International Journal of Biological Macromolecules 135 (2019) 240–245

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

journal homepage: http://www.elsevier.com/locate/ijbiomac

Structural characterization and properties of polyols plasticized

chitosan films
Xianguang Ma a, Congde Qiao a,⁎, Xujie Wang a, Jinshui Yao a, Jing Xu b
a
School of Materials Science and Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250353, PR China
b
School of Chemistry and Pharmaceutical Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250353, PR China

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

Article history: In this study, the influence of different polyols such as glycerol, xylitol and maltitol on the crystalline structure
Received 6 March 2019 and thermal properties of chitosan films were investigated by X-ray diffraction (XRD), Fourier transform infrared
Received in revised form 30 April 2019 spectroscopy (FTIR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The concen-
Accepted 21 May 2019
tration of polyol was fixed at 20 wt%. FTIR result showed that the addition of polyols weakened the hydrogen
Available online 22 May 2019
bonding between chitosan molecules, whereas the electrostatic interactions remained nearly unchanged. Struc-
Keywords:
tural analysis revealed that the plasticizer which promoted the crystallization of chitosan was moisture rather
Chitosan than polyol contained in the polymer films. DSC result indicated that glycerol plasticized film had a lower glass
Polyols transition temperature (Tg) and lower melting temperature (Tm). The low thermal transition temperatures sug-
Plasticizer gested that the moisture content is higher in glycerol plasticized film, which was evidenced by TGA result. In ad-
Microstructure dition, the polyols incorporation resulted in a decrease of the tensile strength of chitosan films, while their
ductility was improved. These observations indicate that the addition of polyols as plasticizers could regulate
the microstructure as well as the properties of chitosan films, which is essential for their usage in food industry.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction plasticizers, are generally added to improve the flexibility of biopoly-

Chitosan is a linear polysaccharide composed of β-1,4-linked-d-
glucosamine and N-acetyl-d-glucosamine [1], which is only dissolved
in acidic solution. It is the only polycationic polysaccharide in nature
[2,3]. Chitosan is one of the most prospective materials due to its avail-
ability, nontoxicity, biodegradability, biocompatibility and antimicro-
bial properties [4]. In addition, thanks to its good film-forming
properties, chitosan has been used as packaging material, especially as
edible films and coatings for fruits and vegetables to extend the shelf
life of foodstuffs [5].
Unfortunately, a disadvantage of chitosan is that it naturally inter-
acts with water, which may result in unexpected changes in its structure
and properties. This is a general phenomenon occurred for almost all of
biopolymers [6]. In addition, the pure chitosan films are relatively brittle
and fragile [7]. Accordingly, the usage of chitosan as packaging material
is hindered by the poor mechanical properties and high hygroscopicity.
Physical blend is a simple but efficient method to improve the prop-
erties of biopolymer films [8–10]. The blending of chitosan with low
molecular weight substances has attracted great interest in the modifi-
cation of chitosan. These small molecules, which are named as
⁎ Corresponding author at: School of Materials Science and Engineering, Qilu University
of Technology (Shandong Academy of Sciences), Daxue Rd. 3501, Jinan 250353, PR China.
E-mail address: cdqiao@qlu.edu.cn (C. Qiao).
mer. This plasticization effect is generally explained by several theories
including the gel theory, the lubrication theory and the free volume the-
ory [5].
Several polyols, such as glycerol, xylitol, sorbitol and maltitol, are
widely used for chitosan plasticization. The performance of plasticized
chitosan films depends on the proportions of plasticizers and their
chemical nature. It was found that the chitosan film plasticized with
20 wt% glycerol showed good mechanical properties [11]. Cerqueira
and coworkers investigated the effect of glycerol on the physicochemi-
cal properties of chitosan films, and found that the addition of glycerol
originated a more hydrophilic structure and an increased affinity of
the film matrix to water [12]. A similar result was also observed for
glycerol-plasticized chitosan samples obtained by mechanical kneading
[13]. Compared to other polyols, sorbitol plasticized chitosan films have
better mechanical and physicochemical properties [7]. It was found that
glycerol plasticized films were more flexible [14]. In addition, the addi-
tion of sorbitol to chitosan could result in a more orderly structure [15].
Matet et al. studied the influences of different polyols plasticizers, and
found that the chitosan films plasticized with the highest molecular
weight polyol displayed the highest thermal, mechanical and rheologi-
cal properties [1]. In addition to polyols, water has notable role in plas-
ticization of biopolymers [16]. It has been found that moisture in
chitosan films could induce significant changes in their structure as
well as properties [3,17,18]. Furthermore, the moisture content can be

https://doi.org/10.1016/j.ijbiomac.2019.05.158
0141-8130/© 2019 Elsevier B.V. All rights reserved.
 X. Ma et al. / International Journal of Biological Macromolecules 135 (2019) 240–245
affected by the addition of these polyols, which are hydrophilic plasti-
cizers. Thus, it is essential to exploit the effects of polyols and water sep-
arately in the plasticization of chitosan. However, the comparisons of
plasticizer efficiencies between these two plasticizers have not been
studied for chitosan films.
The aim of this work was to investigate the influences of three differ-
ent polyols on the microstructure and properties of chitosan films in
wet and dry states. The information about polyols as plasticizers for chi-
tosan films is beneficial for the applications of chitosan as packaging
materials.
2. Experimental
2.1. Materials
Chitosan with degree of deacetylation DD = 90% was purchased
from Sinopharm Chemical Reagent Co., Ltd. The average molecular
weight of chitosan is approximate 160,000. The plasticizers used were
glycerol, xylitol and maltitol, which were also purchased from
Sinopharm Chemical Reagent Co., Ltd. All hydrous solutions were pre-
pared by using ultrapure water (18 MΩ·cm) from a Milli-Q system
(Millipore). All chemicals were analytical grade.
2.2. Film preparation and conditioning
A chitosan or chitosan/plasticizer solution was prepared by dissolv-
ing 0.6 g chitosan powder or 0.72 g chitosan/plasticizer in 30 mL 1% v/v,
solution is here, the concentration of acetic acid aqueous volume con-
centration. The sample solutions were stirred at 50 °C for 6 h to gain ho-
mogenous solutions, and then filtered through a piece of PTFE
membrane with a pore diameter of 0.45 um to remove impurities. In
the mixture, the chitosan concentration was 2%, and the concentration
of plasticizer (glycerol, xylitol, and maltitol) was fixed at 20 wt% (dry
basis of chitosan). Then 30 mL of mixture solutions and neat chitosan
solution were casted on a PTFE mold, respectively, and dried at room
temperature for 72 h. The obtained sample films were dried at 110 °C
for 60 min in a vacuum oven, yielding dry sample films. To investigate
the effect of moisture, a part of these dry films was conditioned at
room temperature (25 °C) in desiccators for at least two weeks at 60%
relative humidity for further analysis.
2.3. Fourier-transform infrared (FTIR) spectroscopy
The FTIR spectra of the films were performed by a Nicolet iS10 spec-
trometer (Thermo Fisher Scientific Inc., Waltham, MA, USA), equipped
with an attenuated total reflection (ATR) accessory. The FTIR spectra
were recorded from wave number 400 to 4000 cm−1 with a resolution
of 4 cm−1.
2.4. X-ray diffraction (XRD)
XRD patterns of film samples were determined on a BDX3300 X-ray
diffractometer (Beijing University Equipment Manufacturer, Beijing,
China) equipped with a multichannel detector by use of a Cu (λ =
0.15406 nm) monochromatic X-ray beam. All the films were performed
within 2θ range of 5–50° with a scan rate of 1°/min.
2.5. Thermogravimetric analysis (TGA)
Thermogravimetric analysis of sample films was performed by a
TGA-1 (Mettler Toledo Instrument, Zurich, Switzerland) from room
temperature to 800 °C with a heating rate of 10 °C/min under a nitrogen
atmosphere. In addition, TGA was also used to accurately determine the
moisture content of the sample films, which were first heated to 120 °C
with a heating rate of 5 °C/min, and equilibrated at this temperature for
241
60 min. The content of moisture was determined from the weight loss at
the end of the experiment.
2.6. Differential scanning calorimetry (DSC)
DSC experiments were carried out by a Q 2000 DSC (TA Instrument,
New Castle, USA) equipped with a refrigerated cooling system. The sam-
ples with mass about 10 mg were hermetically sealed in aluminum her-
metic pans with lids and heated in the DSC cell from −80 to 180 °C at a
heating rate of 10 °C/min. Dry nitrogen was used as the purge gas at a
flow rate of 50 mL/min. DSC experiment was performed at least in trip-
licate on each film.
2.7. Mechanical properties
Tensile tests were carried out on a Universal testing machine (WDL-
005, Jinan Xinshijin Experimental Instrument Co., China) at room tem-
perature. The sample films with typical size of 50 mm × 10 mm
(length × width) were tested at ambient temperature with a constant
deformation rate of 20 mm/min.
3. Results and discussion
3.1. Water content in the plasticized chitosan films
As one of the primary drawbacks of chitosan films is that they natu-
rally interact with water due to their hygroscopic nature, which may
lead to undesired changes in both structure and properties. Hence it is
important to know the exact content of moisture in polymer films.
The moisture uptake study of the sample films conditioned at 60% RH
was carried out. Fig. 1 shows the moisture content in the sample films.
It is observed that the neat chitosan film shows a medium adsorption
activity with water contents of 8% at room temperature. When the plas-
ticizers were added, its moisture content varied with the nature of plas-
ticizers. It decreases from 11.3 wt% for the glycerol-plasticized film
down to 5.1 wt% for the maltitol-plasticized film. This result indicates
that the water content is related to the chemical structure of the plasti-
cizers. Generally, the end hydroxyl groups in plasticizer molecules are
expected to be more accessible to water. The amount of these end hy-
droxyl groups is inverse to the molecular weight of the plasticizers.
For the polyols used in this work, the amount of the end hydroxyl
groups in glycerol is highest, and the moisture content is highest in
glycerol-plasticized chitosan film. A similar result was observed in
polyols-plasticized starch films [19]. In addition, compared to xylitol
and maltitol which are solid plasticizers, glycerol is a liquid, and water
molecules are easily dispersed in glycerol.
12
10
water content(%)
8
6
4
2
0
Neat Chitosan Glycerol Xylitol Maltitol
Fig. 1. The moisture content of the neat and plasticized chitosan films conditioned at 60%
RH.
242 X. Ma et al. / International Journal of Biological Macromolecules 135 (2019) 240–245

1540
1392
3203 groups rather than the NH+3 groups of chitosan. The addition of polyols
results in the disruption of the hydrogen bonding between chitosan
molecules, whereas the electrostatic interactions remained nearly
unchanged.
3226
Intensity(a.u)

3.3. Microstructure of polyols-plasticized films

3219
3215
Neat chitosan Xylitol
Gglycerol Maltitol
4000 3500 3000 2500 2000 1500 1000
-1
Wavenumber(cm )
Fig. 2. FTIR spectra of the neat and plasticized chitosan films conditioned at 60% RH. The
nature of the plasticizer is indicated in the figure.
3.2. Interactions between chitosan and polyols
In order to study the interactions of chitosan with various polyols,
FTIR experiments were performed on chitosan films plasticized by var-
ious polyols. Fig. 2 shows the FTIR spectra of the sample films. A broad
absorption band between 3600 and 3000 cm−1 appears in the neat chi-
tosan film, which is ascribed to the stretching vibration of hydrogen-
bonded hydroxyl groups that overlaps the amino group stretching vi-
bration in the same region [20]. The peak at 1540 cm−1 is attributed
to amide II, indicating the amino group in chitosan is protonated
−1
-NH+ 3 instead of -NH2 [21]. In addition, the peak at 1392 cm is attrib-
uted to -CH2 bending.
When the polyols were added, the broad band at 3000–3600 cm−1
had a slight shift from 3203 cm−1 for the neat chitosan to 3226, 3219
and 3215 cm−1 for glycerol, xylitol and maltitol plasticized samples, re-
spectively. The shift of this broad band indicated that the addition of
polyols weakened the hydrogen bonding between chitosan molecules
[22]. Close examination of the FTIR spectra in Fig. 2 reveals that this
broad absorption band narrowed for glycerol-plasticized film. These re-
sults show that glycerol had a better plasticization effect. In addition, the
absorption band at 1540 cm−1 did not change with polyols addition,
suggesting no significant hydrogen bonds are formed between polyols
molecules and NH+ 3 groups. On the basis of these results it can be de-
duced that, the polyols molecules mainly interact with the hydroxyl
To investigate the effects of polyols and water on the structural
changes of chitosan films, the wide X-ray diffraction patterns of the
neat and various polyol plasticized chitosan films in wet and dry states
are compared, as shown in Fig. 3. For the wet samples as shown in
Fig. 3a, the neat chitosan film displays two main broad peaks: one
peak at around 2θ = 12° and another at 2θ = 20°, which can be assigned
to the diffraction from the chitosan acetate crystal planes of (100) and
(020), respectively. Similar results were reported for chitosan films pre-
500
pared from 9% chitosan solutions [23]. Although chitosan is a semicrys-
talline polymer, the regenerated chitosan film in this study exhibits low
crystallinity, as evidenced by its broad diffraction peaks. Similar behav-
ior has been observed for chitosan film obtained by solvent casting, due
to a partial reorganization of crystalline region of raw powder during
the formation of film [24].
When xylitol is added, three main sharp peaks turn up at 2θ = 9°,
12°and 19° in the scattering curve, agreeing with the pattern of a hy-
drated crystal [25]. It seemed that the addition of xylitol could promote
the crystallization of chitosan. In addition, it was reported that glycerol
could favor the chains mobility and thus the crystallization of chitosan
[13]. However, in this study the enhancement of chitosan crystallization
was not caused solely by polyols as the influence of moisture should be
involved. It was found that the moisture content of chitosan film was in-
creased by the addition of glycerol (Fig. 1). Several studies have shown
that the crystallinity of chitosan films increased with an increase in
water content [18,26].
To eliminate the effect of water, the XRD patterns of the samples at
dry state were determined as shown in Fig. 3b. It was found that the
three sharp peaks disappeared, whereas a wide diffraction peaks at
around 20° appeared for the neat and polyol plasticized chitosan films.
This result was consistent with previously reported studies on chitosan
films cured at 100 °C [27]. These observations confirmed that it was
moisture instead of polyols which resulted in a significant enhancement
of the crystallinity of chitosan.
3.4. Thermogravimetric analysis (TGA)
Fig. 4 shows the thermal degradation curves of the neat and various
polyol plasticized chitosan films. All the sample films displayed a similar
thermal degradation behavior, which underwent an initial slight weight

a Neat chitosan b Neat chitosan

Glycerol Glycerol
Xylitol Xylitol
Maltitol Maltitol
Intensity(a.u)
Intensity(a.u)

10 20 30 40 50 10 20 30 40 50
2θ(degree) 2θ(degree)

Fig. 3. Wide angle X-ray diffraction patterns of the neat and plasticized films: (a) conditioned at 60% RH; (b) treated at 110 °C. The nature of the plasticizer is indicated in the figure.
 X. Ma et al. / International Journal of Biological Macromolecules 135 (2019) 240–245 243

100 When the polyols were added, the Tg decreased from 60 °C for the
Neat chitosan neat chitosan to −27, −15 and 50 °C for glycerol, xylitol and maltitol
Glycerol plasticized samples, respectively. This result indicates that the polyol
Xylitol plasticizer efficiency follows the order glycerol N xylitol N maltitol,
80
Maltitol
Weight(%)

60
40
100 200 300 400 500 600
o It is known that the glass transition behavior of chitosan in hydrated
Temperature( C)
Fig. 4. TGA curve of the neat and plasticized chitosan films. The nature of the plasticizer is
indicated in the figure.
loss at around 120 °C, and then a sharp weight loss from 190 to 350 °C.
The first weight loss at approximately 120 °C was attributed to the vol-
atilization of moisture existed in polymer films. The weight loss of glyc-
erol plasticized film is larger than that of other sample, suggesting that
the water content of this film is higher than that of other films. This re-
sult revealed that the addition of glycerol promoted the hydroscopicity
of chitosan film, due to the highly hydrophilic character of glycerol. The
notable weight loss from 190 to 350 °C was assigned to a complex pro-
cess involving the decomposition of the acetylated as well as
deacetylated units of chitosan and polyols [28–30]. In addition, the de-
composition temperature of chitosan films was almost unchanged for
the addition of polyols. These results hint that the nature of plasticizer
has an insignificant influence on the thermal stability of chitosan films.
3.5. Differential scanning calorimetry (DSC)
The glass transition temperature (Tg) is an important parameter of
polymers, at which their physical properties will undergo significant
changes. The effect of polyols on the Tg of chitosan films was investi-
gated. The DSC thermograms of the neat and various polyol plasticized
chitosan films in wet and dry states were shown in Fig. 5, and the results
are listed in Table 1. For the wet samples as shown in Fig. 5a, it was
found that the glass transition temperature of the neat chitosan film
was 60 °C. This temperature was in good agreement with Tg values of
about 55 °C previously reported for chitosan films stored at 50–60% rel-
ative humidity [31,32].
which decreases with the molecular weight of the plasticizer. The effect
of the molecular weight of the polyols can be explained in term of the
number of effective chitosan/plasticizer interactions. At the same plasti-
cizer content, the amount of polyol molecules interacting with the chi-
tosan chains increases with a decrease in the plasticizer molecular
weight, resulting in a higher plasticizing efficiency. As a result, the Tg
tends to decrease with a decrease of the molecular weight of plasticizer.
This decrease of Tg with the plasticizer molecular weight was also ob-
served for starch films plasticized with these polyols [19]. In addition
to polyols, water molecules also have plasticizing effect in these films.
700 800
films is closely related to the moisture content [3]. In this work, the
lower Tg of glycerol plasticized chitosan film is also related to its higher
water contents, which may be a result of the synergistic effect of polyol
and water.
As the moisture was removed from the polymer films, the effect of
polyols seemed to be negligible (Fig. 5b). The Tg of the neat chitosan
film was observed at 125 °C, which was consistent with that reported
by other researchers [23]. For xylitol or maltitol plasticized films, they
displayed a similar Tg of about 127 °C, whereas glycerol plasticized chi-
tosan film showed a higher Tg of about 165 °C. The higher Tg may be re-
sulted from the antiplasticization effect of glycerol. This
antiplasticization effect has been observed in glycerol plasticized chito-
san or starch systems [33]. In a recent study, Meng et al. found that the
dry chitosan samples still had limited mobility in the temperature range
of 20–200 °C, although they were plasticized with glycerol [34]. These
results revealed that the plasticization effect of polyols was insignificant
in the absence of moisture for chitosan with rigid molecular chains.
Interestingly, the melting behavior of chitosan was also observed in
Fig. 5a. It showed that the melting temperature (Tm) of the neat chito-
san film was about 103 °C. It was almost completely consistent with the
Tm values of 105 °C for chitosan films stored at room temperature [7].
As the polyols were added, the Tm decreased from 103 °C for the neat
chitosan to 83, 90 and 99 °C for glycerol, xylitol and maltitol plasticized
samples, respectively. This decrease of Tm with polyols addition was
also found for glycerol-plasticized films stored at 54% RH [12]. Polyols
show a similar effect on Tm as that on Tg of chitosan films: the Tm of
chitosan tends to decrease with a decrease of the plasticizer molecular
weight. In addition, the melting behavior was not observed for all the
sample films at dry states (Fig. 5b). This is consistent with the X-ray
spectra shown in Fig. 3b, which exhibit completely amorphous patterns
in all cases. Furthermore, chitosan undergoes decomposition prior to

a b
Heat Flow(a.u) Exo-up
Heat Flow (a.u) Exo-up

Neat chitosan Neat chitosan

Glycerol Glycerol
Xylitol Xylitol
Maltitol Maltitol

-50 0 50 100 -50 0 50 o

100 150
o
Temperature ( C) Temperature( C)

Fig. 5. DSC thermograms of the neat and plasticized chitosan films: (a) conditioned at 60% RH; (b) treated at 110 °C. The nature of the plasticizer is indicated in the figure.
244 X. Ma et al. / International Journal of Biological Macromolecules 135 (2019) 240–245

Table 1 remained nearly unchanged. The plasticizer efficiency decreases with

The glass transition temperature (Tg) and the melting temperature (Tm) of sample films the molecular weight of the plasticizer. Glycerin plasticized film with
at wet and dry states (1: wet state; 2: dry state).
the highest moisture content shows a remarkable plasticizing effect,
Tg1 (°C) Tm1 (°C) Tg2 (°C) Tm2 (°C) as evidenced by a lower Tg as well as Tm. In addition, lack of water
Neat chitosan 60 ± 2 103 ± 3 125 ± 4 N may result in the weakening of the plasticization effect of polyols for
Chitosan/glycerol −27 ± 1 83 ± 2 165 ± 5 N chitosan with rigid molecular chains. The chitosan film plasticized
Chitosan/xylitol −15 ± 1 90 ± 2 127 ± 4 N with maltitol has good mechanical properties, whereas a typical rubber-
Chitosan/maltitol 50 ± 2 99 ± 3 127 ± 4 N
like behavior is observed for glycerin plasticized system.
N: not found.

melting due to the presence of the large number of inter- and intramo-
lecular hydrogen bonds in this biopolymer [35]. Consequently, the melt-
ing transition did not occur in these sample films.
3.6. Mechanical properties
The mechanical properties of the plasticized chitosan films were in-
vestigated as a function of the nature of the plasticizer. Fig. 6 displays
the stress-strain curves of the neat and various polyol plasticized chito-
san films at room temperature. It is seen that the neat chitosan film has
the highest tensile strength and lowest elongation at the break, which is
the typical pattern of brittle materials. A similar result was also observed
for the chitosan film conditioned at 50%RH [5]. Compared to other plas-
ticized systems, glycerol plasticized film has the lowest tensile strength
and highest elongation at break. According to the DSC result (in
Table 1), the Tg of this film is −27 °C. Therefore, the glycerol-
plasticized film displays a typical rubberlike behavior with a high strain
at break. This rubberlike behavior was also found for glycerol-
plasticized starch films [19]. This result shows that glycerol is an effec-
tive plasticizer. Furthermore, this sample displays the highest water up-
take, confirmed by the TGA results and also moisture content studies
(Fig. 1). The combination of glycerin and water could result in a remark-
able plasticizing effect. Compare to xylitol plasticized sample, the
maltitol plasticized chitosan film has a higher tensile strength and elon-
gation at break, suggesting that this sample possesses good mechanical
properties. In addition, a “jump” appears in the stress-deformation
curves at low loads for samples plasticized with xylitol and maltitol
(Fig. 6). The origin of this “jump” is unknown at present. It may be re-
lated to the local inhomogeneity of sample films, which need further
study.
4. Conclusions
In polyol plasticized chitosan films, the polyol molecules mainly in-
teract with the hydroxyl groups rather than the NH+ 3 groups of chitosan.
The addition of polyols leads to the disruption of the hydrogen bonding
between chitosan molecules, while the electrostatic interactions
Neat chitosan
Glycerol
30 Xylitol
Maltitol
Stress(MPa)
Acknowledgement
The work was supported by the National Natural Science Foundation
of China (No. 21606138).
References
[1] M. Matet, M.C. Heuzey, E. Pollet, A. Ajji, L. Avérous, Innovative thermoplastic chito-
san obtained by thermo-mechanical mixing with polyol plasticizers, Carbohydr.
Polym. 95 (2013) 241–251.
[2] K. Haxaire, Y. Maréchal, M. Milas, M. Rinaudo, Hydration of polysaccharide
hyaluronan observed by IR spectrometry. I. Preliminary experiments and band as-
signments, Biopolymer 72 (2003) 10–20.
[3] C. Madeleine-Perdrillat, T. Karbowiak, J. Raya, R. Gougeon, P.R. Bodart, F. Debeaufort,
Water-induced local ordering of chitosan polymer chains in thin layer films,
Carbohydr. Polym. 118 (2015) 107–114.
[4] M. Rinaudo, Chitin and chitosan: properties and applications, Prog. Polym. Sci. 31
(2006) 603–632.
[5] N.E. Suyatma, L. Tighzert, A. Copinet, V. Coma, Effects of hydrophilic plasticizers on
mechanical, thermal, and surface properties of chitosan films, J. Agric. Food Chem.
53 (2005) 3950–3957.
[6] I. Yakimets, S.S. Paes, N. Wellner, A.C. Smith, R.H. Wilson, J.R. Mitchell, Effect of water
content on the structural reorganization and elastic properties of biopolymer films:
a comparative study, Biomacromol 8 (2007) 1710–1722.
[7] M. Liu, Y. Zhou, Y. Zhang, C. Yu, S. Cao, Physicochemical, mechanical and thermal
properties of chitosan films with and without sorbitol, Int. J. Biol. Macromol. 70
(2014) 340–346.
[8] M.N. Taravel, A. Domard, Collagen and its interaction with chitosan: II. Influence of
the physicochemical characteristics of collagen, Biomaterials 16 (1995) 865–871.
[9] B. Smitha, S. Sridhar, A.A. Khan, Synthesis and characterization of proton conducting
polymer membranes for fuel cells, J. Membr. Sci. 225 (2003) 63–76.
[10] B. Smitha, G. Dhanuja, S. Sridhar, Dehydration of 1,4-dioxane by pervaporation using
modified blend membranes of chitosan and nylon 66, Carbohydr. Polym. 66 (2006)
463–472.
[11] J.R. Rodríguez-Núñez, T.J. Madera-Santana, D.I. Sánchez-Machado, J. López-
Cervantes, H. Soto Valdez, Chitosan/hydrophilic plasticizer-based films: preparation,
physicochemical and antimicrobial properties, J. Polym. Environ. 22 (2014) 41–51.
[12] M.A. Cerqueira, B.W.S. Souza, J.A. Teixeira, A.A. Vicente, Effect of glycerol and corn oil
on physicochemical properties of polysaccharide films–a comparative study, Food
Hydrocoll. 27 (2012) 175–184.
[13] V. Epure, M. Griffon, E. Pollet, L. Avérous, Structure and properties of glycerol-
plasticized chitosan obtained by mechanical kneading, Carbohydr. Polym. 83
(2011) 947–952.
[14] P.C. Srinivasa, M.N. Ramesh, R.N. Tharanathan, Effect of plasticizers and fatty acids
on mechanical and permeability characteristics of chitosan films, Food Hydrocoll.
21 (2007) 1113–1122.
[15] M. Liu, Y. Zhou, Y. Zhang, C. Yu, S. Cao, Preparation and structural analysis of chito-
san films with and without sorbitol, Food Hydrocoll. 33 (2013) 186–191.
[16] Y.H. Roos, Phase Transitions in Foods, Academic Press, Inc., San Diego, CA, 1995.
[17] S. Alvarado, G. Sandoval, I. Palos, S. Tellez, Y. Aguirre-Loredo, G. Velazquez, The effect
of relative humidity on tensile strength and water vapor permeability in chitosan,
fish gelatin and transglutaminase edible films, J. Food Sci. Technol. 35 (2015)
690–695.
[18] C. Qiao, X. Ma, J. Zhang, J. Yao, Effect of hydration on water state, glass transition dy-

namics and crystalline structure in chitosan films, Carbohydr. Polym. 206 (2019)
20 602–608.
[19] A.P. Mathew, A. Dufresne, Plasticized waxy maize starch: effect of polyols and rela-
tive humidity on material properties, Biomacromoles 3 (2002) 1101–1108.
[20] I. Quijada-Garrido, V. Iglesias-González, J.M. Mazón-Arechederra, J.M. Barrales-
Rienda, The role played by the interactions of small molecules with chitosan and
10 their transition temperatures. Glass-forming liquids: 1,2,3-propantriol (glycerol),
Carbohydr. Polym. 68 (2007) 173–186.
[21] S. Kumar-Krishnan, E. Prokhorov, M. Ramírez, M.A. Hernandez-Landaverde, D.G.
Zarate-Triviño, Y. Kovalenko, Novel gigahertz frequency dielectric relaxations in chi-
0 tosan films, Soft Matter 10 (2014) 8673–8684.
0 20 40 60 80 100 [22] X. Ma, C. Qiao, J. Zhang, J. Xu, Effect of sorbitol content on microstructure and ther-
mal properties of chitosan films, Int. J. Biol. Macromol. 119 (2018) 1294–1297.
Strain(%) [23] N. Mati-Baouche, H. De Baynast, C. Vial, F. Audonnet, S. Sun, E. Petit, F. Pennec, V.
Prevot, P. Michaud, Physico-chemical, thermal, and mechanical approaches for the
Fig. 6. The stress-strain curves of the neat and plasticized chitosan films conditioned at 60% characterization of solubilized and solid state chitosans, J. Appl. Polym. Sci. 132
RH. The nature of the plasticizer is indicated in the figure. (2015) 41257.1–8.
 X. Ma et al. / International Journal of Biological Macromolecules 135 (2019) 240–245
[24] F.S. Kittur, A.B. Vishu Kumar, R.N. Tharanathan, Low molecular weight chitosans—
preparation by depolymerization with Aspergillus niger pectinase, and characteriza-
tion, Carbohydr. Res. 338 (2003) 1283–1290.
[25] M. Fan, Q.L. Hu, K. Shen, Preparation and structure of chitosan soluble in wide pH
range, Carbohydr. Polym. 78 (2009) 66–71.
[26] M.A. Kobaisi, P. Murugaraj, D.E. Mainwaring, Origin and influence of waterinduced
chain relaxation phenomena in chitosan biopolymers, J. Polym. Sci. Phys. 50
(2012) 403–414.
[27] S. Rivero, M.A. García, A. Pinotti, Heat treatment to modify the structural and phys-
ical properties of chitosan-based films, J. Agric. Food Chem. 60 (2012) 492–499.
[28] M. Kurek, C.H. Brachais, C.M. Nguimjeu, A. Bonnotte, A. Voilley, K. Galić, J.P.
Couvercelle, F. Debeaufort, Structure and thermal properties of a chitosan coated
polyethylene bilayer film, Polym. Degrad. Stab. 97 (2012) 1232–1240.
[29] F.H. Abd El-Kader, S.A. Gafer, A.F. Basha, S.I. Bannan, M.A.F. Basha, Thermal and op-
tical properties of gelatin/poly(vinyl alcohol) blends, J. Appl. Polym. Sci. 118 (2010)
413–420.
245
[30] L.S. Guinesi, E.T.G. Cavalheiro, The use of DSC curves to determine the acetylation
degree of chitin/chitosan samples, Thermochim. Acta 444 (2006) 128–133.
[31] J. Bonilla, A.M.Q.B. Bittante, P.J.A. Sobral, Thermal analysis of gelatinchitosan edible
film mixed with plant ethanolic extracts, J. Therm. Anal. Calorim. 130 (2017)
1221–1227.
[32] S.F. Hosseini, M. Rezaei, M. Zandi, F.F. Ghavi, Preparation and functional properties of
fish gelatin-chitosan blend edible films, Food Chem. 136 (2013) 1490–1495.
[33] D. Lourdin, H. Bizot, P. Colonna, “Antiplasticization” in starch-glycerol films, J. Appl.
Polym. Sci. 63 (1997) 1047–1053.
[34] Q.K. Meng, M.C. Heuzey, P.J. Carreau, Hierarchical structure and physicochemical
properties of plasticized chitosan, Biomacromoles 15 (2014) 1216–1224.
[35] C.A. Murray, J.R. Dutcher, Effect of changes in relative humidity and temperature on
ultrathin chitosan films, Biomacromoles 7 (2006) 3460–3465.