Growth of spinel crystals in vanadium slag and their characterization

Morphology of vanadium slags were investigated by scanning electron microscopy (SEM). The mineralogical phases were characterized by energy disperse X‐ray spectrometry (EDS) and powder X‐ray diffraction (XRD). The obtained results show that spinels and silicates are the major phases in the vanadium slag, and V is concentrated in Fe_xV_3‐xO₄ and Mg_x(V, Ti)_3‐xO₄. Both the spinel grain size and volume fraction in the slag with higher V₂O₃ content are much larger than that with lower V₂O₃ content. (Fe, Mn)₂SiO₄ and (Fe, Mn)SiO₃ have a higher proportion in the slag with lower V₂O₃ and higher SiO₂ content. The relation among cooling conditions and grain size and volume fraction of spinels is also discussed. It is found that low cooling rate and long holding time benefit spinel crystal growth, especially for the interval of 1200‐1250 °C. Both mean diameter and volume fraction of spinels could achieve or exceed the industry vanadium slag when holding more than 45 min. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Surface kinetics of nitrogen dissolution and its correlation to the slag structure in the CaO―SiO2, CaO―Al2O3, and CaO―SiO2―Al2O3 slag system

The kinetics of nitrogen dissolution into molten slag at 1873 K was investigated by an isotope exchange technique. Rate constants were correlated with the molten slag structure obtained from FT-IR spectra. The rate constant in the CaO―SiO₂ binary system showed a maximum value at a specific slag composition followed by a decrease in the rate due to excess O²⁻ blocking the surface sites for nitrogen adsorption. The rate constant in the CaO―Al₂O₃ binary system was comparatively constant within the experimental range of 45 mass% to 60 mass%. The rate constant in the CaO―SiO₂―Al₂O₃ ternary slag system was measured within the boundary of the liquidus line and showed a close correlation with the slag structure. Furthermore, the rate constant in the CaO―SiO₂―Al₂O₃ ternary system was found to be significantly higher compared to the binary system due to the correlated effect of lower binding energies of the Al―O bonds and the increased number of reaction sites available when smaller Si―O tetrahedral were simultaneously present with Al―O bonds.     

Effects of passivation and postannealing on the photoluminescence properties of MgO/SiO2 core‐shell nanorods

MgO nanorods were grown by the thermal evaporation of Mg₃N₂ powders on the Si (100) substrate coated with a gold thin film. The MgO nanorods grown on the Si (100) substrate were a few tens of nanometers in diameter and up to a few hundreds of micrometers in length. MgO/SiO₂ core‐shell nanorods were also fabricated by the sputter‐deposition of SiO₂onto the MgO nanorods. Transmission electron microscopy (TEM) and X–ray diffraction (XRD) analysis results indicated that the cores and shells of the annealed core‐shell nanorods were a face‐centered cubic‐type single crystal MgO and amorphous SiO₂, respectively. The photoluminescence (PL) spectroscopy analysis results showed that SiO₂ coating slightly decreased the PL emission intensity of the MgO nanorods. The PL emission of the MgO/SiO₂ core‐shell nanorods was, however, found to be considerably enhanced by thermal annealing and strongly depends on the annealing atmosphere. The PL emission of the MgO/SiO₂ core‐shell nanorods was substantially enhanced in intensity by annealing in a reducing atmosphere, whereas it was slightly enhanced by annealing in an oxidative atmosphere. The origin of the PL enhancement by annealing in a reducing atmosphere is discussed with the aid of energy‐dispersive X‐ray spectroscopy analyses. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dissolution and growth of spinel crystals in a borosilicate glass

The rate of dissolution and growth of settling crystals of spinel was measured optically in a borosilicate melt that was pre-heated at a temperature above liquidus to erase the effects of previous history. The Hixson-Crowell equation, which is based on Fick's first law, was used to determine mass-transfer coefficients (k_H) for dissolution and growth; both were found to fit the same Arrhenius function of temperature (T). An attempt was made to estimate the diffusion coefficient (D) and the concentration-boundary-layer thickness (δ). The calculated values of δ compared well with experimental results and observations. The D vs. T function was similar to a literature function obtained for the dissolution of magnetite in sodium disilicate glass.     

透明MgO·nAl2O3尖晶石陶瓷雾度分析

以高纯超细粉体为原料,采用热压(HP)结合热等静压(HIP)法制备了透明MgO·nAl₂O₃(n=0.98、1、1.1、1.2、1.3)尖晶石陶瓷。雾在透明陶瓷中十分常见,严重云雾的存在大幅降低透光率,影响陶瓷的力学性能。为了获得光学质量优异、力学性能适宜的MgO·nAl₂O₃尖晶石,对尖晶石中的雾度进行了测量,并对雾的形成进行了分析。通过扫描电镜(SEM)发现,在雾较重的富镁半透明样品中,晶界处有许多圆形晶粒。用能谱仪(EDS)测定了圆形晶粒的组成为n=0.41。第二相MgO由于镁过量而易析出,严重降低了晶界强度,影响陶瓷的力学性能。MgO相与尖晶石相具有不同的折射率,会引起严重的光散射,降低样品的透过率。在另一试样中,测得晶界处颗粒组成为n=1.33,测得该富铝试样的抗弯强度远远高于n=1试样和富镁试样。     

Studies on the hydrolysis of {Cu[Al(OPri)4]2}, a single source precursor for CuAl2O4 spinel

Controlled hydrolysis experiments of the heterobimetallic alkoxide {Cu[Al(OPrⁱ)₄]₂}, were investigated. The progress of hydrolysis was monitored by the FT-IR and NMR spectroscopy. A blue colored gel appeared after four days of hydrolysis and the hydrolysis experiments were continued up to ten days. The elemental analysis and FT-IR spectrum revealed the presence of isopropoxy group in the gel obtained even after ten days of hydrolysis. The presence of carbon was further confirmed from the presence of a weak signal at 3.351 ppm in the ¹³C CP-NMR spectrum. The thermal analysis of the hydrolyzed gels in air also suggested that they were not simple hydroxides of copper and aluminum. The gels on one time heat treatment at 900 °C in air yielded inverse spinel CuAl₂O₄ as shown by the PXRD patterns. CuO was observed along with CuAl₂O₄ in the case of the fired product of the gel obtained after five or six days of hydrolysis which was absent in the fired product of ten days hydrolyzed gel. The phase pure spinel was nanocrystalline in nature as revealed by the analysis of PXRD pattern. TEM images revealed porous structured nanocrystallites. The optical property of the spinel was evaluated by the diffuse reflectance spectroscopy. Raman spectrum showed five bands at 767, 698, 595, 450 and 356 cm^?1 conforming to the spinel structure.     

Metal organic vapour phase epitaxy of MgO films grown on c-plane Sapphire

Metal organic vapour phase epitaxy (MOVPE) has been used to epitaxially grow MgO films on c-plane sapphire substrates. Bismethylcyclopentadienyl magnesium (MCP₂Mg) and nitrous oxide (N₂O) were used as the magnesium and the oxygen source, respectively, with nitrogen (N₂) as the carrier gas. The dependence of the growth rate on the partial pressure of magnesium and on the growth temperature was investigated. The growth rate increases with the magnesium partial pressure. The morphological and structural properties of MgO films were investigated using atomic force microscopy and X-ray diffraction. The structural properties are strongly dependent on the growth temperature in the range 400–800 °C. (1 1 1)-oriented MgO layers are observed at growth temperatures above 600 °C whereas no diffraction peak is found at lower growth temperatures. The atomic force microscopy (AFM) images reveal a smooth surface morphology.     

Surface morphology of iron specimens boronized with BCl3-H2 mixtures (II) investigation of short-time gas phase boronized iron surfaces

Specimens made of armco iron or pure iron were boronized during a time ≦; 1 minute with 1.1 vol.% BCl₃ in H₂, and then their surfaces were investigated by scanning electron microscopy and X-ray diffraction. The boride particles consist of FeB and Fe₂B, they crow oriented on the substrate surface, e.g. the Fe₂B (110) crystallographic plane is situated parallel to the (111) plane of α-iron. The polycrystalline substrates are decorated by growing boride particles so that grains, twinning, etc. can be seen. There is a correlation between number per area and size of boride particles in early stages of layer formation and surface morphology in advanced layer growth.     

Structural polymorphism and solubility of medicinal drugs (Using Perindopril as an Example)

The correlation between the structural polymorphism of perindopril salt C₁₉H₃₂N₂O₅ · C₄H₁₁N and its bioavailability has been investigated. During the crystallization of perindopril salt from an organic solvent, a low-symmetry perindopril polymorph is formed when the most polar solvent is used. It is shown that the dissolution rate in water, which is a measure of the bioavailability of any pharmaceutical product, is higher for the perindopril salt grown from the least polar solvent and that the structure has a monoclinic symmetry.     

Epitaxial growth of β-Ga2O3 nanocolumns on MgO substrate

Crystal structure of Ga₂O₃ nanocolumns grown on MgO substrate is analyzed by electron microscopy and electron diffraction study. The nanocolumns have β-Ga₂O₃ structure and the growth direction is [0 0 1] directions. A thin γ-Ga₂O₃ layer grows on the substrate to relax the lattice misfit between MgO and β-Ga₂O₃. The bottom layer of the γ form layer is disordered by {1 1 0} stacking faults. Poly crystalline structure that consists of β-Ga₂O₃ and γ-Ga₂O₃ nanocrystals exists between the β form nanocolumns and the γ form layer. The γ form changes gradually to the β form growing up to the nanocolumn. Though various crystal forms appear in a specimen, oxygen cubic close-packed lattice in crystal structures has always the same orientation in all layers including the MgO substrate.     

Monte Carlo simulations of the dissolution of borosilicate glasses in near-equilibrium conditions

Monte Carlo simulations were performed to investigate the mechanisms of glass dissolution as equilibrium conditions are approached in both static and flow-through conditions. The glasses studied are borosilicate glasses in the compositional range (80 ? x)% SiO₂ (10 + x / 2)% B₂O₃ (10 + x / 2)% Na₂O, where 5 < x < 30%. In static conditions, dissolution/condensation reactions lead to the formation, for all compositions studied, of a blocking layer composed of polymerized Si sites with principally 4 connections to nearest Si sites. This layer forms atop the altered glass layer and shows similar composition and density for all glass compositions considered. In flow-through conditions, three main dissolution regimes are observed: at high flow rates, the dissolving glass exhibits a thin alteration layer and congruent dissolution; at low flow rates, a blocking layer is formed as in static conditions but the simulations show that water can occasionally break through the blocking layer causing the corrosion process to resume; and, at intermediate flow rates, the glasses dissolve incongruently with an increasingly deepening altered layer. The simulation results suggest that, in geological disposal environments, small perturbations or slow flows could be enough to prevent the formation of a permanent blocking layer. Finally, a comparison between predictions of the linear rate law and the Monte Carlo simulation results indicates that, in flow-through conditions, the linear rate law is applicable at high flow rates and deviations from the linear rate law occur under low flow rates (e.g., at near-saturated conditions with respect to amorphous silica). This effect is associated with the complex dynamics of Si dissolution/condensation processes at the glass–water interface.     

Orthophosphate nanostructures in SiO2-P2O5-CaO-Na2O-MgO bioactive glasses

Vibrational spectroscopy, ²⁹Si and ³¹P magic-angle spinning nuclear magnetic resonance spectroscopy and high resolution transmission electron microscopy were used to investigate structural aspects of SiO₂-P₂O₅-CaO-Na₂O-MgO glasses. The experimental results show that for the two compositions, 25.3SiO₂-10.9P₂O₅-32.6CaO-31.2MgO and 33.6SiO₂-6.40P₂O₅-19.0CaO-41.0MgO, phosphorous is present in a nano-crystalline form with interplanar distances in the 0.21-0.26 nm range. The two glasses develop a surface CaP-rich layer and the presence of any intermediate silica-rich layer was not detected. It was suggested that the phosphate nano-regions may play a key role in the initial stages of the bioactive process, acting as nucleation sites for the calcium phosphate-rich layer.     

On‐line monitoring of lithium carbonate dissolution

Dissolution of lithium carbonate (Li₂CO₃) in aqueous solution was investigated using three on‐line apparatuses: the concentration of Li₂CO₃ was measured by electrical conductivity equipment; CLD (Chord Length Distribution) was monitored by FBRM (Focused Beam Reflectance Measurement); crystal image was observed by PVM (Particle Video Microscope). Results show dissolution rate goes up with a decrease of particle size, and with an increase in temperature; stirring speed causes little impact on dissolution; ultrasound facilitates dissolution obviously. The CLD evolution and crystal images of Li₂CO₃ powders in stirred fluid were observed detailedly by FBRM and PVM during dissolution. Experimental data were fitted to Avrami model, through which the activation energy was found to be 34.35 kJ/mol. PBE (Population Balance Equation) and moment transform were introduced to calculate dissolution kinetics, obtaining correlation equations of particle size decreasing rate as a function of temperature and undersaturation. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of various alkali and divalent metal oxides on phase transformations in NiO-doped glasses of the Li2O–Al2O3–SiO2–TiO2 system

Regularities of phase transformations in glasses of the Li₂O–Al₂O₃–SiO₂–TiO₂ system doped with up to 2.5 mol% of alkali- and divalent metal oxides were studied by X-ray diffraction analysis, Raman scattering and optical spectroscopy. Ni(II) ions were used as spectral probes of phase transformations because Ni(II)-ions enter the inhomogeneous regions formed during the phase separation and crystallization, and their absorption spectra change with heat-treatment temperature reflecting formation of aluminotitanate amorphous regions, spinel nanosized crystals and β-quartz solid solutions, consequently.It was demonstrated that the technological additives do not change the sequence of the phases' formation but accelerate the liquid phase separation and crystallization. Addition of MgO and ZnO leads to increasing the temperature range of spinel precipitation. Addition of CaO, BaO and PbO results in increasing the light scattering of prepared glass-ceramics.In selection of the technological additives for decreasing the melting temperature of glass-ceramics for optical and photonic applications the influence of the additives on the structure and optical properties of the prepared material should be considered.     

Aqueous alteration of five-oxide silicate glasses: Experimental approach and Monte Carlo modeling

The alteration behavior of glass comprising five oxides (61 ? x)SiO₂–17B₂O₃–18Na₂O–4CaO–xZrO₂ was studied during static leach tests in a buffer solution at 90 °C and with a glass-surface-area-to-solution-volume (SA/V) ratio of 15 cm^?1. The morphological evolution of altered glasses investigated by small-angle X-ray scattering (SAXS) exhibits a strong dependence with the zirconium content in the glass. The experiments were compared with modeling results using Monte Carlo simulation. The model has been improved to simulate the alteration kinetics and alteration layer morphology, considering zirconium atoms at coordination number 6. The simulations exhibit very good agreement with experimental results, showing relations between the alteration rate and the restructuring altered layer. The model is used to interpret experimental observations by proposing a porosity closure mechanism in the altered layer to account for the diminishing alteration rate. For high zirconium concentrations, the simulation highlights the existence of percolation pathways responsible for a complete alteration of the glass. Zirconium has a hardening effect that limits the dissolution of neighboring atoms; this effect is favorable in terms of the glass alteration kinetics, but by inhibiting silicon recondensation it prevents complete closure of the porosity and the glass is completely altered.     

The effect of composition and temperature on the amount and type of nanoferrite particles inserted in Fe2O3–ZnO–MgO–SiO2 glass–ceramics

Glass–ceramics with the composition 2Fe₂O₃.1ZnO.1MgO.96SiO₂ [4ZnMgFe] and 2Fe₂O₃.2ZnO.3MgO.93SiO₂ [7ZnMgFe] (mol%) were prepared using the sol–gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM), electron diffraction (ED) and Mössbauer spectroscopy (MS) were used to investigate the glass–ceramics structure. The samples contain ferrite nanoparticles embedded in a glass matrix. However, zinc ferrite nanoparticles seems to be the preferential crystalline phase formed. The amount of ferrite particles depends on treatment temperature and sample composition. The Mössbauer spectroscopy measurements show that ferrite nanoparticles can exhibit a ferrimagnetic behaviour combined with superparamagnetism.     

Precipitation selectivity of perovskite phase from Ti-bearing blast furnace slag under dynamic oxidation conditions

The effects of dynamic oxidations on the crystal morphology and the precipitation behavior of the perovskite phase from Ti-bearing blast furnace slag were investigated. Air was blown into the molten slag as an oxygen source through a lance during the dynamic oxidation process. It was found that the dispersed Ti components were selectively taken into the perovskite phase (CaTiO₃), and the perovskite phase could be selectively precipitated and grown. Oxidation of molten slag produced a large amount of heat, which not only increased the temperature of the slag, but also promoted the precipitation and growth of the perovskite phase. It was confirmed by isothermal experiments and non-isothermal pilot experiments that the precipitation of the perovskite (CaTiO₃) in molten slag is obviously affected by operation factors such as oxidizing time, and slag temperature. The perovskite phase precipitation kinetics and mechanisms from molten slag during the dynamic oxidation processes were also investigated.     

Leaching of some lithium silicate glasses and glass-ceramics by HCl

The leaching of some binary and ternary lithium silicate glasses and their respective glass-ceramics by HCl is reported.The leaching rate of lithium silicate glasses gradually decreases with the decrease of the percentage of Li₂O or by the introduction of small amounts of a third component, e.g. Al₂O₃, MgO, ZnO or B₂O₃. With a further increase in the proportions of B₂O₃ or ZnO the rate of leaching increases. The rate of leaching is also substantially modified by the conversion of glasses into glasses-ceramics.The results obtained are discussed in terms of the effects of the different ions on the rate of the interdifussion of the lithium and hydrogen ions in the glass and the leached layer, the phase separation developed in the glass, the type and concentration of crystalline phases developed in glass-ceramics and the composition of the residual glass phase.     

Synthesis and characterization of hexagonal ferrites BaFe12‐2xZnxTixO19 (0 ≤ x ≤ 2) by thermal decomposition of freeze‐dried precursors

Substituted barium hexaferrites, BaFe_12‐2xZn_xTi_xO₁₉ (0 ≤ x ≤ 2), have been synthesized by thermal decomposition of freeze‐dried acetate precursors. Decomposition and phase formation were investigated by means of thermal analysis, XRD and IR spectroscopy. The initially amorphous decomposed precursor reacts to the substituted hexaferrite via a spinel‐like maghemite (γ‐Fe₂O₃) and Zn/Ti containing spinel ferrites. The synthesis method allows a decrease of the reaction temperature and time, necessary for producing a single phase hexaferrite. At relative low reaction temperatures, the substitution rate x shows remarkable differences at different iron sublattices. For x ≤ 0,8 this selective substitution results in an increase of magnetization as x grows. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

High photorefractive sensitivity and fast response time of near‐stoichiometric and MgO doped LiNbO3:Fe crystals

Congruent LiNbO₃:Fe and LiNbO₃:Mg,Fe crystals were grown by Czochralski method, and vapor transport equilibration technique was employed to improve the [Li]/[Nb] ratios of these crystals. The influence of stoichiometry and MgO dopant on the photorefractive sensitivity and response time of LiNbO₃:Fe crystals was investigated. Both stoichiometry and MgO dopant can effectively reduce the amount of intrinsic defects, but MgO can also decrease the concentration of Fe²⁺ ions in Li‐sites. Near‐stoichiometric and MgO doped LiNbO₃:Fe crystal has high photorefractive sensitivity and fast response time. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)