This thesis presents an experimental study which investigates the behaviour of gas bubbles rising in a liquid metal and the related bubble-driven flow under the influence of external DC magnetic fields. The experimental configuration considered here concerns a cylindrical container filled with the eutectic alloy GaInSn. Argon gas bubbles are injected through a single orifice located at the container bottom in the centre of the circular cross-section. A homogeneous magnetic field was generated by a Helmholtz configuration of a pair of water-cooled copper coils. The magnetic field has been imposed either in vertical direction parallel to the main bubble motion or in horizontal direction, respectively. A vertical magnetic field stabilizes and damps the liquid metal flow effectively. The temporal variations of the fluid velocity with time become smaller with increasing magnetic induction. The velocity magnitudes are decreased, and the velocity distributions along the magnetic field lines are smoothed. The flow field keeps the axisymmetric distribution. A horizontal magnetic field destabilizes and enhances the flow within a range of moderate Hartmann numbers (100 < Ha < 400). The flow becomes non-axisymmetric due to the non-isotropic influence of the magnetic field. In the meridional plane parallel to the field lines, the flow changes its direction from a downward to an upward motion. Enhanced downward flows were observed in the meridional plane perpendicular to the field lines. The liquid velocity in both planes shows strong, periodic oscillations. The fluid motion is dominated by large-scale structures elongated along the magnetic field lines over the entire chord lengths of the circular cross-section.

With the discovery of conductivity in doped polyacetylene (PA), a new era in synthetic metals has emerged by breaking the traditionally accepted view that polymers were always insulating. Conducting polymers are essentially characterized by the presence of conjugated bonding on the polymeric back bone, which facilitates the formation of polarons and bipolarons as charge carriers. Among the numerous conducting polymers synthesized to date, polypyrrole (PPy) is by far the most extensively studied because of prodigious number of applications owing to its facile polymerizability, environmental stability, high electrical conductivity, biocompatibility, and redox state dependent physico-chemical properties. Electrochemically prepared PPy is more interesting than the chemically prepared polymer because it adheres to the electrode surface and can be directly used for applications such as supercapacitors, electrochemical sensors, electromechanical actuators and drug delivery systems. In quest for improvement in quality of the device performances in the mentioned applications, micro and nano structured polymeric materials which bring in large surface area are studied. Finding a simple and efficient method of synthesis is very important for producing devices of PPy microstructures. Till date, Hard and soft template methods are the most employed methods for synthesis of these structures. Soft template based electrochemical methods are better than hard template methods to grow clean PPy microstructures on electrode substrates as procedures for removal of hard templates after the growth of microstructures are very complex. As per the literature, there is no unique method available to grow PPy microstructures which can demonstrate several applications. Although gas bubble based soft template methods are exploited to grow conducting polymer microstructures of sizes in few hundreds of micrometers, studies on applications of the same are limited. Hence it is planned to develop procedures to grow microstructures that can be used in several applications. In the current work, PPy microstructures with high coverage densities are synthesized on various electrode substrates by soft template based electrochemical techniques. Hollow, hemispherical and spherical PPy microstructures are developed by a two step method using electro generated hydrogen bubble templates on SS 304 electrodes. In the first step, Hydrogen bubbles are electro generated and stabilized on the electrode in the presence of β- naphthalene sulfonic acid (β-NSA). In the second step, Pyrrole is oxidised over the bubble template to form PPy microstructures. Microstructures (open and closed cups) of average size 15 μm are uniformly spread on the surface with a coverage density of 2.5×105 units /cm2. Globular PPy microstructures are developed by a single step method using concomitantly electro generated oxygen bubble templates on SS 304 electrodes during electropolymerization. Microstructures of average size 4 μm are uniformly spread on the surface with a coverage density of 7×105 units/cm2. Surfactant properties of Zwitterionic 4-(2-hydroxyethyl)-1-piperazine ethane sulfonic acid (HEPES) are exploited for the first time to grow conducting polymer microstructures. Ramekin shaped PPy microstructures are developed using HEPES as the surfactant to stabilize hydrogen bubble templates in a two step electrochemical synthesis method. Microramekins of size 100 µm are uniformly spread on the surface with a coverage density of 3000 units/cm2. Micropipettes and microhorns of PPy are synthesised by a single step electrochemical route using HEPES as a surfactant. Hollow micropipettes of length 7 µm with an opening of 200 nm at the top of the structure are observed. Similarly microhorn/celia structures are observed with length 10-15 µm. Microcelia are uniformly distributed over the surface with each structure having a diameter of 2 µm at the base to 150 nm at the tip. Growth mechanism based on contact angle of the reactant solution droplets on the substrate is proposed. PPy microstructures are characterized by scanning electron microscopy, X-Ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman Spectroscopy and UV-Visible spectroscopy to study morphology, ‘chemical bonding and structure’ , ‘defects and charge carriers’. Applicability of the electrodes with PPy microstructures in supercapacitors is investigated by cyclic voltammetry, chronopotentiometry and electrical impedance spectroscopy. Electrodes developed by all the above methods demonstrated very good supercapacitance properties. Supercapacitor studies revealed very high specific capacitances (580, 915, 728 and 922 F/g,) and specific powers (20, 25, 13.89 and 15.91 kW/kg) for electrodes with PPy microstructures (H2 bubble based two step method, O2 bubble based single step method, HEPES stabilized H2 bubbble method and HEPES based microhorn/celia structures respectively). Supercapacitive behavior of all the electrodes is retained even after an extended charge-discharge cycling in excess of 1500 cycles. Horseradish peroxidase entrapped, bowl shaped PPy microstructures are developed for H2O2 biosensing. Amperometric biosensor has a performance comparable to the sensors reported in the literature with high sensitivity value of 12.8 μA/(cm2.mM) in the range 1.0 mM to 10 mM. Glucose oxidase entrapped PPy amperometric biosensor is developed for Glucose sensing. Sensitivity of 1.29 mA/(cm2.mM) is observed for β-D-Glucose sensing in the 0.1 mM to 5.0 mM range while 58 μA/(cm2.mM) is observed in the 5.0 to 40 mM range. Potentiometric urea sensor with urease entrapped PPy microstructures on SS electrode is developed. It is able to sense urea in the micromolar ranges down to 0.1 μM. It represented an excellent performance with sensitivity of 27 mV/decade. Sensitivity in the micromolar range is 4.9 mV/(μM.cm2). Drug encapsulation and delivery is successfully demonstrated by two actuation means (i) by electrochemical actuation, (ii) by actuation based on pH changes. Concepts are proved by delivering a fluorescent dye into neutral and acidic solutions. Drug delivery is confirmed by UV-Visible spectroscopy and Fluorescence microscopy. Finally, Micro/nanostructures with Tangerine, Hollow globular (Pani Poori), Chip, Flake, Rose, Worm, Horn and Celia shapes are synthesized electrochemically and scanning electron microscopic studies are presented. Controlled growth of microstructures on lithographically patterned gold interdigital electrodes is demonstrated with a future goal of creating addressable microstructures. The studies reported in the thesis provide an insight on various applications of PPy microstructures (supercapacitors, sensors and drug delivery systems) developed by a unique methodology based on electrochemically generated gas bubble templates.

In dieser Arbeit wird ein Simulationsprogramm für das Gas-Verhalten in Heizungssystemen entwickelt. Der Gaseintrag durch das Membranausdehnungsgefäß und Dichtungsstellen, die Entstehung und Ansammlung von Gasblasen und die Funktionen der Heizungsanlage werden in einem Programm dynamisch simuliert. Mit diesem Programm wird eine Parameter-Studie durchgeführt. Die Einflüsse verschiedener Faktoren auf das Vorhandensein des Gases und die Leistung der Heizungsanlage werden ausgewertet, wie zum Beispiel der Druck und Temperatur im Heizungssystem, die Gasgehalten im Füllwasser, die Auswirkung eines atmosphärischen Entgasungsgeräts. Die Ergebnisse zeigen, dass der Einfluss der Gaspermeation auf das Auftreten von Gasblasen im Heizungssystem im Vergleich zum Anfangsgasgehalt im Füllwasser sehr gering ist. Bei höherer Temperatur dringt viel mehr Sauerstoff in das System ein. Die meisten Gasblasen sammeln sich in dem Heizkörper in der höchsten Etage mit dem kürzesten Kreislauf an. Das atmosphärische Entgasungsgerät wirkt besser als das MAG bei der Druckhaltung. Jedoch wird mehr Rost in der Heizungsanlage durch den von dem Behälter des Entgasungsgeräts eingetragenen Sauerstoff erzeugt. / The purpose of this paper is to find out how and how much gas get into the heating system through permeation, when and where the gas bubbles get accumulated in the heating system and how well an atmospheric degassing device works. For this propose a dynamic timestep simulation was made with C# program to simulate heating system and the gas behaviors in the system. Sensibility tests were made for different factors such as sealing material, temperature and gas concentration in water. In addition, the speed of the gas permeation in the dynamic simulation gets compared with the values of static calculation in the literature. The results showed, that different sealing material and different temperature could make a big difference for the amount of gas that permeate in to the system. But compare to the initial gas concentration in the filling water is gas permeation alone is not a decisive factor for the presence of gas bubbles in the heating system and does not have a major impact on the performance of the heating system. More oxygen enters the system and get consumed by corrosion at higher operation temperatures. The results also showed, that the atmospheric degassing device works better than MAG at the pressure maintenance and getting rid of gas bubbles. However, oxygen gets constantly introduced in to the heating system through the container of the atmospheric degassing device. More rust is therefore generated.

This thesis presents an experimental study which investigates the behaviour of gas bubbles rising in a liquid metal and the related bubble-driven flow under the influence of external DC magnetic fields. The experimental configuration considered here concerns a cylindrical container filled with the eutectic alloy GaInSn. Argon gas bubbles are injected through a single orifice located at the container bottom in the centre of the circular cross-section. A homogeneous magnetic field was generated by a Helmholtz configuration of a pair of water-cooled copper coils. The magnetic field has been imposed either in vertical direction parallel to the main bubble motion or in horizontal direction, respectively. A vertical magnetic field stabilizes and damps the liquid metal flow effectively. The temporal variations of the fluid velocity with time become smaller with increasing magnetic induction. The velocity magnitudes are decreased, and the velocity distributions along the magnetic field lines are smoothed. The flow field keeps the axisymmetric distribution. A horizontal magnetic field destabilizes and enhances the flow within a range of moderate Hartmann numbers (100 < Ha < 400). The flow becomes non-axisymmetric due to the non-isotropic influence of the magnetic field. In the meridional plane parallel to the field lines, the flow changes its direction from a downward to an upward motion. Enhanced downward flows were observed in the meridional plane perpendicular to the field lines. The liquid velocity in both planes shows strong, periodic oscillations. The fluid motion is dominated by large-scale structures elongated along the magnetic field lines over the entire chord lengths of the circular cross-section.

Cette thèse se situe dans le cadre du projet ASTRID du CEA. La surveillance de la présence de gaz dans un RNR est importante pour son fonctionnement en toute sécurité. Cette thèse porte sur la détection et la caractérisation de présence de gaz par un débitmètre à distorsion de flux (DDF). Du point de vue technologique, l’objectif est d’évaluer la faisabilité de l’utilisation d’un DDF, et s’il est possible de mesurer le débit et le taux de vide simultanément avec un DDF. Du point de vue de la physique, le DDF mesure la perturbation du flux magnétique due aux courants de Foucault induits par l’hydrodynamique d’un écoulement de liquide conducteur. En présence de vide dans le conducteur, une nouvelle source de perturbation apparaît du fait de la modification, par le taux de vide, de la distribution du champ magnétique. En effet, la présence de vide agit sur les distributions locales de courants électriques dues au couplage des phénomènes d’induction et de forces de Lorentz. Notre objectif est de comprendre la nature de ces couplages et de proposer une méthode qui permette de caractériser la présence de vide à partir du signal de sortie du DDF, de mesurer le taux de vide et d’étudier la sensibilité de cette mesure aux variations des paramètres de l’écoulement et du champ électromagnétique (vitesse et pulsation, en particulier). Dans ce travail, des expériences spécifiques ont été développées pour étudier les effets de la vitesse, du taux de vide et de la pulsation du flux magnétique sur la réponse d’un DDF. Ces expériences modélisent un écoulement diphasique idéal (écoulement piston) consistant en une barre mobile d’aluminium contenant des trous et des cannelures pour simuler le taux de vide. Dans ces expériences la vitesse, le taux de vide et la pulsation sont parfaitement contrôlé et leur domaine de variations sont les suivants : 0<U<1 m/s pour la vitesse, 0< <6.9% pour le taux de vide et 1500<<12000 rad/s pour la pulsation (dans cette gamme de pulsations, on notera que la profondeur de pénétration du champ électromagnétique est de l’ordre de, mais plus petit que, le rayon du barreau d’aluminium). Une méthode d’ellipse-fitting appliqué au signal de sortie du DDF a été utilisée pour caractériser l’effet du taux de vide. Les résultats montrent que le DDF est sensible pour des fractions volumique de vide entre 0.3 % and 6.9% . En outre, la réponse aux variations de taux de vide est insensible à la vitesse du barreau. Cette technique est peu adaptée aux mesures des faibles taux de vide (< 0.1%). Une deuxième approche a été développée, sur la base de l’analyse du signal démodulé du DDF. Cette analyse s’appuie sur un modèle théorique du flux magnétique obtenu par un développement au 1er ordre par rapport à U et a. Ce modèle permet d’interpréter les résultats expérimentaux en termes de contributions de U et a au flux magnétique. Malgré le couplage fort entre l’induction Faraday et les forces de Lorentz, les résultats montrent que les contributions de U et alpha peuvent être séparées correctement pour des petites valeurs du nombre de Reynolds magnétique (Rem < 0.12), et de faible taux de vide ( < 6.9%). Un résultat très important est que la contribution de a sur le flux magnétique est insensible aux variations de vitesse dans cette gamme de Rem . De plus, l’effet de la géométrie du vide a été étudié pour deux configurations : cannelures et trous. Il a été observé que la géométrie du vide n’a pas d’effet sur les variations du flux magnétique avec a. Cette seconde approche est plus sensible aux variations de fraction volumique du vide que la méthode de l’ellipse-fitting. Enfin, des expériences préliminaires avec un liquide métallique (galinstan) contenant des perles de verre, ont été faites et ont montré une bonne sensibilité du signal du DDF avec la vitesse et le taux de vide. En conclusion, ce travail a montré qu’il est possible de mesurer simultanément un taux de vide et un débit pour la gamme de variations des paramètres étudiés. / A Generation IV Sodium cooled Fast Reactor (SFR) is being researched and developed at CEA, Cadarache France under the project named ASTRID. Monitoring gas presence in SFR is important with respect to its safe operation. In accordance with the principles of diversity, techniques based on different measurement principles have been proposed. This thesis concerns the detection and characterization of void using magnetic flux perturbation principle. An Eddy Current Flow Meter (ECFM) device is used for this purpose. From the technological point of view, the objective is to evaluate the feasibility of ECFM as a flow and/or void monitoring/characterizing device; and to determine which parameters are of interest and what are the precision of these measurements; and whether it is possible to measure the flow rate and void fraction simultaneously with the same ECFM device. From the physics point of view, the ECFM system involves the magnetic flux perturbation due to voids in the presence of Faraday induction and Lorentz force effects. Therefore ECFM integrated signal contains informations about the void, Faraday induction and Lorentz force effects based perturbation in magnetic flux and their couplings. Our objective is to understand the nature and extent of these couplings. Specific experiments have been developed to study the effects of flow velocity, void fraction and magnetic flux pulsations on the response of an ECFM. It consists in modeling the two-phase flow by a moving aluminium rod (plug flow) with holes and grooves to simulate voids. Flow velocity range of variation was 0<U<1 m/s, void fraction 0<<6.9% and pulsation 1500<<12000 rad/s (for this range of pulsations the electromagnetic skin depth is of order but smaller than the aluminium rod radius). An ellipse fitting method was proposed to analyze the output signal of the secondary coils. The results show that ECFM is sensitive to void fractions between 0.3 % and 6.9%. Furthermore, the response to void fraction is insensitive to the mean velocity of the twophase medium. A second approach based on demodulation analyses of the secondary coils output signal has been developed. We have proposed a theoretical model based on a first order expansion of magnetic flux in U and a. With this model it was possible to interpret the experimental results in terms of contributions of U and a. Despite the strong coupling between Faraday induction and Lorentz force effects, the results show that the contributions of U and a. can be well separated at low magnetic Reynolds number (Rem < 0.12) and low a values ( < 6.9%). A very important result is that the contribution of _ on magnetic flux is insensitive to variations of velocity in this range of Rem. Moreover, different geometries of void have been studied: grooves and holes. It was observed that the geometry of void do not change the variation of magnetic flux with a. This second approach revealed to be more sensitive to void fraction variations than ellipse fitting method. Finally, preliminary experiments with liquid metal galinstan with glass beads were done, which showed sensitivity of ECFM signal with velocity and void. In conclusion, this work has shown that ECFM can measure simultaneously void and velocity in the range of parameters studied, in particular 0.06%< < 6.9%.