Fabrication and characterization of high flux poly(vinylidene fluoride) electrospun nanofibrous membrane using amphiphilic polyethylene-block-poly(ethylene glycol) copolymer

Electrospun nanofiber membranes (ENM) made of polymers such as polysulfone and poly(vinylidene fluoride) (PVDF) have a much higher contact angle (CA) and also more hydrophobic when compared to the virgin polymers. For water treatment applications, membranes with hydrophilic nature are highly desirable in order to achieve high flux and less fouling potentials. Hence, in the present study, highly hydrophilic electrospun nanofiber membranes (ENMs) were prepared by blending PVDF polymer with amphiphilic polyethylene-block-poly (ethylene glycol) (PE-b-PEG) copolymer. Resulting amphiphilic ENMs were highly porous (77%–92%) and the breaking elongation of 140% with a young's modulus of 2.55 MPa was observed. When compared with the control PVDF membrane, PE-b-PEG blended ENMs revealed higher water permeation flux owing to the enrichment of the hydrophilic PEG segments at the membrane surface, which was confirmed by using X-ray photoelectric spectroscopy and Energy-dispersive spectroscopy measurements. When compared to the phase inversion process (CA of 97.3°) blended ENM had CA of 0°, which indicates that besides hydrophilic block copolymer segments, the nature of membrane formation also contributes its role in influencing the hydrophilicity of the membrane. This improved hydrophilicity in combination with larger pore sizes of the PVDF/ PE-b-PEG membranes have contributed to enhancement of pure water flux, protein solution permeability and water flux recovery, which can be applied potentially for water treatment applications.     

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     

Preparation and characterization of antifouling poly(vinylidene fluoride) blended membranes

Poly(vinylidene fluoride) (PVDF) membranes have been widely used in microfiltration and ultrafiltration because of their excellent chemical resistance and thermal properties. However, PVDF membranes have exhibited severe membrane fouling because of their hydrophobic properties. In this study, we investigated the antifouling properties of PVDF blended membranes. Antifouling PVDF blended membranes were prepared with a PVDF‐g‐poly(ethylene glycol) methyl ether methacrylate (POEM) graft copolymer. The PVDF‐g‐POEM graft copolymer was synthesized by the atom transfer radical polymerization (ATRP) method. The chemical structure and properties of the synthesized PVDF‐g‐POEM graft copolymer were determined by NMR, Fourier transform infrared spectroscopy, and gel permeation chromatography. To investigate the antifouling properties of the membranes, we prepared microfiltration membranes by using the phase‐inversion method, which uses various PVDF/PVDF‐g‐POEM concentrations in dope solutions. The pure water permeabilities were obtained at various pressures. The PVDF/PVDF‐g‐POEM blended membranes exhibited no irreversible fouling in the dead‐end filtration of foulants, including bovine serum albumin, sodium alginate, and Escherichia coli broth. However, the hydrophobic PVDF membrane exhibited severe fouling in comparison with the PVDF/PVDF‐g‐POEM blended membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Hydrophilic modification of high‐strength polyvinylidene fluoride hollow fiber membrane

The polyvinylidene fluoride (PVDF)/polyvinyl alcohol (PVA) polymer solutions were coated on the outer surface of PVDF matrix hollow fiber membrane. On the principle of the homogeneous‐reinforced (HR) membrane technology, the reinforced PVDF/PVA (RFA) hollow fiber membranes prepared through the dry‐wet spinning method. The performance of the RFA membranes varies with the PVA concentration in the polymer solution and is characterized in terms of pure water flux (PWF), porosity, a mechanical strength test, and morphology observations by a scanning electron microscopy (SEM). The results of this study indicate that PVA can apparently improve the hydrophilicity of the PVDF hollow fiber membranes. The growing enrichment of the hydrophilic components PVA on the membrane surface is determined by X‐ray photoelectron spectroscopy. The RFA membranes have a favorable interfacial bonding between the coating layer (PVDF/PVA) and the matrix membrane (PVDF hollow fiber membrane), as shown by SEM. The elongation at break of the RFA membranes increases much more than that of the matrix membrane that is endowed with the better flexibility of the membrane performance. PWF decreases much more compared with that of the matrix membrane. The RFA membranes have a lower flux decline degree during the process of protein solution and ink solution filtration compared with that of the matrix membrane. POLYM. ENG. SCI., 54:276–287, 2014. © 2013 Society of Plastics Engineers     

Fabrication of antifouling membranes by blending poly(vinylidene fluoride) with cationic polyionic liquid

Membrane fouling problem is now limiting the rapid development of membrane technology. A newly synthesized cationic polyionic liquid (PIL) [P(PEGMA-co-BVIm-Br)] was blended with poly(vinylidene fluoride) (PVDF) to prepare antifouling PVDF membranes. The PVDF/P(PEGMA-co-BVIm-Br) exhibited an increased surface hydrophilicity, the water contact angle was reduced from 77.8° (pristine PVDF) to 57.9°. More porous membrane structure was obtained by adding PIL into the blending polymers, as high as 478.0 L/m²·h of pure water flux was detected for the blend PVDF membrane in comparison with pristine PVDF (17.2 L/m²·h). Blending of the cationic PIL with PVDF gave a more positive surface charge than pristine PVDF membrane. Blend membranes showed very high rejection rate (99.1%) and flux recovery rate (FRR, 83.0%) to the positive bovine serum albumin (BSA), due to the electrostatic repulsion between the membrane surface and proteins. After three repeated filtration cycles of positive BSA, the blend PVDF membranes demonstrated excellent antifouling performance, the permeation flux of the membranes was recovered very well after a simple deionized water washing, and as high as 70% of FRR was obtained, the water flux was maintained at above 350 L/m²·h. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48878.     

A novel conductive membrane with RGO/PVDF coated on carbon fiber cloth for fouling reduction with electric field in separating polyacrylamide

Directly applying an electric field on conductive membrane can effectively mitigate membrane fouling. Thus, a conductive reduced graphene oxide/polyvinylidene fluoride (RGO/PVDF) membrane was prepared by casting PVDF and graphene oxide (GO) solution over a selected carbon fiber cloth, then phase inversion and final heat treatment in hydroiodic acid (HI) solution. This method realized uniform and stable presence of RGO in PVDF membrane. Scanning electron microscopy (SEM) images showed addition of GO reduced the pore size of the composite membranes. The thermal HI treatment partially reduced graphene oxide to RGO, and made the membrane more conductive but less hydrophilic [as characterized by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and contact angle (CA)]. From thermogravimetric analysis (TGA), it showed that the addition of GO and RGO improved the thermal stability of the membranes, when temperature was lower than 400 °C. The HI treatment increased the pore size and water flux of the RGO/PVDF membrane (being 71.6% higher than the GO/PVDF membrane). The RGO/PVDF membrane was used in separating polyacrylamide (PAM), a macromolecule pollutant in oil field waste water; when applying a 0.6 V/cm external electric field, its membrane fouling and flux decline was effectively slowed down, as shown in the fitting curves slopes using the classical cake filtration model (t/V–V). Being uniform and stable, the RGO/PVDF membrane had great potential for practical applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43597.     

Hydrophilic modification of poly(vinylidene fluoride) membrane with poly(vinyl pyrrolidone) via a cross‐linking reaction

A highly hydrophilic hollow fiber poly(vinylidene fluoride) (PVDF) membrane [PVDF‐cl‐poly(vinyl pyrrolidone) (PVP) membrane] was prepared by a cross‐linking reaction with the hydrophilic PVP, which was immobilized firmly on the outer surface and cross‐section of the PVDF hollow fiber membrane via a simple immersion process. The cross‐linking between PVDF and PVP was firstly verified via nuclear magnetic resonance measurement on PVP solution after cross‐linking. The hydrophilic stability of the modified PVDF membrane was evaluated by measuring the pure water flux after different times of immersion and drying. The anti‐fouling properties were estimated by cyclic filtration of protein solution. When the cross‐linking time was as long as 6 hr and the PVP content reached 5 wt %, the pure water flux (J_v) was constant as ～ 600 L m^?2 hr^?1. The hydrophilicity of the PVDF‐cl‐PVP membrane was significantly enhanced and exhibited a good stability. The PVDF‐cl‐PVP membrane showed an excellent anti‐protein‐fouling performance during the cyclic filtration of bovine serum albumin solution. Therefore, a highly hydrophilic and anti‐protein‐fouling PVDF hollow fiber membrane with a long‐term stability can be prepared by a simple and economical cross‐linking process with PVP. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

Amphiphilic PVDF-g-PDMAPMA ultrafiltration membrane with enhanced hydrophilicity and antifouling properties

It is easy to adsorb the pollutants from water owning to the hydrophobicity of the poly(vinylidene fluoride) (PVDF) ultrafiltration (UF) membrane. To improve the hydrophilicity of the PVDF UF membrane, a novel amphiphilic copolymer PVDF-g-poly-N-(3-dimethylaminopropyl)methacrylamide] (PDMAPMA) was developed. The amphiphilic PVDF-g-PDMAPMA was synthesized with PVDF and N-(3-dimethylaminopropyl)methacrylamide (DMAPMA) via free-radical polymerization, and characterized by Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance. The scanning electron microscopy and energy dispersive X-ray spectroscopy were used to characterize the structure morphologies and elementals of the blend PVDF membranes, respectively. The pure water flux (PWF), molecular weight cutoff, and bovine serum albumin (BSA) solution filtration experiments were tested to evaluate the permeation performance and antifouling properties of the membranes. The experimental results showed that the PWF was 263.1 L m⁻² h⁻¹, BSA rejection rate was 98.1% and flux recovery rate was 95.1% of the prepared blend membrane which had obvious improvement compared with the pristine PVDF membrane (17.3 L m⁻² h⁻¹, 91.0, and 83.8%, respectively). The antibacterial activity test showed the prepared blend membrane had good potency against microorganisms. A novel hydrophilic PVDF membrane with good antibacterial properties was developed and would be promising for wastewater treatment. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48049.     

Preparation of PVDF ultrafiltration membranes using PVA as pore surface hydrophilic modification agent with improved antifouling performance

Novel polyvinylidene fluoride (PVDF) ultrafiltration (UF) membranes were facilely fabricated using polyvinyl alcohol (PVA) aqueous solution as the coagulation bath through phase inversion method. In the process, PVA was introduced into the pore surfaces of the PVDF membranes via the interdiffusion of the non‐solvent water and the solvent. The effects of PVA content in the coagulation bath on membrane properties were systematically discussed. The results indicated that the increase of PVA content in coagulation bath resulted in the formations of the more sponge‐like structures and the higher surface hydrophilicity. Smaller pore size led to lower water flux and higher bovine serum albumin rejection. Fouling resistance measurement indicated that the membranes made in PVA/water coagulation bath had higher flux recovery ratio (92.1%) than the membrane made in a pure water bath (71.0%). Furthermore, mechanical property test revealed that the resulting membranes had high tensile strength and Young's modulus. In this work, we found that the morphology and the property of the novel PVDF membranes could be determined by the PVA content in the coagulation bath. POLYM. ENG. SCI., 59:E384–E393, 2019. © 2018 Society of Plastics Engineers     

Engineering silver-zwitterionic composite nanofiber membrane for bacterial fouling resistance

Bacterial attachment and fouling compromise material performance in applications ranging from marine equipment and biomedical devices to water treatment systems. For membrane-based water treatment systems, bacterial attachment and biofilm formation decrease water purification efficiency and reduces mechanical durability of the membranes. In this work, we present a concurrent electrospinning and copolymerization approach to engineer composite nanofiber membranes comprising of silver nanoparticle containing poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP-Ag) nanofibers and [copolymerized zwitterionic sulfobetaine methacrylate-methacryl polyhedral oligomeric silsesquioxane]-poly(methyl methacrylate) nanofibers. We characterized the surface morphology, topography, material chemistry, and wettability of the nanofiber membranes with scanning electron microscopy, atomic force microscopy, Fourier transform infrared spectroscopy, and contact angle measurements. We then challenged these nonwoven membranes with two model microbes, Gram-negative Pseudomonas aeruginosa and Gram-positive Staphylococcus aureus, and found that the silver-zwitterionic composite nanofiber membrane exhibited superior bacterial fouling resistance by reducing >90% of bacterial attachment when compared to neat PVDF-HFP and PVDF-HFP-Ag nanofiber membranes. This study demonstrates that concurrent electrospinning enables free-standing nanofiber membranes with sustained bacterial fouling resistance, with potential in applications in filtration and water treatment technologies for which antifouling strategies are imperative. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47580.     

Poly(vinylidene fluoride) hollow‐fiber membranes containing silver/graphene oxide dope with excellent filtration performance

In this study, an antifouling poly(vinylidene fluoride) (PVDF) hollow‐fiber membrane was fabricated by blending with silver‐loaded graphene oxide via phase inversion through a dry‐jet, wet‐spinning technique. The presence of graphene oxide endowed the blended membrane with a high antifouling ability for organic fouling. The permeation fluxes of the blended membrane was 3.3 and 2.9 times higher than those of a pristine PVDF membrane for filtering feed water containing protein and normal organic matter, respectively. On the other hand, the presence of silver improved the antibiofouling capability of the blended membrane. For the treatment of Escherichia coli suspension, the permeation flux of the blended membranes was 8.2 times as high as that of the pristine PVDF membrane. Additionally, the presented blended membrane improved the hydrophilicity and mechanical strength compared to those of the pristine PVDF membrane, with the water contact angle decreasing from 86.1 to 62.5° and the tensile strength increasing from 1.94 to 2.13 MPa. This study opens an avenue for the fabrication of membranes with high permeabilities and antifouling abilities through the blending of graphene‐based materials for water treatment. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44713.     

Preparation of PVDF/poly(tetrafluoroethylene‐co‐vinyl alcohol) blend membranes with antifouling propensities via nonsolvent induced phase separation method

Poly(vinylidene fluoride) (PVDF) was blended with a new amphiphilic copolymer, poly(tetrafluoroethylene‐co‐vinyl alcohol) [poly(TFE‐VA)], via non‐solvent induced phase separation (NIPS) method to make membranes with superior antifouling properties. The effects of the VA/TFE segment ratio of the copolymer and the copolymer/PVDF blend ratio on the properties of the prepared membranes were studied. Membranes with similar water permeabilities, surface pore sizes, and rejection properties were prepared and used in bovine serum albumin (BSA) filtrations with the same initial water flux and almost the same operating pressure, to evaluate the sole effect of membrane material on fouling propensity. While the VA/TFE segment ratio strongly affected the membrane antifouling properties, the effects of the copolymer/PVDF blending ratio were not so drastic. Membrane surface hydrophilicity increased, and BSA adsorption and fouling decreased upon blending a small amount of amphiphilic copolymer with a high VA/TFE segment ratio with PVDF (copolymer/PVDF blending ratio 1:5). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43780.     

Electrospun fiber membranes from blends of poly(vinylidene fluoride) with fouling‐resistant zwitterionic copolymers

Nonwoven super‐hydrophobic fiber membranes have potential applications in oil–water separation and membrane distillation, but fouling negatively impacts both applications. Membranes were prepared from blends comprising poly(vinylidene fluoride) (PVDF) and random zwitterionic copolymers of poly(methyl methacrylate) (PMMA) with sulfobetaine methacrylate (SBMA) or with sulfobetaine‐2‐vinylpyridine (SB2VP). PVDF imparts mechanical strength to the membrane, while the copolymers enhance fouling resistance. Blend composition was varied by controlling the PVDF‐to‐copolymer ratio. Nonwoven fiber membranes were obtained by electrospinning solutions of PVDF and the copolymers in a mixed solvent of N,N‐dimethylacetamide and acetone. The PVDF crystal phases and crystallinities of the blends were studied using wide‐angle X‐ray diffraction and differential scanning calorimetry (DSC). PVDF crystallized preferentially into its polar β‐phase, though its degree of crystallinity was reduced with increased addition of the random copolymers. Thermogravimetry (TG) showed that the degradation temperatures varied systematically with blend composition. PVDF blends with either copolymer showed significant increase of fouling resistance. Membranes prepared from blends containing 10% P(MMA‐ran‐SB2VP) had the highest fouling resistance, with a fivefold decrease in protein adsorption on the surface, compared to homopolymer PVDF. They also exhibited higher pure water flux, and better oil removal in oil–water separation experiments. © 2018 Society of Chemical Industry     

Improving the charged and antifouling properties of PVDF ultrafiltration membranes by blending with polymerized ionic liquid copolymer P(MMA‐b‐MEBIm‐Br)

This study describes the fabrication and properties of poly(vinylidene fluoride) (PVDF) filtration membranes modified by blending with ionic liquid block copolymer P(MMA‐b‐MEBIm‐Br), which is synthesized via reversible addition‐fragmentation chain transfer polymerization method. The attenuated total reflectance‐Fourier transform infrared spectroscopy and X‐ray photoelectron analyses reveal that the ionic liquid block copolymers are immobilized on PVDF membrane surface. The modified PVDF membrane exhibits excellent charged and antifouling properties because of the charged and hydrophilic properties of the copolymer. Scanning electron microscopy and atomic force microscopy also indicate the morphological characteristics of the membrane and demonstrate that the surface porous structure becomes denser after adding the copolymer. The data of filtration and the zeta potential of the membranes suggest that the charged properties of the ionic liquid block copolymers are mainly responsible for the improvement of the reversible fouling ratio and the decrease in the total fouling ratio of the membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44751.     

Peroxopolyoxometalate nanoparticles blended PES membrane with improved hydrophilicity,anti-fouling,permeability, and dye separation properties

Poly(ethersulfone) (PES) is one of the polymers most widely used for the fabrication of ultrafiltration or nanofiltration membranes in various applications, but its membrane suffers from fouling. In this study, preparation, characterization, and performance of PES nanocomposite membrane comprising peroxopolyoxometalate nanoparticles was studied to provide improved permeability and anti-fouling properties. The high oxygen ratio of the PW₄ nanoparticles could enhance the hydrophilicity of the membranes. The PW₄ nanoparticles were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray (EDX), and X-ray diffraction analyses. The mixed matrix membranes were fabricated using a non-solvent induced phase-separation method. The fabricated membranes were characterized using atomic force microscopy, attenuated total reflection, SEM, EDX mapping, total average porosity, thermogravimetric analyze, and water contact angle experiments. The dye flux and rejection, pure water permeability and anti-fouling properties of the membranes were investigated. All of the membranes blended by different contents of the PW₄ nanoparticles presented better performance compared to the unmodified membrane. The filtration performance of the membranes in reactive green 19 (RG19) and reactive yellow 160 (RY160) dye separation showed that all of the PW₄ blended membranes possessed dye rejection greater than 86% and 96% for RY160 and RG19, respectively. The reusability test using bovine serum albumin (BSA) protein and RG19 dye solutions in five cycle experiments presented good reproductivity of the PW₄ blended membranes. The PES membrane containing 1 wt% of PW₄ nanoparticles showed the highest flux recovery ratio (75%) as well as reduced irreversible fouling ratio (8%) through BSA protein filtration.     

Preparation and properties of PVDF/PVA hollow fiber membranes

On principle of polymer blend phase separation, PVDF/PVA hollow fiber membranes were prepared using phase inversion method. The membrane morphology and performance varied with the blending ratio. The PVDF/PVA blends showed incompatibility by the results of dynamic mechanical analysis (DMA) and infrared attenuated total reflection (FTIR-ATR) sampling technique. Based on bursting pressure and tensile strengths results, we suggest that the mechanical properties of PVDF/PVA blend membranes are worse than that of PVDF membrane. PVA can improve the hydrophilicity of PVDF/PVA hollow fiber membranes, which could be illuminated by the decrease in contact angle, the increase in equilibrium water content (EWC) and the variety in dynamic moisture regain. The pure water flux increases while the rejection ratio decreases with PVA content increasing. Moreover, PVA can improve the anti-fouling property of PVDF/PVA hollow fiber membranes, which could be illuminated by the result of increase coefficient of resistance.     

Taurine as an additive for improving the fouling resistance of nanofiltration composite membranes

A hydrophilic compound, taurine, was investigated as an additive in the interfacial polymerization between piperazine (PIP) and trimesoyl chloride (TMC) to prepare thin‐film composite (TFC) membranes. The resulting membranes were characterized by X‐ray photoelectron spectroscopy and attenuated total reflectance–Fourier transform infrared spectroscopy. The morphology and hydrophilicity of the membranes were investigated through scanning electronic microscopy and water contact angle measurements. The separation performance of the TFC membranes was investigated through water flux and salt rejection tests. The protein‐fouling resistance of the films was evaluated by water recovery rate measurements after the treatment of bovine serum albumin. The membrane containing 0.2 wt % taurine showed the best performance of 92% MgSO₄ rejection at a flux of 31 L m^?2 h^?1 and better antifouling properties than the PIP–TMC membranes. An appropriately low concentration of taurine showed the same MgSO₄ rejection as the PIP–TMC membranes but a better fouling resistance performance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41620.     

PVDF/TiO2/graphene oxide composite nanofiber membranes serving as separators in lithium-ion batteries

Improving the electrochemical properties of membranes in lithium-ion batteries (LIBs) is very important. Many attempts have been made to optimize ionic conductivity of membranes. The aim of this study was fabricating composite nanofiber membranes of poly(vinylidene fluoride) (PVDF), containing titanium dioxide (TiO₂) and graphene oxide (GO) nanoparticles to use in LIBs as separators. The morphology, crystallinity, porosity, pore size, electrolyte uptake, ionic conductivity, and electrochemical stability of the membranes were investigated using scanning electron microscopy, wide-angle X-ray diffraction, Fourier transform infrared spectroscopy, electrochemical impedance spectroscopy, and linear sweep voltammetry. The electrolyte uptake and ionic conductivity of the PVDF/TiO₂/GO composite nanofiber membranes containing 2 wt % GO were 494% and 4.87 mS cm⁻¹, respectively, which were higher than those of the other fabricated membranes as well as the commercial Celgard membrane. This could be attributed to the increased porosity, larger surface area, and higher amorphous regions of the PVDF/TiO₂/GO composite nanofiber membranes as a result of the synergistic effects of the nanoparticles. In this work, suitable optimized membranes with greater electrochemical stability compared with the other membranes were presented. Also, it was demonstrated that the incorporation of the TiO₂ and GO nanoparticles into the PVDF nanofiber membranes led to a porous structure where the electrolyte uptake enhanced. These properties made these membranes promising candidates for being used as separators in LIBs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48775.     

Antifouling enhancement of PVDF membrane tethered with polyampholyte hydrogel layers

The preparation and property of antifouling poly(vinylidene fluoride) (PVDF) membrane tethered with polyampholyte hydrogel layers were described in this work. In fabricating these membranes, the [2‐(methacryloyloxy)ethyl] trimethylammonium chloride and 2‐acrylamide‐2‐methyl propane sulfonic acid monomers were grafted onto the alkali‐treated PVDF membrane to yield polyampholyte hydrogel layers via radical copolymerization with N,N′‐methylenebisacrylamide as crosslinking agent. The analyses of fourier transform infrared attenuated total reflection spectroscopy and X‐ray photoelectron spectroscopy confirm the covalent immobilization of polyampholyte hydrogel layer on PVDF membrane surface. The grafting density of polyampholyte hydrogel layer increases with the crosslinking agent growing. Especially for the membrane with a high grafting density, a hydrogel layer can be observed obviously, which results in the complete coverage of membrane pores. Because of the hydrophilic characteristic of grafted layer, the modified membranes show much lower protein adsorption than pristine PVDF membrane. Cycle filtration tests indicate that both the reversible and irreversible membrane fouling is alleviated after the incorporation of polyampholyte hydrogel layer into the PVDF membrane. This work provides an effective pathway of covalently tethering hydrogel onto the hydrophobic membrane surface to achieve fouling resistance. POLYM. ENG. SCI., 55:1367–1373, 2015. © 2015 Society of Plastics Engineers