Fabrication of PVDF-SiO2/PVSQ superhydrophobic compositemembrane via self-assembly with anti-fouling property for membrane distillation

doi:10.11949/j.issn.0438-1157.20180845

Abstract

Abstract:

The SiO₂ was hydrophobically modified by vinyltrimethoxysilane (VTMOS), and the modified SiO₂ was grafted onto the surface of commercial PVDF (polyvinylidene fluoride) membrane by self-assembly method to make the surface superhydrophobic. The VTMOS not only modified the SiO₂ particles changing from hydrophilic into hydrophobicity, but also produced highly monodisperse spherical polyvinylsilsesquioxane (PVSQ) particles by self-hydrolysis and condensation reaction. The achievement of the superhydrophobic membrane surface was attributable to the hierarchical micro/nano rough structure constructed by the random distribution of SiO₂ particles and spherical PVSQ particles, which together with the hydrophobic groups like vinyl groups and methoxyl groups which had low surface tension distributed on the coating surface. The results showed that the maximum water of contact angle modified membrane surface was up to 159.5°, and the sliding angle could reach 8.1°. The anti-fouling properties of the commercial and modified membrane were investigated by direct contact membrane distillation (DCMD) experiments with feed solution containing NaCl, HA and CaCl₂. The results indicated that the modified membrane with superhydrophobic surface was suitable.

Key words: membrane, distillation, silica, superhydrophobic, poly(vinylidene fluoride), self-assembly

摘要：

采用乙烯基三甲氧基硅烷(VTMOS)对SiO₂疏水改性，通过自组装法，将改性SiO₂接枝在商业PVDF(聚偏氟乙烯)膜表面，使其表面达到超疏水。利用场发射电子显微镜、红外光谱仪、接触角测量仪及毛细流孔径分析仪等仪器对改性前后膜的表面形貌、化学组成、接触角及孔径变化等性能参数进行表征。结果表明，VTMOS不仅对SiO₂疏水改性，还通过自身的水解缩聚反应，生成了规整圆球状的聚乙烯基倍半硅氧烷(PVSQ)微粒，纳米级SiO₂分布于微米级PVSQ表面，在改性膜表面构造了多层次微/纳米粗糙表面，在低表面能疏水基团乙烯基和甲氧基的共同作用下，成功实现了超疏水改性，改性膜水接触角达到159.5°，滚动角降至8.1°。以NaCl、HA和CaCl₂混合溶液为进料液，对商业PVDF膜和改性膜进行了长期直接接触式膜蒸馏(DCMD)实验，探究其抗污染性能。结果表明，改性膜适用于长期DCMD实验，并表现出比商业PVDF膜更稳定的通量，截盐率始终大于99.99%，具有良好的稳定性和抗污染性能。

关键词: 膜, 蒸馏, 二氧化硅, 超疏水, 聚偏氟乙烯, 自组装

CLC Number:

TQ 028.8

Kai WANG, Dewu WANG, Deyin HOU, Ziyi YUAN, Jun WANG. Fabrication of PVDF-SiO₂/PVSQ superhydrophobic compositemembrane via self-assembly with anti-fouling property for membrane distillation[J]. CIESC Journal, 2019, 70(1): 298-308.

王凯, 王德武, 侯得印, 袁子怡, 王军. 自组装法制备PVDF-SiO₂/PVSQ超疏水复合膜及膜蒸馏抗污染性能[J]. 化工学报, 2019, 70(1): 298-308.

Figures/Tables 15

Table 1 Alcohol sol compositions and preparation conditions of modified membranes

Alcohol sol compositions(preparation conditions)	Value
concentration of SiO₂/%(mass)	0.5, 1.0, 1.5, 2.0
concentration of VTMOS/%(mass)	2.0, 4.0, 6.0, 8.0
immersion solution temperature/℃	40
dipping time/h	0.5
air-tried temperature/℃	room temperature

Fig.1 Mechanism of preparation of surperhydrophobic PVDF-SiO2/PVSQ membrane

Fig.2 Schematic diagram of direct contact membrane distillation experiment device

Fig.3 Mechanism of modification of SiO2 and formation of spherical PVSQ particles

Fig.4 Schematic diagrams of alkaline treat process of PVDF and mechanism of modified SiO2 grafted on PVDF-OH

Fig.5 SEM images of origin SiO2 and SiO2/PVSQ

Fig.6 SEM images of commercial PVDF membrane and modified membranes

Fig.7 FT-IR spectra of commercial PVDF membrane, PVDF-OH and modified membranes

Fig.8 Water contact angles and sliding angles of commercial PVDF membrane and modified membranes

Fig.9 Schematic diagrams of Cassie-Baxter state

Fig.10 Schematic diagrams of modified superhydrophobic membrane surface

Table 2 Measured data of commercial PVDF membrane and modified membranes with different SiO2 concentrations

Membrane label	Concentration of SiO₂/%	Mean pore size/μm	Bubble pore size/μm	Porosity/%	Membrane thickness/mm
PVDF	0	0.76±0.06	1.13±0.08	77.68±2.23	0.102±0.02
PVDF-M1	0.5	0.75±0.08	1.12±0.11	75.13±1.76	0.118±0.02
PVDF-M2	1.0	0.74±0.07	1.11±0.09	73.30±0.97	0.131±0.02
PVDF-M3	1.5	0.74±0.04	1.09±0.07	71.61±1.15	0.141±0.02
PVDF-M4	2.0	0.72±0.07	1.05±0.10	66.36±1.56	0.174±0.02

Fig.11 Change of DCMD permeate flux and conductivity with operating time

Fig.1 SEM images of membrane surface after anti-fouling DCMD experiment

Fig.13 SEM-EDS analysis of membrane surface after anti-fouling DCMD experiment

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Fabrication of PVDF-SiO₂/PVSQ superhydrophobic compositemembrane via self-assembly with anti-fouling property for membrane distillation

自组装法制备PVDF-SiO₂/PVSQ超疏水复合膜及膜蒸馏抗污染性能

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