纺织学报 ›› 2023, Vol. 44 ›› Issue (09): 223-231.doi: 10.13475/j.fzxb.20220401302

• 综合述评 • 上一篇    下一篇

石墨烯改性蚕丝的制备方法及其应用研究进展

何铠君1, 沈加加2(), 刘国金3   

  1. 1.嘉兴南湖学院 新材料工程学院, 浙江 嘉兴 314001
    2.嘉兴学院 材料与纺织工程学院, 浙江 嘉兴 314001
    3.浙江理工大学 浙江省纤维材料和加工技术研究重点实验室, 浙江 杭州 310018
  • 收稿日期:2022-04-02 修回日期:2022-11-09 出版日期:2023-09-15 发布日期:2023-10-30
  • 通讯作者: 沈加加(1981—),男, 教授,博士。主要研究方向为纳米功能材料。E-mail:jjshen@zjxu.edu.cn。
  • 作者简介:何铠君(1989—),男,讲师,硕士。主要研究方向为生物基功能材料。
  • 基金资助:
    国家自然科学基金项目(52003242);浙江省基础公益研究计划项目(LGG20F020019);嘉兴市产教融合“五个一批”项目(002072101);嘉兴南湖学院科研重点项目(62216ZL)

Progress in preparation and application of graphene modified silk

HE Kaijun1, SHEN Jiajia2(), LIU Guojin3   

  1. 1. School of Advanced Materials Engineering, Jiaxing Nanhu University, Jiaxing, Zhejiang 314001, China
    2. College of Materials and Textile Engineering, Jiaxing University, Jiaxing, Zhejiang 314001, China
    3. Zhejiang Provincial Key Laboratory of Fiber Materials and Manufacturing Technology, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
  • Received:2022-04-02 Revised:2022-11-09 Published:2023-09-15 Online:2023-10-30

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摘要：

为优化蚕丝纤维和石墨烯材料的相互结合作用并进一步增强和丰富蚕丝纤维的性能和用途,扩大其在纺织及生物医疗柔性可穿戴领域的应用,详细介绍了石墨烯及其衍生物材料通过内在改性法和外在改性法制备蚕丝材料的方法及应用,并对比分析了各种方法的优缺点,简要介绍了改性蚕丝材料中氧化石墨烯化学还原法和高温还原法的特点。阐述了在力学性能、导电性能、抗紫外线性能、抗菌性能、防污/防水性能等方面,石墨烯改性蚕丝的工作机制及研究进展。综述了石墨烯改性蚕丝材料的性能及其在智能传感器纺织品领域的应用现状,最后展望了石墨烯改性蚕丝材料的研究及发展方向,以期拓宽其应用。

关键词: 蚕丝, 石墨烯材料, 功能化, 改性蚕丝材料, 柔性可穿戴

Abstract:

Significance Fibers and fabrics are the main components of conventional wearable products because of its good flexibility, air permeability and mechanical properties. However, with the rapid development of science and technology and the improvement of people's living standards, the future textiles need to retain the advantages of conventional fibers and fabrics while providing them multi-functional and intelligent characteristics. Compared with other man-made chemical polymer materials, natural biomaterials have the advantages of being environmentally friendly, biodegradable, and sustainable among many others. Natural silk from silkworms has been used in clothing for thousands of years and can be continuously obtained and used in large quantities. Silk is a natural protein fiber with excellent mechanical properties, good flexibility, biocompatibility and biodegradability. Two-dimensional nano-graphene and its derivative materials with excellent thermal conductivity, biocompatibility and mechanical properties were synergistically combined with silk. By optimizing the interaction between silk and graphene materials, the properties and functions of silk can be further enhanced and enriched, and its applications in the field of textile and biomedical flexible wearables can be expanded. This paper reviews the latest research progress in graphene modified silk materials to identify research gaps for research.

Progress Because of the unique natural layered structure of silk and the excellent functionality of graphene material, graphene modified silk materials have been widely favored in the field of intelligent textiles. This paper firstly introduced the preparation methods of graphene modified silk. While retaining the natural structure and properties of silk, it can also endow silk with new functions. There are mainly two methods for attaching graphene and its derivatives uniformly and stably on silk, that is, internal modification and external modification. The internal modification mainly refers to the in vivo uptake of graphene materials by silkworms during their growth, including feeding method and in vivo injection method, and the external modification, also known as surface finishing method, includes dip-rolling coating method, dip coating method, spraying method, dry coating method and layer self-assembly method. The preparation methods of graphene modified silk materials were compared (Tab. 1), and the improvement of silk properties by graphene materials, including mechanical properties, electrical conductivity and multi-functional wearability, was reviewed. In addition, the applications of graphene modified silk in sensors, including respiratory sensor, gas sensor and infrared sensor, were scrutinized and summarized. It is believed that silk materials have great potential in multi-functional and intelligent textiles.

Conclusion and Prospect Graphene modified silk materials have laid a foundation for the development of flexible electronic wearable field in the fields of mechanical properties, electrical conductivity and biological adaptability. However, the low loading of graphene and the weak interfacial bonding force on silk are still yet satisfy the special required functions in some respects, which is the key and difficult point to be solved. The interfacial forces between graphene materials and silk, such as hydrogen bond, Van Der Waals force, and covalent bond, determine the loading capacity and durability of graphene on silk, and then affect the performance of modified silk. The reviewed researches include the assembly method of graphene on silk, the reduction method of graphene oxide, the pH value of solution, the screening of additives and other processes to obtain graphene modified silk materials with stable structure, excellent performance and complete functions. The preparation method of graphene functionalized silk with low cost, high efficiency and environment friendliness, the interface bonding force and working mechanism between graphene materials and silk, and the changes of secondary structure of modified silk are the main perspectives that has drawn research attention, which also determine the application of graphene modified silk materials in various fields. Researches also shows that single functionalization does not satisfy the application of silk in textile and biomedicine, hence it becomes imperative to develop multi-functionalization of graphene silk materials. For example, it is necessary to build a ternary or multivariate functional modification system, introduce environmentally friendly cross-linking additives, biomolecules and other modified materials with different sizes and functions in the process of modification of silk with graphene, increase the load of graphene on modified silk materials and endow it with multi-function, so as to expand its application in the textile and biomedical fields.

Key words: silk, graphene material, modification, graphene modified silk, flexible and wearable

中图分类号: 

  • TS195.5

表1

石墨烯改性蚕丝方法的比较"

方法 优点 缺点
体内注射法 步骤简单,摄入量可控,牢度高,持久性强 操作较难,对家蚕生长有影响,大规模生产难,摄入量低
添食法 简便,持久,低价高效且生态环保,可大批量生产 转化率低且不可控,对家蚕生长有一定影响,摄入量低
浸轧涂层法 方法简便易操作,负载量大 耗材量大,均匀性难把握,与织物结合强度差
浸渍涂层法 方法简便易操作,多次操作可实现高负载量 需整理液多,时间长影响生产效率,牢度差
喷涂法 成本低,操作简单,无组织结构要求,图案可控制 弹性差,均匀性和持久性较差
干法涂层法 表面吸附量高,厚度可调节 透气率差,耐水洗和持久性较弱,手感较差
层层自组装法 表面吸附量高,厚度可控 循环次数多,时间长影响生产效率,手感较差
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