纺织学报 ›› 2023, Vol. 44 ›› Issue (09): 232-242.doi: 10.13475/j.fzxb.20220708302

• 综合述评 • 上一篇    下一篇

增强纤维用上浆剂的耐高温化改性研究进展

钱晨1,2, 黄博翔1, 李永强2, 万军民2, 傅雅琴1()   

  1. 1.浙江理工大学 材料科学与工程学院, 浙江 杭州 310018
    2.浙江理工大学桐乡研究院, 浙江 桐乡 314500
  • 收稿日期:2022-07-22 修回日期:2023-02-23 出版日期:2023-09-15 发布日期:2023-10-30
  • 通讯作者: 傅雅琴(1965—),女,教授,博士。主要研究方向为纺织复合材料及其复合技术。E-mail:fyq01@zstu.edu.cn。
  • 作者简介:钱晨(1992—),男,讲师,博士。主要研究方向为功能高分子及其复合材料。
  • 基金资助:
    国家自然科学基金项目(52103150);高等学校学科创新引智计划资助项目(D21011)

Research progress on high temperature resistant modified reinforcing fiber sizing agents

QIAN Chen1,2, HUANG Boxiang1, LI Yongqiang2, WAN Junmin2, FU Yaqin1()   

  1. 1. School of Materials Science and Engineering, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
    2. Zhejiang Sci-Tech University Tongxiang Research Institute, Tongxiang, Zhejiang 314500, China
  • Received:2022-07-22 Revised:2023-02-23 Published:2023-09-15 Online:2023-10-30

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摘要：

在高性能热塑性树脂基复合材料的开发与前沿应用中,常规的纤维上浆剂存在耐高温性能不足的问题,因此,耐高温型增强纤维上浆剂的开发与研究引起了广泛关注。基于纤维上浆剂的配方组成,介绍了近年来增强纤维用上浆剂的耐高温化改性研究进展。重点综述了耐高温型上浆剂体系中浆料树脂(成膜剂)的选择与优化方法,探讨了无机纳米杂化对上浆剂耐热性能提升及复合材料界面性能的改善效果,并分析了偶联剂在耐高温型上浆剂体系中的作用与性能。基于产业化应用的考虑,最后指出:深入分子结构设计,开发绿色环保的耐高温型上浆剂将是未来研究的重点;考虑各类纤维及树脂基体的结构性能差别,有针对性地开发耐高温型上浆体系极为必要。

关键词: 纤维上浆剂, 复合材料, 热塑性树脂, 界面强度, 热稳定性

Abstract:

Significance Fiber sizing agent is one of the core technologies in the production of reinforcing fiber (carbon fiber, aramid fiber, glass fiber, etc.) and its composites. The sizing agent coated on the surface of reinforcing fibers facilitates the bundling of filaments, remedies the surface defects of the fibers, and improves the processing property of corresponding fabrics. Moreover, the sizing agent promotes the infiltration and tight binding of the matrix resin on the fibers through physical and chemical effects such as increased compatibility in similar structure, induced crystallization, and crosslinking/reaction. Nevertheless, the stability of the general fiber sizing agents at high temperatures is insufficient to meet the needs for the development and advanced applications of high-performance thermoplastic resin-based composites. Therefore, the development of fiber sizing agents with high temperature resistance has attracted extensive attention. Based on the basic composition of sizing agents, this review reports research and development progress in fiber sizing agents with high temperature resistance, which focuses on the selection and modification of film former of the sizing agents and introduces the effect of the inorganic hybridization on the heat resistance of sizing agents and interfacial properties of composites. The importance and property of coupling agents in the formulations are also discussed.

Progress Fiber sizing agent is a mixed liquor composed of a variety of functional components, including film former, coupling agent, lubricant, antifoaming agent, antistatic agent, pH regulator, and other functional additives. Film former accounts for 70%-90% of the total solid mass of sizing agent which directly affects the wetting ability and compatibility of fiber in resin matrix. To meet both requirements of high temperature resistance and compatibility with the matrix, most research focuses on the development of novel film former based on polyimide and polyarylether, which show high thermal stability and the same or similar chemical structure with the high-performance thermoplastic matrix in composites. However, these sizing agents still have defects in applications, for example, the use of organic solvent, which causes health and environmental risk. Hybrid modification by nano-silica, carbon nanotubes, graphene, and other nanocomponents has become another common strategy to improve the thermal stability and properties of fiber sizing agents. In the high temperature resistant fiber sizing agent system, the nanocomponents show a significant effect on improving the heat resistance and functionalizing the interface of composite. The introduction of nanocomponents inhibits the thermal decomposition of film former and increases the surface roughness of fibers, resulting in improved interface bonding between reinforcing fibers and matrix. Moreover, in consideration of the necessity of adding a coupling agent in the sizing agent for glass fiber and basalt fiber, the thermal decomposition temperature of various silane coupling agents has been systematically studied and summarized with their chemical structure. Despite the complex chemical process, the macromolecular coupling agent that contains both high temperature resistant imide groups and functional siloxane groups holds great potential for the applications of high temperature and high performance.

Conclusion and Prospect The future development of high temperature resistant fiber sizing agents is expected. In view of practical applications, there are still great challenges for novel fiber sizing agents in industrial production, and future breakthroughs are still needed. First of all, an in-depth study on the green synthesis of novel water-soluble/water dispersible film former with high thermal stability is required. The green and environmentally friendly sizing agent with no organic solvent use and satisfactory property will be highly desired in applications. Secondly, it is necessary to develop corresponding high temperature resistant sizing agents that are suitable for each kind of reinforced fiber. Finally, a systematic study is needed to reveal the complex effects of the addition of other functional additives on the stability and properties of the sizing agent in future research.

Key words: fiber sizing agent, composite, thermoplastic, interfacial strength, thermal stability

中图分类号: 

  • TB332

图1

SA-PI涂层改性的CF与PEEK的界面结构示意图"

图2

HPAEK合成路线与化学结构示意图"

表1

部分硅烷偶联剂的化学结构及其25%质量的热分解温度(Td25)"

硅烷偶联剂的化学结构 Td25/℃
ClCH2CH2CH2Si(OCH3)3 360
H2HCH2CH2NHCH2CH2CH2Si(OCH3)3 390
395
435
460
485
495
510
530
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