A new sedimentary benchmark for the Deccan Traps volcanism?

The origin of the Cretaceous-Paleogene boundary (KPB) mass extinction is still the center of acrimonious debates by opposing partisans of the bolide impact theory to those who favored a terrestrial origin linked to the Deccan Traps volcanism. Here we apply an original and high-resolution environmental magnetic study of the reference Bidart section, France. Our results show that the KPB is identified by an abrupt positive shift of the magnetic susceptibility (MS), also observed by others at the KPB elsewhere. In addition, an anomalous interval of very low MS, carried by an unknown Cl-bearing iron oxide similar to specular hematite, is depicted just below the KPB. Grain-size and morphology of the Cl-iron oxide are typically in the range of hematitic dust currently transported by winds from Sahara to Europe. This discovery is confirmed in the referenced Gubbio section (Italy) suggesting a global scale phenomenon. As a conjecture we suggest an origin by heterogeneous reaction between HCl-rich volcanic gas and liquid-solid aerosols within buoyant atmospheric plumes formed above the newly emitted Deccan flood basalts. Based on this hypothesis, our discovery provides a new benchmark for the Deccan volcanism and witnesses the nature and importance of the related atmospheric change.

Capillary bridging and long-range attractive forces in a mean-field approach

When a mixture is confined, one of the phases can condense out. This condensate, which is otherwise metastable in the bulk, is stabilized by the presence of surfaces. In a sphere-plane geometry, routinely used in atomic force microscope and surface force apparatus, it, can form a bridge connecting the surfaces. The pressure drop in the bridge gives rise to additional long-range attractive forces between them. By minimizing the free energy of a binary mixture we obtain the force-distance curves as well as the structural phase diagram of the configuration with the bridge. Numerical results predict a discontinuous transition between the states with and without the bridge and linear force-distance curves with hysteresis. We also show that similar phenomenon can be observed in a number of different systems, e.g., liquid crystals and polymer mixtures. (C). 2004 American Institute of Physics.

Equilibrium self-assembly of colloids with distinct interaction sites: Thermodynamics, percolation, and cluster distribution functions

We calculate the equilibrium thermodynamic properties, percolation threshold, and cluster distribution functions for a model of associating colloids, which consists of hard spherical particles having on their surfaces three short-ranged attractive sites (sticky spots) of two different types, A and B. The thermodynamic properties are calculated using Wertheim's perturbation theory of associating fluids. This also allows us to find the onset of self-assembly, which can be quantified by the maxima of the specific heat at constant volume. The percolation threshold is derived, under the no-loop assumption, for the correlated bond model: In all cases it is two percolated phases that become identical at a critical point, when one exists. Finally, the cluster size distributions are calculated by mapping the model onto an effective model, characterized by a-state-dependent-functionality (f) over bar and unique bonding probability (p) over bar. The mapping is based on the asymptotic limit of the cluster distributions functions of the generic model and the effective parameters are defined through the requirement that the equilibrium cluster distributions of the true and effective models have the same number-averaged and weight-averaged sizes at all densities and temperatures. We also study the model numerically in the case where BB interactions are missing. In this limit, AB bonds either provide branching between A-chains (Y-junctions) if epsilon(AB)/epsilon(AA) is small, or drive the formation of a hyperbranched polymer if epsilon(AB)/epsilon(AA) is large. We find that the theoretical predictions describe quite accurately the numerical data, especially in the region where Y-junctions are present. There is fairly good agreement between theoretical and numerical results both for the thermodynamic (number of bonds and phase coexistence) and the connectivity properties of the model (cluster size distributions and percolation locus).

Percolation of colloids with distinct interaction sites

We generalize the Flory-Stockmayer theory of percolation to a model of associating (patchy) colloids, which consists of hard spherical particles, having on their surfaces f short-ranged-attractive sites of m different types. These sites can form bonds between particles and thus promote self-assembly. It is shown that the percolation threshold is given in terms of the eigenvalues of a m x m matrix, which describes the recursive relations for the number of bonded particles on the ith level of a cluster with no loops; percolation occurs when the largest of these eigenvalues equals unity. Expressions for the probability that a particle is not bonded to the giant cluster, for the average cluster size and the average size of a cluster to which a randomly chosen particle belongs, are also derived. Explicit results for these quantities are computed for the case f = 3 and m = 2. We show how these structural properties are related to the thermodynamics of the associating system by regarding bond formation as a (equilibrium) chemical reaction. This solution of the percolation problem, combined with Wertheim's thermodynamic first-order perturbation theory, allows the investigation of the interplay between phase behavior and cluster formation for general models of patchy colloids.

Sensor de glicose polarimétrico

Esta tese tem como principal objectivo a investigação teórica e experimental do desempenho de um sensor polarimétrico baseado num cristal líquido para medição da concentração de glicose. Recentemente uma série de sensores polarimétricos baseados em cristais líquidos foram propostos na literatura e receberam considerável interesse devido as suas características únicas. De facto, em comparação com outros moduladores electro-ópticos, o cristal líquido funciona com tensões mais baixas, tem baixo consumo de energia e maior ângulo de rotação. Além disso, este tipo de polarímetro pode ter pequenas dimensões que é uma característica interessante para dispositivos portáteis e compactos. Existem por outro lado algumas desvantagens, nomeadamente o facto do desempenho do polarímetro ser fortemente dependente do tipo de cristal líquido e da tensão a ele aplicada o que coloca desafios na escolha dos parâmetros óptimos de operação. Esta tese descreve o desenvolvimento do sensor polarimétrico, incluindo a integração dos componentes de óptica e electrónica, os algoritmos de processamento de sinal e um interface gráfico que facilita a programação de diversos parâmetros de operação e a calibração do sensor. Após a optimização dos parâmetros de operação verificou-se que o dispositivo mede a concentração da glicose em amostras com uma concentração de 8 mg/ml, com uma percentagem de erro inferior a 6% e um desvio padrão de 0,008o. Os resultados foram obtidos para uma amostra com percurso óptico de apenas 1 cm.

Contratos bilaterais em mercados multi-agente de energia eléctrica: protocolo de ofertas alternadas

A liberalização do sector eléctrico, e a consequente criação de mercados de energia eléctrica regulados e liberalizados, mudou a forma de comercialização da electricidade. Em particular, permitiu a entrada de empresas nas actividades de produção e comercialização, aumentando a competitividade e assegurando a liberdade de escolha dos consumidores, para decidir o fornecedor de electricidade que pretenderem. A competitividade no sector eléctrico aumentou a necessidade das empresas que o integram a proporem preços mais aliciantes (do que os preços propostos pelos concorrentes), e contribuiu para o desenvolvimento de estratégias de mercado que atraiam mais clientes e aumentem a eficiência energética e económica. A comercialização de electricidade pode ser realizada em mercados organizados ou através de contratação directa entre comercializadores e consumidores, utilizando os contratos bilaterais físicos. Estes contratos permitem a negociação dos preços de electricidade entre os comercializadores e os consumidores. Actualmente, existem várias ferramentas computacionais para fazer a simulação de mercados de energia eléctrica. Os simuladores existentes permitem simulações de transacções em bolsas de energia, negociação de preços através de contratos bilaterais, e análises técnicas a redes de energia. No entanto, devido à complexidade dos sistemas eléctricos, esses simuladores apresentam algumas limitações. Esta dissertação apresenta um simulador de contratos bilaterais em mercados de energia eléctrica, sendo dando ênfase a um protocolo de ofertas alternadas, desenvolvido através da tecnologia multi-agente. Em termos sucintos, um protocolo de ofertas alternadas é um protocolo de interacção que define as regras da negociação entre um agente vendedor (por exemplo um retalhista) e um agente comprador (por exemplo um consumidor final). Aplicou-se o simulador na resolução de um caso prático, baseado em dados reais. Os resultados obtidos permitem concluir que o simulador, apesar de simplificado, pode ser uma ferramenta importante na ajuda à tomada de decisões inerentes à negociação de contratos bilaterais em mercados de electricidade.

Acompanhamento dos trabalhos de construção de um hotel SANAHotels Amoreiras

Este trabalho final de mestrado baseou-se no acompanhamento da construção do hotel SANA Amoreiras, situado na Avenida Duarte Pacheco nº 12. O empreiteiro geral foi a empresa FDO Construções. Existindo também uma equipa de fiscalização, LMSA, contratada pelo Dono de Obra de forma a efectuar todo o controlo de qualidade. O TFM baseou-se no estágio efectuado para o Dono de obra do hotel onde fui devidamente acompanhada por uma engenheira, orientadora de estágio, que acompanhou de perto o desempenho da minha actividade. Esta função teve como objectivos a gestão de projecto de hotel, interligação entre projectistas e empreiteiro geral, bem prestar o devido acompanhamento de todos trabalhos a realizar. Acompanhei a realização de dois quartos modelo onde o objectivo do Dono de Obra foi testar as diversas soluções ao nível de revestimentos, sanitários, iluminação, mobiliário, decoração e outras soluções de arquitectura, soluções estas a implementar no hotel. Acompanhei também a realização de reuniões de compatibilização e coordenação de todos os projectos de especialidades com o projecto de arquitectura, nomeadamente Avac, Instalações eléctricas, Comunicações, Segurança, Águas, Esgotos, Gás, Incêndio, Cozinhas de forma a ser possível efectuar consultas aos empreiteiros e adjudicar todas estas empreitadas. Foi efectuada uma abordagem à descrição do hotel, suas características, indicação das razões que levaram à sua construção e descrição das várias empreitadas de construção realizadas até então, tal como, demolição, escavação, estrutura, acabamentos e especialidades.

Otimização de sistema de absorção, com coletores solares, para refrigeração de espaços condicionados termicamente (a chiller)

Nos dias que correm questões ambientais e considerações energéticas obrigam a uma inovação constante na procura de soluções de baixo consumo energético e de impacto ambiental baixo, nomeadamente no que diz respeito aos sistemas de climatização e refrigeração. Têm vindo a ser criadas medidas, tanto a nível internacional como nacional, no sentido de reduzir as emissões nocivas para a atmosfera, consequência do excessivo consumo de combustíveis fósseis, e do aumento da rentabilidade da energia e maior utilização de energias renováveis. O presente estudo de dimensionamento de um sistema de absorção, a brometo de lítio/água, com coletores solares, tem por base o sistema de compressão existente num edifício de serviços no centro de Lisboa. Foi efetuada uma analise simplificada dos seus dados de consumo energético, de maneira a verificar a viabilidade económica da substituição do equipamento existente e instalação de um sistema de coletores solares. Concluiu-se que a substituição do equipamento e a instalação de coletores solar, não é atrativa do ponto de vista económico, nesta solução em particular. Contudo, verifica-se uma considerável redução do impacto ambiental do consumo energético do edifício.

KrF pulsed laser deposition of chromium oxide thin films from Cr8O21 targets

Chromium oxides, CrxOy, are of great interest due to the wide variety of their technological applications. Among them, CrO2 has been extensively investigated in recent years because it is an attractive compound for use in spintronic heterostructures. However, its synthesis at low temperatures has been a difficult task due to the metastable nature of this oxide. This is indeed essential to ensure interface quality and the ability to coat thermal-sensitive materials such as those envisaged in spintronic devices. Pulsed Laser Deposition (PLD) is a technique that has the potential to meet the requirements stated above. In this work, we describe our efforts to grow chromium oxide thin films by PLD from Cr8O21 targets, using a KrF excimer laser. The as-deposited films were investigated by X-ray diffraction and Rutherford backscattering spectrometry. Structural and chemical composition studies showed that the films consist of a mixture of amorphous chromium oxides exhibiting different stoichiometries depending on the processing parameters, where nanocrystals of mainly Cr2O3 are dispersed. The analyses do not exclude the possibility of co-deposition of Cr2O3 and a low fraction of CrO2.

The condensation and ordering of models of empty liquids

We consider a simple model consisting of particles with four bonding sites ("patches"), two of type A and two of type B, on the square lattice, and investigate its global phase behavior by simulations and theory. We set the interaction between B patches to zero and calculate the phase diagram as the ratio between the AB and the AA interactions, epsilon(AB)*, varies. In line with previous work, on three-dimensional off-lattice models, we show that the liquid-vapor phase diagram exhibits a re-entrant or "pinched" shape for the same range of epsilon(AB)*, suggesting that the ratio of the energy scales - and the corresponding empty fluid regime - is independent of the dimensionality of the system and of the lattice structure. In addition, the model exhibits an order-disorder transition that is ferromagnetic in the re-entrant regime. The use of low-dimensional lattice models allows the simulation of sufficiently large systems to establish the nature of the liquid-vapor critical points and to describe the structure of the liquid phase in the empty fluid regime, where the size of the "voids" increases as the temperature decreases. We have found that the liquid-vapor critical point is in the 2D Ising universality class, with a scaling region that decreases rapidly as the temperature decreases. The results of simulations and theoretical analysis suggest that the line of order-disorder transitions intersects the condensation line at a multi-critical point at zero temperature and density, for patchy particle models with a re-entrant, empty fluid, regime. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3657406]

Patching up dipoles: can dipolar particles be viewed as patchy colloids?

We investigate whether the liquid-vapour phase transition of strongly dipolar fluids can be understood using a model of patchy colloids. These consist of hard spherical particles with three short-ranged attractive sites (patches) on their surfaces. Two of the patches are of type A and one is of type B. Patches A on a particle may bond either to a patch A or to a patch B on another particle. Formation of an AA (AB) bond lowers the energy by epsilon AA (epsilon AB). In the limit [image omitted], this patchy model exhibits condensation driven by AB-bonds (Y-junctions). Y-junctions are also present in low-density, strongly dipolar fluids, and have been conjectured to play a key role in determining their critical behaviour. We map the dipolar Yukawa hard-sphere (DYHS) fluid onto this 2A + 1B patchy model by requiring that the latter reproduce the correct DYHS critical point as a function of the isotropic interaction strength epsilon Y. This is achieved for sensible values of epsilon AB and the bond volumes. Results for the internal energy and the particle coordination number are in qualitative agreement with simulations of DYHSs. Finally, by taking the limit [image omitted], we arrive at a new estimate for the critical point of the dipolar hard-sphere fluid, which agrees with extrapolations from simulation.

Phase diagrams of binary mixtures of patchy colloids with distinct numbers and types of patches: Theempty fluid regime

We investigate the effect of distinct bonding energies on the onset of criticality of low functionality fluid mixtures. We focus on mixtures ofparticles with two and three patches as this includes the mixture where "empty" fluids were originally reported. In addition to the number of patches, thespecies differ in the type of patches or bonding sites. For simplicity, we consider that the patches on each species are identical: one species has threepatches of type A and the other has two patches of type B. We have found a rich phase behavior with closed miscibility gaps, liquid-liquid demixing, and negative azeotropes. Liquid-liquid demixing was found to pre-empt the "empty" fluid regime, of these mixtures, when the AB bonds are weaker than the AA or BB bonds. By contrast, mixtures in this class exhibit "empty" fluid behavior when the AB bonds are stronger than at least one of the other two. Mixtureswith bonding energies epsilon(BB) = epsilon(AB) and epsilon(AA) < epsilon(BB), were found to exhibit an unusual negative azeotrope. (C) 2011 American Institute of Physics. [doi:10.1063/1.3561396]

Re-entrant phase behaviour of network fluids: A patchy particle model with temperature-dependent valence

We study a model consisting of particles with dissimilar bonding sites ("patches"), which exhibits self-assembly into chains connected by Y-junctions, and investigate its phase behaviour by both simulations and theory. We show that, as the energy cost epsilon(j) of forming Y-junctions increases, the extent of the liquid-vapour coexistence region at lower temperatures and densities is reduced. The phase diagram thus acquires a characteristic "pinched" shape in which the liquid branch density decreases as the temperature is lowered. To our knowledge, this is the first model in which the predicted topological phase transition between a fluid composed of short chains and a fluid rich in Y-junctions is actually observed. Above a certain threshold for epsilon(j), condensation ceases to exist because the entropy gain of forming Y-junctions can no longer offset their energy cost. We also show that the properties of these phase diagrams can be understood in terms of a temperature-dependent effective valence of the patchy particles. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3605703]

Reentrant Phase Diagram of Network Fluids

We introduce a microscopic model for particles with dissimilar patches which displays an unconventional "pinched'' phase diagram, similar to the one predicted by Tlusty and Safran in the context of dipolar fluids [Science 290, 1328 (2000)]. The model-based on two types of patch interactions, which account, respectively, for chaining and branching of the self-assembled networks-is studied both numerically via Monte Carlo simulations and theoretically via first-order perturbation theory. The dense phase is rich in junctions, while the less-dense phase is rich in chain ends. The model provides a reference system for a deep understanding of the competition between condensation and self-assembly into equilibrium-polymer chains.

Chitosan-alginate microparticulate delivery system for an alternative route of administration of BCG vaccine

Immunisation against M. tuberculosis with current available BCG vaccine lacks efficacy in preventing adult pulmonary tuberculosis. Targeting nasal mucosa is an attractive option for a more effective immunization. The delivery of BCG via the intranasal route involves overcoming barriers such as crossing the physical barrier imposed by the mucus layer and ciliar remotion, cellular uptake and intracellular trafficking by antigen presenting cells. Due to its biodegradable, immunogenic and mucoadhesive properties, chitosan particulate delivery systems can act both as vaccine carrier and adjuvant, improving the elicited immune response. In this study, different combinations of Chitosan/Alginate/TPP microparticles with BCG were produced as vaccine systems. The developed microparticle system successfully modulates BCG surface physicochemical properties and promotes effective intracellular uptake by human macrophage cell lines Preliminary immune responses were evaluated after s.c. and intranasal immunisation of BALB/c mice. BCG vaccination successfully stimulated the segregation of IgG2a and IgG1, where intranasal immunisation with chitosan/alginate particulate system efficiently elicited a more equilibrated cellular/humoral immune response.