How patchy can one get and still condense? The role of dissimilar patches in the interactions of colloidal particles

We investigate the influence of strong directional, or bonding, interactions on the phase diagram of complex fluids, and in particular on the liquid-vapour critical point. To this end we revisit a simple model and theory for associating fluids which consist of spherical particles having a hard-core repulsion, complemented by three short-ranged attractive sites on the surface (sticky spots). Two of the spots are of type A and one is of type B; the interactions between each pair of spots have strengths [image omitted], [image omitted] and [image omitted]. The theory is applied over the whole range of bonding strengths and results are interpreted in terms of the equilibrium cluster structures of the coexisting phases. In systems where unlike sites do not interact (i.e. where [image omitted]), the critical point exists all the way to [image omitted]. By contrast, when [image omitted], there is no critical point below a certain finite value of [image omitted]. These somewhat surprising results are rationalised in terms of the different network structures of the two systems: two long AA chains are linked by one BB bond (X-junction) in the former case, and by one AB bond (Y-junction) in the latter. The vapour-liquid transition may then be viewed as the condensation of these junctions and we find that X-junctions condense for any attractive [image omitted] (i.e. for any fraction of BB bonds), whereas condensation of the Y-junctions requires that [image omitted] be above a finite threshold (i.e. there must be a finite fraction of AB bonds).

Self-assembly in chains, rings, and branches: a single component system with two critical points

Agências financiadoras: FCT - PEstOE/FIS/UI0618/2011; PTDC/FIS/098254/2008 ERC-PATCHYCOLLOIDS e MIUR-PRIN

Estudo dos sistema de automação da protecção diferencial de linha e comparação direccional

O tema do sistema de automação da protecção diferencial de linha e comparação direccional é merecedor de uma nova abordagem devido às recentes inovações tecnológicas ocorridas desde o aparecimento dos relés digitais e à consequente comunicação entre os sistemas de protecção, em particular na comunicação entre protecções diferenciais de linha. A protecção diferencial de linha apresenta claras vantagens face às protecções actualmente utilizadas para a protecção de linhas de transmissão e distribuição, tais como, Protecção de Máximo Intensidade de Fase, Máximo Intensidade Homopolar Direccionale Protecção de Distância. Contudo, existem alguns problemas associados a este tipo de protecções, nomeadamente na comunicação entre relés. Para automação e comunicação de protecções diferenciais de linhas de transmissão, no caso da ocorrência de defeitos na zona protegida pelo sistema de protecção diferencial foi empregue um método inovador para este tipo de sistema. Uma vez que a eficácia da actuação das protecções diferenciais depende do rigor das variáveis que são necessárias enviar entre protecções que se encontram localizadas em subestações distintas, recorreu-se à utilização de um automatismo para comunicação entre relés suportado pelo desenvolvimento de novos algoritmos para detectar quase instantaneamente um defeito em qualquer zona de protecção de uma linha de transmissão. Estes algoritmos são baseados na Transformada de Park, pelo que, é introduzido um novo conceito neste tipo de protecções. Através destes algoritmos é possível atenuar os problemas associados à protecção diferencial de linha. No sentido de verificar a aplicabilidade destes algoritmos à protecção diferencial de linha são apresentados diversos casos de estudo. Através dos resultados obtidos também foi possível verificar as vantagens associadas à utilização dos algoritmos propostos.

The K-Th derivatives of the immanant and the X-symmetric power of an operator

In recent papers, formulas are obtained for directional derivatives, of all orders, of the determinant, the permanent, the m-th compound map and the m-th induced power map. This paper generalizes these results for immanants and for other symmetric powers of a matrix.

The norm of the K- Th derivative of the X-symmetric power of an operator

In this paper, the exact value for the norm of directional derivatives, of all orders, for symmetric tensor powers of operators on finite dimensional vector spaces is presented. Using this result, an upper bound for the norm of all directional derivatives of immanants is obtained.

Three-Dimensional patchy lattice model for empty fluids

The phase diagram of a simple model with two patches of type A and ten patches of type B (2A10B) on the face centred cubic lattice has been calculated by simulations and theory. Assuming that there is no interaction between the B patches the behavior of the system can be described in terms of the ratio of the AB and AA interactions, r. Our results show that, similarly to what happens for related off-lattice and two-dimensional lattice models, the liquid-vapor phase equilibria exhibit reentrant behavior for some values of the interaction parameters. However, for the model studied here the liquid-vapor phase equilibria occur for values of r lower than 1/3, a threshold value which was previously thought to be universal for 2AnB models. In addition, the theory predicts that below r = 1/3 (and above a new condensation threshold which is < 1/3) the reentrant liquid-vapor equilibria are so extreme that it exhibits a closed loop with a lower critical point, a very unusual behavior in single-component systems. An order-disorder transition is also observed at higher densities than the liquid-vapor equilibria, which shows that the liquid-vapor reentrancy occurs in an equilibrium region of the phase diagram. These findings may have implications in the understanding of the condensation of dipolar hard spheres given the analogy between that system and the 2AnB models considered here.

Bicontinuous and mixed gels in binary mixtures of patchy colloidal particles

We investigate the thermodynamics and percolation regimes of model binary mixtures of patchy colloidal particles. The particles of each species have three sites of two types, one of which promotes bonding of particles of the same species while the other promotes bonding of different species. We find up to four percolated structures at low temperatures and densities: two gels where only one species percolates, a mixed gel where particles of both species percolate but neither species percolates separately, and a bicontinuous gel where particles of both species percolate separately forming two interconnected networks. The competition between the entropy and the energy of bonding drives the stability of the different percolating structures. Appropriate mixtures exhibit one or more connectivity transitions between the mixed and bicontinuous gels, as the temperature and/or the composition changes.

Properties of patchy colloidal particles close to a surface: a Monte Carlo and density functional study

We investigate the behavior of a patchy particle model close to a hard-wall via Monte Carlo simulation and density functional theory (DFT). Two DFT approaches, based on the homogeneous and inhomogeneous versions of Wertheim's first order perturbation theory for the association free energy are used. We evaluate, by simulation and theory, the equilibrium bulk phase diagram of the fluid and analyze the surface properties for two isochores, one of which is close to the liquid side of the gas-liquid coexistence curve. We find that the density profile near the wall crosses over from a typical high-temperature adsorption profile to a low-temperature desorption one, for the isochore close to coexistence. We relate this behavior to the properties of the bulk network liquid and find that the theoretical descriptions are reasonably accurate in this regime. At very low temperatures, however, an almost fully bonded network is formed, and the simulations reveal a second adsorption regime which is not captured by DFT. We trace this failure to the neglect of orientational correlations of the particles, which are found to exhibit surface induced orientational order in this regime.

Quantitative description of the self-assembly of patchy particles into chains and rings

We numerically study a simple fluid composed of particles having a hard-core repulsion complemented by two patchy attractive sites on the particle poles. An appropriate choice of the patch angular width allows for the formation of ring structures which, at low temperatures and low densities, compete with the growth of linear aggregates. The simplicity of the model makes it possible to compare simulation results and theoretical predictions based on the Wertheim perturbation theory, specialized to the case in which ring formation is allowed. Such a comparison offers a unique framework for establishing the quality of the analytic predictions. We find that the Wertheim theory describes remarkably well the simulation results.

Sistema de auto calibração visual para robots do ISePorto, baseado em EKF

Os sistemas de perceção existentes nos robôs autónomos, hoje em dia, são bastante complexos. A informação dos vários sensores, existentes em diferentes partes do robôs, necessitam de estar relacionados entre si face ao referencial do robô ou do mundo. Para isso, o conhecimento da atitude (posição e rotação) entre os referenciais dos sensores e o referencial do robô é um fator critico para o desempenho do mesmo. O processo de calibração dessas posições e translações é chamado calibração dos parâmetros extrínsecos. Esta dissertação propõe o desenvolvimento de um método de calibração autónomo para robôs como câmaras direcionais, como é o caso dos robôs da equipa ISePorto. A solução proposta consiste na aquisição de dados da visão, giroscópio e odometria durante uma manobra efetuada pelo robô em torno de um alvo com um padrão conhecido. Esta informação é então processada em conjunto através de um Extended Kalman Filter (EKF) onde são estimados necessários para relacionar os sensores existentes no robô em relação ao referencial do mesmo. Esta solução foi avaliada com recurso a vários testes e os resultados obtidos foram bastante similares aos obtidos pelo método manual, anteriormente utilizado, com um aumento significativo em rapidez e consistência.

Variação dos parâmetros paleomagnéticos em perfis dos Tufos de Condeixa (Baixo Mondego, Portugal)

Paleomagnetic parameters measured in 4 outcrops of the Tufos de Condeixa are presented. The directional signatures allow the admission of the Reversed Polarity Criptchron C1n-1 in the Condeixa-a-Velha outcrop. It was possible to discuss the magnetic properties, origin of the magnetic grains and paleoclimatic variation relationships. The downward of the initial magnetization and magnetic susceplibility values in the Condeixa-a-Velha outcrop coincide with the Cln-1 (504-493 Ka) occurrence and may represent a paleoclimatic variation. The Tufos de Condeixa were formed during the Ionian-Tarentian(?).

Liquid-vapor interfaces of patchy colloids

We investigate the liquid-vapor interface of a model of patchy colloids. This model consists of hard spheres decorated with short-ranged attractive sites ("patches") of different types on their surfaces. We focus on a one-component fluid with two patches of type A and nine patches of type B (2A9B colloids), which has been found to exhibit reentrant liquid-vapor coexistence curves and very low-density liquid phases. We have used the density-functional theory form of Wertheim's first-order perturbation theory of association, as implemented by Yu and Wu [J. Chem. Phys. 116, 7094 (2002)], to calculate the surface tension, and the density and degree of association profiles, at the liquid-vapor interface of our model. In reentrant systems, where AB bonds dominate, an unusual thickening of the interface is observed at low temperatures. Furthermore, the surface tension versus temperature curve reaches a maximum, in agreement with Bernardino and Telo da Gama's mesoscopic Landau-Safran theory [Phys. Rev. Lett. 109, 116103 (2012)]. If BB attractions are also present, competition between AB and BB bonds gradually restores the monotonic temperature dependence of the surface tension. Lastly, the interface is "hairy," i.e., it contains a region where the average chain length is close to that in the bulk liquid, but where the density is that of the vapor. Sufficiently strong BB attractions remove these features, and the system reverts to the behavior seen in atomic fluids.

GLODS: Global and Local Optimization using Direct Search

Locating and identifying points as global minimizers is, in general, a hard and time-consuming task. Difficulties increase in the impossibility of using the derivatives of the functions defining the problem. In this work, we propose a new class of methods suited for global derivative-free constrained optimization. Using direct search of directional type, the algorithm alternates between a search step, where potentially good regions are located, and a poll step where the previously located promising regions are explored. This exploitation is made through the launching of several instances of directional direct searches, one in each of the regions of interest. Differently from a simple multistart strategy, direct searches will merge when sufficiently close. The goal is to end with as many direct searches as the number of local minimizers, which would easily allow locating the global extreme value. We describe the algorithmic structure considered, present the corresponding convergence analysis and report numerical results, showing that the proposed method is competitive with currently commonly used global derivative-free optimization solvers.

On derivatives and norms of generalized matrix functions and respective symmetric powers

In recent papers, the authors obtained formulas for directional derivatives of all orders, of the immanant and of the m-th xi-symmetric tensor power of an operator and a matrix, when xi is a character of the full symmetric group. The operator norm of these derivatives was also calculated. In this paper, similar results are established for generalized matrix functions and for every symmetric tensor power.

Dimensionamento do Sistema Híbrido para Alimentação de Energia Elétrica da Escola Rural de Nangade (Cabo Delgado)

Os combustíveis fósseis, como o carvão, o petróleo e o gás, constituem fontes de energia que em breve se esgotarão e que são demasiado caras para serem desperdiçadas pelas centrais elétricas na produção de electricidade. Para além desse facto, existem outros argumentos (sobretudo económicos) que inviabilizam a utilização destas fontes de energia em algumas regiões, abrindo caminho a fontes de energia alternativas (e.g. solar, eólica, biomassa, mini-hídricas, geotérmicas, etc) e preferencialmente com contornos locais. No caso particular de Moçambique, tem-se verificado um interesse crescente por parte do governo e de várias ONGs na promoção do uso de energias alternativas para as zonas onde a energia convencional não chega e não chegará, devido aos custos muito elevados que esse processo acarretaria. Esta dissertação apresenta um estudo aprofundado do dimensionamento dum sistema híbrido de geração de energia elétrica envolvendo gerador FV e grupo eletrogéneo de emergência para a Escola Rural da Nangade, situada no Distrito de Nangade, na Província do Cabo Delgado. São também descritos os diversos componentes e as tecnologias associadas a um sistema deste género, com a inclusão de sistemas inteligentes de controlo de energia com a utilização de inversores bidireccionais (inversores de bateria e carregadores) para sistemas isolados. Os resultados são apresentados de forma a facilitar a aplicação e montagem deste tipo de sistemas in loco. Espera-se que esta dissertação possa servir de base no futuro próximo, para a implementação deste tipo de sistemas para permitir a melhoria da qualidade de ensino através de melhores infraestruturas, democratizando desta forma o acesso à educação para as crianças das zonas rurais das várias províncias de Moçambique. Como as energias renováveis são parte integrante do Sistema Elétrico Nacional, apresenta-se resumidamente, no anexo 17, o “Plano de Desenvolvimento na Área de Energia de Moçambique”.