Pattern formation in nanoparticle suspensions: a Kinetic Monte Carlo approach

Various experimental settings that involve drying solutions or suspensions of nanoparticles often called nano-fluids have recently been used to produce structured nanoparticle layers. In addition to the formation of polygonal networks and spinodal-like patterns, the occurrence of branched structures has been reported. After reviewing the experimental results, the work presented in this thesis relies only on simulations. Using a modified version of the Monte Carlo model first introduced by Rabani et al. [95] the study of structure formation in evaporating films of nanoparticle solutions for the case that all structuring is driven by the interplay of evaporating solvent and diffusing nanoparticles is presented. The model has first been used to analyse the influence of the nanoparticles on the basic dewetting behaviour, i.e., on spinodal dewetting and on dewetting by nucleation and growth of holes. We focus, as well, on receding dewetting fronts which are initially straight but develop a transverse fingering instability. One can analyse the dependence of the characteristics of the resulting branching patterns on the driving effective chemical potential, the mobility and concentration of the nanoparticles, and the interaction strength between liquid and nanoparticles. This allows to understand the underlying fingering instability mechanism. We describe briefly how the combination of a Monte Carlo model with a Genetic Algorithm (GA) can be developed and used to tune the evolution of a simulated self-organizing nanoscale system toward a predefined nonequilibrium morphology. This work has presented evolutionary computation as a method for designing target morphologies of self-organising nano-structured systems. Finally, highly localised control of 2D pattern formation in colloidal nanoparticle arrays via surface inhomogeneities created by atomic force microscope (AFM) induced oxidation is presented and some simulations are shown. Furthermore, the model can be extended further, and by including the second type of nanoparticle, the binary mixture behaviour can be captured by simulations. We conclude that Kinetic Monte Carlo simulations have allowed the study of the processes that lead to the production of particular nanoparticle morphologies

Direct numerical simulation of multi-phase flow in complex media

Tesi en modalitat de compendi de publicacionsIn numerous applications, two-phase liquid-gas transport at sub-millimeter length scales plays a substantial role in the determination of the behavior of the system at hand. As its main application, the present work focuses on the polymer electrolyte membrane (PEM) fuel cells. Desirable performance and operational life-time of this class of high-throughput energy conversion devices requires an effective water management, which per se relies on proper prediction of the water-air transport mechanisms. Such two-phase flow involves interfacial forces and phenomena, like hysteresis, that are associated with the physicochemical properties the liquid, gas, and if present, the solid substrate. In this context, numerical modeling is a viable means to obtain valuable predictive understanding of the transport mechanisms, specially for cases that experimental analyses are complicated and/or prohibitively expensive. In this work, an efficient finite element/level-set framework is developed for three-dimensional simulation of two-phase flow. In order to achieve a robust solver for practical applications, the physical complexities are consistently included and the involved numerical issues are properly tackled; the pressure discontinuity at the liquid-gas interface is consistently captured by utilizing an enriched finite element space. The method is stabilized within the framework of variational multiscale stabilization technique. A novel treatment is further proposed for the small-cut instability problem. It is shown that the proposed model can provide accurate results minimizing the spurious currents. A robust technique is also developed in order to filter out the possible noises in the level-set field. It is shown that it is a key to prevent irregularities caused by the persistent remnant of the spurious currents. It is shown how the well-established contact-line models can be incorporated into the variational formulation. The importance of the inclusion of the sub-elemental hydrodynamics is also elaborated. The results presented in the present work rely on the combination of the linearized molecular kinetic and the hydrodynamic theories. Recalling the realistic behavior of liquids in contact with solid substrates, the contact--angle hysteresis phenomenon is taken into account by imposing a consistent pinning/unpinning mechanism developed within the framework of the level-set method. Aside from the main developments, a novel technique is also proposed to significantly improve the accuracy and minimize the the loss in the geometrical features of the interface during the level-set convection based on the back and forth error compensation correction (BFECC) algorithm. Within the context of this thesis, the numerical model is validated for various cases of gas bubble in a liquid and liquid droplets in a gas. For the latter scenario, besides free droplets, the accuracy of the proposed numerical method is assessed for capturing the dynamics droplets spreading on solid substrates. The performance of the model is then analyzed for the capturing the configuration of a water droplet on an inclined substrate in the presence the contact--angle hysteresis. The proposed method is finally employed to simulate the dynamics of a water droplet confined in a gas channel and exposed to air-flow.Existen numerosas aplicaciones industriales en las que transporte bifásico (líquido-gas) a escalas submilimétricas resulta crucial para la determinación del comportamiento del sistema en cuestión. Entre todas ellas, el presente trabajo se centra en las pilas de combustible con membrana de electrolito polimérico (PEMFC). El rendimiento deseable y la vida útil operativa de esta clase de dispositivos de conversión de energía de alto rendimiento requieren una gestión eficaz del agua (conocida como “water management”), que per se depende de la predicción adecuada de los mecanismos de transporte de agua y aire. Así pues, el análisis del flujo microfluídico de dos fases obliga considerar fuerzas y fenómenos interfaciales, tales como la histéresis, que están asociados con las propiedades fisicoquímicas del líquido, el gas y, si está presente, el sustrato sólido. En este contexto, la modelización numérica es una alternativa viable para obtener una predicción precisa de los mecanismos de transporte, especialmente en aquellos casos en los que los análisis experimentales son prohibitivos, ya sea por su complejidad o coste económico. En este trabajo, se desarrolla un marco eficiente, basado en la combinación del método de elementos finitos y el método de “level-set”, para la simulación tridimensional de flujos bifásicos. Con el fin de lograr una herramienta numérica robusta para aplicaciones prácticas, las complejidades físicas se incluyen consistentemente y los problemas numéricos involucrados se abordan adecuadamente. Concretamente, la discontinuidad de la presión en la interfaz líquido-gas se captura consistentemente utilizando un espacio de elementos finitos enriquecido. La estabilización del método se consigue mediante la introducción de la técnica de multiescalas variacionales. Asimismo, se propone también un tratamiento novedoso para el problema de la inestabilidad de tipo “small-cut”. Se muestra que el modelo propuesto puede proporcionar resultados precisos minimizando las corrientes espurias en la interfaz liquido-gas. Complementariamente, se presenta una nueva metodología para filtrar el ruido en el campo de “level-set”. Esta metodología resulta ser crucial para prevenir las irregularidades provocadas por el remanente persistente de las corrientes espurias. El comportamiento de la línea de contacto es considerado a través de la inclusión los modelos correspondientes en la formulación variacional. A este respecto, el presente trabajo aborda la importancia de la inclusión de la hidrodinámica subelemental. Los resultados presentados se basan en la combinación de la cinética molecular linealizada y las teorías hidrodinámicas. Para representación del comportamiento realista de los líquidos en contacto con sustratos sólidos, el fenómeno de histéresis del ángulo de contacto se tiene en cuenta imponiendo un mecanismo de anclado / desanclado consistente desarrollado en el marco del método de level-set. Aparte de los desarrollos principales, también se propone una técnica novedosa para la convección de la función ”level-set”. Ésta permite mejorar significativamente la precisión, minimizando a su vez la pérdida en las características geométricas de la interfaz asociadas al transporte. Esta nueva metodología está basada en el algoritmo de corrección de compensación de errores (BFECC). La herramienta numérica desarrollada en esta tesis es validada para varios casos que involucran burbujas de gas en un líquido y pequeñas gotas de líquido en un gas. Para el último escenario, además de las gotas libres, se evalúa la precisión de la herramienta propuesta para capturar la dinámica de las gotas sobre sustratos sólidos. A continuación, se analiza el rendimiento del modelo para capturar la configuración de una gota de agua sobre un sustrato inclinado en presencia de la histéresis del ángulo de contacto. El método propuesto finalmente se aplicaPostprint (published version

Modelling of dynamical effects related to the wettability and capillarity of simple and complex liquids

This Thesis explores physical phenomena characteristic for thin liquid films and small droplets of simple and complex liquids on solid substrates for which wettability and capillarity control their statical and dynamical properties. We start by discussing the general concepts of wettability and capillarity and introduce the common mathematical framework of the lubrication approximation for studies of thin liquid films and small contact angle drops. We demonstrate the derivation of the generic equation describing the evolution of a film of simple liquid from the Navier-Stokes equations. We show how this model can be further extended to incorporate various effects relevant to the case of complex liquids. The results described in the Thesis comprise three projects with the common main theme of the influence of wettability and capillarity on the statics and dynamics of the studied systems, namely (i) Evaporating sessile droplets fed through the solid substrate - a geometry that allows us to discuss steady states of the system and their role in the time evolution of freely evaporating droplets without influx in an isothermal case; (ii) The influence of a solute--dependent wettability on the stability, static and dynamical properties of thin films and drops of non-volatile mixtures, suspensions and solutions; (iii) A parameter-passing scheme between particle-based Molecular Dynamics simulations and the continuum lubrication model which allows us to discuss equilibrium properties of small polymeric droplets. We present the physical questions arising in the three systems and discuss approaches and results as well as possible extensions

Time-stepping methods for the simulation of the self-assembly of nano-crystals in MATLAB on a GPU

Partial differential equations describing the patterning of thin crystalline films are typically of fourth or sixth order, they are quasi- or semilinear and they are mostly defined on simple geometries such as rectangular domains. For the numerical simulation of these kind of problems spectral methods are an efficient approach. We apply several implicit-explicit schemes to one recently derived PDE that we express in terms of coefficients of trigonometric interpolants. While the simplest IMEX scheme turns out to have the mildest step-size restriction, higher order SBDF schemes tend to be more unstable and exponential time integrators are fastest for the calculation of very accurate solutions. We implemented a reduced model in the EXPINT package syntax and compared various exponential schemes. A convexity splitting approach was employed to stabilize the SBDF1 scheme. We show that accuracy control is crucial when using this idea, therefore we present a time-adaptive SBDF1/SBDF1-2-step method that yields convincing results reflecting the change in timescales during topological changes of the nanostructures. The implementation of all presented methods is carried out in MATLAB. We used the open source GPUmat package to gain up to 5-fold runtime benefits by carrying out calculations on a low-cost GPU without having to prescribe any knowledge in low-level programming or CUDA implementations and found comparable speedups as with MATLAB's PCT or with GPUmat run on Octave

Computational Study of and Model Development for Morphological Evolution in Metallic-Nanostructure Heteroepitaxy.

In this thesis, we describe computational studies relevant to morphological evolution in metallic-nanostructure heteroepitaxy. Our first contribution focuses on the understanding of the thermodynamic driving force behind morphological evolution of the magnetic thin-film system. Specifically, we study the stability of thin single-crystal, internal-defect-free Fe films on Mo(110) and W(110) substrates through calculations of energetics including contributions from the misfit strain, interfacial misfit dislocations, film surface and interface. It is found that the combined energetics gives rise to a driving force for solid-state dewetting for a single-crystal, internal-defect-free film, i.e., an instability of a flat film that leads to formation of thicker and thinner regions. Our second contribution lies in the development of numerical methods for the classical density functional theory (CDFT) and the phase-field crystal (PFC) method, both of which are promising tools for modeling metallic-nanostructure hetereoepitaxy. We introduce a new approach to represent a two-body direct correlation function (DCF) in order to alleviate the computational demand of CDFT and enhance the predictive capability of the PFC method. The approach utilizes a rational function fit (RFF) to approximate the two-body DCF in Fourier space. We use the RFF to empirically parameterize the two-body DCF allows us to obtain the thermodynamic properties of solids and liquids that agree with the results of CDFT simulations with the full two-body DCF without incurring significant computational costs. In addition, the RFF can also be used to improve the representation of the two-body DCF in the PFC method. Our third contribution involves an investigation of procedures for calculating isothermal elastic constants using the PFC method. We find that the conventional procedure used in the PFC method for calculating the elastic constants are inconsistent with those defined from a theory of thermoelasticity of stressed materials. Therefore, we present an alternative procedure for calculating the elastic constants that are consistent with the definitions from the thermoelasticity theory, and show that the two procedures result in different predictions. The second and third contributions together will provide necessary modeling capability for quantitative and accurate simulations of morphological evolution in metallic thin films.PhDMaterials Science and EngineeringUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/97988/1/nirand_1.pd