Mechanochemical Synthesis and Thermal Behavior of Metastable Mixed Oxides in the CaO–Sb2O3–Bi2O3 System

The phase composition of crystalline mechanochemical synthesis products in the CaO–Sb₂O₃–Bi₂O₃ system was determined. Of the known phases in this system, only three could be prepared mechanochemically: Ca₂Sb₂O₅, CaSb₂O₄, and CaBiO_2.5 (fcc). A new metastable phase, "-Bi₂O₃, with an orthorhombic structure close to that of the high-temperature, fluorite phase -Bi₂O₃, was obtained by mechanical processing at 30°C. A number of new metastable fluorite solid solutions of binary and ternary oxides were obtained as single-phase powders by mechanochemical synthesis. The mechanochemical yield of primary crystalline products was shown to be several times higher than that of secondary products. A broad composition range was revealed in which perovskite and fluorite phases are in mechanochemical equilibrium. The composition dependence of the lattice parameter of the metastable fluorite phase Bi_{2 – x} Sb _x O₃ was found to be the opposite of the one predicted by Vegard's law. Metastable mixed oxides undergo phase transformations during heating (starting at 280°C in the case of the ternary perovskite phase). Bi_{2 – x} Ca _x O_{3 – 0.5x} fluorite solid solutions experience a transformation at 400°C, accompanied by oxygen loss. During heating in air, Sb₂O₃-containing fluorite phases partially stabilize owing to oxidation but, nevertheless, undergo structural transformations above 480°C. The transformation of Sb_{2 – x} Ca _x O_{3 – 0.5x} metastable fluorite solid solutions near 500°C in air is accompanied by the formation of needle-like Sb₂O₃ crystals. A mechanism is proposed for the extremely rapid growth of such crystals: extrusion of the Sb₂O₃ resulting from fluorite decomposition in agglomerates through triple junctions of aggregates and through cracks in the surface layer of agglomerates.     

Mechanochemical Synthesis and Structure of New Phases in the Pb–V–O System

The products of mechanochemical synthesis in the Pb–V–O system were characterized by x-ray diffraction and magnetic resonance spectroscopy techniques. The mechanical processing was found to yield only new crystalline compounds, Pb_2.67V_1.33O_5.96and Pb_3.5V_4.5O_14.75. Structural analysis of these phases revealed a low atomic density, mixed-valent states of the constituent cations, the presence of three of four types of vanadium polyhedra, and splitting of crystallographic sites, in line with the views on the mechanisms of mechanochemical reactions developed in the model for the reaction zone.     

Phase Relations in the Na2O–Al2O3–Nb2O5and CaO–Al2O3–Nb2O5Systems

Phase relations in the Na₂O–Al₂O₃–Nb₂O₅and CaO–Al₂O₃–Nb₂O₅systems were studied. The Na₂O system was found to contain neither ternary compounds nor niobate–aluminate solid solutions. In the CaO system, a ternary compound of composition 4CaO · Al₂O₃·Nb₂O₅was identified (cubic structure, a= 7.628 Å, Z= 2, _meas= _x= 4.43 g/cm³).     

Structure-Sensitive Properties of Melts and Thermal Properties of Glasses in the B2O3–CaO–Al2O3–PbO System

Inorganic Materials - The devitrification, “cold” crystallization, and glass transition temperatures and melting point of samples in the B2O3–CaO–Al2O3–PbO system have...     

Phase Relations in the Systems Al2TiO5–Fe2O3 , Al2O3–TiO2–Fe2O3 , and Al2TiO5–Cr2O3

Phase relations in the systems Al₂TiO₅–Fe₂O₃, Al₂TiO₅–Cr₂O₃, and Al₂O₃–TiO₂–Fe₂O₃ are investigated, and the composition ranges of pseudobrookite Al_{2 – 2x} M_2x TiO₅ (M = Fe, Cr) solid solutions are determined.     

Ion-Conducting Defect Pyrochlore Phases in the K2O–Sb2O3–WO3 System

Potassium tungstate antimonates were prepared by calcining K₂CO₃ + Sb₂O₃ + 2(1 – – )WO₃ mixtures in air. Data on the phase composition of the obtained materials were used to locate the pyrochlore phase region in the Sb₂O _z –W₂O₆ – K₂O composition triangle at 1170 K. The distributions of the constituent ions and lattice defects over the crystallographic positions of space group Fd3m were inferred from structural and gravimetric data. The ac conductivity of the potassium tungstate antimonates was measured from 600 to 1000 K. The conductivity and its activation energy were shown to be correlated with the concentrations of cation (position 16d) and anion (position 8b) defects. The concentration and mobility of K⁺ ions involved in charge transport were determined.     

Phase Transformations in the Systems Y2BaCuO5–“Ba3Cu5O8” and Y2BaCuO5–BaCuO2

Data are presented on the sequence of phase transformations leading to the formation of YBa₂Cu₃O_{7 –} textured ceramics and single crystals in the systems Y₂BaCuO₅–Ba₃Cu₅O₈ and Y₂BaCuO₅–BaCuO₂. During cooling in the Y₂BaCuO₅–BaCuO₂ system, YBa₂Cu₃O_{7 –} crystallization in the range 1260–1210 K occurs through the intermediate phase YBa₄Cu₃O_{9 –} , without an additional oxygen source. In the Y₂BaCuO₅–Ba₃Cu₅O₈ system between 1250 and 1210 K, YBa₂Cu₃O_{7 –} crystallization is accompanied by oxygen absorption.     

Optical properties of Nd3+ and Er3+ ions in TeO2–WO3–PbO–La2O3 glasses

Multicomponent telluride-tungstate glasses containing Nd³⁺ and Er³⁺ ions were studied experimentally at 77 and 293 K using spectroscopic methods. The Judd–Ofelt intensity parameters were derived from the absorption spectra and used to calculate the radiative lifetimes and branching ratios. The quantum efficiency η = 0.95 of the ⁴F_3/2 level of Nd³⁺ ion is higher than the typical value of other tellurite-based glasses. For low concentration of Er³⁺ ions, the luminescence decay of the ⁴S_3/2 and ⁴I_11/2 levels is governed by radiative transitions and multiphonon relaxation involving the Te-O highest energy vibrations.     

High-Pressure Reactions in the CeCo3–H2 and GdNi3–H2Systems

Reactions in the CeCo₃–H₂and GdNi₃–H₂systems were studied at hydrogen pressures of up to 0.2 GPa. Using hydrogen absorption–desorption isotherms, the compositions of the high-pressure hydrides were determined to be CeCo₃H_6.8(–70°C) and GdNi₃H_5.1(–50°C). According to x-ray diffraction studies, high-pressure hydrogen absorption to above the stoichiometry CeCo₃H₄is accompanied by insignificant volume changes. In the GdNi₃–H₂system, the hydride phase amorphizes at high hydrogen contents.     

Influence of Reducing Media on the Structure and Physicomechanical Properties of Ceramics of the ZrO2–Y2O3–Al2O3–NiO – CuO System

Materials Science - We study the regularities of changes in the microstructure, strength, electric conductivity, and micromechanism of fracture of 50% (ZrO2–8 mole% Y2O3–2 wt.% Al2O3) +...     

Formation and transformation of cubic 3PbO·2Ta2O5 solid solution

The formation of lead tantalates in the PbO-rich region is studied using the powders prepared by the simultaneous hydrolysis of lead and tantalum alkoxides. Cubic 3PbO · 2Ta₂O₅ solid solutions crystallize at low temperatures from amorphous materials between 60 and 75 mol% PbO. The lattice parameter,a, increases linearly from 1.0545 to 1.0705 nm with increasing PbO. At higher temperatures the solid solutions above 66.67 mol% PbO are transformed into those of rhombohedral 2PbO · Ta₂O₅. Rhombohedral 5PbO · 2Ta₂O₅ is formed at 850 to 900 °C by transformation of 2PbO·Ta₂O₅ solid solution corresponding to 71.43 mol% PbO. The existence of previously reported 3PbO·Ta₂O₅ is not confirmed.     

Optical,thermal and radiation shielding properties of B2O3–NaF–PbO–BaO–La2O3 glasses

Journal of Materials Science: Materials in Electronics - The techniques of melt-quenching have been used to generate 53B2O3—2NaF—27PbO – $$(20-x)$$...     

Composition and Properties of Layered Compounds in the GeTe–Sb2Te3System

The 620-K section of the Ge–Sb–Te phase diagram was mapped out using x-ray diffraction, microstructural analysis, and microhardness measurements. The transport properties of the layered tetradymite-like compounds nGeTe · mSb₂Te₃(n, m= 1–4) were studied in wide temperature ranges (Hall effect and electrical resistivity, from 77 to 800 K, and thermoelectric power, from 90 to 450 K). The results show that the nGeTe · mSb₂Te₃compounds are degeneratep-type semiconductors with a fairly high hole concentration due to the high density of intrinsic point defects. The temperature dependences of the Hall coefficient and resistivity exhibit anomalies related to solid-state phase transitions. The room-temperature lattice thermal conductivity ofnGeTe · mSb₂Te₃is fairly low, in the range 8–10 mW/(cm K).     

Enhancing the physical,optical and shielding properties for ternary Sb2O3–B2O3–K2O glasses

Ternary Sb₂O₃–B₂O₃–K₂O glass system, with general composition of x Sb₂O₃–(70-x) B₂O₃–30 K₂O (where x?=?0, 10, 20, 30, 40, 50) were prepared using melt-quenching technique. Structures of these glasses were investigated using XRD analysis and FT-IR spectroscopy. The optical properties were investigated using the UV–Vis NIR JASCO (Model V-670) Double Beam Spectrophotometer. Different physical parameters, such as density (ρ), molar volume (V_M), oxygen molar volume (V_O) and oxygen packing density values (OPD) have been estimated. Also, the Gamma radiation shielding ability have been characterized for the investigated glasses using Phy-X/PSD software in the photon energy range (0.015–15 MeV). XRD analysis confirm the amorphous nature of the prepared glasses. The optical energy gap of SBK glasses is decreasing from 4 to 2.63 eV with increasing Sb₂O₃ content while refractive index is increasing from 2.17 to 2.5 because of increasing the non-bridging oxygens (NBOs) in the glass matrix. The molar refractivity (R_m), molar polarizability (α_m) and the third-order nonlinear optical susceptibility values χ³ have been calculated, their values are found to increase with increasing Sb₂O₃ content. Glass density and molar volume values for the SBK glasses increase with increasing Sb₂O₃ content. Increasing the Sb₂O₃ concentration enhance the radiation shielding features of the prepared glasses against gamma rays and neutrons. Hence, the mass attenuation coefficient (MAC) increases from 8.6 to 35.4 cm²/gm while the half value layer (HVL) decreases from 0.036 to 0.0046 cm at 0.015 MeV as the Sb₂O₃ concentration increases from 0 to 50 mol%. The fast neutron cross section of the six investigated SBK glasses are (0.087, 0.092, 0.095, 0.091, 0.094 and 0.092 cm^?1), respectively.

     

Effect of P2O5, B2O3 and PbO on the sinterability of β.quartz solid solution and gahnite glass-ceramics

The effect of P₂O₅, B₂O₃ and PbO additives on the sintering and crystallization behaviour of .quartz solid solution and gahnite glass-ceramics were investigated. According to our results, only the addition of PbO to glasses produces sinterable glass-ceramics containing .quartz solid solution gahnite as the sole crystalline phases, respectively. The nucleation mechanism of the glasses were determined by the Ozawa equation and their activation energy for crystallization were determined by the modified form of the Kissinger, Matusita and Marotta equations. The results indicate that the better sinterability of the lead bearing .q._ss glass-ceramic than the lead free one could be explained by changes of bulk to surface nucleation and increase of its activation energy for crystallization. At the other hand, it could not be observed any differences between the nucleation mechanism and the activation energy for crystallization of the lead bearing and lead free gahnite glass-ceramics. Then the differences in sinterability of the two glass-ceramics could not be explained by comparison of theirs activation energy for crystallization.     

Pore Structure and Transport Properties in Bulk YBa2Cu3O7?δ Doped with Sb2O3

In this work we have studied the pore structure and electrical transport properties of superconducting YBa₂Cu₃O_7?y polycrystalline samples doped by the addition of different Sb₂O₃ concentrations, i.e. resulting in (YBa₂Cu₃O_7?y )_1?x (Sb₂O₃) _x . The samples were prepared through the solid-state reaction method. Rietveld analyses of X-ray diffraction data were used to investigate how the lattice parameters are modified by doping. Specific superficial area measurements identified the principal characteristics of the pore structure of the samples and how these properties change with doping. The superconducting properties were studied by using zero field cooling magnetization and transport critical current measurements. The critical temperature of the samples does not depend on the doping level, but their transport critical current density strongly decreases as the Sb₂O₃ concentration is increased. Our experimental results suggest that for the samples studied here there is not a direct correlation between the modification by doping of both, the pore structure and the transport critical current density.     

Spectroscopic properties of B2O3–PbO–Bi2O3–GeO2 glass doped with Sm3+ and gold nanoparticles

Heavy metal oxide B₂O₃–PbO–Bi₂O₃–GeO₂ transparent glass doped with Sm³⁺ was synthesized and implanted with Au⁺ using energy of 300 keV and fluence of 1 × 10¹⁶ cm⁻². The annealing of the implanted glass at moderate temperature below the glass transition temperature induced the nucleation of gold nanoparticles, confirmed by the characteristic absorption band in the visible range and by transmission electron microscopy. Using Miés and Doylés theories for the surface plasmon resonance, the average size of the gold nanoparticles was about 4.6 nm, similar to the values observed by transmission electron microscopy. It was also observed the crystallization of a thin layer of the glass at the implanted surface after annealing, detected by X-ray diffraction and scanning electron microscope. Visible and near-infrared emission of Sm³⁺ was enhanced after annealing of the glass implanted with gold. Judd–Ofelt parameters and radiative parameters were calculated for the glass doped with Sm³⁺ with and without gold nanoparticles.     

Effect of B2O3 and CuO additions on the sintering temperature and microwave dielectric properties of 3Li2O–Nb2O5–3TiO2 ceramics

The effects of B₂O₃–CuO (BCu, the weight ratio of B₂O₃ to CuO is 1:1) addition on the sintering behavior, microstructure, and the microwave dielectric properties of 3Li₂O–Nb₂O₅–3TiO₂ (LNT) ceramics have been investigated. The low-amount addition of BCu can effectively lower the sintering temperature of LNT ceramics from 1125 to 900 °C and induce no obvious degradation of the microwave dielectric properties. Typically, the 2 wt% BCu-added ceramic sintered at 900 °C has better microwave dielectric properties of ε _r  = 50.1, Q × f = 8300 GHz, τ _f  = 35 ppm/°C. Silver powders were cofired with the dielectric under air atmosphere at 900 °C. The SEM and EDS analysis showed no reaction between the dielectric ceramic and silver powders. This result shows that the LNT dielectric materials are good candidates for LTCC applications with silver electrode.