物理化学学报 >> 2022, Vol. 38 >> Issue (9): 2204059.doi: 10.3866/PKU.WHXB202204059

所属专题： 烯碳纤维与智能织物

论文 上一篇    

石墨烯诱导水凝胶成核的高强韧人造蛛丝

何文倩1, 邸亚2, 姜南2, 刘遵峰1,*(), 陈永胜1,*()   

  1. 1 南开大学药物化学生物学国家重点实验室, 高分子所, 化学学院, 天津 300071
    2 航宇救生装备有限公司武汉创新中心, 武汉 430000
  • 收稿日期:2022-04-30 录用日期:2022-06-15 发布日期:2022-06-22
  • 通讯作者: 刘遵峰,陈永胜 E-mail:liuzunfeng@nankai.edu.cn;yschen99@nankai.edu.cn
  • 基金资助:
    国家自然科学基金(52090034);国家自然科学基金(51973093);国家自然科学基金(51773094);国家重点研发项目(2019YFE0119600);南开大学新有机质前沿科学中心(63181206)

Graphene-Oxide Seeds Nucleate Strong and Tough Hydrogel-Based Artificial Spider Silk

Wenqian He1, Ya Di2, Nan Jiang2, Zunfeng Liu1,*(), Yongsheng Chen1,*()   

  1. 1 State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Functional Polymer Materials, College of Chemistry, Nankai University, Tianjin 300071, China
    2 Innovation Center of Hangyu Lifesaving Equipment, Wuhan 430000, China
  • Received:2022-04-30 Accepted:2022-06-15 Published:2022-06-22
  • Contact: Zunfeng Liu,Yongsheng Chen E-mail:liuzunfeng@nankai.edu.cn;yschen99@nankai.edu.cn
  • About author:yschen99@nankai.edu.cn (Y.C.)
    Email: liuzunfeng@nankai.edu.cn (Z.L.)
  • Supported by:
    the National Natural Science Foundation of China(52090034);the National Natural Science Foundation of China(51973093);the National Natural Science Foundation of China(51773094);the National Key Research and Development Program of China(2019YFE0119600);Frontiers Science Center for New Organic Matter, Nankai University(63181206)

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摘要：

天然蜘蛛丝是由β-sheet交联的蛛丝蛋白溶剂流入S-型导管后经牵引拉伸形成，它显示了高强度与高韧性的完美结合。其优异的力学性质主要源于它的多级结构：交联、线性排列的纳米组装体以及核壳结构。受此启发，我们合成了一种交联的水凝胶，通过牵引拉丝的方法，制备了交联的、含有取向排列的纳米组装体结构以及核壳结构的凝胶纤维，并通过少量引入二维纳米材料—氧化石墨烯(0.01%)，进一步调控纳米组装体的取向和尺寸，实现了蜘蛛丝般优异的力学性能(断裂强度560 MPa，断裂韧性200 MJ·m–3，缓冲能94%)。这种纤维可以用于高速下落物体的能量耗散和降低冲击力。

关键词: 功能纤维, 聚合物复合物, 仿生, 纺丝, 纳米材料, 氧化石墨烯, 缓冲

Abstract:

Natural spider silk is composed of spun spidroin protein containing beta-sheet crosslinking sites drawn from an S-shaped spinning duct. It exhibits an excellent combination of strength (1150 ± 200 MPa) and toughness (165 ± 30 MJ·m–3) that originates from its hierarchical structure, including crosslinking sites, highly aligned nano-aggregates, and a sheath-core structure. In this work, we prepared a hydrogel fiber that contains crosslinking sites, highly aligned nano-aggregates, and a sheath-core structure, by draw-spinning a bulk hydrogel composed of polyacrylic acid crosslinked with vinyl-functionalized silica nanoparticles (SNVs). The core-sheath structure was prepared by the water-evaporation-controlled self-assembly of the polyacrylic hydrogel, while nanometer-sized aggregates were formed by the self-assembly of polyacrylic acid chains. The addition of a tiny amount of graphene oxide (GO: 0.01%), a 2D nanomaterial, enhanced the mechanical properties of the fiber (breaking strength: 560 MPa; fracture toughness: 200 MJ·m–3; damping capacity: 94%). In addition, we investigated the factors responsible for the mechanical properties of the gel fibers, including fiber diameter, drying time in air, relative air humidity, and stretching speed. A higher breaking strength and a lower fracture strain was obtained by decreasing the fiber diameter, increasing the drying time, or increasing the stretching speed, while a lower fracture strain and higher breaking strength were obtained by increasing the relative air humidity. Polarized optical and SEM images revealed that the GO-seeded material is better aligned and contains smaller nano-aggregates, with GO seeding found to play a key role in the formation of nano-aggregates and polymer-chain alignment. The prepared fiber exhibited excellent mechanical properties compared to gel fibers prepared by other methods (e.g., electro-, wet, dry, and microfluidic spinning, as well as templating, and 3D printing, etc.). Repeated mechanical testing involving stretch-release cycles to 70% strain at 20% relative humidity revealed that the fibers have an energy-damping capacity of 93.6%, which exceeds that of natural spider silk and many types of artificial fiber. The relaxed stretched fiber recovered its initial length when exposed to 80% relative humidity, while the fiber recovered its initial mechanical properties when stored for 2 h at room temperature. A yarn composed of three hundred of the prepared gel fibers was shown to lift a 3 kg object without breaking; the prepared fiber was also shown to absorb dynamic energy and lower the impact force of a falling object.

Key words: Functional fiber, Polymer composite, Biomimetic, Spinning, Nanomaterials, Graphene oxide, Damp capacity