Synthesis, characterization and electrochemical behavior of the vanadium pentoxide/cetyl pyridinium chloride hybrid material

In situ and ex situ studies concerning the new hybrid material vanadium pentoxide xerogel in the presence of the cationic surfactant cetyl pyridinium chloride (V(2)O(5)/CPC) are presented. The in situ characterization studies revealed the presence of a lamellar structure for the V(2)O(5)/CPC hybrid material. The intercalation reaction was evidenced on the basis of the increase in the d-spacing as well as the displacement of the infrared bands toward lower energy levels. Electrochemical studies comprising the cyclic voltammetry and the electrochemical impedance spectroscopy techniques showed that the behavior of the hybrid material is considerably influenced by the electrolyte composition. The ion insertion/de-insertion into the V(2)O(5) xerogel structure accompanying the charge transfer process is influenced by the solid-state diffusion process modeled by using the finite-space Warburg element.

Selective entrainment of sediment graded by size and density under waves

The influence of near-bed sorting processes on heavy mineral content in suspension is discussed. Sediment concentrations above a rippled bed of mixed quartz and heavy mineral sand were measured under regular nonbreaking waves in the laboratory. Using the traditional gradient diffusion process, settling velocity would be expected to strongly affect sediment distribution. This was not observed during present trials. In fact, the vertical gradients of time-averaged suspension concentrations were found to be similar for the light and heavy minerals, despite their different settling velocities. This behavior implies a convective rather than diffusive distribution mechanism. Between the nonmoving bed and the lowest suspension sampling point, fight and heavy mineral concentration differs by two orders of magnitude. This discrimination against the heavy minerals in the pickup process is due largely to selective entrainment at the ripple face. Bed-form dynamics and the nature of quartz suspension profiles are found to be little affected by the trialed proportion of overall heavy minerals in the bed (3.8-22.1%).

On the Estimation of the Short-Circuit Impedance of Power Transformers Using Fractional Order Calculus

This paper reports investigation on the estimation of the short circuit impedance of power transformers, using fractional order calculus to analytically study the influence of the diffusion phenomena in the windings. The aim is to better characterize the medium frequency range behavior of leakage inductances of power transformer models, which include terms to represent the magnetic field diffusion process in the windings. Comparisons between calculated and measured values are shown and discussed.

A multi–physics approach applied to masonry structures with non–hydraulic lime mortars

Tese de Doutoramento em Engenharia Civil (área de especialização em Engenharia de Estruturas).

A Rembrandt is a Rembrandt

As paintings are assets, we propose to model a painting's price dynamics as a diffusion process, i.e., as the financial literature models share prices, but correcting by size. We show that the influence of size on the artwork price diminishes as the paintings gets older because 1) prices incorporate progressively more noise and 2) for high quality artists, the relative importance of size on price decreases as the artist consolidates and authorship gains importance as explanatory variable. Our theoretical results are consistent with data from a sample of 19th- and 20th-century Catalan painters of similar quality. These findings suggest that an artist's quality and antiquity should be taken into account in order to obtain more efficient estimates of parameters in hedonic art market models.

Consumer populations and nutritional transition in Spain in the 20th century: a methodology for their reconstruction

One feature of the modern nutrition transition is the growing consumption of animal proteins. The most common approach in the quantitative analysis of this change used to be the study of averages of food consumption. But this kind of analysis seems to be incomplete without the knowledge of the number of consumers. Data about consumers are not usually published in historical statistics. This article introduces a methodological approach for reconstructing consumer populations. This methodology is based on some assumptions about the diffusion process of foodstuffs and the modeling of consumption patterns with a log-normal distribution. This estimating process is illustrated with the specific case of milk consumption in Spain between 1925 and 1981. These results fit quite well with other data and indirect sources available showing that this dietary change was a slow and late process. The reconstruction of consumer population could shed a new light in the study of nutritional transitions.

THE USE OF SIMULATIONS IN EVOLUTIONARY POPULATION GENETICS: APPLICATIONS ON HUMANS, OWLS AND VIRTUAL ORGANISMS

Summary (in English) Computer simulations provide a practical way to address scientific questions that would be otherwise intractable. In evolutionary biology, and in population genetics in particular, the investigation of evolutionary processes frequently involves the implementation of complex models, making simulations a particularly valuable tool in the area. In this thesis work, I explored three questions involving the geographical range expansion of populations, taking advantage of spatially explicit simulations coupled with approximate Bayesian computation. First, the neutral evolutionary history of the human spread around the world was investigated, leading to a surprisingly simple model: A straightforward diffusion process of migrations from east Africa throughout a world map with homogeneous landmasses replicated to very large extent the complex patterns observed in real human populations, suggesting a more continuous (as opposed to structured) view of the distribution of modern human genetic diversity, which may play a better role as a base model for further studies. Second, the postglacial evolution of the European barn owl, with the formation of a remarkable coat-color cline, was inspected with two rounds of simulations: (i) determine the demographic background history and (ii) test the probability of a phenotypic cline, like the one observed in the natural populations, to appear without natural selection. We verified that the modern barn owl population originated from a single Iberian refugium and that they formed their color cline, not due to neutral evolution, but with the necessary participation of selection. The third and last part of this thesis refers to a simulation-only study inspired by the barn owl case above. In this chapter, we showed that selection is, indeed, effective during range expansions and that it leaves a distinguished signature, which can then be used to detect and measure natural selection in range-expanding populations. Résumé (en français) Les simulations fournissent un moyen pratique pour répondre à des questions scientifiques qui seraient inabordable autrement. En génétique des populations, l'étude des processus évolutifs implique souvent la mise en oeuvre de modèles complexes, et les simulations sont un outil particulièrement précieux dans ce domaine. Dans cette thèse, j'ai exploré trois questions en utilisant des simulations spatialement explicites dans un cadre de calculs Bayésiens approximés (approximate Bayesian computation : ABC). Tout d'abord, l'histoire de la colonisation humaine mondiale et de l'évolution de parties neutres du génome a été étudiée grâce à un modèle étonnement simple. Un processus de diffusion des migrants de l'Afrique orientale à travers un monde avec des masses terrestres homogènes a reproduit, dans une très large mesure, les signatures génétiques complexes observées dans les populations humaines réelles. Un tel modèle continu (opposé à un modèle structuré en populations) pourrait être très utile comme modèle de base dans l'étude de génétique humaine à l'avenir. Deuxièmement, l'évolution postglaciaire d'un gradient de couleur chez l'Effraie des clocher (Tyto alba) Européenne, a été examiné avec deux séries de simulations pour : (i) déterminer l'histoire démographique de base et (ii) tester la probabilité qu'un gradient phénotypique, tel qu'observé dans les populations naturelles puisse apparaître sans sélection naturelle. Nous avons montré que la population actuelle des chouettes est sortie d'un unique refuge ibérique et que le gradient de couleur ne peux pas s'être formé de manière neutre (sans l'action de la sélection naturelle). La troisième partie de cette thèse se réfère à une étude par simulations inspirée par l'étude de l'Effraie. Dans ce dernier chapitre, nous avons montré que la sélection est, en effet, aussi efficace dans les cas d'expansion d'aire de distribution et qu'elle laisse une signature unique, qui peut être utilisée pour la détecter et estimer sa force.

Enzyme loading dependence of cellulose hydrolysis of sugarcane bagasse

The enzymatic hydrolysis of steam-pretreated sugarcane bagasse, either delignified or non-delignified, was studied as a function of enzyme loading. Hydrolysis experiments were carried out using five enzyme loadings (2.5 to 20 FPU/g cellulose) and the concentration of solids was 2% for both materials. Alkaline delignification improved cellulose hydrolysis by increasing surface area. For both materials, glucose concentrations increased with enzyme loading. On the other hand, enzyme loadings higher than 15 FPU/g did not result in any increase in the initial rate, since the excess of enzyme adsorbed onto the substrate restricted the diffusion process through the structure.

Rendu de matériaux semi-transparents hétérogènes en temps réel

On retrouve dans la nature un nombre impressionnant de matériaux semi-transparents tels le marbre, le jade ou la peau, ainsi que plusieurs liquides comme le lait ou les jus. Que ce soit pour le domaine cinématographique ou le divertissement interactif, l'intérêt d'obtenir une image de synthèse de ce type de matériau demeure toujours très important. Bien que plusieurs méthodes arrivent à simuler la diffusion de la lumière de manière convaincante a l'intérieur de matériaux semi-transparents, peu d'entre elles y arrivent de manière interactive. Ce mémoire présente une nouvelle méthode de diffusion de la lumière à l'intérieur d'objets semi-transparents hétérogènes en temps réel. Le coeur de la méthode repose sur une discrétisation du modèle géométrique sous forme de voxels, ceux-ci étant utilisés comme simplification du domaine de diffusion. Notre technique repose sur la résolution de l'équation de diffusion à l'aide de méthodes itératives permettant d'obtenir une simulation rapide et efficace. Notre méthode se démarque principalement par son exécution complètement dynamique ne nécessitant aucun pré-calcul et permettant une déformation complète de la géométrie.

Spray Pyrolysed Tin Chalcogenide Thin Films: Optimization of optoelectronic properties of SnS for possible photovoltaic application as an absorber layer

In the early 19th century, industrial revolution was fuelled mainly by the development of machine based manufacturing and the increased use of coal. Later on, the focal point shifted to oil, thanks to the mass-production technology, ease of transport/storage and also the (less) environmental issues in comparison with the coal!! By the dawn of 21st century, due to the depletion of oil reserves and pollution resulting from heavy usage of oil the demand for clean energy was on the rising edge. This ever growing demand has propelled research on photovoltaics which has emerged successful and is currently being looked up to as the only solace for meeting our present day energy requirements. The proven PV technology on commercial scale is based on silicon but the recent boom in the demand for photovoltaic modules has in turn created a shortage in supply of silicon. Also the technology is still not accessible to common man. This has onset the research and development work on moderately efficient, eco-friendly and low cost photovoltaic devices (solar cells). Thin film photovoltaic modules have made a breakthrough entry in the PV market on these grounds. Thin films have the potential to revolutionize the present cost structure of solar cells by eliminating the use of the expensive silicon wafers that alone accounts for above 50% of total module manufacturing cost.Well developed thin film photovoltaic technologies are based on amorphous silicon, CdTe and CuInSe2. However the cell fabrication process using amorphous silicon requires handling of very toxic gases (like phosphene, silane and borane) and costly technologies for cell fabrication. In the case of other materials too, there are difficulties like maintaining stoichiometry (especially in large area films), alleged environmental hazards and high cost of indium. Hence there is an urgent need for the development of materials that are easy to prepare, eco-friendly and available in abundance. The work presented in this thesis is an attempt towards the development of a cost-effective, eco-friendly material for thin film solar cells using simple economically viable technique. Sn-based window and absorber layers deposited using Chemical Spray Pyrolysis (CSP) technique have been chosen for the purpose

Modelo telegráfico de valoración de opciones

En este trabajo construimos un modelo de mercado financiero basado en un proceso telegráfico más un proceso de saltos para la valoración de opciones Europeas. Vamos a asumir que el tamaño de los saltos es constante y después que es aleatorio, en ambos casos estos saltos ocurren cuando la tendencia del mercado cambia. Estos modelos capturan la dinámica del mercado en periodos con presencia de ciclos financieros. Mostraremos la estructura del conjunto de medidas neutrales al riesgo, además, de fórmulas explícitas para los precios de las opciones Europeas de venta y compra.

Static and dynamic bimolecular fluorescence quenching of porphyrin dendrimers in solution

The fluorescence quenching kinetics of two porphyrin dendrimer series (GnTPPH(2) and GnPZn) by different type of quenchers is reported. The microenvironment surrounding the core in GnPZn was probing by core-quencher interactions using benzimidazole. The dependence of quencher binding constant (K(a) ) on generation indicates the presence of a weak interaction between branches and the core of the porphyrin dendrimer. The similar free volume in dendrimers of third and fourth generation suggests that structural collapse in high generations occurs by packing of the dendrimer peripheral layer. Dynamic fluorescence quenching of the porphyrin core by 1,3-dicyanomethylene-2-methyl-2-pentyl-indan (PDCMI) in GnTPPH(2) is a distance dependent electron transfer process with an exponential attenuation factor beta=0.33 angstrom(-1). The quenching by 1,2-dibromobenzene occurs by diffusion process of the quencher toward to the porphyrin core, and its rate constant is practically independent of dendrimer generation.

Modelo de mensuração de mercado para bens duráveis: o caso de condicionadores de ar para uso residencial

Trata de uma proposta de mensuração de mercado de bens duráveis em nível municipal. O processo de modelagem assume que: a função deve ser determinada a partir do análise do estágio do produto em seu processo de difusão n o mercado, cada município é uma unidade representada p o r variáveis obtidas através d e dados secundários e os dados secundários a serem coletados podem determinados através d o conhecimento d o comportamento de compra do produto. No modelo, os resíduos sã o tratados como ferramenta estratégica mercadológica. É apresentada uma aplicação do modelo para condicionadores de ar

Do encontro das águas ao Atlântico negro: organização, difusão de frames e os limites do ativismo transnacional no movimento negro brasileiro

Meu objetivo nesta tese é compreender o processo de transnacionalização do movimento negro brasileiro e as suas consequências para a luta antirracista no Brasil. Em outras palavras, busco compreender como os negros brasileiros se articulam com os negros do mundo para cumprir seus objetivos. Uma vez que hoje a cultura negra global tem sido compreendida a partir da metáfora do “Atlântico Negro”, que representa um espaço de trocas transnacional que conecta todos os sujeitos da diáspora negra, assumo esta mesma metáfora como ponto de partida para minha reflexão. Entretanto, me interessa refletir sob um dos aspectos do Atlântico Negro, que é a sua dimensão organizacional. Se é pelo Atlântico Negro que hoje circulam um conjunto de conteúdos que são compartilhados pela comunidade negra mundial, tais como idéias e práticas que estão relacionadas a religião, a música, a literatura e as formas de organização, então podemos afirmar que a organização do movimento negro brasileiro se alimenta também destas múltiplas dimensões. Para desenvolver esta linha de argumentação, a tese utiliza o caso do movimento negro brasileiro para analisar o processo de difusão de um frame transnacional racialista que é apropriado pelo movimento negro como base para a elaboração de um diagnóstico, prognóstico e ressonância das ações de combate ao racismo no Brasil e para a definição das estruturas de mobilização e das estratégias de ação do movimento. Contudo, esta apropriação não ocorre sem problemas, pois este frame enfrenta outros frames locais, de caráter não-racialista, o que acarreta severas restrições ao ativismo transnacional na medida em que o próprio movimento negro se vê diante do dilema entre manter o alinhamento com o frame transnacional e aproveita as oportunidades políticas oferecidas pelo racialismo, ou relativiza este frame fazendo algumas concessões em suas propostas e na sua organização, a fim de se adaptar aos frames locais, negociando estas oportunidades a partir das restrições existentes. Para entender esta dinâmica, proponho a metáfora do “Encontro das Águas” amazonense, como um ponto de argumentação complementar ao Atlântico Negro, pois leva em conta os aspectos locais da luta antirracista que se apoiam na mestiçagem como identidade autônoma que não se dilui facilmente na identidade negra. Além de desenvolver estes pontos, a tese contribui para compreender melhor a dialética entre o global e local, bem como as tensões advindas dos frames em disputa.

Modelo de volatilidade estocástica com saltos aplicado a commodities agrícolas

Mensalmente são publicados relatórios pelo Departamento de Agricultura dos Estados Unidos (USDA) onde são divulgados dados de condições das safras, oferta e demanda globais, nível dos estoques, que servem como referência para todos os participantes do mercado de commodities agrícolas. Esse mercado apresenta uma volatilidade acentuada no período de divulgação dos relatórios. Um modelo de volatilidade estocástica com saltos é utilizado para a dinâmica de preços de milho e de soja. Não existe um modelo ‘ideal’ para tal fim, cada um dos existentes têm suas vantagens e desvantagens. O modelo escolhido foi o de Oztukel e Wilmott (1998), que é um modelo de volatilidade estocástica empírica, incrementado com saltos determinísticos. Empiricamente foi demonstrado que um modelo de volatilidade estocástica pode ser bem ajustado ao mercado de commodities, e o processo de jump-diffusion pode representar bem os saltos que o mercado apresenta durante a divulgação dos relatórios. As opções de commodities agrícolas que são negociadas em bolsa são do tipo americanas, então alguns métodos disponíveis poderiam ser utilizados para precificar opções seguindo a dinâmica do modelo proposto. Dado que o modelo escolhido é um modelo multi-fatores, então o método apropriado para a precificação é o proposto por Longstaff e Schwartz (2001) chamado de Monte Carlo por mínimos quadrados (LSM). As opções precificadas pelo modelo são utilizadas em uma estratégia de hedge de uma posição física de milho e de soja, e a eficiência dessa estratégia é comparada com estratégias utilizando-se instrumentos disponíveis no mercado.