Microstructure,dielectric and ferroelectric properties of barium zirconate titanate ceramics prepared by microwave sintering

Barium zirconate titanate ceramics were fabricated by microwave sintering. Effects of microwave sintering time on microstructure, dielectric and ferroelectric properties of barium zirconate titanate ceramics have been investigated. The result shows that the ceramic samples sintered at 2.5 kW for 15–30 min are single phase perovskite structure and there is no secondary phase observed. As the microwave sintering time extends, barium zirconate titanate ceramics become more uniform and the grain size increases. The data of dielectric properties indicate that the samples prepared by microwave sintering for 15–30 min are the ferroelectrics with diffuse phase transition and the diffuseness of phase transition weakens with the extending of microwave sintering time. As microwave sintering time increases, the remnant polarization increases initially and then decreases. Moreover, the remnant polarization and the coercive field of the samples sintered for 15 and 20 min decrease as measuring frequency increases, but the measuring frequency has little effect on ferroelectricity of the sample sintered for 30 min. The temperature dependences of hysteresis loops further prove that the samples are ferroelectrics with diffuse phase transition.     

Preparation and properties of barium titanate glass-ceramics sintered from sol–gel-derived powders

Homogeneous Ba–Ti–B–Si, Ba–Ti–Al–Si and Ba–Ti–B gels have been successfully prepared by the sol–gel process. A novel method is presented for fabricating barium titanate glass-ceramics by sintering the gel powders with small barium titanate crystallites. The structural development, grain size, crystallization process and dielectric properties were systematically studied by differential thermal analysis, thermogravimetric analysis, X-ray diffraction techniques, scanning electron microscopy and dielectric measurements. The glass-ceramic samples were sintered at lower temperatures compared to the barium titanate ceramic sintering, and showed improved dielectric properties. It was found that the small size effect of the barium titanate grains on the dielectric constant in the glass-ceramics was quite evident. Ferroelectric hysteresis loop analyses were also performed to manifest the ferroelectric nature of the barium titanate grains in situ grown from the gels. This revised version was published online in November 2006 with corrections to the Cover Date.     

Effect of sintering temperature on the grain growth and electrical properties of barium zirconate titanate ferroelectric ceramics

In the present work, structural, dielectric and ferroelectric properties of barium zirconate titanate ferroelectric ceramics have been investigated. The specimens were synthesized using a solid state reaction technique. The XRD analysis reveals that the synthesized compound was formed with no secondary phases. As the sintering temperature increases from 1,200 to 1,300 °C, the average grain size is observed to increase from ~0.39 to ~6.15 μm. The dielectric measurements as a function of temperature show a decrease in Curie temperature (T_C) on increasing the sintering temperature. The decrease in Curie temperature is attributed to the substitution of Zr⁺⁴ whose ionic radius is larger than Ti⁺⁴. A large increase in the dielectric constant with the increase in grain size is observed. The remanent polarization is also observed to increase with the increase in grain size.     

Effect of crystallizable glass addition on sintering and dielectric behaviors of barium titanate ceramics

A crystallizable glass which can precipitate barium titanate was added to BaTiO₃ ceramics to study its effect on sintering behavior and dielectric properties of the composites. High densification (>95 % theoretical density) was achieved by addition of glass phase and the dielectric constant of composites was enhanced through the crystallization of glass phase. A composite with 90 wt% BaTiO₃ and 10 wt% glass showed a dielectric constant of ~2,300 at room temperature at 1 kHz and a dielectric breakdown strength about 140 kV/cm.     

Synthesis and sintering of barium titanate fine powders by ultrasonic spray pyrolysis

Crystalline, spherical barium titanate fine powders with a narrow particle size distribution were prepared by ultrasonic spray pyrolysis. The stability of the starting solution was influenced by type of barium source and peptizer. The particle structure was influenced by the pyrolysis temperature of the barium source. The particle structure derived from barium acetate was dense, while powders derived from barium nitrate involved a lot of hollow particles. As-prepared powders were crystallized to a perovskite structure. Inductively coupled plasma analysis showed that the BaO/TiO₂ molar ratio of as-prepared powders was 50.5:49.5. The effects of the concentration of the starting fluid, pyrolysis temperature and flow rate of carrier air through the furnace on powder characteristics such as particle size, size distribution and crystal phase were investigated. The particle size depended on the concentration of starting solution and the flow rate of carrier air, but the particle size distribution was independent of these variables. Single-phase BaTiO₃ was obtained at more than 700°C. The relative density of barium titanate sintered at 1200°C was 98%. The hollow particles in the powders resulted in a low sintering density and a large grain size. The dielectric constant and tan δ of barium titanate at 25°C were 4500 and 0.02, respectively.     

Dielectric properties of CaCu3Ti4O12 ceramics: effect of high purity nanometric powders

The dielectric properties of CaCu₃Ti₄O₁₂ ceramics fabricated with nano-size fine powders (~30 nm) are compared with that fabricated with micro-size coarse powders (0.1–0.3 μm). For the same sintering conditions, the ceramic samples with nano-size fine powders have more uniform and denser microstructures and higher room temperature dielectric constant (~10⁵, in the frequency range of 10^?1–10⁵ Hz) than that with micro-size coarse powders. That the use of nano powders facilitates the formation of Cu-rich amorphous phase in the grain boundary led to an increasing dielectric loss in low frequency range. Besides the common intrinsic defect structure of V _O ⁺ and V _O ⁺⁺ , the energy level of ~0.72 eV detected in high temperature range is attributed to the conduction relaxations, and the energy level of 0.30–0.40 eV which is only detected in the sample synthesized by common submicron powders is suggested to originate from the defect level of grain boundary related to Cu ions. This research provides a technical guidance for the application of this material.     

Structure,dielectric property and impedance spectroscopy of La<Subscript>2/3</Subscript>Cu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> ceramics by sol–gel method

La_2/3Cu₃Ti₄O₁₂ (LCTO) precursor powders were synthesized by the sol–gel method. Effect of sol conditions and sintering process on microstructure and dielectric properties of LCTO powders or ceramics were investigated systematically. The optimum sol conditions for the synthesis of precursor powders were as follows: the Ti⁴⁺ concentration of 1.00 mol/L, the molar ratio of water and titanium of 5.6:1 and the sol pH of 1.0, respectively. After sintered at 1105 °C for 15 h, the LCTO ceramics exhibited more homogeneous microstructure, much higher dielectric constant (ca 09–1.6 × 10⁴) and lower dielectric loss (ca 0.057). The higher dielectric constant of the LCTO ceramics might be due to the internal barrier layer capacitor effect. The LCTO ceramics showed two kinds of conductivity activation energy for grain boundary conductivity from complex impedance analysis. The transition temperature of two activation energy values occured between 170 and 210 °C. The temperature range of 170–210 °C was critical pseudocritical region of the dielectric constant, dielectric loss and activation energy. Furthermore, it was concluded that the grain boundary play an important role for electrical properties.     

Characterization,sintering and dielectric properties of nanocrystalline barium titanate synthesized through a modified combustion process

Nanocrystalline barium titanate has been synthesized through a modified combustion process in a single step for the first time. The as-prepared barium titanate powder is cubic perovskite with lattice constant a = 4.018 Å. The phase purity of the nanopowder was examined using thermo gravimetric analysis, differential thermal analysis and Fourier transform infrared spectroscopy. Transmission electron microscopic investigations have shown that the particle size of the as-prepared powder is in the range 20–40 nm. The agglomerate size distribution of the as-prepared powder was studied using atomic force microscopy. The nanoparticles of barium titanate were sintered to 97% of the theoretical density at a temperature of 1350 °C for 3 h. The microstructure of the sintered surface was examined using scanning electron microscopy. The dielectric constant and loss factor of the sintered pellets at 1 MHz measured at room temperature were 1223 and 3.5 × 10^? 3 respectively.     

Electrical hetero-structure of Nd0.1Sr0.9TiO3 ceramic for energy storage applications

Both high dielectric constant and high bulk resistance was required to meet high energy storage density in high-voltage ceramic capacitors. In this paper, Nd_0.1Sr_0.9TiO₃ (NSTO) ceramic with pure tetragonal perovskite structure was prepared by solid state reaction route. Dielectric response of NSTO ceramic was investigated in the temperature range of ?60 to 550 °C over the frequency 20 Hz–1 MHz. Complex impedance spectroscopy (IS) analysis was employed to study the electrical conductive behavior of NSTO ceramic. IS results revealed that the NSTO ceramic showing electrical hetero-structure, which includes semiconducting grains, inter-grains and insulating grain boundaries. The space charge polarization at heterointerfaces by conductive charge carries was contributed to high dielectric constant, while insulating grain boundaries to high bulk resistance for NSTO ceramic. The mechanism of such electrical hetero-structure formation associated with charge compensation induced by trivalent Nd ions substitution for divalent Sr, as well as the first and second ionization of oxygen vacancies was discussed tentatively.     

Effect of pH Variation on Structural and Dielectric Properties of Co-precipitated Nanostructured Multiferroic BiFeO3

Phase pure multiferroic BiFeO₃ (BFO) was prepared by the co-precipitation technique using diverse precursors at a temperature as low as 400 °C. The dependence of structural and dielectric properties was investigated with the variation of pH (8–13, with steps of 1). Uniaxially pressed powders were sintered in air at 500 °C for 2 h. X-ray diffraction analysis determined the amorphous nature of the as-synthesized samples and the perovskite nature of the sintered samples. The crystal structure obtained from the lattice parameters of the BFO specimens was R3c hexagonal. The fractional porosity of the pellets was determined from the measured and theoretical density of the samples. The crystallite size varies from 48–62 nm with the variation of the pH value. SEM micrographs exhibited a grain morphology and a wide size distribution. The dielectric constant, loss tangent, and ac conductivity of the pellets were measured as a function of frequency (20 Hz–3 MHz). A high dielectric constant and dissipation factor for the sample prepared with pH=10 was observed in the low frequency range.     

Structure and dielectric properties of Nd x Sr1−x TiO3 ceramics for energy storage application

Polycrystalline Nd-doped SrTiO₃ ceramics with the formula Nd _x Sr_1?x TiO₃ (NSTO, x = 0, 0.024, 0.056, 0.104, 0.152, 0.200) were prepared by solid state reaction route. X-ray diffraction (XRD) analysis confirmed the formation of monophasic compounds and indicated the structure to be changed from cubic to tetragonal by increasing Nd doping concentrations. A remarkable decrease in grain size from ~30 μm for un-doped SrTiO₃ ceramics to ~1 μm for Nd-doped SrTiO₃ ceramics with x = 0.024 was observed by scanning electron microscopy. The grain size had a degree of increasing with further increasing Nd doping concentration and reached ~3 μm when the x value was 0.200. The dielectric properties of NSTO ceramics were measured at 1 kHz in ambient temperature. It revealed that the dielectric constant dramatically increases for the reason of Nd doping, leading to a maximum value of 19,800 for as-sintered sample with x = 0.104. The breakdown strength of all Nd-doped SrTiO₃ samples was found to be higher than 10 kV/mm. The relationship between dielectric properties and the microstructure feature, as well as the defect structures correlated with the charge compensation induced by trivalent Nd³⁺ doping, was discussed tentatively.     

还原气氛烧成Y5V型瓷粉的结构与介电性能

运用SEM、TEM、XRD等手段研究了掺杂组分对钛酸钡基Y5V陶瓷的结构和性能影响.结果表明:由于掺杂组分的存在,烧结情况得到了明显的改进.掺杂钛酸钡陶瓷的烧结包括固-固烧结和液-固烧结.Zr和稀土元素能够扩散进入钛酸钡晶格并促进固-固烧结,SiO2主要聚集在晶界并促进液-固烧结烧结.Nd5 聚集在晶界并促进针状颗粒生成,XRD的结果表明样品中有新相形成.由于掺杂的引入,材料的居里温度向低温方向移动,材料的介温曲线较纯钛酸钡材料的介温曲线更趋平坦.研究的结果还表明,由于在还原气氛中烧结,材料的介电损耗上升.     

Electrical characterization of BaTiO3 made by hydrothermal methods

The manufacture of multilayer capacitors based on barium titanate requires improved precursor powders. In this paper the dielectric properties of barium titanate ceramics made from hydrothermally precipitated material are compared with those powders obtained commercially and prepared by calcination. The greater porosity of hydrothermal powders tends to reduce their effective dielectric constant but preheating them to 950 C before sintering produced high density ceramic with higher values of _r. The dielectric losses of these materials are higher than those produced by traditional methods. Their low Curie temperatures (106–8 C) are related to the high strontium concentration (4.7 mol%) present in the starting materials. The grain sizes of these ceramics are less sensitive to sintering temperature than those made using calcined powders, with no anomalous grain growth.     

Density variation and piezoelectric properties of Ba(Ti1 − x Sn x )O3 ceramics prepared from nanocrystalline powders

Nanocrystalline powders of tin-doped barium titanate with different concentrations of tin have been synthesized by a combination of solid state reaction and high-energy ball milling. The average particle size of the milled powders as determined from TEM analysis was about 5·96 nm. Analysis of all the milled powders using X-ray diffraction method showed single phase perovskite structure. The density variation of the ceramics with sintering temperature has been studied by sintering the samples at different temperatures. Density variation results show that 1350°C is the optimum sintering temperature for tin-doped barium titanate ceramics. SEM micrographs show high density and increasing trend of grain size with increasing content of Sn. The ferroelectricity decreases with increasing concentration of Sn. The electromechanical coupling coefficient also decreases with increasing Sn content corroborating decreasing trend of ferroelectricity. The bipolar strain curves show piezoelectric properties of the prepared ceramics.     

Structural and dielectric properties of nanocrystalline Nd<Superscript>3+</Superscript> substituted nickel–zinc ferrites

Ferrite samples with general formula Ni_1−xZn_xNd_yFe_2−yO₄ (x = 0, 0.2, 0.4, 0.6, 0.8 and 1; y = 0.01, 0.02 and 0.03) were synthesized by oxalate co-precipitation technique. The X-ray diffraction study confirms the formation of single-phase cubic spinel structure. The lattice constant of the samples increases with increase in zinc content and obeys Vegard’s law. On Nd³⁺ substitution lattice constant of the samples slightly increases except zinc ferrite. The frequency dependence of the dielectric constant, dielectric loss and AC conductivity of the samples were determined in the frequency range from 20 Hz to 1 MHz at room temperature. The experimental results reveal that the dielectric constant and dielectric loss decreases where as AC electrical conductivity increases with increase in frequency. The dielectric loss increases with increase in zinc content whereas it decreases with increase in Nd³⁺ content. There is no appreciable change in permittivity of the samples with increase in Nd³⁺ content. Permeability of all the samples increases with increase in Nd³⁺ content. Because of lower dielectric loss, Nd³⁺ substituted Ni–Zn ferrites are useful in electronic devices.     

The hydroxyl concentration and the dielectric properties of barium titanate nano-powder synthesized by water-based ambient condition sol process

Nanocrystalline barium titanate, BaTiO₃, powders have been successfully synthesized via water-based ambient condition sol (WACS) process, using barium hydroxide and titanium isopropoxide. The properties of the powder were investigated as a function of various processing parameters such as the concentration of Ba²⁺ ions ([Ba²⁺]), the concentration of base, and reaction time. The concentration of hydroxyl (OH⁻) groups in the BaTiO₃ powder was greatly affected by changing the values of each processing parameter. The dielectric constant and tetragonality of the powders which contain lattice OH⁻ more than 0.35 wt% were little affected with further increase in the lattice OH⁻ concentration. The dielectric loss was highly varied with the concentration of the OH⁻ groups, and it was increased with increasing OH⁻ concentration. Calcination treatment significantly improved the dielectric properties of the powder. With higher calcination temperature, the dielectric constant increased and the dielectric loss decreased.     

Structural characteristics and dielectric properties of neodymium doped barium titanate

Neodymium (Nd) doped barium titanate powder (Ba_(1−x)Nd _x TiO₃) with x value varying from 0, 0.01, 0.03, 0.05, 0.07, 0.10 and 0.13 was prepared using the sol gel method. The powder samples were calcined at 700 °C and tetragonal phase appeared in the powders before they were sintered at 1250 °C for 3 h. The undoped samples have a polycrystalline tetragonal structure, but Nd doping into the BaTiO₃ caused phase transformation from tetragonal to cubic. The smaller grains (0.35 μm) produced with the addition of Nd is associated to the inhibition of grain growth of samples. The powders for each composition were pressed into pellets and tested as dielectric resonator antenna (DRA). It was found that on the actual antenna circuit, each sample showed a resonance frequency at X-band application and a dielectric constant value in the range of 51.25–56.89 and tangent loss was 0.039–0.045, depending on the concentration of the Nd at room temperature.     

Dielectric,ferroelectric and optical behaviour of terbium hydrogen tartrate trihydrate crystals

Gel diffusion technique, using agar–agar as gel medium, has been employed to obtain single crystals of terbium hydrogen tartrate trihydrate. The grown crystals are characterised by X-ray diffraction, scanning electron microscopy, CHN technique, thermogravimetric methods and UV–Vis spectroscopy. Dielectric, ferroelectric and optical studies on this metal–organic compound have been carried out. The dielectric constant has been measured as a function of temperature and frequency in the ranges of 20–250 °C and 20 Hz–3 MHz, respectively. The study of dielectric behaviour as a function of temperature reveals two dielectric anomalies at 95 and 198 °C. The dielectric anomaly at 95 °C is suggested to be due to ferroelectric phase transition brought about in the material. The study of polarisation versus electric field shows a hysteresis loop which thereby confirms the ferroelectric nature of terbium hydrogen tartrate trihydrate crystals. The dielectric anomaly at 198 °C is suggested to be due to loss of water molecules in the compound. The results of thermal study show that the material is thermally stable up to temperature of about 200 °C. Optical studies show that the terbium hydrogen tartrate trihydrate crystal has good transparency in the entire visible and infra red range of the spectrum.     

Ferroelectric and piezoelectric properties of (1 − x) (Bi0.5Na0.5)TiO3–xBaTiO3 ceramics

Lead-free ceramics based on bismuth sodium titanate (Bi_0.5Na_0.5TiO₃, BNT)–barium titanate (BaTiO₃,BT) have been prepared by solid state reaction process. The (1?x)BNT–(x)BT (x = 0.01,0.03,0.05,0.07) ceramics were sintered at 1,150 °C for 4 h in air, show a pure perovskite structure. X-ray diffraction analysis indicates that a solid solution is formed in (1?x)BNT–(x)BT ceramics with presence of a morphotropic phase boundary (MPB) between rhombohedral and tetragonal at x = 0.07. Raman spectroscopy shows the splitting of (TO₃) mode at x = 0.07 confirming the presence of MPB region. The temperature dependence dielectric study shows a diffuse phase transition with gradual decrease in phase transition temperature (T_m). The dielectric constant and diffusivity increases with increase in BT content and is maximum at the MPB region. With the increase in BT content the maximum breakdown field increases, accordingly the coercive field (E_c) and remnant polarization (P_r) increases. The piezoelectric constant of (1 ? x)BNT–(x)BT ceramics increases with increase in BT content and maximum at x = 0.07, which is the MPB region. The BNT–BT system is expected to be a new and promising candidate for lead-free dielectric and piezoelectric material.     

Preparation and characterization of PI/PVDF composite films with excellent dielectric property

All-organic polyimide (PI)/poly(vinylidene fluoride) (PVDF) composite materials with high dielectric constant and low dielectric loss were fabricated via solution blending. The dielectric, mechanical, and thermal properties of the PI/PVDF composite films were studied. Results indicated that the dielectric properties of the composites were highly reinforced through the introduction of PVDF, and the composites exhibited excellent thermal stability. When the mass fraction of PVDF was adjusted to 30 wt%, the specimen demonstrated excellent thermal properties, superior mechanical properties, high dielectric constant (5.7, 1 kHz), and low dielectric loss (0.009, 1 kHz). Moreover, the dependence of the dielectric constant and dielectric loss on frequency was investigated. The composite presented stable dielectric constant and dielectric loss that were less than 0.04 within the testing frequency range of 100 Hz–10 MHz. This study demonstrated that the PI/PVDF composites were potential dielectric materials in the field of electronics.