PVDF–TiO2 composite hollow fiber ultrafiltration membranes prepared by TiO2 sol–gel method and blending method

Organic–inorganic polyvinylidene fluoride (PVDF)–titanium dioxide (TiO₂) composite hollow fiber ultrafiltration (UF) membranes were prepared by TiO₂ sol–gel method and blending method, respectively. The membranes were characterized in terms of microstructure, hydrophilicity, permeation performance, thermal stability, and mechanical strength. The experimental results indicated that PVDF–TiO₂ composite UF membranes exhibited significant differences in surface properties and intrinsic properties because of the addition of inorganic particles. The TiO₂ particles improved the membrane strength and thermal stability of PVDF–TiO₂ composite UF membranes. In particular, hydrophilicity and permeability increased dramatically with the increase of TiO₂, whereas the retention property of UF membranes was nearly unchanged. However, high TiO₂ concentration induced the aggregation of particles, resulting in the decline of hydrophilicity and permeability. Compared with PVDF–TiO₂ composite hollow fiber UF membranes prepared by TiO₂ blending method, PVDF–TiO₂ composite hollow fiber UF membranes prepared by TiO₂ sol–gel method formed a dispersed inorganic network, and the stronger interaction between inorganic network and polymeric chains led to TiO₂ particles being uniformly dispersed in UF membranes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Structural and performance properties of UV-assisted TiO2 deposited nano-composite PVDF/SPES membranes

In this research, the surface of poly (vinylidene fluoride) (PVDF)/sulfonated polyethersulfone (SPES) blend membrane prepared via immersion precipitation was modified by depositing of TiO₂ nano-particles followed by UV irradiation to activate their photocatalytic property. The membranes were characterized by FTIR, SEM, AFM, contact angle, dead end filtration (pure water flux and BSA solution flux), antifouling analysis and antibacterial activity. The FTIR spectrum confirmed the presence of OH functional groups on the PVDF/SPES membrane structure, which was the key factor for deposition, and self-assembly of TiO₂ nanoparticles on the membrane surface. The SEM and AFM images indicated that the TiO₂ nanoparticles were deposited on the PVDF/SPES membrane. The contact angle measurements showed that the hydrophilicity of PVDF/SPES membrane was strongly improved by TiO₂ deposition and UV irradiation. The filtration results indicated that the initial flux of TiO₂ deposited PVDF/SPES membranes was lower than the initial flux of neat PVDF/SPES membrane. However, the former membranes showed lower flux decline compared to the neat PVDF/SPES membrane. The BSA rejection of modified membranes was improved. The fouling analysis demonstrated that the TiO₂ deposited PVDF/SPES membranes showed the fewer tendencies to fouling. The results of antibacterial study showed that the UV irradiated TiO₂ deposited PVDF/SPES membranes possess high antibacterial property.     

Synthesis and characterization of low content of different SiO2 materials composite poly (vinylidene fluoride) ultrafiltration membranes

A comparison of the morphology and performance of virgin poly (vinylidene fluoride) (PVDF) ultrafiltration (UF) membrane, and PVDF-composite membranes with low content of two different SiO₂ (N-SiO₂ and M-SiO₂ particles) was carried out. Cross-sectional area and surface morphology of the membranes were observed by scanning electron microscopy and atomic force microscopy. Surface hydrophilicity of the porous membranes was determined through the measurement of a contact angle. Performance tests were conducted on the composite membranes through water flux and bovine serum albumin (BSA) retention. Average pore size and surface porosity were calculated based on the permeate flux. Thermal stability and mechanical stability were determined by thermogravimetric analysis and tensile stress tests. The results indicate that N-SiO₂/PVDF (P-N) membranes possessed larger average pore size and porosity, which led to higher water flux and a slight decline in BSA retention. On the other hand, M-SiO₂/PVDF (P-M) membranes had better mechanical stability and anti-fouling performance with enhanced membrane hydrophilicity and decreased membrane surface roughness. Both of the P-N and P-M membranes exhibited typical asymmetric morphology and improved thermal stability.     

Comparative impact of SiO2 and TiO2 nanofillers on the performance of thin-film nanocomposite membranes

Nanoparticle (NP) additions can substantially improve the performance of reverse osmosis and nanofiltration polyamide (PA) membranes. However, the relative impacts of leading additives are poorly understood. In this study, we compare the effects of TiO₂ and SiO₂ NPs as nanofillers in PA membranes with respect to permeate flux and the rejection of organic matter (OM) and salts. Thin-film nanocomposite (TFN) PA membranes were fabricated using similarly sized TiO₂ 15 nm and SiO₂ (10 – 20 nm) NPs, introduced at four different NP concentrations (0.01, 0.05, 0.2, and 0.5% w/v). Compared with PA membranes fabricated without NPs, membranes fabricated with nanofillers improved membranes hydrophilicity, membrane porosity, and consequently the permeability. Permeability was increased by 24 and 58% with the addition of TiO₂ and SiO₂ , respectively. Rejection performance and fouling behavior of the membranes were examined with salt (MgSO₄ and NaCl ) and OM (humic acid [HA] and tannic acid [TA]). The addition of TiO₂ and SiO₂ nanofillers to the PA membranes improved the permeability of these membranes and also increased the rejection of MgSO₄ , especially for TiO₂ membranes. The addition of TiO₂ and SiO₂ to the membranes exhibited a higher flux and lower flux decline ratio than the control membrane in OM solution filtration. TFN membranes' HA and TA rejections were at least 77 and 71%, respectively. The surface change properties of NPs appear to play a dominant role in determining their effects as nanofillers in the composite membrane matrix through a balance of changes produced in membrane pore size and membrane hydrophilicity.     

Morphological effects of spherical SiO2 and hexagonal mesoporous MCM-41 nanoparticles in polyacrylonitrile mixed matrix membranes on the biofouling mitigation in short-term filtration

In this study, the morphology of the nanostructures is evaluated on the surface characterization and performance of the polyacrylonitrile (PAN) ultrafiltration mixed matrix membranes (MMM). To this end, silica nanoparticles (NPs) such as spherical (SiO₂) and hexagonal mesoporous (MCM-41) with high hydrophilicity were incorporated at 0.5, 1, and 2 wt%. Attenuated total reflectance-Fourier transform infrared analysis illustrated the placement of NP on the surface of the MMM. Atomic force microscopy studies also showed that SiO₂ NP added to PAN exhibited a smoother surface than MCM-41 NP. Field-emission scanning electron microscope analysis of the MMM identified that all membranes are composed of a finger-like porous structure. Contact angle measurements indicate that the morphology of the NPs has no significant effect on MMM hydrophilicity. Moreover, the performance of the MMM was evaluated, and regardless of NP morphology, the MMM showed better permeate flux with increased loading. A higher pure water flux was observed in the PAN-MCM41-1% membrane (237 L/m² h), possibly because of inherent porosity and high hydrophilicity of MCM-41 compared to SiO₂ NP. Further, the PAN-SiO₂-1% membrane exhibited superior antifouling properties due to a lower surface roughness. The present studies reveal that the morphology of the NP greatly influence on the structure, permeation, and antifouling properties of PAN membranes.     

Nanoparticles modified Polyacrylonitrile/Polyacrylonitrile – Polyvinylidenefluoride blends as substrate of high flux anti-fouling nanofiltration membranes

Thin-film composite nanofiltration membranes were prepared by interfacial polymerization reaction of piperazine and trimesoylchloride on virgin and nanoparticles (SiO₂/TiO₂) modified Polyacrylonitrile/70:30 and 30:70 Polyacrylonitrile – Polyvinylidenefluoride blend ultrafiltration substrates. The membranes were characterized for surface hydrophilicity and potential, surface and cross-sectional morphology and equilibrium water content. Pure water permeability and differential rejection of multi (MgSO₄) and monovalent salts (NaCl) of the membranes were studied. Nanofiltration (NF) membranes prepared on nanoparticle modified UF substrates exhibit higher flux than the membranes prepared on virgin UF substrates. NF membranes prepared on TiO₂ modified substrates are exhibiting higher flux than the other membranes. Membrane prepared on TiO₂ modified 70:30 blend substrate exhibits the highest rejection ratio (4.63) of divalent to monovalent salts. Nanofiltration membranes prepared on nanoparticle modified substrates are displaying comparatively higher flux recovery ratio (FRR) and lower total fouling ratio (TFR) values than the NF membranes prepared on virgin ultrafiltration substrates.     

Effect of additives concentration on the surface properties and performance of PVDF ultrafiltration membranes for refinery produced wastewater treatment

The aim of this study was to investigate the effect of pore-forming hydrophilic additives on the porous asymmetric polyvinylideneflouride (PVDF) ultrafiltration (UF) membrane morphology and transport properties for refinery produced wastewater treatment. PVDF ultrafiltration membranes were prepared via a phase inversion method by dispersing lithium chloride monohydrate (LiCl·H₂O) and titanium dioxide (TiO₂) nanoparticles in the spinning dope. The morphological and performance tests were conducted on PVDF ultrafiltration membranes prepared from a different additive content. The top surface and cross-sectional area of the membranes were observed using a field emission scanning electron microscope (FESEM) and energy dispersive X-ray (EDX) analysis. The surface wettability of porous membranes was determined by the measurement of a contact angle. The mean pore size and surface porosity were calculated based on the permeate flux. The results indicated that the PVDF/LiCl/TiO₂ membranes with lower TiO₂ nanoparticles loading possessed smaller mean pore size, more apertures inside the membrane with enhanced membrane hydrophilicity. LiCl·H₂O has been employed particularly to reduce the thermodynamic miscibility of dope which resulted in increasing the rate of liquid–liquid demixing process. The maximum flux and rejection of refinery wastewater using PVDF ultrafiltration membrane achieved were 82.50 L/m² h and 98.83% respectively at 1.95 wt.% TiO₂ concentration.     

Pore morphology control and hydrophilicity of polyacrylonitrile ultrafiltration membranes

The effects of different solvents (dimethyl formamide: DMF and dimethylsulfoxide: DMSO) on the solubility of polyacrylonitrile (PAN) were investigated by the phase diagrams of H₂O/DMF/PAN and H₂O/DMSO/PAN ternary systems through cloud‐point titration method at low polymer concentration. The influences of polymer concentrations and temperatures on the morphologies of PAN ultrafiltration membranes were elucidated. The morphologies of fabricated UF membranes were characterized by scanning electron microscopy (SEM) and atomic force microscope (AFM), and the basic performance of ultrafiltration including pure water flux and rejection of BSA were explored. At 25°C, the pure water flux of ultrafiltration membranes at the lower PAN content (16 wt % PAN in 84 wt % DMSO) reached 213.8 L/m/bar and the rejection of BSA was 100%. Interestingly, the water flux of UF membranes dramatically decreased to 20.6 L/m/bar (20 wt %) and 2.9 L/m/bar (24 wt %) when increasing PAN concentrations in DMSO. On the other hand, the hydrophilicity of membranes can be enhanced by increasing coagulation temperatures and polymer concentrations which were characterized by static contact angle, fitting well with the variation tendency of roughness. Although there are many works concerning on the effects of phase inversion conditions on the performance of PAN UF membranes, to our best knowledge, there is seldom works focusing on investigating the membrane hydrophilicity trend by adjusting phase inversion conditions. To disclose the reason of the enhanced hydrophilicity, the water and glycol contact angles of various membranes were measured and the surface tensions were presented. The results illustrated that the enhanced hydrophilicity of PAN UF membranes fabricated at higher temperatures or higher polymer concentrations was due to the higher polarity on membrane surface. Since the vast majority of ultrafiltration membranes in labs and in industrial scale have been fabricated by immersion phase inversion method, this work can provide a guidance to obtain hydrophilic PAN UF membranes by adjusting the process of phase inversion. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41991.     

Preparation and performance of the novel PVDF ultrafiltration membranes blending with PVA modified SiO2 hydrophilic nanoparticles

In this study, PVA‐SiO₂ was synthesized by modifying silica (SiO₂) with polyvinyl alcohol (PVA), then a novel polyvinylidene fluoride (PVDF) ultrafiltration (UF) membrane was prepared by incorporating the prepared PVA‐SiO₂ into membrane matrix using the non‐solvent induced phase separation (NIPS) method. The effects of PVA‐SiO₂ particle on the properties of the PVDF membrane were systematically studied by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT‐IR), surface pore size, porosity, and water contact angle. The results indicated that with the addition of PVA‐SiO₂ particles in the PVDF UF membranes, membrane mean pore size increased from 80.06 to 126.00 nm, porosity improved from 77.4% to 89.1%, and water contact angle decreased from 75.61° to 63.10°. Furthermore, ultrafiltration experiments were conducted in terms of pure water flux, bovine serum albumin (BSA) rejection, and anti‐fouling performance. It indicated that with the addition of PVA‐SiO₂ particles, pure water flux increased from 70 to 126 L/m² h, BSA rejection increased from 67% to 86%, flux recovery ratio increased from 60% to 96%, total fouling ratio decreased from 50% to 18.7%, and irreversible fouling ratio decreased from 40% to 4%. Membrane anti‐fouling property was improved, and it can be expected that this work may provide some references to the improvement of the anti‐fouling performance of the PVDF ultrafiltration membrane. POLYM. ENG. SCI., 59:E412–E421, 2019. © 2018 Society of Plastics Engineers     

Hydrophilic modification of polyacrylonitrile membranes by oxyfluorination

The surface of polyacrylonitrile (PAN) membranes was modified by oxyfluorination with various conditions to improve its wettability. The membranes were characterized in terms of morphology, structure, hydrophilicity, and membrane performance. The properties and functional groups on the surface of PAN membranes were investigated by contact angle, SEM, ATR-IR and XPS. And permeability of PAN membranes was compared by permeating pure water flux through membrane surface under 100, 150 and 200 kPa pressure. Oxyfluorination introduced oxygen contained functional groups such as the carboxylic acid groups that help increment of wettability on the surface of PAN membrane. Water flux of oxyfluorinated PAN UF membrane increased 20% at pure water permeation pressure 200 kPa compared to that of untreated PAN UF membrane.     

Preparation of photo-catalytic copolymer grafted asymmetric membranes (N-TiO<Subscript>2</Subscript>-PMAA-g-PVDF/PAN) and their application on the degradation of bentazon in water

Nitrogen-doped titanium dioxide (N–TiO₂) was prepared and supported on a novel copolymer grafted membrane matrix to avoid the problems associated with the removal of spent photocatalyst from treated water. Membranes of poly (methacrylic acid) grafted onto poly (vinylidene difluoride) and blended with poly (acrylonitrile) (PMAA-g-PVDF/PAN) were prepared through a dry–wet phase inversion technique. Methacrylic acid side chains were grafted onto an activated PVDF backbone by the method of reversible addition fragmentation chain transfer polymerization and then the novel photocatalytic asymmetric membranes of N–TiO₂–PMAA-g-PVDF/PAN were prepared. The casting solutions were blended with 1–5 % N–TiO₂ before immersion into the coagulation bath. PVDF and PAN offer several advantages which include: mechanical strength and toughness, chemical resistance, unaffected by long-term exposure to UV radiation, low weight, and thermal stability. N–TiO₂ was prepared through sol-gel synthesis. The photocatalytic membranes were evaluated by degradation process of herbicide bentazon in water. Photodegradation studies revealed that the optimum photocatalyst loading was 3 % N–TiO₂ and the optimum pH was 7 for the degradation of bentazon in water. UV–Vis, TOC and LC–MS analyses confirmed the successful photodegradation of bentazon. A bentazon removal efficiency of 90.1 % was achieved at pH 7. N–TiO₂–PMAA-g-PVDF/PAN membranes were successfully prepared and characterized. These photocatalytic membranes showed great potential as a technology for the effective removal of pesticides from water. According to literature, N–TiO₂–PMAA-g-PVDF/PAN asymmetric photocatalytic membranes have not been prepared before for the purpose of treating agricultural wastewater.     

Studies on the surface properties of mixed‐matrix membrane and its antifouling properties for humic acid removal

A major factor limiting the use of ultrafiltration (UF) membrane in water treatment process is the membrane fouling by natural organic matter such as humic acid (HA). In this work, neat PVDF and PVDF/TiO₂ mixed‐matrix membranes were prepared and compared in terms of their antifouling properties. Two commercial types of TiO₂ namely PC‐20 and P25 were embedded to prepare the mixed matrix membranes via in situ colloidal precipitation method. The contact angles for the mixed‐matrix membranes were slightly reduced while the zeta potential was increased (more negatively charged) compared with the neat membrane. Filtration of HA with the presence of Ca²⁺ demonstrated that mixed‐matrix membrane could significantly mitigate the fouling tendency compared with the neat membrane with flux ratio (J/J₀) of 0.65, 0.70, and 0.82 for neat PVDF membrane, PVDF/TiO₂ mixed‐matrix membrane embedded with P25 and PC‐20, respectively. PC‐20 with higher anatase polymorphs exhibited better antifouling properties due to its hydrophilicity nature. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Morphologies and properties of poly(phthalazinone ether sulfone ketone) matrix ultrafiltration membranes with entrapped TiO2 nanoparticles

Poly(phthalazine ether sulfone ketone) (PPESK) is a newly developed membrane material with superior thermal stability and comprehensive properties. Titanium dioxide (TiO₂)‐entrapped PPESK ultrafiltration (UF) membranes were formed by dispersing uniformly nanosized TiO₂ particles in the casting solutions. Initially, the inorganic nanoparticles were organically modified with silane couple reagent to overcome the aggregation and to improve the dispersibility in organic solvent. The membranes were prepared through the traditional phase inversion method. The effects of inorganic TiO₂ nanoparticles on the membrane surface morphology and cross section structure were investigated using scanning electronic microscopy (SEM) and atomic force microscopy (AFM). Water contact angle (CA) measurement was conducted to investigate the hydrophilicity and surface wettability of the membranes. The influence of TiO₂ on the permeability, antifouling, and tensile mechanical properties of the PPESK membranes were evaluated by UF experiments and tensile tests. The experimental results showed that the obtained TiO₂‐entrapped PPESK UF membranes exhibit remarkable improvement in the antifouling and mechanical properties because of the introduction of TiO₂ nanoparticles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3623–3629, 2007     

Preparation and properties of hydrophobic poly(vinylidene fluoride)–SiO2 mixed matrix membranes for dissolved oxygen removal from water

The application of the membrane method for removing dissolved oxygen (DO) from water on the laboratory scale was studied. Flat mixed matrix membranes were composed of poly(vinylidene fluoride) (PVDF) and hydrophobic nanosilica particles, which were used to improve the DO removal process. The SiO₂ particles were modified by a silane coupling agent and examined by Fourier transform infrared spectroscopy. It was shown that the surface of the SiO₂ particles was bonded to hydrophobic long‐chain alkane groups through chemical bonding. The effects of adding SiO₂ particles on the membrane properties and morphology were examined. The results show that the porosity and pore size of the membrane were affected by the introduction of SiO₂ particles, and the cross‐sectional morphology of the PVDF composite membranes changed from fingerlike macrovoids to a spongelike structure. The membrane performance of DO removal was evaluated through the membrane unit by a vacuum degassing process. It was found that the SiO₂/PVDF hybrid membranes effectively improved the oxygen removal efficiency compared with the original PVDF membranes. The maximum permeation flux was obtained when the loading amount was 2.5 wt %. The effect of the downstream vacuum level was also investigated. The experimental results show that the SiO₂/PVDF hybrid membranes had superior performances and could be an alternative membrane for removing DO from water. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40430.     

Facile surface modification of PVDF microfiltration membrane by strong physical adsorption of amphiphilic copolymers

To endow the surface of poly(vinylidene fluoride) (PVDF) microfiltration (MF) membranes with hydrophilicity and antifouling property, physical adsorption of amphiphilic random copolymers of poly(ethylene glycol) methacrylate (PEGMA) and poly(methyl methacrylate) (PMMA) (P(PEGMA‐r‐MMA)) onto the PVDF membrane was performed. Scanning electron microscopy (SEM) images showed that the adsorption process had no influence on the membrane structure. Operation parameters including adsorption time, polymer concentration, and composition were explored in detail through X‐ray photoelectron spectroscopy (XPS), static water contact angle (CA), and water flux measurements. The results demonstrated that P(PEGMA‐r‐MMA) copolymers adsorbed successfully onto the membrane surface, and hydrophilicity of the PVDF MF membrane was greatly enhanced. The antifouling performance and adsorption stability were also characterized, respectively. It was notable that PVDF MF membranes modified by facile physical adsorption of P(PEGMA₅₈‐r‐MMA₃₃) even showed higher water flux and better antifouling property than the commercial hydrophilic PVDF MF membranes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3112–3121, 2013     

PEG/GO/TiO2纳米复合材料改性PVDF膜的制备及其抗污性能

为改善聚偏氟乙烯(PVDF)膜的抗污性能,以聚乙二醇2000接枝的GO/TiO₂(PEG/GO/TiO₂)纳米复合材料为添加剂,通过非溶剂诱导沉淀相分离法制备了一系列PEG/GO/TiO₂/PVDF复合超滤膜。采用FTIR、SEM和接触角测试仪对其结构和形貌进行了表征,采用超滤法评价其纯水通量和抗污性能。结果表明,当PEG/GO/TiO₂纳米复合材料质量分数为0.60%时,制备的PEG/GO/TiO₂/PVDF复合超滤膜(记为0.60%PEG/GO/TiO₂/PVDF)表现出最佳的亲水性和抗污性能,其接触角比PVDF膜下降8.2°,总孔隙率增加13.40%,PEG/GO/TiO₂纳米复合材料在PVDF膜中分散较均匀。在0.08 MPa的工作压力下,0.60%PEG/GO/TiO₂/PVDF的纯水通量高达282.44 L/(m²·h),对腐植酸溶液的过滤通量为131.96 L/(m^2...     

Inorganic nanoparticles incorporated in polyacrylonitrile-based mixed matrix membranes for hydrophilic,ultrafast, and fouling-resistant ultrafiltration

Mixed matrix membrane (MMM) structures and performances are greatly affected by the distribution of nanoparticles in the polymeric matrix. Until now, there has been little research on the effects of nanoparticle distribution states on polyacrylonitrile (PAN)-based MMM structures and performances. In this paper, different intermolecular interactions between nanoparticles and PAN molecules were generated by in situ fabricated amino-functionalized SiO₂ and TiO₂ nanoparticles to create absolutely different distribution states of nanoparticles in a PAN matrix. The results indicated that, due to the strong interactions between amino and cyano groups, SiO₂ is distributed in the PAN membranes homogeneously, while most of the TiO₂ migrates to the membrane's top surfaces or the walls of pores or even escape from the membranes during the nonsolvent index phase separation (NIPS) process. PAN-TiO₂ MMMs have more hydrophilic top surfaces, higher porosity, larger mean pore size, and stronger antifouling performances than pure PAN and PAN-SiO₂ membranes. The PAN-TiO₂ MMMs have an ultrahigh water flux of 1204.6 L/(m² h), which is more than 44 times that of PAN membranes. And the good pore structures and hydrophilicity of the membranes derived from special interactions between in situ TiO₂ nanoparticles and PAN molecules can give high-performance PAN-based ultrafiltration membranes a bright future. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47902.     

Counterion‐Switched Reversibly Hydrophilic and Hydrophobic TiO2‐Incorporated Layer‐By‐Layer Self‐Assembled Membrane for Nanofiltration

The manipulation of surface wettability has been regarded as an efficient strategy to improve the membrane performances. Herein, the counterion‐switched reversibly hydrophilic and hydrophobic surface of TiO₂‐loaded polyelectrolyte membrane are prepared by layer‐by‐layer assembly of poly(sodium 4‐styrene sulfonate) (PSS) and poly(diallydimethyl‐ammoniumchloride (PDDA) containing TiO₂@PDDA nanoparticles (NPs) on the hydrolyzed polyacrylonitrile (PAN) substrate membrane. The obtained polyelectrolyte multilayer (PEM) membranes [PEM‐TiO₂]_4.5⁺X^? (X^? = Cl^?, PFO^? [perfluorooctanoate] etc.) show different hydrophilicity and hydrophobicity with various counterions. The integration of TiO₂ NPs obviously improves the wettability and nanofiltration (NF) performance of PEM membrane for (non)aqueous system of dyes (crystal violet, eriochrome black T) with a high recyclability. The highly hydrophilic [PEM‐TiO₂]_4.5⁺Cl^? (water contact angle [WCA]: 13.2 ± 1.8°) and hydrophobic [PEM‐TiO₂]_4.5⁺PFO^? (WCA: 115.4 ± 2.3°) can be reversibly switched via counterion exchange between Cl^? and PFO^?, verifying the surface with a reversible hydrophilic–hydrophobic transformation. For such membranes, the morphology, wettability, and NF performance rely on the loading of TiO₂@PDDA NPs and surface counterion. Meanwhile, the motion and interaction of water or ethanol in the hydrophilic or hydrophobic membrane are revealed by low‐field nuclear magnetic resonance. This work provides a facile and rapid approach to fabricate smart and tunable wetting surface for potential utilization in (non)aqueous NF separation.     

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.     

Development of mesoporous titanium dioxide hybrid poly(vinylidene fluoride) ultrafiltration membranes with photocatalytic properties

A photocatalytic activity ultrafiltration membrane (UFM) was prepared by the blending of a poly(vinylidene fluoride) (PVDF) polymer with mesoporous titanium dioxide (M‐TiO₂) particles via the phase‐inversion method. The microstructure of the membrane and Ti element distribution were characterized by scanning electron microscopy and energy‐dispersive X‐ray spectroscopy. Their properties were also determined by thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, tensile stress tests, contact angle tests, bovine serum albumin retention, water flux, and permeation flux. When the M‐TiO₂ concentration reached 1 wt %, the thermal stability, mechanical properties, hydrophilicity, flux, and antifouling performance of the M‐TiO₂/PVDF UFM were improved to an optimal value with the M‐TiO₂ particles successfully entrapped and evenly distributed throughout the PVDF polymer matrix. Compared with the P25‐modified PVDF UFM (1 wt %), the M‐TiO₂‐modified PVDF UFM (1 wt %) exhibited better photocatalytic activity and wonderful stability in the UV photocatalytic degradation of the organic dye Rhodamine B. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43427.