Molecular analysis of isotopically enriched <Superscript>28</Superscript>SiF<Subscript>4</Subscript> and <Superscript>28</Superscript>SiH<Subscript>4</Subscript> prepared from it

We have developed analytical techniques for the determination of impurities in isotopically enriched ²⁸SiH₄ and ²⁸SiF₄. The impurities in SiF₄ were first determined by IR spectroscopy, and those in SiH₄, by gas chromatography/mass spectrometry. High-sensitivity determination of organic impurities in SiH₄ and SiF₄ was performed by gas chromatography. SiF₄ was found to contain C₁–C₄ hydrocarbons, hexafluorodisiloxane (Si₂F₆O), hydrogen fluoride, trifluorosilanol (SiF₃OH), fluorosilanes, water, and carbon oxides. The impurities identified in SiH₄ include C₁–C₄ hydrocarbons, disilane (Si₂H₆), inorganic hydrides, Si₂H₆O, alkylsilanes, and fluorinated and chlorinated organics. The detection limits of IR spectroscopy were 3 × 10^?3 to 5 × 10^?5 mol %, those of gas chromatography/mass spectrometry were 8 × 10^?6 to 10^?8 mol %, and those of gas chromatography were 6 × 10^-6 to 2 × 10^?7 mol %.     

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.     

Optical properties of undoped and Yb<Superscript>3+</Superscript>-doped YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystals

The ordinary and extraordinary refractive indices of nominally undoped and Yb³⁺-doped (7 at %) YAl₃(BO₃)₄ crystals have been measured in the visible range at temperatures from 20 to 400°C. The refractive indices are found to increase with temperature. The thermo-optic coefficients are on the order of ～10^?6. The temperature dependences of the refractive indices show a number of anomalies, suggestive of an incommensurate system exhibiting devil’s staircase behavior.     

Efficient Removal of Polyvalent Metal Impurities from KH<Subscript>2</Subscript>PO<Subscript>4</Subscript> by Crystallization

The separation factors of metal impurities for potassium dihydrogen phosphate crystallization from nonstoichiometric solutions have been experimentally determined. Based on the results obtained, a method has been proposed that makes it possible to obtain a material containing aluminum, iron, chromium, and titanium at a level of ~5 × 10^–2 ppm by weight from commercially available raw materials. In this method, a KH₂PO₄ solution is purified due to partial crystallization of the macrocomponent, so that the above impurities are concentrated in the solid phase. The purified solution is then boiled down with KOH additions.     

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.     

Electrical properties of In<Subscript>2</Subscript>Se<Subscript>3</Subscript> layered crystals doped with cadmium,iodine, or copper

The electrical properties of nominally undoped and doped (0.1 wt % Cd, I, and Cu) In₂Se₃ single crystals have been studied in the range 80–400 K. Only iodine doping has been found to have a significant effect on the carrier concentration in In₂Se₃, raising it from 4.9 × 10¹⁷ to 1.6 × 10¹⁸ cm^?3 at 300 K. The observed temperature variation of in-plane electron mobility is interpreted in terms of acoustic phonon and neutral impurity scattering. The three dopants have the strongest effect on the out-of-plane conductivity of In₂Se₃.     

Conductivity of Sm<Subscript>2</Subscript>TiO<Subscript>5</Subscript> and Sm<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript>

The oxygen-ion conductivity of porous materials, the coarse-grained pyrochlore-like Sm₂Ti₂O₇ and fine-grained Sm₂TiO₅ compounds, produced by mechanical activation of initial oxides is studied at 400–1000 °C. The Sm₂TiO₅ samples contain ～15 wt % of the nanosized pyrochlore-like Sm₂TiO₅ phase in addition to the rhombic phase. As determined by impedance spectroscopy, the ionic conductivities of Sm₂TiO₅ and Sm₂Ti₂O₇ at 1000°C are 1.3 × 10^?3 and 1.8 × 10^?4 S cm^?1, and the activation energies of the bulk and grainboundary conductivities of the materials are 1.04 and 1.24 eV for Sm₂TiO₅ and 1.69 and 1.80 eV for Sm₂Ti₂O₇.     

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.     

Microstructure and electrical properties of K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>NbO<Subscript>3</Subscript> lead-free piezoelectric ceramics sintered in low pO<Subscript>2</Subscript> atmosphere

Pure K_0.5Na_0.5NbO₃ lead-free piezoelectric ceramics without any dopants/additives were sintered at various temperatures (950–1125 °C) in low pO₂ atmosphere (pO₂?~?10^?6 atm). All ceramics exhibit high relative densities (>?94%) and low weight loss (<?0.6%). Compared to the ceramics sintered in air, the ceramics sintered in low pO₂ exhibit improved electrical properties. The piezoelectric constant d₃₃ and converse piezoelectric constant d₃₃* are 112 pC/N and 119 pm/V, respectively. The ceramics show typical ferroelectric behavior with the remnant polarization of 21.6 µC/cm² and coercive field of 15.5 kV/cm under measurement electric field of 70 kV/cm. The good electrical properties of the present samples are related to the suppression of volatility of the alkali cations during the sintering process in low pO₂ atmosphere.     

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.     

Rietveld analysis of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> thin films obtained by RF-sputtering

Calcium copper titanate, CaCu₃Ti₄O₁₂, CCTO, thin films with polycrystalline nature have been deposited by RF sputtering on Pt/Ti/SiO₂/Si (100) substrates at a room temperature followed by annealing at 600 °C for 2 h in a conventional furnace. The crystalline structure and the surface morphology of the films were markedly affected by the growth conditions. Rietveld analysis reveal a CCTO film with 100 % pure perovskite belonging to a space group Im3 and pseudo-cubic structure. The XPS spectroscopy reveal that the in a reducing N₂ atmosphere a lower Cu/Ca and Ti/Ca ratio were detected, while the O₂ treatment led to an excess of Cu, due to Cu segregation of the surface forming copper oxide crystals. The film present frequency -independent dielectric properties in the temperature range evaluated, which is similar to those properties obtained in single-crystal or epitaxial thin films. The room temperature dielectric constant of the 600-nm-thick CCTO films annealed at 600 °C at 1 kHz was found to be 70. The leakage current of the MFS capacitor structure was governed by the Schottky barrier conduction mechanism and the leakage current density was lower than 10^?7 A/cm² at a 1.0 V. The current–voltage measurements on MFS capacitors established good switching characteristics.     

Behavior of Am(V) in concentrated HNO<Subscript>3</Subscript> solutions containing potassium phosphotungstate K<Subscript>10</Subscript>P<Subscript>2</Subscript>W<Subscript>17</Subscript>O<Subscript>61</Subscript>

The Am(V) disproportionation in (2–10) × 10^?3 M K₁₀P₂W₁₇O₆₁ (KPW) solutions in 1–7 M HNO₃ was studied spectrophotometrically. Under the experimental conditions, Am(VI) and Am(III) are the final products of Am(V) transformation; the process is described by the rate equation of a reversible reaction. The direct reaction follows the first-order rate equation with respect to Am(V) concentration, and the reverse reaction, the zero-order equation.     

Synthesis and high-temperature electrical conductivity of Ln<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript> and LnYTi<Subscript>2</Subscript>O<Subscript>7</Subscript> (Ln = Dy,Ho)

Ho₂Ti₂O₇ and LnYTi₂O₇ (Ln = Dy, Ho) pyrochlores have been synthesized using hydroxide coprecipitation, mechanical activation, and firing at 1600°C. The bulk and grain-boundary components of their conductivity have been determined for the first time by impedance spectroscopy. The 740°C bulk conductivity of Ho₂Ti₂O₇ is 4 × 10^?4 S/cm, and that of HoYTi₂O₇ is 1 × 10^?3 S/cm, with activation energies E _a = 1.01 and 1.17 eV, respectively, suggesting that these materials are new oxygen-ion conductors. The bulk conductivity of DyYTi₂O₇ (3 × 10^?4 S/cm at 740°C, E _a = 1.09 eV) is almost one order of magnitude lower than that of HoYTi₂O₇ (1 × 10^?3 S/cm at 740°C, E _a = 1.17 eV).     

Enhanced electrochemical performance of Na<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>F<Subscript>3</Subscript> for Na-ion batteries with nanostructure and carbon coating

Carbon-coating Na₃V₂(PO₄)₂F₃ nanoparticles (NVPF@C NP) were prepared by a hydrothermal assisted sol–gel method and applied as cathode materials for Na-ion batteries. The as-prepared nanocomposites were composed of Na₃V₂(PO₄)₂F₃ nanoparticles with a typical size of ~?100 nm and an amorphous carbon layer with the thickness of ~?5 nm. Cyclic voltammetry, rate and cycling, and electrochemical impedance spectroscopy tests were used to discuss the effect of carbon coating and nanostructure. Results display that the as-prepared NVPF@C NP demonstrates a higher rate capability and better long cycling performance compared with bare Na₃V₂(PO₄)₂F₃ bulk (72 mA h g^?1 at 10 C vs 39 mA h g^?1 at 10 and 1 C capacity retention of 95% vs 88% after 50 cycles). The remarking electrode performance was attributed to the combination of nanostructure and carbon coating, which can provide short Na-ion diffusion distance and rapid electron migration.     

Relaxation of optical excitations in crystals of the Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system with radiation defects

The photoluminescence and short-time persistence (afterglow) kinetics in pure and doped Y₂O₃-Al₂O₃ crystals excited with UV laser pulses (12 ns, 337 nm) were studied using samples irradiated with gamma quanta from a ⁶⁰Co source to a dose from 10⁴ to 10⁷ Gy. The relaxation time of the samples studied increases, with decreasing symmetry of the crystal lattice, in the following order: garnet—orthoaluminate—ruby—yttria. The afterglow duration and intensity significantly decrease in gamma-irradiated crystals, which is explained by the predominant recombination of close electron-hole pairs. Garnet-neodymium crystals are characterized by high radiation stability and fast relaxation kinetics.     

Critical Current Densities and Vortex Dynamics in Ba(Fe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>As<Subscript>2</Subscript> Single Crystals

Superconducting properties are evaluated for high-quality single crystals of Ba(Fe_1−x Co _x )₂As₂ in a wide range of doping levels. The critical current density, J _c , in an optimally-doped crystal (T _c ∼24 K) shows a fishtail effect with its value over 10⁵ A/cm² even at 5 T below 10 K. Magneto-optical imaging has clarified rather homogeneous supercurrent flow in the crystal, in spite of a large amount of impurities. In the heavy-ion irradiated sample, the presence of columnar defects are confirmed and J _c has been enhanced by a factor of five at low temperatures, reaching 6×10⁶ A/cm² at 2 K under zero field. Flux creep rate in the heavy-ion irradiated sample has been reduced in accordance with the enhancement of J _c .     

Bridgman growth and defects of Nd<Superscript>3+</Superscript> : Sr<Subscript>3</Subscript>Ga<Subscript>2</Subscript>Ge<Subscript>4</Subscript>O<Subscript>14</Subscript> laser crystals

Nd³⁺ : Sr₃Ga₂Ge₄O₁₄ crystals have been grown by the modified Bridgman method. The growth defects, such as striations, scattering particles and dislocations were investigated. Some featherlike striations were observed in as-grown crystals. EPMA analysis suggested that these inclusions were caused by the segregation of Nd₂O₃ from the melt. Chemical etching results showed that the dislocation density was in the range of 10³ ∼ 10⁵/cm².     

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.     

Physicochemical properties of La<Subscript>3</Subscript>Ga<Subscript>5.5</Subscript>Ta<Subscript>0.5</Subscript>O<Subscript>14</Subscript>

We report the optical and dielectric properties and microhardness of La₃Ga_5.5Ta_0.5O₁₄ lanthanum gallium tantalate (langatate) crystals. Analysis of the optical transmission spectra of the crystals in relation to their refined compositions indicates that the bands at 34000–35000 and 27000–28000 cm⁻¹ are due to lanthanum and oxygen vacancies, respectively, and that the band at 20000–21000 cm⁻¹ is responsible for the yellow (orange) coloration of the crystals. Their resistivity and microhardness decrease with increasing oxygen vacancy concentration.     

Dielectric properties of Be(IO<Subscript>3</Subscript>)<Subscript>2</Subscript>⋅4H<Subscript>2</Subscript>O crystals

The article studies the dielectric properties, dc conductivity and ac conductivity of Be(IO₃)₂⋅4H₂O single crystals. The dielectric constant ε has been defined for the three directions of the vectors a, b and c in the crystals in the temperature interval 280–340 K and frequency range 100 Hz–10⁶ Hz. The crystals show strongly expressed anisotropy, at 20 ^∘C and frequency 100 Hz ε_a = 235, ε_b = 30 and ε_c = 85. The frequency dependence of ε is evidence of the presence of low-frequency relaxation polarization in the crystals. The activation energies of the three directions in the crystals have been derived from the temperature dependence of dc conductivity, and they are 1.03 eV, 0.836 eV and 1.2 eV respectively.