Synthesis and properties of γ-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> solid solutions

The textural and structural properties of mixed oxides Ga₂O₃–Al₂O₃, obtained via impregnating γ-Al₂O₃ with a solution of Ga(NO₃)₃ and subsequent heat treatment, are studied. According to the results from X-ray powder diffraction, gallium ions are incorporated into the structure of aluminum oxide to form a solid solution of spinel-type γ-Ga₂O₃–Al₂O₃ up to a Ga₂O₃ content of 50 wt % of the total weight of the sample, accompanied by a reduction in the specific surface area, volume, and average pore diameter. It is concluded that when the Ga₂O₃ content exceeds 50 wt %, the β-Ga₂O₃ phase is observed along with γ-Ga₂O₃–Al₂O₃ solid solution. ⁷¹Ga and ²⁷Al NMR spectroscopy shows that gallium replaces aluminum atoms from the tetrahedral position to the octahedral coordination in the structure of γ-Ga₂O₃–Al₂O₃.     

Preparation of ceramic γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> nanofiltration membranes for desalination

As one of the most recently developed membrane separation processes, nanofiltration (NF) has found a number of industrial applications. Ceramic NF membranes are also regarded as the appropriate choice in many applications, due to their higher chemical and physical stability. In this study, the rejection of the chloride ion is investigated using bi-layered γ-Al₂O₃-TiO₂ NF membranes based on α-alumina supports. Compression is used in preparation of the supports and sol-gel dip-coating for the top-layer formation. SEM micrographs, XRD, and nitrogen adsorption/desorption isotherms are used for membrane characterisation. The results show that the calcination temperature (600°C) results in different crystal structures including the brookite phase of TiO₂, the γ phase of Al₂O₃, and a combined phase of aluminium-titanium oxides. The average pore size of the membrane was identified as 1.6 nm using an adsorption/desorption isotherm. The rejection was also studied for the chloride ion, using a cross-flow filtration module. Filtration tests were carried out under different pressures, pH values, and salt concentrations; these showed a smoother behaviour particularly around the isoelectric points (IEPs) due to the dual-layer structure, with the best rejection at pH of approximately 5.     

Peculiarities of tetrachloromethane vapor sorption by mesoporous γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> templated at different stages of sol-gel process

The processes of adsorption-desorption of tetrachloromethane vapors by mesoporous -Al₂O₃ were investigated. Aluminum oxide was synthesized by the template method in the presence of micelles of cationic (cetylpyridinium chloride) and nonionic (Tween-85) surfactants added at various stages of sol-gel process. It was revealed that the shape of hysteresis loops depends on the structural peculiarities of the mesophase of template and gel-like boehmite. It was assumed that this effect is associated with the transformation of bottle-shaped mesopores into open cylindrical mesopores.Translated from Kolloidnyi Zhurnal, Vol. 66, No. 6, 2004, pp. 788–792.Original Russian Text Copyright © 2004 by Kuznetsova, Ratko.     

Preparation of Mesoporous γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> from Aluminum Hydroxide Peptized with Organic Acids

The relationships of the formation of aluminum oxide from aluminum hydroxide peptized with organic acids (propionic, maleic, malonic, tartaric) were studied. The pore structure parameters of the hydroxide samples and of aluminum oxide samples obtained from them are strongly influenced by acid peptization. The nature of the acid influences the extent of defectiveness of the γ-Al₂O₃ structure, manifested in the density of aluminum oxide, measured by helium pycnometry. The possibility and conditions for preparing mesoporous γ-Al₂O₃ suitable for use in chemical and petrochemical processes were determined.     

A New Method for Producing a Nanosized γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Powder

A new method for producing a nanosized γ-Al₂O₃ powder was proposed, by which a saturated solution of aluminum oxychloride and sucrose was subjected to sequential heat treatment to 350°C to form a transient species and then to 800°C to form a nanosized γ-Al₂O₃ powder. The optimal treatment parameters were determined. Stages of the process were identified. The transient species and the nanosized γ-Al₂O₃ powder were studied.     

Structure and magnetic properties of the nanocomposites γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript>

The structural features and magnetic properties of composite materials Fe₂O₃-SiO₂ consisting of γ-Fe₂O₃ nanoparticles in an amorphous porous matrix of SiO₂ were considered. The studied samples were synthesized by the sol-gel method. The structure of γ-Fe₂O₃-SiO₂ depending on the heating temperature was studied by electron microscopy, X-ray diffraction analysis, ESR and IR spectroscopy. Magnetic measurements were performed on a SQUID magnetometer in the range 2–350 K.     

Catalytic dehydrogenation of cyclohexene over MoO<Subscript>3</Subscript>/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

A series of MoO₃/γ-Al₂O₃ catalysts with different Mo surface densities (Mo atoms/nm²) has been prepared by incipient wetness impregnation method. Structural characteristics of the prepared catalysts were investigated by atomic absorption spectroscopy, X-ray diffraction, Fourier Transform Infrared spectroscopy, N₂ adsorption at −196 °C, and temperature-programmed reduction (TPR). The catalytic activities of the prepared catalysts were tested by cyclohexene conversion between 200 and 400 °C. XRD results indicated that molybdenum oxide species were dispersed as a monolayer on the support up to 4.04 Mo atoms/nm², and the formation of crystalline MoO₃ was observed above this loading. FTIR and TPR results showed that molybdenum oxide species were present predominantly in tetrahedral form at lower loading, and polymeric octahedral forms were dominant at higher loading. Cyclohexene conversion reaction proceeded mainly through the simple dehydrogenation pathway in the studied temperature range 200–400 °C and was found to be highly dependent on MoO₃ dispersion.     

Influence of the nature of molybdenum compounds on the activity of Mo/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and NiMo/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> hydrotreating catalysts

The influence of the nature of molybdenum compounds on the catalytic activity of sulfided NiMo/γ-Al₂O₃ catalysts was studied. The samples were prepared by impregnating the support with mixed aqueous solutions of nickel nitrate and molybdenum-containing compounds: ammonium paramolybdate and the 6-series heteropoly compounds (HPCs) ammonium 6-molybdonickelate (NiMo₆-HPC) and ammonium 6-molybdoaluminate (AlMo₆-HPC). Complexing agents (tartaric acid or a solution of NH₃) were used for stabilizing mixed aqueous ammonium paramolybdate and nickel nitrate solutions and for simultaneously producing an acidic or alkaline medium. The starting molybdenum compounds and catalysts in the oxide form were characterized using IR spectroscopy and x-ray diffraction analysis. The activity of catalysts based on NiMo₆-HPC in the hydrogenolysis of thiophene and in the hydrotreating of the diesel fraction was higher than that of catalysts based on ammonium paramolybdate: at 320°C, the degree of sulfur removal from the diesel fraction was higher by 13–16% and the average degree of hydrogenation of polycyclic aromatic hydrocarbons was higher by 14–15%. It was also found that the use of AlMo₆-HPC does not cause such an effect.     

Role of ɣ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> on the mechanical and microstructural properties of metakaolin-based geopolymer cements

The main target of this work is to investigate the influence of ?-Al₂O₃ on the properties of metakaolin-based geopolymer cements. The kaolin used as starting material for producing geopolymer cements contains approximately 28 and 64% of gibbsite and kaolinite, respectively. This kaolin was transformed to metakaolins by calcination at 500, 550, 600, 650, and 700?°C for 1?h. Gibbsite contained in kaolin was transformed to γ-Al₂O₃ during the calcination process. The hardener was obtained by mixing commercial sodium silicate and sodium hydroxide solution (10?M) with a mass ratio sodium silicate/sodium hydroxide equal to 1.6:1. Geopolymer cements, GMK-500, GMK-550, GMK-600, GMK-650, and GMK-700, were obtained using the prepared hardener with a mass ratio hardener/metakaolin equal to 0.87:1. It could be seen that the specific surface area of metakaolins decreases with increasing the calcination temperature of kaolin owing to the formation of the particles of γ-Al₂O₃. The compressive strengths 18.21/29.14/36.61/36.51 increase in the course GMK-550/GMK-600/GMK-650/GMK-700. The X-ray patterns and micrograph images of geopolymer cements, GMK-600, GMK-650, and GMK-700, indicate the presence of γ-Al₂O₃ in their structure. It was typically found that γ-Al₂O₃ remains largely unaffected during the geopolymerisation, and therefore could act as an inert filler and reinforce the structure of geopolymer cements.

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The effect of temperature on the formation of titanium dioxide structures on γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> surface

The effect of calcination temperature of hydrated gamma-aluminum oxide on the phase formation of surface structures and the content of titanium in them in the course of successive treatment of the initial matrix with TiCl₄ and H₂O was determined.     

Adsorption of chlorobenzene vapor on V<Subscript>2</Subscript>O<Subscript>5</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst under dynamic conditions

Adsorption dynamics of chlorobenzene vapors on a 5% V₂O₅/Al₂O₃ catalyst has been investigated using the frontal chromatography technique. The uptakes of chlorobenzene have been measured as a function of vapor concentration and adsorption equilibrium has been found to follow formally the Langmuir isotherm. The breakthrough time proved to be a linear function of the column length as expected. Breakthrough profiles have been reported for different experimental conditions and quantitatively fitted by a reduced lumped diffusion model. This model provides an analytical solution that facilitates engineering calculations. Model parameters show complex behavior as functions of stream characteristics and depend on column length. When empirical expressions relating model mass transfer coefficients with influencing variables are found the model demonstrates good accuracy in predicting column performance.     

Adsorption of Cl<Superscript>−</Superscript> ions on γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> oxide from nitrate solutions

The adsorption of chloride ions on γ-Fe₂O₃ oxide (maggemite) from nitrate solution is studied using the method of potentiometric titration and an ion-selective electrode. The specific character of adsorption is determined. It is shown that the maggemite surface coverage with Cl^? ions increases with increasing concentration of ions in the solution, decreasing pH value, and increasing potential. The adsorbability of ions changes drastically in the pH range about pH₀ (γ-Fe₂O₃)6.2. It is found that the adsorption of chloride ions from neutral nitrate solution exponentially increases in the potential range from 0.1 to 1.0 V. The type of adsorption isotherm and the adsorption parameters are determined. It is found that, in the absence of external polarization, the concentration dependences of adsorption of Cl^? ions are complex-shaped, and their initial portions are described by the Langmuir isotherm. Further increase of adsorption is explained by the penetration of Cl^? ions inwards the oxide.     

Thermal properties of Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>–PbO–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glass system

Thermal behavior of xGa₂O₃–(50 − x)PbO–50P₂O₅ (x = 0, 10, 20, and 30 mol.% Ga₂O₃) and xGa₂O₃–(70 − x)PbO–30P₂O₅ (x = 0, 10, 20, 30, and 40 mol.% Ga₂O₃) glassy materials were studied by thermo-mechanical analysis (TMA) and differential thermal analysis (DTA). Replacement of PbO for Ga₂O₃ is accompanied by increasing glass-transition temperature (263 ≤ T _g/°C ≤ 535), deformation temperature (363 ≤ T _d/°C ≤ 672), crystallization temperature (396 ≤ T _c/°C ≤ 640) and decreasing of coefficient of thermal expansion (5.1 ≤ CTE/ppm K⁻¹ ≤ 16.7). Values of Hruby parameter were determined (0.1 ≤ K _H ≤ 1.3). The thermal stability of prepared glasses increases with increasing of concentration of Ga₂O₃.     

Formation of solid solutions of multiferroics in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–Nd<Subscript>2</Subscript>O<Subscript>3</Subscript>–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The sequence of phases appearance during the formation of Bi_1–xNd_xFeO₃ solid solutions in powder oxides mixtures of bismuth, neodymium, and iron has been determined. It has been shown that the closeness of the reaction mixture composition to that of the individual compound (BiFeO₃ or NdFeO₃) is essential for the realization of the series of phase transformations yielding solid solutions of multiferroics Bi_1–xNd_xFeO₃ as the final product, due to the prevalence of various interphase contacts in the starting reaction zone.     

Modifying additives affect the properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> system

The effects caused by modifying additives, namely nonionic surfactants (Tween 80 and Neonol AF 9-6) and oxides (B₂O₃ and HfO₂), on the rheology, film formation, and phase formation in the yttrium aluminum silicate system prepared by sol–gel technology were studied. The effect of 1 wt % HfO₂ additions on the activation energy of crystallization was studied.     

Spectroscopic study of the properties of surface compounds in methanol conversions on Cu/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

The reactions of methanol on the (10% Cu)/γ-Al₂O₃ surface were studied by the spectrokinetic method (simultaneous measurements of the conversion rates of surface compounds and the product formation rates). Bridging and linear methoxy groups result from the interaction of methanol with surface hydroxyl groups. Formate and aldehyde-like complexes form by the oxidative conversion of the linear methoxy groups. Hydrogen forms via the recombination of hydrogen atoms on copper clusters, and the hydrogen atoms result from interconversions of surface compounds. The source of CO₂ in the gas phase is the formate complex, and the source of CO is the aldehyde complex. In the absence of methanol in the gas phase, dimethyl ether forms by the interaction between two bridging methoxy groups. When present in the gas phase, methanol reacts with methoxy groups on the surface. The roles of oxygen and water vapor in the conversions of surface compounds are discussed.     

The character of interactions of CO,H<Subscript>2</Subscript>, and CH<Subscript>3</Subscript>OH with the surface of γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Cu-Zn oxide catalyst

The thermal desorption of CO, H₂, and CH₃OH from the surface of Katalco-58 industrial catalyst for the synthesis of methanol and γ-Al₂O₃ was studied. Weak interaction of the gases with the surface of samples was observed over the temperature range 75–400°C. The desorption of the gases obeyed the second-order Wigner-Polyani equation. The desorption energies of the gases were calculated. The mechanism of dimethyl ether synthesis was studied.     

Physicochemical properties of precursors of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZrO<Subscript>2</Subscript> oxide ceramics prepared by electrochemical method

Scanning electron microscopy, X-ray, and thermal analysis are used to examine the structure and properties of dispersive systems based on aluminum and zirconium oxides prepared electrochemically. The effect the conditions of synthesis have on the structure and morphology of Al₂O₃–ZrO₂ particles is studied. It is shown that the effect of an electric field on the reaction medium allows us to adjust the physicоchemical properties and morphology.