Comprendre l'origine de la fragilisation des aciers austéno-ferritiques utilisés dans les coudes moulés des circuits primaires des centrales nucléaires est une étape clé pour l'anticipation de leur vieillissement. Cette prédiction nécessite une caractérisation et une compréhension du mécanisme de transformation de phase à l'origine de ce constat : la décomposition de la ferrite. Ainsi, de façon duale, des ferrites d'aciers vieillis plus de 20 ans, sur site ou en laboratoire ainsi qu'à différentes températures, ont été analysées par sonde atomique tomographique et un travail de simulation de la décomposition de la ferrite d'alliages modèles Fe-Cr a été initié. Afin de valider les paramètres utilisés en simulation Monte Carlo, une étude expérimentale de la démixtion d'un alliage Fe-20 % at. Cr vieilli à 500°C a été réalisée. Cette étude expérimentale a montré qu'un régime de germination non classique (GNC) intervient dans cet alliage. La simulation de la décomposition de la ferrite dans le même alliage, vieilli à la même température, n'a pas révélé l'enrichissement progressif des précipités de phase α' caractéristique de la GNC. L'étude d'aciers vieillis plus de 20 ans a permis de confirmer que les aciers vieillis en laboratoire sont représentatifs de ceux vieillis sur site (pour T < 350°C), que la phase G (précipitation intermétallique à l'interface des phases α/α') n'influence pas la fragilisation de la ferrite et que la différence de traitement thermomécanique n'est pas déterminante quant à l'écart de décomposition observé dans ces aciers.

Dans ce travail, nous avons utilisé deux techniques pour mesurer les champs magnétiques générés par des couches micro-structurées d'aimants au NdFeB de plusieurs micromètres d'épaisseur: la microscopie par balayage d'une sonde Hall, et la microscopie magnéto-optique (MO). Nous avons proposé et validé une nouvelle approche de la mesure 3D de champ à l'aide d'une seule sonde Hall unidirectionnelle. Nous avons démontré la faisabilité de l'imagerie MO quantitative à l'aide d'un film MO uniaxial dans un champ d'offset. Nous avons extrait de la mesure des profils de champ des informations sur la micro-structure magnétique des micro-aimants. Nous avons exploré les aspects théoriques et expérimentaux de la lévitation diamagnétique de matériaux diamagnétiques sur des réseaux intégrés de micro-aimants, et réciproquement la lévitation de micro-aimants sur des substrats diamagnétiques. Nous avons démontré expérimentalement la lévitation d'un micro-aimant d'aimantation unidirectionnelle.

<p>The transport of elements by streams from headwater regions to the sea is influenced by landscape characteristics. This thesis focuses on the influence of landscape characteristics (e.g. proportion of wetland/forest coverage) on temporal and spatial variations of Fe, Mn, S and trace elements (As, Co, Pb) in streams located in northern Sweden, a boreal region characterized by coniferous forests and peat wetlands.</p><p>Water samples from a network of 15 streams revealed a different hydrogeochemistry in forested catchments compared to wetland catchments. The temporal variation was dominated by spring flood, when concentrations of Fe, Mn and trace elements increased in forested headwaters. However, in streams of wetland catchments concentrations decreased, but Pb concentrations were higher in comparison to other streams. Both Fe and Pb showed positive correlations with wetland area, while Co correlated with forest coverage. The anthropogenic contribution of As and Pb appear to be larger than the supply from natural sources.</p><p>During spring flood SO₄^2- decreased in most streams, although concentrations increased in streams of wetland catchments. Concentrations of SO₄^2-were higher in streams of forested catchments than in wetland dominated streams, the former being net exporters of S and the latter net accumulators. Isotope values of stream water SO₄^2- (δ³⁴S_SO4) were close to that of precipitation during spring flood, indicating that the major source of S is from deposition. The results show that, although emissions of anthropogenic S have been reduced, there is still a strong influence of past and current S deposition on runoff in this region.</p><p>In conclusion, wetlands are key areas for the hydrogeochemistry in this boreal landscape. The findings emphasize the importance of understanding stream water chemistry and element cycling from a landscape perspective. This may be important for predicting how boreal regions respond to environmental disturbances such as climate change.</p>

Ubiquistes, dynamiques et caractérisés par d'importantes capacités de complexation de surface, les colloïdes sont supposés jouer un rôle majeur dans la mobilisation des éléments traces dans les eaux et les sols. Cette étude a pour objectif d'améliorer la compréhension du rôle des colloïdes dans la mobilisation des éléments traces en définissant (a) l'impact de paramètres physico-chimiques sur la composition élémentaire et colloïdale de la phase dissoute d'un sol de zone humide, (b) les modes de genèse de ces colloïdes, ainsi que leur rôle de phases porteuses et vectrices d'éléments traces dans les eaux et les sols. Les différents travaux accomplis mettent en avant un contrôle colloïdal pour de nombreux éléments traces présents dans la solution de sol. Ainsi, certains éléments sont fortement complexés par le compartiment colloïdal (Al, Cr, U, Mo, Pb, Ti, Th, Fe, et les REE), d'autres le sont plus modérément (Cu, Cd, Co, et le Ni) et une autre partie ne réagit pas avec les colloïdes (Li, B, K, Na, Rb, Si, Mg, Sr, Ca, Mn, Ba et le V). Le pH apparaît être un facteur majeur de contrôle de la composition élémentaire de la phase dissoute ; un changement du pH, à la hausse ou à la baisse impactant fortement les concentrations et la composition colloïdale et élémentaire de la solution de sol. De plus, le pH apparaît un acteur non négligeable de la conformation des substances humiques, principales molécules organiques actives dans la mobilisation des éléments traces dans le milieu naturel, impactant ainsi leur mobilité et celles des éléments associés. Les résultats ont confirmé la présence d'associations supramoléculaires de petites molécules organiques au sein des substances humiques, ainsi que la présence de nanoparticules de Fe intimement liées à la matière organique, et pouvant mobiliser certains éléments traces comme le Pb ou le Ti. De plus, ce travail a permis de mesurer l'impact des substances humiques sur la vitesse d'oxydation-hydrolyse du Fe, et sur la taille des oxyhydroxydes formés. Les substances humiques tendent ainsi à ralentir et à diminuer les réactions d'oxydation-hydrolyse du Fe, et impactent directement la taille des oxydes de Fe. Le Fe est ainsi présent soit sous forme ionique et complexé aux substances humiques, soit sous forme de nanoparticules et inclus dans la matrice organique. La biodisponibilité de ces nanoparticules de Fe à être utilisée comme accepteur d'électrons par des bactéries Schewanella putrefaciens a ensuite été testée en comparaison de celle de particules de Fe formées en absence de substances humiques. Les résultats évoquent une biodisponibilité accrue des nanoparticules de Fe associées aux substances humiques lors de la bioréduction. Ce résultat prouve que les colloïdes mixtes Fematière organique représentent dans les zones humides, un stock majeur de fer régulièrement sollicité par la microfaune, bien plus accessible que celui du fonds géochimique.

1. Scope of the Study<BR> ---------------------<BR> In the modern engineering world, technological advancements drive the product design process. Increasingly powerful CAD programs make more complex product designs possible, which in turn boost the demand for more complex prototypes. At the same time, fast-moving competitive markets require frequent design changes, shorter lead times, and tighter budgets. In short, prototyping must be faster, better, and less expensive.<BR> <BR> Within this context, rapid prototyping in sheet metal is highly desirable because the manufacturing of functional prototypes speeds up the time to market. While the market is well developed when it comes to rapid prototyping for plastic parts, the options for prototyping geometrically complicated sheet metal components are more limited and extremely expensive, because all the methods available require expensive tooling, machinery or manual labor.<BR> <BR> Unlike many other sheet metal forming processes, incremental forming does not require any dedicated dies or punches to form a complex shape. Instead, the process uses a standard smooth-end tool, the diameter of which is far smaller than the part being made, mounted on a three-axis CNC milling machine.<BR> <BR> The sheet metal blank is clamped around its edges using a blank-holder. During the forming process, the tool moves along a succession of contours, which follow the final geometry of the part, and deforms the sheet into its desired shape incrementally.<BR> <BR> 2. Context of the Research<BR> --------------------------<BR> The work presented in this thesis was started in October 2003 in the framework of the SeMPeR project (Sheet Metal oriented Prototyping and Rapid manufacturing). This was a four-year-long project, whose purpose was to develop a research platform that would support an in-depth analysis of the incremental forming and laser forming processes. This platform supported experimental, numerical, and analytical research activities, the interaction between which was expected to lead to the design of new and improved process variants and the identification of effective process planning and control strategies.<BR> <BR> Four research partners from three different universities were involved in the project, covering the various academic disciplines required. As project leader, the PMA Department of the Catholic University of Leuven (KUL) provided extensive background knowledge in numerically controlled sheet metal forming processes, as well as long-term experience of experimental hardware development and process planning. This department was in charge of the experimental study of the processes. The MTM Department from the same university studied the processes in detail using accurate finite element models. The MEMC Department of the Free University of Brussels (VUB) provided expertise in in-process strain and displacement measurement, and material characterization by means of inverse method techniques. Finally, the ArGEnCo Department of the University of Liège (ULg), to which the present author is affiliated, undertook the task of developing a finite element code adapted to the incremental forming process.<BR> <BR> Because of its promising outcome, the project held wide industrial interest: several companies assisted in ensuring the ultimate industrial relevance of the research and provided logistical support in terms of hardware, materials, and specific data.<BR> <BR> 3. Objective of the Thesis<BR> --------------------------<BR> Although the SeMPeR project aimed at studying two rapid prototyping processes, the present work focused only on one of those: incremental forming. The goal of the team at the University of Liège was to adapt a department-made finite element code, Lagamine, to the incremental forming process. In particular, the computation time had to be reduced as much as possible while maintaining a sufficient level of accuracy.<BR> <BR> 4. Outline of the Thesis<BR> ------------------------<BR> The body of the text is divided into three parts.<BR> <BR> The first part contains two chapters. The first of these provides a literature review in the field of incremental forming. More specifically, it introduces the process, presents an overview of its practical implementation and experimental setup requirements, and shows its benefits and limitations. Then, the chapter focuses on the latest developments in terms of finite element modeling and analytical computations.<BR> <BR> The second chapter presents the numerical tools used throughout this research. This consists mainly of the finite element code, the elements, and the constitutive laws. Then, this chapter gives an overview of the experimental setup and measuring devices used during the experimental tests performed in Leuven. The second part focuses on dynamic explicit simulations of incremental forming and contains four chapters. The first justifies the use of a dynamic explicit strategy. The second presents the new features added to the finite element code in order to be able to model incremental forming with such a strategy. The third explains the computation of the mass matrix of the shell element used throughout this part of the thesis and justifies this computation. Finally, the fourth chapter analyzes the overall performance of the dynamic explicit simulations both in terms of accuracy and computation time.<BR> <BR> The third part of this thesis contains an in-depth analysis of the incremental forming process using more classic implicit finite element simulations. This analysis is performed in two steps. In a first chapter, the influence of using a partial mesh for the simulations is evaluated in terms of accuracy and computation time. Then, in a second and final chapter, a detailed analysis of the deformation mechanism occurring during this forming process is carried out.<BR> <BR> Finally, this thesis ends with the major conclusions drawn from the research and perspectives on possible means of further improving the simulation tool.<BR> <BR> 5. Original Contributions<BR> -------------------------<BR> Through this research, several major contributions were achieved.<BR> <BR> First, a comprehensive literature review of the incremental forming process was carried out. In particular, the review focused on original articles concerning the limitations of the process and possible ways of bypassing them; on the most recent explanations for the increased formability observed during the process; and on the state of the art in finite element simulations of incremental forming. Understanding the concepts and difficulties inherent in these publications was made possible particularly by the SeMPeR project thanks to the discussions held and the monthly follow-ups on research performed by its members.<BR> <BR> Secondly, Lagamine's shell element was corrected and its mass matrix modified to enable its use with an explicit strategy. Following this, a new approach for modeling the contact between an element and the forming tool during simulations in a dynamic explicit strategy was developed and thoroughly tested. A detailed comparison of the influence of various finite element parameters on the simulations' results was performed, in particular regarding the choice between using the implicit and explicit strategies and the use of mass scaling to reduce the computation time.<BR> <BR> In addition, many simulations were validated thanks to experimental results.<BR> <BR> Moreover, the computation time required for simulations of the forming of parts with rotational symmetry was radically reduced by using a partial model with a new type of boundary conditions.<BR> <BR> Finally, the material behavior occurring during incremental forming was analyzed.

Experiments on the production of porous metallic materials were performed on Fe-base and Al-base alloys. The method involves dissolution of gases in the liquid state and solidification at various cooling rates. The alloy compositions were selected to induce solidification of primary particles intended to control the pore distribution. For the Fe-base alloys, nitrogen was introduced into the melt by dissolution of chromium nitride powder. Fe-Cr-Mn-Si-C alloys featuring M7C3 carbide particles were selected. For the Al-base alloys, hydrogen gas was dissolved into the melt by decomposition of water vapor. Al-Ti and Al-Fe alloys featuring primary Al3Ti and Al3Fe intermetallic particles, respectively, were considered. In the Fe-base alloys, a homogeneous distribution of gas pores through the specimens’ volume was obtained at high cooling rate (water quenching) and after introduction of external nucleating agents. In the case of the Al-base alloys, a good pore distribution was observed at all cooling rates and without addition of nucleating agents. Calculations of the variation of nitrogen (respectively hydrogen) solubility based on Wagner interaction parameters suggest that pore nucleation and growth occur during precipitation of the primary particles (M7C3 carbides, Al3Ti or Al3Fe intermetallics), due to composition changes in the melt and resultant supersaturation with gas atoms. Microscopic analyses revealed that the primary particles control the pore growth in the melt and act as barriers between adjacent pores, thereby preventing pore coalescence and promoting a fine pore distribution. Uniaxial compression testing of the porous Al-Ti and Al-Fe materials showed the typical compressive behavior of cellular metals. Further work is needed to improve the quality and reproducibility of the porous structures which can possibly be used in energy absorption or load-bearing applications. As a corollary result of the quenching of hypereutectic Fe-Cr-Mn-Si-C alloys in the experiments of synthesis of porous metals, a homogeneous featureless structure was observed in some parts of the samples, instead of the equilibrium structure of M7C3 and eutectic phases. Subsequent investigations on rapid solidification of Fe-base alloys at various alloy compositions and cooling rates led to the formation of a single-phase structure for the composition Fe-8Cr-6Mn-5Mo-5Si-3.2C (wt.%), at relatively low cooling rates (≈103 K/s) and for large sample dimensions (2.85 mm). The single phase, which is likely to be the hcp ɛ-phase, was found to decompose into a finely distributed structure of bainite and carbides at ≈600 °C. The annealed structure showed very high hardness values (850 to 1200 HV), which could be exploited in the development of high-strength Fe-base materials. / QC 20100809

Les alliages à base de chrome sont couramment utilisés pour des applications à haute température. Leurs capacités à former une couche d'oxyde thermique protectrice permet de réduire les cinétiques d'oxydation de ces matériaux. En particulier, les alliages Ni-Cr et Fe-Cr forment une couche continue de α-Cr2O3 en surface. La durabilité du système métal/céramique résultant dépend de l'intégrité mécanique de cette couche, et donc des mécanismes d'endommagement susceptibles de se produire lors de l'oxydation ou du refroidissement. L'endommagement est étroitement corrélé au niveau de contraintes résiduelles dans l'oxyde mais aussi à sa microstructure. Dans ces travaux, des alliages Ni-30Cr et Fe-47Cr sont oxydés à l'air à 800, 900 et 1000°C et une approche multi-échelle est proposée pour analyser rigoureusement les contraintes résiduelles aussi bien à des échelles macroscopiques dans le film d'oxyde adhérent qu'à des échelles locales au travers de régions délaminées.A l'échelle macroscopique, les niveaux de contraintes résiduelles sont déterminés grâce à la diffraction des Rayons X conventionnelle et à la spectroscopie Raman. Les taux de délamination des couches d'oxyde et les phénomènes de fluage diffusionnel sont quantifiés en fonction de paramètres métallurgiques conduisant à différents états microstructuraux du système. L'influence de la compétition entre ces deux modes de relaxation de contrainte sur l'endommagement est discutée. A l'échelle microscopique, des cartographies de contraintes résiduelles au travers de différents types de délaminations sont réalisées grâce à la microspectroscopie Raman et à la microdiffraction Synchrotron. En raison de sa résolution latérale, la microspectroscopie Raman est particulièrement appropriée pour analyser les délaminations formées localement. Des observations par microscopie à force atomique ont également été menées afin de décrire la géométrie (dimensions, hauteur) des différents types d'objets délaminés. Ces informations morphologiques complémentaires couplées aux niveaux de contraintes associés permettent une confrontation aux lois de la mécanique du cloquage, et l'extraction de l'adhérence interfaciale. A partir de ces analyses, des schémas et cartes de l'endommagement des couches de chromine sont proposés.

Dans le cadre de ce travail, des composés de formulation Ce1−xFexO2−x2 ont été synthétisésà l'aide de deux protocoles : co-précipitation et synthèse assistée par chauffage micro-ondes.L'utilisation de cette dernière a ainsi conduit à l'obtention de nanoparticules de morphologiescubiques ou " bâtonnets " et ceci pour des temps de synthèse relativement courts. L'analysepar diffraction X a montré notamment que le paramètre de maille diminue en fonction de lateneur en fer, x. L'environnement local et le degré d'oxydation du fer ont été analysés parspectroscopies Mössbauer, RPE et XANES mettant ainsi en évidence la présence d'ions Fe3+isolés au sein de sites octaédriques distordus et sous forme de clusters. Une comparaison entreles deux voies de synthèse a montré que des différences apparaissent à l'échelle locale. Lessolutions solides obtenues ont ensuite été caractérisées au cours du traitement thermique etsous différentes atmosphères. Indépendamment de l'atmosphère de recuit, une démixtion dela solution solide intervient pour des températures proches de 600°C.

A new class of materials, known as multi-functional energetic structural materials (MESMs), has been developed. These materials possess both strength and energetic functionalities, serving as candidates for many exciting applications. One of such applications is ballistic missiles, where these materials serve as part of structural casing as well as explosive payload. In this study, the dynamic compressive behavior of two types of MESMs in the intermediate strain rate regime is investigated. The first type is a thermite mixture of Al and Fe₂O₃ particles suspended in an epoxy matrix. The second type is a shock compacted mixture of Ni and Al powders. Compression experiments on a split-Hopkinson pressure bar (SHPB) apparatus are carried out at strain rates on the order of 103 s-1. In addition, a novel method for investigating the dynamic hardness of the Al + Fe₂O₃ + Epoxy materials is developed. In this method, high-speed digital photography is used to obtain time-resolved measurements of the indentation diameter throughout the indentation process. Experiments show that the shock compacted Ni-Al material exhibits a rather ductile behavior and the deformation of the Al + Fe₂O₃ + Epoxy mixtures is dominated by the polymer phase and significantly modulated by the powder phases. The pure epoxy is ductile with elastic-plastic hardening, softening, and perfectly plastic stages of deformation. The Al and Fe₂O₃ particles in Al + Fe₂O₃ + Epoxy mixtures act as reinforcements for the polymer matrix, impeding the deformation of the polymer chains, alleviating the strain softening of the glassy polymer matrix at lower levels of powder contents (21.6 - 29.2% by volume), and imparting the attributes of strain hardening to the mixtures at higher levels of powder contents (21.6 - 49.1% by volume). Both the dynamic and quasi-static hardness values of the Al + Fe₂O₃ + Epoxy mixtures increase with powder content, consistent with the trend seen in the stress-strain curves. To quantify the constitutive behavior of the 100% epoxy and the Al + Fe₂O₃ + Epoxy materials, the experimentally obtained stress-strain curves are fitted to the Hasan-Boyce model. This model uses a distribution of activation energies to characterize the energy barrier for the initiation of localized shear transformations of long chain polymeric molecules. The results show that an increase in powder content increases the activation energy, decreases the number of transformation sites, causes redistribution of applied strain energy, and enhances the storage of inelastic work. These effects lead to enhanced strength and strain hardening rate at higher levels of powder content.

Metal oxide-facilitated transformation is likely an important degradation pathway of antibacterial agents at soil-water interfaces. Phenolic disinfectants (triclosan and chlorophene), fluoroquinolones (FQs), and aromatic N-oxides are of particular concern due to their widespread usage, potential toxicity and frequent detection in the environment. Results of the present study show that the above antibacterial agents are highly susceptible to metal oxide-facilitated oxidation. The interfacial reactions exhibit complex reaction kinetics, which are affected by solution pH, the presence of co-solutes, surface properties of metal oxides, and structural characteristics of antibacterial agents. Adsorption of the antibacterial agents to Mn and Fe oxide surfaces generally proceeds faster than oxidation reactions of these compounds by Mn and Fe oxides, especially in the case of Fe oxides. Reaction intermediates and end products are identified by GC/MS, LC/MS and/or FTIR. Structurally-related model compounds are examined to facilitate reaction site and mechanism elucidation. On the basis of experimental results and literature, reaction schemes are proposed. In general, the antibacterial agent is adsorbed to the oxide surface, forming a precursor complex. Electrons are transferred within the precursor complex from the antibacterial agent to the oxide, followed by releasing of the radical intermediates which undergo further reactions to generate oxidation products. The precursor complex formation and electron transfer are likely rate-limiting. For triclosan, phenoxy radicals are critical intermediates to form oxidation products through three pathways (i.e., radical coupling, further oxidation of the radical, and breakdown of an ether bond within the radical). The first two pathways are also operative in the oxidation of chlorophene. For FQs, oxidation generates radical intermediates that are most likely centered on the inner N in the piperazine ring. The radical intermediates then undergo three major pathways (i.e., radical coupling, N-dealkylation, and hydroxylation) to yield a variety of products. For aromatic N-oxides, a N-oxide radical intermediate is generated upon oxidation by MnO2, followed by the loss of oxygen from the N-oxide moiety and the formation of a hydroxyl group at the C-atom adjacent to the N-oxide moiety. Overall, a fundamental understanding of the reaction mechanisms between three classes of antibacterial agents and metal oxides has been obtained.