Growth of bulk β-BaB<Subscript>2</Subscript>O<Subscript>4</Subscript> crystals of high optical quality in the BaB<Subscript>2</Subscript>O<Subscript>4</Subscript>-NaBaBO<Subscript>3</Subscript> system

Phase equilibria along the BaB₂O₄-NaBaBO₃ join of the BaO-B 2 O 3 -Na 2 O system are studied by differential thermal analysis and modified visual thermal analysis. The join is shown to be suitable for growing - BaB₂O₄ crystal of high optical quality.Translated from Neorganicheskie Materialy, Vol. 41, No. 1, 2005, pp. 64–69. Original Russian Text Copyright © 2005 by Kokh, Kononova, Fedorov, Bekker, Kuznetsov.     

Synthesis of thorn-like Ca<Subscript>2</Subscript>B<Subscript>2</Subscript>O<Subscript>5</Subscript>·H<Subscript>2</Subscript>O by hydrothermal method

Thorn-like polycrystalline Ca₂B₂O₅·H₂O microspheres with nano-sized slices were synthesized using boric acid and calcium hydroxide as reactants by a facile catalyst-free hydrothermal method at low temperature. The products were characterized by means of X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The XRD pattern reveals that the Ca₂B₂O₅·H₂O is a monoclinic phase polycrystalline with cell parameters a = 0·6702, b = 0·5419 and c = 0·3558 nm. SEM also reveals that the monoclinic phase polycrystalline are thorn-like microspheres composed of many flakes with an average thickness of <100 nm. Possible reaction and growth mechanism were also discussed.     

Effect of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> on the dynamics of Li<Superscript>+</Superscript> ions in Li<Subscript>2</Subscript>O·P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Lithium ion transport has been studied in bismuth lithium phosphate glasses in the frequency range 20 Hz–1 MHz and in the temperature range 423–573 K using impedance spectroscopy. The addition of Bi₂O₃ in Li₂O·P₂O₅ glass is related to the modification of the glass structure and facilitates the Li⁺ ions migration. The ac and dc conductivities, activation energy of the dc conductivity and relaxation frequency are extracted from the impedance spectra. Conductivity of the present glass system is found to be ionic in nature. The electrical response of the glasses has been studied using both conductivity and electric modulus formalisms. A single ‘master curve’ for normalized plots of all the modulus isotherms observed for a given composition indicates the temperature independence of the dynamic processes for ions in these glasses. Nearly identical values of activation energy for dc conduction and for conductivity relaxation time indicate that the ions overcome same energy barrier while conducting and relaxing.     

Variable—Range hopping in Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-K<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript> glasses

The dc conductivity of the glasses in the Fe₂O₃-Bi₂O₃-K₂B₄O₇ system was studied at temperatures between 223 and 393 K. At temperatures from 300 to 223 K, T^–1/4 (T is temperature) dependence of the conductivity was found, however, both Mott variable-range hopping and Greaves intermediate range hopping models are found to be applicable. Mott and Greaves parameters analysis gave the density of states at Fermi level N (E_F) = 3.13 × 10²⁰–21.01 × 10²⁰ and 1.93 × 10²¹–16.39 × 10²¹ cm^–3eV^–1 at 240 K, respectively. The variable-range hopping conduction occurred in the temperature range T = 300–223 K, since W_D was found to be large (W_D = 0.08–0.14 eV for these glasses) and dominated the conduction at T < 300 K.     

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.     

Investigation of solid solution of ZrP<Subscript>2</Subscript>O<Subscript>7</Subscript>–Sr<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

In this study, ZrP₂O₇ was synthesized by the solid state reaction of ZrO₂ and NH₄H₂PO₄ at 900 °C. Then, in set 1; 10, 5, 1, 0.5, 0.1, 0.05, 0.03% previously prepared Sr₂P₂O₇ were doped into ZrP₂O₇, and Sr₂P₂O₇ slightly affect the unit cell parameter of cubic ZrP₂O₇ (a = 8.248(6)–8.233(8) Å). The reverse of this process was also applied to Sr₂P₂O₇ system (set 2). ZrP₂O₇ changes the unit cell parameters of orthorhombic Sr₂P₂O₇ in between a = 8.909(5)–8.877(5) Å, b = 13.163(3)–13.12(1) Å, and c = 5.403(2)–5.386(4) Å. Analysis of the vibrations of the P₂O ₇ ^4? ion and approximate band assignments for IR and Raman spectra are also reported in this work. Some coincidences in infrared and Raman spectra both sets were found and strong P–O–P bands were observed. Surface morphology, EDX analysis, and thermoluminescence properties of both sets were given the first time in this paper.     

Influence of Bi substitution on microwave dielectric properties of BaO–La<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sm<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiO<Subscript>2</Subscript> ceramics

The influences of Bi substitution on microwave dielectric properties of Ba₄(La_0.5Sm_0.5)_9.33Ti₁₈O₅₄ solid solutions were investigated. Dielectric ceramics with general formula Ba₄(La_(0.5−z)Sm_0.5Bi _z )_9.33Ti₁₈O₅₄, z = 0.0–0.2 were prepared by conventional solid state route. The structural analysis of all the samples was carried out by X-ray diffraction and scanning electron microscopy. The dielectric properties were investigated as a function of Bi contents using open-ended coaxial probe method in the frequency range 0.3–3.0 GHz at room temperature. Dielectric constant varies from 83 to 88 and loss tangent from 2.1 × 10⁻³ to 5.5 × 10⁻³ at 3 GHz with temperature coefficient of resonant frequency changing from 106.7 to −8.4 ppm/oC as Bi contents increases from z = 0.00–0.20. It has been found that dielectric constant and temperature coefficient of resonant frequency improve whereas loss tangent is adversely affected with increase in Bi substitution.     

Synthesis and study of uranyl phosphates (UO<Subscript>2</Subscript>)<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>·<Emphasis Type=Italic>n</Emphasis>H<Subscript>2</Subscript>O

Uranyl phosphate (UO₂)₃(PO₄)₂·8H₂O was synthezied. Its dehydration was studied by X-ray diffraction, IR spectroscopy, and thermal and chemical analysis. The dehydration products were isolated and characterized by X-ray diffraction and IR spectroscopy. Their structural features were determined.     

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.     

Thermodynamic properties of Dy<Subscript>2</Subscript>O<Subscript>3</Subscript> · 2ZrO<Subscript>2</Subscript> and Ho<Subscript>2</Subscript>O<Subscript>3</Subscript> · 2ZrO<Subscript>2</Subscript> in the range 10–340 K

The low-temperature heat capacity of Dy₂O₃ · 2ZrO₂ and Ho₂O₃ · 2ZrO₂ has been determined by adiabatic calorimetry in the temperature range 10–340 K. The results have been used to calculate the entropy, enthalpy increment, and reduced Gibbs energy of the zirconates without taking into account their low-temperature magnetic transformations.     

Effect of refractory nitride nanoadditives on the properties of (Bi,Pb)<Subscript>2</Subscript>Sr<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>10+δ</Subscript>

We have investigated the interaction between (Bi,Pb)₂Sr₂Ca₂Cu₃O_10+δ (Bi-2223) and small additions (0.05–0.3 wt %) of nitride powders (TaN, AlN, HfN, NbN, Si₃N₄, TiN, and ZrN) with a particle size from 0.02 to above 0.5 μm and the effect of these nitrides on the microstructure, phase composition, distribution, and morphology of the resulting second-phase inclusions. The concentration and particle size of the nitrides and sintering conditions are shown to influence the superconducting transition temperature T _c, critical current density j _c, irreversible remanent magnetization, bulk density, and mechanical properties of the Bi-2223/nitride composites.     

An Effective Approach to the Synthesis of Nanocrystalline PbMoO<Subscript>4</Subscript> in Na<Subscript>2</Subscript>Mo<Subscript>4</Subscript>O<Subscript>13</Subscript>–PbCO<Subscript>3</Subscript> Melts

This paper presents thermodynamic analysis of reactions of sodium tetramolybdate with Pb₃O₄, PbO₂, PbO, and lead carbonate and describes an effective approach to PbMoO₄ synthesis in melts of the Na₂Mo₄O₁₃–PbCO₃ system, which offers a low synthesis temperature, waste-free character of the process, high rate, and high yield of a reagent-grade synthesis product in a nanocrystalline state. The synthesis product has been identified by chemical analysis, X-ray diffraction, and particle size measurements.     

Kinetics of Thermal Transformation of Mg<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> · 8H<Subscript>2</Subscript>O to Mg<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The kinetics of thermal dehydration of Mg₃(PO₄)₂ · 8H₂O was investigated using thermogravimetry at four different heating rates. The activation energies of the dehydration step of Mg₃(PO₄)₂ · 8H₂O were calculated through the isoconversional Ozawa and Kissinger-Akahira-Sunose (KAS) methods and iterative methods, which were found to be consistent and indicate a single mechanism. The possible conversion function of the dehydration reaction for Mg₃(PO₄)₂ · 8H₂O has been estimated through the Coats and Redfern integral equation, and a better kinetic model such as random nucleation of the “Avrami–Erofeev equation (A _3/2 model)” was found. The thermodynamic functions (ΔH*, ΔG*, and ΔS*) of the dehydration reaction are calculated by the activated complex theory and indicate that it is a non-spontaneous process when the introduction of heat is not connected.     

Synthesis of supported SnO<Subscript>2</Subscript>–CeO<Subscript>2</Subscript> catalysts for the deep oxidation of methane

A new method has been proposed for the synthesis of catalytically active 80 wt % SnO₂ + 20 wt % CeO₂ materials supported on glass fiber, which involves the use of an ethanolic film-forming solution based on cerium(III) nitrate and salicylic acid, with the addition of tin(IV) chloride. We have studied the morphology of the materials thus prepared and assessed their catalytic activity for the deep oxidation of methane. The results indicate that the appreciable catalytic activity of the materials is ensured by their uniform distribution over the support surface and the small oxide aggregate size ( 10 μm), which is due to the use of the filmforming solution of the proposed composition.     

Synthesis and characterization of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZrO<Subscript>2</Subscript> nanocomposite powder by sucrose process

Nanocrystalline alumina–zirconia powders were prepared by a modified chemical route using sucrose, polyvinyl alcohol (PVA) and metal nitrates followed by a post calcination process. The process involved dehydration of Al³⁺–Zr⁴⁺ ions-sucrose–PVA solution to a highly viscous liquid which on decomposition process produced a black precursor material. The obtained precursor were then calcined at various temperatures: 1,050, 1,100, 1,150, 1,200 and 1,250 °C for different soaking times (1, 2, 4 h) in air. The formation of a nanocomposite composed of α-alumina (~20 nm) and tetragonal (t) zirconia (~19 nm) crystallites were confirmed for the sample calcined at 1,200 °C for 2 h, based on our XRD and TEM results. However, for the samples calcined below 1,150 °C the composite formed were composed of metastable alumina (γ, δ, θ) as well as t-zirconia phases. Interestingly, the zirconia phase retained its tetragonal structure for all the samples calcined above 1,050 °C. This is possibly related to the “size effect” and reduction of surface enthalpy of the zirconia crystallites surrounded by Al³⁺ cations.     

Synthesis and properties of nanocrystalline 90 wt % ZrO<Subscript>2</Subscript>〈Y<Subscript>2</Subscript>O<Subscript>3</Subscript>, CeO<Subscript>2</Subscript>〉-10 wt % Al<Subscript>2</Subscript>O<Subscript>3</Subscript> powder

Using hydrothermal treatment of coprecipitated hydroxides, we have prepared nanocrystalline ZrO₂-rich ZrO₂-Y₂O₃-CeO₂-Al₂O₃ powder. The effect of heat treatment on the properties of the powder has been studied in the temperature range 400–1300°C. The powder has been shown to have a metastable phase composition, which is attributable to structural and size factors and also to the fact that the ZrO₂ and Al₂O₃ crystallites inhibit the growth of each other. Sintering the powder under various conditions, we have obtained ceramics with fracture toughnesses from 6.4 to 16.8 MPa m^1/2.     

Crystal Structure of Uranyl Malonate Trihydrate [UO<Subscript>2</Subscript>(OOC)<Subscript>2</Subscript>CH<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)]·2H<Subscript>2</Subscript>O

Single crystals of [UO₂(OOC)₂CH₂(H₂O)]·2H₂O (I) were prepared by recrystallization of finely crystalline uranyl malonate trihydrate under hydrothermal conditions. The crystal structure of I consists of electroneutral [UO₂(OOC)₂CH₂(H₂O)]_n layers and water molecules located between them. The uranium coordination number is 7. The uranium coordination polyhedron is a distorted pentagonal bipyramid with the oxygen atoms of the uranyl group in the apices. The equatorial plane is occupied by four O atoms of three malonate ligands and the water molecule. The malonate anion is coordinated in the bidentate fashion to one uranyl ion to form a six-membered ring and in the monodentate fashion to two other uranyl ions.     

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).