纺织学报 ›› 2024, Vol. 45 ›› Issue (02): 52-58.doi: 10.13475/j.fzxb.20231004801

• 纺织工程 • 上一篇    下一篇

导电微纳纤维复合纱的制备及其气敏特性

周歆如1, 范梦晶1, 岳欣琰1, 洪剑寒1,2(), 韩潇1,2   

  1. 1.绍兴文理学院 纺织服装学院, 浙江 绍兴 312000
    2.浙江省清洁染整技术研究重点实验室, 浙江 绍兴 312000
  • 收稿日期:2023-10-16 修回日期:2023-12-04 出版日期:2024-02-15 发布日期:2024-03-29
  • 通讯作者: 洪剑寒(1982—),男,教授,博士。主要研究方向为新型纺织材料的制备与应用。E-mail:jhhong@usx.edu.cn
  • 作者简介:周歆如(1998—),女,硕士生。主要研究方向为功能纳米纤维材料的开发与应用。
  • 基金资助:
    浙江省自然科学基金探索公益项目(LTGY24E030001)

Preparation of conductive micro-nano fiber composite yarns and their gas-sensitive properties

ZHOU Xinru1, FAN Mengjing1, YUE Xinyan1, HONG Jianhan1,2(), HAN Xiao1,2   

  1. 1. School of Textile and Apparel, Shaoxing University, Shaoxing, Zhejiang 312000, China
    2. Key Laboratory of Clean Dyeing and Finishing Technology of Zhejiang Province, Shaoxing, Zhejiang 312000, China
  • Received:2023-10-16 Revised:2023-12-04 Published:2024-02-15 Online:2024-03-29

摘要:

为开发高质量的气敏传感器,利用水浴静电纺丝法制备以涤纶(PET)为芯纱,聚酰胺6(PA6)纳米纤维为包覆层的微纳纤维复合纱(MNY),基于原位聚合方法对MNY进行连续导电处理,制备微纳米纤维复合纱/聚苯胺(MNY/PANI)复合导电纱,以此作为气敏元件,同时将相同参数下制备的PET/PANI复合导电纱也作为气敏元件进行对照,探究不同结构纱线之间气敏效果的差异。研究结果表明:MNY具备良好的皮芯结构,经导电处理后MNY表面均匀分布了聚苯胺颗粒,MNY/PANI的电导率最高可达7.53 S/cm;相比于PET/PANI气敏元件,MNY/PANI气敏元件因其纳米结构的高比表面积对NH3的灵敏度更高,能表现出更好的响应-恢复效果,重复性和稳定性更好,已初步具备了作为优良气敏元件的条件。

关键词: 静电纺丝, 微纳纤维复合纱, 原位聚合, 气敏传感, 氨气检测, 纤维基气敏传感器

Abstract:

Objective As the key component for gas sensors, the development of gas-sensitive material has attracted much research attention. At present, research on gas-sensitive materials focused mainly on membrane structures, which has poor flexibility and reprocessability. Therefore, in order to meet different needs and expand the applications, this study proposes a one-dimensional structure gas sensor with better flexibility, deformation ability and textile processability.

Method Water bath electrospinning method was used to make the polyamide 6 (PA6) spinning solution with a mass fraction of 12% and 24 kV electrostatic voltage, among other experimental parameters. The micro-nano fiber composite yarn (MNY) with polyester (PET) as the core yarn and PA6 nanofiber as the coating layer was prepared, and the MNY/PANI composite conductive yarn was prepared by a continuous conductive treatment method based on in-situ polymerization. The effect of different reaction liquid concentration on the structure and performance of MNY were studied, and the optimal reaction liquid concentration was achieved for preparing MNY/PANI gas sensing elements. Compared with PET/PANI gas sensing elements under the same parameters, the difference in gas sensitivity effect between yarns with different structures was explored.

Results After studying the surface morphology of MNY and MNY/PANI, materials conductivity, infrared spectrum and gas sensitivity, analysis was carried out. The nanofibers on the surface of MNY were relatively complete, forming a good skin-core structure, and the nanofibers were smooth and orderly. The surface of the conductive-treated MNY/PANI composite conductive yarn was found to adsorb a large number of particles, and the density of adsorbed particles on the yarn surface increased as the concentration of reaction liquid was increased. With the increase of the concentration of reaction liquid, the conductivity of MNY/PANI composite conductive yarn increased first and then decreased, and the conductivity of MNY/PANI-3 reached the maximum value of 7.53 S/cm. The infrared spectra of PET, MNY and MNY/PANI-3 composite conductive yarns were tested and compared. Compared with PET without any treatment, the characteristic peaks of MNY prepared by electrostatic spinning technology appeared at 3 304, 1 672, 1 542 and 1 170 cm-1. This indicated that the surface of MNY after electrostatic spinning was attached with amide group. In addition, MNY/PANI-3 also showed characteristic peaks around 1 611, 1 361 and 810 cm-1, indicating that PANI/MNY-3 composite conductive yarn contained PANI. By comparing the response test of MNY/PANI-3 and PET/PANI composite conductive yarns prepared under the same reaction concentration parameter in NH3 atmosphere, it was found that both reached the maximum sensitivity in the first test, which was 2.70 and 4.62 respectively, and then gradually weakened and eventually plateaued with the increase of the number of cycles. However, the sensitivity of MNY/PANI was consistently better than that of PET/PANI. The difference was that the response curve of PET/PANI had more fluctuations, while the response curve of MNY/PANI was smooth. In addition, with the increase of the number of tests, the response effect of MNY/PANI was better than that of PET/PANI, and the recovery time of MNY/PANI increased with the increase of the number of test cycles, but it was still much smaller than that of PET/PANI.

Conclusion After NH3 detachment, the resistance value of PET/PANI in the air was much different from the initial resistance value, indicating that its reversibility is poor. After repeated testing of MNY/PANI, resistance of gas sensing elements in air could get better recovery, good reversibility and relatively small change in sensitivity. MNY/PANI gas sensor has higher sensitivity to NH3 due to the high specific surface area of its nanostructure, which is due to the uniform distribution of small PANI particles adsorbed by the nanolayer. Therefore, it can show better response-recovery effect, better repeatability and stability, and has initially possessed the conditions as an excellent gas sensor, indicating the feasibility of one-dimensional structure gas sensor.

Key words: electrospinning, micro-nano fiber composite yarn, in-situ polymerization, gas sensing, NH3 detection, fiber based gas-sensitive sensor

中图分类号: 

  • TS195.5

图1

自制多针头连续水浴静电纺丝设备示意图以及针头排列方式 1—电动机;2—旋转支架;3—芯纱筒子;4—高压电源;5—注射喷头;6—水浴接收盘;7—接地铜片;8—干燥装置; 9—电动机;10—旋转支架;11—卷绕辊;12—电动机;13—横移装置;14—电动机。"

图2

MNY/PANI复合导电纱的制备示意图 1—纱筒;2—储纱轮;3—浸渍槽;4—压辊;5—储纱轮; 6—雾化喷枪;7—压辊;8—水槽;9—牵引辊;10—接收盘。"

表1

不同反应液浓度对应的样品名称"

样品名称 An浓度 HCl浓度 APS浓度
MNY/PANI-1 0.5 0.5 0.1
MNY/PANI-2 1.0 1.0 0.2
MNY/PANI-3 1.5 1.5 0.3
MNY/PANI-4 2.0 2.0 0.4

图3

MNY/PANI复合导电纱的实物图 注:图中试样从左至右依次为MNY、MNY/PANI-1、MNY/PANI-2、MNY/PANI-3、MNY/PANI-4。"

图4

气敏传感元件"

图5

MNY及不同反应液浓度下复合导电纱的形貌照片"

图6

MNY和MNY/PANI-3的红外光谱图"

图7

2种气敏传感元件对NH3的传感性能"

表2

PET/PANI和MNY/PANI气敏传感元件在759 mg/m3的NH3中的传感性能"

循环
次数
PET/PANI MNY/PANI
响应
时间/s
恢复
时间/s
灵敏
响应
时间/s
恢复
时间/s
灵敏
1 82.5 115.3 2.70 73.9 58.1 4.62
2 87.8 174.6 1.77 82.0 52.5 3.82
3 75.4 135.1 1.37 64.3 70.2 3.31
4 74.3 140.8 1.36 77.1 76.7 2.73
5 73.4 178.9 1.40 57.1 66.6 2.56
6 97.6 115.9 1.22 48.5 67.1 2.13

图8

PET/PANI复合导电纱的表面形貌"

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