Research progress of waterborne polyurethane-based flexible sensing materials
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摘要: 近年来，柔性传感器在可穿戴电子设备、医疗保健设备、电子皮肤和软体机器人等方面具有广泛的应用前景。聚氨酯(PU)是一类应用于柔性传感领域的基础材料，具有类弹性体、柔韧性及相容性等优势，能满足人们对柔性传感器更好的拉伸性、更高的灵敏度和更宽的工作范围的需求。但随着环保意识的增强，水性聚氨酯(WPU)凭借环保性、低挥发性、易处理性等特性，成为柔性传感领域的研究热点。本文对WPU基柔性传感材料的最新进展进行了跟踪和讨论，包括WPU合成、柔性传感原理、导电填料种类等。最后总结了WPU基柔性传感器独特的多功能性及其广泛应用，并对WPU基柔性传感材料的未来发展前景进行了展望。Abstract: In recent years, flexible sensors have a wide range of applications in wearable electronic devices, healthcare devices, electronic skin and soft robots. Polyurethane (PU) is a class of basic materials used in the field of flexible sensing, with the advantages of elastomer-like, flexibility and compatibility, which can meet the demand for better stretchability, higher sensitivity and wider working range of flexible sensors. However, with the increasing awareness of environmental protection, waterborne polyurethane (WPU) has become a research hotspot in the field of flexible sensing by virtue of its environmental friendliness, low volatility, and ease of handling. In this paper, the recent progress of WPU-based flexible sensing materials is tracked and discussed, including WPU synthesis, flexible sensing principles, and conductive filler types. Finally, the unique multifunctionality of WPU-based flexible sensors and their wide range of applications are summarized, and the future development prospects of WPU-based flexible sensing materials are outlooked.
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图 2 (a) (b) (c)三种主要传感原理示意图
Figure 2. (a) (b) (c) Schematic of the three main sensing principles
图 3 (a) 传感材料的制备过程[36], (b)复合材料的SEM图[36], (c)g-MWCNTs复合材料的制备过程[37], (d)聚合物中均匀分布的g-MWCNT的扫描电镜图[37]
Figure 3. (a) Fabrication process of the sensor[36], (b) SEM image of the composite material[36], (c) Fabrication process of g-MWCNTs composite[37], (d) SEM of the g-MWCNTs distributed in the polymer uniformly[37]
图 4 (a) 红外光谱和核磁共振谱[39], (b)复合材料FGMWPU的制备过程[39], (c)气凝胶的SEM[42], (d)图实时监测各种人体的活动[42], (e)对身体各部位的实时监测[44]
Figure 4. (a) FTIR spectra and 1H NMR spectra[39], (b) Preparation of FGMWPU composite materials[39], (c) SEM image of aerogel[42], (d) Real-time monitoring of various human body activities[42], (e) Real-time monitoring of all body parts[44]
图 5 (a) 由链缠结和多重氢键构建的物理交联网络[46], (b) 不同温度下材料的愈合效果[46], (c)TCNC的SEM和TEM图像[48], (d) 不同TCNC比例的WPU薄膜的代表性应力-应变曲线和力学数据[48]
Figure 5. (a) Physical cross-linking networks constructed by chain entanglements and multiple hydrogen bonds, (b) Healing effect of materials at different temperatures[46], (c) SEM and TEM images[48], (d) Representative stress-strain curves and mechanical data of WPU films with different ratio of TCNCs[48]
图 6 (a) 聚苯胺接枝到WPU表面的过程[52], (b) 传感器结构及工作原理[52], (c) PEDOT:PSS和WPU的化学结构以及生产PEDOT:PSS/WPU复合纤维的湿法纺丝装置示意图[53], (d) 拉伸应变曲线及循环曲线[53]
Figure 6. (a) the process of grafting polyaniline on the WPU surface[52], (b) Sensor structure and working principle [52], (c) Chemical structures of PEDOT:PSS and WPU and schematic illustration of the wet-spinning set-up for producing PEDOT:PSS/WPU composite fibers[53], (d) Tensile Strain Curve and Cycle Curve[53]
图 7 (a) Ti3C2-MXene 纳米片的制备[55], (b) 纯Ti3C2-MXene 沉积层和Ti3C2/CNCs复合沉积层的断裂机制[55], (c)复合材料制备过程[56], (d) 银纳米线和MXene的分布示意图[56]
Figure 7. (a) Preparation of Ti3C2-MXene Nanosheets[55], (b)Fracture mechanism of pure Ti3C2-MXene deposition layer and Ti3C2/CNCs composite deposition layer[55], (c) Composite material preparation process[56], (d) Schematic distribution of silver nanowires and MXene[56]
图 8 (a)实时监测身体部位和响应速度[48], (b) 由蓝牙模块和智能手机组装而成的人体运动传感系统示意图[62], (c) 复合材料在电子皮肤上的应用[59],(d)长时间下与皮肤的黏附测试[60]
Figure 8. (a) Real-time monitoring of body parts and response rate[48], (b) Illustration of human motion sensing system assembled by Bluetooth module and smartphone[62], (c) Composite Materials for Electronic Skin Applications[59], (d) Adhesion test to skin over a long period of time[60]
图 9 (a) 柔性传感器健康监测示意图[58], (b) 实时监测脉搏的反应速度[58], (c) 基于SPRABE的无线监测系统收集心电图和跑步信号的示意图[64], (d) 用于心电图(上)和应变传感(下)模块的皮肤照片[64], (e) 以 2 km·h−1 的速度运行 0、4、8、12、16、20 分钟时的相对阻力变化情况[64]
Figure 9. (a) Flexible Sensor Health Monitoring Schematic[58], (b) Real-time monitoring of pulse response rate[58], (c) Schematic diagram of the SPRABE-skin based wireless monitoring system to collect ECG and running signals[64], (d)Photographs of skin used for ECG (top) and strain sensing (bottom) modules[64], (e) The relative resistance variation at 0, 4, 8, 12, 16, 20 min of 2 km·h−1 running speed[64]
表 1 不同传感原理的优缺点
Table 1. Advantages and disadvantages of different sensing principles
Principle of sensing Advantage Disadvantages Areas of application Piezoresistive Simple structure, easy circuit integration and data processing, flexible structure, and large space for performance adjustment. Less stable, more hysteresis, more affected
by temperatureTactile sensors, pressure sensors Capacitive Simple structure, low temperature influence, low hysteresis, low cost Susceptible to electromagnetic interference, complicated data processing, narrow measurement range Temperature sensors, humidity sensors Piezoelectric Good high-frequency performance, fast response, self-supply of energy Poor static characteristics and small measuring range Energy harvesters, supercapacitors 
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表 2 WPU柔性传感器制备方法与性能总结
Table 2. Summary of WPU flexible sensor preparation methods and performance
Sensor mechanism Preparation process Conductive filler saturation (physics) response
time9(ms)Special performance bibliography Piezoresistive Screen printing g-MWCNTs GF(~2000) 90 — [37] Capacitive Freeze drying GO、MWCNTs GF(~8.37) — Self-healing [39] Piezoresistive Freeze drying GO GF(~0.2) — — [42] Capacitive Dip coating MXene GF(~960) — — [44] Piezoresistive Casting AgNW — — Self-healing [47] Piezoresistive Casting PANI GF(~168.1) 32 High strength [52] Capacitive Wet spinning PEDOT:PSS — Thermoelectric property [53] Capacitive Casting MXene GF(~474) — — [55] Piezoelectric Vacuum filtration AgNW、MXene GF(~1.6×107) 344 — [56] Piezoresistive Vacuum filtration MXene、ILs GF(~1.8) 185 — [58] Piezoresistive Casting PEDOT:PSS GF(~25) — — [59] Capacitive Dip coating rGO、MWCNT GF(~89) — — [60] Notes: MWCNTs—Multi-walled carbon nanotubes; GO—Graphene oxide; PANI—Polyaniline; PEDOT:PSS—Poly(3,4-ethylenedioxythiophene) /poly(styrenesulfonate); ILs—Ionic liquids: rGO—Reduced graphene oxide.
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