Lithium Ion Electro-Insertion and Spectroelectrochemical Properties of Films from Hexaniobate

Layer-by-layer (LbL) films from K(2)Nb(6)O(17)(2-) and polyallylamine (PAH) and dip-coating films of H(2)K(2)Nb(6)O(17) were prepared on a fluorine-doped tin-oxide (FTO)-coated glass. The atomic force microscopy (AFM) images were carried out for morphological characterization of both materials. The real surface area and the roughness factor were determined on the basis of pseudocapacitive processes involved in the electroreduction/electrooxidation of gold layers deposited on these films. Next, lithium ion insertion into these materials was examined by means of electrochemical and spectroelectrochemical measurements. More specifically, cyclic voltammetry and current pulses under visible light beams were used to investigate mass transport and chromogenic properties. The lithium ion diffusion coefficient (D(Li)) within the LbL matrix is significantly higher than that within the dip-coating film, ensuring high storage capacity of lithium ions in the self-assembled electrode. Contrary to the LbL film, the potentiodynamic profile of absorbance change (Delta A) as a function of time is not similar to that obtained in the case of current density for the dip-coating film. Aiming at analyzing the rate of the coloration front associated with lithium ion diffusion, a spectroelectrochemical method based on the galvanostatic intermittent titration technique (GITT) was employed so as to determine the ""optical"" diffusion coefficient (D(op)). In the dip-coating film, the method employed here revealed that the lithium ion rate is higher in diffusion pathways formed from K(2)Nb(6)O(17)(2-) sites that contribute more significantly to Delta A. Meanwhile, the presence of PAH contributed to the increased ionic mobility in diffusion pathways in the LbL film, with low contribution to the electrochromic efficiency. These results aided a better understanding of the potentiodynamic profile of the temporal change of absorbance and current density during the insertion/deinsertion of lithium ions into the electrochromic materials.

O Processo de Concessão dos Sistemas de Transporte de Massa na Região Metropolitana do Rio de Janeiro: Implicações na Organização e na Gestão de Transporte de Passageiros

O presente estudo procurou descrever e analisar o contexto em que se desenvolveu o processo de concessão dos sistemas de transporte de massa na Região Metropolitana do Rio de Janeiro, promovido pelo Programa Estadual de Desestatização ¿ PED, na gestão governamental compreendida entre os anos de 1995 e 1998, bem como avaliar suas implicações sobre o modelo de organização e gestão do transporte público regional então vigente. Seu desenvolvimento enfatizou três aspectos desse processo: a caracterização do cenário anterior à proposta de mudança, a análise substantiva da política representada pelo programa de concessões e a avaliação do novo cenário criado como conseqüência do programa. Sua metodologia pautou-se em consulta bibliográfica, volumosa análise documental, observação dos fatos e entrevistas desestruturadas com administradores e técnicos envolvidos no processo. Seus resultados evidenciaram as limitações dos modelos de análise e de planejamento tradicionalmente adotados para a formulação das políticas setoriais, a precariedade dos sistemas de transporte de passageiros regionais e a situação pelos sistemas de metrô, trens e barcas, consubstanciando um ambiente propício às propostas de sua transferência à gestão privada. Evidenciaram, ainda, que a iniciativa foi influenciada pelo contexto dos projetos de reforma do Estado patrocinados pelo Banco Mundial (BIRD), desenvolvendo-se sem referências relevantes na comunidade técnica setorial e gerando um cenário institucional frágil diante da tarefa de gerir os contratos dela resultantes. Embora pautado em estratégias de retomada de investimentos condizentes com as diretrizes do Plano de Transporte de Massa ¿ PTM, elaborado em 1994, a insipiência do programa não permite constatar, ainda tendências significativas no desempenho dos sistemas concedidos. São evidentes, entretanto, seus reflexos na desentruturação do modelo de gestão pública do transporte metropolitano sob responsabilidade do Estado.

Electrochimie analytique en absence d'electrolyte indiferent : transports de matiere lors de la reduction des acides a une ultramicroelectrode

O transporte de massa por migração relativo à redução do proton em um ultramicroeletrodo de platina foi investigado. O efeito da migração sobre as correntes limite foi primeiramente estudado para uma só espécie eletroativa em solução através da comparação dos voltampérogramas obtidos na ausência de eletrólito suporte assim como na presença de um grande excesso do mesmo (efeito do eletrólito). O comportamento do proton na água e dos ácidos do tipo BH+ e HA- em acetonitrila foi estudado e uma expressão para quantificar o efeito do eletrólito é proposta. Ela considera as condutâncias equivalentes e as cargas das espécies iônicas em solução, o número de elétrons envolvido na reação eletroquímica e o tipo de eletrodo utilisado. Os fenômenos de exaltação da corrente de migração que podem se manifestar quando a redução de uma espécie eletroativa é precedida pela redução de uma segunda espécie presente simultâneamente na solução foram igualmente estudados. Observa-se que a exaltação da corrente de migração de uma espécie iônica ocorre mesmo quando sua transformação eletroquímica precede aquela da espécie molecular. Nêste caso, se as mobilidades iônicas são próximas, a altura da onda da espécie molecular é duas vezes maior que na ausência da espécie iônica.

Estudo comparativo da queima rápida com a queima tradicional nas propriedades de materiais cerâmicos de base argilos

Dutra, R. P. S.; Varela,M. L.; Nascimento, R. M. ; Gomes, U. U. ; Martinelli1, A. E. ; Paskocimas, C. A. Estudo comparativo da queima rápida com a queima tradicional nas propriedades de materiais cerâmicos de base argilosa. Cerâmica [online]. 2009, vol.55, n.333, pp. 100-105. ISSN 0366-6913. doi:Disponivem em: . Acesso em: 04 out. 2010.

Síntese e caracterização de NiO-CGO para anodo e eletrólitos sólidos e base de Céria para SOFC

The direct use of natural gas makes the Solid Oxide Fuel Cell (SOFC) potentially more competitive with the current energy conversions technologies. The Intermediate Temperature SOFC (IT-SOFC) offer several advantages over the High Temperature SOFC (HT-SOFC), which includes better thermal compatibility among components, fast start with lower energy consumption, manufacture and operation cost reduction. The CeO2 based materials are alternatives to the Yttria Stabilized Zirconia (YSZ) to application in SOFC, as they have higher ionic conductivity and less ohmic losses comparing to YSZ, and they can operate at lower temperatures (500-800°C). Ceria has been doped with a variety of cations, although, the Gd3+ has the ionic radius closest to the ideal one to form solid solution. These electrolytes based in ceria require special electrodes with a higher performance and chemical and termomechanical compatibility. In this work compounds of gadolinia-doped ceria, Ce1-xGdxO2-δ (x = 0,1; 0,2 and 0,3), used as electrolytes, were synthesized by polymeric precursors method, Pechini, as well as the composite material NiO - Ce0,9Gd0,1O1,95, used as anode, also attained by oxide mixture method, mixturing the powders of the both phases calcinated already. The materials were characterized by X ray diffraction, dilatometry and scanning electronic microscopy. The refinement of the diffraction data indicated that all the Ce1-xGdxO2-δ powders were crystallized in a unique cubic phase with fluorite structure, and the composite synthesized by Pechini method produced smaller crystallite size in comparison with the same material attained by oxide mixture method. All the produced powders had nanometric characteristics. The composite produced by Pechini method has microstructural characteristics that can increase the triple phase boundaries (TPB) in the anode, improving the cell efficiency, as well as reducing the mass transport mechanism effect that provokes anode degradation

Avaliação cinética e potencial do Nb2O5 obtido a partir de um complexo de nióbio para formação do oleato de metila através da reação de esterificação do ácido oleico

Among the heterogeneous catalysts materials made from niobium show up as an alternative to meet the demand of catalysts for biodiesel production. This study aims to evaluate the potential of a heterogeneous catalyst derived from a complex of niobium in the reaction of methyl esterification of oleic acid. The catalyst was synthesized after calcination at different temperatures of a niobium complex ((NH4)3[NbO(C2O4)3].H2O) generating a niobium oxide nanostructure with a different commercial niobium oxide used to synthesize the complex. The commercial niobium oxide, the complex niobium and niobium catalyst were characterized by thermogravimetry (TG and DTA), surface area analysis (BET), scanning electron microscopy (SEM) and X-ray diffraction (XRD), showing the catalyst has researched morphological and crystallographic indicating a catalytic potential higher than that of commercial niobium oxide characteristics. Factorial with central composite design point, with three factors (calcination temperature, molar ratio of alcohol/oleic acid and mass percentage of catalyst) was performed. Noting that the optimal experimental point was given by the complex calcination temperature of 600°C, a molar ratio alcohol/oleic acid of 3.007/1 and the catalyst mass percentage of 7.998%, with a conversion of 22.44% oleic acid in methyl oleate to 60 min of reaction. We performed a composite linear and quadratic regression to determine an optimal statistical point of the reaction, the temperature of calcination of the complex at 450°C, the molar ratio of alcohol/oleic acid 3.3408/1 and mass percentage of catalyst of 7.6833% . Kinetic modeling to estimate parameters for heterogeneous catalysis it set well the experimental results with a final conversion of 85.01% with 42.38% of catalyst and without catalyst at 240 min reaction was performed. Allowing to evaluate the catalyst catalytic studied has the potential to be used in biodiesel production

Oxidação úmida de fenóis com catalisadores de ferro suportado em argilominerais em reator de leito de lama (slurry)

The wet oxidation of organic compounds with CO2 and H2O has been demonstrated to be an efficient technique for effluent treatment. This work focuses on the synthesis, characterization and catalytic performance of Fe-MnO2/CeO2, K-MnO2/CeO2/ palygorskite and Fe/ palygorskite toward the wet oxidative degradation of phenol. The experiments were conducted in a sludge bed reactor with controlled temperature, pressure and stirring speed and sampling of the liquid phase. Experiments were performed on the following operating conditions: temperature 130 ° C, pressure 20.4 atm, catalyst mass concentration of 5 g / L initial concentration of phenol and 0.5 g / L. The catalytic tests were performed in a slurry agitated reactor provided with temperature, pressure and agitation control and reactor liquid sampling. The influences of iron loaded on the support (0.3; 7 and 10%, m/m) and the initial pH of the reactant medium (3.1; 6.8; 8.7) were studied. The iron dispersion on the palygorskite, the phase purity and the elemental composition of the catalyst were evaluated by X-Ray Difraction (XRD), Scanning Electron Microscopy (SEM) and X-Ray Flourescence (XRF). The use of palygorskite as support to increase the surface area was confirmed by the B.E.T. surface results. The phenol degradation curves showed that the Fe3+ over palygorskite when compared with the other materials tested has the best performance toward the (Total Organic carbonic) TOC conversion. The decrease in alkalinity of the reaction medium also favors the conversion of TOC. The maximum conversion obtained from the TOC with the catalyst 3% Fe / palygorskite was around 95% for a reaction time of 60 minutes, while reducing the formation of acids, especially acetic acid. With products obtained from wet oxidation of phenol, hydroquinone, p-benzoquinone, catechol and oxalic acid, identified and quantified by High Performance Liquid Chromatography was possible to propose a reaction mechanism of the process where the phenol is transformed into the homogeneous and heterogeneous phase in the other by applying a kinetic model, Langmuir-Hinshelwood type, with evaluation of kinetic constants of different reactions involved.

Fast dynamics in the optical storage with Langmuir-Blodgett films of a diazocrown ether molecule

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

Formal verification of PLC programs using the B Method

PLCs (acronym for Programmable Logic Controllers) perform control operations, receiving information from the environment, processing it and modifying this same environment according to the results produced. They are commonly used in industry in several applications, from mass transport to petroleum industry. As the complexity of these applications increase, and as various are safety critical, a necessity for ensuring that they are reliable arouses. Testing and simulation are the de-facto methods used in the industry to do so, but they can leave flaws undiscovered. Formal methods can provide more confidence in an application s safety, once they permit their mathematical verification. We make use of the B Method, which has been successfully applied in the formal verification of industrial systems, is supported by several tools and can handle decomposition, refinement, and verification of correctness according to the specification. The method we developed and present in this work automatically generates B models from PLC programs and verify them in terms of safety constraints, manually derived from the system requirements. The scope of our method is the PLC programming languages presented in the IEC 61131-3 standard, although we are also able to verify programs not fully compliant with the standard. Our approach aims to ease the integration of formal methods in the industry through the abbreviation of the effort to perform formal verification in PLCs

Condicionamento estrutural das zonasa de cisalhamento da região de Forquilha, domínio Ceará Central: uma abordagem integrada de sensoriamento remoto e geologia estrutural

The studied region, named Forquilha and localized in northwestern Central Ceará domain (northern portion of Borborema Province), presents a lithostratigraphic framework constituted by paleoproterozoic metaplutonics, metasedimentary sequences and neoproterozoic granitoids. The metasedimentary rocks of Ceará group occupy most part of the area. This group is subdivided in two distinct units: Canindé and Independência. Canindé unit is represented basically by biotite paragneisses and muscovite paragneisses, with minor metabasic rocks (amphibolite lens). Independência sequence is composed by garnetiferous paragneisses, sillimanite-garnet-quartz-muscovite schists and quartz-muscovite schists, pure or muscovite quartzites and rare marbles. At least three ductile deformation events were recognized in both units of Ceará group, named D1, D2 and D3. The former one is interpreted as related to a low angle tangential tectonics which mass transport is southward. D2 event is marked by the development of close/isoclinal folds with a N-S oriented axis. Refolding patterns generated by F1 and F2 superposition are found in several places. The latest event (D3) corresponds to a transcurrent tectonics, which led to development of mega-folds and several shear zones, under a transpressional regime. The mapped shear zones are Humberto Monte (ZCHM), Poço Cercado (ZCPC) and Forquilha (ZCF). Digital image processing of enhanced Landsat 7-ETM+ satellite images, combined with field data, demonstrate that these penetrative structures are associated with positive and negative geomorphologic patterns, distributed in linear and curvilinear arrangements with tonal banding, corresponding to the ductile fabric and to crests. Diverse color composites were tested and RGB-531 and RGB-752 provided the best results for lineament analysis of the most prominent shear zones. Spatial filtering techniques (3x3 and 5x5 filters) were also used and the application of Prewitt filters generated the best products. The integrated analysis of morphological and textural aspects from filtered images, variation of tonalities related to the distribution of geologic units in color composites and the superposition over a digital elevation model, contributed to a characterization of the structural framework of the study area. Kinematic compatibility of ZCHM, ZCPC, ZCF shear zones, as well as Sobral-Pedro II (ZCSPII) shear zone, situated to the west of the study area, was one of the goal of this work. Two of these shear zones (ZCHM, ZCPC) display sinistral movements, while the others (ZCSPII, ZCF) exhibit dextral kinematics. 40Ar/39Ar ages obtained in this thesis for ZCSPII and ZCPC, associated with other 40Ar/39Ar data of adjacent areas, indicate that all these shear zones are related to Brasiliano orogeny. The trend of the structures, the opposite shear senses and the similar metamorphic conditions are fitted in a model based on the development of conjugate shear zones in an unconfined transpression area. A WNW-ESE bulk shortening direction is infered. The geometry and kinematic of the studied structures suggest that shortening was largely accommodated by lateral extrusion, with only minor amounts of vertical stretch

Effect of lithium additive on the microstructure and electrical responses of 0.9PMN-0.1PT ceramics

Structural effects of lithium additive on 0.9PMN-0.1PT powders prepared by Ti-modified columbite route were studied. The substitution of Li+ ions for Mg2+ ions in the B-site sub-lattice of 0.9PMN-0.1PT perovskite structure was explained in terms of lead and oxygen vacancies generation originated as consequence of the ionic compensation of negatively charged Li'(Mg) sites. The rise in mass transport as consequence of the increasing of Pb2+ and O2- vacancies produces more agglomerated particles during the powder synthesis and changes the mechanical characteristics between grain and grain boundary of sintered ceramic. The relation between K-m and T-m values, the difference between ionic radii of B cation and the molar volume were used to explain the changes in the relaxor behavior and diffusiveness of phase transition as function of lithium doping, which are corroborated by the results obtained through the ferroelectric characterization.

Aspects of solid state formation and properties of Sn(0.9)Ti(0.1)O(2) system doped with CoO and Nb(2)O(5)

The effect of calcination temperature during the formation of the solid solution Sn(0.9)Ti(0.1)O(2) doped with 1.00 mol % CoO and 0.05 mol % Nb(2)O(5) is presented. The structural characteristics of this system were studied using X-ray diffraction, and the changes in phase formation were analyzed using the Rietveld method. With an increase in calcination temperature, there is increasing miscibility of Ti into the (Ti,Sn)O(2) phase and near 1000 degrees C, and the remaining TiO(2) (anatase) was transformed into the rutile phase. The sintering process, monitored using dilatometry, suggests two mass transport mechanisms, one activated close to 900 degrees C associated with the presence of TiO(2) (anatase) and the second mechanism, occurring between 1200 and 1300 degrees C, is attributed to a faster grain boundary diffusion caused by oxygen vacancies. (C) 2008 International Centre for Diffraction Data.

Comportamento voltamétrico da redução de 2-furfuraldeído em etanol utilizando eletrodo de carbono vítreo

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

Sintering of tin oxide and its applications in electronics and processing of high purity optical glasses

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

Sintering of ultrafine undoped SnO2 powder

The sintering process of nanometric undoped SnO2 powder was studied. No macroscopic shrinkage was observed during the sintening process. Grain growth kinetics investigation showed that surface diffusion is the dominant mechanism in the temperature range 500-1300 degreesC. For temperatures higher than 1300 degreesC, high weight loss was measured, suggesting evaporation-condensation as the dominant mass-transport mechanism. Thermogravimetric analysis (TG) and mass spectroscopy studies showed that the surface contamination of the SnO2 particles by chemical species like H2O, OH- and CO2, has a strong influence on the role of mass transport controlled by surface diffusion. (C) 2001 Elsevier B.V. Ltd. All rights reserved.