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.

SrBi2Ta2O9 ferroelectric thick films prepared by electrophoretic deposition using aqueous suspension

SrBi2Ta2O9 ferroelectric thick films were prepared by electrophoretic deposition (EPD). For that, ceramic powders were prepared by chemical method in order to obtain compounds with chemical homogeneity. The polymeric precursor method was used for the synthesis of the SrBi2Ta2O9 powder. The crystallographic structure of the powder was examined by X-ray diffraction, and the surface area was determined by single point BET adsorption. The 0.03 vol.% suspension was formed by dispersing the powder in water using two different polymers as dispersants: an ester polyphosphate (C213) and an ammonium polyacrilate (Darvan 821-A). It was investigated the influence of the different dispersants in the surface properties of the powder by zeta potential measurements. The films were deposited on platinum-coated alumina and Pt/Ti/SiO2/Si substrates by a 4 mA constant current, for 10 min, using two parallel electrodes placed at a separation distance of 3 min in the suspension. Several cycles of deposition-drying of the deposit were carried out until reaching the desired thickness. After thermal treatment at temperatures ranging from 700 to 1000 degreesC, the films were characterized by X-ray diffraction and scanning electron microscopy for the microstructure observation. (C) 2003 Elsevier Ltd. All rights reserved.

Improvement of the Mo/TiO2-Al2O3 catalyst by the control of the sol-gel synthesis

Traditional hydrotreating catalysts are constituted by molybdenum deposited on Al2O3 promoted by nickel and phosphorous. Several studies have shown that TiO2-Al2O3 mixed oxides are excellent supports for the active phases. 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, the titanium one chelated with acetylacetone (acac) to promote similar hydrolysis ratio for both the alcoxides. The effect of nominal molar ratio [Ti]/[Ti+Al] on the microstructural features of nanometric particles was analyzed by X-Ray Diffraction, N-2 Adsorption Isotherms and Transmission Electron Microscopy. The catalytic activity of Mo impregnated supports was evaluated using the thiophene hydrodesulfurization at different temperatures and atmospheric pressure. The pores size distribution curve moves from the micropores to the mesopores by increasing the Ti contents, allowing the fine tuning of average size from 2.5 to 6 nm. Maximal (367 m(2).g(-1)) and minimal (127 m(2).g(-1)) surface area were found for support containing [Ti]/[Ti+Al] ratio equal to 0.1 and 1, respectively. The good mesopore texture of alumina-titania support with [Ti]/[Ti+Al] molar ratio between 0.3 and 0.5 was found particularly valuable for the preparation of well dispersed MoS2 active phase, leading to HDS catalyst with somewhat higher activity than that prepared using a commercial alumina support.

Root growth and cotton nutrition as affected by liming and soil compaction

Soil columns were produced by filling PVC tubes with a Dark Red Latosol (Acrortox, 22% of clay). A compacted layer was established at the depth of 15 cm in the columns. In the compacted layer, soil was packed to 1.13, 1.32, 1.48, and 1.82 Mg kg(-1), resulting in cone resistances of 0.18, 0.43, 1.20, and 2.50 MPa. Cotton was cropped for 30 days. Lime was applied to raise base saturation to 40, 52, and 67%. The highest base saturation caused a decrease in phosphorus (P) and zinc (Zn) concentrations in the plants. A decrease in root dry matter, length and surface area was also observed. This could be a consequence of lime induced Zn deficiency. Root growth was decreased in the compacted layer, and complete inhibition was noticed at 2.50 MPa. Once the roots got through the compacted layer, there was a growth recovery in the bottom layer of the pots. The increase in base saturation up 52% was effective in preventing a decrease in cotton root length at soil resistances to 1.20 MPa. Where the roots were shorter, there was an increase in nutrient uptake per unit of root surface area, which kept the plants well nourished, except for P.

Macrobenthic intertidal communities from wave to tide dominated beach environments. A case study in two Brazilian beaches

Modification showed by intertidal macrofaunal communities between two nearby sites that change from a wave to a tide dominated beach environment, was analyzed on the present study. At each site, eleven intertidal sampling stations were distributed along a transect, from the drift line to the spring low tide water level. Four macrofaunal samples one meter long-shore spaced were collected at, each station with an iron core of 0.05 m(2) surface area, taken to a depth of 20 cm. Major,differences on sediments between sites were the offshore decrease of mean particle size diameter and increase of kurtosis and water content at the tide dominated site. KIDS ordination showed major similarities between the lowest stations of this site, that represents the dissipative low tide-terrace portion of the beach. Two lower station of the wave dominated site presented similarities with this group. The other stations of the tide-dominated site, that represents the reflective high tide beach portion, grouped distant from the former. (canonical Correspondence Analysis (CCA) showed a similar spatial distribution of stations, suggesting the importance of environmental factors on the explanation of species distribution patterns. Sediment water content and water table depth, with the highest inertia value, seems to be the principal physical factor. Increase on water content affects the macrofaunal distribution by the expansion of typical infralitoral species, as was the case of Bathyporeiapus ruffoi, on the dissipative low tide terrace beach portion. A disrupted distribution with the lost of a gradate zonation along a physical gradient is one of the major modification presented by macrobenthic communities on the transition from a wave to a tide dominated beach environment.

Dielectric properties of Na1-xLixNbO3 ceramics from powders obtained by chemical synthesis

Ultra-fine powders of Na1-xLixNbO3 (x=0; 0.06; 0.09; 0.12) were synthesized by the Polymeric Precursors Method. Such powders had their orthorhombic structures determined by X-ray diffraction and their surface area determined by BET isotherms (less than 10 m(2) g(-1)). Densification was followed by dilatometric study. The powders, calcined at 700 degrees C for 5 h, were sintered at 1290 degrees C during 2 h under ambient atmosphere with no application of extra pressure. The samples with relative densities higher than 95% were analyzed by impedance spectroscopy at room temperature, under a signal amplitude of 1 V-rms. Dielectric constants of about 180 and dielectric loss factor of about 0.03 were measured showing small dependence with frequency. The electrical properties were similar to those obtained for samples sintered by hot pressing. (C) 1999 Elsevier B.V. Limited and Techna S.r.l. All rights reserved.

Mechanochemical synthesis of PZT powders

PZT ceramic powders were successfully prepared from the mixture of PbO, ZrO2 and TiO2 by mechanochemical synthesis in a planetary ball mill, under different milling conditions. Phase evolution during synthesis was monitored by X-ray diffraction analysis. Intensive milling resulted in formation of the nanocrystalline, perovskite PZT powders after 1 h of milling. This is a significant improvement in comparison to milling conditions reported by other authors. Depending on milling parameters the presence of some other phases, such as unreacted ZrO2, was also detected in some samples. The changes in powder size and morphology due to intensive milling, were determined by SEM and TEM, while BET analysis was used to determine specific surface area of the powders. Conclusions about processes taking place during mechanochemical synthesis of PZT powders were made based on the results of characterization. (C) 2002 Elsevier B.V. B.V. All rights reserved.

On the stabilizing behavior of zirconia: A combined experimental and theoretical study

Reactive zirconia powder was synthesized by the complexation of zirconium metal from zirconium hydroxide using a solution of 8-hydroxiquinoline. The kinetics of zirconia crystallization was followed by X-ray diffraction, scanning electron microscopy and surface area measured by the nitrogen adsorption/desorption technique. The results indicated that zirconia with a surface area as high as 100 m(2)/g can be obtained by this method after calcination at 500degreesC. Zirconia presents three polymorphic phases (monoclinic, tetragonal and cubic), which are reversibly interconversible. The cluster model Zr4O8 and Z(r)4O(7)(+2) was used for a theoretical study of the stabilization process. The ab initio RHF method was employed with the Gaussian94 program and the total energies and the energy gap of the different phases were calculated and compared with the experimental energy gap. The theoretical results show good reproducibility of the energy gap for zirconia. (C) 2004 Kluwer Academic Publishers.

The role of hydration on the mechanism of allosteric regulation: In situ measurements of the oxygen-linked kinetics of water binding to hemoglobin

We report here the first direct measurements of changes in protein hydration triggered by a functional binding. This task is achieved by weighing hemoglobin (Hb) and myoglobin films exposed to an atmosphere of 98%, relative humidity during oxygenation. The binding of the first oxygen molecules to Hb tetramer triggers a change in protein conformation, which increases binding affinity to the remaining empty sites giving rise to the appearance of cooperative phenomena. Although crystallographic data have evidenced that this structural change increases the protein water-accessible surface area, isobaric osmotic stress experiments in aqueous cosolutions have shown that water binding is linked to Hb oxygenation. Now we show that the differential hydration between fully oxygenated and fully deoxygenated states of these proteins, determined by weighing protein films with a quartz crystal microbalance, agree with the ones determined by osmotic stress in aqueous cosolutions, from the linkage between protein oxygen affinity and water activity. The agreements prove that the changes in water activity brought about by adding osmolytes to the buffer solution shift biochemical equilibrium in proportion to the number of water molecules associated with the reaction. The concomitant kinetics of oxygen and of water binding to Hb have been also determined. The data show that the binding of water molecules to the extra protein surface exposed on the transition from the low-affinity T to the high-affinity R conformations of hemoglobin is the rate-limiting step of Hb cooperative reaction. This evidences that water binding is a crucial step on the allosteric mechanism regulating cooperative interactions, and suggests the possibility that environmental water activity might be engaged in the kinetic control of some important reactions in vivo.

Sol-gel entrapped cobalt complex

This work describes optimized conditions for preparation of a cobalt complex entrapped in alumina amorphous materials in the form of powder. The hybrid materials, CoNHG, were obtained by a nonhydrolytic sol-gel route through condensation of aluminum chloride with diisopropylether in the presence of cobalt chloride. The materials were calcined at various temperatures. The presence of cobalt entrapped in the alumina matrix is confirmed by ultraviolet visible spectroscopy. The materials have been characterized by X-ray diffraction (XRD), surface area analysis, thermogravimetric analysis (TGA), differential thermal analyses (DTA) and transmission electron microscopy (TEM). The prepared alumina matrix materials are amorphous, even after heat treatment up to 750 degreesC. The XRD, TGA/DTA and TEM data support the increase of sample crystallization with increasing temperature. The specific surface area, pore size and pore diameter changed as a function of the heat treatment temperature employed. Different heat treatment temperatures result in materials with different compositions and structures, and influence their catalytic activity. The entrapped cobalt materials calcined at 750 degreesC efficiently catalyzed the epoxidation of (Z)-cyclooctene using iodozylbenzene as the oxygen donor. (C) 2003 Elsevier B.V. All rights reserved.

Synthesis of nanocrystalline tetragonal zirconia by a polymeric organometallic method

A polymeric precursor method based on the Pechini process was successfully used to synthesize zirconia-12 mol% ceria ceramic powders, the influence of the main process variables (citric acid-ethylene glycol ratio, citric acid-total oxides ratio and calcination temperature) on phase formation and powder morphology (surface area and crystallite size) were investigated. The thermal decomposition behavior of the precursor is presented. X-ray diffraction (XRD) patterns of powders revealed a crystalline tetragonal zirconia single-phase, with crystallite diameter ranging from 6 to 15 nm. The BET surface areas were relatively high, reaching 95 m(2) g(-1) Nitrogen adsorption/desorption on the powders suggested that nonaggregated powders could be attained, depending on the synthesis conditions. Copyright (C) 1999 John Wiley & Sons, Ltd.

Low-temperature synthesis of single-phase Co7Sb2O12

Polycrystalline Co7Sb2O12 compounds have been synthesized by a chemical route, which is based on a modified polymeric precursor method. In order to study the physical properties of the samples, X-ray diffraction (XRD), thermal analyses (TG and DSC), infrared spectroscopy (IR), specific surface area (BET), and magnetization measurements were performed on these materials. Characterization through XRD revealed that the samples are single-phase after a heat-treatment at 1100degreesC for 2h, while the X-ray patterns of the samples heat-treated at lower temperatures revealed the presence of additional Bragg reflections belonging to the Co6Sb2O6 phase. These data were analyzed by means of Rietveld refinement and further analyze showed that Co7Sb2O12 displays an inverse spinel crystalline structure. In this structure, the Co2+ ions occupy the eight tetrahedral positions, and the sixteen octahedral positions are randomly occupied by the Sb5+ and Co2+ ions. IR studies disclosed two strong absorption bands, v(1) and v(2), in the expected spectral range for a spinel-type binary oxide with space group Fd3m. Exploratory studies concerning the magnetic properties indicated that this sample presents a spin-glass transition at T-f similar to 64 K. (C) 2004 Elsevier B.V. All rights reserved.