Investigation of the microwave dielectric properties of Ca1−xMgxLa4Ti5O17 ceramics for application in coplanar patch antenna

In this paper, the dielectric properties of Ca_1−xMg_xLa₄Ti₅O₁₇ ceramics at microwave frequency have been studied. The diffraction peaks of Ca_(1−x)Mg_xLa₄Ti₅O₁₇ ceramics nearly unchanged with x increasing from 0 to 0.03. Similar X-ray diffraction peaks of Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic were observed at different sintering temperatures. A maximum density of 5.3 g/cm³ can be obtained for Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h. A maximum dielectric constant (_r) and quality factor (Q × f) of Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h are 56.3 and 12,300 GHz (at 6.4 GHz), respectively. A near-zero temperature coefficient of resonant frequency (τ_f) of −9.6 ppm/°C can be obtained for Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h. The measurement results for the aperture-coupled coplanar patch antenna at 2.5 GHz are presented. With this technique, a 3.33% bandwidth (return loss <−10 dB) with a center frequency at approximately 2.5 GHz has been successfully achieved.     

Synthesis and crystal structure of a new calcium borate, CaB6O10

A new calcium borate, CaB₆O₁₀, has been prepared by solid-state reactions at temperature below 750 °C. The single-crystal X-ray structural analysis showed that CaB₆O₁₀ crystallizes in the monoclinic space group P2₁/c with a = 9.799(1) Å, b = 8.705(1) Å, c = 9.067(1) Å, β = 116.65(1)°, Z = 4. It represents a new structure type in which two [B₃O₇]⁵⁻ triborate groups are bridged by one oxygen atom to form a [B₆O₁₃]⁸⁻ group that is further condensed into a 3D network, with the shorthand notation 6: ∞³[2 × (3:2Δ + T)]. The 3D network affords intersecting open channels running parallel to three crystallographically axis directions, where Ca²⁺ cations reside. The IR spectrum further confirms the presence of both BO₃ and BO₄ groups.     

Conductivity of a new pyrophosphate Sn0.9Sc0.1(P2O7)1−δ prepared by an aqueous solution method

New pyrophosphate Sn_0.9Sc_0.1(P₂O₇)_1−δ was prepared by an aqueous solution method. The structure and conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ have been investigated. XRD analysis indicates that Sn_0.9Sc_0.1(P₂O₇)_1−δ exhibits a 3 × 3 × 3 super structure. It was found that Sn_0.9Sc_0.1(P₂O₇)_1−δ prepared by an aqueous method is not conductive. The total conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ in open air is 2.35 × 10⁻⁶ and 2.82 × 10⁻⁹ S/cm at 900 and 400 °C respectively. In wet air, the total conductivity is about two orders of magnitude higher (8.1 × 10⁻⁷ S/cm at 400 °C) than in open air indicating some proton conduction. SnP₂O₇ and Sn_0.92In_0.08(P₂O₇)_1−δ prepared by an acidic method were reported fairly conductive but prepared by similar solution methods are not conductive. Therefore, the conductivity of SnP₂O₇-based materials might be related to the synthetic history. The possible conduction mechanism of SnP₂O₇-based materials has been discussed in detail.     

Improved high-Q microwave dielectric resonator using ZnO-doped La(Co1/2Ti1/2)O3 ceramics

The microwave dielectric properties and the microstructures of ZnO-doped La(Co_1/2Ti_1/2)O₃ ceramics prepared by conventional solid-state route have been studied. Doped with ZnO (up to 0.75 wt%) can effectively promote the densification of La(Co_1/2Ti_1/2)O₃ ceramics with low sintering temperature. At 1320 °C, La(Co_1/2Ti_1/2)O₃ ceramics with 0.75 wt% ZnO addition possesses a dielectric constant (_r) of 30.2, a Q × f value of 73,000 GHz (at 8 GHz) and a temperature coefficient of resonant frequency (τ_f) of −35 ppm/°C.     

Subsolidus phase relations in the system ZnO–P2O5–MoO3

The subsolidus phase relations of the ternary system ZnO–P₂O₅–MoO₃ were investigated by means of X-ray diffraction (XRD). Seven binary compounds and eight 3-phase regions were determined, and no ternary compound was found in this system. The phase diagram of pseudo-binary system Zn₃(PO₄)₂–Zn₃Mo₂O₉ was also constructed through XRD and differential thermal analysis (DTA) methods, and the result reveals this system is eutectic system. The eutectic temperature is 904 °C and the corresponding component is 30% Zn₃Mo₂O₉ and 70% Zn₃(PO₄)₂.     

Synthesis, structure, and high temperature Mössbauer and Raman spectroscopy studies of Ba1.6Sr1.4Fe2WO9 double perovskite

Ba_1.6Sr_1.4Fe₂WO₉ has been prepared in polycrystalline form by solid-state reaction method in air, and has been studied by X-ray powder diffraction method (XRPD), and high temperature Mössbauer and Raman spectroscopies. The crystal structure was resolved at room temperature by the Rietveld refinement method, and revealed that Ba_1.6Sr_1.4Fe₂WO₉ crystallizes in a tetragonal system, space group I4/m, with a = b = 5.6489(10)Å, c = 7.9833(2)Å and adopts a double perovskite-type A₃B′₂B″O₉ (A = Ba, Sr; B′ = Fe/W, and B″ = Fe/W) structure described by the crystallographic formula (Ba_1.07Sr_0.93)_4d(Fe_0.744W_0.256)_2a(Fe_0.585W_0.415)_2bO₆. The structure contains alternating [(Fe/W)_2aO₆] and [(Fe/W)_2bO₆] octahedra. Mössbauer studies reveal the presence of iron in the 3+ oxidation state. The high temperature Mössbauer measurements showed a magnetic to paramagnetic transition around 405 ± 10 K. The transition is gradual over the temperature interval. The decrease in isomer shift is in line with the general temperature dependence. While the isomer shift is rather linear over the whole temperature range, the quadratic dipolar ΔE temperature dependence shows an abrupt change at 405 K. The latter results allow concluding that a temperature-induced phase transition had occurred. The high temperature Raman study confirms the Mössbauer results on the magnetic to paramagnetic transition.     

Roles of humidity and heat treatment temperatures on YBa2Cu3O7-x coated conductors by trifluoroacetic acid-metal organic deposition process

YBa₂Cu₃O_7−x(YBCO) films were fabricated on an LAO substrate using the trifluoroacetic acid-metal organic deposition (TFA-MOD) method and the effects of the humidity and heat treatment temperatures on the microstructure, degree of texture and critical properties of the films were evaluated. In order to understand the combined effects of the humidity and the calcining and firing temperatures on critical properties, heat-treatment was performed at various temperatures with the other processing variables fixed. The films were calcined at 400–430 and fired at 750–800 °C in a 0–12.1% humidified Ar-O₂ atmosphere. The texture was determined by pole-figure analysis. The amount of the BaF₂ phase was effectively reduced and a sharp and strong biaxial texture was formed under a humidified atmosphere, which led to increased critical properties. In addition, the microstructure varied significantly with firing temperature but changed little with calcining temperature. The highest I_C of 40 A/cm-width, which corresponds to J_C value of 1.8 MA/cm², was obtained for the films fired at 775 (in 12.1% humidity) after calcining at 400–430 °C. It is likely that °C the highest I_C value is due to the formation of a more pure YBCO phase, c-axis grains, and a denser microstructure.     

Synthesis and characterization of Al2O3-Ce0.5Zr0.5O2 powders prepared by chemical coprecipitation method

Al₂O₃-Ce_0.5Zr_0.5O₂ catalytic powders were synthesized by the coprecipitation (ACZ-C) and mechanical mixing (ACZ-M) methods, respectively. As-synthesized powders were characterized by XRD, Raman spectroscopy, surface area and thermogravimetric analyses. It was found that the mixing extent of Al³⁺ ions affected the phase development, texture and oxygen storage capacity (OSC) of the Ce_0.5Zr_0.5O₂ powder. Single phase of ACZ-C could be maintained without phase separation and inhibit α-Al₂O₃ formation up to 1200 °C. The specific surface area value of ACZ-C (81.5 m²/g) was larger than that of ACZ-M (62.1 m²/g) and Ce_0.5Zr_0.5O₂ (17.1 m²/g) powders, which were calcined at 1000 °C. In comparison with ACZ-C and Al₂O₃, which were calcined at high temperature (900–1200 °C), it was found that the degradation rate of specific surface area of ACZ-C was lower than that of Al₂O₃. ACZ-C sample showed a higher thermal stability to resist phase separation and crystallite growth, which enhanced the oxygen storage capacity property for Ce_0.5Zr_0.5O₂ powders.     

Densification, microstructural evolution, and dielectric properties of hexagonal Ba(Ti1−xMnx)O3 ceramics sintered with fluxes

Recently, doped hexagonal BaTiO₃ (6h-BaTiO₃) ceramics have been reported as potential candidates used in microwave dielectric resonators. However, similar to other common microwave ceramics, doped 6h-BaTiO₃ ceramics require a high sintering temperature, greater than 1300 °C. In this study, the effect of sintering aids, including Bi₂O₃, B₂O₃, BaSiO₃, Li₂CO₃, CuO, V₂O₅, 5ZnO·2B₂O₃, and 5ZnO·2SiO₂, on the densification, microstructural evolution, and microwave properties of the 6h-Ba(Ti_0.85Mn_0.15)O₃ ceramics was examined. Results indicate that among the fluxes studied, Bi₂O₃, B₂O₃, and Li₂CO₃ could effectively reduce the sintering temperature of 6h-Ba(Ti_0.85Mn_0.15)O₃ ceramics through liquid phase sintering, while retaining the hexagonal structure and the microwave dielectric properties. The best results were obtained for the 6h-Ba(Ti_0.85Mn_0.15)O₃ with the additions of 5 wt% Bi₂O₃ sintered at 900 °C (_r: 54.7, Qf_r: 1323, and τ_f:183.3 ppm/°C), 10 wt% B₂O₃ sintered at 1100 °C (_r: 54.4, Qf_r: 3448, and τ_f: 254.5 ppm/°C), and 5 wt% Li₂CO₃ sintered at 950 °C (_r: 43.7, Qf_r: 2501, and τ_f: −29.8 ppm/°C).     

Subsolidus phase relations of the ZnO–Li2O–P2O5 system

As a systematic search for suitable flux to grow zinc oxide single crystals, the subsolidus phase relations of the ternary system ZnO–Li₂O–P₂O₅ were investigated by means of X-ray diffraction (XRD). There are 6 binary compounds, 5 ternary compounds and 17 three-phase regions in this system. A new compound, Li₆Zn(P₂O₇)₂, is found in this system based on XRD experiments. The phase diagrams of the pseudo-binary systems Li₃PO₄–ZnO and LiZnPO₄–ZnO are investigated. It shows that the compounds, Li₃PO₄ and LiZnPO₄, are not suitable as flux for the growth of ZnO single crystals below 1250 °C.     

Effect of Ag-doping on crystal structure and high temperature thermoelectric properties of c-axis oriented Ca3Co4O9 thin films by pulsed laser deposition

Ag-doped Ca₃Co₄O₉ thin films with nominal composition of Ca_3−xAg_xCo₄O₉ (x = 0∼0.4) have been prepared on sapphire (0 0 0 1) substrates by pulsed laser deposition (PLD). Structural characterizations and surface chemical states analysis have shown that Ag substitution for Ca in the thin films can be achieved with doping amount of x ≤ 0.15; while x > 0.15, excessive Ag was found as isolated and metallic species, resulting in composite structure. Based on the perfect c-axis orientation of the thin films, Ag-doping has been found to facilitate a remarkable decrease in the in-plane electrical resistivity. However, if doped beyond the substitution limit, excessive Ag was observed to severely reduce the Seebeck coefficient. Through carrier concentration adjustment by Ag-substitution, power factor of the Ag-Ca₃Co₄O₉ thin films could reach 0.73 mW m⁻¹ K⁻² at around 700 K, which was about 16% higher than that of the pure Ca₃Co₄O₉ thin film.     

Thermo-physical and thermal cycling properties of plasma-sprayed BaLa2Ti3O10 coating as potential thermal barrier materials

Increased turbine inlet temperature in advanced turbines has promoted the development of thermal barrier coating (TBC) materials with high-temperature capability. In this paper, BaLa₂Ti₃O₁₀ (BLT) was produced by solid-state reaction of BaCO₃, TiO₂ and La₂O₃ at 1500 °C for 48 h. BLT showed phase stability between room temperature and 1400 °C. BLT revealed a linearly increasing thermal expansion coefficient with increasing temperature up to 1200 °C and the coefficients of thermal expansion (CTEs) are in the range of 1 × 10^− 5–12.5 × 10^− 6 K^− 1, which are comparable to those of 7YSZ. BLT coatings with stoichiometric composition were produced by atmospheric plasma spraying. The coating contained segmentation cracks and had a porosity of around 13%. The microhardness for the BLT coating is 3.9–4.5 GPa. The thermo-physical properties of the sprayed coating were investigated. The thermal conductivity at 1200 °C is about 0.7 W/mK, exhibiting a very promising potential in improving the thermal insulation property of TBC. Thermal cycling result showed that the BLT TBC had a lifetime of more than 1100 cycles of about 200 h at 1100 °C. The failure of the coating occurred by cracking at the thermally grown oxide (TGO) layer due to severe oxidation of bond coat. Based on the above merits, BLT could be considered as a promising material for TBC applications.     

Ethanol-assisted synthesis of Zn0.5Fe2.5O4 nanocrystals in thermal solvent of paraffin

In the atmosphere of N₂, low cost paraffin slices were refined and then successfully utilized as a solvent instead of the expensive high-carbon alkanes or alkenes like 1-octadecene to synthesize Zn_0.5Fe_2.5O₄ nanocrystals at 320 °C. In the experiments, the precursor solutions of ferric and zinc oleates were stoichiometrically prepared and injected by two-step operations into the hot solvent, together with controlled amounts of ethanol to tailor their thermal decomposition performances. The synthesized Zn_0.5Fe_2.5O₄ nanocrystals were characterized by XRD and FESEM, having uniform morphology and a quasi-monodisperse size distribution with a mean value 25 nm and a standard deviation of ±12.3%. The formation and structural characteristics of Zn_0.5Fe_2.5O₄ nanocrystals are attributed to the catalysing function of ethanol and the effective separation of nucleation and growth of nanocrystals via the two-step injections of reactive precursors.     

Subsolidus phase relationships in the system ZnO–Li2O–WO3

The subsolidus phase relationships of the system ZnO–Li₂O–WO₃ have been investigated by X-ray diffraction (XRD) analyses. There are one ternary compound, five binary compounds and eight 3-phase regions in this system. The new ternary compound Li₂Zn₂W₂O₉ was found by the powder diffraction pattern. The corresponding crystal structure of this compound was refined by Rietveld profile fitting method. It belongs to a trigonal system with space group and lattice constants are a = 5.1438(2) Å, c = 14.1052(3) Å, and its thermal property was studied.     

Electrical resistivity, oxidation resistivity and hardness of single crystal compounds in the Er–Rh–B system

Single crystals of ternary borides ErRh₃B (cubic,Pm3m), ErRh₃B₂ (monoclinic, C2/m) and ErRh₄B₄ (tetragonal, P4₂/nmc) have been grown from copper solution by slow cooling method. The electrical resistivity, oxidation resistivity and Vickers microhardness were studied. The electrical resistivities at room temperature of the (100) face of ErRh₃B, (001) face of ErRh₃B₂ and (100) face of ErRh₄B₄ are 25.6 μΩ·cm, 50.0 μΩ·cm and 106.8 μΩ·cm, respectively. According to thermogravimetric and differential thermal analyses, the oxidation of ErRh₃B, ErRh₃B₂ and ErRh₄B₄ start at 1030°C, 373°C and 690°C, respectively. The weight gain of the same compounds after heating in air up to 1200°C is 0.7%, 15.44% and 5.4%, respectively. The values of the Vickers microhardness for the (100) face of ErRh₃B, the (100) face of ErRh₃B₂ and the (110) face of ErRh₄B₄ are 4.8–5.0 GPa, 10.4–10.9 GPa and 10.9–11.3 GPa, respectively. The effect of boron content and crystal structure of each compound on the electrical resistivity, oxidation resistivity and Vickers microhardness are discussed.     

A novel proton conducting Ba0.95K0.05Ce0.6Zr0.2Gd0.16Zn0.04O3−δ for SOFC

A new proton conducting Ba_0.95K_0.05Ce_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ electrolyte membrane was prepared on NiO-based anode support by suspension spray followed by a co-sintering at 1400 °C for 4 h. Chemical stability test shows that this new proton conductor displays adequate chemical stability against CO₂ at intermediate temperatures. The conductivity of Ba_0.95K_0.05Ce_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ in humidified H₂ is about 50% higher than that of BaCe_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ from 500 to 800 °C. With La_0.8Sr_0.2MnO_3−δ cathode, fuel cell with Ba_0.95K_0.05Ce_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ electrolyte shows 1.02 V of OCV and 354 mW/cm² of maximum power density at 700 °C, respectively. And the cell performance did not degrade after running at least for 10 h.     

Phase relations and flux research for zinc oxide crystal growth in the ZnO–K2O–P2O5 system

The subsolidus phase relations of the ternary system ZnO–K₂O–P₂O₅ were investigated by means of X-ray diffraction (XRD). There are 7 binary compounds, 6 ternary compounds and 20 three-phase regions in this system. The phase diagram of the pseudo-binary system KZn₄(PO₄)₃–ZnO was also investigated by means of XRD and differential thermal analysis (DTA) methods. KZn₄(PO₄)₃–ZnO is a eutectic system with eutectic temperature about 952 °C and eutectic point at about 2 mol% ZnO. Only narrow composition range in the KZn₄(PO₄)₃–ZnO system is suitable for the growth of ZnO crystals.     

Synthesis of a NiFe2O4 catalyst for the preferential oxidation of carbon monoxide (PROX)

The aim of this work was to study the NiFe₂O₄ spinel catalyst obtained by combustion reaction in the preferential oxidation of carbon monoxide reaction to conversion reactants H₂, CO and O₂ and to conversion products CH₄, H₂O and CO₂. The powders were prepared according to propellants chemical concept and characterized by XRD, TEM and catalytic tests. The XRD pattern shows the characteristic peaks of the spinel phase. The particle size calculated by TEM was 10.7 nm. The catalyst proved to be more selective to reagents for conversion into O₂ (89.5%) at 350 °C.     

Sinterability and dielectric properties of Ba0.55Sr0.4Ca0.05TiO3-CaTiSiO5-Mg2TiO4 composite ceramics

The composite ceramics of Ba_0.55Sr_0.4Ca_0.05TiO₃-CaTiSiO₅-Mg₂TiO₄ (BSCT-CTS-MT) were prepared by the conventional solid-state route. The sintering performance, phase structures, morphologies, and dielectric properties of the composite ceramics were investigated. The BSCT-CTS-MT ceramics were sintered at 1100 °C and possessed dense microstructure. The dielectric constant was tailored from 1196 to 141 as the amount of Mg₂TiO₄ increased from 0 to 50 wt%. The dielectric constant and dielectric loss of 40 wt% Ba_0.55Sr_0.4Ca_0.05TiO₃-10 wt% CaTiSiO₅-50 wt% Mg₂TiO₄ was 141 and 0.0020, respectively, and the tunability was 8.64% under a DC electric field of 8.0 kV/cm. The Curie peaks were broadened and depressed after the addition of CaTiSiO₅. The optimistic dielectric properties made it a promising candidate for the application of tunable capacitors and phase shifters.