Impedance spectroscopy of V2O5–Bi2O3–BaTiO3 glass–ceramics

The glasses within composition as: (80 − x)V₂O₅/20Bi₂O₃/xBaTiO₃ with x = 2.5, 5, 7.5 and 10 mol% have been prepared. The glass transition (T_g) increases with increasing BaTiO₃ content. Synthesized glasses ceramic containing BaTi₄O₉, Ba₃TiV₄O₁₅ nanoparticles of the order of 25–35 nm and 30–46 nm, respectively were estimated using XRD. The dielectric properties over wide ranges of frequencies and temperatures were investigated as a function of BaTiO₃ content by impedance spectroscopy measurements. The hopping frequency, ω_h, dielectric constant, ε′, activation energies for the DC conduction, E_σ, the relaxation process, E_c, and stretched exponential parameter β of the glasses samples have been estimated. The, ω_h, β, decrease from 51.63 to 0.31 × 10⁶ (s⁻¹), 0.84 to 0.79 with increasing BaTiO₃ respectively. Otherwise, the E_σ, increase from 0.279 to 0.306 eV with increasing BaTiO₃. The value of dielectric constant equal 9.5·10³ for the 2.5BaTiO₃/77.5V₂O₅/20Bi₂O₃ glasses-ceramic at 330 K for 1 KHz which is ten times larger than that of same glasses composition. Finally the relaxation properties of the investigated glasses are presented in the electric modulus formalism, where the relaxation time and the respective activation energy were determined.     

Infrared,Raman and XPS spectroscopic studies of Bi2O3–B2O3–Ga2O3 glasses

Glasses with compositions 60Bi₂O₃–(40?x)B₂O₃–xGa₂O₃ (x = 5, 10, 15, 20 mol%) are prepared by conventional melting method. The thermal properties are investigated by differential thermal analysis (DTA) and the structures of the glasses were probed by Infrared, Raman and X-ray photoelectron spectroscopy (XPS). The results show that density, refractive index and optical basicity increase with the increase of Ga₂O₃. The glass transition temperature (T_g), the onset crystallization temperature (T_x), ΔT (T_x?T_g) decrease with the content of Ga₂O₃. The cut-off edges in ultraviolet and infrared shift to longer wavelength with the increase of Ga₂O₃. On the other hand, the addition of Ga₂O₃ causes a progressive coordination number change of the boron atom from 3 to 4. XPS result indicates both Bi⁵⁺ and Bi³⁺ exist in 5 mol% Ga₂O₃ content, while Bi⁵⁺ amounts decrease with the increase of Ga₂O₃ contents. The glass is mainly composed of [BiO₆], [BO₃], [BO₄] and [GaO₄] polyhedra. Glasses are supposed to have layer structure. [BO₃] triangle and [BO₄] tetrahedra may be located between the [GaO₄] tetrahedral and [BiO₆] octahedra to prevent crystallization and to compensate electric charge.     

ZrO2–Sc2O3 Solid Electrolytes Doped with Yb2O3 or Y2O3

Russian Journal of Electrochemistry - The effects of the Y2O3 and Yb2O3 co-doping impurities on the transport characteristics and stabilization of the cubic phase in solid solutions based on...     

Phase Equilibria in The System La2O3–K2O–P2O5

The ternary system La₂O₃–K₂O–P₂O₅ has been examined by thermal, X-ray, IR and microscopic methods. The existence of three double potassium-lanthanum phosphates, K₃La(PO₄)₂, KLa(PO₃)₄ and K₂La(PO₃)₅ has been confirmed, and the phase diagram of the ternary system La₂O₃–K₂O–P₂O₅ over the composition range LaPO₄–K₃PO₄–P₂O₅ has been determined. This revised version was published online in August 2006 with corrections to the Cover Date.     

Comparative studies in subsolidus areas of ternary oxide systems PbO–V2O5–In2O3 and PbO–V2O5–Fe2O3

Thermal stability of PbO was studied. Reactivity of oxides in the systems PbO–M₂O₃ (M = In, Fe) was investigated up to 650 °C. Using the DTA and XRD methods, parts of investigated ternary oxide systems, labelled by compounds: V₂O₅, Pb₈V₂O₁₃ and M₂O₃ (M = In, Fe), have been divided into partial ternary systems. IR spectra of compounds Pb₂MV₃O₁₁ (M = In, Fe) have been compared.     

Phase equilibria in the oxide system Nd2O3–K2O–P2O5

A phase equilibria diagram of the partial system NdPO₄–K₃PO₄–KPO₃ has been developed as part of the research aimed at determining the phase equilibrium relationships in the oxide system Nd₂O₃–K₂O–P₂O₅. The investigations were conducted using thermoanalytical techniques, X-ray powder diffraction analysis and reflected-light microscopy. Three isopleths existing between: K₃Nd(PO₄)₂–K₄P₂O₇, NdPO₄–K₅P₃O₁₀ and NdPO₄–K₄P₂O₇ have been identified in the partial NdPO₄–K₃PO₄–KPO₃ system. Previously unknown potassium-neodymium phosphate “K₄Nd₂P₄O₁₅” has been discovered in the latter isopleth section. This phosphate exists in the solid phase up to a temperature of 890 °C at which it decomposes into the parent phosphates NdPO₄ and K₄P₂O₇. Four invariant points: two quasi-ternary eutectics, E₁ (1057 °C) and E₂ (580 °C) and two quasi-ternary peritectics, P₁ (1078 °C) and P₂ (610 °C), occur in the NdPO₄–K₃PO₄–KPO₃ region.     

The effect of mechanical activation on the thermal reactions of P2O5–Al2O3–Fe2O3–Na2O phosphate glasses

The effect of mechanical activation on the structure and thermal reactions of glasses has been studied on the example of Na–Al–Fe phosphate glasses. These glasses are used in nuclear technology for immobilization of radioactive waste. The glasses were activated by grinding in a planetary mill. Mechanical activation causes a decrease of the T _g temperature as well as of the glass crystallization temperature. The type of crystalline phases formed and the quantitative proportions between them are changing. Analysis of inter-atomic interactions in the structure of glass was applied to explain the observed regularities governing the crystallization of the activated glasses.     

Kinetics of nonisothermal crystallization of Cs2O–Fe2O3–P2O5 glasses

The crystallization kinetics of Cs₂O–Fe₂O₃–P₂O₅ glasses containing 12.5–27 mol% Cs₂O were studied by using differential scanning calorimetry under nonisothermal conditions. Strong dependence of activation energy with temperature was observed, indicating the complex nature of the crystallization process. The various crystallization products were identified by X-ray diffraction technique. CsFeP₂O₇ was found to be the major crystalline phase in all cases. The overall activation energy obtained by classical model-free kinetic method was compared with that of isoconversional method; and from the results, the dependence of activation energy on extent of reaction and average temperature was delineated.     

Preparation and characterization of SO4 2−/Fe2O3–TiO2–Nd2O3 catalyst

This paper reports on the preparation of SO₄ ^2?/Fe₂O₃–TiO₂–Nd₂O₃ (SFTN) by combustion method. The effect of Nd content on catalytic activity was investigated. The prepared materials doped and undoped by Nd were compared by means of TG-DTG, XRD, FT-IR, NH₃-TPD and TEM techniques. Results indicated that the introduction of Nd improved the catalytic activities of the catalysts. Catalytic activity of SFTN was the highest with 98.3 % menthol conversion when Nd content was at 2 wt%. The introduction of Nd stabilized the coordination bond between the sulfate irons and the metallic oxides, helping in the formation of solid acid sites, enhancing the dispersion of catalyst particles, and inhibiting the growth of catalyst particles under heating.     

Infrared,Raman and XPS spectroscopic studies of Bi2O3–B2O3–GeO2 glasses

Glasses with composition 50Bi₂O₃–(50 ? x) B₂O₃–xGeO₂ (x = 0, 5, 10, 15 mol%) were prepared by conventional melting method. The thermal properties were investigated by differential thermal analysis (DTA) and the structures of the glasses were probed by Infrared, Raman and X-ray photoelectron spectroscopy (XPS). The results show that density, refractive index and optical basicity increase with the increase of GeO₂. The glass transition temperature (T_g), onset crystallization temperature (T_x) and ΔT (T_x ? T_g) increase as well. The cut-off edges in ultraviolet and infrared shift to longer wavelength by the addition of GeO₂. Infrared, Raman and XPS results indicate that the glass network consists of [Bi–O₆] octahedron, [BO₃] triangle, [BO₄] tetrahedron and [GeO₄] tetrahedron and borate oxide mainly exists in [BO₃] units. XPS result indicates Ge⁴⁺ ions form steady [GeO₄] tetrahedra units in the glass network and the number of non-bridging oxygens decreases with the addition of GeO₂.     

Investigation of phase equilibria in the Er2O3–Na2O–P2O5 system: the partial system ErPO4–NaPO3–Er(PO3)3

The partial system ErPO₄–NaPO₃–Er(PO₃)₃ of the Er₂O₃–Na₂O–P₂O₅ oxide system has been investigated by thermoanalytical methods and X-ray powder diffraction. On the basis of the obtained results the phase diagram of the partial system is proposed. The system is bounded by three subsystems: (i) ErPO₄–Er(PO₃)₃, (ii) Er(PO₃)₃–NaPO₃ and (iii) ErPO₄–NaPO₃. Their phase diagrams are proposed. In the Er(PO₃)₃–NaPO₃ subsystem an intermediate compound NaEr(PO₃)₄ occurs; it melts incongruently at 655 °C. It was found that ErPO₄ and NaEr(PO₃)₄ form a section which is a real system only in the subsolidus region (below 646 °C). Two ternary invariant points (one ternary peritectic and one ternary eutectic) occur in the investigated partial system ErPO₄–NaPO₃–Er(PO₃)₃.     

Phase Diagrams of Fullerenol-d–LaCl3–H2O and Fullerenol-d–GdCl3–H2O Systems at 25°С

Russian Journal of Physical Chemistry A - Isothermal phase diagrams of ternary systems fullerenol-d–LaCl3–H2O and fullerenol-d–GdCl3–H2O at 25°C are studied via...     

Effects of nano-YAG (Y3Al5O12) crystallization on the structure and photoluminescence properties of Nd3+-doped K2O–SiO2–Y2O3–Al2O3 glasses

Nd³⁺-doped precursor glass in the K₂O–SiO₂–Y₂O₃–Al₂O₃ (KSYA) system was prepared by the melt-quench technique. The transparent Y₃Al₅O₁₂ (YAG) glass–ceramics were derived from this glass by a controlled crystallization process at 750 °C for 5–100 h. The formation of YAG crystal phase, size and morphology with progress of heat-treatment was examined by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and Fourier transformed infrared reflectance spectroscopy (FT-IRRS). The crystallite sizes obtained from XRD are found to increase with heat-treatment time and vary in the range 25–40 nm. The measured photoluminescence spectra have exhibited emission transitions of ⁴F_3/2 → ⁴I_J (J = 9/2, 11/2 and 13/2) from Nd³⁺ ions upon excitation at 829 nm. It is observed that the photoluminescence intensity and excited state lifetime of Nd³⁺ ions decrease with increase in heat-treatment time. The present study indicates that the incorporation of Nd³⁺ ions into YAG crystal lattice enhance the fluorescence performance of the glass–ceramic nanocomposites.     

Solid Solutions in The Cr2O3–α-Sb2O4–MoO3 System

DTA and XRD methods used to examine the Cr₂O₃–α-Sb₂O₄–MoO₃ system have shown that a substitution solid solution of MoO₃ in CrSbO₄ is formed. A study of all the theoretically possible solid solution models has pointed to the fact that Mo⁶⁺ ions are incorporated into the CrSbO₄ crystal lattice, in the place of Sb⁵⁺ ions and the compensation of redundant charges takes place through cation vacancies arising in an Sb⁵⁺ sub-lattice. The solubility limit for MoO₃ in CrSbO₄ does not exceed 25.00 mol%. CrSbO_4(s.s.) is stable to ~1320°C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structure and properties of glasses in the system Li2O–SnO–B2O3

Glasses in the system Li₂O–SnO–B₂O₃ system were prepared by a melt-quenching method. Thermal and viscous properties and local structure of these glasses were investigated. The SnO–B₂O₃ glasses exhibited relatively low glass-transition temperatures (T_g) around 350 °C and excellent thermal stability against crystallization. Viscosity measurements in the vicinity of T_g indicated that the glasses were considerably fragile compared to alkali borate glasses. Fraction of four-coordinated boron was maximized at the composition with 50 mol% SnO and that of nonbridging oxygen, which is not purely ionic in alkali borate systems but partially covalent, augmented with an increase in the SnO content. Correlation between glass properties and structure was discussed in the SnO–B₂O₃ binary system.     

Ga2O3-La2O3-Yb2O3-Er2O3(HO2O3)体系光谱性质的研究

根据稀土离子能级的特点,对Ga2O3-La2O3-Yb2O3-Er2O3(HO2O3)体系的光谱性质进行了探讨,发现它们有二类发光性质:Stokes发光和反Stokes发光,研究了发光强度和发射波长与掺杂离子的依赖关系,观察到由能量的共振转移引起的荧光浓度猝灭现象,并取得了最大发光强度时的掺杂离子浓度和一些规律性结果.     

Mullitization behavior and microstructural development of B2O3–Al2O3–SiO2 mixtures activated by high-energy ball milling

This paper reports on phase formation and microstructural development of mullite, derived from B₂O₃–Al₂O₃–SiO₂ mixtures activated with different milling methods. It is found that the addition of B₂O₃ has a positive effect on mullite phase formation from the mixture of Al₂O₃–SiO₂, which can be qualitatively attributed to the fact that B₂O₃ brought out higher nucleation density and enhanced reaction kinetics. Anisotropic grain growth of mullite was not observed in the unmilled mixture since mullite phase formation occurred after densification. Dense and interlocking microstructures of mullite ceramics were produced from the mixture activated with stainless steel milling media, whereas mullite whiskers were formed in the samples milled with tungsten carbide media. The high-energy ball milling refined the precursors and thus reduced the mullitization temperature. As a result, anisotropic microstructures and mullite whiskers could be derived from the milled mixtures. This way to produce anisotropic microstructures of mullite ceramics is very simple and requires temperatures much lower than those reported in the literature. This method is believed to be useful to fabricate reinforced mullite or mullite-related materials via in-situ anisotropic grain growth.     

Phases in the subsolidus area of the system CuO–V2O5–Fe2O3

The phase equilibria in the solid state in the system FeVO₄?CCu₃V₂O₈ and FeVO₄?CCuO have been determined. Based on the obtained DTA and XRD analysis results and some additional research, a phase diagram in the whole subsolidus area of the system CuO?CV₂O₅?CFe₂O₃ has been worked out. Eighteen subsidiary subsystems can be distinguished in this ternary system. Basic properties of the obtained phases with howardevansite- and lyonsite-type structure have been investigated by DTA, IR, and SEM methods.     

209Bi NQR in Mixed Oxides 2Bi2O3· B2O3, 3Bi2O3· 5B2O3, and Bi2O3· 3B2O3

It was earlier found from nuclear quadrupole resonance (NQR) measurements and computer modeling that -Bi₂O₃, Bi₃O₄Br and mixed oxides Bi₂O₃· 2Al₂O₃, Bi₂O₃· 2Ga₂O₃, Bi₂O₃· 3GeO₂, and 2Bi₂O₃· 3GeO₂exhibit local ordered magnetic fields from 30 to 200 G. It thus follows that these compounds are not diamagnets in a conventional sence of the word. With the aim of revealing previously unknown magnetic properties in bismuth(III) oxide-based Main Group element compounds, the mixed bismuth–boron oxides 2Bi₂O₃· B₂O₃, 3Bi₂O₃· 5B₂O₃, and Bi₂O₃· 3B₂O₃were prepared and studied using ²⁰⁹Bi NQR. The quadrupole interactions of the ²⁰⁹Bi nuclei and their electronic environment were studied, the crystallochemical features of the compounds were discussed, and the conformity of the ²⁰⁹Bi results to the X-ray structure data was verified. The preliminary tests in the field of a permanent magnet showed that the resonance intensities increase in external magnetic fields, indicating that a magnetism of unknown nature develops in the titled compounds. It was found reasonable to continue studies of the magnetic properties of these compounds using single-crystal ²⁰⁹Bi NQR in external magnetic fields.     

Crystallization mechanism and microstructure evolution of Li2O–Al2O3–SiO2 glass-ceramics with Ta2O5 as nucleating agent

Li₂O–Al₂O₃–SiO₂ glass-ceramics were prepared with Ta₂O₅ as nucleating agent, the crystallization mechanism and microstructure evolution were investigated by DTA, XRD, and SEM technologies. With increasing amount of Ta₂O₅ from 2 to 6 mol%, the crystallization activation energy decreased from 297.73 to 218.66 kJ mol^?1, while the crystallization index increased from 1.76 to 3.39. In addition, the cluster of dendritic crystals and lamellar structure obtained in T-2 glass-ceramics indicated a typical two-dimensional crystallization mechanism, and the formation of spherical β-quartz solid solution in T-4 specimens, with average size of 50–70 nm, was mainly due to bulk crystallization mechanism. It was considered that Ta₂O₅ promoted the nucleation and crystallization of LAS glass by precipitating the crystalline precursor phase of Ta₂O₅, which acted as nuclei for the subsequent crystal growth. Eventually, the diffusion and crystallization process, microstructure morphology, as well as the secondary grain growth were also investigated.