Characterization of partially inverse spinel ZnFe2O4 with high saturation magnetization synthesized via soft mechanochemically assisted route

ZnFe₂O₄ was prepared by a soft mechanochemical route from two starting combinations of powders: (1) Zn(OH)₂/α-Fe₂O₃ and (2) Zn(OH)₂/Fe(OH)₃ mixed in a planetary ball mill. The mechanochemical treatment provoked reaction leading to the formation of the ZnFe₂O₄ spinel phase that was monitored by XRD, TEM, IR and Raman spectroscopy. The spinel phase was first observed after 4 h of milling and its formation was completed after 18 h in both the cases of starting precursors. The synthesized ZnFe₂O₄ has a nanocrystalline structure with a crystallite size of about 20.3 and 17.6 nm, for the cases (1) and (2), respectively. In the far-infrared reflectivity spectra are seen four active modes. Raman spectra suggest an existence of mixed spinel structure in the obtained nanosamples. In order to confirm phase formation and cation arrangement, Mössbauer measurements were done. Estimated degree of inversion is about 0.58 for both starting mixtures. The magnetic properties of the prepared ZnFe₂O₄ powders were also studied. The results show that the samples have a typical superparamagnetic-like behavior at room temperature. Higher values of magnetization in the case of samples obtained with starting mixture (2) suggest somewhat higher degree of cation inversion.     

Single-calcination synthesis of pyrochlore-free Pb(Ni1/3Nb2/3)O3-PbTiO3 using a coating method

Pyrochlore-free 0.64Pb(Ni_1/3Nb_2/3)O₃-0.36PbTiO₃ (0.64PNN-0.36PT) powder has been successfully synthesized by only one calcination step using a coating method. The formation of pyrochlore phase is prevented by coating NiCO₃·2Ni(OH)₂·2H₂O on Nb₂O₅ particles. NiCO₃·2Ni(OH)₂·2H₂O-coated Nb₂O₅ powder is prepared by heterogeneous precipitation method. The coating structure is confirmed by transmission electron microscope (TEM) with energy dispersive spectroscope (EDS). Single calcination treatment of the coating powder mixed with appropriate amounts of Pb₃O₄ and TiO₂ powders at 900 °C for 2 h produces the pure-perovskite 0.64PNN-0.36PT powder. The elimination of the pyrochlore phase can be explained in terms of the separating of Pb₃O₄ and Nb₂O₅ by the NiCO₃·2Ni(OH)₂·2H₂O coating layer.     

Comparative structural and photoluminescent study of Eu-doped La2O3 and La(OH)3 nanocrystalline powders

Eu³⁺-doped La₂O₃ nanocrystalline powder was prepared by polymer complex solution method and further used for preparation of Eu³⁺-doped La(OH)₃. Structural and optical characterization was carried out by powder X-ray diffraction and photoluminescent spectroscopy. XRD measurements confirmed the formation of hexagonal La₂O₃ and its recrystallization into La(OH)₃ in a humid atmosphere. Excitation spectra show redshift of host lattice and charge transfer emission bands in La(OH)₃ while bands that correspond to Eu³⁺f–f transitions are placed at same wavelengths in both samples. Photoluminescence spectra recorded over the temperature range from 10 K to 300 K show that intensities of emission lines in Eu³⁺-doped La₂O₃ do not depend on temperature as much as in La(OH)₃ sample. Observed dominant ⁵D₀→⁷F₂ and markedly visible ⁵D₀→⁷F₀ emissions in doped La₂O₃ indicate that Eu³⁺ ion is located in a structural site without an inversion center. On the other hand, in Eu³⁺-doped La(OH)₃⁵D₀→⁷F₀ transition is barely visible while ⁵D₀→⁷F₂ is not prominent, and with temperature drop three ⁵D₀→⁷F_J (J=1, 2, 4) transitions become almost of the same intensity. In both La₂O₃ and La(OH)₃ structures Eu³⁺ ion replaces La³⁺ in non-centrosymmetric C_3v and C_3h crystallographic sites, respectively, and difference in symmetry of the crystal field around europium ion is explained by comparing shape and volume of these sites. Decay times of the ⁵D₀- level recorded over the temperature range 10−300 K revealed that emission lifetime values in La₂O₃ (~0.7 ms) are almost two times higher than in La(OH)₃ (~0.4 ms), and unlike in La₂O₃, lifetime in La(OH)₃ is temperature dependent.     

Effect of hydroxyl groups on Er doped Bi2O3-B2O3-SiO2 glasses

A series of Er³⁺-doped Bi₂O₃-B₂O₃-SiO₂-Na₂O glasses with different hydroxyl groups were prepared and the interaction between the Er³⁺ ions and OH groups was investigated. Infrared spectra were measured in order to calculate the exact content of OH groups in samples. The observed increase of the fluorescence lifetime with the oxygen bubbling time has been related to the reduction in the OH content concentration evidenced by infrared (IR) absorption spectra, which confirmed that the OH groups were dominant quenching centers of excited Er³⁺ and a cause of concentration quenching of 1.5 μm band emission. Various nonradiative decay rates from ⁴I_13/2 of Er³⁺ with the change of OH content were determined from the fluorescence lifetimes and radiative decay rates, which were calculated on the basis of Judd-Ofelt theory.     

Controllable synthesis and characterization of CuO, β-Ni(OH)2 and Co3O4 nanocrystals in the MCln-NH4VO3-NaOH system

In this study, we demonstrate a general but efficient solution-phase approach for preparing CuO, β-Ni (OH)₂ and Co₃O₄ nanocrystals selectively by simply adjusting the amount of NaOH in the reaction system of MCl_n-NH₄VO₃-NaOH. The experimental results revealed that the amount of NaOH is crucial in the formation of desirable products. The as-obtained nanocrystals were characterized by means of X-ray powder diffraction, transmission electron microscope, high resolution transmission electron microscope, selected area electron diffraction and electrochemical techniques. The as-prepared CuO are nanorods with 15 nm in diameter and 50 nm in length. The as-prepared Ni (OH)₂ nanocrystals have the flocculent feature and Co₃O₄ nanocrystals are composed of irregular particles. It should be pointed out that some traditional metal vanadates occur in these reaction systems, which were usually prepared by the solid-state routes. On the other hand, the electrochemical properties of the obtained products were studied in brief. Electrochemical performances of CuO, β-Ni (OH)₂ and Co₃O₄ nanocrystals were measured with Li metal as the reference anode, which indicates their excellent capacities of Li-deposited for Li-ion batteries.     

The partial 1H NMR spectra of Al–OH and molecular H2O in hydrous aluminosilicate glasses: Component-Resolved analysis of 27Al–1H cross polarization and 1H spin-echo MAS NMR spectra

The Component-Resolved methodology was applied to ¹H spin-echo and ²⁷Al–¹H cross polarization (CP) MAS NMR data of aluminosilicate glasses. The method was able to resolve two components with different T2 relaxation rates, hydroxyl groups (OH) and molecular water (H₂O_mol), from the spin-echo data and to determine partial spectra and the relative abundances of OH and H₂O_mol. The algorithm resolved two to three components with different ²⁷Al–¹H CP dynamics from the ²⁷Al–¹H cross polarization data; the obtained partial NMR spectra for Al–OH are in excellent agreement with those obtained previously from the difference spectra between spectra with various contact times and confirm previous quantitative results and models for the Al–OH, Si–OH and H₂O_mol speciation (Malfait and Xue, 2010).     

Formation pathways of HO2 and OH changing as a function of temperature in photolytically initiated oxidation of dimethyl ether

The time resolved product formation in oxidation of dimethyl ether (DME) has been studied between 298-625 K and 20-90 torr total pressure. Near-infrared frequency modulation spectroscopy (FMS) with Herriott type multi pass optics and UV absorption spectroscopy (UV) were conducted in the same cell. The reaction was initiated by pulsed photolysis in a mixture of Cl₂, O₂, and DME via CH₃OCH₂ radical formation. The reaction process was investigated through FMS measurement of HO₂ and OH, and UV measurement of CH₃OCH₂O₂. The yields of HO₂ and OH are obtained by comparison with reference mixtures, Cl₂, O₂, and CH₃OH for HO₂, and Cl₂, O₂, CH₃OH, and NO for OH, which convert 100% of initial Cl to HO₂ and OH. The CH₃OCH₂O₂ yield is also obtained. It was found that the HO₂ yield increases sharply over 500 K mainly with a longer time constant than that of R + O₂ reaction, while a prompt component exists throughout the temperature range at a few percent yield. OH was found to be produced promptly at a yield considerably larger than that known for the simplest alkanes. The CH₃OCH₂O₂ profile has a prompt rise followed by a gradual decay whose rate is consistent with the slow HO₂ formation. The species profiles were successfully predicted with a model constructed by modifying the existing one to suit the reduced pressure condition. After modification, it was inferred that the HO₂ formation over 500 K is secondary from HCHO + OH and HCO + O₂ and a part of HCO is formed directly from the O₂ adduct, whereas the HO₂ formation below 500 K is governed by CH₃OCH₂O₂ chemistry. The HCO forming pathway via isomerization-decomposition of the O₂ adduct, which was not included in the former models, was supported by our quantum-chemical calculations.     

Evaluation of heat release indicators in lean premixed H2/Air cellular tubular flames

Heat release rate in combustion systems must be understood in order to control thermoacoustic instabilities, flame extinction, and heat losses. Traditionally OH chemiluminescence (OH*) is used to trace heat release rate (HRR) in H₂/air flames, but its accuracy as a tracer has not been assessed. Lean premixed H₂/air cellular tubular flames are a good test case to evaluate HRR tracers due to the presence of highly reactive flame cells surrounded by regions of near extinction. Comparing the calculated heat release rate to OH* concentration, one finds that [OH*] profiles correlate with the regions of high reactivity (flame cells) but the correlation fails in the low reactivity regions where the HRR is much higher than the [OH*] value indicates. Alternate HRR tracers including [H] and pixel-by-pixel products of [O₂]x[H], [OH]x[H₂], and [O]x[H₂] are analyzed with detailed numerical simulations. The chosen products derive from the main chain reaction steps that contribute to overall HRR in lean, premixed H₂/air flames. Findings suggest that [H] is an accurate yet simple way of tracking HRR. Planar measurements of HRR are possible if LIF measurements of [H] are improved.     

Photoluminescence of Y2O3:Eu thin film phosphors by sol-gel deposition and rapid thermal annealing

Y₂O₃:Eu³⁺ phosphor films have been developed by using the sol-gel process. Comprehensive characterization methods such as Photoluminescent (PL) spectroscopy, X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR) spectroscopy were used to characterize the Y₂O₃:Eu³⁺ phosphor films. In this experiment, the XRD profiles show that the Y₂O₃:Eu³⁺ phosphor films crystallization temperature and optimum annealing temperature occur at about 650 and 750 °C, respectively. The optimum dopant concentration is 12 mol% Eu³⁺ and the critical transfer distance (R_c) among Eu³⁺ ions is calculated to be about 0.84 nm. Vacuum environment is more efficient than oxygen and nitrogen to eliminate the OH content and hence yields higher luminescent phosphor films. The PL emission intensity of Y₂O₃:Eu³⁺ phosphor films is also dependent on the annealing time. It was found that the H₂O impurities were effectively eliminated after annealing time of 25 s at 750 °C in vacuum environment. From the experiment results, the schematic energy band diagram of Y₂O₃:Eu³⁺ phosphor films is constructed.     

Surface reaction mechanism of Y2O3 atomic layer deposition on the hydroxylated Si(1 0 0)-2 × 1: A density functional theory study

The surface reaction mechanism of Y₂O₃ atomic layer deposition (ALD) on the hydroxylated silicon surface is investigated by using density functional theory. The ALD process is designed into two half-reactions, i.e., Cp₃Y (Cp = cyclopentadienyl) and H₂O half-reactions. For the Cp₃Y half-reaction, the chemisorbed complex is formed along with the change of metal-Cp bonding from Y-C(π) to Y-C₁(σ). For the H₂O half-reactions, the chemisorbed energies are increased with the relief of steric congestion around yttrium metal center. In addition, Gibbs free energy calculations show that it is thermodynamically favorable for the Cp₃Y half-reactions. By comparing with the reaction of H₂O with {Si}-(O₂)YCp, it is thermodynamically more favorable and kinetically less favorable for the reactions of H₂O with {Si}-OYCp₂ as well as with {Si}-OYCp(OH).     

Mechanism of magnetic field effect on OH density distribution in a methane–air premixed jet flame

The mechanism of magnetic field effect on OH density distribution in a methane-air premixed jet flame was investigated by means of PLIF measurement and numerical simulation. In the experiment, magnetically induced change in the OH density profile in the flame in a N₂ atmosphere was much smaller than that in air (mixture of 80% N₂ and 20% O₂), and such a phenomenon was qualitatively reproduced by solving the equations for reactive gas dynamics and magnetism in the numerical simulation. Here, N₂ is diamagnetic and little affected by the magnetic field, while O₂ is paramagnetic and influenced due to the magnetic field. This provided the experimental and numerical verification for the mechanism of the magnetic field effect suggested in our previous study. That is, the magnetic force does not directly and selectively induce the change in the diffusion velocity of OH itself. Alternatively, the magnetic force acting on O₂ in the surrounding air, whose mass density and magnetic susceptibility are much larger than that of other chemical species in the flame, causes the change in the convection velocity of the gas mixture and displaces the OH density distribution indirectly and passively. In other words, the most important cause of the OH density change is not the diffusion of OH, but the convection of air containing a large amount of O₂. Furthermore, by careful examination of the magnetic field effect on the flame in the N₂ atmosphere, it was found out that the magnetic force does not only act on O₂ in the surrounding air, but also on O₂ in the premixed gas injected from the burner.     

The role of co-adsorbed O2 on the catalytic reduction of NO with C2H5OH on the surface of Pt(3 3 2)

The influence of pre-dosed O₂ on the catalytic reduction of NO with ¹³C₂H₅OH on the surface of stepped Pt(3 3 2) was investigated using Fourier transform infra red reflection-absorption spectroscopy (FTIR-RAS) and thermal desorption spectroscopy (TDS). We show that the oxidation of ¹³C₂H₅OH with O₂ is a very effective reaction, occurring at 150 K and giving rise to acetate. The presence of NO does not lead to any evident oxidation of ¹³C₂H₅OH irrespective of the annealing temperature. For the case of O₂ + ¹³C₂H₅OH + NO co-adlayers, oxidation of ¹³C₂H₅OH also takes place at 150 K. However, no new surface species that are supposed to be an intermediate for the production of N₂ are detected.The influence of O₂ on the production and desorption of N₂ is intimately related to both O₂ and ¹³C₂H₅OH coverage. The presence of pre-dosed O₂ does not greatly promote N₂ desorption. In fact, N₂ desorption is suppressed quantitatively with increasing O₂ coverage, after which unreacted, or left-over O atoms appear and remain on steps. It is concluded that the presence of pre-dosed O₂ does not play a role of activating reactants in the catalytic reduction of NO with ¹³C₂H₅OH on the surface of Pt(3 3 2).     

Study of the Characteristics of Elementary Processes in a Chain Hydrogen Burning Reaction in Oxygen

The characteristics of possible chain explosive hydrogen burning reactions in an oxidizing medium are calculated on the potential energy surface. Specifically, reactions H₂ + O₂ → H₂O + O, H₂ + O₂ → HO₂ + H, and H₂ + O₂ → OH + OH are considered. Special attention is devoted to the production of a pair of fast highly reactive OH radicals. Because of the high activation threshold, this reaction is often excluded from the known kinetic scheme of hydrogen burning. However, a spread in estimates of kinetic characteristics and a disagreement between theoretical predictions with experimental results suggest that the kinetic scheme should be refined.     

Deactivation of TiO2 photocatalytic films loaded on aluminium: XPS and AFM analyses

TiO₂ films were loaded on aluminium substrates by dip-coating method. Based on cyclic photocatalytic degradation experiments using benzamide as model molecule, XPS and AFM tests, the deactivating behaviour of the samples was studied. Experiment results show that the samples with less coating times (one to four times) deactivated very quickly, while the samples coated more than five times did not lose activity. Al element was proved to segregate from substrate and diffuse into TiO₂ films during calcination and annealing treatment, existing as mixture of Al₂O₃ and Al(OH)₃ at the boundaries among TiO₂ particles. During photocatalytic reactions in aqueous phase, the transformation of Al from Al₂O₃ to Al(OH)₃ and the leaching of the latter brought out serious alternation of surface morphology to the samples coated one to three times, on whose surface Ti³⁺ and Ti²⁺ centers were also detected after six cycles of photocatalytic reactions, while fresh films and the tested films which did not deactivate possess unique +4 valence Ti. The alteration of surface morphology, together with the change of valence of surface Ti element, resulted in the deactivation encountered in this research.     

Caloric properties of liquid alcohols - H-bonded liquids continuum or spectroscopic determined mixture model,is that really the question?

It is discussed that the spectroscopic based mixture model of H-bonded liquids is qualified as efficient approximation to calculate caloric properties. The specific heat, enthalpy and heat of evaporization of liquid CH₃OH and C₂H₅OH are calculated from the melting point till overcritical temperature with the spectroscopic determined content O_f of non H-bonded OH groups and the H-bond energy. The good agreement between the results of water and the two alcohols shows the efficiency of the simplified model although O_f, the ratio of van der Waals to H-bond energy and the coordination numbers are totally different in both cases.     

Water enrichment by hydroxyl and hydrogen peroxide due to cavitation treatment: GHz four-wave mixing spectroscopy

Four-waves mixing spectroscopy has been applied to detection of H₂O₂ and OH molecules in water after different treatments in a cavitation jet. The considerable growth of the ortho-H₂O, OH, and H₂O₂ rotational lines amplitude in cavitation water relatively to distilled water and 1% hydrogen peroxide aqueous solution have been found. This fact was interpreted as the exhibition of H₂O molecules dissociation onto atoms and recombination into OH and H₂O₂. Four-waves mixing spectra fitting gives the evaluation of H₂O₂ rotational line’s amplitude increasing in cavitation water by factor of ～3 in comparison to 1% H₂O₂ aqueous solution.     

Multi-species detection in spray flames with tunable excimer lasers

Planar imaging with tunable excimer-laser sheet illumination is used to determine spatial distributions of different species in liquid-fuelled spray flames of commercial oil burning furnaces. Two burner configurations, which differ only in the fuel/air mixing devices, are investigated to understand why one configuration yields 30% less NO_x emission. Iso-octane and n-heptane fuels are used. To understand the origin for NO_x reduction spatial distributions of reactants (fuel, O₂), the reaction intermediate OH and the pollutant NO are recorded. OH and O₂ are measured by LIPF, NO by LIF. Fuel distributions are determined by another broad-band emission, whose origin is not yet identified. Both single shot and averaged distributions are recorded. The averaged distributions are extremely reproducible and depend sensitively on details of the burner geometry and the fuel/air mixing device. They can clearly be used to distinguish fine details in different injection systems. The spatial distribution of different species relative to each other yield considerable insight in the differences between the two combustion processes. On the basis of purely qualitative visualization it is possible to understand the origin for NO_x reduction: it results from faster injection of air in the one fuel/air mixing device.     

包钴型γ-Fe2O3磁粉矫顽力的研究

包钴型γ-Fe₂O₃磁粉分为包钴γ-Fe₂O₃(简记为Co-γ-Fe₂O₃)和包钴包亚铁γ-Fe₂O₃(简记为CoFe-γ-Fe₂O₃)两种,它们的矫顽力可比γ-Fe₂O₃磁粉的提高100至400Oe左右,本工作对这两种磁粉矫顽力增大的原因作了探讨,认为它们矫顽力增大的机制不同:CO-γ-Fe₂O₃矫顽力增大是由于表面包覆一层Co(OH)₂使表面各向异性增大,而CoFe-γ-Fe₂O₃则是由于表面包覆的是钴铁氧体,γ-Fe₂O₃与钴铁氧体之间发生耦合作用,使矫顽力增大。     

Measurement of OH spatially resolved spectrum in a wire-plate pulsed streamer discharge

In this study, spatially resolved measurements of the emission intensity of OH (A²Σ↦X²Π, 0-0) and the vibrational temperature of N₂ (C) have been performed during a positive pulsed streamer discharge with a wire-plate electrode configuration at atmospheric pressure. The effects of pulse peak voltage, pulse repetition rate and the added O₂ flow rate on the spatial distributions of the emission intensity of OH (A²Σ↦X²Π, 0-0) and the vibrational temperatures of N₂ (C) perpendicular to the wire in the direction towards the plate (in the radial direction) are investigated. It has been found that the emission intensity of OH (A²Σ↦X²Π, 0-0) increases with increasing pulse peak voltage and pulse repetition rate and decreases with increasing the distance from the wire electrode. When the different oxygen flows are added in N₂ and H₂O mixture gas, the emission intensity of OH (A²Σ↦X²Π, 0-0) decreases with increasing the flow rate of oxygen. The vibrational temperature of N₂ (C) is nearly independent of pulsed peak voltage and pulsed repetition rate, but increases with increasing the added O₂ flow rate and keeps almost constant in the radial direction under the present experimental conditions. This measurement plays a crucial role in understanding the discharge characters of pulsed streamer discharge and establishing the molecule reaction dynamics model of pulsed streamer discharge.     

Thermal decomposition and electrical conductivity of M(OH)3 and MOOH (M=Y, lanthanide)

The thermal decomposition of M(OH)₃ (M=Y, La, Nd, Sm, Gd) with the Y(OH)₃ structure was examined by the TG and DTA methods. Y(OH)₃, Nd(OH)₃, and Sm(OH)₃ decomposed to MOOH and then to M₂O₃. The decomposition of La(OH)₃ and Gd(OH)₃ occurred via the following schemes: La(OH)₃→LaOOH→La₂O₃·1/2H₂O→La₂O₃, and Gd(OH)₃→Gd₂O₃·3/2H₂O→GdOOH→Gd₂O₃. The highest conductivity of 5.9×1o^?9Scm^?1 at 250°C was found in Gd(OH)₃ and that of 8.9×10^?7 S cm^?1 400°C in GdOOH. The continuous-wave ¹H NMR absorption spectrum of LaOOH at room temperature exhibited no doublet line shape. This shows that protons are magnetically isolated from each other, and very little H₂O and H₃O⁺ can exist.