Facile preparation of low swelling, high strength, self-healing and pH-responsive hydrogels based on the triple-network structure

doi:10.1007/s11706-019-0450-7

Front. Mater. Sci.

2019, Vol. 13

Issue (1) : 54-63 https://doi.org/10.1007/s11706-019-0450-7

RESEARCH ARTICLE

Facile preparation of low swelling, high strength, self-healing and pH-responsive hydrogels based on the triple-network structure

Zhicun WANG¹, Xiaoman HAN¹, Yixi WANG¹, Kenan MEN², Lin CUI³(

), Jianning WU¹, Guihua MENG¹, Zhiyong LIU¹(

), Xuhong GUO^1,⁴

¹. School of Chemistry and Chemical Engineering, Shihezi University/Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan/Key Laboratory of Materials-Oriented Chemical Engineering of Xinjiang Uygur Autonomous Region/Engineering Research Center of Materials-Oriented Chemical Engineering of Xinjiang Bingtuan, Shihezi 832003, China
². Bingtuan Sishi Hospital, Yili 835000, China
³. School of Medicine, Shihezi University, Shihezi 832003, China
⁴. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

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Abstract

A polyacrylic acid (PAA)/gelatin (Gela)/polyvinyl alcohol (PVA) hydrogel was prepared by copolymerization, cooling, and freezing/thawing methods. This triple-network (TN) structure hydrogel displayed superior mechanical properties, low swelling ratio and self-healing properties. The superior mechanical properties are attributed to the triple helix association of Gela and PVA crystallites by reversible hydrogen bonding. The characterization results indicated that the fracture stress and the strain were 808 kPa and 370% respectively, while the compression strength could reach 4443 kPa and the compressive modulus was up to 39 MPa under the deformation of 90%. The hydrogen bonding in PVA contributed to maintain and improve the self-healing ability of hydrogels. Every type of hydrogels exhibited a higher swelling ratio under alkaline conditions, and the swelling ratios of PAA, PAA/PVA and PAA/Gela hydrogels were 27.71, 12.30 and 9.09, respectively. The PAA/Gela/PVA TN hydrogel showed the lowest swelling ratio (6.57) among these hydrogels. These results indicate that the novel TN hydrogels possess good environmental adaptability and have potential applications in the biomedical engineering and sensor field.

Keywords hydrogel triple-network structure mechanical property swelling self-healing

Corresponding Author(s): Lin CUI,Zhiyong LIU

Online First Date: 29 January 2019 Issue Date: 07 March 2019

Cite this article:

Zhicun WANG,Xiaoman HAN,Yixi WANG, et al. Facile preparation of low swelling, high strength, self-healing and pH-responsive hydrogels based on the triple-network structure[J]. Front. Mater. Sci., 2019, 13(1): 54-63.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-019-0450-7
https://academic.hep.com.cn/foms/EN/Y2019/V13/I1/54

Fig.1 Schematic drawing for the synthesis of TN hydrogels.

Tab.1 Hydrogels with various compositions and network structures

Fig.2 FTIR analysis results of Gela, PVA and PAA/Gela/PVA samples.

Fig.3 SEM images: the PAA hydrogel with (a) 200-fold magnification and (b) 400-fold magnification; the PAA/Gela/PVA hydrogel with (c) 500-fold magnification and (d) 2000-fold magnification.

Fig.4 Swelling behaviors of (a) the PAA/Gela/PVA hydrogel and (b) various hydrogels in solutions with different pH values.

Fig.5 Photographs of various hydrogels before swelling (upper) and after swelling (lower): (a) PAA/Gela/PVA hydrogel; (b) PAA/PVA hydrogel; (c) PAA/Gela hydrogel; (d) PAA hydrogel.

Fig.6 (a) Stress–strain curves of stretching of various hydrogels. (b) Stress–strain curves of the compression of various hydrogels. (c) Compression elasticity modulus of various hydrogels. (d) The recovering efficiency of various hydrogel in different compression times.

Tab.2 Summary of mechanical properties of various samples

Fig.7 Schematic drawing for toughening and stiffening mechanisms of PAA/Gela/PVA TN hydrogels.

Fig.8 Photographs showing the macroscopic self-healing behavior: (a) the PAA/Gela/PVA TN hydrogel was cut in the middle and one half was stained with Rhodamine B; (b)(c) the two halves self-healed over a period of 24 h.

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