自组装法制备PVDF-SiO2/PVSQ超疏水复合膜及膜蒸馏抗污染性能

doi:10.11949/j.issn.0438-1157.20180845

化工学报 ›› 2019, Vol. 70 ›› Issue (1): 298-308.DOI: 10.11949/j.issn.0438-1157.20180845

• 材料化学工程与纳米技术 • 上一篇下一篇

自组装法制备PVDF-SiO₂/PVSQ超疏水复合膜及膜蒸馏抗污染性能

王凯^1,²,王德武¹(),侯得印^2,³(),袁子怡⁴,王军³

1. 河北工业大学化工学院，天津 300130
2. 中国科学院生态环境研究中心，中国科学院饮用水科学与技术重点实验室，北京 100085
3. 中国科学院生态环境研究中心，环境水质学国家重点实验室，北京 100085
4. 南昌大学环境学院，江西南昌 330000

收稿日期:2018-07-23 修回日期:2018-09-30 出版日期:2019-01-05 发布日期:2019-01-05
通讯作者: 王德武,侯得印
作者简介:王凯（1993—），男，硕士研究生|王德武（1980—），男，博士，教授，<email>wangdewu@hebut.edu.cn</email>|侯得印（1980—），男，博士，副研究员，<email>dyhou@rcees.ac.cn</email>
基金资助:
国家自然科学基金项目(51478454)

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

Kai WANG^1,²,Dewu WANG¹(),Deyin HOU^2,³(),Ziyi YUAN⁴,Jun WANG³

1. School of Chemical Engineering, Hebei University of Technology, Tianjin 300130, China
2. Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
3. State Key Laboratory of Environment Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
4. School of Resources Environmental & Chemical Engineering, Nanchang University, Nanchang 330000, Jiangxi, China

Received:2018-07-23 Revised:2018-09-30 Online:2019-01-05 Published:2019-01-05
Contact: Dewu WANG,Deyin HOU

摘要/Abstract

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

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

中图分类号:

TQ 028.8

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.

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.

图/表 15

表1 醇溶胶组成与改性膜制备参数

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

图1 PVDF-SiO2/PVSQ超疏水复合膜制备机理

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

图2 直接接触式膜蒸馏装置

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

图3 SiO2疏水改性以及PVSQ形成机理

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

图4 碱处理PVDF膜与改性SiO2接枝PVDF-OH机理

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

图5 原始SiO2与SiO2/PVSQ的SEM图

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

图6 商业PVDF膜与改性膜的SEM图

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

图7 商业PVDF膜、PVDF-OH以及改性膜的红外谱图

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

图8 商业PVDF膜与改性膜的水接触角

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

图9 Cassie-Baxter状态

Fig.9 Schematic diagrams of Cassie-Baxter state

图10 改性膜超疏水表面

Fig.10 Schematic diagrams of modified superhydrophobic membrane surface

表2 商业PVDF膜与不同质量分数SiO2改性膜测试数据

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

图11 直接接触式膜蒸馏抗污染实验通量及

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

图12 长期DCMD抗污染实验后SEM照片

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

图13 长期DCMD抗污染实验后膜表面

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

参考文献 39

1	AlkhudhiriA, DarwishN, HilalN. Membrane distillation: a comprehensive review[J]. Desalination, 2012, 287(8): 2-18.
2	ZhangW, LiY, LiuJ, 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.
3	RenL F, XiaF, ChenV, et al. TiO₂-FTCS modified superhydrophobic PVDF electrospun nanofibrous membrane for desalination by direct contact membrane distillation[J]. Desalination, 2017, 423: 1-11.
4	LinS, NejatiS, BooC, et al. Omniphobic membrane for robust membrane distillation[J]. Environmentalence & Technology Letters, 2014, 1(11): 443-447.
5	GrażYnaL, WojciechB, BartłOmiejM, et al. Application of membrane distillation for ethanol recovery during fuel ethanol production[J]. Journal of Membrane Science, 2011, 375(1/2): 212-219.
6	KhalifaA, AhmadH, AntarM, et al. Experimental and theoretical investigations on water desalination using direct contact membrane distillation[J]. Desalination, 2017, 404: 22-34.
7	GrytaM, TomaszewskaM, GrzechulskaJ, et al. Membrane distillation of NaCl solution containing natural organic matter[J]. Journal of Membrane Science, 2001, 181(2): 279-287.
8	GeQ, PengW, WanC, et al. Polyelectrolyte-promoted forward osmosis-membrane distillation (FO-MD) hybrid process for dye wastewater treatment.[J]. Environmental Science & Technology, 2012, 46(11): 6236.
9	WangZ, LinS. Membrane fouling and wetting in membrane distillation and their mitigation by novel membranes with special wettability[J]. Water Research, 2017, 112: 38-47.
10	EykensL, SitterK D, DotremontC, et al. Wetting resistance of commercial membrane distillation membranes in waste streams containing surfactants and oil[J]. Applied Sciences, 2017, 7(2): 118.
11	KhayetM, MatsuuraT. Preparation and characterization of polyvinylidene fluoride membranes for membrane distillation[J]. Industrial & Engineering Chemistry Research, 2001, 40(24): 5710-5718.
12	GrytaM. Long-term performance of membrane distillation process[J]. Journal of Membrane Science, 2005, 265(1): 153-159.
13	RazmjouA, ArifinE, DongG, et al. Superhydrophobic modification of TiO₂, nanocomposite PVDF membranes for applications in membrane distillation[J]. Journal of Membrane Science, 2012, 415/416(10): 850-863.
14	FüRstnerR, BarthlottW, NeinhuisC, et al. Wetting and self-cleaning properties of artificial superhydrophobic surfaces[J]. Langmuir the ACS Journal of Surfaces & Colloids, 2005, 21(3): 956-961.
15	ZhangJ, PuG, SevertsonS J. Fabrication of zinc oxide/polydimethylsiloxane composite surfaces demonstrating oil-fouling-resistant superhydrophobicity[J]. ACS Applied Materials & Interfaces, 2014, 2(10): 2880-2883.
16	TijingL D, YunC W, ChoiJ S, et al. Fouling and its control in membrane distillation—a review[J]. Journal of Membrane Science, 2015, 475: 215-244.
17	WolfP H, SivernsS, MontiS. UF membranes for RO desalination pretreatment[J]. Desalination, 2005, 182(1): 293-300.
18	BhushanB, HerE K. Fabrication of superhydrophobic surfaces with high and low adhesion inspired from rose petal[J]. Langmuir the ACS Journal of Surfaces & Colloids, 2010, 26(11): 8207-17.
19	WangH, FangJ, ChengT, et al. One-step coating of fluoro-containing silica nanoparticles for universal generation of surface superhydrophobicity[J]. Chemical Communications, 2008, 7(7): 877.
20	MchaleG, ShirtcliffeN J, NewtonM I. Super-hydrophobic and super-wetting surfaces: analytical potential[J]. Analyst, 2004, 129(4): 284-287.
21	KimH, NohK, ChoiC, et al. Extreme superomniphobicity of multiwalled 8 nm TiO₂ nanotubes[J]. Langmuir, 2011, 27(16): 10191-10196.
22	YangH, PiP, CaiZ Q, et al. Facile preparation of super-hydrophobic and super-oleophilic silica film on stainless steel mesh via sol–gel process[J]. Applied Surface Science, 2010, 256(13): 4095-4102.
23	LattheS S, ImaiH, GanesanV, et al. Porous superhydrophobic silica films by sol–gel process[J]. Microporous & Mesoporous Materials, 2010, 130(1): 115-121.
24	PengP, KeQ, ZhouG, et al. Fabrication of microcavity-array superhydrophobic surfaces using an improved template method[J]. J. Colloid Interface Sci., 2013, 395(1): 326-328.
25	SunM, LuoC, XuL, et al. Artificial lotus leaf by nanocasting[J]. Langmuir the ACS Journal of Surfaces & Colloids, 2005, 21(19): 8978.
26	GadelhakM, OchandaF O, SamahaM A, et al. Fabrication of superhydrophobic fiber coatings by DC-biased AC-electrospinning[J]. Journal of Applied Polymer Science, 2011, 123(2): 1112-1119.
27	JiangL, ZhaoY, ZhaiJ. A lotus-leaf-like superhydrophobic surface: a porous microsphere/nanofiber composite film prepared by electrohydrodynamics[J]. Angewandte Chemie, 2004, 43(33): 4338.
28	BarshiliaH C, AnanthA, GuptaN, et al. Superhydrophobic nanostructured Kapton surfaces fabricated through Ar+O₂ plasma treatment: effects of different environments on wetting behaviour[J]. Applied Surface Science, 2013, 268(268): 464-471.
29	FresnaisJ, ChapelJ P, Poncin-epaillardF. Synthesis of transparent superhydrophobic polyethylene surfaces[J]. Surface & Coatings Technology, 2006, 200(18): 5296-5305.
30	ZhangZ, YangW, GuZ, et al. PVDF films with superhydrophobic surface fabricated by plasma-enhanced chemical vapor deposition[J]. Advanced Materials Research, 2009, 79/80/81/82: 1451-1454.
31	HuangL, LauS P, YangH Y, et al. Stable superhydrophobic surface via carbon nanotubes coated with a ZnO thin film[J]. Journal of Physical Chemistry B, 2005, 109(16): 7746-7753.
32	ZhangH, LiuY, YaoD, et al. ChemInform abstract: hybridization of inorganic nanoparticles and polymers to create regular and reversible self-assembly architectures[J]. Chemical Society Reviews, 2012, 43(48): 6066-88.
33	ThorkelssonK, BaiP, XuT. Self-assembly and applications of anisotropic nanomaterials: a review[J]. Nano Today, 2015, 10(1): 48-66.
34	杨辉, 高红芳. 二氧化硅/聚乙烯基倍半硅氧烷超疏水涂层的制备与表征[J].高分子材料科学与工程, 2016, 32(11): 130-134.
	YangH, GaoH F. Preparation and characterization of superhydrophobic coatings with silica/polyvinylsilsesquioxane[J]. Polymer Materials Science & Engineering, 2016, 32(11): 130-134.
35	GuM, ZhangJ, WangX, et al. Formation of poly(vinylidene fluoride)(PVDF) membranes via thermally induced phase separation[J]. Desalination, 2006, 192(1): 160-167.
36	SongZ, XingM, ZhangJ, et al. Determination of phase diagram of a ternary PVDF/γ-BL/DOP system in TIPS process and its application in preparing hollow fiber membranes for membrane distillation[J]. Separation & Purification Technology, 2012, 90(90): 221-230.
37	杨辉, 陈飞. 乙烯基三甲氧基硅烷对二氧化硅的超疏水改性研究[J]. 人工晶体学报, 2015, 44(09): 2597-2605.
	YangH, ChenF. Superhydrophobic modification of silica with VTMO[J]. Journal of Synthetic Crystals, 2015, 44(09): 2597-2605.
38	LiH, YuS. A robust superhydrophobic surface and origins of its self-cleaning properties[J]. Applied Surface Science, 2017, 420: 336-345.
39	SrisurichanS, JiraratananonR, FaneA G. Humic acid fouling in the membrane distillation process[J]. Desalination, 2005, 174(1): 63-72.

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自组装法制备PVDF-SiO₂/PVSQ超疏水复合膜及膜蒸馏抗污染性能

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

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