Preparation of polyacrylonitrile/polyvinylidene fluoride composite fiber membrane by electrospinning and its air filtration performance
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摘要: 以聚偏氟乙烯(PVDF)为芯层，聚丙烯腈(PAN)为皮层，通过同轴法静电纺丝技术制备PAN/PVDF纳米复合纤维膜。通过向纤维膜的皮层中加入纳米硅粉、气相白炭黑、硅溶胶三种不同的纳米粒子和改变皮芯层溶液挤出速度对PAN/PVDF纳米纤维膜进行结构优化。同时，采用BET、SEM、水接触角、纤维强度仪等对纤维膜的孔结构参数、表面形貌、亲水性、力学性能等进行研究。结果表明：在皮层中加入硅溶胶后的溶液导电能力达到32.90 μL/cm，PAN/PVDF纤维膜力学性能最好，纵向断裂强度达到13.02 MPa。含有硅溶胶的口罩布的品质因子达到0.0236，远大于纯聚丙烯(PP)无纺布的品质因子(0.0127)，过滤性显著提高。Abstract: The polyacrylonitrile/polyvinylidene fluoride (PAN/PVDF) nanocomposite fiber membranes were prepared by the coaxial electrospinning technology using PVDF as the core layer and PAN as the skin layer. Structure optimization of PAN/PVDF nanocomposite fiber membrane was carried out by adding three different nanoparticles of nano-silica powder, fumed silica and silica sol to the PAN/PVDF nanocomposite fiber membrane and changing the extrusion speed of the skin-core layer solution. Meanwhile, its pore structure parameters, surface morphology, hydrophilicity and mechanical properties were studied by BET, SEM, water contact angle, fiber strength meter and so on. The results show that the conductivity of the solution after adding silica sol to the solution reaches 32.90 μL/cm, the PAN/PVDF nanocomposite fiber membrane has the best mechanical properties, and the longitudinal breaking strength reaches 13.02 MPa. The quality factor of mask cloth containing silica sol reaches 0.0236, which is much larger than the quality factor of pure polypropylene (PP) non-woven, which is 0.0127, and the filterability is significantly increased.
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Key words:
- coaxial electrospinning /
- nanoparticles /
- filter performance /
- silica sol /
- fiber membrane
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图 1 不同皮层溶液(PAN、Si/PAN、G/PAN、S/PAN)和芯层溶液(PVDF、TiO2/PVDF)的电导率
Figure 1. Conductivity of different skin layer solutions (PAN, Si/PAN, G/PAN, S/PAN) and core layer solutions (PVDF, TiO2/PVDF)
图 2 PAN/PVDF复合纤维膜的吸-脱附曲线及孔容分布
Figure 2. Absorption-desorption curves and pore volume distribution of PAN/PVDF composite fiber membranes
图 3 PAN/PVDF复合纤维膜的SEM图像
Figure 3. SEM images of PAN/PVDF composite fiber membranes ((a), (d) PAN/PVDF5; (b), (e) PAN/PVDF2; (c), (f) PAN/PVDF6)
图 4 PAN/PVDF复合纤维膜的水接触角
Figure 4. Water contact angle of PAN/PVDF composite fiber membranes
表 1 静电纺不同纤维膜时对应的皮层溶液和芯层溶液的组成及推进速度
Table 1. Composition and advancing speed of skin layer solution and core layer solution when preparing different fiber membranes by electrospinning
Serial number Cortical speed/(mL·h−1) Core speed/(mL·h−1) Cortical solution Core solution PAN/PVDF1 0.6 0.6 PAN PVDF PAN/PVDF2 0.6 0.6 Si/PAN TiO2/PVDF PAN/PVDF3 0.4 0.8 Si/PAN TiO2/PVDF PAN/PVDF4 0.8 0.4 Si/PAN TiO2/PVDF PAN/PVDF5 0.6 0.6 G/PAN TiO2/PVDF PAN/PVDF6 0.6 0.6 S/PAN TiO2/PVDF Notes: PAN—Polyacrylonitrile; PVDF—Polyvinylidene fluoride; Si—Nano-silica powder; G—Fumed silica; S—Silica sol; The unit of cortical speed and core speed is mL/h. 
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表 2 PAN/PVDF复合纤维膜的纤维膜孔结构参数
Table 2. Pore structure parameters of PAN/PVDF composite fiber membranes
Serial number SBET/(m2·g−1) Smic/(m2·g−1) Sext/(m2·g−1) Sext/SBET/% Vtotal/(cm3·g−1) PAN/PVDF1 3.453 0 3.453 100.00 6.982×10−3 PAN/PVDF2 8.802 0.092 8.711 98.97 3.938×10−2 PAN/PVDF3 3.764 0 3.764 100.00 2.846×10−2 PAN/PVDF4 10.354 1.886 8.468 81.78 4.025×10−2 PAN/PVDF5 46.749 18.715 28.034 59.97 3.432×10−1 PAN/PVDF6 8.523 1.597 6.926 81.26 3.760×10−2 Notes: SBET—Specific surface area of fiber membrane; Smic—Micropore specific surface area; Sext—External pore surface area; Sextt/SBET—Percentage of external pores in overall surface area; Vtotal—Total pore volume of fiber membrane.
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表 3 PAN/PVDF复合纤维膜的断裂强度和断裂伸长率
Table 3. Breaking strength and elongation at break of PAN/PVDF composite fiber membranes
Serial number Longitudinal breaking strength/MPa Longitudinal elongation at break/% Transverse breaking strength/MPa Transverse elongation at break/% PAN/PVDF1 6.19±0.30 161.50±8.08 2.33±0.12 218.41±10.22 PAN/PVDF2 8.25±0.41 304.30±15.29 5.90±0.28 401.70±14.23 PAN/PVDF3 4.31±0.22 88.30±4.42 2.43±0.14 136.99±9.38 PAN/PVDF4 14.01±0.65 424.30±17.87 8.60±0.36 390.20±19.84 PAN/PVDF5 7.20±0.36 186.16±9.76 3.56±0.16 131.68±12.34 PAN/PVDF6 13.02±0.56 222.69±10.14 10.83±0.54 190.20±14.56
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表 4 PAN/PVDF-PP和PP口罩布的过滤性能
Table 4. Filtration performance of PAN/PVDF-PP and PP non-woven fabric
Serial number Filtration resistance/mm H2O Filtration efficiency/% Quality factor PP 3.3 4.10 0.0127 PAN/PVDF-PP1 151.5 93.28 0.0178 PAN/PVDF-PP2 223.8 97.36 0.0162 PAN/PVDF-PP3 132.6 95.68 0.0236
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