Carbohydrate Polymer Technologies and Applications

Effectiveness of alkaline and hydrothermal treatments on polysaccharide fibers

extracted from the Moroccan  Pennisetum Alopecuroides plant : chemical
and morphological characterization
--Manuscript Draft--

Manuscript Number: CARPTA-D-22-00157R1

Full Title: Effectiveness of alkaline and hydrothermal treatments on polysaccharide fibers

extracted from the Moroccan  Pennisetum Alopecuroides plant : chemical
and morphological characterization

Article Type: Research Paper

Keywords: Vegetal fibers * fibers treatment * fiber characterization * surface properties

Abstract: This work aims to study the physical, chemical, and thermal properties of natural fibers
extracted from the Pennisetum alopecuroides plant. The study was carried out on raw
and treated fibers to assess improvements that facilitate future uses in composites.
The alkaline treatment was carried out using NaOH with different concentrations (1, 3,
5, and 10%) for 2 hours. Hydrothermal treatment was performed at different immersion
times in a water bath at 100 °C. The chemical composition of Pennisetum
alopecuroides fibers, such as cellulose, hemicellulose, lignin, and ash contents, was
evaluated. The structure of the fiber was analyzed by FTIR, SEM, and X-ray diffraction.
Thermogravimetric analysis (TGA) is used to study the thermal stability of the fiber.
The density was also investigated with the pycnometric methode. The results showed
that a concentration of 3% NaOH during the 2h is the most suitable solution to treat the
P.alopecuroides fiber, but the hydrothermal treatment for 1h at 100 °C is also effective
for this fiber. The treated fibers seem viable to be used as reinforcement for
composites production, namely to achieve goals of energy efficiency.

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Detailed Response to Reviewers

Cover letter
18.11.2022

Dr John F Kennedy,
Editor-in-Chief
Carbohydrate polymer technologies and applications
Manuscript ID : CARPTA-D-22-00157
Dear Dr John F Kennedy on behalf of all the author, I am submitting a revision of the manuscript titled
Effectiveness of alkaline and hydrothermal treatments on polysaccharide fibers extracted from the
Moroccan Pennisetum Alopecuroides plant: chemical and morphological characterization for
publication in Carbohydrate polymer technologies and applications.
The authors would like to thank the reviewers for their time and valuable comments.
Please see below, in blue, the response to the reviewers’ comments and concerns.

Hicham Elmoudnia
Phd student
+212670993068
University of Cadi Ayyad, Matériaux Innovants, Énergie et Développement Durable (IMED-Lab),
40000 Marrakech, Morocco
Hicham.elmoudnia@ced.uca.ma (Corresponding author)

Editor and Reviewer Comments:  

I need a polysaccharide name in the title please to be able to process your paper.

Authors’ Response : Thank you for the suggestion, we have made changes in the title of revised
version (page 1, line no. 1).
Revised manuscript clean version Click here to view linked References

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4 1 Effectiveness of alkaline and hydrothermal treatments on polysaccharide fibers extracted from the
5 2 Moroccan Pennisetum Alopecuroides plant : chemical and morphological characterization
6
7 3 Hicham Elmoudnia1⁎ · Paulina Faria2 · Rachid Jalal1 · Mohamed Waqif1 · Latifa Saâdi1
8
9 4 1
Department of chemistry, Faculty of Sciences and Technology, Cadi Ayyad University, Marrakech,
10 5 Morocco.
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12 6 2
Department of Civil Engineering, NOVA School of Science and Technology, NOVA University of
13
14
7 Lisbon, Lisbon, Portugal
15 ⁎
8 Corresponding authors.
16
17 9 E-mail address : hicham.elmoudnia@ced.uca.ma (H. Elmoudnia)
18
19 10 Abstract :
20
21 11 This work aims to study the physical, chemical, and thermal properties of natural fibers extracted from the
22 12 Pennisetum alopecuroides plant. The study was carried out on raw and treated fibers to assess improvements
23
24 13 that facilitate future uses in composites. The alkaline treatment was carried out using NaOH with different
25 14 concentrations (1, 3, 5, and 10%) for 2 hours. Hydrothermal treatment was performed at different immersion
26 15 times in a water bath at 100 °C. The chemical composition of Pennisetum alopecuroides fibers, such as
27 16 cellulose, hemicellulose, lignin, and ash contents, was evaluated. The structure of the fiber was analyzed by
28 17 FTIR, SEM, and X-ray diffraction. Thermogravimetric analysis (TGA) is used to study the thermal stability
29
30 18 of the fiber. The density was also investigated with the pycnometric methode. The results showed that a
31 19 concentration of 3% NaOH during the 2h is the most suitable solution to treat the P.alopecuroides fiber, but
32 20 the hydrothermal treatment for 1h at 100 °C is also effective for this fiber. The treated fibers seem viable to
33 21 be used as reinforcement for composites production, namely to achieve goals of energy efficiency.
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35
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37 22 Keywords vegetal fibers · fibers treatment · fiber characterization · surface properties
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39
40
41 23 1. Introduction :
42
43 24 In recent years, the use of natural fibers as reinforcements for various materials has attracted the attention
44 25 of several researchers (Khoudja et al., 2021; Omrani et al., 2020). The use of natural fibers as reinforcements
45 26 in various matrices to replace commercially available synthetic fibers is mainly due to environmental factors
46
47
27 and marginal costs (Sanjay et al., 2018).
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28 Plant-derived natural fibers have great potential for use in the plastic, automotive, and packaging industries
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50 29 (Arthanarieswaran et al., 2015; Lau et al., 2018; Ravindran et al., 2020), as well as in the construction
51 30 industry (Nunes et al., 2021). Depending on the fibers, they may have excellent characteristics such as low
52 31 density, high specific stiffness, good mechanical properties, biodegradability, being environmentally
53 32 friendly, toxicologically harmless, and contributing for good thermal and acoustic insulation (Ridzuan et
54
33 al., 2016). Plant fibers are composed of celluloses, hemicelluloses, and lignin. Other components are in
55
56 34 small amounts, such as lipids, proteinaceous materials, and mineral materials. The proportion of these
57 35 components depends strongly on the species, climatic conditions, and the plant organ (Yang et al., 2007a).
58
59 36 The main problems with the use of lignocellulosic fibers as reinforcement in mineral or organic matrices
60 37 are the risk for biological colonisation (Cintura et al., 2022) and degradability, and compatibility with the
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4 38 matrices. Particularly the latter remains a weak point. Several treatments have been done to solve this
5 39 problem to improve the compatibility of the fiber/matrix interface and thermal stability. Different chemical
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7 40 and physical treatments of natural fibers have been analyzed in several studies to assess the different
8 41 physical-chemical properties obtained. One of the most used treatments is the alkaline treatment or
9 42 mercerization, which consists of treating the plant biomass in an alkaline solution to remove lignin,
10 43 hemicellulose, waxy substances, and natural oils that coat the outer surface of the fiber cell wall (Cai et al.,
11 44 2015; Faruk et al., 2012). (Pandiarajan et al., 2022) studied the effect of alkali treatment on Thespesia
12
13 45 populnea fiber with 1% sodium hydroxide (NaOH) for a duration of 1h, showing that the crystallinity index
14 46 increased from 41% to 65%. The thermal stability of the fiber was increased from 210 °C for the untreated
15 47 fiber to 230 °C for the fiber treated with NaOH. (Singh et al., 2022) treated corn leaf fibers with NaOH
16 48 solution at different concentrations ranging from 5 to 15% for 90 min at 80 °C and 90 °C, respectively.
17
49 Fourier transform infrared spectroscopy (FTIR) results and chemical composition confirmed the removal of
18
19 50 hemicellulose and lignin and the alkaline treatment at 15% and 90 °C was considered the optimal treatment
20 51 for this fiber. (Umashankaran & Gopalakrishnan, 2021) conducted a study on the chemical modification of
21 52 Pongamia pinnata (L.) fiber with 5% NaOH solution for different immersion times (15, 30, 45, 60, and 75
22 53 min). It was found that the 5% NaOH treatment for 60 min improved the crystallinity index (from 45% to
23
54 52%). The tensile strength and Young's modulus of the modified fiber increased from 322 MPa to 344 MPa,
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25 55 10 GPa to 13 GPa, respectively.
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27 56 Pennisetum alopecuroides, is a member of the grass family (Poaceae) and is native to Africa (1913).
28 57 Centuries ago, this plant was introduced as animal feed in South America, Asia, and Australia. In Morocco,
29 58 this plant grows everywhere with important quantities in the cities at the roadside, and can reach heights up
30 59 to 2 m. Every year the maintenance of public green spaces generates enormous quantities of P.alopecuroides
31 60 plants which are generally rejected in the free surfaces of the city. This cellulose-rich waste could be
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33 61 exploited either as a base material, as reinforcement for composites, or in the elaboration of insulating
34 62 materials. To the authors knowledge, no study has been conducted on the chemical, morphological and
35 63 physical characterization of the Moroccan P.alopecuroides fiber for its application in the field of
36 64 biocomposites, such has been done to other vegetal wastes (de Andrade Silva et al., 2008). It is in this
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65 perspective that the objective of this study lies. Fibers were extracted from the harvested P.alopecuroides
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39 66 and physicochemical analyses before and after chemical treatments were performed to assess the effect and
40 67 optimize the treatment. The aim is to improve the surface adhesion to a matrix, to increase its potential for
41 68 being used as raw material for the manufacture of composites, namely insulating boards for buildings and
42 69 other industries, to contribute for eco-efficiency.
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44 70 2. Materials and methods
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46 71 2.1 Fibers and treatments
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48 72 The leaves of the P.alopecuroides (PA) plant used in this study were harvested after manual pruning from
49 73 the green spaces of the city of Marrakech, Morocco. Afterward, the leaves were washed several times with
50 74 distilled water and dried in an oven at 60°C for 24 h. They were then manually cut to a length of about 5 cm
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52 75 for further use.
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76 Chemical treatments (alkaline and hydrothermal) of the prepared fibers were performed to modify the
55 77 surface and prepare them to have a good adhesion to a matrix.
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4 78 Alkaline treatment :
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7 79 Alkali treatment of natural fibers is expected to promote the ionization of hydroxyl groups to alcohols to
8 80 improve mechanical properties (Ariawan et al., 2020). The treatment was performed with 1%, 3%, 5%, and
9 81 10 wt% NaOH solution, with a solution ratio of 1:25 (w/v) at room temperature for 2 h to remove
10 82 hemicellulose and surface contaminants (Fig.1). Finally, a 1 wt% acetic acid solution was used to neutralize
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83 the fibers immerging them during 5 min, followed by immersion in distilled water. The fibers were then
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13 84 dried in an oven at 60°C for 24 h.(Indran & Raj, 2015)
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46 85 Fig.1. PA fiber extraction process and after NaOH treatment: in nature, cut stem, alkaline treatment, oven
47 86 dried after NaOH treatment and after being crushed
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52 87 Hydrothermal treatment :
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54 88 The treatment was performed according to the protocol described by (Ajouguim et al., 2019). The P.
55 89 alopecuroides fibers were immersed in boiling water at 100°C temperature for the different duration of
56 90 15min, 30min and, 60min. The treated fibers were washed with distilled water and dried at room temperature
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91 for 48 h.
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4 92 After chemical treatment, the raw and treated fibers were ground with an electric mill (Lamacom, model
5 93 BL0153) for characterization.
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9 94 2.2 Characterization techniques
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11 95 2.2.1 Chemical analysis :
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13 96 - Cellulose content :
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97 The cellulose content of the untreated and chemically treated fibers was analyzed by the method of
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16 98 Kushner and Hoffer (Sanjay et al., 2018). The fibers were soaked in a mixture of nitric acid and ethanol
17 99 (HNO3-C2H5OH) with a ratio of 1:4 for 4 h. The samples were then dried in an oven at 60 °C to a constant
18 100 weight. Cellulose content is calculated based on equation 1 :
19
20 W2
21 101 %cellulose   100 (1)
W1
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24 102 being W1 the mass of the fibers before treatment and, W2 after treatment.
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26 103 - Lignin content :
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28 104 The lignin content was estimated according to the ASTM D 1106-96 standard method. The fibers were
29 105 submitted to a treatment with an ethanol-toluene mixture with a ratio of 1:2 by a soxhlet apparatus during
30 106 8h and their mass was assessed.1g of the fibers recovered after treatment with the ethanol-toluene mixture
31 107 was stirred in 15 mL of a 72% sulfuric acid solution (H2SO4) for 2 h. Afterward, 560 mL of distilled water
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108 is added and the mixture is boiled for 4 h. After this hydrolysis, the residue is filtered by vacuum suction
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34 109 and then washed with 500 mL of hot water to remove all traces of acid, and oven-dried at 103±2 °C for 2 h.
35 110 The percentage of extracted lignin can be calculated using the equation 2 :
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W2
37
111 %lignin   (100  W3 ) (2)
38 W1
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40
112 being W1 and W2 the masses of PA fibers before and after treatment, and W3 the mass obtained after the
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42 113 solubility test of the fibers in the ethanol-toluene mixture (%).
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44
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46 114 - Hemicellulose content :
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48 115 Hemicellulose content was determined according to the protocol adopted by Boopathi (Boopathi et al.,
49 116 2012). PA fibers were immersed in a 5% NaOH solution at room temperature for 30 min and then neutralized
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117 with HCl solution. Finally, the fibers were dried in an oven at 105 °C for 2 h. The difference in weight
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52 118 provides the hemicellulose content by equation 3 :
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54 119 %Hemicellulose  (W1  W2 ) 100 (3)
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56 120 being W1 and W2 the masses of the fibers before and after treatment.
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4 121 2.2.2. Physical analysis :
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122 - Diameter and density
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9 123 The diameter of the P.alopecuroides fiber was determined by a digital caliper with an accuracy of 0.001
10 124 mm. Twenty samples were examined and the average diameter was reported. Density was determined
11 125 following the ASTM D578-89 standard method with toluene (866 kg/m3) as the immersion liquid. Fiber
12 126 density was calculated using equation (4) :
13
14 m2  m1
15 127  PA  ( ) toluène (4)
16 (m3  m1 )  (m4  m2 )
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18 128 being m1 the mass of the empty pycnometer (g), m2 the mass of the pycnometer filled with the PA fiber (g),
19 129 m3 the mass of the pycnometer filled with toluene (g) and, m4 the mass of the pycnometer filled with the PA
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21
130 fiber and toluene (g).
22 131
23 132 - Scanning electron microscopy :
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25 133 The morphology of P.alopercuroides fibers before and after treatment was examined using a JEOL JSM-
26 134 5500 (VEGA3 TESCAN) scanning electron microscope equipped with an EDAX detector. To determine
27 135 the atomic percentage of the present elements on the surface of the raw fiber, the energy dispersive X-ray
28 136 spectroscopic technique (SEM-EDX) was used. Before analysis, all samples were coated with carbon using
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137 the sputtering technique (model 108carbon/A).
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32 138 2.2.3. Mineralogical analysis
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34 139 - X-ray diffraction (XRD) :
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36 140 The XRD tests were performed using a Philips X'Pert MPD diffractometer at 40 kV and 15 mA at room
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141 temperature. The anticathode was copper (Kα = 1.5418 Å). The scan angle (2θ) was between 5 and 75°. The
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39 142 treated and untreated fibers were placed on a stainless steel support. The crystallinity index of the PA fiber
40 143 was calculated using the Segal method (Segal et al., 1959) (Eq 5) :
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42 I 200  I am
43 144 I cr   100 (5)
I 200
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46 145 being I200 the maximum intensity of the spectrum (amorphous or crystalline) at 2θ = 22° and Iam the
47 146 minimum intensity of the amorphous part at 2θ = 18° (Hernandez et al., 2018).
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49 147 The Scherrer's formula was used to determine the crystallite size of the PA fiber (Eq 6) (Ahmed et al.,
50 148 2019).
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52 k .
149 Cs  (6)
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 .cos 
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55
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150 being K= 0.89 the Scherrer constant, λ the wavelength of the diffracting ray (Kα1 line), β the width at
57 151 half height of the peak (200) and θ the diffraction angle of the peak (200).
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59 152 The numerical values are λ= 1.54184 A° and 2θ=22.2° (French & Santiago Cintrón, 2013; Maache et al.,
60 153 2017).
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4 154 - FTIR infrared spectroscopy :
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155 The infrared spectra of raw and chemically treated P.alopecuroides were recorded using a Bruker Vertex 70
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8 156 Fourier transform infrared spectrophotometer in the wavelength range 4000-400 cm-1. For this purpose, 1
9 157 mg treated and untreated fibers was ground and mixed with 99 mg of KBr powder and the mixture was
10 158 compressed into plates for FTIR analysis.
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12 159 2.2.3. Thermogravimetric Analysis (TGA) :
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15 160 Thermal stability of P.alopercuroides fiber was performed using a Setaram Setsys 24 Discovery TGA
16 161 thermogravimetric analyzer. The raw fiber was grounded and 23 mg was placed in a platinum crucible and
17 162 heated in the temperature range of 25 °C to 800 °C at a rate of 10 °C per minute under a constant flow of
18 163 nitrogen, which provides an inert atmosphere during pyrolysis.
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22 164 3. Results and discussion :
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165 3.1 Morphological analysis :
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27 166 SEM observations were conducted on the longitudinal (Fig. 2a) and transverse (Fig.2b,c,d) sections of the
28 167 raw fibers. The surface of the longitudinal section (Fig. 2a) clearly shows a layer of wax and other impurities.
29 168 It justifies the need of removal of surface impurities from the fibers by proper chemical treatment to help
30 169 improving fiber adhesion to a matrix..
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32 170 Fig.2b,c,d shows the cross-section of PA fiber, in which the lumen, microfibrils, and cell walls are observed.
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171 They are visible due to the presence of amorphous constituents like hemicellulose, lignin, and wax which
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35 172 help in the formation of this hollow structure. This type of morphology has been observed for other natural
36 173 fibers like Citrullus lanatus climber, Agave Americana, and chloris barbata (Balasundar et al., 2018a; Khan
37 174 et al., 2022; Msahli et al., 2015).
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39 175 Water absorption is highly dependent on the size of the lumen. The larger the lumen and porous are the
40 176 fibers structure, the easier it is for the fiber to absorb more water, and better it is to promote penetration
41 177 when used as reinforcement in composites (Kamaruddin et al., 2021).
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35 178 Fig. 2. SEM micrographs of the longitudinal (a) and transverse section of the raw PA fiber at three
36 179 different magnifications: (b) higher, (c) lower, and (d) medium
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38 180 3.2. Chemical characterization
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40
41
181 The chemical compositions of the raw (untreated) P.alopecuroides fibers, after alkaline treatment with 3%
42 182 NaOH for 2 h at 25 ºC, after hydrothermal treatment in boiling water for 60 min, and of other plant fibers
43 183 from literature are presented in Table 1. The untreated P.alopecuroides fiber contains 40% cellulose,
44 184 29.5% hemicellulose, 19.66% lignin, 6.76% ash. The cellulose content of raw P.alopecuroides fiber is
45 185 close to that of Juncus effusus L fiber (Naili et al., 2017). Raw P.alopecuroides fiber contains a higher
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186 amount of hemicellulose and lignin compared to Agave Americana (15.67% and 4.85%, respectively
48 187 (Moshi et al., 2020) and Sansevieria cylindrica fiber (10.13% and 3.8%, respectively (Manimaran et al.,
49 188 2019).
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4 189 Table 1. : Physical properties and chemical composition of Pennisetum alopecuroides fiber in comparison
5 190 with other natural fibers :
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8
Fiber Chemical properties Physical properties XRD References
9
10
11 Cellulose Hemi Lignin Ash Diameter Density CI CS
(wt.%) cellulose (wt.%) (wt.%) (µm) (g/cm3) (%) (nm)
12 (wt.%)
13
14
15
P.alopecuroides
16 (raw) 40 29.5 19.66 6,76 80-200 0.87 49.14 0.49 In current study
17
PAA3
18 50 23 17.5 3.42 - - 60.02 - In current study
PAH60
19 45 27.2 18.3 4.24 - - 55.24 - In current study
Pennisetum
20 orientale 60.3 16 12.45 - 213.1 1.04 33.5 62.02 (Vijay et al., 2021)
grass
21
Cissus quadrangularis 82.73 7.96 11.27 - 770 - 870 1.220 47.15 31.55 (Indran & Raj, 2015)
22
stem
23
Phaseolus vulgaris 62.17 7.04 9.13 9.02 53.56 0.852 43.02 4.07 (Gurukarthik Babu et al., 2019)
24
25
Furcraea foetida 68.35 11.46 12.32 6.53 12.8 0.780 52.6 28.36 (Manimaran et al., 2018)
26
Chloris
27 barbata 65.37 10.23 9.32 2.52 180-200 0.634 50.29 - (Balasundar et al., 2018b)
Sansevieria
28 cylindrica 79.7 10.13 3.8 - 6-30 915 60 86 (Kathirselvam et al., 2019)
Borassus
29 fruit 68.94 14.03 5.37 - 241 .18 1.256 - - (Manimaran et al., 2019)
30
Agave Americana 68.42 15.67 4.85 - 126-344 1.200 - - (Moshi et al., 2020)
31
32
Albizia amara 64.54 14.32 15.61 4.1 - 1.043 - - (Senthamaraikannan et al., 2019;
33 Senthamaraikannan & Kathiresan, 2018)
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35
Azadiratcha indica 68.42 13.72 13.58 - - 0.740 - 2.75 (Maheshwaran et al., 2018)
36
37 Arabica
Acacia 68.1 9.36 16.86 - - 1.028 51.72 15 (Maheshwaran et al., 2018; Manimaran et
38 al., 2019)
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Perotis
40 indica 68.4 15.7 8.35 - - 0.785 48.3 15 (Prithiviraj et al., 2016)
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Juncus plant 40 21 29 4.41 3300 0.385 - - (Naili et al., 2017)
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4 191 3.3 Physical characterization
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6 192 The diameter of the PA fiber is compared to other lignocellulosic fibers, based in Table 1.
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8 193 The density of the raw PA fibers, measured by the pycnometer method, is equal to 0.97 g.cm-3. This value
9 194 represents one of the lowest values for a lignocellulosic fiber when compared to literature (Table 1); this
10 195 means that the PA fibers will be very useful for the fabrication of lightweight composites.
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12 196 The low density value between natural fibers occurs due to parameters such as extraction methods, the
13 197 presence of pores in the fibers, and environmental conditions (Belouadah et al., 2015; Sathishkumar et al.,
14 198 2013).
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18 199 3.4. Microstructural properties :
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20 200 3.4.1 Raw Pennisetum fibers
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22 201 Figures 3 and 4, represent the infrared spectrum and diffractometer of P.alopecuroides fibers in the raw
23 202 state, respectively. The infrared spectrum analysis shows a band at 3430 cm-1 corresponding to the O-H
24 203 stretching of α-cellulose (Ferreira et al., 2015; Jayaramudu et al., 2010). The two absorption bands at about
25 204 2922 cm-1 and 2853 cm-1 are attributed to the CH and CH2 stretching vibrations of cellulose and
26
27 205 hemicellulose (Ko et al., 2019; Sathishkumar et al., 2013). The absorption band around 1734 cm-1 can be
28 206 attributed to the C=O carbonyl stretching absorption of the ester group or carboxyl group in hemicellulose
29 207 (Bezazi et al., 2014; Morán et al., 2008; Prado & Spinacé, 2019; Reddy et al., 2014).
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51 208 Fig. 3. FTIR spectrum of the raw PA fibers
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26 209 Fig. 4. X-ray diffractogram of the raw PA fiber
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30 210 The significant band noted at 1639 cm-1 can be attributed to the aromatic ring (C=H) of lignin (Chakravarthy
31 211 et al., 2020), while a small band at 1515 cm-1 indicates C=C stretching of the lignin aromatic ring (De Rosa
32 212 et al., 2011; El Achaby et al., 2018). A band at 1460 cm-1 corresponds to the asymmetric bending of CH3 in
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34 213 the methoxyl group (Moosavinejad et al., 2019). The peak at 1320 cm-1 is attributed to the C-O groups of
35 214 the aromatic ring in polysaccharides (Maache et al., 2017).
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37 215 The bands located at 1162 cm-1 and 1250 cm-1 correspond to the antisymmetric deformation of C-O-C
38 216 (cellulose and hemicellulose) and the out-of-plane stretching vibration of the C-O of the aryl group,
39 217 respectively. (Ajouguim et al., 2019; Ibrahim et al., 2010; Saravanakumar et al., 2013).
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41 218 The band at 895 cm-1 is associated with the C-O-C stretching vibration characteristic of β-glycosidic bonds
42 219 between the anhydroglucose units of cellulose (El Achaby et al., 2018; Elanthikkal et al., 2010; Zhou et al.,
43 220 2012).
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45 221 3.4.2. Treated vs untreated Pennisetum fibers
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47 222 Figure 5 shows the FTIR spectra of the raw and treated PA fibers. The band positions and possible
48 223 assignments are shown in Tables 2 and 3. The spectra are identical, except for the disappearance of the band
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50 224 at 1734 cm-1 as a result of hemicellulose removal. From the results of the two treatments, it can be inferred
51 225 that the alkaline treatment provides a good removal of amorphous components than the hydrothermal
52 226 treatment. In addition, the FTIR study confirmed the results on the chemical compositions of the treated and
53 227 untreated PA fiber previously found.
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7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24 228 Fig. 5. FTIR spectrum of raw PAB and treated PA fibers : alkaline (a); hydrothermal (b)
25
26
27
28 229 Table 2. : Band positions and functional group assignments in raw and NaOH treated Pennisetum
29 230 alopecuroides fibers based on literature (El Achaby et al., 2018; Maache et al., 2017; Ramkumar &
30 231 Saravanan, 2021; Reddy et al., 2014; Saravanakumar et al., 2013)
31
32
33 Wave number (cm-1) Assignments
34 PAB PAA1 PAA3 PAA5 PAA10
35
3433 3446 3443 3442 3445 O-H stretching (cellulose & hemicellulose)
36
2924 2925 2924 2923 2923 C-H stretching of alkyls (cellulose & hemicellulose)
37
38 2851 2857 2861 2856 2858 CH2 Symmetric stretching (cellulose &
39 hemicellulose)
40 1734 - - - - Stretching of the C=O of the hemicellulose
41 1635 1650 1640 1643 1646 Stretching of the C-O of lignin
42 1515 1513 1515 1512 1515 Stretching of the C-O of lignin
43 1162 1164 1162 1162 1164 Asymmetric C-O-C stretching (cellulose and
44 hemicellulose)
45 1047 1039 1056 1053 1056 Symmetrical stretching of the C-O of lignin
46 897 899 894 897 897 C-H bonding of the aromatic hydrogen of a lignin
47 compound
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 11
63
64
65
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2
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4 232 Table 3. : Band positions and functional group assignments in raw and boil-treated Pennisetum
5 233 alopecuroides fibers, based on literature (El Achaby et al., 2018; Maache et al., 2017; Ramkumar &
6
7 234 Saravanan, 2021; Reddy et al., 2014; Saravanakumar et al., 2013).
8
9 Wave number (cm-1) Assignments
10 PAB PAH15 PAH30 PAH60
11 3433 3433 3432 3432 O-H stretching (cellulose & hemicellulose)
12 2918 2918 2918 2920 C-H stretching of alkyls (cellulose & hemicellulose)
13 2850 2852 2854 2852 CH2 Symmetric stretching (cellulose & hemicellulose)
14 1734 - - - Stretching of the C=O of the hemicellulose
15 1635 1632 1634 1635 Stretching of the C-O of lignin
16 1515 1513 1512 1512 Stretching of the C-O of lignin
17 1162 1164 1162 1162 Asymmetric C-O-C stretching (cellulose and
18 hemicellulose)
19 1047 1042 1045 1048 Symmetrical stretching of the C-O of lignin
20 897 898 895 896 C-H bonding of the aromatic hydrogen of a lignin compound
21
22
23
24
25
26 235 X-ray diffraction analysis was performed on the PA fibers. From Figure 5, we can observe major peaks are
27 236 present. The first two peaks, observed at 15.02° and 16.18, correspond to the (1-10) and (110) planes
28 237 respectively. This indicates the presence of amorphous components in the PA fiber. In addition to this, a
29 238 sharp peak of high intensity observed at 22.07° corresponds to the (200) plane of cellulose I
30
31 239 (Senthamaraikannan & Kathiresan, 2018; Vinod et al., 2021).
32
240 The crystallinity index value of PA fiber calculated by Segal's method is 49.14%. As shown in Table 1, the
33
34 241 crystallinity index of raw PA fiber is higher than that of Pennisetum oriental grass (33.5%) (Vijay et al.,
35 242 2021), Phaseolus vulgaris (43%) (Gurukarthik Babu et al., 2019) but lower than that calculated for
36 243 Sansevieria cylindrica (60%) (Kathirselvam et al., 2019) and Furcraea foetida (52.6%) (Manimaran et al.,
37 244 2018).
38
39
40
41 245 Figures 6.a and 7 show the X-ray spectra and the evolution of crystallinity of Pennisetum alopecuroides
42 246 fibers as a function of the percentage of alkali treatment respectively. It can be observed that when the fibers
43
44 247 were treated with alkali from 1% to 3% concentration, the crystalline cellulose content increased from
45 248 49.14% to 60.02%. This may be due to the formation of new hydrogen bonds between some cellulose chains
46 249 due to the removal of hemicelluloses and lignin, which usually separate the cellulose chains. On the other
47 250 hand, due to the rearrangement of crystalline regions (Reddy et al., 2014). Treatment with 3% alkali gave
48 251 the best crystallinity index (60.02%). However, when treated with 5% to 10% alkali the crystalline cellulose
49
50 252 content decreased rapidly (55.83%), indicating the polymorphic transformation to cellulose II that causes
51 253 fiber degradation at this concentration (Achour et al., 2017; Ajouguim et al., 2019). Figures 6.b and 8 show
52 254 the X-ray spectra of boiling water-treated fibers and the evolution of the crystallinity of these fibers as a
53 255 function of treatment time. The results of this study show an increase in crystallinity index up to 55.24 for
54 256 60 min. The increase in the crystallinity index is attributed to the removal of amorphous components from
55
56 257 the fiber. Climatic conditions affect not only the fiber structure but also its composition (Mouhoubi et al.,
57 258 2017). A lower hemicellulose content is desirable, as a higher content degrades thermal stability and
58 259 increases moisture absorption capacity (Azwa et al., 2013). On the other hand, Lignin improves fiber
59 260 stiffness by binding the cell wall structures together. It also contributes to polymer bonding when used as
60
261 reinforcement in polymer matrix composites (Beaugrand et al., 2014; Jawaid & Khalil, 2011).
61
62 12
63
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2
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4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24 262 Fig. 6. X-ray diffractograms of raw PA fibers and treated: alkaline (a); hydrothermal (b)
25
26
27
28
29 263 3.4.3. Evolution of the crystallinity index :
30
31
32 264 Using the Scherer equation, the crystallite size (L) of Pennisetum alopecuroides fibers calculated is 0.49
33 265 nm, which is significantly smaller than that determined for flax (2.8 nm), corn (3.8 nm), and cotton (5.5 nm)
34 266 fibers, and quite close to coir (0.43 nm) (Dharmaratne et al., 2021; Indran et al., 2014). Smaller crystal size
35 267 structures tend to absorb more water than higher crystal size structures (Indran et al., 2014).
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55 268
56
57 269 Fig. 7. Evolution of the crystallinity index of PA fibers as a function of alkaline treatment.
58
59
60
61
62 13
63
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2
3
4
5
6
7
8
9
10
11
12
13
14
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16
17
18
19
20
21
22 270 Fig. 8. Evolution of the crystallinity index of PA fibers as a function of the duration of boiling water
23 271 treatment.
24
25 272 3.5. Thermal analysis :
26
27
28 273 The ATG and DTG curves of the Pennisetum alopecuroides fiber are presented in Figure 9. The
29 274 decomposition of the different components of the PA fiber is done in three steps. The first weight loss at
30 275 temperatures below 100 °C corresponds to the loss of water and removal of waxy material from the fiber
31 276 (Maache et al., 2017; Manimaran et al., 2020). The second weight loss at 290 °C related to the decomposition
32
277 of hemicellulose and the glycosidic bonds of cellulose (Balaji & Nagarajan, 2017; Belouadah et al., 2015).
33
34 278 A significant weight loss (70 wt%) was found at 337 °C. This could be attributed to the decomposition of
35
36 279 cellulose I, α cellulose, and lignin (Balaji & Nagarajan, 2017; Fiore et al., 2014; Manimaran et al., 2018;
37 280 Saravanakumar et al., 2013). However, lignin, due to the presence of phenyl groups, is the most difficult to
38 281 decompose and its decomposition extends over the entire temperature range from below 200 °C to 700 °C
39 282 (Reddy et al., 2009; Yang et al., 2007b). Moreover, the degradation temperature of PA is relatively similar
40 283 to that of Okra (220 °C), Hemp (250 °C), Curaua (230 °C), Kenaf (219 °C), Jute (205 °C), (De Rosa et al.,
41
42 284 2011).
43
44 285
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59 286 Fig. 9. ATG and DTG curves of raw Pennisetum alopecuroides fiber
60
61
62 14
63
64
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2
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4 287 3.6. Morphological analysis by EDX
5
6
288 3.6.1. Raw fibers
7
8
9 289 Figure 10 presents the EDX spectrum for the raw PA fiber. The fiber is composed of elements such as
10 290 carbon (C), oxygen (O), a small amount of silicon (Si), and traces of chlorine (Cl), potassium (K), calcium
11 291 (Ca), and aluminum (Al).
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32 292 Fig. 10. EDX analysis of the raw Pennisetum alopecuroides fiber
33
34
35
36 293 Based on the results in Table 4, which show the mass and atomic percentage calculated from the peak areas,
37 294 carbon and oxygen are the main constituents as they are the majority components found in natural fiber
38 295 structures (Kambli et al., 2016). This, is consistent with the known chemical composition of lignocellulosic
39
40 296 fibers. The mass percentage revealed that P. alopecuroides fiber contains less carbon (47.95 wt%) than jute
41 297 fiber (55.68 wt%) and Vascular bundles fiber (50.14 wt%) (Boumediri et al., 2019; Moshi et al., 2020). But
42 298 it has a non-negligible content of silicon (5.56 wt%) and traces of potassium (1.72 wt%), sulfur (0.68 wt%),
43 299 calcium (0.46 wt%), and aluminum (0.23 wt%) compared to other natural fibers.
44
45 300 Table 4. : The mass and atomic percentage of raw Pennisetum alopecuroides fiber and other natural
46 301 fibers:
47
48 302 Pennisetum Vascular bundles Coccinia Grandis Jute
49 alopecruroides (Boumediri et al., 2019) (Moshi et al., 2019) (Moshi et al., 2019)
50 303 (raw)
51 Eléments Weight Atomic Weight Atomic Weight Atomic Weight Atomic
52 304 (%) (%) (%) (%) (%) (%) (%) (%)
53 C 47.95 56.93 50.14 57.88 44.67 51.91 55.68 62.72
54 305 O 44.40 39.57 46.41 40.22 54.38 47.58 43.89 37.11
55 Si 4.56 2.32 0.47 0.23 0.67 0.36 0.11 0.06
56 306 K 1.72 0.63 0.06 0.02 - - - -
57 Cl 0.68 0.27 0.14 0.06 0.38 0.06 - -
58 307 Ca 0.46 0.16 0.05 0.02 - - - -
59 Al 0.23 0.12 0.86 0.44 0.18 0.09 - -
60
61
62 15
63
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4 308 3.6.2. Treated fibers
5
6 309 Figure 11 compares the surface of the untreated and chemically treated fibers. The surface of the untreated
7 310 fiber (Fig. 11a) shows impurities. The micrographs (Fig.11 b, c, d) indicate that the hydrothermal treatment
8
9
311 has removed some of the impurities.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30 312 Fig. 11. SEM micrographs of Pennisetum alopecuroides fiber after hydrothermal (PAH) and alkaline
31 313 (PAA) treatment : (a) untreated (BAP), (b) PAH15, (c) PAH30, (d) PAH60, (e) PAA1, (f) PAA3, (g)
32
33 314 PAA5, (h) PAA10.
34
315 The micrographs (Fig. 11 e, f, g, h) indicate that the alkaline treatment improved the surface morphology of
35
36 316 the fibers. The NaOH treatment acts on the middle lamella and the secondary wall leading to the removal
37 317 of hemicelluloses and the dissolution of pectins, but as soon as the concentration exceeds 3% the degradation
38 318 of the cell wall can be noticed due to the excessive extraction of hemicellulose and lignin.
39
40
41
42 319 4. Conclusions :
43
44 320 In this work, the effect of hydrothermal and alkaline treatments on Pennisetum alopecuroides (PA) fibers
45 321 were analyzed for the first time. For the hydrothermal treatment the effect of the duration of immersion in
46 322 boiling water at 100°C temperature was assessed (15 min, 30 min and 60 min). For the alkaline treatment
47
323 the effect of the NaOH concentrations (1%, 3%, 5%, and 10%) was evaluated.
48
49 324 The physicochemical, morphological, and thermogravimetric characterization was performed for untreated
50
51 325 and treated PA fibers. The following conclusions can be drawn :
52
53
326 - The chemical analysis shows that the PA fibers have cellulose, hemicellulose, and lignin content in the
54 327 order of 49 wt%, 30% and 20% respectively, and these values are comparable to other lignocellulosic fibers
55 328 reported in the literature.
56
57 329 - The density of the PA fibers (870 kg/m3) presents a lower value compared to other cellulosic fibers, namely
58 330 jute fiber (1460 kg/m3), and synthetic fibers, such as glass fiber (2500 kg/m3).
59
60
61
62 16
63
64
65
 1
2
3
4 331 - The FTIR analysis indicates a decrease in hemicellulose and lignin content due to the alkaline and
5 332 hydrothermal treatments.
6
7 333 - XRD analysis shows that the crystallinity index of the PA fibers increases after alkaline (60%) and
8
9
334 hydrothermal (55%) treatments.
10 335 - The results of the thermo-gravimetric analysis reveals that the PA fibers were thermally stable up to 226°C,
11
12 336 which is much higher than the temperature of polymerization process.
13
14
337 - The SEM micrograph reveals a smoother surface morphology for the untreated PA rods. The 3% NaOH
15 338 alkaline and 60 min hydrothermal treatments are optimal for this fiber, since they remove the amorphous
16 339 components and the surface becomes rough, leading to most probable good interfacial adhesion of the fiber
17 340 with a matrix, in case it is used to produce composites.
18
19 341 - The EDX analysis confirms that carbon and oxygen are the main constituents of the PA fiber, which means
20 342 that the fiber keeps its organic nature.
21
22 343 Finally, the characterization results validate the promising use of the PA fibers for various industrial
23 344 applications, namely to produce composites for the construction industry, such as insulation boards
24
25 345 contributing for buildings energy efficiency.
26
27
28 346 Acknowledgments The authors would express their sincere thanks to the Moroccan Center for Analysis
29
30 347 and Characterization (CAC) affiliated to Cadi Ayyad University, for providing some sample
31 348 characterizations.
32
33
34
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