This project encompasses the design of a pretreatment protocol for blood serum and adaption of that protocol to a microfluidic environment in order to optimize key sample characteristics, namely pH, conductivity, and viscosity, to enable on-chip electrokinetic separations. The two major parts of this project include (1) designing a pretreatment protocol to optimize key parameters of the sample solution within a target range and (2) designing /fabricating a microchip that will effectively combine the sample solution with the appropriate buffers to replicate the same bench-scale protocol on the micro-scale. Biomarker detection in complex samples such as blood necessitates appropriate sample “pretreatment” in order for specific markers to be isolated through subsequent separations. This project, though using conventional mixing techniques and buffer solutions, is one of the first to observe the effects of the combination of micro-mixing and sample pretreatment in order to create an all-in-one “pretreatment chip”. Using previous literature related to capillary electrophoresis, a bench-scale pretreatment protocol was developed to tune these parameters to an optimal range. A PDMS device was fabricated and used to combine raw sample with specific buffer solutions. Off-chip electrodes were used to induce electrokinetic micro-mixing in the mixing chamber, where homogeneous analyte mixing was achieved in less than one second using an 800V DC pulse wave. Ultimately, we wish to incorporate this device with pre-fabricated electrokinetic devices to optimize certain bioseparations.

Immunofluorescence assays are capable of both detecting the amount of a protein and the location of the protein within a cell or tissue section. Unfortunately, the traditional technique is not capable of detecting concentrations on the nanoscale. Also, the technique suffers from non-specific attachment, which can cause false-positives, as well as photobleaching when detecting lower concentrations is attempted. There is also a time constraint problem since the technique can take from many hours to a few days in some cases. In this work, metal-enhanced fluorescence (MEF) is used to lower the detection limit and reduce photobleaching. Unfortunately, MEF also increases the intensity of non-specifically bound proteins (NSBPs). Therefore, a surface acoustic wave (SAW) device is used to remove the more weakly bound NSBPs. Previously, this has been shown on lithium niobate, but it is used with a quartz substrate in this work. The SAW device is also used to cause micro-mixing which speeds the process up significantly. In this research, it was found that silver nanocubes can lower the detection limit down to below 1 ng/mL. Quartz SAW devices are shown to remove NSBPs at a power of 10 mW applied for five minutes. Micro-mixing is shown to be improved by a factor of six at 10 mW for 10 minutes by saturating the antibody used in this research, which takes 1 hour without micro-mixing. Finally, all three components are combined. In this work, the whole device is used to detect 50 ng/mL. After micro-mixing, the intensity is the same as with MEF, and, after removal, it has been lowered by 7 a.u.

Environmentally friendly and efficiently produced energy from sustainable and renewable resources is of great importance. Carbon dioxide (CO2) and nitric oxides (NOx) are the main emissions of air-breathing gas turbines in power plants. Gas turbines of the power generation industry are normally fueled with liquid fuels, natural gas or syngas in changing qualities. Syngas can be produced by gasification processes in IGCC power plants and consist of varying percentages of the main fractions hydrogen (H2) and carbon monoxide (CO). CO2 emissions can be reduced by a decrease of the CO-share and an increase of the hydrogen-share in the syngas fuel, and by using pre-combustion carbon capture and sequestration (CCS) technology. For low NOx, current gas turbine combustion chamber technologies require diluents, a rather low H2 content and modifications of the combustor hardware. A feasible solution for low NOx hydrogen and syngas combustion in gas turbines is the Micromix principle developed at Aachen University of Applied Sciences. The goal of this doctoral thesis is the research on a Micromix combustor with increased power densities fueled with hydrogen-rich syngas with about 90% by volume hydrogen, and going up to 100% hydrogen in the fuel. Test burner experiments are used to characterize the combustion and emission properties of a multitude of key drivers. Based on this optimization with a variety of scaled model test burners, a prototype dual-fuel hydrogen/syngas Micromix combustor is designed and integrated into the annular combustion chamber of an industrial gas turbine. In the gas turbine, the performance characteristics of the prototype-combustor are investigated under real operational conditions with hydrogen-rich syngas and pure hydrogen. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

Cette thèse est consacrée à la simulation du mélange de scalaires passifs à grand nombre de Schmidt (faible diffusion), au moyen d’un modèle de sous-maille structurel pour la Simulation aux Grandes Echelles (LES pour Large Eddy Simulation) reposant sur le caractère multifractal des champs de gradient en turbulence. L’analyse multifractale des champs de dissipation scalaire permet, à l’aide d’une description statistique des singularités, de prendre en compte l’intermittence inhérente à ces champs. Des simulations numériques directes du mélange à différents nombres de Schmidt supérieurs à l’unité sont mises en oeuvre. Une analyse multifractale au moyen de différentes méthodes est menée afin d’obtenir les spectres de singularités de la dissipation scalaire. Une implantation du modèle de sous-maille multifractal pour la vitesse, proposé par Burton et al., est d’abord réalisée dans le code volumes finis YALES2.Une modification du modèle équivalent pour les scalaires, reposant sur une cascade multiplicative pour reconstruire la dissipation scalaire de sous-maille, est proposée afin de prendre en compte le micro-mélange à grand nombre de Schmidt. Ce modèle de sous-maille est alors évalué au moyen de tests a priori. / This thesis is focused on the simulation of turbulent mixing of passive scalars at high Schmidt numbers (low diffusivity). The modeling work is based on a structural subgrid-scale model for Large Eddy Simulation relying on the multifractal nature of gradient fields in turbulence.The multifractal formalism provides a mean to handle the characteristic intermittency of scalar dissipation fields through a statistical description of their singularities. Direct Numerical Simulations of mixing at several Schmidt numbers above unity are run with a dedicated code. Different methods are used to perform a multifractal analysis of scalar dissipation. The multifractal subgrid-scale model of Burton et al. for velocity is implemented in the Finite Volume code YALES2. A modification of the equivalent multifractal model for scalars is proposed to take into account micro-mixing at high Schmidt numbers. The model shows satisfactory results when tested a priori against direct simulations.

La simulation devient un outil incontournable pour concevoir ou optimiser les procédés en biotechnologies. Elle est particulièrement pertinente pour permettre le changement d'échelle de l'échelle laboratoire à la mise en œuvre de cultures biologiques industrielles. Cette thèse se concentre sur le développement d'une structure de modèle pour les fermenteurs, qui ne néglige ni les problématiques de mélange, ni la complexité biologique, tout en permettant des simulations rapides. Pour intégrer l'ensemble des phénomènes couplés et dynamiques interagissant dans les bioréacteurs, l'approche proposée couple (i) un modèle métabolique dynamique pour décrire le comportement des cellules, (ii) un modèle de bilan de population pour suivre la diversité biologique et (iii) un modèle de compartiments pour décrire l'hydrodynamique du fermenteur. Une structure de modèle métabolique, générique et numériquement peu couteuse a été appliquée à E. coli et S. cerevisiae et été confrontée avec succès à de nombreuses données expérimentales. Parmi plusieurs méthodes numériques permettant de traiter les équations de bilan de population, la méthode EQMOM a été sélectionnée pour sa stabilité et sa précision et son coût a été réduit d'un facteur 10. L'hydrodynamique gaz-liquide d'un fermenteur industriel a été obtenue par simulations CFD et des outils ont été développés pour en extraire des modèles de compartiments. Le couplage de ces différents aspects a finalement été illustré par la simulation d'une culture industrielle. Ce travail ouvre la voie à la création d'outil de simulation rapide, ce qui permettra des études d'ingénierie de design et d'optimisation de procédés industriels. / Simulations are becoming an essential tool to design and improve processes in the field of biotechnologies. They are especially relevant to facilitate the scale-up of biological cultures from laboratory to industrial scales which is a key difficulty as of now. This thesis focuses on developping a model structure for fermenters, which does not neglect either mixing issues known to occur in industrial bioreactor, nor biological complexity inherent to micro-organisms, while enabling fast and low-cost simulations. To account for all coupled and dynamic phenomena that occur in bioreactors, the developed approach couples (i) a dynamic metabolic model to describe cells behaviour, (ii) a population balance model tracking biological cell-to-cell diversity and (iii) a compartment model to account for fermenter hydrodynamics. A structure for low-cost dynamic metabolic model has been developed, applied to E. coli and S. cerevisiae and successfully challenged against experimental data. Among multiple numerical methods tackling population balance equations, the EQMOM method has been selected for its stability and precision, and its algorithm has been improved by reducing its cost by a factor 10. The gas-liquid hydrodynamics of an industrial fermenter has been obtained through CFD simulations, and tools have been developed to extract compartment model from these simulation results. Finally, the coupling between all these modeling blocks has been demonstrated by simulating an actual industrial culture. This work paves the way to the emergence of fast bioreactor simulation tools, which will then enable new enginnering studies for designing and optimising industrial bio-processes.

Ce travail de thèse est consacré à l'élaboration de membrane photocatalytique à partir de nanoparticules de TiO2 obtenues par voie sol-gel (système TTIP-eau). Les sols sont préparés dans un réacteur à micro-mélange rapide (turbulent). L'effet de l'hydrodynamique au sein de différents mélangeurs (T simple, T chicanes, T rétrécissement) sur la morphologie et l'activité photocatalytique de nanoparticules déposées sur des plaques d'α-alumine a été étudié. Les dépôts de TiO2 ont été réalisés durant la période d'induction de la réaction sol-gel. Le mélange des réactifs a été simulé en utilisant un logiciel de modélisation numérique (modèle k-ε), Les différences hydrodynamiques au sein du micro-mélange a seulement un impact significatif sur le temps de stabilité des nanoparticules (période d'induction). Des couches minces et des membranes photo-actives ont été réalisées en vue du couplage membrane et réaction photocatalytique. Ces membranes ont été caractérisées et testées en photocatalyse. Elles ont montrées de bonnes photo-activités. Des tests de couplage direct séparation/photodégradation ont été réalisés sur des solutions aqueuses d'acide orange 7. Ce dispositif expérimental a permis de mettre en évidence une augmentation de flux de perméation significative avec de l'eau et en présence de colorant en solution. L'effet de la concentration et du pH de la solution a été évalué sur les flux de perméat et sur la photodégradation. / This PhD work is devoted to the elaboration of photocatalytic membranes using TiO2 nanoparticles synthetized by sol-gel process (titanium tetra-isopropoxyde precursor – water). Sols are prepared in sol-gel reactor with rapid turbulent micro-mixing. The effect of hydrodynamic using 3 T mixers (T simple, T with 3 baffles and T with narrow) during the mixing was studied with k-ε modeling Computational fluid Dynamics (CFD), as well as the morphology and the photo-activity of thin layers deposited on alumina support during induction period. Differences on hydrodynamic during micro-mixing have only impact on the time of nanoparticles stability (induction period). Photo-active thin layers and membranes are synthesized for coupling membrane separation and photocatalytic reaction. Photocatalytic activities of thin layers and membranes are performed with an aqueous solution of acid orange 7. Significant increases of permeate flux are observed during the filtration of water and solution containing dye. Effects of concentration and pH are evaluated on permeation flux and photodegradation.

We report the application of a novel optical Raman-based measurement technique for the simultaneous determination of the progress of mixing on the micro- and on the macro-scale. The introduced measurement technique is applicable to mixing systems containing one compound, which potentially can form hydrogen bonds, such as water, alcohols or amines, and does not rely on the addition of traces of indicator compounds. Here we demonstrate its applicability by analyzing the lag of micro-mixing behind macro-mixing when liquid ethanol is injected into a supercritical bulk environment mainly composed of carbon dioxide (CO2). While the degree of mixing on the macro-scale is determined from the ratio of the intensities of characteristic Raman signals of ethanol and CO2, the degree of mixing on the micro-scale is determined from the shape of the OH stretching vibration Raman signal of ethanol, which is a function of the development of hydrogen bonds.