Journal of Textile Research ›› 2024, Vol. 45 ›› Issue (11): 1-9.doi: 10.13475/j.fzxb.20230805601

• Fiber Materials •     Next Articles

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

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

  1. 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 Online:2024-11-15 Published:2024-12-30
  • Contact: PAN Zhijuan E-mail:zhjpan@suda.edu.cn

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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

CLC Number: 

  • TS149

Fig.1

Flow chart of spinning process of RRSF/PVA/SFNF blended fibers"

Fig.2

Macroscopic (a) and microscopic (b) morphology of SFNF and length (c), diameter (d)frequency distribution map"

Fig.3

X-ray diffraction pattern of SFNF"

Fig.4

Rheological properties of RRSF/PVA/SFNF blends. (a) Shear viscosity-shear rate curves; (b) Shear stress-shear rate relationship curves; (c) Energy storage modulus-angular frequency curves; (d) Loss modulus-angular frequency curves"

Fig.5

Picture of blended membrane"

Fig.6

Laser confocal image of RRSF/PVA/SFNF blended membrane. (a) RRSF/PVA blend membrane; (b)RRSF/PVA/SFNF blended membrane; (c) Schematic diagram of capacitive effect of SFNF on blended solution"

Fig.7

Surface (a) and cross section (b) morphology of RRSF/PVA/SFNF blended fibers"

Fig.8

Whole FT-IR spectra of RRSF/PVA/SFNF blended fibers (a) and enlarged view of characteristic peaks (b) of RRSF"

Fig.9

Schematic diagram of fitting molecularconformation peaks of fibroin protein at amide Ⅰ"

Tab.1

Contents of secondary structures of fibroin protein based on amide Ⅰ peak spectrum %"

样品编号 α-螺旋 β-折叠 β-转角 无规卷曲
S0.0 23.61 50.37 13.41 12.62
S0.1 22.38 52.63 14.91 10.07
S0.2 20.03 54.42 13.96 11.59
S0.3 24.79 49.92 12.99 12.30

Fig.10

X-ray diffraction pattern of RRSF/PVA/SFNF blend fibers"

Tab.2

Mechanical properties test results of RRSF/PVA/SFNF blended fibers"

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)
S0.0 499.02 30.17 351.48 90.11
S0.1 481.83 35.62 508.34 116.18
S0.2 443.27 38.98 640.83 133.50
S0.3 402.79 29.00 391.98 80.08
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