Fabrication and characterization of La2O3–Fe2O3–Bi2O3 nanopowders: Effects of La2O3 addition on structure,optical, and radiation-absorption properties

In this study, we fabricated and characterized six new nanopowders representing variations of La₂O₃–Fe₂O₃–Bi₂O₃, i.e., 100Bi₂O₃, 30Fe₂O₃–70Bi₂O₃, 3La₂O₃–27Fe₂O₃–70Bi₂O₃, 7La₂O₃–23Fe₂O₃–70Bi₂O₃, 10La₂O₃–20Fe₂O₃–70Bi₂O₃, and 20La₂O₃–10Fe₂O₃–70Bi₂O₃ (represented by 100B, 30F70B, 3L27F70B, 10L20F70B, and 20L10F70B, respectively). These nanopowders were prepared by the microwave-assisted hydrothermal synthesis method. Saponin extract from soapnuts was used as the nanoparticle capping agent. The structural, optical, and gamma radiation characteristics were measured, calculated, and analysed, respectively. The chemical structures of the nanocomposites influenced their optical and radiation shielding characteristics. The optical bandgaps of the 100B, 30F70B, 3L27F70B, 7L23F70B, 10L20F70B, and 20L10F70B nanopowders were 3.16, 3.13, 3.43, 3.45, 3.46, and 3.58 eV, respectively. The ranges of the mass attenuation coefficients of the nanopowders were computed, using XCOM, to be 0.0412–5.1624, 0.0401–4.5406, 0.0401–4.5285, 0.0401–4.5129, 0.0401–0.5015, and 0.0400–4.4156 cm²/g, respectively, and the ranges of mass energy absorption coefficients were found to be 0.0232–1.7525, 0.0228–1.5484, 0.0228–1.5598, 0.0288–1.5746, 0.0228–1.5853, and 0.0227–1.6192 cm²/g, respectively, for photon energies in the range of 0.1–10 MeV. The order of the dose rate trend was as follows: 30F70B < L27F70B < 7L23F70B < 10L20F70B < 20L10F70B. Analysis of the photon interaction parameters showed that the synthesized nanopowders could function well as fillers in radiation-shielding matrices.     

The influence of microstructure and phase composition of glass ceramics in the VO2–V2O5–P2O5–Cu2O–SnO2 system on the electrical properties related to the metal–semiconductor phase transition

Phase composition, microstructure and electrical conductivity of glass ceramics in the VO₂–V₂O₅–P₂O₅–SnO₂ and VO₂–V₂O₅–P₂O₅–Cu₂O–SnO₂ systems have been studied. Only crystalline phases VO₂, SnO₂ and vanadium phosphate glass of the V₂O₅–P₂O₅ system have been found in glass ceramic compositions in the VO₂–V₂O₅–P₂O₅–SnO₂ system. Besides the above-mentioned phases, probably the X-ray lines of V₃O₅, V₄O₇, V₅O₉, V₆O₁₁, V₇O₁₃, V₄O₉, V₆O₁₃, V₂O₅, SnO₂, SnO, Sn₂O₃, Sn₃O₄ and CuO phases are observed in the X-ray spectra of glass ceramics in the VO₂–V₂O₅–P₂O₅–Cu₂O–SnO₂ system. According to SEM/EDS data, these phases were observed as submicrometer fine-crystalline inclusions in glass on the surface of VO₂ crystallites and between them. The formation of these phases was caused by the redox processes in the liquid phase during glass ceramics synthesis. The important role of tin oxides possessing high electrical conductivity and vanadium oxides exhibiting a low temperature of metal–semiconductor phase transition in the stabilization of glass ceramics electrical properties related to the phase transition in VO₂ has been established.     

Phase equilibrium in binary La2O3-Dy2O3 and ternary CeO2-La2O3-Dy2O3 systems

Cerium oxide doped with oxides of rare earth elements is a multifunctional material, a wide range of uses which is associated with its unique physicochemical properties. Phase diagrams of multicomponent systems are the physicochemical basis for the creation of new materials with improved characteristics.In this work, phase equilibria in ternary CeO₂–La₂O₃–Dy₂O₃ and binary La₂O₃–Dy₂O₃ systems in the whole concentration range were studied. No new phases have been identified in these systems. An isothermal section of the phase diagram of the CeO₂–La₂O₃–Dy₂O₃ system at a temperature of 1500 °С is constructed. No new phases have been detected in the system. It was found that in the studied ternary system solid solutions are formed on the basis of (F) modification of CeO₂ with structure of fluorite type, monoclinic (B), cubic (C) and hexagonal (A) modifications of Ln₂O₃.In the La₂O₃–Dy₂O₃ binary system (1500–1100 °С) three types of solid solutions are formed: based on hexagonal modification A-La₂O₃, monoclinic modification B-Dy₂O₃ and cubic modification C-Dy₂O₃ separated by two-phase fields (A+B) and (B+C), respectively. The boundaries of the regions of homogeneity of solid solutions based on A-La₂O₃ are determined by compositions containing 35–40, 20–25, 15–20 mol% Dy₂O₃ at 1500, 1250, 1100 °C, respectively. From the obtained data it follows that the solubility of Dy₂O₃ in the hexagonal modification of lanthanum oxide is 39 mol% at 1500 °C, 23 mol. % at 1250 °C and 16 mol% at 1100 °C. The limits of existence of solid solutions based on monoclinic B-modification are determined by compositions containing 30–35, 65–60 (1250 °С), 35–40, 55–60 (1100 °С) 40–45, 70–75 (1500 °C) mol% Dy₂O₃.In the studied system, with a decrease in temperature from 1500° to 1100°C, there is a decrease in the solubility of La₂O₃ in the crystal lattice of cubic solid solutions of C-type from 16 to 10 mol%.     

Influence of TiO2, Cr2O3 and ZrO2 on sintering and machinability of fluorophlogopite glass ceramics

Abstract

The influence of Cr₂O₃, TiO₂ and ZrO₂ on the sintering, crystallisation and machinability of SiO₂–Al₂O₃–MgO–K₂O–B₂O₃–F glasses was investigated. Optimum fluoromica glass ceramic compositions with desirable sintering behaviour and machinability were obtained by addition of titanium and chromium oxides to the base glass. Texture and relative intensity of mica phase I_mica/I_Si were determined by XRD analysis and the particle size distribution of chips was studied by drilling. Microhardness and bending strength were also investigated. The relative intensity of mica phase and microhardness were found to be compatible with the experimental results.     

Effect of Alumina Reactivity on the Densification and Properties of Al2O3–Cr2O3 Refractories

Alumina‐chrome (Al₂O₃–Cr₂O₃) refractories with Al₂O₃:Cr₂O₃ molar ratio 1:1 were synthesized in the temperature range of 1400–1700°C by conventional solid–oxide reaction route. The effect of different aluminas (viz., hydrated and calcined) on the densification, microstructure, and properties of Al₂O₃–Cr₂O₃ refractories was investigated without changing the Cr₂O₃ source. The starting materials were analyzed to determine the chemical composition, mineralogy, density, surface area, and particle size. Sintered materials were characterized in terms of densification, phase assemblage, and mechanical strength at room temperature and at higher temperatures. Microstructural evolution at different sintering temperature was correlated with sintering characteristics. It can be concluded that the Al₂O₃–Cr₂O₃ refractories prepared with hydrated alumina as Al₂O₃ source show better densification and hot mechanical strength than corresponding calcined variety.     

Sintering behavior and microwave dielectric characteristics of BaO–Sm2O3–4TiO2 ceramics with B2O3 and BaB2O4 addition

We studied the low temperature sintering and the reaction in BaO–Sm₂O₃–4TiO₂ ceramics with boron-based additives for the application to microwave dielectric devices. The amount of the boride glasses of B₂O₃ and BaB₂O₄ was varied from 1 to 10 wt.% and the green compacts were sintered in the temperature range of 900–1200 °C for 2 h. When B₂O₃ was added, second phases of Sm₂Ti₂O₇, BaTi(BO₃)₂, Ba₂Ti₉O₂₀, and TiO₂ were formed, while BaB₂O₄ addition resulted in the formation of BaSm₂Ti₄O₁₂ single phase without second phases. On the basis of these results, it is regarded that the B₂O₃ is a reactive glass and the BaB₂O₄ is a non-reactive glass. The second-phase development, sintering behavior and microwave dielectric characteristics of BaO–Sm₂O₃–4TiO₂ ceramics were examined.     

Thermal and optical properties of La2O3–Ga2O3– (Nb2O5 or Ta2O5) ternary glasses

La₂O₃–Ga₂O₃–M₂O₅ (M = Nb or Ta) ternary glasses were fabricated using an aerodynamic levitation technique, and their glass‐forming regions and thermal and optical properties were investigated. Incorporation of adequate amounts of Nb₂O₅ and Ta₂O₅ drastically improved the thermal stabilities of the glasses against crystallization. Optical transmittance measurements revealed that all the glasses were transparent over a wide wavelength range from the ultraviolet to the mid‐infrared. The refractive indices of the glasses increased and the Abbe number decreased upon substituting Ga₂O₃ with Nb₂O₅, and the decrease in the Abbe number was significantly suppressed when Ta₂O₅ was incorporated into the glass. As a result, excellent compatibility between high refractive index and lower wavelength dispersion was realized in La₂O₃–Ga₂O₃–Ta₂O₅ glasses. Analysis based on the single‐oscillator Drude–Voigt model provided more systematical information and revealed that this compatibility was due to an increase in the electron density of the glass.     

Microstructure evolution and cooperative reinforcement mechanisms of Al2O3/Al2O3 joints brazed by low-melting borosilicate glass

The Al₂O₃/SiO₂–B₂O₃–Al₂O₃–Na₂O glass/Al₂O₃ joints reinforced cooperatively by glass matrix and in-situ Al₄B₂O₉ whiskers were obtained via a low-melting borosilicate glass braze. The composition of glass seam transformed from SiO₂–B₂O₃–Na₂O to SiO₂–B₂O₃–Al₂O₃–Na₂O due to continuous diffusion and dissolution of Al₂O₃. An appropriate amount of [AlO₄] units introduced into the glass braze played a vital role in strengthening the glass network structure resulting to considerably improved mechanical strength of the glass seam. Meanwhile, plenty of in-situ Al₄B₂O₉ whiskers growing from the Al₂O₃/glass braze interface to the center of glass seam in various directions generated. Three-dimensional crisscross structures were fabricated at the Al₂O₃/glass braze interface domains, where were enhanced by crack-bridging and pull-out effect of the whiskers. Generally, ascribed to the cooperative reinforcement of the glass matrix in the seam and in-situ Al₄B₂O₉ whiskers at Al₂O₃/glass braze interface domains through reactions of Al₂O₃ and borosilicate glass braze, strength of the as-brazed joints was promoted prominently. The shear strength of the joints reached a maximum of 61 MPa brazed at 1050 °C for 60 min.     

Isothermal phase diagram of CaO–SiO2–Nb2O5-5wt% Fe2O3–TiO2 system at 1200 °C

The lack of thermodynamic data such as the phase diagram of CaO–SiO₂–Nb₂O₅–Fe₂O₃–TiO₂ system has seriously hampered the comprehensive utilization of niobium, titanium and other resources in the Bayan Obo tailing. In this study, phase equilibria of the CaO–SiO₂–Nb₂O₅–Fe₂O₃–TiO₂ system at 1200 °C were investigated using high temperature equilibrium experiment for the first time, and the CaTiO₃–Ca₁₀Nb₂Si₆O₂₇–Ca₂SiO₄–Ca₂Nb₂O₇ solid phase coexistence region was determined. Afterwards, based on the high temperature equilibrium experiments, the liquidus surfaces of the liquid + CaTiO₃ and liquid + SiO₂ equilibrium coexistence regions in CaO–SiO₂–Nb₂O₅-5wt% Fe₂O₃–TiO₂ system at 1200 °C were calculated using mathematical methods of interpolation and fitting. Finally, the 1200 °C isothermal phase diagrams of CaO–SiO₂–Nb₂O₅-5wt%Fe₂O₃–TiO₂ system were plotted. The results of the study can provide theoretical guidance for the enrichment and extraction processes of niobium and titanium resources in the Bayan Obo tailing.     

Thermal Stability,Optical Transmittance,and Refractive Index Dispersion of La2O3–Nb2O5–Al2O3 Glasses

La₂O₃–Nb₂O₅–Al₂O₃ high‐refractive‐index glasses were fabricated by containerless processing, and the glass‐forming region was determined. The thermal stability, density, optical transmittance, and the refractive index dispersion of these glasses were investigated. All the glasses were colorless and transparent in the visible to near infrared (NIR) region and had high refractive index with low wavelength dispersion. Some of these glasses were found to have significantly high glass‐forming ability. These results indicate that the ternary glasses are suitable for optical applications in the visible to NIR region. The effects of the substitution of Al₂O₃ for Nb₂O₅ on optical properties were discussed on the basis of the Drude–Voigt equation. It was suggested that the substitution of Al₂O₃ for Nb₂O₅ increased the molecular density and suppressed a decrease in the refractive index, even when both the average oscillator strength and inherent absorption wavelength decreased in La₂O₃–Nb₂O₅–Al₂O₃ glasses. These results are helpful for designing new optical glasses controlled to have a higher refractive index and lower wavelength dispersion.     

The effect of B2O3, PbO and P2O5 on the sintering and machinability of fluormica glass–ceramics

Sintering, crystallization and machinability behavior of the SiO₂–Al₂O₃–MgO–K₂O–B₂O₃–F glasses were investigated. The optimum fluormica glass–ceramics with desirable sintering behavior and machinability were obtained by addition of PbO and P₂O₅ glass formers. Various parameters, e.g. the morphology of the mica crystal, relative intensity of the mica phase, the particle size distribution of chips obtained by drilling, microhardness, and the strength differences of glass–ceramics before and after drilling (Δσ) were investigated and compared with naked eye experiments.     

Integrated experimental phase equilibria study and thermodynamic modelling of the binary ZnO–Al2O3, ZnO–SiO2, Al2O3–SiO2 and ternary ZnO–Al2O3–SiO2 systems

Phase equilibria of the ZnO–SiO₂, Al₂O₃–SiO₂ and ZnO–Al₂O₃–SiO₂ systems at liquidus were characterized at 1340–1740 °C in air. The ZnO–Al₂O₃ subsolidus phase equilibria were derived from the experiments with the SiO₂- and CaO + SiO₂-containing slags. High-temperature equilibration on silica or platinum substrates, followed by quenching and direct measurement of Zn, Al, Si and Ca concentrations in the phases with the electron probe X-ray microanalysis (EPMA) was used to accurately characterize the system. Special attention was given to zincite phase that was shown to consist of two separate ranges of compositions: round-shaped low-Al zincite (<2 mol.% AlO_1.5) and platy high-Al zincite (4–11 mol.% AlO_1.5). A technique was developed for more accurate measurement of the ZnO solubility in the low-ZnO phases (corundum, mullite, tridymite and cristobalite) surrounded by the ZnO-containing slag, using l-line for Zn instead of K-line, avoiding the interference of secondary X-ray fluorescence. Solubility of ZnO was found to be below 0.03 mol.% in corundum and cristobalite, and below 0.3 mol.% in mullite. Present experimental data were used to obtain a self-consistent set of parameters of the thermodynamic models for all phases in this system using FactSage computer package. The modified quasichemical model with two sublattices (Zn²⁺, Al³⁺, Si⁴⁺) (O^2?) was used for the liquid slag phase; the compound energy formalism was used for the spinel (Zn²⁺,Al³⁺)[Zn²⁺,Al³⁺,Va]₂O^2-₄ and mullite Al³⁺₂(Al³⁺,Si⁴⁺) (O^2?,Va)₅ phases; the Bragg-Williams formalism was used for the zincite (ZnO, Al₂O₃); other solid phases (tridymite and cristobalite SiO₂, corundum Al₂O₃, and willemite Zn₂SiO₄) were described as stoichiometric. Present study is a part of the research program on the characterization of the multicomponent Pb–Zn–Cu–Fe–Ca–Si–O–S–Al–Mg–Cr–As–Sn–Sb–Bi–Ag–Au–Ni system.     

Synthesis and microstructure of Gd2O3-doped HfO2 ceramics

The effect of Gd₂O₃-doping on the crystal structure, surface morphology and chemical composition of the Gd₂O₃–HfO₂ system is reported. Gd₂O₃–HfO₂ ceramics with variable composition were prepared by varying the Gd₂O₃ composition in the range of 0–38 mol% balanced HfO₂. X-ray diffraction (XRD) analysis indicates that the Gd₂O₃ concentration influences the crystal structure of the Gd₂O₃–HfO₂ ceramics. Pure HfO₂ and Gd₂O₃ crystallize in monoclinic and body centered cubic structure, respectively. The Gd₂O₃–HfO₂ ceramics exhibit mixed monoclinic and fluorite structure when the Gd₂O₃ concentration is varied from 4 to 12 mol%. At 20 mol% of Gd₂O₃, existence of only the fluorite phase was found. Increasing the Gd₂O₃ concentration to 38 mol% results in the formation of single-phase pyrochlore Gd₂Hf₂O₇ (a = 5.258 Å).     

Attenuation properties of epoxy-Ta2O5 and epoxy-Ta2O5-Bi2O3 composites at γ-ray energies 59.54 and 662 keV

Epoxy resin filled with suitable high Z elements can be a potential shield for X-rays and γ-rays. In this work, we present the γ-ray attenuation properties of epoxy composites filled with (0–30 wt%) Tantalum pentoxide (Ta₂O₅) and Ta₂O₅-Bi₂O_3, which were prepared by open mold cast technique. X-ray diffraction patterns showed crystalline peaks of Ta₂O₅ and bismuth oxide (Bi₂O₃) in the prepared epoxy-Ta₂O₅ and epoxy-Ta₂O₅-Bi₂O₃ composites. Homogeneity of the samples at higher filler wt% was revealed by SEM images. Mechanical characterization showed the enhanced mechanical strength of epoxy-Ta₂O₅-Bi₂O₃ composites compared to epoxy-Ta₂O₅. Higher storage modulus and glass transition temperature of the epoxy-Ta₂O₅-Bi₂O₃ composites showed enhanced stiffness and thermal stability when compared to neat and epoxy-Ta₂O₅. Decrease in the value of tan(δ) at higher content of filler loadings indicated the good adhesion between filler and matrix. Mass attenuation coefficients of epoxy-Ta₂O₅ (30 wt%) composites at γ-ray energies 59.54 and 662 keV were found to be 0.876 cm² g^–1 and 0.084 cm² g^–1, while that of epoxy-Ta₂O₅-Bi₂O₃ (30 wt% Bi₂O₃) composite were 1.271 cm² g^–1 and 0.088 cm² g^–1, respectively. The epoxy-5% Ta₂O₅-30% Bi₂O₃ composites with higher μ/ρ value and tensile strength may be a potential γ-ray shield in various radiation environments.     

Cyclic thermal shock resistance of h-BN composite ceramics with La2O3–Al2O3–SiO2 addition

The effects of La₂O₃–Al₂O₃–SiO₂ addition on the thermal conductivity, coefficient of thermal expansion (CTE), Young's modulus and cyclic thermal shock resistance of hot-pressed h-BN composite ceramics were investigated. The samples were heated to 1000 °C and then quenched to room temperature with 1–50 cycles, and the residual flexural strength was used to evaluate cyclic thermal shock resistance. h-BN composite ceramics containing 10 vol% La₂O₃–Al₂O₃ and 20 vol% SiO₂ addition exhibited the highest flexural strength, thermal conductivity and relatively low CTE, which were beneficial to the excellent thermal shock resistance. In addition, the viscous amorphous phase of ternary La₂O₃–Al₂O₃–SiO₂ system could accommodate and relax thermal stress contributing to the high thermal shock resistance. Therefore, the residual flexural strength still maintained the value of 234.3 MPa (86.9% of initial strength) after 50 cycles of thermal shock.     

Phase relation studies in the CeO2–La2O3–Er2O3 system at 1500°C

Materials based on CeO₂–La₂O₃–Er₂O₃ system are promising candidates for a wide of applications, but the phase relationship has not been studied systematically previously. To address this challenge, the isothermal section of the phase diagram for 1500 °C was investigated. The phase relations in the CeO₂–La₂O₃–Er₂O₃ ternary system at 1500 °C were studied by X-ray diffraction and scanning electron microscopy in the overall concentration range. To study phase relationships at 1500 °C the as-repared samples were thermally treated in two stages: at 1100 °C (for 300 in air) and then at 1500 °C (for 70 h in air) in the furnaces with heating elements based on Fecral (H23U5T) and Superkanthal (MoSi2), respectively. The solid solutions based on various polymorphous forms of constituent phases and with perovskite-type structure of LaErO₃ (R) with orthorhombic distortions were revealed in the system. No new phases were found. The isothermal section of the phase diagram for the CeO₂–La₂O₃–Er₂O₃ system has been constructed. It was established that in the ternary CeO₂–La₂O₃–Er₂O₃ system there exist fields of solid solutions based on hexagonal (A) modification of La₂O₃, cubic modification of CeO₂ with fluorite-type structure (F), cubic modification Er₂O₃ and with perovskite-type structure of LaErO₃ (R) with orthorhombic distortions. The maximal solubility of ceria in LaErO₃ was found to be around ∼ 2 mol% CeO₂ along the section CeO₂–(50 mol % La₂O₃ –50 mol% Er₂O₃).     

Synergetic effect of combined use of Cu–ZnO–Al2O3 and Pt–Al2O3 for the steam reforming of methanol

Commercial Cu–ZnO–Al₂O₃ catalysts are used widely for steam reforming of methanol. However, the reforming reactions should be modified to avoid fuel cell catalyst poisoning originated from carbon monoxide. The modification was implemented by mixing the Cu–ZnO–Al₂O₃ catalyst with Pt–Al₂O₃ catalyst. The Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture created a synergetic effect because the methanol decomposition and the water–gas shift reactions occurred simultaneously over nearby Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalysts in the mixture. A methanol conversion of 96.4% was obtained and carbon monoxide was not detected from the reforming reaction when the Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture was used.     

Synthesis and physicochemical characterizations of Ni/Al2O3–ZrO2 nanocatalyst prepared via impregnation method and treated with non-thermal plasma for CO2 reforming of CH4

Ni/Al₂O₃ and Ni/Al₂O₃–ZrO₂ nanocatalysts synthesized via impregnation and treated with non-thermal plasma were investigated in dry reforming of methane. The results showed that plasma treatment produces highly dispersed nanoparticles with a high surface area. Strong interaction between active phase and support particles in plasma-treated catalysts can be concluded based on XRD and XPS results. Smaller Ni particles with narrow particle size distribution were observed in plasma-treated Ni/Al₂O₃–ZrO₂ nanocatalyst. The catalytic activity of plasma-treated Ni/Al₂O₃–ZrO₂ was higher than that of conventional catalyst, resulting in operating conditions with considerably lower temperatures. Long reaction times confirmed the stability of the plasma-treated Ni/Al₂O₃–ZrO₂ nanocatalyst.