丝素纳米原纤增强再生丝素蛋白/聚乙烯醇纤维的结构与性能

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丝素纳米原纤增强再生丝素蛋白/聚乙烯醇纤维的结构与性能

Structure and properties of fibroin nanofibril reinforced regenerated silk protein/polyvinyl alcohol fiber

丝素纳米原纤增强再生丝素蛋白/聚乙烯醇纤维的结构与性能

Structure and properties of fibroin nanofibril reinforced regenerated silk protein/polyvinyl alcohol fiber

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doi:10.13475/j.fzxb.20230805601

纺织学报 ›› 2024, Vol. 45 ›› Issue (11): 1-9.doi: 10.13475/j.fzxb.20230805601

• 纤维材料 • 下一篇

杨鑫¹, 张昕¹^,², 潘志娟¹^,²()

1.苏州大学纺织与服装工程学院, 江苏苏州 215021
2.苏州大学现代丝绸国家工程实验室, 江苏苏州 215123

收稿日期:2023-08-25 修回日期:2024-04-28 出版日期:2024-11-15 发布日期:2024-12-30
通讯作者: 潘志娟(1967—),女,教授,博士。主要研究方向为新型纺织材料及产品开发。E-mail:zhjpan@suda.edu.cn。
作者简介:杨鑫(1998—),女,硕士生。主要研究方向为新型纺织材料开发。
基金资助:
江苏省卓越博士后计划(2023ZB420);江苏省丝绸工程重点实验室开放课题(KJS2314)

YANG Xin¹, ZHANG Xin¹^,², PAN Zhijuan¹^,²()

1. College of Textile and Clothing Engineering, Soochow University, Suzhou, Jiangsu 215021, China
2. National Engineering Laboratory for Modern Silk, Soochow University, Suzhou, Jiangsu 215123, China

Received:2023-08-25 Revised:2024-04-28 Published:2024-11-15 Online:2024-12-30

摘要： 为拓展废旧蚕丝高值化回收再利用形式,提高再生丝素蛋白纤维的力学性能,以废旧蚕丝为原料制备了丝素纳米原纤(SFNF)、再生废旧蚕丝丝素蛋白(RRSF),并与聚乙烯醇(PVA)共混制备了共混纤维,探究了SFNF作为增强材料对纤维微观结构与力学性能的影响。结果表明:SFNF的加入提高了RRSF与PVA的相容性,共混溶液的均匀性和稳定性显著提高;在RRSF/PVA/SFNF共混纤维中少量添加SFNF可诱导分子构象从α-螺旋向β-折叠转变,提高纤维结晶度,当SFNF的质量分数为0.2%时,共混纤维内β-折叠含量增加,达到最大值54.42%,α-螺旋含量降至20.03%;SFNF显著增强共混纤维的拉伸性能与韧性,断裂应力可达到38.98 MPa,断裂伸长率可达到443.27%,初始模量可达到640.83 MPa,断裂比功可达到133.50 N/mm²。

关键词: 自增强, 丝素纳米原纤, 再生丝素蛋白纤维, 废旧蚕丝, 力学性能, 聚乙烯醇

Abstract:

Objective Extracting silk fibroin protein from waste silk to prepare recycled fiber is one of the approaches to recycle waste silk, but the mechanical properties of recycled fiber are generally poor. Therefore, it is necessary to explore new methods to improve the mechanical properties of recycled silk fibroin fibers and achieve the high-value recovery and reuse of waste silk.

Method The silk fibroin nanofibrillar fiber (SFNF) and the recycled silk fibroin (RRSF) extracted from waste silk were blended with polyvinyl alcohol (PVA) to prepare the blending solution. The effect of SFNF on the properties of the blended solution was investigated, the RRSF/PVA/SFNF blended fibers were prepared by dry spray wet spinning process and the effects of SFNF on the microstructure and mechanical properties of the blended fibers were investigated.

Results The SFNF was obtained after mechanical grinding and filter screen filtration of degumming waste silk, with length distribution between 20 and 90 μm and diameter distribution between 30 and 100 nm. The SFNF crystal obtained by mechanical grinding is not damaged and still retains the original crystalline structure of silk fibroin. RRSF/PVA/SFNF blended solution were non-Newtonian fluids with obvious shear thinning properties. With the increase of SFNF addition, the shear viscosity and shear stress of the blended solution was increased, and the elastic and viscous characteristics of the solution were enhanced. When the amount of SFNF was greater than 0.3%, the viscosity of the solution was obvious and gelation was easy to occur. Besides, SFNF significantly improved the stability and uniformity of the blended membrane. After the addition of SFNF, the pore structure inside the blended fibers was changed and the number of pores were increased. A small amount of SFNF induced the molecular conformation change from α-helix structure to β-fold structure. When the addition amount was 0.2%, the α-helix content reached the minimum of 20.03%, and the β-fold content reached the maximum of 54.42%. The fiber crystallinity was increased first and then decreased with the increase of SFNF addition. The addition of SFNF effectively enhanced the tensile strength and toughness of the blend fibers. When the amount of addition was 0.2%, the RRSF/PVA/SFNF blended fiber demonstrated a breaking strength of 38.98 MPa, an elongation at break of 443.27%, a modulus of elasticity of 640.83 MPa, and a specific work of fracture of 133.50 N/mm².

Conclusion The preparation method of SFNF is environmentally friendly, simple and efficient, which makes it an ideal fiber reinforcement material for regenerative silk fibroin protein. The compatibility of RRSF and PVA was improved, and the uniformity and stability of the blends were enhanced when SFNF was added to the RRSF/PVA blended solution. The compatibility of RRSF and PVA was improved when SFNF was added to the RRSF/PVA blended solution as a reinforcing material. The addition of a small amount of SFNF to RRSF/PVA/SFNF blend fiber was found to have improve the crystallinity of the blend fiber, and significantly improving the tensile properties and toughness of the blend fiber. The SFNF reinforced RRSF/PVA/SFNF blend fiber has good mechanical properties and biocompatibility, which can be further explored in the field of biomedical materials.

Key words: self-reinforce, silk fibroin nanofibril, regenerated silk fibroin fiber, waste silk, mechanical property, polyvinyl alcohol

中图分类号:

TS149

杨鑫, 张昕, 潘志娟. 丝素纳米原纤增强再生丝素蛋白/聚乙烯醇纤维的结构与性能[J]. 纺织学报, 2024, 45(11): 1-9.

YANG Xin, ZHANG Xin, PAN Zhijuan. Structure and properties of fibroin nanofibril reinforced regenerated silk protein/polyvinyl alcohol fiber[J]. Journal of Textile Research, 2024, 45(11): 1-9.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20230805601

http://www.fzxb.org.cn/CN/Y2024/V45/I11/1

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样品编号	α-螺旋	β-折叠	β-转角	无规卷曲
S_0.0	23.61	50.37	13.41	12.62
S_0.1	22.38	52.63	14.91	10.07
S_0.2	20.03	54.42	13.96	11.59
S_0.3	24.79	49.92	12.99	12.30

样品编号	断裂伸长率/ %	断裂应力/ MPa	初始模量/ MPa	断裂比功/ (N·mm^-2)
S_0.0	499.02	30.17	351.48	90.11
S_0.1	481.83	35.62	508.34	116.18
S_0.2	443.27	38.98	640.83	133.50
S_0.3	402.79	29.00	391.98	80.08

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