Preparation and dielectric properties of BaCu(B2O5)-doped SrTiO3-based ceramics for energy storage

BaCu(B₂O₅) (BCB) was used as sintering aids to lower the sintering temperature of multi-ions doped SrTiO₃ ceramics effectively from 1300 °C to 1075 °C by conventional solid state method. The effect of BCB content on crystalline structures, microstructures and properties of the ceramics was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and dielectric measurements, respectively. The addition of BCB enhanced the breakdown strength (BDS) while did not sacrifice the dielectric constant. The enhancement of BDS should be due to the modification of microstructures, i.e., smaller and more homogeneous grain sizes after BCB addition. The dielectric constant of BCB-doped ceramics maintained a stable value with 1.0 mol% BCB, which was dominated by the combination of two opposite effects caused by the presence of second phases and the incorporation of Cu²⁺ and Ba²⁺, while further increase was owing to the increase of dissolved Ba²⁺ ions when the content of BCB is more than 2.0 mol%. The multi-ions doped SrTiO₃ ceramics with 1.0 mol% BCB addition showed optimal dielectric properties as follows: dielectric constant of 311.37, average breakdown strength of 28.78 kV/mm, discharged energy density of 1.05 J/cm³ and energy efficiency of 98.83%.     

Effects of Fe2O3 doping on the microstructure and piezoelectric properties of 0.55Pb(Ni1/3Nb2/3)O3-0.45Pb(Zr0.3Ti0.7)O3 ceramics

0.55Pb(Ni_1/3Nb_2/3)O₃-0.45Pb(Zr_0.3Ti_0.7)O₃(PNN-PZT) ceramics with different concentration of xFe₂O₃ doping (where x = 0.0, 0.8, 1.2, 1.6 mol%) were synthesized by the conventional solid state sintering technique. X-ray diffraction analysis reveals that all specimens are a pure perovskite phase without pyrochlore phase. The density and grain size of Fe-doped ceramics tend to increase slightly with increasing concentration of Fe₂O₃. Comparing with the undoped ceramics, the piezoelectric, ferroelectric and dielectric properties of the Fe-doped PNN-PZT specimens are significantly improved. Properties of the piezoelectric constant as high as d₃₃ ~ 956 pC/N, the electromechanical coupling factor k_p ~ 0.74, and the dielectric constant ε_r ~ 6095 are achieved for the specimen with 1.2 mol% Fe₂O₃ doping sintered at 1200 °C for 2 h.     

Effect of Bi2O3 and Y2O3 doping methods on electrical properties and PTCR behavior of Ba0.95Ca0.05TiO3 ceramics

Lead-free PTCR ceramics based on Bi₂O₃ and Y₂O₃ doped Ba_0.95Ca_0.05TiO₃ were fabricated by the conventional mixed oxide method, while Bi₂O₃ and Y₂O₃ were doped directly or after pre-calcining, in the molar ratio of Bi₂O₃:Y₂O₃ = 1:1. There were two synthesizing route, i.e. the materials were pre-calcined at 900 °C to obtain BiYO₃ firstly and then doped into the basic materials, and the materials were directly doped into the starting materials, both of which could obtain samples with different electrical properties and PTCR behavior. The samples were characterized by using X-ray diffraction, scanning electron microscope, dielectric constant-temperature and resistivity-temperature measurement instrument. It was revealed that the perovskite lattice, the microstructure and the PTCR behavior of Ba_0.95Ca_0.05TiO₃ varied with different doping contents and methods. A further research was conducted so as to study the electrical properties of ceramics by impedance spectroscopy.     

Effects of Y2O3 addition on microwave dielectric characteristics of Al2O3 ceramics

Microwave dielectric characteristics of alumina ceramics with yttria addition were investigated. The sintering temperature was lowered, and the dielectric constant (ε_r) did not remarkably change by adding yttria. The microwave dielectric loss (tan δ) increased from 8.4 × 10^− 5 to 2.2 × 10^− 4, due to the presence of Al₅Y₃O₁₂ secondary phase. The grain size had significant effects on the dielectric loss, and there was an optimum grain size where the dielectric loss reached the minimum.     

The study on electrical behavior of Gd2O3-WO3 complex ceramics at high temperature

Gd₂O₃-WO₃ complex ceramics are fabricated by the conventional solid-state reaction process. The electrical characteristics and dielectric properties of the samples were measured at various ambient temperatures in a low electric field (E < 150 V/mm). As the temperature increases, the dielectric constant and the loss tangent show an obvious change at about 50 °C and 330 °C. When the temperature is above 200 °C, the samples display stable nonlinear electrical properties characterized by semiconductivity, and the nonlinearity increases along with increasing temperature. XRD analysis reveals that Gd₂W₂O₉ is the main phase and Gd₂O₃ is the secondary phase. Based on the phase transition of tungsten trioxide, these electrical properties of Gd₂O₃-WO₃ complex ceramics can be simply explained.     

Dielectric and non-Ohmic properties of CaCu3Ti4O12 ceramics modified with NiO, SnO2, SiO2, and Al2O3 additives

In order to conciliate dielectric and non-Ohmic properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics, NiO, SnO₂, SiO₂, and Al₂O₃ were added as sintering aids to promote the grain growth of CCTO ceramics. Microstructure, dielectric properties, and non-Ohmic behavior of the CCTO ceramics were investigated. Among them, NiO-modified CCTO exhibits good dielectric and non-Ohmic properties (ε = 69833, tanδ = 0.073, α = 3.66 and E _B = 296.7 V/cm), due to NiO is also one of giant dielectric materials. Therefore, it is suitable for applying semiconductor circuits. The relationship between electrical current density (J) and electrical field (E) demonstrated that Schottky barrier should exist at grain boundaries. Non-linear coefficient α was directly proportional to the height of barrier. Depressing barrier width would improve significantly dielectric permittivity but decrease breakdown voltage.     

Effects of Bi2O3 and Cr2Ti3O9 Co-doping on dielectric properties in BaTiO3-based ceramics

A microwave ceramic with general composition (1-x-y) BaTiO₃ + x Cr₂Ti₃O₉ + y Bi₂O₃ has been prepared by solid state synthesis at 1300-1400 °C. The phase composition, perovskite structural parameters and dielectric properties have been obtained by X-ray diffraction and dielectric measurements as a function of chemical composition and temperature. At low doping levels the formation of BaTiO₃-based solid solution has been found. The precipitation of BaCrO₃ has been detected at x = y = 2.0 mol%. A model of the incorporation of Cr³⁺ and Bi³⁺ ions into BaTiO₃-based crystal lattice has been proposed. Diffused phase transition in the temperature range 100-140 °C have been revealed by dielectric measurements for different ceramic composition. As high dielectric constant as 7311 and as low dielectric loss as 0.02 have been found for the composition of 0.98BaTiO₃-0.01Cr₂Ti₃O₉-0.01Bi₂O₃.     

Preparation of Y2O3:Ce phosphors by homogeneous precipitation inside bicontinuous cubic phase

Yttrium oxide doped with cerium (Y₂O₃:Ce³⁺) blue emitting phosphors was prepared by a new method called the bicontinuous cubic phase (BCP) method. The experimental results showed that the prepared precursors were amorphous yttrium hydroxide with a spherical shape and primary size 30-50 nm. After heat treatment, high crystallinity and luminescence efficiency phosphors were obtained. The obtained Y₂O₃:Ce³⁺ phosphors had a strong blue emitting at 400 nm. The optimum Ce³⁺ concentration was 1 mol% to obtain the highest PL intensity. This study indicated that the calcining temperature of 700 °C needed for high luminescence efficiency in this work is much lower than 1000 °C or above needed for the conventional solid-state method.     

Piezoelectric, ferroelectric and dielectric properties of La2O3-doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

La₂O₃ (0–0.8 wt.%)-doped (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (abbreviated as BNBT6) lead-free piezoelectric ceramics were synthesized by conventional solid-state reaction. The influences of La₂O₃ on the microstructure, the dielectric, ferroelectric and piezoelectric properties of the composites were investigated. X-ray diffraction (XRD) patterns indicate that 0.2-0.8 wt.% of La₂O₃ has diffused into the lattice of BNBT6 ceramics. Consequently, a pure perovskite phase is formed. SEM images show that the microstructure of the ceramics is changed with the addition of a small amount of La₂O₃. The temperature dependence of the relative dielectric constant shows that Curie point decreases with the increase of La₂O₃. At room temperature, the ceramics doped with 0.6 wt.% La₂O₃ show superior performance with high piezoelectric constant (d₃₃ = 167 pC/N), high planar electromechanical coupling factor (k_p = 0.30), high mechanical quality factor (Q_m = 118), high relative dielectric constant (ε_r = 1470) and lower dissipation factor (tanδ = 0.056) at a frequency of 10 kHz.     

Microstructure and electrical properties of Sm2O3 doped Bi2O3-based ZnO varistor ceramics

The dependence of the bulk density, microstructure and dc electrical properties of bismuth oxide (Bi₂O₃)-based zinc oxide (ZnO) varistor ceramics for various samarium oxide (Sm₂O₃) contents was investigated. The value of bulk density was found to 5.43-5.50 g cm⁻³ with Sm₂O₃ (mol%) content. The maximum value of bulk density is observed to be 5.50 for 0.30 mol% Sm₂O₃ containing varistor ceramics. The grain sizes for all the samples calculated from the scanning electron micrographs were found to decrease as Sm₂O₃ increases. The presence of ZnO phases, Bi-rich phases, spinel phases and Sm₂O₃ phases were observed in the samples by the energy dispersive X-ray analysis and X-ray diffraction analysis. As the Sm₂O₃ amount increased in the Bi₂O₃-based ZnO varistor ceramics, the nonlinear coefficient, α increased up to 0.10 mol%, reaching a maximum value of 58 and then decreased. The breakdown electric field, E_b, increased with the increase of Sm₂O₃ content with a maximum value of 3220 V cm⁻¹ for the 0.75 mol% Sm₂O₃ doped ZnO varistor ceramics. The leakage current, I_L, showed a minimum value of 1.10 μA for the composition of 0.30 mol% Sm₂O₃ doped Bi₂O₃-based ZnO varistor ceramics. The 0.30 mol% Sm₂O₃-doped Bi₂O₃-based ZnO varistor ceramics sintered at 1200 °C exhibited a good stability for dc accelerated aging stress of 0.90 V_1 mA/90 °C/12 h.     

Dielectric and piezoelectric properties of Y2O3 doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free piezoelectric ceramics

Y₂O₃ doped lead-free piezoelectric ceramics (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (0-0.7 wt%) were synthesized by the conventional solid state reaction method, and the effect of Y₂O₃ addition on the structure and electrical properties was investigated. X-ray diffraction shows that Y₂O₃ diffuses into the lattice of (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ to form a solid solution with a pure perovskite structure. The temperature dependence of dielectric constant of Y₂O₃ doped samples under various frequencies indicates obvious relaxor characteristics different from typical relaxor ferroelectric and the mechanism of the relaxor behavior was discussed. The optimum piezoelectric properties of piezoelectric constant d₃₃ = 137 pC/N and the electromechanical coupling factor k_p = 0.30 are obtained at 0.5% and 0.1% Y₂O₃ addition, respectively.     

Synthesis of CaCu3Ti4O12 ceramic via a sol-gel method

The novel nano-ultrafine powders for the preparation of CaCu₃Ti₄O₁₂ ceramic were prepared by the sol-gel method and citrate auto-ignition method. The obtained precursor powders were pressed, sintered at 1000 °C to fabricate microcrystal CaCu₃Ti₄O₁₂ ceramic. The microcrystalline phase of CaCu₃Ti₄O₁₂ was confirmed by X-ray powder diffraction (XRD). The morphology and size of the grains of the powders and ceramics under different heat treatments were observed using scanning electron microscopy (SEM). The relative dielectric constant of the ceramic sintered at 1000 °C was measured with a magnitude of more than 10⁴ at room temperature, which was approaching to those of Pb-containing complex perovskite ceramics, and the loss tangent was less than 0.20 in a broad frequency region. The relative dielectric constant and loss tangent were also compared with that of CaCu₃Ti₄O₁₂ ceramic prepared by other reported methods.     

Influence of Bi2O3 and CuO addition on low-temperature sintering and dielectric properties of Ba0.6Sr0.4TiO3 ceramics

In this study, we tried to lower the sintering temperature of Ba_0.6Sr_0.4TiO₃ (BST) ceramics by several kinds of adding methods of Bi₂O₃, CuO and CuBi₂O₄ additives. The effects of different adding methods on the microstructures and the dielectric properties of BST ceramics have been studied. In the all additive systems, the single addition of CuBi₂O₄ was the most effective way for lowering the sintering temperature of BST. When CuBi₂O₄ of 0.6 mol% was mixed with starting BST powders and sintered at 1100 °C, the derived ceramics demonstrated dense microstructure with a low dielectric constant (? = 4240), low dielectric loss (tan δ = 0.0058), high tunability (Tun = 38.3%) and high Q value (Q = 251). It was noteworthy that the sintering temperature was significantly lowered by 350 °C compared with no-additive system, and the derived ceramics maintained the excellent microwave dielectric properties corresponding to pure BST.     

Improvement in dielectric properties of Al2O3-doped Li0.30Cr0.02Ni0.68O ceramics

Li_0.30Cr_0.02Ni_0.68O giant dielectric ceramics doped with Al₂O₃ were prepared by solid-state reaction via sol-gel process. The sintered samples were characterized using X-ray powder diffraction and scanning electron microscopy, and dielectric properties were also investigated. All doped samples showed the single phase of cubic rock-salt structure NiO. With increasing Al₂O₃ content, the crystallite size and grain size decreased, possibly due to an occurrence of the secondary phases at grain boundaries which inhibit the grain growth. The sample with 0.2 wt.% Al₂O₃ showed nearly 7 times lower tanδ (2.37) and higher ε_r (7.25 × 10⁶) measured at 1 kHz and room temperature when compared to the pure sample.     

Tunable and microwave dielectric properties of Ba0.5Sr0.5TiO3-BaWO4 composite ceramics doped with Co2O3

Co₂O₃ doped BaWO₄-Ba_0.5Sr_0.5TiO₃ composite ceramics, prepared by solid-state route, were characterized systematically, in terms of their phase compositions, microstructure and microwave dielectric properties. Doping of Co₂O₃ promoted grain growth, reduced Curie temperature and broadened phase-transition temperature range of BaWO₄-Ba_0.5Sr_0.5TiO₃, which were attributed mainly to the substitution of Co³⁺ for Ti⁴⁺ at B site in the perovskite lattice. Dielectric diffusion behaviors of the composite ceramics were discussed. The composite ceramics all had dielectric tunability of higher than 10% at 30 kV/cm and 10 kHz, with promising microwave dielectric properties. Specifically, the sample doped with 0.2 wt.% Co₂O₃ exhibited a tunability of 20%, permittivity of 225 and Q of 292 (at 1.986 GHz), making it a suitable candidate for applications in electrically tunable microwave devices.     

Preparation and characterization of Ag-doped BaTiO3 based X7R ceramics

Ag-doped BaTiO₃ based X7R (temperature coefficient of capacitance within the range of ±15% between −55 and +125 °C) ceramics with different amounts of silver (0.0-20.0 mol%) were prepared in this paper. The X-ray diffraction analysis indicated that no phases other than BaTiO₃ and silver were observed in the ceramics. The energy dispersive X-ray spectroscopy analysis showed that the silver particles presented homogeneous distribution in the BaTiO₃ ceramics. The dielectric properties of Ag-doped ceramics were investigated. A small amount of silver (<0.5 mol%) and a large amount of silver (>2.0 mol%) could both improve the sintered density and permittivity, but more content of silver (0.5-2.0 mol%) would decrease the relative density and permittivity. Specially, the temperature coefficient of capacitors of the ceramics doped with 20 mol% silver still met the X7R characteristics, and the room temperature permittivity of the ceramics was 6823, which was the highest dielectric constant in the BaTiO₃ based X7R ceramics.     

Processing, dielectric properties and impedance characteristics of Na0.5Bi0.5Cu3Ti4O12 ceramics

Na_0.5Bi_0.5Cu₃Ti₄O₁₂ (NBCTO) ceramics were prepared by conventional solid-state reaction method. The phase structure, microstructure and dielectric properties of NBCTO ceramics sintered at various temperatures with different soaking time were investigated. Pure NBCTO phase could be obtained with increasing the temperature and prolonging the soaking time. High dielectric permittivity (13,495) and low dielectric loss (0.031) could be obtained when the ceramics were sintered at 1000 °C for 7.5 h. The ceramics sintered at 1000 °C for 7.5 h also showed good temperature stability (−4.00 to −0.69%) over a large temperature range from −50 to 150 °C. Complex impedances results revealed that the grain was semiconducting and the grain boundaries was insulating. The grain resistance (R_g) was 12.10 Ω cm and the grain boundary resistance (R_gb) was 2.009 × 10⁵ Ω cm when the ceramics were sintered at 1000 °C for 7.5 h.     

Dielectric properties of low temperature sintered LiF doped BaFe0.5Nb0.5O3

Sintering of BaFe_0.5Nb_0.5O₃:BFN requires the use of high temperatures to achieve satisfactory densification of this material. The aim of this study is to determine the effect of LiF on the sintering and electrical properties of BFN ceramics (the LiF was added as a sintering agent). The results show that LiF lowers the sintering temperature by 150-200 °C without affecting the formation of BFN. Ceramics doped with 2-3% LiF show optimum densities of about 93-94% of the theoretical value when sintered at low temperatures (1000-1100 °C). Samples containing 2-3% LiF show the following dielectric behaviour. The dielectric constant curves are very broad over a wide temperature range, with room-temperature values of 7154 in the 2% LiF sample and 2527 in the 3% LiF sample. The dielectric constants gradually increase up to 300 °C to values of about 38,862 in the 2% LiF sample and 40,471 in the 3% LiF sample. Furthermore, the addition of 2-3% LiF to BFN causes a reduction in the room-temperature dielectric loss from 4.29 in undoped BFN to less than 1.2 for LiF-containing samples.     

Synthesis of submicron-sized spherical Y2O3 powder for transparent YAG ceramics

Spherical monodispersed, submicron-sized Y₂O₃ powder was prepared via a homogeneous precipitation method using nitrate and urea as raw materials. The structure, phase evolution and morphology of Y₂O₃ precursor and the calcined powder were studied by FTIR, TG/DTA, XRD and SEM methods. The sphere size of the precursor was about 250 nm and that of Y₂O₃ powder calcined at 800 °C for 2 h was about 200-210 nm. With the spherical Y₂O₃ powder and a commercial Al₂O₃ ultrafine powder, high transparent YAG ceramics was fabricated by vacuum sintering at 1780 °C for 6 h through a solid-state reaction method. The in-line transmittances of the as-fabricated YAG ceramics at the wavelength of 1064 nm and 400 nm were 82.8% and 79.5%, respectively, which were much higher than that of the YAG ceramics with a commercial Y₂O₃ powder and a commercial Al₂O₃ ultrafine powder directly. The superior properties are attributed to the good morphology, dispersibility and uniform grain size of the as-prepared spherical Y₂O₃ powder, which matches that of the commercial Al₂O₃ powder.     

Synthesis and photocatalytic activity of cobalt oxide doped ZnFe2O4-Fe2O3-ZnO mixed oxides

Novel cobalt oxide doped ZnFe₂O₄-Fe₂O₃-ZnO mixed oxides with the Zn/Fe molar ratio of 1/2 were synthesized with a citric acid complex method. The effects of cobalt oxide and calcination temperature on phase composition and photocatalytic activity of the mixed oxides were investigated. X-ray diffraction (XRD) analysis revealed that there were mainly ZnFe₂O₄, α-Fe₂O₃, amorphous ZnO and Fe₂O₃ in the 6 mol% cobalt oxide doped products calcined at 500 °C. 5-10 mol% cobalt oxide doping could significantly enhance the formation of ZnFe₂O₄ and altered the phase composition of the mixed oxides. Experimental results showed that cobalt oxide doping could remarkably improve the photocatalytic activity of the mixed oxides for phenol degradation. The 6 mol% cobalt oxide doped mixed oxides calcined at 500 °C exhibited better photocatalytic activity as compared with other samples.