Journal of Textile Research ›› 2023, Vol. 44 ›› Issue (09): 11-19.doi: 10.13475/j.fzxb.20220309601

• Fiber Materials • Previous Articles     Next Articles

Preparation and properties of regenerated silk fibroin/polyvinyl alcohol blended nanofiber membranes with predesigned orientation

YAO Shuangshuang1,2, FU Shaoju1,2, ZHANG Peihua1,2(), SUN Xiuli3   

  1. 1. Key Laboratory of Textile Science & Technology, Ministry of Education, Donghua University, Shanghai 201620, China
    2. College of Textiles, Donghua University, Shanghai 201620, China
    3. Department of Gynaecology and Obstetrics, Peking University People's Hospital, Beijing 100044, China
  • Received:2022-03-29 Revised:2022-10-12 Online:2023-09-15 Published:2023-10-30

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Abstract:

Objective Non-oriented nanofiber membranes are usually obtained on the receiving device due to instable movement of polymer jet in electrospinning. Oriented nanofiber membranes are obtained by changing the receiving device and other methods.Compared with non-oriented nanofiber membranes,oriented nanofiber membranes have the advantages of regular fiber arrangement and good mechanical properties. The paper proposes the preparation of oriented nanofiber membranes by electrospinning with regenerated silk fibroin (RSF) and polyvinyl alcohol (PVA) as raw materials,and potential applications of oriented nanofiber membranes in the field of textile biomedicine.

Method The optimal spinning parameters were determined by single factor experiment and orthogonal experiment,and the morphology,chemical structure,mechanical properties,thermal stability,pore size distribution of oriented nanofiber membranes were studied with the assistance of scanning electron microscopes,Fourier transform infrared spectrometer,medical multi-function strength tester,synchronous thermal analyzer,and porous material pore size analyzer.

Results Based on the nanofiber membrane morphology obtained from single factor experiment and orthogonal experiment (Fig. 1,Tab. 2 and Fig. 2),it was evident that the optimal electrospinning parameters for preparing RSF/PVA blended oriented nanofiber membranes were as follows, formic acid as the solvent,roller speed of 2 400 r/min,spinning fluid concentration of 0.16 g/mL,spinning voltage of 23 kV,outflow velocity of 0.6 mL/h,and receiving distance of 17 cm.Under these parameters,the oriented nanofiber membranes demonstrated regular morphology and high orientation (Fig. 3 and Tab. 3). It can be seen from the infrared spectra of RSF power,PVA grain and RSF/PVA oriented fiber membranes (Fig. 4) that compared with RSF powder,part of amorphous structure in the oriented nanofiber membranes was transformed into the ɑ helix structure. The stretching effect of the high-speed roller on the fiber was conductive to improving the degree of orientation and crystallinity of nanofiber membranes,thus the breaking strength of the oriented nanofiber membranes obtained under the same spinning time was more than two times that of the non-oriented nanofiber membranes, but the elongation rate at break was lower than that of the latter (Tab. 4).The oriented and non-oriented nanofiber membranes almost coincide,and both begin to decompose at 284 ℃ with their thermal decomposition rates fastest at 312 ℃ (Fig.7),indicating that the thermal stability of the oriented and non-oriented nanofiber membranes was similar,and the stretching and alignment of fibers by the high-speed roller had substantially no effect on the thermal stability of RSF/PVA nanofiber membranes.The pore sizes of oriented and non-oriented nanofiber membranes were distributed in 0.46-1.50 μm and 0.08-0.48 μm, respectively,and were concentrated near 0.5 μm and 0.1 μm, respectively,indicating that oriented nanofiber membranes had larger pore sizes and were expected to be used in the field of textile biomedicines.

Conclusion RSF and PVA were electrospinned into oriented nanofiber membranes.The optimal spinning parameters were determined by single-factor experiment and orthogonal experiment,and the morphology,chemical structure, mechanical properties and thermal stability of nanofiber membranes were studied. The experimental results showed that part of the amorphous structure in the oriented nanofiber membranes was transformed into the ɑ helix structure; and the oriented nanofiber membranes had higher strength than the non-oriented nanofiber membranes,but had lower elongation at break under the same spinning time. And the pore sizes in the oriented nanofiber membranes were larger than that of the non-oriented ones and the oriented structure has substantially no effect on the thermal stability of the nanofiber membranes. The experimental results provided a theoretical basis for further enhancing the application potential of oriented nanofiber membranes in the field of textile biomedicine.

Key words: oriented nanofiber membrane, electrostatic spinning, regenerated silk fibroin, polyvinyl alcohol

CLC Number: 

  • TS101.4

Fig. 1

Influences of spinning process parameters on nanofiber membrane morphology. (a) Different roller speeds;(b) Different solvents;(c) Different spinning fluid concentrations;(d) Different spinning voltages;(e) Different outflow velocities;(f) Different receiving distances"

Tab. 1

Factors and levels table of orthogonal experiment"

水平 A
质量浓度/
(g·mL-1)		 B
电压/kV		 C
出液速度/
(mL·h-1)		 D
接收距离/
cm
1 0.15 23 0.4 15
2 0.16 24 0.6 16
3 0.17 25 0.8 17

Tab. 2

Orthogonal experiment results analysis table"

样品
编号		 A
B		 C D 直径/
μm		 直径
CV值		 45°~135°取向
纤维占比/%		 70°~110°取向
纤维占比/%
1# 1 1 1 1 0.21 0.41 80 48
2# 1 2 2 2 0.16 0.40 88 52
3# 1 3 3 3 0.14 0.38 70 42
4# 2 1 2 3 0.25 0.31 90 56
5# 2 2 3 1 0.27 0.30 84 56
6# 2 3 1 2 0.29 0.33 84 22
7# 3 1 3 2 0.52 0.23 52 26
8# 3 2 1 3 0.18 0.38 90 60
9# 3 3 2 1 0.44 0.58 46 20
直径 K1 0.51 0.98 0.68 0.92 优选工艺A1B3C3D3
K2 0.81 0.61 0.85 0.97
K3 1.14 0.87 0.93 0.57
R 0.63 0.37 0.25 0.40
直径
CV值		 K1 1.19 0.95 1.12 1.29 优选工艺A3B1C3D2
K2 0.94 1.08 1.29 0.96
K3 1.19 1.29 0.91 1.07
R 0.25 0.34 0.38 0.33
45°~135°
取向纤维
占比		 K1 238 222 254 210 优选工艺A2B1C2D3;A3B2C1D3
K2 258 262 224 224
K3 188 200 206 250
R 67 62 48 40
70°~110°
取向纤维
占比		 K1 142 130 130 124 优选工艺A3B2C1D3
K2 134 168 128 100
K3 105 84 124 158
R 37 84 6 58

Fig. 2

Morphologies of nanofiber membrans obtained byorthogonal experiment"

Fig. 3

Surface morphology of oriented (a)and non-oriented (b)nanofiber membranes"

Tab. 3

Measurement results of diameter and proportion of different orientations of nanofibers"

样品名称 直径/
μm		 直径
CV值		 45°~135°取向
纤维占比/%		 70°~110°取向
纤维占比/%
取向
纳米纤维膜		 0.25 0.31 90 56
无取向
纳米纤维膜		 0.15 0.30 66 14

Fig. 4

Infrared spectra of RSF power,PVA grain and RSF/PVA oriented fiber membranes"

Fig. 5

Thickness and surface density of oriented and non-oriented nanofiber membranes"

Tab. 4

Mechanical properties of oriented and non-oriented nanofiber membranes"

样品名称 断裂强力/N 断裂伸长率/%
取向纳米纤维膜 1.96±0.37 5.14±1.75
无取向纳米纤维膜 0.87±0.05 12.61±5.08

Fig. 6

TG (a)and DTG (b)curves of oriented and non-oriented nanofiber membranes"

Fig. 7

Pore size distribution of oriented (a)and non-oriented (b)nanofiber membranes"

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