Preparation and Epidermal Sensing Properties of Hybrid Cross-Linked Network Hydrogel
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摘要: 以丙烯酰胺（AAm）单体和甲基丙烯酰氧乙基三甲基氯化铵（DMC）阳离子单体为共聚单体，添加一定量阴离子聚电解质聚丙烯酸钠（PAAS），制备具有杂化交联网络的离子导电水凝胶P(AAm-DMC)-PAAS。采用万能试验机和电化学工作站对其力学性能和应变敏感性能进行测试。结果表明，水凝胶最大应力可达（88.4±4.7） kPa，最大应变为（1030.8±71.7）%。由于PAAS和DMC能电离出丰富的游离离子，水凝胶无需额外添加导电填料即可保持较高的离子电导率（0.684 S/m）和应变变化的快速响应，灵敏因子约为2.409（0~70%应变范围内）。制备的水凝胶可作为可穿戴应变传感器监测人体运动，还可以组装成表皮电极对人体电生理信号进行准确检测。Abstract: Ionic conductive hydrogels exhibit good electrical conductivity, excellent tensile properties and high biocompatibility, which is of great significance in the fields of flexible electronic equipment, human-machine interface and health monitoring. By using acrylamide (AAm) monomer and methyl acryloxyethyl trimethylammonium chloride (DMC) cationic monomer as copolymers and adding a certain amount of anionic polyelectrolyte sodium polyacrylate (PAAS), ionic conductive hydrogels with hybrid crosslinking network(P(AAm-DMC)-PAAS) are prepared. The mechanical properties of hydrogel can be effectively regulated by changing the density of chemical crosslinking and ionic crosslinking in hydrogel networks. The experimental results show that the maximum stress of the hydrogel can reach (88.4±4.7) kPa and the maximum strain is (1030.8±71.7)%. Because PAAS and DMC can ionize abundant free ions, P(AAm-DMC)-PAAS hydrogel can maintain high ionic conductivity and rapid response to strain without additional conductive filler, with conductivity up to 0.684 S/m and sensitivity factor GF about 2.409(0—70% strain range). The hydrogel can be used as a wearable strain sensor to monitor arm bending, finger bending, knee bending and other human movements through changes in relative resistance. The hydrogel can also be assembled into epidermal electrodes, which can accurately detect human physiological signals. Therefore, the P(AAm-DMC)-PAAS has the potential as a multifunctional sensor, which is expected to broaden its application in flexible electronic equipment, intelligent medical and other fields.
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图 1 离子导电水凝胶制备过程示意图
Figure 1. Schematic diagram of preparation process of ionic conductive hydrogel
图 2 （a）MBA和（b）DMC用量对水凝胶力学性能的影响
Figure 2. Effects of （a）MBA and （b）DMC contents on mechanical properties of hydrogels
图 3 （a） 水凝胶在不同应变下的单次循环拉伸；（b） 不同应变单次循环拉伸的滞后能；（c） 在400%应变下的10次循环拉伸；（d） 400%应变下的10次循环拉伸的滞后能
Figure 3. （a） Single cyclic stretching of hydrogel under different strains; （b） Hysteresis energy of single cyclic stretching under different strains; （c） 10 cycles of tension under 400% strain; （d） Hysteresis energy of 10 cycles of tension under 400% strain
图 4 （a）水凝胶相对电阻随应变的变化;（b）循环拉伸100次的相对电阻变化；（c）输入应变与输出信号之间的关系；（d）小应变拉伸与（e）大应变拉伸相对电阻变化；（f）不同拉伸速率下水凝胶传感器的相对电阻变化
Figure 4. （a） Change of hydrogel relative resistance versus strain range; （b） 100 cycles of tensile relative resistance change; （c） Relationship between input stress and output signal; Changes in the relative resistance of （d） small strain stretching and （e） large strain stretching; （f） Changes in relative resistance of hydrogel sensors at different tensile rates
图 5 水凝胶传感器的相对电阻变化
Figure 5. Changes of relative resistance of hydrogel sensor
a−Bent the arm; b−Bent the knee; c−Bent the finger; d−During walking and running
图 6 （a） 心电检测示意图；使用（b）水凝胶表皮电极和（c）Ag/AgCl商用电极测量的心电图；（d）左手握拳肌电信号检测示意图；使用（e）Ag/AgCl商用电极和（f）水凝胶表皮电极测量的肌电信号
Figure 6. （a） Schematic diagram of ECG detection; Electrocardiogram measured with （b） hydrogel epidermal electrode and （c） Ag/AgCl commercial electrodes; （d） EMG detection schematic diagram of left hand clenched fist; Electromyographic signals measured using （e） Ag/AgCl commercial electrodes and （f） hydrogel skin electrodes
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