Preparation and properties of POSS/sodium polyacrylate conductive composite hydrogels with high stretchability, self-healable and self-adhesive properties
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摘要: 导电水凝胶在柔性可穿戴设备、电子皮肤和生物电极等方面具有很大的应用潜力。然而，复杂多变的应用场景对导电水凝胶在可拉伸性、自愈合性、自黏附性和生物相容性等方面提出了更高的要求。利用水溶性多面体低聚倍半硅氧烷(POSS)与聚丙烯酸钠(PAA-Na)之间的非共价键交联设计了一种具有高可拉伸性、自愈合、自黏附性和良好生物相容性的导电复合水凝胶(OCAPS/PAA-Na)。OCAPS/PAA-Na水凝胶的断裂伸长率为2537.0%~4056.1%；POSS的加入提高了水凝胶的力学性能，拉伸强度由10.5 kPa提高到23.8 kPa，拉伸模量由7.1 kPa提高到27.8 kPa，断裂能由3.7 kJ·m−2提高到6.8 kJ·m−2。OCAPS/PAA-Na水凝胶具有优异的自愈合性能，自愈合效率达97.8%。该水凝胶对有机材料和无机材料均具有良好的黏附性，黏附强度最高分别达到19.6 kPa和18.2 kPa。细胞毒性试验和溶血试验表明，水凝胶具有优异的生物相容性。制备过程中原位生成的NaCl晶体，提高了水凝胶的电导率(由0.165 S·m−1增加到0.290 S·m−1)。OCAPS/PAA-Na水凝胶可作为应变式电阻传感器材料精确地检测一些细微的人体动作，传感灵敏系数值达5.17，在柔性智能可穿戴设备和电子皮肤领域具有良好的应用前景。Abstract: Conductive hydrogels have great potential applications in flexible wearable devices, electronic skin and biological electrodes. However, the complex and changing application scenarios put forward higher requirements on the stretchability, self-healable, self-adhesive and biocompatibility of conductive hydrogels. In this paper, a conductive composite hydrogel (OCAPS/PAA-Na) with high extensibility, self-healable, self-adhesive and excellent biocompatibility was designed by the non-covalent cross-linking between a water-soluble polyhedral oligomeric silsesquioxane (POSS) and sodium polyacrylate (PAA-Na). The elongation at break of OCAPS/PAA-Na hydrogel is 2537.0%-4056.1%. The addition of POSS improves the mechanical properties of hydrogels: The tensile strength increases from 10.5 kPa to 23.8 kPa; The tensile modulus increases from 7.1 kPa to 27.8 kPa; The fracture energy increases from 3.7 kJ·m−2 to 6.8 kJ·m−2. OCAPS/PAA-Na hydrogel has excellent self-healable property, and the self-healable efficiency is up to 97.8%. The hydrogel shows good adhesion to both organic and inorganic materials, with the highest adhesive strength of 19.6 kPa and 18.2 kPa, respectively. Cytotoxicity test and hemolysis test show that the hydrogel has excellent biocompatibility. The conductivity of the hydrogel increases from 0.165 to 0.290 S·m−1 with NaCl crystals is generated in situ during the preparation. OCAPS/PAA-Na hydrogel can be used as a strain resistance sensor material to accurately detect some subtle human actions and the gauge factor value can reach 5.17, which has a good application prospect in the field of flexible intelligent wearable devices and electronic skin.
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图 1 OCAPS/PAA-Na复合水凝胶的制备示意图
Figure 1. Preparation diagram of OCAPS/PAA-Na hydrogel
KPS—Potassium peroxodisulfate
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图 2 (a) OCAPS、PAA-Na和OCAPS/PAA-Na的FTIR图谱；(b) PAA-Na和OCAPS/PAA-Na的XRD图谱
Figure 2. (a) FTIR spectra of OCAPS, PAA-Na and OCAPS/PAA-Na; (b) XRD patterns of PAA-Na and OCAPS/PAA-Na
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图 3 PAA-Na和OCAPS/PAA-Na水凝胶的SEM图像：(a) PAA-Na；(b) 3OCAPS/PAA-Na；(c) 9OCAPS/PAA-Na；(d) 12OCAPS/PAA-Na；(e) 9OCAPS/PAA-Na水凝胶的EDS能谱
Figure 3. SEM images of OCAPS/PAA-Na hydrogel: (a) PAA-Na; (b) 3OCAPS/PAA-Na; (c) 9OCAPS/PAA-Na; (d) 12OCAPS/PAA-Na; (e) EDS spectrum analysis of 9OCAPS/PAA-Na hydrogel
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图 4 PAA-Na和OCAPS/PAA-Na水凝胶在去离子水中的溶胀曲线图(a)和平衡溶胀比(b)
Figure 4. Swelling curves (a) and balanced swelling ratio (b) of PAA-Na and OCAPS/PAA-Na hydrogel in deionized water
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图 5 PAA-Na和9OCAPS/PAA-Na水凝胶第二次升温的DSC曲线
Figure 5. Second heating DSC curves of PAA-Na and 9OCAPS/PAA-Na hydrogels
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图 6 (a) 9OCAPS/PAA-Na水凝胶的的拉伸实物图；(b) PAA-Na和OCAPS/PAA-Na水凝胶的拉伸应力-应变曲线；(c) 拉伸强度；(d) 断裂能；9OCAPS/PAA-Na水凝胶循环拉伸曲线(e)、循环中相应的耗散能(f)和循环压缩曲线(g)
Figure 6. (a) Stretching picture of 9OCAPS/PAA-Na hydrogel; (b) Tensile stress-strain curves of PAA-Na and OCAPS/PAA-Na hydrogel; (c) Tensile strength; (d) Fracture energy; Cyclic tensile curves (e), corresponding dissipated energy in every cycle (f) and cyclic compression curves (g) of 9OCAPS/PAA-Na hydrogel
λ—Stretching factor
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图 7 9OCAPS/PAA-Na水凝胶在不同频率下((a), (b))和不同应变下((c), (d))的流变曲线
Figure 7. Rheological curves of 9OCAPS/PAA-Na hydrogel at different frequencies ((a), (b)) and different strains ((c), (d))
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图 8 9OCAPS/PAA-Na水凝胶的自愈合性能：(a) 样品愈合前；(b) 样品愈合中；((c), (d)) 愈合5 min后的拉伸过程；9OCAPS/PAA-Na水凝胶自愈合前后的应力-应变曲线(e)和压缩曲线(f)
Figure 8. Self-healable property of 9OCAPS/PAA-Na hydrogel: (a) Before the sample healed; (b) During the sample healed; ((c), (d)) Stretching after 5 min; Stress-strain curves (e) and compression curves (f) of 9OCAPS/PAA-Na hydrogel before and after self-healable
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图 9 (a) 9OCAPS/PAA-Na水凝胶黏附不同材料的宏观照片；(b) PAA-Na和9OCAPS/PAA-Na水凝胶对不同材料的黏附曲线；(c) PAA-Na和9OCAPS/PAA-Na对不同材料的黏附强度；(d) 不同水凝胶的黏附强度比较
Figure 9. (a) Photoes of 9OCAPS/PAA-Na hydrogel adhesion to different materials; (b) Adhesive curves of PAA-Na and 9OCAPS/PAA-Na hydrogels to different materials; (c) Adhesive strength of PAA-Na and 9OCAPS/PAA-Na hydrogels to different materials; (d) Comparisons of adhesive strength of different hydrogels
CNC—Carboxylated nano cellulose; MAGP—Microfibrillar-associated glycoprotein; DCMC—Dimethylol dicyanurate; AG—Amino gelatin; PDA—Polydopamine; CS—Chitosan; TA—Tannic acid; PAa—Polyacrylamide/polydopamine
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图 10 (a) PAA-Na和9OCAPS/PAA-Na水凝胶的细胞增殖率和溶血率；(b) 9OCAPS/PAA-Na水凝胶的溶血现象
Figure 10. (a) Cell proliferation rate and hemolysis rate of PAA-Na and 9OCAPS/PAA-Na hydrogels; (b) Hemolysis phenomenon of PAA-Na and 9OCAPS/PAA-Na hydrogels
RGR—Relative growth rate
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图 11 (a) PAA-Na水凝胶导电效果图；(b) 9OCAPS/PAA-Na水凝胶导电效果图；(c) PAA-Na和OCAPS/PAA-Na水凝胶的电导率；(d) PAA-Na和9OCAPS/PAA-Na水凝胶的传感灵敏度(GF)；9OCAPS/PAA-Na水凝胶在不同肢体处的弯曲传感变化：(e) 喉咙循环发“A”时；(f) 食指0°至90°循环弯曲；(g) 肘部0°至60°循环弯曲；(h) 膝盖0°至90°循环弯曲；(i) 手腕0°至60°循环弯曲
Figure 11. (a) Photo of conductive performance of PAA-Na hydrogel; (b) Photo of conductive performance of 9OCAPS/PAA-Na hydrogel; (c) Conductivity of PAA-Na and 9OCAPS/PAA-Na hydrogels; (d) Gauge factor (GF) of PAA-Na and 9OCAPS/PAA-Na hydrogels; The bending sensing changes of 9OCAPS/PAA-Na hydrogel at different limbs: (e) When "A" is circulated for the throat; (f) Cycle the index finger from 0° to 90°; (g) Cycle from the elbow 0° to 60°; (h) Cycle knee flexion from 0° to 90°; (i) Cycle the wrist from 0° to 60°
ΔR—Quantifying the variations in hydrogel impedance pre and post stress application; R0—Impedance characterization of the hydrogel in unstressed state
表 1 样品命名
Table 1 Sample naming
Sample Molar ratio (OCAPS:AA-Na) PAA-Na 0∶100 3OCAPS/PAA-Na 0.3∶100 6OCAPS/PAA-Na 0.6∶100 9OCAPS/PAA-Na 0.9∶100 12OCAPS/PAA-Na 1.2∶100 Notes: PAA-Na—Sodium polyacrylate; OCAPS—Octa(3-chloro-ammoniumpropyl) silsesquioxane 
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