Résumé : Grâce à des caractéristiques physiques particulières, le [indice supérieur 64]Cu (T[indice inférieur 1/2]= 12.7 h; β[indice supérieur+], 0.65 MeV [17.8 %]; β[indice supérieur −], 0.58 MeV [38.4 %]) est un candidat idéal pour l’imagerie TEP et la radiothérapie ciblée du cancer. Son utilisation est actuellement limitée par la disponibilité de chélateurs bi-fonctionnels (CBFs) offrant une résistance élevée aux réactions de transmétallation in vivo. Récemment nous avons développés deux nouveaux CBFs cycliques, DOTHA[indice inférieur 2] et NOTHA[indice inférieur 2], portant des ligands hydroxamates pour la complexation au [indice supérieur 64]Cu. Ces CBFs possèdent une cinétique de marquage rapide dans des conditions très douces, une stabilité élevée in vivo et un profil de biodistribution favorable avec une clairance rapide. Nous proposons maintenant d’étendre notre approche à la préparation de CBFs acycliques plus flexibles et compacts afin de moduler les propriétés biologiques et la pharmacocinétique des traceurs peptidiques. Le but de mon projet de maîtrise est de développer une série de chélateurs acycliques dérivés de l'histidine et de l'acide glutamique et fonctionalisés avec des groupements hydroxamates pour identifier un CBF offrant un complexe stable in vivo avec le [indice supérieur 64]Cu(II). Les CBFs ont été préparés en solution pour faciliter l’optimisation de chaque étape réactionnelle. Les groupements chélatants hydroxamates ont été sélectionnés pour leur habilité à former des complexes stables avec différents métaux et ils ont été liés en position N-terminale et sur la chaîne latérale des acides aminés grâce à des réactions de substitution nucléophile. Les groupements para-methoxy-benzyles ont été judicieusement sélectionnés pour la protection des groupements hydroxamates afin de faciliter, au besoin, une déprotection sélective sous des conditions très douces. L’optimisation du marquage a été effectuée avec l’isotope stable du cuivre et ensuite avec le [indice supérieur 64]Cu en faisant varier le contre ion métallique, le pH, la concentration, et la température. Le CBF offrant la plus grande stabilité, soit celui dérivé de l’histidine, a été conjugué à un peptide, le H[indice inférieur 2]N-PEG-[D-Tyr[indice supérieur 6],βAla[indice supérieur 11],Thi[indice supérieur 13],Nle[indice supérieur 14]]bombesin(6-14) (BBN), se liant fortement aux récepteurs de la relâche de la gastrine surexprimés dans les cancers du sein et de la prostate. La stabilité et l’activité spécifique du CBF-histidine et du radiotraceur marqués au [indice supérieur 64]Cu s’est avérée faible in vitro. Il est connu que l’activité antibactérienne de ligands hydroxamates est associée à leur capacité à complexer le fer. En perspective, comme nos chélateurs complexent très fortement le Fe(III), une alternative pour ces composés serait d’évaluer leur capacité à inhiber la croissance et la prolifération des bactéries. || Abstract : Thanks to its particular physical characteristics, [superscript 64]Cu (T[subscript ½= 12.7 h; β[superscript +], 0.65MeV [17.8 %]; β[superscript −], 0.58MeV [38.4 %]) is an ideal candidate for PET imaging and targeted cancer radiotherapy. Currently, its use is limited by the availability of bi-functional chelators (BFCs) which give high resistance to in vivo transmetallation reactions. Recently, we developed two new cyclic BFCs, DOTHA[subscript 2] and NOTHA[subscript 2], bearing hydroxamate pendant arms for the complexation with [superscript 64]Cu. Those BFCs have fast labeling kinetics under very mild conditions, a high in vivo stability and a biodistribution profile which is favorable with a fast clearance. Now, we propose to expand our approach to the preparation of acyclic BFCs, which are more flexible and compact, in order to better modulate biological properties and the pharmacokinetics of the peptidic tracers. The goal of my Master’s degree project is to develop a series of acyclic chelators derived from histidine and glutamic acid and functionalized with hydroxamate pendant arms to identify a BFC that shows highly stable in vivo complexes with [superscript 64]Cu(II). BFCs have been prepared in solution to facilitate the optimization of each reactive step. Hydroxamate chelating groups have been selected for their ability to form stable complexes with different metals and they have been conjugated in N-terminal position and on the lateral chain of amino acids via nucleophilic substitution reactions. Para-methoxy-benzyl groups have been judiciously selected for the protection of the hydroxamate groups to facilitate, if needed, a selective deprotection under mild conditions. The labeling optimization has been performed with a stable copper isotope, and then with [superscript 64]Cu varying the metallic counter-ion, pH, concentration and temperature. The BFC having the highest stability, the one derived from histidine, was conjugated to a peptide, H[subscript 2]N-PEG-[D-Tyr[superscript 6],βAla[superscript 11],Thi[superscript 13],Nle[superscript 14]]bombesin(6-14) (BBN), strongly bounding the gastrin releasing peptide receptor, which is overexpressed in breast and prostate cancers. Both the stability and specific activity of BFC-histidine of the radiotracer labeled with [superscript 64]Cu were low in vitro. It is known that the antibacterial activity of hydroxamate ligands is associated with their ability to complex iron. In perspective, because our hydroxamate ligands strongly complex Fe(III), an alternative for these compounds would be to assess their ability to inhibit the growth and proliferation of bacteria.

This dissertation constitutes two major sections. In the first major section, a kinetic analysis was established to investigate the electromigration (EM), enhanced intermetallic compound (IMC) growth and void formation for Sn-based Pb-free solder joints to Cu under bump metallization (UBM). The model takes into account the interfacial intermetallic reaction, Cu-Sn interdiffusion, and current stressing. A new approach was developed to derive atomic diffusivities and effective charge numbers based on Simulated Annealing (SA) in conjunction with the kinetic model. The finite difference (FD) kinetic model based on this approach accurately predicted the intermetallic compound growth when compared to empirical observation. The ultimate electromigration failure of the solder joints was caused by extensive void formation at the intermetallic interface. The void formation mechanism was analyzed by modeling the vacancy transport under electromigration. The effects of current density and Cu diffusivity in Sn solder were also investigated with the kinetic model. The second major section describes the integration of Step and Flash Imprint Lithography (S-FIL®) into an industry standard Cu/low-k dual damascene process. The yield on a Back End Of the Line (BEOL) test vehicle that contains standard test structures such as via chains with 120 nm vias was established by electrical tests. S-FIL shows promise as a cost effective solution to patterning sub 45 nm features and is capable of simultaneously patterning two levels of interconnect structures, which provides a low cost BEOL process. The critical processing step in the integration is the reactive ion etching (RIE) process that transfers the multilevel patterns to the inter-level dielectrics (ILD). An in-situ, multistep etch process was developed that gives excellent pattern structures in two industry standard Chemical Vapor Deposited (CVD) low-k dielectrics. The etch process showed excellent pattern fidelity and a wide process window. Electrical testing was conducted on the test vehicle to show that this process renders high yield and consistent via resistance. Discussions of the failure behaviors that are characteristic to the use of S-FIL are provided. / text

Cette thèse est consacrée à l'étude des structures atomiques des phases icosaédriques de type F et leurs dislocations.<br /><br />Dans cette étude nous avons d'abord construit une structure générique permettant de traiter dans un seul schéma les phases icosaédriques de type F connues. Afin de valider ce modèle nous avons synthétisé quelques compositions suggérées par ce dernier. Ces synthèses ont permis entre autres de découvrir deux nouvelles phases quasipériodiques à la stoechiométrie Al66,08Cu21,35Mn8,29Fe4,28 , l'une icosaédrique (métastable) de type F et l'autre décagonale (stable). Elles ont montré, à une composition au-delà de celles déjà étudiées dans le système (Al,Pd,Fe), l'existence d'une phase F-IQC.<br /><br /> Globalement, ces résultats expérimentaux d'études de nouvelles phases icosaédriques ont permis de montrer la fiabilité du modèle : sur les trois essais de nouvelles compositions, deux ont montré l'existence de phases icosaédriques de type F et la troisième a mis en évidence une phase décagonale en relation d'épitaxie canonique avec la phase icosaédrique brut métastable (axe 10 confondu avec un axe 5).<br /><br />Possédant un modèle fiable nous avons donc pu y introduire des dislocations. Nous avons ainsi précisé la géométrie des dislocations à l'échelle atomique, hors de la zone de cœur, dans les phases F-IQC. Dans cette structure nous avons aussi identifié les mouvements des phasons et tenté d'apporter des éléments de réponse aux mouvements de ces dislocations.

Die Motivation zur Untersuchung ternärer und quaternären CuZr-Legierungen bestand in der Annahme, dass die Zugabe von Kobalt den Stabilitätsbereich von B2 CuZr bis zur Raumtemperatur erweitert und Aluminium einen signifikanten Effekt auf die Glasbildungsfähigkeit des CuZr-Systems hat. Die vorliegende Dissertation befasst sich mit der Herstellung und Charakterisierung von Cu50-xCoxZr50 (0 ≤ x ≤ 20) und Cu50-xCoxZr45Al5- (x = 2, 5, 10 und 20) Legierungen. Hierbei wurden die Phasenbildung, die thermische Stabilität, die Mikrostruktur, die Martensitbildung und die mechanischen Eigenschaften der Legierungen untersucht. Die Abhängigkeit der Phasenbildung von der Erstarrungsrate und der thermodynamischen Stabilität von Cu-Co-Zr-Legierungen zeigte, dass die Zugabe von Kobalt die Glasbildungsfähigkeit von Cu-Co-Zr-Legierungen absenkt und die stabilen kristallinen Produkte des Systems von Cu10Zr7 + CuZr2 zu (Cu,Co)Zr Phase mit einer B2 Struktur verändert. Die Ergebnisse weisen darauf hin, dass bei den schmelzgesponnene Bänder mit wenigstens 5 Atom-% Co das Glas direkt in B2 (Cu,Co)Zr kristallisiert, während Massivproben mit Co-Gehalten zwischen 0 ≤ x < 5 die monokline (Cu,Co)Zr Phase und Cu10Zr7 sowie CuZr2 beinhalten, wobei für x ≥ 10 die B2 (Cu,Co)Zr Phase bei Raumtemperatur im Gleichgewicht ist. Des Weiteren werden mit steigendem Co-Gehalt die Martensitumwandlungstemperaturen zu niedrigeren Werten verschoben. Die Phasenbildung im ternären System wird im pseudo-binären (Cu,Co)Zr-Phasendiagramm zusammengefasst, welches die Entwicklung neuer Formgedächtnislegierungen sowie metallischer Glas-Komposite bei Zugabe des Glasbildungselementes Aluminium vereinfacht. In den Vierstofflegierungen erhöht Al die Glasübergangs- und Kristallisationstemperaturen und verbessert dadurch die Glasbildungsfähigkeit des Systems. Die röntgenographische Analyse zeigte, dass die Kristallisationsprodukte der schmelzgesponnenen Bänder variieren: von Cu10Zr7 + CuZr2 + AlCu2Zr zu (Cu,Co)Zr + AlCu2Zr, wenn Co ≤ 5 und Co ≥ 10. Die Herstellung von Massivproben mit unterschiedlichen Durchmessern führte zu einem vollständig amorphen Gefüge, einem metallischen Glas-Komposit oder einem vollständig kristallinen Gefüge. Für Co ≤ 5 tritt neben (Cu,Co)Zr und AlCu2Zr ebenfalls Cu10Zr7 auf. Mittels Rasterelektronen (REM)- und Transmissionselektronenmikroskopie (TEM) erfolgte die Analyse des Einflusses von Al- und Co-Zugaben auf die Mikrostruktur von CuZr-Legierungen. Für die Cu-Co-Zr-Al-Legierungen sowie Cu30Co20Zr45Al5 (ø = 4 mm) und Cu45Co5Zr45Al5 (ø = 2 mm) wurden mikrostrukturelle Untersuchungen mittels TEM durchgeführt. Nachfolgend wurde die Heterogenität der Mikrostruktur in der Cu40Co10Zr45Al5 (ø = 2 mm) untersucht. Der Einfluss von Co auf die mechanischen Eigenschaften von rascherstarrten Cu50-xCoxZr50 (x = 2, 5, 10 und 20 Atom-%) Legierungen zeigt, dass das Verformungsverhalten der Stäbe unter Druckbeanspruchung stark von der Mikrostruktur der (Cu,Co)Zr Phase und somit von der Legierungszusammensetzung abhängt. Kobalt beeinflusst die Bruchfestigkeit der Gussproben. Weiterhin zeigen Proben mit martensitischem Gefüge eine Kaltverfestigung. Neben der Kaltverfestigung zeigen die Legierungen mit hohem Co-Gehalt eine verformungsinduzierte Martensitumwandlung und weisen zwei Streckgrenzen auf. Für die Vierstofflegierungen wurde der Einfluss der Kühlrate und der chemischen Zusammensetzung auf die mechanischen Eigenschaften untersucht. Für Cu48Co2Zr45Al5 (ø = 1.5, 2, 3 und 4 mm) und Cu45Co5Zr45Al5 (ø = 3 mm) wurde der Einfluss der Kühlrate und der Heterogenität diskutiert. Die Ergebnisse zeigen, dass die mechanischen Eigenschaften der Cu50-xCoxZr45Al5-Legierungen stark von der Makrostruktur und dem Volumenanteil der amorphen und kristallinen Phase abhängen. Die verformungsinduzierte Martensitumwandlung in Cu40Co10Zr50- und Cu40Co10Zr45Al5-Gussstäben wurde mittels hochenergetischer Röntgenstrahlung durchgeführt. Die In-situ- Druckversuche erfolgten weg- und kraftkontrolliert. Das makroskopische und mikroskopische Spannung-Dehnungs-Verhalten sowie die Phasenumwandlungskinetik wurden dabei betrachtet. Die relativen Veränderungen der vollständig integrierten Intensität der ausgewählten B2- und Martensitreflexe, die auf die Veränderungen der Volumenanteile der entsprechenden Phasen unter Verformung hinweisen, wurden als Phasenumwandlungsvolumen M/M+B2 beschrieben. / The fact that the presence of Co extends the stability range of B2 CuZr to room temperature, together with the significant effect of Al on improving the glass forming ability of the CuZr system was the motivation to investigate the ternary and quaternary CuZr alloys with the aim of synthesizing BMG composites containing B2 (Cu,Co)Zr crystals. This PhD thesis deals with preparation and characterization of Cu50-xCoxZr50 (0 ≤ x ≤ 20) and Cu50-xCoxZr45Al5 (x = 2, 5, 10 and 20) alloys. The phase formation, thermal stability, microstructure, martensitic transformation and mechanical properties of these alloys were investigated. The dependence of phase formation on solidification rate and the thermodynamically stability of Cu-Co-Zr alloys reveals that the addition of Co decreases the glass forming ability (GFA) of the Cu-Co-Zr alloys and changes the stable crystalline products of the system from Cu10Zr7 + CuZr2 to (Cu,Co)Zr phase with a B2 structure. The results indicate that for the melt-spun ribbons with at least 5 % Co, the glass crystallizes directly into B2 (Cu,Co)Zr, while in the case of bulk specimens, compositions with 0 ≤ x < 5 of Co contain the monoclinic (Cu,Co)Zr phase and Cu10Zr7 and CuZr2, whereas, for x ≥ 10, the B2 (Cu,Co)Zr phase is the equilibrium phase at room temperature. Furthermore, increasing the cobalt content decreases the martensitic transformation temperatures to lower temperatures. The phase formation in the ternary system is summarized in a pseudo-binary (Cu,Co)Zr phase diagram, that helps for designing new shape memory alloys, as well as bulk metallic glass composites with the addition of glass former elements. In the quaternary alloys, Al increases the glass transition and crystallization temperatures and hence improves the GFA of the system. The X-ray analysis illustrates that for the melt-spun ribbons, the crystallization products vary from Cu10Zr7 + CuZr2 + AlCu2Zr to (Cu,Co)Zr + AlCu2Zr when Co ≤ 5 and Co ≥ 10, respectively. Depending on the cooling rates, the bulk samples represent a fully amorphous structure or BMG composites or a fully crystalline structure. For Co ≤ 5, beside (Cu,Co)Zr and AlCu2Zr, Cu10Zr7 exists as well. Scanning (SEM) and transmission (TEM) electron microscopy investigations were done to investigate the effect of Al and Co addition to the microstructure of CuZr alloys. In the case of Cu-Co-Zr-Al alloys, Cu30Co20Zr45Al5 (ɸ = 4 mm) and Cu45Co5Zr45Al5 (ɸ = 2 mm) compositions were selected for the microstructure verification using TEM. Later, the heterogeneity of the microstructure in Cu40Co10Zr45Al5 (ɸ = 2 mm) alloy was considered. The effect of Co on the mechanical properties of rapidly solidified Cu50-xCoxZr50 (x = 2, 5, 10 and 20 at.%) alloys depict that the deformation behavior of the rods under compressive loading strongly depends on the microstructure, and as a results, on the alloy composition. Cobalt affects the fracture strength of the as-cast samples; and deformation is accompanied with two yield stresses for high Co-content alloys, which undergo deformation-induced martensitic transformation. Instead samples with a martensitic structure show a work-hardening behavior. For quaternary alloys, the effects of cooling rate and chemical composition on mechanical properties of the alloys were investigated. Cu48Co2Zr45Al5 (ɸ= 1.5, 2, 3 and 4 mm) and Cu45Co5Zr45Al5 (ɸ = 3 mm) compositions were selected to discuss the effect of cooling rate and heterogeneity, respectively. The results depict that the mechanical properties of Cu50-xCoxZr45Al5 alloys strongly depend on the microstructure and the volume fraction of the amorphous and crystalline phases. The deformation-induced martensitic transformation of Cu40Co10Zr50 and Cu40Co10Zr45Al5 as-cast rods, was studied by means of high-energy X-rays. The in situ compression measurements were performed in track control and load control modes. The macroscopic and microscopic stress-strain behavior, as well as the phase transformation kinetics were considered. The relative changes in the fully integrated intensity of the selected B2 and martensite peaks, which indicate the changes in volume fraction of the corresponding phases under deformation, was described as phase transformation volume, M/M+B2.

L’activité catalytique de l’or en réaction d’oxydation préférentielle du CO (PROX) dépend de plusieurs facteurs tels que la nature du support, l’ajout de promoteurs, la taille des particules ou la nature du prétraitement. L’objectif de cette thèse a donc été de clarifier l’influence de ces paramètres sur cette réaction en utilisant des catalyseurs à base d’or modifiés. Dans une 1ère partie, nous avons étudié un système à base d’or supporté sur des oxydes Ce-Fe préparés par co-imprégnation ou imprégnations successives en faisant varier le rapport Ce/Fe. Le dopage de la cérine par le fer conduit à la formation d’une solution solide qui améliore l’activité en PROX en raison d’une mobilité d’oxygène accrue. Dans une 2ème partie, nous avons évalué une série de supports (Al2O3, CeO2 et Ce2Zr2O7) pour optimiser le dépôt de Au, Cu ou Au-Cu. La combinaison Au-Cu/CeO2 s’est révélée être la meilleure en PROX. Nous avons donc étudié l’influence du rapport Au/Cu (1/3, 1/1 ou 3/1) ainsi que l’influence du pré-traitement (calcination ou réduction) sur ce système. Les catalyseurs ont été systématiquement caractérisés par des méthodes physico-chimiques (BET, DRX, MET, XPS, RTP, FTIR). Les performances catalytiques du système Au-Cu/CeO2 dépendent fortement de la taille des particules, de l’état chimique de l’or déterminé par XPS, de l’interaction Au-support et de la distribution de surface des 2 métaux. Une étude cinétique corrélée à de l’infrarouge à transformée de Fourier a permis d’établir un mécanisme de réaction d’oxydation de CO dans le lequel CO adsorbé réagit avec O2 adsorbé pour conduire à la formation de CO2. / The catalytic activity of gold for CO preferential oxidation in rich hydrogen (PROX) is generally influenced by various parameters such as the nature of support, the addition of a promoter, the particle size or the pre-treatment. Therefore, the objectives of this work were to clarify the influence of these parameters on a series of modified gold catalysts in PROX reaction. In a 1rst part, we have studied a system based on Au supported on Ce-Fe oxides prepared by co-precipitation or impregnation with various Ce/Fe ratios. The doping of CeO2 by iron led to the formation of a solid solution which improved the PROX activity due to an increase of the oxygen mobility. In a 2nd part, a series of supports (Al2O3, CeO2, and Ce2Zr2O7) was evaluated in order to load Au, Cu or Au-Cu. The combination of Au-Cu/CeO2 was shown to be the best system. The influence of Au/Cu (1/3, 1/1 or 3/1) ratio was therefore undertaken along with the effect of the pre-treatment (calcination or reduction). The catalysts have been systematically characterized by physico-chemical techniques (BET, XRD, TEM, XPS, TPR, FTIR). The kinetics of PROX reaction and CO oxidation mechanism on Au-Cu/CeO2 were explored and correlated with an FTIR study. The catalytic performances of these catalysts are strongly dependent upon the particle size of the metal, the chemical state of gold, the gold-support interaction and the surface distribution of Au and Cu. We have proposed a CO oxidation mechanism in which adsorbed CO reacts with adsorbed O2 to produce CO2.

Os fármacos antiinflamatórios não-esteróides (FAINEs) são amplamente utilizados no combate a processos inflamatórios e dores, mas apresentam restrição de uso em razão de sérios efeitos colaterais sobre o trato gastrointestinal. A atividade biológica de complexos metálicos tem sido objeto de pesquisa de grande interesse na área de metalofármacos e compostos do tipo Cu(II)-FAINEs apresentam boa atividade antiinflamatória e efeitos colaterais reduzidos em relação aos fármacos orgânicos. Nesse trabalho, com o objetivo de contribuir para ampliar os estudos sobre o desenvolvimento de alternativas aos FAINEs, foram preparados e caracterizados complexos cobre(lI) com ibuprofeno, indometacina, naproxeno, sulindaco, meloxicam. Os compostos foram imobilizados em Hidrotalcita, um hidróxido duplo lamelar (HDL) de magnésio e alumínio (Mg/AI = 3) que é biocompatível e tem uso como antiácido estomacal. As interações dos metalofármacos com o HDL geraram materiais híbridos bioinorgânicos do tipo Cu-FAINElHDL, nos quais os complexos podem estar presentes de duas maneiras: intercalados entre as Ia meias ou adsorvidos nas superfícies externas do hidróxido duplo lamelar, dependendo do solvente utilizado. A intercalação de complexos neutros é favorecida em solvente misto álcooVamida no qual a Hidrotalcita sofre esfoliação promovida por um processo de hidrólise da amida. A estabilidade alguns dos complexos e dos materiais híbridos em condições gástricas simuladas (pH e temperatura) e as atividades antiinflamatória, analgésica e ulcerogênica in vivo dos sistemas contendo indometacina (Indo) foram investigadas. A intercalação do complexo Cu-Indo no HDL favorece sua estabilização, contribuindo para potencializar a sua atividade farmacolágica. Os materiais híbridos bioinorgânicos obtidos neste trabalho apresentam propriedades interessantes com vistas a potencial aplicação como sistemas de liberação controlada de fármacos. / Non-steroidal anti-inflammatory drugs are widely consumed to treat inflammatory diseases and pain but their clinical use are limited due to serious side-effects on the gastrointestinal tract. The bioactivity of metal complexes exhibits great interest in metal-based drug research. Cu(II)-NSAID compounds show good anti-inflammatory property and decreased side-effects compared to their organic parent drugs. This work aimed to contribute for development of alternative NSAIDs. Cu-NSAlD compounds containing the drugs Ibuprofen, Indomethacin, Naproxen, Sulindac and Meloxicam were synthesized and characterized. The compounds were also immobilized on Hydrotalcite, a layered double hydroxide (LDH) of magnesium and aluminum (Mg/Al = 3), that is biocompatible and used as stomach antacid. The interactions of the copper drugs with LDH led to Cu-NSAID/LDH- bioinorganic hybrid materiais. Two kinds of complex-LDH interactions were observed by changing the solvent: intercalation between LDH layers or adsorption on the LDH external surfaces. The intercalation of neutral complexes is favored in an alcohollamide solvent mixture where Hydrotalcite undergoes exfoliation process promoted by the amide hydrolysis. The stability of some complexes and their correspondent hybrid materials under gastric conditions (pH and temperature) and also in vivo anti-inflammatory, analgesic and ulcerogenic activities for Indomethacin (Indo)-containing systems were investigated. The stabilization of the Cu-Indo structure is promoted by intercalation of the complex into the LDH layers, contributing to increase its pharmacological activity. The bioinorganic hybrid materials here investigated also exhibit interesting properties for applications as controlled drug delivery systems.

A influência de variáveis do banho na composição, microestrutura e nas propriedades magnéticas de filmes de CoB preparados por deposição química foi estudada. Dois diferentes tipos de agentes complexantes foram utilizados: citrato de sódio e Glicina. Filmes com menor teor de boro foram obtidos com o uso de Glicina como complexante. A deposição de Co é acelerada em presença de Glicina ou de amônia no banho, porque ambos evitam a diminuição do pH na interface solução/filme de CoB em crescimento. A coercividade dos filmes variou em função do teor de boro, sendo que filmes com maior teor de boro apresentaram mais baixa coercividade. Catalisadores de Co/Al2O3 são utilizados na síntese de combustíveis à partir de derivados do Gás Natural (Síntese de Fischer-Tropsch - SFT). O processo usual de preparação destes catalisadores, denominado impregnação úmida, consiste na impregnação do substrato em solução de sal de Co(II), secagem/calcinação e redução com H2 a 300/350 &#176;C. Uma fração considerável do Co não é reduzida à fase metálica na etapa de redução, o que resulta em perdas de área ativa para a catálise da SFT. Normalmente pequenas quantidades de metais preciosos tais como Pt, Ru ou Pd são adicionadas para catalisar a redução dos óxidos de cobalto e aumentar a área superficial ativa do catalisador, o que representa um grande incremento no custo destes catalisadores. Nesta tese, foram investigadas duas propostas alternativas de solução para este problema: a preparação de catalisadores de Co por deposição química sobre Al2O3 e a preparação pelo método usual, mas com adição de pequenas quantidades de Cu,Ag e Au, dos quais Cu e Ag têm custo mais baixo do que os metais preciosos normalmente utilizados. Co foi depositado quimicamente sobre &#947;-Al2O3, previamente ativada com pequenas quantidades de Pd, utilizando NaBH4 como redutor. Uma amostra de catalisador de CoB/PdAl2O3 (contendo 13,4 % em massa de Co e c.a. 25% at. de boro) foi obtida e caracterizada por RTP, Quimissorção de H2 e XRD, assim como foram efetuados testes de SFT sob diferentes temperaturas de ativação. Para efeito de comparação, foi preparado por impregnação úmida uma amostra de Co/PdAl2O3 contendo 11% em massa de Co, sobre a mesma alumina ativada com Pd utilizada na preparação dos catalisadores de CoB/PdAl2O3. Embora a amostra de catalisador de CoB/PdAl2O3 tenha tido menor área superficial ativa do que a amostra de catalisador de Co/PdAl2O3, sua atividade catalítica foi sensivelmente maior. Essa diferença pode ser explicada supondo-se que o boro é solubilizado durante a reação, deixando uma fase de Co metálico altamente dispersa. Catalisadores de Co/Al2O3 promovidos por metais do grupo 11 foram preparados por impregnação úmida. Além da caracterização por RTP, Quimissorção de H2/titulação de O2 e XRD, a estrutura das amostras de catalisador foi estudada por XANES/EXAFS. Dos resultados de EXAFS e do fato de que altos teores de Cu e Au levaram à desativação do catalisador, é sugerido que durante a redução, o promotor é segregado para a superfície das partículas de Co. Dos três metais testados, Ag e Au apresentaram maior efeito promotor da atividade catalítica, proporcionando maior área superficial ativa para catálise da SFT. Não houve modificações importantes na seletividade dos catalisadores por conta da presença destes metais. / The influence of bath composition on the boron content, microstructure and magnetic properties CoB films deposited by chemical deposition was studied. Two different complexing agents were used in this study: sodium citrate and Glycine. CoB films with lower boron content were obtained with the use of a Glycine containing bath. The Co deposition is accelerated when either Glycine or ammonia is present in the solution because both substances prevent the decrease of the pH in the region near the CoB film/solution interface. The coercivity of the films varied in function of the boron content, as films with larger boron contents showed lower coercivities. Co/Al2O3 is used as a catalyst for the synthesis of liquid fuels from either coal or natural gas derivatives (Fischer Tropsch Synthesis FTS). The usual preparation procedure of such catalysts, known as wet impregnation, consists in the Al2O3 impregnation with a Co(II) aqueous solution, water evaporation/calcination and reduction with H2 at 300/350 &#176;C. A considerable fraction of the cobalt oxides formed during calcination is not reduced to Co0 during reduction and this leads to active area loss. Normally, small quantities of precious metals like Pt, Ru or Pd are added to promote the reduction of cobalt oxides and therefore increase the active area of the Co/Al2O33 catalyst, yet these metals are extremely expansive. In this thesis, two different approaches to solve this problem are presented: the preparation of Co/Al2O3 by chemical deposition of the metallic phase and the use of Cu, Ag or Au (from which, Cu and Ag are cheaper metals) as promoters on wet impregnation prepared Co/Al2O3 catalysts. Cobalt was chemically deposited on &#947;-Al2O3, activated with a small quantity of Pd, with NaBH4 as a reducing agent. The resulting CoB/PdAl2O3 sample (with 13,4 % wt. Co and approximately 25 % at. of boron) was characterized by TPR, H2 Chemisorption and XRD, as well as SFT tests were made with the catalyst at different pre-reduction temperatures. For the sake of comparison a Co/PdAl2O3 catalyst sample with almost the same Co loading (11 % wt.) was prepared by wet impregnation on the same Pd-activated Al2O3 used to prepare the CoB/PdAl2O3 sample. Although the CoB/PdAl2O3 has a smaller active surface area (measured by H2 Chemisorption) than that of the Co/PdAl2O3 sample, it presented a much higher catalytic activity for the SFT. This difference may be explained assuming that boron impurities (present in the catalyst as boron oxides) is solubilized during the reaction leaving a highly dispersed Co phase. Group 11 promoted Co/Al2O3 catalysts were prepared by wet impregnation and characterized by TPR, H2 Chemisorption/O2 pulse oxidation, XRD and XANES/EXAFS. From the EXAFS results and from the fact that higher loadings of Cu and Au lead to catalyst deactivation, it is proposed that in the reduced catalyst the SFT inactive promoter is segregated to the surface. Silver and Gold were the most active in promoting Co reduction and therefore increasing catalytic activity for the SFT. No important modification in the selectivity of the reaction was observed.

Este trabalho tem como objetivo a obtenção das taxas de sedimentação da plataforma continental e do talude superior, no trecho centro norte do Embaiamento São Paulo (Santos a Cabo Frio), além da verificação do uso do método 210Pb/137Cs, comparados a métodos mais tradicionais como o 14C, para a obtenção destas taxas de sedimentação. Um segundo objetivo é verificar se ocorre a transferência de metais, provenientes da área costeira contígua, para o oceano aberto. Para a realização deste trabalho, foram coletados, em diferentes projetos de pesquisa, 12 testemunhos que foram analisados em função da granulometria e dos teores de CaCO3 e metais (Pb, Cu e Zn). Estes mesmos testemunhos foram submetidos, também, a análise da espectrometria gama para obtenção dos níveis de atividade de 210Pb e 137Cs. A partir da medição destes níveis, após alguns cálculos matemáticos baseados no modelo CIC, puderam ser obtidas as taxas de sedimentação. Os resultados indicaram colunas sedimentares bastante homogêneas, predominantemente siliciclásticas. As taxas de sedimentação obtidas, na ordem de milímetros/ano, são compatíveis com os dados encontrados em outras partes do litoral brasileiro e do mundo, onde o aporte atual de sedimentos não é significativo. Com base nestes dados, pode-se afirmar que o método 210Pb/137Cs é bastante confiável para a obtenção de taxas de sedimentação e identificação dos processos sedimentares atuantes nas áreas costeiras e de plataforma, respeitando-se como limite a isóbata de 100 metros. Em profundidades maiores que esta, a técnica não se mostra um \"proxy\" confiável, pois os dados obtidos foram muito conflitantes, sendo mais recomendado o uso do 14C. Os metais provenientes da zona costeira, aparentemente, não estão alcançando a plataforma continental, mas em alguns pontos isolados, já se nota um aumento em especial do Pb, não atingindo entretanto, os níveis de alerta da resolução CONAMA 344/04. / The objective of the present work is the obtainment of the sedimentation rates of the continental shelf and the upper slope on the central north area from São Paulo Bight (from Santos to Cabo Frio), besides checking the use of the 210Pb/137Cs method when compared to more traditional methods like 14C for obtainment of this sedimentation rates. The second objective is the checking if there is a metal transference deriving from the adjacent coastal area to the open ocean. In this work a total of 12 cores were collected from different research projects and they were analyzed considering the granulometry and CaCO3 and metals (Pb, Cu and Zn) contents. These same samples were also analyzed through gamma spectrometry for obtainment of the activity levels of 210Pb and 137Cs. The sedimentation rates were obtained after mathematical computing based on CIC model. The results indicated rather homogeneous sedimentary columns, predominantly siliciclastics. The obtained sedimentation rates, in a millimeters/year basis, are consistent to the data found in other areas of the Brazilian Coastal and the World Coastal where the actual deposit of sediments is not significant. Based on this data it is possible to state that 210Pb/137Cs method is a really reliable method for obtainment of sedimentation rates and identification of the sedimentary processes occurring on the coastal and shelf areas, respecting 100 meters isobath as the limit. The technique is not a reliable proxy when considering deeper areas as there was much conflict on the resultant data and in this cases, the best recommendation is the use of 14C method. Apparently, the metals deriving from the coastal zone are not reaching the continental shelf, but the growth of Pb can be noticed on some isolated spots although they not reach the warning levels from CONAMA 344/04 resolution

Os depósitos de tipo Cu-Au (Mo) pórfiro de Água Rica e Bajo de la Alumbrera, NW argentino, estão geneticamente associados às atividades do Complexo Vulcânico Farallón Negro, no Mioceno. Estes depósitos de classe mundial estão inseridos no contexto geotectônico dos Andes Centrais, Província Geológica das Serras Pampeanas Ocidentais e são do tipo Cu-Au (Mo) pórfiro, embora o depósito de Água Rica possua uma série de características epitermais e uma fase de enriquecimento supergênico. Estudos isotópicos e geocronologia de alta resolução foram propostos para os dois depósitos, objetivando investigar a fonte da mineralização e a influência crustal em sua gênese, além de idades para os pórfiros de Água Rica. Os isótopos de Pb mostram que as amostras de rocha total de Bajo de la Alumbrera são menos radiogênicas, com valores de razões muito próximos e apresentam-se menos radiogênicas do que as amostras de rocha total de Água Rica. As amostras de rocha total de Água Rica mostram maior dispersão, mas de certo modo alguma relação com o material analisado (pirita, ou rocha total). As amostras de pirita, de ambos os depósitos apresentam valores de razões similares, o que permite agrupá-las. As composições isotópicas de Pb em sulfetos e em rochas hospedeiras para os depósitos de Água Rica e Bajo de la Alumbrera indicaram que, apesar da diferença nas litologias presentes nos dois depósitos, os valores obtidos são próximos e muito homogêneos. As amostras de sulfetos de Bajo de la Alumbrera apresentam razões \'ANTPOT.206 Pb\'/ \'ANTPOT.204 Pb\', \'ANTPOT.207 Pb\'/ \'ANTPOT.204 Pb\' e \'ANTPOT.208 Pb\'/ \'ANTPOT.204 Pb\' muito próximas das razões de rocha total, porém com discreto enriquecimento em Pb radiogênico. As amostras de sulfetos de Água Rica apresentam distribuição pouco mais variável, no entanto, observa-se que as amostras de pirita de diorito e pirita do metarenito encaixante ficam próximas entre si e próximas das razões de pirita de Bajo de la Alumbrera Isto pode ser interpretado como fonte e condições de formação similar para estes sulfetos. Os isótopos de Sr e Nd obtidos e combinados com dados da literatura podem sugerir mais evidências na fonte dos magmas e fluidos para estes depósitos, onde as rochas foram divididas em grupos por afinidades isotópicas. Percebe-se que há rochas de padrão juvenil, incorporadas durante a orogenia Andina, mas também há rochas que indicam a presença de contaminação crustal, não homogênea, com variações nos valores de épsilon Nd(t) positivos e negativos. Idades de U-Pb em zircão SHRIMP-IIe nos pórfiros Trampeadero e Quebrada Seca, do depósito de Água Rica, apresentaram idades de 6,20±0,16 Ma e 5,66±0,22 Ma, respectivamente. Estas idades indicam um intervalo tempo muito curto, de cerca de 0,54 Ma, entre as intrusões que contém as mineralizações de maior teor e sendo as primeiras idades obtidas para as intrusões de Água Rica, por meio de datação por U-Pb SHRIMP em zircão. Estas idades sugerem que as intrusões associadas a mineralizações do depósito Água Rica são as mais jovens das que ocorrem na área do Complexo Farallón Negro. Uma isócrona Re-Os obtida em pirita para o depósito de Água Rica de 6,4±2,8 Ma é condizente com a história evolutiva deste depósito. Esta idade, combinada com a idade U-Pb em zircão condiz com a principal fase magmática ocorrida neste depósito e que é tida como a fase principal da mineralização. Com base nos dados, sugere-se que a gênese do depósito de Água Rica ocorreu concomitantemente aos estágios magmáticos finais de Bajo de la Alumbrera, e que esta marca as idades mais jovens para as rochas do Complexo Vulcânico Farallón Negro. Além disso, a participação crustal foi significativa durante a gênese desses depósitos, com uma componente maior no depósito de Água Rica, devido a maior interação dos fluidos magmáticos e mineralizantes com o embasamento Paleozoico. Com base neste estudo, indicamos que em zonas de subducção com baixo ângulo de mergulho, os depósitos minerais gerados podem apresentar maior interação com fluidos crustais do que aqueles em áreas de com placa de alto ângulo. / The Agua Rica and Bajo de la Alumbrera Cu-Au (Mo) porphyry-type deposits, NW Argentina, are genetically associated with the Farallón Negro Volcanic Complex, Miocene age. These world-class deposits of Bajo de la Alumbrera and Agua Rica, located into the tectonic context of the Central Andes, Geological Province of the Sierras Pampeanas, are Cu-Au (Mo) porphyry-type, although the Agua Rica deposit has a number of epithermal features and a supergene enrichment phase. Isotopic studies and high-resolution geochronology were carried out for the two deposits, aiming to investigate the source of the mineralization and crustal influence in its genesis, and ages for the Agua Rica porphyries. Pb isotopes show that the whole-rock samples from Bajo de la Alumbrera are less radiogenic than those from Agua Rica, with close ratio values. The whole-rock samples from Agua Rica show higher dispersion compared to Bajo de la Alumbrera. The pyrite samples from both deposits present similar ratios, which allows grouping them. The Pb isotopic compositions of sulfides and host rocks for the Agua Rica deposit and Bajo de la Alumbrera indicated that, despite the difference in the lithology present in the two deposits, the values obtained are close and very homogeneous. Sulfide samples from Bajo de la Alumbrera show ratios of \'ANTPOT.206 Pb\'/ \'ANTPOT.204 Pb\', \'ANTPOT.207 Pb\'/ \'ANTPOT.204 Pb\' and \'ANTPOT.208 Pb\'/ \'ANTPOT.204 Pb\' very close to the whole-rock ratios, but with a slight enrichment in radiogenic Pb. Sulfide samples from Agua Rica present variable distribution, however, the pyrite samples from diorite and from metasandstone present ratios close to the pyrite from Bajo de la Alumbrera. This ratios similarity could be interpreted as similar conditions and sources to these sulfides. The Sr and Nd isotopes obtained and combined with literature data may suggest more evidence on the source of magmas and fluids for these deposits. Rocks with juvenile pattern, incorporated during the Andean orogeny, are one group observed, but there are also rocks that indicate the presence of crustal contamination, not homogeneous, with variations in Epsilon Nd(t) positive to negative. U-Pb SHRIMP-IIe zircon ages in the porphyries Trampeadero and Quebrada Seca, from the Agua Rica deposit, presented ages of 6.20 ± 0.16 Ma and 5.66 ± 0.22 Ma, respectively. These ages indicate a short time interval between these intrusions, of about 0.54 Ma, and represent the youngest ages obtained for Agua Rica by U-Pb SHRIMP zircon. A Re-Os isochron obtained in pyrite to the Agua Rica deposit of 6.4 ± 2.8 Ma is consistent with the evolution of this deposit. This age, combined with the U-Pb SHRIMP zircon ages matches the main magmatic phase and shows that the main mineralization phase is coeval to the intrusions. Based on these data, it is suggested that the genesis of the Agua Rica deposit was coeval to the last magmatic stages of Bajo de la Alumbrera, and this marks the youngest ages to the Farallón Negro Volcanic Complex rocks. In addition, the crustal participation was significant in the genesis of these deposits, with a major component in the Agua Rica deposit, because the fluids interaction with the Paleozoic basement. Based on this study, we indicated that in flat-subduction zones, the mineral deposits generated present more significant interaction with the crustal fluids than those normal subduction zones.

Les roches vulcanogéniques de la Mine de Seival appartiennent à la Formation Hilário du Bassin de Camaquã, d’âge Néoprotérozoique. Ces roches contiennent six mines inactives avec diverses prospections de cuivre–argent. Les minéralisations semblent associées à un contrôle structurel intense du régime ruptile. La compréhension de la transformation chimique de l’hydrothermalisme associé aux paléo-contraintes est assez faible dans la région. Nous proposons de caractériser la chimie des minéraux des phases magmatiques, tardi–magmatiques et hydrothermales ainsi que de comprendre les contraintes structurales et la géochimie des veines tardives de barytine et calcite. Pour ce faire, nous avons effectué des analyses minéralogiques, et chimiques des phases magmatiques et d’altération. La chimie minérale associée à la modélisation thermodynamique a permis de caractériser l’altération comme tardi– magmatique. L’albitisation (650 à 350 °C) s’est produite en association avec une chloritisation (312 à 120 °C) et avec de la pyrite et de la chalcopyrite. Les températures les plus basses (150 à 50 °C) ont été reliées à la formation de smectite et d’inter-stratifié de chlorite/smectite et avec de la chalcocite–covellite, chalcocite–bornite ou barytine. Nous effectuons les analyses structurales des mesures de cinématique et de la direction des failles/fractures. L’analyse structurale a montré trois contraintes principales survenant dans la Mine Seival et dans le District Minier de Lavras do Sul : compression NW–SW ; compression NE–SW ; distension ENE–SWS. La contrainte NW–SE est la principale direction de contrainte associée à la minéralisation et aux filons minéralisés dans ces deux régions. / The volcanogenic rocks of the Seival Mine belong to Hilário Formation from Camaquã Basin, with ages Neoproterozoic. These rocks contain six inactive mines with various prospects of copper-silver. Mineralization are associated with intense structural control in brittle regime. Chemical transformation of hydrothermal alteration associated with paleostress is not very well understood in the region. We propose a characterization of mineral chemistry of the magmatic phases, tardi–magmatic and hydrothermal as well as understand the paleostress and geochemistry of late veins. For this, we realized analyses of mineral chemistry of magmatic and alteration phase. Mineral chemistry coupled with thermodynamic modeling allowed to characterize the alteration as tardi–magmatic. The albitization (650 to 350 °C) occurred in association with chloritization (312 to 120 °C), and with pyrite and chalcopyrite. The lowest temperatures (150 to 50 °C) were related to formation of smectite and interlayered chlorite/smectite, and with chalcocite–covellite, chalcocite–bornite or barite. We perform structural analyzes through kinematic measures and failure/fracture directions. The analysis on faults, fractures and mineralization showed three main stresses occurring in the Seival Mine and Lavras do Sul Mining District: NW–SE compression; NE–SW compression; ENE–SWS distension. The NW–SE paleostress is the main effort related to the dikes and mineralization in both areas.