CN115045017A - 一种用于信号监测的传感器织物及其制备方法和应用 - Google Patents
一种用于信号监测的传感器织物及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于柔性传感织物的制备领域,特别涉及一种可用于多重人体信号实时监测的柔性传感器织物及其制备方法和应用。配制防水涂料分散液;准备导电纤维,将制得的涂料分散液,界面微溶嵌入在导电纤维上,得到涂料导电纤维;准备弹力纤维,使用缠绕机将得到的涂料导电纤维缠绕在弹力纤维表面,得到柔性传感器;将得到的柔性传感器进行经纬编织,得到智能传感器织物。作为可实时监测压力、脉搏和运动等多重人体信号的智能传感织物,具有优异的柔性和透气性,还拥有稳定的导电性能、可控的机械性能,以及压力、脉搏等人体生理信号的感知能力,在当前人体健康监测、智能预警、危险求救、可穿戴设备和柔性电子皮肤等领域具有广阔的应用前景。
Description
技术领域
本发明属于柔性传感织物的领域,特别涉及一种可用于多重人体信号实时监测的柔性传感器织物及其制备方法和应用。
背景技术
随着人工智能的蓬勃发展,柔性可穿戴设备在智能终端、仿生电子皮肤、假肢置换、健康监测和加密传输等领域显示出了巨大的应用潜力,个性化的生理信号监测引起了研究者的极大兴趣。为了满足人们对身体健康和美好生活的追求,越来越多的科研工作者立足于柔性电子领域,致力于开发可用于人体生理信号监测的柔性可穿戴器件。但大部分研究人员致力于提高传感器的灵敏度、稳定性和生物相容性,忽视了制备成本、机械性能、重复性和透气性,因此,在保证其稳定优异的传感性能前提下,如何开发一种成本低廉、具有可调机械性能、多重信号捕获和多模态响应的柔性传感器,便成为目前研究的一个重大挑战。
热塑性聚氨酯弹性体(TPU)是介于橡胶和塑料的一类高分子材料,具有轻,薄,柔软,隐藏性好;耐寒,耐热,接触皮肤不刺激,不搔痒;不含对身体有害物质;拉伸力强的特点;并且具有良好的耐磨性、耐药性、柔韧度和伸缩度,是易加工、易制备、易缝制、弹性佳的环保基体,是制备柔性智能织物的理性选择,在柔性可穿戴应变传感器、智能服装等领域被广泛应用。
Wang等人在期刊ACS Applied Materials & Interfaces上发表的《Polyurethane/Cotton/Carbon Nanotubes Core-Spun Yarn as High ReliabilityStretchable Strain Sensor for Human Motion Detection》文章(ACS Appl. Mater.Interfaces, 2016, 8, 37, 24837-24843.)介绍了将天然棉纱缠绕在聚氨酯连续长丝上,并将碳纳米管涂覆在包芯纱表面制成一种核壳式纱线应变传感器,该传感器显示出较大的可拉伸性(300 %),但其灵敏度较低(25 %应变时GF = 2.15),涂层易脱落、稳定性较差,并且该技术需要执行多个准备步骤,技术繁琐。
CN106705829B提出一种柔性可穿戴导电纤维传感器及其制备方法,通过将缠绕纤维螺旋缠绕在弹性芯纱线外表面,并将导电层涂覆在缠绕纤维表面,实现独特的弹性螺旋状双包覆结构,能够感应拉伸应变,弯曲角度,扭转变形,但其上的导电层是涂覆在纤维表面,缠绕之后,再在表面涂覆导电的涂层裸露表面,难免脱落,涂层厚度不能完全一致且涂层容易脱落,影响电信号稳定性进而影响传感器的稳定性和精确度。
发明内容
基于现有技术中存在的上述缺点和不足,本发明的目的之一是至少解决现有技术中存在的上述问题之一或多个,换言之,本发明的目的之一是提供满足前述需求之一或多个的一种可用于多重人体信号实时监测的柔性传感器的制备方法,目的之二是制得智能织物传感器,具有可控的机械性能、稳定的传感性能和多模态响应性能并具有较高的灵敏度和优异的应变范围。
骨架材料,所述骨架材料包括弹力纤维、缠绕在所述弹力纤维表面的导电纤维;和界面微溶嵌入于所述骨架材料的所述缠绕纤维表面的防水绝缘层涂料。
一种可用于多重人体信号实时监测的柔性传感器的制备方法,其具体步骤如下:
(1) 配制防水涂料分散液;
(2) 准备导电纤维,将步骤(1)制得的涂料分散液,均匀地界面微溶嵌入在导电纤维上,风干,得到涂料导电纤维;
(3) 准备弹力纤维,使用缠绕机将步骤(2)得到的涂料导电纤维缠绕在弹力纤维表面,得到柔性传感器;
(4) 将步骤(3)得到的柔性传感器进行经纬编织,得到智能传感器织物。
作为优选方案,所述涂料分散液质量分数为1-40 %,
质量分数低于1%,分散液太稀,不易界面微溶嵌入且影响涂层遮盖力,不能完全覆盖表面,使得自然风干后涂料导电纤维皮层过薄,更易被侵蚀,耐久性不好,皮层质量效果下降;
质量分数高于40%,分散液太稠,粘度高,流动性差,也不易界面微溶嵌入,且会造成涂层过厚,使得皮层过于致密坚硬,纤维过粗,影响柔性和透气性。经过数十次的测试,当涂料分散液质量分数在1-40%范围内,界面微溶嵌入方便,得到的皮层厚度适宜,质量效果好,覆盖性、柔性及透气性最佳。
作为优选方案,所述步骤(3)中涂料导电纤维以60 -200捻/m的公制捻度缠绕在弹力纤维表面。
捻度高于200捻/m时,涂料导电纤维在弹力纤维表面缠绕过多,导电线路长,电阻相对高,不易及时响应信号的变化,从而降低传感器的灵敏度;
捻度低于60捻/m时,涂料导电纤维在弹力纤维表面缠绕过少,卷曲纤维短,可拉伸性降低,无法监测大形变下的信号变化,同样会影响传感器的灵敏度。
选用不同的捻度进行实验,最终发现,在60-200捻/m的公制捻度下,所得到的的传感器无论是对大形变还是小形变,都有很好的信号捕获能力,灵敏度较高。
作为优选方案,所述弹力纤维为聚氨酯弹性纤维、聚醚酯弹性纤维、二烯类弹性纤维或聚氨酯弹力线。
由于聚氨酯弹力线,主要成分为热塑性聚氨酯橡胶,具有极好的弹性、恢复性,测试出来断裂伸长率500%以上,主要作用是作为芯层,提供弹性、柔性、拉伸性、循环性,可用其他弹性好的材料如聚氨酯弹性纤维(氨纶)、聚醚酯弹性纤维、二烯类弹性纤维(橡胶丝)等进行替换;
作为优选方案,所述聚氨酯弹力线的直径为0.5-1.5 mm。
作为优选方案,所述导电纤维为碳纤维丝束、金属纤维铜线、银线或有机高分子导电纤维。
碳纤维,高强高模导电导热,将外界信号转化为电信号显示出来,灵敏度极高,作为功能导电组分,也可用其他功能相似的导电纤维,如金属纤维铜线、银线、有机高分子导电纤维等。
作为优选方案,所述步骤(2)中碳纤维丝束数量为1000-24 000根。
作为优选方案,所述步骤(2)中界面微溶嵌入厚度为0.05-0.25 mm;风干时间为12-24 h。
作为优选方案,所述涂料分散液为聚氨酯防水涂料或聚合物水泥基防水涂料。
水性聚氨酯,防水涂料,耐溶剂、无污染、无毒环保、安全可靠、机械性能优良、相容性好,主要用作碳纤维表面的隔绝层;也可用其他防水涂料,如聚氨酯类防水涂料、聚合物水泥基防水涂料等。
作为优选方案,所述步骤(4)中编织为机织、针织、缝纫中的一种。
作为优选方案,所述多重外界信号包括压力、温度;所述生理信号的实时监测包括脉搏、呼吸、人体各部位运动。
作为优选方案,所述智能传感织物应用于多重外界信号或生理信号的实时监测。
采用编织方法将其织成适当大小的面料,作为可实时监测压力、脉搏和运动等多重人体信号的智能传感织物。
本发明具有的有益效果是:
(1)本发明以聚氨酯弹力线为基体材料,无毒无害,生物相容性好,有一定的柔韧度和伸缩度,耐磨,弹性佳,易加工、易制备、易缝制。
(2)本发明得到的柔性传感器结构稳定,透气性好,应用场景广阔。
(3)本发明制备传感性能优异和机械性能可控的智能传感器,可实现对压力、脉搏和人体运动等多重外界信号或生理信号的实时监测,精度高,稳定性好,制备简单,成本低,有利于实现规模化生产。
附图说明
图1为实施例1制备的柔性传感器的简易实物图。
图2为实施例1制备的柔性传感器的压力传感性能测试图。
图3为实施例1制备的柔性传感器的脉搏传感性能测试图。
图4为实施例1制备的柔性传感器的人体运动监测图。
图5为实施例1制备的柔性智能传感器织物图。
具体实施方式
为了更清楚地说明本发明实施例,下面描述中的是本发明的一些实施例。显而易见地,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些实施例替换获得其他的实施方式。
下面以碳纤维、聚氨酯分散液、聚氨酯弹力线为优选原料,进行解释说明实施。
本发明碳纤维电阻极小,导电性能优异,可以很灵敏感知电阻的变化。在碳纤维表面界面微溶嵌入上一层聚氨酯分散液,作为隔绝层,既能增加导电组分的耐久性,又避免了芯套纱传感响应存在的双解现象,使得信号传输更加稳定、灵敏。
将具有导电功能的聚氨酯碳纤维通过卷曲缠绕结构复合在弹力纤维上,赋予该传感器优异的性能。无形变时,碳纤维丝束内存在较多间隙,导致导电网络连接不良,具有较高的电阻。在拉伸应变作用下,卷曲的聚氨酯碳纤维沿拉伸方向取向伸长,贴合紧密,缝隙消失,导电网络的连通性增强,使得电阻降低。将该传感器附在身体各部位,由于其形变量不同,导电网络的连通性不同,电阻相异,因此对于各种信号有着特定的响应。
本发明优选聚氨酯弹力线作为基体材料,发明人经试验测试偶然发现碳纤维螺旋缠绕上去,分散液界面微溶嵌入在碳纤维表面,起到一定的隔绝作用后,材料是一种理想的柔性传感器材料,既能监测关节运动等大变形,也能监测微小变形,具有良好的灵活性和稳定的信号捕获能力,非常适合实时监测人体运动、脉搏等个性化生理信号。
实施例1
准备直径为1.2 mm的聚氨酯弹力线;取质量分数为40 %的聚氨酯分散液,加水稀释,在25 ℃温度下搅拌5 min,得到搅拌均匀的质量分数为20 %的聚氨酯分散液;准备6 K的碳纤维丝束;将上述得到的聚氨酯分散液,以0.1 mm的厚度均匀地界面微溶嵌入在准备好的碳纤维丝束上,而后自然风干24 h时间,得到具有皮芯结构的聚氨酯/碳纤维;使用缠绕机将上述得到的聚氨酯/碳纤维以60 捻/m的公制捻度在聚氨酯弹力线表面,得到TPU基柔性传感器如图1所示;最后将该TPU基柔性传感器进行机织斜纹设计,即得到智能传感织物如图5所示。
实施例2
准备直径为0.8 mm的聚氨酯弹力线;取质量分数为40 %的聚氨酯分散液,加水稀释,在26 ℃温度下搅拌3 min,得到搅拌均匀的质量分数为5 %的聚氨酯分散液;准备1 K的碳纤维丝束;将上述得到的聚氨酯分散液,以0.05 mm的厚度均匀地界面微溶嵌入在准备好的碳纤维丝束上,而后自然风干12 h时间,得到具有皮芯结构的聚氨酯/碳纤维;使用缠绕机将上述得到的聚氨酯/碳纤维以100 捻/m的公制捻度缠绕在聚氨酯弹力线表面,得到TPU基柔性传感器;最后将该TPU基柔性传感器进行针织双罗纹设计,即得到智能传感织物。
实施例3
准备直径为1.5 mm的聚氨酯弹力线;取质量分数为40 %的聚氨酯分散液,加水稀释,在30 ℃温度下搅拌1 min,得到搅拌均匀的质量分数为35 %的聚氨酯分散液;准备24 K的碳纤维丝束;将上述得到的聚氨酯分散液,以0.25 mm的厚度均匀地界面微溶嵌入在准备好的碳纤维丝束上,而后自然风干20 h时间,得到具有皮芯结构的聚氨酯/碳纤维;使用缠绕机将上述得到的聚氨酯/碳纤维以200 捻/m的公制捻度缠绕在聚氨酯弹力线表面,得到TPU基柔性传感器;最后将该TPU基柔性传感器进行机织平纹设计,即得到智能传感织物。
实施例4
准备直径为0.6 mm的聚氨酯弹力线;取质量分数为40 %的聚氨酯分散液,加水稀释,在28 ℃温度下搅拌2 min,得到搅拌均匀的质量分数为10 %的聚氨酯分散液;准备12 K的碳纤维丝束;将上述得到的聚氨酯分散液,以0.15 mm的厚度均匀地界面微溶嵌入在准备好的碳纤维丝束上,而后自然风干18 h时间,得到具有皮芯结构的聚氨酯/碳纤维;使用缠绕机将上述得到的聚氨酯/碳纤维以80 捻/m的公制捻度缠绕在聚氨酯弹力线表面,得到TPU基柔性传感器;最后将该TPU基柔性传感器进行针织罗纹设计,即得到智能传感织物。
实施例5
准备直径为1.0 mm的聚氨酯弹力线;取质量分数为40 %的聚氨酯分散液,加水稀释,在27 ℃温度下搅拌4 min,得到搅拌均匀的质量分数为1 %的聚氨酯分散液;准备3 K的碳纤维丝束;将上述得到的聚氨酯分散液,以0.2 mm的厚度均匀地界面微溶嵌入在准备好的碳纤维丝束上,而后自然风干16 h时间,得到具有皮芯结构的聚氨酯/碳纤维;使用缠绕机将上述得到的聚氨酯/碳纤维以160 捻/m的公制捻度缠绕在聚氨酯弹力线表面,得到TPU基柔性传感器;最后将该TPU基柔性传感器进行缝纫编织,即得到智能传感织物。
对本发明所获得的TPU基柔性传感器使用万能试验机(Instron 5943, aDivision of Illinois Tool Works Inc)测试复合材料的机械性能;使用多功能数字电表(Agilent Truevolt 34461A DMM)测试复合材料的传感性能,其结果如下:
(1)将样品置于特殊环境中(温度:25℃;湿度:50%)24小时,以消除环境温湿度对材料机械性能的影响。对长度为5 cm的样品进行了拉伸测试,恒定拉伸速率为40 mm/min,两个夹头之间的初始距离为10 mm。万能试验机测得拉伸应力>5Mpa,拉伸应变>100%,表明该传感器材料具有优异的可拉伸性,是由于缠绕螺旋复合结构使其兼具聚氨酯弹力线的优异形变性和碳纤维的高强度。
(2)以80 mm/min的速率对TPU基柔性传感器进行了1500个拉伸释放周期(从0到10%)的测试。通过可逆的螺旋结构,该材料可以连续输出稳定的电信号。多功能数字电表测得的(R-R0)/R0信号非常有规律且保持一致,使得TPU基柔性传感器作为应变信号监测的柔性传感器具有良好的动态稳定性和重复性。
(3)在温度为25℃,湿度为50%的实验环境下,将柔性传感器连接到电路中,通过多功能数字电表测量电阻的变化,测试传感性能。可以发现,材料输出的电子信号是稳定的,在监测大、小变形时都可以很好地恢复到原始值,具有较高的灵敏度(GF = 76.2),且与应变有一定的线性关系。上述结果证明,该材料是一种理想的柔性传感器材料,既能监测关节运动等大变形,也能监测微小变形,具有良好的灵活性和稳定的信号捕获能力,非常适合实时监测人体运动、脉搏等个性化生理信号。
本发明制备的柔性传感器材料具有优异的电导率、可控的机械性能以及灵敏的信号捕获能力,在人体健康监测、智能预警、危险求救、人机交互、可穿戴电子设备和柔性电子皮肤等方面有广阔的应用前景。
对实施例1制备的TPU基柔性传感器进行结构设计,得到如附图1的TPU基柔性传感器的简易实物图,并且可根据不同的使用情况进行编织密度和编织方式的修改。对实施例1制备的TPU基柔性传感器进行压力传感性能测试,如附图2的压力传感测试图,(I-I0)/I0与压力在0-4 kPa之间呈理想的线性关系,灵敏度达到8.59% / kPa,这对压力信号的捕获非常有利;随后对其进行脉搏和人体运动传感性能测试,得到如附图3的脉搏传感测试图和附图4的膝盖传感测试图,脉搏处的(R-R0)/R0>30%,膝盖处的(R-R0)/R0>120%,结果表明,材料输出的信号十分稳定,在监测脉搏及膝盖运动等大小变形时都可以很好的恢复到原始值,对微弱信号及高强信号兼具极佳的响应。
作为一种柔性应变传感器,高灵敏度和大应变范围是至关重要的。Zhang等人在期刊Chemical Engineering Journal上发表的《Reconstructed silk fibroin mediatedsmart wristband for physiological signal detection》文章(Chem. Eng. J. 428(2022) 132362)报道了一种根据SF的重构,用丝材料制作的具有微阵列结构的高灵敏度柔性压力传感器,在0 Pa至1500 Pa的压力下表现出0.48 kPa-1的灵敏度。Xia等人在期刊Chemical Engineering Journal上发表的《Carbon nanotubes reinforced hydrogel asflexible strain sensor with high stretchability and mechanically toughness》文章(Chem. Eng. J. 382 (2020) 122832)设计并制备了一种 PAAm-oxCNTs 水凝胶,该水凝胶具有令人满意的应变敏感性(在250%-700%,应变GF= 3.39 )。Gu等人在期刊ACS AppliedMaterials & Interfaces上发表的《Multifunctional poly(vinyl alcohol)nanocomposite organohydrogel for flexible strain and temperature sensor》文章(ACS Appl. Mater. Interfaces 12 (2020) 40815-40827)制备了具有 3D 蜂窝结构的导电有机水凝胶应变传感器,不仅具有GF = 2.01的高灵敏度,而且具有0-700%的宽传感范围。
综合上述文献调研,将GF与其他技术进行比较,我们的TPU基柔性传感器具有较高的灵敏度(GF = 76.2,应变>15%),优异的应变范围>100%,其中灵敏度是上述现有技术的22-159倍(如表1所示),更易捕获人体运动等个性化生理信号,更有利于柔性纺织传感器作为可穿戴电子器件的构建。
表1 柔性传感器GF对比
本发明制得的柔性传感器作为可实时监测压力、脉搏和运动等多重人体信号的智能传感织物,具有优异的柔性和透气性,还拥有稳定的导电性能、可控的机械性能,以及压力、脉搏等人体生理信号的感知能力,在当前人体健康监测、智能预警、危险求救、可穿戴设备和柔性电子皮肤等领域具有广阔的应用前景。
以上所述仅是对本发明的优选实施例及原理进行了详细说明,对本领域的普通技术人员而言,依据本发明提供的技术构思,在具体实施方式上会有改变之处,而这些改变也应视为本发明的保护范围。
Claims (10)
1.一种柔性智能传感器织物,其特征在于,包括:
弹力纤维、缠绕在所述弹力纤维表面的导电纤维以及界面微溶嵌入于所述导电纤维表面的防水绝缘层涂料。
2.根据权利要求1所述的一种柔性智能传感器织物,其特征在于:所述防水绝缘层涂料为聚氨酯防水涂料分散液或聚合物水泥基防水涂料分散液。
3.根据权利要求1所述的一种柔性智能传感器织物,其特征在于:所述导电纤维为碳纤维丝束、金属纤维铜线、银线或有机高分子导电纤维。
4.根据权利要求1所述的一种柔性智能传感器织物,其特征在于:所述弹力纤维为聚氨酯弹性纤维、聚醚酯弹性纤维、二烯类弹性纤维或聚氨酯弹力线。
5.一种柔性智能传感器织物的制备方法,其特征在于,包括以下步骤:
(1) 配制防水涂料分散液;
(2) 将步骤(1)制得的涂料分散液,界面微溶嵌入在导电纤维上,得到涂料导电纤维;
(3) 使用步骤(2)得到的涂料导电纤维缠绕在弹力纤维表面,得到柔性传感器;
(4) 将步骤(3)得到的柔性传感器进行经纬编织,得到智能传感器织物。
6.根据权利要求5所述的一种柔性智能传感器织物的制备方法,其特征在于:所述步骤(1)涂料分散液质量分数为1-40 %,步骤(3)中涂料导电纤维以60 -200捻/m的公制捻度缠绕在弹力纤维表面。
7.根据权利要求5所述的一种柔性智能传感器织物的制备方法,其特征在于:所述步骤(2)中界面微溶嵌入厚度为0.05-0.25 mm。
8.根据权利要求5所述的一种柔性智能传感器织物的制备方法,其特征在于:所述步骤(4)中编织为机织、针织、缝纫中的一种。
9.根据权利要求1所述的一种柔性智能传感器织物的应用,其特征在于:所述智能传感器织物应用于多重外界信号或生理信号的实时监测。
10.根据权利要求9所述的一种柔性智能传感器织物的应用,其特征在于:所述多重外界信号包括压力、温度;所述生理信号的实时监测包括脉搏、呼吸、人体各部位运动。
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