Formation of V2O3 nanocrystals by thermal reduction of V2O5 thin films

We report the formation of homogeneous and stable V₂O₃ nanocrystals, directly from V₂O₅ thin films, at 600 °C, as observed by using in situ electron microscopy experiments. Thermally-induced reduction of V₂O₅ thin films in vacuum is remarkably different when compared to reduction of V₂O₅ single crystals and results in the formation of nanophase V₂O₃. Thermally grown V₂O₃ nanocrystals exhibit hexagon or square shape and are stable at higher temperature as well as room temperature. The formation of stable nanocrystals through the reduction process in a non-chemical environment (vacuum) could provide a basis for understanding the complex processes of vanadium oxide phase transitions and for controlling the chemical processes to produce oxide nanocrystals.     

Kinetics of thermally stimulated recombination processes in lithium borate crystals

This paper reports on the results of the experimental and theoretical investigations of thermally stimulated recombination processes in crystals of the lithium borates Li₂B₄O₇ and LiB₃O₅. For both types of crystals, the measurements of thermally stimulated luminescence curves, spectra, and temperature dependences of the intensities of steady-state X-ray luminescence have been performed in a single experimental cycle. In the framework of a unified model for the Li₂B₄O₇ and LiB₃O₅ crystals, the thermally stimulated recombination processes have been calculated and the obtained results have been interpreted talking into account all available experimental data.     

Spin-wave resonances in Eu<Subscript>0.8</Subscript>Ce<Subscript>0.2</Subscript>Mn<Subscript>2</Subscript>O<Subscript>5</Subscript> and EuMn<Subscript>2</Subscript>O<Subscript>5</Subscript> multiferroics

Spin-wave resonances have been observed in superlattices arising due to the phase separation and self-organization of charge carriers in Eu_0.8Ce_0.2Mn₂O₅ single crystals. The resonances are found within the 5–80 K temperature range at frequencies close to 30 GHz. Similar resonances with intensities about an order of magnitude lower are also observed in EuMn₂O₅. The latter suggests the existence of charge transfer processes between the manganese ions of different valences in EuMn₂O₅.     

Preparation of MgTi2O5 nanoparticles for sonophotocatalytic degradation of triphenylmethane dyes

MgTi₂O₅ (magnesium dititanate) nanoparticles were prepared by a simple hydrothermal assisted post-annealing method and characterized with various analytical techniques. The catalytic properties (sonocatalytic, photocatalytic and sonophotocatalytic activity) were evaluated using the degradation of triphenylmethane dyes (crystal violet, basic fuchsin, and acid fuchsin). The sonophotocatalytic activity of MgTi₂O₅ nanoparticles towards crystal violet was found to be ~2.9 times higher than the photocatalytic activity and ~20 times higher than that of the sonocatalytic processes. In addition, the sonophotocatalytic efficiency of MgTi₂O₅ nanoparticles was found to be remarkable for the degradation of basic fuchsin (cationic dye) and acid fuchsin (anionic dye). The mechanism of these catalytic activities has been discussed in detail.     

Photocatalytic activity of Nb2O5/SrNb2O6 heterojunction on the degradation of methyl orange

The pure SrNb₂O₆ powders were prepared at 1400 °C by a conventional solid-state method and characterized by X-ray powder diffraction and UV-vis diffuse reflection spectrum. The powders of Nb₂O₅ and SrNb₂O₆ were ball-milled together and annealed to form the Nb₂O₅/SrNb₂O₆ composite. Photocatalytic activities of the composites were investigated on the degradation of methyl orange. The results show that the proportion of Nb₂O₅ to SrNb₂O₆ and the annealing temperature greatly influence the photocatalytic activities of the composites. The best photocatalytic activity occurs when the weight proportion of Nb₂O₅ to SrNb₂O₆ is 30% and the annealing temperature is 600 °C. The tremendously enhanced photocatalytic activity of the Nb₂O₅/SrNb₂O₆ composite compared to Nb₂O₅ or SrNb₂O₆ is ascribed to the heterojunction effect taking place at the interface between particles of Nb₂O₅ and SrNb₂O₆. The powders also show a higher photocatalytic activity than commercial anatase TiO₂.     

Ion-beam reduction of the surface of tantalum higher oxide

The process of reduction of the surface of higher oxide Ta₂O₅ under irradiation by inert gas (Ar⁺) and chemically active gas (O₂⁺) ions with an energy of 3 keV in high vacuum is investigated by X-ray photoelectron spectroscopy at room temperature. It is found that intermediate oxide TaO₂, lower oxide TaO, and metallic Ta form in the surface layers of Ta₂O₅ under Ar⁺ ion bombardment. An insignificant amount of intermediate oxide TaO₂ forms in the surface layers of Ta₂O₅ under O₂⁺ ion bombardment. Ion-beam-induced reduction of the Ta₂O₅ surface is shown to depend on the type of ion and irradiation dose.     

Surface modification of Mg2B2O5 whisker and its effect on the mechanical properties and thermostability of polycarbonate/Mg2B2O5w composites

The Mg₂B₂O₅ whiskers (Mg₂B₂O₅w) were modified by boric acid ester (BE) coupling agent and used to prepare polycarbonate (PC) composites. Surface wettability test and evaluation of dispersibility of BE-modified Mg₂B₂O₅w (BE-Mg₂B₂O₅w) in n-heptane were carried out by water contact angle measurement and polarizing microscopy, respectively. The surface chemical characteristics of BE-Mg₂B₂O₅w and estimation of the amount of tightly bonded organic modifier were examined by Fourier transform infrared spectrometry (FT-IR) and thermogravimetric analysis (TGA), respectively. The influence of BE-Mg₂B₂O₅w on the mechanical property, morphology and thermostability of PC composites was investigated by using universal testing machine, scanning electron microscopy (SEM), dynamic mechanical analysis (DMA) and TGA, respectively. It was found that BE was successfully grafted to the surface of Mg₂B₂O₅w, and the hydrophobic BE-Mg₂B₂O₅w leads to high ratio of adhesion work to interfacial tension between PC and BE-Mg₂B₂O₅w, and its better dispersibility in n-heptane. Furthermore, the incorporation of BE-Mg₂B₂O₅w into PC matrix resulted in higher tensile properties of PC/BE-Mg₂B₂O₅w than that of PC/Mg₂B₂O₅w composites and lower maximum weight loss rate than that of PC. The storage modulus of the PC/Mg₂B₂O₅w composites increased obviously as a function of whisker content, especially for the composites with BE-Mg₂B₂O₅w, but the T_g value changed little.     

The thermochemistry of the hydrogen vanadium bronzes HxV2O5

The enthalpies of formation of seven hydrogen vanadium bronzes, H_xV₂O₅(0<x⩽3.77), prepared at ambient temperature by “hydrogen spillover”, have been determined by solution calorimetry. The enthalpy values obtained for their formation from H₂(g) and V₂O₅(s) at 298.15 K are (in kJ mol⁻¹): H_0.22V₂O₅, −1569.95 ± 1.75; H_0.46V₂O₅, −1589.96 ± 1.69; H_1.43V₂O₅, − 1670.53 ± 1.88; H_1.87V₂O₅, −1700.56 ± 1.58; H_2.79V₂O₅, −1744.23 ± 1.72; H_3.53V₂O₅, −1772.98 ± 2.38; H_3.77V₂O₅, −1781.10 ± 2.27. The stabilities of the compounds towards decomposition, disproportion and oxidation are discussed.     

光腔衰荡光谱法测量大气中的NO3和N2O5

本文应用基于二极管激光器的双路光腔衰荡光谱技术,分别对大气中NO₃和N₂O₅浓度进行监测. 通过使用实验室标准样校正有效吸收腔长比R_L和系统的总损耗系数?,并获得了NO₃有效吸收截面. 该装置在时间分辨率为1 s时,对NO₃的测量灵敏度达到1.1 pptv,N₂O₅被在线转换成NO₃,从而被另一路光腔衰荡光谱装置探测. 利用该装置,对合肥市区冬季夜间大气中的NO₃,N₂O₅浓度进行了实时监测. 通过对比一次大气快速清洁过程中氮氧化物、臭氧、PM_2.5等组分的浓度变化,讨论了大气环境下可能影响NO₃及N₂O₅浓度的因素.     

First-principles study of the effect of iron doping on the electronic and magnetic properties of TbMn2O5

We have studied the electronic and magnetic properties of TbFe_xMn_2−xO₅ (x=0, 0.125, 0.25) samples using first-principles density functional theory within the generalized gradient approximation (GGA) schemes. The crystal structure of TbMn₂O₅ is orthorhombic containing Mn⁴⁺O₆ octahedra and Mn³⁺O₅ pyramids. The structure changes to monoclinic symmetry for the Fe-doping at the Mn sites. Our spin-polarized calculations give an insulating ground state for TbMn₂O₅ and a metallic ground state for Fe-doped TbMn₂O₅. Based on the magnetic properties calculations, it is found that the magnetic moment enhances with increase in the Fe-content in TbMn₂O₅. Most interestingly, the enhanced magnetic moment is due to a substantial reduction of the magnetic moments at the Fe sites.     

Thermochemistry of the high and ambient temperature lithium vanadium bronze phases LixV2O5

The enthalpies of formation of a series of high and low temperature phases in the ternary oxide system Li_xV₂O₅ have been determined by solution calorimetry. Samples of the former, α-Li_0.04V₂O₅, β-Li_0.30V₂O₅, β'-Li_0.48V₂O₅ and γ-LiV₂O₅, were prepared by solid state reaction at 650°C. The ambient temperature materials Li_0.1V₂O₅(I), Li_0.45V₂O₅(II) and Li_1.03V₂O₅(III) were prepared by n-butyl lithiation in hexane. The thermochemistries of the two classes of material were examined and related to structural features and to the observed behaviour of V₂O₅ as a battery cathode material in lithium cells.     

Intensity of the atomic oxygen lines at 8446 and 7771 A in an Ar-O2 d.c. glow discharge

An equation for the intensity ofO(3³P?3³S) at 8446 A and ofO(3⁵P?3⁵S) at 7771 A has been derived as a function of electron-, Ar- and O₂-densities assuming applicability of the excitation processes proposed by Bennett et al. and by Tunitskii and Cherkasov. The electron temperature has been assumed to be constant. The results are compared with experimental data obtained in the d.c. glow discharge of Ar-O₂ mixtures.     

Influence of V2O5 on the densification and the magnetic properties of Ni—Zn ferrite

The effects of V₂O₅ addition on the densification and the magnetic properties of the Ni—Zn ferrites have been studied. The maximum density was observed at a V₂O₅ content of 0.2 mo1% and 0.5 mo1% in iron excess and deficient ferrites respectively. The minimum loss factor occured at a V₂O₅ content of 0.4 mo1% irrespective of sintering temperature in both iron excess and iron deficient compositions. The variation of Curie temperature with the amount of V₂O₅ (? 1 mo1%) added suggests that V₂O₅ goes into solid solution in the Ni—Zn ferrites, though the lattice parameter does not change appreciably with such addition.     

Kinetics of energy deactivation in the O2(1Δ)-I medium

The kinetics of energy-exchange and quenching processes in the O₂(¹Δ)-I medium plays an important role in the operation of the chemical oxygen-iodine laser. However, up to now, many of the key processes in this medium are not fully understood. In this work, the flow tube technique is used to determine the rate of excitation energy deactivation in the O₂(¹Δ)-I medium in the presence of small concentrations of water and carbon dioxide. The concentrations of electronically excited species are measured with spectrometers calibrated in absolute spectral responsivity. The effective rate constant for the deactivation of O₂(¹Δ) molecules in processes involving iodine atoms is determined. The results are compared to those obtained in previous works.     

Ion-beam reduction of the surface of higher niobium oxide

X-ray photoelectron spectroscopy is used to study the process of reduction of the surface of the higher oxide Nb₂O₅ upon bombardment with inert gas ions (Ar⁺) and reactive gas ions (O₂⁺) with an energy of 1 and 3 keV in high vacuum at room temperature. It is found that, upon bombardment with Ar⁺ ions, the lower oxide NbO and the intermediate oxide NbO₂ are formed in the surface layers of the oxide Nb₂O₅. Bombardment with O₂⁺ ions leads to the formation of an extremely insignificant amount of the intermediate oxide NbO₂ in the surface layers of the oxide Nb₂O₅. It is revealed that the process of ion-beam reduction of the surface of the oxide Nb₂O₅ depends on the ion type, dose, and energy of exposure.     

Effects of process parameters on the optical constants of highly textured V2O5 thin films

The optical properties of the highly-textured V₂O₅ thin-films grown on Si(100) by sputter-deposition at various oxygen reactive-pressures were investigated in detail. The profiles of the optical constants, namely the refractive index and extinction coefficient, of V₂O₅ films were evaluated in the photon-energy range of 1–5 eV. At photon-energy above 2.5 eV, the dispersion behavior in optical constants is explained based on Lorentz-Drude model. The refractive index dispersion fits to a Cauchy’s relation at photon-energy below 2.5 eV, where the V₂O₅-film is mostly transparent. The optical transitions across the bandgap occur at energy ～2.5–3.2 eV depending on the V₂O₅ growth conditions and film-microstructure. The highly-textured and c-axis oriented V₂O₅-films, fabricated under optimum conditions of temperature and oxygen partial pressure, exhibit excellent optical characteristics similar to V₂O₅ single crystals.     

In situ RHEED analysis of epitaxial Gd2O3 thin films grown on Si (001)

Epitaxial Gd₂O₃ thin films were successfully grown on Si (001) substrates using a two-step approach by laser molecular-beam epitaxy. At the first step, a ～0.8 nm thin layer was deposited at the temperature of 200 ^°C as the buffer layer. Then the substrate temperature was increased to 650 ^°C and in situ annealing for 5 min, and a second Gd₂O₃ layer with a desired thickness was deposited. The whole growth process is monitored by in situ reflection high-energy electron diffraction (RHEED). In situ RHEED analysis of the growing film has revealed that the first Gd₂O₃ layer deposition and in situ annealing are the critical processes for the epitaxial growth of Gd₂O₃ film. The Gd₂O₃ film has a monoclinic phase characterized by X-ray diffraction. The high-resolution transmission electron microscopy image showed all the Gd₂O₃ layers have a little bending because of the stress. In addition, a 5–6 nm amorphous interfacial layer between the Gd₂O₃ film and Si substrate is due to the in situ high temperature annealing for a long time. The successful Gd₂O₃/Si epitaxial growth predicted a possibility to develop the new functional microelectronics devices.     

Effect of intensifying additives on the degradation of thiamethoxam using ultrasound cavitation

The present study has investigated the degradation of thiamethoxam using ultrasound cavitation (US) operated at a frequency of 20 kHz and its combination with intensifying additives viz. hydrogen peroxide, Fenton and photo-Fenton reagent. At the outset, the performance of US (20 kHz) has been maximised by the optimization of process parameters. Highest rate of degradation of thiamethoxam was observed at the optimum ultrasonic power density of 0.22 W/mL, thiamethoxam concentration of 10 ppm and the pH of 2. The established optimum values of operating parameters were used further in case of combined treatment approaches. The effect of concentration of H₂O₂ on the rate of degradation of thiamethoxam in the case of US + H₂O₂ process has confirmed the existence of optimum concentration of H₂O₂ with the ratio of thiamethoxam: H₂O₂ as 1:10. US + Fenton process indicated the optimal molar ratio of FeSO₄·7H₂O:H₂O₂ as 1:15. The combined processes of US + H₂O_2, US + Fenton and US + photo-Fenton have resulted in the extent of degradation of 20.47 ± 0.61%, 34.41 ± 1.03% and 85.17 ± 2.56% respectively after 45 min. of operation. These combined processes lead to the synergistic index of 2.04 ± 0.06, 2.26 ± 0.07 and 2.42 ± 0.07 in case of US + H₂O₂, US + Fenton and US + photo-Fenton processes respectively over only US/stirring treatment with the additive. Additionally, the extent of mineralization and the energy efficiency of individual and combined processes have been compared. US + photo-Fenton process has been found to be the best strategy for effective degradation of thiamethoxam with a significant intensification benefit. The by-products formed during the ultrasonic degradation of thiamethoxam have been identified by using LC-MS/MS analysis.     

The role of electrolyte in governing the performance of protonic solid state battery

The solid-state proton conductor, P₂O₅.5H₂O, is found very difficult to handle due to presence of a very high content of moisture and corrosive nature. The addition of Al₂O₃ and SiO₂ into P₂O₅.5H₂O, forming composite electrolytes, obviates said drawback. The Zn + ZnSO₄ used as an anode to prepare cells with different cathode viz. I₂, MnO₂, PbO₂, and V₆O₁₃ characterized under different conditions. Open circuit voltage, discharge current and discharge time, on load voltage, discharge capacity, power density, and energy density are evaluated from discharge properties. Protonically conducting composite 70(P₂O₅.5H₂O)/30[(92SiO₂)/08(Al₂O₃)] is found to be the optimum combination with the optimized 50Zn/50ZnSO₄ as anode and 40MnO₂/60 graphite as cathode from secondary battery view point. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006     

Resistive switching functional quantum-dot light-emitting diodes

This study demonstrates quantum-dot light-emitting diodes (QD-LEDs) with a function of resistive switching memory, capable of on/off operation at the same driving current depending on reset/set state. The QD-LEDs were fabricated by spin-coating process and experienced two different annealing conditions, which yielded defective or less-defective V₂O_5–x layer. One of the annealing conditions produced QD-LEDs with the unusual electrical behaviors of negative differential resistance (NDR), capacitance oscillation, and voltage–current hysteresis curves, signifying so-called resistive switching characteristics. X-ray and ultraviolet photoelectron spectroscopies were used to examine the chemical state of the differently annealed V₂O_5–x layers. The less stoichiometric V₂O_5–x layer was found to be responsible for the resistive switching behaviors of the NDR and the low and high resistance states (LRS and HRS, respectively). We discuss the LRS/HRS of V₂O_5–x for resistive switching in terms of a conductive filament effect, induced by microstructural changes caused by oxygen drift and vacancy annihilation processes in the high defect density V₂O_5–x layer.