Electrochemical and structural properties of MoO3–V2O5 nanocomposite thin film electrodes for lithium rechargeable batteries

We have investigated the electrochemical properties of V₂O₅-based thin film electrodes as a function of the amount of MoO₃ by means of X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS), and transmission electron microscopy (TEM). XRD results show that the V₂O₅-based thin film electrodes give an amorphous characteristic. XPS results reveal the formation of V₂O₅ and MoO₃ phases. TEM results show that MoO₃ dots (5–30 nm in size) are embedded in the amorphous V₂O₅ matrix. It is further shown that cells fabricated with the MoO₃–V₂O₅ nanocomposite thin film electrodes give better cycling performance than those made with the single V₂O₅ thin film electrodes. A possible explanation for the MoO₃ nano-dot dependence on the cycling performance of the V₂O₅-based thin film electrodes is described.     

Thermal conductivity of crystalline chrysotile asbestos

The thermal conductivity of crystalline chrysotile asbestos made up of hollow tubular Mg₃Si₂O₅(OH)₄ filaments is measured in the range 5–300 K. The paper discusses the possibility of using this material in studies of the thermal conductivity of thin filaments of metals and semiconductors incorporated into the channels of crystalline chrysotile asbestos tubes.     

Theoretical calculations of N2-broadened half-widths of ν5 transitions of HNO3

A number of satellite instruments are measuring nitric acid, HNO₃, in the Earth's atmosphere. In order to do retrievals of temperature and concentration profiles, the spectral parameters for many thousands of HNO₃ transitions must be known. Currently the HITRAN database uses a constant estimated value for the air-broadened half-width of HNO₃. To help improve the line shape parameters, complex Robert–Bonamy calculations were made to determine N₂-broadened half-widths for some 5000 transitions of HNO₃ in the ν₅ band. The intermolecular potential is a sum of electrostatic terms (dipole–quadrupole and quadrupole–quadrupole) and the atom–atom potential expanded to eighth order. The trajectory parameters were adjusted to yield better agreement with measurement. Velocity integrated calculations were made at seven temperatures in order to determine the temperature dependence of the half-widths. The half-width data are compared with available rotation band measurements. The average percent difference between the measured and calculated half-widths is ?2.38 for N₂-broadening and ?0.65 for air-broadening. The temperature, vibrational, and rotational state dependence of the half-width are investigated.     

Infrared Spectrum of Potassium Pentacyanonitrosylchromate. Normal Coordinate Analysis for [Cr(CN)5NO]−3 Anion

The infrared spectra of pentacyanonitrosyl complexes of iron and manganese have been widely investigated^1–4, and approximate potential field calculated.^2–4 No similar study has been made, however, for the analogous complex K₃Cr(CN)₅NO for which only partial data exist in the literature.^5,6 We report a more extensive investigation making use of ¹⁵NO and single crystal polarised spectra.     

Ternary compounds and isothermal section in Lu–Fe–Ga ternary system at 773 K

The isothermal section of the Lu–Fe–Ga ternary system at 773?K was investigated and constructed based on X-ray powder diffraction analysis. Thirteen binary compounds, Lu₂Fe₁₇, Lu₆Fe₂₃, LuFe₂, LuGa₃, LuGa₂, Lu₃Ga₅, LuGa, Lu₃Ga₂, Lu₅Ga₃, Fe₃Ga, Fe₆Ga₅, Fe₃Ga₄, FeGa₃, nine ternary solid solutions, T₁-LuFe_2–1.43Ga_0–0.57, T₂-LuFe_1.34–0.92Ga_0.68–1.08, T₃-LuFe_0.52–0.26Ga_1.48–1.74, T₅-LuFe_2.04–1.72Ga_0.96–1.28, T₆-Lu₆Fe_23–21.4Ga_0–1.6, T₇-Lu₂Fe_17–14.5Ga_0–3.5, T₈-Lu₂Fe_12.9–8.1Ga_4.1–8.9, T₉-LuFe_6.8–5.5Ga_5.2–6.5, T₁₀-LuFe_5.2–4.5Ga_6.8–7.5, and two ternary compounds, T₄-LuFe_2.35Ga_0.65 and T₁₁-Lu₂FeGa₈ have been confirmed. The structures of the five new ternary compounds or solid solution T₂, T₃, T₄, T₅ and T₈ are determined by Rietveld refinement method.     

New aspects of the rotational model in25Mg

Spin assignments have been made to the²⁵Mg levels in theE _x=5–6 MeV region fromγ-ray angular distributions measured in the²²Ne(α, n y) reaction atE _α=8.0 and 8.8 MeV and fromp-γ angular correlations measured in the²⁴Mg(d, p γ) reaction atE _d=6 MeV. Unique spin assignments ofJ=7/2, 5/2, 5/2, and 9/2 could be made to the levels atE _x=5005, 5511, 5851, and 5967 keV, respectively. Ambigious assignments have been made to the levels atE _x=5245, 5524, 5785, 6032 keV (J=11/2, 7/2), 5455 keVJ=13/2, 9/2), and 5738 keV (J=3/2, 5/2). The present data confirm previous assignments ofJ=1/2 to the levels atE _x=5108 and 5466 keV, respectively. Lifetime estimates have been obtained, using the Doppler-shift attenuation method, for the levels atE _x=5245 keV (τ=30–60 fs), 5785 keV (τ=50–100 fs), 5967 keV (τ=50–100 fs), and 5455 keV (τ>1ps). All other levels in theE _x=5–6 MeV region haveτ<60 fs. A breakdown of theK-selection rule has been observed in theγ-decay of some high spin states, indicating a deviation from the strong coupling model.     

Laser magnetic resonance spectra of NH2 in the 9-μm region: Observation of weak ΔKa = −3 transitions in the ν2 band

Laser magnetic resonance spectra of the ν₂ band of the NH₂ radical have been observed with a CO₂ laser in the 1030–1108-cm^?1 range. The measurements of these weak ΔN = ?1, ΔK_a = ?3 transitions, involving levels with 5 ≤ N ≤ 10, should complement measurements in the higher frequency half of the band (1500–1900 cm^?1) made using CO lasers.     

Isotope shifts in the spectra of LiLuF<Subscript>4</Subscript>:Ho<Superscript>3+</Superscript> crystals due to the isotopic disorder in the lithium sublattice

The isotope shifts of lines in the spectra of the LiLuF₄:Ho³⁺ crystal in the range of the transitions ⁵ I ₈→⁵ I ₇, ⁵ I ₆, and ⁵ I ₅ caused by the isotopic disorder with respect to lithium are measured. The shifts of different lines amount to 0.01–0.036 cm^?1. A comparison with the previously measured isotope shifts in the spectra of the LiYF₄:Ho³⁺ crystal is made.     

Impedance and Modulus studies of the solid electrolyte system 20CdI2–80[xAg2O–y(0.7V2O5–0.3B2O3)], where 1 ≤x/y ≤ 3

In the present work, an evaluation of the transport properties of super ion conducting quaternary system 20CdI₂–80[xAg₂O–y(0.7V₂O₅–0.3B₂O₃)], where 1 ≤ x/y ≤ 3, in steps of 0.25, to study the effect of changing the modifier to former ratio on the conduction phenomena has been undertaken. Electrical conductivity measurements were made using complex impedance method. The electrical conductivity and conductivity relaxation of the system were studied in the temperature range from 303 K to 333 K and in the frequency range from 100 Hz to 10 MHz. The highest conductivity at room temperature is obtained for the system with modifier to former ratio 1.75. Impedance and modulus analyses had indicated the temperature independent distribution of relaxation times and the non-Debye behavior in these materials. The co-operative motion due to strong coupling between the mobile Ag⁺ ions is assumed to give rise to non-Debye type of relaxation. The silver ionic transport number (t_Ag+) obtained by the emf technique suggested the occurrence of silver ion conduction in the CdI₂-doped Ag₂O–V₂O₅–B₂O₃ system.     

Crystallization and conductivity of 2CaO–La2O3–5P2O5 glass–ceramic with Al2O3 addition

Al₂O₃ was added to a 2CaO–La₂O₃–5P₂O₅ metaphosphate, to replace 10% of the Ca²⁺ ions by Al³⁺, forming a phosphate with the nominal composition 1.8CaO–0.1Al₂O₃–La₂O₃–5P₂O₅. The effect of Al₂O₃ addition and heat treatment on the microstructure and conductivity of the resulting glass–ceramics was investigated by XRD, SEM, TEM, and AC impedance spectroscopy. Upon transformation from glass to glass–ceramic, conductivities increased significantly. The glasses were isochronally transformed at 700 and at 800 °C for 1 h or 5 h, in air, following heating at 3 or 10 °C/min. With Al₂O₃ addition, after a heat treatment at 700 °C, 100–300 nm nano-domains of LaP₃O₉ crystallized from the glass matrix. Annealing at 800 °C produced a further order of magnitude conductivity increase for the Al-free glass, but less so for the Al-containing glass.     

Structural and optical properties of WO3–PbO–B2O3 glass-ceramic

The WO₃–PbO–B₂O₃ glasses and glass ceramics are prepared and investigated with the help of XRD, density, molar volume, UV–visible and FTIR spectroscopy. XRD pattern reveals the glassy behavior up to 4% concentration of WO₃ and ceramic behavior of the prepared samples with concentration of WO₃ >4%. Band gap of glass samples decreases with increase in the WO₃ concentration from 0–5%. The samples with WO₃ concentration >5% do not respond to UV–visible absorption. The density and molar volume measurements show the compaction of structure of the samples, which is due to the formation of BO₄ groups. FTIR spectroscopy shows the formation of BO₄ group and W–O–W bending vibration at high concentration of WO₃.     

Electrical properties of the high-pressure phases of gallium and indium tellurides

A study has been made of the resistance ρ, the thermopower S, and magnetoresistance MR of Ga₂Te₃ and α-In₂Te₃ single crystals at pressures P up to 25 GPa. It is found that the resistance ρ and |S| sharply decrease at ∼0–5 and 1.5–3 GPa, respectively. The semiconductor-metal phase transitions in the temperature range from 77 to 300 K are established from the sign reversal of the temperature coefficient of ρ to occur at P>4.4 and >1.9 GPa. The values S ≈+(10–20)μ V/K for the metallic phases with a Bi₂Te₃-type structure agree with those for liquid In₂Te₃ and Ga₂Te₃. Negative MR is revealed in In₂Te₃ at P≈1.9 GPa. No MR is observed in Ga₂Te₃ up to 25 GPa. The variation of the electronic structure of In₂Te₃ and Ga₂Te₃ under pressure is discussed. __________ Translated from Fizika Tverdogo Tela, Vol. 42, No. 6, 2000, pp. 1004–1008. Original Russian Text Copyright ? 2000 by Shchennikov, Savchenko, Popova.     

Theoretical studies on the structures and absorption spectra of–C n R2n+1(R = H,F; n = 1, 2) substituted 5-(2-pyridyl) pyrazolate boron complexes

The molecular structures, electronic structures and absorption characters of–CH₃,–C₂H₅,–CF₃,–C₂F₅ substituted 5-(2-pyridyl) pyrazolate boron complexes were presented by density functional theory (DFT). The ground state structures of the title complexes were optimised at B3LYP/6-31G* level. In addition, a time dependent density functional theory (TD-DFT) method is applied to investigate the properties of absorption spectra and electronic transition mechanism which were based on the ground state geometries. The results show that the chemical bond formed between nitrogen in the pyridyl ring and boron can be attributed to coordination effect. The boron centre has a typical tetrahedral geometry with the adjacent atoms. The calculated absorption wavelengths for–CF₃,–C₂F₅ substituted 5-(2-pyridyl) pyrazolate boron complexes are in good agreement with the experimental data.     

Experimental Study and Modelling of Formation and Decay of Active Species in an Oxygen Discharge

A microwave (2.45 GHz) oxygen discharge (3 hPa, 150 W, 50 mL.min^–1) is studied by optical emission spectroscopy of O(⁵P) (line 777.4 nm) and of the atmospheric system of O₂(head‐line 759.4 nm). Calibration of the spectral response of the optical setup is used to determine the concentrations of O(⁵P) and O₂(b). The concentration of the O(⁵P) atoms is in the range 108–109 cm^–3 and the concentration of the O₂(b) molecules is in the range 10¹⁴ – 2 × 10¹⁴ cm^–3 along the discharge tube. An attempt is made to simulate the experimental results by using coupling the Boltzmann equation, homogeneous energy transfer V‐V and V‐T, heterogeneous reactions on the walls (energy transfer and recombination of atoms) and a kinetic scheme (electronic transfer and chemical reactions). The Boltzmann equation includes momentum transfer, inelastic and superelastic processes and e‐e collisions. V‐V and V‐T transfer equations are obtained from the SSH theory and the kinetic scheme includes 65 reactions with 17 species [electrons e, ions O^– and O₂^–, fundamental electronic neutral species O(³P), O₂, O₂(X,v), O₃ and excited neutral species O₂(a), O₂(b), O₂(A), O(¹D), O(¹S), O(⁵P), O(4d ⁵D^o), O(5s ⁵S^o), O(3d ⁵D^o) and O(4s ⁵S^o)]. A fair agreement between experimental results and modelling is obtained with the following set of fitting values: – heterogeneous deactivation coefficient for O₂(b) γ = 2.6 × 10^–2; – rate constant of reaction [O(¹D) + O(³P) → 2 O(³P)] k₃₄ = 1.4 × 10^–11 cm³.s^–1; – electron concentration in the range 10¹⁰ – 10¹¹ cm^–3. Modelling shows that the recombination coefficient for oxygen atoms on the silica wall (range 1.4 × 10^–3 – 0.2 × 10^–3) is of the same order as the values obtained in a previous paper and that the ratio ([O] / 2 [O₂]initial) is about 33–50%. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Pressure-induced phase transformation in In2Bi

We have made measurements of the pressure dependence of the superconducting transition temperature, T_c, for In₂Bi and related alloys. For In₂Bi- phase alloys, a large discontinuity in T_c is seen at 15–20 kbar, which we associate with a phase transformation first seen by Bridgman [1]. Our measurements suggest that this transformation is produced by the decomposition of In₂Bi into In₅Bi₃ and an In-rich phase. In the low pressure phase, T_c shows a minimum at 9–15 kbar whereas it depends linearly on pressure in the high pressure phase with ?T_c/?P equal to -4.9 × 10^-5 K bar^-1.     

Unexpected Features of the Intramolecular Spin Exchange in Imidazoline Nitroxide Biradicals Dissolved in Ionic Liquids

Three imidazoline-type nitroxide biradicals of the similar composition R ₅ ^NO –CH=N–N=CH–R ₅ ^N , B1, R ₅ ^NO –CH=N–N=C(CH₃)–R ₅ ^N , B2, and R ₅ ^N –C(CH₃)=N–N=C(CH₃)–R ₅ ^N , B3, with R ₅ ^N and R ₅ ^NO denoting, respectively, the nitroxide rings 1-oxyl-2,2,5,5-tetramethyl-3-imidazoline and 1-oxyl-2,2,5,5-tetramethyl-3-N–oxide imidazoline, have been studied by X-band electron paramagnetic resonance (EPR) spectroscopy. Variations of the intramolecular electron spin exchange in these biradicals dissolved in ethanol and the room temperature ionic liquid bmimBF₄ were characterized as a function of temperature by means of the analysis of the EPR lines shape. Thermodynamic parameters of the conformational rearrangements in ethanol were calculated. Analyzing the EPR spectra of these biradicals in bmimBF₄, it was revealed that the two-conformational model does not describe their conformational transitions. Moreover, the observed EPR spectra are not central symmetric especially at low temperatures that cannot be described and explained in the framework of the current theory of the intramolecular spin exchange. Probable reasons of this “strange” behavior are discussed.     

Luminescence properties of Pr3+-doped transparent oxyfluoride glass–ceramics containing BaYF5 nanocrystals

Transparent oxyfluoride glass–ceramics containing BaYF₅ nanocrystals were successfully synthesized by appropriate heat-treatment on the SiO₂–Al₂O₃–Na₂O–BaF₂–Y₂O₃–Pr₆O₁₁ precursor glass. The structure and luminescence properties of the precursor glass and glass–ceramics were investigated by DSC, XRD, TEM, optical transmission, photoluminescence, decay time and radioluminescence spectra. The XRD results indicate that the BaYF₅ nanocrystals can percitated in the precursor glass and the sharper emission peaks of Pr³⁺ in glass ceramic suggests that Pr³⁺ ions are incorporated into the BaYF₅ nanocrystals. The higher the heat-treatment temperature is, the more the Pr³⁺ ions are centered into BaYF₅ nanocrystals, which results in the optimal concentration of Pr³⁺ in glass ceramic changes on heat-treatment temperature. It is notable that the emission intensity of both photoluminescence and radioluminescence for 0.1 mol% Pr³⁺ in the glass ceramic (GC665) are stronger than those in the precursor glass. The mechanism of enhanced luminescence is also discussed.     

Effect of additives on structure and corrosion resistance of ceramic coatings on Mg–Li alloy by micro-arc oxidation

In order to improve the corrosion resistance of ceramic coatings formed on Mg–5mass%Li substrate by micro-arc oxidation (MAO) method, two kinds of additives (Na₂B₄O₇ and EDTA) were doped in Na₂SiO₃–Na₃PO₄ solution system. The surface and cross-section morphology feature, phase composition and elemental composition were examined by SEM, XRD and EDX, respectively. Corrosion resistance of ceramic coating was tested by electrochemical methods. It was revealed that all coatings were composed of MgO and Mg₂SiO₄, and had porous surface structure. Doping of additives had little effect on the elemental composition, while it influenced the morphological feature of the coating. The results of electrochemical tests showed that the coatings prepared in the solutions with additive had good corrosion resistance. The addition of EDTA to the solution made coatings thinner and more uniform which resulted in better general corrosion resistance. The addition of Na₂B₄O₇ to the solution made coatings much thicker and compacter, which improved the pitting corrosion resistance.     

Optical band-gap of Zn3As2

Absorption measurements of single Zn₃As₂ crystals were made at temperatures 5, 80 and 300 K. Free-carrier absorption is interpreted in the simple classical model. Interband absorption shows contributions from Urbach-like excitations. The direct optical gap has been estimated as 0.99 eV at 300 K, 1.09 eV at 80 K and 1.11 eV at 5 K. The linear dependence of band-gap on temperature was found in the range 80–300 K with dE_g/dT = ? 4.55 × 10^?4eVK^?1.     

Photoluminescence and decay behavior of Tb3+ ions in sodium fluoro-borate glasses for display devices

We report the optical absorption, photoluminescence and fluorescence decay properties of Tb³⁺-doped sodium fluoro-borate (SFB) glasses. Different concentrations of Tb³⁺-doped SFB glasses were prepared by conventional melt quenching technique using a chemical composition (in mol%) 25Na₂O–5LaF₃–10CaF₂–10AlF₃–(50?x) B₂O₃?x TbF₃ (0.01≤x≥4). The Judd-Ofelt model has been adopted to determine the radiative parameters of the ⁵D₄→⁷F_6–3 emission transitions. The effect of Tb³⁺ ion concentration on the emission from the ⁵D_3,4 excited levels is discussed in detail. The analysis of optimization of Tb³⁺ ion concentration for efficient green color display devises is reported. The resonance energy transfer mechanism responsible for non-radiative decay rates is clearly explored.