Novel Ag–BaTiO3/PVDF three-component nanocomposites with high energy density and the influence of nano-Ag on the dielectric properties

Novel Ag–BaTiO₃/PVDF (polyvinylidene fluoride) three-component nanocomposites and traditional BaTiO₃/PVDF two-component nanocomposites were prepared by the same procedures. The dielectric properties of these two kinds of composites were compared. The results showed that the kind of three-component nanocomposites had better dielectric properties. The energy density of such kind of composites could reach nearly 10 J/cm³, which indicated that these nanocomposites could be used as the dielectric layers of pulse-power capacitors. The Coulomb blockade effect was used to explain the dielectric breakdown properties and the resistivities under high electric field of such new kind of nanocomposites.     

Enhanced energy storage in polyvinylidenefluoride (PVDF) + BaZrO<Subscript>3</Subscript> electroactive nanocomposites

PVDF + BaZrO₃ electroactive nanocomposite thin film has been prepared by solution casting method. The structural analysis was carried out by using x-ray diffraction pattern and atomic force microscopy (AFM). Generally, the performance of dielectric capacitors toward higher energy density and higher operating temperatures has been drawing increased interest. In this regard, the present study was focussed on the fabrication and characterization of PVDF + BaZrO₃ electroactive nanocomposites in view of enhancing the energy density at elevated temperature. Cole-Cole plot is an agreement with multiple relaxation process in electroactive nanocomposites. Dielectric energy storage performance is assessed for PVDF nanocomposites with different wt% of BaZrO₃ at different frequencies and temperature. It has been observed that with increase of temperature, the permittivity increased while the energy density slightly decreased but significantly higher than pure polymer PVDF. A high energy density of 6.88 J/cm³ was obtained for BaZrO₃ electroactive nanocomposites at 50 °C and 5.06 J/cm³ at 70 °C. Overall, the testing results indicate that using nanocomposites of PVDF and BaZrO₃ as a dielectric component is promising for implementation to preserve high energy density values up to temperatures of 70 °C.The enhancement of dielectric permittivity and the energy density is attributed due to increase of interracial charge density. The effect of BaZrO₃ nanoparticles in energy density of PVDF is first time reported.     

A flexible piezoelectric-triboelectric hybrid nanogenerator in one structure with dual doping enhancement effects

For achieving more effective mechanical energy conversion, based on low-cost and flexible polydimethylsiloxane (PDMS) and polyvinylidene fluoride (PVDF) polymer film as triboelectric and piezoelectric function layer respectively, a polymer-based hybrid piezoelectric-triboelectric nanogenerator (PT-NG) with a structure of Al/PVDF/Cu-PDMS/indium tin oxide (ITO)/polyethylene terephthalate (PET) has been demonstrated. The device has realized the simultaneous triboelectric and piezoelectric conversions in one structure. In addition, when PDMS and PVDF are further modified by graphene quantum dot (GQD) and titanium dioxide (TiO₂) nanoparticles respectively, both triboelectric and piezoelectric outputs of the modified device are greatly enhanced synchronously. The experimental results have indicated that the increase of triboelectric output is due to the improvement of dielectric properties of PDMS film doped with conductive GQDs as well as the enhancement of the effective contact caused by the change of PDMS surface microstructure. While the promotion of piezoelectric output is mainly attributed to the fact that PVDF film after TiO₂ modification induces more polarized β phase with a polarization-free process. Accordingly, the modified device converts mechanical energy into electricity more effectively, which shows a promising prospect in the fields of flexibility display, electronic skin, wearable electronic products and self-powered sensors.     

Giant permittivity of three phase polymer nanocomposites obtained by modifying hybrid nanofillers with polyvinylpyrrolidone

In this work, the combination of graphene decorated with graphene quantum dots (G-D-GQDs) and barium titanate (BaTiO₃) nanoparticles filled poly (vinyledene fluoride) (PVDF) nanocomposites are prepared using solvent casting method. The modification of G-D-GQDs and BaTiO₃ nanoparticles with polyvinyl pyrrolidone (PVP) show finer dispersion in PVDF matrix as compared to unmodified G-D-GQDs and BaTiO₃ nanoparticles in PVDF matrix. XRD of PVDF nanocomposites shows the formation of α and β form of PVDF crystals. The incorporation of the combination of PVP modified BaTiO₃ nanoparticles and G-D-GQDs in PVDF matrix show a decrease in crystallization temperature (T_c), percent crystallinity (X_c) and increase in thermal stability as compared to unmodified PVDF/BaTiO₃/G-D-GQDs nanocomposites, due to interaction of PVP modified nanoparticles with PVDF. Further, the incorporation of the combination of 20 wt.% BaTiO₃ nanoparticles and 3 wt.% G-D-GQDs in PVDF matrix show a giant dielectric constant. The giant dielectric constant is achieved due to accumulation of more charges across conductor-insulator interface, more numbers of microcapacitor formed and enhanced interfacial compatibility between BaTiO₃/G-D-GQDs with PVDF through PVP. The loss tangent (tan δ) of PVP modified G-D-GQDs and BaTiO₃ nanoparticles and its PVDF nanocomposites is low due to lower leakage current, which make the material suitable for various applications.     

Influence of pyrazole on the photovoltaic performance of dye-sensitized solar cell with polyvinylidene fluoride polymer electrolytes

We investigate the influence of the pyrazole content on the polyvinylidene fluoride (PVDF)/KI/I₂ electrolytes for dye-sensitized solar cells (DSSCs). The solid polymer electrolyte films consisting of different weight percentage ratios (0 20, 30, 40, and 50 %) of pyrazole doped with PVDF/KI/I₂ have been prepared by solution casting technique using N,N-dimethyl formamide (DMF) as a solvent. The as-prepared polymer electrolyte films were characterized by various techniques such as Fourier transform infrared spectroscopy (FT-IR spectroscopy), differential scanning calorimetry (DSC), X-ray diffractometer (XRD), alternate current (AC)-impedance analysis, and scanning electron microscopy (SEM). The 40 wt% pyrazole-PVDF/KI/I₂ electrolyte exhibited the highest ionic conductivity value of 9.52?×?10^?5 Scm^?1 at room temperature. This may be due to the lower crystallinity of PVDF and higher ionic mobility of iodide ions in the electrolyte. The DSSC fabricated using this highest ion conducting electrolyte showed an enhanced power conversion efficiency of 3.30 % under an illumination of 60 mW/cm² than that of pure PVDF/KI/I₂ electrolyte (1.42 %).     

Preparation of amino acid nanoparticles at varying saturation conditions in an aerosol flow reactor

In this article, we describe the synthesis of new and ion-selective nanofiltration (NF) membranes using polyvinylidene fluoride (PVDF) nanofibers and hyperbranched polyethylenimine (PEI) as building blocks. These new nanofibrous composite (NFC) membranes consist of crosslinked hyperbranched PEI networks supported by PVDF nanofibrous scaffolds that are electrospun onto commercial PVDF microfiltration (MF) membranes. A major objective of our study was to fabricate positively charged NF membranes that can be operated at low pressure with high water flux and improved rejection for monovalent cations. To achieve this, we investigated the effects of crosslinker chemistry on membrane properties (morphology, composition, hydrophobicity, and zeta potential) and membrane performance (salt rejection and permeate flux) in aqueous solutions (2,000?mg/L) of four salts (NaCl, MgCl₂, Na₂SO₄, and MgSO₄) at pH 4, 6, and 8. We found that an NFC?CPVDF membrane with a network of PEI macromolecules crosslinked with trimesoyl chloride has a high water flux (~30?L?m^?2?h^?1) and high rejections for MgCl₂ (~88 %) and NaCl (~65 %) at pH 6 using a pressure of 7?bar. The overall results of our study suggest that PVDF nanofibers and hyperbranched PEI are promising building blocks for the fabrication of high performance NF membranes for water purification.     

Polyvinylidene Fluoride/Acrylonitrile Butadiene Rubber Blends Prepared Via Dynamic Vulcanization

Dynamically vulcanized blends based on polyvinylidene fluoride (PVDF)/acrylonitrile butadiene rubber (NBR) were prepared and characterized. The mixing torque and dynamic rheology analyses showed that the NBR phase increased the viscosity of the blends. Scanning electron microscopy (SEM) results showed that the NBR phase was in the form of spherical particles dispersed in the PVDF phase during dynamic vulcanization. Comparing PVDF-rich and NBR-rich blends, the size of the rubber particles in the NBR-rich blends were larger than those in PVDF-rich blends. Differential scanning calorimetry (DSC) results showed that the addition of the NBR phase reduced the PVDF crystallinity and T_m. Thermal gravimetric analysis (TGA) results showed that the dynamically vulcanized PVDF/NBR blends had a higher residual char mass than the neat PVDF and NBR. For PVDF-rich blends, the PVDF can be highly toughened by NBR; the Izod impact strength of the PVDF/NBR (70/30) blend was 77.5 kJ/m², which was about six times higher than that of pure PVDF. For rubber-rich blends, the PVDF component was beneficial to the mechanical properties of the blends, which can be used as thermoplastic elastomers.     

Finely-reconciled high dielectric constant and low dielectric loss in ternary polymer/Cr2C3/montmorillonite composite films by filler-synergy strategy

Polymer/conductive ceramic composites with high dielectric constant have become research hotspot of dielectric capacitor materials. However, the conductivity and dielectric loss increase when high dielectric constant is achieved. In order to reconcile high dielectric constant and low dielectric loss, in this study, poly (vinylidene fluoride) (PVDF)/chromium carbide (Cr₂C₃)/montmorillonite (MMT) ternary composite films were prepared by solution cast. Dielectric response based on interfacial polarization was improved and dielectric constant of composites was increased. MMT ceramic was used to suppress interface leakage current. Compared with PVDF/Cr₂C₃ composites, the conductivity and dielectric loss of ternary composites were reduced.     

PVDF-Based Nanocomposite Solid Polymer Electrolytes; the Effect of Affinity Between PVDF and Filler on Ionic Conductivity

Nanocomposite solid polymer electrolytes (NSPEs) based on poly(vinylidene fluoride) (PVDF) were prepared by dispersing two kinds of organoclay (Cloisite^® 30B, Cloisite^® 15A) consisting of silicate layers in the polymer matrix. The effect of affinity between PVDF and organoclay as the filler on ionic conductivity was investigated in relation to its content, dispersed condition of organoclay, and structural changes of nanocomposites. The characterizations of PVDF-based nanocomposites with various organoclay contents were carried out by XRD, TEM, DSC, and DMA. In order to confirm the ion conduction properties of NSPEs with LiCF₃SO₃ at room temperature, ac impedance analyzer and FT-IR spectrometer were used. As a result, a higher ionic conductivity appeared in the case of NSPE with C15A than that with C30B and the maximum conductivity was 1.04 × 10^–3 S/cm for the NSPE containing 5 wt% of C15A and 40 wt% of LiCF₃SO₃.     

SnO2-decorated multiwalled carbon nanotubes and Vulcan carbon through a sonochemical approach for supercapacitor applications

Multiwalled carbon nanotubes (MWCNTs) and Vulcan carbon (VC) decorated with SnO₂ nanoparticles were synthesized using a facile and versatile sonochemical procedure. The as-prepared nanocomposites were characterized by means of transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Fourier transform infra red spectroscopy. It was evidenced that SnO₂ nanoparticles were uniformly distributed on both carbon surfaces, tightly decorating the MWCNTs and VC. The electrochemical performance of the nanocomposites was evaluated by cyclic voltammetry and galvanostatic charge/discharge cycling. The as-synthesized SnO₂/MWCNTs nanocomposites show a higher capacity than the SnO₂/VC nanocomposites. Concretely, the SnO₂/MWCNTs electrodes exhibit a specific capacitance of 133.33 F g⁻¹, whereas SnO₂/VC electrodes exhibit a specific capacitance of 112.14 F g⁻¹ measured at 0.5 mA cm⁻² in 1 M Na₂SO₄.     

Structural, optical and some physical properties of PVDF films filled with LiBr/MnCl2 mixed fillers

Films of polyvinylidene fluoride (PVDF) filled with (X)LiBr(20−X)MnCl₂ mixture, where X=0, 1, 2, 8, 16 and 20 wt%, were prepared by casting method and studied by ultraviolet/visible optical absorption (UV), differential scanning calorimetry (DSC), X-ray diffraction (XRD), infrared transmission (IR) and electron spin resonance (ESR). The optical absorption spectra suggested the presence of an optical gap (E_g) which depends on filler concentration (W) and arises due to the variation in crystallinity within the polymer matrix. Melting and degradation temperatures were identified using DSC. XRD implied a semicrystalline structure (containing α- and β-PVDF phases for all films). Conjugated double bonds and the role of dimethylformamide with a PVDF chain were detected by IR spectra. The ESR analysis revealed the existence of both isolated and aggregated Mn²⁺ ions within the PVDF matrix.     

Phase switching phenomenon in magnetoelectric laminate polymer composites: Experiments and modeling

This article reports on the magnetoelectric (ME) effect observed in bi- and trilayered polymers consisting of polyvinylidene fluoride (PVDF) and polyurethane (PU) filled with magnetically hard magnetite Fe₃O₄ or Terfenol-D(TeD) magnetostrictive material. The samples had the following compositions: (PU+2 wt% Fe₃O₄/PVDF), (PU+2 wt% Fe₃O₄/PVDF/PU+2 wt% Fe₃O₄), (PU+50 wt% TeD/PVDF) and (PU+50 wt% TeD/PVDF/PU+50 wt% TeD). A model, based on a driven damped oscillation system, has been developed to evaluate and study the influence of the first and second-order ME coefficients on the dc magnetic field-induced phase switching phenomenon between dynamic ME current and the applied ac magnetic field. A good agreement between the simulated results and experimental data was obtained and it was found that phase switching characteristics are mainly influenced by the ME losses induced by magnetostriction losses.     

Local variation of the dielectric properties of poly(vinylidene fluoride) during the α- to β-phase transformation

The phase transformation from the non-polar α-phase to the polar electroactive β-phase of polyvinylidene fluoride (PVDF) has been investigated using the fluorescence from Nile red. Films of α-PVDF doped with Nile red were stretched at controlled rates at a temperature of 80 °C to produce the α- to β-phase transition. The thermo/mechanical dependent changes in the crystalline structure are related to the physical rotation of the polar (CH₂-CF₂) group, which can be monitored by steady state fluorescence techniques. The degree of phase transformation is related to variation in the fluorescence, which in turn is linked to local dielectric constant of the polymer. The variation of the refractive index is more associated to the alignment of the polymeric chains than to the phase transformation. Thus, fluorescence is a suitable technique to monitor phase transitions coupled to a variation in the polarity of the dielectric medium.     

Iron oxide nanoparticle synthesis in aqueous and membrane systems for oxidative degradation of trichloroethylene from water

The potential for using hydroxyl radical (OH^?) reactions catalyzed by iron oxide nanoparticles (NPs) to remediate toxic organic compounds was investigated. Iron oxide NPs were synthesized by controlled oxidation of iron NPs prior to their use for contaminant oxidation (by H₂O₂ addition) at near-neutral pH values. Cross-linked polyacrylic acid (PAA) functionalized polyvinylidene fluoride (PVDF) microfiltration membranes were prepared by in situ polymerization of acrylic acid inside the membrane pores. Iron and iron oxide NPs (80–100 nm) were directly synthesized in the polymer matrix of PAA/PVDF membranes, which prevented the agglomeration of particles and controlled the particle size. The conversion of iron to iron oxide in aqueous solution with air oxidation was studied based on X-ray diffraction, Mössbauer spectroscopy and BET surface area test methods. Trichloroethylene (TCE) was selected as the model contaminant because of its environmental importance. Degradations of TCE and H₂O₂ by NP surface generated OH^? were investigated. Depending on the ratio of iron and H₂O₂, TCE conversions as high as 100 % (with about 91 % dechlorination) were obtained. TCE dechlorination was also achieved in real groundwater samples with the reactive membranes.     

Influence of the processing method on the properties of a PVDF film

The main electrophysical properties of polyvinylidene fluoride (PVDF) films produced by two technologies: the solution casting method and the method of hot pressing from the melt are investigated. To analyze the PVDF films, methods of dielectric spectroscopy (DS), IR spectroscopy, TGA/DSC analysis, and x-ray diffraction (XRD) are used. It is demonstrated that the IR spectra of both PVDF films change weakly in comparison with the virgin PVDF film. The absorption bands characteristic for α-, β-, and γ-phases are observed for the virgin and both types of PVDF films. This testifies to the fact that the molecular structure of film samples is practically independent of their processing method. The only difference is that the new absorption band at 1723 cm^–1 arises in the IR spectra of the films produced by the method of hot pressing from the melt. The TGA/DSC analysis demonstrates that the beginning melting temperature, melting temperature, beginning decomposition temperature, and decomposition temperature for the film samples produced by the method of hot pressing from the melt decrease by 8, 2, 10, and 12°C, respectively, compared to the film samples produced by the solution casting method.     

Effects of CNT inclusions on structure and dielectric properties of PVDF/CNT nanocomposites

ABSTRACT

The effects of multiwall carbon nanotube (CNT) inclusions on the crystalline structure of poly(vinylidene fluoride) (PVDF), and on the dielectric properties of PVDF/CNT nanocomposites (NCs), prepared by melt mixing, were investigated by employing X-ray diffraction, differential scanning calorimetry, and dielectric spectroscopy techniques. Our results imply that, in the NCs, the formation of β-phase crystals depends on specific compression treatment in the melt and fast cooling. Dielectric measurements on NCs, with CNT concentrations below the electrical percolation threshold, reveal that the dielectric strength of the two relaxation processes in the amorphous phase and dielectric permittivity, ?′, measured within the broad temperature range from ?150 °C to 60 °C, increase strongly with increasing CNT concentration. This enhancement of amorphous PVDF polarizability has been attributed to the increase of the local electric field, due to local polarization generated at the surface of conductive inclusions/CNT clusters.     

Preparation and electroactive properties of a PVDF/nano-TiO2 composite film

In the present study, poly(vinylidene fluoride) (PVDF)/nano-TiO₂ electroactive film was prepared by coating a substrate with an acetone/DMF solution, which was evaporated at a high temperature (110 °C). The crystallisation behaviour, dynamic mechanical properties and electroactive properties of this PVDF/nano-TiO₂ electroactive film were investigated. The cross-section and surface of the film were observed with a scanning electron microscope (SEM). X-ray diffraction (XRD) results showed that the film containing the PVDF β phase, the desired ferroelectric phase, was obtained by crystallising the mixed solution of nano-TiO₂ and PVDF at 110 °C, while the film containing the α phase was obtained from the crystallisation of the pure PVDF solution at the same temperature. It was found that the storage modulus, the room-temperature dielectric constant and the electric breakdown strength of the composite films were much higher than those of a pure PVDF film. TiO₂ improved the mechanical properties and electroactive properties of the film. The results indicate that PVDF/nano-TiO₂ composite films can be applied to the fabrication of self-sensing actuator devices.     

On the possibility of synthesizing one-dimensional carbon during radiative carbonization of PVDF

The modification of x-ray photoelectron spectra (XPS) and C KVV spectra of a partially crystalline polyvinylidene fluoride (PVDF) film under the long action of soft x-rays and secondary electrons followed by argon ion bombardment of its surface is investigated. Deep radiative carbonization leads to the formation of carbynoid structures (chain carbon) on the PVDF surface. Hence, the carbon XPS of the carbonized sample differs from those obtained for graphite and PVDF. Ion bombardment shows the instability of the carbonized sample surface, giving rise to formation of sp ² hybrid bonds of carbon atoms. The obtained results are indirect experimental evidence that, before ion bombardment, sp-type bonds are dominant on the carbonized PVDF surface.     

Interaction of 157-nm excimer laser radiation with fluorocarbon polymers

Two important fluoropolymers, polytetrafluoroethylene [PTFE—(C₂F₄)_N] and polyvinylidene fluoride [PVDF—(C₂H₂F₂)_N], respond to 157-nm laser radiation in dramatically different ways. At fluences sufficient to produce rapid etching, the volatile emissions from PTFE are dominated by (CF₂)_N fragments. The velocities of the fastest (CF₂)_N molecules at each mass are consistent with kinetic energies on the order of an electron volt—and change little with fluence. This fluence independence suggests that the velocities are not affected by collisions after emission. To account for the high kinetic energies and the unusual, half-monomer mass distribution, we propose that these fragments are produced by photochemical scission of the polymer backbone, and that a fraction of the excitation energy is delivered to each fragment as kinetic energy. In contrast, the principle neutral species from PVDF is HF. HF is produced by the scission of C-F bonds, followed by chemical reactions with nearby hydrogen. This process is accompanied by the conjugation of backbone C-C bonds. The photochemical cleavage of C-C bonds in PTFE and C-F bonds in PVDF is consistent with the lower C-C bond energy of PTFE.     

Properties of gel polymer electrolytes based on poly(butyl acrylate) semi-interpenetrating polymeric networks toward Li-ion batteries

A new type of gel polymer electrolyte (GPE) based on poly(butyl acrylate) (PBA) semi-interpenetrating polymer networks (IPNs) and polyvinylidene fluoride (PVDF) was prepared in different molar ratios ranging from 1:0.5 to 1:1. A series of structure characterizations of PBA/PVDF had been measured using FTIR, XRD, and SEM. The electrolyte uptake test revealed that when the semi-IPNs were swollen with the commercial liquid electrolyte solutions, they showed an outstanding electrolyte uptake of 120% with a chemically cross-linked structure. All results indicated that the GPE exhibited the best performance when the molar ratio of BA and PVDF was 1:0.5. The prototype cell assembled with LiFePO₄ as cathode, lithium metal as anode, and GPE as the electrolyte as well as separator retained 94% of its initial specific capacity after 100 charge-discharge cycles, showing an excellent cycling stability and a high electrochemical window (up to 4.5 V against Li⁺/Li) at room temperature. Compared with the liquid electrolyte, the GPE exhibited a similar stable cycling performance and was suitable for practical application in Li-ion batteries.