O preenchimento dos atuais requisitos industriais para as propriedades das ligas Al-Si exige o controle dos processos de fundição e o conhecimento das relações entre as variáveis de processo e as propriedades finais desejadas. Sabe-se que as propriedades finais dependem fortemente da macroestrutura, especificamente da forma e tamanho dos grãos e da distribuição de porosidade. Embora se conheça a importância do estudo da formação da macroestrutura bruta de solidificação, existem diversos aspectos que foram pouco estudados. O presente trabalho tem como objetivo principal estudar o efeito da adição de inoculante na macroestrutura de grãos, particularmente na transição colunar-equiaxial, formada durante a solidificação unidirecional das ligas Al-3%Si e Al-7%Si. Foram realizados diversos ensaios de solidificação unidirecional ascendente em um forno de aquecimento resistivo adicionando-se diferentes quantidades de inoculante na forma de uma liga-mãe comercial de composição nominal Al-3%Ti-1%B. A solidificação unidirecional foi realizada num cadinho de aço inoxidável com base refrigerada a água e com topo e paredes laterais isolados termicamente. A macroestrutura da seção longitudinal dos lingotes obtidos foi revelada e parâmetros térmicos foram calculados a partir de curvas de resfriamento coletadas por termopares posicionados no interior do cadinho durante a solidificação. O aumento da quantidade de inoculante adicionada resultou em um conjunto de lingotes que apresentaram macroestruturas compostas quase completamente de grãos colunares até estruturas completamente equiaxiais. Sem a adição de inoculante, as macroestruturas mostraram uma transição colunar-equiaxial que não ocorre abruptamente, ao passo que a adição de inoculante resultou no aparecimento de uma região mista contendo simultaneamente grãos colunares e equiaxiais. O aparecimento desta região mista e a diminuição do tamanho dos grãos equiaxiais ocorreram na liga Al-7%Si para maiores quantidades de inoculante do que na liga Al-3%Si. / The development of various industrial sectors, such as the automotive and the aerospace industry, demand premium aluminum castings with strict control of mechanical properties. To fulfill these requirements, the control of solidification processes and the knowledge of relations between the processing variables and the casting properties are necessary. The mechanical properties of a cast part depend strongly on its macrostructure, which are directly related to the grain size and distribution of porosity. Although the study of the macrostructure formation is important to establish the relationship between processing variables and properties, some important effects were not studied thoroughly. The main objective of the present work is to study the effect of inoculant addition on the grain macrostructure, particularly the columnar-to-equiaxial transition, of Al-3%Si and Al-7%Si alloys solidified directionally. Several experiments of directional upwards solidification have been carried out in a electric resistance furnace. Different contents of a master-alloy (Al-3%Ti-1%Ti) traditionally used for grain refining in the aluminum industry were added to the melt before solidification. The directional solidification occurred in a stainless steel crucible with a water-cooled base and with lateral walls and top with thermal insulation. The macrostructures of the longitudinal section of ingots were revealed and thermal parameters, such as isotherm velocity and temperature gradients were calculated from the cooling curves measured during solidification by thermocouples inserted within the crucible. An increase in the inoculant addition resulted in a series of different ingot macrostructures that ranged from completely columnar to completely equiaxed grain structures. Without inoculant addition, the columnar-to-equiaxed transition region was abrupt, whereas the addition of inoculant gave rise to a mixed structure of columnar and equiaxed grains. The amount of inoculant that had to be added to the Al-7%Si to cause this mixed structure and decrease the equiaxed grain size was nearly one order o magnitude larger than the amount of inoculant added to the Al-3%Si alloy.

O preenchimento dos atuais requisitos industriais para as propriedades das ligas Al-Si exige o controle dos processos de fundição e o conhecimento das relações entre as variáveis de processo e as propriedades finais desejadas. Sabe-se que as propriedades finais dependem fortemente da macroestrutura, especificamente da forma e tamanho dos grãos e da distribuição de porosidade. Embora se conheça a importância do estudo da formação da macroestrutura bruta de solidificação, existem diversos aspectos que foram pouco estudados. O presente trabalho tem como objetivo principal estudar o efeito da adição de inoculante na macroestrutura de grãos, particularmente na transição colunar-equiaxial, formada durante a solidificação unidirecional das ligas Al-3%Si e Al-7%Si. Foram realizados diversos ensaios de solidificação unidirecional ascendente em um forno de aquecimento resistivo adicionando-se diferentes quantidades de inoculante na forma de uma liga-mãe comercial de composição nominal Al-3%Ti-1%B. A solidificação unidirecional foi realizada num cadinho de aço inoxidável com base refrigerada a água e com topo e paredes laterais isolados termicamente. A macroestrutura da seção longitudinal dos lingotes obtidos foi revelada e parâmetros térmicos foram calculados a partir de curvas de resfriamento coletadas por termopares posicionados no interior do cadinho durante a solidificação. O aumento da quantidade de inoculante adicionada resultou em um conjunto de lingotes que apresentaram macroestruturas compostas quase completamente de grãos colunares até estruturas completamente equiaxiais. Sem a adição de inoculante, as macroestruturas mostraram uma transição colunar-equiaxial que não ocorre abruptamente, ao passo que a adição de inoculante resultou no aparecimento de uma região mista contendo simultaneamente grãos colunares e equiaxiais. O aparecimento desta região mista e a diminuição do tamanho dos grãos equiaxiais ocorreram na liga Al-7%Si para maiores quantidades de inoculante do que na liga Al-3%Si. / The development of various industrial sectors, such as the automotive and the aerospace industry, demand premium aluminum castings with strict control of mechanical properties. To fulfill these requirements, the control of solidification processes and the knowledge of relations between the processing variables and the casting properties are necessary. The mechanical properties of a cast part depend strongly on its macrostructure, which are directly related to the grain size and distribution of porosity. Although the study of the macrostructure formation is important to establish the relationship between processing variables and properties, some important effects were not studied thoroughly. The main objective of the present work is to study the effect of inoculant addition on the grain macrostructure, particularly the columnar-to-equiaxial transition, of Al-3%Si and Al-7%Si alloys solidified directionally. Several experiments of directional upwards solidification have been carried out in a electric resistance furnace. Different contents of a master-alloy (Al-3%Ti-1%Ti) traditionally used for grain refining in the aluminum industry were added to the melt before solidification. The directional solidification occurred in a stainless steel crucible with a water-cooled base and with lateral walls and top with thermal insulation. The macrostructures of the longitudinal section of ingots were revealed and thermal parameters, such as isotherm velocity and temperature gradients were calculated from the cooling curves measured during solidification by thermocouples inserted within the crucible. An increase in the inoculant addition resulted in a series of different ingot macrostructures that ranged from completely columnar to completely equiaxed grain structures. Without inoculant addition, the columnar-to-equiaxed transition region was abrupt, whereas the addition of inoculant gave rise to a mixed structure of columnar and equiaxed grains. The amount of inoculant that had to be added to the Al-7%Si to cause this mixed structure and decrease the equiaxed grain size was nearly one order o magnitude larger than the amount of inoculant added to the Al-3%Si alloy.

L'objectif de ce travail de thèse a été de développer l'utilisation des isotopes du fer pour le traçage des métaux anciens, principalement ferreux. Notre approche méthodologique s'est articulée autour de trois axes majeurs. Le premier axe a consisté à étudier l'influence potentielle des processus métallurgiques sur la composition isotopique du fer des métaux produits. Pour cela, nous avons mesuré la composition isotopique du fer d'échantillons issus d'expérimentations de réduction de minerai de fer en bas fourneau, réalisées sur un site sidérurgique majeur de la période romaine (la Montagne Noire, Sud-Ouest de la France). Le second axe a eu pour objectif de valider ce nouveau traceur en mesurant la composition des isotopes du fer de minerais, scories et objets en fer issus d'un contexte archéologique connu et dont la provenance avait déjà été identifiée par des analyses élémentaires. Nous avons alors mesuré la composition des isotopes du fer de barres de fer principalement retrouvées dans des épaves romaines au large des Saintes-Maries-de-la-Mer (Bouches-du-Rhône, France). Enfin, le troisième axe a eu pour vocation d'estimer la pertinence, mais aussi les limites de ce nouvel outil en l'appliquant à deux terrains archéologiques très différents, où aucune étude de traçage classique n'avait été utilisée précédemment. Ces deux terrains concernaient la sidérurgie ancienne au Togo et la production de plomb argentifère médiévale au Maroc. Les résultats obtenus montrent que la composition isotopique du fer de la scorie et du métal produit est similaire à celle du minerai correspondant. Il n'y a donc pas de fractionnement des isotopes du fer tout au long de la chaîne opératoire de production de fer. De plus, et contrairement à certains traceurs élémentaires, les isotopes du fer ne sont pas contaminés par la paroi du four très pauvre en cet élément durant la réduction. Ceci permet ainsi d'établir des liens de provenance directs entre un objet en fer et un minerai. L'application de cette méthode de traçage à un contexte archéologique déjà largement étudié a permis de valider les hypothèses de provenance d'objets archéologiques. En outre, les isotopes du fer peuvent être plus discriminants que les éléments en trace car ils permettent notamment de différencier des productions de fer temporellement et géographiquement très proches. Le traçage est ainsi affiné. Enfin, nos résultats préliminaires suggèrent que les analyses des isotopes du fer pourraient également être appliquées à l'étude de la production de métaux non ferreux. Cette étude offre ainsi de nombreuses perspectives, telles que l'étude de la provenance de pièces de musée étant donné la faible quantité de matière nécessaire, l'établissement d'une base de données de composition isotopique du fer de minerais archéologiques et l'élaboration d'une méthode de traçage commune aux métaux ferreux et non ferreux. / The objective of this work was to develop the use of iron isotopes for ancient, essentially ferrous metal tracing. Our methodological approach was based on three major directions. The first one consisted in the assessment of the potential influence of metallurgical processes on iron isotope compositions of the reduction products. For this purpose, we measured the iron isotope composition of materials from experiments of iron ore reduction in bloomery furnace performed in a major site of iron production during the Roman period (Montagne Noire, SW France). The second direction aimed at validating this new tracer through the iron isotope measurement of ores, slags and iron artefact samples from a well-defined archaeological context, and whose provenance was previously investigated by elemental analyses. We thus measured the isotopic composition of iron bars discovered in Roman shipwrecks found offshore Les-Saintes-maries-de-la-Mer (Bouches-du-Rhône, France). Thirdly, we estimated the relevance and limitations of our new tracing approach by applying it to the study of two different archaeological fields, on which no previous provenance study had been performed. These were the ancient iron production from North East Togo and the Medieval lead-silver production in Morocco (Anti Atlas Massif). The results demonstrate that the isotopic composition of slags and metals produced reflect that of their corresponding ores because no iron isotope fractionation occurs along the entire chaîne opératoire of iron production. Moreover, and in contrast to several elemental tracers, iron isotopes are not impacted by iron contribution from the smelting device during the reduction process, which allows to establish provenance links directly between an iron artifact and a specific ore. The application of this tracing method in a well-studied archaeological context has allowed to validate the provenance assumption of several archaeological artifacts. Furthermore, iron isotopes may provide a more discriminative tracer than trace elements because a temporal and geographical distinction is possible between close iron production sites. The tracing is thus more precise. Finally, our results suggest that iron isotope analyses could also be used in the study of non-ferrous metal production. This work offers many perspectives in provenance studies of museum pieces given the very small amount of material needed, in the setup of a database of iron isotope compositions of archaeological iron ores and the establishment of a common tracing approach for both ferrous and non-ferrous metals.