Revised heat capacity and thermodynamic functions of GdVO<Subscript>4</Subscript>

The heat capacity of GdVO₄ has been determined by adiabatic calorimetry in the range 5–345 K. The present experimental data and earlier results have been used to evaluate the thermodynamic functions of gadolinium orthovanadate (C _p ⁰(T), S ⁰(T), H ⁰(T) − H ⁰(0), and Φ⁰(T)) as functions of temperature (5–350 K). Its Gibbs energy of formation is determined to be Δ_f G ⁰(GdVO₄, 298.15 K) = −1684.5 ± 1.6 kJ/mol.     

Heat capacity and thermodynamic functions of LaVO<Subscript>4</Subscript> and LuVO<Subscript>4</Subscript> from 7 to 345 K

The heat capacities of lanthanum and lutetium orthovanadates have been measured at temperatures from 7 to 345 K using an adiabatic calorimeter. No anomalies have been detected in the heat capacity data. The thermodynamic functions (C _p ⁰(T), S ⁰(T), and H ⁰(T) − H ⁰(0)) of the two compounds have been calculated in the temperature range studied, and their Debye characteristic temperatures have been estimated.     

High-temperature thermodynamic properties of LuPO<Subscript>4</Subscript>

The high-temperature enthalpy of lutetium orthophosphate has been determined as a function of temperature in the range 432.92–1744.58 K using drop calorimetry. The present and earlier experimental data have been used to calculate temperature-dependent heat capacity of LuPO₄ in the range 1–1750 K.     

Electrical and thermodynamic properties of Cs<Subscript>0.97</Subscript> Rb<Subscript>0.03</Subscript>H<Subscript>2</Subscript>PO<Subscript>4</Subscript>

The transport properties of Cs_0.97Rb_0.03H₂PO₄ have been studied using polycrystalline samples and single crystals. The mixed salt is isostructural with cesium dihydrogen phosphate and has slightly smaller unitcell parameters. The cation substitution increases the low-temperature ionic conductivity of the material by about two orders of magnitude but has an insignificant effect on the conductivity of the high-temperature phase. The low-temperature conductivity of single-crystal samples exhibits significant anisotropy, with σ _a < σ _b±c . The conductivity of the polycrystalline material is close to σ _b±c . The substitution reduces the temperature of the superionic phase transition by 20°C and enhances the thermal stability of the high-temperature phase at low humidity (1 mol % H₂O).     

Heat capacity and thermodynamic properties of crystalline SrB<Subscript>4</Subscript>O<Subscript>7</Subscript>

The heat capacity of a strontium tetraborate (SrB₄O₇) single crystal has been determined in the temperature range 55–300 K by adiabatic calorimetry, and its Debye characteristic temperature, entropy change, enthalpy increment, and phonon mean free path have been calculated as functions of temperature.     

Vapor pressure determination for solid and liquid La<Subscript>2</Subscript>S<Subscript>3</Subscript> using boiling points

A high-temperature technique was developed for vapor pressure determination of solid and liquid γ-La₂S₃ (we called it the boiling point technique). Melting temperatures and total vapor pressures were measured for incongruently vaporizing γ-La₂S₃ at 1853–2210 K and 0.3–3.0 atm pressures. Having compared the slopes of the log p(S₂) versus 1/T plots measured by various techniques, we recommend the equation log p(S₂) [atm] = (6.31 ± 0.15) ? (12720±310)T ^?1 for T = 1021–2013 K as the most reliable for practical use.     

Compounds WAl<Subscript>4</Subscript>, WAl<Subscript>3</Subscript>, W<Subscript>3</Subscript>Al<Subscript>7</Subscript>, and WAl<Subscript>2</Subscript> and Al-W-N combustion products

X-ray diffraction data are presented for combustion products in the Al-W-N system. New, nonequilibrium intermetallic compounds have been identified, their diffraction patterns have been indexed, and their unit-cell parameters have been determined. The phases α-and β-WAl₄ are shown to exist in three isomorphous forms, differing in unit-cell centering. The phases α′-, α″-, and α?-WAl₄ are monoclinic, with a ₀ = 5.272 Å, b ₀ = 17.770 Å, c ₀ = 5.218 Å, β = 100.10°; point groups C12/c1, A12/n1, I12/a1, respectively. The phases β′-, β″-, and β?-WAl₄ are monoclinic, with a ₀ = 5.465 Å, b ₀ = 12.814 Å, c ₀ = 5.428 Å, β = 105.92°; point groups A112/m, B112/m, I112/m, respectively. The compounds WAl₂ and W₃Al₇, identified each in two isomorphous forms, differ in cell metrics (doubling) but possess the same point group: P222. WAl ₂ ^′ : orthorhombic, a ₀ = 5.793 Å, b ₀ = 3.740 Å, c ₀ = 6.852 Å. WAl ₂ ^″ : orthorhombic, a ₀ = 11.586 Å, b ₀ = 3.740 Å, c ₀ = 6.852 Å. W₃Al ₇ ^′ : orthorhombic, Pmm2, a ₀ = 6.225 Å, b ₀ = 4.806 Å, c ₀ = 4.437 Å. W₃Al ₇ ^″ : orthorhombic, Pmm2, a ₀ = 12.500 Å, b ₀ = 4.806 Å, c ₀ = 8.874 Å. The new phase WAl₃: triclinic, P1, a ₀ = 8.642 Å, b ₀ = 10.872 Å, c ₀ = 5.478 Å, α = 104.02°, β = 64.90°, γ = 107.15°.     

Liquid-phase epitaxy of NdAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> and Yb-doped YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Epitaxial layers of NaAl₃(BO₃)₄ (NAB) and YAl₃(BO₃)₄〈Yb〉 (YAB〈Yb〉) containing up to 10 at % Yb have been grown by liquid-phase epitaxy on YAB substrates. Their growth kinetics have been studied at relative supersaturations of the high-temperature solution from 2 × 10^?2 to 16 × 10^?2. The ytterbium concentration in YAB〈Yb〉 has been shown to vary little during the epitaxial process. Near the edges of the substrate, the surface morphology of the layers is complicated by vicinals, which have a spiral form in the case of YAB〈Yb〉. On \(\{ 10\overline 1 1\} \) YAB substrates, homogeneous single-crystal NAB films have been grown.     

Enhanced photoluminescence of CoWO<Subscript>4</Subscript> in CoWO<Subscript>4</Subscript>/PbWO<Subscript>4</Subscript> nanocomposites

CoWO₄/PbWO₄ nanocomposites were successfully synthesized at room temperature (RT) by co-precipitation route without using any templates or surfactants and sintered at 600 °C for good crystallization. The sintered samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy and Zeta potential measurements. UV–Visible diffuse reflectance spectroscopy, photoluminescence (PL) and PL lifetime were studied at RT. The results indicate that the composites have two-phase composition: CoWO₄ and PbWO₄. SEM micrograph and zeta potential measurements reveal particle agglomeration. The intrinsic PL peak emission at 467 nm of CoWO₄ nano sample was enhanced upto four times by optimizing the atomic ratio of Pb/Co concentration. The interconnected interface of CoWO₄/PbWO₄ nanocomposites could have led to increase in number of recombination of electron hole pairs in CoWO₄ and enhanced its intrinsic PL emission intensity. The mechanism of enhanced PL emission for the CoWO₄/PbWO₄ nanocomposites can be attributed to charge transfer between [WO₄]^2? and [WO₆]^6? complexes due to intra particle agglomeration leading to possible interface.     

Electric-field effect on crystal growth in the Li<Subscript>3</Subscript>PO<Subscript>4</Subscript>-Li<Subscript>4</Subscript>GeO<Subscript>4</Subscript>-Li<Subscript>2</Subscript>MoO<Subscript>4</Subscript>-LiF system

We have studied the electric-field effect on crystallization processes in the Li₃PO₄-Li₄GeO₄-Li₂MoO₄-LiF system. In zero field, Li_3+x P_1?x Ge _x O₄ (x = 0.31) crystals were grown on the cathode under the conditions of this study. At low applied voltages (≤ 0.5 V), we obtained Li₂MoO₄, Li₂GeO₃, and Li_1.3Mo₃O₈. In the range V = 0.5–1 V, crystals of Li_3+x P_1?x Ge _x O₄ solid solutions with x = 0.17, 0.25, 0.28, 0.29, and 0.36 were obtained. An applied electric field was shown to reduce the melting temperature of the starting mixtures and the crystallization onset temperature.     

Na<Subscript>2</Subscript>MoO<Subscript>4</Subscript>-CaMoO<Subscript>4</Subscript>-Ce<Subscript>2/3</Subscript>MoO<Subscript>4</Subscript> scheelite-like solid solutions

We have studied tetragonal scheelite-like solid solutions in the ternary system Na₂MoO₄-CaMoO₄-Ce_2/3MoO₄: Na _0.7Ca_y Ce_{1.1 ? 2y/3} (MoO₄)₂ (0 ≤ y ≤ 0.6) and Na_0.3 Ca_zCe_{1.23? 2z/3} (MoO₄)₂ (0 ≤ z ≤ 1.4). The solid solutions melt congruently at temperatures from 1100 to 1200°C. Their lattice parameters have been determined. Using reflection spectra, we evaluated the color parameters of all the samples studied.     

High-temperature crystal chemistry of Na<Subscript>6</Subscript>(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>O(MoO<Subscript>4</Subscript>)<Subscript>4</Subscript>

Thermal deformations of Na₆(UO₂)₂O(MoO₄)₄ were studied by high-temperature powder X-ray diffraction. The compound crystallizes in the triclinic system, space group Р\(\bar 1\), a = 7.636(7), b = 8.163(6), c = 8.746(4) Å, α = 72.32(9)°, β = 79.36(4)°, γ = 65.79(5)°, V = 472.74(4) ų. It is stable in the temperature interval 20–700°С. The thermal expansion coefficients (TECs) are α₁₁ = 25.5 × 10^–6, α₂₂ = 7.8 × 10^–6, and α₃₃ = 1.1 × 10^–6 (°C)^–1. The orientation of the TEC pattern relative to the crystallographic axes is a₃₃^Z = 45°, a₃₃^X = 122°, a₂₂^Z = 59°, and a₂₂^X = 66°. The anisotropy of the thermal expansion is due to specific features of the crystal structure of the compound.     

Superprotonic CsH<Subscript>2</Subscript>PO<Subscript>4</Subscript>-CsHSO<Subscript>4</Subscript> solid solutions

We have performed partial HSO₄⁻ substitution in CsH₂PO₄ and studied the associated structural changes and the proton conductivity of the resultant (CsH₂PO₄)_{1 − x} (CsHSO₄) _x solid solutions in the range x = 0.01–0.3. The results indicate that, at room temperature, the solid solutions are disordered. In the range x = 0.01–0.1, they are isostructural with the low-temperature phase of CsH₂PO₄ (sp. gr. P2₁/m), and their unit-cell parameters increase with x, whereas in the range x = 0.15–0.3 the solid solutions are isostructural with the high-temperature, cubic phase of CsH₂PO₄ (Pm3m), and their unit-cell parameter decreases. The conductivity of the (CsH₂PO₄)_{1 − x} (CsHSO₄) _x solid solutions with x ≤ 0.3 depends significantly on their composition and increases at low temperatures by up to four orders of magnitude, approaching that of the superionic phase of CsH₂PO₄ in the range x = 0.15–0.3 because of the hydrogen bond weakening and increased proton mobility. The conductivity of the superionic phase decreases with increasing x by no more than a factor of 1.5–2, and the superionic phase transition, which occurs at 231°C in CsH₂PO₄, shifts to lower temperatures and disappears for x ≥ 0.15. The activation energy for low-temperature conduction decreases with increasing x: from 0.9 eV in CsH₂PO₄ to 0.48 eV at x = 0.1.     

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).     

Si<Subscript>3</Subscript>N<Subscript>4</Subscript>/TiN composites produced from TiO<Subscript>2</Subscript>-Modified Si<Subscript>3</Subscript>N<Subscript>4</Subscript> powders

Si₃N₄/TiN composites have been produced by hot pressing at temperatures from 1600 to 1800°C in a nitrogen atmosphere, using silicon nitride powders prepared by self-propagating high-temperature synthesis and surface-modified with titanium dioxide nanoparticles. We examined the effect of TiO₂ content on the microstructure, phase composition, and mechanical strength of the ceramics. It is shown that titanium nitride can be formed by the reaction Si₃N₄ + TiO₂ → TiN + NO + N₂O + 3Si. The Si₃N₄/TiN composites containing 5–20% TiN have a low density, high porosity, and a bending strength of 60 MPa or lower. In Si₃N₄/TiN ceramics produced using calcium aluminates as sintering aids, the silicon nitride grains are densely packed, which ensures an increase in strength to 650 MPa.     

Synthesis and x-ray diffraction study of solid solutions in the Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript>-Zn<Subscript>2</Subscript>TiO<Subscript>4</Subscript>-Zn<Subscript>2</Subscript>ZrO<Subscript>4</Subscript> system

The multicomponent refractory oxide system Zn₂(Ti_aSn_b)_{1 ? x} Zr_xO₄ (a + b = 1; a: b = 1: 5, 1: 4, 1: 3, 1: 2, 1: 1, 1: 0, 2: 1, 3: 1, 4: 1; x = 0?1.0; Δx = 0.05) has been studied by x-ray diffraction, using samples prepared by melting appropriate oxide mixtures in a low-temperature hydrogen-oxygen plasma. Two phases, both with wide homogeneity ranges, have been identified: α-phase, with a cubic inverse spinel structure, and β-phase, with a tetragonal spinel structure. The phase boundaries in the system have been determined. Structural data are presented for about 100 solid solutions of different compositions.     

Vapor growth of SnO<Subscript>2</Subscript> whiskers

Tin dioxide whiskers have been prepared by vapor growth in a tube furnace in flowing argon at a constant evaporation temperature, and the effect of carrier-gas flow rate during growth on their morphology, phase composition, and IR spectrum has been studied. The whiskers are more than 0.5 mm in length and are well crystallized. Reducing the flow rate of the carrier gas during whisker growth makes it possible to reduce the fraction of phases containing tin in lower oxidation states and favors preferential whisker growth along the c axis.     

High-temperature thermodynamic properties of the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

High-temperature mass spectrometry is used to investigate vaporization processes and determine SiO₂ activity in the Al₂O₃-SiO₂ system between 1850 and 1970 K. The results are consistent with the known phase equilibria in this system.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 4, 2005, pp. 434–441.Original Russian Text Copyright © 2005 by Bondar, Lopatin, Stolyarova.     

Microemulsion-based synthesis and luminescence of nanoparticulate CaWO<Subscript>4</Subscript>, ZnWO<Subscript>4</Subscript>, CaWO<Subscript>4</Subscript>:Tb,and CaWO<Subscript>4</Subscript>:Eu

Blue emitting CaWO₄ and greenish blue emitting ZnWO₄ nanoparticles are synthesized via microemulsion techniques applying a cationic (CTAB) as well as a non-ionic surfactant (TritonX-100). The influence of the surfactant on particle size and shape is studied. Scanning electron microscopy and dynamic light scattering confirm the presence of uniform and non-agglomerated nanoparticles, 60–80 nm in diameter. Photoluminescence confirms [WO₄]²⁻-related broad-band emission with its maximum at 440 nm (CaWO₄) and 420 nm (ZnWO₄). The highest quantum yield (QY) is observed for nanoscaled CaWO₄ with a value of 23–25%. Doping of CaWO₄ and ZnWO₄ with Tb³⁺ and Eu³⁺ was performed and in the case of CaWO₄:Tb and CaWO₄:Eu and results in the emission of green and red light, again with comparably high QYs (17–19%).     

Growth of Rare-Earth-Doped K<Subscript>2</Subscript>LaCl<Subscript>5</Subscript>, K<Subscript>2</Subscript>BaCl<Subscript>4</Subscript>, and K<Subscript>2</Subscript>SrCl<Subscript>4</Subscript> Single Crystals

Processes are described for the synthesis and melt growth of rare-earth-doped K₂LaCl₅, K₂BaCl₄, and K₂SrCl₄, using rare-earth oxides as starting materials. The solubility of rare-earth activators in Bridgman-grown crystals are determined, and the spectroscopic properties of K₂LaCl₅〈Nd〉 crystals are investigated.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 6, 2005, pp. 748–752.Original Russian Text Copyright © 2005 by Vinogradova, Galagan, Dmitruk, Moiseeva, Osiko, Sviridova, Brekhovskikh, Fedorov.