Heat transfer and solidification models were developed for use in a numerical model of a continuous caster to provide a means of predicting how the developing shell would react under variable operating conditions. Measurement data of the operating conditions leading up to a breakout occurrence were provided by an industrial collaborator and were used to define the model boundary conditions. Steady-state and transient simulations were conducted, using boundary conditions defined from time-averaged measurement data. The predicted shell profiles demonstrated good agreement with thickness measurements of a breakout shell segment – recovered from the quarter-width location. Further examination of the results with measurement data suggests pseudo-steady assumption may be inadequate for modeling shell and flow field transition period following sudden changes in casting speed. An adaptive mesh refinement procedure was established to increase refinement in areas of predicted shell growth and to remove excess refinement from regions containing only liquid. A control algorithm was developed and employed to automate the refinement procedure in a proof-of-concept simulation. The use of adaptive mesh refinement was found to decrease the total simulation time by approximately 11% from the control simulation – using a static mesh.

This work aims at modelling and evaluating a new type of photocatalytic reactors, named fixed-bed photocatalytic membrane reactor (FPMR). Such reactors are based on the deposition of a thin layer of photocatalysts on a permeable substrate by filtration. This layer serves as a photocatalytic membrane, named fixed-bed photocatalytic mem-brane (FPM), which is perpendicularly passed by the reactant solution and illuminated by a suitable light source. One advantage of FPMs is their renewability. The model, which was developed for this reactor, relates the overall reaction rate in the FPM with the intrinsic reaction kinetic at the catalyst surface and accounts for light intensity, structural and optical layer properties as well as the mass transfer in the pores. The concept of FPMR was realised by using a flat sheet membrane cell. It facilitated principal investigations into the reactor performance and the validity of the model. For this purpose, the photocatalytic degradation of organic compounds, such as meth-ylene blue and diclofenac sodium, was conducted at varying conditions. Pyrogenic ti-tania was used as a photocatalyst. The experimental data support the developed mod-el. They also indicate a significant impact of the flow conditions on the overall photo-catalytic activity, even though the Reynolds number in the FPM was very small; the to-tal mass transfer rate in the FPM amounted to more than 1.0 s−1. The experiments also showed a sufficient structural strength of the FPM and photocatalytic stability. In addi-tion, the renewal and regeneration of FPMs was successfully demonstrated. Furthermore, another FPMR was designed by means of submerged ceramic mem-branes. This reactor was mainly used to assess the effectiveness and efficiency of FPMRs at the example of the photocatalytic degradation of oxalic acid. The correspond-ing reactor was run closed loop and in continuous mode. The effectiveness of the reac-tor was evaluated based on common descriptors, such as apparent quantum yield, photocatalytic space-time yield and light energy consumption. The results showed that the FPMR based on submerged ceramic membrane had a higher efficiency than other reported photocatalytic reactors. The comparison of the different modes of operation revealed that the closed loop FPMR is most efficient with regard to light energy con-sumption. Finally, this work discusses the up-scaling of FPMRs for industrial applications and proposes a solution, which can e.g. be employed for wastewater treatment or CO2 conversion.:Abstract iii Kurzfassung v Acknowledgment vii Contents ix Nomenclature xiii 1 Introduction 1 1.1 Motivation 1 1.2 Aim and objectives of the work 3 1.3 Thesis outline 3 2 Heterogeneous photocatalytic reactors 5 2.1 Introduction to photocatalysis 5 2.2 Processes in heterogeneous photocatalysis 6 2.2.1 Optical phenomena 7 2.2.2 Mass transfer 8 2.2.3 Adsorption and desorption 9 2.2.4 Photocatalytic reactions 10 2.2.5 Factors affecting heterogeneous photocatalysis 12 2.3 Photocatalytic reactor systems towards water treatment 16 2.3.1 Introduction to photocatalytic reactors 16 2.3.2 Development of photocatalytic reactor designs 17 2.3.3 Quantitative criteria for evaluating photocatalytic reactor designs 21 2.4 Cake layer formation in membrane microfiltration 22 2.4.1 Suspension preparation 22 2.4.2 Cake layer formation 23 2.5 Fluid flow through a fixed bed of particles 25 2.5.1 Pressure drop through a fixed-bed 25 2.5.2 Liquid-solid mass transfer correlation in fixed-bed 25 3 Concept and mathematical modelling of FPMRs 29 3.1 Concept of fixed-bed photocatalytic membrane reactors 29 3.2 Modelling of fixed-bed photocatalytic membrane reactors 31 3.3 Model sensitivity analysis 37 3.4 Chapter summary 39 4 FPMR realised with flat sheet polymeric membrane 41 4.1 Introduction 41 4.2 Materials and set-up 41 4.2.1 Materials 41 4.2.2 Experimental set-up 43 4.3 Experiments and methods 48 4.3.1 Formation of fixed-bed photocatalytic membrane 48 4.3.2 Reactor performance 50 4.3.3 Parameters study and model verification 53 4.3.4 Catalyst layer characterisation 56 4.3.5 Measurement and evaluation of photocatalytic activity of FPM 59 4.4 Results and model verification 60 4.4.1 Reactor performance 60 4.4.2 Influence parameters 71 4.4.3 Model verification 79 5 FPMR realised with submerged ceramic membrane 92 5.1 Introduction 92 5.2 Materials and reactor set-up 93 5.2.1 Reactor set-up 93 5.2.2 Chemicals 97 5.3 Experiments and methods 97 5.3.1 Formation of fixed-bed photocatalytic membranes 97 5.3.2 Photocatalytic performance 97 5.3.3 Parameter study 98 5.3.4 Reactor model for calculating reaction rate constant of FPM 99 5.3.5 Comparison of different reactor schemes 102 5.4 Results and discussions 105 5.4.1 Reactor performance 105 5.4.2 Consistency of CPMR and LPMR data 107 5.4.3 Influence of catalyst loading 108 5.4.4 Influence of permeate flux and light intensity 109 5.4.5 Reactor efficiency 111 5.4.6 Comparison of different reactor schemes 113 5.5 Proposed up-scaled FPMR systems 113 5.6 Concluding remarks 116 6 Conclusion and outlook 118 6.1 Summary of thesis contributions 118 6.2 Discussion and outlook 120 References 122 List of Figures 134 List of Tables 138 Appendix A Calibration 139 A.1 Distribution of light intensity on the surface of catalyst layer 139 A.2 Concentration and absorbance of diclofenac 141 A.3 TOC concentration and electrical conductivity of oxalic acid 141 A.4 Concentration and absorbance of methylene blue 142 Appendix B Mathematical modelling 143 B.1 Influence of axial dispersion on the reaction rate 143 B.2 Special case 146 Appendix C Comparison the photocatalytic activity of TiO2 and ZnO 147 Appendix D Mathematical validation of model for LPMR and CPMR 148 D.1 Model for LPMR (cf. Eq. (5 12)):148 D.2 Model for CPMR (cf. Eq. (5 17)) 149 Appendix E Particle size distribution 151

The assessment of performance for PEM Fuel Cells (PEMFC) at the stack, Single Repeating Unit (SRU), and Membrane Electrode Assembly (MEA) level is dominated by the evaluation of polarization curves. However, polarization curves do not provide adequate detail as to the origin of the inefficiencies of the fuel cell performance and information on these sources of origin are critical to understand and address topics such as material selection, optimal operating conditions, and overall robust and reliable cell and stack design characteristics. To the purpose of understanding the origin of the inefficiencies underlying the fuel cell polarization curve a series of additional experimental and analysis techniques must be applied and from the resultant data the origin of the inefficiencies can then be assigned to kinetic, ohmic, and mass transport loss categorizations. Further, through a combination of the diagnostic methods further resolution can be implied down to the contribution of the individual components to the relative voltage loss categories. In this topic, a methodology will be presented and discussed that achieves and demonstrates this process.

In verfahrenstechnischen Anlagen der Flüssig-Flüssig-Stoffübertragung kommt es an der Phasengrenze zwischen den nicht mischbaren Flüssigphasen häufig zur Ausbildung hydrodynamischer Instabilitäten. Sie sind mit komplexen Geschwindigkeitsfeldern in den Flüssigphasen, insbesondere in den grenzschichtnahen Regionen verbunden und führen zu einem starken Anstieg der pro Zeiteinheit übertragenen Stoffmenge. Die Lösung der Diffusionsgleichung reicht in diesem Fall zur Vorausberechnung des für Auslegungszwecke bedeutsamen Stoffdurchgangskoeffizienten nicht mehr aus. Chemische Reaktionen stellen Quellen oder Senken von Wärme und Stoff dar, die das Auftreten von Instabilitäten begünstigen und die mathematische Beschreibung zusätzlich erschweren. Im Rahmen der vorliegenden Arbeit wurden experimentelle und numerische Untersuchungen zum Flüssig-Flüssig-Stoffübergang in einem vertikalen Kapillarspalt durchgeführt. Reaktionsfreie Stoffübergänge und solche mit einer exothermen chemischen Reaktion an der Phasengrenze zeigten eine große Vielfalt von Konvektionsstrukturen, wie Rollzellen, Thermiken und das doppeldiffusive Fingerregime. Die Visualisierung der Transportvorgänge erfolgte durch das Schattenschlierenverfahren. Die Beobachtungen wurden hinsichtlich geometrischer Eigenschaften von Konvektionsstrukturen sowie deren zeitlicher Änderung ausgewertet. Dazu zählten insbesondere das Längenwachstum von Thermiken und horizontale Wellenlängen von Fingerstrukturen. Zur mathematischen Beschreibung der Phänomene im Kapillarspalt wurde ein Modell entwickelt, welches auf den gekoppelten, zweidimensionalen Transportgleichungen von Impuls, Wärme und Stoff beruht. Es berücksichtigt dichte- und grenzflächenspannungsgetriebene Instabilitätsmechanismen sowie die besonderen Durchströmungseigenschaften des Kapillarspalts. Die Phasengrenze wurde als eben angenommen. Die Lösung der Modellgleichungen erfolgt auf numerischem Wege durch ein Computerprogramm. Das Modell ist in der Lage, die beobachteten Instabilitätsphänomene qualitativ richtig wiederzugeben. Mit Hilfe von Simulationsrechnungen konnte der Mechanismus aufgeklärt werden, der zum schnelleren Rückgang des Stoffdurchgangskoeffizienten im Rollzellenregime der rein grenzflächenspannungsgetrieben Instabilität im Vergleich zum Vorgang mit überlagerter Dichtekonvektion führt. Des Weiteren gelang der Nachweis des doppeldiffusiven Fingerregimes beim Stoffübergang mit exothermer Grenzflächenreaktion. Die berechnete Erhöhung des Stoffdurchgangskoeffizienten stimmt mit Angaben in experimentellen Arbeiten anderer Autoren überein.

Eine kompakte und effiziente Wasserstofferzeugung aus verfügbaren Energieträgern ist für die Marktfähigkeit von Brennstoffzellenheizgeräten essentiell. Der Auslegung von Reformern für PEM-Brennstoffzellen kommt eine große Bedeutung zu, da bei diesem Brennstoffzellentyp keine interne Reformierung möglich ist. In dieser Arbeit werden die mathematische Modellierung der Dampfreformierung von Erdgas, die Rolle der eingesetzten Katalysatoren und die Problematik von Wärme- und Stofftransportprozessen untersucht. Für fünf kommerzielle Nickel- und einen Rhodiumkatalysator werden die Kinetik, die effektive Wärmeleitfähigkeit und der Diffusionskoeffizient ermittelt. Unter Verwendung dieser Werte wird in einem Einzelpartikelmodell die Existenz und Signifikanz von intra- und extrapartikulären Stoff- und Temperaturgradienten evaluiert. Daraus werden für ein quasihomogenes Reaktormodell Modellparameter abgeleitet, die eine exakte Simulation unter Berücksichtigung der relevanten Phänomene zulassen. Schließlich wird ein Reaktormodell erstellt, welches mit Messwerten aus einem Versuchsreaktor validiert und für eine Sensitivitätsanalyse verwendet wird.

Boiling is used in a wide variety of industries, including electronics cooling, distillation, and power generation. Fundamental studies on the boiling process are needed for effective implementation. Key performance characteristics of boiling are the heat transfer coefficient, which determines the amount of heat flux that can be dissipated for a given superheat, and critical heat flux(CHF), the failure point that occurs when vapor blankets the surface. The wettability of a surface is one of the key parameters that affects boiling behavior. Wetting surfaces(e.g., hydrophilic surfaces), typically characterized by a static contact angle below 90°,have better critical heat flux due to effective rewetting, but compromised heat transfer coefficients due to increased waiting times between nucleation of each bubble. Meanwhile, nonwetting surfaces (e.g., hydrophobic surfaces), characterized by static contact angles greater than 90°, have better heat transfer coefficients due to improved nucleation characteristic, but reach critical heat flux early due to surface dry out. However, recent studies have shown that the static contact angle alone offers and incomplete, and sometimes inaccurate, description of this behavior, which is instead governed entirely by the dynamic wettability. Specifically, the receding contact angle impacts the size and contact area of bubbles forming on a surface during boiling, while the advancing contact angle determines how the bubble departs. With this more complete set of wettability descriptors, three characteristic wetting regimes define the boiling behavior: hygrophilic surfaces having advancing and receding contact angles both under 90°; hygrophobic surfaces having both these dynamic contact angles over 90°;and ambiphilic surfaces having a receding contact angle less than 90°, but an advancing contact angle greater than 90°.The goal of this thesis is to experimentally characterize and compare the behavior of boiling surfaces in each of these regimes, observe the contact line behavior, and explain the mechanisms for their differences in performance.

<div>A microheater and resistance temperature detector (RTD) are designed and fabricated for various applications. First, a hierarchical manifold microchannel heatsink with an integrated microheater and RTDs is demonstrated. Microfluidic cooling within the embedded heat sink improves heat dissipation, with two-phase operation offering the potential for dissipation of very high heat fluxes while maintaining moderate chip temperatures. To enable multi-chip stacking and other heterogeneous packaging approaches, it is important to densely integrate all fluid flow paths into the device. Therefore, the details of heatsink layouts and fabrication processes are introduced. Characterization of two-phase cooling as well as reliability of the microheater/RTDs are discussed. In addition, another application of microheater for mining particle detection using interdigitated capacitive sensor. While current personal monitoring devices are optimized for monitoring microscale particles, a higher resolution technique is required to detect sub-micron and nanoscale particulate matters (PM) due to smaller volume and mass of the particles. The detection capability of the capacitive sensor for sub-micron and nanoparticles are presented, and an incorporated microheater improved stable capacitive sensor reading under air flow and various humidity. </div><div>This paper also introduces the characterization of nanomaterials such as metallic nanowires (NWs) and single layer graphene. First, the copper nanowire (CuNW)/graphene hybrid networks for transparent conductors (TC) is investigated. Though indium tin oxide (ITO) has been widely used, demands for the next generation of TC is increasing due to a limited supply of indium. Thus, the optical and electrical properties of CuNW/graphene hybrid network are compared with other transparent conductive materials including ITO. Secondly, silver nanowire (AgNW) growth technique using electrodeposition is introduced. A vertically aligned branched AgNW arrays is made using a porous anodic alumina template and the optical properties of the structure are discussed.</div><div><br></div>

Ce travail est dédié à l'étude d'écoulement diphasique sous pression en micro et milli-capillaires pour permettre la mesure efficace de propriétés de mélanges sous pression. Dans un premier temps, un montage expérimental comprenant un micro-dispositif pour des applications allant jusqu'à des pressions de 25 MPa a été développé. Ce micro-dispositif à faible coût et transparent, permet la visualisation de l'écoulement grâce à une caméra rapide. Dans un second temps, l'étude du système diphasique du système CO2 supercritique / liquide ionique (1-Butyl-3-Methyl-Imidazolium hexafluorophosphate, [BMIm][PF6]) sous pression est présentée. L'écoulement est réalisé dans des tubes cylindriques de silice de diamètre intérieur de 536 micromètres. Parmi les différents régimes d'écoulements diphasiques, nous nous sommes intéressés aux écoulements périodiques intermittents ou « Taylor flow ». La zone de conditions opératoires couvertes est la suivante : [308 K - 318 K] x [9 MPa - 18 MPa]. Les films de la caméra rapide sont traités par analyse d'image. Le logiciel« μcap2phase » développé pour traiter les films permet d'accéder aux caractéristiques géométriques de l'écoulement (volume et aire de chaque phase, longueur du motif, longueur de la phase dispersée et vitesse de la phase dispersée). Un comportement atypique est observé avec ce binaire. En effet le transfert unidirectionel du CO2SC dans le [BMIm][PF6] induit des changements importants des propriétés physico-chimiques de la phase continue : abaissement de la viscosité (divisée par 10) et augmentation de la masse volumique (multiplié par 1,5). Ces changements impliquent une modification de la forme et de la taille des bulles au cours de l'écoulement. Une importante vitesse de glissement a été identifiée. Elle est générée par la présence d'un film épais de viscosité plus élevée au niveau des parois du capillaire. Un modèle de transfert de matière prenant en compte certaines des observations expérimentales (variations de la taille du film, de la taille des bulles, et des propriétés de la phase continue tout au long du capillaire) a été développé. Ce modèle intégrera dans le futur la tension interfaciale bulle/phase continue et le facteur de forme de la bulle. / The present work deals with the study of two-phase flow in micro-capillaries under high-pressure to enhance properties measurements. As a first step, an experimental setup consisting of a micro-device has been developed for microfluidics high-pressure applications (P < 25 MPa). The set-up combines good optical access, high-pressure resistance, homogeneous operating conditions, fast process control and detection, and the ability to generate a stable two-phase flow. In the following step, we focused our work on the hydrodynamics features of two-phase flow between supercritical carbon dioxide(SC-CO2) and ionic liquid (1-butyl-3-methyl-imidazolium hexafuorophosphate) ([BMIm][PF6]) .The two-phase flow system is observed with a high-speed camera. The flow is conducted in silica capillary tubing with inner diameter of 536 micrometers. Among the two-phase flow patterns, ours relates to Taylor flow. The range of operating conditions are : [308 K - 318 K] x [9 MPa - 18 MPa]. An image analysis home-made soft, « μcap2phase », has been developed in order to access to the geometric properties and to the velocities of the dispersed phase from images. The two-phase flow presents an unexpected behaviour. In fact, the unidirectional transfer of SC-CO2 in [BMIm][PF6] induces significant changes in physico-chemical properties of continous phase : viscosity decreases(divided by ten) and density increases (1.5 fold). Due to the wide variations of the continuous phase properties along the capillary, size and shape of the dispersed phase bubbles are simultaneously modified. A significant slip velocity has been indentified located between a thick liquid film (at the wall of capillary) and a Taylor flow region (at the center). A mass transfer taking into account some experimental observations (changes in film thickness, in bubble size, and in properties of the continuous phase throughout the capillary) is developed. Further, this model will integrate the interfacial tension between bubbles and continous phase.

<div>This dissertation focuses on a consistent and conservative Phase-Field method for multiphase flow problems, and it includes both model and scheme development. The first general question addressed in the present study is the multiphase volume distribution problem. A consistent and conservative volume distribution algorithm is developed to solve the problem, which eliminates the production of local voids, overfilling, or fictitious phases, but follows the mass conservation of each phase. One of its applications is to determine the Lagrange multipliers that enforce the mass conservation in the Phase-Field equation, and a reduction consistent conservative Allen-Cahn Phase-Field equation is developed. Another application is to remedy the mass change due to implementing the contact angle boundary condition in the Phase-Field equations whose highest spatial derivatives are second-order. As a result, using a 2nd-order Phase-Field equation to study moving contact line problems becomes possible.</div><div><br></div><div>The second general question addressed in the present study is the coupling between a given physically admissible Phase-Field equation to the hydrodynamics. To answer this general question, the present study proposes the <i>consistency of mass conservation</i> and the <i>consistency of mass and momentum transport</i>, and they are first implemented to the Phase-Field equation written in a conservative form. The momentum equation resulting from these two consistency conditions is Galilean invariant and compatible with the kinetic energy conservation, regardless of the details of the Phase-Field equation. It is further illustrated that the 2nd law of thermodynamics and <i>consistency of reduction</i> of the entire multiphase system only rely on the properties of the Phase-Field equation. All the consistency conditions are physically supported by the control volume analysis and mixture theory. If the Phase-Field equation has terms that are not in a conservative form, those terms are treated by the proposed consistent formulation. As a result, the proposed consistency conditions can always be implemented. This is critical for large-density-ratio problems.</div><div><br></div><div>The consistent and conservative numerical framework is developed to preserve the physical properties of the multiphase model. Several new techniques are developed, including the gradient-based phase selection procedure, the momentum conservative method for the surface force, the boundedness mapping resulting from the volume distribution algorithm, the "DGT" operator for the viscous force, and the correspondences of numerical operators in the discrete Phase-Field and momentum equations. With these novel techniques, numerical analyses ensure that the mass of each phase and momentum of the multiphase mixture are conserved, the order parameters are bounded in their physical interval, the summation of the volume fractions of the phases is unity, and all the consistency conditions are satisfied, on the fully discrete level and for an arbitrary number of phases. Violation of the consistency conditions results in inconsistent errors proportional to the density contrasts of the phases. All the numerical analyses are carefully validated, and various challenging multiphase flows are simulated. The results are in good agreement with the exact/asymptotic solutions and with the existing numerical/experimental data.</div><div> </div><div><br></div><div>The multiphase flow problems are extended to including mass (or heat) transfer in moving phases and solidification/melting driven by inhomogeneous temperature. These are accomplished by implementing an additional consistency condition, i.e., <i>consistency of volume fraction conservation</i>, and the diffuse domain approach. Various problems are solved robustly and accurately despite the wide range of material properties in those problems.</div>

<p> With new technologies taking advantages of the rapid miniaturization of devices to microscale across emerging industries, there is an unprecedented increase in the heat fluxes generated. The relatively low phase-change thermal resistance associated with boiling is beneficial for dissipating high heat flux densities in compact spaces. However, for boiling heat transfer, a high degree of geometrical confinement significantly alters two-phase interface dynamics which affects the flow pattern, wetting dynamics, and moreover, the heat transfer rate of the boiling processes. Hence, it is crucial to have a deeper understanding of the mechanistic effects of confinement on two-phase heat dissipation and carefully examine the applicability of boiling correlations developed for unconfined pool boiling to predict and optimize design of extremely compact two-phase thermal management solutions. This dissertation develops and demonstrate a fundamental understanding of the impact of confinement on pool boiling. To elucidate the mechanisms that impact confined boiling, this study experimentally evaluates boiling characteristics through the quantification of boiling curves and high-speed visualization across a range of gap spacing smaller than the capillary length of the working fluid. </p> <p><br></p> <p> This work reveals the existence of two distinct boiling regime uniquely observed in boiling in confined configurations (namely, intermittent boiling and partial dryout). In contrast to pool boiling where the maximum heat transfer coefficient occurs below the critical heat flux limit, the intermittent boiling regime demonstrates the highest heat transfer coefficient in confined boiling. Then, this study provides a mechanistic explanation for the enhanced heat transfer rate due to geometrical confinement. Mainly, small residual pockets of vapor, termed ‘stem bubbles’ herein, remain on the boiling surface through a pinch-off process. These stems bubbles act as seeds for vapor growth in the next phase of the boiling process without the need for active nucleation sites. Furthermore, this dissertation develops a more accurate, mechanistic-based model for the phenomena that occur at CHF in confined configurations. The newly developed mechanistic understanding and model provides guidance on new directions for designing extremely compact two-phase thermal solutions.</p>