Enhancement of the transport and dielectric properties of graphite oxide nanoplatelets‐polyvinyl alcohol composite showing low percolation threshold

Graphite oxide nanoplatelets (GOnP) were prepared using standard method and used to make GOnP‐polyvinyl alcohol (PVA) composites by using solution cast technique. Significant enhancement of electrical conductivity and dielectric permittivity of the GOnP/PVA composites are observed at low GOnP concentration (f_GOnP = f_c∼0.41 vol%) which is the percolation threshold value estimated from the concentration dependent transport and dielectric data. Nearly 300 times increase in dielectric permittivity (compared with that of PVA) is observed in the GOnP/PVA composite around f_c. We notice interesting metal‐insulator like transition (a sudden increase in resistivity) from the temperature dependent resistivity data in the pure GOnP sample around T_MI ∼ 275 K which is shifted to 300 K in the GOnP/PVA composite for f_c = 0.41 vol%, indicating drastic change of sp³/sp² ratio around respective T_MI. The present graphite‐based composite material might be processed for different applications. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Destruction of percolative network using green synthesized gold nanoparticles: Formation of high dielectric material

Gold nanoparticles (AuNPs) of about 5 nm in diameter were biosynthesized at room temperature (300 K). The PVA/2.5 wt% KH₂PO₄ or KDP composite film and PVA/2.5 wt% KDP/AuNPs nanocomposite films with different concentrations of AuNPs were prepared. Interestingly, addition of 0.05 wt% of AuNPs to the PVA/2.5 wt% KDP percolative composite film destroys percolative behavior of this composite film. Furthermore, the PVA/2.5 wt% KDP/0.05 wt% AuNPs nanocomposite film exhibited high room temperature dielectric permittivity (ε′ ∼ 590 at 1 kHz). The behavior of AC conductivity (σ_ac) of the nanocomposite films indicated correlated barrier hopping type of conduction mechanism. The Cole–Davidson dielectric response becomes evident as the interfacial polarization process acquires a more symmetric form, tending to Debye relaxation. High value of ε′ promises direct application in capacitors. Moreover, the novel feature of destroying the percolative behavior by AuNPs may be applied even in other systems.     

Eco-friendly poly(vinyl alcohol)/delaminated V2C MXene high-k nanocomposites with low dielectric loss enabled by moderate polarization and charge density at the interface

High-dielectric-constant (high-k) polymer/conductor composites with low dielectric loss are desirable for energy storage. However, high leakage currents from interfacial regions with high charge density are difficult to handle. In this work, high permittivity and low dielectric loss were achieved in poly(vinyl alcohol) (PVA)/V₂C MXene nanocomposite films fabricated by solution casting by taking advantage of the interfacial compatibility and moderate interfacial charge density of the nanocomposites. Water-soluble PVA was utilized as the polymer matrix. Delaminated V₂C MXene nanosheets with appropriate conductivity were prepared and used as the filler. The mild interface polarization of the nanocomposites was responsible for achieving favourable permittivity values. The small gap between the work functions of PVA and V₂C contributed to moderate interfacial charge density values and thus low dielectric loss values. A proportional correlation between the interfacial charge density and the conductivity of composites was also verified. The depth of charge injection from the MXene to PVA was found to be half of the interlamellar spacing of the delaminated MXene. The dependence of the electrical properties of the nanocomposites on the frequency and MXene content was also studied. The composite with 4 wt% MXene exhibited a permittivity of ~24 (16 times that of PVA) and a dielectric loss of ~0.14 (1.5 times that of PVA) at 1 kHz, as well as breakdown strength of ~31 MV m⁻¹ (63% of PVA). This work might enable environmentally friendly fabrication of promising composite dielectrics.     

Dielectric Relaxation and Electrical Conductivity Study in Thiourea- Doped Poly (Vinyl Alcohol)

Abstract

FT-IR, UV-spectroscopy and X-ray diffraction of thiourea-Poly (vinyl alcohol) (PVA) complexes have been investigated. It was observed that thiourea affected the structure of PVA. X-ray study revealed that as the thiourea salt increases the crystallinity of PVA increases. The dielectric properties of thiourea-PVA complexes were investigated in the frequency range 0.2 to 100 kHz and the temperature range 293 to 433 K. All samples are characterized by high values of dielectric permittivity at low frequencies and high temperatures. The results are discussed in terms of interfacial Maxwell-Wagner-Sillars (MWS) polarization and space-charge polarization. Different relaxation modes, i.e., β and α-relaxations have been observed in pure PVA. AC conductivity measurements of samples showed that the hopping conduction mechanism dominates at low temperature region, from room temperature to the glass transition temperature.     

Anomalous behavior of the dielectric and electrical properties of polymeric nanodielectric poly(vinyl alcohol)–titanium dioxide films

The complex dielectric permittivity, alternating‐current electrical conductivity, electric modulus, and impedance spectra of polymeric nanocomposite (PNC) films consisting of a poly(vinyl alcohol) (PVA) matrix dispersed with nanosize particles of titanium dioxide (TiO₂); (i.e., PVA–x wt % TiO₂, where x is 0, 1, 3, or 5) were investigated in the frequency range 20 Hz to 1 MHz at ambient temperature. A detailed analysis of the results showed that the values of the dielectric and electrical parameters of these PNC‐based nanodielectric films varied anomalously with increasing TiO₂ concentration. The temperature‐dependent dielectric characterization of the PVA–3 wt % TiO₂ film revealed that the dielectric polarization at a fixed frequency increased nonlinearly with increasing temperature. The temperature‐dependent electric modulus relaxation time values of the nanodielectric film obeyed Arrhenius behavior. The X‐ray diffraction study confirmed that the crystalline phase of the PVA matrix decreased with increasing TiO₂ concentration; this suggested that the interaction of the TiO₂ nanoparticles caused some destruction of the hydroxyl group dipolar ordering in the hydrogen‐bonded crystalline structure of the pristine PVA matrix. The intensities of the diffraction peaks of the TiO₂ nanofiller were enhanced as its concentration increased in these nanodielectrics; this confirmed the existence of TiO₂ nanoparticles inside the crystalline phases of the PVA matrix. The surface morphology of the films was examined by the study of their scanning electron micrographs. The feasibility of using these flexible polymeric nanodielectric films as electrical insulators and dielectric substrates in low‐power microelectronic devices operated at audio‐ and radio‐frequency electric fields was explored. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44568.     

Thermal and dielectric properties of the aluminum particle/epoxy resin composites

Microsized aluminum/epoxy resin composites were prepared, and the thermal and dielectric properties of the composites were investigated in terms of composition, aluminum particle sizes, frequency, and temperature. The results showed that the introduction of aluminum particles to the composites hardly influenced the thermal stability behavior, and decreased T_g of the epoxy resin; moreover, the size, concentration, and surface modification of aluminum particles had an effect on their thermal conductivity and dielectric properties. The dielectric permittivity increased smoothly with a rise of aluminum particle content, as well as with a decrease in frequency at high loading with aluminum particles. While the dissipation factor value increased slightly with an increase in frequency, it still remained at a low level. The dielectric permittivity and loss increased with temperature, owing to the segmental mobility of the polymer molecules. We found that the aluminum/epoxy composite containing 48 vol % aluminum‐particle content possessed a high thermal conductivity and a high dielectric permittivity, but a low loss factor, a low electric conductivity, and a higher breakdown voltage. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

High permittivity BaTiO3 and BaTiO3-polymer nanocomposites enabled by cold sintering with a new transient chemistry: Ba(OH)2∙8H2O

Cold sintering process (CSP) offers a promising strategy for the fabrication of innovative and advanced high permittivity dielectric nanocomposite materials. Here, we introduce Ba(OH)₂?8H₂O hydrated flux as a new transient chemistry that enables the densification of BaTiO₃ in a single step at a temperature as low as 150 °C. This remarkably low temperature is near its Curie transition of 125 °C, associated with a displacive phase transition. The cold sintered BaTiO₃ shows a relative density of 95 % and a room temperature relative permittivity over 1000. This new hydrated flux permits the fabrication of a unique dense BaTiO₃-polymer nanocomposite with a high volume fraction of ceramics ((1-x) BaTiO₃ – x PTFE, with x = 0.05). The composite exhibits a relative permittivity of approximately 800, at least an order of magnitude higher than previous reports on polymer composites with BaTiO₃ nanoparticle fillers that are typically well below 100. Unique high permittivity dielectric nanocomposites with enhanced resistivities can now be designed using polymers to engineer grain boundaries and CSP as a processing method opening up new possibilities in dielectric materials design.     

Flexible dielectric ZnO-doped reduced graphene oxide bionanocomposites from solution blending for potential application in bio-related devices

Biocompatible materials with high dielectric constant and low dielectric loss have applications in bio-related electronic devices. Development of flexible materials with those properties is still a challenge. In this work, electrospun membranes and films are prepared from poly(vinyl alcohol) (PVA) and chitosan (CS) solutions, incorporated with a reduced graphene oxide-zinc oxide composite (rGO-ZnO). Blending CS with flexible PVA favors electrospinnability and mechanical properties. ZnO contributes to hinder agglomeration of conductive rGO sheets. The structural, mechanical, dielectric and electrical properties of the hybrid materials are investigated. Infrared spectroscopy reveals interaction between the filler and the polymeric components. For mats and films, the increase in rGO-ZnO content leads to lower crystallinity. The Young's modulus and stress at break values increase with increasing rGO-ZnO content. High dielectric constants (ε' = 132 to ε' = 166, at 10³ Hz), associated with low dielectric loss factor (tan δ = 0.02), are determined for the PVA/CS/rGO-ZnO films.     

Polytetrafluorethylene-based high-k composites with low dielectric loss filled with priderite (K1.46Ti7.2Fe0.8O16)

Composite materials with a high permittivity (high-k) and low dielectric loss represent an important research direction for the rapid development of modern electronic. This article is about high-k composite with low dielectric loss (dielectric constant is approximately 11, and dielectric loss is only 0.02 at 1 MHz and about 50 wt % of filler) based on a polytetrafluorethylene (PTFE) compounded with priderite (K_1.46Ti_7.2Fe_0.8O₁₆). The dielectric permittivity about ε' ≈ 10³ and the dielectric loss of tgδ ≈ 2 have been found for filler content about 50 wt % (30 vol %) and, respectively, ε' ≈ 11 and tgδ ≈ 0.02 for 1 MHz. To produce filler, amorphous potassium polytitanate was synthesized by molten salt method, modified in aqueous solution of iron sulfate, crystallized at 700 °C and further treated in the aqueous dispersion of PTFE. The obtained product was pressured, dried and investigated by X-ray diffraction and scanning electron microscopy. Dielectric properties of the composite with different ceramic filler content (1–90 wt %) were studied using impedance spectroscopy in the frequency range of 10⁻² to 10⁶ Hz. The influence of frequency on electric conductivity, permittivity, and dielectric losses was analyzed taking into account the experimental data on porosity, apparent density obtained for the composites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48762.     

Polydimethylsiloxane–PbZr0.52Ti0.48O3 nanocomposites with high permittivity: Effect of poling and temperature on dielectric properties

Polydimethylsiloxane (PDMS)/lead zirconate titanate (PbZr_0.52Ti_0.48O₃, PZT)-based nanocomposites with high dielectric constant (permittivity, k) are prepared through room temperature mixing. The effect of PZT loading on electrical and mechanical properties of the PDMS–PZT composites is extensively studied. It is found that there is significant increase in permittivity with PZT loading and decrease in volume resistivity. All the composites have low dielectric loss compared to permittivity value. It is observed that there is increase in permittivity and decrease in volume resistivity of composites after poling, which is due to the dipolar polarization. It is found that both permittivity (ε′) and alternating current conductivity (σ_ac) are increased with temperature at low frequency (1 Hz) and decreased with temperature at high frequency (1 MHz). The above composites are sensitive to external pressure and can be used as pressure/force sensor. The tensile strength and % elongation at break decreases with PZT loading, which is due to the nonreinforcing behavior of PZT ceramic. PZT particles distribution and dispersion in PDMS matrix are observed through field emission scanning electron microscopy, high resolution transmission electron microscopy, and atomic force microscopy/scanning probe microscopy. Thermal stability of composites increased with the PZT loading which is due to higher thermal stability of PZT particles compared to PDMS matrix. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47307.     

Studies of dielectric relaxation and a.c. conductivity in [(100−<Emphasis Type="Italic">x</Emphasis>)PEO + <Emphasis Type="Italic">x</Emphasis>NH<Subscript>4</Subscript>SCN]: Al-Zn ferrite nano composite polymer electrolyte

Present work deals with findings on dielectric behaviour and a.c. conduction in a ferrite doped polymer nano composite electrolyte system, namely [(100−x) PEO + xNH₄SCN]: ferrite. The formation of nano composite and structural behavior of electrolyte was studied by XRD and SEM images. The effect of salt and ferrite on conductivity behaviour of PEO based nano composite polymer electrolyte has been investigated by the impedance spectroscopy at room temperature. The variation of dielectric permittivity and dielectric loss with frequency was carried out at ambient temperature. The a.c. conductivity seems to follow the universal power law.     

Frequency and voltage dependence of dielectric properties,complex electric modulus,and electrical conductivity in Au/7% graphene doped‐PVA/n‐Si (MPS) structures

In order to increase the capacitance of Au/n‐Si (MS) structure, 7% graphene doped PVA was coated on n‐Si as an interfacial layer. The measured data of capacitance (C) and conductance (G/ω) of Au/7% graphene doped‐PVA/n‐Si (MPS) structure was utilized for the calculation of real and imaginary parts of complex permittivity (ε^* = ε′ − jε″), loss tangent (tanδ), complex electric modulus (M^* = M′ + jM″), and electrical conductivity (σ). The admittance measurements (C and G/ω) were carried out in the frequency range of 0.5 kHz to 1 MHz at room temperature. Frequency dependence of the dielectric constant (ε′), dielectric loss (ε″) and tanδ shows a dispersive behavior at low frequencies. This behavior was explained by Maxwell–Wagner relaxation. Due to the dipolar and the interfacial polarizations, as well as the surface states (N_ss) and the interfacial PVA layer, the parameters exhibited a strong dependence on frequency and applied bias voltage. The σ versus log(f) plot exhibited both low and high frequency dispersion phenomena such that at low frequencies σ value corresponding to the dc conductivity (σ_dc), but at high frequencies it corresponds to the ac conductivity (σ_ac). M′ and M″, both, have low values in the low frequency region. However, an increase is observed with the increasing frequency due to the short‐range mobility of charge carriers. As a result, the change in dielectric parameters and electric modulus with frequency is the result of relaxation phenomena and surface states. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43827.     

Dielectric and mechanical properties of rubber ferrite composites

Abstract

Rubber ferrite composites (RFCs) containing powdered nickel zinc ferrite (Ni_{1 - x}Zn_xFe₂O₄ ) in a natural rubber matrix have been prepared and their mechanical and dielectric properties have been evaluated. Variations in the relative permittivity of both the ferrite ceramics and RFCs have been studied over a range of frequencies, ceramic compositions, ceramic filler loadings, and temperatures, and the results have been correlated. Appropriate mixture equations have been formulated to calculate the dielectric permittivity of the composite from the dielectric permittivity of its constituents. Values calculated using these equations have been compared with experimental data on relative permittivity, and the two have been found to be in good agreement. In the present investigation it was also observed that for x = 0 4 and for the maximum ferrite loading, the composite sample exhibits maximum magnetisation and optimum flexibility.     

Revisiting the thermal relaxations of poly(vinyl alcohol)

The molecular dynamics of poly(vinyl alcohol) (PVA) were studied by dielectric spectroscopy and dynamic mechanical analysis in the 20–300°C range. The well-established plasticizing effect of water on the glass-transition temperature (T_g) of PVA was revisited. Improper water elimination analysis has led to a misinterpretation of thermal relaxations in PVA such that a depressed T_g for wet PVA films (ca. 40°C) has been assigned as a secondary β relaxation in a number of previous studies in the literature. In wet PVA samples, two different Vogel–Fulcher–Tammann behaviors separated by the moisture evaporation region (from 80 to 120°C) are observed in the low- (from 20 to 80°C) and high- (>120°C) temperature ranges. Previously, these two regions were erroneously assigned to two Arrhenius-type relaxations. However, once the moisture was properly eliminated, a single non-Arrhenius α relaxation was clearly observed. X-ray diffraction analysis revealed that the crystalline volume fraction was almost constant up to 80°C. However, the crystallinity increased approximately 11% when temperature increased to 180°C. A secondary β_c relaxation was observed at 140°C and was related to a change in the crystalline volume fraction, as previously reported. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fabrication of BaTiO3-PTFE composite film for embedded capacitor employing aerosol deposition

The potential for using aerosol deposition (AD) as an alternative fabrication method to the conventional polymer composite process for embedded capacitors was examined. In order to achieve a high relative dielectric permittivity, BaTiO₃-polytetrafluoroethylene (PTFE) composite thick films were attempted by AD at room temperature. For the high dielectric constant, the BaTiO₃-PTFE composite films grown by AD should satisfied the following two critical conditions: a reduced decrement in ceramic particle size and a relieved distortion of the crystal structure. However, the relative permitivity of the composite films was too low compared with that of the BaTiO₃ films grown by AD. By predicting the dielectric constant in several composite models using the Hashin-Shtrikman bounds theory and 3-dimenstional (3-D) electrostatic simulation, we confirmed that the connectivity between ceramic particles is a highly critical factor for achieving a high dielectric constant in composite films.     

Influence of the Strain on Dielectric and Ferroelectric Properties of 0.5BaZr0.2Ti0.8O3–0.5Ba0.7Ca0.3TiO3

0.5BaZr_0.2Ti_0.8O₃‐0.5Ba_0.7Ca_0.3TiO₃ ceramic and its epitaxial films on (0 0 1) SrTiO₃ substrate were prepared to compare their dielectric and ferroelectric properties. The ceramic has a high dielectric permittivity, a weak dielectric relaxation, a low ferroelectric Curie temperature (T_C) of 60°C and a fast polarization relaxation. The films show much lower dielectric permittivities and mild dielectric relaxations. Furthermore, the T_C of film with 40, 100, and 200 nm thickness is 155°C, 110°C, and 60°C, respectively, because the epitaxial strain decreases with the film thickness increasing. The higher the T_C is, the more stable the room‐temperature polarization is.     

Dielectric,Mechanical, and Thermal Properties of Low-Permittivity Polymer–Ceramic Composites for Microelectronic Applications

A new low-permittivity polymer–ceramic composite for packaging applications has been developed. The ceramic-reinforced polyethylene and polystyrene composites were prepared by melt mixing and hot molding techniques. Low-loss, low-permittivity Li₂MgSiO₄ (LMS) ceramics prepared by the solid-state ceramic route were used as the filler to improve the dielectric properties of the composites. The relative permittivity and dielectric loss were increased with the increase in the ceramic loading at radio and microwave frequencies. The mechanical properties and thermal conductivity of the Li₂MgSiO₄-reinforced polymer–ceramic composite were also investigated. The stability of the relative permittivity of polymer–ceramic composites with temperature and frequency was investigated. The experimentally observed relative permittivity, thermal expansion, and thermal conductivity were compared with theoretical models.     

Good dielectric performance and broadband dielectric polarization in Ag,Nb co-doped TiO2

Due to the demand of miniaturization and integration for ceramic capacitors in electronic components market, TiO₂-based ceramics with colossal permittivity has become a research hotspot in recent years. In this work, we report that Ag⁺/Nb⁵⁺ co-doped (Ag_1/4Nb_3/4)_xTi_1−xO₂ (ANTOx) ceramics with colossal permittivity over a wide frequency and temperature range were successfully prepared by a traditional solid–state method. Notably, compositions of ANTO0.005 and ANTO0.01 respectively exhibit both low dielectric loss (0.040 and 0.050 at 1 kHz), high dielectric permittivity (9.2 × 10³ and 1.6 × 10⁴ at 1 kHz), and good thermal stability, which satisfy the requirements for the temperature range of application of X9R and X8R ceramic capacitors, respectively. The origin of the dielectric behavior was attributed to five dielectric relaxation phenomena, i.e., localized carriers' hopping, electron–pinned defect–dipoles, interfacial polarization, and oxygen vacancies ionization and diffusion, as suggested by dielectric temperature spectra and valence state analysis via XPS; wherein, electron-pinned defect–dipoles and internal barrier layer capacitance are believed to be the main causes for the giant dielectric permittivity in ANTOx ceramics.     

Dielectric properties of epoxy/graphite flakes composites: Influence of loading and surface treatment

Epoxy-rich carbon-based composites are well recognized materials in industries owing to their good mechanical properties and thermal stability. Here, dielectric properties of composites based on bisphenol-A-epoxy resin loaded with 5, 6, 10, and 15 wt% of graphite flakes (GF) have been studied. The frequency and temperature dependence of the dielectric permittivity, dielectric loss, and ac conductivity have been examined in temperature (−103 to 97°C) and frequency (20 Hz–200 kHz) range. Influence of the filler surface chemistry have been studied for composites loaded with 5 wt% GF obtained: (i) under wet milling, without or with adding Triton-100x as a surfactant, or (ii) under dry milling in the presence of KOH. The composite made of epoxy loaded with 5 wt% exfoliated expanded graphite flakes (EEG), was also prepared. The surface treatment with KOH notably increased dielectric constant of the composite, keeping low dielectric loss, while treatment with Triton-100x significantly increased tanδ. The composite loaded with exfoliated expanded graphite shows higher ac conductivity than those obtained with flaky graphite, GF. Possibility to change dielectric properties of the composites without changing the loading content can be used as an approach in tailoring one with desired dielectric properties.     

Microstructure and dielectric properties of Ag-BaTiO3 composite ceramics

Di-phase composite ceramics based on BaTiO₃ with 5?vol% of Ag filler have been prepared by sintering the mixture of powders at temperatures above the silver melting point (1000?°C–1300?°C/2?h). As predicted by finite element calculations, the addition of metallic particles should produce a field concentration in some regions of the BaTiO₃ matrix and therefore, an enhanced dielectric response with respect to pure BaTiO₃. The role of oxygen vacancies on the dielectric relaxation mechanisms of Ag-BaTiO₃ composites has been investigated. The sintering temperature of 1200?°C provided optimized ceramics with excellent dielectric properties, i.e. with low losses (tanδ?<?3%) and room temperature permittivity measured at 50?kHz exceeding 6500 (and above 13,000 at the Curie temperature), as result of a good densification (94% relative density) and a synergy effect of the metallic particles inclusions and ceramic grain size in the range of ≈1?μm, where BaTiO₃ has a well-known maximum of its permittivity.