Análise estratigráfica da sequência mesodevoniana-eocarbonífera da Bacia do Parnaíba, nordeste do Brasil

The Middle Devonian-Early Carboniferous sequence of the Parnaíba Basin, lithostratigraphically defined as Canindé Group, has been reinterpreted using the basic model of sequence stratigraphy. Therefore, lithology and gamma ray well-logs and seismic lines of central portion of the basin were analyzed, producing up from there diagrams 1D, isochore maps and stratigraphic sections. As results of this study, were defined two depositional cycles of second order, referred as Depositional Sequence 1 (SEQ1) and the Depositional Sequence 2 (SEQ2). The SEQ1, with interval about 37 Ma, is limited below by Early Devonian Unconformity and is equivalent to the formations Itaim, Pimenteiras and Cabeças. The SEQ2, which follows, comprises a range of about 15 Ma and is equivalent to the Longá Formation The SEQ1 starts with the lowstand systems tract, consisting of progradational parasequence set in the basal part, predominantly pelitic, deposited on a prodelta under influence of storms and the upper part consists in sandstones of deltaic front, with the maximum regressive surface on the upper limit. The transgressive systems tract, deposited above, is characterized by retrogradacional parasequence set composed of shallow shelf mudstones, deposited under storm conditions. The maximum flooding surface, upper limit of this tract, is positioned in a shale level whose radioactivity in gammaray well-log is close to 150 API. The highstand systems tract presents progradational parasequence set, comprising mudstones and sandstones deposited in shelf, fluvial-estuarine or deltaic and periglacial environments, with the upper limit the Late Devonian Unconformity. The SEQ2 was deposited in shelf environment, starting with the lowstand systems tract, that is characterized by a progradational parasequence set, followed by the transgressive systems tract, with retrogradational character. The upper limit of the tract corresponding to the fusion between maximum flooding surface with the upper limit of this sequence, which is the Early Carboniferous Unconformity, where the overlapping section was eroded. This section, which corresponds the highstand systems tract is restricted to portions at which the erosion that generate the Early-Carboniferous Unconformity was less effective, preserving the records of this unit.

Análise estratigráfica da sequência mesodevoniana-eocarbonífera da Bacia do Parnaíba, nordeste do Brasil

The Middle Devonian-Early Carboniferous sequence of the Parnaíba Basin, lithostratigraphically defined as Canindé Group, has been reinterpreted using the basic model of sequence stratigraphy. Therefore, lithology and gamma ray well-logs and seismic lines of central portion of the basin were analyzed, producing up from there diagrams 1D, isochore maps and stratigraphic sections. As results of this study, were defined two depositional cycles of second order, referred as Depositional Sequence 1 (SEQ1) and the Depositional Sequence 2 (SEQ2). The SEQ1, with interval about 37 Ma, is limited below by Early Devonian Unconformity and is equivalent to the formations Itaim, Pimenteiras and Cabeças. The SEQ2, which follows, comprises a range of about 15 Ma and is equivalent to the Longá Formation The SEQ1 starts with the lowstand systems tract, consisting of progradational parasequence set in the basal part, predominantly pelitic, deposited on a prodelta under influence of storms and the upper part consists in sandstones of deltaic front, with the maximum regressive surface on the upper limit. The transgressive systems tract, deposited above, is characterized by retrogradacional parasequence set composed of shallow shelf mudstones, deposited under storm conditions. The maximum flooding surface, upper limit of this tract, is positioned in a shale level whose radioactivity in gammaray well-log is close to 150 API. The highstand systems tract presents progradational parasequence set, comprising mudstones and sandstones deposited in shelf, fluvial-estuarine or deltaic and periglacial environments, with the upper limit the Late Devonian Unconformity. The SEQ2 was deposited in shelf environment, starting with the lowstand systems tract, that is characterized by a progradational parasequence set, followed by the transgressive systems tract, with retrogradational character. The upper limit of the tract corresponding to the fusion between maximum flooding surface with the upper limit of this sequence, which is the Early Carboniferous Unconformity, where the overlapping section was eroded. This section, which corresponds the highstand systems tract is restricted to portions at which the erosion that generate the Early-Carboniferous Unconformity was less effective, preserving the records of this unit.

Petrologia e geoquímica do magmatismo ediacarano Serra do Caramuru, Rio Grande do Norte, NE do Brasil

The Serra do Caramuru and Tapuio stocks, located in the extreme NE of Rio Piranhas-Seridó Domain (RN), are representative of the Ediacaran-Cambrian magmatism, an important magmatic feature of the Brasilian / Panafrican orogeny of the Borborema Province. These bodies are lithologically similar, intrusive in paleoproterozoic gneiss embasement, being separated by a thin belt of mylonitic orthogneiss. The field relations show a magmatic stratigraphy initiated by dioritic facies that coexists with the porphyritic granitic and equigranular granitic I facies, and less frequently with equigranular granitic II facies. These rocks are crosscut by late granitic dykes and sheets with NE-SW / NNE-SSW orientation. The dioritic facies (diorite, quartz diorite, quartz monzodiorites, tonalite and granodiorite) is leucocratic to melanocratic, rich in biotite and hornblende. The granitic facies are hololeucocratic to leucocratic, and have biotite ± hornblende. Petrographic and geochemical (whole rock) data, especially from Serra do Caramuru pluton, suggest fractionation of zircon, apatite, clinopyroxene (in diorites), opaque minerals, titanite, biotite, hornblende, allanite, plagioclase, microcline and garnet (in dykes). The behavior of trace elements such as Zr, La and Yb indicates that the dioritic magma does not constitute the parental magma for the granitic facies. On the other hand, the granitic facies seems to be cogenetic to each other, displaying differentiation trends and very similar rare earth elements (REE) spectra [12.3≤(La/Yb)N≤190.8; Eu/Eu*=0.30-0.68]. Field relationships and REE patterns [6.96≤(La/Yb)N≤277.8; Eu/Eu*=0.18-0.58] demonstrate that the granitic dykes and sheets are not cogenetically related to the Serra do Caramuru magmatism. The dioritic facies is metaluminous (A/CNK = 0.88-0.74) and shoshonitic, whereas the granitic ones are metaluminous to peraluminous (A/CNK = 1.08-0.93) and high potassium calc-alkaline. Dykes and sheets are strictly peraluminous (A/CNK = 1.01-1.04). Binary diagrams relating compatible and incompatible trace elements and microtextures indicate the fractional crystallization as the dominant mechanism of magmatic evolution of the various facies. The Serra do Caramuru and Tapuio stocks have well preserved magmatic fabric, do not show metamorphic minerals and are structurally isotropic, showing crosscutting contact with the ductile fabric of the basement. These observations lead to interpretate a stage of relative tectonic stability, consistent with the orogenic relaxation period of the Brasiliano / Pan-African orogeny. Chemical plots involving oxides and trace elements indicate late to post-collisional emplacement. In this context, the assumed better mechanism to describe the stocks emplacement within an extensional T Riedel joint, with ENE-WSW extensional vector. The U-Pb zircon age of 553 ± 10 Ma allows correlating the Serra do Caramuru magmatism to the group of post-collisional bodies, equigranular high potassium calc-alkaline granites of the NE of Rio Piranhas-Seridó Domain.

Petrologia e geoquímica do magmatismo ediacarano Serra do Caramuru, Rio Grande do Norte, NE do Brasil

The Serra do Caramuru and Tapuio stocks, located in the extreme NE of Rio Piranhas-Seridó Domain (RN), are representative of the Ediacaran-Cambrian magmatism, an important magmatic feature of the Brasilian / Panafrican orogeny of the Borborema Province. These bodies are lithologically similar, intrusive in paleoproterozoic gneiss embasement, being separated by a thin belt of mylonitic orthogneiss. The field relations show a magmatic stratigraphy initiated by dioritic facies that coexists with the porphyritic granitic and equigranular granitic I facies, and less frequently with equigranular granitic II facies. These rocks are crosscut by late granitic dykes and sheets with NE-SW / NNE-SSW orientation. The dioritic facies (diorite, quartz diorite, quartz monzodiorites, tonalite and granodiorite) is leucocratic to melanocratic, rich in biotite and hornblende. The granitic facies are hololeucocratic to leucocratic, and have biotite ± hornblende. Petrographic and geochemical (whole rock) data, especially from Serra do Caramuru pluton, suggest fractionation of zircon, apatite, clinopyroxene (in diorites), opaque minerals, titanite, biotite, hornblende, allanite, plagioclase, microcline and garnet (in dykes). The behavior of trace elements such as Zr, La and Yb indicates that the dioritic magma does not constitute the parental magma for the granitic facies. On the other hand, the granitic facies seems to be cogenetic to each other, displaying differentiation trends and very similar rare earth elements (REE) spectra [12.3≤(La/Yb)N≤190.8; Eu/Eu*=0.30-0.68]. Field relationships and REE patterns [6.96≤(La/Yb)N≤277.8; Eu/Eu*=0.18-0.58] demonstrate that the granitic dykes and sheets are not cogenetically related to the Serra do Caramuru magmatism. The dioritic facies is metaluminous (A/CNK = 0.88-0.74) and shoshonitic, whereas the granitic ones are metaluminous to peraluminous (A/CNK = 1.08-0.93) and high potassium calc-alkaline. Dykes and sheets are strictly peraluminous (A/CNK = 1.01-1.04). Binary diagrams relating compatible and incompatible trace elements and microtextures indicate the fractional crystallization as the dominant mechanism of magmatic evolution of the various facies. The Serra do Caramuru and Tapuio stocks have well preserved magmatic fabric, do not show metamorphic minerals and are structurally isotropic, showing crosscutting contact with the ductile fabric of the basement. These observations lead to interpretate a stage of relative tectonic stability, consistent with the orogenic relaxation period of the Brasiliano / Pan-African orogeny. Chemical plots involving oxides and trace elements indicate late to post-collisional emplacement. In this context, the assumed better mechanism to describe the stocks emplacement within an extensional T Riedel joint, with ENE-WSW extensional vector. The U-Pb zircon age of 553 ± 10 Ma allows correlating the Serra do Caramuru magmatism to the group of post-collisional bodies, equigranular high potassium calc-alkaline granites of the NE of Rio Piranhas-Seridó Domain.

Aplicação informática para verificação de perfis enformados a frio segundo a EN1993-1-3

Os perfis enformados a frio estão em crescente uso na indústria da construção, utilizados como estruturas secundárias e primárias, por apresentar resistência em relação ao baixo peso, facilidade de utilização em obra e sustentabilidade. A norma europeia EN1993-1-3, também adotada em Portugal, que apresenta as especificações normativas sobre o uso estrutural de perfis enformados a frio é de difícil aplicação para os projetistas devido à quantidade e complexidade de cálculos para que sejam efetuadas as verificações de segurança necessárias, pelas limitações dos programas informáticos e complexidade de compreensão dos fenómenos da instabilidade local e distorcional que condicionam o comportamento deste tipo de secções, classificadas como de classe 4. O presente trabalho procura explicar os procedimentos do eurocódigo e os seus aspetos mais controversos, como, por exemplo, o processo de cálculo da distribuição de tensões numa secção arbitrária constituída por segmentos retos, o cálculo de larguras efetivas e espessuras reduzidas e as verificações de segurança em termos de resistência e estabilidade global requeridos pela norma. O principal objetivo deste trabalho é o desenvolvimento um programa de cálculo para verificar barras com secções de classe 4 que tenha a abrangência das especificações do Eurocódigo (EC3-1-3), que possa auxiliar engenheiros no processo de projeto, dimensionamento e verificação regulamentar de estruturas metálicas que utilizem este tipo de secções. Para isso foi criada uma aplicação informática, em ambiente Windows®, que está ligada ao programa Autodesk® Robot Structural Analisys® para obtenção de dados de cálculo e executar os cálculos de secções efetivas e verificações de segurança de acordo com a norma europeia. São apresentados diagramas de blocos com a sequência do procedimento de cálculo das várias fases de cálculo de secções efetivas e de verificação de barras, com vista a mostrar a lógica de funcionamento interno da aplicação criada no âmbito deste trabalho. Por fim desenvolve-se um manual de utilização da aplicação e um exemplo comparativo, de cálculo das propriedades efetivas de uma secção, entre os resultados do programa e documentos de referência com cálculos manuais

Reforço de pilares por confinamento com mantas de fibras de carbono: avaliação de modelos de comportamento

A presente dissertação incide sobre o estudo dos efeitos do confinamento com materiais compósitos de polímeros reforçados com fibras de carbono (CFRP) em pilares de estruturas de betão armado. A motivação para este estudo surge da necessidade de aprofundar conhecimentos acerca do comportamento dos pilares de betão reforçados por confinamento com CFRP, uma vez que a sua aplicação apresenta uma crescente importância, por exemplo, para aumento da resistência e da ductilidade de estruturas de betão armado. Fez-se, inicialmente, uma breve revisão das técnicas de reforço convencionais utilizadas em pilares de betão armado, com ênfase no reforço exterior com polímeros reforçados com fibras. A elevada resistência à tração, à corrosão e à fadiga, o baixo peso volúmico, a versatilidade e a diversidade dos sistemas comercializados com CFRP tornam este material muito competitivo para este tipo de aplicação. Na sequência desse estudo, realizou-se uma revisão bibliográfica acerca dos modelos de comportamento que permitem prever o desempenho de pilares de betão confinados com CFRP, sujeitos a esforços de compressão. Como forma de análise desses modelos, desenvolveu-se uma ferramenta numérica em ambiente Mathworks - Matlab R2015a, que permitiu a obtenção e posterior comparação dos diagramas de tensão-extensão descritos pelos modelos desenvolvidos por Manfredi e Realfonzo (2001), Ferreira (2007) e Wei e Wu (2011). Por fim, comparam-se os resultados experimentais de Paula (2003) e de Rocca (2007) com os dos modelos constitutivos referidos anteriormente, analisando-se também a influência de vários fatores na eficácia do confinamento, tais como o boleamento, o número de camadas de CFRP e a geometria da secção transversal. Foram ainda comparados e discutidos resultados relativos ao confinamento parcial de pilares. Os resultados obtidos indicam que os modelos analíticos representam relativamente bem o andamento das curvas do betão confinado para secções circulares, quadradas e retangulares, verificando-se as principais discrepâncias nestas duas últimas tipologias de secção transversal, dada a dificuldade associada à quantificação de parâmetros associados ao seu comportamento (por exemplo, boleamento de arestas). No entanto, verificou-se igualmente que com um adequado boleamento de arestas (e consequente aumento da relação entre o raio de canto e a largura da secção de betão), bem como com um aumento do número de camadas de material compósito, é possível aumentar a tensão resistente e a extensão axial na rotura do betão à compressão.

Electrolytic cells for plastic waste recycling

The current project assesses potential molten alloy anodes for Solid Oxide Fuel Cells (SOFC) running on solid waste. A detailed phase diagram study was performed to locate probable anode systems. The molten metal oxide system PbO-Sb2O3 was selected as a possible molten alloy anode for this application. A detailed vapour pressure study of this system was performed. Several cells were fabricated to experimentally assess the electrochemical properties of this system. The work reveals several unexpected limiting features such as the incompatibility between the platinum and the chosen alloy. A second cell was built, this time using rhenium wires instead, preventing such reaction. However, the rhenium wire sublimes under oxidizing conditions (air) and the sealing glass and the chosen alloy system react with each other under long term use. Considering all these issues, a third cell design was conceived, surpassing some obstacles and providing some initial information regarding the electrochemical behaviour. The current project shows that many parameters need to be taken into account to ensure materials compatibility. For the PbOSb2O3 system, the high volatility of Sb2O3 was a serious limitation that can only be addressed through the application of new contact wires or sealing materials and conditions. Nonetheless, the project highlights several other potential systems that can be considered, such as Pb11Ge3O17, Pb3GeO5, Pb5Ge3O11, Bi2CuO4, Bi2PdO4, Bi12GeO20.

Towars a chemical reagents and residues management at the teaching laboratories of the Chemistry School of the Universidad Nacional

The academic activities carried out at the School of Chemistry make indispensable to develop actions oriented toward the consolidation of a reagent and residue management system, especially in the teaching laboratories. The project “Management of reagents and residues in the teaching laboratories of the School of Chemistry” works under the Green Chemistry values which designs products and chemical processes that reduce or eliminate the use and production of dangerous substances, to benefit the environment. With a preventive vision, a change from the  laboratory practices is looked to select those with less environmental impact. Additionally, residue quantification is made and its management protocols are developed for each practice. The project has several stages: diagnose, action implementation, student, teacher and administration personnel training and evaluation during the process and at the end of it. The article describes methodological aspects of the project operation emphasizing on reagent and residue quantification through flow diagrams.

Mecanismo genérico para la definición de transformaciones de modelos en el marco de un enfoque multivistas para la generación de aplicaciones con base en la ingeniería dirigida por modelos

La ingeniera de software se enfoca en el desarrollo de aplicaciones desde diferentes puntos de vista usando diversos enfoques, uno de ellos es el Desarrollo de Software Dirigido por Modelos (MDSD, por sus siglas en inglés); al desarrollar soluciones bajo esta propuesta se han visualizado grandes ventajas como velocidad, bajos costos y calidad en los desarrollos, sin embargo también algunas desventajas como la dificultad de intervenir las transformaciones, falta expresividad en los modelos y la generación hacia múltiples plataformas; este último debido a que no es posible delimitar con claridad las características de la plataforma destino al especificar los modelos y las transformaciones que constituyen el proceso de desarrollo. Durante el progreso del presente trabajo se trata de mitigar las tres dificultades antes mencionadas por medio de la construcción de un Lenguaje de Dominio Específico (DSL, por sus siglas en inglés) con toda la información funcional de la aplicación, usando diagramas de paquetes y de clases en UML y diagramas de procesos de negocio en BPMN. Este trabajo hace parte de la macro propuesta Metáfora donde se desarrolló un plugin de Eclipse que está basado en el framework de modelado de eclipse (EMF, por sus siglas en inglés). El plugin tiene las funciones de asistente guiando al usuario a través del proceso iterativo de transformaciones hasta llegar al código fuente. El software que fue desarrollado para que el proceso de generación se pueda parametrizar de acuerdo a los modelos y transformaciones realizadas por el analista de desarrollo con ayuda del analista de negocio. Se tiene la total libertad para configurar las secuencias de transformación y aplicarlas en un orden determinado a un conjunto de modelos específicos con el fin de generar parte de una aplicación.

Estudio del patrón de expresión de microRNAs en el hueso osteoporótico

Objetivos: Identificar microRNAs (miRNAs) diferencialmente expresados en muestras óseas con fractura osteoporótica respecto a huesos sanos. Material y métodos: Se extrajo RNA total a partir de hueso trabecular fresco del cuello femoral de mujeres sometidas a reemplazo de cadera, ya sea debido a fractura osteoporótica (n=6) o por artrosis en ausencia de osteoporosis (según la DMO) (n=6). Las muestras se hibridaron en un array de miRNAs y se realizaron diagramas de PCA y de mapa de calor. Para la comparación de los niveles de expresión, se fijó como significativo un umbral de cambio de >1,5 veces y un valor p<0,05 en la t de Student (corregido para múltiples pruebas). Resultados: Tanto los análisis de PCA como el mapa de calor mostraron una agrupación de las muestras según si eran de fractura o no. Se detectaron 790 miRNAs en las muestras de hueso, 82 de los cuales estaban alterados en las muestras osteoporóticas. Tras la validación en otro panel de 6 muestras osteoporóticas y 6 no osteoporóticas mediante PCR a tiempo real de los miRNAs más significativos, y para los que existía un ensayo disponible, se confirmaron los miRNAs miR-320a y miR-22-3p. Estos dos miRNAs se detectaron en cultivos de osteoblastos primarios, aunque no mantenían el mismo patrón de expresión que en las muestras de hueso total. Conclusiones: Hemos demostrado que existen diferencias en la expresión de miRNAs en muestras con fractura osteoporótica, lo que abre nuevas perspectivas para la investigación y diseño de nuevas terapias.

Coupling of magnetic, strain and electric polarization fields in the structure of multiferroic material

The comprehensive study on the coupling of magnetism, electrical polarization and the crystalline lattice with the off-stoichiometric effects in self-doped multiferroic hexagonal h-LuMnxO3±δ (0.92≤x≤1.12) ceramic oxides was carried out for the PhD work. There is a complex coupling of the three ferroic degrees. The cancelation of the magnetic moments of ions in the antiferromagnetic order, electric polarization with specific vortex/antivortex topology and lattice properties have pushed researchers to find out ways to disclose the underlying physics and chemistry of magneto-electric and magneto-elastic couplings of h-RMnO3 multiferroic materials. In this research work, self-doping of Lu-sites or Mn-sites of h-LuMnxO3±δ ceramics prepared via solid state route was done to pave a way for deeper understanding of the antiferromagnetic transition, the weak ferromagnetism often reported in the same crystalline lattices and the ferroelectric properties coupled to the imposed lattice changes. Accordingly to the aim of the PhD thesis, the objectives set for the sintering study in the first chapter on experimental results were two. First, study of sintering off-stoichiometric samples within conditions reported in the bibliography and also extracted from the phase diagrams of the LuMnxO3±δ, with a multiple firings ending with a last high temperature step at 1300ºC for 24 hours. Second, explore longer annealing times of up to 240 hours at the fixed temperature of 1300 ºC in a search for improving the properties of the solid solution under study. All series of LuMnxO3±δ ceramics for each annealing time were characterized to tentatively build a framework enabling comparison of measured properties with results of others available in literature. XRD and Rietveld refinement of data give the evolution the lattice parameters as a function to x. Shrinkage of the lattice parameters with increasing x values was observed, the stability limit of the solid solution being determined by analysis of lattice parameters. The evolution of grain size and presence of secondary phases have been investigated by means of TEM, SEM, EDS and EBSD techniques. The dependencies of grain growth and regression of secondary phases on composition x and time were further characterized. Magnetic susceptibility of samples and magnetic irreversibility were extensively examined in the present work. The dependency of magnetic susceptibility, Neel ordering transition and important magnetic parameters are determined and compared to observation in other multiferroics in the following chapter of the thesis. As a tool of high sensitivity to detect minor traces of the secondary phase hausmannite, magnetic measurements are suggested for cross-checking of phase diagrams. Difficulty of previous studies on interpreting the magnetic anomaly below 43 K in h-RMnO3 oxides was discussed and assigned to the Mn3O4 phase, with supported of the electron microscopy. Magneto-electric coupling where AFM ordering is coupled to dielectric polarization is investigated as a function of x and of sintering condition via frequency and temperature dependent complex dielectric constant measurements in the final chapter of the thesis. Within the limits of solid solubility, the crystalline lattice of off-stoichiometric ceramics was shown to preserve the magneto-electric coupling at TN. It represents the first research work on magneto-electric coupling modified by vacancy doping to author’s knowledge. Studied lattices would reveal distortions at the atomic scale imposed by local changes of x dependent on sintering conditions which were widely inspected by using TEM/STEM methods, complemented with EDS and EELS spectroscopy all together to provide comprehensive information on cross coupling of distortions, inhomogeneity and electronic structure assembled and discussed in a specific chapter. Internal interfaces inside crystalline grains were examined. Qualitative explanations of the measured magnetic and ferroelectric properties were established in relation to observed nanoscale features of h-LuMnxO3±δ ceramics. Ferroelectric domains and topological defects are displayed both in TEM and AFM/PFM images, the later technique being used to look at size, distribution and switching of ferroelectric domains influenced by vacancy doping at the micron scale bridging to complementary TEM studies on the atomic structure of ferroelectric domains. In support to experimental study, DFT simulations using Wien2K code have been carried out in order to interpret the results of EELS spectra of O K-edge and to obtain information on the cation hybridization to oxygen ions. The L3,2 edges of Mn is used to access the oxidation state of the Mn ions inside crystalline grains. In addition, rehybridization driven ferroelectricity is also evaluated by comparing the partial density of states of the orbitals of all ions of the samples, also the polarization was calculated and correlated to the off-stoichiometric effect.

Resistência de Materiais - Conceitos gerais

Tendo sido interrompido, a partir do ano lectivo de 2015/2016, o 1º Ciclo do Curso de Engenharia Civil, o autor resolveu reunir toda a informação que foi disponibilizada aos alunos da disciplina de Resistência de Materiais, durante os 8 anos em que o curso funcionou na Universidade de Évora. O presente trabalho versa os Conceitos Gerais da Resistência de Materiais e é uma edição revista e acrescentada das edições que foram publicadas em 2010; 2009 e 2008. No curso, a disciplina de Resistência de Materiais tinha a duração de um único semestre (4º semestre), pelo que foi necessário selecionar os temas mais relevantes a ensinar sobre Esforço axial. No último ponto estão incluídos exercícios, abordados nas aulas práticas, sobre diagramas de esforços, tema ministrado na unidade curricular de Mecânica Aplicada que precedia a Resistência de Materiais na Licenciatura em Engenharia Civil.

Extraction and purification of theobromine using ionic liquids

Theobromine is an alkaloid present in cocoa and it is used in the treatment of atherosclerosis, hypertension, angina, among others. Due to its importance, the aim of this work consists on the development of an efficient and sustainable technology for the extraction of theobromine from cocoa beans. For the development of a purification technique for theobromine extracted from cocoa, aqueous biphasic systems (ABS) composed of ionic liquids (ILs) were initially studied to infer on the most promising systems. Cholinium-based ILs, based on a non-toxic and biocompatible cation, were used combined with two polymers (PPG 400 and PEG 400) and an inorganic salt (K3PO4). The respective phase diagrams at 298 K and atmospheric pressure were determined, as well as their extraction efficiencies for theobromine. The results obtained indicate that K3PO4 has a greater ability to induce the formation of ABS compared to PEG 400 and PPG 400. ABS consisting of K3PO4 also have a high potential for the extraction of theobromine, with extraction efficiencies ranging between 96.4 and 99.9 %. Based on the most promising ILs for the purification step, they were further used in aqueous solution to extract theobromine from cocoa beans, with extraction yields ranging between 4.5% and 6.5 wt%. Finally, ABS were applied to the aqueous solutions containing theobromine from the cocoa extract, with extraction efficiencies ranging between 96.7 and 99.0%.

Critical magnetic elds in superconducting systems with semi-metallic bands

In this work, we study the Zeeman splitting effects in the parallel magnetic field versus temperature phase diagram of two-dimensional superconductors with one graphene-like band and the orbital effects of perpendicular magnetic fields in isotropic two-dimensional semi-metallic superconductors. We show that when parallel magnetic fields are applied to graphene and as the intraband interaction decreases to a critical value, the width of the metastability region present in the phase diagram decreases, vanishing completely at that critical value. In the case of two-band superconductors with one graphene-like band, a new critical interaction, associated primarily with the graphene-like band, is required in order for a second metastability region to be present in the phase diagram. For intermediate values of this interaction, a low-temperature first-order transition line bifurcates at an intermediate temperature into a first-order transition between superconducting phases and a second-order transition line between the normal and the superconducting states. In our study on the upper critical fields in generic semi-metallic superconductors, we find that the pair propagator decays faster than that of a superconductor with a metallic band. As result, the zero field band gap equation does not have solution for weak intraband interactions, meaning that there is a critical intraband interaction value in order for a superconducting phase to be present in semi-metallic superconductors. Finally, we show that the out-of-plane critical magnetic field versus temperature phase diagram displays a positive curvature, contrasting with the parabolic-like behaviour typical of metallic superconductors.

Reforço de pilares por confinamento com mantas de fibras de carbono: avaliação de modelos de comportamento

A presente dissertação incide sobre o estudo dos efeitos do confinamento com materiais compósitos de polímeros reforçados com fibras de carbono (CFRP) em pilares de estruturas de betão armado. A motivação para este estudo surge da necessidade de aprofundar conhecimentos acerca do comportamento dos pilares de betão reforçados por confinamento com CFRP, uma vez que a sua aplicação apresenta uma crescente importância, por exemplo, para aumento da resistência e da ductilidade de estruturas de betão armado. Fez-se, inicialmente, uma breve revisão das técnicas de reforço convencionais utilizadas em pilares de betão armado, com ênfase no reforço exterior com polímeros reforçados com fibras. A elevada resistência à tração, à corrosão e à fadiga, o baixo peso volúmico, a versatilidade e a diversidade dos sistemas comercializados com CFRP tornam este material muito competitivo para este tipo de aplicação. Na sequência desse estudo, realizou-se uma revisão bibliográfica acerca dos modelos de comportamento que permitem prever o desempenho de pilares de betão confinados com CFRP, sujeitos a esforços de compressão. Como forma de análise desses modelos, desenvolveu-se uma ferramenta numérica em ambiente Mathworks - Matlab R2015a, que permitiu a obtenção e posterior comparação dos diagramas de tensão-extensão descritos pelos modelos desenvolvidos por Manfredi e Realfonzo (2001), Ferreira (2007) e Wei e Wu (2011). Por fim, comparam-se os resultados experimentais de Paula (2003) e de Rocca (2007) com os dos modelos constitutivos referidos anteriormente, analisando-se também a influência de vários fatores na eficácia do confinamento, tais como o boleamento, o número de camadas de CFRP e a geometria da secção transversal. Foram ainda comparados e discutidos resultados relativos ao confinamento parcial de pilares. Os resultados obtidos indicam que os modelos analíticos representam relativamente bem o andamento das curvas do betão confinado para secções circulares, quadradas e retangulares, verificando-se as principais discrepâncias nestas duas últimas tipologias de secção transversal, dada a dificuldade associada à quantificação de parâmetros associados ao seu comportamento (por exemplo, boleamento de arestas). No entanto, verificou-se igualmente que com um adequado boleamento de arestas (e consequente aumento da relação entre o raio de canto e a largura da secção de betão), bem como com um aumento do número de camadas de material compósito, é possível aumentar a tensão resistente e a extensão axial na rotura do betão à compressão.