A microfluídica atua em áreas como controle de fluxo, e \"química e ciências da vida\". Nesta última área encontram-se dispositivos como micro-agulhas, micro-separadores, microdispensadores, micro-reatores e micromisturadores. Em particular, micromisturadores podem estar presentes nas mais variadas aplicações na industria e na ciência, que necessitam de mistura de fluidos. Uma dessas aplicações é a encapsulação de ativos por uma matriz polimérica (micro-esferas poliméricas) para sistemas de liberação controlada. Nos processos convencionais de encapsulação uma das etapas cruciais é a produção de emulsões simples e múltiplas, que é o resultado do processo de mistura de dois líquidos imiscíveis. A introdução de micromisturadores para formação de emulsões é uma alternativa tecnológica que foi explorada neste trabalho. Portanto, foi realizado um estudo de pré-formulação, no qual foram produzidas micro-esferas poliméricas sem nenhum ativo encapsulado através de n misturadores microfluídicos diferentes. Os dispositivos mais eficientes foram identificados através das características das micro-esferas produzidas, tais como: diâmetro médio de partícula, índice de dispersão da distrib uição de partículas e morfologia (forma geométrica). Identificados os dispositivos, parâmetros de processo foram estudados, tais como: vazão e formulação. Os resultados obtidos indicaram que é possível produzir micro-esferas poliméricas com suas principais características controladas: tamanho e índice de dispersão. / Microfluidics actuates in areas as flow control, and \"chemistry and life sciences\". In this latter area appear devices as microneedles, microseparators, microdispensers, micro-reactors and micromixers. In particular, micromixers can be found in several applications in industry and science where it is needed fluid mixing. One of these applications is the asset encapsulation of a polymeric matrix (polymeric microspheres) for controlled release systems. In conventional processes of encapsulation one of crucial steps is the production of simple or multiple emulsions, which is the result of the mixing process of two immiscible liquids. Utilization of micromixers for emulsion preparation is a technological alternative that is explored in this work. Therefore, it was realized a pre-formulation study, for production of polymeric microspheres without any asset encapsulated, through several microfluidic mixers. The more efficient devices were ident ified through characteristic parameters of produced microspheres, such as: particle average diameter, dispersion index of particle size distribution and morphology (geometric shape). After device identification, process parameters were studied, such as: flow rate and formulation. Obtained results indicated that it is possible to produce polymeric microspheres with its main controlled characteristics: size and dispersion index.

As variáveis de processo determinam as propriedades dos produtos resultantes dos processos de fundição ou de soldagem, que são função da sua macro e microestrutura bruta de solidificação. Um dos parâmetros importantes para se determinar as propriedades de um produto é a posição da transição colunarequiaxial (CET) e, por este motivo, o entendimento dos fenômenos físicos que causam esta transição é essencial. Com o intuito de se prever a formação da CET, surgiram os métodos empíricos e os modelos matemáticos, que são divididos em dois grandes grupos: modelos determinísticos e modelos estocásticos. Estes dois grupos foram bem estudados, porém nunca foram comparados entre si, particularmente em relação à previsão da posição da CET. O presente trabalho tem como um primeiro objetivo preencher esta lacuna através da comparação entre estes modelos. No entanto, o objetivo principal é apresentar, implementar e validar um novo modelo matemático, denominado de híbrido estocástico-determinístico (CADE -\"Cellular Automaton Deterministic\"), que combine características importantes e vantajosas de cada um dos dois grupos de modelos. Inicialmente, um modelo representante do grupo dos modelos estocásticos foi implementado e validado frente a resultados disponíveis na literatura. Durante esta validação, foi necessária a elaboração de um critério baseado na razão de aspecto dos grãos para a identificação da CET nas macroestruturas calculadas pelo modelo. Estes resultados foram então comparados com os resultados de modelos determinísticos para, após cuidadosa discussão, possibilitar a proposta e implementação do modelo híbrido. Os modelos determinísticos que utilizam o critério mecânico para prever o bloqueio de grãos colunares e a ocorrência da CET mostram regiões colunares em geral maiores que as previstas pelo modelo estocástico. Por outro lado, os modelos determinísticos que utilizam um critério de bloqueio a partir da interação do campo de concentração de soluto ao redor dos grãos prevêem uma CET em posições semelhantes às calculadas pelos modelos estocásticos. O modelo implementado no presente trabalho é capaz de prever a macroestrutura bruta de solidificação e ainda utilizar as equações tradicionalmente empregadas nos modelos determinísticos, sem a necessidade de qualquer método extra para prever a posição da frente de crescimento colunar ou o seu bloqueio por grãos equiaxiais. / The processing variables determine many properties of the products obtained by casting and welding processes and these properties, on the other hand, are strongly affected by the as-cast micro and macrostructure. Particularly the position of the columnar-to-equiaxed transition (CET), which determines the amount of columnar and equiaxed grains in the macrostructure, has an important effect on the properties of as-cast parts. Therefore, understanding the important physical phenomena that cause and affect the formation of the CET plays a crucial role in predicting the ascast macrostructure. To predict the CET formation, empirical methods and mathematical models have been developed. These models are frequently divided into two main groups: deterministic and stochastic. Both groups have been thoroughly studied, but a comparison between them was never attempted, especially regarding the prediction of the CET position. One of the main objectives of the present work is to fulfill this gap by carefully comparing these models. Nevertheless, the most important objective is to propose, implement, and validate a hybrid stochastic-deterministic model, referred to as CADE (Cellular Automaton Deterministic), that combines some important and well-known features of each model. Initially, a model from the stochastic group was implemented and validated using results available in the literature and then used to analyze the effects of some processing variables on the CET prediction. To carry out this analyzes, a criteria based on the aspect ratio of the grains was proposed and developed to identify the CET region from macrostructure images calculated by the model. The results were compared with those obtained by deterministic models and finally led to the development of the new proposed model. This new model has some characteristics from each group of mathematical models and, for this reason, was denoted as hybrid. A deterministic model based on a mechanical blocking criterion to block columnar grains and define the CET position showed, for the most part, larger columnar regions than those predicted by the stochastic model. A deterministic model with a solutal blocking criterion to predict the CET showed results similar to those calculated with the stochastic model. The model proposed in the present work (CADE) was able to predict the as-cast macrostructure using the well-established deterministic equations, without the need for a new method to track columnar grains or predict their blocking by equiaxed grains.

<p>Prikazana je procedura modelovanja prekidnog sušenja materijala sfernog oblika u tankom sloju, nakon čega je pokrenuta računarska simulacija procesa na osnovu predloženog modela. Zatim, odrađeno je eksperimantalno istraživanje, za šta su korišćeni svježe ubrani orasi u ljusci, bez komine. Nakon što je statistički potvrđena pouzdanost modela, on je iskorišćen kao baza formiranje modela za simulaciju sušenja u debelom sloju. Posle toga su urađeni eksperimenti i za druge materijale različitih osobina (krompir, bundeva i kestenje), da bi se izveli zaključci o mogućnosti energetske uštede u procesima konvektivnog sušenja u zavisnosti od fizičkih osobina materijala. Ovim istraživanjem pokazano je da su sa stanovišta uštede energije prekidni režimi konvektivnog sušenja preporučljiviji kod materijala koji imaju veću efektivnu difuzivnost.</p> / <p>This research shows the procedure of modeling the intermittent drying of sphereshaped<br />materials in a thin-layer, after which the computer simulation was done, based<br />on the proposed model. Тhe experimental investigation has been done, where the<br />fresh collected in-shell walnuts had served as the main drying material. As the model<br />reliability was experimentally confirmed, it was used as а basis for creating а model for<br />deep-bed drying simulation. Afterwards, the experimental investigation was done for<br />other materials as well (potato, pumpkin and chestnuts), in order to draw the<br />conclusions concerning the possibility of energy saving in convective drying processes,<br />as it depends on physical properties of a material. This research showed that, from the<br />perspective of energy saving, it is more advisable to use an intermittent regime if a<br />material has a higher effective diffusivity.</p>

Future nanofiltration (NF) membranes used for selective separations of ions and small organic molecules must maintain performance in environments where high concentrations of total dissolved solvents or foulants are present. These challenges can be addressed through the development of composite membranes, as well as the engineering of enhanced surface properties and operating conditions for existing commercial membranes. In this work, ion transport through commercial thin film composite (TFC) polyamide NF membranes were studied in both lab-prepared salt solutions and industrial wastewater. The dependence of several variables on ion rejection was investigated, including ion radius, ion charge, ionic strength, and temperature. The impact of scaling and increasing ionic concentration on membrane performance during recovery of industrial wastewater was investigated. Fouling of the membrane surface was reduced by enhancing commercial NF membrane surfaces via aqueous-phase esterification of lignin sulfonate. NF membranes were also created utilizing an ionic liquid solvent (1-ethyl-3-methylimidazolium acetate) to integrate composite materials into cellulose. Composite materials such as graphene oxide quantum dots, iron III particles, and lignin have been shown to be interact strongly with cellulose in solution with ionic liquid and bind together cellulose chains via hydrogen bonds following nonsolvent induced phase inversion. Studies suggest the composite materials modify membrane surface chemistry and improve selectivity of small organic molecules (~300 nm) while allowing for the complete passage of ions.

Mathematical models were developed to understand cavity growth mechanisms, heat and mass transfer in combination with chemical reaction, and the factors which affect gas production from an underground coal gasifier. A model for coal gasification in a one-dimensional spatial domain was developed and validated through comparison with experimental measurements of the pyrolysis of large coal particles and cylindrical coal blocks. The effects of changes in operating conditions and coal properties on cavity growth were quantified. It was found that the operating conditions which have the greatest impact on cavity growth are: temperature, water influx, pressure and gas composition, while the coal properties which have the greatest impact are: the thermo-mechanical behaviour of the coal, the coal composition and the thickness of the ash layer. Comparison of the model results with estimates from field scale trials, indicate that the model predicts growth rates with magnitudes comparable to those observed. Model results with respect to the effect of ash content, water influx and pressure are in agreement with trends observed in field trials. A computational fluid dynamics model for simulating the combined transport phenomena and chemical reaction in an underground coal gasification cavity has been developed. Simulations of a two-dimensional axi-symmetric cavity partially filled with an inert ash bed have shown that when the oxidant is injected from the bottom of the cavity, the fluid flow in the void space is dominated by a single buoyancy force due to temperature gradients established by the combustion of volatiles produced from the gasification of carbon at the cavity walls. Simulations in which the oxidant was injected from the top of the cavity reveal a weak fluid circulation due to the absence of strong buoyancy forces, leading to poor gasification performance. A channel model of gas production from underground coal gasification was developed, which incorporates a zero-dimensional cavity growth model and mass transfer due to natural convection. A model sensitivity study is presented and model simulations elucidate the effects of operating conditions and coal properties on gas production.

This thesis deals with diffusion and flow of sub-critical hydrocarbons in activated carbon by using a differential permeation method. The hydrocarbons are selected according to the effect on environmental concerns and their unique characteristics such as polarity and affinity towards activated carbon. Although it has been known that transport processes in activated carbon consist of Knudsen diffusion, gaseous viscous flow, adsorbed phase diffusion (so called, surface diffusion) and condensate flow, there have been no rigorous models to describe the transport processes in activated carbon with a full range of pressures. In particular among the four processes, the mechanism of adsorbed phase diffusion in activated carbon is still far from complete understanding. Also due to the dispersion interactions between adsorbing molecules and the solid surface, one would expect that Knudsen diffusion is influenced by the dispersive forces. From intensive experimental observations with a great care over a full range of pressures, conventional methods (for example, direct estimation from inert gas experiments) to determine adsorbed phase diffusion are found to be inadequate for strongly adsorbing vapors in activated carbon. By incorporating the effect of adsorbate-adsorbent interactions into Knudsen diffusivity, the general behavior of adsorbed phase diffusion in terms of pressure (or surface loading) can be obtained, showing a significant role in transport at low pressures. For non-polar hydrocarbons such as benzene, carbon tetrachloride and n-hexane, a mathematical model, which accounts for the effects of adsorbate-adsorbent interactions and pore size distribution, is formulated and validated, resulting in a good agreement with experimental data. Moreover, the adsorption and dynamic behaviors of alcohol molecules (which are polar compounds) are investigated with an aim to compare their behaviors against those of non-polar compounds.

Molten carbonate fuel cells (MCFCs) have become an attractive emerging technology for stationary co-generation of heat and power. From a technical perspective, dynamic operation has a significant effect on the fuel cell life cycle and, hence, economic viability of the device. The scope of this thesis is to present an improved understanding of the system behaviour at transient operation that can be used to design a more robust control system in order to overcome the cost and the operating lifetime issues. Hence, a comprehensive multi-component multidimensional transient mathematical model is developed based on the conservation laws of mass, momentum, species, energy and electric charges coupled through the reaction kinetics. In essence, this model is a set of partial differential equations that are discretized and solved using the finite-volume based commercial software, ANSYS FLUENT 12.0.1. The model is validated with two sets of experimental results, available in open literature, and good agreements are obtained. The validated model is further engaged in an extensive study. First, the MCFC behaviour at high current densities or oxidant utilization, when the mass transfer becomes dominant, is investigated using peroxide and superoxide reaction mechanisms. In brief, both mechanisms predicted the linear region of the polarization curve accurately. However, none of these mechanisms showed a downward bent in the polarization curve. A positive exponent for the carbon-dioxide mole fraction is probably essential in obtaining the downward bent (“knee”) at high current densities which is in contrast to what has been reported in the literature to date. Next, a sinusoidal impedance approach is used to examine the dynamic response of the unit cell to inlet perturbations at various impedance frequencies. This analysis is further used to determine the phase shifts and time scales of the major dynamic processes within the fuel cell. Furthermore, numerical simulation is utilized in order to investigate the underlying electrochemical and transport phenomena without performing costly experiments. Results showed that the electrochemical reactions and the charge transport process occur under a millisecond. The mass transport process showed a comparatively larger time scale. The energy transport process is the slowest process in the cell and takes about an hour to reach its steady state condition. Furthermore, the developed mathematical model is utilized as a predictive tool to provide a three-dimensional demonstration of the transient physical and chemical processes at system startiv up. The local distribution of field variables and quantities are presented. The results show that increasing the electrode thickness provides a higher reaction rate, but may lead to larger ohmic loss which is not desirable. The reversible heat generation and consumption mechanisms of the cathode and anode are dominant in the first 10 s while the heat conduction from the solid materials to the gas phase is not considerable. The activation and ohmic heating have the same impact within the anode and cathode because of their similar electric conductivity and voltage loss. Increasing the thermal conductivity of the cathode material will facilitate the process of heat transport throughout the cell. This can also be accomplished by lowering the effects of heat conduction by means of a cathode material with a smaller thickness. In addition, a thermodynamic model is utilized to examine energy efficiency, exergy efficiency and entropy generation of a MCFC. By changing the operating temperature from 883 K to 963 K, the energy efficiency of the unit cell varies from 42.8 % to 50.5 % while the exergy efficiency remains in the range of 26.8% to 36.3%. Both efficiencies initially rise at lower current densities up to the point that they attain their maximum values and ultimately decrease with the increase of current density. With the increase of pressure, both energy and exergy efficiencies of the cell increase. An increase in this anode/cathode flow ratio lessens the energy and exergy efficiencies of the unit cell. Higher operating pressure and temperature decrease the unit cell entropy generation. / UOIT

Polymer electrolyte membrane (PEM) fuel cells have increasingly become promising green energy sources for automobile and stationary cogeneration applications but its success in commercialization depends on performance optimization and manufacturing cost. The activation losses, expensive platinum catalyst, and water flooding phenomenon are the key factors currently hindering commercialization of PEM fuel cells. These factors are associated with the cathode catalyst layer (CCL), which is about ten micrometers thick. Given the small scale of this layer, it is extremely difficult to study transport phenomena inside the catalyst layer experimentally, either intrusively or non-intrusively. Therefore, mathematical and numerical models become the only means to provide insight on the physical phenomena occurring inside the CCL and to optimize the CCL designs before building a prototype for engineering application. In this thesis research, a comprehensive two-phase mathematical model for the CCL has been derived from the fundamental conservation equations using a volume-averaging method. The model also considers several water transport and physical processes that are involved in the CCL. The processes are: (a) electro-osmotic transport from the membrane to the CCL, (b) back-diffusion of water from the CCL to the membrane, (c) condensation and evaporation of water, and (d) removal of liquid water to the gas flow channel through the gas diffusion layer (GDL). A simple analytical model for the activation overpotential in the CCL has also been developed and an optimization study has been carried out using the analytical activation overpotential formulation. Further, the mathematical model has been simplified for the CCL and an analytical approach has been provided for the liquid water transport in the catalyst layer. The volume-averaged mathematical model of the CCL is finally implemented numerically along with an investigation how the physical structure of a catalyst layer affects fuel cell performance. Since the numerical model requires various effective transport properties, a set of mathematical expressions has been developed for estimating the effective transport properties in the CCL and GDL of a PEM fuel cell. The two-dimensional (2D) numerical model has been compared with the analytical model to validate the numerical results. Subsequently, using this validated model, 2D numerical studies have been carried out to investigate the effect of various physical and wetting properties of CCL and GDL on the performance of a PEM fuel cell. It has been observed that the wetting properties of a CCL control the flooding behavior, and hydrophilic characteristics of the CCL play a significant role on the cell performance. To investigate the effect of concentration variation in the flow channel, a three-dimensional numerical simulation is also presented.

Nowadays, the development of novel materials involves diverse branches of science as a consequence of the new requirements imposed by modern society. This includes aspects ranging from the optimization of the manufacturing processes to the durability of the materials themselves. Ideally, some synergism should exist between the durability, the properties of interest in the material. Although metals in their pure state are often desired, the best properties or combination of properties often cannot be satisfactorily achieved with a single metal. In these situations, the desired properties can be attained by the formation of alloys of these metals with others. Ni-Co alloys are no exceptions and so have received considerable attention especially in microsystem technology due to the magnetic properties of cobalt and the corrosion and wear resistance of nickel. Moreover, this interest has been further stimulated by its use in the manufacture of sensors, magnetic devices, microrelays, inductors, actuators, memory devices and hard drives. The fabrication of these alloys (particularly coatings) via electroplating has been shown to be techno-economically feasible in comparison with other processes: capability of high volume production, low cost and the ability to coat thin layers on non-planar substrates. In addition, the materials fabricated by this technology exhibit excellent characteristics such as refined grain structure, smoothness, low residual stress and coercivity, etc., making them advantageous to materials produced by other physical methods of deposition. Nevertheless, one of the biggest problems faced during the formation of Ni-Co alloys is its anomalous behavior whereby cobalt preferentially deposits over nickel under most conditions, even when the Ni(II) concentration is significantly higher than that of Co(II). This problem has complicated the prediction and control of the metal composition in these alloys during their production and as a consequence the ability to obtain the desirable properties associated with high nickel content. Although this problem is not recent, the studies that have been carried out so far to analyze this system have not always been as comprehensive as they could be in terms of the experimental conditions investigated or the reaction mechanisms and mathematical models developed to describe its behavior. Consequently, the origin of this behavior is still not completely understood. Thus, this work presents a contribution in terms of the analysis of the reaction mechanisms for single metal deposition of nickel and cobalt and for the formation of Ni-Co alloys in sulphate media with the intention of gaining a better understanding of the phenomena controlling the anomalous behavior of this system. Analyses of the single metal deposition of nickel and cobalt are first carried out to better understand their reaction mechanisms. Such an approach should allow the contributions of the reduction of each metal ion and interactions between the two systems during alloy co-deposition to be more clearly understood. In order to analyse the aforementioned systems, both steady state and transient techniques are employed. Among these techniques, electrochemical impedance spectroscopy (EIS) is employed since it is a robust and powerful method to quantitatively characterize the various relaxation phenomena occurring during the electrodeposition of metals. The experimental data acquired from this technique are analyzed with comprehensive physicochemical models and the electrochemical processes are quantified by fitting the models to these data to determine the kinetic parameters. During the development of the physicochemical models, several assumptions (e.g. neglect of convection, homogeneous reactions and single electron-transfer steps) made in former models are relaxed in order to investigate their combined impact on the predicted response of the system. Estimates of the kinetic parameters determined by EIS for the deposition of the single metals reveals that the first step of Co(II) reduction is much faaster tha the corresponding step of Ni(II) reduction. Some limitations of the EIS technique (i.e. analysis at high overpotentials) are exposed and compared in the case of the nickel deposition using linear sweep voltammetry (LSV). Likewise, physicochemical models accounting for most of the important phenomena are derived and fitted to experimental data. Ni-Co alloy formation is analyzed using LSV and steady state polarization experiments for different pH, current density and electrolyte composition. Current efficiencies for metal depsoition and alloy composition are also evaluated. To date, no experimental study considering all these variables has been reported in the literature. Then a steady state model is presented to describe the electrode response during alloy formation and used to provide insight into the anomalous behavior of this system. This model is based on information obtained from previous studies reported in the literature and from the current research. After being fitted to the experimental data, the model reveals that the anomalous behavior observed for this alloy is likely caused by the much faster charge-transfer of Co(II) reduction than that of Ni(II) reduction and not by other previously proposed mechanisms such as competition between adsorbed species for surface sites, formation of aqueous hydroxides (MeOH+) or mixed intermediate species (NiCo(III)ads) on the surface of the electrode.

Area averaging is one of the techniques used to solve problems encountered in the transport of momentum, heat, and mass. The application of this technique simplifies the mathematical solution of the problem. However, it necessitates expressing the local value of the dependent variable and/or its derivative(s) on the system boundaries in terms of the averaged variable. In this study, these expressions are obtained by the two-point Hermite expansion and this approximate method is applied to some specific problems, such as, unsteady flow in a concentric annulus, unequal cooling of a long slab, unsteady conduction in a cylindrical rod with internal heat generation, diffusion of a solute into a slab from limited volume of a well-mixed solution, convective mass transport between two parallel plates with a wall reaction, convective mass transport in a cylindrical tube with a wall reaction, and unsteady conduction in a two -layer composite slab. Comparison of the analytical and approximate solutions is shown to be in good agreement for a wide range of dimensionless parameters characterizing each system.