Small angle X-ray scattering and IR spectroscopy study of metal carbonyl complexes immobilized on a silica gel surface chemically modified with piperazine

The carbonyl complexes [WCl(CO)(3)(bipy) (HgCl)] (1), [Fe(CO)(4)(HgCl)(2)] (2) and W(CO)(6)] (3) were immobilized on a silica gel surface organofunctionalized with piperazine groups. The products obtained were studied by IR spectroscopy and small angle X-ray scattering (SAXS) techniques. The IR data show that the immobilization of heterobimetallic compounds 1 and 2, on the functionalized surface, occurred through the mercury atom, while for 3 the displacement of one CO group by the nitrogen of a piperazine molecule was observed. The data obtained from SAXS indicate that particles have a uniform size and reveal suitable modifications on the functionalized surface after immobilization of metal carbonyl complexes. The average intermolecular distance (l(ij)) for piperazine ligands on support is 8.7 Angstrom, for the metal carbonyl complex 1 it is 18.8 Angstrom, for complex 2 it is 16.2 Angstrom and for complex 3 it is 15.3 Angstrom. Copyright (C) 1996 Elsevier B.V. Ltd

Characterization of tin oxide based sol-gel coatings on borosilicate glasses by X-ray reflectivity

The X-ray reflectivity technique was applied in the study of tin oxide films deposited by sol-gel dip-coating on borosilicate glasses. The influence of the withdrawal speed and temperature of thermal treatment on the film structure was analyzed. We have compared the thermal evolution of the density and the shrinkage of the films with these properties measured for the monolithic xerogel by helium picnometry and thermomechanical analysis. In agreement with the Landau-Levich model, the layer thickness increases by increasing the withdrawal speed. Nevertheless, it decreases with the increase of the thermal treatment temperature, due to the densification process. The values of apparent density are smaller than the skeletal density, which shows that the films are porous. The comparison between the film and the monolith indicates that shrinkage during firing is anisotropic, occurring essentially perpendicular to the coating surface.

Density improvement of the sol-gel dip-coated SnO2 films by chemical surface modification

We compare the effect of organic (Tiron (R)) and inorganic (Mn(11)) additives on the low temperature (< 600 degrees C) densification of the sol-gel dip-coated SnO2 films. The structural and compositional properties of the samples were investigated by X-ray reflectometry (XRR), X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). The results suggest that the replacement of hydroxyl groups at the particle surface by Tiron (R) reduces the level of agglomeration of the sol, increasing the particles packing and the apparent density of the coatings. Undoped and Mn-doped films drawn from a Tiron (R) containing suspension show after firing at 500 degrees C a porosity reduction of 12 and 8.6%, respectively. The porosity decrease is less pronounced (4.3%) for the film without additives. Both XAS and XPS data show the presence of trivalent manganese. The formation of a non-homogeneous solid solution characterised by the presence of Mn(111) replacing tin atom near to the crystallite surface was evidenced by XAS. Additionally, XPS results reveal the presence of metallic Sn at the surface of films containing Tirono. (c) 2005 Elsevier Ltd. All rights reserved.

Effect of reaction time on the particle size of ZnO and ZnO : Ce obtained by a sol-gel method

In this work particles of ZnO of size range 33-56 Angstrom were prepared by a sol-gel method. The effect of reaction time on the particle size of ZnO or ZnO:Ce was investigated by transmission electron microscopy measurements, UV-vis absorption and luminescence spectroscopy. A linear increase of the mean particle size is observed as a function of reaction time. The cerium-doped particles are bigger than the pure ZnO ones obtained at the same reaction time. A shift to lower energy at the maximum of the bands is observed in all absorption, emission and excitation spectra as a function of particle growth. From the absorption spectra the optical energy gap values (Eg) for these particles were determined. In the quantum size regime, Eg was found to decrease with particle growth.

Study of the selectivity of SnO2 supported membranes prepared by a sol-gel route

In this work the sol-gel process was used to prepare SnO2 supported membranes with an average pore size of 2.5 nm. The effects of salt concentration (NaCl or CaCl2) and of the pH of the aqueous solutions used on the flux and selectivity through the SnO2 membrane were analyzed by permeation experiments and the results interpreted taking account of the zeta potential values determined from the electrophoretic mobility of the SnO2 powder aqueous dispersion. The results show that the ion flux (Na+, Ca2+ and Cl-) throughout the membrane is determined by the electrostatic repulsion among these species and the surface charge at the tin oxide-solution interface.

Nanostructure and luminescent properties of sol-gel derived europium-doped amine functionalised hybrids

The effect of doping by europium triflate on the nanoscopic structure of organic-inorganic hybrid formed by a siliceous network containing pendant amine-terminated propyl chains, called aminosils, was investigated by Small-Angle X-ray Scattering (SAXS). It appears that the composites exhibit a two-level structure. The first level consists of well-condensed cubic-like siloxane octamers, with a radius of gyration around 2 angstrom. The second level is formed by the aggregation of these siloxane nanodomains to form larger structures, in which the nanodomains are spatially correlated and separated by the organic pendant chains. Europium doping inhibits the aggregation between siloxane octamers, leading to a less compact second-level structure. This can be explained by the Eu3+ stop coordination close to the external surface of the siloxane nanodomains, as detected by luminescence spectroscopy.

Wettability and photodegradation activity of sol-gel dip-coated zinc oxide films

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Small-angle X-ray and nuclear-magnetic resonance study of siloxane-PMMA hybrids prepared by the sol-gel process

Transparent siloxane-polymethylmethacrylate (PMMA) hybrids were synthesized by the sol-gel process through hydrolysis of methacryloxyproyltrimethoxysilane (TMSM), tetramethoxysilane (TMOS) and polymerization of methylmethacrylate (MMA) using benzol peroxide (BPO) as catalyst. These composites have a good chemical stability due to the presence of covalent bonds between the inorganic (siloxane) and organic (PMMA) phases. The effects of siloxane content, pH of the initial sol and BPO content on the structure of the dried gels were analyzed by small-angle X-ray scattering (SAXS). SAXS results revealed the presence of an interference (or correlation) peak at medium q-range for all compositions, suggesting that siloxane groups located at the ends of PMMA chains form isolated clusters that are spatially correlated. The average intercluster distance - estimated from the q-value corresponding to the maximum in SAXS spectra - decreases for samples prepared with increasing amount of TMSM-TMOS. This effect was assigned to the expected increase in the number density of siloxane groups for progressively higher siloxane content. The increase of BPO content promotes a more efficient polymerization of MMA monomers but has no noticeable effect on the average intercluster distance. High pH favors polycondensation reactions between silicon species of both TMOS and TMSM silicon alcoxides, leading to a structure in which all siloxane clusters are bonded to PMMA chains. This effect was confirmed by Si-29 nuclear-magnetic resonance (NMR) measurements.

Gelation and drying of weakly bonded silica-PPO nanocomposites

Silica-poly(oxypropylene) (PPO) nanocomposites containing PPO with weak physical bonds between the organic (PPO) and inorganic (silica) phases were obtained by the sol-gel procedure. Three precursor sols containing silica and PPO with molecular weights of 1000, 2000 and 4000g/mol were prepared. The structure changes during the whole sol-gel process, i.e. sol formation, sol-gel transition and gel aging and drying were investigated in situ by small angle X-ray scattering (SAXS). The experimental SAXS curves corresponding to sols and wet gels containing PPO of molecular weight 1000g/mol indicate that the aggregates formed during the studied process are fractal objects. Close to the sol-gel transition and during gel aging the fractal dimension is D=2.5. A clearly different structure evolution occurs in samples prepared with PPO with molecular weights 2000 and 4000 g/mol. Our SAXS results indicate the presence of two coexisting and well-defined structure levels, one of them corresponding to small silica clusters and the other to large silica aggregates. These two levels remain along the whole transformation. The SAXS curves of all dry samples are similar to those of the corresponding wet gels suggesting that no significant changes at nanoscopic scale occur during the drying process.

Study of the annealing temperature effect on the structural and luminescent properties of SrWO4:Eu phosphors prepared by a non-hydrolytic sol-gel process

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Active planar waveguides based on sol-gel Er3+-doped SiO2-ZrO2 for photonic applications: Morphological, structural and optical properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Succession and management of tropical dry forests in the Americas: Review and new perspectives

Understanding tropical forest succession is critical for the development of tropical forest conservation strategies worldwide, given that tropical secondary forests can be considered the forests of the future. Tropical dry forests (TDF) are among the most threatened tropical ecosystems, there are more secondary forests and forest restoration efforts that require a better understanding of successional processes. The main goal of this synthesis for this special issue on the ecology and management of tropical dry forests in the Americas is to present a summarized review of the current knowledge of the ecology and management implications associated to TDF succession. We explore specific issues associated to tropical dry forest succession with emphasis on the use of chronosequences, plant diversity and composition, plant phenology and remote sensing, pollination, and animal-plant interactions; all under the integrating umbrella of ecosystem succession. We also emphasize the need to conduct socio-ecological research to understand changes in land-use history and its effects on succession and forest regeneration of TDF. We close this paper with some thoughts and ideas associated with the strong need for an integrating dimension not considered until today: the role of cyberinfrastructure and eco-informatics as a tool to support sound conservation, management and understanding of TDF in the Americas. (C) 2009 Elsevier B.V. All rights reserved.

Broadband NIR Emission in Sol-Gel Er(3+)-Activated SiO(2)-Ta(2)O(5) Glass Ceramic Planar and Channel Waveguides for Optical Application

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)