Effects of dissolution conditions on the properties of PVDF ultrafiltration membranes

Poly (vinylidene fluoride) (PVDF) is an important membrane forming material for water treatment. Earlier works have shown that major morphological changes can be achieved when PVDF is dissolved under different conditions with practical applications in membrane distillation and protein attachment. However, no previous report has discussed the effects of dissolution conditions on the performance of PVDF under ultrafiltration, which is one of the most important applications of the polymer. In this work, four different PVDF ultrafiltration membranes were produced from dopes dissolved either by stirring at 24 °C, 90 °C, 120 °C or by sonication. It is shown that dope sonication results in membrane with enhanced thermal and mechanical stability, improved permeate flux during oil emulsion filtration and high flux recovery of ∼63% after cleaning. As a comparison, flux recovery of only ∼26% was obtained for the membrane produced from dope dissolved at 24 °C. The outstanding performance of the dope-sonicated membrane was linked to its slightly lower porosity, narrow distribution of small pores and relatively smooth skin layer. Performance parameters for all membranes showed good correlation to porosity suggesting a tool for membrane design achievable by simple variation in the mode of polymer dissolution. The polymer dissolution effect was related to the degree of unfolding of the polymer molecular chains and their entanglements.     

Role of the polymer matrix in determining the chemical–physical and electrochemical properties of gel polymer electrolytes for lithium batteries

Gel polymer polymer membranes, prepared by immobilizing lithium-conducting solutions in a polymer matrix, are promising electrolyte materials for promoting the advancement of the lithium battery technology. However, so far, not much attention has been devoted to the definition of the role of the constituents in determining the properties of these electrolytes. In this work we have examined the characteristics of three common examples of polymer electrolytes based on a poly(vinylidene fluoride)-fluoropropylene, poly(vinyilidene fluoride)–hexa-fluoropropylene copolymer matrix. The three selected electrolytes differed from the nature of their polymer matrix. The results, based on X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and conductivity tests, show that, indeed, the type of the polymer matrix may influence the properties of the electrolytes, especially in terms of conductivity.     

Crystallizaion and surface morphology of poly(vinylidene fluoride)/poly(methylmethacrylate) films by solution casting on different substrates

The dependence of surface structure of the poly(vinylidene fluoride) (PVDF)/poly(methylmethacrylate) (PMMA) films by solution casting on properties of seven substrates was investigated by wide angle X-ray diffraction (WAXD), Fourier transform infrared (FTIR), scanning electron microscope (SEM) and differential scanning calorimetry (DSC). It was revealed that the polyblend films obtained by casting onto each substrate contained exclusively β phase PVDF. Higher crystallinity of the film was obtained by casting onto ceramic, polytetrafluoroethylene (PTFE), copper (Cu), stainless steel and glass substrates than that by casting onto aluminium (Al) and polypropylene (PP) substrates, depending on the degree of close lattice matching. The surface crystalline structure of PVDF was strongly affected by the wettability of substrate. The largest size of PVDF spherulitic crystal structure with about 6 μm presented in the casting film grown at the air/solution interface on glass substrate, while the smallest spherulite size with about 3 μm was generated by casting onto PTFE, stainless steel and PP substrates. It implied that the higher surface tension the substrate had, the larger PVDF spherulite grew at the air/solution interface.     

Preparation and characterization of modified nano-porous PVDF membrane with high antifouling property using UV photo-grafting

In this study, the poly(vinylidene fluoride) (PVDF) membrane was prepared via immersion precipitation technique and modified by UV photo-grafting of hydrophilic monomers on the top membrane surface. Acrylic acid (AA) and 2-hydroxyethylmethacrylate (HEMA) as acrylic monomers and 2,4-phenylenediamine (PDA) and ethylene diamine (EDA) as amino monomers were used at different concentrations to modify the membrane and improve the hydrophilicity with less fouling tendency. Moreover the presence of benzophenon as photo-initiator for grafting the hydrophilic monomers onto PVDF membrane surface was elucidated. The virgin and modified PVDF membranes were characterized by contact angle, ATR-FTIR, SEM and cross-flow filtration. The contact angle measurements demonstrated that the hydrophilicities of the membranes were significantly enhanced by UV photo-grafting of hydrophilic monomers onto the membrane surface. The ATR-FTIR confirmed the occurrence of modification on PVDF membrane by UV photo-grafting. The pure water flux of membranes was declined by UV photo-grafting but the milk water permeation and protein rejection were slightly improved. Moreover the antifouling properties and flux recovery of PVDF membrane were improved by UV photo-grafting of hydrophilic monomers.     

Electromechanical actuation of CNT/PVDF composite films based on a bridge configuration

Bridged strips consisting of carbon nanotubes and poly(vinylidene fluoride) are developed, which exhibit notable deflection in response to very low driven voltages( 1 V), because of both the excellent conductivity of the unique carbon nanotube film and the powerful thermal expansion capability of the polymer. The actuators demonstrate periodic vibrations motivated by the alternating signals. The amplitude of displacement is dependent not only on the driven voltage but also on the applied frequency. The mechanism of actuation is confirmed to be the thermal power induced by the electrical heating. By accelerating the dissipation of heat, the vibration response at higher frequencies can be significantly enhanced.The useful locomotion shows great promise in potential applications such as miniature smart devices and micro power generators.     

β-Phase of poly(vinylidene fluoride) formation in poly(vinylidene fluoride)/poly(methyl methacrylate) blend from solutions

The effect of single and mixed solvent on the crystallization behavior of the PVDF/PMMA blend from solutions was investigated. The films cast from the good solvent N,N-dimethylformamide (DMF) dominantly yielded the β-phase crystal with the highest crystallinity of PVDF. Those deposited from the methyl ethyl ketone (MEK) and tetrahydrofuran (THF) exhibited a mixture of α- and some extra β-phase crystals and presented the low crystallinity of PVDF. The crystallization behavior and morphology of the films cast from the mixed solvent (THF/DMF) revealed an enormous dependence on the DMF content. The increased DMF content in the mixed solvent enhanced the interactions between polymers and solvents, and favored the β-crystal of PVDF formation but hindered the α-phase of PVDF formation. Thus, the total crystallinity of PVDF in the blend film was decreased with the DMF content increasing, because of the decreased α-phase of PVDF. In addition, the morphological feature revealed that the voids between the PVDF spherulites were eliminated remarkably by blending with PMMA. The average size of the connected spherulite on top surface of the film can grow into larger as DMF content increased.     

Effect of PMMA on crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate) blend prepared in semi-dilute solutions

Films of poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) blend were derived from a special procedure of casting semi-dilute solutions. Hydrophilic character and crystallization of PVDF were optimized by variation of PMMA concentration in PVDF/PMMA blends. It was found that a PVDF/PMMA blend containing 70 wt% PMMA has a good performance for the potential application of hydrophilic membranes via thermally induced phase separation. The films presented β crystalline phase regardless of PMMA content existed in the blends. Thermal analysis of the blends showed a promotion of crystallization of PVDF with small addition of PMMA which induced larger lamellar thickness of PVDF, leading to the largest spherulitic crystal of PVDF (10 wt% PMMA) is about 8 μm. SEM micrographs illustrated no phase separation occurred in blends, due to the high compatibility between PVDF and PMMA.     

Study of a novel porous gel polymer electrolyte based on TPU/PVdF by electrospinning technique

Investigation on a new electrospun gel polymer electrolyte consisting of thermoplastic polyurethane (TPU) and poly(vinylidene fluoride) (PVdF) has been made. Its characteristics were investigated by scanning electron microscopy, FT-IR, Differential Scanning Calorimeter (DSC) analysis. This kind of gel polymer electrolyte had a high ionic conductivity about 3.2 × 10^− 3 S cm^− 1 at room temperature, and exhibited a high electrochemical stability up to 5.0 V versus Li⁺/Li, good mechanical strength and stability to allow safe operation in rechargeable lithium-ion polymer batteries. A Li/GPE/LiFePO₄ cell delivered a high discharge capacity when it was evaluated at 0.1 °C—rate at 25 °C (167.8 mAh g^− 1). And a very stable cycle performance also existed under this low current density.     

P(VDF-TrFE)铁电聚合物薄膜不对称铁电开关现象

报道了铁电聚合物薄膜中观测到的不对称铁电开关双峰现象．当薄膜被略低于其矫顽场的电场极化时可观测到铁电开关双峰,当进一步连续施加超过矫顽场的电场后这一开关双峰现象消失．用空间电荷的注入和再分布模型对这一不对称现象进行了探讨．     

Investigation on crystalline structure and dielectric relaxation behaviors of hot pressed poly(vinylidene fluoride) film

The dielectric relaxation behaviors of hot pressed poly(vinylidene fluoride) (PVDF) film have been studied using dielectric spectroscopy in the frequency domain from 20 Hz to 5 MHz at temperatures between 20 °C and 200 °C. Crystalline/amorphous interphase is suggested with methods of FTIR, XRD, and DSC. Frequency and temperature dependence of dielectric spectroscopy reveals the relaxation behavior and structural dynamics of the samples, and three types of relaxation processes are suggested, α_Ac relaxation process contributed by the hopping transport process near the periphery of conduction band or valence zones at Fermi energy, α_c relaxation process related to the structure change of crystal lattice trapped dipoles in crystalline regions, and α_a relaxation process arising from segmental dipole rearrangement of interphases in amorphous regions. Cole-Cole and Havriliak-Negami experimental equations were utilized to analyze these relaxation processes, and differences of Arrhenius parameters for α_Ac and α_c relaxation processes obtained from Cole-Cole and Havriliak-Negami equations were discussed in detail. Activity energy of different relaxation processes obtained from Arrhenius equation and VFT equation indicates non-single thermal activation mechanism for hot pressed PVDF film.     

Rheological Behaviors of Poly(Vinylidene Fluoride)/“Bud-Branched” Nanotubes Nanocomposites

Bud-branched nanotubes, fabricated by growing metal particles on the surfaces of multiwall carbon nanotubes (MWCNTs), were used to prepare poly(vinylidene fluoride) (PVDF)-based nanocomposites. The melt viscoelastic behaviors of PVDF and its nanocomposites were characterized. The results showed that the introduction of both the MWCNTs and bud-branched nanotubes (MWCNTs-B) increased the storage modulus, loss modulus, and complex viscosity of the nanocomposites. However, the bud-branched nanotubes were more efficient to increase the elasticity than the MWCNTs that have relatively smooth surfaces. In particular, it was observed that the bud-branched nanotubes caused an increase of normal force and crossover modulus, while for MWCNTs, no variation in the normal force and a decrease of the crossover modulus were observed.     

Local vibration assisted molecular configurations in poly(vinylidene fluoride) of ordered ferroelectric phase in N,N-dimethylformamide

Amide-based polymer liquids are important for developing biological and optical colloids or nanofluids. Functionalized properties arise from specific molecular structures. In this investigation, we report model molecular configurations of a polymer liquid, 0.3 g/L poly(vinylidene fluoride) (PVF₂) dissolved in liquid N,N-dimethylformamide (DMF), based on the characteristic IR vibration bands. Peculiarly, a ferroelectric β-PVF₂ phase reorders on a linear configuration in support with the DMF molecules, showing a characteristic band 840 cm^− 1 (CH₂ rocking and CF₂ asymmetric stretching) with the trans band at 1275 cm^− 1. Four CO stretching bands ν₁⁰, ν₁¹, ν₁², and ν₁³ of 1650, 1675, 1725, and 1760 cm^− 1 (bandwidth Δν_½ = 180 cm^− 1 in the four bands) arise in four major configurations of DMF-PVF₂ pairs (or derivatives). Only one prominent ν₁⁰ band 1660 cm^− 1 (Δν_½ = 75 cm^− 1) incurs with a shoulder ν₁¹ of 1725 cm^− 1 (Δν_½ = 25 cm^− 1) in two DMF configurations. A ferroelectric field cased in presence of β-PVF₂ leads to enhance IR absorption by as much as an order of magnitude. It leads to converging non-bonding electron density on the amide moiety.     

Effect of Polyaniline (Emeraldine Base) Addition on α to β Phase Transformation in Electrospun PVDF Fibers

A facile and effective transformation of α to β phase in electrospinning of PVDF was demonstrated by adding emeraldine base polyaniline (PANI). Results from FTIR and X-ray studies revealed that a very large amount of the electraoctive β-phase can be obtained by controlling the amount of PANI loading and the electrospinning parameters, whereas the γ-phase normally showed a very tiny amount, much lower than the β-phase, for all samples with PANI loading. The above results indicate that the addition of PANI into the PVDF solution during electrospinning is a powerful way to enhance the electroactive β-phase of the fibers, which is significant for developing high-performance fiber-based piezoelectric devices.     

Effect of relative humidity on the electrical transport properties of poly(thionaphtheneindole)

Poly(thionaphtheneindole) (pTNI) conducting polymer has previously been observed to undergo a large variation in the electrical conductivity as a function of relative humidity. In this paper the electrical characteristics of this material as a function of the adsorbed water are studied. Isothermal current-time and current-voltage plots can be understood in terms of an ionic charge transfer inside the polymer, controlled by a diffusion limited electrodic process. The charge transfer at the electrodes is probably due to proton reduction at the cathode and water oxidation at the anode.     

Morphology,Crystallization and Formation Mechanism of Poly(Vinylidene Fluoride) Membranes Prepared with Immersion Precipitation: Effect of Maturation Time

Poly(vinylidene fluoride) (PVDF) membranes were prepared by the immersion precipitation method. Effects of the maturation time of dopes on the morphology and crystallization of the prepared membranes were investigated. The analysis showed that the maturation time played an important role in determining the morphology of the prepared membranes. For the dope prepared in the initial day, liquid–liquid demixing preceded solid–liquid demixing in the process of the membrane formation. The morphology of the cross section of the prepared membrane (M1) was finger-like structures with a sponge substrate beneath the porous skin. During the maturation, the dopes underwent a microscopic phase separation and the PVDF crystallized, which resulted in the existence of micro-liquid phases and micro-solid phase crystalline areas in the dopes. In the process of the membrane formation, liquid–liquid demixing took place by nucleation and growth of droplets of the polymer rich phase in the micro-liquid phase. The micro-solid phase crystallites were connected together by the polymer chains, and formed a three-dimensional network gelation morphology. The crystal structure of M1 was mainly β crystals. With increasing maturation time of the dopes, the proportion of β decreased crystals, but that of α crystals increased for the prepared membranes.     

Radical grafting from carbon fiber surface: graft polymerization of vinyl monomers initiated by azo groups introduced onto the surface

This paper describes the radical graft polymerizations of vinyl monomers from carbon fiber surface initiated by azo groups introduced onto the fiber surface. The carbon fiber used in this experiment was the polyacrylonitrile type. The introduction of azo groups onto the carbon fiber surface was achieved by the reaction of 4,4'-azobis (4-cyanopentanoic acid) with isocyanate groups which were previously attached onto the surface by the treatment of the fiber with tolylene 2,4-diisocyanate. The amount of surface azo groups introduced onto nitric acid-treated carbon fiber was determined to be 0.60 x 10^-5 mol 9^-1 by nitrogen analysis. The radical graft polymerization of methyl methacrylate (MMA) was tried. Though the thermal polymerization of MMA proceeded slightly in the absence or in the presence of untreated carbon fiber, the rate of the polymerization was considerably low. In contrast, the graft polymerization of MMA was initiated in the presence of the carbon fiber having surface azo groups, and part of resultant poly(MMA) grafted onto the surface. The percentage of grafting increased with an increase in polymerization time and reached 42.8% after 24 h. The graft polymerizations of other monomers, such as styrene, vinyl acetate, and acrylic acid, were also initiated by the surface azo groups attached onto the carbon fiber, and the corresponding polymer effectively grafted onto the surface.     

Haloform adsorption on crystalline copolymer films of vinylidene fluoride with trifluoroethylene

Reversible bromoform adsorption on crystalline polyvinylidene fluoride with 30% of trifluoroethylene, P(VDF-TrFE 70:30) was examined by photoemission and inverse photoemission spectroscopies. The adsorption of bromoform on this polymer surface is associative and reversible. Molecular bromoform adsorption appears to be an activated process at 120 K with enhanced adsorption following the initial adsorption of bromoform. Strong intermolecular interactions are also implicated in the presence of a weak shake off or screened photoemission final state, whose intensity scales with the unscreened photoemission final state.     

Crystalline Phase Formation of Poly(vinylidene fluoride) from Tetrahydrofuran/N,N‐dimethylformamide Mixed Solutions

The present work focused on the effect of the interactions between poly(vinylidene fluoride) (PVDF) chains and solvent molecules on the structure and crystallization behavior of PVDF in films obtained by solution casting. In a single solvent system, the film cast from the good solvent of N,N‐dimethylformamide (DMF), showed dominantly β‐phase crystals with the highest PVDF crystallinity (50.6%) and the largest spherulite size, about 4 μm, at the top surface. The samples deposited from good swelling agents, such as tetrahydrofuran (THF) and methyl ethyl ketone (MEK), exhibited mainly the original α phase with some amount of β‐phase crystals; the crystallization behavior and the morphology of the surface were similar to the original PVDF resin, because of the only partially dissolved PVDF chains in these two solvents. In a mixed solvent system (THF/DMF), the β phase formation linearly increased as the DMF component increased, determined by Fourier transform infrared spectroscopy (FTIR) techniques, owing to increased interactions between PVDF chains and DMF molecules. The film surface consisted of β spherulites with average size of about 3 μm, which were smaller than those grown from pure DMF, because of the increased crystallization rate in the mixed solvent.     

Enhancement of dielectric constant in PVDF polymer using dendrite-shaped PbS nanostructures

Dendrite-shaped PbS has been successfully synthesized using hydrothermal method on a large scale. The formation of dendrite-shaped PbS was confirmed by scanning electron microscopy (SEM). A detailed study of variations in dielectric properties on frequency and temperature shows that composites of PVDF and dendrite-shaped PbS have significantly higher dielectric constant than PVDF/PbS nanoparticles (NP) nanocomposites due to low percolation threshold.     

Radiation effects on poly(vinylidene fluoride)

Melt-crystallized poly(vinylidene fluoride)s (PVF₂) with different crystallization histories were irradiated with γ-rays within the range of irradiation doses 0–83 Mrad. The effects on the crystalline structure and mechanical properties have been measured, compared, and discussed. The degree of crystallinity of the samples was found to increase with radiation dose. The differential scanning calorimeter scans of the quenched samples indicate that there are two melting peaks, and that the area of the lower temperature peak increases while the area of higher temperature peak decreases with increasing dose. Yield stress and breaking stress for all samples are not significantly affected by irradiation but elongation at break is.