High dielectric permittivity and low loss in PVDF filled by core-shell Zn@ZnO particles

In this study, metal-semiconductor Zn@ZnO core-shell particles were prepared by the heat treatment of raw Zn powder under air atmosphere, and the prepared Zn@ZnO particles were incorporated into poly(vinylidene fluoride) (PVDF) to obtain high dielectric permittivity polymer. The results indicate that the Zn@ZnO particles remarkably increased the dielectric constant of the PVDF composites compared with the raw Zn/PVDF due to the duplex interfacial polarizations induced by ZnO-Zn interface and ZnO-PVDF interface. Moreover, the dielectric permittivity of the Zn@ZnO/PVDF composites can be further optimized by adjusting the thickness of ZnO shell. The dielectric loss and conductivity were still remained at low acceptable level owing to the presence of ZnO shell between Zn core and PVDF matrix which serves as an interlayer between the Zn cores preventing them from contacting with each other. The developed Zn@ZnO/PVDF polymer composites with high dielectric constant and low loss are potential for embedded capacitor applications.     

Novel composites of copper nanowire/PVDF with superior dielectric properties

Novel copper nanowires (CuNWs)/poly(vinylidene fluoride) (PVDF) nanocomposites with high dielectric permittivity (ε′) and low dielectric loss (ε″) were prepared by a precipitation technique followed by melt compression. Their dielectric properties over the broadband frequency range, i.e. 10¹–10⁶ Hz, were compared with multi-walled carbon nanotubes (MWCNT)/PVDF nanocomposites prepared by the same technique. It was observed that the CuNWs/PVDF nanocomposites had higher dielectric permittivity, lower dielectric loss and thus significantly lower dissipation factor (tan δ) than the MWCNT/PVDF nanocomposites at room temperature. This behavior was ascribed to a higher conductivity of the fresh core of the CuNWs relative to the MWCNT, which provided the composites with a higher amount of mobile charge carriers participating in the interfacial polarization. Moreover, the presence of oxide layers on the CuNWs surfaces diminished the conductive network formation leading to a low dielectric loss.     

Fabrication and Dielectric,Mechanical, and Thermal Properties of Low-Density Polyethylene (LDPE) Composites Containing Surface-Passivated Silicon (Si/SiO2 Core/Shell Nanoparticles)

Composites of low-density polyethylene containing between 1 and 5?wt% of Si/SiO₂ core/shell nanoparticles were prepared by ball milling method. The thermal, mechanical, and dielectric properties of composites were investigated in terms of composition, frequency, and temperature. The results showed that the dielectric permittivity increased smoothly with a rise of Si/SiO₂ particle. The dielectric permittivity and loss decreases and increases with temperature, respectively. The resistance of composites to erosion due to partial discharge was significantly improved by adding nanoparticles. The results have demonstrated that ball milling was an effective method for producing relatively homogeneous nanocomposite up to 4?wt% Si/SiO₂.     

Core‐shell structured Al/PVDF nanocomposites with high dielectric permittivity but low loss and enhanced thermal conductivity

Surface modification of core‐shell structured Al (Al@Al₂O₃) nanoparticles was performed using γ‐(Aminopropyl)‐triethoxysilane (APS) and dopamine (DA), respectively, and the microstructures, dielectric properties and thermal conductivities of the Al/poly(vinylidene fluoride) (PVDF) nanocomposites were investigated. Both DA and APS enhance the interfacial bonding strength between the fillers and the matrix, leading to homogeneous dispersion of Al nanoparticles in PVDF matrix. Compared with raw Al nanoparticles, surface‐treated Al/PVDF exhibit much higher dielectric permittivity due to the enhanced interfacial interactions between the two components, whereas, the dielectric loss and electric conductivity of the nanocomposites still remain at rather low levels owing to the insulating alumina shell preventing effectively core Al from direct contact. The dynamic dielectric properties results reveal that dielectric constant and loss increase with temperature due to the gradually enhanced mobility of molecular chain segments of PVDF for the raw Al/PVDF and treated Al/PVDF nanocomposites. Additionally, the PVDF nanocomposites with Al treated with APS and DA show enhanced thermal conductivities compared with raw Al/PVDF under the same filler loading because of reduced thermal interfacial resistance promoting phonon transfer across the interfaces. POLYM. ENG. SCI., 59:103–111, 2019. © 2018 Society of Plastics Engineers     

Effect of calcination temperature of TiO2 on the crystallinity and the permittivity of PVDF‐TrFE/TiO2 composites

Composite membranes of poly(vinylidene‐trifluoroethylene)/titanium dioxide (PVDF‐TrFE/TiO₂) were prepared by the solution cast method. The crystallization behavior and dielectric properties of the composites with TiO₂ calcined at different temperatures were studied. Transmission electron microscopy and X‐ray diffraction (XRD) results showed that the TiO₂ nanoparticles calcined at different temperatures were well dispersed in the polymer matrix and did not affect the structure of the PVDF‐TrFE matrix. XRD and differential scanning calorimeter measurements showed that the crystallinity of PVDF‐TrFE/TiO₂ composites increased as the addition of TiO₂ with different calcination temperatures. The dielectric property testing showed that the permittivity of PVDF‐TrFE/TiO₂ membrane increased rapidly with the increase of TiO₂ content and the calcination temperature of TiO₂ at constant TiO₂ content, but the dielectric loss did not change much. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

High-k composites with sandwich structure by introducing a negative permittivity layer with Ni as conductive filler

Advanced electronic equipment requires new high dielectric constant materials. Nevertheless, the balance of the permittivity and dielectric loss remained a problem. In this work, BFT/PVDF-Ni/PVDF sandwich polymer matrix composites (SPMCs) containing alternating negative dielectric constant and positive dielectric constant layers were fabricated using hot press sintering. The structure and dielectric properties of the composites were investigated. The results indicated that introducing negative dielectric constant layer into SPMCs led to higher dielectric constant (ε′ ≈ 130) and low loss tangent (tanδ ≈ 0.14) at 1 kHz compared with the pristine PVDF (ε′ ≈ 10, tanδ ≈ 0.020). The effective increase of dielectric constant was due primarily to the introduction of a negative dielectric layer into the material. The low loss tangent was caused by the ohm barrier effect between adjacent layers.     

Dielectric and optical properties of a poly(ethylene terephthalate) membrane in the temperature interval 150–400 K

In this study, the dielectric and optical properties of poly(ethylene terephthalate) (PET) membranes were examined. The dielectric measurements were carried out in the temperature interval 150–400 K and in the frequency range 20 Hz–60 kHz. We analyzed in detail the temperature dependences of the dielectric permittivity and dielectric loss (tan δ) at various test frequencies. The relaxation tan δ peak, which appeared in the temperature range 150–300 K, was identified as the secondary β relaxation. The increase in tan δ at temperatures higher than 300 K could be explained as approaching the α relaxation. Optical measurements were performed in the UV–visible region from 200 to 400 nm at various temperatures between 150 and 400 K. The values of the direct and indirect band gaps were calculated at various temperatures. These values were lower for higher temperatures. An absorption peak was observed at a wavelength around of 285 nm at temperatures lower than 300 K. Such insight into the dielectric and optical responses of PET track membranes in a wide temperature range is particularly important when this material is used as a matrix for the semiconductor structure in the development of optoelectronic or microfluid devices. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42834.     

Synthesis and Characterization of Lead-Free Ferroelectric 0.5[Ba(Zr0.2Ti0.8)O3]–0.5[(Ba0.7Ca0.3)TiO3]—Polyvinylidene Difluoride 0–3 Composites

0.5[Ba(Zr_0.2Ti_0.8)O₃]–0.5[(Ba_0.7Ca_0.3)TiO₃]/[BZT–BCT]–polyvinylidene difluoride/[PVDF] 0–3 composites were prepared by uniaxial hot-press method for different volume fractions of BZT–BCT ceramic powder in a PVDF polymer matrix. The structural, microstructural and dielectric properties were investigated and discussed. There was an increase in relative permittivity (ε_r) and dielectric loss (tan δ) of the composites with increase in the volume fraction of the ceramics. At room temperature and at 1 kHz frequency, 0.25[BZT–BCT]–0.75[PVDF] composite showed a highest relative permittivity (ε_r) ~41.     

Improving dielectric properties of poly(vinylidene fluoride) composites: effects of surface functionalization of exfoliated graphene

To investigate the effects of surface functionalization of exfoliated graphene (EG) on the crystalline form of β-phase and dielectric properties of poly(vinylidene fluoride) (PVDF), we prepared PVDF-based composites reinforced by different functionalized EG. The X-ray photoelectron spectroscopy results indicated that a wide variety of chemical functional groups such as C–OH, C–O–C, C=O, COOH and C–F could be introduced on the surface of modified EG. As confirmed by results of Fourier transform infrared spectrum and X-ray diffraction, the β-phase PVDF can be produced in the composites with the incorporation of functionalized EG. In the frequency ranging from 10² to 10⁷ Hz, the dielectric permittivity of PVDF composites shows an obvious increase owing to a variation of the carbonyl group (C=O) content. Among all the composites, the EG grafted with polymethyl methacrylate/PVDF composite has the highest dielectric permittivity and dielectric loss.     

Nickel‐multiwalled carbon nanotubes/polyvinylidene fluoride composites with high dielectric permittivity

Composites with nickel particles coated multiwalled carbon nanotubes (Ni‐MWNTs) embedded into polyvinylidene fluoride (PVDF) were prepared by solution blending and hot‐press processing. The morphology, structure, crystallization behavior, and dielectric properties of composites were studied. The results showed that the crystallization of PVDF was affected by Ni‐MWNTs. With the increment of Ni‐MWNTs, the content of β‐phase in PVDF increased. The dielectric permittivity was as high as 290 at 10³ Hz when the weight fraction of Ni‐MWNTs was 10%. The results can be explained by the space charge polarization at the interfaces between the insulator and the conductor, and the formation of microcapacitance structure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3746–3752, 2013     

Dielectric properties of nanographite‐filled PMMA composites prepared by in situ polymerization

In this work, a series of polymer composites was prepared by in situ polymerization of methylmethacrylate (MMA) as a monomer and sonicated nanographite particles (∼400 nm) as conductive fillers. The concentration of nanographite particles was changed in the step of 0.25 wt% in the monomer and five composites having a filler concentration of 0.25, 0.50, 0.75, 1, and 1.5 wt% respectively were prepared. The composites were characterized for their morphology, thermal, and dielectric behavior. Room temperature dielectric behavior of the composites was studied at six different frequencies of 100 Hz, 1, 10, 100, 500 kHz, and 1 MHz. Temperature‐dependent dielectric properties was studied in the temperature range from 30 to 150°C at the above frequencies. It was interesting to note that at room temperature dielectric constant (ε′) decreased with increasing concentration of nanographite and reached a minimum at a filler concentration of 0.75 wt%. Dielectric relaxation behavior was observed in the temperature versus tan δ curves. The dielectric peak shifted to higher temperatures with increase in frequency and vice‐versa. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Improved dielectric properties of poly(vinylidene fluoride)–BaTiO3 composites by solvent-free processing

Composites of poly(vinylidene fluoride) (PVDF) and BaTiO₃ nanoparticles (average diameter ca. 125 nm) are fabricated by a solvent-free and industrially scalable technique, that is, melt blending, followed by compression molding. The effect of processing parameters on the spectroscopic, microstructural, thermal, mechanical and dielectric properties are evaluated as a function of composition (loading up to 30 vol%). The presence of nanoparticle inclusions as well as specific compression molding parameters demonstrate both to affect the molecular relaxations of the PVDF matrix, studied by correlating the results of different techniques, and to induce the PVDF crystallization as β phase. Processing parameters also play a key role for optimizing the dielectric properties. An improved dielectric behavior of the composites is obtained in terms of both permittivity, whose value increases up to four times that of neat PVDF, and dielectric losses, lower than 5% between 10 and 3·10⁴ Hz. The obtained performances resulted enhanced compared to analogous composites prepared with the use of solvents.     

Polyvinylidene fluoride-modified BaTiO3 composites with high dielectric constant and temperature stability

Polyvinylidene fluoride (PVDF)-modified X7R-type BaTiO₃ (BTO) composites were prepared by hot pressing, and the dielectric properties were investigated. The dielectric constant of the PVDF–BTO composites at 1 kHz increased significantly with increasing the volume fraction of BTO up to 0.5, and good temperature stability of dielectric constant was obtained for the composites, which benefited from the temperature-stable dielectric constant of the modified BaTiO₃. Two significant dielectric relaxations were observed for the PVDF–BTO composites, and they fit the Vogel–Fulcher and Arrhenius fittings, respectively.     

Effect of temperature on electrical behavior of flyash‐filled epoxy gradient composites

Functionally gradient composites of epoxy resin having different weight percentages of flyash were prepared under centrifugal force to obtain gradient in density, hardness, and electrical properties. Effect of temperature and frequency variation on dielectric constant (ε′), tan δ, and ac conductivity was determined by using a 4274 A Multi‐Frequency LCR meter. Electrical measurements were carried out in a temperature range from 40 to 180°C and in a frequency range from 1 to 100 kHz. It was observed that the dielectric constant and tan δ increased with increase in temperature and decreased with increase in frequency. The ac conductivity increases with increase in temperature and frequency. The increased weight percentage of flyash increased the compaction of flyash particle in the flyash‐rich phase of graded composites, which would have increased the dielectric constant (ε′), tan δ, and ac conductivity. Shore D hardness and density of the functionally gradient composites has also been determined and reported. A continuous increase in the hardness from 69 to 76 and density from 1.287 to 1.41 g/cc has been observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1269–1276, 2006     

聚偏氟乙烯/石墨烯复合材料的制备及性能研究

用溶液共混法制备出聚偏氟乙烯/氧化石墨烯复合材料(PVDF/GO),经高温热压将GO还原得到聚偏氟乙烯/还原氧化石墨烯复合材料(PVDF/rGO)。研究了填料种类及含量对复合材料电学性能、热稳定性和力学性能的影响。结果表明：随GO和rGO的添加,两种复合材料的介电常数(ε _r)均变大、介电损耗(tanδ)变化不大;低含量下GO和rGO均能提高PVDF的热稳定性,但rGO对PVDF性能的改善效果更好;随填料含量从0增加到8%(质量),100 Hz下PVDF/rGO复合材料的ε _r从3.60增加到38.30,PVDF/rGO[4%(质量)]复合材料失重率为5%的分解温度较纯PVDF提高了6.44℃。rGO增强了PVDF的刚性,PVDF/rGO复合材料的拉伸强度先增大后减小,杨氏模量逐渐增大,当rGO含量为4%(质量)时拉伸强度最大,拉伸强度和弹性模量分别较纯PVDF提高了35.30%、22.58%。但GO和rGO都降低了复合材料的击穿场强。     

Deposition of platinum on the outer surface of carbon-encapsulated silver nanoparticles

Investigations of the morphological and phase characteristics of silver nanoparticles encapsulated in amorphous carbon shell (Ag@C) during heating, acid treatment and galvanic replacement reactions were carried out. It was found that upon heating of Ag@C nanoparticles up to 800 °C the silver sublimes resulting in the formation of hollow carbon nanocapsules. Washing of Ag@C nanoparticles with nitric or hydrochloric acid solutions also leads to dissolution of encapsulated silver core and formation of hollow carbon nanocapsules. Electron microscopic investigations showed that, for short treatment times of Ag@C nanoparticles with a H₂PtCl₆ solution, nanoparticles of metallic platinum, several nanometers in diameter, are deposited on the outer surface of the carbon shells. With increasing treatment time or concentration of H₂PtCl₆ solution, increasing numbers of noble metal nanoparticles on the surface of the carbon shells, and almost complete dissolution of the metal core, were observed. This process opens broad possibilities for the design and direct preparation of modified by noble metal carbon-based nanomaterials of different compositions for a wide variety of practical applications.     

Measurement of AC conductivity and dielectric properties of flexible conductive styrene–butadiene rubber‐carbon black composites

Flexible conductive polymer composites were prepared using styrene–butadiene rubber (SBR) as a matrix and conductive carbon black as filler. The filler loading was varied from 10 to 60 phr. The effect of frequency, filler loading, temperature, and applied pressure on the AC conductivity, permittivity, and loss factor of the composites was studied. The AC conductivity of low and high loaded composites was found to be frequency dependent and independent respectively. The permittivity and the loss factor were continuously decreasing with increasing frequency. The increase in filler loading increased the AC conductivity, dielectric constant, and loss factor of the composites. Increase in temperature imposed increase in conductivity and permittivity of the composites. With increasing applied pressure the properties showed exponential increase. The effect of time under a constant compressive stress was studied and dielectric relaxation times were evaluated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 986–995, 2007     

Flexible 0–3 Ceramic‐Polymer Composites of Barium Titanate and Epoxidized Natural Rubber

Flexible composites with a high electrical permittivity are pursued in materials research, due to their potential applications in electrical devices. We synthesized such ceramic‐polymer composites from BaTiO₃ and epoxidized natural rubber. The influence of BaTiO₃ concentration on cure characteristics, mechanical (static & dynamic), dielectric, and morphological properties of the composites was investigated. The tensile strength and elongation at break decreased with BaTiO₃ loading, while the storage modulus and permittivity of composites increased. As for dynamic electrical properties, the dielectric loss factor and tan δ of the composites showed a maximum peak within the frequency range extending up to 10⁵ Hz, reflecting the relaxation process of the polymer matrix. All of the composites showed two peaks in the frequency dependence of electric modulus, due to conductivity and molecular relaxation. Scanning electron microscopy micrographs confirmed the 0–3 structure of composites, with isolated BaTiO₃ particles.     

Synthesis and dynamic mechanical study of core–shell structure epoxy/polyacrylate composite particle

A material with high damping property and based on epoxy/polyacrylate (EP/PA) composite particles was synthesized by two-stage emulsion polymerization. Transmission electron microscopy (TEM) showed that the composite particles have a spherical morphology, a core–shell structure and a diameter of 100 nm–130 nm. Fourier transform infrared spectra (FTIR) indicated the cross-linking between EP groups in the core layer and carboxyl groups in the shell layer of the composite particles during film formation. The cross-linking reaction improved the dynamic mechanical property by the interaction of core and shell polymers. The effects of the cross-linking agent and ratio of the two polymers on the damping capacity were studied by dynamic mechanical analysis (DMA). DMA results revealed that a certain amount of acrylic acid could markedly enhance the loss factor (tan δ) and slightly widen the damping temperature range. When the EP/PA ratio was 1:7, peak values for tan δ of the composite materials could reach 2.10, exceeding the value for most damping materials. The result implies that the EP/PA composites have great potential application in damping steel surface coatings.     

Single step densification of high permittivity BaTiO3 ceramics at 300 ºC

Dense nanocrystalline BaTiO₃ ceramics are prepared in a single step by the Cold Sintering Process at 300 °C, under a uniaxial pressure of 520 MPa for 12 h using a molten hydroxide flux. Transmission electron microscopy reveals a dense microstructure with sharp grain boundaries. The average grain sizes are 75−150 nm depending on the flux amount. The dielectric permittivity is 700–1800 at room temperature at 10⁶ Hz, with a dielectric loss, tan δ ∼ 0.04. The difference in permittivity and phase transition behavior are explained in terms of the intrinsic size effect of the BaTiO₃. The nanocrystalline BaTiO₃ ceramics still shows a macroscopic ferroelectric switching via a hysteresis loop. This work demonstrates that cold-sintering process could enable the densification of ferroelectric oxides in a single step. Futhermore, comparable dielectric properties to reported values for nanocrystalline grains are obtained, but at this time, with the lowest processing temperatures ever used.