Alterações de geometria e sinalização rodoviária em zonas consolidadas no contexto da gestão da mobilidade urbana

Relatório de Estágio para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização de Vias de Comunicação e Transportes

Which firms are the most innovative? The importance of multinationals and exporters in Portugal

We test the Global Engagement (GE) hypothesis according to which the most globally engaged firms, whether multinationals or exporters, are the most innovative. The test is applied to data from 4815 Portuguese firms for the period 2002–2004 based on the 4th Community Innovation Survey for Portugal. We estimated several Knowledge Production Functions, assuming that knowledge outputs result from the combination of certain knowledge inputs with the flow of ideas coming from the existing stock of knowledge. We found that the more internationally engaged firms create more knowledge output than their domestic counterparts; indeed, the more globalised firms apply more inputs and have the opportunity to use a larger stock of knowledge. Nevertheless, the relative perceived advantage of the more internationally exposed firms is also the result of their globalised nature,and is not directly connected with knowledge inputs or information flows.

Via Balastrada versus via não balastrada

Trabalho Final de Mestrado para a obtenção do grau de Mestre em Engenharia Civil, na Área de Especialização de Vias de Comunicação e Transportes

Plano de negócios para a construção de uma unidade fabril de misturas complementares

A Cooperativa Agrícola de Vila do Conde desenvolve um negócio de fabrico e comercialização de misturas complementares para alimentação bovina, sobretudo para vacas leiteiras. Há alguns anos a esta parte, esta Cooperativa sabe que terá que deslocalizar a unidade fabril existente devido a imposições da Direção Geral de Alimentação e Veterinária, relacionadas com questões de natureza ambiental. A necessidade de ser realizado um novo investimento, para garantir a sustentabilidade do negócio mais rentável gerido por esta Cooperativa, levou a pensar-se na possibilidade de construção de uma nova unidade fabril, de dimensão superior, capaz de servir outras cooperativas, visando o desejado entendimento das cooperativas em torno de um objetivo comum, logrando a obtenção de economias de escala, de extrema importância para a sobrevivência do setor leiteiro na região do Entre Douro e Minho. Para o efeito será constituída uma nova sociedade por quotas, designada por AGRIVIL XXI, Lda., de capital exclusivamente cooperativo, possibilitando que, em cada momento, se possa aferir a situação económica e financeira do negócio de forma mais rigorosa e autónoma. Esta realidade foi conducente à elaboração do presente Plano de Negócios que se espera profícuo para definição dos objetivos e metas a atingir num futuro próximo pela Cooperativa Agrícola de Vila do Conde. As análises de viabilidade e do risco do projeto demonstraram estarem criadas as condições de aceitação do mesmo, sendo expectável um VAL de 1.371.764 euros, uma TIR de 12,04% e um pay-back period próximo dos 11 anos. No entanto é notório a existência de um risco inerente ao investimento na medida em que o montante dos fluxos gerados tende a aproximar-se dos fluxos investidos, não gerando um excedente de riqueza significativo.

Análise por ultra-sons no controlo de condição

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica

Vision antropologica de la descentralizacion del sistema de salud en Mexico

OBJETIVO: Analizar cambios organizacionales, políticos y económicos resultantes de la descentralización del sistema de salud en la población sin seguridad social en México. METODOS: Se visitaron tres estados del país seleccionados por el número de habitantes en condición de pobreza, el partido político en el poder y la etapa de implementación de la descentralización (la primera fue en 1984 y la segunda en 1997). Se realizaron entrevistas durante 2007 con informantes clave de los servicios de salud de los gobiernos estatales, personas que acudieron a consulta en los servicios estatales de salud y líderes comunitarios. Los datos fueron analizados desde una perspectiva antropológica y económica. RESULTADOS: La descentralización ocurrió de forma heterogénea en cada estado, observándose una transferencia de responsabilidades de la federación a los estados, más no así una ruptura con la dependencia del nivel central - federal. Las reformas impulsadas desde el nivel federal para crear un esquema fundamentado en principios de subsidiaridad financiera y democratización en salud enfrentan retos políticos y organizacionales para su consolidación. CONCLUSIONES: El enfoque antropológico muestra la relevancia de considerar factores organizacionales, políticos y económicos como parte del proceso de descentralización.

Film thickness in a ball-on-disc contact lubricated with greases, bleed oils and base oils

Three different lubricating greases and their bleed and base oils were compared in terms of film thickness in a ball-on-disc test rig through optical interferometry. The theoretical values calculated according to Hamrock's equation are in close agreement with the base oil film thickness measurements, which validates the selected experimental methodology. The grease and bleed oil film thickness under fully flooded lubrication conditions presented quite similar behaviour and levels. Therefore, the grease film thickness under full film conditions might be predicted using their bleed oil properties, namely the viscosity and pressure-viscosity coefficient. The base and bleed oil lubricant parameter LP are proportional to the measured film thickness. A relationship between grease and the corresponding bleed oil film thickness was evidenced.

Influence of grease rheology on thrust ball bearings friction torque

The friction torque and the operating temperatures in a thrust ball bearing were measured for seven different types of greases, including three biodegradable greases having low toxicity. These friction torque tests were performed using a modified Four-Ball machine. Rheological evaluations of the lubricating greases were made using a rheometer. Bleed oils were extracted from the greases and the dynamic viscosities were measured. In order to compare the performance of the lubricant greases in terms of friction, the grease characteristics were related to experimental results, showing that the interaction between thickener and base oil have strong influences in the bearing friction torque.

Detection and diagnosis solutions for fault-tolerant VSI

This paper presents solutions for fault detection and diagnosis of two-level, three phase voltage-source inverter (VSI) topologies with IGBT devices. The proposed solutions combine redundant standby VSI structures and contactors (or relays) to improve the fault-tolerant capabilities of power electronics in applications with safety requirements. The suitable combination of these elements gives the inverter the ability to maintain energy processing in the occurrence of several failure modes, including short-circuit in IGBT devices, thus extending its reliability and availability. A survey of previously developed fault-tolerant VSI structures and several aspects of failure modes, detection and isolation mechanisms within VSI is first discussed. Hardware solutions for the protection of power semiconductors with fault detection and diagnosis mechanisms are then proposed to provide conditions to isolate and replace damaged power devices (or branches) in real time. Experimental results from a prototype are included to validate the proposed solutions.

Experimental measuring procedure for the friction torque in rolling bearings

The reduction of the power loss generated in mechanical transmissions and the use of low friction biodegradable lubricants has been attracting considerable attention in recent times. Therefore, it is necessary to develop methods to test and evaluate the performance of such lubricants and compare them with conventional ones. In this sense, a Four-Ball Machine was modified allowing the test of rolling bearings. A 51107 thrust ball bearing was used to test two different greases and the corresponding base oils. Friction torque and operating temperatures were continuously monitored to quantify the power loss and the heat evacuation for each lubricant tested. Copyright © 2010 John Wiley & Sons, Ltd.

Friction and wear in thrust ball bearings lubricated with biodegradable greases

Thrust ball bearings lubricated with several different types of grease, including three biodegradable low-toxicity greases, were tested in a modified four-ball machine in order to evaluate the bearing friction torque. At the end of each test, grease samples were obtained and analysed through ferrography, allowing the quantification and evaluation of the bearing wear. In order to compare the grease performance in terms of friction and wear, a correlation between the grease characteristics (base oil, bleed oil, thickener structure, and rheological parameters) and the experimental results was established.

Cobalt complexes with pyrazole ligands as catalyst precursors for the peroxidative oxidation of cyclohexane: Z-ray absorption spectroscopy studies and biological applications

[CoCl(-Cl)(Hpz(Ph))(3)](2) (1) and [CoCl2(Hpz(Ph))(4)] (2) were obtained by reaction of CoCl2 with HC(pz(Ph))(3) and Hpz(Ph), respectively (Hpz(Ph)=3-phenylpyrazole). The compounds were isolated as air-stable solids and fully characterized by IR and far-IR spectroscopy, MS(ESI+/-), elemental analysis, cyclic voltammetry (CV), controlled potential electrolysis, and single-crystal X-ray diffraction. Electrochemical studies showed that 1 and 2 undergo single-electron irreversible (CoCoIII)-Co-II oxidations and (CoCoI)-Co-II reductions at potentials measured by CV, which also allowed, in the case of dinuclear complex 1, the detection of electronic communication between the Co centers through the chloride bridging ligands. The electrochemical behavior of models of 1 and 2 were also investigated by density functional theory (DFT) methods, which indicated that the vertical oxidation of 1 and 2 (that before structural relaxation) affects mostly the chloride and pyrazolyl ligands, whereas adiabatic oxidation (that after the geometry relaxation) and reduction are mostly metal centered. Compounds 1 and 2 and, for comparative purposes, other related scorpionate and pyrazole cobalt complexes, exhibit catalytic activity for the peroxidative oxidation of cyclohexane to cyclohexanol and cyclohexanone under mild conditions (room temperature, aqueous H2O2). Insitu X-ray absorption spectroscopy studies indicated that the species derived from complexes 1 and 2 during the oxidation of cyclohexane (i.e., Ox-1 and Ox-2, respectively) are analogous and contain a Co-III site. Complex 2 showed low invitro cytotoxicity toward the HCT116 colorectal carcinoma and MCF7 breast adenocarcinoma cell lines.

Copper-organic frameworks assembled from in situ generated 5-(4-pyridyl) tetrazole building blocks: synthesis, structural features, topological analysis and catalytic oxidation of alcohols

Two new metal- organic compounds {[Cu-3(mu(3)-4-(p)tz)(4)(mu(2)-N-3)(2)(DMF)(2)](DMF)(2)}(n) (1) and {[Cu(4ptz) (2)(H2O)(2)]}(n) (2) {4-ptz = 5-(4-pyridyl)tetrazolate} with 3D and 2D coordination networks, respectively, have been synthesized while studying the effect of reaction conditions on the coordination modes of 4-pytz by employing the [2 + 3] cycloaddition as a tool for generating in situ the 5-substituted tetrazole ligands from 4-pyridinecarbonitrile and NaN3 in the presence of a copper(II) salt. The obtained compounds have been structurally characterized and the topological analysis of 1 discloses a topologically unique trinodal 3,5,6-connected 3D network which, upon further simplification, results in a uninodal 8-connected underlying net with the bcu (body centred cubic) topology driven by the [Cu-3(mu(2)-N-3)(2)] cluster nodes and mu(3)-4-ptz linkers. In contrast, the 2D metal-organic network in 2 has been classified as a uninodal 4-connected underlying net with the sql [Shubnikov tetragonal plane net] topology assembled from the Cu nodes and mu(2)-4-ptz linkers. The catalytic investigations disclosed that 1 and 2 act as active catalyst precursors towards the microwave-assisted homogeneous oxidation of secondary alcohols (1-phenylethanol, cyclohexanol, 2-hexanol, 3-hexanol, 2-octanol and 3-octanol) with tert-butylhydroperoxide, leading to the yields of the corresponding ketones up to 86% (TOF = 430 h(-1)) and 58% (TOF = 290 h(-1)) in the oxidation of 1-phenylethanol and cyclohexanol, respectively, after 1 h under low power ( 10 W) microwave irradiation, and in the absence of any added solvent or additive.

Diethydithiocarbamate complexes with metals used as food suplements show diferente effects in cancer cells

Diethyldithiocarbamate (ditiocarb), a metabolite of the old anti-alcoholic drug disulfiram (Antabuse), forms proteasome-inhibiting metal complexes with copper or zinc that suppress cancer cells both in vitro and in vivo. The drug has been used in a clinical trial (NCT00742911) along with copper gluconate as a dietary supplement in patients with cancer spreading to the liver. In this study, we demonstrate the effect of synthetic complexes of disulfiram with four various metals (Mn, Fe, Cr and Cu) used as food supplements. These complexes may be spontaneously formed in the blood during the use of disulfiram with divalent metals and thus may suppress the growth of cancer in vivo. The cytotoxic effect of the compounds and the compounds' ability to inhibit the cellular proteasome were tested in the osteosarcoma cell line U2OS. After 48 h, copper and manganese complexes exhibited cytotoxic effect on the cell line, in sharp contrast to both iron and chromium complexes. (C) 2014 Faculty of Health and Social Studies, University of South Bohemia in Ceske Budejovice. Published by Elsevier Urban & Partner Sp. z o.o. All rights reserved.

Dinuclear Mn (II,II) complexes: magnetic properties and microwave assisted oxidation of alcohols

A series of six new mixed-ligand dinuclear Mn(II, II) complexes of three different hydrazone Schiff bases (H3L1, H3L2 and H3L3), derived from condensation of the aromatic acid hydrazides benzohydrazide, 2-aminobenzohydrazide or 2-hydroxybenzohydrazide, with 2,3-dihydroxy benzaldehyde, respectively, is reported. Reactions of Mn(NO3)(2) center dot 4H(2)O with the H3L1-3 compounds, in the presence of pyridine (1 : 1 : 1 mole ratio), in methanol at room temperature, yield [Mn(H2L1)(py)(H2O)](2)(NO3)(2) center dot 2H(2)O (1 center dot 2H(2)O), [Mn(H2L2)(py)(CH3OH)](2)(NO3)(2) center dot 4H(2)O (2 center dot 4H(2)O) and [Mn(H2L3)(py)(H2O)](2)(NO3)(2) (3) respectively, whereas the use of excess pyridine yields complexes with two axially coordinated pyridine molecules at each Mn(II) centre, viz. [Mn(H2L1)(py)(2)] 2(NO3)(2) center dot H2O (4 center dot H2O), [Mn(H2L2)(py) H-O (6 center dot 2CH(3)OH), respectively. In all the complexes, the (H2L1-3)-ligand coordinates in the keto form. Complexes 1 center dot 2H(2)O, 2 center dot 4H(2)O, 4 center dot H2O, 5 center dot 2H(2)O and 6 center dot 2CH(3)OH are characterized by single crystal X-ray diffraction analysis. The complexes 1, 2 and 6, having different coordination environments, have been selected for variable temperature magnetic susceptibility measurements to examine the nature of magnetic interaction between magnetically coupled Mn(II) centres and also for exploration of the catalytic activity towards microwave assisted oxidation of alcohols. A yield of 81% (acetophenone) is obtained using a maximum of 0.4% molar ratio of catalyst relative to the substrate in the presence of TEMPO and in aqueous basic solution, under mild conditions.