Efeito da incorporação de resíduos da indústria petrolífera na durabilidade de argamassas de reparação de estruturas de betão

Na presente dissertação, o trabalho desenvolvido teve como objetivo, a avaliação de alguns parâmetros de durabilidade de argamassas com incorporação de catalisador exausto de FCC (do inglês “Fluid Catalytic Cracking”) para serem utilizadas na reparação de estruturas de betão. O catalisador exausto de FCC é um resíduo da indústria petrolífera e o utilizado neste estudo é proveniente da refinaria da Petrogal, S.A. em Sines. A presente investigação baseou-se na preparação, e avaliação de propriedades, de duas séries distintas de argamassas: a série que se denominou “RAS” e a série que se denominou “Durabilidade”, nas quais se substituiu, parcialmente entre 5, 10 e 15%, em massa de cimento por resíduo exausto de FCC. As argamassas de ambas as séries diferenciam-se entre si, sobretudo, pela utilização de areia reativa nas argamassas da série RAS e de areia inerte no caso das argamassas da série durabilidade. Nas argamassas estudadas foram realizados ensaios no estado fresco e ensaios no estado endurecido. Os ensaios no estado fresco incluíram a determinação da consistência por espalhamento, da massa volúmica e do teor de ar. Nos ensaios no estado endurecido foram avaliadas, no caso das argamassas da série RAS a extensão da reação àlcalis-sílica e no caso das argamassas da série Durabilidade as resistências mecânicas - à flexão e à compressão, a resistência à carbonatação acelerada, o módulo de elasticidade à compressão, a absorção capilar, a permeabilidade ao oxigénio, a difusão de cloretos em regime não estacionário. O trabalho desenvolvido nesta dissertação demonstrou que a incorporação de catalisador exausto de FCC, em argamassas à base de cimento, minimiza o efeito de expansão das reações álcalis-sílica, bem como contribui para reduzir a absorção capilar e coeficiente de difusão de cloretos. No entanto, este resíduo quando incorporados em argamassas contribui para a diminuição da resistência à carbonatação acelerada e para o aumento da permeabilidade ao oxigénio.

Dynamical analysis in growth models: Blumberg’s equation

We present a new dynamical approach to the Blumberg's equation, a family of unimodal maps. These maps are proportional to Beta(p, q) probability densities functions. Using the symmetry of the Beta(p, q) distribution and symbolic dynamics techniques, a new concept of mirror symmetry is defined for this family of maps. The kneading theory is used to analyze the effect of such symmetry in the presented models. The main result proves that two mirror symmetric unimodal maps have the same topological entropy. Different population dynamics regimes are identified, when the intrinsic growth rate is modified: extinctions, stabilities, bifurcations, chaos and Allee effect. To illustrate our results, we present a numerical analysis, where are demonstrated: monotonicity of the topological entropy with the variation of the intrinsic growth rate, existence of isentropic sets in the parameters space and mirror symmetry.

Study of the one dimensional and transient bioheat transfer equation: Multi-layer solution development and applications

: In this work we derive an analytical solution given by Bessel series to the transient and one-dimensional (1D) bioheat transfer equation in a multi-layer region with spatially dependent heat sources. Each region represents an independent biological tissue characterized by temperature-invariant physiological parameters and a linearly temperature dependent metabolic heat generation. Moreover, 1D Cartesian, cylindrical or spherical coordinates are used to define the geometry and temperature boundary conditions of first, second and third kinds are assumed at the inner and outer surfaces. We present two examples of clinical applications for the developed solution. In the first one, we investigate two different heat source terms to simulate the heating in a tumor and its surrounding tissue, induced during a magnetic fluid hyperthermia technique used for cancer treatment. To obtain an accurate analytical solution, we determine the error associated with the truncated Bessel series that defines the transient solution. In the second application, we explore the potential of this model to study the effect of different environmental conditions in a multi-layered human head model (brain, bone and scalp). The convective heat transfer effect of a large blood vessel located inside the brain is also investigated. The results are further compared with a numerical solution obtained by the Finite Element Method and computed with COMSOL Multi-physics v4.1 (c). (c) 2013 Elsevier Ltd. All rights reserved.

An application of structural equation modeling of test dispositional optimism as mediator or moderator in quality of life in patients with chronic disease

The aim of the present study was to test a hypothetical model to examine if dispositional optimism exerts a moderating or a mediating effect between personality traits and quality of life, in Portuguese patients with chronic diseases. A sample of 540 patients was recruited from central hospitals in various districts of Portugal. All patients completed self-reported questionnaires assessing socio-demographic and clinical variables, personality, dispositional optimism, and quality of life. Structural equation modeling (SEM) was used to analyze the moderating and mediating effects. Results suggest that dispositional optimism exerts a mediator rather than a moderator role between personality traits and quality of life, suggesting that “the expectation that good things will happen” contributes to a better general well-being and better mental functioning.

Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation

Two multinuclear complexes [Fe-6(mu(3)-O)(2)(mu(4)-O-2)L-10(OAc)(2)(H2O)(2)]center dot 2.625Et(2)O center dot 2.375H(2)O (1) and [(Fe11Cl)-Cl-III-(mu(4)-O)(3)(mu(3)-O)(5)L-16(dmf)(2.5)(H2O)(0.5)]center dot Et2O center dot 1.25dmf center dot 3.8H(2)O (2), where HL = 3,4,5-trimethoxybenzoic acid and dmf = dimethylformamide, have been prepared from trinuclear iron(III) carboxylates via their structural rearrangement in dimethylformamide or diethyl ether-dimethylformamide 9:1, respectively, and slow vapor diffusion of diethyl ether into the reaction mixture. Both compounds have been characterized by X-ray diffraction, optical, Mossbauer spectroscopy, and magnetic measurements. Complex 1 possesses a hexanuclear ferric peroxido-dioxido {Fe-6(O-2)(O)(2)}(12+) core unit, which adopts a recliner conformation, while complex 2 contains an unprecedented {Fe11O8Cl}(16+) core, in which 9 ferric ions are six-coordinate and the remaining two are five-coordinate. Another structural feature of note of the undecanuclear core is the presence of a deformed cubane entity {Fe-4(mu(3)-O)(mu(4)-O)(3)}(4+). Both complexes act as catalyst precursors for the oxidation of cyclohexane to cyclohexanol and cyclohexanone with aqueous H2O2, in the presence of pyrazinecarboxylic acid. Remarkable TONs and TOFs (the latter mainly for 1) with concomitant quite good yields have been achieved under mild conditions. Moreover, 1 exhibits remarkably high activity in an exceptionally short reaction time (45 min), being unprecedented for any metal catalyzed alkane oxidation by H2O2. The catalytic reactions proceed via Fenton type chemistry.

Estudo do tratamento de águas contaminadas com tricloroetileno, usando ferro zerovalente

A tecnologia de barreiras reactivas é uma alternativa possível de ser implementada para tratamento de águas contaminadas com compostos organoclorados, nomeadamente o tricloroetileno (TCE). O recurso a ferro zerovalente (Fe0) como meio reactivo tem na actualidade inúmeras aplicações, tratando-se de uma reacção de desalogenação por mecanismo de oxidação-redução. Neste trabalho fizeram-se estudos em batch da reacção entre o Fe0 e o TCE de forma a conhecer os parâmetros cinéticos. A natureza e a área da superfície do ferro provaram ser determinantes na velocidade da reacção. Foi possível verificar que para o sistema ferro comercial / TCE a ordem da reacção é inferior a um, e a constante cinética da ordem de 10-2 Lm-2h-1. Para simular uma barreira reactiva, projectaram-se e construíram-se colunas, as quais foram cheias com areia e ferro depois de devidamente misturados, uma vez que se tratou da disposição a que corresponderam melhores eficiências de redução do TCE. Não foi possível estabelecer o mecanismo da reacção, nem conhecer os parâmetros cinéticos, pelas dificuldades experimentais encontradas na análise do TCE e pelo facto de se tratar de uma reacção muito lenta. A cromatografia gasosa com detector de ionização de chama provou ser o método mais apropriado para doseamento do TCE em águas contaminadas, nas condições usadas neste estudo. A elevada volatilização do TCE e a baixa solubilidade em água contribuíram para as dificuldades operacionais encontradas.

PPO Reaction Scale-up

O óxido de polifenileno com a marca comercial PPO® é uma das resinas principais produzidas na SABIC IP e o ingrediente principal do plástico de engenharia com a marca registada, Noryl®. A equipa de tecnologia de processo de PPO® desenvolve uma série de novos produtos em reactores de pequena escala, tanto em Selkirk como em Bergen op Zoom. Para se efectuar uma transição rápida da escala laboratorial para a fábrica, é necessário um conhecimento completo do reactor. O objectivo deste projecto consiste em esboçar linhas gerais para o scale-up de novos produtos de PPO1, do laboratório para a escala industrial, baseado no estudo de um tipo de PPO, PPO 803. Este estudo pode ser dividido em duas fases. Numa primeira fase, as receitas e os perfis da reacção são comparados, de onde se retiram as primeiras conclusões. Posteriormente, com base nestas conclusões, é realizado um planeamento experimental. O estudo inicial sugeriu que a receita, a temperatura inicial do reactor e a velocidade do agitador poderiam influenciar o tempo da reacção bem como a queda da velocidade intrínseca do polímero (IV drop). As reacções experimentais mostraram que a receita é o principal factor que influencia, tanto o tempo de reacção, como a queda de viscosidade intrínseca. O tempo de reacção será tanto maior quanto menor a agitação devido à má dispersão do oxigénio na mistura. O uso de temperaturas iniciais elevadas conduz a uma queda maior da viscosidade intrínseca devido à desactivação do catalisador. O método experimental utilizado no laboratório de Bergen op Zoom é um bom exemplo, simulador, do procedimento utilizado na fábrica.

Removal of Cd(II), Zn(II) and Pb(II) from aqueous solutions by brown marine macro algae: kinetic modelling

Specific marine macro algae species abundant at the Portuguese coast (Laminaria hyperborea, Bifurcaria bifurcata, Sargassum muticum and Fucus spiralis) were shown to be effective for removing toxic metals (Cd(II), Zn(II) and Pb(II)) from aqueous solutions. The initial metal concentrations in solution were about 75–100 mg L−1. The observed biosorption capacities for cadmium, zinc and lead ions were in the ranges of 23.9–39.5, 18.6–32.0 and 32.3–50.4 mg g−1, respectively. Kinetic studies revealed that the metal uptake rate was rather fast, with 75% of the total amount occurring in the first 10 min for all algal species. Experimental data were well fitted by a pseudo-second order rate equation. The contribution of internal diffusion mechanism was significant only to the initial biosorption stage. Results indicate that all the studied macro algae species can provide an efficient and cost-effective technology for eliminating heavy metals from industrial effluents.

Determination of ametryn in soils via microwave-assisted solvent extraction coupled to anodic stripping voltammetry with a gold ultramicroelectrode

An extraction-anodic adsorptive stripping voltammetric procedure using microwave-assisted solvent extraction and a gold ultramicroelectrode was developed for determining the pesticide ametryn in soil samples. The method is based on the use of acetonitrile as extraction solvent and on controlled adsorptive accumulation of the herbicide at the potential of 0.50 V (vs. Ag/AgCl) in the presence of Britton-Robinson buffer (pH 3.3). Soil sample extracts were analysed directly after drying and redissolution with the supporting electrolyte but without other pre-treatment. The limit of detection obtained for a 10 s collection time was 0.021 µg g-1. Recovery experiments for the global procedure, at the 0.500 µg g-1 level, gave satisfactory mean and standard deviation results which were comparable to those obtained by HPLC with UV detection.

Determination of polyphenols in wines by reaction with 4-aminoantipyrine and photometric flow-injection analysis

A new flow-injection analytical procedure is proposed for the determination of the total amount of polyphenols in wines; the method is based on the formation of a colored complex between 4-aminoantipyrine and phenols, in the presence of an oxidizing reagent. The oxidizing agents hexacyanoferrate(III), peroxodisulfate, and tetroxoiodate(VII) were tested. Batch trials were first performed to select appropriate oxidizing agents, pH, and concentration ratios of reagents, on the basis of their effect on the stability of the colored complex. Conditions selected as a result of these trials were implemented in a flow-injection analytical system in which the influence of injection volume, flow rate, and reaction- coil length, was evaluated. Under the optimum conditions the total amount of polyphenols, expressed as gallic acid, could be determined within a concentration range of 36 to 544 mg L–1, and with a sensitivity of 344 L mol–1 cm–1 and an RSD <1.1%. The reproducibility of analytical readings was indicative of standard deviations <2%. Interference from sugars, tartaric acid, ascorbic acid, methanol, ammonium sulfate, and potassium chloride was negligible. The proposed system was applied to the determination of total polyphenols in red wines, and enabled analysis of approximately 55 samples h–1. Results were usually precise and accurate; the RSD was <3.9% and relative errors, by the Folin–Ciocalteu method, <5.1%.

Influence of network effects on the diffusion of information systems: the case of open source

Doutoramento em Gestão

Effects of international diffusion of a general purpose technology on wage inequality

This paper studies the effects of the diffusion of a General Purpose Technology (GPT) that spreads first within the developed North country of its origin, and then to a developing South country. In the developed general equilibrium growth model, each final good can be produced by one of two technologies. Each technology is characterized by a specific labor complemented by a specific set of intermediate goods, which are enhanced periodically by Schumpeterian R&D activities. When quality reaches a threshold level, a GPT arises in one of the technologies and spreads first to the other technology within the North. Then, it propagates to the South, following a similar sequence. Since diffusion is not even, neither intra- nor inter-country, the GPT produces successive changes in the direction of technological knowledge and in inter- and intra-country wage inequality. Through this mechanism the different observed paths of wage inequality can be accommodated.

Optimization of QuEChERS procedure coupled to GC-ECD for organochlorine pesticide determination in carrot samples

An optimised version of the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method for simultaneous determination of 14 organochlorine pesticides in carrots was developed using gas chromatography coupled with electron-capture detector (GC-ECD) and confirmation by gas chromatography tandem mass spectrometry (GC-MS/MS). A citrate-buffered version of QuEChERS was applied for the extraction of the organochlorine pesticides, and for the extract clean-up, primary secondary amine, octadecyl-bonded silica (C18), magnesium sulphate (MgSO4) and graphitized carbon black were used as sorbents. The GC-ECD determination of the target compounds was achieved in less than 20 min. The limits of detection were below the EUmaximum residue limits (MRLs) for carrots, 10–50 μg kg−1, while the limit of quantification did exceed 10 μg kg−1 for hexachlorobenzene (HCB). The introduction of a sonication step was shown to improve the recoveries. The overall average recoveries in carrots, at the four tested levels (60, 80, 100 and 140 μg kg−1), ranged from 66 to 111% with relative standard deviations in the range of 2– 15 % (n03) for all analytes, with the exception of HCB. The method has been applied to the analysis of 21 carrot samples from different Portuguese regions, and β-HCH was the pesticide most frequently found, with concentrations oscillating between less than the limit of quantification to 14.6 μg kg−1. Only one sample had a pesticide residue (β-HCH) above the MRL, 14.6 μg kg−1. This methodology combines the advantages of both QuEChERS and GC-ECD, producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.

Determination of ochratoxin A in bread: evaluation of microwave-assisted extraction using an orthogonal composite design coupled with response surface methodology

An analytical method using microwave-assisted extraction (MAE) and liquid chromatography (LC) with fluorescence detection (FD) for the determination of ochratoxin A (OTA) in bread samples is described. A 24 orthogonal composite design coupled with response surface methodology was used to study the influence of MAE parameters (extraction time, temperature, solvent volume, and stirring speed) in order to maximize OTA recovery. The optimized MAE conditions were the following: 25 mL of acetonitrile, 10 min of extraction, at 80 °C, and maximum stirring speed. Validation of the overall methodology was performed by spiking assays at five levels (0.1–3.00 ng/g). The quantification limit was 0.005 ng/g. The established method was then applied to 64 bread samples (wheat, maize, and wheat/maize bread) collected in Oporto region (Northern Portugal). OTAwas detected in 84 % of the samples with a maximum value of 2.87 ng/g below the European maximum limit established for OTA in cereal products of 3 ng/g.

Local fractional variational iteration and decomposition methods for wave equation on cantor sets within local fractional operators

We perform a comparison between the fractional iteration and decomposition methods applied to the wave equation on Cantor set. The operators are taken in the local sense. The results illustrate the significant features of the two methods which are both very effective and straightforward for solving the differential equations with local fractional derivative.