Synthesis and optical properties of Ni/Co/Cr doped BaMg6Ti6O19

Novel green and blue chromophores based on Ni/Co/Cr doped BaMg₆Ti₆O₁₉ solid solutions are successfully synthesized through a solid-state reaction. The crystal structure of all the samples belongs to the magnetoplumbite structure with the space group of P6₃/mmc. The BaMg_6-x/2Ti_6-x/2Ni_xO₁₉ (0 ≤ x ≤ 0.3) compounds exhibit a light green (x = 0.1) to yellow-green (x = 0.3) color. The oxidation state of Ni is confirmed to be +2 valence and the d-d transition of Ni²⁺ in octahedral sites is responsible for color. BaMg_6-x/2Ti_6-x/2Co_xO₁₉ (0 ≤ x ≤ 0.3) series show a blue color and the intensity of blueness is increasing with the increase of Co content. The blue color is due to d-d transitions within Co²⁺ present in the tetrahedral sites. For BaMg_6-x/2Ti_6-x/2Cr_xO₁₉ (0 ≤ x ≤ 2) phases the color varies from light green (x = 0.2) to green (x = 2). Chromium exists in +3 and + 6 oxidation states and the observed color is due to charge transfer transition between Cr³⁺–Ti⁴⁺ and d-d transitions within octahedral Cr³⁺ sites resulting in strong absorption in the visible region. The synthesized colored oxides are mixed with PMMA to prepare novel green and blue PMMA polymer composites to evaluate their compatibility in plastics.     

Synthesis and properties of blue zirconia ceramic based on Ni/Co doped Ba0.956Mg0.912Al10.088O17 blue pigments

Novel blue pigments based on Ba_0.956Mg_0.912Al_10.088-xNi_xO₁₇ (0 ≤ x ≤ 0.3) and Ba_0.956Mg_0.912Al_10.088-xCo_xO₁₇ (0 ≤ x ≤ 0.3) solid solutions were successfully synthesized by solid state method. The XRD results confirmed the structure of the as-synthesized sample belongs to hexagonal β-alumina structure with the space group of P6₃/mmc. The d-d electron transitions in Ni²⁺/Co²⁺ tetrahedral sites in the visible light range are the reason for the blue colors. Then, the as-prepared blue oxides were sintered with ZrO₂ powders at 1400 °C to prepare blue zirconia ceramic materials. Based on XRD and SEM analysis, the pigment phase is stable after high-temperature sintering with ZrO₂, and a clear grain boundary is observed. The XCT results indicate the prepared blue ceramics are dense and very small pores are rarely distributed inside the blue zirconia ceramic body. Additionally, the mechanical properties of the fabricated blue ceramics were maintained compared to pure ZrO₂ ceramic.     

Microwave dielectric properties of Ca1.15RE0.85Al0.85Ti0.15O4 (RE=Nd,La, Y) ceramics prepared by the reaction sintering method

Ca_1.15RE_0.85Al_0.85Ti_0.15O₄ (RE = Nd, La, Y) ceramics were prepared by a reaction sintering method. The sintering behavior, phase composition, microstructure and microwave dielectric performances of ceramics were investigated. X-ray diffraction patterns illustrated that both the Ca_1.15Nd_0.85Al_0.85Ti_0.15O₄(CNAT) and Ca_1.15Y_0.85Al_0.85Ti_0.15O₄(CYAT) ceramics are single-phase structures, and the Ca_1.15La_0.85Al_0.85Ti_0.15O₄(CLAT) ceramic contain LaAlO₃ and CaO phases. The apparent morphology and elemental distribution of the ceramic samples were analyzed by using scanning electron microscope and energy dispersive spectrometer. When the sintering temperature is 1500 °C, the CNAT and CYAT ceramics have the best microwave dielectric properties with ε_r = 19.2, Q × f = 74924 GHz, τ_f = ?1.21 ppm/°C and ε_r = 17.5, Q × f = 27440 GHz, τ_f = ?5.79 ppm/°C, respectively. And the best microwave dielectric properties of ε_r = 17.5, Q × f = 22568 GHz, τ_f = ?14.69 ppm/°C were obtained for the CLAT ceramic sintered at 1525 °C. The reaction sintering method provides a low-cost, economical and straightforward method for the preparation of the Ca_1.15RE_0.85Al_0.85Ti_0.15O₄ (RE = Nd, La, Y) ceramics, which has promising potential for application.     

The electrical properties of (Ba,Ca, Ce,Ti, Zr)O3 thermistor for wide-temperature sensor architecture

A series of new negative temperature coefficient (NTC) thermal materials based on (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ (0.00 ≤ x ≤ 0.20) ceramics were synthesized by a solid-state method. X-ray diffraction, scanning electron microscope and X-ray photoelectron spectroscopy were used to demonstrate the crystal structure, morphology, and composition of the (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ ceramics, which were composed of solid solution based on the BaTiO₃ phase. The average grain size of doped ceramic samples experienced the process of first decreasing and then increasing. The doping of Ce has reduced the sintering temperature. The temperature-dependent resistance analysis revealed that with the change of doping amount x, the thermal constant B_300/1200 (1.21 × 10⁴–1.13 × 10⁴ K) and the activation energy E_a300/1200 (0.9777–1.0471eV) was initially increased to maximum values at x = 0.05, followed by the decreasing when x > 0.05. It has been established that the concentration of oxygen vacancies is affected by the transition between Ce⁴⁺ and Ce³⁺ provided by high levels of Ce doping. (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ ceramics exhibited excellent negative temperature characteristics in the range of 300–1200 °C. Moreover, the temperature resistance linearity was improved after samples were aged. Hence, the (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ ceramics were regarded as a promising material for high-temperature NTC thermistors in a wide temperature range.     

Influence of TiO2 doping on thermo-optical properties of pyrochlore Sm2(Zr1–xTix)2O7 (0≤x≤0.15) ceramics

Sm₂(Zr_1–xTi_x)₂O₇ (0≤x≤0.15) ceramics have been fabricated by pressureless-sintering method at 1973 K for 10 h in air. The influence of TiO₂ doping on microstructure and thermo-optical properties of Sm₂(Zr_1–xTi_x)₂O₇ ceramics is investigated by X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy measurements. The partial substitution of Ti⁴⁺ for Zr⁴⁺ results in a significant increase in emissivity at low wavelengths contrasted with undoped Sm₂Zr₂O₇. Sm₂(Zr_0.85Ti_0.15)₂O₇ ceramic exhibits a high emissivity of above 0.70 at 1073 K in a wavelength range of 3–16 µm, where the highest value at this temperature is more than 0.90 especially in the wavelength range of 9–14 µm. FT-IR spectra and optical absorption spectra unveil the mechanisms of enhanced emissivity in Sm₂(Zr_1–xTi_x)₂O₇ (0.05≤x≤0.15) ceramics in the intermediate infrared range, especially at the wavelengths of 3–8 µm, due to Ti⁴⁺ ion substitution for Zr⁴⁺ ion.     

Effect of substituting Al3+ for Ti4+on the microwave dielectric performance of Mg2Ti1-xAl4/3xO4 (0.01 ≤ x ≤ 0.09) ceramics

In this paper, Mg₂Ti_1-xAl_4/3xO₄ ceramics (0.01 ≤ x ≤ 0.09) were synthesized through conventional solid-state ceramic route. The cubic spinel structure, microstructure and microwave properties of Mg₂Ti_1-xAl_4/3xO₄ (x = 0.01, 0.03, 0.05, 0.07, 0.09) ceramics were investigated by X-ray diffraction, Raman spectra, infrared spectra. Rietveld refinements confirm that a spinel structure phase with space group Fd-3m is formed. The variation of the permittivity was concerned with the ionic polarizability, and the value of τ_f was influenced by the bond valence. Both Q × f values and relative density showed an identical trend. Intrinsic properties of Mg₂Ti_1-xAl_4/3xO₄ ceramics were analyzed by infrared spectra and Raman spectra. In addition, the Mg₂Ti_1-xAl_4/3xO₄ ceramic sintered at 1420 °C for 4 h possessed optimal dielectric properties (ε_r = 14.65, Q × f = 182347 GHz, τ_f = −57.7 ppm/°C) when x = 0.09.     

Karrooite green pigments doped with Co and Zn: Synthesis,color properties and stability in ceramic glazes

The solid-state synthesis and stabilization of Co doped (Mg_1−xCo_xTi₂O₅), Zn doped (Mg_1−xZn_xTi₂O₅) and Co- and Zn-codoped karrooite solid solutions (Mg_0.8−xZn_0.2Co_xTi₂O₅ and (Mg_0.5Zn_0.5)_1−xCo_xTi₂O₅) were investigated. In addition, the optical spectra, color properties and technological performance of (Co,Zn)-karrooite compositions as new green ceramic pigments were also analyzed. XRD characterization revealed for the first time the high solid solubility of Zn²⁺ in MgTi₂O₅ karrooite at 1200 ºC (between 60 and 80 mol% per Mg or karrooite formula unit). In contrast, the reactivity and stabilization of karrooite phase decreased in the case of Co²⁺ doping. Interestingly, codoping with Zn²⁺ ions at high molar ratios (Zn:Mg ratio equal to 1:1) enhanced the reactivity and enabled the stabilization of (Co,Zn)-MgTi₂O₅ karrooite solid solutions, even with high Co²⁺ loadings (20 mol% per karrooite formula unit). The (Co,Zn)-MgTi₂O₅ pigments exhibited yellowish-green colors associated to Co²⁺ ions allocated in octahedral M1 and M2 sites of karrooite lattice, and becoming more intense and less yellow the higher the Co content. However, Zn²⁺ codoping produced less saturated green colors with similar green but lower yellowish hues. The obtained pigments were not stable enough within the tested ceramic glazes, giving rise to turquoise colorations due to cobalt leaching and incorporation into tetrahedral sites of the glassy phase. The stability of Co-karrooite green pigments was higher in a Ca- and Zn-enriched ceramic glaze (B) fired at a higher temperature (1050 °C).     

Thermal stability improvement of dielectric properties and non-ohmic characteristic of CaCu3+xTi4O12 ceramics via a Cu-nonstoichiometric approach

In this work, the effects of Cu composition on the thermal stability of the dielectric and nonlinear properties of CaCu_3+xTi₄O₁₂ (?0.2 ≤ x ≤ 0.2) ceramics obtained via a polymer-pyrolysis chemical process were studied. The mean grain sizes of Cu-stoichiometric (x = 0), Cu-deficient (x < 0) and Cu-excess (x > 0) CaCu_3+xTi₄O₁₂ ceramics were found to be ~3.2, ~3.4 and ~3.7 μm, respectively. Interestingly, very good dielectric properties (0.020 ≤ tanδ ≤ 0.038 and 4000 ≤ ε′ ≤ 7065) were attained in CaCu_3+xTi₄O₁₂ (?0.2 ≤ x ≤ 0.1, excluding x = 0.2) ceramics. Moreover, the variation of dielectric constant (ε′) within a limit of ±15% (Δε′_{± 15%}) over a wide temperature range (T_R) of ?70 – 220 °C with low tanδ < 0.05 (tanδ_<0.05) over a T_R of ?70 to 80 °C were achieved in a CaCu_2.8Ti₄O₁₂ ceramic. These results suggest that this ceramic could be applicable for X9R capacitors and energy storage devices that require high thermal stability. Additionally, the nonlinear properties of Cu-nonstoichiometric ceramics could be improved when compared with those of the Cu-stoichiometric material. The incremental changes of dielectric and nonlinear properties of CaCu_3+xTi₄O₁₂ (?0.2 ≤ x ≤ 0.2) ceramics revealed the significant role of Cu composition on grain boundary resistance (R_gb), which was confirmed by impedance spectroscopy analysis. In addition, XANES results revealed the proper ratios of Cu⁺:Cu²⁺ and Ti³⁺:Ti⁴⁺ found in these ceramics, indicating the semiconducting behavior of these grains.     

Impedance spectroscopy,B-site cation ordering and structure–property relations of (1 − x) La[Al0.9(Mg0.5Ti0.5)0.1]O3–x CaTiO3 ceramics for 5G dielectric waveguide filters

Dense (1 ? x) La[Al_0.9(Mg_0.5Ti_0.5)_0.1]O₃–x CaTiO₃ ceramics were synthesized via solid-state reaction. The crystal structure and microwave dielectric properties of the ceramics were systematically investigated. Rietveld refinement revealed that when x ≤ 0.2, the ceramics had a rhombohedral structure with an R-3c space group. When x ≥ 0.5, the ceramics had an orthorhombic structure with a Pbnm space group. Selected area electron diffraction and Raman spectroscopy analyses proved that the microwave dielectric ceramics had a B-site order, which accounted for the great improvement in microwave dielectric properties. The content of oxygen vacancies was identified through X-ray photoelectron spectroscopy, and the change rule of Q × f was closely related to oxygen vacancy content. The perturbation of A-site cations had an important influence on dielectric constant. Specifically, with the increase in Ti⁴⁺ content, the perturbation effect of the A-site cations was enhanced and dielectric constant increased. When x = 0.65, the temperature coefficient of resonant frequency of the (1 ? x) La[Al_0.9(Mg_0.5Ti_0.5)_0.1]O₃–x CaTiO₃ microwave dielectric ceramics was near zero. The optimal microwave dielectric properties of 0.35LaAl_0.9(Mg_0.5Ti_0.5)_0.1O₃–0.65CaTiO₃ were ε_r = 44.6, Q × f = 32,057 GHz, and τ_f = +2 ppm/°C.     

Crystal structure and luminescence properties of green-emitting Sr1−xAl12O19:xEu2+ phosphors

In this paper, a series of novel luminescent Sr_1−xAl₁₂O₁₉:xEu²⁺ phosphors were synthesized by a high temperature solid-state reaction. The phase structure, photoluminescence (PL) properties, as well as the decay curves were investigated. The quenching concentration of Eu²⁺ in SrAl₁₂O₁₉ was about 0.15 (mol). Upon excitation at 378 nm, the composition-optimized Sr_0.85Al₁₂O₁₉:0.15Eu²⁺ exhibited strong broad-band green emission at 530 nm with the CIE chromaticity (0.2917, 0.5736). The results indicate that Sr_1−xAl₁₂O₁₉:xEu²⁺ phosphors have potential applications as green-emitting phosphors for UV-pumped white-light LEDs.     

The effect of co-substitution on the microwave dielectric properties of Ba6-3xNd8+2xTi18O54(x=2/3) ceramics

In this work, the microwave dielectric properties of Ba₄(Nd_1-yBi_y)_28/3Ti_18-x(Al_1/2Ta_1/2)_xO₅₄(0≤x≤2, 0.05≤y≤0.2) ceramics co-substituted by A/B-site were studied. Firstly, (Al_1/2Ta_1/2)⁴⁺ was used for substitution at B-site. At 0≤x≤1.5, the above mentioned ceramic was found to exist in single-phase tungsten bronze structure, but at x = 2.0, the secondary phase appeared. Although the dielectric constant decreased by doping the (Al_1/2Ta_1/2)⁴⁺, but the quality factor was observed to improve by 40% and the temperature coefficient of resonant frequency decreased by 75%. Based on the above results, Bi³⁺ was introduced to Ba₄Nd_28/3Ti₁₇(Al_1/2Ta_1/2)O₅₄. The introduction of Bi³⁺ reduced the sintering temperature, greatly improved the dielectric constant, and ultimately decreased the temperature coefficient of resonant frequency, but it led to deterioration of quality factor. At last, with appropriate site-substitution content control (x = 1.0,y = 0.15), excellent comprehensive properties (ε_r = 89.0, Q × f = 5844 GHz @ 5.89 GHz，TCF = +8.7 ppm/°C) were obtained for the samples sintered at 1325 °C for 4 h.     

High-Qf value and temperature stable Zn2+-Mn4+ cooperated modified cordierite-based microwave and millimeter-wave dielectric ceramics

Cordierite-based dielectric ceramics with a lower dielectric constant would have significant application potential as dielectric resonator and filter materials for future ultra-low-latency 5G/6G millimeter-wave and terahertz communication. In this article, the phase structure, microstructure and microwave dielectric properties of Mg₂Al_4–2x(Mn_0.5Zn_0.5)_2xSi₅O₁₈ (0 ≤ x ≤ 0.3) ceramics are studied by crystal structure refinement, scanning electron microscope (SEM), the theory of complex chemical bonds and infrared reflectance spectrum. Meanwhile, complex double-ions coordinated substitution and two-phase complex methods were used to improve its Q×f value and adjust its temperature coefficient. The Q×f values of Mg₂Al_4–2x(Mn_0.5Zn_0.5)_2xSi₅O₁₈ single-phase ceramics are increased from 45,000 GHz@14.7 GHz (x = 0) to 150,500 GHz@14.5 GHz (x = 0.15) by replacing Al³⁺ with Zn²⁺-Mn⁴⁺. The positive frequency temperature coefficient additive TiO₂ is used to prepare the temperature stable Mg₂Al_3.7(Mn_0.5Zn_0.5)_0.3Si₅O₁₈-ywt%TiO₂ composite ceramic. The composite ceramic of Mg₂Al_3.7(Mn_0.5Zn_0.5)_0.3Si₅O₁₈-ywt%TiO₂ (8.7 wt% ≤ y ≤ 10.6 wt%) presents the near-zero frequency temperature coefficient at 1225 °C sintering temperature: ε_r = 5.68, Q×f = 58,040 GHz, τ_f = ?3.1 ppm/°C (y = 8.7 wt%) and ε_r = 5.82, Q×f = 47,020 GHz, τ_f = +2.4 ppm/°C (y = 10.6 wt%). These findings demonstrate promising application prospects for 5 G and future microwave and millimeter-wave wireless communication technologies.     

Characterization of Mg1−xNixAl2O4 solid solutions prepared by combustion synthesis

Mg_1−xNi_xAl₂O₄ (x = 0, 0.25, 0.5, 0.75 and 1) solid solutions have been prepared by combustion synthesis. After annealing the combustion synthesized powders at 1000 °C for 3 h single-phase Mg_1−xNi_xAl₂O₄ was obtained over the entire range of compositions. The lattice parameter of Mg_1−xNi_xAl₂O₄ gradually increased from 8.049 Å (NiAl₂O₄) to 8.085 Å (MgAl₂O₄), which certified the formation of the spinel solid solutions. All samples prepared by combustion synthesis had blue color shades, denoting the inclusion of Ni²⁺ in the spinel structure in octahedral and tetrahedral configuration. The crystallite size of Mg_1−xNi_xAl₂O₄ was in the range of 35-39 nm and the specific surface area varied between 5.8 and 7.0 m²/g.     

Sol–gel synthesis and infrared radiation property of Li-substituted cordierite

The Mg_2?xAl_4+1/2xLi_1/2xSi₅O₁₈ (0.1≤x≤1) ceramics with the substitution of (Li_1/2Al_1/2)²⁺ for Mg²⁺ were synthesized by the sol–gel method. The characterization of the modified cordierite included X-ray diffraction, SEM, EDS and infrared radiation. The crystal structure of Mg₂Al₄Si₅O₁₈ with the substitution of (Li_1/2Al_1/2)²⁺ for Mg²⁺ changed and the amount of secondary phase increased with increasing the x value from 0.1 to 1. High infrared emissivity over 0.9 in the band of 8–14 μm at room temperature was obtained in Mg_2?xAl_4+1/2xLi_1/2xSi₅O₁₈ (x=0.1). The material based on cordierite with x=0.1 sintered at 1200 °C maintained a single phase, compact microstructure and good infrared emissivity with potential use in infrared heating.     

Effect of TiO2 Doping on the Structure and Microwave Dielectric Properties of Cordierite Ceramics

The (1?x)Mg₂Al₄Si₅O₁₈–xTiO₂ |(1?x)MAS‐xT| (0 ≤ x ≤ 0.35) cordierite ceramics are fabricated by solid‐state reaction method for obtaining near‐zero temperature coefficient of resonant frequency (τ_f). The XRD and SEM results show that (1?x)MAS‐xT (0 ≤ x ≤ 0.10) ceramics exhibit single cordierite solid solution, whereas as 0.15 ≤ x ≤ 0.35, present composite phases of Mg₂Al₄Si₅O₁₈ solution and TiO₂. Rietveld refinements of XRD data suggest that the [(Si₄Al₂)O₁₈] hexagonal shape in cordierite structure happens to alternate change from nonsymmetrical hexagonal rings to almost centrosymmetrical equilateral rings as x increases to 0.10 comparing to that of x = 0. As Ti⁴⁺ ions squeeze into the [(Si₄Al₂)O₁₈] rings structure, the orientation and shapes of the rings begin to rotate and expand from initial state of [1–20] (x = 0) to near [210] direction (x = 0.10), and then continue to expand toward close to [110] direction (x = 0.25). Due to centrosymmetry adjustment of [(Si₄Al₂)O₁₈] hexagonal rings and of other microstructure factors improvement, the (1?x)MAS‐xT (x = 0.10) cordierite solution achieves optimum quality factor Q_f: ε_r = 6.3, Q_f = 55 400 GHz (17.6 GHz), τ_f = ?21 ppm/°C. The (1?x)MAS‐xT (x = 0.25) composites obtain a near‐zero temperature coefficient of resonance frequency: ε_r = 6.8, Q_f = 37 800 GHz (18.4 GHz), τ_f = ?0.2 ppm/°C.     

Structural and electrical properties of MgO-doped Mn1.4Ni1.2Co0.4−xMgxO4 (0 ≤ x ≤ 0.25) NTC thermistors

We have prepared polycrystalline Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ (0 ≤ x ≤ 0.25) samples using a solid-state reaction process and investigated the MgO doping effect on the microstructure and the electrical properties. It was found that, as the amount of Mg content in the Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ samples increased, both the grain size and density decreased. The as-sintered Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ samples contained Mn- and Ni-rich phases with cubic spinel structure. The MgO-doped Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ negative temperature coefficient (NTC) thermistors provided various electrical properties, depending on Mg content. The electrical resistivity, B_25/85 constant, and activation energy of the Mn_1.4Ni_1.2Co_0.4−xMg_xO₄ NTC thermistors increased with increasing Mg content. The values of ρ₂₅, B_25/85 constant, and activation energy of the NTC thermistors were 11,185–20,016 Ω cm, 3635–4032 K, and 0.313–0.348 eV, respectively.     

Crystal structure and microwave dielectric properties of garnet-type Ca2YZr2-xTixAl3O12 ceramics for dual-band bandpass filters

Microwave dielectric ceramics with a high-quality factor are vital materials for substrates, dielectric resonators, and filters in millimeter-wave communication systems. Here, a novel microwave dielectric ceramic based on a garnet-type Ca₂YZr₂Al₃O₁₂ compound for bandpass filter was prepared using the solid-state reaction method. Sintering the Ca₂YZr₂Al₃O₁₂ ceramics at 1600 ℃ for 5 h resulted in excellent microwave dielectric properties of ε_r = 10.81 ± 0.16, Qf = 87,628 ± 4000 GHz and τ_f = ?34.3 ± 0.5 ppm/℃. Increasing the Ti⁴⁺ content of the Ca₂YZr_2-xTi_xAl₃O₁₂ ceramics significantly improved the sintering process. Superior microwave dielectric properties (ε_r = 11.93 ± 0.15, Qf = 121,930 ± 2600 GHz and τ_f = ?30.8 ± 0.4 ppm/℃) were obtained for Ca₂YZr_2-xTi_xAl₃O₁₂ (x = 0.3) because of its dense microstructure, large grain size and high lattice energy. The Ca₂YZr_2-xTi_xAl₃O₁₂ (x = 0.3) ceramics were used to fabricate a dual-band bandpass filter with a hairpin structure that exhibited a large return loss (|S₁₁| > 12 dB) and a small insertion loss (|S₂₁| < 0.73 dB). The high performance of the Ca₂YZr_2-xTi_xAl₃O₁₂ ceramics and the corresponding bandpass filter makes this material a potential candidate for millimeter-wave devices.     

Microwave dielectric properties of Bi-substituted La(Mg1/2Ti1/2)O3

The system La(Mg_1/2Ti_1/2)O₃–Bi(Mg_1/2Ti_1/2)O₃ (LMT–BMT) was investigated in respect to formation of perovskite solid solutions based on lanthanum magnesium titanate. Single-phase perovskite (1 − x)LMT–xBMT ceramics (0 ≤ x ≤ 0.3) were prepared and their crystal structure and dielectric properties were studied. It has been found that within the solubility range the crystal structure of Bi-substituted LMT remains monoclinic, P2₁/n. Unit cell volume was evaluated to be almost independent on x, varying within the experimental error. Relative permittivity of the ceramics increases by almost a factor of 3 in the range 0 ≤ x ≤ 0.3 and its value is 40–45 at the compositional region where temperature coefficient of the resonant frequency passes a zero-value. Compositional and temperature variations of the dielectric parameters for LMT–BMT estimated at different frequency ranges are considered in comparison with those observed in other Bi-substituted ceramics based on LMT.     

Intrinsic factors affecting the microwave dielectric properties of Mg2Ti1−x(Mg1/3Sb2/3)xO4 ceramics

The effect of crystal structure on the microwave dielectric properties of Mg₂Ti_1−x(Mg_1/3Sb_2/3)_xO₄ (0.025≤x≤0.15) ceramics was investigated. A single phase having a cubic inverse spinel structure formed over the entire range of compositions, in specimens sintered at 1450 °C for 4 h. The structural characteristics of these ceramics were quantitatively evaluated by applying the Rietveld refinement method to the X-ray diffraction data. The largest bond strength between the cation and the oxygen ion and hence the highest quality factor (Qf) of the specimens were obtained at x=0.05. Although the ionic polarizability (3.29 Å³) of (Mg_1/3Sb_2/3)⁴⁺ was larger than that (2.93 Å³) of Ti⁴⁺, the dielectric constant (K) of the specimens decreased owing to the decrease of rattling effect with increasing x. In addition, the temperature coefficient of resonant frequency (TCF) decreased with decreasing K values. Typically, a high Qf value of 229,000 GHz was obtained for the specimens with x=0.05.     

Solubility and microstructural development of TiO2-containing 3Al2O3·2SiO2 and 2Al2O3·SiO2 mullites obtained from single-phase gels

The interdependence of the titanium oxide amount and the anisotropic growth of mullites prepared from single-phase gels were investigated. Gels with stoichiometries 3(Al_2−xTi_xO₃)·2(SiO₂) and 2(Al_2−xTi_xO₃)·(SiO₂), with 0 ≤ x ≤ 0.15 were prepared by the semialkoxide method. Gels and specimens heated at temperatures between 1200 and 1600 °C were characterized by using infrared spectroscopy (IR), X-ray diffraction (XRD) and transmission and field emission scanning electron microscopies (TEM and FESEM). Al₂TiO₅ as minor impurity was detected in both series of mullites for gel precursor compositions x = 0.10 and x = 0.15, obtained at temperatures between 1200 and 1600 °C. Variations of lattice parameters of mullite, processed at temperatures from the range between 1400 and 1600 °C, with the starting nominal amount of titanium oxide indicated that the solubility limit of titanium oxide was in ranges 3.8–4.1 and 4.1–4.4 wt% TiO₂ for 3:2 and 2:1 mullites series, respectively. The anisotropic growth of titanium-doped mullite crystalline grains was significant only when the nominal amount of titanium oxide exceeded the limit of solubility into the mullite structure (for both mullite series). Stronger anisotropy occurred for the 3:2 series specimens, i.e. for the SiO₂-richer mullites. In both series of mullites, the anisotropic grain growth was observed for the process temperatures higher than 1400 °C; the crystalline grains of mullites processed at lower temperatures were equiaxials and of almost the same size.