Montero-Rocca Félix, Badia-Valiente Jose D, Jiménez-Robles Ramón, Martínez-Soria Vicente, Izquierdo Marta
Research Group in Materials Technology and Sustainability (MATS), Department of Chemical Engineering, School of Engineering, University of Valencia, Avda. Universitat s/n, 46100 Burjassot, Spain.
ACS Polym Au. 2025 Jun 20;5(4):353-368. doi: 10.1021/acspolymersau.5c00021. eCollection 2025 Aug 13.
Polyvinylidene fluoride (PVDF) electrospun nanofiber membranes (ENMs) could potentially be used in membrane contactors (MCs) for environmental applications, such as the removal of dissolved CH from anaerobic effluents. In this work, a PVDF flat-sheet ENM fabrication protocol, including the electrospinning processing and the subsequent hot-pressing treatment (HP), has been developed to produce hydrophobic membranes with suitable integrity and pore size distribution for gas-liquid separations in MCs. The HP study explored the effects of pressure (1, 10, and 20 MPa), temperature (25, 60, 80, and 120 °C), and time (2, 4, 6, and 10 min) on the morphological properties and hydrophobicity of the membranes. Our research revealed that fibers in the PVDF ENMs began to sinter at temperatures above 60 °C when hot-pressed between 1 and 20 MPa. ENM samples were prepared at different dope compositions (10-15% PVDF, 0.00-0.043% LiCl). After HP (≥1 MPa, ≥60 °C, and 6 min), the membrane thickness and water contact angle (WCA) decreased considerably, and lower pore sizes with narrower distributions were obtained. At higher pressure (10 MPa), a noticeable decrease in thickness (from 270 to 38 μm) and WCA (from 139 to 110°) was observed. Additionally, pore size distribution shifted toward a predominant narrow peak of around 0.40 μm. HP enhanced the uniformity of the PVDF crystalline structure without altering its overall crystallinity degree (40-42%). The HP ENM exhibited a comparable dissolved CH recovery performance to a commercial PVDF membrane and demonstrated sufficient mechanical integrity to endure operating conditions, maintaining a stable performance for at least 80 h.
聚偏氟乙烯(PVDF)电纺纳米纤维膜(ENMs)有潜力用于膜接触器(MCs)的环境应用,如去除厌氧废水中溶解的CH。在这项工作中,已开发出一种PVDF平板ENM制造方案,包括静电纺丝工艺和随后的热压处理(HP),以生产具有合适完整性和孔径分布的疏水膜,用于MCs中的气液分离。热压研究探讨了压力(1、10和20 MPa)、温度(25、60、80和120°C)和时间(2、4、6和10分钟)对膜的形态特性和疏水性的影响。我们的研究表明,当在1至20 MPa之间进行热压时,PVDF ENMs中的纤维在60°C以上开始烧结。在不同的纺丝原液组成(10 - 15% PVDF,0.00 - 0.043% LiCl)下制备ENM样品。经过热压(≥1 MPa,≥60°C,6分钟)后,膜厚度和水接触角(WCA)显著降低,并获得了孔径更小且分布更窄的结果。在较高压力(10 MPa)下,观察到厚度(从270μm降至38μm)和WCA(从139°降至110°)明显下降。此外,孔径分布向约0.40μm的主要窄峰移动。热压提高了PVDF晶体结构的均匀性,而不改变其整体结晶度(40 - 42%)。热压后的ENM表现出与商用PVDF膜相当的溶解CH回收性能,并显示出足够的机械完整性以承受操作条件,并至少保持80小时的稳定性能。