The horizontal twin-roll casting (TRC) process is an energy saving and cost-efficient method for producing near-net-shape sheets of castable metals for light-weight production. In order to investigate the TRC process numerically, a code is generated in OpenFOAM and the commercial software STAR-CCM+ is used. Both are validated with the Stefan problem, the gallium melting test case, and a continuous casting experiment for magnesium AZ31. Different solidification models are tested that are similar to solution domain definitions and solid-fraction temperature relations. The comparison with temperature measurements of the MgF GmbH Freiberg pilot plant and the final microstructure exhibits good correlation. Sensitivity studies are carried out for thermophysical properties of AZ31 as well as pilot plant parameters. Furthermore, the rolls are incorporated into the simulation to determine the effect of a location-dependent heat-transfer coefficient. Finally, the results are compared to a second pilot plant situated at the Helmholtz-Centre Geesthacht in order to explore differences and similarities. / Das horizontales Gießwalzen ist eine energiesparende und kostengünstige Methode zur Erzeugung von Flachprodukten, die im Leichtbau verwendet werden. Um dieses Verfahren numerisch zu untersuchen wurde ein Programmcode in OpenFOAM entwickelt und die kommerzielle Software STAR-CCM+ verwendet, wobei beide mit dem Stefan Problem, dem Schmelzen von Gallium und Messdaten des Stranggusses von Magnesium AZ31 validiert wurden. Verschiedene Erstarrungsmodelle werden ebenso getestet wie Variationen des Simulationsbereiches und Feststoff-Temperatur-Verläufe. Vergleiche mit Temperaturmessdaten der Pilotanlage MgF GmbH Freiberg und der finalen Mikrostruktur zeigen gute Übereinstimmungen. Sensitivitätsanalysen werden durchgeführt, um die Einflüsse von thermophysikalischen Eigenschaften und Anlagenparametern abzuschätzen. Des Weiteren werden die Walzen in die Simulation mit einbezogen, um den Effekt eines lokal veränderlichen Wärmeübergangskoeffizienten zu beurteilen. Schließlich werden die Ergebnisse mit denen einer zweiten Pilotanlage am Helmholtz-Zentrum Geesthacht verglichen. / Le laminage de coulée continue horizontal possède une faible consommation d’énergie et est bon marché pour la production des feuilles de métaux coulables utilisés dans la construction légère. Afin d’examiner ce processus numériquement, un code est généré dans OpenFOAM et le logiciel commercial STAR-CCM+ est utilisé, tous les deux sont validés en utilisant le problème de Stefan, la fusion du gallium et la coulée continue verticale de magnésium AZ31. Plusieurs modèles de solidification sont testés, ainsi que la variation du domaine de simulation, et des rélations entre la teneur en matière solide et la température. Des comparaisons avec des résultats de mesures de la température à l’installation pilote de MgF GmbH Freiberg ainsi que la microstructure donnent des bons résultats. Des analyses de sensibilité sont effectuées afin d’évaluer l’influence des propriétés thermophysiques et des paramètres de l’installation. De plus, les cylindres sont intégrés dans la simulation pour estimer l’impact du coefficient de transfert de chaleur dépendant du lieu. Finalement, les résultats sont comparés avec ceux du Helmholtz-Centre Geesthacht.

Les phénomènes d’adsorption interviennent dans les processus géochimiques gouvernant ainsi le transport des contaminants. Par ailleurs, les variations de température sont susceptibles d’influencer significativement leur comportement vis-à-vis de la surface des minéraux. Aussi, l'influence de la température sur la sorption doit être étudiée afin de mieux appréhender le devenir des éléments dans l'environnement. Dans cette optique, l'interaction entre un ion modèle, l'uranyle et deux minéraux a été étudiée. Dans un premier temps, un composé méthodologique, la monazite, a été choisi afin de déterminer la démarche à suivre pour étudier l'influence de la température sur la sorption de l'uranyle dans trois milieux plus ou moins complexants. Puis, des tests préliminaires ont été réalisés pour étudier la sorption de l'uranyle sur un composé d'intérêt industriel, la magnétite, en appliquant la démarche mise en place. Le solide a d'abord été caractérisé d'un point de vue massif puis les caractéristiques acido-basiques de sa mise en suspension dans les trois électrolytes (NaClO4, NaNO3 et Na2SO4) ont été étudiées en fonction de la température. Les constantes d'équilibre associées aux réactions de déprotonation des sites de surface ont été déterminées entre 25°C et 95°C par modélisation de courbes de titrages potentiométriques. Les simulations ont été effectuées en limitant au maximum le nombre de degrés de liberté du système. Le modèle 1-pK a donc été préféré au modèle 2-pK en raison du nombre de paramètres ajustables plus limité dans ce modèle. Des contraintes expérimentales telles que le pH de point de charge nulle ou les enthalpies déterminées par mesure directe des chaleurs associées par microcalorimétrie de mélange ont été imposées pour déterminer les constantes d'équilibre acido-basiques. La sorption de l'uranyle en fonction du pH sur le même intervalle de température a été étudiée en alliant l'acquisition de données macroscopiques telles que les sauts de sorption et la spéciation en solution à une étude structurale menée par analyse par spectrofluorimétrie laser permettant l'identification des espèces sorbées. La simulation des sauts de sorption permettant d'accéder aux constantes associées aux réactions de sorption a été réalisée en imposant les caractéristiques acido-basiques préalablement déterminées. Des mesures directes, par microcalorimétrie de mélange, des chaleurs mises en jeu lors de la sorption de l'uranyle ont permis de tester la validité de la loi de Van't Hoff sur ce phénomène. La même démarche a été suivie pour étudier l'influence de la température sur la sorption de l'uranyle sur la magnétite en milieu NaClO4 et NaNO3. Cependant, l'étude structurale par spectrofluorimétrie laser n'a pu être réalisée en raison de la couloration noire de la magnétite. / The migration of radiotoxic elements in the geosphere is mainly regulated by chemical parameters which control the partitioning of the elements between mineral phases and aqueous solutions. Variation in temperature may affect the retention properties of a mineral surface and requires a careful investigation in order to understand the radionuclides behavior in the geosphere. In this way, the interaction mechanisms between uranium(VI) and two minerals (LaPO4 and Fe3O4) have been studied. In a first step, the monazite (LaPO4) has been chosen as methodological solid in order to clearly define all the different stages needed to completely characterize the influence of temperature on the sorption phenomena. To reach that goal, three media, more or less complexants towards aqueous uranyl and the mineral surface, have been considered. Physico-chemical as well as surface acid-base properties of the solid surface have been studied by considering three electrolytes (NaClO4, NaNO3 and Na2SO4) and temperatures ranged from 25°C to 95°C. The point of zero charge has been found to be identical for perchlorate and nitrate media (pHPZC=2.1) but it was found to be one pK unit higher for the sulfate medium indicating a sorption of the background electrolyte ions. The reaction heats associated to the hydration of the solid have been measured by using microcalorimetry and the nature of the reactive surface sites has been determined by carrying out Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS). On the basis of these experimental constraints, the titration curves obtained for the monazite suspensions were fitted by using the Constant Capacitance Model and the 1-pK model was preferred to characterize the surface charge evolution, due to the limited number of adjustable parameters. The surface protonation constants being determined, the behavior of U(VI) towards the monazite surface in the three electrolytes has been investigated. On the basis of both U(VI) speciation in solution and the results of a structural study carrying out by using TRLFS together with calorimetric measurements, the sorption edges have been modeled and the corresponding sorption constants determined. Since these values take into account a wide number of experimental results (both structural and thermodynamical ones) they appear to be accurate and could be extrapolated more confidently to other physico-chemical conditions. The experimental approach being validated with the methodological solid, preliminary tests have been carried out to study uranyl sorption onto a second substrate, the magnetite, more relevant than monazite in the field of radionuclides migration in the geosphere.

The horizontal twin-roll casting (TRC) process is an energy saving and cost-efficient method for producing near-net-shape sheets of castable metals for light-weight production. In order to investigate the TRC process numerically, a code is generated in OpenFOAM and the commercial software STAR-CCM+ is used. Both are validated with the Stefan problem, the gallium melting test case, and a continuous casting experiment for magnesium AZ31. Different solidification models are tested that are similar to solution domain definitions and solid-fraction temperature relations. The comparison with temperature measurements of the MgF GmbH Freiberg pilot plant and the final microstructure exhibits good correlation. Sensitivity studies are carried out for thermophysical properties of AZ31 as well as pilot plant parameters. Furthermore, the rolls are incorporated into the simulation to determine the effect of a location-dependent heat-transfer coefficient. Finally, the results are compared to a second pilot plant situated at the Helmholtz-Centre Geesthacht in order to explore differences and similarities. / Das horizontales Gießwalzen ist eine energiesparende und kostengünstige Methode zur Erzeugung von Flachprodukten, die im Leichtbau verwendet werden. Um dieses Verfahren numerisch zu untersuchen wurde ein Programmcode in OpenFOAM entwickelt und die kommerzielle Software STAR-CCM+ verwendet, wobei beide mit dem Stefan Problem, dem Schmelzen von Gallium und Messdaten des Stranggusses von Magnesium AZ31 validiert wurden. Verschiedene Erstarrungsmodelle werden ebenso getestet wie Variationen des Simulationsbereiches und Feststoff-Temperatur-Verläufe. Vergleiche mit Temperaturmessdaten der Pilotanlage MgF GmbH Freiberg und der finalen Mikrostruktur zeigen gute Übereinstimmungen. Sensitivitätsanalysen werden durchgeführt, um die Einflüsse von thermophysikalischen Eigenschaften und Anlagenparametern abzuschätzen. Des Weiteren werden die Walzen in die Simulation mit einbezogen, um den Effekt eines lokal veränderlichen Wärmeübergangskoeffizienten zu beurteilen. Schließlich werden die Ergebnisse mit denen einer zweiten Pilotanlage am Helmholtz-Zentrum Geesthacht verglichen. / Le laminage de coulée continue horizontal possède une faible consommation d’énergie et est bon marché pour la production des feuilles de métaux coulables utilisés dans la construction légère. Afin d’examiner ce processus numériquement, un code est généré dans OpenFOAM et le logiciel commercial STAR-CCM+ est utilisé, tous les deux sont validés en utilisant le problème de Stefan, la fusion du gallium et la coulée continue verticale de magnésium AZ31. Plusieurs modèles de solidification sont testés, ainsi que la variation du domaine de simulation, et des rélations entre la teneur en matière solide et la température. Des comparaisons avec des résultats de mesures de la température à l’installation pilote de MgF GmbH Freiberg ainsi que la microstructure donnent des bons résultats. Des analyses de sensibilité sont effectuées afin d’évaluer l’influence des propriétés thermophysiques et des paramètres de l’installation. De plus, les cylindres sont intégrés dans la simulation pour estimer l’impact du coefficient de transfert de chaleur dépendant du lieu. Finalement, les résultats sont comparés avec ceux du Helmholtz-Centre Geesthacht.

Diese Dissertation befasst sich mit der industrienahen Herstellung von Katalysatorschichten für Polymer-Elektrolyt-Membran-Brennstoffzellen mit Hilfe des Tiefdrucks als Fertigungsverfahren. Um die Anforderungen an die Katalysatorschicht hinsichtlich der Schichtdicke zu erreichen, wird ein Linienraster für den Tiefdruck entwickelt. Das patentierte und verifizierte Designkonzept des Linienrasters ermöglicht es, trotz Tinten mit geringem Feststoffgehalt hohe Trockenschichtdicken zu erzeugen. Aufgrund des verwendeten Tiefdruckrasters sind Optimierungsschritte an der Fertigungsanlage notwendig, um eine hohe Schichtqualität zu erreichen. Schließlich werden kontinuierlich und industrienah Katalysatorschichten gefertigt, die als Membran-Elektroden-Einheit in einer Polymer-Elektrolyt-Membran-Brennstoffzelle erfolgreich eingesetzt werden. / This work presents an industrial close manufacturing process of active electrodes for Polymer Electrolyte Fuel Cells utilizing an adapted gravure printing process. To meet the requirements of the electrodes regarding the layer thickness (weight) and quality a novel line screen with maximized dipping volume for gravure printing was developed and investigated. A design rule for this kind of screens was realized and verified by a successful manufacturing of electrodes with different dried layer thicknesses. Due to the rough structure and the high dipping volumes of these line screens an adaption and optimization of the machinery and the whole process was necessary to achieve high quality electrodes. Finally, it is shown that it is possible to manufacture continuiously in an industrial close roll-to-roll process platinum loaded electrodes, working successful as cathode in a Membran-Electrode-Assembly.

Extensive theoretical studies on the ground and excited state properties of systems containing heavy atoms have shown that accurate prediction of transition energies and related properties requires the incorporation of both relativistic and higher order correlation and relaxation effects as these effects are strongly inter- wined. The relativistic and dynamical electron correlation effects can be incor- porated in many-electron systems through a variety of many-body methods like configuration interaction (CI), coupled cluster method (CCM) etc. which are very powerful and effective tool for high precision description of electron correlation in many-electron systems. In this thesis, we investigate the relativistic and correlation effects in heavy atomic and molecular systems using these two highly correlated many-body methods. It is well recognized that, heavy polar diatomic molecules such as BaF, YbF, TlF, PbO, etc. are the leading experimental candidates for the search of violation of Parity (P ) and Time-reversal (T ) symmetry. The experimental detection of such P,T-odd effects in atoms and molecules has important consequences for the theory of fundamental interactions or for physics beyond the standard model (SM). For instance, a series of experiments on TlF have already been reported which provide the tightest limit available on the tensor coupling constant C , proton electric dipole moment (EDM) dp , etc. Experiments on YbF and BaF molecules are also of fundamental significance to the study of symmetry violation in nature, as these experiments have the potential to detect effects due to the electron EDMde. It is therefore imperative that high precession calculations are necessary to interpret these ongoing (and perhaps forthcoming) experimental outcome. For example, the knowledge of the effective electric field E(characterized by Wd) at the unpaired electron is required to link the experimentally determined P,T-odd frequency shift with the electron EDM de. We begin with a brief review of P,T-odd effects in heavy atoms and polar diatomics and the possible mechanisms which can give rise to such effects, in particular, the one arises due to the intrinsic electron EDM de. The P,T-odd interaction constant Wd is computed for the ground (2∑ ) state of YbF and BaF molecules using all-electron DF orbitals at the restricted active space (RAS) CI level. The RASCI space used for both systems in this calculation is sufficiently large to incorporate important core-core, core-valence, and valence-valence electron correlation effects. In addition to Wd, we also report the dipole moment (µe ) for these systems to assess the reliability of the method. The basis set dependency of Wd is also analyzed. The single reference coupled cluster (SRCC) method, developed by the cluster expansion of a single determinant reference function, is one of the most sophisticated method for treating dynamical correlation effects in a size-extensive manner. The non-uniqueness of the exponential nature of the wave operator diversifies the methods in multi-reference context. The multi-reference coupled cluster (MRCC) strategies fall within two broad classes: (a) State-Universal (SU), a Hilbert-space approach and (b) Valence-Universal (VU), a Fock-space approach. In this thesis, we shall be mainly concerned with the VU-MRCC which unlike SU-MRCC uses a single wave operator that not only correlates the reference functions, but also all the lower valence (or the so called subdued) sectors, obtained by deleting the occupancies systematically. The linear response theory (LRT) or equation of motion (EOM) method is another possible alternative which is nowadays extensively used to compute the atomic and molecular properties. Although, the CCLRT or EOM-CC method is not fully extensive in nature, this method has some distinct advantages over the traditional VU-MRCC theory. Further, for one-valence problem like ionization processes, the CCLRT/EOM-CC is formally equivalent to VU-MRCC, and hence, size-extensive. In this thesis, the core-extensive CCLRT and core-valence extensive (all electron) VU-MRCC methods are applied to compute the ground and excited state properties of various atomic and molecular systems (HCl, CuH, Ag, Sr, Yb and Hg) using nonrelativistic and relativistic (for heavy atoms) spinors. The similarities and differences in the structure of these two formalisms are also addressed. We also investigate the ground and excited state properties of HCN which is a system of astrophysical importance. This system has raised interest among the astrophysicists due to its detection in the atmosphere of Titan and Carbon stars. HCN has also been identified via radio-techniques in both comets and interstellar atmosphere. In the ash-photolysis of oxazole, iso-oxazole, and thiozole a transient band system was observed in the region 2500-3050 Å. This band system was attributed to a meta-stable form of HCN, i.e, either HNC or triplet HCN. We carry out detailed theoretical investigations using CCLRT and complete active space self-consistent field (CASSCF) method to characterize this unidentified band and other experimentally observed transitions.

Pulse width modulation (PWM) rectifiers are extensively used in battery charger, regulated dc voltage source, UPS systems, ac line conditioner and motor drives. The conventional control schemes for these rectifiers require PLL, transformations, and input voltage sensing, which increase the cost and complexity of the controller. Simple control schemes based on resistance emulation control are developed in this thesis work for different PWM boost rectifiers. Modeling, analysis and design methods for these rectifier systems are presented. The effect of computational delay involved in digital implementation on the performance of the above rectifier systems is studied. A single-switch boost rectifier system is presented, which operates in DCM and in CCM for an output power less than and greater than 50% rated load, respectively, exploiting the best features of both the operating modes. A generalized feedforward control is presented to improve the dynamic response of output voltage of single-phase boost rectifiers against input voltage, load current and reference voltage disturbances. Feedforward control requires additional voltage and/or current measurements. A state observer is presented for estimating the inductor current of a buck rectifier, and two disturbance observers are presented to estimate the input voltage and the load current of a boost rectifier. These observers eliminate the need of additional sensors for implementing the feedforward control. The resistance emulation control is extended to four-wire PWM rectifier. Two control methods are presented. The first method makes the input currents of the rectifier proportional to their respective input voltages, while the second one balances its input currents even under unbalanced input voltage condition. A detailed analysis of line and neutral current distortions of four-wire converter is presented. A three-carrier based PWM scheme is presented, which significantly reduces the neutral current of the rectifier compared to conventional PWM scheme, when three single-phase inductors are used, and considerably reduces both line and neutral current distortions, when a three-limb inductor is used. A regenerative test setup containing two back-to-back connected three-phase PWM converters is presented for testing high-power converters in the active and reactive power circulation mode. The proposed scheme considerably reduces the cost of testing, and hence, the overall production cost of the converters compared to load-bank testing. A mathematical model is presented for the above system. A suitable control method is presented to control the two converters of the back-to-back system. A new PWM scheme is presented, which considerably reduces the requirement of the dc bus voltage of the back-to-back system compared to conventional PWM schemes. All theoretical predictions are experimentally validated. The experimental results are presented.

As the demand for energy continues to increase around the world, more vessels used in the transport of energy, such as Liquid Natural Gas (LNG) and crude oil tankers are being built to transport energy to market overseas. The escort tug has been developed in order to assist in the safe transit of such vessels in confined waterways. Designed to apply emergency braking and steering forces to the stern of a tanker while underway, an escort tug features a hull shape that generates large hydrodynamic lift and drag forces when operating at high angles of attack, this is known as indirect mode. This escorting mode is highly effective at speeds 8 knots and above, often generating towline forces well in excess of bollard pull. Escort performance prediction is a vital aspect of the design of escort tugs. It is important to know a priori if a design will meet the necessary performance criteria. In the past, performance predictions have relied heavily on model testing and empirical methods. With the recent emergence of Computational Fluid Dynamics (CFD) as a commercially viable design tool for naval architects, extensive escort performance predictions can now be carried out more accurately in less time and at less cost than was previously possible. This thesis describes the methodology of a CFD based escort performance prediction method that is accurate and cost effective. / Graduate

The phenomenon of pairing in atomic and nuclear many-body systems gives rise to a great number of different physical properties of matter, from areas as seemingly diverse as the shape of stable nuclei to superconductivity in metals and superfluidity in neutron stars. With the experimental realisation of the long sought BCS-BEC crossover observed in trapped atomic gases - where it is possible to fine tune the s-wave scattering length a of a many-fermion system between a dilute, correlated BCS-like superfluid of Cooper pairs and a densely packed BEC of composite bosons - pairing problems in atomic physics have found renewed interest in recent years. Given the high precision techniques involved in producing these trapped gas condensates, we would like to employ a suitably accurate many-body method to study such systems, preferably one which goes beyond the simple mean-field picture.The Coupled Cluster Method (CCM) is a widely applied and highly successful ab initio method in the realm of quantum many-body physics and quantum chemistry, known to be capable of producing extremely accurate results for a wide variety of different many-body systems. It has not found many applications in pairing problems however, at least not in a general sense. Our aim, therefore, is to study various models of pairing using a variety of CCM techniques - we are interested in studying the generic features of pairing problems and in particular, we are especially interested in probing the collective modes of a system which exhibits the BCS-BEC crossover, in either the BCS or BEC limit. The CCM seems a rather good candidate for the job, given the high precision results it can produce.

The diploma thesis deals with CFD simulating the air flow inside the car using the numerical calculation program Star-CCM+. The aim of the thesis was to prepare 3D geometry, resp. realistic model of the real car, preparing boundary conditions including material properties, simulating the steady state of the environment and evaluating the speed and temperature of the car cabin. The paper presents the results of the temperature distribution and air velocities in the cabin during the winter, spring and summer conditions in HVAC on and HVAC off modes. The monitored air temperatures and surface temperatures of the car parts are compared with the measured data. The average difference between simulation and measurement was at air temperatures of 2.3 °C and surface temperatures of 3.4 °C.

Heat transfer and solidification models were developed for use in a numerical model of a continuous caster to provide a means of predicting how the developing shell would react under variable operating conditions. Measurement data of the operating conditions leading up to a breakout occurrence were provided by an industrial collaborator and were used to define the model boundary conditions. Steady-state and transient simulations were conducted, using boundary conditions defined from time-averaged measurement data. The predicted shell profiles demonstrated good agreement with thickness measurements of a breakout shell segment – recovered from the quarter-width location. Further examination of the results with measurement data suggests pseudo-steady assumption may be inadequate for modeling shell and flow field transition period following sudden changes in casting speed. An adaptive mesh refinement procedure was established to increase refinement in areas of predicted shell growth and to remove excess refinement from regions containing only liquid. A control algorithm was developed and employed to automate the refinement procedure in a proof-of-concept simulation. The use of adaptive mesh refinement was found to decrease the total simulation time by approximately 11% from the control simulation – using a static mesh.