膜科学与技术

NIPS法疏水PVDF膜的结构与性能调控研究进展

作者：徐小洁，于孟超，王钰，王涛，冯英楠，赵之平

单位：北京理工大学化学与化工学院，北京102488

关键词：疏水有机膜；非溶剂致相转化法；喷雾辅助相转化法；膜蒸馏

出版年,卷(期):页码： 2024,44(1):147-156

摘要：

非溶剂致相分离法（NIPS）是制备多孔有机膜一种高效工艺手段，其过程中涉及的热力学与动力学因素对于疏水多孔膜的成膜结构与性质起着至关重要的决定性作用。为此，本文以常用疏水膜制备原材料聚偏氟乙烯（PVDF）为研究对象，系统阐述采用传统浸没沉淀相转化法和新兴喷雾辅助相转化法两种NIPS制膜工艺路线对PVDF疏水膜微纳结构的影响及其内在成膜机理，旨在通过明晰制膜过程中影响因素对成膜疏水性、孔结构参数的作用规律，为疏水膜的可控制备提供理论指导与技术支持。

Non-solvent induced phase separation (NIPS) is an efficient method to prepare porous hydrophobic membranes. It involves thermodynamic and kinetic factors which have deterministic effects on the structure and performance of hydrophobic porous membranes. Hence, a commonly used material for hydrophobic membrane preparation, PVDF, is taken as the research object in this paper. This paper systematically summarizes the influencing factors and membrane formation mechanisms of traditional immersion precipitation method and emerging spray-assisted non-solvent induced phase separation method in the membrane preparation process, focusing on the effects of different fabrication conditions on the membrane structure and performance (hydrophobicity, pore size and porosity, etc.), which could lay a foundation for the controllable preparation of hydrophobic membranes.

徐小洁（2000-），女，河北邯郸人，硕士研究生，研究方向为有机膜制备及应用，E-mail：xxj001221@163.com

参考文献：

[1] Pagliero M, Bottino A, Comite A, et al. Novel hydrophobic PVDF membranes prepared by nonsolvent induced phase separation for membrane distillation[J]. Journal of Membrane Science, 2020, 596: 117575.
[2] Liu F, Hashim N A, Liu Y, et al. Progress in the production and modification of PVDF membranes[J]. Journal of Membrane Science, 2011, 375(1-2): 1-27.
[3] Kang G, Cao Y. Application and modification of poly(vinylidene fluoride) (PVDF) membranes – A review[J]. Journal of Membrane Science, 2014, 463: 145-165.
[4] Shi L, Wang R, Cao Y, et al. Fabrication of poly(vinylidene fluoride-co-hexafluropropylene) (PVDF-HFP) asymmetric microporous hollow fiber membranes[J]. Journal of Membrane Science, 2007, 305(1-2): 215-225.
[5] Wongchitphimon S, Wang R, Jiraratananon R, et al. Effect of polyethylene glycol (PEG) as an additive on the fabrication of polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) asymmetric microporous hollow fiber membranes[J]. Journal of Membrane Science, 2011, 369(1-2): 329-338.
[6] Shi L, Wang R, Cao Y, et al. Effect of additives on the fabrication of poly(vinylidene fluoride-co-hexafluropropylene) (PVDF-HFP) asymmetric microporous hollow fiber membranes[J]. Journal of Membrane Science, 2008, 315(1-2): 195-204.
[7] Gu J, Xu S, Lu X, et al. Study on the membrane formation mechanism of PVDF/PVDF-CTFE blends[J]. Journal of the Taiwan Institute of Chemical Engineers, 2023, 142: 104655.
[8] Saïdi S, Macedonio F, Russo F, et al. Preparation and characterization of hydrophobic P(VDF-HFP) flat sheet membranes using Tamisolve® NxG solvent for the treatment of saline water by direct contact membrane distillation and membrane crystallization[J]. Separation and Purification Technology, 2021, 275: 119144.
[9] Neinhuis C. Characterization and Distribution of Water-repellent, Self-cleaning Plant Surfaces[J]. Annals of Botany, 1997, 79(6): 667-677.
[10] Wang H-T, Lu M-C, Shi M-S, et al. Regulation of the microstructure of polyvinylidene fluoride membrane via incorporation of nano-ZIF-7 for improving hydrophobicity and antiwetting performance[J]. Journal of the Chinese Chemical Society, 2020, 67(5): 732-743.
[11] Li C, Liu W, Mao J, et al. Superhydrophobic PVDF membrane modified by dopamine self-polymerized nanoparticles for vacuum membrane distillation[J]. Separation and Purification Technology, 2023, 304:122182.
[12] Celia E, Darmanin T, Taffin de Givenchy E, et al. Recent advances in designing superhydrophobic surfaces[J]. Journal of Colloid and Interface Science, 2013, 402: 1-18.
[13] 刘敏, 贺兵, 姜馨淳, 等. NIPS法一步制备PVDF疏水分离膜的研究进展[J]. 净水技术, 2020, 39(7): 77-83.
[14] Chung T S, Teoh S K, Hu X. Formation of ultrathin high-performance polyethersulfone hollow-fiber membranes[J]. Journal of Membrane Science, 1997, 133(2): 161-175.
[15] Abdulla AlMarzooqi F, Roil Bilad M, Ali Arafat H. Improving Liquid Entry Pressure of Polyvinylidene Fluoride (PVDF) Membranes by Exploiting the Role of Fabrication Parameters in Vapor-Induced Phase Separation VIPS and Non-Solvent-Induced Phase Separation (NIPS) Processes[J]. Applied Sciences, 2017, 7(2): 181.
[16] 俞三传, 高从堦. 浸入沉淀相转化法制膜[J]. 膜科学与技术, 2000(5): 36-41.
[17] Yeow M L, Liu Y T, Li K. Morphological study of poly(vinylidene fluoride) asymmetric membranes: Effects of the solvent, additive, and dope temperature[J]. Journal of Applied Polymer Science, 2004, 92(3): 1782-1789.
[18] Gregorio R. Determination of the α, β, and γ crystalline phases of poly(vinylidene fluoride) films prepared at different conditions[J]. Journal of Applied Polymer Science, 2006, 100(4): 3272-3279.
[19] Tao M, Liu F, Ma B, et al. Effect of solvent power on PVDF membrane polymorphism during phase inversion[J]. Desalination, 2013, 316: 137-145.
[20] Li Q, Xu Z-L, Yu L-Y. Effects of mixed solvents and PVDF types on performances of PVDF microporous membranes[J]. Journal of Applied Polymer Science, 2010, 115(4): 2277-2287.
[21] Wu C, Tang W, Zhang J, et al. Preparation of super-hydrophobic PVDF membrane for MD purpose via hydroxyl induced crystallization-phase inversion[J]. Journal of Membrane Science, 2017, 543: 288-300.
[22] Toh M J, Oh P C, Chew T L, et al. Antiwettability enhancement of PVDF-HFP membrane via superhydrophobic modification by SiO2 nanoparticles[J]. Comptes Rendus Chimie, 2019, 22(5): 369-372.
[23] Zou L, Zhang G, Yu J. Desirable PVDF hollow fiber membrane engineered with synergism between small molecular weight additives for DCMD treating of a hypersaline brine[J]. Journal of Water Process Engineering, 2022, 45: 102528.
[24] 史艳阳, 陈小乐, 苗闪闪, 等. PVDF超疏水膜的研制及空气过滤初探[J]. 膜科学与技术, 2023: 1-11.
[25] Zhang R, Tang W, Gao H, et al. In-situ construction of superhydrophobic PVDF membrane via NaCl-H2O induced polymer incipient gelation for membrane distillation[J]. Separation and Purification Technology, 2021, 274: 117762.
[26] Zheng L, Wu Z, Wei Y, et al. Preparation of PVDF-CTFE hydrophobic membranes for MD application: Effect of LiCl-based mixed additives[J]. Journal of Membrane Science, 2016, 506: 71-85.
[27] Ouchn R, Chaouqi Y, Louafy R, et al. Polymer Inclusion membranes with long term-stability in desalination via membrane distillation[J]. Chemical Engineering and Processing - Process Intensification, 2023, 191: 109442.
[28] 李硕, 王兴娅, 王文治, 等. 高疏水PVDF微孔膜及其膜蒸馏分离生物质发酵乙醇性能[J]. 膜科学与技术, 2019, 39(3): 110-118.
[29] Munirasu S, Banat F, Durrani A A, et al. Intrinsically superhydrophobic PVDF membrane by phase inversion for membrane distillation[J]. Desalination, 2017, 417: 77-86.
[30] Mazinani S, Darvishmanesh S, Ehsanzadeh A, et al. Phase separation analysis of Extem/solvent/non-solvent systems and relation with membrane morphology[J]. Journal of Membrane Science, 2017, 526: 301-314.
[31] Song H-M, Zhu L-J, Wang G, et al. Salt-induced and alcohol-induced hydrophobic and underoil superhydrophobic poly (vinylidene fluoride) membranes for effective oil collection[J]. Journal of Environmental Chemical Engineering, 2021, 9(1): 104714.
[32] Akbari B, Lashanizadegan A, Darvishi P, et al. Preparation of hydrophobic flat sheet membranes from PVDF-HFP copolymer for enhancing the oxygen permeance in nitrogen/oxygen gas mixture[J]. Chinese Journal of Chemical Engineering, 2020, 28(6): 1566-1581.
[33] Li Q, Xu Z-L, Liu M. Preparation and characterization of PVDF microporous membrane with highly hydrophobic surface[J]. Polymers for Advanced Technologies, 2011, 22(5): 520-531.
[34] 张琳. PVDF平板疏水膜的制备及其应用[D]. 南昌：南昌大学, 2012.
[35] 王兴娅. 超疏水膜的制备及其膜蒸馏分离发酵乙醇的研究[D]. 北京：北京理工大学, 2016.
[36] Lin J, Du J, Xie S, et al. Durable superhydrophobic polyvinylidene fluoride membranes via facile spray-coating for effective membrane distillation[J]. Desalination, 2022, 538: 115925.
[37] Zhang W, Li Y, Liu J, et al. Fabrication of hierarchical poly (vinylidene fluoride) micro/nano-composite membrane with anti-fouling property for membrane distillation[J]. Journal of Membrane Science, 2017, 535: 258-267.
[38] Lu K J, Zhao D, Chen Y, et al. Rheologically controlled design of nature-inspired superhydrophobic and self-cleaning membranes for clean water production[J]. npj Clean Water, 2020, 3(1): 1-10.
[39] Lu K-J, Liang C Z, Chen Y, et al. Unlock the secret of air blowing in developing high strength and superhydrophobic membranes for membrane distillation[J]. Desalination, 2022, 527: 115579.
[40] Yang H-R, Huang Y-H, Wang C-F, et al. Green fabrication of PVDF superhydrophobic membranes using a green solvent triethyl phosphate (TEP) for membrane distillation[J]. Desalination, 2023, 566: 116934.

服务与反馈：

【文章下载】【加入收藏】

《膜科学与技术》编辑部地址：北京市朝阳区北三环东路19号蓝星大厦邮政编码：100029 电话：010-64426130/64433466 传真：010-80485372邮箱：mkxyjs@163.com