Fabrication of poly(vinylidene fluoride) membrane via thermally induced phase separation using ionic liquid as green diluent

Ionic liquid(IL),1-butyl-3-methylimidazolium hexafluorophosphate([BMIM]PF6)as a new and environmentally friendly diluent was introduced to prepare poly(vinylidene fluoride)(PVDF)membranes via thermally induced phase separation(TIPS).Phase diagram of PVDF/[BMIM]PF6 was measured.The effects of polymer concentration and quenching temperature on the morphologies,properties,and performances of the PVDF membranes were investigated.When the polymer concentration was 15 wt%,the pure water flux of the fabricated membrane was up to nearly 2000 L·m-2·h-1,along with adequate mechanical strength.With the increasing of PVDF concentration and quenching temperature,mean pore size and water permeability of the membrane decreased.SEM results showed that PVDF membranes manufactured by ionic liquid(BMIm PF6)presented spherulite structure.And the PVDF membranes were represented asβphase by XRD and FTIR characterization.It provides a new way to prepare PVDF membranes with piezoelectric properties.

High permeability poly(vinylidene fluoride)ultrafiltration membrane doped with polydopamine modified TiO_(2) nanoparticles

In order to improve the water permeability of poly(vinylidene fluoride)(PVDF)ultrafiltration(UF)membranes with low molecular weight cut-off(MWCO),polydopamine(PDA)was employed in the membrane preparation process.Owing to itsmerits of material-independent adhesion,PDAwas coated on inorganic particles or added in coagulation bath to tailor the final membrane structure and property.The introduction of PDA broke through the permeability/selectivity trade-off of the PVDF membrane.By adding the PDA coated titaniumdioxide(PDA/TiO2)nanoparticles,water flux increased by 287% while MWCO kept similar with the pristine PVDF membrane.Thermodynamics and Kinetics of the PVDF/additives/non-solvent were analyzed and shown that nanoparticles reduced the thermodynamic stability and increased the phase separation speed,and the speed can be adjusted using different nanoparticles.Additionally,X-ray diffraction(XRD)test indicated that PVDF crystalline form changed fromαphase to β phase after adding different nanoparticles.Permeability/selectivity trade-offwas broken through by DA addition in coagulation bath.Compared with the original PVDF membrane,when the DA concentration of the coagulation bath was 2.0 g·L^−1,water flux increased by 312%,and MWCO of the PVDF membrane ranged in 10,000 to 20,000 Da as well as contact angle decreased from 81.4°to 45°.

Fabrication of Poly(vinylidene fluoride) /Polysulfone Flat Blend Membranes via Thermally Induced Phase Separation Process for Water Treatment

Poly(vinylidene fluoride) /polysulfone(PVDF/PSF) flat blend membrane was prepared via thermally induced phase separation(TIPS) technique.The membrane formation mechanism and membrane structure were investigated and the effects of PSF/PVDF weight ratio on morphology,crystallinity,porosity,and mechanical properties of the membrane were discussed.The relationship between membrane structure and performances,such as pure water flux and the rejection of carbonic black,was also discussed.It was found that solid-liquid(S-L) phase separation occurred for the PVDF/PSF/diluent system.The addition of PSF influences structure and crystallinity of the membrane,which in turn influences mechanical properties and performances of the membrane.The results reveal that it is possible to obtain network structure via S-L phase separation by blending the polymer,which has a partial compatibility with PVDF.

Preparation and characterization of the antifouling porous membranes from poly(vinylidene fluoride)-graft-poly(N-vinyl pyrrolidone) powders

Porous membranes were prepared using the phase inversion method from poly(vinylidene fluoride)-graftpoly(N-vinyl pyrrolidone)(PVDF-g-PVP) powders, which were synthesized via γ-ray induced graft polymerization(pre-irradiation). Chemical compositions, thermal behavior, morphology and hydrophilicity of the membranes were characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, element analysis, thermalgravimetric analysis, differential scanning calorimetry, scanning electron microscopy and contact angle measurements, respectively. Permeation experiments were conducted to evaluate the water flux,and the dynamic BSA fouling resistance performances were investigated, too. All the experimental results indicate that the PVDF-g-PVP membranes demonstrate better separation performances over the pristine PVDF membrane.

INFLUENCE OF ALCOHOL-BASED NONSOLVENTS ON THE FORMATION AND MORPHOLOGY OF PVDF MEMBRANES IN PHASE INVERSION PROCESS

Through the preparation of PVDF membranes using various nonsolvent coagulation baths following the phase inversion process, the influence of alcohol-based nonsolvents on the formation and structure of PVDF membranes were investigated. The light scattering and light transmission measurements were used to characterize the equilibrium phase diagram and the gelation speed, respectively. The locations of the crystallization-induced gelation boundaries for various systems and precipitation processes were explained from the corresponding thermodynamic and kinetic parameters. It was found that the better affinity between alcohol-based nonsolvents and DMAc solvent caused the gelation boundaries further away from the PVDF-DMAc axis with the coagulation bath varying from water, methanol, ethanol to iso-propanol. Due to the lower exchange rate of DMAc and alcohols, the delayed demixing took place for the membrane-forming using alcohols as baths, and the delayed time became longer when the coagulation bath was changed from methanol, ethanol to iso-propanol. The characterization results of membranes indicate that the influence of nonsolvents on the phase diagram and the precipitation process are in agreement with those on the membrane morphology. The better thermodynamic stability and a low exchange diffusion rate of PVDF/DMAc/alcohols favor the liquid-solid phase separation in gelation process, and therefore yield the membranes with a porous upper surface, a particular bottom surface and symmetrical structure.

Polyaniline-poly(vinylidene fluoride) blend microfiltration membrane and its spontaneous gold recovery application

Structural regular polyaniline was synthesized via a modified-chemical oxidative polymerization reaction. Highly hydrophilic polyaniline(PANi) and polyaniline-poly(vinylidene fluoride) blend(PANi-PVDF) membranes were prepared by solution casting and phase inversion techniques. Both of the mechanical and filtration properties of the membranes depend on the polymer composition and doping level of the blends. The elasticity of the membrane is greatly improved upon introducing poly(vinylidene fluoride) into the blend. The water permeability of the blend membranes is further enhanced when the membranes are doped with hydrochloric acid. The PANi-PVDF blend membranes are capable of recovering metallic gold from the acid/halide leaching streams spontaneous and sustainably, and are promising candidates for wastewater treatments in electronic industries.

Effects of Additives and Coagulant Temperature on Fabrication of High Performance PVDF/Pluronic F127 Blend Hollow Fiber Membranes via Nonsolvent Induced Phase Separation

Poly（vinylidene fluoride） （PVDF） has become one of the most popular materials for membrane preparation via nonsolvent induced phase separation （NIPS） process. In this study, an amphiphilic block copolymer, Pluronic F127, has been used as both a pore-former and a surface-modifier in the fabrication of PVDF hollow fibermembranes to enhance the membrane permeability and hydrophilicity. The effects of 2nd additive and coagulant temperature on the formation of PVDF/Pluronic F 127 membranes have also been investigated. The as-spun hollow fibers were characterized in terms of cross-sectional morphology, pure water permeation （PWP）, relative molecular mass cut-off （MWCO）, membrane chemistry, and hydrolphilicity. It was obsered that the addition of Pluronic F 127 significantly increased the PWP of as-spun fibers, while the membrane contact angle was reduced. However, the size of macrovoids in the membranes was undesirably large. The addition of a 2nd additive, including lithium chloride （LiC1） and water, or an increase in coagulant temperature was found to effectively suppress the macrovoid for- mation in the Pluronic-containing membranes. In addition, the use of LiC1 as a 2nd additive also further enhanced the PWP and hydrophilicity of the membranes, while the surface pore size became smaller. PVDF hollow fiber with a PWP as high as 2330 L·m-2·h-1·MPa-1, a MWCO of 53000 and＇a contact angle of 71 o was successfully fabricated with 3% （by mass） of Pluronic F127 and 3% （by mass） of LiC1 at a coagulant temperature of 25 ℃, which shows better performance as compared with most of PVDF hollow fiber membranes made by NIPS method.

Preparation and characterization of poly （vinylidene fluoride）/ Ti02 hybrid membranes

Poly（vinylidene fluoride） （PVDF）/titanium dioxide （TiO2） hybrid membranes were prepared using nano-TiO2 as the modifier, and characterized by Transmis- sion Electron Microscope （TEM）, Fourier transform infrared spectroscopy （FT-IR）, scanning electron micro- scope （SEM）, atomic force microscope （AFM）, X-ray diffraction （XRD） and X-ray photoelectron spectroscopy （XPS）. The characterization results demonstrated that nano-sized TiO2 particles dispersed homogeneously within the PVDF matrix, contributing to more hydroxyls and smoother surfaces. Moreover, permeate flux, retention factor, porosity, contact angle and anti-fouling tests were carried out to evaluate the effect of TiO2 concentration on the performance of PVDF membranes. Among all the prepared membranes, PVDF/TiO2 membrane containing 10 vol.% TiO2 exhibited the best hydrophilicity with an average pure water flux up to 237 L.mE.h1, higher than that of unmodified PVDF membranes （155L.m2.h ）. Besides, the bovine serum albumin rejection of the hybrid membrane was improved evidently from 52.3% to 70.6%, and the contact angle was significantly lowered from 83° to 60°, while the average pore size and its distribution became smaller and narrower.

SEPARATION OF PROPANE FROM PROPANE/NITROGEN MIXTURES USING PDMS COMPOSITE MEMBRANES BY VAPOR PERMEATION

This study deals with polydimethylsiloxane(PDMS)/polyvinylidene fluoride(PVDF) composite membranes for propane separation from propane/nitrogen mixtures,which is relevant to the recovery of propane in petroleum and chemical industry.The surface and cross-section morphology of PDMS/PVDF composite membranes was observed by scanning electron microscope(SEM).The surface morphology of PDMS/PVDF composite membranes is very dense.There are three layers,the thin dense top layer,finger-like porous middle layer and s...

Poly(vinylidene fluoride-co-hexafluoro propylene) membranes prepared via thermally induced phase separation and application in direct contact membrane distillation

A non-toxic and environmentally safe diluent,acetyl tributyl citrate,was employed to prepare poly(vinylidene fluoride)-co-hexafluoropropylene membranes via thermally induced phase separation.Effects of the polymer concentration on the phase diagram,membrane morphology,hydrophobicity,pore size,porosity and mechanical properties(tensile stress and elongation at break)were investigated.The results showed that the pore size and porosity tended to decrease with increasing polymer concentration,whereas the contact angle,liquid entry pressure and mechanical properties showed the opposite trend.In direct contact membrane distillation operation with 3.5 wt-%sodium chloride solution as the feed solution,the prepared membranes performed high salt rejection(>99.9%).Furthermore,the prepared membranes retained excellent performance in long-term stability tests regarding the permeate flux and salt rejection. ne distillation.

Preparation of PVDF/SiO₂Composite Nanofiber Membrane Using Electrospinning for Polymer Electrolyte Analysis

Superhydrophobic poly(vinylidene fluoride) PVDF-SiO2 composite membranes with different % of SiO2 contents were prepared by electrospinning. The surface morphologies of the membranes are characterized by using scanning electron microscopy. The nanofibers in the membranes were stacked in layers to produce fully interconnected pores that resulted in high porosity. The incorporation of SiO2 into the nanofiber membrane improved the ionic conductivity from 0.2428 × 10-4Scm-1 to 7.731 × 10-4Scm-1 at room temperature. The surface roughness of the membranes increased with increasing the SiO2 content, while the average diameter of nanofibers was rarely affected. Superhydrophobic PVDF membrane with a contact angle larger than 136° was prepared by the electrospinning of the SiO2 functionalized PVDF. The surface composition of the membranes is analyzed by using FTIR and the contact angles and water drops on the surface of the membrane are measured. The contact angle experimental results of PVDF-SiO2 composite membranes showed an improvement of hydrophobicity with % of nano SiO2.

MICROPOROUS PVDF-HFP-BASED POLYMER MEMBRANES FORMED FROM SUPERCRITICAL CO_2 INDUCED PHASE SEPARATION

Microporous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membranes following supercritical CO_2 induced phase separation process were prepared using four solvents.The solid electrolytes of PVDF-HFP were formed by microporous PVDF-HFP membranes filled and swollen by a liquid electrolyte.The effect of the solvents on the morphology and structure,electrolyte absorptions and lithium ionic conductivity of the activated membranes were investigated.It was approved that all the membrane had the similar...

Poly(vinylidene fluoride) membrane based thin film microextraction for enrichment of benzoylurea insecticides from water samples followed by their determination with HPLC

Thin-film microextraction（TFME）,a new geometry for solid-phase microextraction,has become an attractive sample-preparation technique.Compared to other microextraction approaches,the sensitivity of this technique was enhanced without sacrificing the sampling time due to the high surface area-tovolume ratio together with the increase of extraction-phase volume.In this paper,a new TFME method based on poly（vinylidene fluoride） membrane was developed for the extraction of benzoylurea insecticides（diflubenzuron,triflumuron,hexaflumuron and teflubenzuron） from water samples followed by their determination with high performance liquid chromatography-diode array detection.Under the optimal conditions,good linearity was observed over the concentration range of 0.5-100.0 ng/mL with correlation coefficient greater than 0.9994.The limits of detection（S/N = 3） of the method for the target analytes were 0.1 ng/mL.Mean recoveries ranged from 87.7% to 103.9% with relative standard deviations lower than 6.5%.The results indicated that the developed TFME method is simple,efficient,and cost effective.

PREPARATION AND CHARACTERIZATION OF PVDF-HFP MICROPOROUS MEMBRANE BY TEMPLATE METHOD

Porous poly（vinylidene fluoride-co-hexafluoropropylene） （PVDF-HFP） membranes were successfully prepared using dibutyl phthalate （DBP）, polyvinylpyrrolidone （PVP-K30）, polyethylene glycol 200 （PEG200） as templates. SEM was used to examine the morphology of the PVDF-HFP porous membranes. It was found that these membranes have an asymmetric structure and the blends of PVDF-HFP/DBP formed nanoporous membranes, whereas the blends of PVDF- HFP/PVP-K30 formed ＂sponge-like＂ and microporous membranes. Moreover, the average pore size and porosity was about 0.3 μm and 48.7%, respectively. The crystallinity, thermal stability and mechanical strength of membranes were characterized by XRD, DSC, TGA and stress-strain tests. The results showed that the membranes are a crystals with excellent thermal stability. It was an effective way to regulate pore size and morphology of the PVDF-HFP membranes.

SPES/PVDF Binary Membrane as an Alternative Proton Exchange Membrane in Vanadium Redox Flow Battery Application

SPES/PVDF blends were employed to prepare the ion exchange membranes for vanadium redox flow battery(VRB) application for the first time. The addition of the highly crystalline and hydrophobic PVDF effectively limited the swelling behavior of SPES. The vanadium ion permeability of SPES/PVDF membranes was one order of magnitude lower than that of Nafion 117 membrane and pristine SPES membrane. Single cells with SPES/PVDF composite membranes showed significantly lower capacity loss, higher coulombic efficiency and higher energy efficiency than that with Nafion117 and pristine SPES membranes. The blend membrane with 40 wt% of PVDF(denoted as S_(0.6) P_(0.4)) showed energy efficiency of 83.2% at 30 mA?cm^(-2), which was superior to that of the Nafion117 and SPES membranes. In the self-discharge test, S_(0.6) P_(0.4) membrane showed twice longer duration in open circuit decay than that with Nafion 117 membrane. With all the good properties and low cost, the SPES/PVDF membranes are expected to have excellent commercial prospects as ion exchange membranes for VRB system.

PVDF/SiC疏/亲水Janus复合膜的制备及其膜蒸馏处理酸性废水性能

着眼于采用直接接触式膜蒸馏(DCMD)技术对酸性废水进行处理和资源再利用,针对传统蒸馏膜机械稳定性不高、通量低等问题,使用刮涂法和非溶剂致相分离(NIPS)法在亲水碳化硅(SiC)微滤膜表面构建疏水聚偏氟乙烯(PVDF)多孔薄层,制备得到具有不对称润湿性的PVDF/SiC疏/亲水双层Janus复合膜,用于DCMD性能研究.使用N,N-二甲基乙酰胺(DMAc)为溶剂,水-乙醇体系为非溶剂凝固浴,探究了制膜过程中PVDF铸膜液浓度、凝固浴成分、凝固浴温度等因素对PVDF层表面形貌和浸润性的影响,研究了复合膜在DCMD浓缩稀硫酸和处理模拟酸性矿山废水中的性能.结果表明,铸膜液中质量分数10%PVDF和纯乙醇凝固浴为最佳制膜条件,所得复合膜水接触角达140°,分离层孔隙率为45%,平均孔径为0.6μm,并且PVDF层与SiC基体结合力强.复合膜在DCMD浓缩质量分数10%(107 g/L)稀硫酸溶液和处理模拟酸性矿山废水实验中水的膜通量均达10 L/(m^(2)·h)以上,对非水组分截留率近100%,并具有长期运行稳定性,表现出DCMD处理酸性废水的应用潜力.

聚偏氟乙烯及其共聚物涂覆聚烯烃隔膜的研究进展

隔膜是锂离子电池(LIB)的重要组成部分,对电池的容量、循环、耐久性以及安全性能等特性有较大影响。聚烯烃微孔膜具有良好的机械强度、化学和电化学稳定性高、低成本、高孔隙率和适当的热关断性能,,被广泛用作LIB隔膜。但聚烯烃微孔膜存在高温热收缩和电解液润湿性差等问题,降低了电池的安全性和电化学性能。聚偏氟乙烯(PVDF)及其共聚物具有优异的电化学稳定性、化学稳定性、加工性能、介电性能等,通过在聚烯烃隔膜上涂覆PVDF及其共聚物,可显著改善隔膜的热稳定性和润湿性能。本文综述了PVDF及其共聚物涂覆聚烯烃隔膜的研究进展,并对PVDF及其共聚物涂覆聚烯烃隔膜的发展方向进行了展望。

以聚偏氟乙烯为基底的高渗透选择性聚酰胺/酯纳滤膜的制备与表征

以亲水性聚(N-羟乙基丙烯酰胺)(PHEAA)、疏水性聚甲基丙烯酸甲酯(PMMA)为链段的两亲性三嵌段共聚物PHEAA-b-PMMA-b-PHEAA(PHMH)为改性剂,以聚偏氟乙烯(PVDF)为基底膜材料,利用非溶剂诱导相分离法制备了PVDF/PHMH基底.与未改性PVDF基底相比,PVDF/PHMH基底表面孔径变小,孔隙率和亲水性增加;与PVDF基底纳滤膜N0相比,通过界面聚合制备的PVDF/PHMH基底纳滤膜N1表面粗糙度大、亲水性强、截留分子量小,N1纳滤膜对Na_(2)SO_(4)的截留率为96.0%,水渗透通量高达304 L·m^(-2)·h^(-1)·MPa^(-1),优于商业化纳滤膜的渗透选择性.

聚偏氟乙烯微孔膜的亲水化改性及功能化研究进展

聚偏氯乙烯(PVDF)微孔膜的亲水化改性方法有物理共混、化学共聚、表面涂覆、表面化学处理、表面接枝等几种。其中物理共混和表面涂覆法比较成熟且已获得应用,而PVDF微孔膜的表面化学处理、等离子体或光引发改性技术以及环境敏感性等将成为PVDF微孔膜的改性和功能化研究的主要方向。

聚偏氟乙烯微孔膜的改性和应用研究进展

简要介绍了聚偏氟乙烯(PVDF)微孔膜的制备原理、平板式和中空纤维式两类膜的制备方法,及其改性研究的最新进展和应用现状,并展望其研究与应用的发展趋势。