Preparation and properties of 3D printed polypyrrole nanotube/polydimethylsiloxane composite strain sensing composites
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摘要: 柔性电阻式应变传感器作为柔性传感器中重要的一类，具有柔性好、结构简单、数据读取便捷等优点，在多个领域中已有广泛应用。现有研究中，用于填充型应变传感器复合材料的导电填料多以金属导电粉末和碳系导电粉末为主，较少有单独使用导电聚合物的报道。本文以甲基橙(MO)为掺杂剂，无水三氯化铁(FeCl3)为氧化剂，通过化学氧化法聚合制得聚吡咯(PPy)纳米管，电导率高达121.70 S·cm−1。以PPy纳米管为导电填料和增稠剂，聚二甲基硅氧烷(PDMS)为基体，通过机械共混制成打印墨水，利用直写式3D打印机和智能流变仪表征墨水的可打印性和流变性能；利用扫描电子显微镜(SEM)、智能拉伸机、数字万用表、差示扫描量热仪(DSC)等仪器对3D打印固化后的试样进行表征和性能测试，研究PPy纳米管的浓度对PPy/PDMS复合材料微观形貌、电学性能、力学性能、差热性能、动态热力学性能和应变传感性能的影响。结果表明，PPy纳米管浓度达到7~9wt%时，墨水具有良好的打印能力。其中7wt%的墨水在连续20层打印测试中表现出优异的打印性能，所打印哑铃型拉伸试样在单一拉伸测试中的抗拉强度和断裂伸长率可达3.02 MPa和178.64%，敏感因子(GF, Gauge Factor)高达36.14；在100次循环拉伸测试中具有较低的电阻信号峰值稳定系数(α，1.714)和肩峰比例(Psp，9.8%)，在1000次循环拉伸测试中表现出较好的耐久性和稳定性。用该墨水所制备的人体皮肤传感贴片在对手指、手腕、手肘和膝盖关节的运动监测中具有良好的信号稳定性和可重复性，证明了3D打印PPy/PDMS复合材料在柔性电子、可穿戴设备和人体运动监测领域中具有一定的应用前景。Abstract: Flexible resistive strain sensors, as an important category of flexible sensors, have been widely applied across various fields due to their good flexibility, simple structure, and easy data readout. In existing studies, conductive fillers used in composite materials for filled strain sensors mainly consist of metallic conductive powders and carbon-based conductive powders, with few reports on the use of conductive polymers alone. Polypyrrole (PPy) nanotubes were synthesized by chemical oxidation polymerization using methyl orange (MO) as a dopant and anhydrous ferric chloride (FeCl3) as an oxidant, with a high conductivity of up to 121.70 S·cm-1. PPy nanotubes were used as conductive fillers and thickeners, and polydimethylsiloxane (PDMS) was used as the matrix to prepare printing ink by mechanical blending. The printability and rheological properties of the ink were characterized using a direct-writing 3D printer and an intelligent rheometer. The 3D printed samples were characterized and tested using scanning electron microscopy (SEM), intelligent tensile tester, digital multimeter, differential scanning calorimeter (DSC) and other instruments to investigate the effect of PPy nanotube concentration on the microstructure, electrical properties, mechanical properties, differential thermal properties, dynamic thermodynamic properties, and strain sensing properties of PPy/PDMS composite materials. The results show that the ink exhibits good printability when the concentration of PPy nanotubes reaches 7~9 wt%. The ink with 7 wt% shows superior performance in 20-layer continuous printing tests, with the printed dumbbell-shaped tensile specimens achieving a tensile strength of 3.02 MPa and an elongation at break of 178.64%, and a high gauge factor (GF) of 36.14. In 100-cycle tensile tests, the ink shows low resistance signal peak stability coefficient (α, 1.714) and shoulder peak proportion (Psp, 9.8%). It also exhibits good durability and stability in 1000-cycle tensile tests. The skin sensor patches made from this ink exhibit good signal stability and repeatability in monitoring finger, wrist, elbow, and knee joint movements, indicating that 3D-printed PPy/PDMS composites have potential applications in flexible electronics, wearable devices, and human motion monitoring.
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图 2 PPy-N/PDMS复合材料打印墨水的制备流程
Figure 2. Preparation process of the PPy-N/PDMS composite material printing ink
图 4 不同PPy-N浓度墨水的光学图像和打印效果图
Figure 4. Optical images and printing results of inks with different PPy-N concentrations
图 5 不同PPy-N浓度墨水随剪切速率变化的黏度曲线
Figure 5. Viscosity curves of inks with different PPy-N concentrations as a function of shear rate
图 6 不同PPy-N浓度墨水随角频率变化的储能模量曲线
Figure 6. Storage modulus curves of inks with different PPy-N concentrations as a function of angular frequency
图 7 不同PPy-N浓度墨水的剪切屈服强度
Figure 7. Shear yield strength of inks with different PPy-N concentrations
图 8 3D打印墨水打印20层矩形结构的顺序快照
Figure 8. Sequential snapshots of printing a rectangular structure with 20 layers using 3D printing ink
图 9 未添加MO制备得到的PPy-B(a)、添加MO制备得到的PPy-N(b)、PPy-N在透射电子显微镜下的微观形貌(c)和PPy-N在打印墨水中的分布示意图(d)
Figure 9. PPy-B prepared without MO(a), PPy-N prepared with MO(b), Microstructure of PPy-N under transmission electron microscope(c) and Schematic diagram of the distribution of PPy-N in printing ink(d).
图 10 PPy-B和PPy-N粉末样品平均电导率对比图
Figure 10. Comparison of average electrical conductivity of PPy-B and PPY-N powder samples
图 11 PP7 (a)、PP8 (b)和PP9 (c)试样中PPy-N的分散情况和PPy-N在PDMS中微观形貌(d)的SEM图像
Figure 11. SEM images of PP7(a), PP8(b), and PP9(c) samples, and the microscopic morphology of PPy-N in PDMS(d).
图 12 PPy-N/PDMS复合材料电导率曲线
Figure 12. Electrical conductivity curve of PPy-N/PDMS composites
图 13 力电性能测试仪器连接示意图(a)和打印的哑铃型拉伸试样及涂有导电银浆的试样(b)
Figure 13. Schematic diagram of the piezoelectric performance testing instrument connection (a) and Printed dumbbell-shaped tensile specimen and specimen coated with conductive silver paste (b)
图 14 PP7、PP8和PP9试样拉伸应力应变曲线
Figure 14. Tensile stress-strain curves for PP7, PP8 and PP9 samples
图 15 PP7、PP8和PP9试样在0~80%应变范围内的相对电阻变化曲线
Figure 15. The relative resistance changes curve of PP7, PP8 and PP9 samples in the strain range of 0~80%
图 16 PP7、PP8和PP9试样热流随温度变化的DSC曲线
Figure 16. DSC curves of heat flow with temperature for PP7, PP8 and PP9 samples
图 17 PP7、PP8和PP9试样储能模量随温度变化的DMA曲线
Figure 17. DMA curves of storage modulus with temperature for PP7, PP8 and PP9 samples
图 18 PP7、PP8和PP9试样损耗因子随温度变化的DMA曲线
Figure 18. DMA curves of loss factor with temperature for PP7, PP8 and PP9 samples
图 19 PP7、PP8和PP9试样100次循环拉伸应变传感信号结果
Figure 19. Results of 100 cycles of tensile strain sensing signal for PP7, PP8 and PP9 samples
图 20 PP7试样100次循环拉伸肩峰放大图
Figure 20. Magnification of acromion for 100 cycles of tensile strain for PP7 samples
图 21 PP7试样1000次循环拉伸/释放传感信号结果
Figure 21. Results of 1000 cycles of strain sensing signals for PP7 sample
图 22 PP7试样皮肤传感贴片监测手指(a)、手腕(b)、手肘(c)、膝盖(d)关节弯曲的电信号
Figure 22. Electrical signals monitoring finger flexion(a), wrist flexion(b), elbow flexion(c), and knee flexion(d) for the PP7 specimen skin sensing patch
表 1 聚吡咯纳米管/聚二甲基硅氧烷(PPy-N/PDMS)复合材料配方
Table 1. Formulation of polypyrrole nanotube/polydimethylsiloxane (PPy-N/PDMS) composite material
Inks PDMS/g PPy-N/g Curing agent /g PP5 10 0.5 1 PP6 10 0.6 1 PP7 10 0.7 1 PP8 10 0.8 1 PP9 10 0.9 1 PP10 10 1.0 1 
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表 2 DSC测试中PP7、PP8和PP9试样的玻璃化转变温度($ {T}_{\mathrm{g}} $)以及熔融峰值温度$ ({T}_{\mathrm{m}}) $
Table 2. The glass transition temperature ( $ {T}_{\mathrm{g}}) $ and peak melting temperature $ \left({T}_{\mathrm{m}}\right) $ of PP7, PP8 and PP9 samples in DSC test
Samples $ {\mathit{T}}_{\mathbf{g}} $/℃ $ {\mathit{T}}_{\mathbf{m}} $/℃ PP7 −122.4 −46.2 PP8 −121.6 −45.5 PP9 −121 −42.2
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