Carbohydrate Polymers 129 (2015) 156–167

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

Bio-nanocomposite films reinforced with cellulose nanocrystals:

Rheology of film-forming solutions, transparency, water vapor barrier
and tensile properties of films
Nassima El Miri a,b , Karima Abdelouahdi c , Abdellatif Barakat d , Mohamed Zahouily a,b ,
Aziz Fihri b , Abderrahim Solhy e,∗ , Mounir El Achaby e,∗
a
Laboratoire de Matériaux, Catalyse & Valorisation des Ressources Naturelles, FST Mohammedia, Université Hassan II de Casablanca, Rue Tarik Bnou Ziad,
Mers Sultan, 9167 Casablanca, Morocco
b
MAScIR Foundation, Rabat Design, Rue Mohamed El Jazouli, Madinat Al Irfane, 10100 Rabat, Morocco
c
Division UATRS, Centre National pour la Recherche Scientifique et Technique (CNRST), Angle Allal Fassi/FAR, Hay Riad, 10100 Rabat, Morocco
d
INRA, UMR 1208 Ingénierie des Agropolymères et Technologies Emergentes (IATE), 2, place Pierre Viala, 34060 Montpellier Cedex 1, France
e
Center For Advanced Materials, Université Mohammed VI Polytechnique, Lot 660-Hay Moulay Rachid, 43150 Ben Guerir, Morocco

a r t i c l e i n f o a b s t r a c t

Article history: This study was aimed to develop bio-nanocomposite films of carboxymethyl cellulose (CMC)/starch (ST)
Received 29 January 2015 polysaccharide matrix reinforced with cellulose nanocrystals (CNC) using the solution casting method.
Received in revised form 22 April 2015 The CNC were extracted at the nanometric scale from sugarcane bagasse via sulfuric acid hydrolysis
Accepted 26 April 2015
and used as reinforcing phase to produce CMC/ST-CNC bio-nanocomposite films at different CNC load-
Available online 30 April 2015
ing levels (0.5–5.0 wt%). Steady shear viscosity and dynamic viscoelastic measurements of film-forming
solution (FFS) of neat CMC, CMC/ST blend and CMC/ST-CNC bio-nanocomposites were evaluated. Vis-
Keywords:
cosity measurements revealed that a transition from Newtonian behavior to shear thinning occurred
Bio-nanocomposite
Cellulose nanocrystals when CNC were added. The dynamic tests confirmed that all FFS have a viscoelastic behavior with an
Rheology entanglement network structure, induced by the hydrogen bonding. In regard to the cast film quality, the
Solvent casting rheological data showed that all FFS were suitable for casting of films at ambient temperature. The effect
Optical transparency of CNC addition on the optical transparency, water vapor permeability (WVP) and tensile properties of
Tensile properties bio-nanocomposite films was studied. It was found that bio-nanocomposite films remain transparent
due to CNC dispersion at the nanoscale. The WVP was significantly reduced and the elastic modulus
and tensile strength were increased gradually with the addition of CNC. Herein, the steps to form new
eco-friendly bio-nanocomposite films were described by taking advantage of the combination of CMC, ST
and CNC. The as-produced films exhibited good optical transparency, reduced WVP and enhanced tensile
properties, which are the main properties required for packaging applications.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction applications, especially in the field of biomaterials and packaging

The use of biopolymers for sustainable development and envi-
ronmental preservation has become ubiquitous in the last 20 years,
due to their several advantages including non-toxicity, biodegrad-
ability, wide availability and biocompatibility, especially when
compared to their synthetic counterparts (Rodríguez-González
et al., 2012). Biopolymers such as proteins and carbohydrates are
widely used as materials for both conventional and innovative
∗ Corresponding authors. Tel.: +212 662010620.
E-mail addresses: abderrahim.solhy@um6p.ma (A. Solhy),
Mounir.elachaby@um6p.ma (M. El Achaby).
applications (Rhim, Park, & Ha, 2013). In this context, biopolymers
are considered potential replacements for conventional plastic
materials; nevertheless, some of their properties must be improved
to position them as potential candidates that can be competed with
fossil derivatives (Kanmani & Rhim, 2014), especially, mechanical
and water vapor permeability properties, which are the properties
required for packaging applications (Rhim et al., 2013). How-
ever, the blending of biopolymers and/or adding of nanofillers
represents an effective way to improve the properties of biopoly-
mers, and therefore, broadens their fields of application (Reddy,
Vivekanandhan, Misra, Bhati, & Mohanty, 2013; Rhim et al., 2013).
Biopolymer blending is one of the most effective methods to
create new biomaterials with desired properties. Films produced

http://dx.doi.org/10.1016/j.carbpol.2015.04.051
0144-8617/© 2015 Elsevier Ltd. All rights reserved.
 N. El Miri et al. / Carbohydrate Polymers 129 (2015) 156–167
from the blending of biopolymers usually exhibit modified prop-
erties as compared to films made from an individual component
(Ghanbarzadeh, Almasi, & Entezami, 2010; Sionkowska, 2011).
Recently, there has been a noticeable increase in interest in the
use of biodegradable films made from modified biopolymers or
biopolymer based blends for packaging applications. Because they
offer many advantages over synthetic or non-biodegradable films
for coating applications on foodstuff (BenBettaïeb, Karbowiak,
Bornaz, & Debeaufort, 2015; Ghanbarzadeh et al., 2010; Silva-
Pereira, Teixeira, Pereira-Júnior, & Stefani, 2015; Van den Broek,
Knoop, Kappen, & Boeriu, 2015).
On the other hand, the bio-nanocomposite technology with low
loading of nanofillers (5 wt%) has already been proven as an effec-
tive way to produce new biomaterials with specific properties and
high performances for packaging applications (Reddy et al., 2013;
Rhim et al., 2013). The inclusion of well-dispersed nanofillers into
a polymeric matrix may result in improving the physicochemi-
cal properties of the resulted bio-nanocomposites, especially the
mechanical, optical, thermal and barrier properties.
Among the most studied biopolymers for packaging applications
are the starch (ST) and cellulose derivatives, such as carboxymethyl
cellulose (CMC) (Rhim et al., 2013). Despite their good film-forming
abilities, films made from CMC or ST have poor mechanical and
water vapor permeability properties, but these can be enhanced
by mixing them together to produce biodegradable blended films
with modified properties (Ghanbarzadeh et al., 2010; Peressini,
Bravin, Lapasin, Rizzotti & Sensidoni, 2003; Tongdeesoontorn,
Mauer, Wongruong, Sriburi, & Rachtanapun, 2011) or by adding
nanofillers to produce CMC or ST based bio-nanocomposite films
with improved properties (Chen, Liu, Chang, Cao, & Anderson, 2009;
Oun & Rhim, 2015; Savadekar, Karande, Vigneshwaran, Kadam, &
Mhaske, 2014; Yadollahi, Namazi, & Barkhordari, 2014).
The CMC biopolymer contains hydroxyl and carbonyl groups
and it is potentially miscible with ST biopolymer, due to
the formation of hydrogen bonds (Ghanbarzadeh et al., 2010;
Rodríguez-González et al., 2012; Tongdeesoontorn et al., 2011).
Indeed, the combination of their properties allows the forma-
tion of a CMC/CST blend that may lead to the preparation of
a new biocompatible and a homogeneous blend matrix for bio-
nanocomposite development (Almasi, Ghanbarzadeh, & Entezami,
2010; Rodríguez-González et al., 2012). Ghanbarzadeh et al.
(2010) studied CMC/ST blend films, and the effect of CMC con-
tent (0–20 wt%) on the physicochemical properties of the resulted
CMC/ST blend films was evaluated. It was found that the CMC/ST
blend films showed better mechanical and barrier properties than
neat ST film.
Accordingly, the current research is focused on the use
of CMC/ST blend as a biopolymer matrix for developing bio-
nanocomposite films with improved water vapor permeability
(WVP) and mechanical properties. Recently, Almasi et al. (2010)
incorporated nanoclay within a CMC/ST blend to produce high per-
formance nanoclay filled CMC/ST bio-nanocomposite films with
improved properties. In the same context, Rodríguez-González
et al. (2012) developed bio-nanocomposites of CMC/ST blend
reinforced with graphene oxide and keratin-grafted graphene
oxide. From their results, the thermomechanical properties of the
blends were drastically enhanced with addition of modified and
unmodified graphene oxide. Thus, with an aim to transform the
biopolymers into materials with high structural and mechanical
properties that can be competitive with the fossil derivatives, the
researches on biopolymer blend based bio-nanocomposites have
gained considerable interest in the recent years.
Recently, the use of elongated cellulose nanocrystals (CNC) for
bio-nanocomposites development has attracted more and more
attention in the field of nanotechnology. It has been widely demon-
strated that the incorporation of CNC into biopolymer can result in
157
bio-nanocomposite materials with high mechanical, optical, ther-
mal, and barrier properties (Alves, dos Reis, Menezes, Pereira, &
Pereira, 2015; Azizi-Samir, Alloin, Sanchez, & Dufresne, 2004; Chen
et al., 2009; El Miri et al., 2015; Fortunati et al., 2015, 2013; Kamal
& Khoshkava, 2015; Mariano, El Kissi, & Dufresne, 2014), which
are the main properties required for packaging applications (Rhim
et al., 2013). The adhesion properties and the large-number func-
tional groups that are present in the CNC’s surface and biopolymer
matrices can be exploited to improve the interfacial interactions
between the CNC and biopolymer matrices (El Miri et al., 2015).
This study examines bio-nanocomposite films based on CNC-
filled CMC/ST biopolymer blend. The CNC were extracted from
sugarcane bagasse (SCB) via sulfuric acid hydrolysis process and
successfully characterized. Then, the as-extracted CNC were dis-
persed into CMC/ST (70/30, w/w) biopolymer blend in order to
fabricate CMC/ST-CNC bio-nanocomposite films using the solvent
casting method, which is the frequently used method for processing
of biopolymer blend and bio-nanocomposite films for packag-
ing applications. CMC and ST are biopolymers that have hydroxyl
and carboxyl groups in their macromolecular chains; these groups
could be useful to link the functional groups of CNC with CMC and ST
macromolecules. The rheological properties of film-forming solu-
tions (FFS) of CMC/ST blend and CMC/ST-CNC bio-nanocomposites
were studied and their relation with the casting process was
evaluated. Structural, optical transparency, WVP and mechanical
properties of the prepared bio-nanocomposite films were evalu-
ated and studied in this report. The high performances of these
bio-nanocomposite films are expected to have potential in bioma-
terials or packaging applications.
2. Materials and experimental details
2.1. Materials
The SCB was provided by a SUNABEL-COSUMAR Group, a
company located in the region of Gharb-Loukkos, Morocco. The
moisture content of the raw SCB was about 7 wt%. The car-
boxymethyl cellulose sodium salt powder (CAS 9004-32-4) was
purchased from Alfa Aesar and corn starch (CAS 9005-25-8) was
purchased from Sigma–Aldrich. Analytical grade chemicals used
for CNC extraction were purchased from Sigma–Aldrich and used
without further purification.
2.2. Isolation of CNC
CNC were extracted from SCB through three well-known steps:
alkali and bleaching treatments and sulfuric acid hydrolysis,
according to the procedure reported by Siqueira et al. (2013).
Briefly, the raw SCB fibers were washed with distilled water for 1 h
at 60 ◦ C under mechanical stirring. Then, the prewashed SCB fibers
were treated three times with 4 wt% NaOH solution at 80 ◦ C for 2 h
under stirring and bleached with a solution made by equal parts
of acetate buffer, aqueous chlorite (1.7 wt% in water) and distilled
water. The bleaching treatment was performed four times at 80 ◦ C,
under mechanical stirring, during 4 h for each one. Acid hydrol-
ysis was achieved at 55 ◦ C with 64 wt% sulfuric acid for 30 min
under mechanical stirring. The suspension was diluted with ice
cubes to stop the reaction and was washed by successive centrifu-
gations at 12,000 rpm at 15 ◦ C for 30 min at each step and dialyzed
against distillated water until neutral pH. Afterward, the obtained
CNC suspension was sonicated (Branson sonifier model 450) for
5 min in an ice bath to avoid overheating, which can cause desul-
fation of the sulfate groups on the surface of cellulose. Then, the
obtained sonicated suspension was freeze-dried (Christ Alpha 2-4
LD Freeze Dryer) to remove water. The freeze drying process was
158 N. El Miri et al. / Carbohydrate Polymers 129 (2015) 156–167
used to obtain the CNC in solid form in order to measure their mass
fractions with accuracy for bio-nanocomposites preparation.
2.3. Preparation of bio-nanocomposite films
The CMC/ST-CNC bio-nanocomposite films were prepared by
using the solvent casting method (Table 1). Firstly, the CMC solu-
tion was prepared by mixing the desired amount of CMC powder
with 350 mL of distilled water and kept under vigorous stirring for
2 h at ambient temperature. Afterwards, the ST solution was sepa-
rately prepared by dissolving the desired amount of ST in 65 mL of
distilled water and kept under stirring for 30 min at 90 ◦ C. During
the heating process, 0.5 g of glycerol was added to the ST solution
as plasticizer. The CMC/ST mass ratio was fixed at 70/30 in accor-
dance to the work published by Rodríguez-González et al. (2012).
The aqueous suspension of CNC was prepared separately by mix-
ing the desired amount of freeze dried CNC with 65 mL of distilled
water, followed by ultrasonic treatment (Branson sonifier model
450) for 30 min in an ice bath in order to homogenize the disper-
sion of CNC in water. The obtained ST solution and CNC suspension
were then mixed and stirred for 30 min at ambient temperature.
Next, the resulting ST/CNC mixture was added to the pre-prepared
CMC solution and stirred for 1 h at 25 ◦ C. Finally, the CMC/ST-CNC
mixture was casted onto Petri dishes and the water evaporated
at ambient temperature for 3 days, and the obtained films were
dried for 3 h at 80 ◦ C to completely remove the water. Neat CMC
and CMC/ST blend films were also prepared according to the same
process mentioned above, without the addition of CNC. The load-
ing levels of CNC in CMC/ST-CNC bio-nanocomposite films were
fixed at 0.5, 2.5 and 5.0 wt%. The films were coded as CMC, CMC/ST,
CMC/ST-CNC-0.5, CMC/ST-CNC-2.5 and CMC/ST-CNC-5.0. The num-
ber in each code name indicates the weight fraction of CNC in each
formulation. Film codes and details of the formulations of each film
are shown in Table 1.
2.4. Characterization techniques
2.4.1. Characterization of CNC
Atomic Force Microscopy (AFM) measurements of CNC were
carried out using a Veeco Dimension ICON. The tapping mode was
used to capture height images at a scan rate of 1.5 Hz. Samples
for AFM observations were prepared by depositing a droplet of
a diluted CNC suspension onto freshly cleaved mica sheets, after
being sonicated for 30 min, and allowing the solvent to dry in air.
The zeta potential measurement of CNC suspension was carried out
using a Malvern Zetasizer Nano ZS instrument. For this measure-
ment, capillary cell was used and the CNC suspension was diluted
and sonicated for 30 min before being analyzed. X-ray diffraction
(XRD) characterizations of freeze-dried CNC were carried out using
a Bruker D8 Discover using the Cu K␣ radiation ( = 1.54184 nm) in
the 2 range of 2–60◦ , while the voltage and current were held at
45 kV and 100 mA.
Table 1
Sample codes and the composition of each formulation of films.
Film code CMC ST CNC Total mass
(g)/H2 O (g)/H2 O (g)/H2 O (g)/H2 O (mL)
(mL) (mL) (ml)
CMC 5.000/350 0.000/65 0.000/65 5/500 (1%, w/v)
CMC/ST 3.500/350 1.500/65 0.000/65 5/500 (1%, w/v)
CMC/ST-CNC-0.5 3.482/350 1.492/65 0.025/65 5/500 (1%, w/v)
CMC/ST-CNC-0.5 3.412/350 1.463/65 0.125/65 5/500 (1%, w/v)
CMC/ST-CNC-0.5 3.325/350 1.425/65 0.250/65 5/500 (1%, w/v)
2.4.2. Rheological measurements of FFS
Steady state flow and dynamic viscoelasticity measurements of
nanocomposites’ FFS were performed at 20 ◦ C, using a rotational
Physica MCR500 rheomter equipped with concentric cylinder
geometry (CC27). The temperature was regulated by a PaarPhys-
ica circulating bath and a controlled Peltier system (TEZ 150P-C).
Firstly, steady shear flow measurement from 0.01–100 s−1 was per-
formed and flow curves of all FFS were obtained. Secondly, strain
sweep measurement was performed, at a frequency of 0.75 Hz,
in order to determine the appropriate strain of linear-viscoelastic
region of the studied FFS. The storage or elastic modulus (G ) and
loss or viscous modulus (G ) as a function of strain were mea-
sured. Finally, frequency sweep was carried out over a range of
0.01–100 Hz at a strain of 1%. Dynamic G and G moduli as a func-
tion of frequency were measured.
2.4.3. FTIR analysis of films
Transform Infrared Spectroscopy (FTIR) characterizations of bio-
nanocomposite films were performed on an ABB Bomem FTLA 2000
spectrometer equipped with a Golden Gate single attenuated total
reflection (ATR) cell. The experiments were carried out in the range
from 4000 to 400 cm−1 with a 4 cm−1 resolution and an accumula-
tion of 32 scans. The FTIR spectra were taken in the transmittance
mode.
2.4.4. Morphology of films
Morphology of bio-nanocomposite films was evaluated at their
cryo-fractured surfaces, using scanning electron microscope (SEM)
(FEI, Quanta 200-ESEM) operated at 20 kV. The samples were frozen
in liquid nitrogen and cryo-fractured before being coated by a thin
conductive carbon layer to help improve SEM observations.
2.4.5. UV–vis spectroscopy analysis of films
The UV–vis spectroscopy analysis of bio-nanocomposite films
was carried out using a PerkinElmer LAMBDA 1050 UV/vis/NIR
spectrophotometer. The film samples were placed directly in the
spectrophotometer test cell and the air was used as reference. The
optical absorbance/transmittance of the films were measured in
the wavelength range of 200–800 nm.
2.4.6. Tensile properties of films
Tensile tests were performed using an Instron 8821S tensiome-
ter according to our previous work (El Achaby et al., 2014). The
tensile specimens were cut in rectangular shapes with dimensions
of 80 mm in length and 10 mm in width. The gauge length was fixed
at 30 mm and the cross head speed was 5 mm/min at room tem-
perature. All tests were carried out on a minimum of five samples
and the reported results are average values.
2.4.7. Water vapor permeability (WVP) of films
The determination of the WVP of the CMC/ST-CNC bio-
nanocomposite films was carried out according to the standard
method E96-E95 (ASTM method 1995) with some modifications
(Ghanbarzadeh et al., 2010). Glass bottles, with diameter of 20 mm
and depth of 45 mm, were used to accomplish the test. After posi-
tioning 4 g of anhydrous CaCl2 inside each glass bottle and thus
for maintaining a relative humidity (RH) of 0%. The glass bottles
were covered with the elaborated films, weighted and inserted in
climatic chamber with RH of 50% and temperature of 32 ◦ C. The
weighting process was made each hour over the duration of 7 h. The
changes in the weight of the glass bottle were recorded as a function
of time. Slopes were calculated by linear regression (weight change
versus time). The water vapor transmission rate (WVTR) was deter-
mined as the slope of the straight line (g/h) divided by the area of
 N. El Miri et al. / Carbohydrate Polymers 129 (2015) 156–167 159

the glass bottle mouth (m2 ). Finally, the WVP (g m/m2 h Pa) was
calculated as follows:
WVTR WVTR
WVP = X= X treatment yielded about 45% yellow colored fibers (Fig. 1b), which
p S(R1 − R2)
where X is the thickness of the film (m), S is the saturation vapor
pressure (Pa) at the test temperature (32 ◦ C), R1 and R2 are the
relative humidity in the climatic chamber and in the glass bottle,
respectively.
3. Results and discussions
3.1. Extraction and characterization of CNC
The CNC used as nano-reinforcing agents were extracted from
SCB via alkali and bleaching treatments followed by acid hydrol-
ysis. Visually, the initial ground SCB fibers had a yellow-brown
color (Fig. 1a). Beginning with the alkali treatment of the raw
SCB fibers, the main focus of this step was to eliminate the whole
non-cellulosic components (lignin, hemicelluloses and pectin) (Dos
Santos et al., 2013). With the subsequent treatment of alkali, some
alkali-labile linkages (ether and ester linkages) between lignin
monomers or between lignin and polysaccharides may have been
broken, which helped in the partial defibrillation of fibers. This
was calculated by the weight of the treated fibers divided by the ini-
tial weight of SCB. The next step was the bleaching treatment, with
the aim to purify the cellulosic fibers from any residual lignin or
other impurities obtained after the alkaline treatment. This bleach-
ing treatment can result in the total defibrillation of fibers into
individual microfibrils with smaller diameter. The bleached fibers
may have contained pure cellulose, as shown by a clearly white
color (Fig. 1c), thus confirming that the residual non-cellulosic ele-
ments were totally removed under the bleaching treatment. The
yield of this bleached product was about 33% with respect to the
initial amount of SCB. This yield is close to the values reported
in the literature for treated rice straw (36%) (Lu & Hsieh, 2012)
and treated pineapple leaf (40%) (Dos Santos et al., 2013). The
third and final step was the acid hydrolysis, which was carried out
under appropriate conditions that allowed the removal of amor-
phous domains from the bleached cellulose. The acid hydrolysis
and removal of amorphous domains was performed by cleaving

Fig. 1. Digital images of (a) raw SCB, (b) alkali-treated SCB, (c) bleached SCB and (d) freeze dried CNC samples; and (e) CNC suspension (7.6 mg/ml) and (f and g) high and
low scale AFM images of CNC and (h) XRD pattern of CNC.
160 N. El Miri et al. / Carbohydrate Polymers 129 (2015) 156–167
cellulose microfibrils into bundles of CNC with nanometric dimen-
sions, becoming more or less individualized by sonication with the
ability to be obtained in a clearly white powdered form via a freeze-
drying process (Fig. 1d). The yield of CNC was 15% with respect to
the initial amount of dried SCB fibers, and 45% with respect to the
amount of bleached cellulose. Comparatively, this yield is similar
to the CNC derived from corncob (46–50%) (Silvério, Flauzino-Neto,
Dantas, & Pasquini, 2013), higher than that obtained from rice straw
(13–18%) (Lu & Hsieh, 2012) and smaller than that obtained for CNC
extracted from pineapple leaf (55–77%) (Dos Santos et al., 2013),
and SCB (50–58%) (Teixeira et al., 2011).
The stability of the CNC suspension is crucial in the preparation
of nanocomposites and can be derived from the zeta potential of the
CNC suspension. It is well-known that the stability of CNC depends
strongly on its aspect ratio, surface functionalization, and the ability
of the solvent and surface groups to counterbalance the attrac-
tive hydrogen-bond interactions exerted by the abundant hydroxyl
groups (Espinosa, Kuhnt, Foster, & Weder, 2013). Fig. 1e shows a
photograph illustrating the CNC aqueous suspension stability, in
which a white gel appearance is observed. To note, this suspension
was prepared by redispersing of freeze dried CNC in water via ultra-
sonic treatment. Some suggested reasons for good stability of CNC
suspension is the exclusion of apolar components, the insertion of
polar sulfate groups, and the exposition of OH groups from the
cellulose structure. For our CNC suspension, the zeta potential had
a mean value of −61.9 mV. The suspension of CNC was considered
stable because the absolute value was higher than 25 mV (Morais
et al., 2013).
The morphology and size of the as-obtained CNC was char-
acterized by AFM analysis; the micrographs are shown in Fig. 1f
and g. To note, the AFM is an appropriate method to characterize
CNC because it provides accurate information about the diame-
ter, length and shape of the CNC (Flauzino-Neto, Silvério, Dantas,
& Pasquini, 2013). The AFM images showed that the as-isolated
CNC had needle-like shape, confirming that their extraction from
the treated SCB was successful. These images showed individ-
ual CNC and some aggregates through transverse height profiles.
The appearance of laterally aggregated CNC in AFM images was
expected due to the high specific area and strong hydrogen bonds
established between the CNC. Additionally, AFM images showed
that CNC are uniform in diameter and irregular in length. In general,
the exact dimensions of CNC depend on the nature of the original
raw material and hydrolysis conditions or pretreatments (Eichhorn
et al., 2010). Herein, the average diameter of the as-extracted CNC
was 5 ± 1.1 nm and the average length was 275 ± 73 nm, giving rise
to an average aspect ratio of about 55. Comparatively, the mea-
sured aspect ratio was similar to nano-sized CNC derived from
other sources such as SCB (32–64) (Teixeira et al., 2011), Corconob
(52–63) (Silvério et al., 2013), sisal (43–60) (Garcia de Rodriguez,
Thielemans, & Dufresne, 2006) and pineapple leaf (50–60) (Dos
Santos et al., 2013); and higher than that measured for CNC from
rice straw (9–10.5) (Lu & Hsieh, 2012), cotton (9.5–12.5) (Espinosa
et al., 2013) or cotton linters (20–24) (Morais et al., 2013), coconut
husks (35–44) (Rosa et al., 2010), ramie (12) (De Menezes, Siqueira,
Curvelo, & Dufresne, 2009) and Luffa cylindrica fibers (46) (Siqueira
et al., 2013). Contrastingly, it was smaller than that of CNC from
tunicate (70) (Azizi-Samir et al., 2004) and (148) (Sacui et al., 2014)
and bacteria (60–94) (Olsson et al., 2010; Sacui et al., 2014). Con-
sequently, it has been reported in the literature that the efficient
reinforcement effect of CNC in nanocomposite materials can be
guaranteed when CNC with an aspect ratio around 50 are incor-
porated into a polymer matrix (Eichhorn et al., 2010).
Fig. 1h shows the XRD pattern of CNC. The XRD patterns show
that the major intensity peak is located at a 2 value of around
22.6◦ , which is related to the crystalline structure of cellulose I
(Teixeira et al., 2011). Additionally, it has been reported that the
peaks observed at 14–16◦ and 34.5◦ are also characteristic of cel-
lulose I (Flauzino-Neto et al., 2013). The crystallinity index (CrI)
of CNC was found to be 65% according to calculations using the
equation CrI = ((I0 0 2 − Iamorph )/I0 0 2 ) × 100, where I0 0 2 and Iamorph
are the peak intensities of crystalline and amorphous cellulose,
respectively (Flauzino-Neto et al., 2013; Teixeira et al., 2011).
3.2. Stability of film-forming solutions
Owing to the hydrophilic nature of CMC, ST and CNC, their
mixture in water can be easily achieved in controlled conditions,
enabling the formation of a homogeneous and stable aqueous mix-
ture. Fig. 2a shows the photographs of neat CMC, CMC/ST blend
and CMC/ST-CNC bio-nanocomposites FFS. The photographs were
recorded at room temperature 15 days after preparation of the
mixtures, showing high stability and good homogeneity. This is
attributed to the good compatibility and the strong interactions
between CMC and ST in the blend and between CMC, ST and CNC
in the bio-nanocomposites. CMC and ST are miscible polymers via
hydrogen bonding interactions, because the hydroxyl groups of ST
are able to form hydrogen bonds with the hydroxyl and carboxyl
groups of the CMC macromolecules (Ghanbarzadeh et al., 2010;
Rodríguez-González et al., 2012; Tongdeesoontorn et al., 2011).
Very interestingly, the sulfuric acid hydrolyzed CNC exhibited free
hydroxyl and inserted anionic sulfate groups on their surfaces,
which can also strongly interact with the hydroxyl groups and the
carboxyl groups of CMC and ST. In this way, when CNC were incor-
porated into CMC/ST polymeric blend, a fine dispersion of CNC can
be achieved.
3.3. Steady shear viscosity of FFS
Fig. 2b shows the dependence of the steady shear viscosity
() on the shear rate ()˙ for FFS of neat CMC, CMC/ST blend and
CMC/ST-CNC bio-nanocomposites at different CNC loading levels
(0.5–5.0 wt%). As seen in Fig. 2b, neat CMC FFS exhibited a Newto-
nian behavior at low shear rates, which was characterized by the
shear rate-independent viscosity. At high shear rates, the most pro-
nounced shear-thinning behavior was also observed for the neat
CMC FFS. This result indicates that as shear rate increases, the inter-
molecular junctions are disrupted at a rate faster than their rate
of reformation, resulting in a decrease in the junction density and
hence a drop in the viscosity. The same behavior was previously
observed for neat CMC FFS (Florjancic, Zupancic, & Zumer, 2002).
These results indicate that the CMC FFS behaves as an entangle-
ment network system (or a concentrated solution) (Florjancic et al.,
2002; Kulicke, Kull, Kull, & Thielking, 1996). The CMC/ST blend
FFS showed the same behavior observed for neat CMC (Newto-
nian behavior at low shear rate and shear-thinning behavior at high
shear rate) with a slight increase in the shear viscosity at low shear
rate values; this is due to interfacial interactions between macro-
molecular chains of CMC and ST via the hydrogen bonding. The
decrease of the viscosity at high shear rates for CMC/ST blend may
be explained by the disruption of the formed interactions between
CMC and CMC or CMC and ST macromolecular chains during the
rotational measurements.
For FFS of CMC/ST-CNC bio-nanocomposites, it was observed
that the steady shear viscosity of CMC/ST blend was significantly
influenced by the addition of CNC. At the low shear rate region, the
viscosity increased gradually with the increase of CNC loading; this
is due to the flow-impeding effect induced by the presence of CNC
(Wu, Wang, Zhang, & Zhou, 2012). Furthermore, the presence of
CNC restrained the shear flow of the CMC and ST macromolecules
because the CNC’s average size is larger than that of the chain seg-
ments of the CMC and ST biopolymers, resulting in an increase of
shear viscosity (Wu et al., 2012).
 N. El Miri et al. / Carbohydrate Polymers 129 (2015) 156–167
Fig. 2. (a) Digital images, (b) shear viscosity versus shear rate and (c) zero shear viscosity of FFS based on (A) CMC, (B) CMC/ST, (C) CMC/ST-CNC-0.5, (D) CMC/ST-CNC-2.5 and
(E) CMC/ST-CNC-5.0.
As a result, the FFS of CMC/ST-CNC-0.5 bio-nanocomposite
showed a Newtonian behavior at very low shear rate; but the shear
thinning behavior became more pronounced than that observed
for FFS of neat CMC and CMC/ST blend, because this trend is
still controlled by the CMC behavior (Florjancic et al., 2002). The
FFS of CMC/ST-CNC-2.5 and CMC/ST-CNC-5.0 bio-nanocomposites
showed only the shear thinning behavior in the full shear rate
range, indicating that a network structure is formed by CNC within
the bio-nanocomposite FFS, which is constructed by strong hydro-
gen interactions and consequently causes the viscosity to increase
(Zhou, Wang, & Wu, 2012). A similar trend was reported for poly
(ethylene oxide) solutions containing different contents of CNC, in
which the addition of CNC causes the transition from Newtonian
behavior observed in polymer solution, to shear thinning behavior
in the full range of shear rate (Zhou et al., 2012). This transition was
attributed to the formation of a network structure of CNC within
the polymer solution (Bercea & Navard, 2000; Liu, Chen, Yue, Chen,
& Wu, 2011; Zhou et al., 2012).
The zero shear viscosity 0 was estimated by extrapolation
along the low shear rate plateau, and the 0 values determined
for the neat CMC, CMC/ST blend and CMC/ST-CNC FFS were plot-
ted in Fig. 2c. The 0 showed a significant increase when CNC
were added. Consequently, this 0 enhancement suggests that the
CMC, ST and CNC are perfectly compatible phases. Therefore, a net-
work structure was assumed to have been formed in CMC/ST-CNC
bio-nanocomposite solutions (Zhou et al., 2012). The formation of
this network could be related to the special nanometric rod-like
morphology of the CNC as well as their functionalized surfaces, pro-
viding a well homogeneous dispersion of CNC within the polymer
matrix, and thus leading to a high contact area at the CNC-polymer
chains interface.
161
In relation to the casting film quality, FFS based on neat CMC,
CMC/ST blend and CMC/ST-CNC bio-nanocomposites were homo-
geneous and without bubbles. Excellent stability without phase
separation was observed in all FFS studied. It has been reported
that a high-viscosity FFS of biopolymers would make it difficult
to remove air bubbles and hinder casting in thin layers (Cuq,
Aymard, Cuq, & Guilbert, 1995). According to Cuq et al. (1995), it
is very difficult to cast a consistent film from high-viscosity FFS
and the process needs a dispersing machine (spreader). Neverthe-
less, the FFS must be characterized by a relatively low viscosity
in order to avoid retention of air bubbles. Silva-Weiss, Bifani, Ihl,
Sobral, and Gómez-Guillén (2014) studied the viscosity of FFS
based on CMC/ST and CMC/modified ST and observed a shear thin-
ning behavior for these FFS. It was found that, at a shear rate of
2 s−1 , the apparent viscosity of CMC, CMC/ST and CMC/modified
ST was 8.49, 7.02 and 4.77 Pa s−1 , respectively; these values were
found to be suitable for the casting process at ambient tempera-
ture. Moraes, Carvalho, Bittante, Solorza-Feria, and Sobral (2009)
demonstrated that the low viscosity with Newtonian behavior
of FFS based on gelatin/polyvinyl alcohol facilitated the cast-
ing process. In this present study, the viscosity values observed
for all studied FFS were higher than those observed by Moraes
et al. (2009) and smaller than that observed by Silva-Weiss et al.
(2014). Consequently, the observed shear viscosity for all FFS
was suitable for the casting process since uniform layers of FFS
were spread on the plate, covering the entire surface at room
temperature. The dried films were smooth, homogeneous, trans-
parent and easily peeled off from the plate surface. Additionally,
these films were optically transparent, as confirmed by UV–vis
absorbance/transmittance measurements and visual observations
(see below).
162 N. El Miri et al. / Carbohydrate Polymers 129 (2015) 156–167

Fig. 3. (a and b) Storage (G ) and loss (G ) moduli versus strain and (c and d) G and G versus frequency of FFS based on neat CMC, CMC/ST blend and CMC/ST-CNC
bio-nanocomposites.

3.4. Viscoelastic behavior of FFS
To help select the strain appropriate for the linear viscoelas-
tic behavior of the studied FFS, dynamic strain sweeps were
first collected for all FFS at 0.75 Hz and 20 ◦ C. Fig. 3a and b
shows the strain dependence of dynamic storage (G ) and loss
(G ) moduli for neat CMC, CMC/ST and CMC/ST-CNC FFS. The
behavior illustrated in these Figures is typical of many viscoelas-
tic materials: the dynamic moduli remain constant in the linear
range and decreases above a critical shear strain ( crit ) (Kamal &
Khoshkava, 2015; Silva-Weiss et al., 2014). From Fig. 3a and b,
the  crit , G and G at  crit are extracted and presented in Table 2.
For the neat CMC and CMC/ST blend FFS, both moduli (G and
G ) started to decrease when the strain exceeded  crit = 63.94%,
indicating that the material structure starts to destroy. In CMC/ST-
CNC FFS, G and G increased monotonously with the increase
of CNC loading, and the  crit decreased more dramatically with
the increase of CNC loading from 0.5 to 5.0 wt%. A  crit of 17.5%
was observed for CMC/ST-CNC-5.0 bio-nanocomposite FFS, indi-
cating that the structure of the bio-nanocomposite FFS containing
a high CNC loading level started to destroy rapidly in compar-
ison with that of neat CMC and CMC/ST FFS. The decreasing of
 crit with the addition of CNC was recently observed by Kamal
and Khoshkava (2015) in CNC filled PLA bio-nanocomposite sys-
tems. It is also noted that below  crit , all the studied FFS exhibited
G higher than G , indicating that the viscous behavior is pre-
dominant over the elastic one in the linear viscoelastic range
(at low frequency) (Table 2). Consequently, to avoid structural
breakdown, a strain of 1% was chosen as an appropriate strain to
study the linear viscoelastic behaviors in all studied FFS. Dynamic
frequency sweeps with an applied strain level of 1% were then
collected. The storage modulus (G ) and loss modulus (G ) were
measured as a function of frequency in the linear viscoelastic
region.

Table 2
Viscoelastic parameters of FFS of neat CMC, CMC/ST blend and CMC/ST-CNC bio-nanocomposites.

Film code Strain sweep Frequency sweep

 crit (%) G at  crit (Pa) G at  crit (Pa) G at f = 0.1 Hz (Pa) G at f = 0.1 Hz (Pa) G = G (Pa) f at G = G (Hz)

CMC 63.94 0.70 1.07 0.01 0.13 1.35 1.39

CMC/ST 50.22 0.76 1.14 0.02 0.15 1.60 1.53
CMC/ST-CNC-0.5 31.36 0.93 1.58 0.03 0.21 2.38 1.58
CMC/ST-CNC-2.5 20.03 1.27 1.83 0.10 0.32 2.42 1.48
CMC-ST-CNC-5.0 17.52 1.99 2.64 0.24 0.59 2.91 1.33

 crit : critical strain from G curves; f: frequency.

 N. El Miri et al. / Carbohydrate Polymers 129 (2015) 156–167 163

Dynamic frequency sweep results can be used to characterize

or classify polymer based solutions (Clark & Ross-Murphy, 1987).
The four most traditional classifications are: a dilute solution, an
entanglement network system, a weak gel and a strong gel. A dilute
solution shows loss modulus (G ) larger than storage modulus (G )
over the entire frequency range, yet the moduli approach each other
at higher frequencies (Clark & Ross-Murphy, 1987). The entangle-
ment network system is characterized by the intersecting of both
moduli (G = G ) at the middle of the frequency range, indicating a
clear tendency for more solid like behavior at higher frequencies
(Clark & Ross-Murphy, 1987; Silva-Weiss et al., 2014; Xu, Liu, &
Zhang, 2006).
According to the G and G curves presented in Fig. 3c and
d, it is clear that all FFS show predominantly viscous behavior
at low frequencies (G < G ) and elastic behavior at high frequen-
cies (G > G ) (Table 2). According to the classifications mentioned
above, all FFS can be classified as an entanglement network system,
with the intersection of G and G (G = G ) at a frequency of about
1.3 Hz. The intersection points and the corresponding frequency
are summarized in Table 2. These results strongly align with the
results of Florjancic et al. (2002), Kulicke et al. (1996), Peressini
et al. (2003) and Silva-Weiss et al. (2014). At low frequencies,
there was enough time for entanglement to occur and be disrupted
during the oscillation period, which allowed viscous flow to pre-
dominate over the elastic behavior (G < G ). With an increase in
frequency, the time became insufficient for disruption of the entan-
glement; and the dispersion behaved as a cross-linked network
with the elastic response predominating over viscous flow (G > G )
(Ghasemlou, Khodaiyan, & Oromiehie, 2011; Peressini et al., 2003).
Silva-Weiss et al. (2014) studied the dynamic rheological proper-
ties of a series of polysaccharides FFS. They showed that neat CMC
and CMC/ST exhibited an entanglement network system caused
by physical cross-linking through polymer–polymer interactions.
The same trend was previously observed in film-forming disper-
sions of ST-methylcellulose (Peressini et al., 2003). It has been
reported that the elastic behavior is a function of the number of
effective chains participating in the formation of a network struc-
ture (Peressini et al., 2003). Herein, the increase in G values with
the addition of ST to CMC solution, or with the dispersion of CNC Fig. 4. SEM micrographs of (a) CMC/ST, (b) CMC/ST-CNC-0.5, (c) CMC/ST-CNC-2.5
into CMC/ST solution, suggested the presence of a greater num- and (d) CMC/ST-CNC-5.0 films and (e) FTIR spectra of neat CMC, CMC/ST and CMC/ST-
CNC films.
ber of interacting chains than the neat CMC solution. In the FFS of
neat CMC and CMC/ST blend, the entangled network was caused
by inter-chain interactions between CMC-CMC and CMC-ST. How- directly correlated with its effectiveness in improving the proper-
ever, in the FFS of CMC/ST-CNC bio-nanocomposite, the dispersion ties of bio-nanocomposite films.
of CNC can cause additional interfacial interactions between their Fig. 4e shows the FTIR spectra of neat CMC, CMC/ST blend and
functionalized surfaces and the macromolecular chains of CMC and CMC/ST-CNC bio-nanocomposite films. For neat CMC film spec-
ST. Alternatively, the increase of G and G with the increase of fre- trum, the band at 1055 cm−1 can be associated to C O stretching
quency when CNC were added, suggests that the CNC were well vibration of ether groups, while the bands at 1434 and 1604 cm−1
dispersed at the nanometric scale within the CMC/ST blend solu- can be attributed to the asymmetric and symmetric modes of
tion. stretching vibration of carboxylate groups (C O), respectively, and
the broad band centered at 3338 cm−1 is attributed to the stretching
of OH groups and intermolecular and intramolecular hydrogen
3.5. FTIR and SEM analysis of films bonds (Layek, Kundu, & Nandi, 2013; Luna-Martínez et al., 2011).
Owing to the chemical similarities between CMC and ST and
The SEM photographs of cryo-fractured sections of CMC/ST the relatively low content (5.0 wt%) of CNC within the CMC/ST
blend and CMC/ST-CNC bio-nanocomposite films are shown in blend matrix, the FTIR spectra of CMC/ST blend and CMC/ST-CNC
Fig. 4a–d. It was observed that the cross-section of unloaded bio-nanocomposite films showed similar characteristics of neat
CMC/ST film was smooth and without any cracks or pores (Fig. 4a), CMC film. By adding ST biopolymer and CNC nanofillers to CMC
which revealed a better film homogenization of CMC/ST blend. film, the band observed at 3338 cm−1 in neat CMC spectrum ( OH
Comparatively, the cross-section of the CMC/ST film was not group) was shifted to lower frequencies (3293 cm−1 in CMC/ST
strongly affected by the addition of CNC (Fig. 4b–d). In the bio- and 3299–3287 cm−1 in CMC/ST-CNC). In the same way, the band
nanocomposite films, polymers chains encapsulated the CNC. This observed at 1604 cm−1 in neat CMC spectrum ( C O groups) was
indicates that CNC were dispersed uniformly within the CMC/ST shifted to lower frequencies (1592 cm−1 in CMC/ST and 1587 cm−1
blend, and thus formed a stronger interaction and adhesion on the in CMC/ST-CNC). These results were attributed to the formation of
interfaces between CNC and macromolecular chains of CMC/ST. The hydrogen bonds between hydroxyl groups in ST and hydroxyl and
excellent dispersion of CNC within the polymeric blend matrix was carboxyl groups in CMC, and the abundant hydroxyl groups that
164 N. El Miri et al. / Carbohydrate Polymers 129 (2015) 156–167
are present in the surface of CNC. These trends have been previ-
ously observed in CMC/ST blend (Tongdeesoontorn et al., 2011),
CNC-filled ST bio-nanocomposite films (Chen et al., 2009) and
nanoclay-filled CMC/ST blend bio-nanocomposites (Almasi et al.,
2010).
3.6. Transparency properties of films
The optical absorbance, transparency and local dispersion of
CNC for the films of neat CMC, CMC/ST blend and CMC/ST-CNC
bio-nanocomposites were investigated using UV–vis spectroscopy.
The UV–vis absorbance spectra of such films are presented in
Fig. 5a. The absorbance at an arbitrarily chosen wavelength of
600 nm was also extracted and plotted for all studied films (Fig. 5b).
The absorbance of all films was dominated by the Raleigh scat-
tering component (the 1/4 tail), characterized by a decrease of
the absorbance with the increase of the wavelength (El Achaby,
Arrakhiz, Vaudreuil, Essassi, & Qaiss, 2012). The absorbance level of
neat CMC film was slightly affected by its blending with ST, because
the neat ST film showed a relatively high level in its absorbance
spectra (not shown) with respect to neat CMC film, resulting in
increased absorbance for the CMC/ST blend film, in agreement with
the observation of Silva-Weiss et al. (2014) for the CMC/ST blend
film. Furthermore, when CNC were dispersed into CMC/ST blend, all
the investigated CMC/ST-CNC bio-nanocomposite films maintained
the same absorbance level of the CMC/ST blend film, as can be seen
in Fig. 5b for a wavelength of 600 nm, in which the absorbance
level is not largely affected by the addition of CNC. The average
size of CNC was about 275 nm in length, as observed by AFM anal-
ysis (Fig. 1); its presence in bio-nanocomposite films is responsible
Fig. 5. (a) UV–vis absorbance spectra, (b) plot of absorbance at 600 nm, (c) UV–vis transmittance and (d) digitals images of neat CMC, CMC/ST, CMC/ST-CNC films.
to scatter and/or absorb the light and to increase the absorbance
level of the films. However, no scattering and/or absorbance dif-
ference were found between the CMC/ST blend and CMC/ST-CNC
bio-nanocomposites, indicating that the CNC were well dispersed
at the nanometric scale within the CMC/ST polymeric blend (El
Achaby et al., 2012).
Fig. 5c shows the optical transparency of the studied films,
which was performed by acquiring transmittance spectra in the
wavelength region of 200–800 nm. It is clear that all studied films
exhibited optical transmittance between 95% and 80% under the
visible light region. It is well documented that the neat CMC
film exhibits a high transparency level (>90%) in the visible light
region (Luna-Martínez et al., 2011; Yadollahi et al., 2014). This
transparency level of CMC was not largely affected by its blend-
ing with ST, and the resulting CMC/ST blend film exhibited the
same transparency level with a very slight decrease of optical
transmittance. Importantly, the CMC/ST-CNC bio-nanocomposite
films maintained the transparency properties of the CMC/ST
blend matrix, confirming that CNC were well dispersed in bio-
nanocomposite films (Fortunati et al., 2015, 2013). It also confirmed
that CNC have a good compatibility with the CMC/ST polymeric
blend matrix to avoid CNC aggregation, thus reducing the amount
of light scattering and favoring the transmittance of visible light
through the bio-nanocomposite films. Indeed, a good transparency
for bio-nanocomposite films is an important property required for
packaging applications (Rhim et al., 2013).
The results obtained from UV–vis absorbance/transmittance
were also supported by the visual observations of the bio-
nanocomposite films (Fig. 5d). The images illustrated in this figure
clearly show that the transparent level of CMC/ST blend film was
 N. El Miri et al. / Carbohydrate Polymers 129 (2015) 156–167 165

140
15.0
13.5 120
WVP (10 .g.m/m².h.Pa)

12.0 CMC/ST-CNC-5.0

10.5 100 CMC/ST-CNC-2.5

Stress (MPa)
9.0 CMC/ST-CNC-0.5
80
CMC
7.5
-7

6.0
4.5
3.0
1.5
0.0
A B C D E
Fig. 6. WVP of (A) neat CMC, (B) CMC/ST blend, (C) CMC/ST-CNC-0.5, (D) CMC/ST-
CNC-2.5 and (E) CMC/ST-CNC-5.0.
not affected by the addition of CNC due to its dispersion at nano-
metric scale (Fortunati et al., 2013, 2015).
3.7. WVP of films
In packaging applications, film should to avoid or at least
decrease moisture transfer between food and surrounding atmo-
sphere; the WVP should be as low as possible. The WVP of neat
CMC, CMC/ST blend and CMC/ST-CNC bio-nanocomposite films
are shown in Fig. 6. The WVP of the neat CMC film was found
to be 13.6 × 10−7 g m/m2 h Pa and it was influenced by blending
with the ST biopolymer and then by adding of CNC. This WVP
value is smaller than that observed by Oun and Rhim (2015)
(50.4 ×10−7 g m/m2 h Pa) and comparable to that observed by
Yadollahi et al. (2014) (15.2 × 10−7 g m/m2 h Pa) for neat CMC film.
It is well known that the polysaccharides are highly sensitive to
moisture and exhibit poor water vapor barrier properties due to
their hydrophilic character (BenBettaïeb et al., 2015). Importantly,
when CMC is blended with ST, the WVP decreased significantly to
6.05 × 10−7 g m/m2 h Pa, this is might be explained by the interac-
tion between both biopolymers via hydrogen bonding, which lead
to decrease of the number of free hydroxyl groups that give the
hydrophilic character to biopolymers, and thus decrease of WVP of
the CMC/ST blend. This result is in agreement with results previ-
ously reported for polymer blends which are studied for packaging
applications (BenBettaïeb et al., 2015; Ghanbarzadeh et al., 2010).
On the other hand, the addition of CNC into CMC/ST blend showed a
positive effect on the WVP of the resulted bio-nanocomposite films.
The WVP of bio-nanocomposite films decreased to 4.22 × 10−7 ,
4.01 × 10−7 and 5.24 × 10−7 g m/m2 h Pa when 0.5, 2.5 and 5.0 wt%
CNC were added, respectively.
From these results, the decrease in the WVP was attributed
to the impermeable CNC which were well dispersed/distributed
through the blend matrix to form a tortuous path for water vapor
transmission and to increase the effective diffusion path length
(Bai, Sun, Xu, Dong, & Liu, 2015; Kanmani & Rhim, 2014; Yadollahi
et al., 2014). This trend has been recently reported by Oun and
Rhim (2015) in cellulose nanofibril (CNF) reinforced CMC and by
Savadekar et al. (2014) in CNC reinforced ST bio-nanocomposite
films.
CMC/ST
60
40
20
0
0 5 10 15 20 25 30 35 40
Strain (%)
Fig. 7. Typical stress-strain curves of neat CMC, CMC/ST blend and CMC/ST-CNC
bio-nanocomposite films.
and the polymer matrix are the key points needed to achieve poly-
mer nanocomposite films with enhanced final properties (Habibi,
Lucia, & Rojas, 2010). Herein, the tensile properties of the neat
CMC, CMC/ST blend and CMC/ST-CNC films were investigated by
uni-axial tensile tests and the obtained stress-strain curves are pre-
sented in Fig. 7. From the stress-strain curves, the elastic modulus
(Young’s modulus), tensile strength and elongation at break of the
films were extracted and presented in Table 3.
According to these results, it is clear that the selected tensile
properties of CMC were affected by its blending with ST and then by
the addition of different contents of CNC. The neat CMC film exhib-
ited an elastic modulus of 1066.16 MPa, a tensile stress of 76.23 MPa
and an elongation at break of 22.99%. These obtained values are the
characteristics of high molecular weight CMC biopolymer (Layek
et al., 2013). When CMC was blended with ST, the elastic modulus
and tensile strength were decreased from 1066.16 to 847.23 MPa
and from 76.23 to 66.82 MPa, respectively. The elongation at break
of CMC (22.99%) was not affected in the CMC/ST blend (23.88%)
(Table 3). This variation in the tensile properties of CMC was not
surprising because of the lower tensile properties of ST biopolymer
with respect to the CMC biopolymer. These results agree with those
observed by Ghanbarzadeh et al. (2010) and Tongdeesoontorn et al.
(2011) in term of the variation of tensile properties of CMC/ST com-
pared to those of neat CMC.
With respect to the CMC/ST blend film, the elastic modulus
and tensile strength of the CMC/ST-CNC bio-nanocomposite films
increased gradually with increasing of CNC content from 0.5 to
5.0 wt%. When 5.0 wt% CNC was added (CMC/ST-CNC-5.0), the elas-
tic modulus and tensile strength were increased from 847.23 to
1650.19 MPa (94.77%), and from 66.82 to 110.83 MPa (65.86%),
respectively (Table 3). Such improvements confirmed that CMC/ST-
CNC bio-nanocomposite films are mechanically strong materials.
The elongation at break of CMC/ST was not largely affected by the
addition of CNC; a decrease from 23.88% for unloaded CMC/ST to
19.01% for CMC/ST-CNC-5.0 occurred (Table 3), indicating that the
Table 3
Elastic modulus, tensile strength and elongation at break of neat CMC, CMC/ST blend
and CMC/ST-CNC bio-nanocomposite films.

Film code Elastic Tensile Elongation at

3.8. Tensile properties of films modulus (MPa) strength (MPa) break (%)

CMC 1066.16 ± 53.30 76.23 ± 3.81 22.99 ± 0.91

The relatively large aspect ratio and high elastic modulus of CMC/ST 847.23 ± 42.35 66.82 ± 3.34 23.88 ± 0.95
CNC should have a significant reinforcing impact on the mechanical CMC/ST-CNC-0.5 1225.41 ± 61.25 83.56 ± 4.17 21.27 ± 0.85
properties of the polymer. Homogenous dispersion/distribution of CMC/ST-CNC-2.5 1375.34 ± 68.80 99.06 ± 4.95 20.88 ± 0.83
CMC/ST-CNC-5.0 1650.19 ± 82.51 110.83 ± 5.54 19.01 ± 0.76
CNC along with the favorable interfacial interactions between CNC
166 N. El Miri et al. / Carbohydrate Polymers 129 (2015) 156–167
CMC/ST-CNC bio-nanocomposite films are mechanically flexible
materials. For CMC/ST based bio-nanocomposites, the reinforcing
ability of CNC is comparable to that observed for nanoclay
nanofillers at the same loading level (Almasi et al., 2010).
The main reason for the improvement of the mechanical prop-
erties is the strong interfacial interactions between the CMC/ST
blend matrix and CNC, which was due to the high contact area
exposed on the CNC and their functionalized surfaces. During the
processing and drying of the bio-nanocomposite films, the origi-
nal hydrogen bonds formed between the macromolecular chains of
CMC were replaced by new hydrogen bonds that formed between
the hydroxyl and carboxyl groups in CMC chains, the hydroxyl
groups in ST chains and the hydroxyl groups in CNC. The existence
of these new hydrogen bonds improved the tensile properties of
the resulted CMC/ST-CNC bio-nanocomposite films.
4. Conclusions
By using the solvent casting method, new eco-friendly bio-
nanocomposite film materials that were based on carboxymethyl
cellulose (CMC)/starch (ST) biopolymer blend filled with cellulose
nanocrystals (CNC) have been developed and studied through this
paper. In particular, the rheology of film-forming solution (FFS) and
the structural, transparency, water vapor permeability and ten-
sile properties of resulting solid cast films were examined. It was
found that the steady shear viscosity showed that the dispersion
of CNC turned CMC and CMC/ST FFS from a Newtonian behavior
into a shear thinning behavior, especially at low shear rate val-
ues, and the zero shear viscosity increased with the increase of the
CNC content. Dynamic tests showed that all the studied FFS had a
viscoelastic behavior with an entanglement network structure, as
characterized by the intersecting of G and G at the middle of the
frequency range. In relation to the cast film quality, it was found
that the measured rheological properties were suitable for casting
all the FFS to form solid films with high quality and smooth surface.
Due to the homogeneous dispersion of CNC into CMC/ST blend, the
as-produced CMC/ST-CNC bio-nanocomposite films showed a good
optical transparency (80–95%). At the same time, the presence of
CNC in bio-nanocomposite films reduced significantly the water
vapor permeability of the neat CMC and the CMC/ST blend. Ten-
sile tests showed that the elastic modulus and tensile strength of
CMC/ST blend based bio-nanocomposite films increased by 94.77%
and 65.86%, respectively, when 5.0 wt% CNC were added. The
enhancement of the properties of bio-nanocomposite films was
due to strong interfacial interactions generated from the hydro-
gen bonding between the functional groups that are present in
the mixed components (CMC, ST and CNC). The as-produced bio-
nanocomposite films exhibited good optical transparency, reduced
WVP and enhanced tensile properties, which are the main proper-
ties required for packaging applications.
Acknowledgments
The financial assistance of the Office Chérifien des Phosphates
(OCP Group) in the Moroccan Kingdom toward this research is
hereby acknowledged. This work was supported also by grant
from the OCP Foundation. The authors would like to acknowl-
edge SUNABEL-COSUMAR Company in Morocco for providing us
the raw sugarcane bagasse. This work was performed as part of a
collaboration between the Mohammed VI Polytechnic University
and INRA-Montpellier. Financial support of the INRA-Montpellier
is acknowledged. We equally thank all administrative and tech-
nical support teams of the Université Mohammed VI Polytechnique,
especially Mrs Khadija Ait Hadouch et Mrs Loubnae Choukard.
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