Structural modifications in stretch-induced crystallization in PVDF films as measured by small-angle X-ray scattering

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

A Raman and dielectric study of a diffuse phase transition in (Pb1-xCax)TiO3 thin films

Dielectric and Raman scattering experiments were performed on polycrystalline Pb1-xCaxTiO3 thin films (x=0.10, 0.20, 0.30, and 0.40) as a function of temperature. The results showed no shift in the dielectric constant (K) maxima, a broadening with frequency, and a linear dependence of the transition temperature on increasing Ca2+ content. on the other hand, a diffuse-type phase transition was observed upon transforming from the cubic paraelectric to the tetragonal ferroelectric phase in all thin films. The temperature dependence of Raman scattering spectra was investigated through the ferroelectric phase transition. The temperature dependence of the phonon frequencies was used to characterize the phase transitions. Raman modes persisted above the tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of a breakdown of the local cubic symmetry due to chemical disorder. The lack of a well-defined transition temperature and the presence of broad bands in some temperature interval above the FE-PE phase transition temperature suggested a diffuse-type phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in these thin films.

Global and diffuse solar irradiances in urban and rural areas in southeast Brazil

The seasonal evolution of daily and hourly values of global and diffuse solar radiation at the surface are compared for the cities of São Paulo and Botucatu, both located in Southeast Brazil and representative of urban and rural areas, respectively. The comparisons are based on measurements of global and diffuse solar irradiance carried out at the surface during a six year simultaneous period in these two cities. Despite the similar latitude and altitude, the seasonal evolution of daily values indicate that São Paulo receives, during clear sky days, 7.8% less global irradiance in August and 5.1% less in June than Botucatu. on the other hand, São Paulo receives, during clear sky days, 3.6% more diffuse irradiance in August and 15.6% more in June than Botucatu. The seasonal variation of the diurnal cycle confirms these differences and indicates that they are more pronounced during the afternoon. The regional differences are related to the distance from the Atlantic Ocean, systematic penetration of the sea breeze and daytime evolution of the particulate matter in São Paulo. An important mechanism controlling the spatial distribution of solar radiation, on a regional scale, is the sea breeze penetration in São Paulo, bringing moisture and maritime aerosol that in turn further increases the solar radiation scattering due to pollution and further reduces the intensity of the direct component of solar radiation at the surface. Surprisingly, under clear sky conditions the atmospheric attenuation of solar radiation in Botucatu during winter - the biomass burning period due to the sugar cane harvest - is equivalent to that at São Paulo City, indicating that the contamination during sugar cane harvest in Southeast Brazil has a large impact in the solar radiation field at the surface.

Analysis of hourly global, direct and diffuse solar radiations attenuation as a function of optical air mass

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

Annual evolution of global, direct and diffuse radiation and fractions in tilted surfaces

Avaliou-se a evolução anual das componentes global, direta e difusa da radiação solar incidente em superfícies inclinadas a 12,85; 22,85 e 32,85º, com face voltada ao Norte, em Botucatu-SP. Foram obtidas frações radiométricas para cada componente da radiação nas superfícies supracitadas, através de razões com a radiação global e a do topo da atmosfera. A sazonalidade foi avaliada através das médias mensais dos valores diários. As medidas ocorreram entre 04/1998 e 07/2001, em 22,85º; 08/2001 e 02/2003, em 12,85º; e de 03/2003 a 12/2007, em 32,85º, com medidas concomitantes no plano horizontal (referência). Os níveis das radiações global e direta nos planos inclinados foram inferiores no período de verão e superiores entre os equinócios, quando comparadas ao plano horizontal. A radiação difusa nas superfícies inclinadas foi inferior na maioria dos meses, com perdas de até 65%. Ocorreu uma tendência de aumento das diferenças entre as superfícies horizontal e inclinada com o incremento do ângulo em todas as componentes e frações da radiação incidente. A evolução anual das precipitações pluviométricas e da razão de nebulosidade afetou diretamente a transmissividade atmosférica das componentes direta e difusa na região.

The role of clouds in improving the regression model for hourly values of diffuse solar radiation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Estimativas das componentes da radiação solar incidente em superfícies inclinadas baseadas na radiação global horizontal

Statistics equations and validations with groups of annual and monthly data were evaluated for global, direct and diffuse solar radiation components incident on the tilted surface to 12.85, 22.85 and 32.85 degrees with the face North, in climate and geographical conditions of Botucatu, SP. It was employed the fractions of three components of extraterrestrial radiation in correlation with the coefficient clearness index horizontal plane, in a database of April/1998 to December/2007, whose measures at different periods in three inclinations, however concomitant to the horizontal plane. Increasing the angle of the surface led to increased scattering of the daily values of clearness index for inclined and horizontal surfaces. In annual groups, the lower performances were observed in the estimation of inclined daily diffuse radiation, with maximum Root Mean Square Error to 3.89 MJ m(-2) d(-1) (43.65%) and adjustments around 62%. In estimates of global and direct components of solar radiation on inclined planes, both annual and monthly equations can be applied, with performance dependents to climatic conditions.

Estimativa da radiação global incidente em superfícies inclinadas por modelos isotrópicos e índice de claridade

O objetivo deste trabalho foi avaliar o desempenho de modelos isotrópicos de estimativa do total de radiação incidente em superfícies inclinadas e propor estimativas com base nas correlações entre os índices de claridade horizontais e inclinados, em diferentes condições de cobertura de céu, em Botucatu, SP. Foram avaliadas superfícies com inclinação de 12,85º, 22,85º e 32,85º, pelos modelos isotrópicos propostos por Liu & Jordan, Revfeim, Jimenez & Castro, Koronakis, a teoria Circunsolar, e a correlação entre os índices de claridade horizontais e inclinados, para diferentes condições de cobertura de céu. O banco de dados de radiação global utilizado corresponde ao período de 1998 a 2007, com intervalos de 4/1998 a 8/2001 para a inclinação de 22,85º, de 9/2001 a 2/2003 para 12,85º e de 1/2004 a 12/2007 para 32,85º. O desempenho dos modelos foi avaliado pelos indicadores estatísticos erro absoluto médio, raiz quadrada do quadrado médio do erro e índice d de Wilmott. Os modelos de Liu & Jordan, Koronakis e de Revfeim apresentaram os melhores desempenhos em dias nublados, em todas as inclinações. As coberturas de céu parcialmente difuso e parcialmente aberto, nos maiores ângulos de inclinação, apresentaram as maiores dispersões entre valores estimados e medidos, independentemente do modelo. As equações estatísticas apresentaram bons resultados em aplicações com agrupamentos de dados mensais.

Surface-enhanced Raman scattering and micro-Raman imaging of Langmuir-Blodgett films of rhodium phthalocyanine

Rhodium phthalocyanine (RhPc) was synthesized and ultra thin Langmuir-Blodgett (LB) films of RhPc were successfully fabricated. The LB film characterization was carried out using both UV-vis absorption spectra and Raman scattering. The Raman spectroscopy was carried out using 633 and 780 nm laser lines. LB films were deposited onto Ag nanoparticles to achieve the surface-enhanced pre-resonance Raman scattering (pre-SERRS) and surface-enhanced Raman scattering (SERS) for both laser lines, respectively, which allowed the characterization of the RhPc ultra thin films. The morphology of the LB RhPc neat film is extracted from micro-Raman imaging. (C) 2003 Elsevier B.V. All rights reserved.

Surface-enhanced resonance Raman scattering: Single-molecule detection in a Langmuir-Blodgett monolayer

Surface-enhanced resonance Raman scattering (SERRS) is used for single-molecule detection from spatially resolved 1-mum(2) sections of a Langmuir-Blodgett (LB) monolayer deposited onto a Ag film. The target molecule, his (benzimidazo) thioperylene (BZP), is dispersed in an arachidic acid monomolecular layer containing one BZP molecule per mum(2) which is also the probing area of the Raman microscope. For concentrated samples (attomole quantities in the field of view), average SERRS, surface-enhanced fluorescence (SEF), and Raman imaging, including line mapping and global images at different temperatures, were recorded. Single-molecule SERRS spectra, obtained using an LB monolayer, present changes in bandwidth and relative intensities, highlighting the properties of single-molecule SERRS that are lost in average SERRS measurements of mixed LB monolayers obtained at the same temperatures. Also, the dilute system phenomenon of blinking is discussed with regard to results obtained from LB monolayers. The dilution process used in the single-molecule LB SERRS work is independently supported by fluorescence results obtained from very dilute solutions with monomer concentrations down to 10(-12) M.

Incorporation of Ag nanoparticles into membrane mimetic systems composed by phospholipid layer-by-layer (LbL) films to achieve surface-enhanced Raman scattering as a tool in drug interaction studies

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

Coupling Surface-Enhanced Resonance Raman Scattering and Electronic Tongue as Characterization Tools to Investigate Biological Membrane Mimetic Systems

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

Surface-enhanced raman scattering: metal nanostructures coated with langmuir-blodgett films

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

Self-assembling of phenothiazine compounds investigated by small-angle X-ray scattering and electron paramagnetic resonance spectroscopy

Small-angle X-ray scattering (SAXS) and electron paramagnetic resonance (EPR) have been carried out to investigate the structure of the self-aggregates of two phenothiazine drugs, chlorpromazine (CPZ) and trifluoperazine (TFP), in aqueous solution. In the SAXS studies, drug solutions of 20 and 60 mM, at pH 4.0 and 7.0, were investigated and the best data fittings were achieved assuming several different particle form factors with a homogeneous electron density distribution in respect to the water environment. Because of the limitation of scattering intensity in the q range above 0.15 angstrom(-1), precise determination of the aggregate shape was not possible and all of the tested models for ellipsoids, cylinders, or parallelepipeds fitted the experimental data equally well. The SAXS data allows inferring, however, that CPZ molecules might self-assemble in a basis set of an orthorhombic cell, remaining as nanocrystallites in solution. Such nanocrystals are composed of a small number of unit cells (up to 10, in c-direction), with CPZ aggregation numbers of 60-80. EPR spectra of 5- and 16-doxyl stearic acids bound to the aggregates were analyzed through simulation, and the dynamic and magnetic parameters were obtained. The phenothiazine concentration in EPR experiments was in the range of 5-60 mM. Critical aggregation concentration of TFP is lower than that for CPZ, consistent with a higher hydrophobicity of TFP. At acidic pH 4.0 a significant residual motion of the nitroxide relative to the aggregate is observed, and the EPR spectra and corresponding parameters are similar to those reported for aqueous surfactant micelles. However, at pH 6.5 a significant motional restriction is observed, and the nitroxide rotational correlation times correlate very well with those estimated for the whole aggregated particle from SAXS data. This implies that the aggregate is densely packed at this pH and that the nitroxide is tightly bound to it producing a strongly immobilized EPR spectrum. Besides that, at pH 6.5 the differences in motional restriction observed between 5- and 16-DSA are small, which is different from that observed for aqueous surfactant micelles.

Investigation in SrTiO3-CaTiO3-PbTiO3 ternary thin films by dielectric proprieties and Raman spectroscopy

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