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.     

Thermal study of boehmite nanofibers with controlled particle size

Boehmite nanofiber materials with controlled particle size were synthesized without any surfactant by careful tuning of the hydrothermal temperatures, and followed by a series of characterizations. It was found that the boehmite nanofibers became shorter and coarser with the increase of temperature, and resulted in a gradual decrease of their specific surface areas. Moreover, the thermal stability of the boehmite nanofibers was studied by in situ HT X-ray diffraction and thermogravimetry–differential scanning calorimetry. All materials showed the phase transition from γ-Al₂O₃ to other forms. Yet the transition temperature was increased with the increase of hydrothermal temperature. The boehmite nanofibers with the largest diameter showed the best thermal stability.     

Synthesis of corundum doped with cerium in supercritical water fluid

The properties of fine crystalline corundum doped with cerium (α-Al₂O₃: Ce³⁺) during synthesis in a supercritical fluid have been studied. The synthesis of corundum has been carried out by the thermal treatment of hydrargillite, Al(OH)₃, at T = 415°C and {ie290-1} MPa in reaction media that contained from 0.001 to 0.25 wt % of cerium. Cerium ions are incorporated into the boehmite lattice during the transformation of hydrargillite into boehmite, which forms fine monocrystals of the doped corundum with a size from 20 to 50 μm. The size of the corundum crystals increases with increasing pressure and increasing concentration of cerium. The synthesized α-Al₂O₃: Ce³⁺ reveals a luminescent band in the UV region at 352 nm and a blue band at 421 nm. The intensity of the cerium ion luminescence in corundum increases with an increase in the water fluid pressure during synthesis. The follow-up annealing of α-Al₂O₃: Ce³⁺ at 1400°C in a vacuum leads to a decrease in the luminescence. It has been concluded that spectrally active complex structures that include cerium ions, oxygen vacancies, and hydroxyl groups are produced in the media of a supercritical water fluid upon the synthesis of boehmite and corundum. Exposure to high temperatures causes their transformation.     

On the nature of phase conversions and transformations in porous system in hydrothermal processing of χ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> into boehmite

Study of the influence exerted by conditions of hydrothermal treatment of χ-Al₂O₃ on the phase composition and porous system parameters of the resulting products at T = 150–200°C and P = 0.5–1.5 MPa demonstrated the products formed in hydrothermal treatment of χ-Al₂O₃ are the bayerite and boehmite phases formed simultaneously in parallel pathways. Bayerite crystals have a needle-like shape and length of about 10 nm. 3D boehmite crystals are formed as parallelepipeds with edge size exceeding 200 nm in an alkaline medium at pH 8.0–9.2 and as 2D particles having the shape of rhombic plates with edge size of 80–500 nm and thickness of 20–100 nm at Ph 4.0–6.0. The crystallization of coarse boehmite particles favors formation of coarse mesopores and a low-porous system. A full phase transition of χ-Al₂O₃ to boehmite occurs at 180–200°C in 180–240 min.     

An insight into the changes in the thermal analysis curves of boehmite with mechanical activation

This study deals with the changes in the thermal transformation behaviour of boehmite with mechanical activation (MA), carried out in planetary mill. Observed changes in the TG-DTG–DTA curves are: shifting of the desorption of physically adsorbed water to higher temperature, decrease in the γ-Al₂O₃ transformation temperature and its peak area, formation of α-Al₂O₃, not observed for unmilled boehmite upto 1,200 °C, for milling time ≥60 min. Reasons for such changes are explored on the basis of physicochemical changes occurring as a result of high energy milling. Structural degradation is found to increase with increase in milling time. As a consequence of structural changes, Al–OH bonds get stronger, whereas the hydrogen bonds get weaker. Stronger Al–OH bonding and enhanced surface energy increase water affinity and delays its removal. Decreased hydrogen bond strength, easy exit of dehydroxylation product (water) and displacement of Al to tetrahedral positions make the γ-Al₂O₃ transformation easier. Ease of removal of residual hydroxyls from small crystallite transition alumina from MA boehmite, as a result of shorter diffusion path, ensures α-Al₂O₃ transformation at lower temperature.     

The dehydration of boehmite, γ-AlOOH,to γ-Al2O3

Electron microscopic observations of microstructure, together with studies of the evolution of X-ray and electron diffraction patterns, have been used to provide mechanistic information on the dehydration of boehmite to γ-Al₂O₃. Firing boehmite in air at 400°C produces slow development of a fine, lamellar, porous microstructure, oriented parallel to (001)_γ, the dimensions of which are consistent with the loss of one-quarter of the oxygen atoms of the boehmite lattice. The mechanism proposed for the dehydration is controlled by diffusion in a direction determined by the hydrogen bond chains in the boehmite structure and involves countermigration of the Al cations and protons with crystallographic formation of voids in a coherent cubic close-packed matrix. Final reorganization to give the spinel structure of γ-Al₂O₃ is suggested to involve gradual filling of the tetrahedral cation sites.     

Real structure of metastable forms of aluminum oxide

Differences in the real structure of γ-Al₂O₃ samples obtained by the thermal decomposition of pseudoboehmite and boehmite prepared by the hydrothermal treatment of bayerite were found. The transformations of these structures during their conversion to δ-Al₂O₃ as the treatment temperature increased were studied. The rate of conversion of metastable alumina species into the stable α-Al₂O₃ phase significantly depends on the real structure of samples. The rate of this transformation is drastically retarded in the presence of extended defects in the oxides originated from boehmite, and the stability of metastable alumina species increased as the degree of surface dehydroxylation increased.     

前躯体-喷雾干燥法制备氧化铝超细粉体

以六水氯化铝和氨水为原料,采用化学沉淀法结合喷雾干燥技术制备了氧化铝超细粉体。 实验结果表明,沉淀过程中反应体系的pH值对沉淀产物的结晶度有较大的影响。 采用喷雾干燥技术对前躯体进行干燥处理,将干燥后的粉体在管式炉中不同温度下进行煅烧,得到氧化铝超细粉体,用XRD、BET、SEM等测试技术对超细粉体性能进行了表征。 结果表明,在碱性条件下进行沉淀反应更有利于产物结晶度的提高;粉体在热处理过程的物相变化次序为：AlOOH→无定形氧化铝+γ-Al₂O₃→θ-Al₂O₃→α-Al₂O₃;通过喷雾干燥所得粉体,外形是规则的圆盘状或圆钵状,外形均一,无团聚,粒径分布范围窄,在4~10 μm之间,比表面积为391 m²/g,于1200 ℃、2 h处理后粉体的比表面积仍可达到185 m²/g。     

Synthesis of α-alumina from a less common raw material

A nanostructured α-Al₂O₃ with particle size lower than 100 nm was obtained from a hazardous waste generated in slag milling process by the aluminium industry. The route developed to synthesize alumina consisted of two steps: in the first one, a precursor of alumina, boehmite, γ-AlOOH was obtained by a sol–gel method. In the second step, the alumina was obtained by calcination of the precursor boehmite (xerogel). Calcination in air was performed at two different temperatures, i.e. 1,300 and 1,400 °C, to determine the influence of this parameter on the quality of resulting alumina. X-Ray diffraction patterns and transmission electron microscopy images of calcined powers revealed beside corundum the presence of transition aluminas and some rest of amorphous phase in the sample prepared at 1,300 °C. The increase of the calcinations temperature to 1,400 °C favors the formation of an almost single-phase corundum powder. The transition of θ- to α-Al₂O₃ was followed by means of infrared spectroscopy, since it is accompanied by the disappearance of the IR band frequencies associated with tetrahedral sites (AlO₄ sites), giving rise to a spectrum dominated by Al³⁺ ions in octahedral sites (AlO₆) characteristic of corundum.     

Preparation of unsupported alumina membrane by sol-gel techniques

Unsupported alumina membranes were prepared by sol-gel technique using aluminum isoproxide. The influence of the hydrolysis conditions, the type and concentration of peptizant acid on the boehmite sols has been studied. The suitable hydrolysis temperature for the aluminum isoproxide was above 50°C. Crack-free unsupported alumina membranes were obtained by rapid gelation processing of sols. The boehmite gel membrane and γ-Al₂O₃ membrane formed exhibited (020) and (440) preferred orientation.     

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.     

Biomolecule-Assisted Synthesis of Hierarchical Multilayered Boehmite and Alumina Nanosheets for Enhanced Molybdenum Adsorption

The effective utilization of various biomolecules for creating a series of mesoporous boehmite (γ-AlOOH) and gamma-alumina (γ-Al₂O₃) nanosheets with unique hierarchical multilayered structures is demonstrated. The nature and concentration of the biomolecules strongly influence the degree of the crystallinity, the morphology, and the textural properties of the resulting γ-AlOOH and γ-Al₂O₃ nanosheets, allowing for easy tuning. The hierarchical γ-AlOOH and γ-Al₂O₃ multilayered nanosheets synthesized by using biomolecules exhibit enhanced crystallinity, improved particle separation, and well-defined multilayered structures compared to those obtained without biomolecules. More impressively, these γ-AlOOH and γ-Al₂O₃ nanosheets possess high surface areas up to 425 and 371 m² g⁻¹, respectively, due to their mesoporous nature and hierarchical multilayered structure. When employed for molybdenum adsorption toward medical radioisotope production, the hierarchical γ-Al₂O₃ multilayered nanosheets exhibit Mo adsorption capacities of 33.1–40.8 mg g⁻¹. The Mo adsorption performance of these materials is influenced by the synergistic combination of the crystallinity, the surface area, and the pore volume. It is expected that the proposed biomolecule-assisted strategy may be expanded for the creation of other 3D mesoporous oxides in the future.     

Kinetic Analysis Crystallization of α-Al2O3 by Dynamic DTA Technique

The phase transformation of seeded (5 mass% Fe₂O₃ as a Fe(NO₃)₃ solution) boehmite derived alumina gel to α-Al₂O₃ was studied with DTA technique and compared with unseeded and α-Al₂O₃ seeded boehmite gels. Data for kinetic analysis of α-Al₂O₃ crystallization were obtained from quantitative DTA curves. The kinetic parameters were analysed by traditional Kissinger analysis and Friedman and Ozawa-Flynn-Wall methods using the Netzsch Thermokinetics program. Results of the comparison of values of activation energies for all three gels and methods are the process of α-Al₂O₃ transformation for originally γ-AlOOH/Fe(NO₃)₃ gels goes like that of unseeded boehmite gels,only under lower temperatures (lower about 200°C). This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal stability and glass transition behavior of PANI/γ-Al2O3 composites

Polyaniline/γ-Al₂O₃ (PANI/γ-Al₂O₃) composites were synthesized by in-situ polymerization at the presence of HCl as dopant by adding γ-Al₂O₃ nanoparticles into aniline solution. The composites were characterized by FTIR and XRD. The thermogravimetry (TG) and modulated differential scanning calorimetry (MDSC) were used to study the thermal stability and glass transition temperature (T _g) of the composites, respectively. The results of FTIR showed that γ-Al₂O₃ nanoparticles connected with the PANI chains and affected the absorption characteristics of the composite through the interaction between PANI and nano-sized γ-Al₂O₃. And the results of XRD indicated that the peaks intensity of the PANI/γ-Al₂O₃ composite were weaker than that of the pure PANI. From TG and derivative thermogravimetry (DTG) curves, it was found that the pure PANI and the PANI/γ-Al₂O₃ composites were all one step degradation. And the PANI/γ-Al₂O₃ composites were more thermal stable than the pure PANI. The MDSC curves showed that the nano-sized γ-Al₂O₃ heightened the glass transition temperature (T _g) of PANI.     

Structural thermal and textural studies on cobalt oxide/alumina supported catalysts

CoO/Al₂O₃ catalysts containing amounts of cobalt ranging form 2 to 20% were prepared atpH 11 from neutral mesoporous alumina composed of γ-Al₂O₃ and poorly crystalline boehmite, and were then dried at 80?C. X-ray diffraction, DTA and TG techniques were used to study the structural changes produced upon thermal treatment up to 700?C. Soaking of the alumina in cobalt ammine complex solutions for a period of 10 days (the time required for equilibrium) resulted in a series of catalyst samples (I–V). Another sample (III-a) was soaked for a period of 5 days only in order to study the effect of the soaking time upon the equilibrium conditions. Cobalt aluminate (CoAl₂O₄) bands were characterized in all catalyst samples except III-a. They increased in intensity with increasing cobalt content. Surface species appeared in samples heated to 80?C, and others persisted at 150?C. Heating to temperatures above 200?C resulted in the formation of cobalt oxides, due to decomposition of the surface compounds. DTA and TG studies showed that this was more pronounced at higher concentrations of cobalt. Samples heated at 500?C and above did not undergo any further structural changes, except that the boehmite in the support was converted to γ-Al₂O₃. The variations in the surface parameters followed the same pattern as found previously [1], demonstrating that the catalyst samples are mesoporous, with retention of two ranges of pore size in most cases.     

The Role of Lewis Acid Sites in γ-Al2O3 Oligomerization

Olefin oligomerization by γ-Al₂O₃ has recently been reported, and it was suggested that Lewis acid sites are catalytic. The goal of this study is to determine the number of active sites per gram of alumina to confirm that Lewis acid sites are indeed catalytic. Addition of an inorganic Sr oxide base resulted in a linear decrease in the propylene oligomerization conversion at loadings up to 0.3 wt %; while, there is a >95 % loss in conversion above 1 wt % Sr. Additionally, there was a linear decrease in the intensity of the Lewis acid peaks of absorbed pyridine in the IR spectra with an increase in Sr loading, which correlates with the loss in propylene conversion, suggesting that Lewis acid sites are catalytic. Characterization of the Sr structure by XAS and STEM indicates that single Sr²⁺ ions are bound to the γ-Al₂O₃ surface and poison one catalytic site per Sr ion. The maximum loading needed to poison all catalytic sites, assuming uniform surface coverage, was ∼0.4 wt % Sr, giving an acid site density of ∼0.2 sites per nm² of γ-Al₂O₃, or approximately 3 % of the alumina surface.     

Sol–gel synthesis, characterization and catalytic activity of γ-alumina with bimodal mesopore distribution

In this study, boehmite sols were used for preparation of mesoporous γ-alumina with bimodal mesopore distribution. Superfine nanospheres of poly(methyl methacrylate) (PMMA) prepared by water based emulsion polymerization method were used as a template. Nitrogen sorption revealed that aluminas prepared using this approach demonstrated bimodal mesopore size distribution with maxima at 3.8 and 25.7 nm, respectively. Catalytic tests showed that bimodal mesopore distribution within γ-Al₂O₃ prepared with PMMA nanospheres as a template provides improved catalytic activity in the methanol dehydration reaction.     

Sorption of Ponceau 4R anionic dye from aqueous solutions on aluminum oxide and polyurethane foam

The sorption of Ponceau 4R (E-124) anionic dye on polyurethane foam based on ethers and γ-Al₂O₃ from aqueous solutions is studied. It is established that sorption is highest in the range of 0.5 M HCl, pH 2 on polyurethane foam and 0.2 M HCl, pH 6.5 on γ-Al₂O₃. Under optimum conditions, the degrees of recovery on polyurethane foam and γ-Al₂O₃ are 20–30 and 70–85%, respectively. A possible scheme of interactions between the dye and the surfaces of sorbents is proposed.     

Catalytic Combustion of Styrene over the Binary Mixture of Manganese and Copper Based Catalyst in the Absence and Presence of Water Vapor

MnO _x and MnCu based catalysts prepared by ultrasonic impregnation methods were characterized by XRD, TPR-H₂, XPS and N₂ adsorption and tested for styrene combustion in the presence and absence of water vapor. Results showed that the loading of binary mixtures of manganese oxide and copper oxide on γ-Al₂O₃ increased the ratio of Cu⁺/Cu²⁺ of the defect spinel of Cu_1.5Mn_1.5O_4–x and the reducibility of the catalyst and in this way increased the catalytic activity of the catalysts for styrene combustion. The catalyst MnCu/γ-Al₂O₃ (20%/l) with 20 wt % loading amount and the Mn/Cu ratio of 1 : 1 showed the highest catalytic activity with T₉₀ = 214°C. Water vapor in feed steam decreased the activity of the catalysts MnCu/γ-Al₂O₃ (20%/l) and Mn₂O₃/γ-Al₂O₃ (10%). The catalyst MnCu/γ-Al₂O₃ (20%/l) had more resistant to negative influence of water vapor. Upon addition of 2.94 vol % water vapor to the feed stream a 6.5% decrease in styrene conversion was observed whereas for the catalyst Mn₂O₃/γ-Al₂O₃ (10%) a 14% reduction in conversion at the same condition was recorded. Higher resistance to the negative influence of water vapor could be due to weaker interactions between water molecules and the surface of catalyst.     

Dynamic study of ammonium dawsonite doped with yttrium transformation at elevated temperatures

Co-precipitation of alumina/YAG precursor from aluminum and yttrium nitrates solution with ammonium carbonate results in dawsonite (NH₄Al(OH)₂CO₃). Its crystallographic parameters differ from the compound precipitated without the yttrium additive. It indicates that yttrium ions become incorporated into the dawsonite structure. The DSC/TG and X-ray measurements show decomposition of dawsonite at elevated temperature resulting in γ-Al₂O₃ which transforms to δ and θ modifications at still higher temperatures. The full transformation to α-Al₂O₃ and YAG occurs at temperatures higher than 1,230 °C.