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We explore a specific small geometry containing a single thin bounded grain on a substrate with a hole at its center. By employing a mathematical model based on surface diffusion, no flux boundary conditions, and prescribed contact angles, we study the evolution of the hole as well as the exterior surface of the grain, based on energetic considerations and dynamic simulations. Our results regarding the formation and evolution of holes in thin films in small geometries shed light on various nonlinear phenomena associated with wetting and dewetting.

Lors d'un accident grave dans un réacteur à neutrons rapides refroidi au sodium, le combustible fondu peut entrer en contact avec le sodium environnant, conduisant alors à une interaction communément appelée Interaction Combustible-Réfrigérant. L'objectif de ce travail est d'améliorer la connaissance relative aux transferts thermiques en régime d'ébullition en film du sodium, essentielle pour étudier les risques liés à une éventuelle explosion de vapeur. Peu d'études, tant expérimentales que théoriques, ont été menées sur l'ébullition en film du sodium. Une unique expérience permet d'étudier l'ébullition en film du sodium en convection naturelle. Lors de l'analyse de ces essais, deux sous-régimes d'ébullition en film, non identifiés par l'auteur mais déjà observés pour l'eau, ont été mis en évidence : un régime de film qualifié de stable, sans contact liquide-solide, et un régime de film qualifié d'instable, avec contacts. D'un point de vue théorique, un seul modèle dédié à l'ébullition en film du sodium est proposé dans la littérature, dont l'analyse a révélé de nombreux défauts. Dans un premier temps, une analyse d'échelles du problème a été effectuée en convection naturelle et en convection forcée, en distinguant les cas d'un fort et d'un faible sous-refroidissement. Cette approche simplifiée, cohérente avec les résultats expérimentaux, a permis de définir les nombres adimensionnels pertinents pour l'établissement de corrélations. Un modèle a ensuite été développé pour traiter l'ébullition en film du sodium autour d'une sphère dans le cas le plus général - en convection naturelle ou forcée, pour un métal liquide saturé ou sous-refroidi. Ce modèle est basé sur l'approximation de double couche limite et met en œuvre une méthode intégrale en considérant les termes inertiels et convectifs, classiquement négligés, dans les équations de bilan de l'écoulement de vapeur. Par ailleurs, le rayonnement est pris en compte de manière couplée à l'interface liquide-vapeur et contribue directement à la production de vapeur. Ce modèle permet d'évaluer correctement le flux de chaleur perdu par un corps chaud en comparaison aux résultats des essais, en particulier lorsque ceux-ci sont corrigés des biais expérimentaux. La partition du flux de chaleur, entre chauffage et vaporisation, est également estimée : il s'agit d'une information indispensable à la description d'une explosion de vapeur et non accessible expérimentalement. En outre, l'influence de différents paramètres - sous-refroidissement du sodium, surchauffe et diamètre de la sphère, vitesse de l'écoulement externe, pression du système - dans les conditions pouvant être celles d'un accident grave a été étudiée. Enfin, un modèle simplifié a été utilisé pour étudier la transition entre les deux sous-régimes d'ébullition en film identifiés dans l'expérience. Les tendances obtenues par cette approche sont analogues à celles observées expérimentalement. / During a severe accident in a sodium-cooled fast reactor, molten fuel may come into contact with the surrounding liquid sodium, resulting in a so-called Fuel-Coolant Interaction. This work aims at providing a better understanding and knowledge of the associated heat transfer, likely to be in the film-boiling regime and required to study the risks related to a vapor explosion. Scarce literature has been found on sodium film boiling, both from an experimental and a theoretical point of view. Only one experiment has been conducted to investigate sodium pool film-boiling heat transfer. In our analysis of the experiment, two film-boiling regimes have been identified: a stable film boiling regime, without liquid-solid contact, and an unstable film-boiling regime, with contacts. Besides, the only theoretical model dedicated to sodium film boiling has shown some weaknesses. First, a scaling analysis of the problem has been proposed for free and forced convection, considering the two extreme cases of saturated and highly subcooled liquid. This simplified approach, which shows a good agreement with the experimental data, provides the dimensionless numbers which should be used to build correlations. A theoretical model has been developed to describe sodium film-boiling heat transfer from a hot sphere in free and forced convection, whatever the liquid subcooling. It is based on a two-phase laminar boundary layer integral method and includes the inertial and convective terms in the vapor momentum and energy equations, usually neglected. The radiation has been taken into account in the interfacial energy balance and contributes directly to produce vapor. This model enables to predict the heat lost from a hot body within an acceptable error compared to the tests results especially when the experimental uncertainties are considered. The heat partition between liquid heating and vaporization, essential to study the vapor explosion phenomenon, is also estimated. The influence of different parameters - sodium subcooling, sphere superheat and diameter, external flow velocity, system pressure - under accident conditions has been studied. Eventually, a simplified model has been used to investigate the transition between the two film boiling regimes identified in the experiment. The trends obtained with this approach are similar to those observed experimentally.

abstract: This dissertation presents methods for the evaluation of ocular surface protection during natural blink function. The evaluation of ocular surface protection is especially important in the diagnosis of dry eye and the evaluation of dry eye severity in clinical trials. Dry eye is a highly prevalent disease affecting vast numbers (between 11% and 22%) of an aging population. There is only one approved therapy with limited efficacy, which results in a huge unmet need. The reason so few drugs have reached approval is a lack of a recognized therapeutic pathway with reproducible endpoints. While the interplay between blink function and ocular surface protection has long been recognized, all currently used evaluation techniques have addressed blink function in isolation from tear film stability, the gold standard of which is Tear Film Break-Up Time (TFBUT). In the first part of this research a manual technique of calculating ocular surface protection during natural blink function through the use of video analysis is developed and evaluated for it's ability to differentiate between dry eye and normal subjects, the results are compared with that of TFBUT. In the second part of this research the technique is improved in precision and automated through the use of video analysis algorithms. This software, called the OPI 2.0 System, is evaluated for accuracy and precision, and comparisons are made between the OPI 2.0 System and other currently recognized dry eye diagnostic techniques (e.g. TFBUT). In the third part of this research the OPI 2.0 System is deployed for use in the evaluation of subjects before, immediately after and 30 minutes after exposure to a controlled adverse environment (CAE), once again the results are compared and contrasted against commonly used dry eye endpoints. The results demonstrate that the evaluation of ocular surface protection using the OPI 2.0 System offers superior accuracy to the current standard, TFBUT. / Dissertation/Thesis / Ph.D. Industrial Engineering 2012

With continued shrinking of CMOS technology to reduce the gate delay times, an increase in the resistivity of the metal corresponding to the wire dimension is a concern. This phenomenon of increase in resistivity with decreasing dimension of the thin metallic film or interconnect is known as the "classical size effect". Various theories have been postulated to explain the phenomenon of classical size effect; these theories can be broadly classified as resistivity due to scattering arising from surface and grain boundaries. The total resistivity of metals depends on the electron scattering due to impurities, phonons, surfaces, grain boundaries, and other crystal defects. Managing the size effect in a practical and manufacturing way is of major concern to the microelectronics industry. Since each of the processes (phonon, surface and grain boundary scattering) adds to the resistivity and are interrelated, it further complicates managing the size effect. However, these effects have been separately studied. In this work, the effect of annealing on the classical size effect in Cu thin films deposited on SiO2 substrate is investigated. Polycrystalline Cu thin films having thicknesses in the range of 10nm to 200nm were ultra high vacuum sputter deposited on thermally grown SiO2 surfaces. The films were annealed at temperatures in the range of 150°C to 800°C in argon and argon+3% hydrogen gases. The un-annealed Cu thin films exhibit higher resistivity than the annealed films. The resistivities of un-annealed films were in good agreement with Mayadas and Shatzkes model. When annealed the films undergoes grain growth resulting in lowering the resistivities by about 20%-30% thereby confirming the role of grain size on resistivity of the film. However, there is a limit to annealing, i.e. agglomeration phenomenon. Agglomeration is a thermally activated process resulting in a reduction of the free energy of the film–substrate system and can occur well below the melting point of the material by surface and interfacial diffusion. The reduction of film-substrate interfacial energy, film-surface interfacial energy and stresses within the film are possible driving forces for agglomeration. This work also includes the study of agglomeration phenomenon. The agglomeration behavior of Cu is investigated and compared with that of Ru, Au and Pt thin films with thicknesses in the range of 10 nm to 100 nm UHV deposited on thermally grown SiO2 substrate. The films were annealed at temperatures in the range of 150°C to 800°C in argon and argon+3% hydrogen gases. Scanning electron microscopy was used to investigate the agglomeration behavior, and transmission electron microscopy was used to characterize the microstructure of the as-deposited and annealed films. The agglomeration sequence in all the films is found to follow a two step process of void nucleation and void growth. However, void growth in Au and Pt thin films is different from Cu and Ru thin films. Residual stress and adhesion were observed to play important part in deciding the mode of void growth in Au and Pt thin films. Lastly, it is also observed that the tendency for agglomeration can be reduced by encapsulating the metal film with an oxide overlayer, which in turn improves the resistivity of the thin film due to prolonged grain growth without film breakup.

In the present article, electrodes containing a composite of platinum on top of a plasma-oxidized multi-layer graphene film are investigated as model electrodes that combine an exceptional high platinum utilization with high electrode stability. Graphene is thereby acting as a separator between the phosphate-based electrolyte and the platinum catalyst. Electrochemical impedance measurements in humidified hydrogen at 240 °C show area-normalized electrode resistance of 0.06 Ω·cm−2 for a platinum loading of ∼60 µgPt·cm−2, resulting in an outstanding mass normalized activity of almost 280 S·mgPt−1, exceeding even state-of-the-art electrodes. The presented platinum decorated graphene electrodes enable stable operation over 60 h with a non-optimized degradation rate of 0.15% h−1, whereas electrodes with a similar design but without the graphene as separator are prone to a very fast degradation. The presented results propose an efficient way to stabilize solid acid fuel cell electrodes and provide valuable insights about the degradation processes which are essential for further electrode optimization.

L’interaction statique et dynamique entre une sonde locale et un film de liquide provoque la déformation de ce dernier. Ce phénomène a été décrit par des équations analytiques, qui ont été analysées et résolues numériquement. Les potentiels d’interaction sonde/liquide et liquide/substrat ont été déduits à partir de l’intégration des forces de dispersion. La différence de pression à travers l’interface air/liquide a été calculée avec une équation de Young-Laplace modifiée, qui prend en compte les effets de la gravité, de tension superficielle, ainsi que les potentiels d’interaction liquide/substrat et sonde/liquide. Pour le cas statique, l’équation modifiée de Young-Laplace en équilibre a été examinée. La théorie de la lubrification a été utilisé pour décrire l’évolution du film liquide, afin d’analyser le phénomène dynamique. Des simulations numériques de la forme de la surface d’équilibre et de l’évolution dynamique du film ont été réalisées. Des comportements stables et instables ont été discernés, et les résultats ont confirmé l’existence d’une distance de seuil, pour le cas statique, et d’une combinaison de paramètres d’oscillation, pour la situation dynamique, pour lesquelles le saut du liquide vers la sonde se produit. Une analyse théorique a confirmé l’existence de conditions critiques qui séparent les régimes de comportement. Ces conditions critiques indiquent le rôle des paramètres physiques et géométriques dans la stabilité du système. Pour le cas dynamique, les résultats préliminaires sont rapportés et une interprétation qualitative du phénomène est formulée. En outre, des expériences de spectroscopie AFM de force et amplitude ont été effectuées et comparées avec les résultats numériques. / The static and dynamic interaction between a local probe and a liquid film provokes the deformation of the latter. This phenomenon has been described by means of analytical equations, which had been analyzed and numerically solved. Probe/liquid and liquid/substrate interaction potentials have been deduced from the integration of the dispersion forces. The pressure difference across the air/liquid interface has been calculated with a modified Young-Laplace equation, which takes into account the effects of gravity, surface tension, the liquid film/substrate and the probe/liquid interaction potentials. For the static case, the equilibrium modified Young-Laplace equation has been considered. The lubrication theory has been used to describe the liquid film evolution, in order to analyze the dynamic phenomenon. Numerical simulations of the equilibrium surface shape and the dynamic evolution of the film have been performed. Stable and unstable behaviors had been discerned, and results confirmed the existence of a threshold distance, for the static case, and a combination of oscillation parameters, for the dynamic situation, for which the jump of the liquid to contact the probe occurs. A theoretical analysis confirmed the existence of critical conditions separating the behavior regimes. This critical conditions indicate the role of the physical and geometric parameters in the system stability. For the dynamic case, preliminary results are reported and a qualitative interpretation of the phenomenon is formulated. In addition, AFM force and amplitude spectroscopy experiments had been performed and compared with the numerical results.