The ζ-adsorption isotherm was used along with Gibbsian thermodynamics to determine an expression for the surface tension of solid-vapour interface. This expression was examined at low pressures to predict the surface tension of solids in the absence of adsorption, γS0. The method indicated the same value of γS0 for a solid using different vapour adsorption isotherms. A method based on the system stability was developed to predict the contact angle. The findings indicated that the contact angle is a thermodynamic property which depends on the state of the system. Furthermore, the dependence of contact angle on the curvature of three-phase contact line was described by the adsorption at the solid-liquid interface without the introduction of line tension. The energy transport mechanisms during steady-state evaporation of water-sessile droplets were studied. By suppressing the buoyancy-driven convection, the active modes of energy transport were thermal conduction and thermocapillary convection. The experiments on Cu, Au (111) and PDMS showed that the dominant mode of energy transport varies along the liquid-vapor interface. Near the droplet apex, thermal conduction provides enough energy for the evaporation. However, close to three-phase contact line where most of the evaporation occurs, thermocapillary convection is by far the dominant mode of energy transport. In the evaporation experiments on PDMS, the measured directions of thermocapillary convection were opposite of the predicted ones by other studies, since the energy carried by thermocapillary convection was neglected in the previous studies. The study was followed by examination of temperature boundary condition and energy transport at the solid-liquid interface. It was concluded that there is an adsorbed layer at the solid-liquid interface with different thermal properties compared to those of bulk liquid phase. This layer causes a resistance (Kapitsa resistance) and consequently a temperature discontinuity at the adsorbed layer-bulk liquid interface. Due to the high resistance at this interface, only a small portion of energy conducted by solid substrate enters directly to the bulk liquid phase. The remainder was transported through the adsorbed layer to the three-phase contact line. This energy was then distributed along the liquid-vapour interface by thermocapillary convection to be consumed by the evaporation process.

The ζ-adsorption isotherm was used along with Gibbsian thermodynamics to determine an expression for the surface tension of solid-vapour interface. This expression was examined at low pressures to predict the surface tension of solids in the absence of adsorption, γS0. The method indicated the same value of γS0 for a solid using different vapour adsorption isotherms. A method based on the system stability was developed to predict the contact angle. The findings indicated that the contact angle is a thermodynamic property which depends on the state of the system. Furthermore, the dependence of contact angle on the curvature of three-phase contact line was described by the adsorption at the solid-liquid interface without the introduction of line tension. The energy transport mechanisms during steady-state evaporation of water-sessile droplets were studied. By suppressing the buoyancy-driven convection, the active modes of energy transport were thermal conduction and thermocapillary convection. The experiments on Cu, Au (111) and PDMS showed that the dominant mode of energy transport varies along the liquid-vapor interface. Near the droplet apex, thermal conduction provides enough energy for the evaporation. However, close to three-phase contact line where most of the evaporation occurs, thermocapillary convection is by far the dominant mode of energy transport. In the evaporation experiments on PDMS, the measured directions of thermocapillary convection were opposite of the predicted ones by other studies, since the energy carried by thermocapillary convection was neglected in the previous studies. The study was followed by examination of temperature boundary condition and energy transport at the solid-liquid interface. It was concluded that there is an adsorbed layer at the solid-liquid interface with different thermal properties compared to those of bulk liquid phase. This layer causes a resistance (Kapitsa resistance) and consequently a temperature discontinuity at the adsorbed layer-bulk liquid interface. Due to the high resistance at this interface, only a small portion of energy conducted by solid substrate enters directly to the bulk liquid phase. The remainder was transported through the adsorbed layer to the three-phase contact line. This energy was then distributed along the liquid-vapour interface by thermocapillary convection to be consumed by the evaporation process.

Dans cette thèse, la dynamique d'évaporation de gouttes sessiles de solutions salines sur des surfaces planes inertes et métalliques a été étudiée et le phénomène de corrosion pour les surfaces ferriques caractérisé. En premier lieu, nous nous sommes intéressés à la dynamique d'évaporation de gouttes sessiles salées sur des surfaces inertes pour une large gamme de concentrations en sel, d'humidité relatives, de tailles de goutte et d'angles de contact. Notre étude révèle les domaines de validité du modèle classique d'évaporation, processus contrôlé par la diffusion de la vapeur dans l'air et met en évidence l'impact de flux (de Marangoni) induits par des gradients de concentration (tension de surface) en sel sur la dynamique d'évaporation et les dépôts salins obtenus après évaporation de la goutte. De plus, nous nous sommes consacrés à l'évolution spatio-temporelle de gouttes sessiles de solutions salines sur des surfaces métalliques. Contrairement au modèle simplifié de la goutte d'Evans, nous avons montré que le processus de corrosion s'étend aux abords de la ligne de contact, avec la formation d'un film périphérique. La ligne triple est déstabilisée par des gradients de tension de surface induits par des variations de composition ionique au cours du processus de corrosion et la migration des cations vers la périphérie de la goutte. Enfin nous avons étudié le phénomène de corrosion du métal induit par l'évaporation de gouttes sessiles salées. Le processus de corrosion, en particulier la localisation des réactions anodiques et cathodiques sur la surface métallique en contact avec la goutte est corrélée à la distribution spatiale du sel au sein de la goutte s'évaporant. / In this thesis we investigate the evaporation behaviour of sessile droplets of aqueous saline solutions on planar inert and metallic surfaces and characterise the corrosion phenomenon for iron surfaces. First we study the evaporation behaviour of sessile salty droplets on inert surfaces for a wide range of salt concentrations, relative humidities, droplet sizes and contact angles. Our study reveals the range of validity of the well-accepted diffusion-controlled evaporation model and highlights the impact of salt concentration (surface tension) gradients driven Marangoni flows on the evaporation behaviour and the subsequent salt deposit patterns. Furthermore we study the spatial-temporal evolution of sessile droplets from saline solutions on metallic surfaces. In contrast to the simple, generally accepted Evans droplet model, we show that the corrosion spreads ahead of the macroscopic contact line with a peripheral film. The three-phase contact line is destabilized by surface tension gradients induced by ionic composition change during the course of the corrosion process and migrations of cations towards the droplet perimeter. Finally we investigate the corrosion behaviour under drying salty sessile droplets on metallic surfaces. The corrosion process, in particular the location of anodic and cathodic activities over the footprint droplet area is correlated to the spatial distribution of the salt inside the drying droplet.

We employ molecular dynamics simulations to investigate the evaporation process of nanosized droplets adsorbed on a substrate. Beads interacting with each other via Lennard-Jones (LJ) potentials are used to construct the simulation systems. The solid substrate contains 6 layers of beads forming a face-centered-cubic lattice. The bottom 3 layers are held rigid while the rest is kept at a constant temperature with a Langevin thermostat. A liquid droplet, consisting of LJ beads as well, is placed on top of the substrate. An appropriate amount of vapor beads are also supplied to the simulation box to help establish liquid-vapor equilibrium. To ensure adsorption, a stronger attraction is rendered between the droplet and a circular patch of 3 layers of beads at the center of the substrate surface while the rest of the substrate is made non-sticky for the fluid beads. During equilibration, the droplet and vapor are maintained at the same temperature as the thermalized substrate. After relaxation, the droplet adheres to the attractive patch as expected. Then a deletion zone is introduced into the top part of the vapor region. Fluid beads in this zone are removed at a given rate. To ensure that the evaporation dynamics and kinetics are properly captured, only the thermalized substrate is kept at the constant temperature during droplet evaporation. To carry out steady-state evaporation, the removed beads are reintroduced into a channel through the substrate and right below the droplet's center. These beads are then supplied to the droplet, compensating for the evaporation loss at the droplet surface. When the evaporation rate and the insertion rate are balanced, the system enters a steady state with the droplet undergoing continuous evaporation and its contact line pinned at the boundary of the attractive patch on the substrate. A one-to-one correspondence is found between the evaporation rate and the total number of fluid beads in the simulation box, as well as the contact angle of the droplet. Using this steady nonequilibrium system, we have mapped out the flow, temperature, and density fields inside and around the evaporating droplet as well as the local evaporation flux along the droplet surface with unprecedented resolutions. The results are used to test the existing theories on sessile droplet evaporation. / Master of Science / Droplet evaporation is a widespread natural phenomenon with numerous applications across various fields. While there has been extensive research on droplet evaporation, it remains a challenge to characterize the interior of the droplet and the local evaporation behavior on the droplet surface. Here we employ molecular dynamics (MD) simulation to model a nanosized droplet adsorbed on a substrate, which evaporates continuously while maintains a constant shape. This is realized by supplying the evaporated fluid back to the bottom of the droplet through an in-silico approach. Such a steady-evaporation system allows us to accurately map out the internal capillary flow of the evaporating droplet with a pinned contact line, where the droplet, vapor, and substrate meet. We find that local evaporation occurs faster near the contact line than at the apex of the droplet.

Present work is focused on the numerical study of evaporation of sessile liquid droplets on top of smooth solid substrates. The process of evaporation of a sessile liquid droplet has lots of different applications both in industry and research area. This process has been under study for many years, and still it is an actual problem, solution of which can give answers on some fundamental and practical questions. Instantaneous distribution of mass and heat fluxes inside and outside of an evaporating sessile droplet is studied in this research using computer simulations. The deduced dependences of instantaneous fluxes are applied for self-consistent calculations of time evolution of evaporating sessile droplets. The proposed theory of evaporating sessile droplets of liquid has been validated against available experimental data, and has shown a good agreement. Evaporation of surfactant solution droplets is studied experimentally. The theory, proposed for two stages of evaporation, fits experimental data well. An additional evaporation stage, specific for surfactant solutions, is observed and described. Mathematical modelling of this stage requires further research on surfactant adsorption and its influence on the value of receding contact angle. Numerical study of the evaporation of microdroplets is conducted in order to evaluate the significance of different evaporation mechanisms (diffusive and kinetic models of evaporation) and different physical phenomena (Kelvin s equation, latent heat of vaporization, thermal Marangoni convection, Stefan flow).

L’évaporation de gouttes de liquides contenant des particules non volatiles représente un phénomène largement présent dans la vie quotidienne, à l’image des traces laissées par le marc de café après séchage. L’étude de la morphologie des dépôts de particules présente un grand intérêt dans les domaines de la biologie et trouve de nombreuses applications dans l’industrie. De ce fait, elle a fait l’objet de nombreuses recherches durant les dernières décennies. Malgré les nombreuses récentes recherches sur les morphologies des dépôts de particules, les mécanismes les contrôlant restent encore non complétement expliqués. Certains facteurs influençant les morphologies des dépôts sont nombreux (température de substrats…) mais restent encore peu documentés dans la littérature. Cette étude expérimentale s’intéresse à l’influence de la température du substrat sur la morphologie des dépôts de nanoparticules après séchage de gouttes sessiles de liquides. L’augmentation de la température du substrat accélère le processus d’évaporation et entraine des morphologies de dépôts très différentes de celles obtenues sur des substrats à température ambiante. Dans cette étude, la microscopie combinée à la thermographie infrarouge et à l’interférométrie ont permis d’expliquer la dynamique de formation de dépôts. De plus, l’étude a permis d’analyser les effets d’autres paramètres sur la morphologie des dépôts, tel que la composition chimique du liquide composant les gouttes. / Evaporation of liquid droplets containing non-volatile solutes is an omnipresent phenomenon in daily life, e.g., coffee stains on solid surfaces. The study of pattern formation of the particles left after the evaporation of a sessile droplet has attracted the attention of many researchers during the past two decades due to the wide range of biological and industrial applications. Despite the significance of controlling the deposition morphology of droplets, the underlying mechanisms involved in pattern formation are not yet fully understood. There is a varied range of factors that affect the final deposition patterns and some, e.g., substrate temperature, are poorly studied in the literature. This experimental study investigates the effect of a wide range of substrate temperatures on the deposition patterns of nanoparticles from drying sessile droplets. Increasing substrate temperature and accelerating the drying process lead to the formation of the patterns not observed on non-heated substrates. This research elucidates the formation mechanisms of these patterns by optical microscopy, infrared thermography, and white light interferometry techniques. Furthermore, the combined effects of substrate temperature and other factors such as chemical composition of base fluid and particle size on the dried patterns are studied. The underlying mechanisms involved in the formation of the patterns influenced by the combined factors are also discussed and presented.

Droplet evaporation is ubiquitous to multitude of applications such as microfluidics, surface patterning and ink-jet printing. In many of the process like food processing tiny concentrations of suspended particles may alter the behavior of an evaporating droplet remarkably, leading to partially viscous and partially elastic dynamical characteristics. This, in turn, may lead to some striking mechanical instabilities, such as buckling and rupture. In this thesis, we provide a comprehensive physical description of the vaporization, self-assembly, agglomeration and buckling kinetics of sessile nanofluid droplet pinned on a hydrophobic substrate in various configurations. We have deciphered five distinct regimes of droplet lifecycle. Regime I-III consists of evaporation induced preferential agglomeration that leads to the formation of unique dome shaped inhomogeneous shell with stratified varying density liquid core. Regime IV involves capillary pressure initiated shell buckling and stress induced shell rupture. Regime V marks rupture induced cavity inception and growth. We provide a regime map explaining the droplet morphology and buckling characteristics for droplets evaporating on various substrates. Specifically, we find that final droplet volume and radius of curvature at buckling onset are universal functions of particle concentration. Furthermore, flow characteristics inside the heated and unheated droplets are investigated and found to be driven by the buoyancy effects. Velocity magnitudes are observed to increase by an order at higher temperatures with self-similar flow profiles. With an increase in the surface temperature, droplets exhibit buckling from multiple sites over a larger sector in the top half of the droplet. In addition, irrespective of the initial nanoparticle concentration and substrate temperature, hydrophobicity and roughness, growth of daughter cavity (subsequent to buckling) inside the droplet is found to be controlled by the solvent evaporation rate from the droplet periphery. The results are of great significance to a plethora of applications like DNA deposition and nanofabrication. In the next part of the thesis, we deploy the droplet in a rectangular channel. The rich physics governing the universality in the underlying dynamics remains grossly elusive. Here, we bring out hitherto unexplored universal features of the evaporation dynamics of a sessile droplet entrapped in a 3D confined fluidic environment. Increment in channel length delays the completion of the evaporation process and leads to unique spatio-temporal evaporation flux and internal flow. We show, through extensive set of experiments and theoretical formulations, that the evaporationtimescale for such a droplet can be represented by a unique function of the initial conditions. Moreover, using same theoretical considerations, we are able to trace and universally merge the volume evolution history of the droplets along with evaporation lifetimes, irrespective of the extent of confinement. These results are explained in the light of increase in vapor concentration inside the channel due to greater accumulation of water vapor on account of increased channel length. We have formulated a theoretical framework which introduces two key parameters namely an enhanced concentration of the vapor field in the vicinity of the confined droplet and a corresponding accumulation lengthscale over which the accumulated vapor relaxes to the ambient concentration. Lastly, we report the effect of confinement on particle agglomeration and buckling dynamics. Compared to unconfined scenario, we report non-intuitive suppression of rupturing beyond a critical confinement. We attribute this to confinement-induced dramatic alteration in the evaporating flux, leading to distinctive spatio-temporal characteristics of the internal flow leading to preferential particle transport and subsequent morphological transitions. We present a regime map quantifying buckling & non-buckling pathways. These results may turn out to be of profound importance towards achieving desired morphological features of a colloidal droplet, by aptly tuning the confinement space, initial particle concentration, as well as the initial droplet volume. These findings may have implications in designing functionalized droplet evaporation devices for emerging engineering and biomedical applications.

The present thesis deals with two-phase electrohydrodynamic simulations of bubble and droplet dynamics under externally applied electric fields. We used the Coupled Level-Set and Volume-of-fluid method (CLSVOF) and two different electrohydrody-namic formulations to study the process of bubble and drop formation from orifices and needles, the interactions of two conducting drops immersed in a dielectric medium, and the oscillations of sessile drops under two different ways of applying external elec-tric field. For the process of bubble formation in dielectric liquids due to the injection of air from submerged orifices and needles, we show that a non-uniform electric field pro-duces smaller bubbles while a uniform electric field changes only the bubble shape. We further explain the reason behind the bubble volume reduction under a non-uniform electric field. We show that the distribution of the electric stresses on the bubble inter-face is such that very high electric stresses act on the bubble base due to a non-uniform electric field. This causes a premature neck formation and bubble detachment lead-ing to the formation of smaller bubbles. We also observe that the non-uniform elec-tric stresses pull the bubble interface contact line inside the needle. With oscillatory electric fields, we show that a further reduction in bubble sizes is possible, but only at certain electric field oscillation frequencies. At other frequencies, bubbles bigger than those under a constant electric field of strength equal to the amplitude of the AC electric field, are produced. We further study the bubble oscillation modes under an oscillatory electric field. We implemented a Volume-of-fluid method based charge advection scheme which is charge conservative and non-diffusive. With the help of this scheme, we were able to simulate the electrohydrodynamic interactions of conducting-dielectric fluid pairs. For two conducting drops inside a dielectric fluid, we observe that they fail to coalesce when the strength of the applied electric field is beyond a critical value. We observe that the non-coalescence between the two drops occur due to the charge transfer upon drop-drop contact. The electric forces which initially bring the two drops closer, switch direction upon charge transfer and pull the drops away from each other. The factors governing the non-coalescence are the electric conductivity of the drop’s liquid which governs the time scale of charge transfer relative to the capillary time scale and the magnitude of the electric forces relative to the capillary and the viscous forces. Similar observations are recorded for the interactions of a charged conducting drop with an interface between a dielectric fluid and a conducting fluid which is the same as the drop’s liquid. For the case of a pendant conducting drop attached to a capillary and without any influx of liquid from the capillary, we observed that the drop undergoes oscillations at lower values of electric potential when subjected to a step change in the applied electric potential. At higher values of electric potential, we observed the phenomenon of cone-jet formation which results due to the accumulation of the electric charges and thus the electric forces at the drop tip. For the formation of a pendant conducting drops from a charged capillary due to liquid injection, we observed that the drops are elongated in presence of an electric field. This happens because the free charge which appears at the drop tip is attracted towards the grounded electrode. This also leads to the formation of elongated liquid threads which connect the drop to the capillary during drop detachment. We plotted the variation of total electric charge inside the drops with respect to time and found the charge increases steeply as the drop becomes elongated and moves towards the grounded electrode. For sessile drop oscillations under an alternating electric field, two different modes of operations are studied. In the so called ‘Contact mode’ case, the droplet is placed on a dielectric coated grounded electrode and the charged needle electrode remains in direct contact with the drop as it oscillates. In the ‘Non-contact mode’ case, the drop is placed directly on the grounded electrode and electric potential is applied to a needle electrode which now remains far from the drop. We show that the drop oscillations in the contact mode are caused by concentration of electric forces near the three phase contact line where the electric charge accumulates because of the repulsion from the needle. For the non-contact mode, we observe that the electric charge is attracted by the needle towards the drop apex resulting in a concentration of the electric forces in that region. So the drop oscillates due to the electric forces acting on a region near the drop tip. We also present the variation of the total electric charge inside the drop with respect to time for the two cases studied.