Large-size-mismatch co-dopants for colossal permittivity rutile TiO2 ceramics with temperature stability

Colossal permittivity (CP) in donor-accepter co-doped rutile TiO₂ has attracted significant interest. Here, the CP behavior of (Ta?+?La) co-doped rutile TiO₂ ceramics were studied, where the ionic radii of Ta⁵⁺ and La³⁺ are much larger than that of Ti⁴⁺. The ceramics with an extremely low doping exhibit colossal dielectric permittivity (～2.6?×?10⁴) with an acceptable low dielectric loss (<0.07) in the frequency range from 40 to 10⁶?Hz. The CP properties obtained in (Ta?+?La) co-doped TiO₂ ceramics show excellent temperature stability over a wide temperature range of 20–400?°C. The X-ray diffraction analysis and the density functional theory calculation illustrates that the La₂³⁺${\text{V}}_{\text{o}}^{??}$Ti₂³⁺ and Ta₂⁵⁺Ti³⁺Ti⁴⁺ defect complexes with the lowest energy are responsible for the enhanced dielectric properties. Moreover, the defect complex formed by large-size trivalent substitutions and oxygen vacancy is very stable, and assists in improving temperature stability of the dielectric properties of co-doped rutile TiO₂ ceramics.     

Temperature stable 0.35Ag2MoO4-0.65Ag0.5Bi0.5MoO4 microwave dielectric ceramics with ultra-low sintering temperatures

In this study, the novel temperature-stable (1-x)Ag₂MoO₄-xAg_0.5Bi_0.5MoO₄ microwave dielectric ceramics were prepared by a modified solid-state reaction method. The phase composition, microstructures and microwave dielectric properties of the (1-x)Ag₂MoO₄-xAg_0.5Bi_0.5MoO₄ ceramics were investigated. All the compounds can be sintered well at ultra-low temperatures (<540 °C). The XRD and SEM analysis indicate that the Ag₂MoO₄ and the Ag_0.5Bi_0.5MoO₄ can coexist with each other. When x = 0.65, the ceramics exhibit the best microwave dielectric properties with a relative permittivity of 23.9, a Q × f value of 16,200 GHz (at 7.3 GHz) and a near-zero TCF value of -2.4 ppm/°C at 520 °C. The results indicate that temperature-stable (1-x)Ag₂MoO₄-xAg_0.5Bi_0.5MoO₄ ceramics are promising candidates for low temperature co-fired ceramics (LTCC) applications.     

Effects of sintering method and BiFeO3 dopant on the dielectric and ferroelectric properties of BaTiO3–BiYbO3 based solid solution ceramics

(0.95–x) BaTiO₃–0.05 BiYbO₃–x BiFeO₃ (x?=?0, 0.01, 0.02, and 0.04) (abbreviated as (0.95–x) BT–0.05 BY–x BFO) ceramics were fabricated by conventional sintering (CS) and microwave sintering (WS) methods. Effects of sintering method and BFO dopant on the microstructure and electric properties of (0.95–x) BT–0.05 BY–x BFO ceramics were comparatively investigated. X-ray diffraction showed that all CS and WS samples presented a single perovskite phase. It was also found that WS ceramics possessed denser microstructure and finer grains compared to CS samples as indicated by the surface morphology characterization. Dielectric measurements revealed that all samples exhibited the weak relaxation behavior; however, the degree of relaxation behavior of BT–BY based ceramic could be strengthened by addition of BFO and by WS method. Moreover, the temperature and frequency stability could be improved with doped BFO. The density of 0.93BT–0.05BY–0.02BFO ceramic was found to be the largest while that of 0.94BT–0.05BY–0.01BFO ceramic was the smallest, thus, the dielectric constant of 0.93BT–0.05BY–0.02BFO was significantly larger than that of 0.94BT–0.05BY–0.01BFO and 0.94BT–0.05BY–0.04 BFO ceramics. minimum dielectric constant of (0.95–x) BT–0.05 BY–x BFO ceramic was obtained at x?=?0.01. Ferroelectric measurements indicated that all samples showed the slim hysteresis loop. The remnant polarization (P_r) and coercive field (E_C) of (0.95–x) BT–0.05 BY–x BFO ceramics first decreased and then increased with increasing x,the minimum values were obtained at x?=?0.01. Moreover, P_r and E_C of WS ceramics were slightly larger than those of CS ceramics, indicating that higher density and larger grain sizes contributed to enhancing the ferroelectric characteristic. These findings indicate that addition of moderate amount of BFO and use of WS technique can strengthen the degree of relaxation behavior and improve the ferroelectric properties of BT–BY based ceramics.     

Hot corrosion behavior of TiO2 doped,Yb2O3 stabilized zirconia exposed to V2O5 + Na2SO4 molten salt at 700–1000 °C

3.5 mol% Yb₂O₃ stabilized zirconia (YbSZ) doped with 10 mol% TiO₂ (Ti-YbSZ) was produced, and its hot corrosion behavior exposed to Na₂SO₄ + V₂O₅ molten salt was investigated. The as-fabricated ceramic mainly consists of metastable tetragonal (t′) phase. When exposed to the molten salt at 700 °C, 800 °C, 900 °C and 1000 °C for 2 h and 10 h, YbVO₄ and m-ZrO₂ formed as corrosion products due to chemical reactions between the ceramics and the salt. Ti⁴⁺ in Ti-YbSZ solid solution keeps stable during the hot corrosion tests, which acts as a stabilizer for ZrO₂, preventing total decomposition of the t′ phase. After the hot corrosion tests, Ti-YbSZ has an apparently lower m phase content than Y₂O₃ doped Zirconia and YbSZ, indicative of better corrosion resistance. The hot corrosion mechanism of Ti-YbSZ is proposed based on Lewis acid-base rule, phase diagrams and thermodynamics.     

Structural,infrared reflectivity spectra and microwave dielectric properties of the Li7Ti3O9F ceramic

A cubic rock salt structured ceramic, Li₇Ti₃O₉F, was fabricated via the conventional solid-state reaction route. The synthesis conditions, sintering characteristics, and microwave dielectric properties of Li₇Ti₃O₉F ceramics were investigated by X-ray diffraction (XRD), thermal dilatometer, Scanning Electron Microscopy (SEM) accompanied with EDS mapping, and microwave resonant measurements. Rietveld refinement, selected area electron diffraction (SAED) pattern and high-resolution transmission electron microscopy (HRTEM) confirmed that Li₇Ti₃O₉F adopts a cubic rock-salt structure. The ceramic sintered at 950?°C presented the optimal microwave properties of ε_r?=?22.5, Q×f?=?88,200?GHz, and τ_f?=??24.2?ppm/^oC. Moreover, good chemical compatibility with Ag was verified through cofiring at 950?°C for 2?h. These results confirm a large potential for Li₇Ti₃O₉F ceramic to be utilized as substrates in the low temperature cofired ceramic (LTCC) technology. This work provides the possibility to exploit low-temperature-firing ceramics through solid solution between oxides and fluorides.     

Al2O3-Ce:GdYAG composite ceramic phosphors for high-power white light-emitting-diode applications

In order to meet the increasing demand of high-power light-emitting-diode (LED) lighting, state-of-the-art white light-emitting diode technology needs phosphors with high thermal conductivity and high luminous efficacy as color converters. In this work, translucent Al₂O₃-Ce:GdYAG composite phosphors were prepared by solid-state reactive sintering. The microstructure shows that the Al₂O₃ particles are uniformly dispersed in the Ce:GdYAG matrix. These particles can not only improve the thermal conductivity of the ceramics, but also promote the extraction efficacy. The luminous characteristics of the Ce:GdYAG and Al₂O₃-Ce:GdYAG ceramics were analyzed after being packaged with blue LED. When the molar ratio of Al₂O₃/Ce:GdYAG is 0.8, a high luminous efficacy value of 112.6 lm/W is achieved by the Al₂O₃-Ce:GdYAG composite ceramic phosphor with the thickness of 0.4 mm, as well as the highest CRI valve of 71.4. The appropriate photoelectric properties of this kind of ceramic phosphor make it a promising candidate for high-power LED device.     

Two–step processing of thermoelectric (Ca0.9Ag0.1)3Co4O9/nano–sized Ag composites with high ZT

A two–step processing method, spark plasma sintering (SPS) combined with a heat–treatment, was used to fabricate (Ca_0.9Ag_0.1)₃Co₄O₉/nano–sized Ag composites. Sliver within the lattice generated hole carriers, and silver along the grain boundaries improved the transport path of the charge carriers. Samples sintered using SPS at different temperatures had very different thermoelectric properties. The results showed that when the sample was sintered at 1233 K, the maximum power factor reached 0.43 mW/(m·K²) along with an electrical resistivity of 8.61 mΩ·cm and a Seebeck coefficient of 196.90 μV/K, and the corresponding lattice thermal conductivity was 1.86 W/(m·K). This study shows how to improve the properties and broaden the application of Ca₃Co₄O₉ thermoelectric ceramics.     

A new family of sodium niobate-based dielectrics for electrical energy storage applications

Although tremendous achievements have been made in enhancing recoverable energy storage density (W_rec) of lead-free dielectric ceramics for electrical energy storage applications in recent years, these ceramics with high W_rec still have two disadvantages: complex chemical composition and difficult preparation process. In this work, we selected NaNbO₃ (NN)-based ceramics as base materials and used Bi₂O₃ as a sintering aid to reduce porosity and enhance dielectric breakdown strengths. Encouragingly, high W_rec, simple chemical composition and facile preparation process were simultaneously realized in 0.77NaNbO₃-0.23BaTiO₃ (0.77NN-0.23BT) ceramics. A large W_rec of 1.5 J cm^?3 at 175 kV cm^?1 and excellent thermal stability (variation of W_rec < 15% over the temperature range of 20?140 °C) were simultaneously achieved in 0.77NN-0.23BT ceramics. More importantly, this work could bring out the development of a series of NN-based ceramics for electrical energy storage in the future such as NN-ABO₃ (A = Ca and Sr; B = Ti and Zr).     

Microwave dielectric properties of low firing temperature stable scheelite structured (Ca,Bi)(Mo,V)O4 solid solution ceramics for LTCC applications

In the present work, a systematic study on microwave properties of Ca_1-xBi_xMo_1-xV_xO₄ (0.2 ≤ x ≤ 0.5) solid solution ceramics synthesized by using the traditional solid-state reaction method was conducted. A scheelite structured solid solution was formed in the composition range 0.2 ≤ x ≤ 0.5. We successfully prepared a microwave dielectric ceramic Ca_0.66Bi_0.34Mo_0.66V_0.34O₄ with a temperature coefficient of resonant frequency (TCF) near to zero and a low sintering temperature by using (Bi, V) substituted (Ca, Mo) in CaMoO₄ to form a solid solution. The Ca_0.66Bi_0.34Mo_0.66V_0.34O₄ ceramic can be well sintered at only 870 °C and exhibits good microwave dielectric properties with a permittivity (ε_r) ?21.9, a Qf ?18,150 GHz (at 7.2 GHz) (Q = quality factor = 1/dielectric loss; f = resonant frequency), a TCF ? + 0.1 ppm/°C. The chemical compatibility with silver indicated that the Ca_0.66Bi_0.34Mo_0.66V_0.34O₄ ceramic might be a good candidate for the LTCC applications.