Wrinkled structure conductive hydrogels of chitosan-Fe3+-Polyacrylic acid for sensors
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摘要: 壳聚糖基导电水凝胶兼具抗菌和导电等多功能，在电子皮肤、生物电子器件等领域具有广阔的应用前景。在实际应用中，要求导电水凝胶具有优异的力学性能和传感灵敏度。本工作将三氯化铁水溶液滴加到壳聚糖丙烯酸水溶液中，接着将丙烯酸原位聚合成聚丙烯酸，利用壳聚糖铁离子微凝胶和聚丙烯酸的溶胀行为的差异性，构建了褶皱结构的壳聚糖-铁离子-聚丙烯酸导电水凝胶(CS-Fe3+-PAA)。得益于壳聚糖铁离子微凝胶的能量耗散作用及其带来的褶皱结构，CS-Fe3+-PAA具有优异的力学性能和高灵敏度。在800%~
1000 %的大应变范围内，CS-Fe3+-PAA的灵敏因子(GF)值高达25.32，其韧性为2.54 MJ·m−3，断裂应变为1100 %，断裂应力为0.6 MPa。CS-Fe3+-PAA应变传感器被成功用于检测人体多种活动，如手指、手肘和膝盖等关节弯曲活动，以及说话和吞咽等细微活动。独特的褶皱结构为高韧性和高灵敏度的壳聚糖基导电水凝胶提供设计思路和方法。Abstract: Chitosan-based conductive hydrogels have been applied in the fields of electronic skin and biomedical devices due to their antibacterial and conductivity properties. It is demanded that conductive hydrogels process excellent mechanical properties and sensing sensitivity in practical applications. In this work, ferric chloride aqueous solution was dripped into a solution of chitosan and acrylic acid, after which the acrylic acid was in situ polymerized to synthesis the chitosan-Fe3+-polyacrylic acid hydrogels (CS-Fe3+-PAA). The differential swelling behavior between chitosan ferric ion microgels and polyacrylic acid was used to construct a wrinkled structure of CS-Fe3+-PAA. The energy dissipation effect of chitosan ferric ion microgels and the resulting wrinkled structure enabled CS-Fe3+-PAA to exhibited excellent mechanical properties and high sensitivity. In the large strain range of 800%~1000 %, the sensitivity factor (GF) of CS-Fe3+-PAA reached a value of 25.32. The toughness of hydrogels was 2.54 MJ·m−3, with elongation at break of1100 % and tensile strength of 0.6 MPa. The CS-Fe3+-PAA strain sensor has been successfully used to detect various human activities, including bending movements of joints such as fingers, elbows, and knees, as well as subtle actions such as speaking and swallowing. The unique wrinkled structure provides design ideas and methods for chitosan-based conductive hydrogels with high toughness and sensitivity.-
Key words:
- Chitosan /
- Fe3+ /
- Conductive hydrogels /
- Wrinkled structure /
- Sensing performance
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图 1 壳聚糖-铁离子-聚丙烯酸水凝胶(CS-Fe3+-PAA)的合成示意图
Figure 1. Schematic illustration of the synthesis of chitosan- Fe3+-Polyacrylic acid hydrogels(CS-Fe3+-PAA)
图 2 (a) CS、Fe3+-PAA和CS-Fe3+-PAA的FTIR图谱；(b) CS-Fe3+-PAA的XPS图谱和(c) N 1s图谱
Figure 2. (a) FTIR spectra of chitosan, Fe3+-PAA and CS-Fe3+-PAA; (b) XPS spectra of CS-Fe3+-PAA and (c) N 1s
图 3 样品的SEM图像：(a)膜表面；(b) CS-Fe3+-PAA表面；(c) CS-Fe3+-PAA截面
Figure 3. SEM images of the sample: (a) membrane surface; (b) CS-Fe3+-AA surface; (c) CS-Fe3+-AA section
图 4 不同CS含量的CS-Fe3+-PAA的(a)拉伸应力-应变曲线和(b)相应的弹性模量和韧性；不同FeCl3浓度的CS-Fe3+-PAA的(c)拉伸应力-应变曲线和(d)相应的弹性模量和韧性；(e) CS-Fe3+-PAA悬挂砝码、扭转、打结和拉伸的照片
Figure 4. (a) Tensile stress-strain curves and (b) corresponding elastic modulus and toughness of CS-Fe3+-PAA with different content of CS; (c) Tensile stress-strain curves and (d) corresponding elastic modulus and toughness of CS-Fe3+-PAA with different concentrations of FeCl3; (e) Photographs of CS-Fe3+-PAA hanging weights, twisting, knotting and stretching
图 5 流变测试中CS-Fe3+-PAA的储能模量(G')和损耗模量(G″)：(a)频率；(b)应变
Figure 5. Storage modulus (G') and loss modulus (G") of CS-Fe3+-PAA in rheological rheological measurements: (a) frequency; (b) strain
图 6 CS-Fe3+-PAA在50%~300%应变下(a)连续加载-卸载曲线和(b)相应的耗散能与应力曲线；CS-Fe3+-PAA在100%应变下(c)连续10次加载-卸载曲线和(d)相应的耗散能与应力曲线
Figure 6. (a) Successive loading–unloading curves and (b) corresponding dissipated energy and stress curve of CS-Fe3+-PAA at strain of 50%~300%; (c) Ten successive loading–unloading curves and (d) corresponding dissipated energy and stress curves of CS-Fe3+-PAA at strain of 100%
图 7 CS-Fe3+-PAA循环拉伸的相对电阻变化曲线：(a)小应变、(b)大应变和(c)拉伸速率；(d)水凝胶循环拉伸600次的相对电阻变化曲线；(e)0%~
1000 %拉伸应变下水凝胶的相对电阻变化与GF值；(f)本工作水凝胶的GF值和断裂应变与已报道的水凝胶的比较[34,35,42-48]Figure 7. The relative resistance variation curves under cyclic tensile of CS-Fe3+-PAA: (a) small strain, (b) large strain and (c) tensile rate; (d) The relative resistance variation curves of the hydrogel at 600 cycles; (e) The relative resistance variation and GF value of the hydrogel under 0%~
1000 % tensile strains; (f) Comparison of GF value and elongation strain of the hydrogel in this work with reported hydrogels[34,35,42-48]
图 8 CS-Fe3+-PAA作为可穿戴应变传感器，用于监测人体活动：(a)手指弯曲，(b)手肘弯曲，(c)膝盖弯曲，(d)手腕弯曲，(e)吞咽水，(f)说“Hello”
Figure 8. The CS-Fe3+-PAA as a wearable strain-sensor for human movements monitoring: (a) finger bend, (b) Elbow joint bend, (c) Knee bend, (d) Wrist bend, (e) swallowing, (f) Saying “Hello”
表 1 不同CS含量的样品名称
Table 1. Sample names for different CS content
Sample CS/g FeCl3/(mol·L−1) Fe3+-PAA 0 0.1 CS0.05-Fe3+-PAA 0.05 0.1 CS0.1-Fe3+-PAA 0.1 0.1 CS0.2-Fe3+-PAA 0.2 0.1 CS0.3-Fe3+-PAA 0.3 0.1 CS0.4-Fe3+-PAA 0.4 0.1 Notes: CS-Fe3+-PAA—Chitosan-Fe3+-polyacrylic acid hydrogels. 
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表 2 不同FeCl3浓度的样品名称
Table 2. Samples name for different FeCl3 concentrations
Sample CS/g FeCl3/(mol·L−1) CS-Fe3+0.05-PAA 0.2 0.05 CS-Fe3+0.1-PAA 0.2 0.1 CS-Fe3+0.2-PAA 0.2 0.2 CS-Fe3+0.3-PAA 0.2 0.3 CS-Fe3+0.4-PAA 0.2 0.4
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