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     

Nano SiO2 and TiO2 embedded polyacrylonitrile/polyvinylidene fluoride ultrafiltration membranes: Improvement in flux and antifouling properties

Polyvinylidene fluoride (PVDF) and polyacrylonitrile (PAN) ultrafiltration (UF) membranes are widely used in drinking water and wastewater applications. These membranes are prone to fouling and membrane efficiency decreases with time under constant operation. Significant improvements/modifications are necessary to apply these polymers as sustainable membrane materials. In this study, PVDF and PAN UF membranes were modified through incorporation of nanoparticles (NPs) namely SiO₂ and TiO₂. PVDF and PAN UF membranes were prepared by phase inversion method from polymer solutions having dispersed SiO₂ and TiO₂ NPs in it. Membrane surface hydrophilicity, charge, roughness, and morphology were studied. Equilibrium water content and molecular weight cut-off of the membranes were also measured. Addition of NPs increased membrane surface hydrophilicity, equilibrium water content, and surface potential. NPs modified membranes exhibited better membrane flux (35–79% higher) and antifouling properties (flux recovery ratio values 28–41% higher) than the virgin membranes.     

Synthesis and Characterization of Polycarbonate/TiO2 Ultrafiltration Membranes: Critical Flux Determination

A novel polycarbonate (PC) membrane was modified with titanium dioxide via nonsolvent-induced phase separation method to improve its hydrophilicity and antifouling properties in a submerged membrane system for the removal of humic acid (HA) both with and without polyaluminum chloride (PAC) coagulant. The effect of TiO₂ additive on the morphology and performance of the nanocomposite membranes was studied by atomic force microscopy, field emission scanning electron microscopy, energy dispersive X-ray, mechanical properties, water contact angle, porosity, pure water flux, rejection tests, and antifouling parameters. The obtained results revealed that a higher critical flux was achieved by the PC/TiO₂ nanocomposite membrane. The flux recovery ratio of the neat PC membrane increased with the addition of TiO₂ nanoparticles and without PAC coagulant. HA removal for the PC nanocomposite membrane was higher than that of the neat PC membrane with and without PAC coagulant.     

Poly(arylene sulfide sulfone) hybrid ultrafiltration membrane with TiO2‐g‐PAA nanoparticles: Preparation and antifouling performance

Poly(arylene sulfide sulfone) (PASS) is a kind of newly developed polymeric membrane material which has excellent mechanical strength, thermal stability, and solvent resistance. And, it would be a potential material for high temperature ultrafiltration and organic solvent filtration. In this article, PASS hybrid ultrafiltration membrane with improved antifouling property was prepared by mixing TiO₂ nanoparticles which were grafted with polyacrylic acid (PAA). These membranes were prepared by a phase inversion technique and their separation performance and antifouling property of the prepared membranes were investigated in detail by SEM, FTIR, EDS, contact angle goniometry, filtration experiments of water, and BSA solution. The results shown that the TiO₂‐g‐PAA nanoparticles dispersed well in membrane matrix, the hydrophilicity of the membranes prepared within TiO₂‐g‐PAA nanoparticles have been improved and these membranes exhibited excellent water flux and antifouling performance in separation than that of the pure PASS membranes and PASS membranes with TiO₂ nanoparticles. More specifically, among membrane sample M0, M1.5, and MP1.5, MP1.5 which contained 1.5 wt% TiO₂‐g‐PAA exhibited the highest water permeation (190.4 L/m² h at 100 kPa), flux recovery ratio, and the lowest BSA adsorption amount. POLYM. ENG. SCI., 55:2829–2837, 2015. © 2015 Society of Plastics Engineers     

Preparation and characterizations of a new PS/TiO2 hybrid membranes by sol-gel process

New organic-inorganic hybrids based on PS/TiO₂ hybrid membranes were prepared by sol-gel and phase inversion process. The membranes were characterized in terms of morphology, structure, hydrophlicity, UF performance and thermal stability. The results showed that macrovoids were nearly suppressed with formation of a sponge like membrane structure. The TiO₂ particles were uniformly dispersed in membrane. The nanodispersed inorganic network formed after sol-gel process and the strong interaction between inorganic network and polymeric chains led to the improvement of porosity and thermal stability. In particular hydrophilicity and permeability increased drastically with the increasing of TiO₂ content in the range of 0-9.3 wt%, without changing retention properties of membrane. However, high-TiO₂ concentration induces nanoparticles aggregate, resulting in the decline of hydrophilicity and permeability. Thus, PS/TiO₂ hybrid membranes with proper TiO₂ content are desirable to meet some specific requirements in industrial separation.     

Antifouling behaviour of PVDF/TiO2 composite membrane: a quantitative and qualitative assessment

The composite membranes of PVDF/TiO₂ were prepared by a phase-inversion technique. Different amounts of TiO₂ with respect to the weight of the polymer were incorporated in the casting solution to study qualitatively and quantitatively the antifouling property of the membrane. The membrane morphology was studied using a high-resolution scanning electron microscopy and atomic force microscopy, whereas the crystalline nature was studied using X-ray diffraction method. The interfacial interactions between foulants and TiO₂ immobilized membranes were also evaluated using the extended Derjaguin–Landau–Verwey–Overbeek (XDLVO) approach. The XDLVO theory revealed an increase in repulsive interactive energy barrier with an increase in TiO₂ loading, thus causing to improve the antifouling property of the membrane. Intercalation of TiO₂ nanoparticles efficiently improved the porosity and wettability of the polymeric membranes, which could be confirmed by the contact angle analyzer analysis. The modified PVDF membranes exhibited excellent antimicrobial properties against Gram-negative Escherichia coli as confirmed from the halo zone and activity test. The permeation experimental results also showed high protein rejection of bovine serum albumin and humic acid (foulant) for membranes with optimum TiO₂ loading of 0.01 g/g of PVDF polymer. However, at a concentration of 0.02 g TiO₂/g of PVDF a negative effect on the membrane property was observed due to the former non-uniform distribution.

     

Application of Colloidal Precipitation Method Using Sodium Polymethacrylate as Dispersant for TiO2/PVDF Membrane Preparation and Its Antifouling Properties

Immobilized titanium dioxide (TiO₂) nanoparticles on flat sheet polymeric membranes have been found effective for fouling reduction in recent researches. The main challenge in this field is to obtain ultrafine and stable nanodispersions. In this study, composite polyvinylidene fluoride/TiO₂ (PVDF/TiO₂) ultrafiltration membranes were prepared via phase inversion and colloidal precipitation method. Stable TiO₂ suspensions were prepared using sodium polymethacrylate as dispersant and sonication without altering of the coagulation bath pH. The effect of different concentrations of TiO₂ nanoparticles in the coagulation bath was also investigated. The membrane morphology (distribution of nanoparticles on the membrane surface) was observed by scanning electron and atomic force microscopy. Properties of the neat and the composite membranes were also characterized using energy dispersive X‐ray spectroscopy and contact angle and membrane porosity measurements. The neat and the composite membranes were further investigated in terms of bovine serum albumin rejection and flux decline in cross flow filtration experiments. The results showed that the PVDF/TiO₂ composite membrane using dimethylacetamide/triethyl phosphate as solvent and 0.05 g/L of TiO₂ in the coagulation bath exhibits improved antifouling properties. POLYM. ENG. SCI., 59:E422–E434, 2019. © 2018 Society of Plastics Engineers     

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.     

Synthesis of enhanced urea–formaldehyde resin microcapsules doped with nanotitania

Urea–formaldehyde (UF) resin microcapsules doped with TiO₂ nanoparticles were prepared by in situ polymerization, and the properties of the microcapsules, such as the surface morphologies, thermal properties, and chemical elemental composition, were measured by optical microscopy, scanning electron microscopy, thermogravimetric analysis, and energy‐dispersive X‐ray spectrometer analysis. The effects of the presence of ammonium chloride and its concentration and the concentrations of UF resin prepolymer and TiO₂ nanoparticles during the reaction and deposition of UF on the microcapsule surface on the properties of the microcapsules were investigated. Enhanced UF resin microcapsules with more stability and mechanical strength could be obtained under the optimal conditions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Surface modification of TiO2 nanoparticles and preparation of TiO2/PDMS hybrid membrane materials

TiO₂ nanoparticles were surface‐modified by a convenient and mild sol–gel method. A novel hybrid membrane material was prepared by crosslinking reaction based on poly(dimethylsiloxane) (PDMS) as organic matrix and TiO₂ nanoparticles as inorganic filler as well as a crosslinking agent. The chemical structure, mechanical and thermal properties, swelling performance and morphology of the hybrid membranes were characterized and investigated by FTIR, SEM, TG, and so on. The results showed that the surface modification method could make the compatibility between organic component and inorganic component good. The ultrathin PDMS hybrid membrane could easily be prepared by crosslinking reaction at room temperature and the conventional solution casting method. The preparation technology enhanced forming‐membrane ability of the hybrid membrane, shortened reaction time, and decreased some by‐products. In addition, the stress at break and the elongation at break of the hybrid membranes increased significantly with increasing TiO₂ contents. The enhanced mechanical properties of the hybrid membranes will develop potential application of PDMS membranes. POLYM. COMPOS., 38:1541–1548, 2017. © 2015 Society of Plastics Engineers     

Synergistic effects of organic and inorganic additives in preparation of composite poly(vinylidene fluoride) antifouling ultrafiltration membranes

Composite ultrafiltration membranes were successfully fabricated by blending a nonionic surfactant and inorganic nanoparticles via a nonsolvent-induced phase separation (NIPS) method. Brij35 was used as the nonionic surfactant and silica (SiO₂) nanoparticles from rice husk ash, a low cost and widely available material, were used as the inorganic nanoparticles. The synergetic effect of both additives was used to tailor the membrane structure and properties because the selected additives showed completely different or, in some cases, the opposite effect on the membrane properties and structure. The combined effects of Brij and SiO₂ resulted in a membrane with a noticeable improvement in membrane overall performance including pure water permeability, hydrophilicity, antifouling properties, long-term stability, tensile strength, on the cost of a slight decrease in membrane elongation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47737.     

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     

Preparation and characterization of a poly(vinyl alcohol)/tetraethoxysilane ultrafiltration membrane by a sol–gel method

Using poly(vinyl alcohol) (PVA) with highly hydrophilic properties as membrane material and poly(ethylene glycol) (PEG) as an additive, we prepared PVA/tetraethoxysilane (TEOS) ultrafiltration (UF) membranes with good antifouling properties by a sol–gel method. The PVA/TEOS UF membranes were characterized by X‐ray diffraction patterns, Fourier transform infrared spectroscopy, scanning electron microscopy, and static contact angle of measurement of water. The hybridization of TEOS to PVA for preparing the PVA/TEOS UF membranes achieved the required permeation performance and good antifouling behaviors. The morphology and permeation performance of the PVA/TEOS membranes varied with the different TEOS loadings and PEG contents. The pure water fluxes (J_W) increased and the rejections (Rs) decreased with increasing TEOS loading and PEG content. The PVA/TEOS UF membrane with a PVA/TEOS/PEG/H₂O composition mass ratio of 10/3/4/83 in the dope solution had a J_W of 66.5 L m^?2 h^?1 and an R of 60.3% when we filtered it with 300 ppm of bovine serum albumin aqueous solution at an operational pressure difference of 0.1 MPa. In addition, the filtration and backwashing experiment proved that the PVA/TEOS membranes possessed good long‐term antifouling abilities. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4066–4074, 2013     

Synthesis and characterization of PVA/PES thin film composite nanofiltration membrane modified with TiO2 nanoparticles for better performance and surface properties

Novel polyethersulfone (PES)/poly (vinyl alcohol) (PVA)/titanium dioxide (TiO₂) composite nanofiltration membranes were prepared by dip-coating of PES membrane in PVA and TiO₂ nanoparticles aqueous solution. Glutaraldehyde (GA) was used as a cross-linker for the composite polymer membrane in order to enhance the chemical, thermal as well as mechanical stabilities. TiO₂ nanoparticles with different concentrations (0, 0.05, 0.1, 0.5 wt.%) were coated on the surface of PVA/PES composite membrane. The morphological study was investigated by atomic force microscopy (AFM), scanning surface microscopy (SEM) and along with X-ray diffraction (XRD). In addition, the membranes performances, in terms of permeate flux, ion rejection and swelling factor were also investigated. It was found that the increase in TiO₂ solution concentration can highly affect the surface morphology and filtration performance of coated membranes. The contact angle measurement and XRD studies indicated that the TiO₂ nanoparticles successfully were coated on the surface of PVA/PES composite membranes. However, rougher surface was obtained for membranes by TiO₂ coating. The filtration performance data showed that the 0.1 wt.% TiO₂-modified membrane presents higher performance in terms of flux and NaCl salt rejection. Finally, TiO₂ modified membranes demonstrated the lower degree of swelling.     

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.     

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.     

Synergistic effect of silica nanoparticles in the matrix of a poly(ethylene glycol) diacrylate coating layer for the surface modification of polyamide nanofiltration membranes

In this study, a commercial polyamide nanofiltration membrane was modified by a combination of poly(ethylene glycol) diacrylate (PEGDA) in situ polymerization and silica (SiO₂) nanoparticles. The PEGDA layer was polymerized on the surface of the membranes alone or mixed with SiO₂ nanoparticle. The surface modification influence on the water flux, salt rejection, and antifouling behavior was investigated. The effects of the nanoparticles and PEGDAylation on the membrane properties were characterized by Fourier transform infrared spectroscopy, contact angle measurement, and scanning electron microscopy analyses. The membranes that were in contact with 30 wt % PEGDA and then treated with ultraviolet light for 5 min had a better water flux than the unmodified membrane. The fouling resistance of the membranes to a foulant solution containing bovine serum albumin, humic acid, and sodium sulfate were studied, and the results show that the membrane with 30 wt % PEGDA had better antifouling properties. After the weight percentage of PEGDA for the prepolymerization solution was optimized (30 wt % was the best), the SiO₂ nanoparticle concentration in the prepolymerization matrix was optimized. The presence of SiO₂ nanoparticles in the PEGDA layer increased the membrane flux. The maximum water flux and good antifouling properties were obtained for 0.5 wt % SiO₂ nanoparticles in a 30 wt % PEGDA layer. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43793.     

The effect of TiO2 nanoparticles on the properties of sulfonated block copolymers

Block copolymers composed of styrene and different elastomeric blocks were sulfonated to high ion exchange capacities (IECs). Titanium dioxide (TiO₂) nanoparticles were added to these polymers to improve their mechanical and thermal stabilities, while influencing their transport properties for direct methanol fuel cell (DMFC) applications. Materials properties as proton exchange membranes (PEMs) were analyzed using: FT‐IR, water absorption, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), IEC, methanol permeability, and proton conductivity studies. Although there was no effect of TiO₂ nanoparticles on the thermal stability of the membranes, significant changes were observed in the mechanical properties of both sulfonated block copolymers studied. Water absorption increased at low TiO₂ content, but was then reduced with the incorporation of more nanoparticles. To enhance the interaction between the inorganic fillers and the polymers, sulfonic and amino groups were attached to the surface of the titania nanoparticles. The effect of sulfonated nanoparticles on the properties of the materials was more significant than the effect of the amino functionalized nanoparticles on all the properties evaluated, suggesting enhanced chemical interactions with the ionic domains of the polymer membranes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42651.     

Synthesis,structural characterization and properties of novel functional poly(ether imide)/titania nanocomposite thin films

In this study, the synthesis, morphology, and thermal properties of new poly(ether imide)/titania nanohybrid films were investigated. The novel diamine containing functional nitrile groups was prepared in two steps by the nucleophilic substitution reaction and it was fully characterized by different techniques. Reaction of this diamine with pyromellitic dianhydride and 4-aminobenzoic acid gave poly(ether imide) with carboxylic acid end groups. This acid functionalized poly(ether imide) was condense with different amount of TiO₂ nanoparticles to provide organic-inorganic bonding, and the flexible films of these hybrid were prepared. The obtained materials were characterized by Fourier transform-infrared spectroscopy, thermogravimetry analysis (TGA), differential scanning calorimetry, X-ray powder diffraction, UV–Vis spectroscopy, field emission-scanning electron microscopy, and transmission electron microscopy (TEM) techniques. TEM of the nanohybrid films with 12% of TiO₂ contents confirms well dispersion of nanoparticles in the polymer matrix. TGA data indicated that the thermal behavior of the hybrid materials was increased with an increasing the content of TiO₂ nanoparticles. The tensile stress–strain of the hybrids was investigated and the resulting nanocomposites showed good mechanical properties. The permeability and selectivity of the PEI/TiO₂ membranes as a function of the titania weight percentage were study and the results indicated that the permeabilities of CO₂ and N₂ increase with increasing the titania content.     

Tannic acid coating and in situ deposition of silver nanoparticles to improve the antifouling properties of an ultrafiltration membrane

The construction of antifouling membranes has been a desirable approach for addressing membrane-fouling issues in the ultrafiltration (UF) process. Antifouling means antiadhesive and antimicrobial; however, few researchers have achieved both properties in a facile and effective manner. In this article, we report a direct tannic acid (TA) coating method combined with the in situ deposition of silver nanoparticles (Ag NPs); this was used to improve the antifouling properties of a positively charged polymeric UF membrane. The results show that the TA–Ag NP modified membranes showed improved protein resistance (flux recovery rate = 71.2% after modification vs 17.8% before modification) and less attachment of bacteria (Escherichia coli K1) on the membrane surface and reduced cell viability in the resulting bacterial suspension (reduced by ≥90%) because of the combined antimicrobial properties of both the TA and Ag NPs. This indicated that our modification method was promising for UF membrane antifouling applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47314.