Au cours des dernières décennies, l'utilisation de l'aluminium n'a cessé d'augmenter dans différents secteurs industriels. Par ailleurs, dans le domaine de la Conception Assistée par Ordinateur (C.A.O.), les opportunités de développement d'outils de design de l'aluminium sont encore nombreuses. Le présent mémoire propose une méthodologie générale permettant la conversion de pièces structurelles de l'acier vers l'aluminium. Une démarche définie par cinq étapes principales est élaborée à l'aide de différents algorithmes : (1) Analyse mécanique d'une pièce structurelle en acier ; (2) Définition des critères de conception ; (3) Paramétrage de la pièce ; (4) Analyses itératives de pièces d'aluminium ; (5) Élaboration des alternatives retenues et rejetées du design en aluminium. Parallèlement au développement de la méthodologie, les possibilités d'implémentation sont étudiées. Certains concepts d'automatisation sont proposés à l'aide du logiciel CATIA. Un exemple général est proposé, à la fin du mémoire, afin d'illustrer les différentes étapes de la méthodologie.

The Tamengo Formation holds important and well preserved sedimentological and paleontological records of Upper Ediacaran Period. Previous works had centred on Corcal Mine, Saladeiro (now Sobramil Port) and Laginha Sections. However, there is no reports of detailed sedimentological and geochemical surveys on those and other outcrops of the Tamengo Formation at Corumbá-Ladário escarpment located at Paraguay River margins where the paleontological occurrences are concentrated. In the aim of contribute to the understanding of the paleo-environmental conditions, paleontological occurrences and its relationship at Tamengo Formation, detailed stratigraphic columns, description and interpretation of sedimentary facies, sampling, petrography, C and O isotope analysis along with other geochemical analysis were carried out on Corcal Mine, Sobramil Port and six new sections located along the Escarpment. From the obtained data, eight different facies and its C isotope signature were recognized: Wavy Bedding Mudstone (mean \'delta 13C, PDB\' =3.83%o PDB), Hummocky/Cross-Stratified Wackestone (mean \'delta 13C, PDB\' =3.98%o PDB), Cloudina Grainstone (mean \'delta 13C, PDB\' =4.36%o PDB), Intraclastic Packstone-Grainstone (mean \'delta 13C, PDB\' =4.19%o PDB), Low-Angle Cross-Laminated/Laminated Wackestone (mean \'delta 13C, PDB\'=4.93%o PDB), Cloudina Packstone (mean \'delta 13C, PDB\' =4.74%o PDB), Pelite, and Reworked Volcanic Tuff Facies, in which the Formation was dated by other authors, yielding an approximated age of 542 Ma. Also, very well-preserved C and O isotopic signatures were recognized. The carbon isotope data reveal more positive \'delta 13C, PDB\' values on coarser facies (Grainstone, Wackestone, Packstone) and in the calcareous beds overlying the Pelite facies, conforming six main distinctive patterns for carbonate facies that match with coarsening upwards cycles composing the Tamengo Formation. A ramp context of sedimentation has been interpreted for the Tamengo Formation, under strong storms influence, with a progressive tendency towards more positive \'delta 13C, PDB\' values from the deepest to shallower facies. A mid to outer ramp context was inferred for the Ladário-Corumbá, Goldfish, Sobramil and lower part of the Corcal Mine sections, with a mean \'delta 13C, PDB\' value of 3.97%o. For the mid part of the ramp two settings were interpreted; bioclastic lens represented by the Cloudina Grainstone and Intraclastic Packstone-Grainstone Facies and subcoastal setting, represented by the Low-Angle Cross-Laminated/Laminated Wackestone and Cloudina Packstone Facies with mean \'delta 13C, PDB\' values of \'delta 13C, PDB\' =4.33%o and \'delta 13C, PDB\' =4.87%o respectively, represented in the middle and upper part of the Corcal Mine Section. Also, the commonly addressed distribution of Cloudina and Corumbella on different facies could be the reflex of the oscillation between storms and fair-weather conditions; periodic influence of storm-waves or even typhoons in the ramp could avoid Cloudina fixation promoting constantly reworking and accumulating the shells on carbonate facies, while Corumbellas, probably restricted to deepest part of the ramp, expanded to the shallow parts of the ramp on fair weather conditions between storms, as settling by decantation of the Pelite Facies take place at the ramp, explaining the typic distribution of Cloudina restricted to carbonate facies and Corumbella to the interbedded Pelite Facies. / A Formação Tamengo possui importantes e bem preservados registros sedimentológicos e paleontológicos da parte superior do período Ediacarano. Trabalhos anteriores centraram-se nas secções das minas Corcal, Saladeiro (atual Porto Sobramil) e Laginha. No entanto, não há descrições de levantamentos sedimentológicos e geoquímicos detalhados sobre esses e outros afloramentos da Formação Tamengo na escarpa de Corumbá- Ladário, as margens do Rio Paraguai, onde as ocorrências paleontológicas estão concentradas. Com o objetivo de contribuir para o entendimento das condições paleoambientais, ocorrências paleontológicas e sua relação com a Formação Tamengo, perfis estratigráficos, amostragem, petrografia, análises de isótopos C e O e outras investigações geoquímicas foram realizadas na mina Corcal e Porto Sobramil e seis novas seções localizadas ao longo da referida escarpa. A partir dos dados obtidos, oito diferentes facies foram reconhecidas com suas respectivas assinaturas de isótopos de C: Wavy Bedding Mudstone (média \'delta 13C, PDB\'=3.83%o PDB), Hummocky/Cross-Stratified Wackestone (média \'delta 13C, PDB\' =3.98%o PDB), Cloudina Grainstone (média \'delta 13C, PDB\' =4.36%o PDB), Intraclastic Packstone-Grainstone (média \'delta 13C, PDB\' =4.19%o PDB), Low-Angle Cross-Laminated/Laminated Wackestone (média \'delta 13C, PDB\' =4.93%o PDB), Cloudina Packstone (média \'delta 13C, PDB\' =4.74%o PDB),Pelite e Reworked Volcanic Tuff Facies, na qual o topo da Formação Tamengo foi datada por outros autores, com idade aproximada de 542 Ma . Os valores de isótopos revelam valores de \'delta 13C, PDB\' mais positivos nas facies carbonáticas sobrepostas às Facies Pelito e nas de granulação mais grossa (Grainstone, Packstone, Wackstone), configurando seis padrões distintos para as fácies carbonáticas que coincidem, por sua vez, com os ciclos de raseamento ascendentes que compõem a Formação Tamengo. A Formação Tamengo tem sido interpretada como depositada em rampa carbonática sob ação de tempestades, onde se observa uma tendência para valores mais positivos do \'delta 13C, PDB\' das partes mais profundas para as partes rasas da rampa. Um contexto de rampa média para externa foi inferido para as seções Ladário-Corumbá, Goldfish, Sobramil e parte inferior da Mina Corcal, com um valor médio de \'delta 13C, PDB\' = 3,97 %o. Para a parte media da rampa, duas configurações foram interpretadas; lentes bioclásticos marcada pela presença das facies Cloudina Grainstone e Intraclastic Packstone-Grainstone e sublitoraneo marcada pela presença das facies Low-Angle Cross-Laminated/Laminated Wackestone e Cloudina Packstone, as duas configurações com valores médios de \'delta 13C, PDB\' = 4,33 e \'delta 13C, PDB\' = 4,87%o, respectivamente, representados na parte média e superior da Seção Mina Corcal. Além disso, a distribuição comumente observada de Cloudina e Corumbella em diferentes fácies poderia ser o reflexo da oscilação entre tempestades e condições de bom tempo; a influência periódica das ondas de tempestades ou possível tufões na rampa, teriam evitado a fixação das Cloudinas e promovido o constante retrabalhamento de suas caparaças, acumuladas nas fácies carbonáticas. Enquanto os Corumbellas provavelmente restritas às partes profundas da rampa, avançavam para as partes mais rasas durantes os intervalos das tempestades, quando se estabeleciam também, as condições de decantação de argila na rampa (Fácies Pelito), o que explicaria a típica distribuição de Cloudinas, apenas nas fácies carbonáticas, e Corumbella restritas às intercalações de pelitos.

Integrated sequence stratigraphy and geochemistry has significantly improved our knowledge of the formation and distribution of early and late diagenetic products in North American Mississippian carbonates. Deposition of the Madison Limestone occurred in concert with a major perturbation to the global C-pool, the timing of which was constrained by comparing secular variations in the delta13C values from the Madison Limestone with limited biostratigraphy. These early constraints were then improved by peak matching of 87Sr/86Sr values from this study with European brachiopod 87Sr/86Sr. The secular variations in the delta13C values were then applied as a chronostratigraphic tool to outcrops and subsurface core. As a result, our sequence stratigraphic interpretations and knowledge regarding lateral facies variability in carbonate rocks is significantly improved. Geographic variability in the magnitude of the delta13C values is also documented along the dip-transects which suggests that marine waters experienced increasing restriction in a landward direction. These results show how local changes to the C-pool are controlled by the morphology of the depositional system which can significantly affect the original signal of the global carbon pool. The geographic variability in the delta13C and delta18O values from reservoir quality dolomites along the mid-to-upper Madison ramp suggest they also precipitated from a restricted water mass with increased salinity, temperature and alkalinity which in turn, were responsible for the distribution of massive quantities of strataform dolomite deposited during the continental transgression at the beginning of the Mississippian. Trace element and 87Sr/86Sr values from strataform dolomite suggest initial formation from Mississippian seawater and slight resetting during shallow burial diagenesis. Petrography indicates that the formation of this dolomite ceased in the shallow burial environment, between the Mississippian and Permian. These dolomites are cross-cut by comparatively small volumes of geothermal-hydrothermal dolomite associated with Laramide-age breccias and fractures. Tectonic-hydrothermal activity associated with the Laramide Orogeny was responsible for late stage calcite cemented fractures and breccias which cross-cut all carbonate rocks discussed in this thesis. Radiogenic 87Sr/86Sr, depleted delta18O and enriched delta13C values and the hottest fluid inclusions measured in this study suggest the late stage calcite formed in the hydrothermal environment and under the most open-system and water-dominated conditions. Tectonic-diagenesis is ultimately responsible for establishing vertical barriers in the otherwise porous and permeable strataform dolomites.

Made available in DSpace on 2014-06-12T18:00:43Z (GMT). No. of bitstreams: 2 arquivo2387_1.pdf: 2279965 bytes, checksum: e284563f82f7e35a8f004516bbc691ea (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2009 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Neste trabalho é apresentada a evolução do conhecimento paleontológico e as evidências até hoje registradas de paleoambientes marinhos na Bacia do Araripe, nordeste do Brasil, bem como a descrição e análises de isótopos de C e O de uma nova espécie de molusco biválvio, objetivando contribuir para o conhecimento da paleomalacofauna e do paleoambiente da Formação Santana (Eocretáceo). No primeiro trabalho procurou-se reconstituir a história dos primeiros 150 anos do conhecimento paleontológico da Bacia do Araripe e em qual cenário da cultura geocientífica nacional ocorreram as diversas etapas deste desenvolvimento, através da análise de publicações que mencionam sua paleobiota e de relatos históricos. No trabalho seguinte foi realizada uma análise crítica da biota possivelmente marinha dos depósitos cretáceos da Bacia do Araripe registrada na literatura, objetivando oferecer uma visão integrada da ocorrência de organismos indubitavelmente marinhos na bacia, como subsídio para direcionar futuras investigações paleontológicas. Há citações de formas marinhas apenas na Formação Santana (membros Crato e Romualdo), confirmando-se como realmente marinhos somente alguns organismos deste último membro estratigráfico, ainda que mais investigações sejam necessárias para elucidar esta questão. Dessa forma, no último trabalho é efetuado um estudo taxonômico e geoquímico de uma nova espécie de biválvio baquevelídeo proveniente dos estratos mais superiores da Formação Santana (membro Romualdo, Pseudoptera beurleni n.sp.), que revelou ser um habitante de ambientes mixohalinos rasos e bem oxigenados. Pertencendo a um gênero predominantemente tethiano, sem ocorrências assinaladas no Atlântico Sul, P. beurleni possivelmente habitou uma extensão rasa do mar de Tethys, registrada pela deposição de carbonatos de mesma idade nas bacias do Araripe (Formação Santana) e Grajaú (Formação Codó)

Constructing C-C and C-heteroatom bonds is of the utmost importance in organic chemistry. Cross-coupling is a reaction where a transition metal catalyst facilitates the formation of a C-C or C-heteroatom bond between two coupling partners. Cross-coupling reactions are often very robust and reliable and thus have established themselves as one of the most powerful and versatile tools for the modern synthetic organic chemist. A great area of modern cross-coupling research has been the expansion of electrophiles that can participate in cross-coupling reactions. By expanding the scope of available electrophiles, one can access a greater variety of products from simpler starting materials. Esters are relatively robust scaffolds and are difficult to engage in cross-coupling reactions due to the substantial double-bond character of the C(acyl)-O bond. Developing methods to functionalize esters via cross-coupling reactions would be highly beneficial as esters are ubiquitous and readily available. The cross-coupling of phenyl esters has been relatively well established throughout the past decade. The cross-coupling of simple methyl esters largely remains elusive in the primary literature. Chapter 1 of this thesis provides a detailed literature background on the field of carboxylic acid derivative cross-coupling, with a primary focus on esters. Chapter 2 describes our efforts in discovering new methodologies for methyl ester cross-coupling reactions. We invoked the use of high throughput experimentation (HTE) studies to facilitate our search for novel methyl ester cross-coupling reactivity. Chapter 3 describes our efforts in developing an additive free, Ni-catalyzed transesterification reaction of methyl esters. The use of alcohols as nucleophilic coupling partners for methyl esters has yet to be reported. We obtained a scope of 20 isolated examples and were able to identify scaffolds that could not be tolerated under our reaction conditions. Lastly, we began preliminary reaction kinetics studies in order to gain useful mechanistic insights for methyl ester cross-coupling reactions.

Les variations des eaux intermédiaires constituent un point important dans la compréhension des<br />réponses de l'océan aux changements rapides du climat. Cependant, la variabilité de ces masses d'eau<br />est encore peu documentée en raison du manque d'enregistrements fiables et pouvant être datés de<br />manière précise. C'est pour répondre à cette attente que cette étude à été proposée : il s'agissait de<br />développer l'utilisation des coraux profonds et en particulier de leur signal isotopique pour les<br />reconstitutions paléo-océanographiques.<br />Dans un premier temps, une méthode de calcul des températures à partir des données isotopiques (CO)<br />des coraux a été mise au point. Cette méthode a été testée sur 6 coraux prélevés vivants dans<br />différents sites où les conditions environnementales étaient connues (T-S). Une fois la méthode<br />établie, elle a été appliquée, dans un deuxième temps, à une carotte sédimentaire du chenal de Rockall<br />contenant des coraux. Le signal ainsi obtenu a permis de dégager la forte variabilité isotopique des<br />coraux sur l'Holocène. Ce signal a été interprété en terme de fluctuations de la contribution des eaux à<br />composante méditerranéennes par rapport aux eaux du Labrador selon des oscillations climatiques<br />propres à l'Atlantique Nord. En parallèle de ces études, un grand nombre de datations ont été<br />effectuées sur des coraux des différentes carottes de la marge irlandaise afin de définir le cadre<br />stratigraphique représenté par ces coraux. Aucun corail d'âge glaciaire n'a été identifié sur ce site,<br />dégageant ainsi la sensibilité de ce matériel aux variations paléo- environnementales. Un scénario de<br />développement et de mise en place des coraux selon les conditions hydrographiques a été proposé<br />pour expliquer la dynamique de croissance des monts carbonatés sur lesquels se développent les<br />coraux de l'Atlantique Nord-Est. Par ailleurs, les datations au 14C des foraminifères des carottes<br />montrent la complexité de l'enregistrement sédimentaire pour ces sites de haute énergie et soulignent<br />l'intérêt des coraux profonds pour reconstruire la variabilité rapide des eaux intermédiaires.

Η παρούσα εργασία έχει σαν σκοπό την μελέτη των σπηλαιοθεμάτων από το σπήλαιο του Αγίου Γεωργίου στην περιοχή του Κιλκίς. Με αυτή την μελέτη διαπιστώθηκαν οι μεταβολές των περιβαλλοντικών συνθηκών με το πέρασμα των ετών, οι οποίες αποτυπώνονται στα στρώματα δημιουργίας των σπηλαιοθεμάτων. Η αποπεράτωση της εργασίας έγινε σε στάδια. Αρχικά υπήρξε υπαίθρια εργασία που χωρίστηκε σε δύο φάσεις. Στην πρώτη φάση έγινε συλλογή υδάτων της ευρύτερης περιοχής για περαιτέρω αξιολόγηση τους, και κατά την δεύτερη πραγματοποιήθηκε δειγματοληψία των ανθρακικών(σταλακτιτών) μέσα από το σπήλαιο. Στο επόμενο στάδιο πραγματοποιήθηκαν εργαστηριακές έρευνες. Έτσι από τα δείγματα που συλλέχθηκαν από την περιοχή του αμέσου ενδιαφέροντος φτιάχτηκαν λεπτές τομές, που μελετήθηκαν μικροσκοπικά. Για να γίνει ακριβής προσδιορισμός των ορυκτών πραγματοποιήθηκε ορυκτολογική ανάλυση με την μέθοδο της περιθλασιμετρίας, και ακολούθησαν μια σειρά από ορυκτοχημικές αναλύσεις. Παράλληλα με αυτές τις εργασίες πραγματοποιήθηκαν αναλύσεις υδάτων τόσο την χημική όσο και για την ισοτοπική σύσταση τους. Επιπλέον με δειγματοληψία στα ανθρακικά(σταλακτιτών) με κατάλληλη μέθοδο, προσδιορίστηκε και η ισοτοπική σύσταση των ανθρακικών(σταλακτιτών) με σκοπό την αποτύπωση των μεταβολών του κλίματος. / -

Made available in DSpace on 2014-06-12T18:04:15Z (GMT). No. of bitstreams: 2 arquivo5700_1.pdf: 7439252 bytes, checksum: 72266a142680c6c6406a1fa462f4c7f6 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2011 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / A Bacia da Paraíba, localizada no nordeste do Brasil, contém uma sucessão carbonática completa com registros da transição Cretáceo Paleógeno, englobando as formações Itamaracá (Campaniano), Gramame (Maastrichtiano) e Maria Farinha (Daniano). Nesta pesquisa foram estudados o comportamento de isótopos de C e O, elementos maiores e traços, química de elementos terras raras e mercúrio de três poços (Itamaracá, Poty e Olinda). As microfácies destas sucessões são representadas por arenitos calcíferos, calcários dolomíticos com siliclastos e calcários dolomíticos (Formação Itamaracá), wackestone, packstone e mudstone (formações Gramame e Maria Farinha). A deposição desses carbonatos iniciou-se durante uma transgressão marinha no final do Campaniano. Dos resultados isotópicos deduziu-se que durante o evento transgressivo no qual se depositou a Formação Itamaracá, o clima era relativamente frio. Aumento de temperatura e bioprodutividade foram registrados no início do Maastrichtiano (Formação Gramame) e queda gradual durante o resto desse período. Observou-se excursão positiva de &#948;13C (+2 ) próximo a passagem Cretáceo-Paleógeno, seguida de queda para valores em torno de +1 após essa passagem com um aumento de SiO2 e Al2O3 associado ao influxo de terrígenos. Após essa passagem iniciou-se um período de regressão marinha, queda da biprodutividade registrado nos resultados de &#948;13C (+1 ) e sedimentos carbonáticos com altas razões de Mg/Ca possivelmente depositados em ambiente marinho raso. No poço Poty, observa-se anomalias negativas de &#948;13C, possivelmente relacionadas a múltiplos impactos/vulcanismo que antecederam a transição Cretáceo-Paleógeno. No poço Itamaracá há um aumento de mercúrio após a transição K-T, e nos poços Poty e Olinda este enriquecimento é encontrado antes e após essa transição, sugerindo registro de vulcanismo/impactos de meteoritos antecedendo o K-T. Elementos terras raras permitem fazer a reconstrução do paleoambiente de deposição destes carbonatos, comprovando a origem marinha e as condições de deposição, tanto na passagem Campaniano-Maastrictiano quanto na passagem Cretáceo- Paleógeno. Ausência a fraca anomalia positiva de Ce (-0,1 e 0,002) próxima do K-T coincide com queda nos valores de &#948;13C (2,3 para 1,8 ) seguida do aumento destes para 2,3 , e aumento na concentração de mercúrio (de 0,4 para 2.7 ng.g&#8722;1). Presença de nódulos de pirita, associado com fraca anomalia de Eu apontam para condições anóxicas próximas ao K-T

This research examines the history and events that shaped the people and community of Lost Cove, an isolated Appalachian settlement. Chapter 1 surveys previous written and oral accounts of Lost Cove and the physical/cultural attributes of the community. Chapter 2 explores Lost Cove's identity, name, and first settlers. Chapter 3 explores the community's buildings and the families' livelihood. Chapter 4 examines the effect that the CC & O Railway and the sawmills had on the community. Chapter 5 examines moonshine selling in Lost Cove. Chapter 6 reveals how the church and school acted as a gathering place and how sermons and funerals were conducted. Chapter 7 explains why Lost Cove became a ghost town. Much of the information in chapters 3 through 7 is based on oral history interviews that the author did with former residents of the cove.

This dissertation develops a systematic targeting method based on the C-H-O ternary diagram for the conceptual design of gasification-based biorefineries. The approach is applied using dimethyl ether (DME) as case study. A stoichiometric equilibrium model is presented for calculation of the C-H-O chemical equilibria to evaluate and predict equilibrium syngas composition, operating temperature, type and amount of oxidant required in biomass gasification. Overall atomic species balances are developed and process targets are plotted on the C-H-O ternary diagram. Sustainability metrics are incorporated to provide useful insights into the efficiency of biorefinery process targets. It was found that syngas at 1200 and 1500 K is predominantly H2 and CO. Moreover, DME biorefineries have two main process targets, based on the indirect and direct synthesis routes. Gasification at 1200 K and 1 atm. using H2O/CO2 = 2.642 (w/w) and H2O/CH4 = 1.645 (w/w) achieved syngas composition targets for the direct and indirect methods respectively. Comparatively, the integrated biorefinery based on indirect route was more efficient, producing 1.903 ton of DME per ton of biomass feedstock. The process is 100% carbon-efficient and recycles 1.025 tons of H2O. / Civil and Chemical Engineering / M. Tech. (Chemical Engineering)