Calculation of the Cellular Structure of Detonation of Sprays in an H2—O2 System

On the basis of the mathematical model of a two–phase two–velocity medium, detonation of a cryogenic mixture (gaseous hydrogen—drops of liquid oxygen) was studied numerically. The dynamics of formation and the special features of the structure of the two–dimensional reaction zone of the detonation wave are discussed. The cellular structure of detonation is modeled for the first time for a cryogenic hydrogen—oxygen spray.     

Chemical Removal of CeO2 Segregated on the Surface of CeO2–ZrO2 Binary Oxides for Improvement of OSC

A chemical treatment to remove residual CeO₂ phase on CeO₂–ZrO₂ (CZ) solid solution was carried out. A CZ was treated by H₂O₂ for the reduction of Ce⁴⁺ to Ce³⁺ and then HNO₃ for the dissolution of Ce³⁺ compounds (H–CZ). H₂-TPR, TEM-EDX and XPS analyses revealed the removal of CeO₂ phase and the homogeneous distribution of Ce species. About 20% improvement in oxygen storage capacity (OSC) of H–CZ was confirmed at 773 K by the weight measurements under H₂/N₂ and air atmospheres, indicating that the HNO₃/H₂O₂ treatment was effective to avoid the deterioration of the OSC by segregated CeO₂ on the CZ binary oxides.     

Effect of P2O5 on evolution of microstructure of MgO–Al2O3–SiO2 glass ceramics

Abstract

MgO–Al₂O₃–SiO₂ (MAS) cordierite based glass ceramics were prepared by volume crystallisation. X-ray diffraction, Scanning electron microscopy and Energy diffraction scanning were used to investigate crystallisation behaviour and the influence of P₂O₅ on microstructure MAS based glass ceramics. The results showed that P⁵⁺ could promote the phase separation of MAS glass and that the glass was divided into two areas, such as Mg₄Al₂Ti₉O₂₅ and the containing P⁵⁺ area at <900°C. Mg₄Al₂Ti₉O₂₅ and Mg₃(PO₄)₂ in the area were both advantageous to the precipitation of μ cordierite, which further transformed to α cordierite due to P⁵⁺ in the residual glassy phase. However, P⁵⁺ inhibited the presence of cordierite when the heat treatment temperature was >900°C.     

Formation of anisaldehyde via hydroxymethylation of anisole over SnO2–CeO2 catalysts

Hydroxymethylation of anisole has been carried out over SnO₂–CeO₂ catalysts in the temperature range 623–723 K. Methoxybenzaldehyde (anisaldehyde) and condensation products were formed along with minor quantities of methoxybenzyl alcohol, o‐cresol, phenol and 2,6‐xylenol. A maximum anisaldehyde selectivity of 64% was obtained at 623 K at an anisole conversion of 46% under optimized conditions. Catalytic activity of these systems in the formation of aldehyde is ascribed to the presence of weak acid sites and redox metal sites. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis of TS-1 by microwave heating of template-impregnated SiO2–TiO2 xerogels

TS-1 was prepared by microwave heating of a SiO₂–TiO₂ xerogel dry-impregnated with the template, TPAOH. A highly crystalline product was obtained within 30 min after microwave irradiation with yields over 90%. These are significant advantages over the TS-1 obtained by conventional oven heating using alkoxide precursors in liquid phase, which requires 1–2 day crystallization time with low product yields. Characterization of the TS-1 obtained was carried out using XRD, SEM, FT-IR, and UV-vis spectroscopy, and catalytic activity was examined for 1-hexene epoxidation using H₂O₂ as oxidant. These studies revealed that the material obtained by microwave heating of the mixed oxide gel shows essentially identical physicochemical properties to those prepared by conventional means.     

Influence of CeO2 addition on crystal growth behavior of CeO2–Y2O3–ZrO2 solid solution

Nanopowders with cubic fluorite-type structure as well as uniform distribution in particle size were synthesized by hydrothermal method in the ternary oxide zirconia–yttria–ceria system with ceria content of 0–25 mol%. X-ray diffraction (XRD), thermogravimetric analysis/differential scanning calorimeter (TG/DSC), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy (Raman), specific surface area (S_BET) and high resolution transmission electron microscopy (HRTEM) were applied to characterize the structure, thermal decomposition, morphological characteristic and crystal growth of the produced powders. Qualitative analyses indicate that the as-synthesized nanoparticles are single-phase crystallites with an average particle size of 4–9 nm. The specific surface area, lattice parameter and microstrain are closely related to Ce⁴⁺ concentration. Moreover, activation energy of crystal growth is significantly dependent on the dopant (CeO₂) concentration. It firstly increased and then decreased with increasing dopant concentration, and the maximum value was observed at the dopant concentration of 5 mol%.     

Influence of annealing treatment on magnetic properties of Fe2O3/SiO2 and formation of ε-Fe2O3 phase

Magnetic properties of Fe₂O₃/SiO₂ samples were studied after being produced by sol-gel synthesis and formation of ε-Fe₂O₃ polymorph. Samples were thermally treated, using different annealing temperatures and annealing times. The size and morphological characteristics of the iron oxide nanoparticles were examined using a TEM microscope. We used the “ellipticity of shapes”, which is a measure of how much the shape of a nanoparticle differs from a perfect ellipse, in order to quantitatively describe morphological properties of nanoparticles. Coercivity measurements were used to identify and monitor the formation of the epsilon-iron oxide phase during the thermal treatments (annealing). Coercivity values were in the range from 1.2 to 15.4 kOe, which is in accordance with previous experience regarding the existence of ε-Fe₂O₃. We have determined the optimal formation conditions for the ε-Fe₂O₃ polymorph (t=1050 °C for 7 h, H_C=15.4 kOe), as well as the narrow temperature interval (1050–1060 °C) in which the polymorph abruptly vanished (H_C=2300 Oe), on the basis of results of the magnetic properties. The threshold temperature for the ε-Fe₂O₃ phase transformation was measured as 1060 °C. We found that different annealing temperatures and annealing times significantly affected magnetic properties of the examined samples.     

Mechanism of Self-Propagating High-Temperature Synthesis of AlB2–Al2O3 Composite Powders

Refractories and Industrial Ceramics - The mechanism of self-propagating high-temperature synthesis (SHS) of AlB2–Al2O3 composite powders was studied using the combustion front quenching...     

Possibility of Initiation of Combustion of CH4–O2 (Air) Mixtures with Laser‐Induced Excitation of O2 Molecules

The possibility of initiation of combustion of CH₄–O₂ mixtures with excitation of O₂ molecules to the states a¹_g and b¹⁺ _g by laser radiation with wavelengths of 1.268 m and 762 nm is considered. It is shown that excitation of O₂ molecules significantly decreases the induction period and ignition temperature because of accelerated formation of active atoms and radicals and intensification of the chain mechanism of the process. Even if the specific energy of laser radiation absorbed by the gas is low ( 0.1 eV per molecule), the ignition temperature of the CH₄–O₂ mixture with a ratio of 1:2 can be reduced from 1000 to 300 K.     

Effect of addition of TiO2 on reaction sintered MgO–Al2O3 spinels

Three different spinel compositions with MgO:Al₂O₃ molar ratios 2:1, 1:1 and 1:2 were studied using TiO₂ as an additive up to 2 wt.%. Solid state reaction sintering technique was employed for all the compositions in the temperature range of 1550–1650°C. Attrition milling was done for the reduction of particle size. Sintered products were characterised in terms of densification and shrinkage studies, phase analysis, strength evaluation both at ambient temperature and at elevated temperature, strength retention after different number of thermal cycles at 1000°C, quantitative elemental analysis and microstructural studies.     

Effect of CeO2 and La2O3 on the Activity of CeO2−La2O3/Al2O3-Supported Pd Catalysts for Steam Reforming of Methane

The effect of the addition of CeO₂ or La₂O₃ on the surface properties and catalytic behaviors of Al₂O₃-supported Pd catalysts was studied in the steam reforming of methane. The FTIR spectroscopy of adsorbed CO and the Pd dispersion suggest the partial coverage of Pd⁰ by ceria or lanthana species. This could lead to the formation of an adduct MPd _x O (M = Ce or La) at the surface of the metal crystallites. The addition of ceria or lanthana resulted in an increase of the turnover rate and specific rate for steam reforming of methane. One possible explanation if that the Pd⁰*Pd^δ+O–M interfacial species (M = Ce or La) are oxidized by H₂O or CO₂, promoting the O* transfer to the metal surface. This could facilitate the removal of C* species from the metal surface, resulting in the increase of specific reaction rate and increase of the accessibility of CH₄ to metal active sites.     

Enhanced Activity of Spinel-type Ga2O3–Al2O3 Mixed Oxide for the Dehydrogenation of Propane in the Presence of CO2

Catalytic performance of a series of Ga₂O₃–Al₂O₃ mixed oxides prepared by alcoholic-coprecipitation method for the dehydrogenation of propane in the presence of CO₂ was investigated. It is shown that the combination of Ga and Al oxides greatly improved the performance of the Ga₂O₃-based materials for catalytic dehydrogenation of propane, with the highest performance attainable at a Ga₂O₃–Al₂O₃ catalyst with a 20 mol% aluminum content. While the same tendency was observed for the specific activity normalized by BET surface area, significantly enhanced stability was achieved for Ga₂O₃–Al₂O₃ with higher aluminum content. X-ray diffraction (XRD) revealed that a homogeneous spinel-type Ga₂O₃–Al₂O₃ solid solution is uniformly formed by substitution of Ga³⁺ for Al³⁺ in the Al₂O₃ lattice. The enhanced activity of Ga₂O₃–Al₂O₃ mixed oxides was accounted for by the abundance of surface weak acid sites due to the synergetic interaction between Ga₂O₃ and Al₂O₃ in the solid solution systems.     

Influence of mechanical activation of reactive mixtures on the microstructure and properties of SHS-ceramics MoSi2–HfB2–MoB

In this work, the influence of modifications of SHS-process on the microstructure and performance characteristics of composite ceramics MoSi₂-HfB₂-MoB with two-level structure was studied. Partial texturing of MoSi₂ grains in samples obtained by force SHS pressing technology was revealed. The effect of preliminary mechanical activation on the macrokinetic parameters of combustion and on the microstructure of the synthesized ceramics was studied. A significant grinding of the synthesized ceramics grain and an increasing of physical-mechanical properties are achieved by increasing the velocity and lowering the combustion temperature of the activated mixtures. The sample obtained by hot pressing of SHS powder from MA reaction mixture showed the most optimal combination of hardness (19.5 GPa), porosity (0.4%) and oxidation resistance (1.82∙10^-6 mg/(cm²∙s)).     

Synthesis of ZrO2 -SiC Composite by Carbothermal Reduction of Zircon

Zircon （mesh size ≤ 44μm ） and carbon black （mesh size ≤30μm ） were used as the starting materials, weighed with re（zircon） ： re（carbon black） of 100 ： 20 and mixed fully. The specimens with the diameter of 20ram and length of 5ram were prepared by pressing at 100 MPa, then dried at 120℃ for 12h, put into a furnace with 1. 5L ·min^-1 argon gas and fired at 1450℃, 1500℃, 1550℃, 1600℃ and 1650℃ for 4h, respectively. The chemical composition, phase composition and microstructure of the specimens were studied by chemical analysis, X-ray diffraction and scanning electronic microscope, and the carbothermal reduction reaction process was discussed by thermodynamic analysis. The results showed that the ZrO2-SiC composite could be synthesized by carbothermal reduction reaction using zircon and carbon black as the starting materials in argon atmosphere. The composite with different composition was obtained by controlling the firing temperature and partial pressure of CO gas. The proper temperature to synthesize ZrO2-SiC composite was 1600℃ in this experiment.     

Effect of Dehydration of VOPO4⋅2H2O on the Preparation and Reactivity of Vanadium Phosphate Catalyst for the Oxidation of n-Butane

The effect of drying of VOPO₄2H₂O on the preparation of vanadium phosphate catalysts for the selective oxidation of n-butane to maleic anhydride is described and discussed. It is found that partially dehydrated samples of the dihydrate containing small amounts of _I-VOPO₄ are formed when the material is initially dried. The presence of this impurity leads to a final catalyst containing trace amounts of _I-VOPO₄ in combination with (VO)₂P₂O₇ and this combination leads to a catalyst with a higher activity but with a lower selectivity to maleic anhydride. The drying stage is also found to influence the surface area and intrinsic activity of the activated catalyst.     

Catalytic Performance of B2O3/TiO2–ZrO2 for Vapor-Phase Beckmann Rearrangement of Cyclohexanone Oxime: The Effect of Boria Loading

A series of boria catalysts supported on titania–zirconia mixed oxide (B₂O₃/TiO₂–ZrO₂) with different boria loadings (8–20 wt%) were prepared and characterized by X-ray diffraction, adsorption of nitrogen, ¹¹B magic angle spinning (MAS) NMR measurements and temperature-programmed desorption (TPD) of ammonia. The catalytic performance of B₂O₃/TiO₂–ZrO₂ for vapor-phase Beckmann rearrangement of cyclohexanone oxime to -caprolactam was studied at 300°C. It was found that the lactam selectivity increased with increasing of boria loading, whereas a maximum oxime conversion was obtained at the boria loading of 12 wt%. The acid sites of medium strength on the surface of the catalyst play an important role in the selective formation of lactam.     

Investigation of cation distribution and magnetocrystalline anisotropy of NixCu0.1Zn0.9−xFe2O4 nanoferrites: Role of constant mole percent of Cu2+ dopant in place of Zn2+

Co-precipitated and 800 °C heat treated Ni-Cu-Zn nanoferrites with chemical formula Ni_xCu_0.1Zn_0.9-xFe₂O₄ (x=0.5, 0.6, 0.7) were prepared because of their potential use as multilayer chip inductors in electromagnetic applications. Their structural, magnetic properties and phase formation were studied using X-ray diffractometer (XRD), field emission scanning electron microscope (FE–SEM), vibrating sample magnetometer (VSM), Mössbauer spectrometer, thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC). The XRD patterns confirm the cubic spinel structure of the ferrite phase belonging to Fd3m space group. Lattice parameters and cation distributions were obtained by Rietveld refinement of the XRD patterns. The lattice parameter decreases with increase in Ni²⁺ ion concentration. Rietveld analysis indicates that Cu²⁺ ions predominantly occupy the B-sites and Ni²⁺ ions partly going into B-sites but predominantly into A-sites. An excellent agreement is observed between the experimental lattice parameters and lattice parameters theoretically calculated using this cation redistribution. The inversion parameter (λ) observed for Fe³⁺ ions by Mössbauer spectroscopy is different from that of Rietveld analysis. Magnetization and Mössbauer spectroscopic measurements indicate that the ferrite nanoparticles are mostly superparamagnetic. The cation redistribution is supposed to alter the magnetocrystalline anisotropy which in turn affects the magnetic parameters of the present ferrite samples. The reduced magnetization is attributed to core-shell interactions and possible canting of A- and B-shell magnetizations. TGA-DSC studies indicate that ferrite formation in the 800 °C heat treated samples is completed but grain growth increases as the particles are subject to the increased temperature.     

Effect of adding Y2O3 on structural and mechanical properties of Al2O3–ZrO2 ceramics

The effects of adding 1–8 wt% Y₂O₃ on phase formation and fracture toughness of Al₂O₃–xZrO₂–Y₂O₃(AZY) ceramics were studied. Phase formations of the samples were characterized by the X-ray diffraction (XRD) technique. It was found that the major phase was rhombohedral-Al₂O₃, while the minor phase consisted of the monoclinic-ZrO₂, tetragonal-ZrO₂ and monoclinic-Y₂O₃. It was found that Y₂O₃ contents did not clearly influence grain shape of AZY ceramics. The results obtained from the microhardness test could be used to evaluate the fracture toughness. It was found that the smaller grains had high fracture toughness. The maximum fracture toughness of 4.827 MPa m^1/2 was obtained from 4 wt% Y₂O₃. Refinement of lattice parameters using Rietveld analysis revealed the quantitative phases of AZY ceramics. This shows that under adding Y₂O₃ conditions the proportion of tetragonal-ZrO₂ phase plays an important role for the mechanical properties of AZY ceramics.