超疏水聚偏氟乙烯复合微孔膜的制备及性能

提出了一种超疏水聚偏氟乙烯（PVDF）复合微孔膜的制备方法。以相转化法制备的PVDF膜为基膜,通过恒压过滤将多壁碳纳米管（MWCNTs）沉积到PVDF基膜表面,再经聚二甲基硅氧烷（PDMS）溶液修饰,可制得接触角达162°、滚动角约10°的PVDF复合微孔膜。用原子力显微镜和扫描电镜对膜表面进行结构分析,并测试了膜的接触角、气通量和机械强度等性能,考察了MWCNTs及PDMS浓度对膜结构和性能的影响。研究表明,CNTs在具有微米级粗糙度的基膜上强化了纳米结构,提高了膜的粗糙度,PDMS降低了膜的表面能,二者协同作用使复合膜的接触角大幅提高,滚动角显著下降。与高度疏水的PVDF基膜相比,PVDF复合膜的疏水性大幅提高,断裂伸长率加倍,在模拟海水真空膜蒸馏过程中,保持了较高的传质通量和截留率,具有更好的操作稳定性和抗污染性能。     

Fabrication of self‐cleaning poly(vinylidene fluoride) membrane with micro/nanoscaled two‐tier roughness

Based on the “lotus effect” principle, smooth microreliefs of polyvinylidene fluoride (PVDF) membrane were prepared via thermally induced phase separation process. Hydroxyl groups were introduced into PVDF membrane by pretreatment with KOH/alcohol solution. Subsequently, these hydroxyl groups grafted with (CH₃)₂SiCl₂/CH₃SiCl₃ to form nano‐clusters, which were decorated on the microreliefs of PVDF membrane. Scanning Electronic Microscopy (SEM) and Atomic Force Microscope (AFM) analysis showed the micro‐ and nano‐scale structures, similar to lotus leaf, were successfully fabricated on the PVDF membrane surface. The water contact angle and sliding angle on the fabricated lotus‐leaf‐like PVDF membrane surface were 154 and 4°, respectively. Self‐cleaning test indicated that the lotus‐leaf‐like surface of PVDF membrane has excellent superhydrophobic and self‐cleaning properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

自组装法制备PVDF-SiO2/PVSQ超疏水复合膜及膜蒸馏抗污染性能

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。     

Preparation of a hydrophobically enhanced antifouling isotactic polypropylene/silicone dioxide flat‐sheet membrane via thermally induced phase separation for vacuum membrane distillation

Isotactic polypropylene (iPP) hydrophobic flat‐sheet membranes were fabricated for use in vacuum membrane distillation (VMD) through a thermally induced phase‐separation process with dispersing hydrophobically modified SiO₂ nanoparticles in the casting solution to achieve a higher hydrophobicity and to sustain a stable flux in VMD. The contact angle (CA) measurements indicated that the incorporation of nano‐SiO₂ into a casting solution mixture containing 20 wt % iPP had a 20.9% higher CA relative to that of SiO₂‐free membranes. The addition of nano‐SiO₂ also induced morphological changes in the membrane structure, including changes in the pore size distribution, porosity, and suppression of macrovoids. The pore size distribution of the iPP–SiO₂ membranes became narrower compared with that of the SiO₂‐free membranes, and the porosity also improved from 35.45 to 59.75% with SiO₂ addition. The average pore size and maximum pore size of the iPP–SiO₂ membranes both decreased. The ability of the membranes to concentrate an astragalus aqueous solution (a type of traditional Chinese medicine) with VMD was investigated. The surface hydrophobicity and antifouling performance of the iPP–SiO₂ membranes improved with nano‐SiO₂ addition to the membrane casting solution. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42615.     

PDMS/PVDF microporous membrane with semi‐interpenetrating polymer networks for vacuum membrane distillation

In this article, using the non‐solvent induced phase separation process, a new microporous membrane with the semi‐interpenetrating polymer network (semi‐IPN) structure was produced. For this membrane, polydimethylsiloxane (PDMS) polymer is crosslinking and poly(vinylidene fluoride) (PVDF) polymer is linear, by changing the mass ratio of PDMS/PVDF, the structure and the performance of the prepared membranes were studied. The membranes were also investigated by attenuated total reflection‐Fourier transform infrared (ATR‐FTIR), scanning electron microscopy–energy‐dispersive X‐ray spectroscopy, X‐ray diffraction, thermogravimetric analysis, and water contact angle, etc. ATR‐FTIR spectroscopy confirmed the formation of semi‐IPN; compared with the PDMS/PVDF polymer without semi‐IPNs structure, the viscosity of the semi‐IPNs structured casting solution increased, membrane mechanical property increased but its hydrophobicity decreased. Using the resulting membranes for the vacuum membrane distillation desalt of the NaCl solution (30 g/L), 99.9% salt rejection and reasonable flux were obtained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45792.     

Fabrication and characterization of hydrophobic PVDF hollow fiber membranes for desalination through direct contact membrane distillation

The mixture of inorganic salt LiCl and soluble polymer polyethylene glycol (PEG) 1500 as non-solvent additive was introduced to fabricate hydrophobic hollow fiber membrane of polyvinylidene fluoride (PVDF) by phase inversion process, using N,N-dimethylacetamide (DMAc) as solvent and tap water as the coagulation medium. Compared with other three membranes from PVDF/DMAc, PVDF/DMAc/LiCl and PVDF/DMAc/PEG 1500 dope solution, it can be observed obviously by scanning electron microscope (SEM) that the membrane spun from PVDF/DMAc/LiCl/PEG 1500 dope had longer finger-like cavities, ultra-thin skins, narrow pore size distribution and porous network sponge-like structure owing to the synergistic effect of LiCl and PEG 1500. Besides, the membrane also exhibited high porosity and good hydrophobicity. During the desalination process of 3.5 wt% sodium chloride solution through direct contact membrane distillation (DCMD), the permeate flux achieved 40.5 kg/m² h and the rejection of NaCl maintained 99.99% with the feed solution at 81.8 °C and the cold distillate water at 20.0 °C, this performance is comparable or even higher than most of the previous reports. Furthermore, a 200 h continuously desalination experiment showed that the membrane had stable permeate flux and solute rejection, indicating that the as-spun PVDF hollow fiber membrane may be of great potential to be utilized in the DCMD process.     

疏水石墨烯膜的制备及其用于膜蒸馏脱盐的研究进展

膜蒸馏技术由于理论截盐率高、操作条件温和及对盐浓度灵敏度低等优势，在脱盐领域中展现出巨大潜力。近年来，人们开始关注石墨烯材料在膜蒸馏脱盐领域中的应用。本文首先概述膜蒸馏技术的基本原理及常用膜材料；接着介绍石墨烯的疏水性质和疏水石墨烯膜的制备；再详细综述石墨烯混合基质膜、石墨烯复合膜及石墨烯纯膜这三类疏水石墨烯膜在膜蒸馏脱盐中的应用；最后总结疏水石墨烯用于膜蒸馏脱盐面临的主要挑战及未来研究方向。     

Porous poly(vinylidene fluoride) membrane with highly hydrophobic surface

The preparation of very hydrophobic poly(vinylidene fluoride) (PVDF) membranes was explored by using two methods. The first one was the modified phase inversion method using a water/N,N‐dimethylacetamide (DMAc) mixture instead of pure water as a soft precipitation bath. The second method was a precipitation‐bath free method, that is, the PVDF/DMAc casting solution underwent gelation in the open air instead of being immersed into a precipitation bath. The morphology of the surface and cross section of the membranes was investigated by using scanning electron microscopy (SEM). It was found that the membranes exhibited certain micro‐ and nanoscale hierarchical roughness on the surface, which brought about an enhanced hydrophobicity of the membrane. The contact angle (CA) of the samples obtained by the second method was as high as 150° with water. The conventional phase inversion method preparing PVDF porous membrane using pure water as precipitation bath usually results in an asymmetric membrane with a dense skin layer having a CA close to that of a smooth PVDF surface. The modified approach avoided the formation of a skin‐layer and resulted in a porous and highly hydrophobic surface of PVDF. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1358–1363, 2005     

凝固浴组成和温度对PVDF疏水微孔膜结构与性能的影响

利用非溶剂相转化法(NIPS),以聚偏氟乙烯(PVDF)/磷酸三乙酯(TEP)-N,N-二甲基乙酰胺(DMAc)为铸膜液体系,乙醇水溶液为凝固浴制备高性能的PVDF疏水微孔膜。考察了凝固浴中乙醇(EtOH)含量及凝固浴温度对PVDF成膜分相速率、膜结构和膜疏水性的影响。实验结果表明,在20℃的凝固浴温度下,凝固浴中乙醇含量的升高减慢了铸膜液体系的分相速率,提高了PVDF膜的孔隙率;在凝固浴中添加60%(wt)的乙醇,可形成表面荷叶状结构和截面对称的海绵状结构,膜表面的接触角为130.3°,呈很强的疏水性,并具有较优的膜强度。     

Hydrophobic polyethersulfone porous membranes for membrane distillation

Membrane distillation (MD) is a thermal, vapor-driven transportation process through micro porous hydrophobic membranes that is increasingly being applied to seawater and brine desalination processes. Two types of hydrophobic microporous polyethersulfone flat sheet membranes, namely, annealed polyethersulfone and a polyethersulfone/tetraethoxysilane (PES/TEOS) blend were prepared by a phase inversion process. The membranes were characterized and their performances were investigated using the vacuum membrane distillation of an aqueous NaCl solution. The performances of the prepared membranes were also compared with two commercially available hydrophobic membranes, polytetrafluorethylene and polyvinylidene fluoride. The influence of operational parameters such as feed temperature (25–65 °C), permeate vacuum pressure (200–800 mbar), feed flow rate (8–22 mL/s) and feed salt concentration (3000 to 35000 mg/L) on the MD permeation flux were investigated for the four membranes. The hydrophobic PES/TEOS membrane had the highest salt rejection (99.7%) and permeate flux (86 kg/m²·h) at 65 °C, with a feed of 7000 ppm and a pressure of 200 mbar.     

溶胀辊轧法PVDF膜表面的疏水强化：溶胀剂的影响

提出了一种简便、低成本的聚偏氟乙烯（PVDF）微孔膜表面疏水增强方法——溶胀辊轧法,以微结构辊筒对表面喷涂溶胀剂的PVDF成品微孔膜辊轧后,采用浸没凝胶法成膜。以N-甲基吡咯烷酮/水（非溶剂）为溶胀体系,采用扫描电子显微镜（SEM）、原子力显微镜（AFM）、水接触角（WCA）、最大孔径、平均孔径、N₂通量、耐磨性、液体穿透压（LEP）等表征手段,系统地研究了溶胀剂体系、溶胀剂容量对PVDF微孔膜结构与性能的影响。结果表明：辊轧膜表面呈现微米-亚微米层次特征,溶胀辊轧操作起到了疏水增强、透过能力提升的效果。溶胀剂中水（非溶剂）质量分数为6%、喷涂密度为0.03mL/cm²时,膜性能最优。连续运行30h的真空膜蒸馏（VMD）对比实验表明,辊轧膜较未辊轧膜具有更高的产水通量、脱盐率及更好的耐污染性能。该方法为低成本、连续化进行成品膜表面疏水强化提供了一种新选择。     

Preparation of superhydrophobic nanocomposite fiber membranes by electrospinning poly(vinylidene fluoride)/silane coupling agent modified SiO2 nanoparticles

Superhydrophobic nanocomposite fiber membranes were prepared by blend electrospinning of poly(vinylidene fluoride) (PVDF) mixed with silane coupling agent modified SiO₂ nanoparticles. The nanoparticles were prepared by the sol–gel method, and the average particle diameter was measured by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The effects of the type of silane coupling agent, such as n‐octyltriethoxysilane, vinyltrimethoxysilane (A‐171), and vinyltriethoxysilane (A‐151), and the mass ratio of the modified silica particles and PVDF on the surface wettability of the composite fiber membrane were investigated. The results indicated that the incorporation of silane coupling agent modified silica particles into the PVDF membrane increased the roughness of the surface and formed micro/nano dual‐scale structure compared to the pristine PVDF membrane, which was responsible for the superhydrophobicity and self‐cleaning property of the nanocomposite fiber membranes. The value of water contact angle (CA) increased with the increase of the content of modified SiO₂ nanoparticles in the nanocomposite membrane, ranging from 149.8° to 160.1° as the mass ratio of modified 170 nm SiO₂ with PVDF matrix increased from 0.5:1 to 5:1, indicating the membrane possesses a superhydrophobic surface. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44501.     

Poly(vinylidene difluoride) Membrane Assisted by Modified ZnO/ZIF Nanoparticles for Membrane Distillation

Poly(vinylidene difluoride) (PVDF) polymeric membranes incorporated by synthesized hydrophobic agents were applied for membrane distillation. ZnO nanoparticles were modified with a silane coupling agent (n‐octyltriethoxysilane) and coupled by zeolite imidazole framework (ZIF)‐8 crystals. In particular, hydrophobic and porous membranes were prepared with ZIF crystals and modified ZnO/ZIF‐coupled nanoparticles. The influences of feed concentration and temperature of NaCl solution and seawater during filtration were evaluated. The hydrophobic modified membranes showed a higher permeate flux than pure PVDF membranes at different feed concentrations and feed temperatures. After modification, the porosity increased significantly and the contact angle became larger.     

Fouling evaluation on membrane distillation used for reducing solvent in polyphenol rich propolis extract

Membrane distillation (MD) has not been widely studied in the concentrate of phenolic rich solution in comparison to osmotic distillation.In this work,the potential of MD to reduce solvent in the polyphenol rich propolis extract was further investigated.Polyvinylidene fluoride (PVDF) membranes were engineered with the smaller pore size for the less hydrophobic surface in order to avoid wetting,allowing only the solvent vapor to be transferred from the warm feed into the cold permeate.All the membranes exhibited more than 95％ rejection of phenolic and flavonoid compounds.Although the hydrophilic membranes exhibited less fouling,they displayed a lower flux than the hydrophobic membrane due to the hindrance in the wetted pores.The hydrophobic membrane was seriously fouled by the phenolic acid as shown in the Fourier transform infrared spectroscopy spectrum.Pore plugging occurred on these hydrophobic membranes as confirmed in the scanning electron microscope images.     

Effect of the exposure time on the structure and performance of hydrophobic polydimethylsiloxane–poly(vinylidene fluoride) membranes via a non‐solvent‐induced phase separation process in a clean room

The objective of this study was to investigate the effects of the exposure time on the properties and permeability of polydimethylsiloxane (PDMS)–poly(vinylidene fluoride) (PVDF) blend hydrophobic microporous membranes, which were fabricated via a non‐solvent‐induced phase separation process at 25 °C and 60% relative humidity in a clean‐room circumstance. For the prepared PDMS–PVDF membranes, the membrane morphologies were observed by scanning electron microscopy. Crystalline structures were observed by X‐ray diffraction. Pore structures were analyzed by membrane porosity and mean pore size. Hydrophobicity was measured by contact angle measurement, and the mechanical properties were characterized by tensile strength testing. Our study results show that with increasing exposure time from 10 to 110 s, all of the membranes showed a similar pore structure: a spongelike substrate layer with a thin realm of fingerlike structures under the top surface. Phase separation between PDMS and PVDF occurred. The membrane porosity and mean pore radius decreased, and the membrane thickness increased. The membrane hydrophobicity decreased, and the mechanical properties first increased and then decreased. In addition, vacuum membrane distillation experiments were conducted. With the increase in the exposure time from 10 to 110 s, the membrane permeate flux decreased from 16.54 to 6.65 kg m⁻²·h⁻¹, and the salt rejection was higher than 99.9%. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43842.     

PVDF-ZrO2复合中空纤维膜在乳化油废水中的应用

针对普通聚偏二氟乙烯(PVDF)中空纤维膜具有疏水性强、易污染的应用缺陷,在制备纳米粒子掺杂改性的PDVF-ZrO2复合中空纤维膜前期工作基础上,表征了其微观结构,并考察了其在油水体系中的分离效果。微观结构检测表明,随着ZrO2含量的增大,复合膜的断面微观结构完成由指状大孔向海绵状结构的转化。PDVF-ZrO2复合膜的接触角和牛血清蛋白(BSA)吸附实验结果显示其亲水性及抗污染性能均得到了提高。进一步考察了PDVF-ZrO2复合中空纤维渗透分离性能,ZrO2纳米粒子质量分数为0.3%时,显示了最佳的渗透性能。在乳化油废水处理过程中,在油质量浓度为1 g/L,操作压力为0.1MPa、搅拌强度为20 r/min条件下,通量为105 L/(m2.h),TOC去除率为95.4%,表明具有较好的废水处理效果。     

Modified poly(vinylidene fluoride) hollow fiber composite membranes reinforced by hydroxyapatite nanocrystal whiskers

The modified poly(vinylidene fluoride) (PVDF) hollow fiber composite membranes reinforced by hydroxyapatite (HAP) nanocrystal whiskers were fabricated with wet‐spinning method. The PVDF/HAP/N‐methyl‐2‐pyrrolidone dope solutions experienced delayed demixing mechanism, and the precipitation rate slightly increased as the HAP whisker content increased. The cross sections of PVDF‐HAP and neat PVDF hollow fiber composite membranes were composed of five distinct layers: two skin layers, two finger‐like sublayers, and a sponge‐like layer. The Young's modulus of and tensile strength of the PVDF‐HAP hollow fiber membranes gradually increased with the addition of nano‐HAP whiskers. The elongation ratio was also improved, which was different from the polymeric membranes modified by other inorganic nanofillers. The permeation flux of the PVDF‐HAP hollow fiber membranes slightly increased with the increase of HAP content in the composite membranes as its hydrophilicity was improved. The crystallization behaviors of PVDF in the composite membranes were also investigated. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Innovative hydrophobic/hydrophilic perfluoropolyether (PFPE)/polyvinylidene fluoride (PVDF) composite membrane for vacuum membrane distillation

Though membrane distillation (MD) has gained more and more attention in the field of desalination, the wetting phenomenon was still a non-negligible problem. In this work, a method combined dip-coating and UV in situ polymerization for preparing hydrophobic/hydrophilic perfluoropolyether (PFPE)/polyvinylidene fluoride composite membranes. This composite membrane consisted of a top thin hydrophobic coating layer and hydrophilic substrate membrane. In terms of anti-wetting properties, contact angle and liquid entry pressure of all composite membranes (except for those based on 0.45 μm) exceeded 160° and 0.3 MPa, respectively. In particular, the desalination performance was tested in vacuum membrane distillation tests by feeding 3.5% (mass) saline solution (NaCl) at 60 ℃. The composite membranes with larger support pore size and lower PFPE content had higher membrane distillation flux. And for stability tests (testing the 0.22 μm membrane coated by 5% (mass) PFPE), the highest MD flux 29.08 kg·m^-2·h^-1 and stable salt rejection (over 99.99%) during the period. Except that, the effects of coating material concentration and pore sizes of substrate membrane were also investigated for surface morphology and topography, porosity, mechanical strength and pore size characteristics. This work provided a simple and effective alternative to prepare excellent hydrophobic composite membranes for MD applications.     

亲水改性PVDF膜材料及其膜生物反应器应用

膜生物反应器（MBR）技术中最常用的膜材料是聚偏氟乙烯（PVDF）,然而由于PVDF膜的疏水性,使其在用于MBR的运行过程中存在易污染、通量低等缺陷,因此对PVDF膜材料进行亲水改性是近年来国内外研究的热点。本文首先介绍了PVDF膜材料典型的表面涂覆改性和表面化学接枝改性这两种亲水改性方法,然后概述了随着纳米科学技术的兴起,采用无机纳米材料如碳材料氧化石墨烯（GO）、无机抑菌材料纳米银粒子及二氧化钛纳米颗粒等进行功能化复合制备PVDF膜材料等亲水改性方法。研究进展表明,新型亲水改性PVDF膜材料不仅在MBR污/废水处理中优势明显,而且在可再生生物能源生产等可持续发展领域极具潜力。     

表面沉积化镁合金基底上超疏水聚偏氟乙烯微孔膜的制备与性能

用一步浸泡法制得表面沉积化镁合金板，再以此镁合金板为制膜基底，以聚偏氟乙烯（PVDF）/N,N-二甲基乙酰胺（DMAc）/辛醇/水为制膜体系，采用干-湿相转化法制备了超疏水PVDF膜，该膜的水接触角可达160°。用粗糙度仪、扫描电镜、能谱仪、红外光谱仪等对镁合金表面和PVDF膜底面的微观结构、化学组成进行表征和分析。研究表明，一步浸泡处理过的镁合金表面生成了均匀的十四酸铁沉积物，该沉积物可在膜制备中部分嵌入膜底面，增加了膜底面的粗糙度，从而使PVDF膜的疏水性大幅提高。对PVDF膜的磨损试验表明，所制备的超疏水膜表面具备良好的机械稳定性。真空膜蒸馏实验表明，所制备的PVDF膜具有较高的通量和截留率，在运行中保持了更好的操作稳定性。