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Power distribution network (PDN) design was a non-existent entity during the early days of microprocessors due to the low frequency of operation. Once the switching frequencies of the microprocessors started moving towards and beyond MHz regions, the parasitic inductance of the PCB tracks and planes started playing an important role in determining the maximum voltage on a PDN. Voltage regulator module (VRM) sup-plies only the DC power for microprocessors. When the MOSFETs inside a processor switches, it consumes currents during transition time. If this current is not provided, the voltage on the supply rails can go below the specifications of the processor. For lower MHz processors few ceramic-capacitors known as ‘decoupling capacitors’ were connected between power and ground to provide this transient current demand. When the processor frequency increased beyond MHz, the number of capacitors also increased from few numbers to hundreds of them. Nowadays, the PDN is said to be comprising all components from VRM till the die location. It includes VRM, bulk capacitors, PCB power planes, capacitor mounting pads and vias, mount for the electronic package, package capacitors, die mount and internal die capacitance. So, the PDN has evolved into a very complex system over the years. A PDN should provide three distinct roles; 1) provide transient current required by the processor 2) act as a stable reference voltage for processor 3) filter out the noise currents injected by the processor. The first two are required for the correct operation of the processor. Third one is a requirement from analog or other sensitive circuits connected to the same PDN. If the noise exits the printed circuit board (PCB), it can result in conducted and radiated EMI, which can in turn result in failure of a product in EMC testing. Every PDN design starts with the calculation of a target impedance which is given as the ratio of maximum allowed ripple voltage to the maximum transient current required by the processor. The transient current is usually taken as half the average input current. The definition of target impedance assumes that the PDN is flat over the entire frequency of operation, which is true only for a resistive network. This is seldom true for a practical PDN, since it contains inductances and capacitances. Because of this, a practical PDN has an uneven impedance versus frequency envelope. Whenever two capacitors with different self resonant frequencies are connected in parallel, their equivalent impedance produces a pole between the self resonant frequencies known as antiresonance peaks. Because of this, a PDN will have phase angles associated with them. Also, these antiresonance peaks are energy reservoirs which will be excited during the normal operation of a processor by the varying currents. The transient current of a microprocessor is modeled as a gamma function, but for practical cases it can be approximated as triangular waveforms during the transition time which is normally 10% of the time period. Depending upon the micro-operations running inside the processor, the peak value of this waveform varies. This is filtered by the on-chip capacitors, package inductance and package capacitors. Due to power gating, clock gating, IO operations, matrix multiplications and magnetic memory readings the waveforms at the board will be like pulse type, and their widths are determined by these operations. In literatures, these two types of waveforms are used for PDN analysis, depending upon at which point the study is conducted. Chapter 1 introduces the need for PDN design and the main roles of a PDN. The issue of antiresonance is introduced from a PDN perspective. Different types of capacitors used on a PDN are discussed with their strengths and limitations. The general nature of the switching noise injected by a microprocessor is also discussed. This chapter discusses the thesis contributions, and the existing work related to the field. Chapter 2 introduces a new method to calculate the target impedance (Zt ) by including the phase angles of a PDN which is based on a maximum voltage calculation. This new Zt equals to conventional Zt for symmetrical triangular switching current waveforms. The value of new Zt is less than the conventional Zt for trapezoidal excitation patterns. By adding the resonance effects into this, a maximum voltage value is obtained in this chapter. The new method includes the maximum voltage produced on a PDN when multiple antiresonance peaks are present. Example simulations are provided for triangular and pulse type excitations. A measured input current wave-form for PIC16F677 microcontroller driving eight IO ports is provided to prove the assumption of pulse type waveforms. For triangular excitation waveform, the maximum voltage predicted based on the expression was ¡0.6153 V, and the simulated maximum voltage was found to be at ¡0.5412 V which is less than the predicted value. But the predicted value based on Zt method was 1.9845 V. This shows that the conventional as well as the new target impedance method leads to over estimating the maximum voltage in certain cases. This is because most of the harmonics are falling on the minimum impedance values on a PDN. If the PDN envelope is changed by temperature and component tolerances, the maximum voltage can vary. So the best option is to design with the target impedance method. When pulse current excitation was studied for a particular PDN, the maximum voltage produced was -139.39 mV. The target impedance method produced a value of -100.24 mV. The maximum voltage predicted by the equation was -237 mV. So this shows that some times the conventional target impedance method leads to under estimating the PDN voltage. From the studies, it is shown that the time domain analysis is as important as frequency domain analysis. Another important observation is that the antiresonance peaks on a PDN should be damped both in number and peak value. Chapter 3 studies the antiresonance peak suppression methods for general cases. As discussed earlier, the antiresonance peaks are produced when two capacitors with different self resonant frequencies are connected in parallel. This chapter studies the effect of magnetic coupling between the mounting loops of two capacitors in parallel. The mounting loop area contribute to the parasitic inductance of a capacitor, and it is the major contributing factor to it. Other contributing factors are equivalent series inductance (ESL) and plane spreading inductance. The ESL depends on the size and on how the internal plates of the capacitors are formed. The spreading inductance is the inductance contributed by the parts of the planes connecting the capacitor connector vias to the die connections or to other capacitor vias. If the power and ground planes are closer, the spreading inductance is lower. On one/two layer boards dedicated power/ground planes are absent. So the spreading inductance is replaced by PCB track inductances. The inductance contributed by the mounted area of the capacitor is known as mounting inductance. On one/two layer boards dedicated power/ground planes are absent. So the spreading inductance is replaced by PCB track inductances. The dependencies of various circuit parameters on antiresonance peak are studied using circuit theory. A general condition for damping the antiresonance is formulated. The antiresonance peak reduces with Q factor. The conventional critical condition for antiresonance peak damping needs modification when magnetic coupling is present between the mounting loops of two parallel unequal value capacitors. By varying the connection geometry it is possible to obtain negative and positive coupling coefficients. The connection geometries to obtain these two are shown. An example is shown for positive and negative coupling coefficient cases with simulation and experimental results. For the example discussed, RC Æ 32 - for k Æ Å0.6 and RC Æ 64 - for k Æ ¡0.6, where RC is the critical damping value and k is the magnetic coupling coefficient between the two mounting loops. The reason for this is that, the antiresonance peak impedance value is higher for negative coupling coefficient case than that for positive coupling coefficient case. Above the self resonant frequencies of both the capacitors, the equivalent impedance of the parallel capacitors become inductive. This case is studied with two equal value capacitors in parallel. It is shown that the equivalent inductance is lower for negative coupling coefficient case as compared to positive coupling coefficient case. An example is provided with simulation and experimental results. In the experimental results, parasitic inductance is observed to be 2.6 times lower for negative coupling coefficient case than that for positive coupling coefficient case. When equal value capacitors are connected in parallel, it is advantageous to use a negative coupling geometry due to this. Chapter 4 introduces a new method to damp the antiresonance peak using a magnet-ically coupled resistive loop. Reducing the Q factor is an option to suppress the peak. In this new method, the Q factor reduction is achieved by introducing losses by mag-netically coupling a resistive loop. The proposed circuit is analyzed with circuit-theory, and governing equations are obtained. The optimum value of resistance for achieving maximum damping is obtained through analysis. Simulation and experimental results are shown to validate the theory. From the experimental results approximately 247 times reduction in antiresonance peak is observed with the proposed method. Effectiveness of the new method is limited by the magnetic coupling coefficient between the two mounting loops of capacitors. The method can be further improved if the coupling coefficient can be increased at the antiresonance frequency. Chapter 5 focuses on the third objective of a PDN, that is to reduce the noise injected by the microprocessor. A new method is proposed to reduce the conducted noise from a microprocessor with switched super capacitors. The conventional switched capacitor filters are based on the concept that the flying capacitor switching at high frequency looks like a resistor at low frequency. So for using at audio frequencies the flying capacitors were switching at MHz frequencies. In this chapter the opposite of this scenario is studied; the flying capacitors are the energy storage elements of a switched capacitor converter and they switch at lower frequencies as compared to the noise frequencies. Two basic circuits (1:1 voltage conversion ratio) providing noise isolation were discussed. They have distinct steady state input current waveforms and are explained with PSPICE simulations. The inrush current through switches are capable of destroying them in a practical implementation. A practical solution was proposed using PMOS-PNP pair. The self introduced switching noise of the converter is lower when switching frequency is low and turn ON-OFF time is higher. If power metal oxide semiconductor field effect transistor (MOSFET)s are used, the turn ON and turn OFF are slow. The switching frequency can be lowered based on the voltage drop power loss. The governing equations were formulated and simulated. It is found that the switching frequency can be lowered by increasing the capacitance value without affecting the voltage drop and power loss. From the equations, it is found that the design parameters have a cyclic dependency. Noise can short through the parasitic capacitance of the switches. Two circuits were proposed to improve the noise isolation: 1) T switch 2) ¦ switch. Of these, the ¦ switch has the higher measured transfer impedance. Experimental results showed a noise reduction of (40-20) dB for the conducted frequency range of 150 kHz - 30 MHz with the proposed 1:1 switched capacitor converter. One possible improvement of this method is to combine the noise isolation with an existing switched capacitor converter (SCC) topology. The discussed example had a switching frequency of 700 Hz, and it is shown that this can isolate the switching noise in kHz and MHz regions. In a PDN there are antiresonance peaks in kHz regions. If the proposed circuit is kept close to a microprocessor, it can reduce the excitation currents of these low frequency antiresonance peaks. Chapter 6 concludes the thesis by stating the major contributions and applications of the concepts introduced in the thesis. This chapter also discusses the future scope of these concepts.

Magister Scientiae - MSc (Biotechnology) / Soybean have been listed as a priority commodity crop in South Africa (SA) and provide a good source of protein to the population. Therefore, soybean has been earmarked as an important food security crop and strategies are currently being discussed at governmental level to increase and sustain soybean production. However, the SA landscape poses many challenges to the agricultural sector such as prolong drought periods, flooding, nutrient poor soils, saline soils and heavy metal contaminated soils. Heavy metal (HM) contamination is becoming a serious concern and is aggravated by historical mining in SA. Indeed, SA has established itself as the number one ranked mining country in the world and is frequently mining metals such as chromium, vanadium, gold, zirconium, platinum, and antimony. Prolong rainfall near mining areas leads to acid mine drainage which lowers the soil pH to approximately two. These highly acidic soils will solubilize the metals and cause the metals to leach into river systems as well as the water table leading to increase heavy metal contamination in nearby soil sites. This increase metal content negatively affects seed germination and overall plant development. Nonetheless, plants have evolved numerous internal mechanisms that help them to survive HM toxicity; by either avoiding or tolerating the stress. Two stress-activated pathways that help the plant tolerate stress have attracted much interest i.e. the glyoxalase system and reactive oxygen species (ROS) - antioxidant system as they detoxify methylglyoxal (MG) and ROS. / 2021-08-31

La sûreté des installations de stockage profond des déchets radioactifs repose sur l’évaluation des propriétés de confinement de la barrière géologique et des processus qui y régissent le transport des radionucléides. La thèse est menée dans le cadre de l’expérience Deep Borehole du projet Mont Terri. Elle vise à renforcer l’évaluation de l’importance relative des phénomènes de transfert convectifs et diffusifs au sein de l’Argile à Opalines (OPA) et à apporter des éclaircissements concernant l’impact des phénomènes transitoires chimique et hydraulique sur ces transferts et la génération d’anomalies de pression. Un premier volet expérimental a permis d’acquérir les paramètres de transport advectifs, diffusifs, et les forces motrices associées, nécessaires à l’estimation des flux d’eau et de solutés entre l’OPA et les aquifères adjacents. Les données de température et de pression révèlent un gradient géothermique de 8.5°C/100 m et un excès de charge d’au moins 60 m. L’inversion du profil de chlorure par méthode Bayésienne de type Monte Carlo Markov Chain valide l’évolution paléohydrogéologique du site proposé dans la littérature en considérant un transport diffusif pur à travers la formation. La contribution des phénomènes de transport osmotique a été déterminée en interprétant le profil de pression à l’aide de simulations transitoires considérant l’évolution temporelle de la chlorinité et de la pression au cours du scénario géologique et de simulations en pseudo régime permanent. Ce profil est reproduit en évaluant le flux advectif couplé incluant l’advection de Darcy, la chemo-osmose et la thermo-osmose, avec une contribution majeure de ce dernier processus. / The safety of radioactive waste disposal facilities in deep geological formation depends on the evaluation of the rock confining properties and the processes governing radionuclides transfer. The thesis is conducted in the framework of Deep Borehole experiment of the Mont Terri project. The purpose of this research is to build confidence with regard to understanding relative importance of diffusive and convective phenomena withine the Opalinus Clay (OPA) and to identify the impact of a hydraulic and chemical transient behaviour on the transfers of fluid and solutes, and anomalous pressures generation.A first experimental stage enabled to acquire the advective and diffusive transport parameters, and the associated driving forces, necessary to the evaluation of fluid and solute fluxes between the OPA and its adjacent aquifers. Temperature and pressure measurements revealed a geothermal gradient of 8.5 °C/100 m and an excess of hydraulic head of at least 60 m.The chloride profile inversion by a Bayesian method with a Monte Carlo Markov Chain algorithm validates the paleohydrological evolution proposed in the litterature, considering a pure diffusive transport through the argillaceous formation. The contribution of osmotic transport phenomena was assessed by interpreting the pressure profile, using transient simulations that takes into account the temporal evolution of chlorinity and pressure during the geological scenario, and pseudo steady-state simulations. This profile is reproduced by evaluating the coupled advective flux, including pure advection, chemo-osmosis and thermo-osmosis, with a major contribution of the latter process.

This thesis describes a computational investigation of the mutagenicity of 5-bromouracil (BrU). In Chapter 1, three models of spontaneous and BrU-induced base mispairing (rare tautomer, wobble pair, and ion) are reviewed. Chapter 2 presents the computational techniques used: electronic structure methods (Hartree–Fock-based and density functional theory) and molecular dynamics. Chapter 3 presents optimisations of the keto and enol tautomers of BrU and uracil (U) in water clusters. The enol tautomer of BrU is found to be more stable than that of U. Chapter 4 is a molecular dynamics study of the keto-enol tautomerism of BrU and U in a periodic water box. The pKₐ of BrU at N3 is found to be lower than that of U. Chapter 5 is a study of stacked base dimers containing BrU, U, or thymine (T) stacking with natural bases. Some structures were taken from the Protein Data Bank, while others were generated using an in-house methodology. BrU is found to stack more strongly than T in vacuo, but solvation and thermal effects nullify this difference. Chapter 6 discusses the significance of the results in Chapters 3–5 in terms of BrU-induced mutagenesis. Appendices A and B–D provide supplementary material to Chapters 2 and 5, respectively. Appendix E is an investigation of the “base flipping” pathway of 2-aminopurine (2AP). Both 2AP/N and A/N dinucleosides (N = thymine or guanine) are found to adopt a wide range of energy-minimum conformations – not only stacked and “flipped”, but also intermediate – and the stacked are not the most favourable by free energy. Appendix F is a list of publications and papers in preparation. One publication concerns BrU stacking. The other is a conformational study of the dipeptide tyrosine-glycine: the theoretical results are shown to be consistent with experiment (R2PI spectra) if thermal effects are taken into account.

The need for miniaturized, and high performance microwave devices has focused significant attention onto new fabrication technologies that can simultaneously achieve high performance and low manufacturing complexity. Additive manufacturing (AM) has proven its capability in fabricating high performance, compact and light weight microwave circuits and antennas, as well as the ability to achieve designs that are complicated to fabricate using other manufacturing approaches. Direct print additive manufacturing (DPAM) is an emerging AM process that combines the fused deposition modeling (FDM) of thermoplastics with micro-dispensing of conductive and insulating pastes. DPAM has the potential to jointly combine high performance and low manufacturing complexity, along with the possibility of real-time tuning. This dissertation aims to leverage the powerful capabilities of DPAM to come-up with new designs and solutions that meet the requirements of rapidly evolving wireless systems and applications. Furthermore, the work in this dissertation provides new techniques and approaches to alleviate the drawbacks and limitations of DPAM fabrication technology. Firstly, the development of 3D packaged antenna, and antenna array are presented along with an analysis of the inherent roughness of 3D printed structures to provide a deeper understanding of the antenna RF performance. The single element presents a new volumetric approach to realizing a 3D half-wave dipole in a packaged format, where it provides the ability to keep a signal distribution network in close proximity to the ground plane, facilitating the implementation of ground connections (e.g. for an active device), mitigating potential surface wave losses, as well as achieving a modest (10.6%) length reduction. In addition, a new approach of implementing conformal antennas using DPAM is presented by printing thin and flexible substrate that can be adhered to 3D structures to facilitate the fabrication and reduce the surface roughness. The array design leverages direct digital manufacturing (DDM) technology to realize a shaped substrate structure that is used to control the array beamwidth. The non-planar substrate allows the element spacing to be changed without affecting the length of the feed network or the distance to the underlying ground plane. The second part describes the first high-Q capacitively-loaded cavity resonator and filter that is compatible with direct print additive manufacturing. The presented design is a compromise between quality factor, cost and manufacturing complexity and to the best of our knowledge is the highest Q-factor resonator demonstrated to date using DPAM compatible materials and processes. The final version of the single resonator achieves a measured unloaded quality factor of 200-325 over the frequency range from 2.0 to 6.5 GHz. The two pole filter is designed using a coupled-resonator approach to operate at 2.44 GHz with 1.9% fractional bandwidth. The presented design approach simplifies evanescent-mode filter fabrication, eliminating the need for micromachining and vias, and achieving a total weight of 1.97 g. The design is fabricated to provide a proof-of-principle for the high-Q resonator and filter that compromises between performance, cost, size, and complexity. A stacked version of the two-pole filter is presented to provide a novel design for multi-layer embedded applications. The fabrication is performed using an nScrypt Tabletop 3Dn printer. Acrylonitrile Butadiene Styrene (ABS) (relative permittivity of 2.7 and loss tangent of 0.008) is deposited using fused deposition modeling to form the antenna, array, resonator, and filter structures, and Dupont CB028 silver paste is used to form the conductive traces conductive regions (the paste is dried at 90 °C for 60 minutes, achieving a bulk DC conductivity of 1.5×106 S/m.). A 1064 nm pulsed picosecond Nd:YAG laser is used to laser machine the resonator and filter input and output feedlines.

[pt] A grande maioria dos problemas de estabilidade de poços de petróleo ocorre em trechos de folhelhos, rochas nas quais, uma especificação eficiente da pressão do fluido de perfuração requer previamente uma especificação correta da concentração salina e da temperatura. Todavia, para um dimensionamento adequado das características do fluido de perfuração necessárias à estabilidade do poço, é necessário o uso de modelos matemáticos que considerem um acoplamento adequado entre efeitos poroelásticos, químicos e térmicos. Entretanto, a complexidade matemática das equações de modelos acoplados normalmente leva à adoção de soluções numéricas, que consomem um tempo computacional muito grande e, por isso, esses modelos não são atrativos à aplicação na análise da estabilidade de poços. Este trabalho apresenta um modelo acoplado termo-químico-poroelástico representado por duas soluções, uma numérica, que utiliza o método dos elementos finitos, e outra analítica, baseada no método das transformadas de Laplace. Ao comparar ambas as soluções é demonstrado que a solução analítica consegue representar tão bem quanto à solução numérica os principais processos acoplados presentes durante a perfuração de folhelhos e que influenciam na sua estabilidade e, por esta razão, pode ser utilizada na análise de estabilidade de poços em folhelhos. Através de um estudo de caso, é verificado que um controle eficiente da estabilidade do poço é obtido especificando a pressão do fluido de perfuração em função da sua temperatura e concentração salina. Estes resultados também indicam as razões de alguns problemas não previstos por modelos desacoplados, e que quase sempre ocorrem durante a perfuração em folhelhos. / [en] Wellbore stability problems are most common when drilling through shales. In order to avoid such problems in this kind of rocks the solute concentration and temperature must be properly defined in the drilling fluid composition, which requires considering poroelastic, thermal and chemical effects in a coupled way. The equations complexity of coupled models usually results in numerical solutions that are very time consuming, thus, unattractive for stability analysis. In an opposite way, it is very difficult to develop closed- form solutions for coupled models. This work presents a thermochemoporoelastic model represented by a numerical solution based upon the finite element method and an analytical solution based upon the Laplace transform method. A comparison between the results of the numerical solution and analytical solution shows that the later can reproduce the coupled processes involved in the wellbore stability problem in shales as well as the former, and for this reason the closed-form solution can be applied as a practical tool in wellbore stability analysis. The analysis of a typical wellbore drilled through shales showed that an efficient control of wellbore stability can be obtained through an adequate specification of the drilling fluid pressure when taking in account its solute concentration and temperature. The model was also able to explain some problems not predicted by uncoupled models, but almost always seen while drilling through shales.

This work presents a strategy for the coupled poro-elasto-plastic formulation. The Finite Element Method (FEM) is used to solve the differential equations, interpolating displacement and pore pressure fields. This problem is solved fully coupled, based on an only one system of equations. The nonlinear problem is globally solved by the Newton-Raphson procedure, and the Closest Point algorithm is implemented for the returning map in the elasto-plastic models. Based on a computational module that has already been developed (PORO), which is written using C++ language and Object-Oriented Programming (OOP), this work expands this program creating new classes for different elasto-plastic constitutive models. The program is verified by classical examples in the literature such as the poro-elastic column and the problem of Schiffman. Some strategies for optimization the computational cost are presented, which use specialized math libraries (MKL) and code parallelization (OpenMP). / Este trabalho apresenta, discute e implementa a formulação poro-elastoplástica fortemente acoplada. A discretização espacial das equações diferenciais governantes é realizada através do Método dos Elementos Finitos (MEF), com interpolação do campo de deslocamento e da poropressão. O problema poro-mecânico é resolvido de forma totalmente acoplada, com base em um único sistema de equações. O método iterativo de Newton-Rhapson é empregado para a solução global do problema não linear, tendo ainda o algoritmo implícito iterativo Closest Point para a integração local das equações da plasticidade. Baseando-se em um programa computacional pré-existente denominado PORO, escrito na linguagem C++ e que utiliza o paradigma de Programação Orientada a Objetos (POO), faz-se a adaptação desse código através da criação de novas classes para permitir o uso de modelos constitutivos elastoplásticos e lei de fluxo associada no acoplamento poro-mecânico. Para verificação do programa são analisados problemas clássicos da literatura, a exemplo da coluna poro-elástica e o caso de Schiffman. Descrevem-se ainda algumas estratégias de otimização do custo computacional, implementando-se o uso de bibliotecas matemáticas (MKL) e paralelização do código (OpenMP).

Le procédé VAR (Vacuum Arc Remelting ou refusion à l'arc sous vide en français) est employé dans la production d'alliages à haute performance pour les industries aéronautique (aciers spéciaux, superalliages et alliages de titane) et nucléaire (alliage de zirconium). Comme pour tous les procédés de fonderie, la maîtrise de l'homogénéité chimique et de la structure métallurgique des lingots coulés par le procédé VAR constitue un enjeu industriel important. Les travaux présentés dans ce mémoire visent à identifier, pour les alliages de zirconium en particulier, les effets de la convection naturelle et de la convection forcée due au brassage électromagnétique sur la macroségrégation. Dans ce but, un modèle numérique a été développé. Il est basé sur la résolution couplée des équations de conservation d'énergie, de quantité de mouvement et de solutés, dans des conditions d'écoulement laminaire ou turbulent. La modélisation de la solidification tient compte du couplage fort entre le transport d'énergie et de solutés dans la zone pâteuse. Afin de décrire la microségrégation, la diffusion restreinte des solutés dans les phases liquides et solides peut être prise en compte. Parallèlement, deux électrodes chimiquement homogènes d'alliages Zircaloy-4 et M5® ont été spécialement refondues dans un four VAR industriel sur le site de CEZUS à Ugine (Savoie, France). La macroségrégation des lingots obtenus a été caractérisée.La comparaison entre les mesures expérimentales et les résultats de simulation a montré que pour un alliage dont l'intervalle de solidification est important (comme l'alliage Zircaloy-4), la convection solutale dans la zone pâteuse peut avoir une influence essentielle sur la macroségrégation de la région centrale du lingot. Par ailleurs, le mouvement de grains équiaxes lors de l'application d'un brassage électromagnétique de forte intensité semble accentuer significativement la macroségrégation dans la région externe du lingot. Pour un alliage dont l'intervalle de solidification est faible (comme l'alliage M5®), nous avons montré que la macroségrégation dépend plus spécifiquement de la convection forcée due au mode de brassage électromagnétique appliqué au cours de la refusion / Vacuum Arc Remelting (VAR) is used to produce high performance alloys for the aeronautic (special steels, superalloys, titanium alloys) and nuclear (zirconium alloys) industries. As for all casting processes, the control of the chemical homogeneity and the metallurgical structure in VAR ingots is an important industrial issue. The goal of this thesis is to identify, for zirconium alloys in particular, the effects of the natural convection and the forced convection due to the electromagnetic stirring on macrosegregation. To this purpose, a numerical model has been developed. It is based on the solution of the coupled transient energy, momentum and solute transport equations, under laminar or turbulent flow conditions. The solidification modeling accounts for a full coupling between energy and solute transport in the mushy zone. The finite diffusion of solutes in both solid and liquid phases can be taken into account to describe microsegregation. In addition, chemically homogeneous Zircaloy-4 and M5® electrodes have been specially remelted in an industrial VAR furnace at the CEZUS plant in Ugine (Savoie, France). The macrosegregation of the ingots has been measured. The comparison between the experimental measurements and the simulation results showed that for an alloy with a large solidification interval (like Zircaloy-4), the solutal convection in the mushy zone could have an essential influence on the macrosegregation in the inner part of the ingot. Furthermore, the motion of equiaxed grains caused by a strong stirring seems to seriously intensify macrosegregation in the outer part of the ingot. For an alloy with a small solidification interval (like M5®), we have shown that the macrosegregation depends more specifically on the forced convection due to the type of stirring applied during the remelting

Ce mémoire reporte dans une première partie les études menées sur des polymères à empreintes moléculaires (MIP) en extraction solide-liquide (SPE). La nature des interactions polymère-analyte, l’influence de la composition de la matrice de l’échantillon et la sélectivité des MIPs sont étudiés.La première application concerne l’extraction de molécules ciblées dans un extrait de plante. Deux MIPs respectivement préparés à partir de l’acide méthacrylique (MAA) et l’acide itaconique (IA) et avec respectivement la catharanthine et la vindoline comme molécule empreinte ont montré leur sélectivité sur des solutions standards puis sur un extrait de plante. Des expériences de réactivité croisée réalisées sur des molécules analogues à la molécule empreinte (alcaloïdes dimères) montrent la spécificité de reconnaissance des analytes par les MIPs. Le MIP-catharanthine est caractérisé par les isothermes de Scatchard et sa capacité est évaluée en SPE à partir de l’extrait de Catharanthus roseus. Un MIP préparé à partir de MAA avec la vinorelbine comme molécule empreinte a été appliqué à des matrices aqueuses salines pour l’extraction de la vinflunine et de son métabolite dans du plasma bovin et de l’urine. Des rendements d’extraction élevés ont été atteints grâce à une étude de l’impact des sels et au choix de solvants de lavage adaptés à la matrice. Une deuxième partie montre la simplicité d’utilisation et la sensibilité de la détection conductimétrique sans contact à couplage capacitif (C4D) lors de l’analyse du contre-ion et du principe actif dans des composés pharmaceutiques en électrophorèse capillaire (EC). La technique de la double injection a permis l’analyse simultanée des cations et des anions. La méthode EC-C4D développée est appliquée aux alcaloïdes Vinca et à différents médicaments avec des contre-ions anioniques ou cationiques. / This thesis reports in a first part results obtained with molecularly imprinted polymers (MIP) during solid liquid extraction. Polymer-analyte interactions, composition of the sample matrix and selectivity of MIPs have been studied.The first application concerned the extraction of molecules in a plant extract. Two MIPs respectively prepared from the methacrylic acid (MAA) and itaconic acid ( IA) and with respectively catharanthine and vindoline as template showed their selectivity on standard solutions then on a plant extract. Experiments of cross reactivity performed with analogue of the template (dimers alkaloids) have proved the specificity of analytes recognition by the MIPs. The MIP-catharanthine is characterized by Scatchard isotherms and its capacity was estimated from the extract of Catharanthus roseus. A MIP prepared from MAA with the vinorelbine as template was applied in salt aqueous matrices for the extraction of vinflunine and its metabolite in bovine plasma and urine. High extraction recoveries were reached with a study of the impact of salts and the choice of washing solvents adapted to the matrix. The second part showed the simplicity of use and the sensibility of capacitively coupled contactless conductivity detection (C4D) for the analysis of counter-ion and active principle in pharmaceutical compounds in capillary electrophoresis (CE). The technique of double injection allowed the simultaneous analysis of cations and anions. The developed method EC-C4D was applied to Vinca alkaloids and various medicines with anionic or cationic counter-ions.