Sol-gel synthesis of titania-alumina catalyst supports

Titanium oxide is a good candidate as new support for hydrotreating (HDT) catalysts, but has the inconvenience of presenting small surface area and poor thermal stability. To overcome these handicaps TiO2-Al2O3 mixed oxides were proposed as catalyst support. Here, the results concerning the preparation, characterization and testing of molybdenum catalyst supported on titania-alumina are presented. The support was prepared by sol-gel route using titanium and aluminum isopropoxides, chelated with acetylacetone (acac) to promote similar hydrolysis ratio for both the alcoxides. The effect of nominal complexing ratios [acac]/[Ti] and of sol aging temperature on the structural features of nanometric particles was analyzed by quasi-elastic light scattering (QELS) and N-2 adsorption isotherm measurements. These characterizations have shown that the addition of acac and the increase of aging temperature favor the full dispersion of primary nanoparticles in mother acid solution. The dried powder presents a monomodal distribution of slit-shaped micropores, formed by irregular packing of platelet primary particles, surface area superior to 200 m(2) g(-1) and mean pore size of about 1 nm. These characteristics of porous texture are preserved after firing at 673 K. The diffraction patterns of sample fired above 973 K show only the presence of anatase crystalline phase. The crystalline structure of the support remained unaltered after molybdenum adsorption, but the surface area and the micropore volume were drastically reduced. (C) 2002 Published by Elsevier B.V. B.V.

Colonization of a 'Lost World': Encrustation patterns in modern subtropical brachiopod assemblages.

The encrustation of Paleozoic rhynchonelliform brachiopods has been studied for decades, but modern brachiopods have not received similar scrutiny. The discovery of abundant subtropical brachiopods from the Southeast Brazilian Bight provides an unprecedented opportunity to assess epibiont abundance, diversity, and encrustation patterns in modern brachiopod assemblages. Across the outer shelf, encrustation frequencies vary among taxa, from mean values of 0.45% for Platidia to 9.3% for Argyrotheca. Encrustation frequencies for Bouchardia increase from 1.6% on the outer shelf to 84% on the inner shelf Larger valves are encrusted more frequently, and epibionts preferentially colonize valve interiors. Increased encrustation on the inner shelf may reflect the greater surface area of larger hosts, longer exposure of dead shells, water-mass characteristics, sedimentation rates, productivity, or other factors that vary with depth. Inner-shelf brachiopods exhibit encrustation frequencies comparable to those reported for epifaunal bivalves. The epibiont fauna is dominated by bryozoans and serpulids, with minor roles played by spirorbids, bivalves, barnacles, foraminifera, algae, and other taxa. Epibiont abundance at each site is highly variable, but sites are similar in rank importance of epibiont taxa. A different suite of epibionts colonized Paleozoic brachiopods, but similar patterns of encrustation have been observed, including preferential settlement according to valve morphology. These results provide a baseline for evaluating the encrustation of modern bivalves and ancient brachiopods, and may elucidate the macroevolutionary history of epibionts and their relationship to their hosts.

Mechanically activating formation of layered structured bismuth titanate

Bismuth titanatc-Bi(4)Ti(3)O(12) (BIT) with wide application in the electronic industry as capacitors, memory devices and sensors is the simplest compound in the Aurivillius family, which consists of (Bi(2)O(2))(2+) sheets alternating with (Bi(2)T(i)3O(10))(2-) perovskite-like layers. The synthesis of more resistive BIT ceramics would be preferable advance in obtaining of well-densified ceramic with small grains randomly oriented to limit the conductivity along the (Bi(2)O(2))(2+) layers. Having in mind that the conventional ceramic route for the synthesis can lead to non-stoichiometry in composition, in consequence of the undesirable loss in bismuth content through volatilization of Bi(2)O(3) at elevated temperature, our efforts were addressed to preparation of BIT by mechanical activation the constituent oxides. The nucleation and phase formation of BIT, crystal structure, microstructure, powder particle size and specific surface area were followed by XRD, Rietveld refinement analysis, thermal analysis, scanning electron microscopy (SEM) and the BET specific surface area measurements. (c) 2005 Elsevier B.V. All rights reserved.

Preparation and characterization of LiNi0.8Co0.2O2/PANI microcomposite electrode materials under assisted ultrasonic irradiation

A preparation method for a new electrode material based on the LiNi0.8Co0.2O2/polyaniline (PANI) composite is reported. This material is prepared by in situ polymerization of aniline in the presence of LiNi0.8Co0.2O2 assisted by ultrasonic irradiation. The materials are characterized by XRD, TG-DTA, FTIR, XPS, SEM-EDX, AFM, nitrogen adsorption (BET surface area) and electrical conductivity measurements. PANI in the emeraldine salt form interacts with metal-oxide particles to assure good connectivity. The dc electrical conductivity measurements at room temperature indicate that conductivity values are one order of magnitude higher in the composite than in the oxide alone. This behavior determines better reversibility for Li-insertion in charge-discharge cycles compared to the pristine mixed oxide when used as electrode of lithium batteries. (c) 2005 Elsevier B.V. All rights reserved.

High volume peritoneal dialysis for acute renal failure

Background. Peritoneal dialysis (PD) is still widely used for acute renal failure (ARF) in developing countries despite concerns about its inadequacy. Continuous PD has been evaluated in ARF by analyzing the resolution of metabolic abnormality and normalization of plasma pH, bicarbonate, and potassium.Methodology: A prospective study was performed on 30 ARF patients who were assigned to high-dose continuous PD (Kt/V = 0.65 per session) via a flexible catheter (Tenckhoff) and automated PD with a cycler. Fluid removal, pH and metabolic control, protein Loss, and patient outcome were evaluated.Results: Patients received 236 continuous PD sessions; 76% were admitted to ICUs. APACHE II score was 32.2 +/- 8.65. BUN concentrations stabilized after 3 sessions, creatinine after 4, and bicarbonate and pH after 2. Fluid removal was 2.1 +/- 0.62 L/day. Creatinine and urea clearances were 15.8 +/- 4.16 and 17.3 +/- 5.01 mL/minute respectively. Normalized creatinine clearance and urea Kt/V values were 110.6 +/- 22.5 L/week/1.73 m(2) body surface area and 3.8 +/- 0.6 respectively. Solute reduction index was 41% +/- 6.5% per session. Serum albumin values remained stable in spite of considerable protein tosses (median 21.7 g/day, interquartile range 9.1 - 29.8 g/day). Regarding ARF outcome, 23% of patients presented renal function recovery, 13% remained on dialysis after 30 days of follow-up, and 57% died.Conclusion: High-dose continuous PD by flexible catheter and cycler was an effective treatment for ARF. It provided high solute removal, allowing appropriate metabolic and pH control, and adequate dialysis dose and fluid removal. Continuous PD can therefore be considered an alternative to other forms of renal replacement therapy in ARF.

Influence of milling time on mechanically assisted synthesis of Pb0.91Ca0.1TiO3 powders

Pb0.91Ca0.1TiO3 powders (PCT) were prepared by mechanochemical synthesis from high-energy ball milling process. The influence of milling time on the phase formation, crystal structure, specific surface area, density and powder morphology was observed. We adopted the Rietveld refinement technique to investigate the crystal structure of the PCT powders. Scanning electron microscopy (SEM) analysis revealed that PCT powders milled for 5 h showed a wide distribution of particle agglomerates while milled for 35 h showed a decrease in agglomerates size. Further prolongation of milling time resulted in the agglomerates growth. (C) 2006 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Comparative study of digestive cells in different midgut regions of stingless bees (Hymenoptera: Apidae: Meliponinae)

Ultrastructure of the digestive cells was analyzed in three midgut regions (anterior, middle and posterior) of stingless bees. Variations occurs in the presence of lipid inclusions in the cells from posterior midgut and presence of double-membraned vesicles associated to microvilli in the anterior midgut. However, basal plasmic membrane infoldings and augmentation of surface area achieved by microvilli ale very similar in all midgut regions. These results not supported the existence of fluid fluxes in the ectoperitrophic space and suggest that digestive cells in stingless bees are polifunctional, that is, there is not midgut region specialized in secretion ol absorption as observed in other insects.

Evaporative water loss and oxygen uptake in two casque-headed tree frogs, Aparasphenodon brunoi and Corythomantis greeningi (Anura, Hylidae)

Evaporative water loss (EWL) and oxygen uptake ((V) over dot o(2)) was measured in two species of tree frogs with cranial co-ossification, Aparasphenodon brunoi and Corythomantis greeningi. Both species use their head to seal the entrance of bromeliads, tree holes or rocky crevices used as shelters. EWL was significantly reduced in sheltered individuals of both species as compared with those exposed nude to desiccation. EWL per unit area through the head surface was significantly lower than the body skin for A. brunoi but not for C., greeningi. EWL per unit surface area through C. greeningi body skin was about 50% that of A. brunoi, indicating a less permeable skin in the former species. The relationship between cranial coossification and EWL is discussed. ((V) over dot o(2)) in A. brunoi was comparable with other anurans of similar size, whereas in C. greeningi, it was lower than predicted from body mass. Moreover, ((V) over dot o(2)), in C. greeningi showed less sensitivity to temperature increase than in A. brunoi. C. greeningi occurs in a drier environment than A. brunoi, and this appears to be reflected in their EWL and ((V) over dot o(2)) characteristics. (C) 1997 Elsevier B.V.

Structural characteristics of gels prepared from sonohydrolysis and conventional hydrolysis of TEOS: an emphasis on the mass fractal as determined from the pore size distribution

Silica gels were preparated from fixed proportion mixtures of tetraethoxysilane, water and hydrocloric acid, using either ultrasound stimulation (US) or conventional method (CO) in the hydrolysis step of the process. Wet gets were obtained with the same silica volume concentration and density. According to small-angle X-ray scattering, the structure of the wet gels can be described as mass fractal structures with mass fractal dimension D = 2.20 in a length scale xi = 7.9 nm, in the case of wet gels US, and D = 2.26 in a length scale 6.9 nm, in the case of wet gels CO. The mass fractal characteristics of the wet gels US and CO account for the different structures evolved in the drying of the gels US and CO in the obtaining of xerogels and aerogels. The pore structure of the dried gels was studied by nitrogen adsorption as a function of the temperature. Aerogels (US and CO) present high porosity with pore size distribution (PSD) curves in the mesopore region while xerogels (US and CO) present minor porosity with PSD curves mainly in the micropore region. The dried gels US (aerogels and xerogels) generally present pore volume and specific surface area greater than the dried gels CO. The mass fractal structure of the aerogels has been studied from an approach based on the PSD curves exclusively. (c) 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of the porosity developed in a new titania-alumina catalyst support prepared by the sol gel route

Titanium oxide (TiO2) is a good candidate for support of hydrotreating catalysts but has the disadvantage of presenting a low surface area and a poor thermal stability when compared with Al2O3. A mixed TiO2-Al2O3 support was proposed as an alternative that is expected to be free from these drawbacks. The variation during firing of the nanoporous texture of supports composed of TiO2-Al2O3, TiO2 and Al2O3 was studied by small angle X-ray scattering (SAXS). The supports were prepared by the sol-gel route using Ti and Al isopropoxides. We have particularly analyzed the effects of acid and basic hydrolysis on the nanostructural features of catalyst supports fired at different temperatures. The nanopore radius distribution functions were determined from SAXS results assuming a simple model of spherical nanopores embedded in a homogeneous solid matrix. The modal pore radius in both pure TiO2 and pure Al2O3 supports grows from 1.3 to 2.2 nm as the firing temperature increases from 673 to 973 K. on the other hand, the modal pore radius in the mixed TiO2-Al2O3 support remains below 1.2 nm over the same range of firing temperatures. These results demonstrate the good thermal stability of the nanoporous texture of mixed TiO2-Al2O3 supports.

Synthesis and characterization of Li2ZnTi3O8 spinel using the modified polymeric precursor method

In this work we report the synthesis procedure, crystallographic, structural and magnetic properties of the Li2ZnTi3O8 spinel obtained using a modified polymeric precursor method. This synthesis method generates very reactive and property-controlled nanoparticles. The samples were characterized using X-ray powder diffraction (XRD) associated to the Rietveld refinement method, thermogravimetric analysis (TG), specific surface area, scanning electron microscopy (SEM) and magnetic susceptibility measurements.The phase formation temperature of the lithium zinc titanate spinel was observed to decrease due to the homogeneity and highly controlled nanometric particle size. (C) 2003 Elsevier B.V. All rights reserved.

Mass fractal characteristics of sonogels prepared from sonohydrolysis of tetraethoxysilane with additions of dimethylformamide

Wet silica gels with similar to 1.4 x 10(-3) mol SiO2/cm(3) and similar to 90 vol.% liquid phase were prepared from the sonohydrolysis of tetraethoxysilane (TEOS) with different additions of dimethylformamide (DMF). Aerogels were obtained by CO2 supercritical extraction. The samples were studied mainly by small-angle X-ray scattering (SAXS) and nitrogen adsorption. Wet gels exhibit a mass fractal structure with fractal dimension D increasing from 2.23 to 2.35 and characteristic length xi decreasing from similar to 9.4 nm to similar to 5.1 nm, as the DMF/TEOS molar ratio is increased from 0 to 4. The supercritical process apparently eliminates some porosity, shortening the fractality domain in the mesopore region and developing an apparent surface/mass fractal (with correlated mass fractal dimension D-m similar to 2.6 and surface fractal dimension D-s similar to 2.3) in the micropore region. The fundamental role of the DMF addition on the structure of the aerogels is to diminish the porosity and the pore mean size, without, however, modify substantially the specific surface area and the average size of the silica particle of the solid network. (c) 2006 Elsevier B.V. All rights reserved.

Characterization of bismuth titanate ceramics derived by mechanochemical synthesis

Bismuth titanate, Bi(4)Ti(3)O(12) (BIT) nanosized powders have been successfully synthesized via high energy mechanochemical activation. The phase formation of BIT, crystal structure, microstructure, crystallite size and specific surface area were followed by XRD, scanning electron microscopy (SEM) and the BET specific surface area measurements. The BIT milled 2 h shows the orthorhombic crystalline structure with small amount of amorphous phase. The microstructure of Bi(4)Ti(3)O(12) ceramics sintered at 1000 degrees C for 12h exhibit plate-like grain structure.

Effect of ceria content on the sintering of ZrO2 based ceramics synthesized from a polymeric precursor

Zirconia-ceria powders with ceria concentration varying from 0 to 12 mol% were synthesized using a polymeric precursor route based on the Pechini process. Powder characteristics were evaluated with regard to the crystallite size, BET surface area, phase distribution, nitrogen adsorption/desorption behavior, and agglomeration state. Sintering was studied considering the shrinkage rate, densification, grain size, and phase evolution. It was demonstrated that the synthesis method is effective to prepare nanosized powders of tetragonal zirconia single-phase. Sinterability mainly depended on the agglomeration state of powders and the monoclinic phase content, fully tetragonal zirconia ceramic, with grain size of 2.4 mu m, was obtained after addition of at least 9 mol% ceria and sintering at 1500 degrees C for 4 h. (C) 2000 Elsevier B.V. Ltd. All rights reserved.

SAXS study of formation and growth of tin oxide nanoparticles in the presence of complexing ligands

The effect of acetylacetone (acac) complexing ligand on the formation and growth of tin oxide-based nanoparticles during thermohydrolysis at 70 degreesC of a tin precursor SnCl4-n(acac)(n) (0 less than or equal to n less than or equal to 2) solution was analyzed by in situ small-angle X-ray scattering. A. transparent and stable sol was obtained after 2 h of thermohydrolysis at 70 degreesC, allowing the quantitative determination of the particle volume distribution function and its variation with the reaction time. The number of colloidal particles for equivalent thermohydrolysis temperature and time decreases as the [acac]/[Sn] ratio in initial solution increases from 0.5 to 6. Instead, the amount of soluble species remaining in solution increases for increasing [acac]/[Sn] ratio within the same range. This indicates that increasing amounts of Sn-acetylacetone complexes partially prevent the hydrolysis and consequent formation of colloidal particles. The N-2 adsorption isotherm characterization of freeze-dried powders demonstrates that the average pore size is approximately equal to the average size (approximate to9 Angstrom) of the colloidal primary particles in the sol, and that the porosity and surface area (approximate to200 m(2) g(-1)) are independent of the acac content in the initial solution.