Understanding flow and transport in porous media is critical as it plays a central role in many biological, natural, and industrial processes. Such processes are not limited to one length or time scale; they occur over a wide span of scales from micron to Kilometers and microseconds to years. While field-scale simulation relies on a continuum description of the flow and transport, one must take into account transport processes occurring on much smaller scales. In doing so, pore-scale modeling is a powerful tool for shedding light on processes at small length and time scales.<br><br>In this work, we look into the multi-phase flow and transport through porous media at two different scales, namely pore- and Darcy scales. First, using direct numerical simulations, we study pore-scale Eulerian and Lagrangian statistics. We study the evolution of Lagrangian velocities for uniform injection of particles and numerically verify their relationship with the Eulerian velocity field. We show that for three porous media velocity, probability distributions change over a range of porosities from an exponential distribution to a Gaussian distribution. We thus model this behavior by using a power-exponential function and show that it can accurately represent the velocity distributions. Finally, using fully resolved velocity field and pore-geometry, we show that despite the randomness in the flow and pore space distributions, their two-point correlation functions decay extremely similarly.<br><br>Next, we extend our previous study to investigate the effect of viscoelastic fluids on particle dispersion, velocity distributions, and flow resistance in porous media. We show that long-term particle dispersion could not be modulated by using viscoelastic fluids in random porous media. However, flow resistance compared to the Newtonian case goes through three distinct regions depending on the strength of fluid elasticity. We also show that when elastic effects are strong, flow thickens and strongly fluctuates even in the absence of inertial forces.<br><br>Next, we focused our attention on flow and transport at the Darcy scale. In particular, we study a tertiary improved oil recovery technique called surfactant-polymer flooding. In this work, which has been done in collaboration with Purdue enhanced oil recovery lab, we aim at modeling coreflood experiments using 1D numerical simulations. To do so, we propose a framework in which various experiments need to be done to quantity surfactant phase behavior, polymer rheology, polymer effects on rock permeability, dispersion, and etc. Then, via a sensitivity study, we further reduce the parameter space of the problem to facilitate the model calibration process. Finally, we propose a multi-stage calibration algorithm in which two critically important parameters, namely peak pressure drop, and cumulative oil recovery factor, are matched with experimental data. To show the predictive capabilities of our framework, we numerically simulate two additional coreflood experiments and show good agreement with experimental data for both of our quantities of interest.<br><br>Lastly, we study the unstable displacement of non-aqueous phase liquids (e.g., oil) via a finite-size injection of surfactant-polymer slug in a 2-D domain with homogeneous and heterogeneous permeability fields. Unstable displacement could be detrimental to surfactant-polymer flood and thus is critically important to design it in a way that a piston-like displacement is achieved for maximum recovery. We study the effects of mobility ratio, finite-size length of surfactant-polymer slug, and heterogeneity on the effectiveness of such process by looking into recovery rate and breakthrough and removal times.

The sea-surface microlayer (SML) is the boundary layer at the air-sea interface where many biogeochemical processes occur. Many organisms (e.g., bacteria) produce surface active agents (surfactants) for life processes, which accumulate in the SML and dampen short gravity-capillary waves, resulting in sea surface slicks. Synthetic aperture radar (SAR) is capable of remotely sensing these features on the sea surface by measuring reflected backscatter from the ocean surface in microwaves. This study coordinates SAR overpasses with in situ SML and subsurface (SSW) microbial sample collection to guide subsequent analysis after 16s rRNA sequencing on the Illumina MiSeq. In April 2017, 138 SML and SSW samples were collected near a targeted oil-seep where the Taylor Platform was knocked down in the Gulf of Mexico, both in and out of visually-observed oil slicks. In July and August 2018, 220 SML and SSW samples were collected near the Looe Key coral reef and a coastal seagrass area. Analysis of microbial abundance and diversity between the two experiments shows that within oil slicks, surfactant- and oil-associated bacteria prefer to reside within the SSW rather than in the SML. In natural slicks in the coastal seagrass area, these bacteria are more abundant in the SML. Outside of these slicks, surfactant-associated bacteria are more abundant within the SML than the SSW. This suggests that the presence of oil reduces the habitability of the SML, whereas natural slicks created by foam and other surfactants creates a more habitable environment in the SML. With lower wind speed, abundance of these bacteria are greater, as increased wind speed results in a harsher environment. The diurnal cycle had an effect on the relative abundance of surfactant-associated bacteria in the SML and SSW. Our results demonstrate the usefulness of synthetic aperture radar to remotely sense sea surface slicks in coordination with in situ surfactant-associated bacteria data collection of the sea surface slicks.

L'utilisation des microcapsules fabriquées à partir de matériaux respectueux de l'environnement pour des applications textiles médicales a été étudiée et développée fortement au cours des dernières années. Le but de cette thèse est d'élaborer les textiles anti-inflammatoires à base de microcapsules respectueuses de l'environnement, utilisant trois types de matériaux textiles (coton, peco 65/35 et polyester) et cinq niveaux de longueur de boucle (2.81, 2.83, 2.87, 2,96 et 3,05 mm) sur étoffes tricotées à verrouillage de coton (nombre de fils Ne40). Les influences de la concentration en saponine, de la vitesse d'agitation au cours de l'étape d'émulsification et du volume d'éthyle acétate ajouté à la phase aqueuse sur les caractéristiques des microcapsules ont été étudiées. L'étude a également étudié les effets du rapport massique du coton et de la longueur de boucle des étoffes tricotées sur la distribution des microcapsules, la capacité de chargement des microcapsules et la capacité de libération de l'ibuprofène des étoffes tricotées traités par microcapsules. Les microcapsules d'Eudragit RSPO contenant de l'ibuprofène ont été élaborées par la technique d'évaporation de solvant, en utilisant le tensioactif bio-sourcé quillaja saponine et le solvant non halogéné d'éthyle acétate. Les microcapsules obtenues présentaient les formes sphériques avec un diamètre d (0,5) de 21,5 μm, approprié pour les applications textiles. Il a été trouvé que, pour empêcher la déformation des microcapsules pendant la traitement du textile, la séchage doit être effectuée sous vide à 45 ° C. Lorsque le rapport de teneur en fibres de coton dans le tissu augmentait, la distribution des microcapsules était moins régulière, ce qui entraînait un taux de libération plus faible de l'ibuprofène à partir des étoffes tricotées traités aux microcapsules. En outre, lorsque la longueur de la boucle augmente, la capacité de chargement des microcapsules des étoffes tricotées traités augmente, la distribution des microcapsules sur le tissu devient moins régulière et la vitesse de libération de l'ibuprofène des tissus traités aux microcapsules diminue. De plus, l'augmentation de l'extension du étoffes tricotées a favorisé la libération d'ibuprofène à partir des étoffes tricotées traités par les microcapsules à travers la peau de porc / The use of the microcapsules made from eco-friendly materials for medical textile applications has been researched and developed strongly in recent years. The aim of this thesis is to elaborate the anti-inflammatory textiles basing on eco-friendly microcapsules,using three kinds of textile materials (cotton, peco 65/35 and polyester)and five levels of the loop length (2.81, 2.83, 2.87, 2.96 and 3.05 mm) on the cotton interlock knitted fabrics (yarn count Ne40). The influences of the saponin concentration, the stirring rate during the emulsification step and the volume of ethyl acetate added to the aqueous phase on the characteristics of the microcapsules were studied. The influence of condition in drying on microcapsule’s morphology was also investigated.The thesis also researched the effects of cotton mass ratio and loop length of fabric on the microcapsule distribution, the microcapsule loading capability and the release capability of ibuprofen from the microcapsule treated fabrics. The Eudragit RSPO microcapsules containing ibuprofen were successfully elaborated by solvent evaporation technique, using the bio-sourced surfactant quillajasaponin and the non-halogenated solvent ethyl acetate. The obtained microcapsules exhibited the spherical shapes with d(0.5) diameter of 21.5 m, suitable for the textile applications. It was found that in order to keep the microcapsules from deformation during the textile finishing, the drying stage should be carried out in vacuum at 45oC. When the content ratio of cotton fibers in the fabric increased,the microcapsule distribution was less even, resulting in the lower release rate of ibuprofen from the microcapsule-treated fabrics. Besides, when the loop length increased, the microcapsule loading capability of the treated fabrics increased, the microcapsule distribution on the fabric became less even and the release rate of ibuprofen from the microcapsule-treated fabrics decreased. Furthermore, increasing the fabric extension favored the release of ibuprofen from the microcapsule-treated fabrics through the pigskin

In dieser Arbeit wurden die komplexen Mechanismen für den Einbau von Mg und In in (Ga,In)N/GaN(0001)-Heterostrukturen, die mittels PA-MBE hergestellt wurden, mit morphologischen, optischen und elektrischen Charakterisierungsmethoden untersucht. Darüber hinaus wurde die Verwendung von (Ga,In)N/GaN SPSLs als HIL oder als aktiver Bereich in herkömmlichen LED-Strukturen untersucht. In-situ-Messungen zeigten, dass die Desorption von In in Gegenwart von N und Mg auf der GaN(0001)-Oberfläche zunimmt. Ferner wurden Mg-dotierte (Ga,In)N/GaN-SLs mittels PAMBE gezüchtet und mittels QMS, XRD und SIMS charakterisiert. Die (Ga,In)N/GaN-SLs zeigten eine bessere Oberflächenmorphologie als die (Ga,In)N-Schichten, die homogen mit Mg dotiert wurden. Jedoch wurde eine deutliche Abnahme des In-Gehalts in der (Ga,In)N ML festgestellt, wenn Mg gleichzeitig mit In zugeführt wurde. Gleichzeitig nahm die Mg-Konzentration in Gegenwart von In zu, was möglicherweise auf eine Wirkung als oberflächenaktive Substanz zurückzuführen ist. Für das SL, bei dem nur die (Ga,In)N-QWs mit Mg dotiert waren, wurde vom Messergebnis von SIMS eine maximale Mg-Konzentration von 2,6 × 1022 cm-3 für eine 1 ML dicke (Ga,In)N:Mg-Schicht deduziert. Zusätzlich haben andere Experimente ähnliche Ergebnisse aufgezeigt. Thermoleistung-Studien zeigten, dass das Delta-dotierte SL und die SL-Strukturen mit Mg-Dotierung in 20% der QB p-leitfähig sind. Zusätzlich wurde ein Gleichrichterverhalten der (Ga,In)N/GaN SL-Strukturen mit einem Idealitätsfaktor von weniger als 10 für die QW-dotierten SLs demonstriert. Ausgehend von der elektrischen Charakterisierung wurden drei verschiedene LED-Strukturen, die auf den vielver-sprechendsten Mg-dotierten (Ga,In)N SL-Strukturen (Delta-dotiertes SL und 20% QB-dotiertes SL) basierten, hergestellt und charakterisiert. / In this thesis, the complex mechanisms for the incorporation of Mg and In in (Ga,In)N/GaN(0001) heterostructures prepared by PA-MBE were investigated by morphological, optical, and electrical characterization methods. Furthermore, the implementation of (Ga,In)N/GaN SPSLs as a HIL or as the active region in conventional LED structures have been studied. In-situ measurements demonstrate that the desorption of In increases in the presence of both, N and Mg on the GaN(0001) surface. Further, (Ga,In)N/GaN SLs with Mg-doping grown by PAMBE and their characterization was carried out by QMS, XRD, and SIMS. A better surface morphology was obtained for the (Ga,In)N/GaN SLs in comparison to a (Ga,In)N layer homogeneously doped with Mg. Although, a notable decrease of the In content in the (Ga,In)N ML was revealed when Mg was supplied simultaneously to In. At the same time, the Mg concentration increased in the presence of In, which can possibly be attributed to a surfactant effect. For the SL that had only its (Ga,In)N QWs doped with Mg, a maximum Mg concentration of 2.6 × 1022 cm 3 for a 1 ML thick (Ga,In)N:Mg layer was deduced from SIMS measurements. Additionally, similar results have achieved later by another set of experiments. Thermopower studies revealed the p-type conductivity of the delta doped SL and of the SL structures with 20% of the QB doped by Mg. Additionally, a rectifying behavior with an ideality factor lower than 10 was demonstrated for the (Ga,In)N/GaN SL structures with QW fully doped. Based on the electrical characterization, three different LED structures were fabricated based on the most promising Mg-doped (Ga,In)N SL structures (delta doped SL, and 20% QB doped SL) and characterized.

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[ES] La presente tesis doctoral se centra en la obtención, vía síntesis directa, de materiales zeolíticos nanocristalinos con propiedades fisicoquímicas y catalíticas mejoradas respecto a los materiales de referencia. Para ello se ha hecho uso de tensioativos creados específicamente para cada una de las estructuras zeolíticas estudiadas, evitando el uso de procesos post-sintéticos que conllevan una pérdida de material cristalino. En la primera parte del trabajo se ha estudiado la obtención de la zeolita ITQ-2 deslaminada por síntesis directa (DS-ITQ-2) mediante el uso de varios tensioactivos, siendo el C16DC1 (N-Hexadecil-N'-metil-1,4-diazabiciclo[2.2.2]octano) con el que mejores resultados se han obtenido. Se ha estudiado la influencia de la longitud de la cadena alifática y la concentración del agente director de estructura orgánico (ADEO) en el gel de síntesis sobre la cinética del proceso de cristalización y las implicaciones sobre las características fisicoquímicas del material obtenido. Mediante el control de la concentración del tensioactivo en el gel de síntesis, ha sido posible dirigir el grado de deslaminación del material final. Las propiedades fisicoquímicas del material considerado como óptimo se han comparado con las de las zeolitas MCM-22, MCM-56 e ITQ-2, todas ellas con la misma estructura cristalina (MWW). Por último, la actividad catalítica de la zeolita DS-ITQ-2 se ha estudiado en dos reacciones, la alquilación de benceno con propileno para la obtención de cumeno y la reacción de 2,5-dimetilfurano con etileno para la obtención de p-xileno, obteniendo en ambos casos unos resultados de conversión y selectividad excelentes. La segunda parte de la tesis se ha centrado en la preparación de la zeolita ferrierita en su forma nanocristalina por síntesis directa mediante la utilización de tensioactivos. Se han estudiado tensioactivos con tres partes polares diferentes obtenidos a partir de las correspondientes aminas utilizadas como ADEOs. Además, también se ha estudiado el efecto de la longitud de la cadena del tensioactivo entre los 6 y los 16 átomos de carbono. La modificación de parámetros del gel de síntesis como por ejemplo la relación molar entre la piperidina o el tensioactivo y la sílice ha resultado ser determinante a la hora de conseguir una composición óptima para la obtención de la zeolita nanocristalina con las propiedades fisicoquímicas deseadas. La optimización de la temperatura de síntesis y la introducción de cristales de siembra en el gel de síntesis ha permitido mejorar las propiedades finales del material. La actividad catalítica de las nanoferrieritas se ha estudiado en dos reacciones diferentes, la oligomerización de 1-penteno y la isomerización de 1-buteno. Se ha mostrado la importancia de reducir el tamaño del cristal de la ferrierita, obteniéndose materiales con actividad y selectividad muy superior a los descritos en la bibliografía abierta y de patentes. / [CA] La present tesis doctoral es centra en l'obtenció, via síntesi directa, de materials zeolítics nanocristalins amb propietats fisicoquímiques i catalítiques millorades respecte als materiales de referència. Per a això s'ha fet ús de tensioatius creats específicament per a cadascuna de les estructures zeolítiques estudiades, evitant l'ús de processos post-sintètics que comporten una pèrdua de material cristal·lí. En la primera part del treball s'ha estudiat l'obtenció de la zeolita ITQ-2 deslaminada per síntesi directa (DS-ITQ-2) mitjançant l'ús de diversos tensioactius, essent el C16DC1 (N-Hexadecil-N'-metil-1,4-diazabiciclo[2.2.2]octà) amb el que millors resultats s'han obtés. S'ha estudiat la influència de la longitud de la cadena alifàtica i la concentració de l'agent director d'estructura orgànic (ADEO) en el gel de síntesi sobre la cinètica del procés de cristal·lització i les implicacions sobre les característiques fisicoquímiques del material obtés. Mitjançant el control de la concentració del tensioactiu en el gel de síntesi, ha sigut possible dirigir el grau de deslaminació del material final. Les propietats fisicoquímiques del material considerat com òptim s'han comparat amb les de les zeolites MCM-22, MCM-56 i ITQ-2, totes elles amb la mateixa estructura cristal·lina (MWW). Per íltim, l'activitat catalítica de la zeolita DS-ITQ-2 s'ha estudiat en dos reaccions, l'alquilació de benzé amb propilé per a l'obtenció de cumé i la reacció de 2,5-dimetilfurà amb etilé per a l'obtenció de p-xilé, obtenint en tots dos casos uns resultats de conversió i selectivitat excel·lents. La segona part de la tesi s'ha centrat en la preparació de la zeolita ferrierita a la seua forma nanocristal·lina per síntesi directa mitjançant la utilizació de tensioactius. S'han estudiat tensioactius amb tres parts polars diferents obtesos a partir de les corresponents amines utilitzades com a ADEOs. A més a més, també s'ha estudiat l'efecte de la longitud de la cadena del tensioactiu entre els 6 i els 16 àtoms de carboni. La modificació de paràmetres del gel de síntesi com per exemple la relació molar entre la piperidina o el tensioactiu i la sílice ha resultat ser determinant a l'hora de conseguir una composició òptima per a l'obtenció de la zeolita nanocristal·lina amb les propietats fisicoquímiques desitjades. L'optimització de la temperatura de síntesi i la introducció de cristalls de sembra en el gel de síntesi ha permés millorar les propietats finals del material. L'activitat catalítica de les nanoferrierites s'ha estudiat en dos reaccions diferents, l'oligomerizació de l'1-penté i la isomerització de l'1-buté. S'ha mostrat la import`ancia de reduir el tamany del cristall de la ferrierita, obtenint-se materials amb activitat i selectivitat molt superior als descrits en la bibliografia oberta i de patents. / [EN] This doctoral thesis focuses on obtaining, via direct synthesis, nanocrystalline zeolite materials with improved physicochemical and catalytic properties compared to reference materials. For this, surfactants created specifically for each of the zeolite structures studied have been used, avoiding the use of post-synthetic processes that lead to a loss of crystalline material. In the first part of the work, the obtaining of the delaminated ITQ-2 zeolite by direct synthesis (DS-ITQ-2) through the use of various surfactants, being C16DC1 (NHexadecyl-N'-methyl-1,4-diazabiciclo[2.2.2]octane) with which the best results have been obtained. The influence of the length of the aliphatic chain and the concentration of the organic structure directing agent (OSDA) in the synthesis gel on the kinetics of the crystallization process and the implications on the physicochemical characteristics of the obtained material have been studied. By controlling the concentration of the surfactant in the synthesis gel, it has been possible to direct the degree of delamination of the final material. The physicochemical properties of the material considered optimal have been compared with those of the zeolite MCM-22, MCM-56 and ITQ-2, all of them with the same crystalline structure (MWW). Finally, the catalytic activity of the zeolite DS-ITQ-2 has been studied in two reactions, the alkylation of benzene with propylene to obtain cumene and the reaction of 2,5-dimethylfuran with ethylene to obtain p-xylene, obtaining excellent conversion and selectivity results in both cases. The second part of the thesis has focused on the preparation of ferrierite zeolite in its nanocrystalline form by direct synthesis using surfactants. Surfactants with three different polar parts, obtained from the corresponding amines used as OSDAs, have been studied. In addition, the effect of the chain length of the surfactant between 6 and 16 carbon atoms has also been studied. Modifying the parameters of the synthesis gel, such as the molar ratio between piperidine or surfactant and silica, has turned out to be decisive when it comes to achieving an optimal composition for obtaining nanocrystalline zeolite with the desired physicochemical properties. The optimization of the synthesis temperature and the introduction of seed crystals in the synthesis gel have allowed to improve the final properties of the material. The catalytic activity of nanoferrierites has been studied in two different reactions, the oligomerization of 1-pentene and the isomerization of 1-butene. The importance of reducing the size of the ferrierite crystal has been shown, obtaining materials with activity and selectivity much higher than those described in the open and patent literature. / Margarit Benavent, VJ. (2023). Síntesis directa de zeolitas monolámina (zeolitas 2D) y sus aplicaciones catalíticas [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/192880

The Thesis describe my studies based on self-assembly and co-assembly of block copolymer micelles that I conducted at the Department of Physical and Macro- molecular Chemistry at the Charles University, Prague in the research group of my supervisor, Prof. Dr. Karel Procházka, DrSc. The Thesis based on my publications and consists of four parts. Here I studied the formation of polymeric nanoparticles in aqueous solutions formed by polyelectrolytes with hydrophobic backbones by a combination of several experimental methods. The achieved results enabled me to explain the structure and properties of studied self- and co-assembled nanoparticles and to outline the decisive trends of their behavior. The spontaneous formation, sol- ubility and stability of complex nanoparticles depend not only on the electrostatic attractive forces but also on the hydrophobic effects. As the enthalpy-to-entropy interplay is very complex, a number of external factors such as temperature, pH, salinity and concentration affect the assembling process and structure of formed nanoparticles. 1

[pt] As propriedades reológicas na interface ar/água de modelos de surfactantes pulmonares (DPPC, DPPC:DPPG, DPPC:DPPG:Colesterol, Survanta e Curosurf) foram investigadas utilizando técnicas de cisalhamento superficiais (reometria de cisalhamento interfacial) e dilatacionais (tensiometria da gota pendente). Assim, alguns parâmetros de interesse foram obtidos para o estudo da viscoelasticidade das amostras (como viscosidade e módulos de armazenamento e perda) e as limitações das técnicas também foram analisadas. Os experimentos foram realizados de forma dinâmica, em que a faixa de frequência de interesse abrange, inclusive, a frequência respiratória de um atleta. Os resultados obtidos mostram a maior viscosidade do Survanta, frente ao Curosurf, e mostram o caráter intermediário do DPPC, que pode ser alterado pela adição de DPPG (aumentando a elasticidade) e Colesterol (aumentando a viscosidade), sugerindo que a mistura DPPC:DPPG pode ser mais adequada do que com DPPC:DPPG:COL para simular o comportamento do surfactante pulmonar. A reometria dilatacional não se mostrou aplicável ao estudo dos surfactantes, o que pode ser causado pela alta viscoelasticidade e relativa instabilidade do Survanta. / [en] The interfacial rheological properties of lung surfactants models (DPPC, DPPC:DPPG, DPPC:DPPG:Cholesterol, Survanta and Curosurf) at the air/water interface were investigated using shear (interfacial shear rheometry) and dilatacional (pendent drop tensiometry) techniques. Thus, some parameters of interest were obtained to study the viscoelasticity of the samples (such as viscosity and storage and loss modules) and the limitations of the techniques were also analyzed. The experiments were carried out dynamically, in which the interest frequency range includes the respiratory rate of an athlete. The results obtained show the higher viscosity of Survanta, compared to Curosurf, and show the intermediate character of DPPC, which can be altered by addition of DPPG (increasing the elasticity) and Cholesterol (increasing the viscosity), suggesting the DPPC:DPPG mixture may be more suitable than with DPPC:DPPG:CHOL to simulate the lung surfactant behavior. The dilatacional rheometry does not shown to be applicable for surfactants studies, which can be caused by the high viscoelasticity and relative instability of Survanta.