Made available in DSpace on 2016-06-02T20:36:14Z (GMT). No. of bitstreams: 1 1918.pdf: 4286869 bytes, checksum: 966235f0d23c7aa4e3030eccc751c2a4 (MD5) Previous issue date: 2008-02-29 / Universidade Federal de Sao Carlos / PbO2 films were grown on different substrates (Ti-Pt, ADE, FC and Pb), at constant current density of 20 mA cm-2, using two methodologies: electrodepositon from 0.1 mol L-1 Pb(NO3)2, 1.7 mmol L-1 LSS and 0.1 mol L-1 HNO3 solution and lead anodization in 3 mol L-1 H2SO4 solution. All PbO2 films presented important characteristics such as: homogeneous and compact morphology, quite uniform growth and good adherence. MnO2-composite film was prepared from electrolytic MnO2 powder [80 % (m/m)], carbon black [10 % (m/m)] e PVDF [10 % (m/m)] and then applied on carbon fibre (FC). The physical and electrochemical properties of these different electrode materials were characterized by scanning electronic microscopy, X-ray diffratometry, linear potential scan and cyclic voltammetry. The PbO2 films obtained by electrodeposition presented mainly the tetragonal phase â-PbO2, while the PbO2 film obtained by anodization presented an oxide mixture with the following phases: tetragonal â-PbO2, orthorhombic á-PbO2, PbO and also PbSO4. The electrolytic MnO2 was obtained mainly with the phase å- MnO2. The Pb/PbO2 electrode presented the best performance regarding OER. Among the electrodes obtained by electrodeposition (Ti-Pt/PbO2, ADE/PbO2 and FC/PbO2), the FC/PbO2 electrode presented higher values of superficial area and overpotential for the OER. The FC/MnO2 did not present good performance regarding OER. The Pb/PbO2 electrode was applied, at constant current density of 5 mA cm-2, in the oxidation of 0.05 mol L-1 Cr3+ ions solution, presenting a conversion efficiency of Cr3+ to Cr6+ ions of 90 %. The FC/PbO2 was also applied in the decolorization of the BR 19 dye solution (100 mg L-1), using a filter-press reactor. A decolorization efficiency of 99.5 % was obtained in the following experimental conditions: flow rate of 7.0 L min-1, current density of 30 mA cm-2 and chloride concentration of 70 mmol L-1. At the end of the oxidation process, a value of the German parameter DFZ 10 times lower than the maximum value (3 m-1) established before discarding in the environment was found. / Filmes de PbO2 foram crescidos sobre diferentes substratos (Ti-Pt, ADE, FC e Pb), a densidade de corrente constante de 20 mA cm-2, usando duas metodologias: eletrodeposição a partir de solução de Pb(NO3)2 0,1 mol L-1, LSS 1,7 mmol L-1 e HNO3 0,1 mol L-1 e anodização de chumbo em solução de H2SO4 3 mol L-1. Todos os filmes de PbO2 apresentaram características importantes, tais como: morfologia homogênea e compacta, crescimento bastante uniforme e boa aderência. O filme compósito de MnO2 foi preparado a partir de pó de MnO2 eletrolítico [80 % (m/m)], negro de acetileno [10 % (m/m)] e PVDF [10 % (m/m)] e então aplicado sobre fibra de carbono (FC). As propriedades físicas e eletroquímicas destes diferentes materiais de eletrodo foram caracterizadas por microscopia eletrônica de varredura, difratometria de raios X, varredura linear de potencial e voltametria cíclica. Os filmes de PbO2 obtidos por eletrodeposição apresentaram principalmente a fase â-PbO2 tetragonal, enquanto que o filme de PbO2 obtido por anodização apresentou uma mistura de óxidos com as seguintes fases: â-PbO2 tetragonal e á-PbO2 ortorrômbica, PbO e PbSO4. O MnO2 eletrolítico foi obtido principalmente com a fase å-MnO2. O eletrodo Pb/PbO2 apresentou um bom desempenho em relação à RDO. Dentre os eletrodos obtidos por eletrodeposição (Ti-Pt/PbO2, ADE/PbO2 e FC/PbO2), o eletrodo FC/PbO2 apresentou os maiores valores de área superficial e sobrepotencial para a RDO. O eletrodo FC/MnO2 não apresentou um bom desempenho em relação à RDO comparado com os demais eletrodos estudados. O eletrodo Pb/PbO2 foi aplicado, a densidade de corrente constante de 5 mA cm-2, na oxidação de uma solução contendo 0,05 mol L-1 de íons Cr3+, apresentando uma eficiência de conversão de íons Cr3+ a Cr6+ de cerca de 90%. O eletrodo de FC/PbO2 também foi aplicado na descoloração de uma solução de corante AR 19 simulada (100 mg L-1), utilizando um reator tipo filtro prensa. Uma eficiência de descoloração de 99,5% foi obtida nas seguintes condições experimentais: fluxo de eletrólito de 7,0 L min-1, densidade de corrente de 30 mA cm-2 e concentração de cloreto de 70 mmol L-1. Ao final do processo de oxidação foi encontrado um valor do parâmetro alemão DFZ 10 vezes menor que o valor máximo (3 m-1) estabelecido antes do descarte no meio ambiente.

La connaissance des coefficients de partage des éléments traces à haute pression et haute température est aujourd'hui requise afin de tester les différents modèles géochimiques d'évolution du manteau terrestre. Etant données les difficultés inhérentes à l'évaluation de ces coefficients de partage lors d'expériences d'équilibre dans différentes conditions (pression, température, composition chimique, ... ), la modélisation de la distribution de ces éléments traces est nécessaire. Cependant, celle-ci passe par la compréhension des phénomènes microscopiques qui contrôlent l'incorporation de l'élément. Ce travail a porté sur la détermination des différents sites d'accueil du chrome trivalent dans des minéraux du manteau à partir de l'étude de sa luminescence. Cette spectroscopie de luminescence, mise en oeuvre à haute pression en cellule à enclumes de diamant, permet de suivre l'évolution des niveaux d'énergie du cr3+ en fonction de la pression. Nous avons ainsi acquis des données de luminescence sur plusieurs phases cristallines de basse pression (spinelles, pyroxènes, forstérite), de haute pression (grenats, ilménite, pérovskites), et sur des verres silicatés de composition chimique simple. Les résultats obtenus sur les minéraux montrent que le Cr3+ s'incorporent majoritairement dans les sites octaédriques, ,nécessitant, dans certains cas, une compensation locale des charges. Les mécanismes de substitution", mais aussi l'énergie de stabilisation de l'élément trace dans la structure, dépendent alors fortement de la nature des cations disponibles pour assurer l'équilibre électrostatique. Dans les verres, nous mettons en évidence des variations importantes de la distribution de sites d'accueil en fonction de la composition chimique. La modélisation des paramètres thermodynamiques qui participent au partage du chrome à partir de nos données de haute pression est alors discutée.

In this dissertation, we show the effectiveness of the exploitation of the Circular Restricted Three - Body Problem (CR3BP) in the Earth - Moon framework. We study the motion of a massless particle under the gravitational attraction of Earth and Moon, either to design missions in the new era of lunar exploration and simulate the behaviour of minor bodies that get close to the Earth.A fundamental role is played by the five equilibrium, or libration, points that appear in the rotating reference system. We focus on two, L(1) and L(2), unstable collinear libration points, taking advantage of the central and hyperbolic invariant manifolds, which exist in their neighborhood. Various types of periodic and quasi-periodic orbits, to be conceived as station locations for a spacecraft, occupy the central manifold. A stable and an unstable invariant manifold are associated with any of these orbits: they serve as channels to get far or close to the central orbits for t > / = 0. We exploit the corresponding dynamics to construct transfers from either Earth and Moon to a libration point orbit (LPO) and to investigate some paths that might guide asteroids impacting onto the Moon.We are witnesses of a recent enthusiasm on a possible return to the Moon. Several space agencies have designed unmanned missions that have just achieved observations around the Moon, in view of a future human installation. Besides, the space tourism companies are planning to extend their potentiality by offering lunar trips. In this context, the neighborhood of L(1) seems to be an appropriate place to put a space hub. Instead, L(2) would be profitable to monitor the lunar farside.In Chapter 1, we explain the CR3BP and how to compute, with different methodologies, central orbits along with their associated hyperbolic manifolds and the transit trajectories lying inside them. Then, two more elaborate dynamical systems are introduced, the Bicircular Restricted Four - Body Problem and the Restricted n - Body Problem.In Chapter 2, we use the stable and the unstable manifolds associated with L1/L2 central orbits to connect the lunar surface with such LPOs. We see that almost no effort should be put to follow these transfers thanks tothe natural dynamics we consider.In Chapter 3, we study how to depart from a nominal orbit around the Earth and arrive to a L1/L2 LPO. This case requires two maneuvers, one to leave the Low Earth Orbit and another to insert into the stable manifold associated with the given LPO.In Chapter 4, we wonder how the above reference solutions can change whenever different forces are added to the dynamical model. We describe two possible approaches that can be implemented, namely an optimal control strategy and a multiple shooting procedure. The results demonstrate that also in the Earth - Moon framework the CR3BP gives solutions close to the ones to be used in reality.In Chapter 5, we cope with the collision of asteroids onto the Moon. Such phenomenon happens continuously on all the rocky bodies populating the Solar System, as it can be inferred from the craters that mould their surface, and it is widely studied by several branches of science, since it provides information on the target and on the impactors in dynamical, astronomical and geological terms.We analyze the role played, in the creation of lunar impact craters, by low-energy transit trajectories which approach the neighborhood of L(2). It turns out that in the most likely case the collisions are focused on the apex of the Moon. Summing up the gravitational force exerted by the Sun, we notice that the relative Earth-Moon-Sun configuration can change dramatically the percentage and the region of impact.KEYWORDS: Circular Restricted Three-Body Problem, Lunar Impact Dynamics, Low-Energy Transfers, Optimal Control / L'objectiu d'aquest treball és mostrar la utilitat de l'explotació del Problema Circular Restringit dels Tres Cossos (CR3BP) pel sistema Terra - Lluna. Aquest sistema dinàmic considera el moviment d'una partícula amb massa negligible sota l'atracció gravitatòria de Terra i Lluna i pot ser usat pel disseny de missions espacials a la nova era d'exploració lunar, així com per simular el comportament d'asteroides i cometes que s'apropen a la Terra.Els cinc punts d'equilibri, o de libració, del CR3BP que apareixen al sistema de referència giratori, juguen un paper fonamental: ens centrarem en dos punts de libració col·lineals inestables, L(1) i L(2).Convé tenir en compte les varietats invariants centrals i hiperbòliques que hi ha a l'entorn de L(1) i L(2). La varietat central està ocupada per diversos tipus d'òrbites periòdiques i quasi-periòdiques, que poden ser concebudes com a solucions d'estacionament per a un vehicle espacial. Qualsevol d'aquestes òrbites té associada una varietat estable i una d'inestable, que serveixen com a canals per arribar lluny o prop de les òrbites centrals per t >/= 0.Farem ús de la dinàmica associada a aquestes varietats per a la construcció de transferències des de la Terra i la Lluna a una òrbita de libració i per investigar alguns camins que podrien guiar asteroides que impacten amb la Lluna.Pel que fa a la primera qüestió, l'entorn de L(1) sembla ser el lloc més apropiat per posar una estació espacial. D'altra banda, L(2) seria útil per observar i/o controlar la cara oculta de la Lluna.A la segona part de la tesi, investiguem la col·lisió d'asteroides amb la Lluna. Aquest fenòmen té lloc contínuament a tots els cossos rocosos del Sistema Solar, com es pot deduir dels cràters que modelen les seves superfícies. El procés de formació de cràters proporciona informació sobre el cos objectiu i sobre els asteroides,en termes dinàmics, astronòmics i geològics. Nosaltres estem interessats en el desenvolupament d'una metodologia diferent que pot ajudar en aquesta recerca.En la obra, explotem les eines de Teoria de Sistemes Dinàmics i estratègies de control òptim.

The theoretical part of the thesis contains a brief overview of some experimental methods that are used in machining technologies. The experimental part at first elaborates on the analysis of two titanium alloys. The actual experiment, which consists of milling of the two aforementioned materials with the use of several tools and holders, is then described. It was conducted in collaboration with the company Frentech Aerospace s.r.o. When milling, forces were measured with piezoelectric dynamometer. Further, the analysis of acquired data that is followed with discussion about its main findings, is provided. The conclusion of the thesis deals with the found facts corresponding with the information obtained by analysis of materials. The main results arise out of the comparison of used combinations of tools and holders for milling of material Ti-Al6-V4, observation of impact of particular factors on measured force, or out of different values of measured forces when milling two given materials.