From sol to aerogel: a study of the nanostructural characteristics of TEOS derived sonogels

The nanostructural characteristics of acid-catalyzed sonogels are studied along the aging process at 60 degreesC in saturated conditions and after the CO, supercritical extraction (aerogel). The structural evolution was studied by means of small-angle X-ray scattering (SAXS) and UV-Visible absorption techniques. The sonogel exhibits a mass fractal structure in a length scale between zeta - 1/q(0) similar to 5.3 and a(1) similar to 1/q(m) similar to 0.22 nm, as the length scale probed by SAXS. The apparent mass fractal dimension lightly increases from 2.0 for fresh gel until 2.2 for 14 days aging in wet conditions. The UV absorption also increases with the aging time in wet conditions. Both observations are consistent with the syneresis process accompanying the polycondensation progress during aging in saturated conditions. For long aging times, the wet sonogels show a light transition from a mass to a surface fractal. in a very small interval of the length scale, developing an extremely rough surface with fractal dimension D-S similar to 2.9, the fractal characteristics of the sonogels practically do not change with the alcohol exchange. With the CO2 supercritical extraction (aerogel). The interval in the length scale in which the surface fractal is defined increases, while the surface fractal dimension diminishes to D-S similar to 2.5. The mass fractal characteristics are less apparent in the aerogels. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Nanocrystalline anatase thin films prepared from redispersible sol-gel powders

Transparent thin films of nanocrystalline anatase were obtained by dip-coating process using an ethanolic suspension of redispersed nanoparticles. This suspension was prepared by sol-gel route and their redispersability achieved by surface grafting of para-toluene-sulfonic acid and acetylacetone. The effects of the acetylacetone content on the powder redispersibility and on the structural evolution of films were determined by small angle X-ray scattering, X-ray reflectometry and X-ray diffraction for different firing temperatures. The results demonstrated that the porous structure of the studied films consist of agglomerates of primary particles with two levels of porosity. The control of the amount of capping ligand allows for a fine-tuning of the average pore size of the dried films. Upon increasing the firing temperature up to 500 degrees C, progressive increase in apparent density, average pore size of films and average crystallite size of powders were observed. (c) 2005 Elsevier Ltd. All rights reserved.

Small-angle X-ray scattering and nitrogen adsorption study of the nanoporosity elimination in TEOS sonohydrolysis-derived xerogels

Small-angle X-ray scattering (SAXS) and nitrogen adsorption techniques were used to study the temperature and time structural evolution of the nanoporosity in silica xerogels prepared from acid- and ultrasound-catalyzed hydrolysis of tetraetboxysilane (TEOS). Silica xerogels present a structure of nanopores of fully random shape, size, and distribution, which can be described by an exponential correlation function gamma(r) = exp (-r/a), where a is the correlation distance, as predicted by the Debye, Anderson, and Brumberger (DAB) model. The mean pore size was evaluated as about 1.25 nm from SAXS and about 1.9 nm from nitrogen adsorption. The nanopore elimination in TEOS sonohydrolysis-derived silica xerogels is readily accelerated at temperatures around 900 degrees C probably by the action of a viscous flow mechanism. The nanopore elimination process takes place in such a way that the pore volume fraction and the specific surface are reduced while the mean pore size remains constant. (c) 2005 WILEY-VCH Verlag GmbH S Co. KGaA, Weinheim.

SAXS study of gelation, aging and drying of silica-polypropyleneglycol hybrid materials

New silica-polypropyleneglycol ormosils (organically modified silicates) with covalent bends between the organic (polymer) and inorganic (silica) phases have been prepared by the sol-gel process. Their structural evolution during sol formation, sol-gel transition, gel aging and drying has been studied in situ by small-angle X-ray scattering (SAXS). The experimental SAXS curves corresponding to sols and gels exhibit features expected from fractal objects. Clusters of size around 55 Angstrom with an initial fractal dimension D = 2.4 are formed in the sol. They are constituted of small primary silica particles chemically crosslinked at the end of the polymer chains. A strong liquid-like spatial correlation between the silica particles develops during drying due to the shrinkage of the polymeric network induced by water and ethanol evaporation. The continuous increase in SAXS intensity during drying, while the interparticle distance remains constant, is a consequence of the progressive growth of the dry fraction of the total volume. After drying, the gel structure consists of a rather compact arrangement of silica particles embedded in the polypropyleneglycol matrix.

Experimental and theoretical investigation of the room-temperature photoluminescence of amorphized Pb(ZrTi)O-3

Ultrafine PbZr0.20Ti0.80O3 was omorphized through high-energy mechanical milling. The structural evolution through the omorphization process was accompanied by various characterization techniques, such as X-ray diffraction, Fourier-transformed IR spectroscopy (FTIR), high-resolution transmission electron microscopy (HR-TEM), and Raman spectroscopy. A strong photoluminescence was measured at room temperature for amorphized PbZr0.20Ti0.80O3, and interpreted by means of high-level quantum mechanical calculations in the density functional theory frame-work. Three periodic models were used to represent the crystalline and amorphized PbZr0.20Ti0.80O3, and they allowed the calculation of electronic properties that are consistent with the experimental data and that explain the appearance of photoluminescence.

Disorder-dependent photoluminescence in Ba0.8Ca0.2TiO3 at room temperature

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

Strong violet-blue light photoluminescence emission at room temperature in SrZrO3: Joint experimental and theoretical study

Ultrafine ordered and disordered SrZrO3 powders were prepared by the polymeric precursor method. The structural evolution from structural disorder to order was monitored by X-ray diffraction and X-ray absorption near-edge spectroscopy. Complex cluster vacancies [ZrO5 center dot V-O(Z)] and [SrOII center dot V-O(Z)] (where V-O(Z) = V-O(X), V-O(center dot) and V-O(center dot center dot)) were proposed for disordered powders. The intense violet-blue light photoluminescence emission measured at room temperature in the disordered powders was attributed to complex cluster vacancies. High-level quantum mechanical calculations within the density functional theory framework were used to interpret the experimental results. (C) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Synthesis and photoluminescence behavior of Bi4Ti3O12 powders obtained by the complex polymerization method

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Photoluminescent properties of lead zirconate powders obtained by the polymeric precursor method

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Spectroscopic characterization of SnO2 gels - Code: CP11

Excitation and dynamic emission spectra of Eu3+ ions were simultaneously used with FTIR and Raman spectroscopy to study the structural evolution during SnO2 sol → gel → xerogel conversion. Results make evident an increase of the surroundings symmetry for the Eu3+ ions dissolved in SnO2 matrix and a decrease of the amount of hydroxo groups (Sn-OH) during drying. These phenomena were associated to the pursuit of the condensation reaction after gelation. © 1994 Kluwer Academic Publishers.

Northwestern overthrusting and related lateral escape during the Brasiliano orogeny north of the Patos lineament, Borborema province, northeast Brazil

The Borborema province (BP) of northeastern Brazil, located between the São Luís and São Francisco cratons, represents a branching system of Precambrian orogens of the South American platform. It is composed of segments of Archean and Proterozoic crust that were deformed by the convergence of the West African and São Francisco-Congo cratons during assembly of the Brasiliano collage (650 to 500 Ma), a period of intense orogenic activity considered to be the strongest and most pervasive tectonic event that affected the Precambrian of the South American platform. The tectonic and kinematic history of the Brasiliano/Panafrican orogeny is fundamental for reconstructing South American and African Precambrian geology. The correlation between Neoproterozoic tectonic processes occurring in both continents should use structural elements, of regional or local character, with identical kinematic and metamorphic conditions manifested in both basement and supracrustal units. North of the Patos shear zone, subhorizontal Brasiliano thrusts (0.65 to 0.58 Ga) affected the basement and the supracrustal Seridó belt with such related regional D1/D2 structures as foliation, lineation, isoclinal folds, and related metamorphism. Overprinting the previous structures, regional folding with a vertical S3 foliation and an associated strike-slip shear zone were developed (0.58 to 0.52 Ga). The metamorphism is similar for all deformation phases, ranging from upper-greenschist to amphibolite facies with mineral assemblages including biolite and garnet throughout the Seridó fold belt. We propose, on the basis of deformational and kinematic reconstructions, that the structural evolution of the Seridó fold belt was characterized by transition from a syn-collisional to a strike-slip regime. The transition between regimes occurred, progressively or instantaneously, by the switching of the maximum and intermediary strain axes of the strain ellipsoid. The entire tectonic history can be related to a frontal or oblique collision and lateral escape tectonics, with local, syn-collisional transpression and transtension. The Patos shear zone represents a final vertical shearing, juxtaposing different terranes of the northern and southern Borborema province.

Study of Hybrid Silica-Polyethyleneglycol Xerogels by Eu3+ Luminescence Spectroscopy

Good optical quality Eu3+-doped silica-polyethyleneglycol hybrids were prepared by the sol-gel process. Thermomechanical analysis showed an increase of the glass transition temperature, due to the stiffness of the polymeric network, as the amount of Eu3+ increased. Europium luminescent properties were used to study structural evolution during the sol-gel transition. For lower doping concentrations dried gels present statistical distributions of Eu3+, typical of an amorphous environment, while for higher concentrations a crystalline-like environment of Eu3+ was observed. A broad emission band was observed in the visible part of the electromagnetic spectrum and assigned to the intrinsic emission from the hybrid polymeric network.

Contexto tectônico dos granitóides neoproterozóicos da faixa de dobramentos paraguai, MS e MT

The Neoproterozoic Granitic Province from the southeast of Mato Grosso and Mato Grosso do Sul region is constituted by seven distinctive granitic bodies, emplaced in the epimetamorphic rocks of the Cuiabá Group and related to the evolution of Paraguai Folded Belt. The Northern portion crops out in Mato Grosso State and is constituted by São Vicente, Araguaiana and Lajinha batholiths; the Southern portion crops out in the Mato Grosso do Sul State and is represented the Sonora, Coxim Rio Negro and Taboco massifs. The structural evolution is evidenced by the presence of three deformational phases, the first one is characterized by axial planar foliation (S 1), parallel or sub parallel to S 0, with attitude N60E/70NW; the second constitutes the most important phase for the tectonic arrangement and is defined by a slaty and/or crenulation cleavages (S 2), with attitude N10W/30SW and contact metamorphism associated to the emplacement of granitic bodies, the third phase is characterized by a weak retrometamorphic cleavage (S 3) with attitude N10E/ 80NW, that evolves local and gradually to strike-slip shear zones. The geological data suggest that this province was formed syn- to post tectonic to the D2 deformational set associated to the end of the collisional event in the Southeastern of the Amazonian Craton.

Contexto geológico e estrutural do Maciço Rio Apa, sul do Cráton amazônico - MS

Rio Apa Massif crops out in the Mato Grosso do Sul state and corresponds to the southeastern portion of the Amazonian Craton dominantly Paleoproterozoic in age. Rio Apa Complex is oldest and it is composed mainly by migmatitic orthogneisses, beyond amphybolites, tonalities and granodiorite. Alto Tererê Group is composed by schists, biotitemuscovite gneisses and micaceous quartzites generally rich in garnets, beyond metabasic rocks of low amphibolite facies. The Amoguijá Group is constituted by Alumiador Intrusive Suite, which is represented by a sieno to monzogranitic batholith and Serra da Bocaina Volcanic Suite composed of volcanoclastic rocks of alkali riolites to monzoriolites compositions and pyroclastic products. Overlaying towards East and South occurs Neoproterozoic metasedimentary rocks from the Paraguai Folded Belt (Cuiabá, Corumbá and Jacadigo Groups - Urucum Formation). Structural-metamorphic framewok is identified by five deformational phases but the actual tectonic and metamorphic structure shows the superposed tectonic array of the Paraguai Folded Belt. Rocks from Rio Apa Complex, Alto Tererê Group and Amoguijá Group record an older structural evolution defined by (Dn-1 and Dn). The deformational phases (Dn+1 and Dn+2) are visible mainly in rocks of Paraguai Folded Belt beyond the last deformation (Dn+3) that imprints all sequences.

Propriedades estruturais de géis obtidos a partir de sono-hidrólise de TEOS e troca de fase líquida por acetona

Pós-graduação em Física - IGCE