Cette étude s’inscrit dans une problématique d’économie d’énergie à travers l’augmentation des rendements des turbines à gaz. L’objectif est alors de mettre au point un procédé permettant la croissance et la mise en forme de céramiques d’oxydes à la composition eutectique pour l’élaboration d’aubes de turbine. En conservant leurs propriétés mécaniques jusqu’à 1700°C et en présentant une densité plus faible que les superalliages actuellement utilisés dans les aubes, ces nouveaux matériaux seraient une solution potentielle pour augmenter notablement le rendement global des turboréacteurs. Dans ce contexte, le procédé EFG utilisé pour la production de saphir a été identifié comme le procédé d’élaboration le plus prometteur, et la céramique Al2O3/YAG/ZrO2 comme la composition présentant les meilleurs propriétés mécaniques.Dans un premier temps une étude approfondie du procédé EFG utilisé par RSA le Rubis, l’entreprise dans laquelle s’est déroulé ce travail, a été menée. Nous avons alors réalisé un modèle analytique de résolution du point de fonctionnement du procédé. Ce modèle est basé sur nos connaissances dans la cristallisation de saphir et nécessite des ajustements pour convenir à la cristallisation de la céramique.Nous avons donc mesuré les propriétés de mouillage du matériau. La densité liquide et la tension de surface ont été mesurées à l’aide d’une méthode dérivée de la méthode de Wilhelmy. En outre, une simulation numérique du procédé, accompagnée de mesures de températures par thermocouple, a permis de connaitre plus précisément la distribution thermique à proximité de la zone de cristallisation. Cette étude complète les résultats du modèle.Ainsi, nous avons pu solidifier des plaques en céramique eutectique avec le procédé EFG. Plusieurs essais ont été nécessaires au dimensionnement d’une zone chaude assurant le maintien géométrique des plaques, puis de nombreux essais d’optimisation ont permis de prolonger les tirages et ainsi produire des plaques de plus grandes dimensions.Enfin, nous nous sommes intéressés à la caractérisation des céramiques. L’analyse des microstructures définit la vitesse de cristallisation maximale admissible pour réaliser des cristaux sans colonie, qui sont les défauts principaux dans ce type de microstructure. Une campagne d’essais mécaniques a également été effectuée, révélant des problématiques d’usinage nouvelles et particulièrement importantes. / This study is a part of an energy saving issues through an increase of gas turbine yields. The objective is to adapt a process for the growth of oxide ceramics with eutectic composition for the manufacture of turbine blades. Sustaining their mechanical properties up to 1700 ° C and with a lower density than superalloys which are currently used in the blades, these new materials are a potential solution to significantly increase the overall efficiency of jet engines. In this context, the EFG process used for the production of sapphire has been identified as the most promising process, and the eutectic composition Al2O3/YAG/ZrO2 as the ceramic with the best mechanical properties.First, a thorough study of the EFG process used by RSA le Ruby, the company where this work was conducted, was done. An analytic model to resolve the setting point of the process was realized. This model is based on the RSA le Rubis’s knowledge in the sapphire crystallization.The wetting properties of the material were measured to fit the model. The liquid density and surface tension were measured using a method derived from the Wilhelmy method. In addition, a numerical simulation of the process, accompanied by temperature measurement by thermocouple, was done. It allows to know the temperature distribution close to the crystallization zone with a better accuracy.Thus, eutectic ceramic plates were solidified with the EFG process. Several tests were necessary in order to design a process ensuring the solidification of net shaped plates. Then lot of optimization pulls have been done to extend the plate’s dimensions.Finally, some characterizations were achieved on the plates. Analysis of the microstructure defines the maximum rate of crystallization to produce crystals without colonies, which are the main defect in these kinds of microstructures. A campaign of mechanical testing was also performed, revealing new machining problems which are particularly important.

A planta Syzygium aromaticum L. produz os botões secos do cravo da índia, do qual se extrai o óleo essencial. O componente majoritário deste óleo é o eugenol, cujas algumas de suas propriedades farmacológicas são atividades fungicida, bactericida, anestésico, entre outros. No entanto, o eugenol (EUG) foi convertido a acetato de eugenila (AE) pela adição do íon acetato, na ligação do grupo hidroxila. Esta modificação foi realizada devido aos problemas relacionados à solubilidade, o que estabelece uma difícil relação com sua biodisponibilidade, e então, limitando sua utilização em preparações farmacêuticas. Em seguida, uma mistura eutética foi preparada empregando o acetato de eugenila como princípio ativo, e o polietilenoglicol 3350 (PEG) como carreador hidrofílico. O diagrama de fases apontou a mistura eutética com composição de 80% de AE e 20% PEG. As características térmicas no ponto eutético foram de 21,33° C para temperatura de pico e 5,71Jg-1 a energia envolvida no processo de fusão. Dessa maneira, a taxa de permeabilidade e a solubilidade do acetato de eugenila serão aprimoradas, contribuindo para o aumento de sua biodisponibilidade e assim, viabilizando sua utilização em formulações farmacêuticas. / The Syzygium aromaticum L. plant produces the cloves buds which are dried. From these dried buds the essential oil is extracted. The major compound is eugenol. Some of eugenol\'s pharmacological properties include fungicidal, bactericidal, anesthetic, and other activities. However, eugenol (EUG) was modified to eugenyl acetate (EA) by adding the acetate group to the bound hydroxyl. The modification was performed in order to eliminate the solubility problems which cause a difficult relationship with bioavailability. The solubility problem restrains its use in pharmaceutical formulations. A eutectic mixture was prepared using the eugenyl acetate as the principal active ingredient and a polyethyleneglycol 3350 (PEG) as the hydrophilic carrier. The phase diagram demonstrated that the eutectic mixture occurred with 80% EA and 20% PEG composition. The thermal characteristics at the eutectic point were 21.33°C for the peak temperature and 5.71Jg-1 for the energy of fusion. Thus, the rate of permeability and solubility of eugenyl acetate will be enhanced. This will contribute to an increase in its bioavailability, thus promoting its use in pharmaceutical formulations.

Understanding the fundamental mechanisms of solidification and the relative significance of different parameters governing these mechanisms is of vital importance for controlling the evolution of microstructure during solidification, and consequently, for improving the efficacy of a casting process. Towards achieving this goal, the present work attempts to study the effect of convection and shrinkage on solidification and microstructure formation primarily through the development of computational models which are complemented with experimental investigations and analytical solutions. Convection strongly influences the solutal and thermal distribution adjacent to the solidification interface and affects the growth rate and morphology of dendrites. To investigate this, a numerical model based on the enthalpy method is developed for binary alloy dendrite growth in presence of convection. The model results are validated with corresponding predictions using level-set method and micro-solvability theory. Subsequently, the model is applied for studying the effect of convection on the growth morphology of single dendrites. Results show that the presence of flow significantly affects the thermo-solutal distribution and consequently the growth rate and morphology of dendrites. Parametric studies performed using the model predict that thermal and solutal Peclet number and melt undercooling strongly influence the tip velocity of dendrites. Additionally, an analytical model is developed to quantify the effect of convection on dendrite tip velocity through the definition of an equivalent undercooling. An expression for this equivalent undercooling is derived in terms of the flow Nusselt and Sherwood numbers and the analytical equivalent undercooling values are compared with corresponding predictions obtained using the numerical model. Subsequently, the interaction of multiple dendrites growing in close proximity is studied. It is observed that the presence of neighbouring dendrites strongly influences the thermo-solutal distribution in the domain leading to significant changes in growth pattern. The effect of seed density on the growth morphology is investigated and it is observed that a higher initial seeding density leads to more spherical dendritic structure. Comparison with results from chilled casting of Al-6.5% Cu alloy with and without grain refiners show qualitative similarity in both the cases. The next part of the thesis presents a eutectic solidification model developed using the general enthalpy-based framework for dendritic solidification. New parameters and rules are defined and suitable modifications are made to incorporate the physics of eutectic solidification and account for the additional complexities arising due to the presence of multiple solid phases. The model simulates the presence of buoyancy driven convection and its interaction with the solidification process. i The model predictions are found to be in good agreement with the Jackson-Hunt theory. At first, the model is applied to simulate regular eutectic growth in a purely diffusive environment and it is observed that the model predicts the variation in interface profile with change in lamella width similar to those observed in experimental studies on eutectic solidification. Subsequently, a few case studies are performed to demonstrate the ability of the model in handling complex scenarios of eutectic growth such as width selection, lamella division and presence of solutal buoyancy. It is observed that solutal buoyancy gives rise to flow cells ahead of the eutectic interface facilitating the transfer of solute between the two phases. Apart from forced and natural convection, another important factor affecting solidification is the presence of shrinkage. Currently, solidification shrinkage is mostly modelled using empirical relations and criteria functions. In the present work, a phenomenological model for shrinkage driven convection is developed by incorporating the mechanism of solidification shrinkage in an existing framework of enthalpy based macro-scale solidification model. The effect of shrinkage flow on the free surface deformation is accounted for by using the volume-of-fluid method. The results predicted by the model are found to be in excellent agreement with analytical solutions for one-dimensional solidification with unequal phase densities. A set of controlled experiments are designed and executed for validating the numerical model. The experiments involve in-situ X-ray imaging of casting of pure aluminium in a rectangular cavity. The numerical predictions for solidification rate, free surface movement and temperature profiles are compared with corresponding experimental results obtained from the in-situ X-ray images and thermocouple data. Subsequent case studies, performed using the model, show significant influence of applied heat flux and mould geometry on the formation of shrinkage cavities. The shrinkage flow model provides the foundation for development of a generalized model to accurately predict the formation and morphology of internal porosity. The validated macro-scale shrinkage model is extended to the microscopic scale to study the influence of shrinkage flow on the growth rate of dendrites. Results demonstrate that shrinkage driven convection towards the dendrite strongly influences the solutal and thermal distribution adjacent to the solidification interface and consequently decreases the growth rate of the dendrite. Additionally, an analytical model is developed to quantify the effect of shrinkage driven convection through the definition of an equivalent undercooling for shrinkage flow. The present models provide significant physical insight into various mechanisms governing the process of solidification. Moreover, due to their similar framework, the individual models have the potential to be an effective foundation for the development of a generalized multi-scale solidification model incorporating the presence of important phenomena such as shrinkage and convection.

This thesis investigates how well the Alexandria (WBK) force-field can predict themelting point for multi-cation chloride salts with molecular dynamic (MD) simulationsin Gromacs 4.6.7. Researched is the eutectic ternary salt LiCl-NaCl-KCl(53.5-8.6-37.9 mol%) and its binary eutectic constituents(NaCl-LiCl: 22.5-77.5, KCl-NaCl: 50-50, LiCl-KCl: 58.5-41.5 mol%). The choosen salt mixtures are all promising candidates for use as electrolyte in liquidmetal batteries, a potential future power grid storage system. Simulation of the ternary salt's bulk at 298 K over 100 simulations with its ionsdifferently arranged within the crystal lattice for each simulation all resulted in stablecrystalline structures. This indicates that the WBK force-field properly andconsistently can produce stable crystalline structures not just for pure salts, but alsowithin multi-component ones. The melting point for the ternary and first binary combination was determined to550 K (12.9 % lower than experimental) and 950 K (12.6 % higher than experimental). No melting point could be determined for the last two binary combinations, as theymelted in their entire simulated temperature intervals. The ternary salt showcased acrystalline/amorphous mixture at solid phase temperatures when simulating with thesolid/liquid coexistence method. These simulation anomalies show that modeling ofmulti-cation chloride salts may not be as straight forward as it is with pure salts,despite using a force-field parameterized specifically for alkali halides.

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第22798号 / エネ博第412号 / 新制||エネ||79(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー応用科学専攻 / (主査)教授 平藤 哲司, 教授 土井 俊哉, 教授 馬渕 守 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Sn/Pb solders are widely used by the electronics industry to provide both mechanical and electrical interconnections between electronic components and printed circuit boards. Solders with enhanced mechanical properties are required for high reliability for Surface Mount Technology (SMT) applications. One approach to improve the mechanical properties of solder is to add metallic or intermetallic particles to eutectic 63Sn/37Pb solder to form composite solders. Cu6Sn5 and Cu3Sn form and grow at the solder/copper substrate interface. The formation and growth of these intermetallics have been proposed as controlling mechanisms for solderability and reliability of solder/copper joints. The goal of this study was to investigate the diffusion kinetics and microstructures of six types of composite solder/copper joints.

The goal of this work is to investigate the capabilities of two different commercial codes, OpenFOAM and ANSYS CFX, to predict forced convection heat transfer in low Prandtl number fluids and investigate the sensitivity of these predictions to the type of code and to several input parameters.The goal of the work is accomplished by predicting forced convection heat transfer in two different experimental setups with the codes OpenFOAM and ANSYS CFX using three different turbulence models and varying the input parameters in an extensive sensitivity analysis. The computational results are compared two the experimental data and analyzed for qualitative and quantitative parameters, such as shape of velocity and temperature profiles, thickness of the boundary layers and wall temperatures.The results show that predictions of the temperature and velocity field are generally sufficient to good, however, the sensitivity especially to the turbulent Prandtl number has to be taken into account when computing forced convection heat transfer in low Prandtl number fluids. The results also show that methods applied to OpenFOAM cannot directly be applied to ANSYS CFX. / <p>QC 20130531</p> / GENIUS

The thesis has been divided in two chapters: Chapter I describes the preparation of primary-amine monocarbamates from enantiopure trans-cyclohexane-1,2-diamines and their use as chiral organocatalysts in the enantioselective Michael addition reaction of aldehydes and ketones to maleimides, to synthesize enantiomerically enriched substituted succinimides. In the conjugate addition reaction of aldehydes to maleimides in conventional volatile organic solvents, it has been found that these organocatalysts are able to generate both enantiomers of the corresponding succinimide using only one enantiomeric form of the catalyst, just by changing the polarity of the solvent. Theoretical calculations justify the mechanism through which this inversion of enantioinduction occurred. In addition, these organocatalysts were used in the enantioselective Michael addition reaction of aldehydes to maleimides, using Deep Eutectic Solvents (DES) as recyclable and environmentally sustainable reaction medium, yielding the corresponding succinimides with excellent yields and high enantioselectivities (up to 94%). The succinimides can be extracted from the DES, which retains the chiral organocatalyst, allowing to reuse both solvent and catalyst. Moreover, the conjugate addition of ketones to maleimides using conventional solvents, allows obtaining the corresponding succinimides with excellent yields but with moderate enantioselectivities (up to 66%). Chapter II shows the results obtained in the enantioselective Michael addition reaction of aldehydes and ketones to nitroalkenes, using the former trans-cyclohexane-1,2-diamine-derived aminocarbamates as chiral organocatalysts, obtaining enantioenriched γ-nitrocarbonyl compounds. In the conjugate addition of isobutyraldehyde to nitroalkenes, the corresponding γ-nitroaldehydes were obtained with enantioselectivities up to 84%. In addition, the enantioselective conjugate addition reaction of ketones to nitroalkenes allowed to obtain interesting γ-nitroketones with high enantioselectivities (up to 96%). Theoretical calculations justify the mechanism involved during this enantioselective process.

<p>The lack of a thorough understanding of the solidification behaviors of the proeutectic Al₃Sc and the Al-Al₃Sc eutectic in a hypereutectic Al-Sc alloy stimulates the present dissertation. The major findings for the single-phase growth of the proeutectic Al₃Sc is summarized as follows: At a low cooling rate (~1 ºC·s^-1), the proeutectic Al₃Sc phase’s formation was governed by the lateral growth, exposing six flat {100} facets. At an intermediate cooling rate (~400 ºC·s^-1), the proeutectic Al₃Sc grew in a dendritic manner, with well-defined backbones extending in eight <111> directions and paraboloidal dendrite tips, although the dendrite tips and side-branches turned into faceted steps at a late growth stage,when the lateral growth prevailed. At a high cooling rate (~1000 ºC·s^-1), the proeutectic Al₃Sc primarily crystallized into an entirely seaweed-structured particle, which was composed of interior compact seaweeds and exterior fractal seaweeds. In order to verify the proposed dendritic and seaweed growth mechanisms for the proeutectic Al₃Sc, various morphological stability criteria were used, and fair agreement between the observed and the estimated characteristic length scales was reached.</p><p>On the Al-Al₃Sc eutectic side, it was found that a rod-typed Al₃Sc eutectic phase prevalently existed in an as-cast hypereutectic Al-Sc alloy that solidified via both slow cooling in air (~1 ºC·s⁻¹) and rapid cooling in a wedge-shaped copper mold (up to ~3000 ºC·s⁻¹). Al-Al₃Sc eutectic dendrites were identified within a narrow region near the edge of the wedge. The eutectic dendrites had an equiaxed dendritic contour and a rod eutectic structure inside. Quantitative assessments revealed that an interface undercooling of 48.2 ºC was required to form the eutectic dendrites, or in other words, to enter the coupled zone of the Al-Al₃Sc phase diagram. Furthermore, a phenomenon of scientific interest was discussed: When crystallizing under a near-equilibrium condition, the eutectic Al₃Sc phase formed a non-faceted morphology, in contradiction to its faceted nature. Based on the competitive growth criterion, it was deduced that the non-faceting of the eutectic Al₃Sc phase essentially reduced the interface undercooling for the resultant regular eutectic, in comparison to an otherwise irregular eutectic that would contain a faceted eutectic Al₃Sc phase.</p>

Master‘s thesis deals with the forming of hypereutectic aluminium alloys using sacrificial coatings. Literature research is focused on analysing the characteristics of aluminium and its alloys. Attention is also focused to the heat treatment of aluminium alloys and the influence of alloying elements on these alloys. Analysis of characteristics and increase the useful properties of Al - Ni alloys is another object of literary research. Attention is also focused to the analysis of thermal spraying methods by focusing on the principle of individual methods and the characteristics of the coatings made by these methods. The object of experimental part is to prepare the hypereutectic aluminium alloys using sacrificial nickel based coatings. This is an unconventional manufacturing process comprising coating the surface of the aluminium substrate with using HVOF technology and subsequent thermal exposure. Furthermore, the work deals with the metallographic evaluation of prepared samples with a particular focus on the influence of temperature and time of heat treatment on the final structure of the experimental samples.