纺织学报 ›› 2024, Vol. 45 ›› Issue (05): 35-42.doi: 10.13475/j.fzxb.20221105701

• 纤维材料 • 上一篇    下一篇

包载型聚丙烯腈/SiO2气凝胶复合纳米纤维制备及其隔热性能

王新庆1, 季东圣1, 李舒畅1, 杨晨1, 张宗宇1, 刘实诚2, 王航1,3(), 田明伟1,4   

  1. 1.青岛大学 纺织服装学院, 山东 青岛 266071
    2.江苏百护纺织科技有限公司, 江苏 宿迁 223800
    3.青岛大学 山东省特型非织造材料工程研究中心, 山东 青岛 266071
    4.青岛大学 智能可穿戴技术研究中心, 山东 青岛 266071
  • 收稿日期:2022-11-21 修回日期:2023-09-07 出版日期:2024-05-15 发布日期:2024-05-31
  • 通讯作者: 王航(1990—),男,副教授,博士。主要研究方向为功能纳米纤维与智能纺织品。E-mail: wanghang@qdu.edu.cn。
  • 作者简介:王新庆(2002—),男。主要研究方向为功能纳米纤维与非织造材料。
  • 基金资助:
    国家自然科学基金项目(22208178);山东省科技型中小企业创新能力提升工程项目(2023TSGC0344);山东省青创科技创新团队项目(2023KJ223);青岛市关键技术攻关及产业化示范类项目(23-1-7-zdfn-2-hz);宿迁市重点研发计划(H202310);泰山学者工程专项经费支持项目(tsqn202211116)

Preparation and thermal insulation properties of encapsulated polyacrylonitrile/SiO2 aerogel composite nanofibers

WANG Xinqing1, JI Dongsheng1, LI Shuchang1, YANG Chen1, ZHANG Zongyu1, LIU Shicheng2, WANG Hang1,3(), TIAN Mingwei1,4   

  1. 1. College of Textiles & Clothing, Qingdao University, Qingdao, Shandong 266071, China
    2. Jiangsu Baihoo Textiles Technology Co., Ltd., Suqian, Jiangsu 223800, China
    3. Shandong Province Special Nonwoven Materials Engineering Research Center, Qingdao University, Qingdao, Shandong 266071, China
    4. Smart Wearable Technology Research Center, Qingdao University, Qingdao, Shandong 266071, China
  • Received:2022-11-21 Revised:2023-09-07 Published:2024-05-15 Online:2024-05-31

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摘要：

针对传统气凝胶纤维后处理操作复杂、加工不稳定等问题,且为有效集成纳米气凝胶与纳米纤维功能和结构优势,本文围绕新型气凝胶复合纳米纤维成形与结构调控的关键难题,利用溶液喷射同轴纺丝技术将聚丙烯腈(PAN)与SiO2气凝胶通过一步法制备PAN/SiO2气凝胶复合纳米纤维,研究了复合纳米纤维中SiO2气凝胶质量浓度对纤维形态结构、稳定性、孔径分布、隔热性能的影响。结果表明:所制备的PAN/SiO2气凝胶复合纳米纤维形态结构上呈三维卷曲状,SiO2气凝胶的引入使纤维表面形成多孔褶皱型结构,且纤维表面的微孔、介孔含量随SiO2气凝胶质量浓度的增加逐渐增多;该气凝胶复合纳米纤维具有优异的隔热性能,当SiO2气凝胶质量浓度为6 mg/mL时,PAN/SiO2气凝胶复合纳米纤维在40 ℃的导热系数低至0.037 38 W/(m·K),未来在服用保暖、工业隔热、军用热红外屏蔽等方面具有广阔的应用前景。

关键词: 聚丙烯腈, 纳米纤维, 溶液喷射同轴纺丝技术, 气凝胶复合纤维, SiO2气凝胶, 隔热材料

Abstract:

Objective Aerogel is a novel class of three-dimensional network solid materials, which are porous, high in thermal resistance, and low in volume density, and can be prepared by sol-gel method under the action of gaseous dispersion medium. Aerogels therefore have enormous application potential in the area of thermal insulators, energy conservation because they can effectively delay and block heat flow and reduce heat loss. However, low mechanical strength, high brittleness and easy breakage would hinder the actual aerogel applications. One-step forming of aerogel composite fiber can be achieved by using polymer solution and aerogel powder, and the synergistic improvement of thermal insulation/warmth retention performance can be further achieved by regulating the microstructure of monomer fiber and the macro structure of fiber assembly. However, there are few reports on this aspect.

Method In order to effectively integrate the functional and structural advantages of nano-aerogel and nanofiber, a new production technology was designed and developed to prepare polyacrylonitrile (PAN)/SiO2 aerogel composite nanofibers by one-step method using coaxially solution blowing process. In spinning process, the SiO2 aerogel and the PAN were served as core layer and skin layer respectively, at the speed of 2 mL/h and 12 mL/h. The influences of SiO2 aerogel content in composite fibers on fiber morphology, structure, stability, mechanical properties, and thermal insulation properties were specifically studied.

Results The PAN/SiO2 aerogel composite nanofibers prepared by coaxially solution blown spinning were continuous, uniform and loosely arranged, and the fiber diameter was distributed primarily in the range of 100-400 nm. Furthermore, three-dimensional crimps were shown in morphology and structure due to the disordered shearing effect of high-speed airflow during the fiber forming process. The introduction of SiO2 aerogel significantly affected the surface morphology of the fibers, forming a porous fold structure. PAN/SiO2 aerogel composite nanofibers were heated up in an oven at 180 ℃ for 240 min to evaluate their thermal stability. After heating, the fibers still retained their porous fold structure, showing good thermal stability. Moreover, the contents of micropores and mesoporous pores on the fiber surface were gradually increased with the increase of SiO2 aerogel content. The obtained PAN/SiO2 aerogel composite nanofibers demonstrated excellent thermal insulation, and the thermal conductivity of the sample with SiO2 aerogel mass concentration of 6 mg/mL was as low as 0.037 38 W/(m·K) at 40 ℃. Under the condition of 50 ℃, the surface temperature of the fiber tested by thermal infrared was 32.5 ℃, and under the condition of 65 ℃, the surface temperature of the fiber tested by thermal infrared was 37.5 ℃. In addition, the weighed PAN/SiO2 aerogel composite nanofibers had a low gram weight (about 70 g/m2), and felt soft and fluffy. Owing to its excellent thermal insulation and convenient and stable production process, PAN/SiO2 aerogel composite nanofibers indicate a broad future market in aspects of thermal insulation, field survival and industrial thermal insulation.

Conclusion This paper reported a new route of macro quantization preparation of aerogel composite nanofibers by "one-step method". Specifically, PAN/SiO2 aerogel composite nanofibers were prepared by solution blowing coaxial spinning technology using PAN and SiO2 aerogel particles. In conclusion, the prepared solution blown aerogel fiber has the advantages of low weight and flexible manufacture process, and the spinning efficiency can reach 8-12 times that of electrospinning. It can play a broad application prospect in the aspects of thermal insulation, industrial thermal insulation, and military thermal infrared shielding. In the future, an important development direction of aerogel fibers and their products is to utilize simple fiber processing technology to realize one-step integrated processing.

Key words: polyacrylonitrile, nanofiber, coaxially solution blowing process, aerogel composite fiber, SiO2 aerogel, thermal insulation material

中图分类号: 

  • TQ342.3

图1

纺丝流程示意图"

图2

包载型PAN/SiO2气凝胶纳米纤维宏观集合体及表面微观结构"

图3

包载型PAN/SiO2气凝胶纳米纤维截面微观结构"

图4

高温加热后包载型PAN/SiO2气凝胶纳米纤维表面微观结构"

图5

包载型PAN/SiO2气凝胶纳米纤维和PAN纳米纤维孔径分布曲线 注:V表示孔体积;D表示孔径。"

表1

包载型气凝胶纤维导热系数"

样品编号 测试温度/℃ 导热系数/(W·m-1·K-1)
PAN/SiO2-1 40 0.042 72
80 0.046 37
PAN/SiO2-2 40 0.040 06
80 0.044 72
PAN/SiO2-3 40 0.037 38
80 0.039 15
PAN 40 0.055 49
80 0.059 74

图6

不同温度下PAN/SiO2-3与普通无胶棉样品表面的热红外成像图"

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