Complex materials via colloidal crystallization

The work presented in this thesis deals with complex materials, which were obtained by self-assembly of monodisperse colloidal particles, also called colloidal crystallization. Two main fields of interest were investigated, the first dealing with the fabrication of colloidal monolayers and nanostructures, which derive there from. The second turned the focus on the phononic properties of colloidal particles, crystals, and glasses. For the fabrication of colloidal monolayers a method is introduced, which is based on the sparse distribution of dry colloidal particles on a parent substrate. In the ensuing floating step the colloidal monolayer assembles readily at the three-phase-contact line, giving a 2D hexagonally ordered film under the right conditions. The unique feature of this fabrication process is an anisotropic shrinkage, which occurs alongside with the floating step. This phenomenon is exploited for the tailored structuring of colloidal monolayers, leading to designed hetero-monolayers by inkjet printing. Furthermore, the mechanical stability of the floating monolayers allows the deposition on hydrophobic substrates, which enables the fabrication of ultraflat nanostructured surfaces. Densely packed arrays of crescent shaped nanoparticles have also been synthesized. It is possible to stack those arrays in a 3D manner allowing to mutually orientate the individual layers. In a step towards 3D mesoporous materials a methodology to synthesize hierarchically structured inverse opals is introduced. The deposition of colloidal particles in the free voids of a host inverse opal allows for the fabrication of composite inverse opals on two length scales. The phononic properties of colloidal crystals and films are characterized by Brillouin light scattering (BLS). At first the resonant modes of colloidal particles consisting of polystyrene, a copolymer of methylmethacrylate and butylacrylate, or of a silica core-PMMA shell topography are investigated, giving insight into their individual mechanical properties. The infiltration of colloidal films with an index matching liquid allows measuring the phonon dispersion relation. This leads to the assignment of band gaps to the material under investigation. Here, two band gaps could be found, one originating from the fcc order in the colloidal crystal (Bragg gap), the other stemming from the vibrational eigenmodes of the colloidal particles (hybridization gap).

Thermal Casimir effect at fluid interfaces: Fluctuation-induced forces between anisotropic colloids

We study the effective interaction between two ellipsoidal particles at the interface of two fluid phases which are mediated by thermal fluctuations of the interface. Within a coarse-grained picture, the properties of fluid interfaces are very well described by an effective capillary wave Hamiltonian which governs both the equilibrium interface configuration and the thermal fluctuations (capillary waves) around this equilibrium (or mean-field) position. As postulated by the Goldstone theorem the capillary waves are long-range correlated. The interface breaks the continuous translational symmetry of the system, and in the limit of vanishing external fields - like gravity - it has to be accompanied by easily excitable long wavelength (Goldstone) modes – precisely the capillary waves. In this system the restriction of the long-ranged interface fluctuations by particles gives rise to fluctuation-induced forces which are equivalent to interactions of Casimir type and which are anisotropic in the interface plane. Since the position and the orientation of the colloids with respect to the interface normal may also fluctuate, this system is an example for the Casimir effect with fluctuating boundary conditions. In the approach taken here, the Casimir interaction is rewritten as the interaction between fluctuating multipole moments of an auxiliary charge density-like field defined on the area enclosed by the contact lines. These fluctuations are coupled to fluctuations of multipole moments of the contact line position (due to the possible position and orientational fluctuations of the colloids). We obtain explicit expressions for the behavior of the Casimir interaction at large distances for arbitrary ellipsoid aspect ratios. If colloid fluctuations are suppressed, the Casimir interaction at large distances is isotropic, attractive and long ranged (double-logarithmic in the distance). If, however, colloid fluctuations are included, the Casimir interaction at large distances changes to a power law in the inverse distance and becomes anisotropic. The leading power is 4 if only vertical fluctuations of the colloid center are allowed, and it becomes 8 if also orientational fluctuations are included.

Dynamic wetting of complex liquids

A simple dependency between contact angle θ and velocity or surface tension has been predicted for the wetting and dewetting behavior of simple liquids. According to the hydrodynamic theory, this dependency was described by Cox and Voinov as θ ∼ Ca^(1/3) (Ca: Capillary number). For more complex liquids like surfactant solutions, this prediction is not directly given.rnHere I present a rotating drum setup for studying wetting/dewetting processes of surfactant solutions on the basis of velocity-dependent contact angle measurements. With this new setup I showed that surfactant solutions do not follow the predicted Cox-Voinov relation, but showed a stronger contact angle dependency on surface tension. All surfactants independent of their charge showed this difference from the prediction so that electrostatic interactions as a reason could be excluded. Instead, I propose the formation of a surface tension gradient close to the three-phase contact line as the main reason for the strong contact angle decrease with increasing surfactant concentration. Surface tension gradients are not only formed locally close to the three-phase contact line, but also globally along the air-liquid interface due to the continuous creation/destruction of the interface by the drum moving out of/into the liquid. By systematically hindering the equilibration routes of the global gradient along the interface and/or through the bulk, I was able to show that the setup geometry is also important for the wetting/dewetting of surfactant solutions. Further, surface properties like roughness or chemical homogeneity of the wetted/dewetted substrate influence the wetting/dewetting behavior of the liquid, i. e. the three-phase contact line is differently pinned on rough/smooth or homogeneous/inhomogeneous surfaces. Altogether I showed that the wetting/dewetting of surfactant solutions did not depend on the surfactant type (anionic, cationic, or non-ionic) but on the surfactant concentration and strength, the setup geometry, and the surface properties.rnSurfactants do not only influence the wetting/dewetting behavior of liquids, but also the impact behavior of drops on free-standing films or solutions. In a further part of this work, I dealt with the stability of the air cushion between drop and film/solution. To allow coalescence between drop and substrate, the air cushion has to vanish. In the presence of surfactants, the vanishing of the air is slowed down due to a change in the boundary condition from slip to no-slip, i. e. coalescence is suppressed or slowed down in the presence of surfactant.

Bislug flow in circular and noncircular channels and the role of interface stretching on energy dissipation

The area of microfluidics has increased in popularity with such fields as MEMS, microreactors, microscaleheat exchangers, etc. A comprehensive understanding of dissipation mechanisms for fluid flow in microchannels is required to accurately predict the behavior in these small systems. Tests were performed using a constant pressure potential created by two immiscible fluids juxtaposed in a microchannel. This study focused on the flow and dissipation mechanisms in round and square microchannels. There are four major dissipation mechanisms in slug flow; wall shear, dissipation at the contact line, menisci interaction and the stretching of the interface. A force balance between the internal driving potential, viscous drag and interface stretching was used to develop a model for the prediction of the velocity of a bislug in a microchannel. Interface stretching is a dissipation mechanism that has been included due to the unique system properties and becomes increasingly more important as the bislug decreases in length.

Análisis de la durabilidad de la cubierta plana invertida, a través del estudio de las interacciones e incompatibilidades entre las membranas sintéticas y el poliestireno extrusionado

La cubierta plana invertida se forma, cuando sobre una membrana impermeable se coloca un aislamiento térmico. Estos materiales pueden separarse con capas auxiliares que impiden el contacto directo entre ellos. Muchos de los materiales que forman esta solución constructiva pueden ser polímeros, como lo son algunas membranas impermeables, las capas auxiliares separadoras o el poliestireno extrusionado (XPS). La mayoría de los polímeros son incompatibles entre sí, por lo que en esta tesis se plantea como hipótesis la posibilidad de que se produzcan interacciones e incompatibilidades entre algunos de estos materiales. Por ello se hace una búsqueda bibliográfica y documental de otras investigaciones que pudieran estar relacionadas con el tema, y se estudian y analizan normas y documentación facilitada por fabricantes. Sin embargo, tras consultar toda la bibliografía y documentación que se referencia en esta tesis doctoral, no fue encontrado ningún trabajo de investigación sobre la influencia de la interacción entre los materiales que componen las cubiertas planas invertidas, y de cómo afecta esta a la durabilidad de las mismas. El propósito de esta tesis es el análisis de la durabilidad de la cubierta plana invertida, desde el punto de vista de las interacciones e incompatibilidades que pueden producirse entre los materiales formantes de esta solución constructiva. Además de este objetivo general, se estudian alternativas que puedan prolongar el ciclo de vida de la cubierta plana invertida. Para ello, se desarrolla un plan experimental con el fin de analizar dichas incompatibilidades, y estudiar los factores que las condicionan. Algunos de los resultados obtenidos, muestran que determinadas láminas impermeables utilizadas normalmente para la construcción de cubiertas planas, pueden interactuar con el XPS y sufrir deterioro. El contacto con el mismo, la incorrecta separación, la presión y el calor, son factores determinantes para que se produzca deterioro. Se puede señalar como una de las conclusiones de esta investigación, que la protección térmica que proporciona el XPS a la cubierta plana invertida, puede no ser suficiente (dependiendo del espesor del mismo, y de la ubicación de la cubierta fundamentalmente), para reducir la cantidad de calor que alcanza la línea de contacto entre los materiales, y por tanto paliar las interacciones que se producen. Además, aunque los geotextiles utilizados como capas auxiliares separadoras, en los gramajes por metro cuadrado, recomendados por algunas de las normas reguladoras de este tipo de cubiertas minoran las interacciones, estas siguen produciéndose. ABSTRACT The inverted flat roof is formed from a waterproofing membrane on which the thermal insulation is placed. These materials may be separated with auxiliary layers, which prevent the direct contact between them. Many of the materials forming this constructive solution can be polymers, such as some waterproofing membranes, the auxiliary separating layers, or the extruded polystyrene board (XPS). Most polymers are incompatible, so this thesis hypothesized that interactions and incompatibilities between some of these materials might be possible. Therefore, a literature search, and other documentation that could be related to the topic, are studied and analyzed, as well as, standards and documentation provided by manufacturers. However, after consulting all literature and documents referenced in this dissertation, it was not found any research about the influence of interaction between the materials forming the inverted flat roof, and how this affects to the durability of them. The purpose of this thesis is the analysis of the durability of the inverted flat roof, from the point of view of interactions and incompatibilities may occur between the materials setting up this constructive solution. Along with this general objective, alternatives that can prolong the life cycle of the inverted roof are studied. To get this, an experimental plan is developed, in order to analyze these incompatibilities, and study the factors conditioning them. Some of the results show, that certain normally used waterproofing laminas for building flat roofs, may interact with XPS producing lamina deterioration. Contact, incorrect separation, pressure and heat, are determinant factors for degradation. It can be pointed out, as one of the conclusions of this research, that the thermal protection provided by XPS to the inverted flat roof, cannot be enough (depending on the XPS thickness, and the location of the flat mainly) to reduce the amount of heat that reaches the contact line between materials, and thus to cut down interactions. Furthermore, although geotextiles used as auxiliary separating layers, within the weights per square meter recommended by some of the regulating rules of this type of roofs reduce interactions, these still occur.

Análisis y simulación numérica de problemas electrohidrodinámicos relacionados con el electrospray

La presente tesis es un estudio analítico y numérico del electrospray. En la configuración más sencilla, un caudal constante del líquido a atomizar, que debe tener una cierta conductividad eléctrica, se inyecta en un medio dieléctrico (un gas u otro líquido inmiscible con el primero) a través de un tubo capilar metálico. Entre este tubo y un electrodo lejano se aplica un voltaje continuo que origina un campo eléctrico en el líquido conductor y en el espacio que lo rodea. El campo eléctrico induce una corriente eléctrica en el líquido, que acumula carga en su superficie, y da lugar a un esfuerzo eléctrico sobre la superficie, que tiende a alargarla en la dirección del campo eléctrico. El líquido forma un menisco en el extremo del tubo capilar cuando el campo eléctrico es suficientemente intenso y el caudal suficientemente pequeño. Las variaciones de presión y los esfuerzos viscosos asociados al movimiento del líquido son despreciables en la mayor parte de este menisco, siendo dominantes los esfuerzos eléctrico y de tensión superficial que actúan sobre la superficie del líquido. En el modo de funcionamiento llamado de conochorro, el balance de estos esfuerzos hace que el menisco adopte una forma cónica (el cono de Taylor) en una región intermedia entre el extremo del tubo y la punta del menisco. La velocidad del líquido aumenta al acercarse al vértice del cono, lo cual propicia que las variaciones de la presión en el líquido generadas por la inercia o por la viscosidad entren en juego, desequilibrando el balance de esfuerzos mencionado antes. Como consecuencia, del vértice del cono sale un delgado chorro de líquido, que transporta la carga eléctrica que se acumula en la superficie. La acción del campo eléctrico tangente a la superficie sobre esta carga origina una tracción eléctrica que tiende a alargar el chorro. Esta tracción no es relevante en el menisco, donde el campo eléctrico tangente a la superficie es muy pequeño, pero se hace importante en el chorro, donde es la causa del movimiento del líquido. Lejos del cono, el chorro puede o bien desarrollar una inestabilidad asimétrica que lo transforma en una espiral (whipping) o bien romperse en un spray de gotas prácticamente monodispersas cargadas eléctricamente. La corriente eléctrica transportada por el líquido es la suma de la corriente de conducción en el interior del líquido y la corriente debida a la convección de la carga acumulada en su superficie. La primera domina en el menisco y la segunda en el chorro lejano, mientras que las dos son comparables en una región intermedia de transferencia de corriente situada al comienzo del chorro aunque aguas abajo de la región de transición cono-chorro, en la que el menisco deja de ser un cono de Taylor. Para un campo exterior dado, la acumulación de carga eléctrica en la superficie del líquido reduce el campo eléctrico en el interior del mismo, que llega a anularse cuando la carga alcanza un estado final de equilibrio. El tiempo característico de este proceso es el tiempo de relajación dieléctrica, que es una propiedad del líquido. Cuando el tiempo de residencia del líquido en la región de transición cono-chorro (o en otra región del campo fluido) es grande frente al tiempo de relajación dieléctrica, la carga superficial sigue una sucesión de estados de equilibrio y apantalla al líquido del campo exterior. Cuando esta condición deja de cumplirse, aparecen efectos de relajación de carga, que se traducen en que el campo exterior penetra en el líquido, a no ser que su constante dieléctrica sea muy alta, en cuyo caso el campo inducido por la carga de polarización evita la entrada del campo exterior en el menisco y en una cierta región del chorro. La carga eléctrica en equilibrio en la superficie de un menisco cónico intensifica el campo eléctrico y determina su variación espacial hasta distancias aguas abajo del menisco del orden de su tamaño. Este campo, calculado por Taylor, es independiente del voltaje aplicado, por lo que las condiciones locales del flujo y el valor de la corriente eléctrica son también independientes del voltaje en tanto los tamaños de las regiones que determinan estas propiedades sean pequeños frente al tamaño del menisco. Los resultados experimentales publicados en la literatura muestran que existe un caudal mínimo para el que el modo cono-chorro que acabamos de describir deja de existir. El valor medio y la desviación típica de la distribución de tamaños de las gotas generadas por un electrospray son mínimos cuando se opera cerca del caudal mínimo. A pesar de que los mecanismos responsables del caudal mínimo han sido muy estudiados, no hay aún una teoría completa del mismo, si bien su existencia parece estar ligada a la aparición de efectos de relajación de carga en la región de transición cono-chorro. En esta tesis, se presentan estimaciones de orden de magnitud, algunas existentes y otras nuevas, que muestran los balances dominantes responsables de las distintas regiones de la estructura asintótica de la solución en varios casos de interés. Cuando la inercia del líquido juega un papel en la transición cono-chorro, los resultados muestran que la región de transferencia de corriente, donde la mayor parte de la corriente pasa a la superficie, está en el chorro aguas abajo de la región de transición cono-chorro. Los efectos de relajación de carga aparecen de forma simultánea en el chorro y la región de transición cuando el caudal se disminuye hasta valores de un cierto orden. Para caudales aún menores, los efectos de relajación de carga se notan en el menisco, en una región grande comparada con la de transición cono-chorro. Cuando el efecto de las fuerzas de viscosidad es dominante en la región de transición, la región de transferencia de corriente está en el chorro pero muy próxima a la región de transición cono-chorro. Al ir disminuyendo el caudal, los efectos de relajación de carga aparecen progresivamente en el chorro, en la región de transición y por último en el menisco. Cuando el caudal es mucho mayor que el mínimo del modo cono-chorro, el menisco deja de ser cónico. El campo eléctrico debido al voltaje aplicado domina en la región de transferencia de corriente, y tanto la corriente eléctrica como el tamaño de las diferentes regiones del problema pasan a depender del voltaje aplicado. Como resultado de esta dependencia, el plano caudal-voltaje se divide en diferentes regiones que se analizan separadamente. Para caudales suficientemente grandes, la inercia del líquido termina dominando frente a las fuerzas de la viscosidad. Estos resultados teóricos se han validado con simulaciones numéricas. Para ello se ha formulado un modelo simplificado del flujo, el campo eléctrico y el transporte de carga en el menisco y el chorro del electrospray. El movimiento del líquido se supone casi unidireccional y se describe usando la aproximación de Cosserat para un chorro esbelto. Esta aproximación, ampliamente usada en la literatura, permite simular con relativa facilidad múltiples casos y cubrir amplios rangos de valores de los parámetros reteniendo los efectos de la viscosidad y la inercia del líquido. Los campos eléctricos dentro y fuera del liquido están acoplados y se calculan sin simplificación alguna usando un método de elementos de contorno. La solución estacionaria del problema se calcula mediante un método iterativo. Para explorar el espacio de los parámetros, se comienza calculando una solución para valores fijos de las propiedades del líquido, el voltaje aplicado y el caudal. A continuación, se usa un método de continuación que permite delinear la frontera del dominio de existencia del modo cono-chorro, donde el método iterativo deja de converger. Cuando el efecto de la inercia del líquido domina en la región de transición cono-chorro, el caudal mínimo para el cual el método iterativo deja de converger es del orden del valor estimado del caudal para el que comienza a haber efectos de relajación de carga en el chorro y el cono. Aunque las simulaciones no convergen por debajo de dicho caudal, el valor de la corriente eléctrica para valores del caudal ligeramente mayores parece ajustarse a las estimaciones para caudales menores, reflejando un posible cambio en los balances aplicables. Por el contrario, cuando las fuerzas viscosas dominan en la región de transición, se pueden obtener soluciones estacionarias para caudales bastante menores que aquel para el que aparecen efectos de relajación de carga en la región de transición cono-chorro. Los resultados numéricos obtenidos para estos pequeños caudales se ajustan perfectamente a las estimaciones de orden de magnitud que se describen en la memoria. Por último, se incluyen como anexos dos estudios teóricos que han surgido de forma natural durante el desarrollo de la tesis. El primero hace referencia a la singularidad en el campo eléctrico que aparece en la línea de contacto entre el líquido y el tubo capilar en la mayoría de las simulaciones. Primero se estudia en qué situaciones el campo eléctrico tiende a infinito en la línea de contacto. Después, se comprueba que dicha singularidad no supone un fallo en la descripción del problema y que además no afecta a la solución lejos de la línea de contacto. También se analiza si los esfuerzos eléctricos infinitamente grandes a los que da lugar dicha singularidad pueden ser compensados por el resto de esfuerzos que actúan en la superficie del líquido. El segundo estudio busca determinar el tamaño de la región de apantallamiento en un chorro de líquido dieléctrico sin carga superficial. En esta región, el campo exterior es compensado parcialmente por el campo que induce la carga de polarización en la superficie del líquido, de forma que en el interior del líquido el campo eléctrico es mucho menor que en el exterior. Una región como ésta aparece en las estimaciones cuando los efectos de relajación de carga son importantes en la región de transferencia de corriente en el chorro. ABSTRACT This aim of this dissertation is a theoretical and numerical analysis of an electrospray. In its most simple configuration, a constant flow rate of the liquid to be atomized, which has to be an electrical conductor, is injected into a dielectric medium (a gas or another inmiscible fluid) through a metallic capillary tube. A constant voltage is applied between this tube and a distant electrode that produces an electric field in the liquid and the surrounding medium. This electric field induces an electric current in the liquid that accumulates charge at its surface and leads to electric stresses that stretch the surface in the direction of the electric field. A meniscus appears on the end of the capillary tube when the electric field is sufficiently high and the flow rate is small. Pressure variations and viscous stresses due to the motion of the liquid are negligible in most of the meniscus, where normal electric and surface tension stresses acting on the surface are dominant. In the so-called cone-jet mode, the balance of these stresses forces the surface to adopt a conical shape -Taylor cone- in a intermediate region between the end of the tube and the tip of the meniscus. When approaching the cone apex, the velocity of the liquid increases and leads to pressure variations that eventually disturb the balance of surfaces tension and electric stresses. A thin jet emerges then from the tip of the meniscus that transports the charge accumulated at its surface. The electric field tangent to the surface of the jet acts on this charge and continuously stretches the jet. This electric force is negligible in the meniscus, where the component of the electric field tangent to the surface is small, but becomes very important in the jet. Far from the cone, the jet can either develop an asymmetrical instability named “whipping”, whereby the jet winds into a spiral, or break into a spray of small, nearly monodisperse, charged droplets. The electric current transported by the liquid has two components, the conduction current in the bulk of the liquid and the convection current due to the transport of the surface charge by the flow. The first component dominates in the meniscus, the second one in the far jet, and both are comparable in a current transfer region located in the jet downstream of the cone-jet transition region where the meniscus ceases to be a Taylor cone. Given an external electric field, the charge that accumulates at the surface of the liquid reduces the electric field inside the liquid, until an equilibrium is reached in which the electric field induced by the surface charge counters the external electric field and shields the liquid from this field. The characteristic time of this process is the electric relaxation time, which is a property of the liquid. When the residence time of the liquid in the cone-jet transition region (or in other region of the flow) is greater than the electric relaxation time, the surface charge follows a succession of equilibrium states and continuously shield the liquid from the external field. When this condition is not satisfied, charge relaxation effects appear and the external field penetrates into the liquid unless the liquid permittivity is large. For very polar liquids, the field due to the polarization charge at the surface prevents the external field from entering the liquid in the cone and in certain region of the jet. The charge at the surface of a conical meniscus intensifies the electric field around the cone, determining its spatial variation up to distances downstream of the apex of the order of the size of the meniscus. This electric field, first computed by Taylor, is independent of the applied voltage. Therefore local flow characteristics and the electric current carried by the jet are also independent of the applied voltage provided the size of the regions that determine these magnitudes are small compared with the size of the meniscus. Many experiments in the literature show the existence of a minimum flow rate below which the cone-jet mode cannot be established. The mean value and the standard deviation of the electrospray droplet size distribution are minimum when the device is operated near the minimum flow rate. There is no complete explanation of the minimum flow rate, even though possible mechanisms have been extensively studied. The existence of a minimum flow rate seems to be connected with the appearance of charge relaxation effects in the transition region. In this dissertation, order of magnitude estimations are worked out that show the dominant balances in the different regions of the asymptotic structure of the solution for different conditions of interest. When the inertia of the liquid plays a role in the cone-jet transition region, the region where most of the electric current is transfered to the surface lies in the jet downstream the cone-jet transition region. When the flow rate decreases to a certain value, charge relaxation effects appear simultaneously in the jet and in the transition region. For smaller values of the flow rate, charge relaxation effects are important in a region of the meniscus larger than the transition region. When viscous forces dominate in the flow in the cone-jet transition region, the current transfer region is located in the jet immediately after the transition region. When flow rate is decreased, charge relaxation effects appears gradually, first in the jet, then in the transition region, and finally in the meniscus. When flow rate is much larger than the cone-jet mode minimum, the meniscus ceases to be a cone. The electric current and the structure of the solution begin to depend on the applied voltage. The flow rate-voltage plane splits into different regions that are analyzed separately. For sufficiently large flow rates, the effect of the inertia of the liquid always becomes greater than the effect of the viscous forces. A set of numerical simulations have been carried out in order to validate the theoretical results. A simplified model of the problem has been devised to compute the flow, the electric field and the surface charge in the meniscus and the jet of an electrospray. The motion of the liquid is assumed to be quasi-unidirectional and described by Cosserat’s approximation for a slender jet. This widely used approximation allows to easily compute multiple configurations and to explore wide ranges of values of the governing parameters, retaining the effects of the viscosity and the inertia of the liquid. Electric fields inside and outside the liquid are coupled and are computed without any simplification using a boundary elements method. The stationary solution of the problem is obtained by means of an iterative method. To explore the parameter space, a solution is first computed for a set of values of the liquid properties, the flow rate and the applied voltage, an then a continuation method is used to find the boundaries of the cone-jet mode domain of existence, where the iterative method ceases to converge. When the inertia of the liquid dominates in the cone-jet transition region, the iterative method ceases to converge for values of the flow rate for which order-of-magnitude estimates first predict charge relaxation effects to be important in the cone and the jet. The electric current computed for values of the flow rate slightly above the minimum for which convergence is obtained seems to agree with estimates worked out for lower flow rates. When viscous forces dominate in the transition region, stationary solutions can be obtained for flow rates significantly smaller than the one for which charge relaxation effects first appear in the transition region. Numerical results obtained for those small values of the flow rate agree with our order of magnitude estimates. Theoretical analyses of two issues that have arisen naturally during the thesis are summarized in two appendices. The first appendix contains a study of the singularity of the electric field that most of the simulations show at the contact line between the liquid and the capillary tube. The electric field near the contact line is analyzed to determine the ranges of geometrical configurations and liquid permittivity where a singularity appears. Further estimates show that this singularity does not entail a failure in the description of the problem and does not affect the solution far from the contact line. The infinite electric stresses that appear at the contact line can be effectively balanced by surface tension. The second appendix contains an analysis of the size and slenderness of the shielded region of a dielectric liquid in the absence of free surface charge. In this region, the external electric field is partially offset by the polarization charge so that the inner electric field is much lower than the outer one. A similar region appears in the estimates when charge relaxation effects are important in the current transfer region.

Optimización multiobjetivo inteligente del dimensionamiento energético en sistemas ferroviarios señalizados y en plataformas software de tiempo real

La capacidad de transporte es uno de los baremos fundamentales para evaluar la progresión que puede llegar a tener un área económica y social. Es un sector de elevada importancia para la sociedad actual. Englobado en los distintos tipos de transporte, uno de los medios de transporte que se encuentra más en alza en la actualidad, es el ferroviario. Tanto para movilidad de pasajeros como para mercancías, el tren se ha convertido en un medio de transporte muy útil. Se encuentra dentro de las ciudades, entre ciudades con un radio pequeño entre ellas e incluso cada vez más, gracias a la alta velocidad, entre ciudades con gran distancia entre ellas. Esta Tesis pretende ayudar en el diseño de una de las etapas más importantes de los Proyectos de instalación de un sistema ferroviario: el sistema eléctrico de tracción. La fase de diseño de un sistema eléctrico de tracción ferroviaria se enfrenta a muchas dudas que deben ser resueltas con precisión. Del éxito de esta fase dependerá la capacidad de afrontar las demandas de energía de la explotación ferroviaria. También se debe atender a los costes de instalación y de operación, tanto costes directos como indirectos. Con la Metodología que se presenta en esta Tesis se ofrecerá al diseñador la opción de manejar un sistema experto que como soluciones le plantee un conjunto de escenarios de sistemas eléctricos correctos, comprobados por resolución de modelos de ecuaciones. Correctos desde el punto de vista de validez de distintos parámetros eléctrico, como de costes presupuestarios e impacto de costes indirectos. Por tanto, el diseñador al haber hecho uso de esta Metodología, tendría en un espacio de tiempo relativamente corto, un conjunto de soluciones factibles con las que poder elegir cuál convendría más según sus intereses finales. Esta Tesis se ha desarrollado en una vía de investigación integrada dentro del Centro de Investigaciones Ferroviarias CITEF-UPM. Entre otros proyectos y vías de investigación, en CITEF se ha venido trabajando en estudios de validación y dimensionamiento de sistemas eléctricos ferroviarios con diversos y variados clientes y sistemas ferroviarios. A lo largo de los proyectos realizados, el interés siempre ha girado mayoritariamente sobre los siguientes parámetros del sistema eléctrico: - Calcular número y posición de subestaciones de tracción. Potencia de cada subestación. - Tipo de catenaria a lo largo del recorrido. Conductores que componen la catenaria. Características. - Calcular número y posición de autotransformadores para sistemas funcionando en alterna bitensión o 2x25kV. - Posición Zonas Neutras. - Validación según normativa de: o Caídas de tensión en la línea o Tensiones máximas en el retorno de la línea o Sobrecalentamiento de conductores o Sobrecalentamiento de los transformadores de las subestaciones de tracción La idea es que las soluciones aportadas por la Metodología sugieran escenarios donde de estos parámetros estén dentro de los límites que marca la normativa. Tener la posibilidad de tener un repositorio de posibles escenarios donde los parámetros y elementos eléctricos estén calculados como correctos, aporta un avance en tiempos y en pruebas, que mejoraría ostensiblemente el proceso habitual de diseño para los sistemas eléctricos ferroviarios. Los costes directos referidos a elementos como subestaciones de tracción, autotransformadores, zonas neutras, ocupan un gran volumen dentro del presupuesto de un sistema ferroviario. En esta Tesis se ha querido profundizar también en el efecto de los costes indirectos provocados en la instalación y operación de sistemas eléctricos. Aquellos derivados del impacto medioambiental, los costes que se generan al mantener los equipos eléctricos y la instalación de la catenaria, los costes que implican la conexión entre las subestaciones de tracción con la red general o de distribución y por último, los costes de instalación propios de cada elemento compondrían los costes indirectos que, según experiencia, se han pensado relevantes para ejercer un cierto control sobre ellos. La Metodología cubrirá la posibilidad de que los diseños eléctricos propuestos tengan en cuenta variaciones de coste inasumibles o directamente, proponer en igualdad de condiciones de parámetros eléctricos, los más baratos en función de los costes comentados. Analizando los costes directos e indirectos, se ha pensado dividir su impacto entre los que se computan en la instalación y los que suceden posteriormente, durante la operación de la línea ferroviaria. Estos costes normalmente suelen ser contrapuestos, cuánto mejor es uno peor suele ser el otro y viceversa, por lo que hace falta un sistema que trate ambos objetivos por separado. Para conseguir los objetivos comentados, se ha construido la Metodología sobre tres pilares básicos: - Simulador ferroviario Hamlet: Este simulador integra módulos para construir esquemas de vías ferroviarios completos; módulo de simulación mecánica y de la tracción de material rodante; módulo de señalización ferroviaria; módulo de sistema eléctrico. Software realizado en C++ y Matlab. - Análisis y estudio de cómo focalizar los distintos posibles escenarios eléctricos, para que puedan ser examinados rápidamente. Pico de demanda máxima de potencia por el tráfico ferroviario. - Algoritmos de optimización: A partir de un estudio de los posibles algoritmos adaptables a un sistema tan complejo como el que se plantea, se decidió que los algoritmos genéticos serían los elegidos. Se han escogido 3 algoritmos genéticos, permitiendo recabar información acerca del comportamiento y resultados de cada uno de ellos. Los elegidos por motivos de tiempos de respuesta, multiobjetividad, facilidad de adaptación y buena y amplia aplicación en proyectos de ingeniería fueron: NSGA-II, AMGA-II y ɛ-MOEA. - Diseño de funciones y modelo preparado para trabajar con los costes directos e indirectos y las restricciones básicas que los escenarios eléctricos no deberían violar. Estas restricciones vigilan el comportamiento eléctrico y la estabilidad presupuestaria. Las pruebas realizadas utilizando el sistema han tratado o bien de copiar situaciones que se puedan dar en la realidad o directamente sistemas y problemas reales. Esto ha proporcionado además de la posibilidad de validar la Metodología, también se ha posibilitado la comparación entre los algoritmos genéticos, comparar sistemas eléctricos escogidos con los reales y llegar a conclusiones muy satisfactorias. La Metodología sugiere una vía de trabajo muy interesante, tanto por los resultados ya obtenidos como por las oportunidades que puede llegar a crear con la evolución de la misma. Esta Tesis se ha desarrollado con esta idea, por lo que se espera pueda servir como otro factor para trabajar con la validación y diseño de sistemas eléctricos ferroviarios. ABSTRACT Transport capacity is one of the critical points to evaluate the progress than a specific social and economical area is able to reach. This is a sector of high significance for the actual society. Included inside the most common types of transport, one of the means of transport which is elevating its use nowadays is the railway. Such as for passenger transport of weight movements, the train is being consolidated like a very useful mean of transport. Railways are installed in many geography areas. Everyone know train in cities, or connecting cities inside a surrounding area or even more often, taking into account the high-speed, there are railways infrastructure between cities separated with a long distance. This Ph.D work aims to help in the process to design one of the most essential steps in Installation Projects belonging to a railway system: Power Supply System. Design step of the railway power supply, usually confronts to several doubts and uncertainties, which must be solved with high accuracy. Capacity to supply power to the railway traffic depends on the success of this step. On the other hand is very important to manage the direct and indirect costs derived from Installation and Operation. With the Methodology is presented in this Thesis, it will be offered to the designer the possibility to handle an expert system that finally will fill a set of possible solutions. These solutions must be ready to work properly in the railway system, and they were tested using complex equation models. This Thesis has been developed through a research way, integrated inside Citef (Railway Research Centre of Technical University of Madrid). Among other projects and research ways, in Citef has been working in several validation studies and dimensioning of railway power supplies. It is been working by a large range of clients and railways systems. Along the accomplished Projects, the main goal has been rounded mostly about the next list of parameters of the electrical system: - Calculating number and location of traction substations. Power of each substation. - Type of Overhead contact line or catenary through the railway line. The wires which set up the catenary. Main Characteristics. - Calculating number and position of autotransformers for systems working in alternating current bi-voltage of called 2x25 kV. - Location of Neutral Zones. - Validating upon regulation of: o Drop voltages along the line o Maximum return voltages in the line o Overheating/overcurrent of the wires of the catenary o Avoiding overheating in the transformers of the traction substations. Main objective is that the solutions given by the Methodology, could be suggest scenarios where all of these parameters from above, would be between the limits established in the regulation. Having the choice to achieve a repository of possible good scenarios, where the parameters and electrical elements will be assigned like ready to work, that gives a great advance in terms of times and avoiding several tests. All of this would improve evidently the regular railway electrical systems process design. Direct costs referred to elements like traction substations, autotransformers, neutral zones, usually take up a great volume inside the general budget in railway systems. In this Thesis has been thought to bear in mind another kind of costs related to railway systems, also called indirect costs. These could be enveloped by those enmarked during installation and operation of electrical systems. Those derived from environmental impact; costs generated during the maintenance of the electrical elements and catenary; costs involved in the connection between traction substations and general electric grid; finally costs linked with the own installation of the whole electrical elements needed for the correct performance of the railway system. These are integrated inside the set has been collected taking into account own experience and research works. They are relevant to be controlled for our Methodology, just in case for the designers of this type of systems. The Methodology will cover the possibility that the final proposed power supply systems will be hold non-acceptable variations of costs, comparing with initial expected budgets, or directly assuming a threshold of budget for electrical elements in actual scenario, and achieving the cheapest in terms of commented costs from above. Analyzing direct and indirect costs, has been thought to divide their impact between two main categories. First one will be inside the Installation and the other category will comply with the costs often happens during Railway Operation time. These costs normally are opposed, that means when one is better the other turn into worse, in costs meaning. For this reason is necessary treating both objectives separately, in order to evaluate correctly the impact of each one into the final system. The objectives detailed before build the Methodology under three basic pillars: - Railway simulator Hamlet: This software has modules to configure many railway type of lines; mechanical and traction module to simulate the movement of rolling stock; signaling module; power supply module. This software has been developed using C++ and Matlab R13a - Previously has been mandatory to study how would be possible to work properly with a great number of feasible electrical systems. The target comprised the quick examination of these set of scenarios in terms of time. This point is talking about Maximum power demand peaks by railway operation plans. - Optimization algorithms. A railway infrastructure is a very complex system. At the beginning it was necessary to search about techniques and optimization algorithms, which could be adaptable to this complex system. Finally three genetic multiobjective algorithms were the chosen. Final decision was taken attending to reasons such as time complexity, able to multiobjective, easy to integrate in our problem and with a large application in engineering tasks. They are: NSGA-II, AMGA-II and ɛ-MOEA. - Designing objectives functions and equation model ready to work with the direct and indirect costs. The basic restrictions are not able to avoid, like budgetary or electrical, connected hardly with the recommended performance of elements, catenary and safety in a electrical railway systems. The battery of tests launched to the Methodology has been designed to be as real as possible. In fact, due to our work in Citef and with real Projects, has been integrated and configured three real railway lines, in order to evaluate correctly the final results collected by the Methodology. Another topic of our tests has been the comparison between the performances of the three algorithms chosen. Final step has been the comparison again with different possible good solutions, it means power supply system designs, provided by the Methodology, testing the validity of them. Once this work has been finished, the conclusions have been very satisfactory. Therefore this Thesis suggest a very interesting way of research and work, in terms of the results obtained and for the future opportunities can be created with the evolution of this. This Thesis has been developed with this idea in mind, so is expected this work could adhere another factor to work in the difficult task of validation and design of railway power supply systems.

Crystallization on the Mesoscale : Self-Assembly of Iron Oxide Nanocubes into Mesocrystals

Self-assembly of nanoparticles is a promising route to form complex, nanostructured materials with functional properties. Nanoparticle assemblies characterized by a crystallographic alignment of the nanoparticles on the atomic scale, i.e. mesocrystals, are commonly found in nature with outstanding functional and mechanical properties. This thesis aims to investigate and understand the formation mechanisms of mesocrystals formed by self-assembling iron oxide nanocubes. We have used the thermal decomposition method to synthesize monodisperse, oleate-capped iron oxide nanocubes with average edge lengths between 7 nm and 12 nm and studied the evaporation-induced self-assembly in dilute toluene-based nanocube dispersions. The influence of packing constraints on the alignment of the nanocubes in nanofluidic containers has been investigated with small and wide angle X-ray scattering (SAXS and WAXS, respectively). We found that the nanocubes preferentially orient one of their {100} faces with the confining channel wall and display mesocrystalline alignment irrespective of the channel widths.  We manipulated the solvent evaporation rate of drop-cast dispersions on fluorosilane-functionalized silica substrates in a custom-designed cell. The growth stages of the assembly process were investigated using light microscopy and quartz crystal microbalance with dissipation monitoring (QCM-D). We found that particle transport phenomena, e.g. the coffee ring effect and Marangoni flow, result in complex-shaped arrays near the three-phase contact line of a drying colloidal drop when the nitrogen flow rate is high. Diffusion-driven nanoparticle assembly into large mesocrystals with a well-defined morphology dominates at much lower nitrogen flow rates. Analysis of the time-resolved video microscopy data was used to quantify the mesocrystal growth and establish a particle diffusion-based, three-dimensional growth model. The dissipation obtained from the QCM-D signal reached its maximum value when the microscopy-observed lateral growth of the mesocrystals ceased, which we address to the fluid-like behavior of the mesocrystals and their weak binding to the substrate. Analysis of electron microscopy images and diffraction patterns showed that the formed arrays display significant nanoparticle ordering, regardless of the distinctive formation process.  We followed the two-stage formation mechanism of mesocrystals in levitating colloidal drops with real-time SAXS. Modelling of the SAXS data with the square-well potential together with calculations of van der Waals interactions suggests that the nanocubes initially form disordered clusters, which quickly transform into an ordered phase.

Solid-liquid interactions in microscale structures and devices

Liquid-solid interactions become important as dimensions approach mciro/nano-scale. This dissertation focuses on liquid-solid interactions in two distinct applications: capillary driven self-assembly of thin foils into 3D structures, and droplet wetting of hydrophobic micropatterned surfaces. The phenomenon of self-assembly of complex structures is common in biological systems. Examples include self-assembly of proteins into macromolecular structures and self-assembly of lipid bilayer membranes. The principles governing this phenomenon have been applied to induce self-assembly of millimeter scale Si thin films into spherical and other 3D structures, which are then integrated into light-trapping photovoltaic (PV) devices. Motivated by this application, we present a generalized analytical study of the self-folding of thin plates into deterministic 3D shapes, through fluid-solid interactions, to be used as PV devices. This study consists of developing a model using beam theory, which incorporates the two competing components — a capillary force that promotes folding and the bending rigidity of the foil that resists folding into a 3D structure. Through an equivalence argument of thin foils of different geometry, an effective folding parameter, which uniquely characterizes the driving force for folding, has been identified. A criterion for spontaneous folding of an arbitrarily shaped 2D foil, based on the effective folding parameter, is thus established. Measurements from experiments using different materials and predictions from the model match well, validating the assumptions used in the analysis. As an alternative to the mechanics model approach, the minimization of the total free energy is employed to investigate the interactions between a fluid droplet and a flexible thin film. A 2D energy functional is proposed, comprising the surface energy of the fluid, bending energy of the thin film and gravitational energy of the fluid. Through simulations with Surface Evolver, the shapes of the droplet and the thin film at equilibrium are obtained. A critical thin film length necessary for complete enclosure of the fluid droplet, and hence successful self-assembly into a PV device, is determined and compared with the experimental results and mechanics model predictions. The results from the modeling and energy approaches and the experiments are all consistent. Superhydrophobic surfaces, which have unique properties including self-cleaning and water repelling are desired in many applications. One excellent example in nature is the lotus leaf. To fabricate these surfaces, well designed micro/nano- surface structures are often employed. In this research, we fabricate superhydrophobic micropatterned Polydimethylsiloxane (PDMS) surfaces composed of micropillars of various sizes and arrangements by means of soft lithography. Both anisotropic surfaces, consisting of parallel grooves and cylindrical pillars in rectangular lattices, and isotropic surfaces, consisting of cylindrical pillars in square and hexagonal lattices, are considered. A novel technique is proposed to image the contact line (CL) of the droplet on the hydrophobic surface. This technique provides a new approach to distinguish between partial and complete wetting. The contact area between droplet and microtextured surface is then measured for a droplet in the Cassie state, which is a state of partial wetting. The results show that although the droplet is in the Cassie state, the contact area does not necessarily follow Cassie model predictions. Moreover, the CL is not circular, and is affected by the micropatterns, in both isotropic and anisotropic cases. Thus, it is suggested that along with the contact angle — the typical parameter reported in literature quantifying wetting, the size and shape of the contact area should also be presented. This technique is employed to investigate the evolution of the CL on a hydrophobic micropatterned surface in the cases of: a single droplet impacting the micropatterned surface, two droplets coalescing on micropillars, and a receding droplet resting on the micropatterned surface. Another parameter which quantifies hydrophobicity is the contact angle hysteresis (CAH), which indicates the resistance of the surface to the sliding of a droplet with a given volume. The conventional methods of using advancing and receding angles or tilting stage to measure the resistance of the micropatterned surface are indirect, without mentioning the inaccuracy due to the discrete and stepwise motion of the CL on micropillars. A micronewton force sensor is utilized to directly measure the resisting force by dragging a droplet on a microtextured surface. Together with the proposed imaging technique, the evolution of the CL during sliding is also explored. It is found that, at the onset of sliding, the CL behaves as a linear elastic solid with a constant stiffness. Afterwards, the force first increases and then decreases and reaches a steady state, accompanied with periodic oscillations due to regular pinning and depinning of the CL. Both the maximum and steady state forces are primarily dependent on area fractions of the micropatterned surfaces in our experiment. The resisting force is found to be proportional to the number of pillars which pin the CL at the trailing edge, validating the assumption that the resistance mainly arises from the CL pinning at the trailing edge. In each pinning-and-depinning cycle during the steady state, the CL also shows linear elastic behavior but with a lower stiffness. The force variation and energy dissipation involved can also be determined. This novel method of measuring the resistance of the micropatterned surface elucidates the dependence on CL pinning and provides more insight into the mechanisms of CAH.

Fingering Instabilities in Dewetting Nanofluids

The growth of fingering patterns in dewetting nanofluids (colloidal solutions of thiol-passivated gold nanoparticles) has been followed in real time using contrast-enhanced video microscopy. The fingering instability on which we focus here arises from evaporatively-driven nucleation and growth a nanoscopically thin "precursor" solvent film behind the macroscopic contact line. We find that well-developed isotropic fingering structures only form for a narrow range of experimental parameters. Numerical simulations, based on a modification of the Monte Carlo approach introduced by Rabani et al. [Nature 426, 271 (2003)], reproduce the patterns we observe experimentally.

Reducing electrowetting-on-dielectric actuation voltage using a novel electrode shape and a multi-layer dielectric coating

This paper presents design and fabrication of an electrowetting-on-dielectric (EWOD) device using a novel electrode shape and a multi-layer dielectric coating that reduce the actuation voltage of the device to less than 12.6 V. The fabrication of the EWOD electrodes is carried out in several steps including laser exposure, wet developing, etching, and stripping. A high-dielectric-constant multi-layer dielectric coating containing a 770 nm thick Polyvinylidene difluoride (PVDF) layer and a 1 µm thick Cyanoethyl pullulan (CEP) layer, is deposited on the EWOD electrodes for insulation. This multi-layer dielectric structure exhibits a high capacitance per unit area, and the novel electrode shape changes the actuation force at the droplet contact line reducing the voltage required to operate the device. In addition, an overlaying Teflon layer of 50 nm is placed on top of the dielectric structure to provide a hydrophobic surface for droplet manipulation. It is observed from the experiments that the electrode shape and the dielectric structure have contributed to the reduction of the actuation voltage of the EWOD device.