Computing the phase diagram of binary mixtures: A patchy particle case study

We investigate the phase behaviour of 2D mixtures of bi-functional and three-functional patchy particles and 3D mixtures of bi-functional and tetra-functional patchy particles by means of Monte Carlo simulations and Wertheim theory. We start by computing the critical points of the pure systems and then we investigate how the critical parameters change upon lowering the temperature. We extend the successive umbrella sampling method to mixtures to make it possible to extract information about the phase behaviour of the system at a fixed temperature for the whole range of densities and compositions of interest. (C) 2013 AIP Publishing LLC.

Biaxial Nematic Order in the Hard-boomerang Fluid

We consider a fluid of hard boomerangs, each composed of two hard spherocylinders joined at their ends at an angle Psi. The resulting particle is nonconvex and biaxial. The occurence of nematic order in such a system has been investigated using Straley's theory, which is a simplificaton of Onsager's second-virial treatment of long hard rods, and by bifurcation analysis. The excluded volume of two hard boomerangs has been approximated by the sum of excluded volumes of pairs of constituent spherocylinders, and the angle-dependent second-virial coefficient has been replaced by a low-order interpolating function. At the so-called Landau point, Psi(Landau)approximate to 107.4 degrees, the fluid undergoes a continuous transition from the isotropic to a biaxial nematic (B) phase. For Psi not equal Psi(Landau) ordering is via a first-order transition into a rod-like uniaxial nematic phase (N(+)) if Psi > Psi(Landau), or a plate-like uniaxial nematic (N(-)) phase if Psi < Psi(Landau). The B phase is separated from the N(+) and N(-) phases by two lines of continuous transitions meeting at the Landau point. This topology of the phase diagram is in agreement with previous studies of spheroplatelets and biaxial ellipsoids. We have checked the accuracy of our theory by performing numerical calculations of the angle-dependent second virial coefficient, which yields Psi(Landau)approximate to 110 degrees for very long rods, and Psi(Landau)approximate to 90 degrees for short rods. In the latter case, the I-N transitions occur at unphysically high packing fractions, reflecting the inappropriateness of the second-virial approximation in this limit.

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.

Thermal Residual Stresses in Functionally Graded Structures: a Didactic Case Study

Conferência: 2nd Experiment at International Conference - 18-20 September 2013

Sistema de animação de personagens virtuais para comunicação não verbal

O principal objectivo da animação de personagens virtuais é o de contar uma história através da utilização de personagens virtuais emocionalmente expressivos. Os personagens têm personalidades distintas, e transmitem as suas emoções e processos de pensamento através dos seus comportamentos (comunicação não verbal). As suas acções muitas das vezes constituem a geração de movimentos corporais complexos. Existem diversas questões a considerar quando se anima uma entidade complexa, tais como, a posição das zonas móveis e as suas velocidades. Os personagens virtuais são um exemplo de entidades complexas e estão entre os elementos mais utilizados em animação computacional. O foco desta dissertação consistiu na criação de uma proposta de sistema de animação de personagens virtuais, cujos movimentos e expressões faciais são capazes de transmitir emoções e estados de espírito. Os movimentos primários, ou seja os movimentos que definem o comportamento dos personagens, são provenientes da captura de movimentos humanos (Motion Capture). As animações secundárias, tais como as expressões faciais, são criadas em Autodesk Maya recorrendo à técnica BlendShapes. Os dados obtidos pela captura de movimentos, são organizados numa biblioteca de comportamentos através de um grafo de movimentos, conhecido por Move Tree. Esta estrutura permite o controlo em tempo real dos personagens através da gestão do estado dos personagens. O sistema possibilita também a transição eficaz entre movimentos semelhantes e entre diferentes velocidades de locomoção, minimizando o efeito de arrastamento de pés conhecido como footskate. Torna-se assim possível definir um trajecto que o personagem poderá seguir com movimentos suaves. Estão também disponíveis os resultados obtidos nas sessões de avaliação realizadas, que visaram a determinação da qualidade das transições entre animações. Propõem-se ainda o melhoramento do sistema através da implementação da construção automática do grafo de movimentos.

A transição do pré-escolar para o 1ºCEB: uma preocupação de todos

Relatório da Prática Profissional Supervisionada Mestrado em Educação Pré-Escolar

Thermodynamic pathway for the formation of SnSe and SnSe2 polycrystalline thin films by selenization of metal precursors

In this work, tin selenide thin films (SnSex) were grown on soda lime glass substrates by selenization of dc magnetron sputtered Sn metallic precursors. Selenization was performed at maximum temperatures in the range 300 °C to 570 °C. The thickness and the composition of the films were analysed using step profilometry and energy dispersive spectroscopy, respectively. The films were structurally and optically investigated by X-ray diffraction, Raman spectroscopy and optical transmittance and reflectance measurements. X-Ray diffraction patterns suggest that for temperatures between 300 °C and 470 °C, the films are composed of the hexagonal-SnSe2 phase. By increasing the temperature, the films selenized at maximum temperatures of 530 °C and 570 °C show orthorhombic-SnSe as the dominant phase with a preferential crystal orientation along the (400) crystallographic plane. Raman scattering analysis allowed the assignment of peaks at 119 cm−1 and 185 cm−1 to the hexagonal-SnSe2 phase and those at 108 cm−1, 130 cm−1 and 150 cm−1 to the orthorhombic-SnSe phase. All samples presented traces of condensed amorphous Se with a characteristic Raman peak located at 255 cm−1. From optical measurements, the estimated band gap energies for hexagonal-SnSe2 were close to 0.9 eV and 1.7 eV for indirect forbidden and direct transitions, respectively. The samples with the dominant orthorhombic-SnSe phase presented estimated band gap energies of 0.95 eV and 1.15 eV for indirect allowed and direct allowed transitions, respectively.

Photoluminescence and electrical study of fluctuating potentials in Cu2ZnSnS4-based thin films

In this work, we investigated structural, morphological, electrical, and optical properties from a set of Cu2ZnSnS4 thin films grown by sulfurization of metallic precursors deposited on soda lime glass substrates coated with or without molybdenum. X-ray diffraction and Raman spectroscopy measurements revealed the formation of single-phase Cu2ZnSnS4 thin films. A good crystallinity and grain compactness of the film was found by scanning electron microscopy. The grown films are poor in copper and rich in zinc, which is a composition close to that of the Cu2ZnSnS4 solar cells with best reported efficiency. Electrical conductivity and Hall effect measurements showed a high doping level and a strong compensation. The temperature dependence of the free hole concentration showed that the films are nondegenerate. Photoluminescence spectroscopy showed an asymmetric broadband emission. The experimental behavior with increasing excitation power or temperature cannot be explained by donor-acceptor pair transitions. A model of radiative recombination of an electron with a hole bound to an acceptor level, broadened by potential fluctuations of the valence-band edge, was proposed. An ionization energy for the acceptor level in the range 29–40 meV was estimated, and a value of 172 ±2 meV was obtained for the potential fluctuation in the valence-band edge.

Study of optical and structural properties of Cu2ZnSnS4 thin films

Cu2ZnSnS4 is a promising semiconductor to be used as absorber in thin film solar cells. In this work, we investigated optical and structural properties of Cu2ZnSnS4 thin films grown by sulphurization of metallic precursors deposited on soda lime glass substrates. The crystalline phases were studied by X-ray diffraction measurements showing the presence of only the Cu2ZnSnS4 phase. The studied films were copper poor and zinc rich as shown by inductively coupled plasma mass spectroscopy. Scanning electron microscopy revealed a good crystallinity and compactness. An absorption coefficient varying between 3 and 4×104cm−1 was measured in the energy range between 1.75 and 3.5 eV. The band gap energy was estimated in 1.51 eV. Photoluminescence spectroscopy showed an asymmetric broad band emission. The dependence of this emission on the excitation power and temperature was investigated and compared to the predictions of the donor-acceptor-type transitions and radiative recombinations in the model of potential fluctuations. Experimental evidence was found to ascribe the observed emission to radiative transitions involving tail states created by potential fluctuations.

O percurso escolar de adolescentes com síndrome de asperger

Dissertação apresentada à Escola Superior de Educação de Lisboa Para obtenção de grau de mestre em Ciências da Educação, Especialidade em Educação Especial – Problemas de Cognição e Multideficiência

Online intra-task device scheduling for hard real-time systems

A large part of power dissipation in a system is generated by I/O devices. Increasingly these devices provide power saving mechanisms, inter alia to enhance battery life. While I/O device scheduling has been studied in the past for realtime systems, the use of energy resources by these scheduling algorithms may be improved. These approaches are crafted considering a very large overhead of device transitions. Technology enhancements have allowed the hardware vendors to reduce the device transition overhead and energy consumption. We propose an intra-task device scheduling algorithm for real time systems that allows to shut-down devices while ensuring system schedulability. Our results show an energy gain of up to 90% when compared to the techniques proposed in the state-of-the-art.

Transitional justice in the judiciary: lessons from the portuguese democratisation

The nature of the Portuguese transition to democracy and the following state crises (1974-1975) created a ‘window of opportunity’ in which the ‘reaction to the past’ was much stronger than in the other Southern or even of Central and Eastern European transitions. In Portugal, initiatives of symbolic rupture with the past began soon after the April 25, 1974, coup d’état and transitional justice policies assumed mainly three formulas. First, the institutional reforms directed primarily to abusive state institutions such as the political police (PIDE-DGS) and political courts (Plenary courts) in order to dismantle the repressive apparatus and prevent further human rights abuses and impunity. Secondly, the criminal prosecutions addressed to perpetrators considered as being the most responsible for repression and abuses. Finally, lustration or political purges (saneamentos, the term used in Portugal to designate political purges) which were, in fact, the most common form of political justice in Portuguese transition to democracy. This paper deals with the peculiarities of transitional justice in Portugal devoting a particular attention to the judicial, a key sector to understand the way the Portuguese dealt with their authoritarian past.

Global-EDF scheduling of multimode real- time systems considering mode independent tasks

Embedded real-time systems often have to support the embedding system in very different and changing application scenarios. An aircraft taxiing, taking off and in cruise flight is one example. The different application scenarios are reflected in the software structure with a changing task set and thus different operational modes. At the same time there is a strong push for integrating previously isolated functionalities in single-chip multicore processors. On such multicores the behavior of the system during a mode change, when the systems transitions from one mode to another, is complex but crucial to get right. In the past we have investigated mode change in multiprocessor systems where a mode change requires a complete change of task set. Now, we present the first analysis which considers mode changes in multicore systems, which use global EDF to schedule a set of mode independent (MI) and mode specific (MS) tasks. In such systems, only the set of MS tasks has to be replaced during mode changes, without jeopardizing the schedulability of the MI tasks. Of prime concern is that the mode change is safe and efficient: i.e. the mode change needs to be performed in a predefined time window and no deadlines may be missed as a function of the mode change.

Broad-temperature range spectroscopy of the two-centre modular redox metalloprotein Desulfovibrio desulfuricans desulfoferrodoxin

Dalton Trans., 2003, 3328-3338

Chiroptical and emissive properties of a calix[4]arene-containing chiral poly (P-phenylene ethynylene) with enantioselective recognition ability

Supramolecular chirality was achieved in solutions and thin films of a calixarene-containing chiral aryleneethynylene copolymer. The observed chiroptical activity, which is primarily allied with the formation of aggregates of high molecular weight polymer chains, is the result of a combination of intrachain and interchain effects. The former arises by the adoption of an induced helix-sense by the polymer main-chain while the latter comes from the exciton coupling of aromatic backbone transitions. The co-existence of bulky bis-calixKlarene units and chiral side-chains on the polymer skeleton prevents efficient pi-stacking of neighbouring chains, keeping the chiral assembly highly emissive. In contrast, for a model polymer lacking calixarene moieties, the chiroptical activity is dominated by strong interchain exciton couplings as a result of more favourable packing of polymer chains, leading to a marked decrease of photoluminescence in the aggregate state. The enantiomeric recognition abilities of both polymers towards (R)- and (S)-alpha-methylbenzylamine were examined. It was found that a significant enantiodiscrimination is exhibited by the calixarene-based polymer in the aggregate state.