Low Temperature Synthesis and Characterization of AlScMo3O12

Recent interest in low and negative thermal expansion materials has led to significant research on compounds that exhibit this property, much of which has targeted the A₂M₃O₁₂ family (A = trivalent cation, M = Mo, W). The expansion and phase transition behavior in this family can be tuned through the choice of the metals incorporated into the structure. An undesired phase transition to a monoclinic structure with large positive expansion can be suppressed in some solid solutions by substituting the A-site by a mixture of two cations. One such material, AlScMo₃O₁₂, was successfully synthesized using non-hydrolytic sol-gel chemistry. Depending on the reaction conditions, phase separation into Al₂Mo₃O₁₂ and Sc₂Mo₃O₁₂ or single-phase AlScMo₃O₁₂ could be obtained. Optimized conditions for the reproducible synthesis of stoichiometric, homogeneous AlScMo₃O₁₂ were established. High resolution synchrotron diffraction experiments were carried out to confirm whether samples were homogeneous and to estimate the Al:Sc ratio through Rietveld refinement and Vegard’s law. Single-phase samples were found to adopt the orthorhombic Sc₂W₃O₁₂ structure at 100 to 460 K. In contrast to all previously-reported A₂M₃O₁₂ compositions, AlScMo₃O₁₂ exhibited positive thermal expansion along all unit cell axes instead of contraction along one or two axes, with expansion coefficients (200–460 K) of α_a = 1.7 × 10⁻⁶ K⁻¹, α_b = 6.2 × 10⁻⁶ K⁻¹, α_c = 2.9 × 10⁻⁶ K⁻¹ and α_V = 10.8 × 10⁻⁶ K⁻¹, respectively.     

Al-Doped SrMoO3 Perovskites as Promising Anode Materials in Solid Oxide Fuel Cells

Two perovskite materials with SrMo_1−xAl_xO_3−δ (x = 0.1, 0.2) compositions have been synthesized by reduction from the corresponding scheelite phases, with SrMo_1−xAl_xO_4−δ stoichiometry; the pertinent characterization shows that the defective perovskites can be used as anode materials in solid oxide fuel cells, providing maximum output power densities of 633 mW/cm² for x = 0.2. To correlate structure and properties, a neutron powder diffraction investigation was carried out for both perovskite and scheelite phases. Both perovskites are cubic, defined in the Pm-3m space group, displaying a random distribution of Mo and Al cations over the 1a sites of the structure. The introduction of Al at Mo positions produced conspicuous amounts of oxygen vacancies in the perovskite, detected by neutrons. This is essential to induce ionic diffusion, providing a mixed ionic and electronic conduction (MIEC), since in MIEC electrodes, charge carriers are combined in one single phase and the ionic conductivity can be one order of magnitude higher than in a conventional material. The thermal expansion coefficients of the reduced and oxidized samples demonstrated that these materials perfectly match with the La_0.8Sr_0.2Ga_0.83Mg_0.17O_3−δ electrolyte, La_0.4Ce_0.6O_2−δ buffer layer and other components of the cell. Scanning electron microscopy after the test in a real solid oxide fuel cell showed a very dense electrolyte and porous electrodes, essential requirements for this type of fuel. SrMo_1−xAl_xO_3−δ perovskites are, thus, a good replacement of conventional biphasic cermet anodes in solid oxide fuel cells.     

An A- and B-Site Substitutional Study of SrFeO3−δ Perovskites for Solar Thermochemical Air Separation

An A‑ and B‑site substitutional study of SrFeO_3−δ perovskites (A’_xA_1−xB’_yB_1−yO_3−δ, where A = Sr and B = Fe) was performed for a two‑step solar thermochemical air separation cycle. The cycle steps encompass (1) the thermal reduction of A’_xSr_1−xB’_yFe_1−yO_3−δ driven by concentrated solar irradiation and (2) the oxidation of A’_xSr_1−xB’_yFe_1−yO_3−δ in air to remove O₂, leaving N₂. The oxidized A’_xSr_1−xB’_yFe_1−yO_3−δ is recycled back to the first step to complete the cycle, resulting in the separation of N₂ from air and concentrated solar irradiation. A-site substitution fractions between 0 ≤ x ≤ 0.2 were examined for A’ = Ba, Ca, and La. B-site substitution fractions between 0 ≤ y ≤ 0.2 were examined for B’ = Cr, Cu, Co, and Mn. Samples were prepared with a modified Pechini method and characterized with X-ray diffractometry. The mass changes and deviations from stoichiometry were evaluated with thermogravimetry in three screenings with temperature- and O₂ pressure-swings between 573 and 1473 K and 20% O₂/Ar and 100% Ar at 1 bar, respectively. A’ = Ba or La and B’ = Co resulted in the most improved redox capacities amongst temperature- and O₂ pressure-swing experiments.     

Crystal Structure and Concentration-Driven Phase Transitions in Lu(1−x)ScxFeO3 (0 ≤ x ≤ 1) Prepared by the Sol–Gel Method

The structural state and crystal structure of Lu_(1−x)Sc_xFeO₃ (0 ≤ x ≤ 1) compounds prepared by a chemical route based on a modified sol–gel method were investigated using X-ray diffraction, Raman spectroscopy, as well as scanning electron microscopy. It was observed that chemical doping with Sc ions led to a structural phase transition from the orthorhombic structure to the hexagonal structure via a wide two-phase concentration region of 0.1 < x < 0.45. An increase in scandium content above 80 mole% led to the stabilization of the non-perovskite bixbyite phase specific for the compound ScFeO₃. The concentration stability of the different structural phases, as well as grain morphology, were studied depending on the chemical composition and synthesis conditions. Based on the data obtained for the analyzed samples, a composition-dependent phase diagram was constructed.     

Metastable Materials Accessed under Moderate Pressure Conditions (P ≤ 3.5 GPa) in a Piston-Cylinder Press

In this review, we describe different families of metastable materials, some of them with relevant technological applications, which can be stabilized at moderate pressures 2–3.5 GPa in a piston-cylinder press. The synthesis of some of these systems had been previously reported under higher hydrostatic pressures (6–10 GPa), but can be accessed under milder conditions in combination with reactive precursors prepared by soft-chemistry techniques. These systems include perovskites with transition metals in unusual oxidation states (e.g., RNiO₃ with Ni³⁺, R = rare earths); double perovskites such as RCu₃Mn₄O₁₂ with Jahn–Teller Cu²⁺ ions at A sites, pyrochlores derived from Tl₂Mn₂O₇ with colossal magnetoresistance, pnictide skutterudites M_xCo₄Sb₁₂ (M = La, Yb, Ce, Sr, K) with thermoelectric properties, or metal hydrides Mg₂MH_x (M = Fe, Co, Ni) and AMgH₃ (A: alkali metals) with applications in hydrogen storage. The availability of substantial amounts of sample (0.5–1.5 g) allows a complete characterization of the properties of interest, including magnetic, transport, thermoelectric properties and so on, and the structural characterization by neutron or synchrotron X-ray diffraction techniques.     

Low-Temperature Rapid Sintering of Dense Cubic Phase ZrW2−xMoxO8 Ceramics by Spark Plasma Sintering and Evaluation of Its Thermal Properties

In this study, we report a low-temperature approach involving a combination of a sol–gel hydrothermal method and spark plasma sintering (SPS) for the fabrication of cubic phase ZrW_2−xMo_xO₈ (0.00 ≤ x ≤ 2.00) bulk ceramics. The cubic-ZrW_2−xMo_xO₈ (0.00 ≤ x ≤ 1.50) bulk ceramics were successfully synthesized within a temperature range of 623–923 K in a very short amount of time (6–7 min), which is several hundred degrees lower than the typical solid-state approach. Meanwhile, scanning electron microscopy and density measurements revealed that the cubic-ZrW_2−xMo_xO₈ (0.00 ≤ x ≤ 1.50) bulk ceramics were densified to more than 90%. X-ray diffraction (XRD) results revealed that the cubic phase ZrW_2−xMo_xO₈ (0.00 ≤ x ≤ 1.5) bulk ceramics, as well as the sol–gel-hydrothermally synthesized ZrW_2−xMo_xO₇(OH)₂·2H₂O precursors correspond to their respective pure single phases. The bulk ceramics demonstrated negative thermal expansion characteristics, and the coefficients of negative thermal expansion were shown to be tunable in cubic-ZrW_2−xMo_xO₈ bulk ceramics with respect to x value and sintering temperature. The cubic-ZrW_2−xMo_xO₈ solid solution can thus have potential applications in electronic devices such as heat sinks that require regulation of thermal expansion.     

Structural,Magnetic, Dielectric and Piezoelectric Properties of Multiferroic PbTi1−xFexO3−δ Ceramics

PbTi_1−xFe_xO_3−δ (x = 0, 0.3, 0.5, and 0.7) ceramics were prepared using the classical solid-state reaction method. The investigated system presented properties that were derived from composition, microstructure, and oxygen deficiency. The phase investigations indicated that all of the samples were well crystallized, and the formation of a cubic structure with small traces of impurities was promoted, in addition to a tetragonal structure, as Fe³⁺ concentration increased. The scanning electron microscopy (SEM) images for PbTi_1−xFe_xO_3−δ ceramics revealed microstructures that were inhomogeneous with an intergranular porosity. The dielectric permittivity increased systematically with Fe³⁺ concentration, increasing up to x = 0.7. A complex impedance analysis revealed the presence of multiple semicircles in the spectra, demonstrating a local electrical inhomogeneity due the different microstructures and amounts of oxygen vacancies distributed within the sample. The increase of the substitution with Fe³⁺ ions onto Ti⁴⁺ sites led to the improvement of the magnetic properties due to the gradual increase in the interactions between Fe³⁺ ions, which were mediated by the presence of oxygen vacancies. The PbTi_1−xFe_xO_3−δ became a multifunctional system with reasonable dielectric, piezoelectric, and magnetic characteristics, making it suitable for application in magnetoelectric devices.     

High-Temperature Chemical Stability of Cr(III) Oxide Refractories in the Presence of Calcium Aluminate Cement

Al₂O₃-CaO-Cr₂O₃ castables are used in various furnaces due to excellent corrosion resistance and sufficient early strength, but toxic Cr(VI) generation during service remains a concern. Here, we investigated the relative reactivity of analogous Cr(III) phases such as Cr₂O₃, (Al_1−xCr_x)₂O₃ and in situ Cr(III) solid solution with the calcium aluminate cement under an oxidizing atmosphere at various temperatures. The aim is to comprehend the relative Cr(VI) generation in the low-cement castables (Al₂O₃-CaO-Cr₂O₃-O₂ system) and achieve an environment-friendly application. The solid-state reactions and Cr(VI) formation were investigated using powder XRD, SEM, and leaching tests. Compared to Cr₂O₃, the stability of (Al_1−xCr_x)₂O₃ against CAC was much higher, which improved gradually with the concentration of Al₂O₃ in (Al_1−xCr_x)₂O₃. The substitution of Cr₂O₃ with (Al_1−xCr_x)₂O₃ in the Al₂O₃-CaO-Cr₂O₃ castables could completely inhibit the formation of Cr(VI) compound CaCrO₄ at 500–1100 °C and could drastically suppress Ca₄Al₆CrO₁₆ generation at 900 to 1300 °C. The Cr(VI) reduction amounting up to 98.1% could be achieved by replacing Cr₂O₃ with (Al_1−xCr_x)₂O₃ solid solution. However, in situ stabilized Cr(III) phases as a mixture of (Al_1−xCr_x)₂O₃ and Ca(Al_12−xCr_x)O₁₉ solid solution hardly reveal any reoxidation. Moreover, the CA₆ was much more stable than CA and CA₂, and it did not participate in any chemical reaction with (Al_1−xCr_x)₂O₃ solid solution.     

Electrical and Structural Properties of Li1.3Al0.3Ti1.7(PO4)3—Based Ceramics Prepared with the Addition of Li4SiO4

The currently studied materials considered as potential candidates to be solid electrolytes for Li-ion batteries usually suffer from low total ionic conductivity. One of them, the NASICON-type ceramic of the chemical formula Li_1.3Al_0.3Ti_1.7(PO₄)₃, seems to be an appropriate material for the modification of its electrical properties due to its high bulk ionic conductivity of the order of 10⁻³ S∙cm⁻¹. For this purpose, we propose an approach concerning modifying the grain boundary composition towards the higher conducting one. To achieve this goal, Li₄SiO₄ was selected and added to the LATP base matrix to support Li⁺ diffusion between the grains. The properties of the Li_1.3Al_0.3Ti_1.7(PO₄)₃−xLi₄SiO₄ (0.02 ≤ x ≤ 0.1) system were studied by means of high-temperature X-ray diffractometry (HTXRD); ⁶Li, ²⁷Al, ²⁹Si, and ³¹P magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR); thermogravimetry (TG); scanning electron microscopy (SEM); and impedance spectroscopy (IS) techniques. Referring to the experimental results, the Li₄SiO₄ additive material leads to the improvement of the electrical properties and the value of the total ionic conductivity exceeds 10⁻⁴ S∙cm⁻¹ in most studied cases. The factors affecting the enhancement of the total ionic conductivity are discussed. The highest value of σ_tot = 1.4 × 10⁻⁴ S∙cm⁻¹ has been obtained for LATP–0.1LSO material sintered at 1000 °C for 6 h.     

Formation of Solid Solutions and Physicochemical Properties of the High-Entropy Ln1−xSrx(Co,Cr,Fe,Mn,Ni)O3−δ (Ln = La,Pr, Nd,Sm or Gd) Perovskites

Phase composition, crystal structure, and selected physicochemical properties of the high entropy Ln(Co,Cr,Fe,Mn,Ni)O_3−δ (Ln = La, Pr, Gd, Nd, Sm) perovskites, as well as the possibility of Sr doping in Ln_1−xSr_x(Co,Cr,Fe,Mn,Ni)O_3−δ series, are reported is this work. With the use of the Pechini method, all undoped compositions are successfully synthesized. The samples exhibit distorted, orthorhombic or rhombohedral crystal structure, and a linear correlation is observed between the ionic radius of Ln and the value of the quasi-cubic perovskite lattice constant. The oxides show moderate thermal expansion, with a lack of visible contribution from the chemical expansion effect. Temperature-dependent values of the total electrical conductivity are reported, and the observed behavior appears distinctive from that of non-high entropy transition metal-based perovskites, beyond the expectations based on the rule-of-mixtures. In terms of formation of solid solutions in Sr-doped Ln_1−xSr_x(Co,Cr,Fe,Mn,Ni)O_3−δ materials, the results indicate a strong influence of the Ln radius, and while for La-based series the Sr solubility limit is at the level of x_max = 0.3, for the smaller Pr it is equal to just 0.1. In the case of Nd-, Sm- and Gd-based materials, even for the x_Sr = 0.1, the formation of secondary phases is observed on the SEM + EDS images.     

Effect of Sintering Process on Ionic Conductivity of Li7-xLa3Zr2-xNbxO12 (x = 0, 0.2, 0.4, 0.6) Solid Electrolytes

Garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is considered as a promising solid electrolyte. Nb-doped LLZO ceramics exhibit significantly improved ion conductivity. However, how to prepare the Nb-doped LLZO ceramics in a simple and economical way, meanwhile to investigate the relationship between process conditions and properties in Li_7-xLa₃Zr_2-xNb_xO₁₂ ceramics, is particularly important. In this study, Li_7-xLa₃Zr_2-xNb_xO₁₂ (LLZN_xO, x = 0, 0.2, 0.4, 0.6) ceramics were prepared by conventional solid-state reaction. The effect of sintering process on the structure, microstructure, and ionic conductivity of LLZN_xO (x = 0, 0.2, 0.4, 0.6) ceramics was investigated. Due to the more contractive Nb-O bonds in LLZN_xO ceramics, the cubic structures are much easier to form and stabilize, which could induce the decreased preparation time. High-performance garnet LLZN_xO ceramics can be obtained by optimizing the sintering process with lower calcining temperature and shorter holding time. The garnet samples with x = 0.4 calcined at 850 °C for 10 h and sintered at 1250 °C for 4 h exhibit the highest ionic conductivity of 3.86 × 10⁻⁴ S·cm⁻¹ at room temperature and an activation energy of 0.32 eV, which can be correlated to the highest relative density of 96.1%, and good crystallinity of the grains.     

The Gd2−xMgxZr2O7−x/2 Solid Solution: Ionic Conductivity and Chemical Stability in the Melt of LiCl-Li2O

Materials with pyrochlore structure A₂B₂O₇ have attracted considerable attention owing to their various applications as catalysts, sensors, electrolytes, electrodes, and magnets due to the unique crystal structure and thermal stability. At the same time, the possibility of using such materials for electrochemical applications in salt melts has not been studied. This paper presents the new results of obtaining high-density Mg²⁺-doped ceramics based on Gd₂Zr₂O₇ with pyrochlore structure and comprehensive investigation of the electrical properties and chemical stability in a lithium chloride melt with additives of various concentrations of lithium oxide, performed for the first time. The solid solution of Gd_2−xMg_xZr₂O_7−x/2 (0 ≤ x ≤ 0.10) with the pyrochlore structure was obtained by mechanically milling stoichiometric mixtures of the corresponding oxides, followed by annealing at 1500 °C. The lattice parameter changed non-linearly as a result of different mechanisms of Mg²⁺ incorporation into the Gd₂Zr₂O₇ structure. At low dopant concentrations (x ≤ 0.03) some interstitial positions can be substituted by Mg²⁺, with further increasing Mg²⁺-content, the decrease in the lattice parameter occurred due to the substitution of host-ion sites with smaller dopant-ion. High-density ceramics 99% was prepared at T = 1500 °C. According to the results of the measurements of electrical conductivity as a function of oxygen partial pressure, all investigated samples were characterized by the dominant ionic type of conductivity over a wide range of pO₂ (1 × 10^–18 ≤ pO₂ ≤ 0.21 atm) and T < 800 °C. The sample with the composition of x = 0.03 had the highest oxygen-ion conductivity (10⁻³ S·cm⁻¹ at 600 °C). The investigation of chemical stability of ceramics in the melt of LiCl with 2.5 mas.% Li₂O showed that the sample did not react with the melt during the exposed time of one week at the temperature of 650 °C. This result makes it possible to use these materials as oxygen activity sensors in halide melts.     

Sr and Zr Co-Doped CaCu3Ti4O12 Ceramics with Improved Dielectric Properties

The dielectric constant of CCTO materials can be as high as 10⁴, which makes it suitable for use in electronic devices but the high dielectric loss limits its application. In this paper, a series of Sr and Zr co-doped CCTO ceramics having the formula Ca_0.8Sr_0.2Cu₃Ti_4−xZr_xO₁₂ (x = 0.1, 0.2, 0.3, 0.4) were obtained via a solid-state reaction technique. We force the effect of the Zr content on the phase composition, microstructure, cationic valence states, impedance, and dielectric properties of the as-prepared ceramics to reduce dielectric loss. The results demonstrate that Sr and Zr co-doping increases dielectric constant and reduces dielectric loss simultaneously, and the maximum dielectric constant (1.87 × 10⁵, 1 Hz) and minimum dielectric loss (0.43, 10² Hz) are obtained when x = 0.3. Mixed Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺ valence states are observed to coexist in the co-doped material lattices, which promote dipole polarization, and thereby increase the dielectric constant of the ceramics. The dielectric properties of the materials are analyzed according to the internal barrier layer capacitance model, which elucidates the contributions of the grains and grain boundaries to dielectric performance. The maximum grain boundary resistance (3.7 × 10⁵ Ω) is obtained for x = 0.3, which contributes toward the minimum dielectric loss (0.43) obtained for this ceramic at a frequency less than 1 kHz. The average grain sizes of the samples decrease with increasing Zr content, which is the primary factor increasing the grain boundary resistance of the co-doped ceramics.     

Linking the Electrical Conductivity and Non-Stoichiometry of Thin Film Ce1−xZrxO2−δ by a Resonant Nanobalance Approach

Bulk ceria-zirconia solid solutions (Ce_1−xZr_xO_2−δ, CZO) are highly suited for application as oxygen storage materials in automotive three-way catalytic converters (TWC) due to the high levels of achievable oxygen non-stoichiometry δ. In thin film CZO, the oxygen storage properties are expected to be further enhanced. The present study addresses this aspect. CZO thin films with 0 ≤ x ≤ 1 were investigated. A unique nano-thermogravimetric method for thin films that is based on the resonant nanobalance approach for high-temperature characterization of oxygen non-stoichiometry in CZO was implemented. The high-temperature electrical conductivity and the non-stoichiometry δ of CZO were measured under oxygen partial pressures pO₂ in the range of 10⁻²⁴–0.2 bar. Markedly enhanced reducibility and electronic conductivity of CeO₂-ZrO₂ as compared to CeO_2−δ and ZrO₂ were observed. A comparison of temperature- and pO₂-dependences of the non-stoichiometry of thin films with literature data for bulk Ce_1−xZr_xO_2−δ shows enhanced reducibility in the former. The maximum conductivity was found for Ce_0.8Zr_0.2O_2−δ, whereas Ce_0.5Zr_0.5O_2-δ showed the highest non-stoichiometry, yielding δ = 0.16 at 900 °C and pO₂ of 10⁻¹⁴ bar. The defect interactions in Ce_1−xZr_xO_2−δ are analyzed in the framework of defect models for ceria and zirconia.     

The Dielectric Constant of Ba6−3x(Sm1−yNdy)8+2xTi18O54 (x = 2/3) Ceramics for Microwave Communication by Linear Regression Analysis

The electronics related to the fifth generation mobile communication technology (5G) are projected to possess significant market potential. High dielectric constant microwave ceramics used as filters and resonators in 5G have thus attracted great attention. The Ba_6−3x(Sm_1−yNd_y)_8+2xTi₁₈O₅₄ (x = 2/3) ceramic system has aroused people’s interest due to its underlying excellent microwave dielectric properties. In this paper, the relationships between the dielectric constant, Nd-doped content, sintering temperature and the density of Ba_6−3x(Sm_1−yNd_y)_8+2xTi₁₈O₅₄ (x = 2/3) ceramics were studied. The linear regression equation was established by statistical product and service solution (SPSS) data analysis software, and the factors affecting the dielectric constant have been analyzed by using the enter and stepwise methods, respectively. It is found that the model established by the stepwise method is practically significant with Y = −71.168 + 6.946x₁ + 25.799x₃, where Y, x₁ and x₃ represent the dielectric constant, Nd content and the density, respectively. According to this model, the influence of density on the dielectric constant is greater than that of Nd doping concentration. We bring the linear regression analysis method into the research field of microwave dielectric ceramics, hoping to provide an instructive for the optimization of ceramic technology.     

Lattice-Matched AlInN/GaN/AlGaN/GaN Heterostructured-Double-Channel Metal-Oxide-Semiconductor High-Electron Mobility Transistors with Multiple-Mesa-Fin-Channel Array

Multiple-mesa-fin-channel array patterned by a laser interference photolithography system and gallium oxide (Ga₂O₃) gate oxide layer deposited by a vapor cooling condensation system were employed in double-channel Al_0.83In_0.17N/GaN/Al_0.18Ga_0.82N/GaN heterostructured-metal-oxide-semiconductors (MOSHEMTs). The double-channel was constructed by the polarized Al_0.18Ga_0.82N/GaN channel 1 and band discontinued lattice-matched Al_0.83In_0.17N/GaN channel 2. Because of the superior gate control capability, the generally induced double-hump transconductance characteristics of double-channel MOSHEMTs were not obtained in the devices. The superior gate control capability was contributed by the side-wall electrical field modulation in the fin-channel. Owing to the high-insulating Ga₂O₃ gate oxide layer and the high-quality interface between the Ga₂O₃ and GaN layers, low noise power density of 8.7 × 10⁻¹⁴ Hz⁻¹ and low Hooge’s coefficient of 6.25 × 10⁻⁶ of flicker noise were obtained. Furthermore, the devices had a unit gain cutoff frequency of 6.5 GHz and a maximal oscillation frequency of 12.6 GHz.     

New Solid Solution and Phase Equilibria in the Subsolidus Area of the Three-Component CuO–V2O5–Ta2O5 Oxide System

The results of the study of the three-component system of CuO–V₂O₅–Ta₂O₅ oxides showed, inter alia, that in the air atmosphere in one of its cross-sections, i.e., in the CuV₂O₆–CuTa₂O₆ system, a new substitutional solid solution with the general formula CuTa_2−xV_xO₆ and homogeneity range for x > 0.0 and x ≤ 0.3 is formed. The influence of the degree of incorporation of V⁵⁺ ions into the CuTa₂O₆ crystal lattice in place of Ta⁵⁺ ions on the unit cell volume, thermal stability and IR spectra of the obtained solid solution was determined. Moreover, the value of the band gap energy of the CuTa_2−xV_xO₆ solid solution was estimated in the range of 0.0 < x ≤ 0.3, and on this basis, the new solid solution was classified as a semiconductor. On the basis of the research results, the studied system of CuO–V₂O₅–Ta₂O₅ oxides was also divided into 12 subsidiary subsystems.     

Hf1−xSixO2 Nanocomposite Coatings Prepared by Ion-Assisted Co-Evaporation Process for Low-Loss and High-LIDT Optics

Hf_1−xSi_xO₂ nanocomposites with different SiO₂ doping ratios were synthesized using an ion-assisted co-evaporation process to achieve dense amorphous Hf_1−xSi_xO₂ coatings with low loss and a high laser-induced damage threshold (LIDT). The results showed that the Hf_1−xSi_xO₂ nanocomposites (x ≥ 0.20) exhibited excellent comprehensive performance with a wide band gap and a dense amorphous microstructure. High-temperature annealing was carried out to ensure better stoichiometry and lower absorption. Precipitation and regrowth of HfO₂ grains were observed from 400 °C to 600 °C during annealing of the Hf_0.80Si_0.20O₂ nanocomposites, resulting in excessive surface roughness. A phenomenological model was proposed to explain the phenomenon. The Hf_1−xSi_xO₂ nanocomposites (x = 0.3 and 0.4) maintained a dense amorphous structure with low absorption after annealing. Finally, a 1064-nm Hf_0.70Si_0.30O₂/SiO₂ high-performance reflector was prepared and achieved low optical loss (15.1 ppm) and a high LIDT (67 J/cm²).     

Solid-State-Activated Sintering of ZnAl2O4 Ceramics Containing Cu3Nb2O8 with Superior Dielectric and Thermal Properties

Low-temperature co-fired ceramics (LTCCs) are dielectric materials that can be co-fired with Ag or Cu; however, conventional LTCC materials are mostly poorly thermally conductive, which is problematic and requires improvement. We focused on ZnAl₂O₄ (gahnite) as a base material. With its high thermal conductivity (~59 W·m⁻¹·K⁻¹ reported for 0.83ZnAl₂O₄–0.17TiO₂), ZnAl₂O₄ is potentially more thermally conductive than Al₂O₃ (alumina); however, it sinters densely at a moderate temperature (~1500 °C). The addition of only 4 wt.% of Cu₃Nb₂O₈ significantly lowered the sintering temperature of ZnAl₂O₄ to 910 °C, which is lower than the melting point of silver (961 °C). The sample fired at 960 °C for 384 h exhibited a relative permittivity (ε_r) of 9.2, a quality factor by resonant frequency (Q × f) value of 105,000 GHz, and a temperature coefficient of the resonant frequency (τ_f) of −56 ppm·K⁻¹. The sample exhibited a thermal conductivity of 10.1 W·m⁻¹·K⁻¹, which exceeds that of conventional LTCCs (~2–7 W·m⁻¹·K⁻¹); hence, it is a superior LTCC candidate. In addition, a mixed powder of the Cu₃Nb₂O₈ additive and ZnAl₂O₄ has a melting temperature that is not significantly different from that (~970 °C) of the pristine Cu₃Nb₂O₈ additive. The sample appears to densify in the solid state through a solid-state-activated sintering mechanism.     

Layered Perovskites BaM2In2O7 (M = La,Nd): From the Structure to the Ionic (O2−, H+) Conductivity

The design of new oxide compounds that can be used as oxygen- or proton-conducting electrolytes for solid oxide fuel cells is actively in progress. Despite the intensive research activities regarding electrolytes with perovskite/fluorite structures, the search for other structural alternatives is of paramount importance. In this study we focus on a novel material with significantly improved properties for the electrochemical purposes. The two-layered BaNd₂In₂O₇ perovskite with a Ruddlesden–Popper structure was investigated as a protonic conductor for the first time. In detail, its local structure, water uptake, and the ionic (O²⁻, H⁺) conductivity were comprehensively studied. The nature of rare-earth elements (M = La, Nd) in the structure of BaM₂In₂O₇ on the structural and transport properties was revealed. The presented analysis showed that the composition of BaNd₂In₂O₇ is nearly pure proton conductor below 350 °C. This work opens up a new way in the design of protonic conductors with double-layered perovskite structure.