PVDF-PFTS/SiO2膜制备及抗混合污染性能

doi:10.16085/j.issn.1000-6613.2021-1238

摘要/Abstract

摘要：

采用表面接枝技术制备了PVDF-PFTS/SiO₂超疏水复合膜，通过扫描电子显微镜（SEM）和红外光谱（FTIR）分析了膜污染前后的表面结构和组成，考察了直接接触式膜蒸馏（DCMD）装置出水电导率和膜通量的变化，利用XDLVO理论分析了PVDF-PFTS/SiO₂超疏水复合膜的抗混合污染性能和机理。结果表明：在1H, 1H, 2H, 2H-全氟辛基三氯硅烷（PFTS）和SiO₂共同作用下，PVDF-PFTS/SiO₂超疏水复合膜表面形成微纳米复合乳突结构，水接触角（WCA）由99°增至155°。与PVDF基膜相比，PVDF-PFTS/SiO₂超疏水复合膜对混合污染物具有较好的抗污染性能；连续运行10h，膜通量和截留率分别保持在10.06kg/(m²·h)和99.80%。XDLVO理论分析表明，PVDF-PFTS/SiO₂超疏水复合膜表面与污染物之间的作用力由引力转变为斥力是其抗混合污染性能增强的主要原因之一。

关键词: PVDF-PFTS/SiO₂膜, 超疏水性, 膜污染, 膜制备, 复合材料

Abstract:

The PVDF-PFTS/SiO₂superhydrophobic composite membrane was prepared by surface grafting technology. The surface structure and the composition of the membrane before and after contamination were analyzed by scanning electron microscopy (SEM) and infrared spectroscopy (FTIR). The change of the effluent conductivity and membrane flux of the device in direct contact membrane distillation (DCMD) was investigated. The anti-mixed fouling performance and mechanism of the superhydrophobic PVDF-PFTS/SiO₂ superhydrophobic composite membrane were analyzed by XDLVO theory. The results showed that under the combined action of 1H, 1H, 2H, 2H-perfluorooctyltrichlorosilane (PFTS) and SiO₂, a micro-nano composite papillary structure was formed on the surface of the PVDF-PFTS/SiO₂ superhydrophobic composite membrane. The water contact angle (WCA) increased from 99° to 155°. Compared with the PVDF base membrane, the PVDF-PFTS/SiO₂ superhydrophobic composite membrane had a better anti-fouling performance against mixed pollutants. After 10h continuous operation, the membrane flux and rejection rate were maintained at 10.06kg/(m²·h) and 99.80%, respectively. The theoretical analysis of XDLVO showed that the transformation of the force between the surface of the PVDF-PFTS/SiO₂ superhydrophobic composite membrane and the pollutants from gravitational force to repulsive force was one of the main reasons for its enhanced anti-mixed fouling performance.

Key words: PVDF-PFTS/SiO₂ membrane, superhydrophobicity, membrane fouling, membrane preparation, composite material

中图分类号:

TQ028.8

李正, 牛静东, 何广泽, 张兰河, 张海丰. PVDF-PFTS/SiO₂膜制备及抗混合污染性能[J]. 化工进展, 2022, 41(5): 2713-2721.

LI Zheng, NIU Jingdong, HE Guangze, ZHANG Lanhe, ZHANG Haifeng. Preparation of PVDF-PFTS/SiO₂ membrane and its resistance mixed fouling performance[J]. Chemical Industry and Engineering Progress, 2022, 41(5): 2713-2721.

图/表 13

图1 直接接触式膜蒸馏装置

表1 膜表面组成

样品	元素含量/%
样品	C	N	F	O	Si	F/C
PVDF基膜	53.81	1.60	42.20	2.39	—	0.78
PVDF-PFTS/SiO₂	32.99	1.46	38.77	17.76	9.02	1.18

图2 PVDF基膜、PVDF-PFTS/SiO2膜的XPS结果

表2 PVDF基膜和PVDF-PFTS/SiO2膜的基本参数

样品	膜厚/μm	最大孔径/nm	平均孔径/nm	水接触角/（°）	进水压力/kPa
PVDF基膜	100±1	652	543	99±1	204
PVDF-PFTS/SiO₂膜	101±1	664	561	153±2	235

图3 PVDF基膜和PVDF-PFTS/SiO2膜膜通量和电导率的变化

图4 PVDF基膜和PVDF-PFTS/SiO2膜透过液中BSA浓度的变化

图5 DCMD实验前后PVDF基膜和PVDF-PFTS/SiO2膜红外光谱

图6 DCMD实验前后PVDF基膜[(a)、(b)]和PVDF-PFTS/SiO2膜[(c)、(d)]表面SEM图

图7 DCMD实验前后PVDF基膜和PVDF-PFTS/SiO2膜表面成分分析

表3 三种测试液体的表面张力参数

液体	总表面张力γ/mN·m^-1	非极性表面张力γ^LW/mN·m^-1	电子供体表面张力γ^-/mN·m^-1	电子受体表面张力γ⁺/mN·m^-1
水	72.80	21.80	25.50	25.50
二碘甲烷	50.80	50.80	0.00	0.00
乙二醇	48.00	29.00	47.00	1.90

表4 PVDF基膜、PVDF-PFTS/SiO2膜和污染物（BSA+Ca2+）的表面性质及zeta电位

样品	接触角/（°）			非极性表面张力γ^LW /mN·m^-1	电子供体表面张力γ^-/mN·m^-1	电子受体表面张力γ⁺/mN·m^-1	极性表面张力γ^AB/mN·m^-1	总表面张力γ^TOT/mN·m^-1	zeta电位 /mV
样品	θ_w	θ_D	θ_E	非极性表面张力γ^LW /mN·m^-1	电子供体表面张力γ^-/mN·m^-1	电子受体表面张力γ⁺/mN·m^-1	极性表面张力γ^AB/mN·m^-1	总表面张力γ^TOT/mN·m^-1	zeta电位 /mV
PVDF基膜	98	65	71	22.401	3	0.102	1.106	23.507	-36.787
PVDF-PFTS/SiO₂膜	152	140	136	7.058	6.646	0.003	0.282	7.340	-40.130
BSA+CaCl₂	25	44	30	37.540	63.282	0.017	2.074	39.614	-11.581

表5 污染物（BSA-CaCl2）与膜界面相互作用自由能

膜材料	极性作用能ΔG $m l f A B$ /mJ·m^-2	范德华作用能ΔG $m l f L W$ /mJ·m^-2	静电作用能ΔG $m l f E L$ /mJ·m^-2	总作用能ΔG $m l f T O T$ /mJ·m^-2
PVDF基膜	-5.156	-0.186	2.59×10^-6	-5.342
PVDF-PFTS/SiO₂膜	4.704	5.868	3.55×10^-6	10.572

表5 污染物（BSA-CaCl2）与膜界面相互作用自由能

膜材料	极性作用能ΔG $m l f A B$ /mJ·m^-2	范德华作用能ΔG $m l f L W$ /mJ·m^-2	静电作用能ΔG $m l f E L$ /mJ·m^-2	总作用能ΔG $m l f T O T$ /mJ·m^-2
PVDF基膜	-5.156	-0.186	2.59×10^-6	-5.342
PVDF-PFTS/SiO₂膜	4.704	5.868	3.55×10^-6	10.572

图8 PVDF-PFTS/SiO2膜和PVDF基膜表面与污染物的相互作用

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PVDF-PFTS/SiO₂膜制备及抗混合污染性能

Preparation of PVDF-PFTS/SiO₂ membrane and its resistance mixed fouling performance

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