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The collisions frequency of dispersed phases (particles, droplets, bubbles) in a turbulent carrier phase is a fundamental quantity that is needed for modeling multiphase flows with applications to chemical processes, minerals flotation, food science, and many other industries. In this dissertation, numerical simulations are performed to determine collisions frequency of bi-dispersed particles (solid particles and bubbles) in homogeneous isotropic turbulence. Both direct numerical simulations (DNS) and Large Eddy simulations (LES) are conducted to determine velocity fluctuations of the carrier phase. The DNS results are used to validate existing theoretical models as well as the LES results. The dissertation also presents a CFD-based flotation model for predicting the pulp recovery rate in froth flotation machines. In the direct numerical simulations work, particles and bubbles suspended in homogeneous isotropic turbulence are tracked and their collisions frequency is determined as a function of particle Stokes number. The effects of the dispersed phases on the carrier phase are neglected. Particles and bubbles of sizes on the order of Kolmogorov length scale are treated as point masses. Equations of motion of dispersed phases are integrated simultaneously with the equations of the carrier phase using the same time stepping scheme. In addition to Stokes drag, the pressure gradient in the carrier phase and added-mass forces are also included. The collision model used here allows overlap of particles and bubbles. Collisions kernel, radial relative velocity, and radial distribution function found by DNS are compared to theoretical models over a range of particle Stokes number. In general, good agreement between DNS and recent theoretical models is obtained for radial relative velocity for both particle-particle and particle-bubble collisions. The DNS results show that around Stokes number of unity particles of the same group undergo expected preferential concentration while particles and bubbles are segregated. The segregation behavior of particles and bubbles leads to a radial distribution function that is less than one. Existing theoretical models do not account for effects of this segregation behavior of particles and bubbles on the radial distribution function. In the large-eddy simulations efforts, the dissertation addresses the importance of the subgrid fluctuations on the collisions frequency and investigates techniques for predicting those fluctuations. The cases studied are of particles-particles and particles-bubbles collisions at Reynolds number Re_λ = 96. A study is conducted first by neglecting the effects of subgrid velocity fluctuations on particles and bubbles motions. It is found that around Stokes number of unity solid particles of the same group undergo the well known preferential concentration as observed in the DNS. Effects of pressure gradient on the particles are negligible due to their small sizes. Bubbles as a low inertia particles are very sensitive to subgrid velocity and acceleration fields where the effects of pressure gradient in the carrier phase are dominant. However, particle-bubble radial distribution functions from LES are not as low as that from DNS. To account for the effects of subgrid field on the dispersion of particles and bubbles, a new multifractal methodology has been developed to construct a subgrid vorticity field from the resolved vorticity field in frame work of LES. A Poisson's solver is used to obtain the subgrid velocity field from the subgrid vorticity field. Accounting for the subgrid velocity fluctuations (but neglecting pressure gradient) produced minor changes in the radial distribution function for particle-particle and particle-bubble collisions. We conclude from this study that for accurate particle tracking in LES the subgrid velocity fluctuations must be dynamically realizable field (temporally and spatially correlated with the large scale motion). Adding random SGS velocity fluctuations is not enough to capture the correct radial distribution functions of dispersed phases especially for bubbles-particles collisions where the pressure gradient term ( or acceleration Du_f′/Dt) is responsible for particle-bubble segregation around particle Stokes number near one. A CFD-based model for minerals flotation machines has been developed in this dissertation. The objective of flotation models is to predict the recovery rate of minerals from a flotation cell. The developed model advances the state-of-the-art of pulp recovery rate prediction by incorporating validated theoretical collisions frequency models and detailed hydrodynamics from two-phase flow simulations. Spatial distributions of dissipation rate and air volume fraction are determined by the two-phase hydrodynamic simulations. Knowing these parameters throughout the machine is essential in understanding the effectiveness of different components of flotation machine (rotor, stator or disperser, jets) on the flotation efficiency. The developed model not only predicts the average pulp recovery rate but also it indicates regions of high/low recovery rates. The CFD-based flotation model presented here can be used to determine the dependence of recovery rate constant at any locality within the pulp based on particle diameter, particle specfic gravity, contact angle, and surface tension. / Ph. D.

The behavior of repairable equipment is often modeled under assumptions such as perfect repair, minimal repair, or negligible repair. However the majority of equipment behavior does not fall into any of these categories. Rather, repair actions do take time and the condition of equipment following repair is not strictly "as good as new" or "as bad as it was" prior to repair. Non-homogeneous processes that reflect this type of behavior are not studied nearly as much as the minimal repair case, but they far more realistic in many situations. For this reason, the quasi-renewal process provides an appealing alternative to many existing models for describing a non-homogeneous process. A quasi-renewal process is characterized by a parameter that indicates process deterioration or improvement by falling in the interval [0,1) or (1,Infinity) respectively. This parameter is the amount by which subsequent operation or repair intervals are scaled in terms of the immediately previous operation or repair interval. Two equivalent expressions for the point availability of a system with operation intervals and repair intervals that deteriorate according to a quasi-renewal process are constructed. In addition to general expressions for the point availability, several theoretical distributions on the operation and repair intervals are considered and specific forms of the quasi-renewal and point availability functions are developed. The two point availability expressions are used to provide upper and lower bounds on the approximated point availability. Numerical results and general behavior of the point availability and quasi-renewal functions are examined. The framework provided here allows for the description and prediction of the time-dependent behavior of a non-homogeneous process without the assumption of limiting behavior, a specific cost structure, or minimal repair. / Ph. D.

El proceso de atomización desde una vena o lámina líquida hasta multitud de gotas dispersas en un medio gaseoso ha sido un fenómeno de interés desde hace varias décadas, especialmente en el campo de los motores de combustión interna alternativos. Multitud de estudios experimentales han sido publicados al respecto, pues una buena mezcla de aire-combustible asegura una evaporación y combustión mucho más eficientes, aumentando la potencia del motor y reduciendo la cantidad de contaminantes emitidos. Con el auge de las técnicas computacionales, muchos modelos han sido desarrollados para estudiar este proceso de atomización y mezcla. Uno de los últimos modelos que han aparecido es el llamado ELSA (Eulerian-Lagrangian Spray Atomization), que utiliza un modelo Euleriano para la parte densa del chorro y cambia a un modelo Lagrangiano cuando la concentración de líquido es suficientemente pequeña, aprovechando de esta manera las ventajas de ambos. En el presente trabajo se ha desarrollado un modelo puramente Euleriano para estudiar la influencia de la geometría interna de la tobera de inyección en el proceso de atomización y mezcla. Se ha estudiado únicamente el proceso de inyección diésel. Este modelo permite resolver en un único dominio el flujo interno y el externo, evitando así las comunes simplificaciones y limitaciones de la interpolación entre ambos dominios resueltos por separado. Los resultados actuales son prometedores, el modelo predice con un error aceptable la penetración del chorro, el flujo másico y de cantidad de movimiento, los perfiles de velocidad y concentración, así como otros parámetros característicos del chorro. / Martí Gómez-Aldaraví, P. (2014). DEVELOPMENT OF A COMPUTATIONAL MODEL FOR A SIMULTANEOUS SIMULATION OF INTERNAL FLOW AND SPRAY BREAK-UP OF THE DIESEL INJECTION PROCESS [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/43719 / Premios Extraordinarios de tesis doctorales

Die Doktorarbeit beschäftigt sich mit der Synthese von mono- und bimetallischen Katalysatoren basierend auf Iridium, Rhodium und Palladium. Dabei wurden die zweizähnigen Phosphane Bis(diphenylphosphino)methan (dppm), Bis(di-iso-propylphosphino)methan (dippm), Diphenyl-2-pyridylphosphin (PPh2py), 2-(Di-iso-propylphosphino)imidazol (PiPr2Imd) und 2-(Di-iso-propylphosphino)-1-methylimidazol (PiPr2Imd-Me) zur Synthese von monometallischen Ir- und Rh-Komplexen eingesetzt. Diese monometallische Komplexe konnten dann als Präkursoren für die Synthese bimetallischer Komplexe ([M1M2], M1 = Ir, Rh, M2 = Rh, Pd) verwendet werden. Für die später untersuchten Katalysen wurden auch zu den heterobimetallischen IrPd-Komplexen analoge monometallische Pd-Komplexe dargestellt. Die hergestellten Komplexe wurden mittels 1H-NMR-, 31P{1H}-NMR- und IR-Spektroskopie sowie LIFDI-TOF-Massenspektrometrie charakterisiert. Für einige Verbindungen wurden Einkristalle für die Röntgenkristallstrukturanalyse erhalten. Die verschiedenen Komplexe wurden in unterschiedlichen Katalysen erfolgreich als Präkatalysator eingesetzt. So konnten verschiedene Reaktionen wie die Hydrodefluorierung von 1,2-Difluorbenzol, die Transferhydrierung von Acetophenon, die ß-Alkylierung von 1-Phenylethanol und die Phenoxycarbonylierung von p-Iodtoluol mit hohen Umsätzen durchgeführt werden. Dabei wurde gezeigt, dass die bimetallischen Präkatalysatoren gegenüber den monometallischen in der Hydrodefluorierung, der Transferhydrierung und der ß Alkylierung schnellere Reaktionszeiten und höhere Ausbeuten ermöglichen. In der Phenoxycarbonylierung waren die mono- sowie heterobimetallischen Pd-Komplexe am effizientesten. Durch den Einsatz des heterobimetallischen IrPd-Präkatalysators [IrPdCl3(CO)(PiPr2Imd)2] oder der analogen monometallischen Präkatalysatoren [IrCl(CO)(PiPr2Imd)2] und E-[PdCl(PiPr2Imd+-H)(PiPr2Imd-kP,kN1)]Cl konnten zwei Methoden zur Synthese des Esters 1,3-Diphenylpropyl-4-methylbenzoat entwickelt werden. / The doctoral thesis focuses on the synthesis of mono- and bimetallic catalysts based on iridium, rhodium, and palladium. Bidentate phosphines, namely bis(diphenylphosphino)methane (dppm), bis(di-iso-propylphosphino)methane (dippm), diphenyl-2-pyridylphosphine (PPh2py), 2-(di-iso-propylphosphino)imidazole (PiPr2Imd), and 2-(di-iso-propylphosphino)-1-methylimidazole (PiPr2Imd-Me) were employed for the synthesis of monometallic Ir and Rh complexes. These monometallic complexes were then utilized as precursors for synthesizing bimetallic complexes ([M1M2], M1 = Ir, Rh, M2 = Rh, Pd). For the subsequently investigated catalysis, analogous monometallic Pd complexes to the heterobimetallic IrPd complexes were also prepared. The synthesized complexes were characterized using 1H NMR, 31P{1H} NMR, and IR spectroscopy, as well as LIFDI-TOF mass spectrometry. Single crystals of some compounds were obtained for X-ray crystallographic analysis. These various complexes were successfully employed as precatalysts in different catalytic reactions. Various reactions such as the hydrodefluorination of 1,2-difluorobenzene, transfer hydrogenation of acetophenone, ß-alkylation of 1-phenylethanol, and phenoxycarbonylation of p-iodotoluene were conducted with high turnovers. It was demonstrated that the bimetallic precatalysts, compared to their monometallic counterparts, enable faster reaction times and higher yields in hydrodefluorination, transfer hydrogenation, and ß-alkylation. In phenoxycarbonylation, the mono- and heterobimetallic Pd complexes were most efficient. Two methodologies were developed for the synthesis of the ester 1,3-diphenylpropyl-4-methylbenzoate, using either the heterobimetallic IrPd precatalyst [IrPdCl3(CO)(PiPr2Imd)2] or the respective analogous monometallic precatalysts trans-[IrCl(CO)(PiPr2Imd)2] and E-[PdCl(PiPr2Imd+-H)(PiPr2Imd-kP,kN1)]Cl.

The field of robotics has witnessed significant advancements in recent years, with robotic arms playing a pivotal role in various industrial and research applications. In large-scale manufacturing, manual labour has been replaced with robots due to their efficiency in time and cost. However, in order to replace human labour, the robots need to collaborate in a way that humans do. This master's thesis, conducted at the Cyber-physical Systems Lab (CPS-Lab) at Uppsala University, delves into the intricacies of cooperative interactions between two homogenous robotic arms powered by machine learning algorithms, aiming to explore their collective capabilities. The project will focus on implementing a multi-agent cart-pole experiment that will challenge the two robotic arms' cooperative abilities. First, the problem is simulated, and afterwards implemented in real life. The experiment will be evaluated by the performance of various tested machine learning algorithms. In the end, The simulation yielded poor results due to the complexity of the problem and the lack of proper hyperparameter tuning. The real life experiment failed instantly, caused by the robotic arms not being designed for this application, a large simulation gap, and latency in the controller design. Overall, the results show that the experiment was challenging for the robotic arms, but that it might be possible under different circumstances.

Nowadays, the requirement to design highly valuable compounds is undoubtedly one of the major challenges in the field of organic and organometallic chemistry. The use of the versatile and efficient N-heterocyclic carbenes (NHCs) combined with transition metals represents a key feature in modern organometallic chemistry and homogeneous catalysis. In the course of this thesis, the straightforward design and synthesis of a library of Pd(0) bearing NHC ligands was achieved. Their catalytic performances (Chapter 1) and their phosphorescence properties in solution (Chapter 2) were disclosed. Currently, cross-couplings are some of the most important types of reaction in palladium catalysis. The formation of highly hindered biaryls substrates is one of the main requirements in cross-coupling chemistry. The design and synthesis of a palladium dimer bearing a bulky NHC ligand can fulfil this proposal (Chapter 4). The development of new classes of ligands is a topic of interest. For this reason, normal, abnormal, remote and mesoionic N-heterocyclic carbenes copper complexes were investigated and their reactivity compared in the [3+2] cycloaddition of azides and alkynes (Chapter 7). Air and moisture stable Cu(I)-NHC species have also been compared to their silver analogues for the alkynylation of ketones (Chapter 9). The different reactivity of the two latter organometallic species (Cu and Ag) with ethyldiazoacetate reagent via the formation of carbenes or C-H activated product is presented in Chapter 8. Recently, the development of a bimetallic catalytic system is strongly considered and has high impact. For this reason, two dual catalytic transformations (Pd-NHC and Cu-NHC) were studied for the C-H arylation (Chapter 5) and the synthesis of substituted alkenes products via a relay or cooperative mechanisms (Chapter 6). The isolation of intermediates and mechanistic studies were examined in each of these studies.

Aqueous-biphasic organometallic catalysis is, as illustrated by the industrial hydroformylation of propene and butene, one of the most promising ways to overcome the intrinsic problem of catalyst separation in organometallic catalysis. However, for poorly water-soluble substrates, mass transfer limitations bring the reaction rate below any that could be economically viable, greatly limiting the scope of this elegant technology. We have studied three different strategies to overcome this limitation. We developed additives that speed up the reaction whilst retaining fast phase separation and good metal retention. Evidence suggests that those additives affect the reaction by forming emulsions with poor stability under the reaction conditions These emulsions increase the interfacial surface area but break after settling for a short time. We also developed ligands that allow the catalyst to be reversibly transported between an aqueous and an organic phase upon addition and removal of carbon dioxide. This allows the reaction to be carried out under homogeneous conditions, only limited by intrinsic kinetics, and the catalyst to be separated by aqueous extraction triggered by carbon dioxide. The catalyst can be returned to a fresh organic phase by flushing out the carbon dioxide. By applying this methodology for the hydroformylation of medium chain length alkenes, very high reaction rates were obtained and the catalyst could be recycle three times with excellent retention of activity and low metal leaching. This methodology could also be reversed with the reaction being carried out in an aqueous phase in the presence of carbon dioxide and extracting the catalyst into an organic solvent using nitrogen flushing. Finally, we briefly investigated the use of an oscillatory baffled reactor as a mean for mass transfer improvement for aqueous-biphasic hydroformylation. This new type reactor did not improve the performance of the system under the investigated conditions, but may require less energy input for equivalent agitation and mixing.

Several ligands derived from D-glucosamine, designed for different catalytic reactions havebeen synthesized. The ligands for homogeneous catalysis based on 1,2-glucodiamine wereprepared, and used in reactions of allylic alkylation, hydrogenation and Michael addition.Supported Aqueous Phase Catalyst (SAPC) system was prepared from D-glucosamine anduse with very good results in Suzuki Miyaura cross coupling reactions. Catalyst was alsorecycled. Attempt to prepare ligands grafted on SBA-silica matrix were made as well asligands containing poly(ethylene) glycol moiety.

In this work, we wish to determine the free energy landscape and the nucleation rate associated with the process of homogeneous ice nucleation. To do this, we simulate the homogeneous nucleation of ice with the mW monatomic model of water and with all-atom models of water using primarily the umbrella sampling rare event method. We find that the use of the mW model of water, which has simpler dynamics compared to all-atom models of water, but is nevertheless surprisingly good at reproducing experimental data, results in very reasonable agreement with classical nucleation theory, in contrast to some previous simulations of homogeneous ice nucleation. We suggest that previous simulations did not observe the lowest free energy pathway in order parameter space because of their use of global order parameters, leading to a deviation from classical nucleation theory predictions. Whilst monatomic water can nucleate reasonably quickly, all-atom models of water are considerably more difficult to simulate, primarily because of their slow dynamics of ice growth and the fact that standard order parameters do not work well in driving nucleation when such models are being used. In this thesis, we describe a local, rotationally invariant order parameter that is capable of growing ice homogeneously in a biassed simulation without the unnatural effects introduced by global order parameters, and without leading to non-physical chain-like growth of 'ice' clusters that results from a naïve implementation of the standard Steinhardt-Ten Wolde order parameter. We have successfully used this order parameter to force the growth of ice clusters in simulations of all-atom models of water. However, although ice growth can be achieved, equilibrating simulations with all-atom models of water is extremely difficult. We describe several approaches to speeding up the equilibration in all-atom models of water to enable the computation of free energy profiles for homogeneous ice nucleation.