Submitted by Cleide Dantas (cleidedantas@ufpa.br) on 2014-04-10T14:42:57Z No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_InfluenciaConveccaoTermossolutal.pdf: 2004245 bytes, checksum: ffa9b9a4cf0968080a0cf43f957949cf (MD5) / Approved for entry into archive by Ana Rosa Silva (arosa@ufpa.br) on 2014-08-29T16:35:23Z (GMT) No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_InfluenciaConveccaoTermossolutal.pdf: 2004245 bytes, checksum: ffa9b9a4cf0968080a0cf43f957949cf (MD5) / Made available in DSpace on 2014-08-29T16:35:23Z (GMT). No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_InfluenciaConveccaoTermossolutal.pdf: 2004245 bytes, checksum: ffa9b9a4cf0968080a0cf43f957949cf (MD5) Previous issue date: 2011 / Este trabalho apresenta um estudo teórico-experimental sobre os efeitos da convecção termossolutal sobre os espaçamentos dendríticos primários de ligas hipoeutéticas Sn-Pb. Assim, um dispositivo experimental de configuração horizontal refrigerado a água foi construído e amostras do referido sistema de ligas foram solidificadas direcionalmente sob condições transientes de extração de calor. Um método teórico-experimental é aplicado para determinar as velocidades de deslocamento da isoterma liquidus, os gradientes térmicos e as taxas de resfriamento. São também apresentados resultados para os respectivos coeficientes de transferência de calor na interface metal/molde os quais foram calculados a partir de uma análise comparativa realizada entre os perfis experimentais de temperatura e valores teóricos fornecidos por um método numérico baseado em volumes finitos. Alguns modelos teóricos para a previsão dos espaçamentos dendríticos primários são comparados com os resultados experimentais obtidos. Finalmente, um estudo comparativo é realizado entre resultados encontrados neste trabalho e aqueles apresentados na literatura para os espaçamentos dendríticos primários das ligas Sn-Pb investigadas quando solidificadas direcionalmente nos sistemas verticais ascendente e descendente, sob as mesmas condições. A análise das microestruturas indica que os espaçamentos dendríticos primários são bastante influenciados pela direção de crescimento do sólido. / In order to investigate the effect of thermosolutal convection on the primary dendritic spacings of Pb–Sn hypoeutectic alloys, horizontal directional solidification experiments have been carried out. For this purpose, a water-cooled solidification experimental apparatus was developed and specimens were solidified in unsteady state heat flow conditions. A combined theoretical and experimental approach is developed to quantitatively determine the solidification thermal parameters: tip growth rates, thermal gradients and cooling rates. The results also include transient metal/mold heat transfer coefficients, determined from comparisons between the experimental thermal profiles in castings and the simulations provided by a finite difference heat flow program. A comparison between theoretical models that predict primary dendritic spacings with the experimental results generated in this study is conducted. A comparative study between some experimental data of this work and those from the literature proposed to predict the primary dendritic spacings during upward and downward vertical unsteady-state directional solidification of Sn–Pb alloys have is presented. The observation of the microstructures has indicated that the primary dendritic spacings have been affected by the direction of growth, increasing in conditions of horizontal solidification when compared with those obtained during upward and downward vertical solidification of Sn–Pb hypoeutectic alloys analyzed.

Submitted by Cleide Dantas (cleidedantas@ufpa.br) on 2014-04-11T12:08:27Z No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_InfluenciaParametrosTermicos.pdf: 3274679 bytes, checksum: 67a56351708ea6a0728c738561741289 (MD5) / Approved for entry into archive by Ana Rosa Silva (arosa@ufpa.br) on 2014-08-29T17:08:58Z (GMT) No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_InfluenciaParametrosTermicos.pdf: 3274679 bytes, checksum: 67a56351708ea6a0728c738561741289 (MD5) / Made available in DSpace on 2014-08-29T17:08:58Z (GMT). No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_InfluenciaParametrosTermicos.pdf: 3274679 bytes, checksum: 67a56351708ea6a0728c738561741289 (MD5) Previous issue date: 2007 / CEFET/PA - Centro Federal de Educação Tecnológica do Pará / O principal objetivo deste trabalho é desenvolver um estudo teórico/experimental sobre a influência dos parâmetros térmicos de solidificação (V L e T) na transição colunar/equiaxial das ligas Sn 5%Pb, Sn 15%Pb, Sn 20%Pb e Sn 25%Pb sob condições de solidificação unidirecional horizontal refrigerada à água. Inicialmente, são calculadas experimentalmente as velocidades da isoterma líquidus e as taxas de resfriamento das ligas em questão cujos resultados são comparados com as previsões teóricas de um modelo numérico. Em seguida, a posição da transição colunar/equiaxial é determinada por meio da análise macroestrutural assim como são avaliados os efeitos impostos por correntes convectivas devido ao efeito do soluto no comportamento da transição colunar/equiaxial das referidas ligas. Finalmente, é realizado um estudo experimental comparativo para as ligas estudadas quando solidificadas unidirecionalmente em diferentes sistemas refrigerados à água. / This work carry out a theoretical experimental study about the influence of solidification thermal parameters on the columnar to equiaxed transition of Sn 5%Pb, Sn 15%Pb, and Sn 20% Pb and Sn 25% Pb alloys during the horizontal unidirectional solidification process cooled by water which considers the solute convection effects. The tip growth rates and cooling rates have been experimentally calculated and the obtained results are compared with those of a numerical model. The columnar to equiaxed transition position is determined through the macrostructure characterization of the studied alloys. The experimental results have shown that the thermosolutal convection influences the CET occurrence. Finally, a comparative experimental study is done for the studied alloys when directionally solidified in different water-cooled systems.

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The Coeur d'Alene district in northern Idaho is a world class Pb-Ag mesothermal vein system that has produced about 360 million ounces of silver, lead, and zinc since the 1880s. Despite the long history of exploration and production, the district does not have a predictive model for exploration based on a sound understanding of structural controls on the silver ore deposits; this is certainly the case for the Sunshine Mine and surrounding area. Fault kinematic history in the district shows a regional scale fault system reactivated over time with dextral, sinistral, and dip-slip displacement. The fault system is superimposed on regional deformation fabrics that were examined for this study in the Sunshine Mine area. Cleavage sets observed in the Sunshine mine area, distinguished by orientation and superposition relationships, are consistent with the findings of Smith (2004) which defined cleavage sets referred to as S1, S2, and S3. Two additional deformation fabrics that appear spatially tied to fault zones formed between development of cleavages S2 and S3. The multiple cleavages, fault zones, and their intersections are interpreted to act as pathways for hydrothermal fluids associated with vein formation and silver ore deposition. Thin section kinematic analysis of vein and shear zone samples defined a dip-slip sense of shear associated with the Sterling vein. Electron Backscatter Diffraction (EBSD) analysis of vein and shear zone samples failed to define a lattice preferred crystallographic orientation that defined shear sense. Similarly, cathodoluminescence (CL) analysis of thin section textures failed to define a dominant shear sense and fault kinematics. Nevertheless, additional study using these techniques is warranted. Both field observation and thin section analysis demonstrate a direct relationship between shear zones, veins, and mineralization potential, clarifying the need for detailed fault maps for the Sunshine Mine area and Coeur d'Alene district.

The Wrangellia composite terrane is one of the largest fragments of juvenile crust added to the North American continent since Mesozoic time, and refining its accretionary history has important implications for understanding how continents grow. New U-Pb geochronology and Hf isotopes of detrital zircons from Late Jurassic-Late Cretaceous strata from the forearc of the Wrangellia composite terrane allows more insight on the tectonic and paleogeographic history of the terrane. Our stratigraphically oldest samples from the Late Jurassic Naknek Formation have a detrital zircon U-Pb signature dominated by Early and Late Jurassic grains (195-190 Ma; 153-147 Ma). Hf isotopic compositions of these grains are juvenile to intermediate (εHf(t)=4.5-14.7). Disconformably above the Naknek Formation are two poorly understood units Ks and Kc. The Ks unit is dominated by Early to Late Jurassic grains (159-154 Ma) with a few Paleozoic grains (347-340 Ma). Hf isotopic compositions of Carboniferous-Jurassic grains are juvenile to intermediate (εHf(t)=6.0-18.8). The overlying Kc unit has Late to Early Jurassic zircons (198-161 Ma), and an increase in Paleozoic ages (374-323 Ma). Hf isotopic compositions of these grains are juvenile to intermediate (εHf(t)=4.5-14.7). Samples from the Matanuska Formation have major Late Cretaceous grains (90-71 Ma), and minor Early Cretaceous (137-106 Ma), Late to Early Jurassic (200-153 Ma), Paleozoic (367-277 Ma), and Precambrian grains (2597-1037 Ma). Hf compositions have a wider range from both the Late Cretaceous grains (εHf(t)=-1.5-14.9) and Paleozoic-Precambrian grains (εHf(t)=-23.7-16.3). Our results suggest an evolving provenance from Late Jurassic to Late Cretaceous time for the Wrangellia composite terrane forearc basin. The Late Jurassic Naknek Formation samples were dominantly derived from a juvenile to intermediate Jurassic igneous sediment source. During Early Cretaceous time, there is a slight increase in the number of Paleozoic grains in the Ks and Kc unit samples. The Early Cretaceous sediments have a mostly positive Hf isotopic compositions suggesting exhumation of Jurassic and Paleozoic juvenile igneous sediment sources. By Late Cretaceous time, our data illustrates another increase in Paleozoic grain abundances, in addition to the introduction of Precambrian grains, all with widely variable Hf isotopic compositions. We interpret this to reflect a larger sediment flux from the interior of Alaska where more evolved igneous rocks of that age are found.

L'objectif de cette étude a été de déterminer le mécanisme d'oxydation de l'acier martensitique T91 dans l'alliage eutectique Pb-Bi liquide saturé en oxygène, à 470°C, et ceci afin de développer un modèle prédictif de cinétique d'oxydation de l'acier à long terme. Ce travail se situe dans le cadre des études de durée de vie du démonstrateur de module de spallation MEGAPIE dédié aux recherches sur les réacteurs hybrides. La démarche scientifique suivie au cours de ce travail repose sur une caractérisation expérimentale des couches d'oxyde et de la cinétique d'oxydation de l'acier T91. A partir de ces résultats expérimentaux un mécanisme d'oxydation a été élaboré puis simulé. La couche d'oxyde formée à la surface du T91 présente une structure duplex constituée d'une couche externe de magnétite et d'une couche interne de spinelle Fe-Cr. Un mécanisme de croissance des couches d'oxyde a été proposé: la croissance de la couche de magnétite paraît limitée par la diffusion du fer dans le réseau de la couche d'oxyde duplex. En parallèle, un mécanisme d'auto-régulation semble régir la croissance de la couche de spinelle Fe-Cr. Ce mécanisme comprend une étape non limitante de diffusion de l'oxygène dans la couche d'oxyde, effectuée par voie liquide dans des nano-canaux de plomb, ainsi qu'une étape limitante de diffusion du fer dans le réseau de la couche d'oxyde. En considérant les mécanismes d'oxydation proposés, une simulation de la croissance des deux couches d'oxyde est effectuée puis comparée aux cinétiques de croissance expérimentales sur de longues durées d'oxydation. Le bon accord entre les résultats expérimentaux et la simulation permet, finalement, d'appuyer notre proposition de mécanisme d'oxydation ainsi que de prédire la cinétique de croissance des couches d'oxyde à long terme.

L'île de la Martinique a connu l'histoire volcanique la plus complète de l'arc des Petites Antilles, de 25 Ma à l'actuel. L'hétérogénéité chimique et isotopique des laves de l'île est très importante non seulement par rapport aux autres îles de l'arc mais aussi par rapport aux autres arcs intra-océaniques. L'objectif de ces travaux est d'expliquer la variabilité géochimique des laves de la Martinique et de caractériser les processus de genèse des produits volcaniques émis sur l'île. Pour cela, nous avons effectué une étude géochimique approfondie (éléments majeurs, éléments traces, rapports isotopiques du Pb, Sr, Nd et Hf) sur des échantillons de laves représentatifs de toute l'histoire volcanique de la Martinique. Grâce à une collaboration avec Aurélie Germa et Xavier Quidelleur de l'université Orsay - Paris XI, l'étude géochimique a été couplée à une datation des laves par méthode K-Ar. Les laves martiniquaises forment des droites et hyperboles de mélanges entre pôles appauvris mantelliques et pôle enrichis crustaux. Il apparaît que deux mélanges distincts sont visibles, un premier mélange est formé par les laves « anciennes » (entre 25 et 7 Ma) et un deuxième mélange est formé par les laves « récentes » (entre 5 Ma et l'actuel). Les pôles mantelliques et les pôles crustaux impliqués dans les sources des magmas ne sont pas les mêmes avant et après 6 Ma. Ce changement de source est probablement lié au passage de la ride asismique qui a décalé la moitié nord de l'arc des Petites Antilles. L'origine de la signature crustale des laves martiniquaises est testée en comparant un modèle de mélange à la source entre des sédiments de la plaque plongeante et le coin mantellique et un modèle d'assimilation de la croûte de l'arc par les magmas mantelliques ascendants. Le modèle d'assimilation intra-crustale ne peut pas reproduire les tendances décrites par les laves alors que le modèle de mélange à la source le fait parfaitement. La comparaison entre les pôles crustaux impliqués dans les mélanges et les sédiments entrants dans la subduction indique qu'il n'y a pas de fractionnement entre le Pb, le Sr, le Nd et l'Hf ce qui implique que les sédiments sont probablement ajoutés à la source par fusion partielle et non par déshydratation. Le rapport La/Yb des laves martiniquaises apparait comme un proxy de la proportion de sédiments dans la source des magmas et non du taux de fusion partielle ou de la nature de la phase alumineuse du manteau bien que la fusion, de l'ordre de 10%, ait lieu dans la zone de stabilité du grenat. Le gradient géographique du rapport La/Yb au sein de l'île traduit donc un gradient géographique de la proportion de sédiments, et montre que la proportion de sédiments dans la source augmente avec l'éloignement à la fosse.

An acid rock drainage (ARD) stream emanating from the Zn-Pb XY-deposit in the Yukon Territory was examined in order to evaluate the physico-chemical and geochemical processes governing the distribution of dissolved elements from the creek. The creek showed very high concentrations of metals (300 mg/L Fe, 500 mg/L Zn, 15 000 µg/L Ni, 1300 µg/L Cu and 4500 µg/L Cd), low water temperatures (1 – 12°C) and was acidic to moderately acidic (pH 3.1 – 5.0). It was found that this stream experienced a strong seasonal evolution, with increased sulphate and metal concentrations and decreased pH over the course of the summer. The mineral precipitates that formed under low pH conditions were a mixture of schwertmannite, goethite, jarosite and barite, while those that formed under moderately acidic conditions were a mixture of jurbanite, hydrobasaluminite, gibbsite and an X-ray amorphous Al-sulphate phase. Most of the mineral precipitates were of inorganic origin, although microbes may have played a role in mineral formation and trace metal sequestration in some of the precipitates. All of the mineral precipitates contained anomalous concentrations of trace elements (up to 1.5 % wt Zn) and showed a seasonal evolution in their mineralogy, both of which were determined to be a function of the pH and prevailing geochemical conditions. The geochemistry of the ARD creek draining the XY-deposit was compared to another ARD creek in the area that was likely draining shales. The two creeks were compared in order to determine if ARD geochemical characteristics can be used as a tool for the mineral exploration industry.

The 87Rb-86Sr system is a widely used long-lived isotope geochronometer. 87Rb, the naturally occurring radioactive isotope of Rb, undergoes beta-decay to stable 87Sr with a half-life of approximately 50 Ga. Decay of 87Rb to 87Sr results in variable 87Sr/86Sr in minerals with different Rb/Sr, and measurement of 87Rb/86Sr and 87Sr/86Sr allows for the determination of the age of the rock. Accurate ages depend both on the quality of the isotopic analysis and on the accuracy of the 87Rb decay constant, lambda87. Although the currently accepted value for lambda87 of 1.42 × 10-11a-1 has been in use for over 30 years, there is growing evidence that it is not accurate. Recent attempts to refine lambda87 and its precision have not reached a consensus. This thesis describes a new experiment to measure lambda87 by 87Sr accumulation over a period of about 30 years, and the preparation of a 84-86Sr double-spike in conjunction with that experiment. Radiogenic 87Sr produced in aliquots of a RbClO4 salt was measured by isotope dilution thermal ionization mass spectrometry. An average of 31 measurements yields a value of 1.398 ± 0.003 × 10-11a-1 . This requires a substantial revision from the previously accepted decay constant and makes Rb-Sr ages calculated with it 1.5% older. A Rb-Sr and U-Pb isotopic chronometry study was carried out on thirteen ordinary chondrites – the most common type of meteorite, the origin and history of which are still unclear. Some meteorites appear disturbed, possibly by recent shock during breakup of the parent body, whereas others yielded accurate and precise U-Pb and Pb-Pb ages. For example, L5 Elenovka yielded distinct ages for silicates (4555 Ma) and phosphates (4535 Ma), allowing the cooling rate of this meteorite from approximately 1055 K to 759 K to be constrained to 15 ± 3 K/Ma. Rb-Sr yielded less precise ages than U-Pb, but using the new decay constant allows accurate comparison between the two methods. This study creates a firm foundation for future studies in thermal history of chondrites and terrestrial metamorphic complexes using Rb-Sr together with other isotopic chronometers.

The 87Rb-86Sr system is a widely used long-lived isotope geochronometer. 87Rb, the naturally occurring radioactive isotope of Rb, undergoes beta-decay to stable 87Sr with a half-life of approximately 50 Ga. Decay of 87Rb to 87Sr results in variable 87Sr/86Sr in minerals with different Rb/Sr, and measurement of 87Rb/86Sr and 87Sr/86Sr allows for the determination of the age of the rock. Accurate ages depend both on the quality of the isotopic analysis and on the accuracy of the 87Rb decay constant, lambda87. Although the currently accepted value for lambda87 of 1.42 × 10-11a-1 has been in use for over 30 years, there is growing evidence that it is not accurate. Recent attempts to refine lambda87 and its precision have not reached a consensus. This thesis describes a new experiment to measure lambda87 by 87Sr accumulation over a period of about 30 years, and the preparation of a 84-86Sr double-spike in conjunction with that experiment. Radiogenic 87Sr produced in aliquots of a RbClO4 salt was measured by isotope dilution thermal ionization mass spectrometry. An average of 31 measurements yields a value of 1.398 ± 0.003 × 10-11a-1 . This requires a substantial revision from the previously accepted decay constant and makes Rb-Sr ages calculated with it 1.5% older. A Rb-Sr and U-Pb isotopic chronometry study was carried out on thirteen ordinary chondrites – the most common type of meteorite, the origin and history of which are still unclear. Some meteorites appear disturbed, possibly by recent shock during breakup of the parent body, whereas others yielded accurate and precise U-Pb and Pb-Pb ages. For example, L5 Elenovka yielded distinct ages for silicates (4555 Ma) and phosphates (4535 Ma), allowing the cooling rate of this meteorite from approximately 1055 K to 759 K to be constrained to 15 ± 3 K/Ma. Rb-Sr yielded less precise ages than U-Pb, but using the new decay constant allows accurate comparison between the two methods. This study creates a firm foundation for future studies in thermal history of chondrites and terrestrial metamorphic complexes using Rb-Sr together with other isotopic chronometers.