Redox processes in fine-particle TiO<Subscript>2</Subscript>-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> oxides

We have studied the stability of the Cr⁶⁺ ion in fine-particle TiO₂-Cr₂O₃ oxides during storage after calcination in air. The results indicate that, during storage under normal conditions for 720 days, Cr⁶⁺ is reduced to Cr³⁺. The redox process is due to partial surface hydration of the Cr₂O₃ and TiO₂ crystallites.     

Formation of solid solutions in the TiO<Subscript>2</Subscript>-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The phase formation and reaction kinetics in the TiO₂-Cr₂O₃ system have been studied by x-ray diffraction and electron microscopy. The Cr₂O₃ solubility in TiO₂ has been accurately determined, and the rate parameters of the formation of solid solutions in this system have been evaluated. The results demonstrate that Cr₂O₃ dissolves in rutile and not in anatase. Cr₂O₃ markedly reduces the temperature of the anatase-rutile phase transition.     

Phase composition and microstructure of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> solid solutions prepared by self-propagating high-temperature synthesis

The combustion synthesis, microstructure, chemical composition, and phase composition of cast Al₂O₃-Cr₂O₃ materials are described. The synthesized solid solutions are based on corundum or chromia, depending on the Al₂O₃ and Cr₂O₃ contents. Using self-propagating high-temperature synthesis, a cast aluminum oxynitride is obtained for the first time.     

Annealing behavior of TiO<Subscript>2</Subscript>-sheathed Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires

TiO₂-sheathed Ga₂O₃ one-dimensional (1D) nanostructures were synthesized by thermal evaporation of GaN powders and then sputter-deposition of TiO₂. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis results indicate that the Ga₂O₃ cores are of a single crystal nature with a monoclinic structure while the TiO₂ shells are amorphous. Photoluminescence (PL) emission is slightly decreased in intensity by TiO₂ coating, but it is significantly increased by thermal annealing in an oxygen atmosphere. The emission peak is also shifted from ~500 to ~550 nm by oxygen annealing. The increase in the green emission is due to the increase in the concentration of the Ga vacancies in the cores by the inflow of oxygen during oxygen annealing. On the other hand, annealing in a nitrogen atmosphere leads to a red shift of the emission to ~700 nm originating from nitrogen doping.     

Formation and structural phase transitions of mesoporous Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and TiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> xerogels under hydrothermal conditions

We have studied the effect of the hydrothermal synthesis temperature on Al₂O₃ structure formation and examined the role of the phase composition of the precursor gel and surfactant in the formation of the pore structure of Al₂O₃. A technique has been proposed for the synthesis of TiO₂/Al₂O₃ binary xerogels, and the effect of TiO₂ content on the pore structure parameters and adsorption properties of TiO₂/Al₂O₃ has been investigated.     

Electrical conductivity of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-Tm<Subscript>2</Subscript>O<Subscript>3</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> solid solutions

New solid solutions, Bi_2?x?y Tm _x Nb _y O_3+δ, with tetragonal and cubic structures have been synthesized in the Bi₂O₃-Tm₂O₃-Nb₂O₅ system, and their electrical conductivity has been measured at temperatures from 670 to 1020 K. The 1020-K conductivity of the tetragonal solid solution Bi_1.8Tm_0.15Nb_0.05O_3+δ is comparable to that of Bi_1.75Tm_0.25O₃, the best conductor in the Bi₂O₃-Tm₂O₃ system.     

Production and characterization of metastable Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiO<Subscript>2</Subscript> ceramic materials

Producing nanostructured materials through metastable phases is interesting in the field of ceramic materials. Metastable phases can be obtained by the Atmospheric Plasma Spray (APS) technique which, is a well-known technique to produce coatings. The initial powders are melted during the spraying obtaining a homogenized phase due to their solubility in the liquid state. Afterwards, the molten droplets are quenched in a cooled medium, producing the sought metastable phases. Finally, during material consolidation, the metastable structure evolves due to a dual structure. A suppression of the grain growth is produced as a consequence of the immiscibility of both phases in the solid state. Due to their small grain size and uniform structure, these nanostructured materials exhibit very interesting properties such as higher hardness and toughness. The aim of this research has been to produce nanostructured Al₂O₃–TiO₂ ceramic powders through APS + quenching route, starting from commercially available micron-sized powders. A complete characterization of the obtained structures using XRD, SEM, FESEM and EDS has been carried out in the Thermal Spray Center (CPT) of the University of Barcelona.     

Effect of Eu<Subscript>2</Subscript>O<Subscript>3</Subscript> doping on the crystallization behavior of BaO-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

We gave studied the crystallization behavior of 30BaO · 25Bi₂O₃ · 45B₂O₃ glasses doped with Eu₂O₃ to different levels. At a Eu₂O₃ content of 7 mol % or higher, the glasses undergo volume crystallization. The only precipitating phase is a solid solution between europium and bismuth oxides. With increasing europium concentration in the glass, the structure of the crystallites changes from cubic to rhombohedral. We have investigated the morphology, physicochemical properties, and luminescence spectra of the glasses and glass-ceramics.     

Preparation of magnetic composites through SrO-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> glass crystallization

Glasses with nominal compositions 11SrO · 5.5Fe₂O₃ · 4.5Al₂O₃ · 4B₂O₃ (1) and 15SrO · 5.5Fe₂O₃ · 4.5Al₂O₃ · 4B₂O₃ (2) were prepared by rapidly quenching oxide melts between counterrotating steel rollers. The glasses were then heat-treated in the range 650–950°C to produce glass-ceramic samples. The samples were characterized by X-ray diffraction, electron microscopy, and magnetic measurements. The phase composition of the glass-ceramics was determined, and their microstructure and magnetic properties were studied. The annealing temperature was shown to have a strong effect on the coercivity of the materials, which reaches 650 and 570 kA/m for compositions 1 and 2, respectively.     

Fabrication of Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite nanofibers by electrospinning

PVA(Polyvinyl alcohol)/chromium nitrate/aluminum nitrate composite nanofibers were prepared by using sol–gel processing and electrospinning technique. By high temperature calcinating the above precursor fibers, Cr₂O₃/Al₂O₃ composite nanofibers were successfully obtained. The fibers were characterized by XRD, IR, and SEM, respectively. The results showed that the crystalline phase and the morphology of the fibers depended on the calcination temperatures.     

Y<Subscript>2</Subscript>O<Subscript>3</Subscript> and Nd<Subscript>2</Subscript>O<Subscript>3</Subscript> co-stabilized ZrO<Subscript>2</Subscript>-WC composites

Y₂O₃ + Nd₂O₃ co-stabilized ZrO₂-based composites with 40 vol% WC were fully densified by pulsed electric current sintering (PECS) at 1350 °C and 1450 °C. The influence of the PECS temperature and Nd₂O₃ co-stabilizer content on the densification, hardness, fracture toughness and bending strength of the composites was investigated. The best combination of properties was obtained for a 1 mol% Y₂O₃ and 0.75 mol% Nd₂O₃ co-stabilized composite densified for 2 min at 1450 °C under a pressure of 62 MPa, resulting in a hardness of 15.5 ± 0.2 GPa, an excellent toughness of 9.6 ± 0.4 MPa.m^0.5 and an impressive 3-point bending strength of 2.04 ± 0.08 GPa. The hydrothermal stability of the 1 mol% Y₂O₃ + 1 mol% Nd₂O₃ co-stabilized ZrO₂-WC (60/40) composites was compared with that of the equivalent 2 mol% Y₂O₃ stabilized ceramic. The double stabilized composite did not degrade in 1.5 MPa steam at 200 °C after 4000 min, whereas the yttria stabilized composite degraded after less than 2000 min. Moreover, the (1Y,1Nd) ZrO₂-WC composites have a substantially higher toughness (~9 MPa.m^0.5) than their 2Y stabilized equivalents (~7 MPa.m^0.5).     

Temperature-stable and low loss Fe-containing dielectrics in BaO-Ln<Subscript>2</Subscript>O<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Polycrystalline samples of Ba₄Ln₂Fe₂Ta₈O₃₀ (Ln = La and Nd) were prepared by a high temperature solid-state reaction technique. The formation, structure, dielectric and ferroelectric properties of the compounds were studied. Both compounds are found to be paraelectrics with filled tetragonal tungsten bronze (TB) structure at room temperature. Dielectric measurements revealed that the present ceramics have exceptional temperature stability, a relatively small temperature coefficient of dielectric constant (τ _ε ) of −25 and −58 ppm/°C, with a high dielectric constant of 118 and 96 together with a low dielectric loss of 1.2 × 10⁻³ and 2.8 × 10⁻³ (at 1 MHz) for Ba₄La₂Fe₂Ta₈O₃₀ and Ba₄Nd₂Fe₂Ta₈O₃₀, respectively. The measured dielectric properties indicate that both materials are possible candidates for the fabrication of discrete multilayer capacitors in microelectronic technology.     

Luminescence of europium-doped BaO-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

We have prepared europium-doped BaO-Bi2O₃-B2O₃ glasses and investigated the doping effect on the main physicochemical properties and local structure of the glasses. Using Judd-Ofelt analysis, we calculated intensity parameters (Ω₂, Ω₄, and Ω₆), spontaneous emission probabilities, the radiative lifetime, luminescence branching factors, the quantum yield of luminescence, and the stimulated emission cross sections for ⁵ D ₀ → ⁷ F _J transitions.     

Plasma parameters and volume kinetics in Cl<Subscript>2</Subscript>/O<Subscript>2</Subscript> mixtures

We investigated plasma characteristics, plasma mass content and kinetic dependencies of both neutral and charged particle formation and decay in Cl₂/O₂ gas mixture. For these purposes we used a combination of experimental methods (optical emission spectroscopy, Langmuir probe) and a plasma modeling on the base of self-consistent solution of Boltzmann kinetic equation together with balance kinetic equations for neutral and charged particles in a quasi-stationary approximation. It was found that the change of O₂/(Cl₂+O₂) mixing ratio from 0 to 0.2 leads to an increase of electron average energy and electron energy distribution function (EEDF) deformation. The main mechanisms of Cl and O atom formation are the direct electron impact dissociation of corresponding molecules while the contribution of all possible “secondary” processes is not significant in the case of a relatively low O₂ addition.     

Subsolidus phase relations in the system Tm<Subscript>2</Subscript>O<Subscript>3</Subscript>-Rh<Subscript>2</Subscript>O<Subscript>3</Subscript>

The Tm₂O₃-Rh₂O₃ system has been studied by x-ray diffraction, thermal analysis, and chemical analysis of annealed and quenched samples. The results have been used to construct a schematic subsolidus phase diagram of the system. Only one double oxide, TmRhO₃, has been identified. Some of its physicochemical properties are reported.     

Properties of nanocrystalline ZrO<Subscript>2</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-CeO<Subscript>2</Subscript>-CoO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> powders

We have studied the properties of nanocrystalline ZrO₂-Y₂O₃-CeO₂-CoO-Al₂O₃ powders prepared via hydrothermal treatment of a mixture of coprecipitated hydroxides at 210°C. A number of general trends are identified in the variation of the properties of the synthesized powders during heat treatment at temperatures from 500 to 1200°C. Our results demonstrate that the addition of 0.3 mol % CoO to nanocrystalline ZrO₂-based powders containing 1 to 5 mol % Al₂O₃ allows one to obtain composites with good sinterability at a reduced temperature (1200°C).     

Effect of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> on the crystallization behavior of SiO<Subscript>2</Subscript>–MgO–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

A series of glass comprising of SiO₂–MgO–B₂O₃–Y₂O₃–Al₂O₃ in different mole ratio has been synthesized. The crystallization kinetics of these glasses was investigated using various characterization techniques such as differential thermal analysis (DTA), thermo gravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Crystallization behavior of these glasses was markedly influenced by the addition of Y₂O₃ instead of Al₂O₃. Addition of Y₂O₃ increases the transition temperature, T _g, crystallization temperature, T _c and stability of the glasses. Also, it suppresses the formation of cordierite phase, which is very prominent and detrimental in MgO-based glasses. The results are discussed on the basis of the structural and chemical role of Y³⁺ and Al³⁺ ions in the present glasses.     

Glass formation in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-BaO system

The physicochemical properties of BaO-Bi₂O₃-B₂O₃ glasses have been studied. The effect of KBF₄ additions on the properties of the glasses has been examined. The transmission of the glasses has been correlated with their local structure and composition.     

Calcium bismuth borates in the CaO-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The 600°C (subsolidus) section of the CaO-Bi₂O₃-B₂O₃ phase diagram has been studied by x-ray diffraction and differential thermal analysis. A new calcium bismuth borate of composition CaBi₂B₄O₁₀ has been identified, and the existence of CaBi₂B₂O₇ has been confirmed. According to T-x phase diagram data, these compounds form peritectically at 700±5 and 783±5°C, respectively.     

Subsolidus Phase Relations in the System Dy<Subscript>2</Subscript>O<Subscript>3</Subscript>-Rh<Subscript>2</Subscript>O<Subscript>3</Subscript>

The Dy₂O₃-Rh₂O₃ system is studied by thermal analysis, x-ray diffraction, and chemical analysis of annealed and quenched samples. The results are used to construct a schematic subsolidus phase diagram of the system. Only one double oxide, DyRhO₃, is obtained. Some of its physicochemical properties are reported.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 8, 2005, pp. 960–965.Original Russian Text Copyright © 2005 by Skrobot, Ugolkov, Grebenshchikov, Gusarov.