Understanding deformations during interaction of colloidal or nano droplets. has important implications in a wide range of applications such as flotation collection and emulsion stability. The present work is important and necessary because current models are unable to properly describe recent experimental results obtained using the Atomic Force Microscope (AFM) and Surface Force Apparatus (SFA). We revisit and improve on theories involving interacting deformable droplets. A detailed theoretical model of the experiments, which accounts for surface forces, hydrodynamic interactions, droplet deformation and AFM cantilever detection, has been developed. The new feature of the model is the use of matched asymptotic expansions to derive a new boundary condition at constant volume to obtain results that are independent of the size of the computational domain. The AFM experiments provide measurements of dynamical forces between two interacting droplets as well as between a drop and a colloidal particle of micrometre radii in solution when they are driven together and then are retracted from each other. The SFA experiments measure (time dependent) surface profiles of a millimetre size mercury drop interacting with a mica surface. Different configurations have been studied including mechanical and electrical perturbations to a thin film stabilized by double layer repulsion. Interesting experimental features were observed when approaching or retracting the mica from the mercury drop.

Le sujet de cette thèse s'inscrit dans le cadre de l'étude de la matière active. Ces systèmes sont composés de "particules actives" capables de s'organiser spontanément (transition de phase), et de manière autonome (sans application d'un champs extérieur), créant ainsi des dynamiques complexes comme les transition de phase dynamiques, synchronisation, instabilités etc...De nombreuses études tendent à montrer le rôle important des interactions entre particules active dans l'émergence de ces dynamiques. Nous avons abordé ces questions à travers l'étude d'une suspension de micro-algues Chlamydomonas reinhardtii. Il s'agit d'un système modèle de micro-nageur couramment utilisé pour l'étude des suspensions actives. Nous avons notamment étudié un phénomène de migration spontanée de la suspension, permettant de concentrer des micro-algues grâce à une source de lumière. Puis nous avons étudié le processus de dispersion d'un amas concentré de micro-algues. Nous avons notamment mis en évidence le rôle des interactions hydrodynamiques entre micro-algues dans cette dynamique de dispersion. / The subject of this thesis is part of the study of the active matter. These systems are composed of "active particles" capable of organizing themselves spontaneously (phase transition), and autonomously (without application of an external field), thus creating complex dynamics such as dynamical phase transition, synchronization, instabilities etc ...Numerous studies tend to show the important role of interactions between active particles in the emergence of these dynamics. We have addressed these issues through the study of a suspension of microalgae Chlamydomonas reinhardtii. It is a model system of micro-swimmer commonly used for the study of active suspensions. We studied in particular a phenomenon of spontaneous migration of the suspension, allowing to concentrate micro-algae thanks to a light source. We then studied the dispersal process of a concentrated bloom of microalgae. In particular, we have highlighted the role of hydrodynamic interactions between micro-algae in this dispersion dynamics.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20415号 / 工博第4352号 / 新制||工||1675(附属図書館) / 京都大学大学院工学研究科化学工学専攻 / (主査)教授 山本 量一, 教授 宮原 稔, 教授 稲室 隆二 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24646号 / 工博第5152号 / 新制||工||1984(附属図書館) / 京都大学大学院工学研究科化学工学専攻 / (主査)教授 山本 量一, 教授 外輪 健一郎, 教授 松坂 修二 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

The thermal velocity fluctuations of microscopic particles mediate the transition from microscopic statistical mechanics to macroscopic long-time diffusion. Prior to this work, detection methods lacked the sensitivity necessary to resolve motion at the length and time scales at which thermal velocity fluctuations occur. This dissertation details two experiments which resulted in velocity measurement of the thermal motion of dielectric microspheres suspended by an optical trap in gases and liquids. First, optical tweezers were used to trap glass microspheres in air over a wide range of pressures and a detection system was developed to track the trapped microspheres' trajectories with MHz bandwidth and <100 fm/rt(Hz) position sensitivity. Low-noise trajectory measurements allowed for observation of fluctuations in the instantaneous velocity of a trapped particle with a signal to noise ratio (SNR) of 26 dB, and provided direct verification of the equipartition theorem and of the Maxwell-Boltzmann velocity distribution for a single Brownian particle. Next, the detection technology was further optimized and used to track optically trapped silica and barium titanate glass microspheres in water and acetone with >50 MHz bandwidth and <3 fm/rt(Hz) sensitivity. Brownian motion in a liquid is influenced by hydrodynamic, time-retarded coupling between the particle and the fluid flow its motion generates. Our measurements allowed for instantaneous velocity measurement with an SNR of up to 16 dB and confirmed the Maxwell Boltzmann distribution for Brownian motion in a liquid. The measurements also revealed several unusual features predicted for Brownian motion in the regime of hydrodynamic coupling, including faster-than-exponential decay of the velocity autocorrelation function, correlation of the thermal force and non-zero cross-correlation between the particle's velocity and the thermal force preceding it. / text

The advent of microfluidic technology presents many difficulties but also many opportunities for separation science. Leveraging the potential of micro- and nanofluidic geometries is not only a matter of shrinking systems. Miniaturization can shift the relative importance of physical phenomena leading to separation. Theoretical and computational studies into the consequences of miniaturization are vital. Mesoscopic, multi-particle collision dynamics simulations are performed on polyelectrolytes and hard, colloidal solutes. Multiple variations of this simulation algorithm are implemented to achieve versatility for simulating non-equilibrium flows and dispersed solutes. The algorithm is extended to simulate the effects of finite Debye layers on the electro-hydrodynamics of electrophoresing macromolecules and used to study the electrophoresis of charged oligomers, polyelectrolytes and polyampholytes in both free-solution and confined geometries. Multi-particle collision dynamics simulations of hydrodynamic chromatography and field-flow fractionation are also performed to test the predictions of the derived unified, ideal retention theory. This unified, ideal retention predicts the transitions between multiple operational modes, including Faxén-mode FFF. Simulations and the theory show that increases in drag due to hydrodynamic interactions with microfluidic channel walls perturb the retention curves from the ideal predictions at large particle sizes. Further complications to field-flow fractionation including undesirable forces perpendicular to the flow direction, slip at channel walls and rectangular channel geometries are investigated. These theoretical studies lead to the proposal of several novel fractionation techniques, namely adverse-mode FFF, slip-mode FFF and polymer/depletant HC.

L'enjeu principal de cette thèse est de comprendre et prédire les propriétés structurales et rhéologiques de suspensions colloïdales en tenant compte d'éléments complexes tels que (1) les interactions hydrodynamiques (IHs) et/ou (2) des forces extérieures. Nous employons dans cette thèse deux des techniques numériques les plus rapides de la littérature: la dynamique brownienne standard (BD), pour les systèmes où les IHs peuvent être ignorées; et la technique hybride "stochastic rotation dynamics - molecular dynamics" (SRD-MD), pour les systèmes où les IHs doivent être incorporées.Trois systèmes colloïdaux différents ont été étudiés. Le premier est un système de sphères dures soumis à un cisaillement, où le but a été de vérifier que l'introduction des IHs dans la SRD-MD peut correctement reproduire la relation entre la viscosité et la fraction volumique. Les résultats de viscosité sont en accord avec les résultats connus, qu'ils soient analytiques, numériques et expérimentaux. Le second système consiste en une suspension d'alumine, pour laquelle les interactions sont décrites par la théorie DLVO (Derjaguin-Landau-Verwey-Overbeek). Les simulations montrent que le seuil de percolation (phi_c) diminue lorsque la profondeur du puits de potentiel augmente. De plus, nous observons que la prise en compte des IHs tend à former des structures plus allongées également, par rapport aux structures obtenues sans les IHs. Les valeurs de phi_c obtenues dans les simulations sont en bon accord avec celles estimées par le modèle de la contrainte seuil (YODEL) établi par Flatt et Bowen. Le troisième système comporte deux types de colloïdes qui interagissent par un potentiel de Yukawa. Ce système binaire est soumis à l'influence d'un mur attractif. Nous montrons que la présence d'un mur attractif peut altérer la structure cristalline des agrégats à la surface telle qu'une structure de type CsCl qui se forme au lieu de la structure métastable de type NaCl. Finalement, nous avons réalisé une étude préliminaire par SRD-MD de suspensions soumises à un cisaillement oscillant. Nous montrons que lorsque la suspension est soumise au cisaillement oscillant en même temps que l'agrégation se produit, des structures plus compactes se forment. / The main objective of this thesis is to predict and understand the structural and rheological properties of colloidal suspensions when (1) hydrodynamic interactions (HIs) and/or (2) external forces are present. We employ two of the fastest techniques in literature: Brownian dynamics (BD), for systems without HIs; and the hybrid "stochastic rotation dynamics - molecular dynamics" (SRD-MD) for systems with HIs. Three different systems were studied. The first is a system of hard spheres subjected to shear, where the goal was to ensure that SRD-MD can correctly reproduce the viscosity vs. volume fraction relationship. The results are consistent with known analytical, numerical and experimental data. The second system is an alumina suspension described by the DLVO theory (Derjaguin-Landau-Verwey-Overbeek). The simulations show that the percolation threshold (phi_c) decreases as the depth of the potential well increases. Moreover, we note that HIs tend to form more elongated structures compared to the systems without HIs. The phi_c values ​​obtained are in good agreement with those estimated by Flatt and Bowen's yield stress model (YODEL). The third system consists of binary colloids that interact by Yukawa potential and subjected to the influence of an attractive wall. We show that the presence of an attractive wall may alter the crystalline structures such that CsCl crystals are formed instead of the metastable NaCl crystals. Finally, we conducted a preliminary study of suspensions under an oscillating shear. We show that when the aggregation process suspension coincides with the oscillatory motion, more compact structures are formed.

The advent of microfluidic technology presents many difficulties but also many opportunities for separation science. Leveraging the potential of micro- and nanofluidic geometries is not only a matter of shrinking systems. Miniaturization can shift the relative importance of physical phenomena leading to separation. Theoretical and computational studies into the consequences of miniaturization are vital. Mesoscopic, multi-particle collision dynamics simulations are performed on polyelectrolytes and hard, colloidal solutes. Multiple variations of this simulation algorithm are implemented to achieve versatility for simulating non-equilibrium flows and dispersed solutes. The algorithm is extended to simulate the effects of finite Debye layers on the electro-hydrodynamics of electrophoresing macromolecules and used to study the electrophoresis of charged oligomers, polyelectrolytes and polyampholytes in both free-solution and confined geometries. Multi-particle collision dynamics simulations of hydrodynamic chromatography and field-flow fractionation are also performed to test the predictions of the derived unified, ideal retention theory. This unified, ideal retention predicts the transitions between multiple operational modes, including Faxén-mode FFF. Simulations and the theory show that increases in drag due to hydrodynamic interactions with microfluidic channel walls perturb the retention curves from the ideal predictions at large particle sizes. Further complications to field-flow fractionation including undesirable forces perpendicular to the flow direction, slip at channel walls and rectangular channel geometries are investigated. These theoretical studies lead to the proposal of several novel fractionation techniques, namely adverse-mode FFF, slip-mode FFF and polymer/depletant HC.

The Dynamic Positioning (DP) System is responsible for the station keeping of vessels in several offshore operations. The forces required by the DP System are distributed among the available thrusters by a thrust allocation algorithm which should be accurate, efficient and robust. This means that the effective forces match the required forces while power consumption is minimized. Additionally, in case of impossibility of generating the required forces the heading of the vessel is maintained to avoid increasing environmental forces. To accurately generate the required forces, the physical limitations of the thrusters and the hydrodynamic interactions must be considered. The hydrodynamic interactions are consistently modelled to accommodate the following typical effects: thruster-hull, thruster-current and thruster-thruster interaction. The result of this modeling is a nonlinear optimization problem, which is solved using the Sequential Quadratic Programming (SQP) algorithm with slack variables. The DP simulation carried out show that by considering the hydrodynamic interactions on thrust allocation the overall performance (controllability and power consumption) of the DP system is improved. / O Sistema de Posicionamento Dinâmico (DP) é responsável pela manutenção da posição de embarcações em diversas operações offshore. As forças requeridas pelo Sistema DP são distribuídas entre os propulsores disponíveis por um algoritmo de alocação de empuxo que deve ser preciso, eficiente e robusto. Isso significa que as forças efetivas correspondem às forças solicitadas, enquanto o consumo de energia é minimizado. Além disso, em caso de impossibilidade de gerar as forças necessárias, o rumo da embarcação é mantido para evitar o aumento das forças ambientais. Para gerar com precisão as forças necessárias, as limitações físicas dos propulsores e as interações hidrodinâmicas devem ser consideradas. As interações hidrodinâmicas são modeladas de forma consistente para acomodar os seguintes efeitos típicos: interação entre casco e propulsor, correnteza e propulsor e entre propulsores. O resultado desta modelagem é um problema de otimização não linear, que é resolvido usando o algoritmo de Programação Quadrática Sequencial (SQP) com variáveis de relaxamento. As simulações de posicionameto dinâmico realizadas mostram que, ao considerar as interações hidrodinâmicas na alocação de empuxo, o desempenho geral (controlabilidade e consumo de energia) do sistema DP melhora.

Micro- and nano-fluidic devices represent an exciting field with a wide range of possible applications. These devices, typically made of either silica or glass, ionize when placed in contact with water. Upon the application of an electric field parallel to the wall, a flow is produced by the charged walls called the electro-osmotic flow (EOF). Since electric fields are so often used as the driving force in these devices, EOF is an extremely common phenomenon. For this reason it is highly desirable to be able to control EOF in order to optimize the functioning of these devices. One method which is quite common experimentally is the modification of the surface using polymer coatings. These coatings can be either adsorbed or grafted, and charged or neutral. The first part of this thesis looks at the role of neutral adsorbed polymer coatings for the modulation of EOF. Specifically our simulation results show that for adsorbed coatings made from a dilute polymer solution the strongest quenching of EOF is found for an adsorption strength at the phase transition for adsorption of the polymers. Further evidence is presented that shows that by using a high density of polymer solution and a polymer which has a strong attraction to the surface a very thick polymer layer can be created. Next the case of charged grafted polymer coatings is examined. The variation of the EOF with respect to several key parameters which characterize the polymer coating is investigated and compared to theory. The prediction that the electrophoretic velocity of the polymers is the same as the EOF generated by a coating made up of the same polymers is found to be false though the two values are quite close. The last section presents results which show how hydrodynamic interactions in charged polymer systems can be modeled mesoscopically without the use of explicit charges by forcing a slip between monomers and the surrounding fluid. This model is validated by simulating some surprising predictions made in the literature such as an object with no net charge having a non-zero force when subjected to an electric field, and how the velocity can even be perpendicular to the applied electric field. The thesis can be roughly divided into two topics: using polymer coatings to modulate EOF, and the free solution electrophoresis of polyelectrolytes. While EOF and free solution electrophoresis might seem unrelated it will be shown that the concepts are the same in both cases. In fact while not investigated in this thesis, the mesoscopic simulation methods for electrophoresis could be applied to the modulation of EOF with polymer coatings allowing for the simulation of longer length and time scales or more complex systems such as heterogeneously grafted colloids.