to C=O (ester stretching 1730 cm-1). The PLA straw (biodegradable)
had changes only in the intensity of the bands, the C=O and COC, and in the presence of a
new arising OH band. The starch/PP straw spectrum maintained almost intact its CH2
bands of the fossil polymer with no appearance of the OH groups. In this case, the main
damage due to degradation were done in the COC and C=O bands of the biodegradable
phase since there was a reduction in intensity of them. In the starch/polyester straw
spectrum the following features in intensity were observed: 1) decrease of OH bands, 2)
increase of C=O and 3) no changes in the CH which are related to the no degradation of
the fossil part. From these results is evident that the degradation straws are mainly in
either ester or glycosidic bond. If the straw is partially biodegradable, the fossil polymer
did not change significantly after twelve weeks. This is confirmed in the fully fossil PP
straw shown in Figure 1e, in which, there is almost no evidence of changes in its
functional group bands.

The thermal stability of the straw was also modified after being degraded.
Cellulose display no degradation temperature and higher wt.% at the end due to the soil
particles incrusted in it (Figure 2a). The reduction in stability of PLA straw is
demonstrated in the TGA/DTA curves since it exists a loss in stability of ~ 38 °C (DTA
peaks at 290 °C) (Figure 2b). Starch/PP (Figure 2c) apparently only showed the
transitions of the fossil part since there is an improvement in the stability of ~ 60 °C (DTA
peak at 430 °C). On the contrary, the DTA peak of biodegradable phase disappears
remaining only the fossil at 470 °C in the starch/polyester straw; the stability in this case
is improved by 130 °C (Figure 2d). Finally, the PP straw did not show a significant
change after this process since it has the same DTA peak at 425 °C (Figure 2e).
The evolution of weight loss % under aerobic degradation is shown in Figure
3. According to the results, the straws percentage of biodegradation is c.a. 86.25 wt. %
(cellulose), 1.078 wt. % (PLA), 2.81 wt. % (starch/PP), 26.55 wt. % (starch/polyester) and
0.64 wt. % (PP). PLA, starch/PP and PP straws displayed a gain in wt.% after the 8th week
which could be due to the humidity and soil present in them. The following order in
degradation was obtained: cellulose > starch/polyester> PP> PLA > starch/PP.
6
250
Cellulose
Starch/Polyester
200 PP
PLA
Weight loss (%) Starch/PP
150
100
50
0
0 4 8 12
Week
Figure 3. Weight loss (%) evolution at 4th, 8th and 12th weeks of anaerobic degradation
The morphological features of selected samples (PLA, starch/PP and

starch/polyester) were assessed by SEM analyses. Results are shown in Figure 4, which
are described below. The surface morphology of PLA shows a smooth surface with some
cracks that favor the biodegradation process (Figure 4a). After 12 th week, there is the
presence of some holes as well as particles whose origin could be from the same polymer
and soil (Figure 4b). Corn starch/PP also presented a smooth surface with spherical
particles that could come from the starch the polymer, which are not visible at the end of
the test, and apparently are replaced by others coming either from the material or the soil
(Figure 4c-d). Avocado starch/Polyester shows a smooth surface with few porous (Figure
4e) but after being degraded the surface became rough with the presence of fibers and
loose globular particles suggesting the possible biodegradation of the straw. These
features have been previously reported in polymer degradation [14].
Figure 4. SEM micrographs of a-b) PLA, c-d) starch/PP and e-f) starch/ polyester before and after
being subjected to biodegradation
7
CONCLUSIONS
The assignation of functional groups and decomposition temperatures of the

straws allowed to identify the type of polymers used in their fabrication as well as if they
were from either renewable or fossil nature. Some of the straws that were commercially
tagged as biodegradable were found to be a mixture of biodegradable and non-
biodegradable resources (starch/PP and starch/polyester). There was only detected two of
them that meet the biodegradable tag (cellulose and PLA). From the aerobic
biodegradation test, the main structurally and thermally changes less stable were found in
those in bio-based straws (cellulose, PLA) which is directly related to the presence of
ester and glycosidic bonds. These samples showed degradation features such cracks and
holes after twelve weeks. Then, this work highlights the importance to study the single-
use products, such as the straws, which are tagged as biodegradable in order to have a
better understanding before being composted.
ACKNOWLEDGEMENTS
Andrea de la Luz Ramos is grateful for her postgraduate fellowship through

CONACyT. Authors are also grateful for the financial support provided by the Instituto
Politécnico Nacional through the SIP20201565 and SIP20200909 projects as well as SNI-
CONACyT.
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MRS Advances © The Author(s), 2020, published on behalf of Materials

Structural, thermal and morphological

A. De la Luz Ramos1, G. Pineda Flores1*, D. Palma-Ramírez1**, H. Dorantes-

Corresponding authors: E-mail*gpineda@ipn.mx ** dpalmar@ipn.mx

Five commercial straws were acquired from different suppliers dedicated to

RESULTS AND DISCUSSIONS

Table I. FT-IR assignments corresponding to the straw’s spectra

C=O ν --- 1750 1754 1645 ---

CH2 ρ 712 --- --- --- ---

Additionally, to the structural features, the thermal stability through the

a) Cellulose b)120 Polylactic Acid

0 100 200 300 400 500 600

functional group bands.

The morphological features of selected samples (PLA, starch/PP and

The assignation of functional groups and decomposition temperatures of the

Andrea de la Luz Ramos is grateful for her postgraduate fellowship through

[1] T. M. Karlsson, L. Arneborg, G. Broström, B. C. Almroth, L. Gipperth,

[10] T. Tesfaye, M. Gibril, B. Sithole, D. Ramjugernath, R. Chavan, V.

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