Phase transitions and high-temperature crystal chemistry of polymorphous modifications of Cs<Subscript>2</Subscript>(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)

Phase transitions and thermal deformations of - and -Cs₂(UO₂)₂(MoO₄)₃ were studied by high-temperature X-ray diffraction analysis. In heating of -Cs₂(UO₂)₂(MoO₄)₃ to 625 ± 25°C, the reconstructive phase transition proceeds. -Cs₂(UO₂)₂(MoO₄)₃ is stable up to 700 ±25°C. The thermal expansion of both phases is sharply anisotropic: ₁₁ = 10 × 10^–6, ₂₂ = 33 × 10^–6, ₃₃ = 10 × 10^–6, _V = 53 × 10^–6 deg^–1 for -Cs(UO₂)₂(MoO₄)₃ and ₁₁ = 13 × 10^–6, ₃₃ = 3 × 10^–6, _V = 31 × 10^–6 deg^–1 for -Cs₂ (UO₂)₂ (MoO₄)₃. The anisotropy of thermal expansion is explained by features of the crystal structure of the compounds.Translated from Radiokhimiya, Vol. 46, No. 5, 2004, pp. 405–407.Original Russian Text Copyright © 2004 by Nazarchuk, Krivovichev, Filatov.     

Erbium zirconium phosphate Er<Subscript>0.33</Subscript>Zr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> of the NaZr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> family. Structure contraction on heating

Erbium zirconium phosphate Er_0.33Zr₂(PO₄)₃, a member of the family of structural analogs of NaZr₂(PO₄)₃ (NZP), was prepared by the sol-gel process and studied by X-ray phase analysis, IR spectroscopy, and differential scanning calorimetry. The behavior of erbium zirconium phosphate on heating in the temperature interval from 25 to 625°C was studied by high-temperature X-ray diffraction. Expansion and contraction along different crystallographic directions and contraction of the structure as a whole were found. The overall contraction is due to higher contribution of the negative axial thermal expansion coefficients α _a and α _b to α_av and hence to the volume expansion of the phosphate. On heating to 900°C, the NZP structure is preserved.     

Synthesis and crystal structure of [UO<Subscript>2</Subscript>(OH)(CO(NH<Subscript>2</Subscript>)<Subscript>2</Subscript>)<Subscript>3</Subscript>]<Subscript>2</Subscript>(ClO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The complex [UO₂(OH)(CO(NH₂)₂)₃]₂(ClO₄)₂ (I) was synthesized. A single crystal X-ray diffraction study showed that compound I crystallizes in the triclinic system with the unit cell parameters a = 7.1410(2), b = 10.1097(2), c = 11.0240(4) Å, α = 104.648(1)°, β = 103.088(1)°, γ = 108.549(1)°, space group \(P\bar 1\), Z = 1, R = 0.0193. The uranium-containing structural units of the crystals are binuclear groups [UO₂(OH)· (CO(NH₂)₂)₃] ₂ ²⁺ belonging to crystal-chemical group AM²M ₃ ¹ [A = UO ₂ ²⁺ , M² = OH^?, M¹ = CO(NH₂)₂] of uranyl complexes. The crystal-chemical analysis of nonvalent interactions using the method of molecular Voronoi-Dirichlet polyhedra was performed, and the IR spectra of crystals of I were analyzed.     

Synthesis and structure of multi-layered WS<Subscript>2</Subscript>(CoS), MoS<Subscript>2</Subscript>(Mo) nanocapsules and single-layered WS<Subscript>2</Subscript>(W) nanoparticles

Multi-layered MoS₂ (or WS₂) nanocages stuffed with Mo (or CoS/CoO) nanocrystals have been synthesized by using the reaction between metal nanoparticles and sulfur powders. This simple synthesis method, different from the conventional methods for synthesizing pure inorganic fullerenes, is also potentially important for large-scale synthesis of nanoparticles of other metal dichalcogenide. Besides the multi-layered WS₂ nanocapsules, we have successfully fabricated nanocapsules with a single-layered WS₂ sheet encapsulating W by using the arc-discharge method. We discuss possible mechanisms for the formation of the unique core-shell structured nanocapsules.     

Strain localization in compressed ZrO<Subscript>2</Subscript>(Y<Subscript>2</Subscript>O<Subscript>3</Subscript>) ceramics

Spatiotemporal distributions of local components of the distortion tensor of a nonplastic material—yttria partially stabilized tetragonal zirconia (YTZ) ceramics—have been studied under active compressive straining conditions using double-exposure speckle photography techniques. The strain localization patterns are presented and the features of macroscopic strain inhomogeneity in the elastic state of YTZ ceramics are considered.     

Synthesis and crystal structure CoNi<Subscript>2</Subscript>(BO<Subscript>3</Subscript>)<Subscript>2</Subscript>

A new metal orthoborate compound, cobalt dinickel orthoborate, CoNi₂(BO₃)₂ has been successfully synthesized for the first time. The title compound was synthesized by thermally-induced solid-state chemical reaction at 900°C between the initial reagents of Co(NO₃)₂ · 6H₂O, Ni(NO₃)₂ · 6H₂O and H₃BO₃ which were mixed with the mol ratio of 1: 2: 2 respectively. The obtained product was structurally characterized by X-ray powder diffraction technique. It has been found that the CoNi₂(BO₃)₂ crystallizes in the kotoite type and isostructural with the compounds having the chemical formula M₃(BO₃)₂ where M—Mg, Co and Ni. The synthesized compound belongs to the orthorhombic crystal system with the refined unit cell parameters of a = 5.419(9) Å, b = 8.352(0) Å, c = 4.478(8) Å and Z = 2. The space group was determined as Pnmn. Further characterizations by FTIR, elemental analysis and thermal analysis were also performed.     

Electrical and magnetic properties of (BiNa)<Subscript>1/2</Subscript>(FeV)<Subscript>1/2</Subscript>O<Subscript>3</Subscript>

Potential multiferroic material, (BiNa)_1/2(FeV)_1/2O₃, synthesized using solid-state route is investigated. The phase formation was confirmed by X-ray diffraction and surface morphology by scanning electron microscopy (SEM). Structural data reveal the single phase formation corroborated by SEM. The grain distribution is uniform with an average grain size of 3·6 μm. Electrical properties were investigated in a frequency range (1 kHz–1 MHz) by complex impedance spectroscopy (CIS) technique. The material showed negative temperature coefficient of resistance (NTCR) reflecting semiconductor behaviour. A.C. conductivity was found to obey Johnscher’s law. Conductivity mechanism is discussed and activation energy estimated (1·17 eV) for the conduction process is associated with Fe^3 +→ Fe^2 + variable state. The M–H curve showed the presence of ferromagnetism in the studied material.     

In-situ elevated-temperature TEM study of (AgSbTe<Subscript>2</Subscript>)<Subscript>15</Subscript>(GeTe)<Subscript>85</Subscript>

(AgSbTe₂)₁₅(GeTe)₈₅ (TAGS-85) is a p-type semiconductor characterized by a maximum dimensionless thermoelectric figure of merit of 1.4–1.7 at elevated temperature. In this study, the microstructure of as-solidified TAGS-85 at room temperature and elevated temperature (160 °C) was investigated using TEM. At room temperature, pervasive twinning was observed throughout the specimen. Upon heating to above 120 °C, some of the twins dissolved and new point defects began to nucleate. The mechanisms responsible for formation of high temperature defects are discussed.     

Thermodynamic properties of NaZr<Subscript>2</Subscript>(AsO<Subscript>4</Subscript>)<Subscript>3</Subscript>

The heat capacity C _p ⁰ of crystalline NaZr₂(AsO₄)₃ has been measured in the range 7–650 K using precision adiabatic calorimetry and differential scanning calorimetry. The experimental data have been used to calculate the standard thermodynamic functions of the arsenate: C _p ⁰, enthalpy H ⁰(T) − H ⁰(0), entropy S ⁰(T), and Gibbs function G ⁰(T) − H ⁰(0) from T → 0 to 650 K. The standard entropy of its formation from elements is Δ_f S ⁰(NaZr₂(AsO₄)₃, cr, 298.15 K) = −1087 ± 1 J/(mol K).     

Crystal structure of a complex of Pu(VI) nitrate with triphenylphosphine oxide, [PuO<Subscript>2</Subscript>(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>(OP(C<Subscript>6</Subscript>H<Subscript>5</Subscript>)<Subscript>3</Subscript>)<Subscript>2</Subscript>]

Single crystals of [PuO₂(NO₃)₂(TPPO)₂] (TPPO = OPPh₃) isostructural to the related compounds of uranyl and neptunyl were isolated, and the structure of this complex was determined. Contrary to the complexes [AnO₂(TPPO)₄](ClO₄)₂ studied previously, the interatomic distances and volumes of coordination polyhedra of An in these compounds somewhat decrease in the series U-Np-Pu. This difference was attributed to a change in the number of TPPO ligands in the compounds and weakening of their interaction with oxygen atoms of the AnO ₂ ²⁺ groups in passing from [AnO₂(TPPO)₂](ClO₄)₂ to [AnO₂(No₃)₂(TPPO)₂].     

Synthesis and structure of (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>[UO<Subscript>2</Subscript>(CH<Subscript>3</Subscript>COO)<Subscript>3</Subscript>]<Subscript>2</Subscript>(NCS)

The compound (NH₄)₃[UO₂(CH₃COO)₃]₂(NCS) (I) was synthesized and examined by single crystal X-ray diffraction analysis. The compound crystallizes in the rhombic system with the unit cell parameters a = 11.5546(4), b = 18.5548(7), c = 6.7222(3) Å, V = 1441.19(10) ų, space group P2₁2₁2, Z = 2, R = 0.0345. The uranium-containing structural units of crystals of I are isolated mononuclear groups [UO₂(CH₃COO)₃]^? belonging to crystal-chemical group AB ₃ ⁰¹ (A = UO ₂ ²⁺ , B⁰¹ = CH₃COO^?) of uranyl complexes. The specific features of packing of the uranium-containing complexes in the crystal structure are considered.     

Elastic properties of Li<Subscript>2</Subscript>Zn<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript> single crystals

The complete elastic modulus matrix of Li₂Zn₂(MoO₄)₃ single crystals has been measured for the first time. The sound velocity has been measured in different directions of the crystals by a pulse-phase method. The measurement results have been used to calculate elastic moduli. The sound velocity has been calculated in the three main crystallographic planes of the crystals.     

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.     

Preparation and Thermal Expansion of Calcium Iron Zirconium Phosphates with the NaZr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> Structure

Ca_{0.5(1 + x)}Zr_2–xFe _x (PO₄)₃ phosphates have been synthesized by a sol–gel process. The individual compounds and solid solutions obtained crystallize in the NaZr₂(PO₄)₃ structure (trigonal symmetry, sp. gr. R\(\bar 3\)). Using high-temperature X-ray diffraction, we have determined their thermal expansion parameters in the temperature range from 25 to 800°C. With increasing x, the magnitudes of their linear thermal expansion coefficients and thermal expansion anisotropy decrease. Most of the synthesized phosphates can be rated as low-thermal-expansion compounds and can be regarded as materials capable of withstanding thermal “stress.”     

Thermodynamic functions of germanium oxide molecules in the gaseous phase: GeO<Subscript>2</Subscript>(g), Ge<Subscript>2</Subscript>O<Subscript>2</Subscript>(g), and Ge<Subscript>3</Subscript>O<Subscript>3</Subscript>(g)

Critical analysis of experimental and theoretical data on the structure and vibrational frequencies of GeO₂, Ge₂O₂, and Ge₃O₃ molecules is performed. The values of molecular constants are chosen, and thermodynamic functions in the rigid rotator–harmonic oscillator approximation are calculated in temperature interval Т = 298.15–3000 K. The values obtained are introduced into the data base of the IVTANTERMO program complex.     

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.     

Partially ordered organic-inorganic nanocomposites in the system UO<Subscript>2</Subscript>SeO<Subscript>4</Subscript>-H<Subscript>2</Subscript>O-NH<Subscript>3</Subscript>(CH<Subscript>2</Subscript>)<Subscript>9</Subscript>NH<Subscript>3</Subscript>

The compound [NH₃(CH₂)₉NH₃]₂[(UO₂)₃(SeO₄)₅(H₂O)₂](H₂O)_x (1) was prepared by isothermal evaporation from aqueous uranyl selenate solutions containing 1,9-diaminononane. A structural study showed that the compound is a partially ordered organic-inorganic nanocomposite. The structural model of the inorganic complex was determined by single crystal X-ray diffraction a = 19.5572(5), c = 47.878(2) Å, V= 15859.1(9) ų, Z= 12; R₁ = 0.1318, wR₂ = 0.3186 for 2808 reflections with |F_o| ≥ 4σ_F). The structure consists of double hydrogen-bonded [(UO₂)₃(SeO₄)₅(H₂O)₂]^2- layers parallel to the (001) plane. The disordered protonated 1,9-diaminononane molecules and water molecules are arranged between the layers. The inorganic layered complex [(UO₂)₃(SeO₄)₅(H₂O)₂]^2- belongs to a new type that was not observed previously in the structures of inorganic and organometallic compounds.     

Low-loss,high-purity (TeO<Subscript>2</Subscript>)<Subscript>0.75</Subscript>(WO<Subscript>3</Subscript>)<Subscript>0.25</Subscript> glass

By melting a mixture of high-purity oxides in a platinum crucible under flowing purified oxygen, we have prepared (TeO₂)_0.75(WO₃)_0.25 glass with a total content of 3d transition metals (Fe, Ni, Co, Cu, Mn, Cr, and V) within 0.4 ppm by weight, a concentration of scattering centers larger than 300 nm in size below 10² cm⁻³, and an absorption coefficient for OH groups (λ ∼ 3 μm) of 0.008 cm⁻¹. The absorption loss in the glass has been determined to be 115 dB/km at λ = 1.06 μm, 86 dB/km at λ = 1.56 μm, and 100 dB/km at λ = 1.97 μm. From reported specific absorptions of impurities in fluorozirconate glasses and the impurity composition of the glass studied here, the absorption loss at λ ∼ 2 μm has been estimated at ≤100 dB/km. The glass has been drawn into a glass-polymer fiber, and the optical loss spectrum of the fiber has been measured.     

Bingham viscosity and yield stress of molten (TeO<Subscript>2</Subscript>)<Subscript>0.78</Subscript>(WO<Subscript>2</Subscript>)<Subscript>0.22</Subscript> glass

The flow of molten (TeO₂)_0.78(WO₂)_0.22 glass in a circular-cylindrical channel has been studied at temperatures from 390 to 430°C. The variation of the measured volumetric flow rate with the gas pressure over the melt attests to non-Newtonian flow behavior. The flow rates calculated in the pseudoplastic model were used to determine the yield stress and plastic (Bingham) viscosity of the melt.     

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.