Porous pyridine based polyimide–silica nanocomposites with low dielectric constant

Highly porous polymer–silica hybrid materials were prepared based on the organo-soluble polyimides of four various dianhydride and 2,5-diaminopyridine. 3-Aminopropyltriethoxysilane (APS) was used to increase the intrachain chemical bonding and interchain hydrogen bonding between the polyimide and silica moieties, respectively. The chemical interaction would significantly affect the morphologies and properties of the prepared films. The produced polyimide–silica composites were investigated by X-ray diffraction analysis, scanning electron microscope and thermal analysis tecniques. The effect of silica modified with functional group of 3-aminopropyltriethoxy silane on the porous structure and dielectric properties as well as the thermal stability of films were investigated. Capacitances were determined with a HP4294A at a frequency between 1 kHz and 1 MHz. The dielectric constant was significantly reduced with increasing silica modified with APS. The result indicates that the composite materials are potentially useful in low dielectric materials.     

Correlation of boron content and high temperature stability in Si–B–C–N ceramics

The preparation and characterization of precursor derived Si–B–C–N ceramics with similar Si/C/N ratios but variable boron content are reported. The polymeric precursors were prepared via hydroboration of poly(methylvinylsilazane) using different BH₃·SMe₂/polymer stoichiometries. High temperature thermogravimetric analysis of as-pyrolysed ceramics as well as XRD studies of post-annealed samples display a retarding effect of boron on both crystallization of SiC and Si₃N₄ and stabilization of crystalline β-Si₃N₄.     

Remarkably enhanced dielectric stability and energy storage properties in BNT–BST relaxor ceramics by A-site defect engineering for pulsed power applications

Lead-free bulk ceramics for advanced pulsed power capacitors show relatively low recoverable energy storage density(Wrec)especially at low electric field condition.To address this challenge,we propose an A-site defect engineering to optimize the electric polarization behavior by disrupting the orderly arrangement of A-site ions,in which Ba_0.105Na_0.325Sr_0.245−1.5x□_0.5xBi_0.325+xTiO₃(BNS_0.245−1.5x□_0.5xB_0.325+xT,x=0,0.02,0.04,0.06,and 0.08)lead-free ceramics are selected as the representative.The BNS_0.245−1.5x□_0.5xB_0.325+xT ceramics are prepared by using pressureless solid-state sintering and achieve large W_rec(1.8 J/cm³)at a low electric field(@110 kV/cm)when x=0.06.The value of 1.8 J/cm3 is super high as compared to all other W_rec in lead-free bulk ceramics under a relatively low electric field(<160 kV/cm).Furthermore,a high dielectric constant of 2930 within 15%fluctuation in a wide temperature range of 40–350℃is also obtained in BNS_0.245−1.5x□_0.5xB_0.325+xT(x=0.06)ceramics.The excellent performances can be attributed to the A-site defect engineering,which can reduce remnant polarization(P_r)and improve the thermal evolution of polar nanoregions(PNRs).This work confirms that the BNS_0.245−1.5x□_0.5xB_0.325+xT(x=0.06)ceramics are desirable for advanced pulsed power capacitors,and will push the development of a series of Bi0.5Na0.5TiO3(BNT)-based ceramics with high W_rec and high-temperature stability.     

Synthesis and characterizations of BNT–BT and BNT–BT–KNN ceramics for actuator and energy storage applications

Dielectric and ferroelectric properties of 0.93Bi_0.5Na_0.5TiO₃–0.07BaTiO₃ (BNT–BT) and 0.93Bi_0.5Na_0.5TiO₃–0.06BaTiO₃–0.01K_0.5Na_0.5NbO₃ (BNT–BT–KNN) ceramics were studied in detail. An XRD analysis confirmed the single perovskite phase formation in both the samples. Room temperature (RT) dielectric constant (ε_r) ~1020 and 1370, respectively at 1 kHz frequency were obtained in the BNT–BT and BNT–BT–KNN ceramics. Temperature dependent dielectric and the polarization vs. electric field (P–E) studies confirmed the coexistence of ferroelectric (FE) and anti-ferroelectric (AFE) phases in the BNT–BT and BNT–BT–KNN ceramics. Substitution of KNN into the BNT–BT system decreased the remnant polarization, coercive field and the maximum strain percentage. The energy storage density values ~0.485 J/cm³ and 0.598 J/cm³ were obtained in the BNT–BT and BNT–BT–KNN ceramics, respectively. High induced strain% in the BNT–BT ceramics and the high energy storage density in the BNT–BT–KNN ceramics suggested about the usefulness of these systems for the actuator and the energy storage applications, respectively.     

The origin of the electric and dielectric behavior of expanded graphite–carbon nanotube/cyanate ester composites with very high dielectric constant and low dielectric loss

High performance expanded graphite (EG)–multiwalled carbon nanotube (MWCNT)/cyanate ester (CE) composites with very high dielectric constant, low dielectric loss and low percolation threshold were developed. In order to understand the electric and dielectric behavior of EG–MWCNT/CE composites, EG/CE and MWCNT/CE binary composites were also prepared for comparison. Results show that the ternary composites have greatly different electric and dielectric properties from the binary composites. The percolation threshold of the EG–MWCNT/CE composite is much lower than that of either the EG/CE or MWCNT/CE composite. With the same content of conductive fillers, the EG–MWCNT/CE composite shows a much higher dielectric constant than EG/CE and MWCNT/CE composites. In addition, to obtain the same dielectric constant, the dielectric loss of the EG–MWCNT/CE composite is lower than that of either binary composite. The difference is attributed to the synergistic effect between EG and MWCNT. The addition of EG not only improves the dispersion of MWCNTs in the resin matrix, but also helps to form conductive networks. An equivalent circuit model is proposed.     

Growth,microstructure, energy–storage and dielectric performances of chemical–solution NBT–based thin films: Effect of sodium nonstoichimometry

Na_0.5+δBi_0.5(Ti_0.96W_0.01Ni_0.03)O₃ thin films with various Na contents (abbreviated as Na_.5+δBTWN, δ?=?? 3.0, ??1.5, 0, 1.5%) were fabricated on ITO/glass substrates using a chemical–solution process. The effects of Na nonstoichiometry on the microstructure, insulating, ferroelectric and dielectric performances are investigated. The pure perovskite phase can be obtained in Na_0.5BTWN and Na_0.515BTWN, while for Na_0.470BTWN or Na_0.485BTWN, the main composition contains secondary phase of TiO₂. The grain size increases from 30?nm at δ?=?? 3.0% to 55?nm at δ?=?0%, then decreases to 52?nm with δ?=?1.5%. The leakage current of Na_0.485BTWN sample is reduced dramatically in comparison with Na_0.5+δBTWN (δ?=?? 3.0, 0, 1.5%). The big recoverable energy–storage density of 63.1?J/cm² and high energy–storage efficiency of 55.0% can be obtained for Na_0.485BTWN due to the improved electric break–down strength and large difference value between the remanent polarization and maximum polarization. Enhanced dielectricity is achieved in Na_0.485BTWN with a high tunability of 36.0% and a figure of merit of 4.0 at 450?kV/cm and 500?kHz. These results demonstrated that the crystallization, micrographs and energy storage and dielectric properties of Na_0.5Bi_0.5TiO₃ are highly sensitive to low levels of Na–site nonstoichiometry.     

Influences of crystallization temperature on the structure,dielectric, and energy storage characteristics of KBaSrNb5O15-based glass–ceramics

Glass–ceramics capacitors have great application potential in pulsed power systems, due to ultrafast discharge speed and high dielectric breakdown strength (BDS). Here, lead-free niobate glass–ceramic dielectric materials were synthesized, and the effects of heat treatment temperature on the dielectric, ferroelectric, and energy storage properties of glass–ceramics were investigated comprehensively. The results exhibit that the dielectric permittivity first increases and then decreases as the crystallinity increases; however, the dielectric BDS diminishes. At the optimum crystallization temperature of 740°C, the maximum value of discharge energy density is 2.2 J/cm³ at 600 kV/cm, which is about 7.6 times that of mother glass. Furthermore, an ultrahigh power density of about 380.9 MW/cm³ and ultrafast discharge speed of about 11.2 ns were achieved simultaneously. Meanwhile, great thermal stability of charge–discharge property was verified in this glass–ceramics. According to P–E loops and dielectric test result, a high dielectric constant (∼207) and low dielectric loss (<0.005) as well as high energy storage efficiency of about 94.9% were achieved for G740 sample. The previous results make the obtained glass–ceramic as potential candidates in dielectric capacitors.     

High quality microwave dielectric ceramic sintered at extreme-low temperature below 200° and co-firing with base metal

Ultra-low temperature co-fired ceramics technology (ULTCC) requires the microwave dielectric ceramics with lower intrinsic sintering temperature than the melting point of inner electrodes. In the present work, a novel HBO₂ ceramic was found to be densified at extreme-low temperature below 200 °C, with pores, residual H₃BO₃, amorphous B₂O₃ inside, with a relative permittivity ∼2.12 ± 0.02, a Qf value ∼32,700 ± 300 GHz and a temperature coefficient of resonant frequency value ∼ − 43 ± 3 ppm/°C. This material can be easily obtained by dehydration from H₃BO₃ by sintering at low temperature below 200 °C. Its extreme-low sintering temperature and water solubility also provides the possibility to achieve some novel multi-functional inorganic-organic composite in the future.     

Synthesis and evaluation of water-reducible acrylic–alkyd resins with high hydrolytic stability

Relatively poor hydrolytic stability is one of the major drawbacks of waterborne alkyd resins. Therefore, the shelf life of the paints containing these kinds of resins is usually short. In this research, the hydrolytic stability of water-reducible alkyd resins has been improved by employing polyacid acrylic copolymers in alkyd resins structure. In addition, the effect of other raw materials (such as neutralizing agent) and synthesis conditions on the resins properties was investigated. The results showed that the optimum synthesized water-reducible acrylic–alkyd resins had a high hydrolytic stability and their acid values increased only 23.5% after 4 months storage at ambient temperature. The synthesized resin was also used in an air-drying water-reducible lacquer formulation and its physical and mechanical properties were evaluated.     

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.     

Phase structure and energy storage performance for BiFeO3–BaTiO3 based lead-free ferroelectric ceramics

Recently, BiFeO₃–BaTiO₃ (BF-BT) lead-free ferroelectric ceramics have been widely concerned and deemed as one of the most promising candidates for lead-free energy-storage material because of their high spontaneous polarization and excellent energy storage properties. Herein, a series of Bi_1-zLa_zFeO₃-xBaTiO₃+yMnO₂ (BL_zF-xBT-yMn at 0.45 ≤ x ≤ 0.60 mol, 0.0 ≤ y ≤ 0.4% mol and z = 0 or 0.02 mol) ceramics were prepared to reveal their energy-storage performance. With increasing x, the breakdown strength (BDS) increases, while the maximum polarization (P_max), remanent polarization (P_r), and the difference value between P_max and P_r (ΔP) decrease. Because of the high BDS and ΔP, a large energy storage density W_re = 1.08 J/cm³ is achieved in BF-0.48BT ceramics as the electric field is 130 kV/cm. In addition, with increasing y and z, the increasing BDS and ΔP have been observed. Due to the improvement in BDS and ΔP, an excellent W_re = 1.22 J/cm³ was achieved in Bi_1-zLa_zFeO₃-xBaTiO₃+yMnO₂ ceramics at x = 0.48, y = 0.3% and z = 0.02. This work provides the clue for application of the high-power-energy BF-BT ceramics.     

Shock wave-material interaction in ZrB2–SiC based ultra high temperature ceramics for hypersonic applications

We investigate the thermochemical stability of ZrB₂–SiC based multiphase ceramics to hypersonic aerothermodynamic conditions in free piston shock tube with an objective to understand quantitatively the role of thermal shock and pressure. The developed ceramics sustained impulsive thermomechanical shock, under reflected shock pressure of 6.5 MPa and reflected shock temperature of 4160 K in dissociated oxygen, without structural failure. The conjugate heat transfer analysis predicts the surface temperature of ZrB₂–SiC to reach a maximum of 693 and 865 K, for ZrB₂–SiC–Ti. The transient shock-material response is characterized by surface oxidation of the investigated ceramics, when exposed to high enthalpy gaseous environment, as a consequence of the interaction with ultrafast-heated (10⁶ K/s) gas for ~5 ms. Spectroscopic and structural characterization reveals that addition of Ti improves thermomechanical shock resistance, which is attributed to the assemblage of refractory phases. Taken together, ZrB₂–SiC–Ti based multiphase ceramics exhibit favorable shock-material response under impulse loading.     

Design and magneto-optical characteristics of Ge–Sb–S–PbI2 chalcogenide glasses with a high Verdet constant

To develop high-performance magneto-optical chalcogenide glasses and clarify the mechanisms of the Verdet constant, a series of GeS₂–Sb₂S₃–PbI₂ chalcogenide glasses were designed and fabricated, and their Faraday effects were investigated at a wavelength of 980 nm. A new parameter, that is, average polarizability, was proposed, and the results show that the Verdet constant has a good linear relationship with average polarizability, meaning that the Verdet constant of a chalcogenide glass can be directly estimated by its chemical constituents. The Verdet constant is as large as 0.200 min G⁻¹ cm⁻¹ at 980 nm for 22.5GeS₂–67.5Sb₂S₃–10PbI₂ composition glass, which is the largest value reported thus far for sulfide glasses; this glass also possesses good thermal and optical properties and therefore might be an attractive candidate for mid-infrared magneto-optical device applications.     

Core–shell NTC materials with low thermal constant and high resistivity for wide-temperature thermistor ceramics

Core–shell structures have been proposed to improve the electrical properties of negative-temperature coefficient (NTC) thermistor ceramics. In this work, Al₂O₃-modified Co_1.5Mn_1.2Ni_0.3O₄ NTC thermistor ceramics with adjustable electrical properties were prepared through citrate-chelation followed by conventional sintering. Co_1.5Mn_1.2Ni_0.3O₄ powder was coated with a thin Al₂O₃ shell layer to form a core–shell structure. Resistivity (ρ) increased rapidly with increasing thickness of the Al₂O₃ layer, and the thermal constant (B) varied moderately between 3706 and 3846 K. In particular, Co_1.5Mn_1.2Ni_0.3O₄@Al₂O₃ ceramic with 0.08 wt% Al₂O₃ showed the increase of ρ double, and the change in its B was less than 140 K. The Co_1.5Mn_1.2Ni_0.3O₄@Al₂O₃ NTC ceramics showed high stability, and their grain size was relatively uniform due to the protection offered by the shell. The aging coefficient of the ceramic was less than 0.2% after aging for 500 hours at 125°C. Taken together, the results indicate that as-prepared Co_1.5Mn_1.2Ni_0.3O₄@Al₂O₃ NTC ceramics with a core–shell structure may be promising candidates for application as wide-temperature NTC thermistor ceramics.     

Excellent thermal stability,high efficiency and high power density of (Sr0.7Ba0.3)5LaNb7Ti3O30–based tungsten bronze ceramics

A series of (1-x)(Sr_0.7Ba_0.3)₅LaNb₇Ti₃O₃₀–x(Bi_0.5Na_0.5)TiO₃ (x = 0.1–0.4) ceramics with tungsten bronze structure were prepared by solid state reaction. Phase composition, microstructure and energy storage properties were studied. When x = 0.3, excellent thermal stability satisfying the X7R specification was obtained and its energy storage as well as charge-discharge performances were further evaluated. Release energy density (W_re) of 0.77 J/cm³ and an energy storage efficiency of 97.3 % were detected at a low electric field of 20 kV/mm. Under the electric field of 10 kV/mm, the change of W_re in the temperature range of −55 °C to 125 °C is less than 15 % compared to room temperature. Short discharge period (∼0.17 μs), high power density (61.2 MW/cm³) and high discharge energy density (2.45 J/cm³) were evaluated by charge-discharge tests. Excellent thermal stability, high energy storage efficiency and high power density indicate that 0.7(Sr_0.7Ba_0.3)₅LaNb₇Ti₃O₃₀–0.3(Bi_0.5Na_0.5)TiO₃ ceramic is a promising pulse capacitor for working over a wide temperature range.     

Dielectric behavior and impedance spectroscopy in lead-free BNT–BT–NBN perovskite ceramics for energy storage

The dielectric behavior, impedance spectroscopy and energy-storage properties of 0.85[(1−x)Bi_0.5Na_0.5TiO₃–xBaTiO₃]–0.15Na_0.73Bi_0.09NbO₃ [(BNT–xBT)–NBN] ternary ceramics were investigated. Temperature dependent permittivity curves displayed two depressed anomalies, resulting in significantly improved dielectric temperature stability. (BNT–9BT)–NBN showed a permittivity of 1680 at 150 °C with Δε/ε_150 °C varying no more than ±10% up to 340 °C. From the complex impedance analysis, grain and grain boundary shared the same time constant. The high temperature resistivity followed the Arrhenius law with E_a=1.7–2.0 eV, suggesting intrinsic band-type electronic conduction. The maximum energy-storage density of all the samples reached 1.1–1.4 J/cm³, accompanied with good temperature stability in the range of 25–140 °C. These results indicate that (BNT–xBT)–NBN system should be a promising lead-free material for energy-storage capacitor applications.     

An experimental model for predicting the piezo and dielectric constant of PVDF-PZT nanocomposite fibers with 0–3 and 1–3 connectivity

Energy harvesting from mechanical energy around ambient by flexible nanogenerators is one of the most efficient ways to generate green and renewable energy. Lead zirconate titanate (PZT) particles were embedded into a polyvinylidene fluoride (PVDF) polymer matrix to prepare mixed 0–3 and 1–3 connectivity nanocomposite fibers by electrospinning method. Various theoretical models of Maxwell-Garnett, Rayleigh, and Tinga etc were presented at two different Classes to predict the dielectric constant of PVDF-PZT nanocomposite fibers and compared the predicted results with the experimental results. Also, the piezoelectric properties like the piezoelectric coefficient (d₃₃) and piezoelectric voltage coefficient (g₃₃) were predicted by the Furukawa model and the predicted values were compared with the experimental values. Finally, the experimental model was derived to predict the dielectric constant of binary composites with mixed 0–3 and 1–3 connectivity. Compared to well-known models, the proposed experimental model accurately predicted the dielectric constant of PVDF-PZT nanocomposite fibers. The highest and lowest difference between the theoretical and the experimental results were obtained 12.24% and 0.12% for PZT volume fractions 1.1 and 17, respectively. Also, due to the linear relationship between the dielectric constant and piezoelectric coefficients, this model was generalized to predict the piezoelectric coefficients.     

The magnetization reversal and high temperature dielectric response in Y1−xHoxFe0.5Cr0.5O3

The structural, magnetic, and dielectric properties of the Y_1−xHo_xFe_0.5Cr_0.5O₃ (x=0, 0.05, 0.1, 0.3, and 0.5) compounds have been investigated. Rietveld refinement of the XRD patterns shows that the compounds possess orthorhombic perovskite structure. The dual magnetization reversal is observed in the samples with x=0.05 and 0.1, and it vanishes when x≥0.3. Ferromagnetic-like behavior with large coercive fields is observed in all Ho³⁺ doped YFe_0.5Cr_0.5O₃ samples, indicating a doping induced metamagnetic behavior. This abnormal magnetization behavior can be explained by the antiparallel magnetic coupling between the Ho³⁺ and the canted Cr³⁺/Fe³⁺ moments, as well as the Ho–O–Ho magnetic interaction. The dielectric behavior in the frequency range from 100 Hz to 10 MHz is investigated. The low doped samples (x=0, 0.05, and 0.1) exhibit relaxation-like dielectric behavior and colossal dielectric constant in a wide temperature and frequency range. The dual magnetization reversal under low magnetic field makes these materials attractive candidates for the magnetic dual sensor devices.