<div>The evaporation of a liquid drop containing particles resting on a substrate have diverse industrial applications including inkjet printing, spray coating, fabrication of functional nanomaterials, disease diagnosis, among others. In addition to these wide ranging practical applications, the sessile drop evaporation can be observed in everyday life with dew drops, coffee spills, and the dry patterns of other beverages.</div><div><br></div><div>The self-assembly of particles during drop evaporation is a process that is affected by various factors, such as contact line (CL) behaviors, microfluidic flows, short-range interactions of particle-interface and particle-particle. Each of these factors are complicated enough to study, let alone the total effects on the process. The primary goal of this work is to investigate the influence of microfluidic flows and the particle-interface interaction, viz. the evaporation process was subject to a pinned CL and the particle-particle interaction was neglected under dilute particle concentration. </div><div>To accomplish this goal, the Galerkin/Finite Element Method (G/FEM) is used to solve for the flow, the temperature and the particle concentration profiles. </div><div><br></div><div><br></div><div>The complexity of the problems comes from various surface phenomena, one of which is the surface tension. The surface tension brings capillary force in the normal direction and capillary flow toward the CL, which results in the well-known coffee-ring effect. Moreover, the surface tension changes with temperature, surfactant concentration, etc. resulting in Marangoni stresses in the tangential direction. The Marangoni stress on the surface leads to circulations of flow inside the drop and the circulation can be either clockwise or counterclockwise depending on the direction of the stress. </div><div><br></div><div>When the Marangoni stress is merely caused by temperature change, the circulation direction changes not only in time but also in space. At late stage of evaporation, i.e. with a small contact angle (CA), multi-circulation flow profiles emerge. This flow profiles are featured with stagnation points and transition points. The stagnation points can be further categorized into capillary-induced stagnation points and Marangoni-induced stagnation points. By introducing the concept of capillary-induced stagnation points, the simulations reached agreement with experiments in terms of the radial location of the observed stagnation points.</div><div><br></div><div><br></div><div>The multi-circulation flow profiles implied regional segregation inside the drop. When a large circulation is observed in most part of the drop and a small circulation exists near the CL, particle concentrations are relatively uniform in each individual region but differs significantly across the two regions. Transition points are used to characterize the location of the regional segregation, which can be adjusted by Marangoni stress.</div><div><br></div><div><br></div><div>Marangoni circulations in different directions revealed distinct influences on particle distribution and deposition. First, while both directions facilitate even distribution of particles, a clockwise circulation strengthens CL accumulation for a small Marangoni stress. Second, a counterclockwise circulation with a small Marangoni stress impedes the deposition rate of particles, while a clockwise circulation facilities the deposition no matter how small the Marangoni stress is. This results is under a condition of a strong adsorption between particles and substrates. </div><div><br></div><div>The analysis and understanding of the above results are crucial to elucidating and controlling the final deposition patterns of particles. Thus, the focus of this research is to understand the combined effect of Marangoni stress and capillary flow on particle deposition during sessile drop evaporation.</div><div><br></div>

Le couplage entre processus physico-chimiques et le transfert de matière ou de chaleur peuvent donner lieu à des structures spatio-temporelles induites par des flux convectifs. Ces flux peuvent résulter de gradients de densité ou de tension superficielle et sont l'expression de la conversion d'énergie chimique en énergie mécanique. Quand la tension superficielle est à l'origine de ces mouvements, les effets correspondants sont connus sous le nom d'effet Marangoni. Ils jouent un rôle dans de nombreuses applications comme les procédés industriels d'extraction en amplifiant notablement la vitesse des processus de transfert. Les systèmes réels, trop complexes, doit être simplifiés par le développement de systèmes modèles afin d'établir au niveau fondamental la théorie sous-jacente à de telles dynamiques. Une succession de régimes dynamiques est observée lors de la dissolution d'une goutte de dichlorométhane (DCM) déposée sur une solution aqueuse de tensioactif (bromure de céthytriméthylammonium, CTAB). La succession remarquable de formes et de mouvements induits est déterminée par la concentration du tensioactif qui joue le rôle de paramètre de contrôle. A faible concentration en CTAB, un mouvement de translation ou des pulsations. Aux concentrations plus élevées, la goutte entre en rotation ou forme des structures polygonales. Bien que chimiquement simple, le système est complexe et implique plusieurs processus physico-chimiques : évaporation, solubilisation, transfert de tensioactifs, adsorption aux interfaces et agrégation. Les effets thermiques et de transport qui en résultent sont à l'origine des variations locales de tension interfaciale donnant lieu aux effets Marangoni. Nous nous sommes concentrés sur le comportement de la goutte quand la concentration en tensioactif conduit au régime de pulsation. Nous avons tout d'abord analysé le comportement de la goutte pendant la période d'induction qui précède le régime instable. L'analyse de la forme de la goutte corrélée à des mesures d'Imagerie par Vélocimétrie de Particules (PIV), ont montré que les flux créés par la dissolution du DCM limitent dans un premier temps l'adsorption du CTAB à l'interface eau/huile. L'instabilité ne démarre que lorsque la dissolution est réduite et que l'adsorption devient effective. La phase d'induction apparait comme une transition lente entre un coefficient d'étalement négatif (goutte ayant la forme d'une lentille) vers un coefficient d'étalement positif qui entraine l'expansion du film et les pulsations suivantes. Ces pulsations sont accompagnées par l'éjection de gouttelettes qui se forment à partir d'un bourrelet apparaissant au bord du film pendant la phase d'expansion. La rupture de ce bourrelet ressemble au phénomène connu sous le nom d'instabilité de Rayleigh-Plateau (RP). Cependant, la longueur d'onde caractéristique de formation des gouttelettes est deux fois plus faible que celle attendue dans le cas d'une instabilité de RP classique. L'origine de cet écart réside dans la modulation du bourrelet avant sa rupture. Cette modulation est en fait déterminée par des ondulations apparaissant à la surface du film et formant des rides en direction radiale. Ces rides pourraient être attribuées à un effet Marangoni thermique connu sous le nom d'instabilité de Bénard-Marangoni. Elles jouent également un rôle important dans la formation de la structure de démouillage hautement organisée décrite dans le dernier chapitre. L'ajout de CTAB dans la phase organique (goutte) donne lieu à des oscillations plus rapides qui, après une phase d'expansion de grande amplitude et l'éjection d'une couronne parfaite de gouttelettes, résultent lors de la phase de démouillage en une structure dont la forme rappelle une fleur. Une interprétation qualitative permettant d'identifier les principaux processus à l'œuvre et basée sur des mesures indépendantes de tension interfaciale apporte une explication des pulsations observées et de l'auto-organisation induite. / Far-from-equilibrium systems exhibit a wide variety of spatial and temporal patterns known as dissipative structures. The interplay between physico-chemical processes and mass or heat transfer can give rise to spatio-temporal structures induced by convective flows. These flows may result from density or surface tension gradients. They are the expression of the conversion from chemical into mechanical energy. When surface tension is the driving force, the corresponding effects are known as Marangoni effects. They are at play in numerous applications as extraction processes, oil recovery, and chemical reactors at all scales and noticeably modify transfer rates. The complexity of real systems deserves the development of model systems, essentials to settle, on a fundamental level, the theory governing the related dynamics. A succession of dynamical regimes is observed during the dissolution of a dichloromethane drop deposited on aqueous solutions of a cationic surfactant (cetyltrimethylammonium bromide, CTAB). The remarkable range of shapes and motion patterns that emerges is related to the surfactant concentration, which is used as a control parameter. For low surfactant concentrations, we observe translational motion and pulsations of the drop. At intermediate concentrations the drop transforms and starts to rotate. At higher concentrations polygonal shapes are observed. Although chemically simple and of easy implementation, the system is relatively complex and involves several processes: evaporation, solubilization, surfactant mass transfer, interfacial adsorption and self-aggregation. Thermal and transport effects induced are at the origin of local variations of interfacial tension leading to the Marangoni flows. In this thesis, we focused on the behavior of the dichloromethane drop when the aqueous surfactant concentration (0.5 mM) leads to the pulsating regime. At this concentration, we have first analyzed the behavior of the drop during the induction period that precedes the instable regime. Drop shape analysis, correlated to Particle Image Velocimetry (PIV) measurements, showed that dissolution flows initially hinder adsorption of CTAB at the water/oil interface. The instability is only triggered when dissolution is reduced and water/oil adsorption becomes effective. The induction period appears as a slow transition from an initial negative spreading coefficient (a lens shape drop) towards a positive spreading coefficient that triggers film expansion and following pulsations. These pulsations are accompanied by the ejection of smaller droplets which are formed from a toroidal rim that is created during the expanding phase of the drop. The break-up of this toroidal rim, resembles to what is known as the Rayleigh-Plateau (RP) instability. Nevertheless, the observed characteristic wavelength is a factor of 2 too small in respect to the classical RP instability. We have found the origin of this discrepancy in the fact that modulations that appear on the rim before it transforms into droplets are settled by deformations arising at the surface of the expanding film. They appear as wrinkles that form in the film and may be related to thermal Marangoni effects known as Benard-Marangoni instability. These wrinkles play an important part in the highly organized dewetting structure described in the last chapter of the thesis. The addition of CTAB also in the organic (drop) phase leads to faster pulsations which, after a very high amplitude expanding stage and the ejection of a perfect crown of droplets, result during the film receding stage in the formation of a pattern which symmetry is reminiscent of a flower. A qualitative interpretation aimed at identifying the main processes at play and based on independent surface tension data gives a consistent explanation of the observed pulsations and related self-organized patterns.

Les bactéries se répandent aux interfaces en formant des colonies, qui peuvent être considérées comme des suspensions denses actives. L'objet de cette thèse est le développement et l'analyse de modèles simples pour élucider le rôle des phénomènes physico-chimiques et passifs - tels que l'osmose, la tension de surface et le mouillage - dans l'expansion des colonies bactériennes aux interfaces solide/air. Les modèles sont basés sur une description hydrodynamique des couches minces de suspensions liquides, qui est complété par des processus bioactifs.Dans un premier temps, nous nous sommes intéressés à l'expansion osmotique des biofilms. Dans ce mécanisme, la bactérie sécrète une matrice polymérique qui agit comme un osmolyte et entraîne un afflux d'eau, riche en nutriments, du substrat humide vers le biofilm. Nous avons constaté que la mouillabilité du substrat est une des déterminantes principales de la vitesse d'expansion du biofilm. En-dessous d'une mouillabilité critique l'expansion s'interrompt, bien que la colonie soit biologiquement active. Cependant, une légère réduction de la tension de surface et une amélioration de la mouillabilité qui en résulte suffisent à induire un étalement continu. Les bactéries peuvent activement contrôler la tension de surface par la production de bio-surfactants.Dans un deuxième temps, nous avons étudié l'expansion de colonies bactériennes aidée par des molécules biologiques tensioactives auto-produites. Dans ce mécanisme, des flux de Marangoni résultant d'une concentration non uniforme de molécules tensioactives aux bords de la colonie peuvent favoriser l'expansion coopérative et provoquer une instabilité de la forme axi-symétrique des colonies bactériennes. Notre modèle nous a permis de reproduire quatre modes de développement différentes, à savoir l'étalement arrêté et continu des colonies circulaires, l'étalement des colonies avec des bords légèrement modulées et la formation de doigts prononcés.Dans la dernière partie, nous avons fait un premier pas vers l'incorporation de la motilité actif des bactéries dans notre modèle et présentons donc un modèle phénoménologique pour un film mince active. / Bacteria colonise interfaces by the formation of dense aggregates. In this thesis, we develop and analyse simple models to clarify the role of passive physico-chemical forces and processes - such as osmosis, surface tension effects and wettability - in the spreading of bacterial colonies at solid-air interfaces. The models are based on a hydrodynamic description for thin films of liquid suspensions that is supplemented by bioactive processes.We first focus on the osmotic spreading mechanism of bacterial colonies that relies on the generation of osmotic pressure gradients. The bacteria secrete a polymeric matrix which acts as an osmolyte and triggers the influx of nutrient-rich water from the moist substrate into the colony. We find that wettability crucially affects the spreading dynamics. At low wettability, the lateral expansion of the colony is arrested, albeit the colony is biologically active. However, a small reduction of the surface tension and the resulting improvement of the wettability suffices to induce continuous spreading. This can, e.g., result from the production of bio-surfactants by the bacteria.Next, we study passive liquid films covered by insoluble surfactants before developing a model for the surfactant-driven spreading of bacterial colonies. In this spreading mechanism, Marangoni fluxes arising due to a non-uniform surfactant concentration at the edges of the colony drive cooperative spreading and may cause an instability of the circular colony shape. We find that variations in wettability and surfactant production suffice to reproduce four different types of colony growth, namely, arrested and continuous spreading of circular colonies, slightly modulated front lines and the formation of pronounced fingers.In the final part, we take a first step towards the incorporation of active collective bacterial motion in the employed thin-film framework and present a phenomenologically derived model for active polar films.

This thesis examines the mechanisms of magnetic particle deposition and retention in human airways for magnetically targeted drug delivery. As this is a novel application, fundamental studies were performed to establish the necessary background knowledge for further development. Magnetic particle deposition from an aerosol in simulated airway conditions was studied using numerical and experimental models. The model results showed qualitative agreement; discrepancies were due to particle aggregation, which enhances deposition. Aerosol flow rate had a limited effect; the main factor in effective deposition was the proximity of the particle trajectories to the magnets. This spatial bias shows the importance of particle distribution in the flow as well as magnetic field geometry. These studies demonstrated the feasibility of capturing magnet particles from aerosol in airway conditions. For retention, clearance of particles due to motion of the mucus lining of the airways must be overcome. Particle retention was studied in vitro using various liquids to simulate mucus and identify relevant parameters. An ex vivo animal tissue model was used to demonstrate feasibility. Retention of 3-5 m diameter iron particles was achieved at reduced liquid/mucus viscosities. Larger (~100 m) particles were retained at normal mucus viscosities. The size dependence shows that particle aggregation after deposition is crucial for effective retention. In vitro retention experiments showed aggregate size is correlated with liquid viscosity, i.e. formation of aggregates is limited by forces opposing particle motion along the mucus layer interface. To determine these forces, particle motion on various air-liquid interfaces, chosen to simulate different mucus properties in isolation, was studied. When surfactants are present, as in the mucus layer, particle motion is limited by a velocity-dependent surface tension gradient as well as viscous drag. Pulling particles through the mucus layer into the tissue beneath was also considered as a potential retention strategy. The force required to pull particles through the mucus layer was also studied using various liquids to simulate mucus properties. In addition to the surface tension force holding the particles at the interface, hydrodynamic forces must be overcome to pull particles into or out of a liquid film such as the mucus layer.

A droplet may be prevented from wetting a solid surface by the existence of a lubricating film of air, driven by theromcapillary convection, between liquid and solid surfaces. The noncontact nature and the load-carrying capability of a nonwetting droplet lead to potential engineering applications, e.g., low-friction bearings. The present research consists of two thrusts. The first is aimed at quantifying nonwetting-system failures (film and pinning) triggered by application of a mechanical load, gaining insights to failure mechanisms. Experimental results show that film failure occurs over a wide range of droplet volumes when the temperature difference between the droplet and the plate, the driving potential of the free-surface motion, is small. Interferometric observations reveal flow instability just prior to film failure, with the growth of a nonaxisymmetric disturbance on a free surface (m = 1). Pinning failure becomes more prevalent as the temperature difference is increased, stabilizing the film flow. As part of the present investigation, a system was devised, allowing an oscillating free-surface to be reconstructed from a series of interferograms. The dynamic responses of the free surface reveal mode coupling, with harmonics of the input frequency excited through nonlinearity. The second thrust of the research succeeded in levitating and translating a droplet using the mechanism of permanent nonwetting. In this scheme, the droplet is heated by a CO2 laser and is placed above a cooled glass surface in order to drive the lubricating film that supports the weight of the drop. Furthermore, the position of the droplet can be controlled by moving the heating location, which leads to an asymmetry of the flow fields, driving air from the cooler-end of the droplet and propelling it towards the heat source. These demonstrations suggest the techniques potential use as a liquid-delivery scheme in a Lab-On-a-Chip system. Modeling is carried out to estimate propulsive forces on the droplet and to explain oscillatory behavior observed when excessive heating is applied on the drop. The concept to sandwich a droplet between two plates, a necessary configuration for levitating smaller droplets (less than mm-scale), is also discussed.

No description available.

Au cours des dernières années, les exigences croissantes en matière de dissipation thermique à haut rendement pour la microélectronique, les engins spatiaux, les réacteurs nucléaires, etc., encouragent le développement d'échangeurs de chaleur de nouvelle génération. Le caloduc est l’un des équipements de refroidissement efficaces et potentiels. La plupart du transfert de masse et de chaleur se fait au niveau de la micro-région près de la ligne triple de contact (solide, liquide, vapeur), qui est essentielle à l'amélioration de la performance thermique du caloduc. Cette étude se concentre sur le processus d'évaporation de gouttes sessiles de deux nouveaux fluides de travail (solution binaire et nanofluide), qui possèdent une micro-région similaire à celle du caloduc. Le flux de Marangoni induit par le gradient de concentration et la conductivité thermique exceptionnelle devraient améliorer significativement le débit evaporé du mélange alcool-eau et du nanofluide de graphène, respectivement. Une combinaison de techniques acoustiques et infrarouges est développée pour suivre la variation de la concentration d'alcool pendant l'évaporation des gouttes des mélanges 1-butanol-eau et éthanol-eau. Selon l'observation du comportement d'évaporation à différentes températures du substrat, une série d'équations empiriques est suggérée pour prédire le taux d'évaporation de la solution binaire de 1-butanol-eau en considérant l'effet Marangoni thermal et solutal. De plus, l'effet de la PEGylation, de la concentration des nanoparticules et de la température du substrat sur l'évaporation de gouttes de graphène nanofluide est étudié par des méthodes microscopiques, optiques et infrarouges. Les résultats expérimentaux et l'analyse thermodynamique peuvent contribuer à la compréhension complète du mécanisme impliqué concernant les performances d'évaporation du nanofluide de graphène. / In recent years, increasing requirement in high efficient heat dissipation for micro-electronics, spacecraft, nuclear reactors etc., encourage the development of next generation heat exchanger. Heat pipe is one of potential effective cooling equipments and most of mass and heat transfer take place at micro-region near triple phase (solid, liquid, vapor) contact line of working fluid, which is essential to thermal performance improvement of heat pipe. This study focuses on the evaporation process of sessile droplets of two novel working fluids (binary solution and nanofluid), which possess similar micro-region to that in heat pipe. Concentration gradient induced Marangoni flow and exceptional thermal conductivity are expected to significantly enhance evaporation rate of alcohol-water mixture and graphene nanofluid, respectively. A combination of acoustic and infrared techniques is developed to track alcohol concentration variation during evaporation of 1-butanol and ethanol aqueous droplets. According to observation of evaporation behavior at different substrate temperature, a series of empirical equations is suggested to predict evaporation rate of 1-butanol-water binary solution droplet considering thermal and solutal Marangoni effect. In addition, the effect of PEGylation, nanoparticle concentration and substrate temperature on drop evaporation of graphene nanofluid are investigated by microscopic, optical and infrared methods. Experimental results and thermodynamic analysis can contribute to the full understanding of involved mechanism concerning evaporation performance of graphene nanofluid.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19706号 / 工博第4161号 / 新制||工||1642(附属図書館) / 32742 / 京都大学大学院工学研究科原子核工学専攻 / (主査)教授 功刀 資彰, 教授 杉本 純, 教授 福山 淳 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

The study presented in this dissertation concerns the evaporation, in normal ambient conditions, of sessile droplets (pinned and freely receding) of various HFE liquids (instead of the widely used water), which are considered so far as environmentally friendly and are often used as heat-transfer fluids in thermal management applications. They are pure perfectly-wetting and volatile liquids with low thermal conductivity and high vapor density. These properties affect in their own way many aspects concerning droplet evaporation such as the evaporation-induced contact angles, evaporation rate of a droplet, contact line pinning and Marangoni flow, all of which are treated in the present dissertation.<p>In general, the thesis starts with a general introduction including but not limited to sessile droplets (Chapter 1). In Chapter 2 we provide a general overview of capillarity-related concepts. Then, in Chapter 3 we present the interferometric setup, along with the liquids and the substrate that is used in the experiments, and also explain the reasons why this particular method is chosen. In Chapter 4 we address, among others, the issue of evaporation-induced contact angles under complete wetting conditions. The behavior of the global evaporation rate is also examined here, whereas in Chapter 5 we discuss the influence of thermocapillary stresses on the shape of strongly evaporating droplets. Finally, before concluding in Chapter 7, we address in Chapter 6 the still open question of the influence of non-equilibrium effects, such as evaporation, on the contact-line pinning at a sharp edge, a phenomenon usually described in the framework of equilibrium thermodynamics. The experimental results obtained are also compared with the predictions of existing theoretical models giving rise to interesting conclusions and promising perspectives for future research.<p> / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

No description available.