柔性多孔导电聚合物复合材料的制备及其压阻效应研究
发布时间：2018-11-25 07:56
【摘要】：柔性多孔导电聚合物复合材料(PCPC)可具有显著的压阻效应,是“可穿戴”器件的重要材料,在机器人、健康监测等领域都有着巨大的应用前景。目前,PCPC的制备方法主要有“浸渍法”及“冰固态模板法”,所制材料虽然具有低密度及压缩回弹性良好的特性,但材料的应变敏感系数(GF值)最高仅为3左右。论文提出并研究了一种以高内相乳液,“一步法”制备PCPC的新方法:分别以氧化石墨烯(GO)水分散液和柔性单体为高内相乳液的分散相和连续相;在聚合反应中,原位还原GO,增强的疏水性驱使还原氧化石墨烯(rGO)向“油/水”界面迁移;干燥后,rGO附着于材料腔壁表面,从而得到柔性PCPC。本文分别以0.5-5μm及2-10μm两种片层尺寸的GO为导电填料的前驱体,系统研究了Vitamin C还原GO的反应过程,进而考察了GO的尺寸及浓度,乳化剂的浓度及种类对PCPC微观形貌、力学性能、导电性能及压阻性能的影响。得出如下结论:1.GO的还原反应研究:聚合反应中,GO可被Vitamin C同步还原为具有优良导电性能的rGO;2.当GO的片层尺寸为0.5-5μm时:(1)同步还原得到的rGO覆盖材料的腔壁表面;rGO致使腔壁增强,PCPC形成闭孔结构;(2)材料的电导率均随着压缩应变而增大,具有压阻性能;(3)随着GO用量的增高(0.wt%~0.91 wt%,基于最终材料质量):材料的平均孔径略有降低,平均孔径介于37μm与87μm之间;材料电导率由4.70×10-5 S/m增大至5.93×10-3 S/m;应变灵敏度因子GF值呈现先减小后增大的趋势,但最大值仅为1.03;(4)提高乳化剂Span80用量(8 wt%~23 wt%):材料的平均孔径减少,比表面积增大,填料面密度降低,因此电导率降低,GF值呈现先减小后增大的趋势,但最大值仅为1.22;(5)以高表面活性乳化剂Hypermer A70替代Span80后,乳化剂用量对孔径的影响与Span80相同,但材料的平均孔径可降至7μm,因此相比Span80,材料模量更高,电导率降低两个量级;电导率随应变呈现无规改变;稀疏的填料网络对应变的响应灵敏度很低,GF值仅为0.2;加入增塑剂水杨酸甲酯后,SEM表明材料内rGO填料连通性增高,电导率增大,GF值略有增高。3.采用片层尺寸为2-10μm的GO时,材料的性能明显提升:(1)虽然GO用量对材料电导率的影响与片层尺寸为0.5-5μm的GO影响相同,但GO用量为0.59 wt%(0.048 vol%)时,材料出现渗流现象,此时材料的应力及应变灵敏度最大,5%应变时的灵敏度因子GF值高达6.0;(2)材料受循环应变时,电阻响应稳定,具有优良的机电稳定性,在可穿戴传感器件及医疗领域具有较大的应用潜力。
[Abstract]:Flexible porous conductive polymer composite (PCPC) has a significant piezoresistive effect and is an important material for wearable devices. It has great application prospects in robot, health monitoring and other fields. At present, the preparation methods of PCPC are mainly "impregnation method" and "ice solid template method". Although the prepared materials have the characteristics of low density and good compression resilience, the maximum strain sensitivity coefficient (GF) of the materials is only about 3. In this paper, a new method of preparing PCPC with high internal phase emulsion and "one step method" was proposed and studied. The dispersion phase and continuous phase of high inner phase emulsion were composed of graphene oxide (GO) aqueous dispersion and flexible monomer, respectively. In the polymerization reaction, the hydrophobicity enhanced by in-situ reduction of GO, leads to the migration of reduced graphene (rGO) to the "oil / water" interface. After drying, the rGO adheres to the surface of the cavity wall of the material, and a flexible PCPC. is obtained. In this paper, the process of reducing GO by Vitamin C was systematically studied with GO of 0.5-5 渭 m and 2-10 渭 m as the precursor of conductive filler, and the size and concentration of GO, the concentration and type of emulsifier on the micromorphology of PCPC were investigated. Effects of mechanical properties, electrical conductivity and piezoresistive properties. The conclusion is as follows: the reduction reaction of 1.GO: in the polymerization reaction, GO can be simultaneously reduced by Vitamin C to rGO;2. with excellent conductivity. When the lamellar size of GO is 0.5-5 渭 m: (1) the surface of the cavity wall of the rGO coating material obtained by synchronous reduction, the cavity wall is enhanced by rGO, and the structure of PCPC is obturated; (2) the conductivity of the material increases with the compression strain and has the piezoresistive property; (3) with the increase of GO content (0.wt%~0.91 wt%, based on the final material quality): the average pore size of the material decreases slightly, and the average pore size is between 37 渭 m and 87 渭 m; The conductivity of the material increased from 4.70 脳 10 ~ (-5) S / m to 5.93 脳 10 ~ (-3) S / m, and the GF value of strain sensitivity factor decreased first and then increased, but the maximum value was 1.03. (4) increasing the amount of emulsifier Span80 (8 wt%~23 wt%): the average pore size of the material decreased, the specific surface area increased, the density of filler surface decreased, so the conductivity decreased, the GF value decreased first and then increased, but the maximum value was only 1.22; (5) after replacing Span 80 with high surface active emulsifier Hypermer A70, the effect of emulsifier dosage on pore size is the same as that of Span80, but the average pore size of the material can be reduced to 7 渭 m, so the modulus of the material is higher than that of Span80, and the conductivity is two orders of magnitude lower than that of Span80,. The sensitivity of the sparse packing network to the strain is very low, and the GF value is only 0.2. When the plasticizer methyl salicylate was added, SEM showed that the connectivity of rGO filler increased, the electrical conductivity increased, and the GF value increased slightly. The properties of GO with lamellar size of 2-10 渭 m were significantly improved: (1) although the effect of the amount of GO on the conductivity of the material was the same as that of GO with the lamellar size of 0.5-5 渭 m, However, when the amount of GO was 0.59 wt% (0.048 vol%), the material appeared percolation, the sensitivity of stress and strain of the material was the highest, and the sensitivity factor GF value of 5% strain was as high as 6.0; (2) when the material is subjected to cyclic strain, the resistance response is stable and has excellent electromechanical stability. It has great application potential in wearable sensor devices and medical field.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB332
本文编号：2355373
[Abstract]:Flexible porous conductive polymer composite (PCPC) has a significant piezoresistive effect and is an important material for wearable devices. It has great application prospects in robot, health monitoring and other fields. At present, the preparation methods of PCPC are mainly "impregnation method" and "ice solid template method". Although the prepared materials have the characteristics of low density and good compression resilience, the maximum strain sensitivity coefficient (GF) of the materials is only about 3. In this paper, a new method of preparing PCPC with high internal phase emulsion and "one step method" was proposed and studied. The dispersion phase and continuous phase of high inner phase emulsion were composed of graphene oxide (GO) aqueous dispersion and flexible monomer, respectively. In the polymerization reaction, the hydrophobicity enhanced by in-situ reduction of GO, leads to the migration of reduced graphene (rGO) to the "oil / water" interface. After drying, the rGO adheres to the surface of the cavity wall of the material, and a flexible PCPC. is obtained. In this paper, the process of reducing GO by Vitamin C was systematically studied with GO of 0.5-5 渭 m and 2-10 渭 m as the precursor of conductive filler, and the size and concentration of GO, the concentration and type of emulsifier on the micromorphology of PCPC were investigated. Effects of mechanical properties, electrical conductivity and piezoresistive properties. The conclusion is as follows: the reduction reaction of 1.GO: in the polymerization reaction, GO can be simultaneously reduced by Vitamin C to rGO;2. with excellent conductivity. When the lamellar size of GO is 0.5-5 渭 m: (1) the surface of the cavity wall of the rGO coating material obtained by synchronous reduction, the cavity wall is enhanced by rGO, and the structure of PCPC is obturated; (2) the conductivity of the material increases with the compression strain and has the piezoresistive property; (3) with the increase of GO content (0.wt%~0.91 wt%, based on the final material quality): the average pore size of the material decreases slightly, and the average pore size is between 37 渭 m and 87 渭 m; The conductivity of the material increased from 4.70 脳 10 ~ (-5) S / m to 5.93 脳 10 ~ (-3) S / m, and the GF value of strain sensitivity factor decreased first and then increased, but the maximum value was 1.03. (4) increasing the amount of emulsifier Span80 (8 wt%~23 wt%): the average pore size of the material decreased, the specific surface area increased, the density of filler surface decreased, so the conductivity decreased, the GF value decreased first and then increased, but the maximum value was only 1.22; (5) after replacing Span 80 with high surface active emulsifier Hypermer A70, the effect of emulsifier dosage on pore size is the same as that of Span80, but the average pore size of the material can be reduced to 7 渭 m, so the modulus of the material is higher than that of Span80, and the conductivity is two orders of magnitude lower than that of Span80,. The sensitivity of the sparse packing network to the strain is very low, and the GF value is only 0.2. When the plasticizer methyl salicylate was added, SEM showed that the connectivity of rGO filler increased, the electrical conductivity increased, and the GF value increased slightly. The properties of GO with lamellar size of 2-10 渭 m were significantly improved: (1) although the effect of the amount of GO on the conductivity of the material was the same as that of GO with the lamellar size of 0.5-5 渭 m, However, when the amount of GO was 0.59 wt% (0.048 vol%), the material appeared percolation, the sensitivity of stress and strain of the material was the highest, and the sensitivity factor GF value of 5% strain was as high as 6.0; (2) when the material is subjected to cyclic strain, the resistance response is stable and has excellent electromechanical stability. It has great application potential in wearable sensor devices and medical field.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB332
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