Industrial Crops & Products 112 (2018) 499–510

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Industrial Crops & Products

journal homepage: www.elsevier.com/locate/indcrop

Alfa fibers as viable sustainable source for cellulose nanocrystals extraction: T

Application for improving the tensile properties of biopolymer
nanocomposite films
⁎
Mounir El Achabya, , Zineb Kassaba,b, Abdelatif Barakatc, Adil Aboulkasd
a
Materials Science and Nanoengineering Department, Mohammed VI Polytechnic University, Lot 660–Hay Moulay Rachid, 43150, Benguerir, Morocco
b
Laboratoire d'Ingénierie et Matériaux (LIMAT), Faculté des Sciences Ben M'sik, Université Hassan II de Casablanca, B.P.7955, Casablanca, Morocco
c
IATE, CIRAD, Montpellier SupAgro, INRA, Université de Montpelier, 34060, Montpellier, France
d
Laboratoire des procédés chimiques et matériaux appliqués (LPCMA), Faculté polydisciplinaire de Béni-Mellal, Université Sultan Moulay Slimane, BP 592, 23000 Béni-
Mellal, Morocco

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

Keywords: Due to its renewability, availability and high cellulose content (≈45%), Alfa fibers (Stipa tenacissima) have been
Lignocellulosic fibers identified as a sustainable source for cellulose microfibers (CMF) and cellulose nanocrystals (CNC) production.
Cellulose nanocrystals Subjecting raw Alfa fibers to alkali, bleaching and sulfuric acid hydrolysis treatments allowed producing CMF
Biopolymer nanocomposites and CNC with high yields. The fluorescence microscopy confirmed that CMF, with average diameter of 10 μm,
Tensile properties
were successfully obtained after bleaching treatments. TEM and AFM showed that the CNC exhibit needle-like
shape with an average diameter and length of 5 ± 3 nm and 330 ± 30 nm, respectively, giving rise to an aspect
ratio of about 66. XPS measurement confirmed the presence of sulfate groups on the surface of CNC with 2.04
sulfate groups per 100 anhydroglucose units, confirming the negatively charged surface of CNC, with zeta po-
tential value of − 47.39 mV. XRD studies showed that CMF and CNC exhibit cellulose I structure with crys-
tallinity index of 71% and 90%, respectively. FTIR and TGA analyses were used to identify the chemical com-
position and thermal stability changes during different chemical treatments, suggesting that all non-cellulosic
compounds were removed after alkali and bleaching treatments. The obtained CNC were dispersed into three
different biopolymer matrices, e.g. chitosan, alginate, and k-carrageenan, at various CNC loadings (1, 3, 5 and
8 wt%), to evaluate their ability to enhance the tensile properties of biopolymers and, at the same time, to
produce new biopolymer-based nanocomposite films. It was found that the tensile properties of the as-produced
nanocomposite films were largely improved with addition of CNC, resulting in mechanically strong and flexible
ecofriendly nanocomposite films.

1. Introduction been devoted to use lignocellulosic fibers as renewable raw materials

Natural lignocellulosic fibers are the most abundant renewable raw
materials on earth, and mainly consists of cellulose, hemicelluloses and
lignin as major constituents, and pectin, waxes, proteins, lipids, ash,
pigments and extractive compounds can be found as minor constituents
(Malherbe and Cloete, 2002). In general, the composition and propri-
eties of lignocellulosic fibers vary depending on the origin and the type
of fibers, species of plant, and the environment in which the original
plant is growing (Trache et al., 2016). Most of the lignocellulosic fibers
such as cotton, flax, hemp, jute, kenaf, sisal, ramie, curaua, pineapple,
bamboo, coir can be isolated, treated and functionalized before used in
various applications such as textiles (Yu, 2015) and polymer composites
(Pickering et al., 2016). More importantly, considerable efforts have
for the production of cellulose, lignin and hemicellulose, as high value-
added materials or polymers (Bian et al., 2012; Nadji et al., 2009;
Trache et al., 2016). However, it is well known that lignocellulosic fi-
bers exhibit a complex hierarchal structure in which the constituents
are linked with each other, making it difficult to fractionate these ori-
ginal fibers into value added materials (Rangan et al., 2017).
From lignocellulosic materials, the pure cellulose fibers can be
prepared using physical, mechanical and/or chemical routes (Trache
et al., 2016). In this case, the emphasis is to remove lignin and hemi-
cellulose and focus on getting a maximum yield of pure cellulose, which
is a hierarchically structured material that contains both highly crys-
talline domains (ordered cellulose chains stabilized by inter and in-
tramolecular hydrogen bonding), and amorphous domains (disordered

⁎
Corresponding author.
E-mail address: mounir.elachaby@um6p.ma (M. El Achaby).

https://doi.org/10.1016/j.indcrop.2017.12.049
Received 29 July 2017; Received in revised form 25 November 2017; Accepted 19 December 2017
Available online 04 January 2018
0926-6690/ © 2017 Elsevier B.V. All rights reserved.
M. El Achaby et al.
cellulose chains). Pure cellulose fibers can be chemically or mechani-
cally disintegrated yielding in nanosized cellulose called nanocelluloses
(NC), cellulose nanocrystals (CNC) or cellulose nanowhiskers (CNC),
having very interesting properties such as high aspect ratio (10–100),
large specific surface area (∼250–500 m2/g), low density (∼1.6 g/
cm3), high crystallinity (up to 90%), and high tensile strength
(7.5 GPa), and very high elastic modulus (approximately 100–140 GPa)
(Bandera et al., 2014; Buffiere et al., 2017; Grishkewich et al., 2017;
Tan et al., 2015). Recently, mechanical treatments such as high shear
homogenization, ball-milling or grinding processes have shown to be
efficient in producing nanometer or micrometer sized cellulose parti-
cles, with relatively high aspect ratio (Bandera et al., 2014; Buffiere
et al., 2017; Phanthong et al., 2017; Sofla et al., 2016). For example, it
has been reported that cellulose whiskers with average aspect ratio of
52 can be extracted from microcrystalline cellulose by using high shear
homogenization process (Bandera et al., 2014). They demonstrated that
these mechanically obtained cellulose whiskers performed a similar
reinforcing potential to commercially available whiskers. Regarding to
the chemical treatment, the sulfuric acid hydrolysis represents the most
effective process for obtaining CNC, because it produces CNC with
sulfate-modified surface, high crystallinity and good colloidal stability
in water (Habibi et al., 2010). However, it should be noted that the
morphology, the surface charge density (sulfur content), and the
properties of acid hydrolyzed-CNC depend on the source of the original
cellulose and on the hydrolysis conditions, such as time, temperature,
agitation and acid concentration (Martins et al., 2015; Sapkota et al.,
2017a; Trache et al., 2017; Yao et al., 2017).
“Alfa” fibers are considered as the most important lignocellulosic
fibers feedstocks. “Alfa” is the Arabic name of Stipa tenacissima plant,
which is a fast growing perennial plant that thrives in dry regions of
North Africa (mainly in the Maghreb) and southeast Spain (Trache
et al., 2014). Its fibers rich leaves can reach 1000 mm in length, with
spherical shape. In North African countries, it covers a large area esti-
mated to about 3,186,000 ha in Morocco, 4,000,000 ha in Algeria,
400,000 ha in Tunisia and 350,000 ha in Libya (Marrakchi et al., 2012;
Paiva et al., 2007). Alfa is considered as one of the most interesting
annual plants for the production of fibers for papermaking (Marrakchi
et al., 2011) and polymer composites development (Brahim and Cheikh,
2007; Maafi et al., 2010; Omri et al., 2016).
Alfa fibers are composed mainly of cellulose (44–48 wt%), hemi-
celluloses (27–22 wt%) and lignin (12–18 wt%) (Belkhir et al., 2013;
Hanana et al., 2015), making them a promising substrate for the pro-
duction of carbohydrate derivatives with good performances. Recently,
Alfa fibers have been used for the production of microcrystalline and
nanofibrillated cellulose (Besbes et al., 2011; Trache et al., 2014) and
lignin-based biopolymers (Nadji et al., 2009). Importantly, the high
content of cellulose in Alfa fibers make them a very interesting bio-
sourced raw material for the production of CNC with high reinforcing
potential for biopolymers based nanocomposite development.
Due to their main advantages including nontoxicity, biodegrad-
ability, wide availability and biocompatibility, the biopolymers can be
considered as good candidates for the replacement of petroleum-based
polymers; however, their mechanical, thermal, and barrier properties
must be enhanced to make them attractive materials for various ap-
plications (El Miri et al., 2015a,b). Nevertheless, the nanoreinforcement
strategy, by adding suitable reinforcing nanofillers, is an effective way
to enhance the physico-chemical properties of biopolymers, by produ-
cing high performance biopolymer-based nanocomposite materials (El
Miri et al., 2015a). Indeed, the potential for achievement of useful
biopolymer based nanocomposites must be driven by the excellent in-
trinsic properties of nanofillers and their nanoscale dispersion within
biopolymer matrix (El Miri et al., 2015a). In this context, various bio-
polymers have been used as polymeric matrices to develop bionano-
composite materials with high mechanical, optical, thermal, and barrier
properties, using CNC as nanoreinforcing fillers (El Achaby et al., 2017;
El Miri et al., 2015a,b). Among such biopolymers, chitosan (CH),
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Industrial Crops & Products 112 (2018) 499–510
alginate (ALg) and k-Carrageenan (k-CA) have been used extensively for
the preparation of biopolymer-based nanocomposite films because of
their excellent film forming properties (Huq et al., 2012; Khan et al.,
2012; Sánchez-García et al., 2010).
CH is a linear biopolymer and deacetylated derivative of chitin. It is
composed of β-(1,4)-2-acetamido-2-deoxy-D-glucose and β-(1,4)-2-
amino-2-deoxy-D-glucose units (El Achaby et al., 2014). This biopo-
lymer is one of the most interesting polymers due to its advanced ap-
plications that range from pharmaceuticals to materials science (El Miri
et al., 2015b). ALg is a water soluble biopolymer derived from brown
seaweed such as Laminaria hyperborea, Macrocystis pirifera, Laminaria
digitata, and Ascophyllum nodosum (Remminghorst and Rehm, 2006).
ALg is composed of β-D-mannuronic acid and a-L-glucuronic acid, which
are linked together in varying proportions by 1–4-linkages
(Remminghorst and Rehm, 2006). Owing to its good film forming
ability, ALg biopolymer has been used in various industrial applications
such as food additives and gelling agents, emulsifier, food packaging
(Carneiro-da-Cunha et al., 2010; Shankar et al., 2016). k-CA is also a
water soluble biopolymer extracted from various species of red algae
(Rhodophyta). It is composed of long linear chains of D-galactose and D-
anhydrogalactose with anionic sulfate groups (Liu et al., 2015). This
biopolymer has good gel and film forming properties and has been used
in various applications particularly as a food additive or as a stabilizer
(Dafe et al., 2017).
The objective of this work was to exploit raw Alfa fibers, harvested
from the oriental region of eastern Morocco, for the production of pure
cellulose microfibers and cellulose nanocrystals (CNC) using alkaliza-
tion, bleaching and sulfuric acid hydrolysis treatments. Indeed, the
valorization of the Alfa fibers for the production of cellulose nano-
crystals using such processes should contribute to the economic viabi-
lity and the sustainability of this largely available lignocellulosic bio-
mass. After their successful characterization, the as-extracted CNC were
dispersed into three different biopolymer matrices, e.g. chitosan (CH),
alginate (AL), and k-carrageenan (k-CA), to evaluate their ability to
reinforce of biopolymers with different surface functionalities and
properties and, at the same time, to produce new biopolymer-based
nanocomposite films. Herein, the adhesion properties and the functio-
nalized surface of sulfuric acid hydrolyzed CNC can be widely exploited
to enhance the interfacial interactions between the dispersed CNC and
the biopolymer matrices (CH, ALG and k-CA).
2. Materials and experimental details
2.1. Materials
The raw Alfa fibers (AF) used in this work was collected from the
oriental region of eastern Morocco. The as-received AF (up to 1000 mm
fiber long) (Fig. 1) were cut into 50–100 mm small fibers, and then they
were ground using a knife mill (Retch SM100) with a screen size of
2 mm (Fig. 1). Chitosan (740063 Aldrich), alginate (W201502 Aldrich)
and k-carrageenan (22048 Sigma) were purchased from Sigma Aldrich.
All analytical grade chemicals used for the treatment of raw fibers and
for the extraction of cellulosic materials were also purchased from
Sigma–Aldrich.
2.2. Extraction of cellulose microfibers (CMF)
Pure cellulose microfibers (CMF) were firstly extracted from raw AF
according to our previous works (El Achaby et al., 2017; El Miri et al.,
2016, 2015a). Briefly, ground raw AF (2 mm) were treated in distilled
water for 1 h at 60 °C. Then, the resulted AF were treated three times
with 4 wt% NaOH solution at 80 °C for 2 h under stirring, resulting in
alkali treated Alfa fibers (ATAF) (Fig. 1), after which bleaching treat-
ment was carried out using a solution made up of equal parts (v:v) of
acetate buffer (27 g NaOH and 75 mL glacial acetic acid, diluted to 1 L
of distilled water) and aqueous sodium chlorite (1.7 wt% NaClO2 in
M. El Achaby et al.
water). This treatment was done three times, resulting in pure white
colored cellulose microfibers (Fig. 1). In these treatments the ratio of
the fibers to liquor was 1/20 (g/mL).
2.3. Extraction of cellulose nanocrystals (CNC)
CNC were successfully extracted from the as-extracted cellulose
microfibers (CMF) by acid hydrolysis process, as described in our pre-
vious works (El Achaby et al., 2017; El Miri et al., 2016, 2015b). For
that, CMF were subjected to preheated 64 wt% sulfuric acid hydrolysis
at 50 °C for 30 min under mechanical stirring. Then, the mixture was
diluted with ice cubes to stop the reaction and was washed by succes-
sive centrifugations at 12000 rpm at 15 °C for 20 min at each step, re-
sulting in white CNC suspension, which was subjected to a dialysis
against distillated water until it reached neutral pH. Afterward, the
obtained CNC aqueous suspension was homogenized by the use of a
probe type ultrasonic homogenizer (BRANSON, Sonifier 250) for 5 min
in an ice bath, resulting white stable CNC suspension, in the form of a
gel (Fig. 1). The concentration of CNC aqueous suspension was calcu-
lated gravimetrically. Finally, by using freeze drying process a small
quantity of homogenized CNC suspension was transformed into solid
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Industrial Crops & Products 112 (2018) 499–510
Fig 1. Photographs of (a) raw and (b) crushed alfa fibers (AF), (c)
alkali treated alfa fibers (ATAF), (d) bleached cellulose microfibers
(CMF) and (e) suspended and (f) freeze dried cellulose nanocrystals
(CNC).
material for different physico-chemical characterizations (Fig. 1).
2.4. Preparation of nanocomposite films
Nanocomposite films based on chitosan (CH), alginate (ALg) and k-
carrageenan (k-CA) polysaccharides as biopolymeric matrices filled
with 1; 3; 5 and 8 wt% CNC, as nanodispersed phase, were prepared
using solvent casting method (Fig. 2). For CH-CNC nanocomposite
films, the desired amount of CNC (1; 3; 5 and 8 wt%) was dispersed into
250 mL of 1% acetic acid aqueous solutions and stirred for 5 min at
65 °C. Then, CH powder was slowly added to CNC suspensions and the
resulting mixture (3 g total dry mass) was stirred for 2 h at 65 °C, then
cooled to room temperature under stirring. For ALg-CNC or k-CA-CNC
nanocomposite films, the desired amount of CNC (1; 3; 5 and 8 wt%)
was dispersed into 250 mL in aqueous solutions containing 1 g of gly-
cerol and stirred for 5 min at 65 °C. Then, AL (or k-CA) powder was
slowly added to CNC suspensions and the resulting mixture was stirred
for 2 h min at 65 °C, then cooled to room temperature under stirring.
After cooling to room temperature, all mixtures were casted onto
Petri dishes and the water evaporated at ambient temperature for
3 days. Neat CH, ALg and k-CA films were also prepared according to
M. El Achaby et al.
Fig. 2. Schematic representation of the processing of nanocomposite films based on CNC as nanofillers and ALg, k-CA and CH as biopolymer matrices.
the same procedures mentioned above, without the addition of CNC.
The produced nanocomposite films were coded as Y-CNC-X, with Y
referred to biopolymeric matrix CH, ALg or k-CA and the X referred to
CNC weight fractions (1, 3, 5 and 8 wt%) in each nanocomposite for-
mulations.
2.5. Measurement and characterization techniques
The morphology of samples was evaluated by using an inverted
Nikon A1 laser scanning confocal microscope (LSCM). The samples
were stained with Congo Red (Merck CI22120) by incubating them in a
0.01% solution in distilled water for 20 min. X-ray diffraction (XRD)
characterizations of samples was performed on a Bruker diffractometer
D8 Advance using Cu-Kα radiation. The diffraction profiles were ob-
tained at diffraction angles between 5 and 50° at room temperature.
Atomic Force Microscopy (AFM) images of CNC was recorded using a
BioScope Catalyst AFM (Bruker AXS, Santa Barbara, CA). Samples for
AFM observations were prepared by depositing a droplet of a diluted
CNC suspension onto freshly cleaved mica sheets, after being sonicated
for 5 min, and allowing the solvent to dry in air. The measurements
were conducted in tapping mode under ambient temperature at a scan
rate of 1.5 Hz. Transmission electron microscopy (TEM) for CNC char-
acterization was performed using JEOL JEM-1230 (Jeol, Japan) oper-
ated at 80 kV and equipped with a LaB6 filament. Droplets of CNC
suspensions were deposited on glow-discharged carbon-coated grids.
The liquid in excess was blotted away with filter paper and a drop of 2%
(w/v) uranyl acetate negative stain was added prior to air drying. The
zeta potential measurement of CNC suspension was measured using a
NICOMP ZLS Z3000 Zeta sizer apparatus. For this measurement, ca-
pillary cell was used and the CNC suspension was diluted and sonicated
for 5 min before being analyzed. The thermal degradation behaviors of
all cellulosic materials were characterized using a thermogravimetric
analyzer (METTLER TOLEDO, TGA2). All tests were conducted under a
nitrogen atmosphere, at a flow rate of 25 mL/min, from 25 to 800 °C
with heating rate of 10 °C/min.
Fourier transform infrared spectroscopy (FTIR) was performed on a
Bruker Tensor 27 spectrometer equipped with a Golden Gate single
reflection ATR accessory. The experiments were carried out in the range
from 4000 to 400 cm−1 with a resolution of 4 cm−1 and an
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Industrial Crops & Products 112 (2018) 499–510
accumulation of 16 scans. The FTIR spectra were taken in the trans-
mittance mode. The XPS analysis of freeze dried CNC was conducted on
an Escalab 250 apparatus (Thermo Electron) equipped with a mono-
chromatic Al Kα radiation at 1486.6 eV. The area of analysis was
400 μm diameter. The spectra were modified by setting the CeC con-
tribution in the C1 s emission to 285.0 eV. The thickness of nano-
composite films was determined using a Hanatek Variable Force
Precision Thickness Gauge (FT3-V). Tensile tests for all bionano-
composite films were performed at room temperature using texture
Analyser (TA.XT plus). The specimens were cut in rectangular shapes
with 80 mm in length and 10 mm in width. The gauge length was fixed
at 30 mm and the crosshead speed was 5 mm/min. All tests were carried
out on a minimum of five samples and the reported results are average
values.
3. Results and discussions
3.1. Extraction of CMF and CNC
Micro and nanosized cellulose (CMF and CNC) were successfully
extracted from raw AF, using the three well known steps that involves a
combination of alkali, bleaching and acid hydrolysis treatments, ac-
cording to our previous works (El Achaby et al., 2017; El Miri et al.,
2016, 2015a). In order to remove the noncellulosic components, espe-
cially the hemicellulose and lignin molecules, the ground raw AF
(2 mm) were firstly subjected to washing treatment using distilled
water followed by three subsequent alkali treatments to ensure at least
partial removal of the hemicellulose and lignin molecules. These
treatments yielded about 51% yellow colored fibers (Fig. 1), which was
calculated by the weight of the obtained fibers divided by the initial
weight of AF. The alkali treated Alfa fibers (ATAF) were then subjected
to a bleaching treatment to degrade the residual lignin molecules and
others impurities, resulting in solid pure cellulose microfibers (CMF),
shown by a clearly white color (Fig. 1), confirming that the all non-
cellulosic compounds were totally removed after bleaching treatment.
Herein, the yield of these CMF was about 39% in regard to the initial
amount of AF. Finally, the resulting bleached CMF were hydrolyzed
with sulfuric acid, which was performed under appropriate conditions
that allowed the removal of amorphous domains from the bleached
M. El Achaby et al.
Fig. 3. Laser scanning confocal fluorescence microscopy images of (a,b) AF, (c,d) ATAF and (e,f) CMF samples.
cellulose (Kargarzadeh et al., 2012). The removal of amorphous do-
mains, via acid hydrolysis, was performed by cleaving CMF into bundles
of CNC with nanometric dimensions. As shown in Fig. 1, a viscous gel
for CNC suspension and a clearly white powder were obtained after
homogenization and freeze drying processes, respectively. The yield of
CNC was 21% with respect to the initial amount of dried AF fibers, and
57% with respect to the amount of bleached CMF.
3.2. Morphological analysis of raw and treated cellulosic fibers
Fig. 3 represents the fluorescence microscopy images of raw AF,
ATAF and CMF. These images show that the morphology of fibers, in
terms of the size and the defibrillation level, was changed from compact
fibrous structure for raw AF into totally defibrillated structure (micro-
fibers) for bleached cellulose. For the raw AF, it is worth noting that the
presence of lignin, hemicelluloses and other noncellulosic components
act as cementing agent around the cellulose fibrils and help in the
formation of compact structure (Fig. 3a–b). With the subsequent
treatment of alkali, some alkali labile linkages (ether and ester linkages)
between lignin monomers or between lignin and other carbohydrates
may have been broken (El Miri et al., 2015b; Trache et al., 2014), which
helped in the partial defibrillation of fibers, as shown in Fig. 3c–d. The
laser scanning fluorescence microscopy micrographs obtained for CMF
(Fig. 3e–f) show that the bleaching treatment resulted in the total de-
fibrillation of fibers into individual microfibers with smaller diameter
(average diameter of 10 μm), confirming the all noncellulosic com-
pounds were totally removed after bleaching treatment, which was
suitable for acid hydrolysis process to produce CNC. These results are in
good agreement with literature for obtaining pure CMF from lig-
nocellulosic fibers using the same bleaching treatment (Cudjoe et al.,
2017; El Miri et al., 2015b; Thambiraj and Ravi Shankaran, 2017;
Trache et al., 2014).
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3.3. TEM and AFM analysis of CNC
TEM and AFM microscopies were used to examine the morphology
and dimensions of CNC. The shape and the aspect ratio of CNC played
an important role in determining reinforcing capability of the CNC for
polymer nanocomposite application (Sapkota et al., 2017a,b; Trache
et al., 2017). Thus, these parameters are evaluated from TEM and AFM
observations (Fig. 4). From this result, it was observed that the CNC are
well separated and exhibited a needle-like shape, which is a well known
morphology for CNC extracted from lignocellulosic materials using acid
hydrolysis process (El Miri et al., 2015b; Kargarzadeh et al., 2012;
Mariano et al., 2016). This shape can be considered as a special char-
acteristic to be taken into account to use the needle-like CNC for de-
veloping CNC-based polymer nanocomposite materials.
The average diameter and length of CNC were measured from AFM
and TEM observations at 5 ± 3 nm and 330 ± 30 nm, respectively,
giving rise to an average aspect ratio of about 66, which is calculated as
the length (L) divided by the diameter (D) for individual CNC, in-
dicating the potential application of CNC as nanoreinforcing agents in
composite materials (Sapkota et al., 2017a,b,c; Trache et al., 2017).
Indeed, it is widely accepted that the starting raw material and the
pretreatment and acid hydrolysis conditions are the most important
factors affecting the dimensions of the produced CNC (Trache et al.,
2017). Herein, the aspect ratio obtained for the as-extracted CNC is
comparable to the values reported in the literature for CNC extracted
from various sources such as sugarcane bagasse (L/D = 32–64)
(Teixeira et al., 2011), corncob (52–63) (Silvério et al., 2013), sisal
(43–60) (Garcia de Rodriguez et al., 2006) and pineapple leaf (50–60)
(Marcos dos Santos et al., 2013); and higher than that measured for
CNC from rice straw (9–10.5) (Lu and Hsieh, 2011), cotton (9.5–12.5)
(Camarero Espinosa et al., 2013) or cotton linters (20–24) (Paulo et al.,
2013), coconut husks (35–44) (Rosa et al., 2010), ramie (12) (Junior De
Menezes et al., 2009) and Luffa cylindrica fibers (46) (Siqueira et al.,
2013). Contrastingly, it was smaller than that of CNC from tunicate
(148) (Sacui et al., 2014) and bacteria (60–94) (Olsson et al., 2010;
M. El Achaby et al.
Sacui et al., 2014).
3.4. Zeta potential and aqueous colloidal stability of CNC
The zeta potential is an important parameter to evaluate the dis-
persion state of CNC and its aqueous suspension stability. In this study,
the average value of zeta potential obtained for aqueous CNC suspen-
sion was found to be − 47.39 mV, which can be explained by effective
electrostatic repulsions created by the presence of negatively charged
surface of CNC (Camarero Espinosa et al., 2013), restricting them to
coagulate or flocculate, as schematically illustrated in Fig. 5. This result
confirms that the as-extracted CNC suspension has a good stability,
because the absolute value is higher than 25 mV, as previously high-
lighted in our previous works (El Miri et al., 2016, 2015a,b). Fig. 5
shows a photograph illustrating the CNC aqueous suspension stability,
Fig. 5. Aqueous suspension of CNC at 5.30 mg/mL and schematic representation of
possible electrostatic repulsions between indvidual CNC.
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Industrial Crops & Products 112 (2018) 499–510
Fig. 4. (a,b) TEM and (c,d) AFM images of CNC.
in which a white gel appearance is observed for the as-isolated CNC
suspension, showing a good stability. It should be noted that the sta-
bility of aqueous CNC suspensions is crucial in the preparation of
polymer based nanocomposites, especially when water soluble poly-
mers are used as polymeric matrices and the nanocomposite systems are
made by the solvent casting method.
3.5. XPS analysis of CNC
XPS analysis was carried out to better identify the presence of sul-
fate groups on the surface of CNC and to quantify the surface chemical
composition in terms of oxygen, carbon and sulfur. Fig. 6a shows the
XPS survey spectra peaks of the as-extracted CNC. The peaks at 533.00,
286.44, and 169.07 eV generated from O 1s, C 1s, and S 2p, respectively
(Li et al., 2015; Thambiraj and Ravi Shankaran, 2017). The peak at
1071.8 which can be generated from Na 1 s was not detected con-
firming that the Na atoms were not presented in CNC sample. From the
survey spectra, the S 2p peak region was further determined using high
resolution analysis, and the obtained result is shown in Fig. 6b. The
atomic concentration was determined at 57.10 and 42.50 for C and O
respectively. The O/C ratio was calculated at 0.74, wherein 0.83 is the
theoretical value of pure cellulose (Zoppe et al., 2014). The atomic
concentration of S was found to be 0.40%, corresponding to 2.04 sulfate
groups per 100 anhydroglucose units, basing on the calculation pro-
cedure described elsewhere (Hamad and Hu, 2010; Li et al., 2015). This
result is comparable with that reported by Li et al. (2015) for sulfuric
acid hydrolyzed CNC.
3.6. XRD diffraction and FTIR analysis of raw and treated cellulosic fibers
Fig. 7a shows the XRD profiles of freeze dried CNC in comparison to
the raw and treated fibers (AF, ATAF and CMF). From this result, all
cellulosic materials present the same cellulose I characteristic peaks at
2θ of around 14.9°, 16.3° and 22.5°, corresponding to the cellulose I
M. El Achaby et al.
Fig. 6. (a) XPS survey spectrum and (b) high-resolution of S2p photoelectron spectrum of CNC sample.
crystallographic planes 11̅0, 110 and 200, respectively (El Miri et al.,
2015b; Flauzino Neto et al., 2013). As expected, the magnitude of the
observed crystalline peaks increased after different chemical treatments
because of the removal of amorphous lignin and hemicellulose
(Kargarzadeh et al., 2012). It is worth noting that the crystal structure
of cellulose component was not affected during the alkali, bleaching
and acid hydrolysis treatments. From the XRD data, the crystallinity
index (CrI) was calculated using the Segal equation as previously de-
scribed in our works (El Miri et al., 2015b). The CrI was found to be
about 42%, 56%, 71%, and 90% for raw AF, ATAF, CMF, and CNC
samples, respectively. The increasing of CrI from raw AF to CMF was
ascribed to the progressive removal of amorphous noncellulosic mate-
rials (lignin, hemicellulose and others) (El Miri et al., 2015b;
Kargarzadeh et al., 2012), and from CMF to CNC the increasing of CrI
was attributed to the hydrolysis of amorphous regions of CNC, resulting
in CNC with relatively high crystallinity (90%). Thus, the as-obtained
CNC exhibit a high crystallinity, which is a required property for using
CNC as nanofillers for nanocomposites development (Paulo et al.,
2013).
The FTIR is a very powerful technique to study the changes in the
chemical composition during different stages of treatment (Flauzino
Neto et al., 2013; Marcos dos Santos et al., 2013). Fig. 7b shows the
FTIR spectra of raw AF, ATAF, CMF and CNC. For raw AF, the peak at
1729 cm−1 is attributed to the acetyl and uronic ester groups of
hemicellulose or the ester linkage of carboxylic group of ferulic and p-
coumaric acids of lignin and/or hemicelluloses (Flauzino Neto et al.,
Fig. 7. (a) XRD patterns and (b) FTIR spectra of raw AF, ATAF, CMF and CNC samples.
505
Industrial Crops & Products 112 (2018) 499–510
2013; Kargarzadeh et al., 2012; Rosa et al., 2010). The peaks at 1511
and 1246 cm−1 can be assigned to the C]C stretching vibrations from
the aromatic ring and CeO out-of-plane-stretching-vibration of the aryl
group in lignin and hemicelluloses molecules (Kargarzadeh et al., 2012;
Rosa et al., 2010). However, the mentioned peaks were not detected in
bleached CMF and hydrolyzed CNC spectra, suggesting that the lignin
and hemicelluloses were successfully removed after alkali and
bleaching treatments (Kargarzadeh et al., 2012; Mariano et al., 2016).
Commonly, in all spectra the broad peaks observed at
3370–3250 cm−1 was attributed to the stretching vibrations of CH and
OH groups from the principal functional groups present in lig-
nocellulosic materials (Barakat et al., 2014). Additionally, the peak
detected at 1633 cm−1 is due to the bending mode of the absorbed
water (Barakat et al., 2014; Flauzino Neto et al., 2013). Besides, in all
studied samples, the peak at 1159 cm−1 was associated to CeOeC
asymmetric stretching of the cellulose (Chen et al., 2016). Remarkably,
the intensity of this peak was gradually increased indicating that the
cellulose content was increased after different chemical treatments
starting from raw AF to the production of CNC. Moreover, the peaks
observed at 1033 and 899 cm−1 in all spectra could be attributed to the
CeOeC pyranose ring skeletal vibration and the glycosidic C1eH de-
formation with ring vibration contribution and OH bending, respec-
tively, which is characteristic of β-glycosidic linkages between glucose
in the cellulose (Chuan-Fu Liu et al., 2006). In addition, the peaks at
1426 cm−1, 1370 cm−1 and 1315 cm−1 were contributed to the CH2
symmetric bending of cellulose, CeH asymmetric deformation and CeO
M. El Achaby et al.
Fig. 8. (a) TGA and (b) DTG curves of AF, ATAF, CMF and CNC samples.
symmetric stretching within the polysaccharide aromatic rings of cel-
lulose and CeH bending of cellulose, respectively (Chen et al., 2016).
These peaks are observed in all spectra with increased intensity in the
case of bleached CMF and hydrolyzed CNC samples. Finally, the small
peak at 1202 cm−1 in the CNC spectrum is attributed to S]O vibration,
due to the insertion of sulfate groups on the surface of CNC during the
hydrolysis process (Lu and Hsieh, 2010). Consequently, the FTIR results
are in accord with other literatures, in which the extracted pure CMF
and acid hydrolyzed CNC showed a similar spectra (Chen et al., 2016;
Kargarzadeh et al., 2012; Lu and Hsieh, 2011, 2010; Mariano et al.,
2016; Rosa et al., 2010). This suggesting that the produced pure CMF
and CNC have been successfully isolated from cellulose rich AF.
3.7. Thermal stability of raw and treated cellulosic fibers
TGA/DTG analysis was conducted under nitrogen atmosphere to
evaluate the thermal degradation of all cellulosic materials at different
stages of treatment. The obtained results are shown in Fig. 8. It is well
known that the lignocellulosic materials degrade at low to moderate
temperature (Hajaligol et al., 2001). In general, the thermal decom-
position of such materials begins at lower temperature for hemi-
celluloses followed by an early stage of degradation of lignin molecules
and then decomposition of cellulose (Kargarzadeh et al., 2012; Mariano
et al., 2016).
From the results shown in Fig. 8 all of the samples showed a small
weight loss around 100 °C as a result of the evaporation of adsorbed
moisture, which is related to the hydrophilic nature of these cellulosic
materials (Kargarzadeh et al., 2012; Trache et al., 2014). The raw AF
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Industrial Crops & Products 112 (2018) 499–510
undergo two step degradation process, which confirmed by the ob-
servation of two peaks in DTG curve, with Tmax1 and Tmax2 of 279 °C
and 340 °C. The first degradation stage of AF sample, which began at
Tonset of 217 °C, was attributed to the degradation of hemicelluloses and
lignin molecules. The second degradation stage (Tmax2 = 340 °C) can be
attributed to the degradation of cellulose (Mariano et al., 2016). It has
been reported that the degradation of cellulose starts with the genera-
tion of glucose units followed by the depolymerization and dehydration
process, and then completed by the oxidation and breakdown of the
charred residue to lower molecular weight gaseous products (Flauzino
Neto et al., 2013; Mariano et al., 2016; Trache et al., 2014).
It is noted that the degradation of ATAF and CMF samples follow
almost identical degradation mechanism, as demonstrated by TGA/DTG
curves (Tonset = 235 °C; Tmax = 354 °C), with Tonset is 18 °C higher than
that observed for raw AF sample (217 °C); indicating that the major
parts of hemicelluloses and lignin were removed after alkali treatment,
because their degradation at relatively low temperature was not de-
tected in ATAF sample, regarding to raw AF sample. The same trend
was reported for sugarcane bagasse and kenaf bast fibers after alkali
and bleaching treatments (El Miri et al., 2015b; Kargarzadeh et al.,
2012). Remarkably, the high percentage of residue at high tempera-
tures observed in raw AF as compared to that in the ATAF was due to
the presence of ash and lignin (Kargarzadeh et al., 2012).
For CNC two degradation stages were detected, which start at a low
Tonset of 170 °C, with Tmax1 and Tmax2 of 262 °C and 354 °C, respectively.
These results agreed with many conducted works in the literature for
CNC extracted by sulfuric acid hydrolysis (Kargarzadeh et al., 2012;
Mariano et al., 2016; Paulo et al., 2013). The first degradation me-
chanism (Tmax1 = 262 °C) of CNC can be explained by the presence of
sulfate groups on the surface of CNC, which are capable to catalyze the
primary dehydration phase in the cellulose component at the relatively
lower temperature. Afterwards, the second degradation stage occurred
at the higher temperature (Tmax2 = 354 °C) was attributed to degrada-
tion of cellulose chains that slowly degraded and formed char products.
In regard to the thermal degradation behavior of bleached cellulose
(CMF) (Tonset = 235 °C), the thermal stability of CNC decreased as a
result of the presence sulfate groups, which considered as a major
drawback for CNC extracted by sulfuric acid hydrolysis.
3.8. Processing of nanocomposite films
The CNC were dispersed into Chitosan (CH), alginates (ALg) and k-
carrageenan (k-CA) biopolymer matrices at various CNC loadings for
objective to evaluate their ability to improve the tensile properties of
biopolymers and to produce new biopolymers based nanocomposite
films. CH, ALg and k-CA polysaccharides are the water soluble polymers
and their treatment in water can easily be achieved due to their hy-
drophilic nature. CH, AL and k-CA have also many functional groups,
such as hydroxyl groups (CH, ALg, CA), carboxylic groups (ALg), sulfate
groups (CA) and amino groups (CH) that could be useful to create
strong interfacial interactions between CNC and biopolymer matrices.
On the other hand, the sulfuric acid hydrolyzed CNC exhibit free hy-
droxyl and inserted anionic sulfate groups on their surfaces, which
make them highly water dispersible nanomaterials (Fig. 5). This com-
patibility between the CNC and these biopolymers can cause a good
dispersion/distribution of CNC, and therefore driving the formation of a
complex network in the final polymeric systems, thus improving the
properties of the resulted composite film materials. Accordingly, the
mixture of such polymers and CNC in water can be easily done in
controlled conditions, enabling the formation of a homogeneous and
stable aqueous CNC-biopolymers mixtures. By casting these latter on
petri dishes and evaporating of water, films with high quality, smooth
surface, good flexibility, and about 70-μm-thick were produced, ex-
ample of these films are presented in Fig. 2.
M. El Achaby et al.
Fig. 9. Typical stress-strain curves of (a) ALg-CNC, (b) k-CA-CNC and (c) CH-CNC na-
nocomposite films at different CNC loadings (1, 3, 5 and 8 wt%).
3.9. Tensile properties of nanocomposite films
Biopolymer-based films usually suffers from low tensile properties,
which limit their applications in various fields. However, these draw-
backs can be overcome by adding suitable nanoreinforcing fillers into
biopolymers for enhancing their tensile properties. Indeed, it has been
reported that CNC have a significant reinforcing impact on the tensile
properties of biopolymers (El Achaby et al., 2017; El Miri et al., 2015a;
Wang et al., 2017), due to their relatively large aspect ratio and high
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Industrial Crops & Products 112 (2018) 499–510
elastic modulus. Herein the aim is to evaluate the ability of CNC from
Alfa fibers as nanoreinforcing fillers to improve the tensile properties of
some biopolymers (ALg, k-CA and CH). For that, the tensile properties
of neat ALg, k-CA and CH and its nanocomposite films, with different
CNC loadings (1, 3, 5 and 8 wt%), were investigated by uniaxial tensile
testing. The obtained typical stress–strain curves of all studied ALg-, k-
CA- and CH-based nanocomposite films are presented in Fig. 9a–c, re-
spectively, and the measured tensile parameters, such as Young’s
modulus, tensile strength, toughness and elongation at break are ploted
in Fig. 10a–c. The toughness is defined as the work of fracture, and was
calculated from the area under the stress–strain curve. From these data,
it can be seen that all nanocomposite films exhibited superior tensile
properties than those observed for neat CH, ALg and k-CA biopolymers,
thus confirming that the incorporation of CNC (up to 8 wt%) had a
positive effect on the improving of tensile properties of the selected
biopolymers.
For ALg-CNC nanocomposites, the modulus, strength and toughness
increased gradually with increasing of CNC content from 1 to 8 wt%.
Indeed, when 8 wt% CNC was added (i.e. ALg-CNC-8), the modulus,
strength and toughness were increased from 1310 to 2846 MPa (117%),
from 50 to 97 MPa (94%) and from 5.3 to 8.3 MJ/m3 (56%), respec-
tively (Fig. 10). In contrast, it have been reported that when high
content of CNC (6–8 wt%) was incorporated in ALg nanocomposite the
modulus and strength start to decrease in regard to nanocomposite
containing 4–5 wt% CNC. It was claimed that the increasing of these
tensile parameters is related to the agglomeration phenomenon of CNC
within the ALg matrix at high CNC contents (Huq et al., 2012; Wang
et al., 2017). Herein, in our research the incorporation of CNC at re-
latively high content (8 wt%) resulted in more increasing of the selected
tensile parameters in regard to 5 wt% CNC, which can be attributed to
the original source and high crystallinity of CNC and their inherent
properties, such as high aspect ratio. It has been reported that cellulose
derivatives are compatible with ALg biopolymer due to their similar
structures (Abdollahi et al., 2013; Huq et al., 2012), suggesting that the
incorporation of cellulose-based nanomaterial into ALg matrix can re-
sulted in good dispersion/distribution of the nanoreinforcing phase
within ALg biopolymer matrix, and thus improving the tensile proper-
ties of the resulted nanocomposite systems. Herein, the interesting
combination of improved modulus, strength and toughness in the ALg-
CNC nanocomposites is due to the nanoscale dispersion of CNC, and the
unique characteristics provided by the dispersed CNC. The same trend
was reported by Svagan et al. (2007) for microfibrillated cellulose
(MFC) filled glycerol-plasticized amylopectin nanocomposites, in which
the modulus, strength and toughness are together increased after the
addition of MFC fillers. The fine dispersion of CNC within ALg biopo-
lymer is ensured by strong interfacial hydrogen and ionic interactions
between the free hydroxyl groups, which are naturally available on the
surface of CNC, and the functional groups of ALg biopolymer, including
hydroxyl and carboxyl groups. Similarly, it have been reported that the
improving of tensile properties of CNC-reinforced ALg nanocomposites
is attributed to the interfacial hydrogen and ionic bonding between
both phases (Abdollahi et al., 2013; Wang et al., 2017).
The same trend was found for k-CA-CNC nanocomposite films, in
which the modulus, strength and toughness were also increased with
increasing of CNC content from 1 to 8 wt%. The addition of 8 wt% CNC
(i.e. k-CA-CNC-8) resulted in increasing of the modulus and strength
from 1510 to 3089 (104%) and from 48 to 118 (145%), respectively
(Fig. 10). Furthermore, it should be noted that in regard to the neat k-
CA biopolymer, the k-CA-CNC nanocomposites not only have a higher
strength and modulus but also a higher toughness that reached a
maximum value of 11.1 MJ/m3 for the k-CA nanocomposite containing
3 wt% CNC, which is higher than that determined for MFC filled gly-
cerol-plasticized amylopectin nanocomposites (9.4 MJ/m3) (Svagan
et al., 2007). It is worth noting that no comparable results were pre-
viously reported in the literatures regarding CNC-filled k-CA nano-
composite films. Savadekar et al. (2012) prepared k-CA nanocomposites
M. El Achaby et al.
Fig. 10. (a) Young’s modulus, (b) tensile strength, (c) toughness and (d) elongation at break of neat ALg, k-CA and CH and their nanocomposites with different contents of CNC (1, 3, 5
and 8 wt%).
filled with 0.1-1.0 wt% mechanically produced nanofibrated cellulose
(NFC) (average diameter of 242 nm). They found that the strength was
increased by 44% with increasing of NFC content up to 0.4 wt% and
starts to decrease when 0.5-1.0 wt% NFC content was incorporated, due
to the agglomeration phenomenon of NFC within k-CA biopolymer
matrix. Shankar et al. (2015) reported k-CA nanocomposite reinforced
with 0.5–10 wt% hydrochloric acid hydrolyzed chitin nanofibrils (CNF)
(average diameter of 5–10 nm and average length of 150–200 nm).
From their results, the strength was increased by 42% at 5 wt% CNF
content and then decreased with more addition of CNF (10 wt%);
whereas the modulus was linearly increased with increasing of CNF
content from 0 to 10 wt% (with maximum increase of 65%), attributing
this improvement to the formation of a percolating network based on
hydrogen bonding interactions.
Herein, the modulus, strength and toughness are together improved
in the k-CA nanocomposites containing CNC, suggesting that CNC are
homogeneously dispersed within k-CA biopolymer. Might be the for-
mation of hydrogen bonding in k-CA-CNC nanocomposite films are
responsible for creating interfacial interaction between CNC and k-CA
biopolymer. Additionally, the presence of glycerol in these nano-
composite systems can help increase dispersion and interaction with
CNC, as previously highlighted in the literature for MFC filled glycerol-
plasticized amylopectin nanocomposites (Svagan et al., 2007), hence,
the improvement of the tensile parameters of k-CA-CNC nanocompo-
sites prepared with glycerol could be attributed to these explanations.
For CH-based nanocomposite systems, the addition of 5 wt% CNC
shows a more pronounced reinforcing effect than that of 8 wt%
(Fig. 10), which is related to the agglomeration phenomenon of CNC
within the CH biopolymer matrix, leading to a less pronounced increase
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Industrial Crops & Products 112 (2018) 499–510
of the modulus, strength and toughness parameters (El Achaby et al.,
2017). In regard to neat CH, the addition of 5 wt% CNC resulted in
increasing of the modulus and strength from 1392 to 2506 MPa (80%)
and from 46 to 92 MPa (100%), respectively. The toughness parameter
was reached its maximum value for the CH nanocomposite containing
3 wt% CNC. In these nanocomposite systems, the fact that 5 wt% CNC is
the optimum loading for increasing of modulus and strength was also
reported in the literatures (Borysiak and Grząbka-Zasadzińska, 2016;
Khan et al., 2012). Khan et al. (2012) reported that the increase of the
strength in CNC-filled CH nanocomposites was attributed to (i) the fa-
vorable interactions between the macromolecular chains of CH and
CNC, which is generated from the interactions between the anionic
sulfate groups of CNC and the cationic amine groups of CH, favoring a
good interface interaction between CH and CNC, in line with the work
reported by de Mesquita et al. (2010), and (ii) the nanoreinforcing ef-
fect of CNC occurred through effective stress transfer at CNC-CH in-
terface (Khan et al., 2012). This trend is in agreement with our previous
work when CNC from sugarcane bagasse were incorporated in CH-
Polyvinyl alcohol blend polymeric matrix (El Miri et al., 2015b).
On the contrary, the addition of CNC had a great impact on the
elongation at break values for all prepared biopolymer-based nano-
composites (Fig. 10). With the incorporation of CNC, the elongation at
break dropped from 17%, 27% and 22% for neat ALg, k-CA and CH
biopolymers to 12%, 12% and 11% for their nanocomposites containing
8 wt% CNC, respectively. The decrease of the elongation at break
parameter with incorporating CNC nanofiller is a well known phe-
nomenon, which may be ascribed to the rigid behavior of CNC and their
interfacial interactions with biopolymer matrices, which prevent the
motion of the macromolecular chains of biopolymers (Abdollahi et al.,
M. El Achaby et al.
2013; Borysiak and Grząbka-Zasadzińska, 2016; Shankar et al., 2015;
Wang et al., 2017).
Apparently, the special morphology (needle-like shape), large as-
pect ratio (66) and the functionalized surface of the as-produced sul-
furic acid hydrolyzed CNC are responsible for the significant re-
inforcement impact on tensile properties of the studied biopolymers
(ALg, k-CA and CH). Additionally, homogeneous and fine dispersion of
CNC along with favorable interfacial interactions between the func-
tional groups of CNC and those of biopolymer matrices is essential to
achieve improvement in the final tensile properties of the as-developed
biopolymer-based nanocomposite films. These ideal conditions result in
mechanically strong and flexible ecofriendly nanocomposite films, with
a very interesting combination of high modulus, high strength and high
toughness. From these very important results, CNC produced from raw
lignocellulosic AF have a good ability to improve the properties of
biopolymers.
4. Conclusion
Pure cellulose microfibers (CMF) with a diameter of 10 μm and yield
of 39% have been extracted from Alfa fibers (Stipa tenacissima plant) by
using alkali and bleaching treatments. After subjecting the as-extracted
CMF to sulfuric acid hydrolysis, cellulose nanocrystals (CNC) have been
successfully obtained with a yield of 57% (in regard to initial weight of
CMF), a needle-like shape, a crystallinity of 90%, an aspect ratio of 66,
negatively charged surface (zeta potential of −41.39 mV and 2.04
sulfate groups per 100 anhydroglucose units) and a good aqueous col-
loidal stability. Due to their excellent inherent properties and functio-
nalized surface, the as-extracted CNC showed a high ability to improve
the tensile properties of various biopolymers with different function-
alities. The incorporation of 1, 3, 5 and 8 wt% CNC into alginate, k-
carragennan and chitosan matrices, via solvent casting method, resulted
in nanocomposite films with largely improved Young’s modulus, tensile
strength and toughness parameters. An increase of 117% and 94%,
104% and 145% and 60% and 85% were reached for Young’s modulus
and tensile strength in the case of alginate-, k-carragennan- and chit-
osan-based nanocomposite films containing 8 wt% CNC, respectively.
This large improvement of tensile parameters was attributed to the
homogeneous and fine dispersion of CNC along with favorable inter-
facial interactions between the functional groups of CNC and those of
biopolymer matrices, resulting in mechanically strong and flexible
ecofriendly nanocomposite films.
Through this study, we have demonstrated a possible strategy to
give an added value to raw Alfa plant which is a fast growing perennial
plant, rich in cellulose, inexpensive and renewable source. The ex-
traction of CNC, with excellent properties, from Alfa fibers can be
considered as moderately-feasible source. Indeed, the extracted CNC
and the used method (sulfuric acid hydrolysis) are very attractive for
the realization of a sustainable and economically viable bio-sourced
nanomaterials for future growth of CNC applications in the industry. As
stated above, the raw Alfa fibers are abundant in nature, covering large
areas in North African countries, which can be ensure the availability of
this source for its utilization for the production of CNC for various in-
dustrial applications.
Acknowledgments
The financial assistance of the Office Chérifien des Phosphates (OCP
S.A.) in the Moroccan Kingdom toward this research is hereby ac-
knowledged. This work was performed as part of collaboration between
the INRA of Montpellier and the Materials Science and
Nanoengineering department (MSN) of the Mohamed 6 Polytechnic
University (UM6P) in Morocco. The authors would like to thank Dr.
Cédric Gaillard from INRA-Nantes, France for their help to achieve this
work. The authors would also like to thank Pr. Jones Alami, head of
MSN Department of UM6P, for his help to improve this work.
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Industrial Crops & Products 112 (2018) 499–510
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