Evidence of fluoride oxidation for development of the electrochemically-induced crystallization observed in lead oxyfluoroborate glasses

This work reports on a distinct experimental procedure conceived to closely approach the question of development of crystallization in lead oxyfluoroborate glasses in the presence of an electric field. After proposing earlier that this phenomenon should involve occurrence of redox-type electrochemical reactions occurring at the electrodes. it was in fact recently shown that a direct contact of the glasses with both the cathode and anode revealed essential, provided that crystallization did not develop when ions migration to these electrodes became frustrated. The present study demonstrates that. even in Pt,Ag/Glass/YSZ:PbF(2)/Ag,Pt-type electrochemical cells subjected to electric field action, where YSZ:PbF(2) represents composite-like mixtures (formed by Y(2)O(3)-doped ZrO(2) and PbF(2)) placed between the glass and anode. crystallization was observable in given cases. In summary, supported by (micro)structural and electrical characterizations, clear evidence is provided here that, besides Pb(2+) reduction at the cathode, crystallization really involves simultaneous F(-) oxidation at the anode, completing thus the whole redox electrochemical reaction so far postulated. In these cases, F(-) migration to the anode was achievable following PbF(2) percolative-like paths through the YSZ:PbF(2) mixtures. (C) 2010 Elsevier B.V. All rights reserved.

Elastomeric Composites Based on Ethylene-Propylene-Diene Monomer Rubber and Conducting Polymer-Modified Carbon Black

Thermally stable elastomeric composites based on ethylene-propylene-diene monomer (EPDM) and conducting polymer-modified carbon black (CPMCB) additives were produced by casting and crosslinked by compression molding. CPMCB represent a novel thermally stable conductive compound made via ""in situ"" deposition of intrinsically conducting polymers (ICP) such as polyaniline or polypyrrole on carbon black particles. Thermogravimetric analysis showed that the composites are thermally stable with no appreciable degradation at ca. 300 degrees C. Incorporating CPMCB has been found to be advantageous to the processing of composites, as the presence of ICP lead to a better distribution of the filler within the rubber matrix, as confirmed by morphological analysis. These materials have a percolation threshold range of 5-10 phr depending on the formulation and electrical dc conductivity values in the range of 1 x 10(-3) to 1 x 10(-2) S cm(-1) above the percolation threshold. A less pronounced reinforcing effect was observed in composites produced with ICP-modified additives in relation to those produced only with carbon black. The results obtained in this study show the feasibility of this method for producing stable, electrically conducting composites with elastomeric characteristics. POLYM. COMPOS., 30:897-906, 2009. (C) 2008 Society of Plastics Engineers

Aplicações da teoria da percolação à modelagem e simulação de reservatórios de petróleo

In this thesis we study some problems related to petroleum reservoirs using methods and concepts of Statistical Physics. The thesis could be divided percolation problem in random multifractal support motivated by its potential application in modelling oil reservoirs. We develped an heterogeneous and anisotropic grid that followin two parts. The first one introduce a study of the percolations a random multifractal distribution of its sites. After, we determine the percolation threshold for this grid, the fractal dimension of the percolating cluster and the critical exponents ß and v. In the second part, we propose an alternative systematic of modelling and simulating oil reservoirs. We introduce a statistical model based in a stochastic formulation do Darcy Law. In this model, the distribution of permeabilities is localy equivalent to the basic model of bond percolation

Fractais e Percolação na Recuperação de Petróleo

The complex behavior of a wide variety of phenomena that are of interest to physicists, chemists, and engineers has been quantitatively characterized by using the ideas of fractal and multifractal distributions, which correspond in a unique way to the geometrical shape and dynamical properties of the systems under study. In this thesis we present the Space of Fractals and the methods of Hausdorff-Besicovitch, box-counting and Scaling to calculate the fractal dimension of a set. In this Thesis we investigate also percolation phenomena in multifractal objects that are built in a simple way. The central object of our analysis is a multifractal object that we call Qmf . In these objects the multifractality comes directly from the geometric tiling. We identify some differences between percolation in the proposed multifractals and in a regular lattice. There are basically two sources of these differences. The first is related to the coordination number, c, which changes along the multifractal. The second comes from the way the weight of each cell in the multifractal affects the percolation cluster. We use many samples of finite size lattices and draw the histogram of percolating lattices against site occupation probability p. Depending on a parameter, ρ, characterizing the multifractal and the lattice size, L, the histogram can have two peaks. We observe that the probability of occupation at the percolation threshold, pc, for the multifractal is lower than that for the square lattice. We compute the fractal dimension of the percolating cluster and the critical exponent β. Despite the topological differences, we find that the percolation in a multifractal support is in the same universality class as standard percolation. The area and the number of neighbors of the blocks of Qmf show a non-trivial behavior. A general view of the object Qmf shows an anisotropy. The value of pc is a function of ρ which is related to its anisotropy. We investigate the relation between pc and the average number of neighbors of the blocks as well as the anisotropy of Qmf. In this Thesis we study likewise the distribution of shortest paths in percolation systems at the percolation threshold in two dimensions (2D). We study paths from one given point to multiple other points

Fractais e percolação na recuperação de Petróleo

The complex behavior of a wide variety of phenomena that are of interest to physicists, chemists, and engineers has been quantitatively characterized by using the ideas of fractal and multifractal distributions, which correspond in a unique way to the geometrical shape and dynamical properties of the systems under study. In this thesis we present the Space of Fractals and the methods of Hausdorff-Besicovitch, box-counting and Scaling to calculate the fractal dimension of a set. In this Thesis we investigate also percolation phenomena in multifractal objects that are built in a simple way. The central object of our analysis is a multifractal object that we call Qmf . In these objects the multifractality comes directly from the geometric tiling. We identify some differences between percolation in the proposed multifractals and in a regular lattice. There are basically two sources of these differences. The first is related to the coordination number, c, which changes along the multifractal. The second comes from the way the weight of each cell in the multifractal affects the percolation cluster. We use many samples of finite size lattices and draw the histogram of percolating lattices against site occupation probability p. Depending on a parameter, ρ, characterizing the multifractal and the lattice size, L, the histogram can have two peaks. We observe that the probability of occupation at the percolation threshold, pc, for the multifractal is lower than that for the square lattice. We compute the fractal dimension of the percolating cluster and the critical exponent β. Despite the topological differences, we find that the percolation in a multifractal support is in the same universality class as standard percolation. The area and the number of neighbors of the blocks of Qmf show a non-trivial behavior. A general view of the object Qmf shows an anisotropy. The value of pc is a function of ρ which is related to its anisotropy. We investigate the relation between pc and the average number of neighbors of the blocks as well as the anisotropy of Qmf. In this Thesis we study likewise the distribution of shortest paths in percolation systems at the percolation threshold in two dimensions (2D). We study paths from one given point to multiple other points. In oil recovery terminology, the given single point can be mapped to an injection well (injector) and the multiple other points to production wells (producers). In the previously standard case of one injection well and one production well separated by Euclidean distance r, the distribution of shortest paths l, P(l|r), shows a power-law behavior with exponent gl = 2.14 in 2D. Here we analyze the situation of one injector and an array A of producers. Symmetric arrays of producers lead to one peak in the distribution P(l|A), the probability that the shortest path between the injector and any of the producers is l, while the asymmetric configurations lead to several peaks in the distribution. We analyze configurations in which the injector is outside and inside the set of producers. The peak in P(l|A) for the symmetric arrays decays faster than for the standard case. For very long paths all the studied arrays exhibit a power-law behavior with exponent g ∼= gl.

Efeito das condições de preparação na condutividade elétrica de blendas de poli(fluoreto de vinilideno) e poli(o-metoxianilina)

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

ELECTROACTIVE BLENDS OF POLY(VINYLIDENE FLUORIDE) AND POLYANILINE DERIVATIVES

The conditions for processing and doping of blends of poly(o-alkoxyaniline)s and poly(vinylidene fluoride) were investigated. Flexible, free-standing and stretchable films of blends of various compositions were obtained by casting. A low percolation threshold was observed with the onset of conductivity at low polyalkoxyaniline contents (i.e. 5%). Interestingly, these blends displayed electrochromism with colour changes similar to those of the parent conducting polymer, as observed from cyclic voltammetry measurements. This behaviour is seen even for low contents of the conducting polymer, indicating that a continuous conducting pathway, which is capable of exchanging charge, is formed within the insulating matrix.

Morphology of poly(vinylidene fluoride) and poly(o-metoxyaniline) blends

Blends of poly(o-methoxyaniline) - POMA - and poly(vinylidene fluoride) - PVDF - of various compositions were prepared from organic solvent solutions. Flexible, free-standing and stretchable films were obtained by casting, which were characterized by conductivity measurements, electron microscopy and differential scanning calorimetry. As expected, the blends conductivity increases with increasing contents of the conducting polymer. The onset of the conductivity at low contents of conducting polymer indicates a low percolation threshold for the blends. Despite the presence of the conductive host, the blends displayed the crystalline spherulitic morphology and the beta-phase characteristic of pure PVDF. This morphology appears to be destroyed, however, if the film is stretched by zone-drawing.

Spectroscopic properties of polycarbonate and poly(methyl methacrylate) blends doped with Europium(III) acetylacetonate

Spectroscopic properties of blends formed by bisphenol-A polycarbonate (PC) and poly(methyl methacrylate) (PMMA) doped with Europium (III) acetylacetonate [Eu(acac)(3)], have been studied by photoacoustic spectroscopy (PAS) and photoluminescent (PL) spectroscopy. Emission and excitation spectra, excited state decay times, and quantum efficiency have been evaluated as well. PAS studies evidenced chemical interactions between the Europium complex and the PC/PMMA blend, which presented typical percolation threshold behavior regarding the Eu3+ content. PL spectra evidenced the photoluminescence of the Eu3+ incorporated into the blend. Photoluminescence property enhancement was observed for the composite in comparison with the precursor compound. Optimized emission quantum efficiency was observed for the 60/40 blend doped with 2% and 4% Europium (III) acetylacetonate. (c) 2005 Elsevier B.V. All rights reserved.

Study of ITO@PMMA composites by transmission electron microscopy

ITO nanowires were synthesized by carbothermal reduction process, using a co-evaporation method, and have controlled size, shape, and chemical composition. The electrical measurements of nanowires showed they have a resistance of about 102 Ω. In order to produce nanocomposites films, nanowires were dispersed in toluene using an ultrasonic cleaner, so the PMMA polymer was added, and the system was kept under agitation up to obtain a clear suspension. The PMMA polymer was filled with 1, 2, 5 and 10% in weight of nanowires, and the films were done by tape casting. The results showed that the electrical resistance of nanocomposites changed by over 7 orders of magnitude by increasing the amount of filler, and using 5 wt% of filler the composite resistance decreased from 1010 Ω to about 104 Ω, which means that percolation threshold of wires occurred at this concentration. This is an interesting result once for nanocomposites filled with ITO nanoparticles is necessary about 18% in weight to obtain percolation. The addition of filler up to 10 wt% decreased the resistance of the composite to 103 Ω, which is a value close to the resistance of wires. The composites were also analyzed by transmission electron microscopy (TEM), and the TEM results are in agreement with the electrical ones about percolation of nanowires. These results are promising once indicates that is possible to produce conductive and transparent in the visible range films by the addition of ITO nanowires in a polymeric matrix using a simple route. © 2011 Materials Research Society.

Modelo estatístico de rede de resistores para o estudo de processos de condução em nanocompósitos poliméricos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Síntese e caracterização elétrica de compósitos poliméricos condutores com o poliuretano derivado de óleo de mamona como matriz

Pós-graduação em Ciência dos Materiais - FEIS

Preparação e caracterização do compósito poli (fluoreto de vinilideno) / polianilina com partículas de níquel

Pós-graduação em Ciência dos Materiais - FEIS

Electrical and Thermal study of carbon nanotubes reinforced poly (phenylene sulfide) nanostructured composites

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

Electrical, mechanical, and thermal analysis of natural rubber/polyaniline-DBSA composite

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)