Pressure dependence of the β molecular relaxation process and dielectric properties of polyvinylidene fluoride

The effects of hydrostatic pressure to 20 kbar on the β molecular relaxation process of polyvinylidene fluoride (PVDF) and on the dielectric properties in the neighborhood of this relaxation have been investigated. This relaxation has a strong influence on the electrical and mechanical properties of PVDF. Pressure causes a large shift to higher temperatures (～ 10K/kbar) of the dielectric relaxation peak and a decrease in the width of the distribution of relaxation times. This slowing down of the relaxation process is discussed in terms of the Vogel–Fulcher equation and related models, and it results from an increase in both the energy barrier to dipolar motion and the reference temperature (T₀) for the kinetic relaxation process which represents the “static” dipolar freezing temperature for the process. The general applicability of the Vogel–Fulcher equation to relaxional processes in polymers and other systems is briefly discussed. The pressure dependence of the dielectric constant both above and below the relaxation peak temperature (T_max) is found to be dominated by the change in polarizability. The effect is larger above T_max because of the relatively large decrease in the dipolar orientational polarizability with pressure.     

Elasto-viscoplastic behaviour of a polyvinylidene fluoride (PVDF) in tension

The present paper is concerned with the plasticity of a polyvinylidene fluoride (PVDF) in tension. Strain rate strongly influences the plastic behaviour, but the variation of the elastic properties is almost negligible within the range of strain rates considered in the study (from 1.6 × 10⁻⁴ s⁻¹ up to 1.6 × 10⁻¹ s⁻¹). In particular, the yield stress and the ultimate tensile strength are strongly rate-dependent. A one-dimensional elasto-viscoplastic phenomenological model is proposed and analysed. Despite the nonlinearity of the model equations, only one tensile test performed with variable strain rate is sufficient to identify all material parameters. Model predictions are compared with experiments showing good agreement.     

Investigation of the dielectric,mechanical, and thermal properties of noncovalent functionalized MWCNTs/polyvinylidene fluoride (PVDF) composites

To improve the dispersion of multi‐walled walled carbon nanotubes (MWCNTs) and investigate the effect of dispersant for MWCNTs functionalization on the dielectric, mechanical, and thermal properties of Polyvinylidene fluoride (PVDF) composites, two different dispersants (Chitosan and TritonX‐100) with different dispersion capability and dielectric properties were used to noncovalently functionalize MWCNTs and prepare PVDF composites via solution blending. Fourier transform infrared, X‐Ray diffraction, and Raman spectroscopy indicated that TritonX‐100 and Chitosan were noncovalent functionalized successfully on the surface of MWCNTs. With the functionalization of Chitosan and TritonX‐100, the dispersion of MWCNTs changed in different extent, which was investigated by dynamic light scattering and confocal laser scan microscopy. The dielectric, mechanical, and thermal properties of PVDF composites were also improved. Meanwhile, it was also found that the dielectric properties of PVDF composites are closely related to the dielectric properties of dispersant. High dielectric constant of dispersant contributes to the grant dielectric constant of PVDF composites. The mechanical and thermal properties of MWCNTs/PVDF composites largely depend on the dispersion of MWCNTs in PVDF, interfacial interactions and the residual solvent. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation and characterization of polyvinylidene fluoride (PVDF) hollow fiber membranes

Polyvinylidene fluoride (PVDF) hollow fiber membranes were prepared by dry/wet and wet phase inversion methods. In spinning these PVDF hollow fibers, dimethylacetamide (DMAc) and polyvinyl pyrrolidone (PVP) were used as a solvent and an additive, respectively. Water was used as the external coagulant. Water or ethanol was used as the internal coagulants. The membranes were characterized in terms of water flux, molecular weight cut-off for the wet membranes. Gas permeation fluxes and effective surface porosity were determined by a gas permeation method for the dried membranes. The cross-sectional structures were examined by scanning electron microscopy. The effects of polymer concentration, air-gap, PVP molecular weight, PVP content in the polymer dope, and the internal coagulant on the permeation properties and membrane structures were examined. Highly permeable PVDF hollow fiber membranes could be prepared from a polymer dope containing low molecular weight PVP and using ethanol as the internal coagulant.     

High electrochemical stability of polyvinylidene fluoride (PVDF) porous membranes using phase inversion methods for lithium-ion batteries

Journal of Solid State Electrochemistry - Polyvinylidene fluoride (PVDF) porous membranes were prepared by non-solvent-induced phase separation (NIPS) method. The membranes were made by different...     

A simple and convenient route to prepare poly(vinylidene fluoride trifluoroethylene) copolymer nanowires and nanotubes

Poly(vinylidene fluoride trifluoroethylene) copolymer nanowires and nanotubes have been prepared for the first time via a high temperature (相似文献   

Single-step synthesis of proton conducting poly(vinylidene fluoride) (PVDF) graft copolymer electrolytes

The single-step synthesis of proton conducting poly(vinylidene fluoride) (PVDF) graft copolymer electrolytes is demonstrated. The graft copolymers of PVDF backbone with poly(sulfopropyl methacrylate) (PVDF-g-PSPMA) and poly(styrene sulfonic acid) (PVDF-g-PSSA) were synthesized using PVDF as a macroinitiator for atom transfer radical polymerization (ATRP). ¹H NMR and FT-IR spectroscopy show that the “grafting from” method using ATRP was successful and the maximum grafting degrees were 35 and 25 wt% for PVDF-g-PSPMA and PVDF-g-PSSA, respectively. The IEC values were 0.63 and 0.45 meq/g, the water uptakes were 46.8 and 33.4 wt% and the proton conductivities were 0.015 and 0.007 S/cm at room temperature, for PVDF-g-PSPMA and PVDF-g-PSSA, respectively. Both membranes exhibited excellent thermal stability up to around 350 °C, verified by thermal gravimetric analysis (TGA).     

Hydrophilic modification of polyvinylidene fluoride membrane by blending amphiphilic copolymer via thermally induced phase separation

A new amphiphilic copolymer TD‐A is melt‐blended with polyvinylidene fluoride to fabricate hollow fiber membranes in order to improve the hydrophilicity and anti‐fouling property. Membrane samples with different blending ratios are prepared via thermally induced phase separation method. An optimum blending ratio of TD‐A (10 wt%) is determined by a series of characterizations to evaluate the effects of TD‐A contents on membrane properties. The hydrophilicity of the blended membrane samples increases with the increasing blending ratio, but excessive content of TD‐A in blended membranes can lead to structural defects and reduction of mechanical properties. TD‐A blended hollow fiber membrane with optimum blending ratio shows excellent bi‐continuous structure and high water flux. Membrane fouling is remarkably reduced due to the incorporation of TD‐A by static absorption and cyclic filtration tests of bovine serum albumin. Moreover, constant surface chemical compositions and stable flux during long‐term chemical cleaning demonstrate the hydrophilic stability of the blended membrane.     

Pressure dependence of phase transitions in two diacetylene crystals

The phase transitions which occur in a diacetylene polymer crystal (PTS) at 195 K and a diacetylene monomer crystal (DCH) at 142 K have been studied as a function of pressure. For the second-order phase transition in PTS the pressure dependence of the transition temperature was found to be less than 0.05 K MPa^?1; for the first-order transition in DCH it was 0.63 ± 0.08 K MPa^?1.     

Ferroelectric switching characteristics of 73/27 copolymer of vinylidene fluoride and trifluoroethylene

Ferroelectric polarization-reversal switching of vinylidene fluoride—trifluoroethylene copolymer with 73 mol % of vinylidene fluoride is investigated under a variety of conditions in an attempt to derive detailed information on the polarization reversal of the polymer. The electric-field dependence of switching time t_s obeys an exponential law. The temporal change of switching current density J is presented in the form J/(P_s ? P) versus time (P is the polarization, and P_s is its saturation value), which is free of the depolarization-field effect and discriminates in a straightforward manner between acceleration and deceleration of switching. Effects of the annealing of samples upon t_s are observed together with changes in the degree of crystallinity. Effects of space charge distribution upon t_s are investigated by applying two successive pulses, positive and negative, with varied intervals t_w between the two. The dynamics of space charge redistribution is elucidated from the t_w dependence of the t_s of the second pulse. The temperature dependence of t_s indicates that the switching becomes critically fast as the phase-transition temperature is approached.     

Vibronic coupling in the valence band photoemission of the ferroelectric copolymer: poly(vinylidene fluoride) (70%) and trifluoroethylene (30%)

Two different vibrational contributions to the photoemission fine structure of the ferroelectric copolymer poly(vinlylidene fluoride) with trifluoroethylene (CH2-CF2:CHF-CF2, 70%:30%) are identified. The vibrational contributions at the higher photoemission binding energies are associated with two closely placed upsilon(a,s) (CH2) stretching modes while at the smaller photoemission binding energies, the fine structure is due to a delta (CH2) bending mode. The contribution of the delta (CH2) mode to the photoemission fine structure decreases with decreasing temperature. We associate this temperature dependence to the importance of symmetry in vibronic coupling to the photoemission process and increased dipole ordering with decreasing temperature in this organic ferroelectric system.     

Effects of a static electric field upon dielectric properties of poly(vinylidene fluoride) and poly(vinyl fluoride)

Dielectric measurements on poly(vinylidene fluoride) at higher temperatures result in anomalously large values of ε′ and ε″ at lower frequencies. When a static field is applied, a drastic decrease of ε′ and ε″ occurs. The effects of a static field can be summarized as follows: (1) the field effect upon ε′and ε″ is more significant at lower frequencies; (2) with increasing field strength, the rate of decrease of ε′and ε″ with time becomes greater and the ultimate values are smaller; (3) when the field is removed, ε′and ε″ recover but the ultimate recovery is incomplete; (4) the field effect depends strongly on temperature. Such behavior seems to be attributable to the displacement of ionic impurities and to their electrolysis. These results provided a method to remove the contribution of ionic impurities to ε′and ε″ and to measure the relaxation process due only to dipoles of a polymer. The application of this method revealed the dielectric high temperature absorption which had been masked by the ionic conduction in poly(vinyl fluoride).     

Dependence of the dielectric constant on the structure of extruded polyvinylidene fluoride films

The structure of extruded polyvinylidene fluoride films obtained at different die drawing ratios and melt temperatures was studied by X-ray scattering, differential scanning calorimetry, and gravimetry. Their dielectric constant and mechanical properties were examined. The influence exerted by the structure of the amorphous phase and by the molecular weight of the polymer on the dielectric constant of the samples was revealed.     

Thermal properties and structure of electrospun blends of PVDF with a fluorinated copolymer

We report the structure and thermal properties of blends comprising poly(vinylidene fluoride) (PVDF) and a random fluorinated copolymer (FCP) of poly(methyl methacrylate)‐random‐1H,1H,2H,2H‐perfluorodecyl methacrylate, promising membrane materials for oil–water separation. The roles of processing method and copolymer content on structure and properties were studied for fibrous membranes and films with varying compositions. Bead‐free, nonwoven fibrous membranes were obtained by electrospinning. Fiber diameters ranged from 0.4 to 1.9 μm, and thinner fibers were obtained for PVDF content >80%. As copolymer content increased, degree of crystallinity and onset of degradation for each blend decreased. Processing conditions have a greater impact on the crystallographic phase of PVDF than copolymer content. Fibers have polar beta phase; solution‐cast films contain gamma and beta phase; and melt crystallized films form alpha phase. Kwei's model was used to model the glass transition temperatures of the blends. Addition of FCP increases hydrophobicity of the electrospun membranes. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 312–322     

Functional polymers and sequential copolymers by phase transfer catalysis. XXII. Vinylidene fluoride–trifluoroethylene copolymers by surface modification of polyvinylidene fluoride

Polyvinylidene fluoride films and powders have been used to synthesize vinylidene fluoride-trifluoroethylene copolymers. The synthetic procedure involves a phase transfer catalyzed heterogenous dehydrofluorination, followed by electrophilic chlorination or bromination. A phase transfer catalyzed displacement of bromine or chlorine by fluoride ion completes the synthesis. Dehydrofluorinations were up to 40% complete at room temperature and up to 100% complete at 90°C. Electrophilic chlorination of the resulting carbon–carbon double bonds were complete on both powder or films. The bromination of dehydrohalogenated polymers does not go to completion even when the reaction is carried out in solution. Displacement reactions were incomplete and resulted in further dehydrohalogenation when tetrabutylammonium hydrogen sulfate (TBAH) or 18-crown-6 and KF were used in organic solvents. Using TBAH, KHF₂, and water, high degrees of displacement were achieved only on the brominated compounds. The chlorinated products gave both displacement and elimination.     

Microwave frequency dielectric properties of poly(vinylidene fluoride) films

The frequency dependence of dielectric constant ?′, dielectric loss ?″, and dielectric anisotropy were determined for poly(vinylidene fluoride) (PVDF) in microwave frequencies from 4 to 13 GHz. The ?′ and ?″ for PVDF films decreased with increasing frequency. Both ?′ and ?″ were larger in the transverse direction than in the machine direction or draw direction, but the values at 12 GHz were smaller than those observed at 4.0 GHz. The angular dependence of ?″ at microwave frequency reflects the orientational distribution of molecules in the amorphous region. The orientation function was determined to be about 0.04 and 0.01 for uniaxially and biaxially stretched PVDF, respectively. © 1995 John Wiley & Sons, Inc.     

Crystal‐structure dependence of electroactive properties in differently prepared poly(vinylidene fluoride/hexafluoropropylene) copolymer films

The electroactive properties of two random copolymers of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) were studied. The compositions were 95/5 and 85/15 mol % P(VDF/HFP). For each composition, three different film‐preparation methods were used—solvent casting, melt‐pressed quenched, and melt‐pressed slow‐cooled. The ferroelectric properties observed were strongly dependent on the preparation methods of the films as well as the HFP molar content of the samples. The highest remanent polarizations (P_r) obtained from electric displacement versus electric field (D‐E) hysteresis data are 80 and 50 mC/m² for the 5 and 15% HFP solvent‐cast samples, respectively. The slow‐cooled samples do not exhibit any ferroelectric behavior for either the 5 or 15% HFP copolymers. It was also observed that both the 5 and 15% HFP slow‐cooled samples have a smaller electrostrictive response relative to the other two types of samples. Wide‐angle X‐ray diffraction and DSC results suggest that the 5% HFP sample has a higher crystallinity relative to the 15% HFP sample for each preparation method. In addition, different crystal phases form in the samples resulting from the different preparation methods. Fourier transform infrared results suggest that the slow‐cooled samples are in the nonpolar α phase, whereas the quenched and solvent‐cast samples are more likely in the polar β phase. The slow‐cooled samples do not show a switching peak in their nonpolar α‐phase crystalline state. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2793–2799, 2001     

Investigation of dielectric relaxations associated with the glass transition of vinylidene fluoride and trifluoroethylene copolymers by thermally stimulated current

Thermostimulated current (TSC) spectroscopy was applied to the characterization of dielectric relaxations associated with the glass transition of a series of P(VDF/TrFE) copolymers. The maximum temperature of the β-mode increases slightly as the TrFE unit content is increased, in the same manner as the glass transition temperature. By using the technique of fractional polarizations to the resolution of this relaxation mode, we have isolated, for all the polymers investigated, a series of elementary relaxation times that obey a compensation law. This behavior is characteristic of the free amorphous phase of polymers. The mean activation energy of this mode increases as the TrFE unit content is increased, due to a stiffening of molecular chains. Annealing of the copolymers above their ferroelectric-to-paraelectric transition induces a strong crystallinity increase of the materials. As a matter of fact, the amorphous phase is squeezed in to dimensions lower than the characteristic length scale associated with the glass transition. © 1995 John Wiley & Sons, Inc.     

Enhanced dielectric properties of polyethylene glycol (PEG) modified BaTiO<Subscript>3</Subscript> (BT)-poly(vinylidene fluoride) (PVDF) composites

To improve the compatibility between the ceramic particle and polymer matrix, the surface modifier polyethylene glycol (PEG) was used for the modification of BaTiO₃ (BT) particles as fillers in the poly(vinylidene fluoride) (PVDF) matrix via solution casting techniques. The structural analysis of the composite characterized by X-ray diffraction confirms the tetragonal structure. The results showed that the PEG modified BT-PVDF composites had a higher dielectric constant (≈192) and relatively lower dielectric loss value at 1000 Hz. The Nyquist plot suggests the contribution of only bulk effect present in the composites. The AC electrical conductivity studies obey Jonscher’s universal power law by fitting AC conductivity data which reveals the potential utility of the composites for ideal capacitor and microscopic reasons for this improvement were presented. Furthermore, the remnant polarization was significantly improved and maximum polarization was observed for PEG modified BT-PVDF composites.     

Heat capacity and vibrational dynamics of polyvinylidene fluoride (β-form)

Polyvinylidene fluoride (PVDF) is a polymer of industrial importance, mainly due to its piezoelectric and pyroelectric properties. A comprehensive study of the normal modes and their dispersion in PVDF (β-form) has been reported in the reduced zone scheme using Wilson’s GF matrix method as modified by Higgs. A Urey-Bradley force field has been used. The evaluation of normal modes and their dispersion has been taken to logical conclusion by calculating the heat capacity as a function of temperature. The extent of agreement with the experimental data supports the potential field. Characteristic features of the dispersion curves such as repulsion and exchange of character have also been discussed.