Phase Equilibria in the Cu<Subscript>2</Subscript>Se–Cu<Subscript>3</Subscript>AsSe<Subscript>4</Subscript>–Se System and Thermodynamic Properties of Cu<Subscript>3</Subscript>AsSe<Subscript>4</Subscript>

The Cu₂Se–Cu₃AsSe₄–Se system has been studied using differential thermal analysis, X-ray diffraction, and emf measurements on concentration cells using Cu₄RbCl₃I₂ as a solid electrolyte. We have constructed a number of vertical sections through the phase diagram, the room-temperature solid-state phase compatibility diagram, and a projection of the liquidus surface. The primary crystallization fields of the phases present and the types and coordinates of in- and univariant equilibria in the system have been identified. The system has been shown to contain a broad liquid–liquid immiscibility region. Using emf data, we evaluated the standard thermodynamic functions of formation and standard entropy of the Cu₃AsSe₄ compound.     

Phase equilibria in the Tl<Subscript>5</Subscript>Te<Subscript>3</Subscript>–Tl<Subscript>9</Subscript>BiTe<Subscript>6</Subscript>–Tl<Subscript>9</Subscript>TbTe<Subscript>6</Subscript> system

Phase equilibria in the Tl₅Te₃–Tl₉BiTe₆–Tl₉TbTe₆ system have been studied using differential thermal analysis, X-ray diffraction, and microhardness measurements. We have mapped out a number of vertical sections, the 760-K isothermal section of its phase diagram, and projections of its liquidus and solidus surfaces. The composition dependences of lattice parameters and microhardness have been obtained. The system has been shown to contain a continuous series of solid solutions, which crystallize in a tetragonal structure (Tl₅Te₃ type, sp. gr. I4/mcm).     

Optical properties and crystallization of glasses in the system Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–MoO<Subscript>3</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The purpose of this work is to study the optical properties and crystallization of glasses in the ternary system Bi₂O₃–MoO₃–B₂O₃. In order to verify the obtaining of bismuth borate crystal phases several glass compositions have been selected for crystallization. The obtained samples were characterized by X-ray diffraction, scanning electron microscopy and UV–Vis spectroscopy. The UV–Vis spectroscopy showed that the obtained glasses are transparent in the visible region. The values of optical band gap (E _opt) and changes in cut-off (λ_c) depending on composition are reported. It was established that the increase in the MoO₃ content led to decreasing the transmittance of the glasses. Moreover, the absorption edge shifts towards longer wavelength.     

Structure–property correlations in the SiO<Subscript>2</Subscript>–PbO–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

SiO₂–PbO–Bi₂O₃ glasses having the composition of 35SiO₂–xPbO–(65−x)Bi₂O₃ (where x = 5, 10, 15, 20, 25, 35, 45; in mol%) have been prepared using the conventional melting and annealing method. Density, molar volume and Vickers microhardness of the prepared glasses were measured. Infrared (IR) and UV–visible spectroscopic techniques were used for structural studies of these glasses. Density as well as the microhardness increase systematically and, conversely, the molar volume decreases with increasing the lead oxide content. This behavior can be explained by the correlation with the glass structure. Increasing the lead oxide content (≥20 mol%) increases the network former PbO₄ groups which can play an important role in increasing the connectivity and compactness of the glass matrix via increasing the cross-linking with the other constituent silicate and bismuthate structural units. The increased compactness may explain, in turn, the increase of the density and microhardness. IR spectra reinforce the idea that bismuth participates in the glassy network predominantly as BiO₆ octahedral structural units. UV–VIS optical absorption spectra revealed UV-charge transfer absorption bands related to the contribution of Pb²⁺ ions in the region 350–385 nm; in addition to the extrinsic absorption of trace iron impurities in the range 220–290 nm. In the visible region, three optical bands in the ranges 415–435, 605–650 and 880–890 nm were correlated with the contribution of electronic transitions in Bi³⁺ ions. Calculation of the optical mobility gap and the width of the energy tail of glass from the UV–VIS absorption indicated a slight increase followed by a decrease in their values. The behavior change occurred at the glass in which PbO content is 20 mol% where lead oxide starts to participate into the glassy matrix as a network former. The combination of analytical FTIR and UV–visible spectroscopy provided a consistent picture of structure–property relations in this glass system.     

Glasses formation,characterization, and crystal-structure determination in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sb<Subscript>2</Subscript>O<Subscript>3</Subscript>–TeO<Subscript>2</Subscript> system prepared in an air

A glass-forming domain is found and studied within Bi₂O₃–Sb₂O₃–TeO₂ system. The glasses composition were obtained in pseudo-binary xSbO_1.5, (1−x)TeO₂ for 0.05 ≤ x ≤ 0.20. The constitution of glasses in the system Sb₂O₃–TeO₂ was investigated by DSC, Raman, and Infrared spectroscopy. The influence of a gradual addition of the modifier oxides on the coordination geometry of tellurium atoms has been elucidated based Infrared and Raman studies and showed the transition of TeO₄, TeO₃₊₁, and TeO₃ units with increasing Sb₂O₃ content. XRD results reveal the presence of three crystalline: γ-TeO₂, α-TeO₂, and SbTe₃O₈ phases during the crystallization process. The density of glasses has been measured. The investigation in the ternary system by the solid state reaction using XRD reveals the existence of a solid solution Bi_1−x Sb_1−x Te_2x O₄ isotopic to BiSbO₄ with 0 ≤ x ≤ 0.1.     

Phase formation and dielectric properties of ceramics in the BiFeO<Subscript>3</Subscript>–BaTiO<Subscript>3</Subscript>–Bi(Mg<Subscript>0.5</Subscript>Ti<Subscript>0.5</Subscript>)O<Subscript>3</Subscript> system

We have studied the effect of Bi(Mg_0.5Ti_0.5)O₃ additions on the phase formation, structural parameters, microstructure, and dielectric properties of solid solutions in the region of a morphotropic phase boundary in the BiFeO₃–BaTiO₃ system. Single-phase samples with the perovskite structure have been obtained and the addition of Bi(Mg_0.5Ti_0.5)O₃ has been shown to raise the Curie temperature of the ceramics and improve their dielectric properties.     

Phase equilibria in the Tl<Subscript>2</Subscript>Te–Tl<Subscript>5</Subscript>Te<Subscript>3</Subscript>–Tl<Subscript>9</Subscript>TbTe<Subscript>6</Subscript> system

The Tl₂Te–Tl₅Te₃–Tl₉TbTe₆ system has been studied using differential thermal analysis, X-ray diffraction, and microhardness measurements. We have mapped out a number of vertical sections, the 680 K isothermal section of its phase diagram, and projections of its polythermal projections of its liquidus and solidus surfaces. The field of solid solutions with the Tl₅Te₃ structure (δ-phase) has been shown to account for more than 90% of the area of the composition triangle. Tl₂Te-based solid solutions (α-phase) exist in a narrow composition region.     

Synthesis,bioactivity and preliminary biocompatibility studies of glasses in the system CaO–MgO–SiO<Subscript>2</Subscript>–Na<Subscript>2</Subscript>O–P<Subscript>2</Subscript>O<Subscript>5</Subscript>–CaF<Subscript>2</Subscript>

New compositions of bioactive glasses are proposed in the CaO–MgO–SiO₂–Na₂O–P₂O₅–CaF₂ system. Mineralization tests with immersion of the investigated glasses in simulated body fluid (SBF) at 37°C showed that the glasses favour the surface formation of hydroxyapatite (HA) from the early stages of the experiments. In the case of daily renewable SBF, monetite (CaHPO₄) formation competed with the formation of HA. The influence of structural features of the glasses on their mineralization (bioactivity) performance is discussed. Preliminary in vitro experiments with osteoblasts’ cell-cultures showed that the glasses are biocompatible and there is no evidence of toxicity. Sintering and devitrification studies of glass powder compacts were also performed. Glass-ceramics with attractive properties were obtained after heat treatment of the glasses at relatively low temperatures (up to 850°C).     

Thermal and dielectric properties of the LTCC composites based on the eutectic system BaO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The low-temperature co-fired ceramic (LTCC) composites containing quartz based on the eutectic system BaO–Al₂O₃–SiO₂–B₂O₃ are fabricated at the sintering temperature below 980 °C. Preparation process and sintering mechanism were described and discussed, respectively. The results indicated that the addition of quartz to the eutectic system can availably improve dielectric properties of the LTCC composites. In addition, The LTCC composites with optimum compositions, which were obtained by the regulation of an Al₂O₃ content in the composite, can express excellent dielectric properties (permittivity: 5.94, 5.48; loss: 7 × 10⁻⁴, 5 × 10⁻⁴), considerable CTE values (11.7 ppm. °C⁻¹, 10.6 ppm. °C⁻¹) and good mechanical properties (128 MPa,133 MPa).     

Vaporization in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–MgO system

The pseudobinary system Al₂O₃–MgO has been studied in the temperature range 1750–2100 K by the Knudsen effusion method in combination with mass spectrometric analysis of the vapor phase. Over the entire composition range, except for the 100 mol % Al₂O₃ boundary, the vapor phase over the system consists of three species: Mg, O₂, and O. The partial pressures obtained have been used to construct a p–x section through the Al₂O₃–MgO phase diagram at 1900 K. The standard enthalpy of formation of the MgAl₂O₄ spinel at 298 K has been determined by third-law calculations:–2301.61 ± 11.00 kJ/mol. We have derived equations for the temperature dependences of the partial pressures of the vapor species over the Al₂O₃–MgO system.     

Compositional dependence of the structural and dielectric properties of Li<Subscript>2</Subscript>O–GeO<Subscript>2</Subscript>–ZnO–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

(10Li₂O–20GeO₂–30ZnO–(40-x)Bi₂O₃–xFe₂O₃ where x = 0.0, 3, 6, and 9 mol%) glasses were prepared. A number of studies, viz. density, differential thermal analysis, FT-IR spectra, DC and AC conductivities, and dielectric properties (constant ε′, loss tan δ, AC conductivity, σ _ac, over a wide range of frequency and temperature) of these glasses were carried out as a function of iron ion concentration. The analysis of the results indicate that, the density and molar volume decrease with an increasing of iron content indicates structural changes of the glass matrix. The glass transition temperature T _g and onset of crystallization temperature T _x increase with the variation of concentration of Fe₂O₃ referred to the growth in the network connectivity in this concentration range, while glass-forming ability parameter ΔT decrease with increase Fe₂O₃ content, indicates an increasing concentration of iron ions that take part in the network-modifying positions. The FT-IR spectra evidenced that the main structural units are BiO₃, BiO₆, ZnO₄, GeO₄, and GeO₆. The structural changes observed by varying the Fe₂O₃ content in these glasses and evidenced by FTIR investigation suggest that the iron ions play a network modifier role in these glasses while Bi₂O₃, GeO₂, and ZnO play the role of network formers. The temperature dependence of DC and AC conductivities at different frequencies was analyzed using Mott’s small polaron hopping model and, the high temperature activation energies have been estimated and discussed. The dielectric constant and dielectric loss increased with increase in temperature and Fe₂O₃ content.     

Preparation and properties of Bi<Subscript>6</Subscript>Ti<Subscript>5</Subscript>WO<Subscript>22</Subscript>: a new phase in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiO<Subscript>2</Subscript>–WO<Subscript>3</Subscript> system

In a recent report, the evaluation of the phase relations in the Bi₂O₃–TiO₂–WO₃ ternary system has shown the existence of a new phase with nominal composition close to Bi₆Ti₅WO₂₂. In the present contribution we attempt to prepare this single phase by using a solid state route. Although XRD analyses also show traces of two minority Aurivillius-type phases in the synthesized materials, the crystal structure of the Bi₆Ti₅WO₂₂ phase has been determined by Rietveld analyses revealing a complex structure similar to that of Bi₃(AlSb₂)O₁₁ and PbHoAl₃O₈ related compounds. The electrical response of this new phase was characterized as well. Three peaks are observed in its dielectric response: two of them positioned around 0 °C and can be assigned to this Bi₆Ti₅WO₂₂ structure. The third one rises up to 665 °C and confirms the presence of the Aurivillius-type phases.     

Crystallization and microstructural evolution of MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript>–La<Subscript>2</Subscript>O<Subscript>3</Subscript> glass-ceramics

Crystallization and microstructure of glasses with the molar compositions 1MgO·1.2Al₂O₃·2.8SiO₂·1.2TiO₂·xLa₂O₃ (x = 0.1 and 0.4) were thermally treated at different temperatures in the range from 950 to 1250 °C and then analyzed by X-ray diffraction and scanning electron microscopy, in combination with energy-dispersive X-ray spectroscopy and electron backscatter diffraction. It was found that the microstructure is first homogeneous with the precipitation of randomly distributed crystals and then indialite domains with embedded perrierite and rutile crystals are formed. For higher temperatures or prolonged times, more domains appear and expand into the bulk of the sample. Finally, the entire sample consists of the indialite domains and the boundaries that are enriched in rutile, perrierite, and magnesium aluminotitanate. Nevertheless, very distinct differences are observed between the samples with different La₂O₃ concentrations. For the sample with x = 0.4, the domains were detected at lower temperatures, while the quantity and size of the domains increase faster due to the promoted precipitation of indialite. For the sample with x = 0.1, in addition to the domain boundaries, secondary boundaries between the “regions” (assemblages of the domains) are observed in a larger length scale. The average size of the crystalline phases found between the “regions” is larger than that typically observed at the domain boundaries. The sizes of the crystals at the boundaries decrease with higher concentrations of La₂O₃, and the crystals (especially perrierite) within the domains become larger, resulting in a more homogeneous microstructure. This results in better dielectric properties, i.e., much higher quality factor for the sample with x = 0.4 in comparison to that with x = 0.1 after heat-treatment at 1150 or 1250 °C.     

The crystallographic orientation relationship between Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> in the composite material Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Al–Mg–Si alloy

The formation mechanism of spinels on Al₂O₃ particles in the Al₂O₃/Al–1.0 mass% Mg₂Si alloy composite material has been investigated by transmission electron microscopy (TEM) in order to determine the crystallographic orientation relationship. A thin sample of the Al₂O₃/Al–Mg–Si alloy composite material was obtained by the FIB method, and the orientation relationship between Al₂O₃ and MgAl₂O₄, which was formed on the surface of Al₂O₃ particles, was discovered by the TEM technique as follows:

Formation of Compounds in the Ag<Subscript>2</Subscript>O–Sb<Subscript>2</Subscript>O<Subscript>3</Subscript>–MoO<Subscript>3</Subscript> System on Heating

This paper presents a detailed study of phase formation processes in the AgNO₃–Sb₂O₃–MoO₃ system during heating in air. The compositions of the solid-state reaction products have been determined using thermogravimetry and qualitative X-ray diffraction. The results demonstrate that, at a final heat treatment temperature of 1023 K, synthesis yields a range of Ag_2–xSb_2–xMo _x O₆ compounds with the pyrochlore structure and 0.0 ≤ x ≤ 2.0. The structural parameters of the synthesized phases have been refined by the Rietveld method in space group Fd3?m and their electrical conductivity has been measured.     

Synthesis and characterization of TiO<Subscript>2</Subscript>–NiO and TiO<Subscript>2</Subscript>–WO<Subscript>3</Subscript> nanocomposites

TiO₂–NiO and TiO₂–WO₃ nanocomposites were prepared by hydrothermal and surface modification methods. The samples were analyzed using X-ray diffraction, Scanning Electron Microscope images, Transmission Electron Microscope, Energy dispersive analysis, Zeta potential, Electrophoretic mobility and Photocatalysis activity measurement. XRD data sets of TiO₂–NiO, TiO₂–WO₃ powder nanocomposite have been studied for the inclusion of NiO, WO₃ on the anatase-rutile mixture phase of TiO₂ by Rietveld refinement. The cell parameters, phase fraction, the average grain size, strain and bond lengths between atoms of individual phases have been reported in the present work. Shifted positional co-ordinates of individual atoms in each phase have also been observed.     

High-temperature heat capacity of the oxide compounds in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–V<Subscript>2</Subscript>O<Subscript>5</Subscript> system

The compounds BiVO₄, Bi₄V₂O₁₁, and Bi₁₂V₂O₂₃ have been prepared by solid-state synthesis using stoichiometric mixtures of Bi₂O₃ and V₂O₅. The effect of temperature on the heat capacity of the synthesized bismuth vanadates has been studied by differential scanning calorimetry in the range 350–950 K. The C _p (T) curves have extrema at 531.7 K for BiVO₄ and at 725.2 and 852.8 K for Bi₄V₂O₁₁, which are due to polymorphic transformations of these compounds.     

Phase relations in the K<Subscript>2</Subscript>MoO<Subscript>4</Subscript>–Ln<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript>–Zr(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> (Ln = La–Lu,Y) systems

We have studied phase relations in the K₂MoO₄–Ln₂(MoO₄)₃–Zr(MoO₄)₂ (Ln = La–Lu, Y) systems by the method of “intersecting cuts,” identified pseudobinary joins in their composition triangles, and constructed their phase compatibility diagrams. The systems have been shown to contain new ternary molybdates with the general formula K₅LnZr(MoO₄)₆ (Ln = Dy–Lu and Y). The thermal characteristics of the synthesized compounds have been studied by differential scanning calorimetry in the temperature range 25–700°C. The new ternary molybdates crystallize in a trigonal structure (sp. gr. R\(\bar 3\)c, Z = 6).