Article

Preparation and Characterization of Blended Films

from Quaternized Hemicelluloses and
Carboxymethyl Cellulose
Xian-Ming Qi 1 , Shi-Yun Liu 1 , Fang-Bing Chu 1 , Shuai Pang 1 , Yan-Ru Liang 1 , Ying Guan 2 ,
Feng Peng 1, * and Run-Cang Sun 1
Received: 29 October 2015; Accepted: 15 December 2015; Published: 23 December 2015
Academic Editor: Jun-ichi Anzai
1 Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing 100083, China;
qxmfly@foxmail.com (X.-M.Q.); Liushiyun_Daisy@163.com (S.-Y.L.); chufangbingcfb@163.com (F.-B.C.);
pangshuai2012@126.com (S.P.); l8141586@163.com (Y.-R.L.); rcsun3@bjfu.edu.cn (R.-C.S.)
2 School of Forestry and Landscape Architecture, Anhui Agricultural University, Hefei 230036, China;
xiaomi1231@163.com
* Correspondence: fengpeng@bjfu.edu.cn; Tel.: +86-10-6233-7250

Abstract: Utilization of hemicelluloses from biomass energy is an important approach to explore

renewable resources. A convenient, quick, and inexpensive method for the preparation of blended
films from quaternized hemicelluloses (QH) and carboxymethyl cellulose (CMC) was introduced
into this study. QH and CMC solution were first mixed to form homogeneous suspension, and then
were dried under vacuum to fabricate the blended films. The FT-IR and XRD results indicated that
the linkage between QH and CMC was due to the hydrogen bonding and electrostatic interaction.
From the results of mechanical properties and water vapor permeability (WVP), the tensile strength of
the blended films increased with the QH/CMC content ratio increasing in appropriate range, and the
WVP of the blended films decreased. The maximum value of tensile strength of blend film achieved
was 27.4 MPa. In addition, the transmittances of the blended films increased with the decreasing of
QH/CMC content ratio. When the weight ratio (QH: CMC) was 1:1.5, the blend film showed the best
light transmittance (45%). All the results suggested that the blended films could be used in areas of
application in the coating and packaging fields from the good tensile strength, transmittance, and
low WVP.

Keywords: blend film; quaternized hemicelluloses; carboxymethyl cellulose

1. Introduction
With the decrease in fossil fuels, much attention has been paid to investigate the new
biodegradable materials. The increased social awareness for sustainable development gather
momentum in favor of materials from renewable resources [1–3]. Therefore, polysaccharides have
become the main part of natural-based materials which are particularly advantageous due to their
biocompatibility, biodegradability, and non-toxicity [4–6]. Production of environmentally friendly
packaging materials based on polysaccharides from renewable resources are also expected to substitute
for petroleum-based packaging materials [7]. Cellulose and hemicelluloses are the most and the
second most abundant polysaccharides in biomass, respectively [8–11]. Some studies have been widely
studied for preparing films from them. Biocomposite films based on quaternized hemicelluloses
and montmorillonite showed good thermal properties by the addition of clay nanoplatelets [12].
Bacterial cellulose as reinforcement was added in the arabinoxylan films, it could effectively increase
the stiffness and strength of the films [13]. In addition, hydrophobic films formed by acetylated

Materials 2016, 9, 4; doi:10.3390/ma9010004 www.mdpi.com/journal/materials

Materials 2016, 9, 4 2 of 12

bleached hemicelluloses and acetylated cellulose showed the improvement of thermal and mechanical
properties [14]. Therefore, the films based on hemicelluloses and cellulose have a prospective
application in many fields.
Various derivatives of cellulose have been synthesized and used in practical applications.
Carboxymethyl cellulose (CMC) is one of the most widely applied cellulose derivatives and it
has good film forming property, which can form transparent films and possess high mechanical
strength [15,16]. It contains a hydrophobic polysaccharide backbone and many hydrophilic carboxyl
groups, showing amphiphilic characteristic [17]. CMC is an acidic polysaccharide, due to its a number
of carboxylic substituents [18]. In addition, hemicelluloses are also the excellent materials for the film
preparation [19–21]. Quaternized hemicelluloses (QH) are derivative of hemicelluloses which have
highly solubility and cationic property because of the cationic agents and hydroxide radical in QH [22].
Blending is a main method for fabricating films by mixing two components, which is a simple and
effective method to improve the properties of films [23,24]. When the two components are compatible,
more homogeneous structure and better physicochemical properties of the blended films can be
obtained than that of films from individual components [25]. In this article, quaternized hemicelluloses
(QH) were obtained from bamboo hemicelluloses by esterified with 2,3-epoxypropyltrimethyl
ammonium chloride [26]. Then, QH and CMC as the positive and negative charged polyelectrolyte,
respectively, could form the polyelectrolyte complex through intermolecular hydrogen bonding and
strong electrostatic attraction. A series of novel blended films that are non-toxic, renewable, and
biodegradable were prepared from the two kinds of biopolymer according to a predetermined ratio.
The structural analyses of the blended films were determined by FT-IR and XRD. The morphological
structure was demonstrated by scanning electron microscopy (SEM) and atomic force microscopy
(AFM). The mechanical properties and light transmittance were studied by tensile test and UV/Vis
spectrophotometer. The water vapor permeability (WVP) of the blended films was performed
according to the standard ASTM E 96/E 96M-05 [27]. The relationship between the structure and their
physicochemical properties of the blended films was also discussed in this study.

2. Experimental Section

2.1. Materials
The hemicelluloses was extracted and purified from the phyllostachys pubescens (Meishan,
Sichuan Province, China). The sugar composition of hemicelluloses was 83.6% xylose, 5.1% arabinose,
4.2% glucose, 0.4% galactose, and 6.8% glucuronic acid (relatively molar percent). The molecular
weight obtained by gel permeation chromatography (GPC) showed that the native hemicelluloses had
an average molecular weight (Mw) of 13,420 g¨ mol´1 and a polydispersity of 4.1, corresponding
to a degree of polymerization of 88. Sodium hydroxide was purchased from Beijing Chemical
Works (Beijing, China). 2,3-epoxypropyltrimethyl ammonium chloride (ETA) was obtained from
Sigma-Aldrich Co., Ltd. (St. Louis, MO, USA) CMC, the degree of substitution is 0.78, was supplied
by Tianjin Jinke Fine Chemical Research Institute (Tianjin, China). The weighed average molecular
weight of CMC is 1.9 ˆ 104 , and the viscosity is 800–1200 Pa¨ s. All reagents mentioned above were
directly used without further purification.

2.2. Preparation of Quaternized Hemicelluloses

The synthesis of QH was carried out in a three-necked flask fitted with a mechanical stirrer and
a reflux condenser. 0.66 g of dried hemicelluloses were dissolved in 5 mL distilled water at 60 ˝ C for
30 min. An aqueous solution of sodium hydroxide (the molar ratio of NaOH to ETA, 0.75) was added,
followed by adding of ETA (the molar ratio of ETA to anhydroxylose units in hemicelluloses, 2.0).
The mixture was stirred at 60 ˝ C, for a total period of 5 h. Upon completion of the reaction, the mixture
was cooled to ambient temperature. Then, the reaction mixture was filtered off and thoroughly washed
with ethanol, and dried in a vacuum oven at 45 ˝ C for 24 h.
Materials 2016, 9, 4 3 of 12

2.3. Preparation of Blended Films

QH were dissolved in distilled water and stirred for 6 h. The suspension was centrifuged at
4000 rpm for 10 min, and the supernatant was stored in refrigerator at 4 ˝ C for the use of film
preparation. The insoluble solids were dried to calculate concentration of the supernatant. CMC was
dissolved in distilled water at 60 ˝ C for 30 min under magnetic stirring to prepare the solution with
concentration of 2 wt %. The QH and CMC solution concentrations were all 2 wt %, and they were
mixed under magnetic stirring energetically at 60 ˝ C. The mixing solution was degassed by rotary
evaporator at room temperature for 2 h, after which per 10 mL solution was cast into a 5.5 cm diameter
plastic petri dishes and dried under vacuum at 40 ˝ C for 36 h. Then the blended films were obtained
and peeled off carefully. The different volume ratios of QH to CMC are shown in Table 1.

Table 1. Composition of the blended films.

Sample Code QH: CMC (V/V)

Film 1 1.0:1.0
Film 2 1.0:1.5
Film 3 2.0:1.0
Film 4 1.5:1.0

2.4. FT-IR Spectroscopy

FT-IR spectra of QH, CMC, and QH/CMC blended films were recorded using a Nicolet iN
10 Fourier transform infrared spectrometer (Thermo Nicolet Corporation, Madison, WI, USA). QH and
CMC powder were prepared by grinding with potassium bromide and laminating. FT-IR spectra were
recorded in the spectra range from 4000–650 cm´1 . The blended film samples were measured under
the ATR mode with spectral range of 4000–650 cm´1 .

2.5. X-ray Diffraction

X-ray diffraction patterns of QH, CMC, and QH/CMC blended films were recorded with
a XRD-6000 X-ray diffractometer (Shimadzu, Kyoto, Japan), using Nickel-filtered Cu Kα radiation
(λ = 0.154 nm) at 40 kV and 30 mA in the 2θ range of 5˝ –45˝ at a speed of 5˝ ¨ min´1 .

2.6. Atomic Force Microscopy (AFM)

Surface roughness of the films was measured using a Multimode 8 (Bruker, Billerica, MA, USA),
Atomic force microscope (AFM), operated in tapping mode. Silicon cantilever was used throughout
the study with the nominal tip radius of 10 nm curvature. All scans were performed in air, at room
temperature. Height and phase contrast images were recorded simultaneously with a resonance
frequency between 250 and 300 kHz and a scan angle of 0˝ .

2.7. Scanning Electron Microscopy (SEM)

Scanning electron micrographs of the films, brittle fractured in liquid nitrogen, were taken with
S-3400N scanning electron microscope (Hitachi, Tokyo, Japan). Prior to the SEM analysis, the films were
sputter coated with a thin layer of gold. The acceleration voltage was set to 15 kV and magnification
was 1500ˆ.

2.8. Light Transmittance

The light transmittance of the blended films were performed by a UV-Vis spectrophotometer
(UV 2300, Tech Comp, Shanghai, China) at wavelength of 200–800 nm. The films strips were attached
to the surface of the cuvette with the size of 12 mm ˆ 60 mm, taking cuvette as a reference.
Materials 2016, 9, 4 4 of 12

2.9. Tensile Properties

Tensile strength and breaking elongation of films were measured using a miniature universal
testing machine (CMT6503, SANS Technology stock Co., Ltd., Shenzhen, China), with a load cell
of 100 N, operating in tension mode. The initial grip distance was 20 mm, and the rate of grip
separation was 5 mm/min. The specimens were cut to the size of 30 mm ˆ 10 mm. At least three
repeated measurements of each film were tested and the average value was used to determine
mechanical properties.

2.10. Water Vapor Permeability

The standard ASTM E 96/E 96M-05 was used to determine water vapor permeability (WVP) [27].
Aluminum cups were filled with 15 g anhydrous calcium chloride as desiccant and the film samples
were mounted over the cups at room temperature. The desiccant was dried at 240 ˝ C for 3–5 h before
use. Aluminum cups were then placed in a cabinet containing water. WVP was determined by

qd
WVP “
ts∆P
where q/t, d, s, ∆P are the slope of the weight increase versus time (g/s), the film thickness (cm), the
film area exposed to moisture (4.91 cm2 ), and the difference of the vapor pressure between the two
sides of films (23.76 mmHg), respectively.

3. Results and Discussion

3.1. FT-IR Analysis

Figure 1 shows the FT-IR spectra of CMC and QH. As can be seen, the absorption band at
1592 cm´1 is assigned to asymmetrical COO– stretching of CMC [28]. The signals at 1414 and
1320 cm´1 are related to the symmetrical stretching vibrations of the carboxylate groups and C–H
bending, respectively [29]. The broad peak at 1059 cm´1 is attributed to the stretching of C–O–C [30].
In the spectrum of QH, the absorption band at 3354 cm´1 corresponds to –OH stretching vibration,
and the vibration at 1609 cm´1 reflects the blending mode of absorbed water [31]. The stretching
vibration at 1034 cm´1 and 894 cm´1 which can be ascribed the C–O–C and the β-glycosidic bond,
respectively [32]. In addition, a new absorption peak at 1475 cm´1 appeared in QH, which originates
from the bending vibration of –CH3 and –CH2 in quaternary ammonium group. It suggests that the
hemicelluloses were modified successfully [33]. Compared with the FT-IR spectra of pure CMC and
QH, the spectra of blended films are shown in Figure 2. The stretching vibration of the C–O–C was
broadened and shifted evidently to the 1100 cm´1 , which was caused by the overlap of the ether bond
in both CMC and QH. The absorption peaks at 1597 cm´1 and 896 cm´1 of blended films are attributed
to asymmetrical COO– stretching and β-glycosidic bond, respectively. The broad absorption band
at 3300–3500 cm´1 is also assigned to –OH stretching of hydrogen bonds. The blended films were
fabricated by mixing the QH with CMC, abundant hydrogen bonds were therefore formed between
the QH and CMC chains. Furthermore, plenty of ammonium cations are on the surface of QH, and
there are many carboxyl anions in CMC chains. This resulted in the electrostatic interactions that were
formed between the QH and CMC. Therefore, the blending of QH and CMC was mainly due to the
hydrogen bonds and electrostatic interactions between them.
Materials 2016, 9, 4 5 of 12
Materials 2016, 9, page–page
Materials 2016, 9, page–page

Figure 1. The FT‐IR spectra of CMC and QH.

Figure 1. The FT-IR spectra of CMC and QH.
Figure 1. The FT‐IR spectra of CMC and QH.

Figure 2. The FT‐IR spectra of four blended films.

Figure 2. The FT‐IR spectra of four blended films.
3.2. X‐ray Analysis Figure 2. The FT-IR spectra of four blended films.
3.2. X‐ray Analysis
The impact of chemical modification on the crystal structure was further evaluated by using
3.2. X-ray Analysis
X‐ray diffraction
The impact of analysis.
chemical The X‐ray diffraction
modification on thepatterns of QH and
crystal structure was CMC are evaluated
further shown in Figureby using 3.
The
X‐ray diffraction
diffraction peak of
analysis.QH is
The at 2θ
X‐ray = 19.9° [34].
diffraction It was
patterns found
of
The impact of chemical modification on the crystal structure was further evaluated by QH thatandthe diffraction
CMC are peak
shown intensity
in Figure of
3. using
QH was lowerpeak
The diffraction thanofthatQH of CMC,
is at 2θ = which
19.9° [34].wasIt due
was to the that
found amorphism of hemicelluloses.
the diffraction peak intensityThe of
X-ray diffraction analysis. The X-ray diffraction patterns of QH and CMC are shown in Figure 3.
diffraction
QH was lowerof CMC consists
than that ofof two
CMC, major
which crystalline
was due peaks are at
to the 2θ = 18.9° of
amorphism andhemicelluloses.
32.6°, respectively, The
The diffraction peak of QH is at of
2θ = 19.9 ˝ [34]. It was found that the diffraction peak intensity of QH
which are
diffraction the characteristic
of CMC consists of cellulose
two major I [35,36]. Moreover,
crystalline peaks are the at
intensity
2θ = 18.9° of CMC diffraction
and 32.6°, peak at
respectively,
was lower2θ
which=than
arethat
28.2° the of CMC,
andcharacteristic
38.7° which
become of weak,was due
because
cellulose tothe
I [35,36].the amorphism
hydroxyl
Moreover, in of hemicelluloses.
thecellulose
intensity are substituted
of CMC The diffraction
by carboxyl
diffraction peak at of
CMC consists
groups.
2θ = 28.2° of two
It could major crystalline
be partially
and 38.7° become explained peaks
weak, because are
the at
by molecular 2θrearrangement
hydroxyl= 18.9 ˝ and of
in cellulose 32.6 ˝
CMC.
are ,substituted
respectively,
The XRDby which
patterns
carboxylof are the
the
characteristic blended
groups. filmsbe
ofIt cellulose
could showed
partiallythat
I [35,36]. the majorbydiffraction
explained
Moreover, molecular peaks
the intensity are
of at
rearrangement
CMC 2θ = of19.0°,
CMC. 33.0°,
diffraction The34.2°,
XRDand
peak 37.8°
patterns
at 2θ in ˝ and
of
= 28.2
Figure 4. It suggested that the diffraction peaks of composite films were overlapped and shifted.
the blended films showed that the major diffraction peaks are at
38.7˝ become weak, because the hydroxyl in cellulose are substituted by carboxyl groups.inIt could 2θ = 19.0°, 33.0°, 34.2°, 37.8°
The
Figure degree
4. It of crystallinities
suggested haddiffraction
that the the following order:
peaks CMC > Film
of composite 4 > were
films Film 3overlapped
> Film 2 > Film
and 1shifted.
> QH,
be partially
The
explained
and degree
the crystallinity
by values
molecular
of crystallinities of
hadthem
rearrangement
the were present
following
ofCMC
in Table
order:
CMC. The4 XRD
2.> Film
Theoretically,
patterns
> Film 3the
of the blended
crystallinity
> Film 2 > Film value
1 > QH,of
films
showed thethat the major diffraction peaks are at 2θ = 19.0 ˝ , 33.0˝ , 34.2˝ , and 37.8˝ in Figure 4. It suggested
and blended films should
the crystallinity valuesincrease
of themwith werethe increase
present of CMC
in Table amount, because
2. Theoretically, CMC is crystalline
the crystallinity value of
that the and
diffraction
the blended peaksshould
QH is amorphous.
films of composite
However,
increase the films
with XRD were
the overlapped
results
increase CMC and
ofofblended shifted.
films
amount, indicate
becauseThe degree
that
CMC of crystallinities
theiscrystallinity
crystalline
had thevalue
and QHof the
following blended
order: films
is amorphous. CMC do> not
However, show
the
Film 4XRD>the obvious
results
Film 3> of positive
blended
Film 2 correlation
>films
Film 1 with
indicate
> QH, CMC
that theamount.
and The
crystallinity
the crystallinity
values ofintermolecular
value
them of the
were hydrogen
blended
present bonding
films
indo notand
Table 2. electrostatic
show the obvious
Theoretically, interaction
positive are the driving
correlation
the crystallinity withforce
valueCMCof
ofblended
amount.
the blendedfilms
The films
between QH and
intermolecular CMC, which
hydrogen bonding may andchange the crystal
electrostatic structure
interaction areofthethedriving
blended films.
force The intensity
of blended films
should increase with the increase of CMC amount, because CMC is crystalline and QH is amorphous.
of the driving
between QH and force
CMC,is different
which may with the increase
change of QH/CMC
the crystal structure of content. Moreover,
the blended films.the
Thecrystalline
intensity
However, of the
region XRD
of CMC
the driving results
andis
force of
theblended
amorphous
different films
with indicate
region
the of QH
increase that the have
also
of QH/CMC crystallinity value
influenceMoreover,
content. on the of final
the
the blended
degree offilms do
crystalline
not show the obvious
region of CMC positive correlationregion
and the amorphous with CMC of QHamount.
also have The intermolecular
influence on the final hydrogen
degree of bonding
and electrostatic interaction are the driving force of5 blended films between QH and CMC, which may
change the crystal structure of the blended films. The5 intensity of the driving force is different with the
increase of QH/CMC content. Moreover, the crystalline region of CMC and the amorphous region
of QH also have influence on the final degree of crystallinity of the blended films. Therefore, the
crystallinity values of the blended films do not show obvious regular change with the QH/CMC
content ratio.
Materials 2016, 9, page–page
Materials 2016, 9, page–page

crystallinity of the blended films. Therefore, the crystallinity values of the blended films do not
crystallinity
Materials 2016, 9,of
the blended films. Therefore, the crystallinity values of the blended films do
4 6 ofnot
12
show obvious regular change with the QH/CMC content ratio.
show obvious regular change with the QH/CMC content ratio.

Figure 3.The
The XRDpatterns
patterns ofQH
QH andCMC.
CMC.
Figure 3. The XRD
Figure 3. XRD patterns of
of QH and
and CMC.

Figure 4. The XRD patterns of Film 1, Film 2, Film 3, and Film 4.

Figure 4.
Figure 4. The
The XRD patterns of
XRD patterns of Film
Film 1,
1, Film
Film 2,
2, Film
Film 3,
3, and
and Film
Film 4.
4.

Table 2. The degree of crystallinity of QH, CMC, and the blended films.
Table 2. The
Table 2. The degree
degree of
of crystallinity
crystallinity of
of QH,
QH, CMC,
CMC, and
and the
the blended
blended films.
films.
Sample Code QH CMC Film 1 Film 2 Film 3 Film 4
Sample Code QH CMC Film 1 Film 2 Film 3 Film 4
Crystallinity(%)
Sample Code QH 9 84.6 27.7 Film33.4 Film34 35.9
Crystallinity(%) 9 CMC
84.6 Film27.7
1 2
33.4 343 Film
35.94
Crystallinity(%) 9 84.6 27.7 33.4 34 35.9
3.3. Morphology of Blended films
3.3. Morphology of Blended films
The SEM of
3.3. Morphology images
Blended offilms
the surface and cross section of the blend film are present in Figure 5.
The SEM images of the surface and cross section of the blend film are present in Figure 5.
As can be seen from Figure 5a, the surface of the film is smooth and homogeneous without any
As canThebe seen
SEM from of
images Figure 5a, theand
the surface surface
cross of the film
section is blend
of the smooth filmandarehomogeneous
present in Figure without
5. As any
can
aggregation. It suggested that the QH and CMC were diffused evenly in the film. In the microstructure
aggregation.
be seen fromItFigure
suggested
5a, thethat the QH
surface of and CMCiswere
the film smooth diffused evenly in the film.
and homogeneous In the
without anymicrostructure
aggregation.
of the film cross section in Figure 5b, a dense and smooth structure of blended film suggested that
of suggested
It the film cross
thatsection
the QHinand Figure
CMC 5b,were
a dense and smooth
diffused evenly in structure
the film. of In
blended film suggested
the microstructure of that
the
strong interaction force existed between QH and CMC. QH and CMC have a positive charge and
strong
film interaction
cross section in force
Figureexisted
5b, abetween
dense and QH and CMC.
smooth QH and
structure CMC have
of blended a positive charge
film suggested and
that strong
negative charge, respectively. In addition, abundant of hydroxyl groups were existed in the surface
negative charge,
interaction respectively.
force existed betweenIn addition,
QH and CMC. abundant QH of andhydroxyl
CMC have groups were existed
a positive charge in andthenegative
surface
of QH and CMC. Therefore, hydrogen bonding and electrostatic attraction between the oppositely
of QH and
charge, CMC. Therefore,
respectively. hydrogen
In addition, abundantbonding and electrostatic
of hydroxyl groups were attraction
existed between the oppositely
in the surface of QH
charged polymers are the driving force for the formation of tight and smooth films.
charged
and CMC. polymers
Therefore,arehydrogen
the driving force for
bonding andtheelectrostatic
formation of tight andbetween
attraction smooththe films.
oppositely charged
The surface nanotopography and toughness of the four blended films were investigated by
The surface
polymers nanotopography
are the driving force for theand toughness
formation of the
of tight andfour blended
smooth films.films were investigated by
AFM. The height images, 3D topography, and phase topography of the films are shown in Figure 6.
AFM.The Thesurface
heightnanotopography
images, 3D topography, and phase
and toughness of thetopography
four blended of films
the films
wereare shown in Figure
investigated by AFM. 6.
From the height images and 3D topography of films, it was obviously found that the surfaces of
From
The the height
height images,images and 3D topography
3D topography, of films, it of
and phase topography wastheobviously
films are shownfoundinthat the 6.
Figure surfaces
From the of
blended Film 1 and Film 2 were more flat than those of blended Film 3 and Film 4. The roughness
blended
height Film 1and
images and 3DFilm 2 were more
topography flat itthan
of films, wasthose of blended
obviously found Film 3 and
that the Film of
surfaces 4. The
blendedroughness
Film 1
values were calculated in the areas of 2 μm × 2 μm, and the roughnesses of Film 1, Film 2, Film 3,
values
and Filmwere calculated
2 were in the
more flat areas
than of 2ofμm
those × 2 μm,
blended and3 the
Film androughnesses
Film 4. TheofroughnessFilm 1, Film 2, Film
values were 3,
and Film 4 were 11.4, 3.48, 40.7, and 57.3 nm, respectively. The roughnesses of the blended films
and Film 4inwere
calculated 11.4,of3.48,
the areas 2 µm40.7,
ˆ 2andµm, 57.3 nm,roughnesses
and the respectively.ofThe Filmroughnesses
1, Film 2, Film of 3,
the
and blended
Film 4 films
were
increased with the increase of QH relative content ratio from 1:1.5 (Film 2), 1:1 (Film 1) to 1.5:1 (Film 4).
increased
11.4, 3.48, with
40.7, the
andincrease
57.3 nm, of respectively.
QH relative content ratio from 1:1.5
The roughnesses of the(Film 2), 1:1films
blended (Filmincreased
1) to 1.5:1with
(Filmthe4).
6
6
Materials 2016, 9, 4 7 of 12

increase of QH
Materials 2016,relative content ratio from 1:1.5 (Film 2), 1:1 (Film 1) to 1.5:1 (Film 4). It was due to that
9, page–page
Materials
QH have many2016, branch
9, page–page
chains on its backbone, which resulted in the roughness of the blended films
It was due to that QH have many branch chains on its backbone, which resulted in the roughness of
increased. When the ratio of QH/CMC reached up to 2:1, the roughness of blend Film 3 had a little
It was
the due tofilms
blended that QH have many
increased. Whenbranch chains
the ratio on its backbone,
of QH/CMC reachedwhich
up to resulted in the roughness
2:1, the roughness of
of blend
decrease compared with Film 4, but still higher than that of Film 1 and Film 2.
the blended films increased. When the ratio of QH/CMC reached up to 2:1, the roughness of blend
Film 3 had a little decrease compared with Film 4, but still higher than that of Film 1 and Film 2.
Film 3 had a little decrease compared with Film 4, but still higher than that of Film 1 and Film 2.

Figure 5. SEM images of the surface (a) and cross section (b) of Film 4.
Figure 5. SEM
Figure images
5. SEM imagesofofthe
thesurface (a) and
surface (a) andcross
crosssection
section(b)(b) of Film
of Film 4. 4.

Figure 6. AFM height images (A, D, G, J), 3D topography (B, E, H, K), and phase topography (C, F, I, L)
Figure
of
Figure 6. AFM
theAFM
6. blend height
Film
height images
1,images
Film (A, 3,
2, Film D,and
G, J),
(A,D,G,J), 3Dtopography
Film
3D topography (B,
4. E, H, K), and
(B,E,H,K), andphase
phasetopography (C, (C,F,I,L)
topography F, I, L) of
of the blend Film 1, Film 2, Film 3, and Film 4.
the blend Film 1, Film 2, Film 3, and Film 4.
7
7
Materials 2016, 9, 4 8 of 12

3.4. Mechanical Properties

The tensile stress, tensile strain at break, and Young’s modulus of films are shown in Table 3, and
Materials
the tensile 2016, 9, page–page
stress-strain curves of the blended films are shown in Figure 7. As can been seen, it was
found that the tensile strength of blended films increased with the increase of QH/CMC content ratio
3.4. Mechanical Properties
from 1:1.5 (Film 2), 1:1 (Film 1) to 1.5:1 (Film 4), and the maximum value 27.4 MPa was obtained in
The tensile stress, tensile strain at break, and Young’s modulus of films are shown in Table 3,
Film 4; nevertheless, the tensile strength of Film 3 (QH/CMC, 2:1) reduced obviously when the QH
and the tensile stress‐strain curves of the blended films are shown in Figure 7. As can been seen, it
relative was
content
found further
that theincreased. It was mainly
tensile strength of blended caused
filmsby the intermolecular
increased hydrogen
with the increase bonding and
of QH/CMC
electrostatic interaction between QH and CMC. That is to say, the miscibility of
content ratio from 1:1.5 (Film 2), 1:1 (Film 1) to 1.5:1 (Film 4), and the maximum value 27.4 MPa was the films increases
with theobtained
QH/CMC in Film content in the appropriate
4; nevertheless, range. of
the tensile strength From
Film Film 2 to Film
3 (QH/CMC, 2:1)1reduced
to Filmobviously
4, the quantity
when the
and intensity QH hydrogen
of the relative content
bondingfurther
andincreased.
electrostaticIt was mainly caused
interaction by thewith
increased intermolecular
the QH content
hydrogen bonding and electrostatic interaction between QH
increasing. Therefore, the tensile strength of the films increased consequently. However,and CMC. That is to say, the with the
miscibility of the films increases with the QH/CMC content in the appropriate range. From Film 2 to
relative content of QH further increasing, the miscibility of the films decreased, which resulted in the
Film 1 to Film 4, the quantity and intensity of the hydrogen bonding and electrostatic interaction
hydrogen bonding
increased with and
theelectrostatic force were
QH content increasing. not formed
Therefore, enough
the tensile between
strength QH
of the andincreased
films CMC because
of the relatively small amount of CMC. That is to say, the formed interaction
consequently. However, with the relative content of QH further increasing, the miscibility of the force was too weak
to support
filmsthe structure
decreased, whichof resulted
the Filmin 3,theresulting
hydrogen in the sharp
bonding decrease of
and electrostatic tensile
force strength
were not formedof Film
enough discussed
3. The results between QHabove and CMC becausethat
indicated of thethe
relatively
mechanicalsmall amount of CMC.
properties Thatblended
of the is to say,films
the were
formed interaction force was too weak to support the structure of the Film 3, resulting in the sharp
greatly affected by the QH content, and the excess QH would reduce the mechanical property of the
decrease of tensile strength of Film 3. The results discussed above indicated that the mechanical
blendedproperties
films. of the blended films were greatly affected by the QH content, and the excess QH would
reduce the mechanical property of the blended films.
Table 3. Tensile testing results of the four blended films.
Table 3. Tensile testing results of the four blended films.
Sample Tensile Strength (MPa) Tensile Strain at Break (%) Young‘s Modulus (MPa)
Sample Tensile Strength (MPa) Tensile Strain at Break(%) Young‘s Modulus (MPa)
FilmFilm
1 1 25.2 ˘±2.3
25.2 2.3 2.8±˘0.7
2.8 0.7 1319.9
1319.9 ˘ 102.7
± 102.7
FilmFilm
2 2 14.2 ˘±0.9
14.2 0.9 2.6±˘0.9
2.6 0.9 842.0
842.0 ˘ 11.1
± 11.1
FilmFilm
3 3 14.8 ˘±1.6
14.8 1.6 1.7±˘0.5
1.7 0.5 1177.2
1177.2 ˘ 126.5
± 126.5
Film 4 27.0 ˘ 1.5 3.9 ˘ 0.8 1118.5 ˘ 53.5
Film 4 27.0 ± 1.5 3.9 ± 0.8 1118.5 ± 53.5

FigureFigure
7. The7. The tensile stress‐strain curves of Film 1, Film 2, Film 3, and Film 4.
tensile stress-strain curves of Film 1, Film 2, Film 3, and Film 4.
3.5. UV‐Vis Transparency of Films
3.5. UV-Vis Transparency of Films
Generally, transparency of film is an assistant criterion to judge the miscibility of blended films.
The lighttransparency
Generally, transmittances of of the
filmblended films at wavelength
is an assistant of 200–800
criterion to judge thenmmiscibility
are shown in ofFigure 8. films.
blended
It can be seen obviously that the transmittance curve of each film rose gradually
The light transmittances of the blended films at wavelength of 200–800 nm are shown in Figure 8. with the increase of
wavelength. Comparing the four blended films, the transparencies of the blended films increased
It can be seen obviously that the transmittance curve of each film rose gradually with the increase of
with the QH/CMC content ratio decreasing in visible light spectrum, and it had the following order:
wavelength.
Film 2Comparing the 4four
> Film 1 > Film blended
> Film films,
3. In other the transparencies
words, a relatively high of the blended
content of CMC in films
the increased
blended with
the QH/CMC content ratio decreasing in visible light spectrum,
films is beneficial for the transparency of the blended films. and it had the following order: Film 2
> Film 1 > Film 4 > Film 3. In other words, a relatively 8 high content of CMC in the blended films is
beneficial for the transparency of the blended films.
Materials 2016, 9, 4 9 of 12
Materials
Materials 2016,
2016, 9, 9, page–page
page–page

Figure 8. UV‐Vis spectra of blend Film 1, Film 2, Film 3, and Film 4.

Figure 8. UV-Vis spectra of blend Film 1, Film 2, Film 3, and Film 4.
Figure 8. UV‐Vis spectra of blend Film 1, Film 2, Film 3, and Film 4.
3.6. Water Vapor Permeability (WVP)
3.6.3.6.
Water Vapor
Water Permeability
Vapor Permeability(WVP)
(WVP)
The WVP values of the blended films are important measures for the applications of packaging
TheTheWVP
materials.WVP values
One of the
values ofofthetheblended
main functions
blended films are
are important
of food
films measures
packaging measures
important is to avoidfor for
or thetheapplications
minimizeapplications
moisture ofof packaging
transfer
packaging
between
materials. One food of and
the the
mainsurrounding
functions atmosphere.
of food Low
packaging WVP
materials. One of the main functions of food packaging is to avoid or minimize moisture transfer widens
is to the
avoid application
or minimize of the composite
moisture transfer
betweenpackaging
between foodfood andfilm,
and especially
the thesurrounding in a highly
surroundingatmosphere. humid environment.
atmosphere. Low WVP WVP widens The WVP
widensthe curves
theapplication of the
applicationofofthe four theblended
composite
composite
films are
packaging
packaging shown
film,
film, in Figureinin
especially
especially 9.aIt was
ahighly
highly found that environment.
humid
humid all the four blended
environment. The
TheWVP films
WVPshowed curves
curvesof aofrelatively
thethefourfour lower
blended
blended
WVP,
films suggesting that the fabricated films have the capability to withstand water vapor. The WVP
films areare shown
shown ininFigure
Figure9.9.ItItwas wasfoundfound that
that all
all the four
four blended
blendedfilms filmsshowedshoweda arelatively relatively lower
lower
values of blended films had the following order: Film 2 > Film 3 > Film 1 > Film 4, indicating that
WVP, suggesting that the fabricated films have the capability
WVP, suggesting that the fabricated films have the capability to withstand water vapor. The WVP to withstand water vapor. The WVP
the WVP values decreased with the increase of QH/CMC content ratio from 1:1.5 (Film 2), 1:1 (Film 1)
values
values of blended films hadthethe following order: Film > 2 Film
> Film 3 >Film
Film1 > 1 >Film
Film4,4,indicating
indicatingthat thatthe
to of blended
1.5:1 (Film 4). films had
However, an following
interesting order:
resultFilm
was2observed. 3 When
> the QH/CMC content ratio
the
WVPwas WVP
values values
decreased decreased with the increase of QH/CMC content ratio from 1:1.5 (Film 2), 1:1 (Film 1) 1)
further increasedwith to 2:1 the increase
(Film 3), theof QH/CMC
WVP value of content ratio from
Film 3 increased 1:1.5The
instead. (Film 2), 1:1
causes (Film
of this
to
to 1.5:11.5:1 (Film
(Film 4). are 4). However,
However, an interesting
an interesting result
result was observed. When the QH/CMC content ratio
phenomenon the different densification of thewas
fourobserved.
blended films. When As the QH/CMC
discussed in thecontent
analysis ratio
waswas further
further increasedtoto2:1
increased 2:1(Film
(Film3), 3),the
theWVP
WVP valuevalue of of Film
Film 33 increased
increased instead. The Thecauses of of
this
of the blended films’ mechanical properties, the quantity and intensity ofinstead.
the hydrogen causes
bonding this
phenomenon
and are
electrostatic the different
force increased densification
with the of the
QH/CMC four blended
content films.
ratio As
increasing,discussed
which in the
led analysis
to the
phenomenon are the different densification of the four blended films. As discussed in the analysis of
of tightness
the blended films’ mechanical
of internal structure of properties,
blendedthe theItquantity
films. and intensity
also prevented water of the hydrogen bonding
the blended films’ mechanical properties, quantity and intensity ofmolecules
the hydrogen from diffusing
bonding and
and electrostatic
through forcethe films. force increased
Therefore, with the QH/CMC content ratio increasing, which led to the
electrostatic increased withthe theWVP QH/CMC of filmscontent
decreased ratiowith QH/CMCwhich
increasing, contentled ratio increasing.
to the tightness of
tightness of internal structure of blended films. It also prevented
When the QH/CMC content ratio was further increased to 2:1 (Film 3), the hydrogen bonding and water molecules from diffusing
internal structure of blended films. It also prevented water molecules from diffusing through the films.
through the films.
electrostatic Therefore,
interaction were the not WVP formed of enough
films decreased
between QH withand QH/CMC
CMC because contentofratio increasing.
the relatively
Therefore,
When
the WVP of content films decreased with QH/CMC content ratio increasing. Whenbonding the QH/CMC
small amount of CMC. Then, the structure of blend Film 3 became loose again and the WVP of Filmand
the QH/CMC ratio was further increased to 2:1 (Film 3), the hydrogen
content ratio was
electrostatic
3 increased. further increased
interaction
Therefore, werethe not to 2:1 (Film
formed
interactions enough3), the
between hydrogen
between
components QH bonding
and
have CMC and
obvious electrostatic
because of the on
influence interaction
relatively
the
were
smallnot formed
densification
amount ofofCMC. enough between
the blended
Then, the filmsQH and CMC
[37]. Theofresults
structure because
blend indicated of the
Film 3 became relatively
that thelooseWVP small
again amount
of the
andblended
the WVPof CMC.
films isThen,
of Film
the3 structure
related
increased. of
to the blend Film
intensity ofthe
Therefore, 3 became
interaction
interactions loose again
force between and
between QH the WVP
and CMC, have
components of Film 3
and it obvious increased.
is in accordanceinfluenceTherefore,
withon thethethe
interactions between
tensile strength
densification of the ofcomponents
the blended
blended films have
films.[37].obvious influence
The results on thethat
indicated densification
the WVP of of the
the blended
blended films films is
[37].
Therelated
resultstoindicated
the intensity thatofthe WVP of the
interaction forceblended
between films
QHisand related
CMC,toand the itintensity of interaction
is in accordance with the force
between
tensile QH and CMC,
strength and it isfilms.
of the blended in accordance with the tensile strength of the blended films.

Figure 9. The water vapor permeability of blend Film 1, Film 2, Film 3, and Film 4.
9

Figure
Figure 9.9.The
Thewater
watervapor
vaporpermeability
permeability of
of blend
blend Film
Film1,1,Film
Film2,2,Film
Film3,3,and
andFilm 4. 4.
Film
9
Materials 2016, 9, 4 10 of 12

4. Conclusions
A series of blended films of QH and CMC were successfully fabricated in this study, and they
were linked by the hydrogen bonding and electrostatic interaction. The blended films with different
proportions of QH and CMC were also studied to determine their properties. From the results of
mechanical properties and water vapor permeability, it was found that the intensity of hydrogen
bonding and electrostatic interaction between QH and CMC increased with the increasin QH/CMC
content ratio in the appropriate range, which made the film structurally dense, resulting in the tensile
strength increase and WVP film decrease, respectively. However, hydrogen bonding and electrostatic
interaction were not formed enough to support the structure of the film when excess QH was added,
which led to the film tensile strength decrease and the WVP increase. The light transmittances of the
blended films increased with the decrease of the QH/CMC content ratio. The prepared films show
good strength, low WVP, and good light transmittances, which are beneficial for the applications of
films as packaging materials. Besides, compared with the petroleum-based plastics, the films fabricated
from QH and CMC have biocompatible, nontoxic, and biodegradable properties. Therefore, the films
fabricated by blending CMC with QH might become attractive in the application of packaging materials
to replace the traditional petroleum-based packaging materials.

Acknowledgments: This work was supported by Grants from State Forestry Administration (201404617), 2014
Beijing Student Research Training Program (S201410022044), National Natural Science Foundation of China
(21406014), Ministries of Education (NCET-13-0670), and Author of National Excellent Doctoral Dissertations of
China (201458).
Author Contributions: Shiyun Liu and Fangbing Chu performed the experiments; Yanru Liang and Shuai Pang
analyzed the data; the paper was written under the direction and supervision of Feng Peng and Runcang Sun;
Xianming Qi and Ying Guan are responsible for the writing of this work.
Conflicts of Interest: The authors declare no conflict of interest.

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