膜科学与技术

位置：首页 >> 期刊内容阅读

PVDF聚多巴胺共混超滤膜结构及性能影响因素研究

作者：苗瑞，屈佳妮，王思雨，万家麟，樊莉，王磊

单位： 1. 西安建筑科技大学环境与市政工程学院，西北水资源与环境生态教育部重点实验室，陕西省膜分离重点实验室，西安 710055； 2. 陕西省膜分离技术研究院，西安 710055

关键词：超滤膜；聚多巴胺；氧化自聚；膜性能

DOI号： 10.16159/j.cnki.issn1007-8924.2025.05.005

分类号： TQ028.4

出版年,卷(期):页码： 2025,45(5):42-50

摘要：

本研究将多巴胺（DA）溶于聚偏氟乙烯(PVDF)铸膜液中，以NaClO溶液为凝胶浴，用浸没沉淀相转化法制备PVDF-聚多巴胺(PDA)共混超滤膜；系统研究了铸膜液中DA含量、预蒸发时间及NaClO浓度对共混膜性能和结构的影响。结果表明，共混膜中PDA形成速率随着DA含量、蒸发时间及NaClO浓度的增大而显著提升。当铸膜液中DA含量达到3%(质量分数)、蒸发时间为60 s及NaClO质量浓度为20 mg/L时，所得PVDF-PDA共混膜综合性能最佳，纯水通量较PVDF超滤膜增加了95%，接触角由81°降至48°，拉伸强度从2.7 MPa 提升至3.0 MPa。然而，当DA含量和蒸发时间继续增加，延迟相分离现象加剧，膜表面及断面出现孔道缺陷，导致共混膜的拉伸强度开始衰退；特别是较高浓度NaClO (>20 mg/L) 会损伤PVDF基体，导致共混膜出现严重的结构劣化。

In this study, polyvinylidene fluoride (PVDF)-polydopamine (PDA) blend ultrafiltration membranes were prepared via the immersion precipitation phase inversion method by dissolving dopamine (DA) in a PVDF casting solution with NaClO solution as the gelation bath. The results demonstrated that the formation rate of PDA in the blend membranes increased significantly with the increase of DA content, evaporation time and NaClO concentration. When the DA content in the casting solution reached 3% （mass fraction）, the evaporation time was 60 s, and the NaClO mass concentration was 20 mg/L, the PVDF-PDA blend membrane exhibited optimal comprehensive performance: its pure water flux increased by 95% compared to the pristine PVDF ultrafiltration membrane, the contact angle decreased from 81° to 48°, and the tensile strength improved from 2.7 MPa to 3.0 MPa. However, further increases in DA content or evaporation time intensified delayed phase separation, leading to microporous defects on the membrane surface and cross-section, which consequently reduced the tensile strength of the blend membrane. Notably, excessive NaClO concentration (>20 mg/L) damaged the PVDF matrix and severely compromised the structural integrity of the blend membrane.

基金项目：

国家自然科学基金面上项目（52370049）; 陕西高校青年创新团队资助项目(2023-2026)

作者简介：

苗瑞（1986-）,陕西榆林人,女, 博士,教授,主要从事膜法水处理技术研究

参考文献：

[1]王宗恒, 于滨玮, 章小同, 等. 絮凝/陶瓷超滤组合工艺用于微污染地表水处理的中试研 [J]. 膜科学与技术, 2024, 44(5): 156-163.
[2]Lin Y C, Liu K M, Chao C M, et al. Enhanced anti-protein fouling of PVDF membrane via hydrophobic-hydrophobic adsorption of styrene-terminated amphiphilic linker[J]. Chem Eng Res Des, 2020, 156: 273-280.
[3]李玉懂, 张晶, 李妍妍, 等. 基于多巴胺亲水改性的聚丙烯中空纤维膜及油水分离性能研究[J]. 膜科学与技术, 2024, 44(5): 20-31.
[4]Xi Z Y, Xu Y Y, Zhu L P, et al. A facile method of surface modification for hydrophobic polymer membranes based on the adhesive behavior of poly(DOPA) and poly(dopamine)[J]. J Membr Sci, 2009, 327(1/2): 244-253.
[5]Yan Z, Zhang Y, Yang H, et al. Mussel-inspired polydopamine modification of polymeric membranes for the application of water and wastewater treatment: A review[J]. Chem Eng Res Des, 2020, 157: 195-214.
[6]Yang H C, Luo J, Lyu Y, et al. Surface engineering of polymer membranes via mussel-inspired chemistry [J]. J Membr Sci, 2015, 483: 42-59.
[7]Chen H, Li Y, Wang Q G, et al. Modified polyvinylidene fluoride ultrafiltration membrane coated with polydopamine/3-(2,3-epoxypropoxy) propyl triethoxy silane[J]. Polym Adv Technol, 2020, 32(4): 1597-1603.
[8]Yang H C, Waldman R Z, Wu M B, et al. Dopamine: Just the right medicine for membranes[J]. Adv Funct Mater, 2018, 28(8): 1705327.
[9]Rui M, Yue M, Xin Z, et al. One-step preparation of PVDF-polydopamine blend ultrafiltration membranes via nonsolvent-induced phase separation and their characterization and antifouling mechanism analysis[J]. J Membr Sci, 2025:124029.
[10]Liu Y, Zhou T, Yin G, et al. Membrane fouling mitigation in Anoxic-Oxic membrane bioreactor with carbon nanotube/dopamine modification[J]. J Water Process Eng, 2025, 71:107231.
[11]苗瑞, 王磊, 田丽, 等. 海藻酸及腐殖酸共存对PVDF超滤膜的污染行为[J]. 中国环境科学, 2014, 34(10): 2568-2574.
[12]Shah V, Prasetya N, Li K. Polydopamine modification of high-performance PVDF ultrafiltration membranes prepared by the combined crystallisation and diffusion (CCD) method[J]. J Membr Sci, 2021, 635: 119538.
[13]Kasemset S, Wang L, He Z, et al. Influence of polydopamine deposition conditions on hydraulic permeability, sieving coefficients, pore size and pore size distribution for a polysulfone ultrafiltration membrane[J]. J Membr Sci, 2017, 522: 100-115.
[14]Shao L, Wang Z X, Zhang Y L, et al. A facile strategy to enhance PVDF ultrafiltration membrane performance via self-polymerized polydopamine followed by hydrolysis of ammonium fluotitanate[J]. J Membr Sci, 2014, 461: 10-21.
[15]Zhang L, Cui Z, Hu M, et al. Preparation of PES/SPSf blend ultrafiltration membranes with high performance via H2O - induced gelation phase separation [J]. J Membr Sci, 2017, 540: 136-145.
[16]Zhu G D, Yin Y R, Li Z N, et al. Organic acids interacting with block copolymers have broadened the window that retains isoporous structures[J]. J Membr Sci, 2019, 582: 391-401.
[17]Wu Q, Xie W, Wu H, et al. Effect of volatile solvent and evaporation time on formation and performance of PVC/PVC-g-PEGMA blended membranes [J]. RSC Adv, 2019, 9(59): 34486-34495.
[18]Wang C, Ma Z, Qiu Y, et al. Patterned dense Janus membranes with simultaneously robust fouling, wetting and scaling resistance for membrane distillation[J]. Water Res, 2023, 242: 120308.
[19]Qiu Z, Lei T, Li S, et al. Insights into polymorphic transition of PVDF during nonsolvent-induced phase separation[J]. Macromolecules, 2024, 57(3): 1159-1168.
[20]Wang M, Huang Y W, Chen Y, et al. Poly(vinylidene fluoride) membranes fabricated by vapor-induced phase separation (VIPS) for the adsorption removal of VB12 from aqueous solution[J]. J Appl Polym Sci, 2019, 136(45): 48179.
[21]Wang Q, Zeng H, Wu Z, et al. Impact of sodium hypochlorite cleaning on the surface properties and performance of PVDF membranes[J]. Appl Surf Sci, 2018, 428: 289-295.

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