聚丙烯酸-Al<sup>3+</sup>/壳聚糖复合双网络水凝胶的制备与性能

鲁程程; 于振坤; 杨园园; 张玉红

doi:10.13801/j.cnki.fhclxb.20211119.004

聚丙烯酸-Al³⁺/壳聚糖复合双网络水凝胶的制备与性能

doi: 10.13801/j.cnki.fhclxb.20211119.004

湖北大学　化学化工学院，有机化工新材料省部共建协同创新中心，功能材料绿色制备与应用教育部重点实验室，武汉 430062

基金项目: 湖北省高等学校优秀中青年创新团队项目：功能涂料研发(T201801)

详细信息

通讯作者:
张玉红，博士，教授，硕士生导师，研究方向为功能高分子　E-mail：zhangyuhong@hubu.edu.cn

中图分类号: O631
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- 被引次数: 0
出版历程
- 收稿日期: 2021-09-26
- 修回日期: 2021-11-01
- 录用日期: 2021-11-10
- 网络出版日期: 2021-11-22
- 刊出日期: 2022-12-01

Preparation and performances of polyacrylic acid-Al³⁺/chitosan composite double network hydrogel

Collaborative Innovation Center for Advanced Organic Chemical Materials Co-constructed by the Province and Ministry, Key Laboratory for the Green Preparation and Application of Functional Materials, College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, China

摘要

摘要: 水凝胶材料具有独特的仿生结构、性能及生物相容性，在可穿戴应变传感器中的应用越来越广泛。然而，制备出具有良好的力学性能和高电导率的水凝胶传感器仍然是一项很大的挑战。本文通过简单的两步法，制备了完全物理交联的、高强度和敏感性的聚丙烯酸-Al³⁺/壳聚糖复合双网络水凝胶传感器。首先将壳聚糖(CS)、聚丙烯酸(PAA)和离子交联剂Al³⁺在水中物理混合为预凝胶，然后用预凝胶进行无机盐溶液浸泡而制备出所提出的水凝胶传感器。所得的离子水凝胶传感器显示出优异的力学性能(抗拉强度高达765.4 kPa，断裂伸长率至1025%，韧性为4.13 MJ/m³)。同时，基于该水凝胶应变传感器表现出较出色的拉伸灵敏度(灵敏因子约为1.54)，使其能够重复稳定地检测人体大应变和微小应变。因此，通过金属盐的作用引入物理交联网络可以提高水凝胶的性能，为多功能材料的设计及在电子皮肤、可穿戴设备和生物传感器上的应用提供了新的视角。
- 双网络水凝胶 /
- 可穿戴应变传感器 /
- 壳聚糖 /
- 力学性能 /
- 传感性能
Abstract: Hydrogel materials are widely used in wearable strain sensors due to they have unique biomimetic structure, performances and biocompatibility. However, it is still a big challenge to prepare a hydrogel sensor with good mechanical properties and high conductivity. In this paper, a fully physically crosslinked, high-strength and sensitive polyacrylic acid-Al³⁺/chitosan composite double network hydrogel sensor was prepared by a simple two-step method. Firstly, chitosan (CS), polyacrylic acid (PAA) and ionic crosslinker Al³⁺ were physically mixed in water to form a pre-gel, and then the pre-gel was immersed in NaCl solution to prepare the target hydrogel sensor. The obtained ionized hydrogel sensor shows excellent mechanical properties (tensile strength as high as 765.4 kPa, elongation at break to 1025%, and toughness of 4.13 MJ/m³). At the same time, the strain sensor based on the hydrogel exhibits excellent tensile sensitivity (sensitivity factor is about 1.54). The hydrogel sensor can repeatedly and stably detect large and small strains of human body. Therefore, the introduction of physical cross-linking network through the action of metal salts can improve the performances of hydrogels, which providing a new perspective for the design of multifunctional materials and their applications in electronic skins, wearable devices, and biosensors.
- double network hydrogel /
- wearable strain sensor /
- chitosan /
- mechanical properties /
- sensing property

HTML全文

图 1 聚丙烯酸-Al³⁺/壳聚糖单网络(PAA-Al³⁺/CS SN)和聚丙烯酸-Al³⁺/壳聚糖复合双网络(PAA-Al³⁺/CS DN)水凝胶制备过程示意图

Figure 1. Schematic illustration of the preparation process for the polyacrylic acid-Al³⁺/chitosan composite single network hydrogel (PAA-Al³⁺/CS SN) and polyacrylic acid-Al³⁺/chitosan composite double network hydrogel (PAA-Al³⁺/CS DN) hydrogel

AA—Acrylic acid

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图 2 (a) PAA-Al³⁺/CS SN和PAA-Al³⁺/CS DN水凝胶的典型拉伸应力-应变曲线；(b) PAA-Al³⁺/CS SN和PAA-Al³⁺/CS DN水凝胶的韧性和应力值

Figure 2. (a) Typically tensile curves of PAA-Al³⁺/CS SN and PAA-Al³⁺/CS DN; (b) Corresponding toughness and stress of the PAA-Al³⁺/CS SN and PAA-Al³⁺/CS DN hydrogels

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图 3 PAA-Al³⁺/CS SN和PAA-Al³⁺/CS DN水凝胶的储能模量(G')和损耗模量(G'')与剪切应变(γ) (a) 和角频率 (b) 的关系

Figure 3. Storage modulus (G') and loss modulus (G'') versus shear strain (γ) (a) and angular frequency (b) for the PAA-Al³⁺/CS SN and PAA-Al³⁺/CS DN hydrogels

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图 4 PAA-Al³⁺/CS SN水凝胶 (a) 和PAA-Al³⁺/CS DN水凝胶 (b) 的SEM图像

Figure 4. SEM images of PAA-Al³⁺/CS SN hydrogel (a) and PAA-Al³⁺/CS DN hydrogel (b)

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图 5 不同AlCl₃浓度的PAA-Al³⁺/CS DN水凝胶的特征性应力-应变拉伸曲线 (a) 和相应应力和韧性数值 (b)

Figure 5. Typically tensile curves (a) and corresponding stress and toughness (b) of the PAA-Al³⁺/CS DN hydrogels with different AlCl₃ concentrations

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图 6 (a) 不同浸泡时间下得到的PAA-Al³⁺/CS DN水凝胶的应力-应变曲线；(b) 水凝胶相应的应力和韧性数值

Figure 6. Typically tensile curves (a) and corresponding stress and toughness (b) of the PAA-Al³⁺/CS DN hydrogels with different soaking time

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图 7 (a) PAA-Al³⁺/CS DN水凝胶在不同静置时间下的自恢复性能；(b) 拉伸应力和耗散能随时间延长的恢复率；(c) 连续10次的循环拉伸和松弛曲线；(d) 每次循环中相应的耗散能

Figure 7. (a) Self-recovery properties of the PAA-Al³⁺/CS DN hydrogels in different resting times; (b) Time-dependent recovery efficiency of tensile stress and hysteresis energy; (c) 10 continuous tension and relaxation cycles of the PAA-Al³⁺/CS DN hydrogels; (d) Corresponding dissipated energy in every cycle

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图 8 PAA-Al³⁺/CS DN水凝胶传感器的机电性能：(a) 相对电阻变化(ΔR/R₀)与应变的关系图；(b) PAA-Al³⁺/CS DN水凝胶传感器对重复的大应变(200％、300％)的实时响应信号；(c) PAA-Al³⁺/CS DN水凝胶传感器对微小应变(1％、2％、3％、4％和 5％)的实时响应信号；(d) 微小应变下的灵敏因子(GF)

Figure 8. Electromechanical properties of PAA-Al³⁺/CS DN hydrogel sensors: (a) Plot of the relative resistance variation (ΔR/R₀) versus strain; (b) and (c) Real-time response signals of the synthesized hydrogel sensors to repeated large strains (400%, 500%) and subtle strains (1%, 2%, 3%, 4% and 5%), respectively; (d) Gauge factor (GF) of subtle strains

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图 9 (a) PAA-Al³⁺/CS DN水凝胶传感器在不同速率下被循环拉伸至 100％时的ΔR/R₀(%)曲线图；(b) 100％恒定应变下对于200次循环拉伸和释放的响应信号

Figure 9. (a) ΔR/R₀ (%) of the PAA-Al³⁺/CS DN hydrogel sensors when stretched to 100% at different rate; (b) Response of the synthesized PAA-Al³⁺/CS DN hydrogel sensors to repeated stretching and releasing of 100% strain for 200 cycles

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图 10 PAA-Al³⁺/CS DN水凝胶传感器贴附于人体不同关节的实时相对电阻变化：(a) 指关节；(c) 腕关节；(d) 肘关节；(e) 膝关节

Figure 10. Real-time relative resistance variations of the PAA-Al³⁺/CS DN hydrogel sensors attachedon the different body joints: (a) Finger joint; (b) Wrist joint; (c) Elbow joint; (d) Knee joint

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