Carbohydrate Polymers 211 (2019) 181–194

Contents lists available at ScienceDirect

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

Cellulose nanocrystals reinforced κ-carrageenan based UV resistant T

transparent bionanocomposite films for sustainable packaging applications
Mithilesh Yadava, Fang-Chyou Chiua,b,
⁎

a
Department of Chemical and Materials Engineering, Chang Gung University, Taoyuan, 333, Taiwan
b
Department of General Dentistry, Chang Gung Memorial Hospital, Taoyuan, 333, Taiwan

ARTICLE INFO ABSTRACT

Keywords: In this work, κ-carrageenan bionanocomposite films were prepared by solution casting of a mixture of κ-car-
Fourier-transform infrared spectral analysis rageenan, glycerol, and various amounts of cellulose nanocrystals (CNCs, 0–9 wt.%). The structure and mor-
Mechanical property phology of the bionanocomposite films were characterized by Fourier-transform infrared spectroscopy, X-ray
Nanocomposite diffraction, transmission electron microscopy, and scanning electron microscopy. Compared with κ-carrageenan
Cellulose nanocrystal
films, the κ-carrageenan bionanocomposite films showed better mechanical and barrier properties (water and
UV) and thermal stability. The water contact angle increased from 23.30° to 71.80° and the water vapor per-
meation decreased from 8.93 gm−1 s−1 Pa−1 to 4.69 × 10−11 gm−1 s−1 Pa−1 in the κ-carrageenan films loaded
with 9–7 wt.% CNCs, respectively. The tensile strength and elongation at break of the films increased from
38.33 ± 3.79 MPa to 52.73 ± 0.70 MPa and from 21.50 ± 3.72% to 28.27 ± 2.39%, respectively, after CNC
loading increased from 0 wt.% to 7.0 wt.%. These results indicated that the κ-carrageenan nanocomposite films
have potential applications in food packaging.

1. Introduction for preventing dehydration (Karbowiak, Debeaufort, Champion, &

Petrochemical-based plastic films composed of polyethylene, poly-
vinylchloride (PVC), polypropylene (PP), and polystyrene (PS) are
widely used as packaging materials because of their low cost, light
weight, good mechanical behavior, water resistance, and heat seal
ability. However, these materials are conditioned first before use be-
cause of their non-biodegradable nature (Sorrentino, Gorrasi, &
Vittoria, 2007). Therefore, researchers have developed packaging ma-
terials (Youssef & El- Sayed, 2018; Youssef et al., 2018; Youssef, EL-
Sayed, Salama, EL-Sayed, & Dufresne, 2015; Youssef, EL-Sayed, EL-
Sayed, Salama, & Dufresne, 2016) from sustainable biomass sources
that are environmentally friendly, inexpensive, light weight, possess
good thermomechanical properties, and provide a reasonable barrier to
the transfer of liquids and gases (Khan et al., 2010). Natural films based
on polysaccharides are biodegradable films that have been widely
studied (Dou, Zhang, He, Yin, & Cui, 2016; Xie et al., 2019). Carra-
geenans are sulfated polysaccharides that are derived from the cell
walls of red sea weeds (Roy, Shankar, & Rhim, 2019) and are composed
of a linear chain of sulfated galactans. Carrageenans are categorized
into three types according to their sulfate content: κ (20%), ι (33%), and
γ (41%). Carrageenans show a high potential as a film-forming mate-
rial. Edible carrageenan films can be applied in meat, poultry, and fish
Voilley, 2006). Park (1996) found that κ-carrageenan transparent films
show a higher tensile strength (TS) than ι- and γ-carrageenan films. Fan,
Peng, Li, Wang, and Wang (2013) concluded that the optimal TS and
elongation at break (EB) of blend films of κ-carrageenan and alginate
can be achieved when the κ-carrageenan content is 30 wt.%. Lafargue,
Lourdin, and Doublier (2007) reported the mechanical properties of κ-
carrageenan/pea starch blend films. Larotonda, Torres, Goncalves,
Sereno, and Hilliou (2016) reported that the thin, flexible, and trans-
parent films of κ-carrageenan/rice starch show higher rheological, ul-
traviolet (UV) barrier, oxygen barrier, and hydrophobic properties than
commercial κ-carrageenan. Park, Lee, Jung, and Park (2001) reported
that adding ascorbic acid can affect the TS, EB, and water vapor per-
meability (WVP) of κ-carrageenan/chitosan blend. However, the ap-
plications of κ-carrageenan films are limited by their poor mechanical,
thermal, and barrier properties. Thus, κ-carrageenan has been re-
inforced by preparing nanocomposites with various nanofillers. Wahab
and A B D Razak (2016) revealed that κ-carrageenan/clay bionano-
composite films exhibit optimum tensile properties at 3 wt.% of HNT.
Another study found that κ-carrageenan/SiO2 films as a packaging
material demonstrate enhanced mechanical and antimicrobial proper-
ties (Venkatesan, Rajeswari, & Thiyagu, 2017). Compared with κ-car-
rageenan films, κ-carrageenan/ZnO films show higher mechanical and

⁎
Corresponding author at: Department of Chemical and Materials Engineering, Chang Gung University, Taoyuan, 333, Taiwan.
E-mail address: maxson@mail.cgu.edu.tw (F.-C. Chiu).

https://doi.org/10.1016/j.carbpol.2019.01.114
Received 12 December 2018; Received in revised form 29 January 2019; Accepted 31 January 2019
Available online 01 February 2019
0144-8617/ © 2019 Elsevier Ltd. All rights reserved.
M. Yadav, F.-C. Chiu
solubility properties in food packaging applications (Saputri,
Praseptiangga, Rochima, Panatarani, & Joni, 2018). Rhim (2012)
evaluated the mechanical, water vapor barrier, and water resistance
properties of κ-carrageenan/agar blend films prepared by solution
casting with and without nanoclay.
Although numerous studies reported on κ-carrageenan nano-
composites with different types of fillers, few used cellulose nanocrys-
tals (CNC) as a nanofiller to reinforce κ-carrageenan. Cellulose is the
structural component of the primary cell wall of green plants. It con-
stitutes the most abundant renewable polymer resource on earth. Two
types of nanocellulose can be obtained from cellulose: whiskers and
nanofibrils (Azizi Samir, Alloin, & Dufresne, 2005). The term “whis-
kers” (or “nanowhiskers/nanocrystals”) refers to nanoparticles that
exhibit a needle-like appearance, whereas the term “nanofibrils” (or
“microfibrillated cellulose”) refers to long and flexible nanoparticles
composed of alternating amorphous and crystalline domains (Khalil,
Bhat, & Yusra, 2012). CNCs as sustainable nanomaterials show abun-
dance, renewability, and biodegradability, high mechanical properties,
high reinforcing capability, and low density (Rescignano et al., 2014).
As the main components of cellulose fibers (Veluswamya et al., 2016,
2017), the crystalline and amorphous parts can be generally separated
by mechanical and chemical processes. The amorphous regions of cel-
lulose can be broken under controlled conditions to liberate colloidal
particles known as CNCs. This process is achieved by acid hydrolysis,
which entails the destruction of the surrounding amorphous regions
between the microfibrils of cellulose while the crystalline segments
remain intact. This breakdown of CNCs is attributed to the fact that the
kinetics of hydrolysis is faster in the amorphous region than in the
crystalline domains because of the higher permeability of the former
than the latter (Azizi Samir et al., 2005). The geometric dimensions
depend on the initial source of cellulose, which accounts for widths
(5–20 nm) and lengths (100 nm–2 μm). CNCs do not flocculate with
water because of the electrostatic repulsion arising from the surface,
leading to suspensions that are stable for several months (Tingaut,
Zimmermann, & Sèbe, 2012). Azizi and Mohamad (2018) studied the
effect of CNC loading on the mechanical and barrier properties of κ-
carrageenan bionanocomposite films. The addition of 4% CNC in κ-
carrageenan improves the mechanical properties of biodegradable
composite films based on κ-carrageenan reinforced by CNCs from kenaf
fibers (Zarina and Ahmad, 2015). Garcia, Hilliou, and Lagaron (2010)
concluded that κ-carrageenan/cellulose bionanocomposites containing
3 wt.% cellulose nanowire exhibit the lowest reduction in WVP, that is,
ca. 71%, and largely attributed this reduction to a filler-induced water
solubility reduction. However, the effect of CNCs on the UV properties
of carrageenan was not analyzed. Many studies focused on κ-carra-
geenan/CNC nanocomposites (Azizi & Mohamad, 2018; Garcia et al.,
2010; Zarina & Ahmad, 2015), but information about the UV barrier
properties of κ-carrageenan/CNC films remains lacking to date. Thus,
the present study characterized the UV barrier properties of κ-carra-
geenan/CNC films and fabricated κ-carrageenan/CNC bionanocompo-
site films by using a simple solution mixing technique. The effects of
CNCs on the water solubility, water absorbency, moisture content, and
mechanical and thermal properties of κ-carrageenan films were also
systematically explored. Results showed that the synthesized κ-carra-
geenan/CNC nanocomposite films can serve as sustainable packaging
materials because of their enhanced physico-chemical properties.
2. Materials and methods
2.1. Materials
Glycerol and κ-carrageenan were purchased from Sigma Aldrich and
used as received. Ultra-fine microcellulose (ARBOCEL UFC) was pur-
chased from J. RETTENMAIER & SÖHNE France (JRS). Sulfuric acid
(Merck) was used to maintain acid concentration. The other chemical
reagents were of analytical grade. Millipore water was used for all
182
Carbohydrate Polymers 211 (2019) 181–194
experiments.
2.2. Synthesis of CNCs
CNCs were synthesized using sulfuric acid hydrolysis (Korolovych
et al., 2018). Cellulose microcrystalline (CMC, 3 g) was hydrolyzed with
sulfuric acid solution (20 mL, 64 wt.%) at 48 ℃. The resultant suspen-
sion was added to 200 mL of cold water (4 ℃). The reaction was per-
formed for 60 min under continuous magnetic stirring and then stopped
by adding 200 mL of cold water (4 ℃). After the reaction product
precipitated, the supernatant was decanted. This suspension was wa-
shed by centrifugation at 10,000 rpm for 5 min at room temperature.
The washing was repeated three times before the product was dialyzed
in millipore water. The millipore water was changed daily until the pH
reached 7. Subsequently, the suspension was subjected to ultra-soni-
cation (DELTA Ultrasonic Cleaner DC300 H) for 1 h at an operating
frequency of 40 kHz and a power dissipation of 300 W to break down
the unfractionated cellulose into small nanoparticles. Finally, the
sample was freeze dried. The final product was CNCs with a length of
200–500 nm and a diameter of 20–50 nm. Details about the preparation
of CNCs are discussed in S1. The obtained yield of the CNCs was ap-
proximately 65%.
2.3. Synthesis of κ-carrageenan/CNC nanocomposite films
In accordance with S2, κ-carrageenan/CNC films were fabricated as
follows. The κ-carrageenan solution was prepared by dissolving 1 g of κ-
carrageenan powder in 100 mL of distilled water under magnetic stir-
ring for 30 min. The glycerol plasticizer (25% of κ-carrageenan) was
then mixed with the κ-carrageenan solution while stirring for another
30 min. Nanocomposite samples were fabricated by dispersing different
amounts of CNCs (0, 1, 3, 5, 7, and 9 wt.%) in 100 mL of distilled water
for 30 min at room temperature. The obtained suspension was added to
the κ-carrageenan solution, stirred for 1 h at room temperature, and
then sonicated for 20 min at 25 ℃ in a bath-type ultrasound sonicator.
The κ-carrageenan/CNC suspensions were then poured into a glass petri
dish and dried at 40 ℃ for 24 h until the solvent was completely eva-
porated and a self-standing film was achieved. The resultant κ-carra-
geenan/CNC nanocomposite film with 0, 1, 3, 5, 7, and 9 wt.% loading
of CNCs were coded as CNC0, CNC1, CNC3, CNC5, CNC7, and CNC9,
respectively. The thickness of the films (0.020–0.040 mm) was mea-
sured with the help of a Teclock dial thickness gauge (SM-112, Japan),
and triplicate measurements were taken.
2.4. Fourier-transform infrared spectroscopy (FTIR)
FTIR spectra were recorded using a BRUKER, TENSOR 27 IR spec-
trometer. The samples were analyzed at a range of 400–4500 cm−1.
Prior to the experiment, the samples were dried in an air circulation
oven at 40 ℃.
2.5. Field emission scanning electron microscopy (FESEM)
The surface morphology and cross section of the prepared samples
were examined via SEM (Jeol JSM-7500F).
2.6. Transmission electron microscopy (TEM)
Carbon film-covered copper grids (5–6 nm film thickness, 200 mesh,
EMS FF200) were used for imaging CNC samples. One drop of the CNC
suspension (0.1 mg/mL) was placed on a grid for 30 min and wicked
away with a filter paper. Further, the samples were stained by depos-
iting a drop of (2 wt.%) phosphotungstic acid solution on the grid for
20 min and wicking the excess solution away with a wet filter paper.
The grid was dried in the oven at 70 ℃ before insertion into the mi-
croscope. Finally, the CNCs were analyzed by a JEOL (JEM-1230
M. Yadav, F.-C. Chiu
electron microscope, Tokyo, Japan) operated at an accelerating voltage
of 200 kV.
2.7. Optical microscopy (OM)
The selected samples were dried in an air-circulating oven for 6 h at
40 ℃ and used for microscopic analysis. An optical microscope
(Olympus BX-50) was used to examine the phase morphology and
dispersion status of the nanofillers.
2.8. X-ray diffraction (XRD)
XRD was measured by an X-ray diffractometer (D2, Bruker,
Germany). The X-ray source was CuKα radiation operating at 40 kV and
40 mA. The degree of crystallinity was calculated using the following
equation (Segal, Creely, Martin, & Conrad, 1959):
I002 Iam
CI(%) = × 100,
(1)
I002
where I002 is the intensity of the crystalline region of cellulose
(2θ = 22.5°) and Iam is the intensity of the amorphous region
(2θ = 16.3°).
2.9. Thermogravimetric analysis (TGA)
The thermal stability of the samples was characterized using a
thermogravimetric analyzer on a TA Q50 system. The samples were
scanned from room temperature to 700 ℃ at a heating rate of 10 ℃
/min under a nitrogen environment.
2.10. Density
Film density was determined from the specimen weight and volume.
The specimen was weighed using an analytical balance (A & D Co., Ltd.,
Japan) with a precision of 0.1 mg. The specimen volume was calculated
from specimen area and thickness. The thickness was measured using a
Teclock dial thickness gauge (SM-112, Japan) with a precision of
0.01 mm at five different positions in each specimen, and the average
values were taken. The densities of the CNC0, CNC1, CNC3, CNC5,
CNC7, and CNC9 films are presented in Table 2. The data were calcu-
lated as the mean value of three specimens of each film type. All films
showed almost the same density, suggesting that the incorporation of
CNCs did not significantly affect the density of the films. This result can
be attributed to the low amount of loaded CNCs.
2.11. Opacity and UV visibility
Opacity was determined by measuring the film absorbance at
600 nm using a UV spectrophotometer (JASCO, V-650) and calculating
by the following equation:
Opacity = Abs600/d (2)
Where, Abs600 is the value of absorbance at 600 nm and d is the film
thickness (mm).
2.12. Water absorbency
Water absorbency of the bionanocomposite films was tested in
terms of swelling. Film samples were sectioned into 2 × 2 cm2 pieces
and pre-weighed (5 mg). Each sample was immersed in a petri dish
filled with 20 mL of deionized water and remained undisturbed for 24 h
at room temperature until an equilibrium swelling was reached. The
swollen samples were removed from deionized water, quickly wiped
with filter paper to remove droplets on the surface, and then weighed.
Tests were repeated four times to minimize error. The swelling ratio
(Sr) can be calculated using the following expression (Yadav,
183
Carbohydrate Polymers 211 (2019) 181–194
Seongcheol, Hyun, & Kim, 2015):
Ws Wd
Swelling Ratio (%) = Sr(%) = × 100,
Wd (3)
Where, Ws is the weight of the swollen samples and Wd is the weight of
the dry samples. All measurements were performed in three replicates.
2.13. Film water solubility (FWS)
The solubility of the films was calculated as the percentage of dis-
solved dry matter after immersion in water in accordance with a pre-
viously described method (Orsuwan, Shankar, Wang, Sothornvit, &
Rhim, 2016). For this calculation, film samples were sectioned into
2 × 2 cm2 pieces and dried at room temperature for 24 h to determine
the initial dry weight (Wi). Then, the film samples were immersed in
20 mL of distilled water with mild shaking, removed, and then dried at
40 ℃ for 24 h to determine the undissolved final dry weight (Wf). FWS
was calculated using the following equation (Noshirvani,
Ghanbarzadeh, Fasihi, & Almasi, 2016):
Wi Wf
FWS= × 100.
Wi (4)
2.14. Moisture absorption
Moisture absorption was measured as described by Almasi,
Ghanbarzadeh, and Entezami (2010). Dried CNC0, CNC1, CNC3, CNC5,
CNC7, and CNC9 films of size 2 × 2 cm2 were preconditioned at 0%
relative humidity (RH) for 24 h. After weighing, they were conditioned
in a humid chamber (Giant Force, Taiwan) at 25 ℃ to ensure 98% RH.
The samples were weighed at desired intervals of time until the equi-
librium state was reached. The moisture absorption of the samples was
calculated as follows (Noshirvani et al., 2016):
Wt Wo
Moisture absorption(%) = × 100,
(5)
Wo
Where, Wo is the initial weight of the samples and Wt is the weight
of the samples after time at 98% RH. All measurements were performed
in three replicates.
2.15. Water vapor permeation (WVP)
The WVP of the κ-carrageenan nanocomposite films was determined
by the gravimetric method in accordance with the ASTM-E96/E96-05
Standard (ASTM-E96/E96-05, 2005). The water method described in
this standard was implemented in the current work. Petri dishes of 6 cm
diameter were used as test dishes. In each test dish, 20 mL of distilled
water were added, leaving a distance of approximately 1 cm between
the water surface and the film. The film samples were sealed to the dish
mouth by a water-resistant sealant. The dishes were placed in a con-
trolled-environment room with 30 ℃ temperature and 78% RH, and
their weight was measured at intervals of 12 h over a 48 h period on a
balance. The weight of each dish linearly decreased with time. The
WVP was calculated using Eq. (6). The parameter weight loss/time was
obtained from the slope of weight loss vs. time plot. The WVP of the
film was calculated using the following formula:
WVP (g m−1 s−1 Pa−1) = (w/t). γ. (A)−1 (Δp)−1, (6)
where w is the weight loss of the Petri dishes (g), γ is the film thickness
(m), A is the cross- section area of the film (m2), t is the time (s), and Δp
is the vapor pressure difference (3167.2 Pa at 25 ℃). Each sample was
measured in triplicate.
2.16. Water contact angle
The hydrophilicity of the polymer blend and polymer
M. Yadav, F.-C. Chiu
Fig. 1. FTIR spectra of CMC, CNC, CNC0, κ-carrageenan and CNC9.
nanocomposites films was evaluated by contact angle measurements
using a Drop Shape Analysis System (model DIGIDROP GBX instrument,
France). Deionized water was used to evaluate the hydrophilic prop-
erties of these films. Angle measurements were performed in triplicate,
and their average values were taken.
2.17. Mechanical properties
Tensile tests of the CNC0, CNC1, CNC3, CNC5, CNC7 and CNC9
films (according to ASTM D638) were conducted at a crosshead speed
of 10 mm/min by using a Gotech AI-3000 system.
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Carbohydrate Polymers 211 (2019) 181–194
3. Results and discussion
3.1. Preparation of cellulose nanocrystals, homogenous suspension, and κ-
carrageenan/CNC nanocomposite films
Strong acid hydrolysis with H2SO4 is usually performed prior to or
after mechanical, high-pressure homogenizer, ultrasonic, or hydro-
dynamic cavitation treatment (Majoinen, Kontturi, Ikkala, & Gray,
2012) to yield CNCs. The hydrolysis process basically involves re-
moving the amorphous regions present in the CNCs, leaving the crys-
talline regions intact. Hence, the dimensions of the cellulose whiskers
obtained after hydrolysis are mainly dependent on the percentage of
amorphous regions that varies for each organism. The fabrication of
renewable biopolymer films by a process other than casting is not re-
ported due to its thermosensitivity. Other film-forming procedures,
M. Yadav, F.-C. Chiu
such as slit-die extrusion, blown-film extrusion, and calendaring, in-
volve high temperatures, which consequently lead to undesirable re-
actions such as biopolymer degradation.
3.2. Fourier transform infrared spectroscopy
Many studies (Turquois, Acquistapace, Vera, & Welti, 1996) have
performed infrared spectroscopy of polysaccharides. The FTIR tech-
nique is widely used to investigate the miscibility of renewable poly-
mers and nanomaterials due to its rapid, non-destructive, and powerful
nature. When chemical functional groups interact, changes such as
shifting of absorption bands can be detected in FTIR spectra. These
changes can indicate good miscibility of polymers. The FTIR spectra of
the fabricated CNCs showed that the sharp peak at 3350 cm−1 might be
due to the OeH vibrations in hydrogen bonds (Li & Renneckar, 2011).
The absorption bands between 2800–3000 cm−1 originated from C–H
stretching and bending vibrations (Wang & Roman, 2011). Some other
absorption bands were assigned at 567 (OeH out of plane bending vi-
brations), 1058 (C–O stretching at C-3 position), and 1163 cm−1
(C–OeC stretching motion) (Nikonenko, Buslov, Sushko, & Zhbankov,
2005). Aside from these peaks, the CNCs showed two more peaks at
1645 and 1240 cm−1, confirming that the acidification of the CMCs was
successfully performed (Lu & Hsieh, 2010). Furthermore, the abundant
oxygen functional groups rendered the CNCs hydrophilic, which im-
proved their solubility in water. In κ-carrageenan (Sen & Erboz, 2010),
the characteristic peaks at 3362 cm−1 (OeH stretching vibration),
2978 cm−1 (CeH stretching vibration) (Cerqueira et al., 2011),
1279 cm−1 (presence of ester sulfate group), 912 cm−1 (3, 6-anhy-
drogalactose group), and 835 cm−1 (galactose-4-sulfate group) were
assigned. After adding glycerol in κ-carrageenan (κ-carrageenan con-
taining glycerol = CNC0), the peaks at 3362, 2978, 1279, 912, and 835
cm−1 shifted to 3342, 2982, 1288, 943, and 867 cm−1, suggesting that
glycerol interacted with κ-carrageenan through intermolecular hy-
drogen bonds and indicating the good miscibility between them. When
CNC was added in CNC0 (κ-carrageenan containing glycerol), the peaks
at 3342–3416 cm−1 (OeH stretching vibration), 2982–2932 cm−1
(CeH stretching vibration), 1288–1261 cm−1 (presence of ester sulfate
group), 943–924 cm−1 (3,6-anhydrogalactose group), and
867–851 cm−1 (galactose-4-sulfate group) sharpened, indicating that
CNC interacted with CNC0 through intermolecular hydrogen bonds and
suggested the good miscibility (Xu, Li, Kennedy, Xie, & Huang, 2007)
between κ-carrageenan and the CNCs. The FTIR spectra of CMC, CNC,
CNC0, κ-carrageenan and CNC9 are shown in Fig. 1.
3.3. Morphology
Fig. 2(a) shows the FESEM image of the CNCs in powder form. After
acid hydrolysis, the microfibrils of the cellulose converted into nano-
fibrils in needle shape. (Fig. 2b). The TEM image of the CNCs confirmed
that the lengths and widths of the needles are 200–500 nm and
20–50 nm, respectively (Fig. 2b). The needle shape-like CNCs appeared
longer under the SEM, with lengths up to several microns. Some ag-
gregations of CNC needles formed larger bundles during freeze drying.
However, these bundles of CNC needles were loosely packed and easily
separated by water in preparing the TEM sample for observation
(Fig. 2b). The FESEM image of the CN0 and CN9 films showed a
homogeneous and smooth surface structure (Fig. 3(a) and (c)), sug-
gesting the homogeneous un-agglomerated dispersion of CNCs in the κ-
carrageenan matrix, resulting in good adhesion between the fillers and
the matrix. The optical microscope (OM) images of the CNCs in dry
form (c) and in wet form (d) at 20× magnification are presented in
Fig. 2. Cross-sectional FESEM micrographs of CN0 and CN9 are shown
in Fig. 3(b) and (d), respectively. The cross-section images confirmed
that the smoothness of the κ-carrageenan increased upon the addition of
CNC nanoparticles, suggesting the influence of the un-aggregation of
CNC particles. The images also showed no indication of phase
185
Carbohydrate Polymers 211 (2019) 181–194
separation, indicating good adhesion between the κ-carrageenan and
the CNCs. This adhesion was found due to the presence of hydrogen
bonding and was beneficial to the mechanical properties of the nano-
composite films (Kang et al., 2018). The TEM images also confirmed the
good mixing of the CNCs in the κ-carrageenan matrix. As shown in
Fig. 3(e), the rod-like CNCs were well distributed in the κ -carrageenan/
CNC films. However, some agglomerates were observed in the micro-
structure as the CNC concentration reached 9 wt.%. This agglomeration
was found due to the presence of hydrogen-bonded free hydroxyl
groups within the CNCs. Similar results were reported in previous re-
search papers (Garcia et al., 2010). The uniform and homogeneous
distribution of the CNCs in the nanocomposite film is responsible for the
enhanced physico-mechanical properties of the film.
3.4. XRD
To confirm the presence of crystalline, CMC, CNC, κ-carrageenan,
CNC0, CNC1, CNC3, CNC5, CNC7, and CNC9 were characterized by
XRD, and the diffractogram is shown in Fig. 4. XRD patterns were
collected from 10° to 60° (2θ). The CMCs exhibited characteristic
crystalline peaks at around 2θ = 22.5°, 15.2°, 16.4°, and 34.8°. How-
ever, the CNCs showed four characteristic crystalline peaks at around
2θ = 22.9°, 15.5°, 16.3°, and 34.7°, which corresponded to (2 0 0), (−1
1 0), (1 1 0), and (4 0 0) lattice planes, respectively, which is a char-
acteristic of cellulose I structure (Khilil, Borges, Almeida, Boukherroub,
& Omrani, 2018). The peak at 22.9° was broader in the CNCs than in the
CMCs, indicating that the crystallite size of the CNCs was smaller than
that of the CMCs. The crystallinity index (CI) of the CMCs and CNCs
were 0.49 and 0.52, respectively. The increase in the CI of the CNCs was
probably due to the acid treatment of the CMCs.
The κ-carrageenan and CNC0 did not show any clear peaks in XRD,
indicating its amorphous structure. After the loading of CNC with
CNC0, the strong peak of CNC at 22.9° almost disappeared. Similar
results were observed by Arrieta, Fortunati, Dominici, Lopez, and
Kenny (2015). They found that the expected diffraction peaks of cel-
lulose I are not found in poly(lactic acid) films containing low contents
of CNCs (up to 5 wt.%). In another study, Cao, Chen, Chang, Muir, and
Falk (2008) reported that the XRD patterns of polyurethane films
containing < 10% CNCs are amorphous. These results indicate that
incorporating small contents of CNCs (up to 3 wt.%) can only slightly
increase the intensity of the characteristic peaks of κ-carrageenan,
whereas adding large contents of CNCs (9 wt.%) can obviously increase
the intensity of the characteristic peaks of κ-carrageenan. The XRD
pattern of CNC9 is nearly the same as that of the CNCs, implying that
CNCs were well dispersed in the κ-carrageenan matrix and that the
amorphous structure of κ-carrageenan was not affected by the in-
corporation of CNCs.
3.5. TGA
Vegetable-based food packaging films are widely used in the in-
dustry because of their less processing time, high yield, and less pro-
duction cost, but temperatures lower their stability in terms of de-
gradation. The thermogravimetric behavior of these films has been
reported by many papers (Martelli, Barros, de Moura, Mattoso, & Assis,
2013; Otoni et al., 2017). Thermal analysis techniques measure thermal
transitions, chemical reactions and decompositions, viscoelastic prop-
erties, and thermal conductivity as a function of temperature, heating
rate, deformation, and atmosphere. These techniques give insight into
the specific thermal properties of polymer materials and products. More
importantly, they can be used to determine the composition of plastic
and rubber compounds and to gain information regarding the condition
or processing history of specific samples relative to reference samples.
The TGA/DTGA curve was used to determine the thermal stability of
CMC, CNC, κ-carrageenan, CNC0, CNC1, CNC3, CNC5, CNC7, and
CNC9 by monitoring the weight change that occurred when the samples
M. Yadav, F.-C. Chiu
Fig. 2. (a) FESEM image of CNC (b) TEM image of CNC (c) OM images of CNC in dry form and in wet form (d) at Magnification 20×. All optical microscopy samples
of the fractions were made from dispersions of 5 g dm−3.
were heated in an inert atmosphere. The mass loss (TGA) and derivative
mass loss (DTGA) curves of the samples are given in Figs. 5 and 6. The
CMCs and CNCs showed similar weight loss in the given TGA/DTGA
curve. Two-step degradations were observed during the thermal ana-
lysis of the samples. The first degradation, which occurred at 30–200 ℃,
is attributable to the evaporation of residual water present in the ma-
terial. The second degradation at 346 ℃, which occurred at 230–400 ℃,
is characterized by a series of degradation reactions of cellulose, in-
cluding dehydration, decomposition, and depolymerization of the gly-
coside units (Vasconcelos et al., 2017).
For κ-carrageenan (Fig. 6), the smaller DTGA peak between 33 ℃
and 150 ℃ with a weight loss represented the evolution of light vola-
tiles together with an additional removal of bound moisture. Between
150 ℃ and 222 ℃, a second peak with a loss of 8.4% at 215 ℃ in mass
showed the devolatilization of more thermally stable heavy volatiles in
κ-carrageenan. A further increase in temperature to 700 ℃ showed a
third peak at around 237 ℃ (222 ℃–260 ℃) with the highest rate of
weight loss (Martins et al., 2012). This last step with a mass loss of
9.38% corresponded to the decomposition of carbonaceous materials.
The degradation of CNC0 occurred in three steps. It degraded differ-
ently at 35 ℃–130 ℃, 150 ℃–238 ℃, and 238 ℃–300 ℃, with Tmax
values of 45 ℃, 220 ℃, and 242 ℃ identified in the three-step de-
gradation (DTGA Fig. 6). The degradation of CNC1 occurred in four
186
Carbohydrate Polymers 211 (2019) 181–194
steps rather than one. In specific, CNC1 degraded differently at 36
℃–100 ℃, 100 ℃–208 ℃, 208 ℃–240 ℃, and 240 ℃–300 ℃, with Tmax
values of 48 ℃, 180 ℃, 221 ℃, and 245 ℃ identified in the four-step
degradation (DTGA Fig. 6). The three other samples CNC3, CNC5, and
CNC7 showed multi-step thermal degradation. The first degradation
step was found in the range of 32 ℃–124 ℃, which was assigned to
water desorption; the second degradation step, in the range of 124
℃–242 ℃, resulted from dehydration of the fiber-forming material
(Islam & Karim, 2010). The last process over 242 ℃ is attributable to
the evaporation of carbonaceous char material (Zhang, Ji, Wang, Tan, &
Xia, 2012). Furthermore, the given TGA/DTGA curve shows that the
thermal stability of CNC9 (190–236 at 227 ℃, 236–282 at 243 ℃) is
almost same as those of the CNC1, CNC3, CNC5, and CNC7. The ob-
tained TGA/DTGA results in the present work suggest that the thermal
stability of the nanocomposite films was retained.
3.6. Barrier properties
Water sorption is one factor that governs the final product quality,
considering that the films should be exposed with the outer environ-
ment. Decrease in water sorption facilitates better product quality. The
equilibrium water absorption rate of neat κ-carrageenan films (CNC0)
was 885.94%, which decreased to 561.79% after the incorporation of
M. Yadav, F.-C. Chiu
Fig. 3. (a) FESEM surface image of κ-carrageenan (b) FESEM cross section image of κ-carrageenan (c) FESEM surface image of CNC9 (d) FESEM cross section image of
CNC9 (e) TEM image of CNC9 (f) Digital image of CNC9.
CNCs in the κ-carrageenan film (Table 1). The decrease in water ab-
sorption of the κ-carrageenan nanocomposite film is because cellulose is
more crystalline than κ-carrageenan and, upon reinforcement, it acts as
a barrier to κ-carrageenan molecules to swell and thereby decrease the
water sorption.
A decreased water solubility of hydrophilic materials is also im-
portant because a certain degree of water resistance is desirable for
most food applications to avoid film disintegration when in contact
with humid food surfaces, such as meat and fresh-cut fruits. Table 1
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Carbohydrate Polymers 211 (2019) 181–194
shows the water solubility of the CNC0, CNC1, CNC3, CNC5, CNC7 and
CNC9 nanocomposite films. As CNC content was increased from 0% to
9%, the water solubility decreased from 60.94% to 47.97%. This result
was due to the hydrogen bonding generated between hydroxyl groups
of κ-carrageenan and CNCs, which led to the formation of 3D networks
of cellulose. The generated 3D networks limit the solubility of the
polymer and lead to further reinforcement, which restricts the move-
ment of low-molecular-weight polymers and other compounds to the
water (Oleyaei, Zahedi, Ghanbarzadeh, & Moayedi, 2016). The
M. Yadav, F.-C. Chiu
Fig. 4. XRD patterns of κ-carrageenan, CNC, CMC, CNC0, CNC1, CNC3, CNC5, CNC7 and CNC9.
solubility of a κ-carrageenan nanocomposite film with (0.5 wt.%) ZnO is
higher than that of neat κ-carrageenan film (Saputri et al., 2018).
The WVP of food packaging films depends on the film purity, the
hydrophilic–hydrophobic ratio, the ratio between crystalline and
amorphous zones, and the polymeric chain mobility (Souza, Cerqueira,
Teixeira, & Vicente, 2010). One of the major purposes of edible films is
to block moisture transfer between the food and the surrounding at-
mosphere. Therefore, the WVP should be as low as possible. Perme-
ability is the contribution of diffusivity and solubility of the permeant
through the solid matrix, and this parameter is changed by the structure
of the matrix when using the same permeant. The WVP values of the κ-
carrageenan nanocomposites with different CNC loadings are given in
the Table 1. The WVP of κ-carrageenan containing glycerol films
188
Carbohydrate Polymers 211 (2019) 181–194
8.93 × 10−11gm-1 s-1 Pa-1, which reduced by 7.37, 6.25, 5.36, and
4.69 × 10−11gm-1 s-1 Pa-1 after the addition of 1, 3, 5, and 7 wt.%
CNCs, respectively. The reduction of WVP in the κ-carrageenan nano-
composites can be explained by the physical barrier to the passage of
water provided by CNC. That is, the water must flow along the surface
of CNC; failure to pass through slows down diffusion and thus reduces
permeability (Azeredo et al., 2009). The barrier properties are en-
hanced if the filler is less permeable and has a good dispersion into the
matrix (Lagaron, Catala, & Gavara, 2004). However, at 9 wt.% loading
of CNC, the permeability increases (4.69–9.15 × 10−11 gm−1
s−1 Pa−1) drastically because of the increased chances of agglomera-
tion at high filler loading (Chang, Ruijuan, Zheng, Yu, & Ma, 2010).
Garcia et al. (2010) also reported the same agglomeration behavior
M. Yadav, F.-C. Chiu
Fig. 5. TGA curve of CMC, CNC, κ-carrageenan, CNC0, CNC1, CNC3, CNC5, CNC7 and CNC9.
upon loading of more than (1 wt.%) CNC fiber in κ carrageenan-con-
taining glycerol films. Other research papers also showed improvement
in the moisture barrier properties of polymer films with the in-
corporation of CNCs (Paralikar, Simonsen, & Lombardi, 2008; Svagan,
Hedenqvist, & Berglund, 2009). These improved moisture barrier
properties of CNC-incorporated κ-carrageenan would certainly increase
the shelf life of food in packaging applications.
Liquid creates a spherical droplet with a small surface area if the
solid liquid interfacial energy is high. The contact angle between a li-
quid and solid becomes zero or close to zero that the liquid spreads over
the solid easily during wetting. In non-wetting, the contact angle is
greater than 90° so that the liquid tends form a sphere and run off the
surface easily. In the present study, the contact of κ-carrageenan was
not found due to the substantial spreading of liquid over the surface of
κ-carrageenan/CNC nanocomposites. The contact angles for the CNC0,
CNC1, CNC3, CNC5, CNC7, and CNC9 films were 23.30°, 23.70°,
46.45°, 55.65°, 57.75°, and 71.80°, respectively (Table 1). CNC0 and
189
Carbohydrate Polymers 211 (2019) 181–194
CNC9 exhibited the highest and lowest hydrophilicity among all tested
films, respectively (Table 1). The decreased hydrophilicity of the
composite film may be attributed to the 3D cellulosic network of CNCs,
which reduced the number of hydroxyl groups participating in hy-
drogen bonding with the CNCs. The contact angle of CNC9 was lower
than that of CNC0. The hydrophilicity of the composite films can be
controlled by adjusting the amount of CNCs dispersed on the CNC0
surface. Furthermore, the work of adhesion (W12) depends on the
contact angle and surface tension of the liquid. In the present study,
W12 is the work that must be done to separate two adjacent phases 1
and 2 of a liquid–liquid or liquid–solid phase boundary from one an-
other. Conversely, it is the energy that is released during wetting.
Work of adhesion = W12 = (1 + Cos ϴ) Y. (7)
W12 (Jose, George, Maya, & Thomas, 2015) can be correlated to the
interaction of the filler with the matrix and to the interaction of the
filler with a liquid that is comparable with the matrix polymer. The
M. Yadav, F.-C. Chiu Carbohydrate Polymers 211 (2019) 181–194

Fig. 6. DTGA curve of CMC, CNC, κ-carrageenan, CNC0, CNC1, CNC3, CNC5, CNC7 and CNC9.

Table 1
Physical Properties of κ-carrageenan nanocomposite films.
Samples Code Water absorbency Film solubility WVP (×10−11gm−1 s−1 Pa−1) Water Contact Angle(°) Work of Adhesion

CNC0 885.94 60.94 8.93 23.30 139.69

CNC1 825.00 54.63 7.37 23.70 139.38
CNC3 821.43 53.97 6.25 46.45 122.97
CNC5 778.05 51.22 5.36 55.65 113.88
CNC7 761.54 49.23 4.69 57.75 111.60
CNC9 561.79 47.97 9.15 71.80 95.54

work of adhesion of all selected samples is shown in Table 1. CNC0 and
CNC9 showed the highest (139.69°) and lowest (95.54°) work of ad-
hesion, respectively. The work of adhesion decreased with the increase
in CNC concentration. Thus, the effective dispersion of nanofillers into
the matrix might have decreased the work of adhesion, which is the
work required to separate the liquid from the solid surface (Thomas,
Thomas, Abraham, & Bandyopadhyay, 2008). In addition, a previous
study (Shang, Williams, & Soderholm, 1994) found that TS is inversely
proportional to work of adhesion, implying that hydrophilic films show
high TS.
Moisture absorption is a key factor that influences the performance
of nanocomposite films for food packaging applications. A natural
abundant biopolymer polymer, κ-carrageenan, limits its application due
to its hygroscopic nature. In the present work, κ-carrageenan was re-
inforced with CNCs. Due to the better interaction of κ-carrageenan and
CNCs by hydrogen bonding, the chances to absorb moisture is

190
M. Yadav, F.-C. Chiu Carbohydrate Polymers 211 (2019) 181–194

Table 2 spectroscopy. A JASCO UV/Vis Spectrometer was used to measure the

Values of thickness, Density, Opacity, tensile strength (TS) and elongation-at- light transmittance of the films in a light wavelength area from 190 nm
break (EB) obtained for κ-carrageenan/CNC films. to 900 nm. The scan speed used in the analysis was 1000 nm/min, and
Samples Thickness Density Opacity Tensile Elongation at three replicates of each material were measured. The absorbance of the
Code (mm) (g/cm3) (Abs600/ Strength Break (%) κ-carrageenan/CNC nanocomposite films is presented in Fig. 8P. To
mm) (MPa) avoid the oxidative rancidity catalyzed by UV light, the packaging film
could able to absorb UV light (Chen et al., 2013). When the films are
CNC0 0.020 1.700 3.781 38.33 ± 3.79 21.50 ± 3.72
CNC1 0.030 1.705 6.422 38.43 ± 5.94 22.93 ± 1.50 not UV responsive, the packaging films must be irradiated with UV light
CNC3 0.040 1.710 10.410 39.83 ± 0.38 23.83 ± 2.71 to destroy microbial charge (Narayanan, Loganathan, Valapa, Thomas,
CNC5 0.025 1.720 11.239 40.07 ± 2.80 24.33 ± 3.00 & Varghese, 2017). In the present study, the absorbance of nano-
CNC7 0.025 1.730 22.224 52.73 ± 0.70 28.27 ± 2.39
composites near the UV region (270–300 nm) increased with increasing
CNC9 0.035 1.750 22.254 39.10 ± 1.04 25.83 ± 2.61
fiber loading, and CNC loading did not significantly affect the UV re-
sponse of the prepared nanocomposites films. Thus, this nanocomposite
film did not cause yellowing or de-coloration when exposed to light
because the nanocomposites were not affected by photo-oxidation re-
action. The UV spectra of CNC0, CNC1, CNC3, CNC5, CNC7, and CNC9
are shown in Fig. 8. The spectra of all films exhibited lower transmit-
tance values at UV light (190–380 nm) than that at visible light
(380–750 nm). Fig. 8Q confirms that the UV light transmittance of the
κ-carrageenan nanocomposite films continuously decreases compared
with that of κ-carrageenan films due to the UV-shielding ability of
CNCs. This decrease in transmittance with the CNC content is indicative
of the uniform dispersion of CNCs in the κ-carrageenan matrix. The
supplied figure shows that the UV light transmittance of CNC0 at
820 nm is 76.28% and decreases to 21.40% as the CNC content of
composites is increased to 9 wt.%. The reduction in light transmittance
in all films still maintained optical transparency, and no visual ag-
gregates were observed (Fig. 8S). The order of optical transparency of
films is as follows:

CNC0 > CNC1 > CNC3 > CNC5 > CNC7 > CNC9

Fig. 7. Moisture absorption of CNC0, CNC1, CNC3, CNC5, CNC7 and CNC9
films.
decreased. Composites with poor adhesion between the matrix and the
filler allow moisture to enter the composite material and thereby in-
crease the moisture sensitivity (Balakrishnan, Gopi, Sreekala, &
Thomas, 2018). The effect of CNC content on the moisture absorption of
films is shown in Fig. 7. The moisture absorption of the bionano-
composite films was lower than that of κ-carrageenan film. This result
may be due to the less availability of free hydroxyl groups of the matrix
that participated in hydrogen bonding with the CNCs. Thus, the effect
of time on moisture absorption was studied by varying its time from
12 h to 96 h, and results are presented in Fig. 7. The moisture absorp-
tion increased as the time was prolonged from 12 h to 60 h, and this
increase can be explained due to the greater availability of −OH groups
of κ-carrageenan. Beyond 60 h, the decrease in moisture absorption
which might be due to the 3D cellulosic network of CNCs, which re-
stricts the chain mobility and reduces the number of hydroxyl groups
(Das et al., 2011). The equilibrium moisture uptake value depends on
hydrophilicity and morphology (macro-voids, free volume, crystal size,
and crystallinity degree. Recently, Venkatesan et al. (2017) have re-
ported that the moisture uptake of κ-carrageenan nanocomposite films
decreases when SiO2 is introduced into the neat polymer matrix.
3.7. Opacity and UV visibility
Transparent food packaging secures the visual evidence of the food
content, which is an essential factor that affects the consumers’ sensi-
bility of food quality. Transparent food packaging clubbed with light
labelling appeals to consumers because it provides a clear view of the
food content and its condition. Opacity is an important factor that de-
termines the quality of nanocomposite films. The opacity of all required
samples is presented in Table 2. The transparency of the CNC0, CNC1,
CNC3, CNC5, CNC7, and CNC9 films was studied using UV/Visible light
76.28 > 63.52 > 48.14 > 46.06 > 21.42 > 21.40.
The transmittance spectra clearly show that the transmittance re-
duced with increasing CNC content because of light scattering. Similar
results were found in recent papers (Hietala, Mathew, & Oksman,
2013). The blocking effect (Beff) of CNCs for κ-carrageenan nano-
composites were calculated using the following formula (Castillo et al.,
2013):
T carrageenan T carrageenan/CNC
Beff =
Percentage of CNC with respect to the carrageenan
,
(8)
where T κ-carrageenan and T κ-carrageenan/CNC are the transmittance of κ-
carrageenan film and the κ-carrageenan/CNC nanocomposites, respec-
tively.
Fig. 8R shows the Beff of the CNCs at 300, 700, and 750 nm (UV-B,
UV-A, and visible regions, respectively).
Furthermore, the transmittance of light decreased in the κ-carra-
geenan/CNC nanocomposites after a certain value of visible light
(500 nm) compared with the κ-carrageenan films, confirming the UV
absorption potential of the former. The above findings clearly show that
κ-carrageenan/CNCs can be used to protect food materials from UV
degradation.
3.8. Mechanical properties
Good mechanical properties are among the basic requirements for
food packaging films, considering that poor flexibility or strength may
lead to premature failure or cracking during production, handling,
storage, or use (Sothornvit & Rodsamran, 2008). The most investigated
mechanical properties of packaging films are TS and EB. These prop-
erties support the correlation of the mechanical properties of films to
their compositions and chemical structures. The fabricated bionano-
composite films were sectioned into rectangular shapes with a size of
10 mm × 60 mm × 0.02 mm for tensile tests. The tensile tests of the

191
M. Yadav, F.-C. Chiu
Fig. 8. UV spectra of CNC0, CNC1, CNC3, CNC5, CNC7 and CNC9 (P) Absorbance curve (Q) Percentage transmittance curve (R) Blocking effect at different
wavelengths and (S) Visual appearance.
CNC0, CNC1, CNC3, CNC5, CNC7, and CNC9 films (in accordance with
ASTM D638) were conducted at a crosshead speed of 10 mm/min by
using a Gotech AI-3000 system. The TS and EB were taken to be the
average value of the five tests for each composition. Tensile properties
(TS and EB) of the CNC0, CNC1, CNC3, CNC5, CNC7, and CNC9 bio-
nanocomposites films are shown in Table 2. Loading with a small
amount of CNC significantly improved the tensile properties. The TS of
CNC0 (κ-carrageenan containing glycerol) (38.33 ± 3.79 MPa) is evi-
dently lower than those of CNC1 (38.43 ± 5.94 MPa), CNC3
(39.83 ± 0.38 MPa), CNC5 (40.07 ± 2.80 MPa), CNC7
(52.73 ± 0.70 MPa), and CNC9 (39.10 ± 1.04 MPa). These results
can be attributed to the strong hydrogen bonding between the CNCs
and the κ-carrageenan matrix phase due to their chemical similarity
(Huq et al., 2012). Furthermore, the tensile strengths of the films de-
creased from 52.73 ± 0.70 MPa to 39.10 ± 1.04 MPa when the
loading amount of the CNC was increased from 7 wt.% to 9 wt.%. This
result is caused by the agglomeration of CNCs in the κ-carrageenan
matrix. The aggregation of CNCs may occur while the fiber is in na-
nophase, and the tendency to form large macroscopic fibers increases at
high filler loading. These phenomena result in inter-fiber interaction
due to hydrogen bonding-induced self-association (Dorigato, Dzenis, &
Pegoretti, 2013). Similar results were previously reported (Wu, Zhang,
Rong, & Friedrich, 2005). The TS of the κ-carrageenan control film
(38.33.MPa) obtained in this study was similar to those of films in
previous reports, such as 23.4 MPa (Zarina & Ahmad, 2015), 28.1 MPa
(Wahab & A B D Razak, 2016), 30.68 MPa (Saputri et al., 2018),
39.44 MPa (Rhim, 2012), 42.5 MPa (Larotonda et al., 2016), and 46.8.
192
Carbohydrate Polymers 211 (2019) 181–194
MPa (Venkatesan et al., 2017). The TS values of all selected films are
comparable to those of plastic-based films, such as films based on LDPE
(8–10 MPa), HDPE (19–31 MPa), EVOH (6–19 MPa), PCL (4 MPa), PS
(31–49 MPa), PLA (45 MPa), PVC (42–55 MPa), PP (27–98 MPa), and
PET (157–177 MPa) (Otoni et al., 2017). The κ-carrageenan/SiO2 na-
nocomposite films showed higher TS (53.9 MPa) than the κ-carrageenan
neat polymer (46.8 MPa) (Venkatesan et al., 2017). The fabricated κ-
carrageenan nanocomposite film loaded with 0.5 wt.% ZnO showed
highest TS for food packaging applications (Saputri et al., 2018).
Similar to the TS results, the EB values of CNC0, CNC1, CNC3,
CNC5, CNC7, and CNC9 also increased, with 21.50 ± 3.72,
22.93 ± 1.50, 23.83 ± 2.71, 24.33 ± 3.00, 28.27 ± 2.39, and
25.83 ± 2.61%, respectively (Table 2). In specific, the EB values of the
CNC1, CNC3, CNC5, CNC7, and CNC9 films were 6.67%, 10.85%,
13.18%, 31.47%, and 20.16% higher than that of the κ-carrageenan
film, respectively. Furthermore, the EB of the films decreased from
28.27 ± 2.39% to 25.83 ± 2.61% when the loading amount of the
CNCs was increased from 7 wt.% to 9 wt.%. The decrease in EB of the
nanocomposite films can be explained by the restrictions to the se-
quential motion at the filler–polymer interface (Wang et al., 2005). The
EB of the prepared nanocomposites is comparable to those of films
based on LDPE (300%–900%), HDPE (20%–50%), PCL (800%–1000%)
(Bastarrachea, Dhawan, & Sablani, 2011), PS (2%–3%), PVC
(20%–180%), PP (200%–1000%), PET (70%), and PVDC (10%–40%).
However, the TS and EB of the bionanocomposites with high CNCs
content were still higher than those of the neat matrix. Thus, the CNCs
acted as good reinforcing agents in the κ-carrageenan films.
M. Yadav, F.-C. Chiu
4. Conclusion
The needle-shaped Cellulose nanocrystals (CNCs) were synthesized
from ultra-fine microcellulose by using acid hydrolysis. The CNCs re-
inforced κ-carrageenan transparent bionanocomposite films were pre-
pared by using solution casting method. FTIR analysis revealed the
formation of hydrogen bond at the interface of κ-carrageenan and
CNCs. The XRD and FESEM studies showed the homogeneous disper-
sion of the CNCs in the κ-carrageenan matrix, without any aggregation.
The effects of CNCs concentration on the physical and mechanical
properties (density, moisture content, opacity, color, water solubility,
WVP, TS, and EB) of κ-carrageenan film were systematically studied.
TGA data showed that the thermal stability of all selected samples was
retained. The WVP decreased from 8.93 to 4.69 × 10−11gm-1 s-1 Pa-1
after 7 wt.% CNC loading. With the incorporation of 7 wt.% CNC, the TS
and EB of the films increased from 38.33 ± 3.79 MPa to
52.73 ± 0.70 MPa and from 21.50 ± 3.72% to 28.27 ± 2.39%, re-
spectively. Compared with the κ-carrageenan film, the κ-carrageenan/
CNC films had higher water barrier properties and mechanical prop-
erties. Therefore, the obtained κ-carrageenan/CNC bionanocomposite
films have potential applications in food packaging.
Acknowledgments
Mithilesh Yadav thanks to Chang Gung Memorial Hospital
(BMRP392) for providing the Post-doctoral fellowship. The financial
support from Ministry of Science and Technology (Taiwan) under
contract MOST 107-2811-E-182-503 is appreciated as well.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.carbpol.2019.01.114.
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