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Facile preparation and characterization of super tough chitosan/poly(vinyl al-

cohol) hydrogel with low temperature resistance and anti-swelling property

Xiaotong Xiang, Guoqi Chen, Kai Chen, Xiancai Jiang, Linxi Hou

PII: S0141-8130(19)35205-5
DOI: https://doi.org/10.1016/j.ijbiomac.2019.09.132
Reference: BIOMAC 13377

To appear in: International Journal of Biological Macromole-

cules

Received Date: 7 July 2019

Revised Date: 14 September 2019
Accepted Date: 29 September 2019

Please cite this article as: X. Xiang, G. Chen, K. Chen, X. Jiang, L. Hou, Facile preparation and characterization
of super tough chitosan/poly(vinyl alcohol) hydrogel with low temperature resistance and anti-swelling property,
International Journal of Biological Macromolecules (2019), doi: https://doi.org/10.1016/j.ijbiomac.2019.09.132

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 Facile preparation and characterization of super tough

chitosan/poly(vinyl alcohol) hydrogel with low temperature

resistance and anti-swelling property

Xiaotong Xiang, Guoqi Chen, Kai Chen, Xiancai Jiang*, Linxi Hou*

College of Chemical Engineering, Fuzhou University, Fuzhou 350108, People’s Republic of China

Corresponding author: Xiancai Jiang & Linxi Hou; Phone: +8618850767279; Email:

jiangxc@fzu.edu.cn; lxhou@fzu.edu.cn

Abstract: Facile preparation of super tough hydrogels with low temperature tolerance and
anti-swelling property is still a challenging task for researchers. Meanwhile, the vast majority of

tough hydrogels were obtained though chemical crosslinking and complicated synthesis or

processing method accompanying a large number of harmful chemical reagents. Herein, the super

tough chitosan/poly(vinyl alcohol) (CS/PVA) hydrogels (the maximum compressive strength of

18.97 MPa at a strain of 80% and the maximum tensile strength of 4.02 MPa at a strain of 406.4%)

were successfully prepared via a simple post-treatment method. CS/PVA hydrogels were firstly

prepared by freezing-thawing process and then soaking in saturated sodium chloride aqueous

solution. The resultant hydrogels possess excellent swelling resistance and low temperature

tolerance. This work shows that the post-treatment of immersing in saline solution is a feasible

way to prepare super tough hydrogels with low temperature tolerance and anti-swelling property.

This also would enlarge the application areas of CS.

Keywords: Chitosan; Poly(vinyl alcohol); Toughness; Anti-swelling; Low temperature tolerance

1. Introduction
Hydrogel is composed of three-dimensional polymer network and a certain amount of water

inside the polymer network [1]. Due to its good biocompatibility and “soft and wet” nature,

hydrogels have attracted increasing attention for its multifarious applications in many areas such

as medical, pharmaceutical and tissue engineering areas [2]. However, the poor mechanical

property and the instability at high or low temperatures [3] of the hydrogel have limited the

applications of hydrogel in many areas. Composition and preparation method also have important

impacts on the properties of hydrogel, therefore many tactics have been developed for improving

the mechanical properties of hydrogel or directly synthesis of tough hydrogel, such as design of

1
double network (DN) structure [4], nanocomposites reinforcing [5, 6], topological entanglement [5,

7], and other strategies [6]. Despite the satisfaction of the mechanical performance requirements

of hydrogel, it has to acknowledge that the complex design procedures, processing methods, and a

large number of harmful reagents utilized in those strategies also would limit the industrialization

and generalization of hydrogel application. Saline immersion is one of the simplest methods in

preparation of tough hydrogel, which has been widely used in the field of hydrogel. Ionic effects,

also named as Hofmeister effects, were firstly induced by Hofmeister on the study of the

aggregation of egg white proteins with the addition of various salts in 1888 [8, 9]. The addition of

salt can not only affect the egg white proteins, but also the polymer system for a variety of aims,

such as the change of electron transfer [8], chemoresistive responses [10], the improvement of

properties of biocatalytic hydrogel [11] and mechanics enhancement [12, 13]. Homeister series, an

order of ions, is capable of changing the solubility of protein and polymer. The common order of

both anions and cations is respectively lined up as follow: SO42- > HPO42- > F- > Cl- > Br- >

NO3- > ClO4->SCN-, Ca2+ > K+ > Na+ > Li+ [8, 9, 11, 12, 14, 15]. The effect of anions is stronger

than that of the cations, the left side anions known as kosmotropes are able to decrease the

solubility of proteins while the right side anions named chaotropes are capable of promoting

dissolution of proteins. As a common and non-toxic chemical, NaCl has been proved to be able to

improve various properties of hydrogel [8, 13].

Both natural and synthetic polymers are common sources of hydrogel. Natural polymers are

featured by its regenerability, abundance and low cost, which have been widely used as

biomaterials. Besides the good mechanical property, the non-toxicity, degradability and good

shape designability are also essential for the hydrogel [16]. Thus the natural polymers based

hydrogel could show higher application value than synthetic polymers based hydrogels.

Nevertheless, the natural polymers still are not an ideal choice for fabricating tough hydrogels for

its high viscosity even at a low concentration. Recently many researchers have developed DN

hydrogel by integrating the physically crosslinked natural polymers such as alginate [17], agar

[18], konjac glucomannan [19], gellan gum [20], carrageenan [21] and chitosan (CS) [22] with the

synthetic poly(acrylic amide) and poly(acrylic acid) network. However, the introduction of the

synthetic, non-degradable and inflammatory PAA and PAM network would damage the

biodegradability and biocompatibility of the hydrogel and impair the application in many areas.

2
Thus the preparation of completely degradable and bio-compatible natural polymer based high

strength hydrogel is essential and meaningful.

CS is the N-deacetylated derivative of chitin which ranks second just next to cellulose in the

gross of biopolymer on the earth [23]. CS-based hydrogels have been widely studied and

researched owing to it’s nontoxicity, biocompatibility, hemocompatibility and biodegradability [16,

24]. However, the solubility of CS greatly limits its application in some respects [25]. Usually CS

can only be dissolved in acidic solution. CS is usually dissolved by acetic acid aqueous solution.

Many routes also have been developed to improve the solubility of CS or explore the new solvent

for CS.

Poly(vinyl alcohol) (PVA) is an important water soluble polymer with a great number of

hydroxy groups on its chains. Different from other synthetic polymers, PVA has nontoxicity, good

biodegradability and biocompatibility which make it extensively useful for the preparation of

hydrogel. Moreover, PVA hydrogel can be prepared by repeated freezing-thawing processes and

has good mechanical property. Thus the CS/PVA hydrogel has attracted more and more attention

due to its combinative advantages of both CS and PVA.

In our research group AlCl3·6H2O aqueous solution was used as the solvent for CS and the

high performance PVA/SA blend hydrogels were obtained after immersion post-treatment [22, 25].

For the simple chain structure of both CS and PVA in the CS/PVA hydrogel network, Hofmeister

effect can also be utilized to enhance its performance. However, the high performance CS/PVA

hydrogel was still not reported. In this paper, we focused on a new way for the preparation of ultra

high tough CS/PVA hydrogel and effects of soaking time on the hydrogel properties. The tensile

testing, swelling testing and anti-low temperature measurements were carried out. The

corresponding results showed that CS/PVA hydrogels treated with different treatment time possess

superior anti-low temperature property, anti-swelling property and stability. It is believed that this

novel high performance CS/PVA hydrogel may have potential applications in a wide range of

fields.

2. Experimental and materials

2.1. Materials
CS (degree of deacetylation≥95%, the viscosity of 100-200 mPa·s) was purchased from

Aladdin Chemical Reagent (China). AlCl3·6H2O and NaCl were provided by Zhiyuan Chemical

3
Co. (Tianjin, China). PVA (1799, MW: 75,000 g/mol, >99% hydrolysis) was supplied by Sichuan

Vinylon Factory. All the reagents were used as received.

2.2. Hydrogel preparation

CS/PVA hydrogels were synthesized firstly by the freezing-thawing method and subsequently

soaking in saturated NaCl aqueous solution. Firstly, 2.0 g PVA was dissolved in 12 ml distilled

water under intense stirring at 90 oC, after that 0.2 g AlCl3·6H2O and 0.4 g CS were added into

PVA solution. Then the solution was continued to stir for 1 h at 90 oC and the homogeneous

CS/PVA complex solution was obtained. After eliminating the bubble, the resulting CS/PVA

complex solution was frozen at -20 oC for 3 h and thawed at room temperature. The as-prepared

hydrogel was thereafter immersed into saturated sodium chloride solution with various soaking

time which was set as 3, 6, 12, 24 h, respectively. Finally, the hydrogels with high performance

were obtained and named as CS/PVA-X (X represents immersion time in the unit of hour). The

as-prepared hydrogel without the soaking process was taken as the contrast sample and referred as

CS/PVA.

2.3. Hydrogel characterization

2.3.1. Water content
The hydrogel samples were put into an oven at a temperature of 80 °C for 48 h, and then the

dry sample was weighed. Water retention (WR) of the hydrogels was defined as follows:

WR(%)=((Wi-Wd)/Wi)*100

where Wd was the weight of dried hydrogel and Wi was the weight of the initial hydrogel.

2.3.2. Density
Method of drainage was used to measure the density of hydrogel with different soaking time.

The weighed hydrogel was put in definite volumetric deionized water, and the fore-and-aft

volumetric difference was the volume of corresponding hydrogel, the density was determined by

the following equation:

Density =Wi/Vd

where Vd is the volumetric difference before and after the gel is placed in deionized water, Wi is

the weight of hydrogel before the gel is placed in deionized water.

2.3.3. Tensile testing

The uniaxial tensile testing was implemented on tensile tester (MTS CMT4104) at a

4
crosshead speed of 100 mm/min by using dumbbell-liked gel specimens of 4 mm width, 75 mm

length and 2 mm thickness. The Young’s modulus was calculated from the initial linear part of

stress-strain curve. The fracture energy of the hydrogels is the work needed until fracture and was

calculated from the integration of the stress-strain curve. The tensile testing was performed at

room temperature and relative humidity of 54%.

2.3.4. Compress testing

The cylinder-shaped gel samples (diameter=20 mm and height=20 mm) were put on disc

platform to implement uniaxial compression test with a maximum strain of 80% at a crosshead

speed of 5 mm/min. The compression testing was carried out at room temperature with 54 %

relative humidity.

2.3.5. X-ray diffraction (XRD)

XRD patterns for series CS/PVA samples were obtained on a diffractometer (DY5261/Xpert3,

CEM, America) with Cu Kα radiation (1.542 nm) at 40 kV and 40 mA in the 2 theta range of 5-65
o at room temperature.

2.3.6. Dynamic mechanic analysis (DMA)

DMA was conducted on DMA1 (METTLER TOLEDO, Switzerland) in the tension mode at

the temperature rate of 3 oC/min and 1 Hz frequency. The rectangle specimens of 4 mm width, 2

mm thickness and 25 mm length were carried out in a wide temperature range from -30 to 80 °C

under a sinusoidal force.

2.3.7. Low temperature resistance

For the purpose of inquiring the low temperature resistance, the series CS/PVA hydrogels

were placed at a -23 °C freezer for 24 h, and then tensile testing for CS/PVA hydrogels were

immediately carried out.

2.3.8. Swelling properties

Swelling measurement was carried out to explore the swelling properties of hydrogels. The

weighed columnar samples were placed in excess amount deionized water at room temperature for

a certain time until the mass balance is reached. The immersing specimens were taken out for

weigh again with draining the surface water at a fixed interval. The swelling ratio (SR) [27] can be

estimated using the following equation:

SR(%)=((Wt-Wi)/Wi) * 100

5
where Wi is the initial weight of hydrogels, and Wt is the wet weight of hydrogels at different

intervals during the immersing process.

2.3.9 Statistical analysis

Results are expressed as means and standard deviations of at least duplicate measurements.

Treatment means were tested separately for least significant difference (LSD) with SPSS 18.0

statistical software. The significance level was set at p < 0.05.

3. Results and discussion

3.1. Hydrogel preparation
The preparation process of high toughness CS/PVA hydrogel was presented in Fig. 1. There

are no other harmful reagents except for deionized water as solvent, AlCl3·6H2O as co-solvent, CS

and PVA as solutes in the whole system. Freezing-thawing approach, as a green method, was used

to prepare as-hydrogel coupled with just a certain time of saturated sodium chloride solution

immersing post treatment, and then high toughness CS/PVA hydrogel was obtained. Through

freezing at -20 oC for 3 h and thawing at room temperature, the pale yellow and weak CS/PVA

hydrogel without any chemical crosslinking agent was formed. This strategy makes use of

crystallization of PVA chains after freezing-thawing treatment [28], the entanglement and the

inter/intra-hydrogen bonds between CS and PVA chains. Due to the poor mechanical properties,

the pristine CS/PVA hydrogel is not strong enough to apply in various fields, hence one step of

ionic post-treatment was conducted to improve the properties of CS/PVA hydrogel. After

immersing in the saturated sodium chloride solution for a certain time, the macroscopic reflection

is the shrinkage and more opaque appearance of hydrogel sample as shown in Fig. 1(a).

The high performance of series CS/PVA hydrogel was also demonstrated in Fig. 1(b).

CS/PVA, CS/PVA-3, CS/PVA-6, CS/PVA-12 and CS/PVA-24 were lined up in turn from left to

right. For better observation, all of the hydrogels were colored by methyl orange. Hanging with a

200 g weight, the 1 mm thick hydrogels were elongated to different extent. It is clear to see that

the pristine CS/PVA hydrogel was elongated almost to 19 cm. After the immersing process, the

elongated length of the CS/PVA hydrogels largely decreased. This proves that CS/PVA hydrogel

has a higher tensile strength after soaking into the saturated sodium chloride solution.

6
Fig. 1. Schematic illustration of the preparation process of high performance CS/PVA hydrogel (a);

the photographs of the series CS/PVA hydrogels under the pulling at the bottom by a 200 g weight

(b).

3.2. XRD
The mechanical properties of hydrogel would be affected by it’s crystallinity. In order to

figure out the mechanism for the improved mechanical properties and more clearly understand the

crystalline change of the hydrogel during the soaking process, the X-ray diffraction measurement

for the CS/PVA hydrogels was conducted and the XRD patterns were recorded in Fig. 2. Except

for a broad and strong peak at 2θ=27o, the XRD pattern of CS/PVA hydrogel also reveals weak

crystalline reflections at the peak of 2θ=19.5o and 40.8o related to the crystalline peaks of PVA,

which indicates the semi-crystalline state of CS/PVA hydrogel [28-31] and. After immersing in

saturated sodium chloride solution, the intensity of the diffraction peaks at 2θ=19.5o and 40.8o on

XRD patterns increased, suggesting that the immersing process not only lead to the reinforced

inter and intra-molecular interactions and entanglement between CS and PVA chains, but also the

7
enhanced crystallinity. This result manifests that saline solution could be able to induce crystallize

and entanglement of CS and PVA chains. Meanwhile, the strong hump at 2θ=27o almost

disappeared on the XRD curves of CS/PVA-3, CS/PVA-6, CS/PVA-12 and CS/PVA-24 hydrogels.

This could be attributed to more uniform and denser entanglement of CS and PVA [32]. In general,

the immersing post treatment in the sodium chloride aqueous solution could induce the tight and

homogeneous entanglement of CS and PVA chains in addition to the increased crystallinity, which

is conducive to the enhancement of mechanical properties of hydrogel.

Fig. 2. X-ray diffraction patterns of CS/PVA, CS/PVA-3, CS/PVA-6, CS/PVA-12 and CS/PVA-24

hydrogels.

3.3. Tensile testing

Tensile testing was conducted on dumbbell-liked series CS/PVA hydrogel to quantitatively

characterize its mechanical properties. The corresponding typical tensile stress–strain curves of

series CS/PVA hydrogel samples were presented in Fig. 3(a). The pristine CS/PVA specimen was

soft and weak with the tensile strength of 0.24 MPa and elongation at break of 262.8%,

respectively. However, after immersion post-treatment the CS/PVA hydrogels had much better

tensile properties. Both the tensile strength and elongation at break of the CS/PVA hydrogel

increased extensively after the soaking process. It is clear to see that CS/PVA-X hydrogels became

strong and tough. When soaking time grew up to 24 h, the tensile fracture stress of CS/PVA-24

would reach to 4.02 MPa and the tensile fracture strain reached up to 406.4%. Meanwhile,

Young’s modulus and work of extension of CS/PVA hydrogel also increased with the expanding

soaking time, which was high up to 2.07 MPa and 9.31 MJ m-3 for CS/PVA-24, respectively. The

8
water content declined from 82 % to 53 % after saline ions post treatment but the density went the

other way which increased from 1.08 g/cm3 to 1.18 g/cm3 as shown in Table 1. The tensile testing

results indicate that sodium chloride aqueous solution contributes to the improvement of

mechanical properties such as the higher energy dissipation, enhanced strength, strain, work of

extension at break and Young’s modulus. The previous research work showed that pure PVA

hydrogel showed the strength of 1.61 MPa after soaking in saturated NaCl solution [33]. It proved

that the rigid CS chain would contribute to the high strength of CS/PVA hydrogel.

Cylinder shaped CS/PVA hydrogels were tested for uniaxial compression, as depicted in Fig.

3(b). With the increased immersion time, the larger compression stress was shown at the same

compression strain. When the compression testing was carried out at the strain of 80%, the

maximum compression stress was observed to be 18.97 MPa for CS/PVA-24 while the minimum

compression stress was 1.9 MPa for CS/PVA. The compression test results are coincident with

tensile testing results. This further proved that NaCl aqueous solution post treatment resulted in

the promotion of mechanical properties of hydrogels.

Fig. 3. The typical tensile testing stress–strain curves for series CS/PVA hydrogels (a); Uniaxial

compression curves for series CS/PVA hydrogels (b).

Table 1

The parameters of density, water content, and mechanical properties of CS/PVA hydrogel.

Water Tensile strength Elongation at Young’s modulus Work of extension

Sample Density (g/cm3)
content (%) (MPa) break (%) (MPa) (MJ m-3)

CS/PVA 1.08 (±0.04e) 82 (±0.11a) 0.24 (±0.06b) 262.8 (±19.10c) 0.07 (±0.01c) 0.29 (±0.08c)

9
CS/PVA-3 1.14 (±0.07d) 64 (±1.17a) 2.71 (±0.02b) 332.6 (±17.80c) 1.39 (±0.01c) 5.62 (±0.30c)

CS/PVA-6 1.15 (±0.04c) 59 (±1.28a) 3.48 (±0.06b) 420.6 (±19.44b) 1.69 (±0.10c) 8.28 (±0.25c)

CS/PVA-12 1.17 (±0.02b) 53 (±0.33a) 3.68 (±0.04a) 427.9 (±23.17a) 1.77 (±0.15b) 8.63 (±0.25b)

CS/PVA-24 1.18 (±0.02a) 53 (±1.66a) 4.02 (±0.15a) 406.4 (±9.58c) 2.07 (±0.07a) 9.31 (±0.43a)

1. CS/PVA-X: CS/PVA =CS and PVA blend hydrogel, X=different salt soaking time.

2. All data are averages of triplicate measurements with standard deviation. Means in a column with

different letters are significantly different (p < 0.05) by the least significant difference (LSD) test.

3.4. DMA
The dynamic mechanical analysis was utilized to further determine the mechanic property of

hydrogels. The curves of storage modulus (E’) and loss modulus (E’’) versus temperature were

presented in Fig. 4(a) and Fig. 4(b). Fig. 4(a) showed that the CS/PVA hydrogel presented a lower

E’ than CS/PVA-3 hydrogel at the temperature above 8 oC. The E’ of CS/PVA hydrogels increased

with the immersing time. CS/PVA has the minimum E’ and CS/PVA-24 has a maximum E’. This is

in accordance with the tensile testing results at room temperature. However, when the temperature

deceased to below 8 oC, the E’ of CS/PVA hydrogel remarkably increased. This was mainly

because of a large amount of water contained in the CS/PVA hydrogel. At the temperature below 8
oC
the frozen free water would lead to increase of the stiffness of CS/PVA hydrogel. This indicated

that CS/PVA hydrogel had a low tolerance for cold environment [34, 35]. After the immersing

process, NaCl would integrate into the CS/PVA hydrogel network and decrease the freezing point

of the free water molecules. This indicated that the immersing process made the CS/PVA hydrogel

flexible in cold environment.

Fig. 4. The DMA curves of series CS/PVA hydrogel: (a) The storage modulus (E′) and (b) loss

modulus (E″) versus temperature.

10
3.5. Low temperature resistance
Except the excellent mechanical properties, the series CS/PVA-X hydrogels also have the low

temperature resistance as shown in DMA studies. The CS/PVA and CS/PVA-3 hydrogels were

firstly subjected to freezing at the temperature of -23 oC for 24 h. It could be seen that after the

freezing process the appearance of flavescent CS/PVA-3 hydrogel did not change, while the

CS/PVA hydrogel frozen and became white. CS/PVA-3 still maintained good flexibility while

CS/PVA became stiff and fragile. By twisting and folding, CS/PVA-3 remained intact, however,

CS/PVA broke into two pieces as shown in Fig. 5(a-b). The tensile testing measurements were

performed to further study the mechanical properties of series CS/PVA hydrogels at -23 oC and

room temperature. The detailed mechanical property data of various CS/PVA hydrogels were

recorded in Table 2 and the typical tensile stress-strain curves were shown in Fig. 5(c-g). Basically

CS/PVA-3, CS/PVA-6, CS/PVA-12 and CS/PVA-24 hydrogels would show a similar mechanical

property at -23 oC to that of room temperature, but the tensile strength slightly increased and the

elongation at break slightly decreased. Take CS/PVA-24 hydrogel for example, the tensile strength

reached up to 5.2 MPa and the elongation at break slightly decreased to 402% after 24 h storage at

a freezer, compared with 4.2 MPa and 406.4% at room temperature. The tensile testing result

suggests that the saturated sodium chloride solution post treatment would impart the CS/PVA

hydrogel the low temperature resistance. This can be attributed to the tighter chains entanglement,

increased PVA crystallinity and increased ion-water hydrogen bond in the chain network.

11
Fig. 5. Illustration of the twisting and bending behaviors of CS/PVA-3 (a) and CS/PVA (b) after

storing in a freezer at -23 oC for 24 h; The typical tensile testing curves at 25 and -23 oC for (c)

CS/PVA; (d) CS/PVA-3; (e) CS/PVA-6; (f) CS/PVA-12; (g) CS/PVA-24.

Table 2

The parameters of mechanical properties of CS/PVA hydrogel after 24 h freezing.

Tensile strength Elongation at break Young’s Work of extension

Sample
(MPa) (%) modulus (MPa) (MJ m-3)

CS/PVA 0.18 (±0.02d) 175.4 (±78.60d) 0.16 (±0.03d) 0.15 (±0.05c)

CS/PVA-3 3.58 (±0.28d) 386.9 (±56.18b) 1.60 (±0.15d) 7.20 (±1.44c)

12
 CS/PVA-6 3.99 (±0.19c) 384.3 (±35.62c) 2.20 (±0.07c) 8.46 (±0.45b)

CS/PVA-12 4.44 (±0.16b) 382.0 (±11.70d) 2.21 (±0.09b) 9.50 (±0.53a)

CS/PVA-24 4.75 (±0.36a) 411.9 (±13.00a) 2.48 (±0.29a) 10.96 (±0.80a)

All data are averages of triplicate measurements with standard deviation. Means in a column with

different letters are significantly different (p < 0.05) by the least significant difference (LSD) test.

3.6. Swelling behavior

In order to understand more clearly the effect of saturated sodium chloride solution post

treatment on the hydrogel properties, the swelling behavior of hydrogels was investigated. The

CS/PVA hydrogels were placed in deionized water for swelling at room temperature and the

corresponding swelling curves were recorded in Fig. 6. The pristine CS/PVA hydrogel expanded

quickly at the first 24 h and then gradually reached the swelling equilibrium. The equilibrium

swelling ratio of CS/PVA hydrogel was 175%. After the soaking process, the swelling ratio of

CS/PVA hydrogels distinctly decreased, indicating a good anti-swelling property. With the

increasing of soaking time, the equilibrium swelling ratio of CS/PVA hydrogels decreased. The

swelling ratio of CS/PVA-3 was about 54 % and the minimum swell ratio was 45% possessed by

CS/PVA-24. The significant enhanced swelling resistance is ascribed to the tight entanglement and

increased crystallinity induced by saturated sodium chloride solution and reduced passage for

water molecules [36]. All these results demonstrated excellent swelling resistance of soaking

hydrogels.

The corresponding tensile test after swelling in deionized water for 72 h was conducted to

further investigate the swell behavior. As it shown in Fig. 6(c), the tensile strength for both

CS/PVA and CS/PVA-12 declined dramatically compared with the slight change of the elongation

at break before and after swelling in deionized water for 72 h. For CS/PVA, the tensile strength

decreased from 0.24 MPa to 0.07 MPa, meanwhile the tensile strength of CS/PVA-12 decreased

from 3.68 MPa to 0.50 MPa. Water molecules permeate into the hydrogel network resulting to the

unwinding and arrangement of CS and PVA chains, which account for the decrease of mechanical

properties of CS/PVA and CS/PVA-12. Although enormous decrement of tensile strength of both

CS/PVA and CS/PVA-12 after swelling in deionized water, the tensile strength of CS/PVA-12 is

still 6 times larger than that of CS/PVA. This further illustrates that ion post treatment is able to

13
enhance the anti-swelling property of hydrogel.

14
Fig. 6. The swelling curves of series CS/PVA hydrogels at room temperature (a); The digital photo

of CS/PVA and CS/PVA-12 before and after swelling (b); The typical tensile stress–strain curves

for CS/PVA and CS/PVA-12 hydrogel after swelling in deionized water for 72 h (c).

3. Conclusion
To sum up, a simple and generalizable method for preparing high toughness hydrogel with

low temperature tolerance and anti-swelling property, via post treatment of immersing in saturated

sodium chloride aqueous solution, was developed and the high toughness CS/PVA hydrogels were

obtained in this work. The experimental results proved that the CS/PVA hydrogel became much

more stiff and tough after the immersing process. The high toughness CS/PVA hydrogel with the

tensile strength of 3.68 (±0.04) MPa, elongation at break of 427.9 (±23.17)% and fracture energy

of 8.63 (±0.25) MJ m-3 could be obtained. Moreover, the immersing process would endow the low

temperature tolerance and anti-swelling properties to CS/PVA hydrogel. After immersing process,

CS/PVA hydrogel could still maintain excellent flexibility at the low temperature of -23 oC. The

CS/PVA hydrogel showed high anti-swelling properties in the aqueous solution after the

immersing treatment. This paper provided a facile route for the preparation of high-performance

CS/PVA hydrogel, which would have a large potential application in the area of tissue engineering,

drug delivery, and hydrogel electrolyte for supercapacitor. This paper provided a new utilization

route for CS.

15
Acknowledgements
This work was financially supported by the Opening Project of State Key Laboratory of

Polymer Materials Engineering (Grant No. sklpme 2019-4-25) and Natural Science Foundation of

Fujian Province (No. 2017J05023).

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 The super tough hydrogel with low temperature resistance and anti-swelling property was

prepared from CS and PVA.

 The CS/PVA hydrogels were prepared by freezing/thawing process and subsequently

immersing in saturated NaCl aqueous solution.

 The tensile strength and elongation at break of CS/PVA could reach to 4.02 MPa and 406.4%,

respectively.

20