Synthesis and high-temperature heat capacity of Yb<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript> and Lu<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

Yb₂Sn₂O₇ and Lu₂Sn₂O₇ have been prepared by solid-state reactions, by firing mixtures of Yb₂O₃ or Lu₂O₃ and SnO₂ at 1473 K, and the molar heat capacity of these compounds (pyrochlore structure) has been determined by differential scanning calorimetry. The C _p (T) data have been used to evaluate the thermodynamic properties of the stannates: enthalpy increment, entropy change, and reduced Gibbs energy.     

Etching behavior of CdTe in aqueous H<Subscript>2</Subscript>O<Subscript>2</Subscript>-HI-C<Subscript>6</Subscript>H<Subscript>8</Subscript>O<Subscript>7</Subscript> solutions

This paper examines the dissolution behavior of the (111)A, (111)B, (110), and (100) surfaces of CdTe single crystals in aqueous H₂O₂-HI-C₆H₈O₇ (citric acid) solutions. We have determined the dissolution rate of the crystals as a function of temperature and solution concentration, located the composition regions of polishing and selective etchants, and studied the microstructure and roughness of surfaces polished with optimized etchants. The etching behavior of CdTe is shown to depend on its crystallographic orientation.     

Synthesis and high-temperature heat capacity of Gd<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

Gd₂Sn₂O₇ gadolinium stannate with the pyrochlore structure has been prepared by solid-state reaction and its high-temperature heat capacity has been determined by differential scanning calorimetry in the temperature range 350–1020 K. The C_p(T) data are shown to be well represented by the classic Maier–Kelley equation. The experimental C_p(T) data have been used to evaluate the thermodynamic functions of gadolinium stannate: enthalpy increment H°(T)–H°(339 K), entropy change S°(T)–S°(339 K), and reduced Gibbs energy Ф°(Т).     

High-temperature heat capacity and vibrational spectra of Eu<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Eu₂Sn₂O₇ compound has been prepared by solid-state reaction (by sequentially firing a stoichiometric mixture of Eu₂O₃ and SnO₂ in air at 1273 and 1473 K) and its heat capacity has been determined by differential scanning calorimetry in the temperature range 370–1000 K. The heat capacity data have been used to evaluate the thermodynamic properties of europium stannate: enthalpy increment H°(T)–H°(370 K), entropy change S°(T)–S°(370 K), and reduced Gibbs energy Ф°(T). Raman spectra of Eu₂Sn₂O₇ polycrystals with the pyrochlore structure have been measured in the range 200–1200 cm^–1.     

High-temperature heat capacity and thermodynamic properties of Tb<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

Tb₂Sn₂O₇ has been prepared by solid-state reaction in air at 1473 K over a period of 200 h and its isobaric heat capacity has been studied experimentally in the range 350–1073 K. The C _p(T) data for this compound have no extrema and are well represented by the classic Maier–Kelley equation. The experimental C _p(T) data have been used to evaluate the thermodynamic properties of terbium stannate (pyrochlore structure): enthalpy increment H°(T)–H°(350 K), entropy change S°(T)–S°(350 K), and reduced Gibbs energy Ф°(Т).     

Morphology and optical properties of Sb<Subscript>2</Subscript>O<Subscript>3</Subscript>

The chemical and phase compositions of antimony(III) oxide samples prepared under various conditions have been determined. The size and shape of their particles have been assessed by scanning electron microscopy, and the effect of UV irradiation on their diffuse reflectance spectra has been studied. The results are used to determine the whiteness index, integrated reflectance, and lightfastness of the samples.     

Plutonium dioxide catalyzed reaction between H<Subscript>2</Subscript> and O<Subscript>2</Subscript>

The kinetic characteristics of the reaction between H₂ and O₂ were calculated to more adequately simulate the radiolysis of water adsorbed on PuO₂. The rate constants of this reaction were determined via comparison of the calculated results with the published experimental data. It was found that, with the amount of the adsorbed water increasing from 2 × 10^?4 to 5 × 10^?3%, the rate constant of the reaction decreases from 6.0 × 10^?4 to 1.7 × 10^?5 mol^?1 s^?1. At the water content over 5 × 10^?3%, the rate constant is ≤1 × 10^?5 mol^?1 s^?1. A new mathematical model of the radiation-chemical and physicochemical processes occurring in the PuO₂-H₂O system was presented; the amounts of hydrogen and oxygen yielded by α-radiolysis of the adsorbed water were calculated, taking into account the reaction between H₂ and O₂.     

Synthesis,crystal structure,and proton conductivity of KFe(H<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>)<Subscript>2</Subscript>

KFe H₂P₂O7)₂ is synthesized at 443 K in molten polyphosphoric acids containing K and Fe ions, and its crystal structure is determined: triclinic unit cell with a = 4.9974(6) Å, b = 7.4766(9) Å, c = 7.8185(9) Å, = 82.29(2)°, = 83.37(2)° , = 74.13(2)° ; Z = 1, sp. gr. P . The structure is made up of infinite ribbons formed by corner-shared PO₄ tetrahedra and FeO₆ octahedra, with the K atoms in between. Neighboring ribbons are linked by hydrogen bonds. The proton conductivity of potassium iron(III) dihydrogen diphosphate is rather low.Translated from Neorganicheskie Materialy, Vol. 41, No. 1, 2005, pp. 74–77. Original Russian Text Copyright © 2005 by Chudinova, Murashova, Ilyukhin, Tarnopolskii, Yaroslavtsev.     

Synthesis and High-Temperature Heat Capacity of Dy<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript> and Ho<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Dy₂Ge₂O₇ and Ho₂Ge₂O₇ pyrogermanates have been prepared by solid-state reactions in several sequential firing steps in the temperature range 1237–1473 K using stoichiometric mixtures of Dy₂O₃ (or Ho₂O₃) and GeO₂. The heat capacity of the synthesized germanates has been determined as a function of temperature by differential scanning calorimetry in the range 350–1000 K. The experimentally determined C _p (T) curves of the dysprosium and holmium germanates have no anomalies and are well represented by the Maier–Kelley equation. The experimental C _p (T) data have been used to evaluate the thermodynamic functions of the Dy₂Ge₂O₇ and Ho₂Ge₂O₇ pyrogermanates: enthalpy increment H°(T)–H°(350 K), entropy change S°(T)–S°(350 K), and reduced Gibbs energy Ф°(T).     

Synthesis and High-Temperature Heat Capacity of Sm<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript> and Eu<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Sm₂Ge₂O₇ and Eu₂Ge₂O₇ germanates have been prepared by solid-state reactions via multistep firing of stoichiometric mixtures of Sm₂O₃ (Eu₂O₃) and GeO₂ in air at temperatures from 1273 to 1473 K. The molar heat capacity of the samarium and europium germanates has been determined by differential scanning calorimetry in the range 350–1000 K and the C _p (T) data have been used to evaluate their thermodynamic properties.     

Aging of ITO anodes treated by supercritical CO<Subscript>2</Subscript>/H<Subscript>2</Subscript>O<Subscript>2</Subscript> fluids for OLEDs

The aging behaviors of indium tin oxide (ITO) anodes treated by supercritical CO₂/H₂O₂ (SCCO₂/H₂O₂) fluids were investigated. As the SCCO₂/H₂O₂-treated ITO anodes were aged, the contact angle and surface energy were analyzed and compared with those of the ITO anodes treated by oxygen plasma. The SCCO₂/H₂O₂ pretreatment yielded a stable polar component of the ITO surfaces after 48 h of aging. The energy reduction in the polar component of the oxygen-plasma-treated ITO due to aging was 20 %, as compared with the 1.1 % decrease in ITO treated with the SCCO₂/H₂O₂ fluids at 4000 psi for 15 min. The X-ray photoelectron spectroscopy analysis revealed that the oxygen content of the ITO surfaces with the SCCO₂/H₂O₂ pretreatment was significantly higher than that of the ITO treated by oxygen plasma. This could result from the formation of hydroxyl products that functioned as a stable buffer layer against further contamination during aging. In addition, the correlated dependence of the OLED performance on the aged ITO anodes was also studied. The OLEDs with the SCCO₂/H₂O₂ pretreatment showed an improved degradation of I–V characteristics and brightness in comparison with those of the devices treated with oxygen plasma after aging the treated ITO anodes for 6 and 12 h. The obtained results suggested that the ITO anodes treated by the SCCO₂/H₂O₂ fluids exhibited a stable surface chemistry and could be useful for OLED applications.     

Impedance analysis of Pb<Subscript>2</Subscript>Sb<Subscript>3</Subscript>LaTi<Subscript>5</Subscript>O<Subscript>18</Subscript> ceramic

Polycrystalline sample of Pb₂Sb₃LaTi₅O₁₈, a member of tungsten- bronze (TB family, was prepared using a high temperature solid- state reaction technique. XRD analysis indicated the formation of a single-phase orthorhombic structure. The dielectric studies revealed the diffuse phase transition and the transition temperature was found to be at 52° C. Impedance plots were used as tools to analyse the sample behaviour as a function of frequency. Cole-Cole plots showed Debye relaxation. The activation energy was estimated to be 0·634 eV from the temperature variation of d.c. conductivity. The nature of variation of d.c. conductivity with temperature suggested NTCR behaviour.     

Addition of Sb<Subscript>2</Subscript>O<Subscript>5</Subscript> into MgB<Subscript>2</Subscript> Superconductor Obtained by Spark Plasma Sintering

High-density (92–98 % of the theoretical density) MgB ₂ samples added with Sb ₂ O ₅ ((MgB ₂)+ (Sb ₂ O ₅) _x ,x= 0, 0.0025, 0.005, 0.015) were obtained by Spark Plasma Sintering. A higher amount of additive decreases density. In added samples, grains of secondary phases are located at MgB ₂ grain boundaries and they are of large size. Hence, Sb ₂ O ₅ does not promote effective flux pinning, connectivity is lower, and this suppresses the critical current density and the irreversibility field. Pinning force-related parameters indicate that added samples are close to the point pinning region and they show a higher grain boundary pinning contribution when compared with pristine MgB ₂ sample and when temperature is lower. It is speculated that for fixed processing conditions and Sb-oxide phases, a lower stability of the additive, reflected by a lower melting temperature, may promote reactive processes to start earlier leading to coarsening of the grains belonging to secondary phases.     

MgB<Subscript>2</Subscript> with addition of Sb<Subscript>2</Subscript>O<Subscript>3</Subscript> obtained by spark plasma sintering technique

Superconducting bulks of MgB₂ with addition of Sb₂O₃ and Sb with different stoichiometric compositions ((MgB₂) + (Sb₂O₃) _x , x = 0.0025, 0.005, 0.015, and (MgB₂) + (Sb)_y, y = 0.01) were obtained by the Spark Plasma Sintering (SPS) technique. All added samples have high density, above 95% and critical temperature, T _c, of 38.1–38.6 K. This result and XRD data suggest that Sb does not enter the lattice of MgB₂. Impurity phases are Mg₃Sb₂, MgO, and MgB₄. The optimum addition is Sb₂O₃ for x = 0.005. This sample shows the critical current density, J _c(5 K, 0 T) = 4 × 10⁵ A/cm² and J _c(5 K, 7 T) = 6 × 10² A/cm², while the irreversibility field, H _irr (5 K, 100 A/cm²) = 8.23 T. Indicated values of J _c and H _irr are higher than for the pristine sample. The mechanism of J _c and H _irr increase in the Sb₂O₃ added samples is complex and composed of opposite effects most probably involving morphology elements, the presence of nano metric MgB₄ and the indirect influence of oxygen or oxygen and Sb. Crystallite size of MgB₂ is decreasing when Sb-based additions are introduced and the effect is stronger for the Sb-metal addition. The sample with Sb-metal addition does not improve J _c and H _irr when compared with pristine sample.     

Characterization and electrical properties of semiconducting 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

Semiconducting glasses of the Fe₂O₃-Bi₂O₃-K₂B₄O₇ system were prepared by the press-quenching method and their dc conductivity in the temperature range 223–393 K was measured. The glass transition temperature values (T_g) of the present glasses were larger than those of tellurite glasses. This indicates a higher thermal stability of the glass in the present system. The density for these glasses was consistent with the ionic size, atomic weight and amount of different elements in the glasses. Mössbauer results revealed that the relative fraction of Fe increases with increasing Fe₂O₃ content. Electrical conductivity showed a similar composition dependency as the fraction of Fe. The glasses had conductivities ranging from 10 to 10 Scm at temperatures from 223 to 393 K. Electrical conduction of the glasses was confirmed to be due to non-adiabatic small polaron hopping and the conduction was primarily determined by hopping carrier mobility.     

Crystal and molecular structure of uranyl acetylacetonate dimer, [UO<Subscript>2</Subscript>(C<Subscript>5</Subscript>H<Subscript>7</Subscript>O<Subscript>2</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>

The crystal and molecular structure of uranyl acetylacetonate dimer was determined by single crystal X-ray diffraction. The compound crystallizes in the tetragonal system, a = 7.9420(2), c = 40.1240(13) Å (at 100 K), Z = 4, space group P4₁2₁2. Dimeric uranyl acetylacetonate molecules in the crystal are formed by bridging bonding of one of O atoms of the acetylacetonate ligands with U atoms, so that the coordination polyhedra of U atoms (distorted pentagonal bipyramids) share a common equatorial edge. The dimer has a nonplanar structure, being significantly bent along the conventional line connecting the bridging O atoms.     

Molybdenum dissolution in mixtures of H<Subscript>2</Subscript>O<Subscript>2</Subscript> and concentrated HNO<Subscript>3</Subscript> and H<Subscript>2</Subscript>SO<Subscript>4</Subscript> in the presence of tungsten

The oxidation of molybdenum and tungsten in hydrogen peroxide solutions and the effect of H₂O₂ on the selectivity of Mo and W dissolution in mixtures of concentrated nitric and sulfuric acids have been studied.     

The calculation of liquid-vapor phase equilibrium in H<Subscript>2</Subscript>O-H<Subscript>2</Subscript>O<Subscript>2</Subscript> two-component system

The dependences of total pressure and equilibrium composition of vapors on temperature and mole fraction of hydroperoxide in solution are calculated for a water-hydroperoxide two-component two-phase system. It is assumed that the relaxation to concentration equilibrium in gas at the surface of solution is attained quite rapidly compared to the half-life of hydroperoxide. Three independent approximate methods are used to calculate the total pressure. The ideal gas approximation for the gas phase is not used in two of these methods. Approximation formulas are suggested, which explicitly express the dependence of pressure and composition of gas on relative concentration of hydroperoxide in solution and on temperature. The accuracy of the methods and the range of their validity are discussed.     

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.