Detailed understanding of bubbles growing on a solid surface is a fundamental requirement in many technological domains, with particular application to water electrolysis in relation to the present-day socio-economic significance of clean energy transition. Evolution of bubbles at the electrode surface greatly determines the overall efficiency and throughput of an electrolysis cell. Bubbles residing on the electrode surface creates resistance to the flow of electric current and reduces the active electro-catalytic area. Therefore, fast removal of the bubbles is desirable for efficient operation. With this motivation, this dissertation aims to build deeper understanding of the bubble dynamics during the pre-detachment and detachment stage. To this end, single hydrogen bubbles grown on microelectrodes are chosen as the object of study. Thermocapillary and electric forces acting on an electrolytic bubble are introduced and a thorough account of the forces acting on the bubble is taken. A dynamical model of the bubble motion is developed. By means mathematical and physical modeling of the forces, working mechanism is provided for a novel mode of bubble detachment, namely oscillatory bubble detachment. The model predictions of oscillation parameters are in good correlation with experimental observations. Furthermore, the equation of motion of the bubble is shown to undergo bifurcation thus providing mathematical reasoning behind the existence of different detachment modes. A deeper look is taken specifically at the oscillatory mode. The electrolyte flow velocity is computed and compared with PTV based measurements. Force variation during one oscillation cycle is characterized and correlated with relevant geometric and operational parameters. Based on dynamical conditions of the bubble motion, the surface charge at the bubble interface is quantified. The calculated values match with literature values from bubble electrophoresis experiments. A detailed look is also taken at the effect of electrode size on the thermocapillary effect. The temperature and flow velocity field in the electrolyte is computed for various electrode size. Additional details regarding the flow structure were found. The location of the interfacial temperature hotspot was quantified. The current density distribution along the electrode surface was found to be strongly non-uniform. The Marangoni and the hydrodynamic force acting on the bubble was quantified at various electrode sizes. Further a model was developed to approximate the thermocapillary effect of a bubble on a large electrode. The location of temperature hotspot was found to be different when compared to bubbles on a microelectrode. This influences the Marangoni flow structure and also the Marangoni force on the bubble. Overall, this dissertation provides a systematic framework for characterizing forces acting on the bubble and investigating the dynamics of the bubble motion, which adds to our current understanding of bubble evolution and, takes one step towards predictive detachment models.

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Cette étude concerne la physique des écoulements convectifs résultant d’une instabilité d’évaporation de fluides binaires. Ce problème a de nombreuses applications, l’enrobage par centrifugation, le dépôt de films, les caloducs, etc, pour lesquels le changement de phase et la convection jouent un rôle prépondérant dans la conception et la qualité des procédés. Le système physique étudié est un mélange liquide sous sa propre vapeur, confiné par deux plaques conductrices de chaleur et des bords latéraux isolants. Les plaques sont utilisées pour appliquer un gradient thermique. Aucun gradient de concentration n’est imposé au système. Ces gradients sont induits par les différentes vitesses d’évaporation des composés. Dans ce système, il est important de comprendre comment la dynamique des fluides et les transferts de masse et de chaleur entrent en compétition pour la formation de structures. Le principal objectif de ce travail est d’identifier les conditions pour que le système évolue d’un état conductif vers un état de convection lorsque le gradient vertical de température dépasse une certaine valeur critique.Dans le système, la convection s’installe par trois mécanismes distincts : évaporation, gradients de densité et gradients de tension interfaciale. Trois forces convectives s’opposent aux effets de diffusion qui tendent à garder le système en état conductif. Le seuil d’apparition de la convection dépend de quelques variables, comme les dimensions du contenant, les propriétés thermophysiques des phases liquide et vapeur, la fraction massique, et les caractéristiques de perturbations. L’effet de chacune de ces variables sur le seuil est étudié en présence ou non de gravité.Pour représenter la physique, un modèle mathématique non linéaire complet est développé, basé sur les conservations de quantité de mouvement, d’énergie et de masse dans chaque phase avec les conditions aux limites appropriées. Le fluide binaire est composé de deux alcools légers comme l’éthanol et le sec-butanol. Dans les équations du modèle, la masse volumique ainsi que la tension interfaciale sont fonctions à le fois de la température et de la concentration. Pour la recherche du seuil de transition, les équations sont linéarisées autour d’un état de base connu. Dans notre cas, il s’agit de l’état conductif. Le système d’équations linéaires résultant est résolu par une méthode de collocation spectrale Chebyshev.Nous obtenons quatre résultats principaux. Premièrement, dans un système multi-composants sans gravitation, une instabilité n’apparaît que lorsque le système est chauffé du côté de la phase vapeur contrairement à un système mono-composant. Cela implique que, si on souhaite éviter les instabilités, il vaut mieux un apport de chaleur par la phase liquide en cas de processus d’évaporation en couches minces ou en micro-gravité.Deuxièmement, en présence de gravité, un système multi-composants peut devenir instable quelle que soit la direction du chauffage. Si la convection thermique est négligeable, alors nous montrons que le chauffage par la phase vapeur est la configuration la plus instable. Sinon, les deux modes de chauffage sont à même de produire une instabilité. Ce résultat implique que le gradient thermique appliqué doit être inférieur à une valeur seuil pour éviter les instabilités quelle que soit la direction du chauffage.Troisièmement, lorsque l’instabilité apparaît en absence de gravité, des structures n’apparaitront pas dans le cas de fluide pur mais apparaitront dans le cas d’un fluide multi-composants. De même, des structures apparaitront en présence de gravité en fonction du facteur d’aspect du confinement. Les facteurs d’aspect peuvent être choisis pour éviter des structures multi-cellulaires même en cas d’apparition d’instabilités durant l’évaporation.Enfin, des structures oscillantes ne sont pas prédites de façon générale malgré les effets opposés des convections solutale et thermique dans le problème d’évaporation. / This study focuses on understanding the physics of the convective flow resulting from evaporative instability in binary mixtures. This problem has wide applications in spin coating, film deposition, heat pipes, etc. where phase change and convection play a very important role in the design process and also final quality of the product. The physical system of interest consists of a liquid mixture underlying its own vapor sandwiched between two conducting plates with insulated sidewalls in a closed container. The conducting plates are used to apply a vertical temperature gradient while there is no applied concentration gradient in the system. Concentration gradients are induced by the different evaporation rate of the components. In this system it is important to understand how the fluid dynamics and the heat and mass transfer interact competitively to form patterns. The main goal of this work is to identify the conditions for the system going from the conductive no-flow state to a convection state when the applied vertical temperature gradient exceeds a certain value called the critical value.In the system convection arises due to three distinct phenomena; evaporation, density gradients, and interfacial tension gradients. These convective forces are opposed by the diffusion effects that try to keep the system in the conductive no-flow state. The onset point depends upon several variables such as the dimensions of the container, thermo-physical properties of both liquid and vapor phases, mass fraction, and the characteristic of the disturbance given to the system. The effects of each of these variables on the onset point are investigated both in the presence and in the absence of gravity. To represent the physics a complete non-linear mathematical model is developed including momentum, energy, and mass balances in both phases with appropriate boundary conditions. The binary mixture is assumed to be made up of two low weight alcohols such as ethanol and sec-butanol. In the modeling equations the density and the interfacial tension are taken to be function of both temperature and concentration. To identify the onset point the non-linear equations are linearized around a known base state. In this case the base state is the conductive no-flow state. The resulting set of linear equations is solved using a spectral Chebyshev collocation method. Four major results arise from this work. First, in a multi-component system in the absence of gravity, an instability arises only when the system is heated from the vapor side as opposed to evaporation in a single-component. The implication is that evaporative processes in thin layers or in micro-gravity are best conducted with heat from the liquid side if instabilities are to be avoided.Second, in the presence of gravity, a multi-component system may become unstable no matter the direction of heating. If thermal buoyancy is negligible then it is shown in this study that heating from the vapor side is the unstable arrangement. Otherwise either heating style can produce an instability. This result means that the applied temperature difference must be kept below a threshold in order to avoid flow instabilities no matter the heating direction.Third, whenever instability occurs in the absence of gravity, patterns will not result in the case of a pure component but may result in the case of multi-components. Likewise, patterns will result when gravity is taken into account provided the aspect ratio of the container lies in a suitable range. As a result, aspect ratios can be chosen to avoid multi-cellular patterns even if convective flow instabilities arise during evaporation.Lastly, oscillations are not ordinarily predicted despite opposing effects of solutaland thermal convection in the evaporation problem.

The flow in a layer of volatile fluid driven by a horizontal temperature gradient is a fundamental transport model for numerous evaporative passive cooling applications. When a thin film of a volatile liquid is subject to a horizontal temperature gradient, changes in the surface tension at the free surface lead to Marangoni stresses that drive the flow. In a thicker liquid layer, the flow is also affected by buoyancy. This thesis describes experimental studies of convection driven by a combined action of Marangoni stresses and buoyancy in simple and binary volatile liquid layers confined in a sealed rectangular cavity heated at one end and cooled at the other. Experiments with varying concentrations of noncondensables (i.e., air) ca were performed to investigate their effect on the phase change and heat and mass transport. In the simple liquid, thermocapillary stresses drive the liquid near the free surface away from the heated end. Varying ca is shown to strongly affect the stability of this buoyancy-thermocapillary flow for Marangoni numbers Ma = 290 - 3600 and dynamic Bond numbers BoD = 0.56 - 0.82: removing air suppresses transition to multicellular and unsteady flow. The results are compared with numerical simulations and linear stability analysis. In the binary liquid considered here, a methanol-water (MeOH-H2O) mixture, solutocapillary stresses drive the flow near the free surface towards the heated end. Four distinct flow regimes are identified for this complex flow driven by thermocapillarity, solutocapillarity, and buoyancy, and are summarized in a flow regime map as a function of ca and the liquid composition (MeOH concentration). At low ca, solutocapillary effects are strong enough to drive the liquid near the free surface towards the heated end over the entire liquid layer, suggesting that binary-fluid coolants could significantly reduce film dryout.

The aim of this PhD thesis is to find out mechanisms of the ripple initiation and formation in the chromium thin film on the glass substrate. To learn to control the ripple formation and to apply it for fabrication of diffraction gratings. In this thesis, the experimental and theoretical results of new self-organization effect of the metal thin film on the glass substrate under irradiation with a sequence of partially overlapping laser pulses are presented. The method for formation of the regular ripples and results on investigation of diffractive properties of the self-organized gratings is presented. Different types of metals are used in experiments in order to understand the reasons of regular structure formation in chromium film. A diverse behavior of the films under laser irradiation is observed depending on the metal when burst of partially overlapping pulses was applied. Experimental data is compared with simulations based on different physical phenomena in order to develop and confirm a model of ripple formation in thin chromium film under its irradiation with pulses of a nanosecond laser. The Plateau-Rayleigh instability of the cylindrical ridge formation during laser ablation appears to be the most probable process responsible for initiation of the ripple formation. The Marangoni convection of the molten metal from hot areas to cold is the stabilizing process of steady ripple formation. / Disertacijos darbo tikslas yra suprasti pagrindinius fizikinius mechanizmus, lemiančius raibulių susidarymą. Išmokti kontroliuoti raibulių formavimąsi. Panaudoti raibulių formavimąsi difrakcinių gardeliu gamybai. Rasti sąlygas, kada raibulių formavimosi galima išvengti, siekiant sumažinti kodinės stiklinės liniuotės periodą. Ištirti galimą raibulių formavimąsi skirtingų metalų dangose. Šioje daktaro disertacijoje pristatomi eksperimentiniai ir teoriniai rezultatai naujo savi-organizacijos reiškinio metalo dangos ant stiklo padėklo nanosekundinio lazerio į juostą sufokusuoto pluošto spinduliuotės poveikyje. Pristatomas naujas difrakcinių gardelių formavimo metodas panaudojant metalo savitvarką. Siekiant suprasti kas inicijuoja raibulių formavimąsi ir ar jis įmanomas visiems metalams, dangos apdribimas persiklojančiais lazerio impulsais aštriai į juostą sufokusuotu lazerio pluoštu išbandytas skirtingiems metalams. Skirtingas dangos elgesys stebimas kiekvienam metalui. Nagrinėjami pagrindiniai fizikiniai mechanizmai sukeliantys griežtai periodinių raibulių formavimąsi. Parodoma, kad raibulių formavimosi pradžia atsiranda dėl Plato-Reilio nestabilumo cilindrinės užvartos susidarymo metu. Taip pat parodoma, kad Marangoni konvekcija skystame metale yra pagrindinė jėga, lemianti nusistovėjusį periodinių raibulių formavimąsi.

Disertacijos darbo tikslas yra suprasti pagrindinius fizikinius mechanizmus, lemiančius raibulių susidarymą. Išmokti kontroliuoti raibulių formavimąsi. Panaudoti raibulių formavimąsi difrakcinių gardeliu gamybai. Rasti sąlygas, kada raibulių formavimosi galima išvengti, siekiant sumažinti kodinės stiklinės liniuotės periodą. Ištirti galimą raibulių formavimąsi skirtingų metalų dangose. Šioje daktaro disertacijoje pristatomi eksperimentiniai ir teoriniai rezultatai naujo savi-organizacijos reiškinio metalo dangos ant stiklo padėklo nanosekundinio lazerio į juostą sufokusuoto pluošto spinduliuotės poveikyje. Pristatomas naujas difrakcinių gardelių formavimo metodas panaudojant metalo savitvarką. Siekiant suprasti kas inicijuoja raibulių formavimąsi ir ar jis įmanomas visiems metalams, dangos apdribimas persiklojančiais lazerio impulsais aštriai į juostą sufokusuotu lazerio pluoštu išbandytas skirtingiems metalams. Skirtingas dangos elgesys stebimas kiekvienam metalui. Nagrinėjami pagrindiniai fizikiniai mechanizmai sukeliantys griežtai periodinių raibulių formavimąsi. Parodoma, kad raibulių formavimosi pradžia atsiranda dėl Plato-Reilio nestabilumo cilindrinės užvartos susidarymo metu. Taip pat parodoma, kad Marangoni konvekcija skystame metale yra pagrindinė jėga, lemianti nusistovėjusį periodinių raibulių formavimąsi. / The aim of this PhD thesis is to find out mechanisms of the ripple initiation and formation in the chromium thin film on the glass substrate. To learn to control the ripple formation and to apply it for fabrication of diffraction gratings. In this thesis, the experimental and theoretical results of new self-organization effect of the metal thin film on the glass substrate under irradiation with a sequence of partially overlapping laser pulses are presented. The method for formation of the regular ripples and results on investigation of diffractive properties of the self-organized gratings is presented. Different types of metals are used in experiments in order to understand the reasons of regular structure formation in chromium film. A diverse behavior of the films under laser irradiation is observed depending on the metal when burst of partially overlapping pulses was applied. Experimental data is compared with simulations based on different physical phenomena in order to develop and confirm a model of ripple formation in thin chromium film under its irradiation with pulses of a nanosecond laser. The Plateau-Rayleigh instability of the cylindrical ridge formation during laser ablation appears to be the most probable process responsible for initiation of the ripple formation. The Marangoni convection of the molten metal from hot areas to cold is the stabilizing process of steady ripple formation.

L’évaporation d’une solution solvant/soluté est un processus transitoire qui prend fin lorsque le solvant a totalement disparu. Le refroidissement créé par le changement de phase provoque des gradients à la fois thermiques et de concentration en solvant. Ces homogénéités diffusent ensuite dans l’épaisseur de la solution et sont susceptibles d’engendrer un écoulement fluide. L’origine de cette convection peut être liée à des variations de tension de surface ou de densité. Des travaux expérimentaux ont montré que l’épaisseur des dépôts issus de séchages de solutions solvant/soluté semblait pouvoir être corrélée avec les cellules de convection de la zone fluide. Une compréhension approfondie des phénomènes à l’origine de la convection devrait donc participer à un meilleur contrôle de la qualité des dépôts.Sur la base de travaux numériques et expérimentaux publiés, nous avons étudié l’apparition de la convection pour trois types de modèles représentant le processus d’évaporation d’une solution de Polyisobutylène-Toluène : un modèle purement thermique qui s’applique pour les temps courts, un modèle solutal qui est valable sur les temps longs et enfin un modèle couplé thermique/solutal qui représente les transferts sur l’ensemble de la gamme des temps étudiés. Le caractère transitoire de l’évaporation induit une difficulté pour caractériser la naissance de la convection à partir d’un régime de conduction. En effet, cette convection apparaît à partir d’un germe qui est une petite perturbation de la solution diffusive. Si l’amplitude de cette perturbation est trop faible, son amplification à des intensités suffisantes ne pourra pas avoir lieu avant la fin du régime transitoire et l’écoulement ne deviendra donc jamais convectif. Le rôle de la perturbation est donc primordial. Dans des travaux numériques antérieurs, cette perturbation a été imposée à l’état initial, généralement avec une distribution aléatoire du champ thermique ou de vitesse. Lors de cette thèse, nous avons opté pour un modèle plus physique, basé sur l’introduction d’un transfert thermique sur les parois latérales qui joue le rôle de perturbateur de l’écoulement diffusif transitoire.Dans cette thèse, nous avons établi par voie numérique les seuils de transition entre une solution diffusive et un écoulement convectif pour les modèles thermique, solutal et couplé, dans le cas d’une approximation bidimensionnelle du film liquide et des simulations pleinement tridimensionnelles. Des diagrammes spatio-temporels et l’étude des cellules à la surface libre par des reconstructions de Voronoï nous ont permis de mieux comprendre la naissance et la propagation des instabilités dans la solution fluide / The evaporation of a solvent/solute solution is a transient phenomenon which ends when the whole solvent has disappeared. Phase change generates a cooling of the liquid-gas interface, and consequently, it creates thermal and solutal gradients. These homogeneities spread in the core solution and produce, eventually, a fluid flow. This convection can be due to the surface tension and/or buoyancy variations. Experimental works have shown that some coating thicknesses stemming from drying processes are correlated to the size of the convection cells in the fluid region. A thorough understanding of the physical phenomena responsible to fluid convection should contribute to improve the control of deposit quality.Based on numerical and experimental works, we have studied the onset of convection for three kinds of models for the drying process of a Polyisobutylene-Toluène solution: A pure thermal model which is valid for short times, a solutal model devoted to the simulation of long times, only, and a thermal/solutal coupled model which takes into account the heat and mass transfer over a long time period of the evaporation process. The transient nature of the evaporation problem raises the issue of how to define the onset of the convective flow from a diffusive solution. Indeed, this flow motion occurs from a seed which is a small perturbation of the transient diffusive solution. If the perturbation is too weak, the necessary time interval for a significant growing of its magnitude will be greater than the time scale of the transient regime: thus the solution will never be considered as convective. Consequently, the influence of the perturbation is fundamental. In previous numerical works, this perturbation was imposed at the initial state, often through a random spatial distribution applied to the velocity or temperature field. In the present contribution, we have adopted a physical model where the adiabatic lateral walls have been replaced by diathermal walls: The local thermal inhomogeneities create a very weak flow acting as a small disturbance for the transient diffusive solution.In this thesis, we have developed a numerical model to evaluate the thresholds between the diffusive solutions and the convective flows, for the thermal, solutal and thermal/solutal coupled models, for two- and three-dimensional approximations of the Polyisobutylene-Toluène liquid film. Space-time diagrams and convective cell reconstructions at the liquid-gas interface by a Voronoï algorithm allowed us to get a better understanding of the way the disturbances propagate from the lateral walls for finally giving rise to a convective flow in the core fluid

This dissertation aims to better understand the evolution of single hydrogen gas bubbles evolved during the water electrolysis at microelectrodes. In particular, the growth and detachment processes were studied in detail experimentally by means of electrochemical and optical methods in terrestrial, micro-, and hypergravity conditions. The combination of microelectrode and sulfuric acid promoting the bubble coalescence results in a periodical growth and the detachment of single bubbles. This provides a systematic view on the phenomena under study. A shadowgraphy system was used to provide general insight into the bubble behaviour, while Particle Tracking Velocimetry (PTV) was used for the flow velocity measurements around the growing hydrogen bubble. By applying high electric potentials considerably exceeding that in industrial electrolysers, it is possible to analyse the evolution of hydrogen bubbles under extreme conditions and for a wide range of electrolyte concentrations, overall shedding more light on bubble dynamics in general, and especially the underlying balance of forces. The growth of single hydrogen bubbles at micro-electrodes was studied in an acidic electrolyte over a wide range of concentrations and cathodic potentials. New bubble growth regimes were identified which differ in terms of whether the bubble evolution proceeds in the presence of a monotonic or oscillatory variation in the electric current and a carpet of microbubbles underneath the bubble. Key features such as the growth law of the bubble radius, the dynamics of the microbubble carpet, the onset time of the oscillations and the oscillation frequencies were characterised as a function of the concentration and electric potential. Furthermore, the system's response to jumps in the cathodic potential was studied. The electrode, tilted to the horizon, promotes faster growth and, therefore, earlier detachment at the smaller volume of the bubble. During its evolution, the bubble moves laterally from the electrode centre, releasing the electrode area and enabling higher electric current, therefore faster hydrogen generation and bubble-bubble coalescence rates. The duration of the bubble position oscillations found on the horizontal electrode gradually reduces upon tilt angle increase, with an almost complete disappearance at 5°. Based on the analysis of the forces involved and their scaling with the concentration, potential and electric current, a sound hypothesis was formulated regarding the mechanisms underlying the micro-bubble carpet and oscillations. A detailed look was also taken on the dynamics of single hydrogen bubbles in microgravity during parabolic flights. Three bubble evolution scenarios were identified depending on the electric potential applied and the acid concentration. The dominant scenario, characterised by lateral detachment of the grown bubble, was studied in detail. For that purpose, the evolution of the bubble radius, electric current and bubble trajectories as well as the bubble lifetime were comprehensively addressed for different potentials and electrolyte concentrations. The bubble-bubble coalescence events, which are responsible for reversals of the direction of bubble motion, were particularly analysed. Finally, as parabolic flights also permit hypergravity conditions, a detailed comparison of the characteristic bubble phenomena at various levels of gravity was drawn. Finally, the Marangoni convection at the foot of hydrogen gas bubbles mainly induced by the thermocapillary effect is systematically studied during the bubble evolution, the bubble position oscillations, at horizontal and tilted electrodes both in terrestrial and hyper-g environments. The flow structure progressively modifies with the bubble evolution or during the bubble position oscillations, i.e. as per electric current and bubble geometry variation. The velocity increases both with the bubble size and the electric current magnitude. It reaches up to 50 mm/s and 125 mm/s shortly before the bubble detachment at horizontal and tilted electrodes, correspondingly. The bubble position oscillations characterised by the large variation of the electric current govern the velocity of around ~80 mm/s at the highest and ~40 mm/s at the lowest positions. In the case of tilted electrodes, both in terrestrial and hyper-g environments, the lateral movement of the bubble enables higher values of the current and, therefore, stronger convection. The non-homogeneous distribution of the electric current lines at the tilted electrode results in the asymmetrical Marangoni convection around the bubble. There is a certain limitation in terms of the maximal magnitude of the velocity at different tilt angles, governed by the optimal size of the bubble and electric current. At last, the effects of the particles and laser used for PTV measurements were shown to reduce the duration of the oscillations and to retard the bubble evolution. Both effects were considered during the measurements.