Synthesis, structure, and optical properties of an alternating calix[4]arene-based meta-linked phenylene ethynylene copolymer

Novel alternating copolymers comprising biscalix[4]arene-p-phenylene ethynylene and m-phenylene ethynylene units (CALIX-m-PPE) were synthesized using the Sonogashira-Hagihara cross-coupling polymerization. Good isolated yields (60-80%) were achieved for the polymers that show M-n ranging from 1.4 x 10(4) to 5.1 x 10(4) gmol(-1) (gel permeation chromatography analysis), depending on specific polymerization conditions. The structural analysis of CALIX-m-PPE was performed by H-1, C-13, C-13-H-1 heteronuclear single quantum correlation (HSQC), C-13-H-1 heteronuclear multiple bond correlation (HMBC), correlation spectroscopy (COSY), and nuclear overhauser effect spectroscopy (NOESY) in addition to Fourier transform-Infrared spectroscopy and microanalysis allowing its full characterization. Depending on the reaction setup, variable amounts (16-45%) of diyne units were found in polymers although their photophysical properties are essentially the same. It is demonstrated that CALIX-m-PPE does not form ground-or excited-state interchain interactions owing to the highly crowded environment of the main-chain imparted by both calix[4]arene side units which behave as insulators inhibiting main-chain pi-pi staking. It was also found that the luminescent properties of CALIX-m-PPE are markedly different from those of an all-p-linked phenylene ethynylene copolymer (CALIX-p-PPE) previously reported. The unexpected appearance of a low-energy emission band at 426 nm, in addition to the locally excited-state emission (365 nm), together with a quite low fluorescence quantum yield (Phi = 0.02) and a double-exponential decay dynamics led to the formulation of an intramolecular exciplex as the new emissive species.

Grid structure impact in sparse point representation of derivatives

In the Sparse Point Representation (SPR) method the principle is to retain the function data indicated by significant interpolatory wavelet coefficients, which are defined as interpolation errors by means of an interpolating subdivision scheme. Typically, a SPR grid is coarse in smooth regions, and refined close to irregularities. Furthermore, the computation of partial derivatives of a function from the information of its SPR content is performed in two steps. The first one is a refinement procedure to extend the SPR by the inclusion of new interpolated point values in a security zone. Then, for points in the refined grid, such derivatives are approximated by uniform finite differences, using a step size proportional to each point local scale. If required neighboring stencils are not present in the grid, the corresponding missing point values are approximated from coarser scales using the interpolating subdivision scheme. Using the cubic interpolation subdivision scheme, we demonstrate that such adaptive finite differences can be formulated in terms of a collocation scheme based on the wavelet expansion associated to the SPR. For this purpose, we prove some results concerning the local behavior of such wavelet reconstruction operators, which stand for SPR grids having appropriate structures. This statement implies that the adaptive finite difference scheme and the one using the step size of the finest level produce the same result at SPR grid points. Consequently, in addition to the refinement strategy, our analysis indicates that some care must be taken concerning the grid structure, in order to keep the truncation error under a certain accuracy limit. Illustrating results are presented for 2D Maxwell's equation numerical solutions.

Optimal design of piezolaminated structures using B-spline strip finite element models

A package of B-spline finite strip models is developed for the linear analysis of piezolaminated plates and shells. This package is associated to a global optimization technique in order to enhance the performance of these types of structures, subjected to various types of objective functions and/or constraints, with discrete and continuous design variables. The models considered are based on a higher-order displacement field and one can apply them to the static, free vibration and buckling analyses of laminated adaptive structures with arbitrary lay-ups, loading and boundary conditions. Genetic algorithms, with either binary or floating point encoding of design variables, were considered to find optimal locations of piezoelectric actuators as well as to determine the best voltages applied to them in order to obtain a desired structure shape. These models provide an overall economy of computing effort for static and vibration problems.

Completion problems for real matrices, II

Thirty years ago, G.N. de Oliveira has proposed the following completion problems: Describe the possible characteristic polynomials of [C-ij], i,j is an element of {1, 2}, where C-1,C-1 and C-2,C-2 are square submatrices, when some of the blocks C-ij are fixed and the others vary. Several of these problems remain unsolved. This paper gives the solution, over the field of real numbers, of Oliveira's problem where the blocks C-1,C-1, C-2,C-2 are fixed and the others vary.

From unthinned continent to ocean: The deep structure of the West Iberia passive continental margin at 38 degrees N

The crustal and lithospheric mantle structure at the south segment of the west Iberian margin was investigated along a 370 km long seismic transect. The transect goes from unthinned continental crust onshore to oceanic crust, crossing the ocean-continent transition (OCT) zone. The wide-angle data set includes recordings from 6 OBSs and 2 inland seismic stations. Kinematic and dynamic modeling provided a 2D velocity model that proved to be consistent with the modeled free-air anomaly data. The interpretation of coincident multi-channel near-vertical and wide-angle reflection data sets allowed the identification of four main crustal domains: (i) continental (east of 9.4 degrees W); (ii) continental thinning (9.4 degrees W-9.7 degrees W): (iii) transitional (9.7 degrees W-similar to 10.5 degrees W); and (iv) oceanic (west of similar to 10.5 degrees W). In the continental domain the complete crustal section of slightly thinned continental crust is present. The upper (UCC, 5.1-6.0 km/s) and the lower continental crust (LCC, 6.9-7.2 km/s) are seismically reflective and have intermediate to low P-wave velocity gradients. The middle continental crust (MCC, 6.35-6.45 km/s) is generally unreflective with low velocity gradient. The main thinning of the continental crust occurs in the thinning domain by attenuation of the UCC and the LCC. Major thinning of the MCC starts to the west of the LCC pinchout point, where it rests directly upon the mantle. In the thinning domain the Moho slope is at least 13 degrees and the continental crust thickness decreases seaward from 22 to 11 km over a similar to 35 km distance, stretched by a factor of 1.5 to 3. In the oceanic domain a two-layer high-gradient igneous crust (5.3-6.0 km/s; 6.5-7.4 km/s) was modeled. The intra-crustal interface correlates with prominent mid-basement, 10-15 km long reflections in the multi-channel seismic profile. Strong secondary reflected PmP phases require a first order discontinuity at the Moho. The sedimentary cover can be as thick as 5 km and the igneous crustal thickness varies from 4 to 11 km in the west, where the profile reaches the Madeira-Tore Rise. In the transitional domain the crust has a complex structure that varies both horizontally and vertically. Beneath the continental slope it includes exhumed continental crust (6.15-6.45 km/s). Strong diffractions were modeled to originate at the lower interface of this layer. The western segment of this transitional domain is highly reflective at all levels, probably due to dykes and sills, according to the high apparent susceptibility and density modeled at this location. Sub-Moho mantle velocity is found to be 8.0 km/s, but velocities smaller than 8.0 km/s confined to short segments are not excluded by the data. Strong P-wave wide-angle reflections are modeled to originate at depth of 20 km within the lithospheric mantle, under the eastern segment of the oceanic domain, or even deeper at the transitional domain, suggesting a layered structure for the lithospheric mantle. Both interface depths and velocities of the continental section are in good agreement to the conjugate Newfoundland margin. A similar to 40 km wide OCT having a geophysical signature distinct from the OCT to the north favors a two pulse continental breakup.

Enhanced short wavelength response in laser-scanned-photodiode image sensor using an a-SiC : H/a-Si : H tandem structure

We report in this paper the recent advances we obtained in optimizing a color image sensor based on the laser-scanned-photodiode (LSP) technique. A novel device structure based on a a-SiC:H/a-Si:H pin/pin tandem structure has been tested for a proper color separation process that takes advantage on the different filtering properties due to the different light penetration depth at different wavelengths a-SM and a-SiC:H. While the green and the red images give, in comparison with previous tested structures, a weak response, this structure shows a very good recognition of blue color under reverse bias, leaving a good margin for future device optimization in order to achieve a complete and satisfactory RGB image mapping. Experimental results about the spectral collection efficiency are presented and discussed from the point of view of the color sensor applications. The physics behind the device functioning is explained by recurring to a numerical simulation of the internal electrical configuration of the device.

Novel structure for large area image sensing

This work presents preliminary results in the study of a novel structure for a laser scanned photodiode (LSP) type of image sensor. In order to increase the signal output, a stacked p-i-n-p-i-n structure with an intermediate light-blocking layer is used. The image and the scanning beam are incident through opposite sides of the sensor and their absorption is kept in separate junctions by an intermediate light-blocking layer. As in the usual LSP structure the scanning beam-induced photocurrent is dependent on the local illumination conditions of the image. The main difference between the two structures arises from the fact that in this new structure the image and the scanner have different optical paths leading to an increase in the photocurrent when the scanning beam is incident on a region illuminated on the image side of the sensor, while a decreasing in the photocurrent was observed in the single junction LSP. The results show that the structure can be successfully used as an image sensor even though some optimization is needed to enhance the performance of the device.

Projecto de reabilitação e reforço de um túnel ferroviário

As obras de arte e as demais estruturas, são dimensionadas para um tempo de vida útil em serviço. Com o passar do tempo as estruturas começam a apresentar patologias e assim sendo há que intervir em serviços de manutenção ou, no limite, de recuperação e reforço. Estas intervenções servem para beneficiar ou reforçar as estruturas, com o intuito de evitar acidentes, pois estes, levariam a grandes prejuízos e contratempos, principalmente quando estas obras se situam em meios urbanos. Os problemas patológicos que surgem numa estrutura são ocasionados pela sua antiguidade, por manutenção inadequada ou mesmo ausência de total de manutenção, têm na sua origem o desconhecimento técnico e/ou problemas financeiros. Este trabalho consiste num projecto de beneficiação e reforço de um túnel ferroviário, fazendo uma abordagem das patologias existentes nos vários elementos construtivos e uma apresentação das técnicas de reabilitação e reforço utilizadas.

Influence of growth temperature and carrier flux on the structure and transport properties of highly oriented CrO2 on Al2O3 (0001)

In this work we report on the structure and magnetic and electrical transport properties of CrO2 films deposited onto (0001) sapphire by atmospheric pressure (AP)CVD from a CrO3 precursor. Films are grown within a broad range of deposition temperatures, from 320 to 410 degrees C, and oxygen carrier gas flow rates of 50-500 seem, showing that it is viable to grow highly oriented a-axis CrO2 films at temperatures as low as 330 degrees C i.e., 60-70 degrees C lower than is reported in published data for the same chemical system. Depending on the experimental conditions, growth kinetic regimes dominated either by surface reaction or by mass-transport mechanisms are identified. The growth of a Cr2O3 interfacial layer as an intrinsic feature of the deposition process is studied and discussed. Films synthesized at 330 degrees C keep the same high quality magnetic and transport properties as those deposited at higher temperatures.

A New Modular Marx Derived Multilevel Converter

A new Modular Marx Multilevel Converter, M(3)C, is presented. The M(3)C topology was developed based on the Marx Generator concept and can contribute to technological innovation for sustainability by enabling wind energy off-shore modular multilevel power switching converters with an arbitrary number of levels. This paper solves both the DC capacitor voltage balancing problem and modularity problems of multilevel converters, using a modified cell of a solid-state Marx modulator, previously developed by authors for high voltage pulsed power applications. The paper details the structure and operation of the M(3)C modules, and their assembling to obtain multilevel converters. Sliding mode control is applied to a M(3)C leg and the vector leading to automatic capacitor voltage equalization is chosen. Simulation results are presented to show the effectiveness of the proposed M(3)C topology.

Damage detection and quantification using transmissibility

Structures experience various types of loads along their lifetime, which can be either static or dynamic and may be associated to phenomena of corrosion and chemical attack, among others. As a consequence, different types of structural damage can be produced; the deteriorated structure may have its capacity affected, leading to excessive vibration problems or even possible failure. It is very important to develop methods that are able to simultaneously detect the existence of damage and to quantify its extent. In this paper the authors propose a method to detect and quantify structural damage, using response transmissibilities measured along the structure. Some numerical simulations are presented and a comparison is made with results using frequency response functions. Experimental tests are also undertaken to validate the proposed technique. (C) 2011 Elsevier Ltd. All rights reserved.

Positive solutions of fourth order problems with clamped beam boundary conditions

n this paper we make an exhaustive study of the fourth order linear operator u((4)) + M u coupled with the clamped beam conditions u(0) = u(1) = u'(0) = u'(1) = 0. We obtain the exact values on the real parameter M for which this operator satisfies an anti-maximum principle. Such a property is equivalent to the fact that the related Green's function is nonnegative in [0, 1] x [0, 1]. When M < 0 we obtain the best estimate by means of the spectral theory and for M > 0 we attain the optimal value by studying the oscillation properties of the solutions of the homogeneous equation u((4)) + M u = 0. By using the method of lower and upper solutions we deduce the existence of solutions for nonlinear problems coupled with this boundary conditions. (C) 2011 Elsevier Ltd. All rights reserved.

O trabalho de projeto no desenvolvimento da cidadania

Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Educação Matemática na Educação Pré-Escolar e nos 1º e 2º Ciclos do Ensino Básico

Projeto de estruturas e fundações de um edifício de serviços

O presente trabalho é o culminar de um percurso académico cheio de aprendizagens que me preencheu por completo. A realização de um projeto de estruturas como trabalho final de mestrado (TFM) foi uma escolha fácil, pois, na minha opinião, permite fazer a transição entre os conceitos adquiridos durante o curso e os métodos utilizados no ambiente não académico. O objetivo do trabalho é realizar o projeto de estruturas e fundações de um edifício destinado a serviços. Foram aplicados os conhecimentos adquiridos ao longo de todo o curso de Engenharia Civil, em especial das Unidades Curriculares de dimensionamento de estruturas. Foi elaborado um modelo da estrutura num programa de cálculo automático: SAP2000. Assim, de acordo com os resultados fornecidos pelo programa e através da consulta dos regulamentos nacionais (REBAP e RSA) e internacionais (Eurocódigos), foi possível dimensionar todos os elementos estruturais. Os diferentes aspetos condicionantes no projeto foram devidamente analisados e discutidos, por forma a encontrar a solução que mais se adequa ao pretendido. Todas as opções tomadas são devidamente justificadas, procurando-se elaborar um trabalho detalhado e, acima de tudo, correto. É importante dizer ainda que, a permanente troca de ideias e conhecimentos entre colegas e, como é óbvio, com o orientador do trabalho, foi muito relevante na realização deste trabalho. Uma parte essencial de um projeto são, sem dúvida, as peças desenhadas. Nesse capítulo tentou-se atingir um nível de detalhe e simplicidade que permita uma interpretação inequívoca dos mesmos.

Execução da Augi 42, Casal do Sapo, Sesimbra

O estágio desenvolvido na empresa de construção Manuel da Graça Peixito, incidiu sobre Direcção e Gestão de Obra na execução de um projecto de reconversão urbanística a aplicar na AUGI 42 localizada no Casal do Sapo em Sesimbra. As áreas urbanas de génese ilegal, denominadas de AUGI, surgiram no inicio da década de 60, como um fenómeno que surgiu de forma a colmatar a carência no parque habitacional das periferias das grandes áreas metropolitanas do território nacional. O ambiente urbano gerado pela existência das AUGI, muitas vezes de proporções de grande dimensão, evidencia inúmeras carências e problemas a níveis sociais, económicos, urbanísticos e legais. A gestão de obra é uma actividade essencial na execução da obra e no planeamento de todas as tarefas a realizar com o melhor tratamento económico e financeiro. A direcção de obra tem como principais funções a selecção de recursos humanos, escolha e montagem dos órgãos de apoio logístico, a aquisição atempada e negociação de materiais. O Gestor e Director de Obra é colocado num ciclo operacional de optimização de recursos e eficiências, em que as duas funções, gestão e direcção de obra, são complementares e a abordagem do contexto interactivo do controlo da obra, em termos da produção, da gestão económica e financeira, da gestão do tempo, do cumprimento das normas de saúde e segurança no trabalho e no assegurar da qualidade, são claramente identificadas, enquanto veículo indispensável do cumprimento do contrato de empreitada. O processo de reconversão urbanística aplicado na AUGI 42 teve como estrutura de proposta a seguinte base: primeiro na recolha de dados relativo à AUGI 42 e na definição de um planeamento do faseamento numa estratégia de execução da empreitada; segundo na constituição e caracterização da execução de variadas infra-estruturas (rede de drenagem de esgotos domésticos e pluviais, rede de abastecimento de águas, rede de telecomunicações, rede eléctrica, rede de gás, rede viária e arranjos de espaços exteriores). Este processo e consequente proposta surgem como um contributo fundamental na melhoria da qualidade de vida das populações, como também da funcionalidade do sistema urbano que compõe as AUGI.