Sol–gel derived mesoporous and microporous alumina membranes

Stable polymeric and colloidal boehmite sols were prepared by sol–gel process through controlled hydrolysis/condensation reactions. The particle sizes of the colloidal sols were in the 12–25 nm range depending on the process parameters and about 2 nm for polymeric sols. The presence of a significant increase in the microporosity content of the heat treated polymeric membranes relative to the mesoporous colloidal membranes might make the design of thermally stable microporous alumina membranes with controlled pore structures possible. The phase structure evolution in the 600–800 °C range had shown that the crystallization of the gamma alumina in the amorphous matrix starts at about 800 °C. This indicated that the pore structure stability may be enhanced through processing up to this relatively high temperature in polymeric alumina derived unsupported membranes. The permeance values of the two and three layered colloidal alumina membranes were observed to be independent of pressure which implies that the dominant gas transport mechanism is Knudsen diffusion in these structures. This was also supported by the 2.8 nm BJH pore sizes of the colloidal membranes. The Knudsen diffusion equation derived permeances of the polymeric alumina membranes with thicknesses of about 300 nm were determined to be very close to the experimentally determined permeance values.     

Synthesis of boehmite and hematite by joint hydrolysis of carbamide,aluminum chloride,and iron(III) chloride under hydrothermal conditions

The formation of boehmite and hematite in dependence of the conditions of joint hydrothermal hydrolysis of carbamide and a mixture of aluminum and iron(III) chlorides in the presence of K, Na, Ca, and Mg chlorides at T = 160–200°C and P = 0.6–1.6 MPa was studied. It was shown that the amount of boehmite and hematite being formed in hydrolysis of Al and Fe chlorides strongly depends on pressure, temperature, hydrolysis duration, and composition of the model mixture of Al, Fe, Mg, Ca, K, and Na chlorides. It was found that a complete hydrolysis of AlCl₃ and FeCl₃ with 99% yield of boehmite and hematite occurs at the stoichiometric ratio between carbamide and aluminum and iron chlorides in the starting solution, whereas mostly iron oxyhydroxide [goethite FeO(OH)] and aluminum oxychloride [Al₁₇O₁₆(OH)₁₆Cl₃] are formed at nonstoichiometric ratios.     

Effect of Solution Chemistry on Preparation of Boehmite by Hydrothermal Assisted Sol-Gel Processing of Aluminum Alkoxides

Various aluminum alkoxide precursors have been used for the preparation of boehmite by hydrothermal assisted sol-gel processing. The coordination status of aluminum in solution for all precursors employed for the preparation of boehmite phase was determined by ²⁷Al NMR and correlation between coordination status of aluminum atoms of precursors and development of boehmite phase has been investigated. Hydrothermal assisted hydrolysis of aluminum alkoxides where the aluminum atoms are four or five coordinated in solution resulted in the formation of boehmite. In contrast, hydrothermal hydrolysis of aluminum alkoxides where the aluminum atoms are six coordinated resulted in the formation of amorphous gel. Development of boehmite phase by hydrothermal hydrolysis of aluminum alkoxides at various temperatures was pursued by X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR) spectroscopy.     

An efficient route to aqueous phase synthesis of nanocrystalline γ-Al2O3 with high porosity: from stable boehmite colloids to large pore mesoporous alumina

In this paper we emphasise the important role of Pluronic F127 on the porosity of mesoporous alumina prepared from boehmite colloids. By focusing on the F127/boehmite interactions we show how the concepts of interface science may help to predict and improve the textural characteristics of mesoporous alumina. By varying the synthetic parameters, in particular the copolymer content, we show that the porosity of γ-Al(2)O(3) can be enhanced by 400% and the average pore diameter can be expanded from 5 to 14 nm. These results are discussed in terms of interactions between the Pluronic F127 and boehmite colloids, and are correlated to the critical micelle concentration (CMC) of the copolymer. The textural characteristics of the mesoporous alumina can be further improved either by introducing hydrocarbons in the preformed boehmite/copolymer sols or by concentrating the sols. In comparison with as-synthesised alumina, those prepared with F127 showed improved thermal stability. Furthermore, boehmite/copolymer sols were stable for all surfactant concentrations investigated and can give high quality coatings suitable for catalytic applications.     

The role of precursors in the structure of SiO2-Al2O3 sols and gels by the sol-gel process

Binary sols and gels of SiO₂-Al₂O₃ were prepared using tetraethyl orthosilicate and each of four aluminum compounds; aluminum di (sec-butoxide) ethylacetoacetic ester chelate (AC), aluminum nitrate nonahydrate (AN), aluminum formoacetate (AF), and boehmite sol (BS) made from aluminum i-propoxide. The structure and the evolution of the Si-O-Al bonds in SiO₂-Al₂O₃ sols and gels were investigated by ²⁷Al nuclear magnetic resonance (NMR), Infrared absorption spectra, DTA, and X-ray diffraction. The formation of Si-O-Al bonds differs depending on the aluminum compounds used as raw materials. The ratio of Al(IV) to {Al(IV) + Al(VI)} is related to the microstructural homogeneity of the gels. When AC is used as a raw material, the Si-O-Al bonds are formed in the sol state and resultant gel shows good microstructural homogeneity. In case of AN, the Si-O-Al bonds are not formed either in the sol or the wet gel state. The bonds are formed by drying the gel before heat-treatment temperature reaches 300 400°C, resulting in good microstructural homogeneous gel. When AF is used, the Si-O-Al bonds are formed in the sol state but the ratio of Al(IV) to {Al(IV) + Al(VI)} is lower than when using AC. Microstructural homogeneity of the gel is ranked between AC or AN and BS. Using BS, the Si-O-Al bonds are not formed in the sol solution, and the change in the coordination number of the gel is similar to that of boehmite gel. The Microstructural homogeneity of the gel is the worst among the BS gels, which were prepared by using the four aluminum raw materials.     

Preparation of aqueous sols containing well-shaped boehmite crystals

The paper describes the preparation of aqueous sols of crystalline boehmite, containing about 70 grams of AlOOH per liter from three different starting materials; gels of Al(OH)₂Ac are obtained and are hydrolyzed by thermal aging into sols of fibrillar pseudoboehmite. The pseudoboehmite fibrils are hydrothermally recrystallized at 200°C producing well-shaped hexagonal laths of boehmite, also as stable sols.     

Coating of Sol Particles for Membrane Applications

For improving chemical and thermal stability of γ-Al₂O₃ membranes boehmite (AlOOH) sol-particles are coated with Zr⁴⁺-species with two techniques. These techniques are heterogeneous precipitation (HP-method) and “surface-reaction-followed-by-polycondensation” (SRPC-method). A continuous coating layer is formed at relative low Zr⁴⁺-concentration, about one monolayer coverage of boehmite particles, and with the HP-method. For large concentrations and for the SRPC-method small particles (order 1 nm) of Zr⁴⁺-species are formed on the surface of the boehmite particles. After drying and calcination up to 1000°C no continuous layer of a zirconia phase could be detected for all samples. However the thermal stability of the porous structure is improved. Phase transitions of alumina occur at temperatures of 1100°C and the porous structure of the membrane material is then destabilized.     

Porous Al2O3/Al Metal Ceramics Prepared by the Oxidation of Aluminum Powder under Hydrothermal Conditions Followed by Thermal Dehydration: II. Composition and Microtexture of the Composites

The microtexture of Al₂O₃/Al composites with different oxide contents formed in the hydrothermal treatment of aluminum followed by thermal decomposition of boehmite is examined by a set of adsorption and structural analysis techniques. Two main types of alumina microtexture are found: relatively loose agglomerates of amorphous particles and highly ordered aggregates of well-crystallized primary blocks of a larger size, the fraction of which increases with the oxide content of the composite leads to an increase in the fraction of micropores and a decrease in the fraction of mesopores. The mechanism of thermal decomposition of boehmite prepared by the hydrothermal oxidation of aluminum is refined.     

Hydrothermally stable silica–alumina composite membranes for hydrogen separation

A thin layer (30–40 nm) of a dual-element silica–alumina composition was deposited on a porous alumina support by chemical vapor deposition (CVD) in an inert atmosphere at high temperature. Prior to CVD, an intermediate layer of γ-alumina was coated on the macroporous alumina support. The intermediate layer was prepared by the dip-coating and calcination of boehmite sols of different sizes to give a graded structure that was substantially free of defects. The resulting supported composite membrane had high permeance for hydrogen in the order of 2–3 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ at 873 K with selectivities of H₂ over CH₄, CO and CO₂ of 940, 700 and 590, respectively. The membrane operated by a hopping mechanism involving jumps of permeating molecules between solubility sites. The presence of aluminum improved the hydrothermal stability of the membranes for periods in excess of 500 h at 873 K in 16% steam, allowing the permeance to remain above 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹, although with decreased selectivities.     

SiO2-TiO2 membranes by the sol-gel process

The use of membranes for gas separation represents an important alternative from the viewpoint of energy conservation in industrial separation processes. Polymeric Si-Ti sols prepared from titanium isopropoxide (Ti(OPrⁱ)₄) and tetraethoxysilane (TEOS) were used to deposit membranes on α-Al₂O₃ supports. Acetylacetone (2,4 pentanedione, acacH) and isoeugenol (2-methoxy-4-propenylphenol, isoH) were employed separately to chelate the Ti precursor in order to slow down the chemical reactivity, avoiding precipitation. The radial distribution functions (RDF) of the gels aging at room temperature were obtained. The xerogels were studied by Thermal Gravimetric (TGA) and Differential Thermal (DTA) Analysis in air. The Microporosity of the solids calcined at 773 K was determined by N₂-adsorption at 77 K. The membrane thickness was determined from SEM photographs. Preliminary permeance results of the supported membranes on commercial alumina support were obtained for He, N₂ and CO₂ in a single gas equipment. At 773 K the separation factors α(He/CO₂) and α(N₂/CO₂) for both membranes exceeds the theoretical Knudsen limit.     

Influence of peptization on the properties of alumina produced from boehmite sols

Formation of boehmite sols from aluminium alkoxides was studied by X-ray diffraction, IR-spectroscopy, DLS (Dynamic Light Scattering) and other methods. It was found that the distortion of the boehmite crystal lattice occurs under the electrolyte sol formation processes. The surface charges were evaluated to explain the observed changes in X-ray patterns and IR-spectra of the boehmite samples and the causes that bring about these changes. The influence of the peptizing process on -Al₂O₃ specific surface was also studied.     

The Effect of Nanoscaled Metal Oxide Sols on the Structure and Properties of Glycidoxypropyltrimethoxysilane Derived Sols and Gels

Glycidoxypropyltrimethoxysilane (GPTS) is frequently used as precursor for the preparation of sol-gel derived nanoscaled hybrid polymers. The influence of nanoscaled metal oxide sols of silica, boehmite, zirconia and ceria on reactions of GPTS in ethanolic hydrolysates and in corresponding gels (epoxide ring-opening, condensation degree) was examined by liquid- and solid-state ¹³C and ²⁹Si NMR with regard to a better correlation between structure and material properties. Generally, a higher condensation degree of RSi(O_0.5)₃ units of GPTS is found after addition of metal oxide sols compared to GPTS without additives. The metal oxide sols (10 mole% series) cause an epoxide ring-opening up to 20% in GPTS hydrolysates after 24 h. A nearly complete ring opening was found in the boehmite and silica containing hybrid gels whereas gels containing ceria and other types of silica only show a low degree of ring-opening. The results show an accelerated ring-opening with increasing content of AlO/OH-species in silica sols. ¹³C NMR studies reveal that the epoxide ring-opening does not completely lead to polyether structures but to considerable amounts (up to 40%) of ethylether groups which can influence the material properties (hardness).     

Alumina cryogels with superior thermal stability for catalyst supports

Alumina cryogels were synthesized from a colloidal boehmite sol through a sol–gel processing and subsequent freeze drying, and thermal stability was examined by comparison to that of the corresponding xerogel, precipitate and commercial alumina. N₂ adsorption, X-ray powder diffraction and transmittance electron micrography observations revealed that the stability was higher for the cryogel than for others in particular at temperatures above 1,000 °C. The higher stability was ascribed to the fine and uniform primary particles with fibrous shapes formed by the sol–gel technique and furthermore to the suppression of aggregation of the primary particles owing to the subsequent freeze drying. It was also found that aluminum sec-butoxide employed as a precursor for the preparation of boehmite sol was preferable compared to aluminum iso-propoxide.     

The conversion of an organometallic compound into an intercalated thin‐layer amorphous structure

A thin alumina‐hydrotalcite (Al‐HT) film was fabricated from the synthesized boehmite and HT sol samples. The sols were a Newtonian fluid within 12 h of the sol synthesis and pseudo‐plastic flow thereon. Co‐precipitated HT demonstrated poorly crystallized periclase and spinel structures and apparent doublet peak of hydrotalcite at 2θ = 39–44°, indicative of a disordered structure. The heated Al‐HT sample demonstrated highly amorphous structure with single hydrotalcite peak but barely observed γ‐alumina and γ‐boehmite phases. The exfoliation of the spinel, gibbsite and periclase in the Al‐HT was caused by the intercalation of boehmite into the HT layers that impeded the formation of the oxides phases. Copyright © 2009 John Wiley & Sons, Ltd.     

Untersuchungen an oxidischen Katalysatoren. XIV. Die katalytische Aktivität verschiedener Übergangsformen des Aluminiumoxids bei der Dehydratisierung von Isopropanol

Studies on Oxide Catalysts. XIV. The catalytic Activity of some transient Forms of Alumina in the Dehydration of Isopropanol In order to give statements about the influence of the method of preparation of aluminum hydroxides and oxide hydroxides on the catalytic properties of alumina obtained from these compounds in the dehydration of ispropanol, bayerite, nordstrandite, and boehmite were prepared by several methods, carefully excluding impurity ions. Also, hydrargillite containing alkali was included in the investigations. By calcination in oxygen at 550 and 950°C, respectively, two groups of alumina were obtained. The catalytic properties of the oxides in the dehydration of isopropanol were examined by an apparatus working according to the dynamic principle. The specific activities of the different transient forms of alumina were found to vary according to the sequence η-;≈γ->?-≈δ->??(>??-)Al₂O₃.     

Polymer approach to supported silica membranes

Polymeric silica sols were used to prepare membranes on commercial -Al₂O₃ supports with nominal support pore diameters of 4.0 nm. Aging of the silica sols was shown to be effective to form discrete membrane layers. He/N₂ selectivity factors exceeding ideal Knudsen values were observed when the sols were prepared under conditions in which the condensation rate was minimized. We propose that the average pore size of the membrane depends on the balance of capillary pressure and modulus during membrane deposition. The condensation rate might influence the breadth of the pore size distribution.     

Tentative links between thermal diffusivity and fire-retardant properties in poly(methyl methacrylate)-metal oxide nanocomposites

Possible relationships between fire-retardant properties and thermal diffusivity for poly(methyl methacrylate) (PMMA) filled by melt blending with titanium dioxide (TiO₂), alumina (Al₂O₃) and boehmite (AlOOH) were investigated for a better understanding of the mode of action of metal oxides as fire-retardants (FR) in PMMA. Fire-retardancy was measured with a cone calorimeter and thermal diffusivity (α) by Laser Flash Analysis (LFA). LFA measurements have shown that heat dispersion is higher with titanium dioxide and boehmite than with alumina despite a larger surface area. For thermal diffusivity, discrepancies between the different nanofillers were only visible from 10 wt% onwards. Thermal degradation of PMMA-oxide nanocomposites and their thermal diffusivity could be linked. Moreover, a bi-linear relationship between the peak of heat release rate (pHRR) and the average of heat release rate (AHRR) showed the occurrence of a barrier effect.     

A new way to spinnable sols derived from modified aluminumalkoxides

The preparation of spinnable sols has been developed to obtain a new type of sol-gel derived pure alumina fiber. The starting material was aluminum sec-butoxide, which was modified in a first step with glycolether, e.g., isopropoxyethanol. This leads to a partial replacement of alkoxy groups via alcoholysis and a change of the precursor structure from a trimeric to a tetrameric one. In the second step, carboxylation, the transformation to six-coordinated aluminum could be observed. Due to the formation of a sol with Newtonian flow behavior after hydrolysis, gel fibers up to several kilometers long could be drawn directly from the clear colorless sol with spinning velocities up to 200 m/min. The addition of an organic filament-forming polymer is not necessary. The sol is spinnable for periods up to one year. The transformation of the gel fiber to -Al₂O₃ occurs at 1150° C.     

Sol–gel synthesis,characterization and catalytic activity of mesoporous γ-alumina prepared from boehmite sol by different methods

In this study, boehmite sols were used as alumina precursors for preparing mesoporous γ-aluminas by two different methods. In one case polyethylenimine was used as a structure-directing agent, and in another case ultrasound treatment was applied. Nitrogen physisorption showed that aluminas that had been prepared by these methods demonstrated different porous structures. The sample obtained without additional treatment had closely packed spherical particles and pores had ink-bottle neck morphology. Ultrasound treatment led to the transformation of ink-bottle pores into cylindrical form and to the increase in surface area and pore volume. Aluminas prepared using polyethylenimine as a template showed larger cylindrical wormhole-like mesopores with a broader pore size distribution, high surface area and pore volume. Catalytic tests showed that textural properties as well as crystallite size were very important parameters of synthesized samples which affected the catalytic activity in the methanol dehydration reaction. It was found that γ-Al₂O₃ prepared by ultrasound treatment had large crystallite size and demonstrated high catalytic activity.     

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.