14 resultados para polymer gel dosimetry
em Repositório Institucional UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho"
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
Small-angle X-ray scattering study of sol-gel-derived siloxane-PEG and siloxane-PPG hybrid materials
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Hybrid organic-inorganic two-phase nanocomposites of siloxane-poly(ethylene glycol) (SiO3/2-PEG) and siloxane-poly(propylene glycol) (SiO3/2-PPG) have been obtained by the sol-gel process. In these composites, nanometric siloxane heterogeneities are embedded in a polymeric matrix with covalent bonds in the interfaces. The structure of these materials was investigated in samples with different molecular weights of the polymer using the smalt-angle X-ray scattering (SAXS) technique. The SAXS spectra exhibit a well-defined peak that was attributed to the existence of a strong spatial correlation of siloxane clusters. LiClO4-doped siloxane-PEG and siloxane-PPG hybrids, which exhibit good ionic conduction properties, have also been studied as a function of the lithium concentration [O]/[Li], O being the oxygens of ether type. SAXS results allowed us to establish a structural model for these materials for different basic compositions and a varying [Li] content. The conclusion is consistent with that deduced from ionic conductivity measurements that exhibit a maximum for [O]/[Li] =15.
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The aggregation, gelation, and aging of urea-cross-linked siloxane-poly(oxyethylene) nanohybrids [(U600)-n] containing two different amounts of europium triflate initially dissolved in an ethanol-water mixture were investigated by in situ small-angle X-ray scattering (SAXS). For both low (n = [O]/[Eu] = 80) and high (n = 25) europium contents, the SAXS intensity was attributed to the formation of siloxane clusters of about 8-11 Angstrom in size. Siloxane cluster formation and growth is a rapid process in hybrids with low Eu contents and slow in Eu-rich hybrids. An additional contribution to the scattering intensity at very low angles was attributed to the formation of a coarse structure level. At this secondary level, the structure can be described as a set of dense domains containing siloxane clusters embedded in a depleted matrix composed of unfolded polymer chains and solvent. By fitting a theoretical function for this model to the experimental SAXS curves, relevant structural parameters were determined as functions of time during the sol-gel transition and gel aging. For hybrids with low europium contents (n = 80), the size of the siloxane clusters remains essentially invariant, whereas the dense segregation domains progressively grow. In hybrids with high doping contents (n = 25), the preponderant structure variation during the first stages of the sol-gel transformation is the slow growth of siloxane clusters. For these hybrids, the segregation of siloxane clusters forming dense domains occurs only during advanced stages of the process.
EXAFS, SAXS and Eu3+ luminescence spectroscopy of sol-gel derived siloxane-polyethyleneoxide hybrids
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Hybrid Eu3+-doped silica-poliethyleneoxide (PEO) nanocomposites with covalent bonds between the inorganic (siloxane) and organic (PEO) phases have been obtained by sol-gel process. These materials are transparent, flexible and present high Eu3+ luminescence output. Their luminescence properties, local environment around europium ions and structure have been investigated as a function of europium content. EXAFS measurements indicate that the increase in Eu-doping induces a decrease in Eu3+ coordination number. An increase in symmetry degree around the metal ion is also observed for increasing Eu3+ concentration, while non radiative decay paths from the D-5(0) excited state become more important. SAXS results suggest the preferential interaction of europium ions with ether-type oxygens of the polymer chains. However, the existence of interactions between the cations and the carbonyl groups from urea bridges located at the siloxane-PEO interface can not be excluded.
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The absorption and luminescence spectra for the poly(p-phenylene vinylene)/sol-gel silica with different thermal treatments were measured. A considerable increase in the luminescence was observed for the polymer introduced into SiO2 matrix with thermal treatment at 120 degreesC. The thermal diffusivity of these samples was measured using the thermal lens technique, and the obtained value 3.3 x 10(-5) cm(2)/s (sample treated at 37 degreesC) is practically independent of the thermal treatment (37-150 degreesC). (C) 2003 Elsevier B.V. All rights reserved.
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A potentiometric sensor for the perchlorate anion was developed by mixing chemically modified silicagel with pyridinium perchlorate, with an epoxy polymer and graphite. The electrode showed Nernstian response between 1.0 × 10-2 and 1.0 × 10-3M perchlorate concentrations. The electrode showed high selectivity to this ion at solutions pH between 5.5 and 8.0. The presence of IO4 -, NO3 -,Br-, IO3 -, Cl- and SO4 2- ions in the solutions, had only small interference in the electrode response in the range mentioned. © 1995 Springer-Verlag.
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The magnetic and structural properties of sol-gel derived organic/inorganic nanocomposites doped with Fe(II), Fe(III), Nd(III) and Eu (III) ions are discussed. These hybrids consist of poly(oxyethylene)-based chains grafted onto siloxane nanodomains by urea cross-linkages. Small angle X-ray scattering data show the presence of spatial correlations of siloxane domains embedded in the polymer matrix. The magnetic properties of rare-earth doped samples are determined by single ion crystal-field-splitted levels (Eu3+ J=0; Nd3+ J=9/2) and the small thermal irreversibility is mainly associated to structural effects. Fe2+ -doped samples behave as simple paramagnet with residual antiferromagnetic interactions. Fe3+-doped hybrids are much more complex, with magnetic hysterisis, exchange anisotropy and thermal irreversibility at low temperatures. Néel temperatures increase up to 14K for the highest (∼5.5%) Fe3+ mass concentration.
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This work describes a modified sol-gel method for the preparation of V 2O 5/TiO 2 catalysts. The samples have been characterized by N 2 adsorption at 77K, x-ray diffractometry (XRD) and Fourier Transform Infrared (FT-IR). The surface area increases with the vanadia loading from 24 m 2 g -1, for pure TiO 2, to 87 m 2 g -1 for 9wt.% of V 2O 5. The rutile form is predominant for pure TiO 2 but became enriched with anatase phase when vanadia loading is increased. No crystalline V 2O 5 phase was observed in the catalysts diffractograms. Two species of surface vanadium observed by FT-IR spectroscopy a monomeric vanadyl and polymeric vanadates, the vanadyl/vanadate ratio remains practically constant.
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Pós-graduação em Física - IGCE
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Fabrication of optoelectronic devices requires the employment of at least one transparent electrode. Usually, commercially transparent electrodes have been made by deposition of indium tin oxide (ITO) films by RF-Sputtering technique. These commercial electrodes have sheet resistance of about 100 Ω/sq and optical transmittance of 77% at the wavelength of 550 nm. The poly(3,4-ethylenedioxythiophene):polystyrene-sulfonate (PEDOT:PSS) is an alternative material to fabricate transparent electrodes due to its high conductivity (about 600 S/cm) and solubility in water. Soluble conductive materials exhibits advantages for processing of electrode layers, however there is a disadvantage during devices fabrication once materials with the same solvent of the electrode material cannot be coated one over the other. Alternatively, organic/Silica hybrid materials prepared by sol-gel process allow producing bulks and films with high chemical durability. In order to obtain transparent electrodes with high chemical durability, we introduced a blended material comprising the high UV-VIS transparency of organic/Silica sol-gel material and a high conductivity polymer PEDOT:PSS. The organic/Silica sol was obtained using two different molar concentrations (1:1 and 4:1), of tetraethylorthosilicate (TEOS) and 3-glycidoxypropyltrimethoxysilane (GPTS). Amounts of PEDOT:PSS solutions were added to the sol material, resulting in different weight fractions of sol and polymer. G:T/P:P were deposit onto glass substrates by spray-coating. In order to perform electrical characterization of the blended material, gold electrodes were thermally evaporated onto the films. The electrical characterization was performed using a Keithley 2410 source/meter unity and the optical characterization, using a Cary50 UV-Vis spectrophotometer. The absorption coefficient and electric conductivity of the different compositions blends, as function of the PEDOT:PSS concentration, were...
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Pós-graduação em Química - IQ