Orientador: Paulo Roberto Mei / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-12T11:09:37Z (GMT). No. of bitstreams: 1 Bubani_FrancodeCastro_M.pdf: 7334881 bytes, checksum: 9cc4f96ceff0972bc2552404b4ccee84 (MD5) Previous issue date: 2008 / Resumo: Os efeitos da adição de níquel e da temperatura em ligas ferro-cromo foram estudados. Sete ligas de base ferro, com 18% Cr e teores de níquel variando entre zero e 60%, foram utilizadas no estudo (0, 10, 20, 30, 40, 50 e 60% Ni). Foram realizados ensaios de tração em temperatura ambiente, 350 e 700 ºC; simulação por termodinâmica computacional; microscopia ótica no estado recozido, nas amostras de quick stop, após deformação a frio, a 350 e a 700 ºC; difração de raios X no estado recozido, após deformação a 350 e a 700 ºC; ensaio de dureza a quente a 100, 200, 300 e 400 ºC; ensaio de impacto Charpy em temperatura ambiente e a -196 ºC; e ensaio de quick stop; análise térmica por DTA; ensaios de dureza no estado recozido, nos cavacos obtidos em torneamento, após deformação a 350 e 700 ºC. Os resultados dos ensaios de tração a 350 ºC foram correlacionados com os dados obtidos por Marques (2007), visando relacionar propriedades mecânicas e usinabilidade. A tendência geral de redução da usinabilidade com o aumento do teor de níquel foi relacionada com o aumento da resistência mecânica e da ductilidade a quente, proporcionados pelo níquel. A alta usinabilidade observada na liga 30% Ni foi relacionada com a presença de inclusões com cálcio nesta liga, o que proporcionou ganhos muito expressivos em usinabilidade, mas sem prejudicar as propriedades mecânicas avaliadas. / Abstract: The effects of nickel addition and temperature in iron-chromium alloys have been studied. Seven iron-base alloys with 18% Cr and nickel content varying from zero to 60% were used in the study (0, 10, 20, 30, 40, 50 and 60% Ni). The alloys were submitted to tension tests at room temperature, 350 and 700 ºC; computational thermodynamics simulations; optical metallography observations in annealed state, after deformation at room temperature, 350 and 700 oC, and in quick stop samples; x-ray diffraction, annealed and after deformation at 350 and 700 ºC; hot hardness test at 100, 200, 300 and 400 ºC; Charpy impact tests at room temperature and at -196 ºC; quick stop test; differential thermal analysis tests; Vickers hardness tests: annealed, on chips, after deformation at 350 and 700 ºC. The results of the tension tests at 350 ºC were correlated with the data obtained by Marques (2007), aiming at reaching a relationship between mechanical properties and machinability. The general tendency of reduction in machinability with the increase of nickel content was related to the increase in mechanical strength and hot ductility provided by nickel. The high machinability observed in the 30% Ni alloy was related with the presence of calcium inclusions in this alloy, which allowed for significant gains in machinability, but without loss to the evaluated mechanical properties. / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

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The development of the construction industry brought the new methods of structural design, which have been introduced to engineers, although overall this phenomenon has increased building costs. A cost-effective construction is one of the major decision points during the definition of any engineering project, therefore, due to the opposing concepts of these two statements, revising design standards and codes are essential in order to provide adequate and cost-effective design requirements. A single-ply roof system is a relatively new method of roof construction that has been used in the building industry in recent decades, which seems to have undergone dramatic changes due to significant structural failures that have occurred through the years. Wind-induced damage on flat roofs is a common problem for low-rise buildings and much of this damage is initiated when the steel deck roof fails, leading to the overall roofing system collapse. The FM (Factory Mutual) design recommendations, which is a standard that recommends allowable dimensions and wind rating for the roofing products, have provided tabulated steel deck span dimensions and fasteners distance for many years. To update the FM design recommendations extensive experimental and analytical investigations are required. In the current study an experimental program was conducted at the National Research Council of Canada (NRC) on flat roofing systems, for simulating the wind uplift effect on several roofing systems samples, as recommended by FM design recommendations. A Finite Element Model (FEM) of the same roofing systems as those used in the experimental cases was developed and different loading patterns were analysed for providing a better simulation of the deflection, moments and forces responses, as measured during the experiments. The FEM was validated with the experimental results and was further employed for applying the FE analysis for more steel deck span dimensions and wind rating cases, as provided in the FM design recommendations tables. These results were reported to the Single Ply Roof Industry (SPRI) Committee where the updating of the FM design tables is currently under discussion.

Au cours de cette thèse, nous avons développé la réaction d'hydroamination d'arylacétylènes en présence de quelques amines secondaires aliphatiques. Dans un premier temps, nous avons pu montrer que cette réaction peut être catalysée par différents sels de cuivres. L'utilisation catalytique de CuCN a permis la formation régio- et stéréosélective d'énamines issues d'addition d'orientation de type anti-Markovnikov d'isomèrie (E). Les conditions développées n'ont pas permis la purification des énamines observées. Pour cette raison une réduction en présence de l'agent réducteur NaBH3CN a été effectuée afin de pouvoir isoler les amines correspondantes. L'utilisation catalytique de CuCl a permis à son tour, dans certaines conditions, la synthèse régio-et stéréosélective de 1,3-diènes (1E,3E)-1,4-disubstitués. La nature des électroniques des substituants des noyaux aromatiques des alcynes employés a joué un rôle majeur en ce qui concerne la chimiosélectivité de la réaction. Dans un second temps, nous nous sommes concentrés sur l'amélioration des conditions développées et la recherche d'autres moyens plus efficaces, moins coûteux et plus verts, nous avons été en mesure de montrer que la réaction étudiée peut également s'effectuer uniquement en présence d'éthylène glycol employé en tant que solvant et promoteur de la réaction. Cette méthode permet l'accès direct aux énamines issues de l'addition d'orientation de type anti-Markovnikov d'isomérie (E) avec d'excellents rendements isolés sans qu'il soit nécessaire de purifier les énamines obtenues. / In this thesis, we developed the hydroamiantion arylacétylènes reaction in the presence of some aliphatic secondary amines. At first, we could show that this reaction can be catalyzed by various copper salts. The catalytic use of CuCN allowed the regional training and sétéréosélective enamines derived from anti-Markovnikov addition type orientation isomerism (E). Developed conditions have not allowed the purification of the observed enamines. For this reason a reduction in the presence of the reducing agent NaBH3CN was performed in order to isolate the corresponding amines. The catalytic use of CuCl enabled in turn, under certain conditions, the regio-and stereoselective synthesis of 1,3-dienes (1E, 3E) -1,4-disubstituted oxanilides. The electronic nature of substituents of the aromatic rings alkynes employed played a major role as regards the chemoselectivity of the reaction.Secondly, we concentrate developed to improve conditions and find other more efficient ways, cheaper and greener, we were able to show that the test reaction can also be carried out only in the presence ethylene glycol used as solvent and the reaction promoter. This method allows direct access to enamines from the addition anti-Markovnikov orientation type of isomerism (E) with excellent isolated yields without the need to purify the resulting enamines.

Cette étude aborde le problème de l’aggravation du risque de fractures de côtes chez les automobilistesâgés en choc frontal. L’analyse de la bibliographie fait ressortir que les moyens actuels d’évaluationdu risque de fractures ne permettent pas de prendre en compte les différences anatomiques et depropriétés mécaniques du thorax observées chez les personnes âgées. Les modèles éléments finis (EF)personnalisés du corps humain offrent un grand potentiel en tant qu’outil avancé d’évaluation durisque de blessures. Toutefois, des données expérimentales sont nécessaires pour valider ces modèlesdans des conditions réalistes. De plus, le choix du niveau de personnalisation et la sensibilité de laréponse du modèle à celle-ci doivent être évaluées.Des expérimentations in vivo menés sur des volontaires ceinturés en choc léger, de différents âges etanthropométries, ont été réalisées. Ces tests ont permis d’étudier l’influence de l’âge et de lacorpulence sur la réponse mécanique du thorax et ont permis l’obtention de corridors nécessaires à lavalidation de modèles EF personnalisés. La géométrie du modèle numérique THUMS a été adaptée àcelle des volontaires et les propriétés mécaniques du thorax ont été modifiées au vu du vieillissementpour effectuer une analyse similaire dans le domaine lésionnel. Les simulations numériques ont mis enévidence un risque accru de fracture de côtes pour certains modèles personnalisés.Cette étude devrait permettre de mieux estimer le risque de blessure pour les automobilistesvulnérables. Elle devrait contribuer ainsi à promouvoir les modèles personnalisés du corps humaincomme outil avancé d’évaluation du risque de blessures. / This study deals with the topic of increased risk of rib fractures among elderly drivers infrontal impact. The analysis of the literature reveals that actual thorax injury assessment tools do nottake into account for the differences in anatomical features and biological material properties observedbetween adults and elderly. Personalized human body finite element (FE) models have great potentialas improved thorax injury assessment tools. However, experimental data are needed to validate thesemodels under real-world conditions. In addition, the choice of the level of personalization of the modeland the sensibility of the model response to this personalization must be assessed to predict thoracicinjury risk.In vivo sled tests were performed on belted volunteers of various anthropometries and age. These testswere used to assess the influence of age and corpulence on thorax mechanical response and allowed toobtain corridor responses needed to validate personalized FE models. The geometry of the FE modelTHUMS was adapted to the volunteers and the thorax material properties were modified consideringaging to carry out a similar analysis in the injurious domain. Numerical simulations highlighted anincreased risk of rib fractures for specific personalized models.This study should help to better estimate the injury risk for car occupants. It should contribute topromote personalized human body models as attractive thorax injury assessment tool ofvulnerable individuals.

Mainly two different morphologies of martensite can be obtained in steels depending on the amount of alloying elements. The first morphology, referred to as lath martensite, forms in low alloy, low carbon steels. It is, by far, the most extensively studied form of martensite due to its industrial applications. The second morphology of martensite, referred to as plate martensite, forms in highly alloyed and in high carbon steels and in particular in Fe-High Ni alloys. In this case, the transformation product is disc shaped and internally twinned. This morphology is the only form of martensite that has the potential to exhibit shape memory properties. It is therefore of great interest to understand the mechanisms of its formation. This is investigated in the present dissertation through the study of the martensitic transformation occurring in a Fe-30.5%Ni-0.155%C alloy. More precisely, the influence of stress and grain size on the crystallography of plate martensite is discussed in the general framework of the phenomenological theory of martensite crystallography. This theory allows associating a unique shape deformation to each orientational variant. In this way, the experimental observations carried out at different length scales by means of optical microscopy, EBSD and TEM can be used to infer the transformation path followed under different conditions. Firstly, the burst configurations of variants observed in coarse-grained austenite under stress free conditions are rationalized by considering the mechanical couplings between the variants. It is shown that self-accommodating and autocatalytic couplings are responsible for the formation of hierarchical configurations of variants. More precisely, the transformation is shown to occur through the alternate formation of perpendicular plate groups of variants. Self-accommodation is the dominant coupling between variants of the same plate group while autocatalytic couplings are responsible for the transfer of the transformation from one generation to the next. It is suggested that the plastic accommodation of the shape deformation plays a dominant role in propagating the transformation to a lower length scales. Secondly, the influence of a uniaxial stress state on the transformation is studied. It is seen experimentally that only the most favoured variants are systematically formed in coarse Cube grains while coarse non-Cube grains generally transform into plate groups of variants that are only moderately favoured by the stress. These observations are well explained by considering the interaction energy between the applied stress and the shape deformation associated with the transformation. Thirdly, the influence of the austenitic grain size on the transformation is also studied. A decrease in grain size is seen to decrease the martensite start temperature. For a grain size below about 10µm, the thermal transformation in liquid nitrogen is indeed suppressed in the present alloy. This observation is related to the increasing yield strength of austenite as the grain size is reduced. A noticeable change in the morphology of martensite also accompanies the decrease in grain size. Indeed, martensite forming in coarse-grained austenite is mostly lens shaped and partially twinned while it appears plate shaped and fully twinned in smaller grains. Furthermore, martensite forming in fine-grained austenite develops self-accommodating configurations suggesting that most of the transformation deformations are elastically accommodated in this case. This is believed to be related to the observance of a shape memory effect in the present alloy in its fine-grained condition. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

L’objectif de ce travail est le développement de dispositifs de contrôle de la diffusion des ondes acoustiques à l’aide de surfaces hétérogènes, pour des applications à l’acoustique urbaine. Pour remplir cet objectif, deux méthodes sont employées. La première à l’aide d’une métasurface, la direction d’une onde réfléchie est contrôlée. La seconde étude concerne l’influence d’un traitement inhomogène aux parois d’un guide ouvert sur les effets conjoints ou compétitifs d’absorption, de confinement et de rayonnement de l’onde. Nous montrons expérimentalement la possibilité de dissimuler un objet disposé sur un mur pour une onde acoustique audible. Pour y parvenir, une métasurface composée de différents résonateurs de Helmholtz est conçue et est réalisée de façon à être la plus fine possible. Ces travaux sont réalisés dans le domaine fréquentiel mais également dans le domaine temporel, ce qui permet de mettre en avant le caractère large bande de la métasurface. Il est démontré numériquement et expérimentalement que la direction des ondes réfléchies peut être contrôlée. Enfin la dernière partie est consacrée à l’influence d’une paroi hétérogène sur la propagation d’une onde acoustique à l’intérieur d’une rue. Une rue pouvant être assimilée à un guide d’onde ouvert engendre donc des modes de propagation complexes, dus aux pertes par rayonnement. La présence d’un matériau poreux sur les parois d’un guide vient perturber fortement la localisation spatiale des modes, ce qui les rend plus ou moins fuyants. / The aim of this thesis is to develop a scheme for controling the propagation of acoustic waves using heteregenous surfaces. Its results can be applied in the field of urban acoustic. The thesis is composed of two sections, each of them employing a different method. The first section focuses on controling the direction of a reflected wave, using a metasurface. The second concentrates on the influence of an inconsistent treatment to the side of an open waveguide on the wave joint and competitive effects of absorption, confinement and radiation. Part one provides experimental evidence that it is possible to conceal an object placed on a wall from an audible acoustic wave. To prove it, the thinest possible metasurface was constructed with Helmholtz resonators. The experimental results were compared to a numerical study realized with finite elements. This work was made in both temporal and frequency domains, allowing to point out the wide frequency characteristics of the metasurface. The numerical and experimental results show that the direction of a reflected wave can, indeed, be controled. Part two analyse the impact of a heterogeneous wall on the spreadinf of an acoustic wave in a street. Due to radiation losses, the street produces complex ways of propagation. The presence of a porous material on a waveguide‘ side deeply disrupt the spatial location of these waves, making them more or less fleeting. In particular, depending on the position of the material in the street, certain waves will be more confined to the inside of the street, radiating less towards the open external environment. They are consequently, less cushioned.

Memoria (licenciado en ciencias jurídicas y sociales) / No autorizada por el autor para ser publicada a texto completo / La presente tesis se centrará en el análisis de la aplicación de la teoría de los actos propios por parte de nuestros Tribunales Superiores de Justicia para resolver cuestiones de carácter laboral sometidas a su decisión, referentes principalmente a reclamos efectuados por trabajadores sujetos a contrato de prestación de servicios a honorarios que con posterioridad al término de la vigencia de su contrato, alegan la existencia con la empresa de una relación laboral propiamente tal, incluyendo nuestro estudio una referencia especial para las razones que esgrimen los autores que se han manifestado en contra de la operación de esta teoría en la órbita laboral, realizándose una recopilación de la jurisprudencia más relevante e ilustrativa generada al respecto y precisando un análisis jurisprudencial pormenorizado y con explicaciones precisas de los diferentes fallos recogidos en donde los tribunales de justicia han dado procedencia a la teoría presentada. De esta forma, esta investigación dará al lector las ideas fundamentales que informan la recepción por parte de nuestros Tribunales Superiores de Justicia en sede laboral, de una postura no explorada anteriormente, y que se encuentra en germen potencial, de desarrollo creciente y que se perfila como una de las soluciones más novedosas para resolver conflictos laborales en donde se discute la existencia de la subordinación y dependencia y otros temas propios del Derecho del Trabajo, convirtiéndose en poco tiempo en una poderosa herramienta de defensa que han hecho suyas las empresas principalmente, a través del hecho de que la teoría en estudio posibilita, en el caso de los trabajadores que prestan servicios a honorarios y que con posterioridad a la vigencia de su vínculo reclaman la existencia con la empresa de una relación laboral tipo, la inadmisibilidad del reclamo posterior por parte de los trabajadores que se obligaron de conformidad a un contrato a honorarios, justificando esta ilicitud de contravenir la conducta que observaron durante el periodo en que prestaron sus servicios, en el principio de la buena fe y en el deber jurídico de no contrariar conductas pasadas, piedra angular de la teoría del propio acto.

Memoria (licenciado en ciencias jurídicas y sociales) / Esta memoria se enmarca en un proyecto realizado por el Departamento de Derecho Privado de la Facultad de Derecho de la Universidad de Chile, para la actualización del Repertorio de Legislación y Jurisprudencia del Código Civil, consistiendo en las fichas de análisis de sentencias de diversos tópicos, los extractos realizados respecto a la buena fe contractual que modificarán el Repertorio en cuestión y por último una monografía en la cual se examina la jurisprudencia respecto al tema. Las sentencias que se analizaron para extractar fueron 99, de las cuales sólo algunas fueron pertinentes al tema en cuestión, siendo sólo 54 los extractos que finalmente terminaron modificando en algún sentido la jurisprudencia del artículo 1546

Raman spectroscopy provides characteristic peaks of the target molecules that can be observed with appropriate laser, spectrometer and detector. These characteristic peaks can reveal ‘fingerprint’ information of a molecule even in a myriad of cases and combinations. It makes Raman spectroscopy a highly sensitive and selective analytical technique. Raman spectroscopy has a variety of chemical, environmental and biological applications. In this dissertation, modified Raman method are applied in life sciences and pharmaceutical studies. The major challenge against development of Raman spectroscopy is how to improve the intensity of Raman signal. Surface Enhance Raman Scattering (SERS) and resonance Raman(RR) are utilized for conquer this obstacle. In SERS technique, Raman signal is enhanced by introducing metal surface. SERS has a great potential for trace molecular detection since it’s sensitive enough to detect a single molecule. In RR, wavelength is carefully chosen to overlap with (or very near to) an electronic transition of a target molecule. With such overlap, Raman intensity can be increased by factors of 102-106, thus detection limit of target molecule can be significantly decreased. SERS and RR are applied for trace bio-marker detection and bio-system analysis in this study. In the first chapter, the history, principles and applications of SERS and RR are introduced. Second chapter emphases on instrumental information and experimental methods of the techniques were applied in this study. The third chapter focuses on establishing novel SERS method to detect Alzheimer’s disease related biomarker, melatonin. A novel SERS substrate, Fe3O4/Ag nanostructures is developed, and SERS experimental conditions, such as aggregating agents and pH, are optimized to achieve the most sensitive detection of melatonin. In the fifth chapter, resonance Raman is served as an important analytical tool to identify metal binding and structure-activity relationship of metalloantibiotic, bacitracin. In the last chapter, Raman spectroscopy are applied in material science. Two solar cell materials, regioregular poly(3-hexylthiophene) films and Cu2ZnSnSe4 are characterized by Raman spectroscopy.