Dissertations / Theses: 'Liquid phase content'

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Lauermann, Felix, Fanny Finger, André Ehrlich, and Manfred Wendisch. "Analysis of Water Content Profiles in Arctic Mixed-Phase Clouds during VERDI." Universität Leipzig, 2016. https://ul.qucosa.de/id/qucosa%3A16700.

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Airborne measurements of liquid water content (LWC) and ice water content (IWC) were performed in mixed-phase clouds during the field campaign VERDI in Canada in April and May 2012. In single-layer and multi-layer clouds different vertical profiles of LWC and IWC could be observed. For single layer clouds the maximum LWC occurred in the upper half of the clouds while the IWC had a maximum near the cloud base. This pattern was attributed to the sedimentation of ice particles. In the lowest cloud layer of a multi-layer system both LWC and IWC reached a maximum near cloud top. Together with measured particles size distributions this suggests the presence of the seeder-feeder-process described by Fleishauer et al. (2012) for mid-level clouds.
Im Rahmen der VERDI-Kampagne im April und Mai 2012 in Kanada wurden flugzeuggetragene Messungen von Flüssigwassergehalt (LWC) und Eiswassergehalt (IWC) durchgeführt. Für Einschicht- und Mehrschichtwolkensysteme konnten unterschiedliche Vertikalprofile von LWC und IWC nachgewiesen werden. In Einschichtsystemen wurden die größten Flüssigwassergehalte in der oberen Wolkenhälfte und die größten Eiswassergehalte nahe der Wolkenunterkante gemessen. Diese Verteilung wurde auf die Sedimentation von Eispartikeln zurückgeführt. In der untersten Wolkenschicht eines Mehrschichtsystems befanden sich die Maxima von LWC und IWC nahe der Wolkenoberkante. Diese Beobachtung deutet zusammen mit gemessenen Partikelgrößenverteilungen auf das Vorhandensein des Seeder-Feeder- Prozesses hin, welcher von Fleishauer et al. (2012) für mittelhohe Wolken beschrieben wurde.

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Chen, Jingjing. "Water repellency effects on liquid- and vapor-phase water exchange in soil and clay minerals." Diss., Virginia Tech, 2019. http://hdl.handle.net/10919/87583.

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Drought conditions and wildfires can induce soil water repellency. Precipitation shifts are expected to exacerbate drought and wildfire in regions such as the southeastern United States, making it critical to understand how repellency affects water exchange processes in soil. The objectives of this dissertation were to 1) quantify the water vapor sorption dynamics of two clay minerals in which water repellency was induced; 2) identify if and for how long wildfires in humid hardwood forests induce water repellency, 3) evaluate if organic carbon content and hydrophobic functional groups explain actual and potential soil water repellency; and 4) understand how vertical position (i.e., depth) of water repellent layers affect infiltration processes. To meet these objectives, a laboratory test was first conducted examining water vapor sorption processes in water-repellent clay minerals. Next, a field study occurred in two forests that experienced wildfires in late 2016: Mount Pleasant Wildfire Refuge, Virginia, and Chimney Rock State Park, North Carolina, United States. Measurements include water drop penetration time, soil water content, and tension infiltration. Complimentary laboratory tests quantified potential soil water repellency, soil organic carbon content and hydrophobic functional groups. Results showed that water repellency inhibited water vapor condensation because of altered mineral surface potentials and decreased surface areas. Burned hardwood forest soils presented water repellency for > 1 year, though laboratory measurements presented different trends than in situ measurements. Total organic carbon content and hydrophobic functional groups correlated with soil water repellency measured in the laboratory but not the field. Soil water content was lower in burned than unburned soils, and negatively correlated with water repellency. Water repellency in the surface layers significantly reduced relative water infiltration rates, whereas subsurface water repellency did not, and water repellency persisted longer in sites with surface compared to subsurface water repellency. Finally, while the wildfires increased the occurrence of water repellency, they did not alter the underlying relationship between relative infiltration and surface water repellency. Altogether, this study provided new insight into water repellency effects on water partitioning at soil-atmosphere interfaces, and presented evidence of soil and hydrological changes induced by wildfires in humid hardwood forests.
PHD
Rising temperatures and shifting precipitation patterns that result from global climate change have the potential to induce long-term droughts, which may induce soil water repellency, as can wildfires that become more prevalent and damaging. Water repellency can alter the physical, chemical, and hydraulic properties of soil. These alterations may drive soil erosional processes and increase the mobility of surface-bound pollutants with the potential to reduce water quality and degrade down-gradient aquatic ecosystems. Thus, it is critical to understand how water repellency affects water movement in and through soils. Despite several decades of research towards this topic, some critical questions still remain. For example, how does water repellent soil influence water characteristics in the vapor phase (which is increasingly important under drought conditions)? Do wildfires in humid hardwood forests cause soil water repellency? If so, how long does water repellency persist? Do water repellency measurements using field and laboratory techniques correspond to one another? How does the depth of water repellent soil layer(s) affect water movement? In order to solve this questions, several tests were conducted in both field and laboratory. The field experiments occurred within forested hillslopes that underwent varying degrees of burning during widespread wildfires that affected the Southeastern United States in late 2016. Choosing two forested locations, we measured actual water repellency, soil moisture, and infiltration in burned and unburned sites after wildfire, and took loose samples for laboratory tests. In the lab, we tested potential water repellency on air-dried soil samples, soil organic carbon content and hydrophobic substance percentage. We also conducted water vapor sorption experiments to quantify water vapor exchange in two types of water repellent minerals: kaolinite and montmorillonite. The results showed that water repellency can affect water exchange between the subsurface and the atmosphere, by both limiting water vapor sorption and reducing liquid water infiltration. Soil organic matter and composition correlate well with potential water repellency measured in the laboratory, though less so with actual water repellency measured in the field. Instead, soil water content provided a high and inverse correlation with actual water repellency. Finally, water infiltration rates were influenced by the vertical position (depth) of water repellent layers, with water repellency at the soil surface causing much reduced initial infiltration rates compared to water-repellent layers in the subsurface.

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Vilč, Ladislav. "Vliv teploty a času na podíl krystalické a amorfní fáze v polypropylenu." Doctoral thesis, Vysoké učení technické v Brně. Fakulta chemická, 2010. http://www.nusl.cz/ntk/nusl-233299.

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is is a study of the relationship between structure, mechanical properties and relaxing behavior of the polypropylene. The structure was evaluated by the quantity the solid phase content (SPC). This was defined as mathematical result of free induction decay (FID) signal from pulsed 1H-NMR. The solid phase content is a quite new structural parameter representing the quantity for description of semi-crystalline polymers. Whereas pulsed 1H-NMR is non-destructive, accurate and repeatable, it becomes a unique tool for a description of mechanical, structural, physical-mechanical changes of polypropylene within the time and temperature. Particularly, this method registers the small changes in the time-dependant shipments during secondary crystallization with small structure changes.

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Alford, Shannon Recca. "Analytical method for detecting PCB derivatives at low levels in surface water samples by solid phase extraction-liquid chromatography/mass spectrometry." Mississippi State : Mississippi State University, 2005. http://library.msstate.edu/content/etd/show.asp?etd=etd-12142004-142520.

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DUMAS, HERBIN CHRISTINE. "Chromatographie en phase liquide et synthese organique, exemple d'un produit industriel : la cylcododecanone oxime." Paris 6, 1987. http://www.theses.fr/1987PA066104.

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Les techniques de la chromatographie en phase liquide ont permis de mettre au point une separation optimisee des impuretes de la cyclododecanone oxime. La methode la plus performante est la chromatographie de partage a polarite de phases inversee sur un gel de silice greffee octadecyle avec une phase mobile ayant la composition suivante : methanol-acetonitrile-tetrahydrofurane-eau 33:24:3,5:39,5 (v/v). Une trentaine d'impuretes sont ainsi mises en evidence grace a l'emploi d'une colonne de petit calibre de 1 metre de long et de 1 millimetre de diametre interieur. Cette colonne contient 30000 plateaux theoriques. La duree de la separation est de 3,5 heures. L'identification d'un certain nombre de ces impuretes a ete effectuee par la conjonction de differentes methodes : couplage en ligne avec la spectrometrie de masse et chromatographie semi-preparative permettant d'isoler des quantites notables de certaines impuretes identifiees par la spectrometrie de masse differee de meme on a pu appliquer a ces impuretes la spectrometrie infrarouge par transformee de fourier

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Zhao, Lei. "Dynamics and Statics of Three-Phase Contact Line." Diss., Virginia Tech, 2019. http://hdl.handle.net/10919/102649.

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Wetting, which addresses either spontaneous or forced spreading of liquids on a solid surface, is a ubiquitous phenomenon in nature and can be observed by us on a daily basis, e.g., rain drops falling on a windshield and lubricants protecting our corneas. The study of wetting phenomena can be traced back to the observation of water rising in a capillary tube by Hauksbee in 1706 and still remains as a hot topic, since it lays the foundation for a wide spectrum of applications, such as fluid mechanics, surface chemistry, micro/nanofluidic devices, and phase change heat transfer enhancement. Generally, wetting is governed by the dynamic and static behaviors of the three-phase contact line. Therefore, a deep insight into the dynamics and statics of three-phase contact line at nanoscale is necessary for the technological advancement in nanotechnology and nanoscience. This dissertation aims to understand the dynamic wetting under a molecular kinetic framework and resolve the reconfiguration of liquid molecules at the molecular region of contact line. Water spreading on polytetrafluoroethylene surfaces is selected as a classical example to study the dynamic behaviors of three-phase contact line. To accommodate the moving contact line paradox, the excess free energy is considered to be dissipated in the form of molecular dissipation. As-formed contact line friction/dissipation coefficient is calculated for water interacting with PTFE surfaces with varying structures and is found to be on the same order of magnitude with dynamic viscosity. From an ab initio perspective, contact line friction is decomposed into contributions from solid-liquid retarding and viscous damping. A mathematical model is established to generalize the overall friction between a droplet and a solid surface, which is able to clarify the static-to-kinetic transition of solid-liquid friction without introducing contact angle hysteresis. Moreover, drag reduction on lotus-leaf-like surface is accounted for as well. For the first time, the concept of contact line friction is used in the rational design of a superhydrophobic condenser surface for continuous dropwise condensation. We focus on the transport and reconfiguration of liquid molecules confined by a solid wall to shed light on the morphology of the molecular region of a three-phase contact line. A governing equation, which originates from the free energy analysis of a nonuniform monocomponent system, is derived to describe the patterned oscillations of liquid density. By comparing to the Reynolds transport theorem, we find that the oscillatory profiles of interfacial liquids are indeed governed in a combined manner by self-diffusion, surface-induced convection and shifted glass transition. Particularly for interfacial water, the solid confining effects give rise to a bifurcating configuration of hydrogen bonds. Such unique configuration consists of repetitive layer-by-layer water sheets with intra-layer hydrogen bonds and inter-layer defects. Molecular dynamics simulations on the interfacial configuration of water on solid surfaces reveal a quadratic dependence of adhesion on solid-liquid affinity, which bridges the gap between macroscopic interfacial properties and microscopic parameters.
Doctor of Philosophy

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Herbaut, Rémy. "Dynamique des liquides sur substrat froid, avec solidification." Thesis, Sorbonne Paris Cité, 2019. http://www.theses.fr/2019USPCC006.

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Nous étudions l’étalement de liquides sur une surface froide, avec solidification. L’application visée est le secteur aéronautique qui est confronté à des problèmes de givrage lorsque l’avion est au sol. Le dégivrage s’effectue actuellement par un jet d’éthylène glycol, qui contribue à un surcoût pour les compagnies et une pollution non négligeable. Nos objectifs portent tout d’abord sur des questions fondamentales d’étalement d’une goutte sur un substrat à une température inférieure à la température de solidification. Sur une surface donnée, est-on capable de prédire si la goutte se solidifie ou s’étale dès son impact ? Quelles sont les formes prises par celle-ci, avant, pendant et après la solidification? Quel est le mécanisme de solidification et son influence sur la dynamique d’étalement ? Quel sont les paramètres qui contrôlent la dynamique des processus mis en jeu ? Plusieurs dispositifs et modélisations seront mis en œuvre en vue d’apporter des éléments de réponses à ces questions. Nos objectifs portent aussi sur des stratégies en vue d’éviter la congélation des gouttes et leur permettre de glisser avant leur congélation. La mise en oscillation d’une goutte ou le greffage de polymère en vue modifier l’état de surface seront également envisagés. Cette thèse tente d’apporter quelques éléments de compréhension nouveaux en se concentrant sur deux types d’écoulements très différent. Premièrement, l’avancée d’une ligne de contact en présence de solidification. Deuxièmement, la croissance d’une goutte solide sous alimentation continue en liquide
We study the liquids spreading on cold substrate, with solidification. The intended application is the aeronautical sector, which faces icing problems when the aircraft is on the ground. The deicing is currently carried out by an ethylene glycol jet, which contributes to an additional cost for the companies and a significant pollution. Our objectives focus on fundamental issues of spreading a drop on a substrate at a temperature below the solidification temperature. On a given surface, is it possible to predict whether the drop solidifies or spreads as soon as it is impacted ? What are the forms taken by it, before, during and after solidification? What is the solidification mechanism and its influence on the spreading dynamics? What are the parameters that control the dynamics of the processes involved ? Several devices and models will be implemented to provide some answers to these questions. Our goals also include strategies to avoid freezing drops and allowing them to slide before freezing. Oscillation of a droplet or grafting of polymer to modify the surface condition will also be considered. This thesis attempts to bring some new elements of understanding by focusing on two very different types of flows. First, the advance of a line of contact in the presence of solidification. Second, the growth of a solid drop under continuous liquid feed

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Oprisan, Ana. "Fluctuations, Phase Separation and Wetting Films near Liquid-Gas Critical Point." ScholarWorks@UNO, 2006. http://scholarworks.uno.edu/td/435.

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Gravity on Earth limits the study of the properties of pure fluids near critical point because they become stratified under their own weight. Near the critical point, all thermodynamic properties either diverge or converge and the heating and cooling cause instabilities of the convective flow as a consequence of the expansibility divergence. In order to study boiling, fluctuation and phase separation processes near the critical point of pure fluids without the influence of the Earth's gravity, a number of experiments were performed in the weightlessness of Mir space station. The experimental setup called ALICE II instrument was designed to suppress sedimentation and buoyancy-driven flow. Another set of experiments were carried out on Earth using a carefully density matched system of deuterated methanolcycloxexane to observe critical fluctuations directly. The set of experiments performed on board of Mir space station studied boiling and wetting film dynamics during evaporation near the critical point of two pure fluids (sulfur hexafluoride and carbon dioxide) using a defocused grid method. The specially designed cell containing the pure fluid was heated and, as a result, a low contrast line appeared on the wetting film that corresponded to a sharp change in the thickness of the film. A large mechanical response was observed in response to the cell heating and we present quantitative results about the receding contact lines. It is found that the vapor recoil force is responsible for the receding contact line. Local density fluctuations were observed by illuminating a cylindrical cell filled with the pure fluid near its liquid- gas critical point and recorded using a microscope and a video recorder. Microscopic fluctuations were analyzed both in sulfur hexafluoride and in a binary mixture of methanol cyclohexane. Using image processing techniques, we were able to estimate the properties of the fluid from the recorded images showing fluctuations of the transmitted and scattered light. We found that the histogram of an image can be fitted to a Gaussian relationship and by determining its width we were able to estimate the position of the critical point. The characteristic length of the fluctuations corresponding to the maximum of the radial average of the power spectrum was also estimated. The power law growth for the early stage of the phase separation was determined for two different temperature quenches in pure fluid and these results are in agreement with other experimental results and computational simulations.

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Solomenko, Zlatko. "Two-phase flows over complex surfaces : towards bridging the gap between computations and experiments with application to structured packings." Thesis, Lyon, 2016. http://www.theses.fr/2016LYSEC047/document.

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Ces travaux de thèse s'incrivent dans le cadre du traitement de gaz acides et captage CO2 dans les colonnes à garnissages structurés. Les gaz à traiter réagissent avec un liquide s'écoulant à contre-courant sur des plaques métalliques dont la compléxité géométrique permet d'accroître l'aire d'échange, et donc l'efficacité du procédé. Dans un contexte de modélisation multi-échelles des contacteurs à garnissages structurés, les écoulements gaz-liquide à la plus petite échelle géométrique des plaques de garnissages (de l'ordre de l'épaisseur du film liquide) sont étudiés, pour améliorer la compréhension et la modélisation des écoulements diphasiques et phénomènes de mouillage dans les garnissages. L'objectif final est de développer une méthodologie CFD pour reproduire des écoulements diphasiques 3D sur des géométries complexes telles que les plaques de garnissages. Pour ce faire, il est nécessaire de progresser en méthodes numériques et de proposer des méthodes expérimentales pour observer des écoulements de film liquide sur des géométries complexes. Ces travaux comprennent une partie numérique et une partie expérimentale. Un écoulement sur une plaque de garnissage structuré peut présenter des zones sèches, et donc des lignes de contact (dynamiques), ce qui présente un défi en simulation numérique à cause des différentes échelles de l'écoulement. La méthodologie employée ici en simulation numérique consiste à résoudre l'écoulement jusqu'à une échelle intermédiaire en modélisant les effets des plus petites échelles. Le code de calcul Two-Phase Level-Set a été utilisé et modifié dans ce but. Différentes méthodes level-set ont d'abord été testées de manière à identifier une méthode satisfaisante quant à la réduction des erreurs de conservation de masse, un problème rencontré en level-set. Il est ici montré que certaines combinaisons de schémas de discrétisation spatiale et temporelle permettent de réduire considérablement ces erreurs de conservation de masse. Après avoir réalisé de nombreux tests de validation, une nouvelle méthode numérique est proposée pour simuler les grandes échelles d'écoulements diphasiques 3D avec ligne de contact dynamique en level-set, dans des conditions réalistes. La méthode est ici validée pour des écoulements axisymétriques de gouttes simulés en 3D, en régime visqueux et en régime inertiel, et pour des écoulements de gouttes sur plan incliné. Les résultats sont en très bon accord avec d'autres travaux numériques et expérimentaux. Afin de faciliter l'utilisation de cette méthodologie pour des applications industrielles, un modèle sous-maille similaire a été implémenté dans un code VOF commercial; les résultats sont aussi en très bon accord avec d'autres travaux. En plus de ces développements numériques, une campagne expérimentale est mise en oeuvre pour observer des écoulements de film liquide sur une plaque de garnissage structuré. Les méthodes expérimentales employées sont d'abord testées et validées pour des écoulements de film plat ou ondulé sur plan incliné, et ensuite utilisées pour observer des écoulements de film sur des plaques de garnissage. L'épaisseur de film liquide est mesurée aux creux et aux crêtes des picots des plaques de garnissages, pour différents débits, par imagerie confocale chromatique. Des lois de puissance de l'épaisseur de film en fonction du Reynolds sont proposées; celles-ci sont très différentes suivant la position des relevés de mesure, aux creux ou aux crêtes des picots. La vitesse à l'interface de l'écoulement gaz-liquide est aussi mesurée, par PIV et PTV, en utilisant des particules hydrophobes. Les résultats montrent que le liquide a tendance à dévier du creux des canaux (corrugations), et la norme de la vitesse semblent présenter des extremums correspondant aux creux et crêtes des picots. [...]
The work described in this thesis is motivated by the use of structured packing columns in acid gas treatment and post-combustion CO2 capture. In a counter-current mode, flue gases react with the liquid that flows down over metal sheets, the geometrical complexity of which allows increasing the specific interfacial area, and thereby the overall efficiency of the process. In the context of multiscale modeling of structured-packing contacting devices, the focus in this work is on the gas-liquid flows at the smallest geometrical scale of packing sheets, of the order of the liquid film thickness, aiming to improve understanding and modeling of two-phase flows and wetting phenomena in structured packings. The ultimate objective is to build up a CFD methodology to reproduce 3D two-phase flows over complex surfaces such as structured packing sheets. For this purpose, progress is necessary both in pertinent computational methods and in the adaptation of experimental methods for observing liquid film flows over complex surfaces. This thesis therefore consists of computational and experimental parts. Flows over structured packing sheets may exhibit dry zones, and hence (moving) contact lines, the numerical simulation of which presents a computational challenge due to the disparity in length scales involved. Here, the methodology for large-scale numerical simulations of flows with moving contact lines consists in resolving the flow down to an intermediate scale and modeling effects of smaller ones. The parallelized freeware Two-Phase Level-Set has been extended for this purpose. First though, because some level-set methods have been reproached to yield mass conservation issues, an assessment is made of the mass conservation properties of a range of level-set methods. It is demonstrated that the combined use of some spatial and temporal discretization schemes allows to drastically reduce mass conservation errors in level-set methods. Having thus implemented a level-set method with satisfactory performance at such tests (and others), a novel numerical method is proposed to perform 3D large-scale simulations of flows with moving contact lines in level-set, under realistic conditions. Validation tests of axisymmetric droplet spreading in a viscous, and in an inertial regime, simulated in 3D, and sliding drops are shown to be in excellent agreement with prior experimental and numerical work. The results show that complex contact-line dynamics observed in prior experimental studies on sliding droplets can be simulated using the present large-scale methodology. To facilitate dissemination of this work in industrial applications, a similar subgrid model has been implemented in a commercial volume-of-fluid code; results of validation tests are shown to be in excellent agreement with other work. These computational developments are accompanied by an experimental campaign to observe liquid film flows over structured packing sheets. All experimental methods used herein are tested and validated for flat and wavy films down an inclined plane before being used for observing liquid film flows over packing sheets. The film thickness is measured at local troughs and crests of small-scale corrugations of the structured packing sheet, for different flow rates, by Chromatic Confocal Imaging. Power laws of the Reynolds number for the mean liquid film thickness are suggested, with significant differences for measurements at crests compared to that at troughs. Interface velocity measurements are also performed by PIV and PTV using hydrophobic particles. Results reveal that the liquid tends to deviate from troughs of large-scale corrugations, and seems to exhibit local extrema of the velocity magnitude corresponding to troughs and crests of small-scale corrugations. [...]

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Garcin-Beyssac, Isabelle. "Contribution à l'étude du contenu hormonal des extraits placentaires par chromatographie liquide haute performance." Lyon 1, 1985. http://www.theses.fr/1985LYO1W037.

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Muchena, John Kailemia. "Studies of Capsaicinoids Contents of Locally Grown and Commercial Chilies Using Reversed-Phase High Performance Liquid Chromatography." Digital Commons @ East Tennessee State University, 2009. https://dc.etsu.edu/etd/1800.

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Capsaicinoids are a class of compounds responsible for the "heat" of hot peppers. Capsaicin and dihydrocapsaicin have the highest burning effect. The aim of this work is to separate and quantify the two major capsaicinoids in fruits harvested at different stages of development and at different seasons. Simple and rapid HPLC method involves 73:27% methanol water mobile phase with C18 stationary phase and UV-Vis detector set at 210 nm. The method showed good reproducibility with 1.74% - 4.72% relative standard deviations, a linear response within 0.65–45.5 and 0.25-17.5 μg/mL for capsaicin and dihydrocapsaicin, respectively. The method achieved average recovery of 106% for capsaicin and 102% dihydrocapsaicin. Determination of capsaicinoids in four naturally grown chili and commercial source habanero were analyzed. The amount in the sample ranged from 1184-8156 μg/g for capsaicin and 430-3299 μg/g for dihydrocapsaicin.

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Gonçalves, Daniel. "Citrus essential oil fractionation using ethanol with different water contents as solvents: phase equilibrium, physical properties and continuous equipment extraction." Universidade de São Paulo, 2017. http://www.teses.usp.br/teses/disponiveis/74/74132/tde-22092017-150246/.

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Essential oils are featured commodities in the global market due their many applications in food and chemical industries, in different medicine areas, and as antibacterial, antifungal, and antioxidant agent. One of the phenomena accountable for the loss of essential oils quality may be associated with the degradation of terpene hydrocarbons by oxidation when exposed to air, light or heat, causing disagreeable odors. The procedure of terpenes content reducing, known as deterpenation, can be performed by diverse techniques, among which the liquid-liquid extraction can be highlighted since this process can be operated without the use of heating and pressure changes, causing low impact on the essential oil sensory qualities and low energy consumption. This research was focused on the fractionation process of citrus essential oils, by liquid-liquid extraction, using ethanol/water mixtures as solvents. Experimental liquid-liquid equilibrium data of model and real citrus systems were obtained. The aroma profile of the crude citrus essential oils (orange - Citrus sinensis and lime - Citrus aurantifolia) and the phases from the liquid-liquid equilibrium was also evaluated. Moreover, the crude citrus essential oils were fractionated in a continuous operation equipment (perforated rotating disc contactor, PRDC). It was verified that the water has an important influence over the fractionation performance, but not over the aroma profile of the phases. The experimental data from the model systems (citrus essential oil model mixture + ethanol + water) were used to adjust parameters of empirical and thermodynamic models, which provided satisfactory results on the calculation of physical property values and compositions of the phases from the real systems (crude citrus essential oil + ethanol + water). The fractionation of citrus essential oils by liquid-liquid extraction technology was technically feasible and can be accomplished into continuous apparatus such as PRDC column. The solvents employed provided extract phases enriched in oxygenated compounds.
Óleos essenciais são importantes produtos comercializados mundialmente devido às suas diversas aplicações em indústrias alimentícias e químicas, em diferentes áreas da medicina, e como agentes antibacteriano, antifúngico e antioxidante. Um dos fenômenos responsáveis pela sua perda de qualidade pode estar associado à degradação dos hidrocarbonetos terpênicos por oxidação, quando estes são expostos ao ar, luz ou calor, ocasionando odor desagradável. O procedimento para redução do teor de terpenos no óleo essencial, conhecido como desterpenação, pode ser realizado por diferentes técnicas, entre as quais a extração líquido-líquido se destaca uma vez que pode ser conduzida sem o emprego de calor e mudanças na pressão, o que atenua o impacto nas qualidades sensoriais e demanda menor gasto energético. Este estudo se concentrou no processo de fracionamento de óleos essenciais cítricos, pela técnica de extração líquido-líquido, empregando misturas de etanol e água como solventes. Foram obtidos dados de equilíbrio líquido-líquido de sistemas cítricos modelo e reais. O perfil de aroma dos óleos essenciais brutos (laranja - Citrus sinensis e lima ácida Citrus latifolia) e das fases provenientes do equilíbrio líquido-líquido também foram avaliados. Além disso, os óleos essenciais brutos foram submetidos ao processo de fracionamento em equipamento de operação contínua (coluna de discos rotativos perfurados, PRDC). Verificou-se que a água possui uma importante influência sobre o desempenho do processo de fracionamento, mas não afetou o aroma das fases. Os dados experimentais dos sistemas modelo (mistura modelo de óleo essencial cítrico + etanol + água) foram utilizados para o ajuste de parâmetros de modelos empíricos e termodinâmicos, os quais apresentaram bons resultados no cálculo de valores de propriedades físicas e da composição das fases oriundas dos sistemas reais (óleo essencial cítrico bruto + etanol + água). O fracionamento de óleos essenciais cítricos pela tecnologia de extração líquido-líquido mostrou-se tecnicamente viável e pode ser conduzido em equipamentos contínuos como a coluna de extração PRDC. Os solventes empregados permitiram a obtenção de fases extrato enriquecidas com compostos oxigenados.

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Sun, Jiong. "Contribution à l'étude des transferts de chaleur par contact direct entre deux liquides avec changement d'état liquide-vapeur de la phase dispersée." Aix-Marseille 1, 1989. http://www.theses.fr/1989AIX11260.

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Un modele est etabli pour les echangeurs a contact direct avec le changement de phase liquide-vapeur afin de generaliser et d'extrapoler les resultats experimentaux. Le systeme d'equations differentielles est developpe et resolu numeriquement. Les resultats obtenus montrent l'importance capitale du phenomene de coalescence due a la turbulence et au phenomene de vaporisation. Des lois empiriques ou semi-empiriques ont ete proposees pour tenir compte de cet effet. L'influence de cette loi sur les resultats est analysee et divers comportements sont observes. Un bon accord avec l'experience est obtenu pour un choix convenable de la loi de coalescence. A partir de ce modele l'evolution des divers parametres dans la colonne d'echange est predite. Un bon accord entre les resultats numeriques et experimentaux est observe quelque soit le regime d'ecoulement pour les grandeurs de sortie. Pour le taux de vide local, les courbes obtenues experimentalement et numeriquement ont la meme allure dans la majeure partie de la colonne d'echange. Le decalage spatial peut etre attribue aux hypotheses simplificatrices du modele qui supposent principalement l'existence de trois zones distinctes et un ecoulement diphasique unidimensionnel, ce qui n'est pas le cas dans la realite. On observe par ailleurs une accumulation de vapeur a la sortie de la colonne d'echange. Cet effet n'est pas pris en compte par le modele

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Alves, Kelly Cristina Nascimento. "Modelagem termodinâmica de sistemas aquosos bifásicos contendo sais e polímeros." Universidade de São Paulo, 2008. http://www.teses.usp.br/teses/disponiveis/3/3137/tde-30052008-164131/.

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Neste trabalho estudou-se a modelagem termodinâmica do equilíbrio de fases de sistemas aquosos bifásicos formados por um polímero neutro, especificamente o poli(etileno glicol), e um sal. O modelo implementado é baseado na equação de Pitzer para soluções de eletrólitos, dele diferindo ao considerar a influência das propriedades do polímero no cálculo da constante dielétrica e da densidade do meio, presentes no cálculo do termo relativo às interações de longo alcance da energia de Gibbs excedente. Além disso, procurou-se também considerar a dependência dos parâmetros relativos ao polímero com respeito ao tamanho de sua cadeia. Dados experimentais obtidos da literatura foram utilizados para a obtenção dos parâmetros ajustáveis do modelo, em cuja implementação foi utilizada a linguagem FORTRAN. A alteração nas propriedades do meio modificou o estado de equilíbrio calculado, fato que pôde ser observado por meio da análise de fatores como o desvio entre a composição calculada pelos modelos e os valores experimentais em cada fase e a inclinação da linha de amarração. Em alguns sistemas o desempenho do modelo modificado foi superior nesses parâmetros, mas em termos gerais a modificação no cálculo da constante dielétrica e da densidade não resultou em melhora no cálculo do equilíbrio de fases, por vezes piorando-o, de modo que investigações específicas sobre o termo de longo alcance foram conduzidas para verificar a razão deste comportamento. A inclusão de parâmetros ternários aumentou a capacidade de correlação de ambos os modelos. No que diz respeito à possibilidade de correlação dos parâmetros de interação como função do tamanho da cadeia polimérica, que poderia levar a um modelo preditivo, observou-se que somente para tamanhos grandes de cadeia foi possível estabelecer uma dependência direta e inequívoca.
The thermodynamic modeling of phase equilibrium in aqueous two phase systems containing the neutral polymer poly(ethylene glycol) and a salt was studied in this work. The implemented model is based on the Pitzer equation for electrolytes solutions, modified in order to account for the influence of polymer properties in both the medium dielectric constant and the medium density, values which are present in long range term of the excess Gibbs energy. The dependence of the adjustable parameters on the polymer molecule size was also investigated. Experimental data from literature were used to obtain the adjustable parameters of the model, in whose implementation the FORTRAN computer language was used. The changes introduced into the long range term resulted in a shift of the calculated equilibrium compositions, which could be observed by analyzing the deviation between calculated and experimental compositions and tie-line slopes. For some systems the performance of the modified model was superior, but in most cases the changes introduced did not result in a significant improvement in phase equilibrium calculations, and even worsened them. Specific investigations on the long range term were carried out to verify the reason for such behavior. The insertion of ternary parameters increased the correlation capacity of both models. Concerning the hypothesis that the interaction parameters can be directly related to the polymer chain size, which might eventually lead to a predictive model, it was noticed that a direct dependency holds only for larger chain sizes.

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Mourah, Moustafa. "Modélisation des équilibres de phases liquide-liquide et liquide-vapeur des mélanges contenant de l'eau, des alcools et des hydrocarbures." Paris 13, 2009. http://www.theses.fr/2009PA132023.

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Le sujet de cette thèse concerne la modélisation thermodynamique ‘prédictive’ des équilibres de phases liquide-liquide et liquide-vapeur de systèmes contenant du méthanol, de l'éthanol et/ou de l'eau (molécules polaires et associatives). Le modèle utilisé se base sur une version de l’équation d’état théorique SAFT, combinée à une méthode de contribution de groupe. Cette méthode a été étendue aux composés polaires par Nguyen-Huynh (GC-PPC-SAFT). Dans le cadre de nos travaux, nous avons appliqué une méthode de contribution de groupes développée par Tamouza, avec une méthode prédictive pour évaluer les paramètres d'interaction binaire (basée sur la théorie de London). Après avoir déterminé les paramètres spécifiques de ces composés, ceux-ci ont été étudiés en mélange, en mettant l'accent sur les équilibres liquide-liquide observés en présence d’hydrocarbures. Les paramètres d'interaction binaires ont un effet très important sur ces équilibres, mais peuvent être calculés de manière prédictive. Cette approche ne dégrade que très légèrement la qualité des équilibres liquidevapeur. La description des mélanges de composés polaires et associatifs nécessite une étude du phénomène d'association croisée (eau + alcool). Finalement, nous avons testé la qualité de notre modèle GC-PPC-SAFT sur des systèmes ternaires et les résultats obtenus sont prometteurs dans le but de développer un modèle qui soit le plus prédictif possible. Mots clés: Equilibres de phases liquide-liquide, équation d’état, GC-PPC-SAFT, méthanol, éthanol, eau, simulation moléculaire, associations croisées
This dissertation studies a ‘predictive’ thermodynamic modeling of liquid-liquid and/or liquid-vapor phase equilibria of mixtures containing methanol, ethanol and/or water (polar and associative compounds). The model used is based on a SAFT equation of state combined with a group contribution method. Nguyen-Huynh (GC-PPC-SAFT) has extended this method to polar compounds. In this study, we have applied a group contribution method proposed by Tamouza, with a predictive method to estimate the binary interaction parameter (based on the London theory). Specific parameters of these compounds have been determinated using fundamentally the liquid-liquid phase equilibria data with hydrocarbons. The binary interaction parameters have very important effect on the representation of this phase equilibria. Nevertheless, it is possible to calculate this parameter with a predictive method. This approach weakly degrades the quality of the liquid-vapor phase equilibria. The description of the mixtures containing polar and associative compounds requires to study the cross-associating effect. Finally, we tested the performance of the model GC-PPC-SAFT on ternary systems. The results can be considered promising towards a fully predictive model development

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Bahsoun, Hadi. "Electronic strong coupling of molecular materials in the liquid phase." Thesis, Strasbourg, 2017. http://www.theses.fr/2017STRAF030/document.

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Cette thèse contribue à la compréhension fondamentale du phénomène de couplage fort de la lumière avec des molécules organiques en mettant en œuvre de nouveaux systèmes et de nouvelles techniques, afin d'étudier les modifications de propriétés de molécules couplées à des résonances photoniques. Nous présentons des techniques de nanofabrication avancées pour la création de grands réseaux de trous sur des métaux et de cavités de Fabry-Pérot (FP) nanofluidiques. Ces systèmes sont ensuite utilisés pour étudier, sous régime de couplage fort, les modifications des propriétés de surface et de volume de molécules organiques en phase solide et liquide. En particulier les transitions électroniques de molécules du colorant cyanine en solution liquide ont été couplées à des modes photoniques résonants de cavités FP nanofluidiques spécialement conçues. Leur couplage fort a conduit à une amélioration du rendement quantique d'émission, mettant en évidence la nature radiative des états polaritoniques
This thesis contributes to the fundamental understanding of the phenomenon of strong coupling of light with organic molecules by implementing new systems and techniques in order to investigate property modifications of molecules coupled with photonic resonances. State-of-the-art nanofabrication techniques for the formation of large hole-array gratings in metals and nanofluidic Fabry-Perot (FP) cavities are presented. These systems were then invested to study, under strong coupling, surface and bulk properties modifications of organic molecules in the solid and liquid phase. In particular, electronic transitions of cyanine dye molecules in liquid solutions were coupled to resonant photonic modes of specially designed nanofluidic FP cavities. Their strong coupling has led to an enhancement of the emission quantum yield, highlighting the radiative nature of the associated polaritonic states

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Tang-Mu, Wei. "Oxydation photocatalytique d'hydrocarbures cycliques en phase liquide à température ambiante au contact de TiO2." Lyon 1, 1992. http://www.theses.fr/1992LYO10137.

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L'oxydation menagee d'hydrocarbures cycliques, satures ou non, a ete realisee a temperature ambiante et en phase liquide par photocatalyse heterogene au contact de tio#2 en utilisant l'oxygene de l'air. Contrairement a certaines methodes d'oxydation ce procede evite la formation de rejets polluants. Les influences de divers parametres sur le regime photocatalytique ont ete determines dans le cas du cyclohexane. La proportionnalite entre l'activite et la masse en dessous d'un seuil correspondant a la saturation d'absorption des photons montre qu'il s'agit d'un phenomene catalytique. L'absence d'influence de la temperature prouve que la reaction n'est pas activee et qu'elle est donc de nature photocatalytique. Les variations de la vitesse avec la concentration initiale de cyclohexane dans l'acetonitrile correspondent a une loi du type langmuir-hinshelwood avec reaction en phase adsorbee entre l'hydrocarbure non dissocie et une espece oxygene activee qui d'apres des etudes anterieures du laboratoire serait monoatomique. La proportionnalite entre la vitesse de reaction et le flux energetique pour les faibles valeurs de ce dernier montre que la reaction est proportionnelle a la concentration en trous positifs formes. Pour les flux plus importants, la variation de la vitesse avec la racine carree de montre que la recombinaison electron-trou peut devenir preponderante. Le produit principal d'oxydation menagee du cyclohexane est la cyclohexanone (selectivite de 85%). Il se forme 3% de cyclohexanol et 12% de co#2. L'isomere le plus abondamment forme a partir du methylcyclohexane est la methyl-3 cyclohexanone (selectivite de 53%). La decaline fournit principalement la decalone-2 (selectivite de 86%). Ces selectivites pourraient s'expliquer par les modes d'adsorption de ces hydrocarbures a la surface de tio#2. Le cyclohexene reagit principalement en position allylique avec formation de 56% de cyclohexanone et 27% de cyclohexenol; il se forme egalement 9% d'epoxyde. La tetraline (tetrahydronaphtalene) s'oxyde en position 1 en formant la tetralone-1 (76%) et le tetralol-1 (23%); la formation de seulement 0,8% co#2 illustre la stabilite introduite par le noyau aromatique. Le dopage cationique substitutionnel de tio#2 et le depot de platine a la surface de ce semiconducteur favorisent les recombinaisons electron-trou et donc inhibent la reaction. En conclusion, ces resultats montrent que la photocatalyse heterogene peut etre une methode interessante pour oxyder selectivement en certaines cetones des hydrocarbures cycliques, satures ou non, en phase liquide

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Muller, Julie. "Spéciation dans les phases organiques des systèmes d'extraction liquide-liquide contenant un malonamide et un acide dialkylphosphorique." Phd thesis, Université Pierre et Marie Curie - Paris VI, 2012. http://tel.archives-ouvertes.fr/tel-00833286.

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Le but de la thèse est d'améliorer la compréhension des équilibres chimiques mis en jeu lors de l'extraction des actinides(III) et des lanthanides(III) dans le procédé hydrométallurgique DIAMEX-SANEX de retraitement du combustible nucléaire usé. Il s'agit de décrire au mieux les différents équilibres chimiques pour améliorer la modélisation des propriétés extractantes de ce procédé. La phase organique est constituée d'un mélange d'extractants : un malonamide, le DMDOHEMA, et un acide dialkylphosphorique, le HDEHP, dilués dans un alcane. Ce mélange extractant présente un comportement singulier comparé au comportement des deux extractants seuls. On observe un effet synergique vis-à-vis de l'extraction d'Eu(III) et Am(III) en milieu acide (HNO3 ≈ 1 mol/L en phase aqueuse) et un effet antagoniste à faible acidité (pH < 1). Dans le but de comprendre ce comportement, des études de spéciation moléculaires ont été réalisées après extraction de Ln(III) et Am(III) par diverses techniques spectroscopiques complémentaires (spectrométrie de masse à ionisation électrospray, spectroscopie IR, spectrométrie RMN, spectrofluorimétrie laser à résolution temporelle, spectrophotométrie UV-Visible) mais également par des calculs de chimie quantique pour optimiser la géométrie des complexes formés. Les différentes techniques ont montré l'existence de complexes mixtes incluant les deux extractants, thermodynamiquement plus stables que les complexes unitaires, permettant d'expliquer la synergie sur l'extraction des cations métalliques. L'existence d'un adduit entre les deux extractants, venant consommer les extractants libres, expliquerait l'effet antagoniste observé à faible acidité.

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Said-Bacar, Zabardjade. "Elaboration et caractérisations de silicium polycristallin par cristallisation en phase liquide du silicium amorphe." Phd thesis, Université Paris Sud - Paris XI, 2012. http://tel.archives-ouvertes.fr/tel-00680303.

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L'objectif de ce travail de thèse est l'élaboration du silicium polycristallin en phase liquide, sur substrat de verre borosilicate, en utilisant l'irradiation par laser continu de forte puissance d'un film de silicium amorphe. Des simulations numériques modélisant l'interaction laser-silicium amorphe ont été effectuées grâce à un modèle que nous avons développé sur l'outil COMSOL. Nous avons ainsi pu suivre l'évolution des transferts thermiques dans les différentes structures Si/verre irradiées par laser et ainsi pu évaluer l'impact des paramètres expérimentaux tels que la vitesse de balayage, la puissance du laser, la température du substrat sur les seuils de transition de phase du Si amorphe (fusion, cristallisation, évaporation). Ces résultats de simulation ont été confrontés à des données réelles obtenues en réalisant différentes expériences d'irradiation de films Si amorphe. Les résultats de cette comparaison ont été largement discutés. Dans une deuxième partie, nous avons étudié les propriétés structurales et morphologiques de films Si polycristallin obtenus par l'irradiation laser de films Si amorphe. En particulier, nous avons mis en évidence les effets de la présence d'impuretés tels que l'hydrogène ou l'argon présent dans les couches Si amorphe préalablement au traitement laser. Nous avons également montré que la croissance des cristaux silicium s'opère par épitaxie à partir d'un effet de gradient thermique latéral et longitudinal, produit respectivement par le profil énergétique du faisceau laser et la diffusion thermique par conduction, et par convection thermique dans la direction de balayage. L'optimisation des conditions opératoires nous a permis de réaliser des films Si polycristallin à larges grains, jusqu'à plusieurs centaines de µm de long sur plusieurs dizaines de µm de large. Ces structures sont très intéressantes pour des applications en électronique et en photovoltaïque.

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Soulé, Paul. "Étude des Bords des Phases de l’Effet Hall Quantique Fractionnaire dans la Géométrie d’un Contact Ponctuel Quantique." Thesis, Paris 11, 2014. http://www.theses.fr/2014PA112215/document.

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Dans cette thèse, je présente une étude que j'ai réalisée à l'université Paris-sud sous la direction de Thierry Jolicœur sur les phases des Hall Quantiques Fractionnaire (HQF) dans la géométrie du cylindre.Après une rapide introduction dans le premier chapitre, je présente dans le second quelques concepts de base de l'effet HQF et j'introduit certains aspects de la géométrie cylindrique.Le chapitre 3 est consacré à l'étude de la limite du cylindre fin, c'est à dire lorsque la circonférence du cylindre est de l'ordre de quelques longueurs magnétiques. Dans cette limite, on sait que la fonction d'onde de Laughlin au remplissage 1/q se réduit à un cristal unidimensionnel, où une orbitale sur q est occupée. Dans le but d'étudier un limite intermédiaire, nous conservons les quatre premiers termes du développement de l’Hamiltonien lorsque la circonférence est petite devant la longueur magnétique. On trouve alors une expression exacte de l'état fondamental au moyen d'opérateurs de "squeezing" ou de produits de matrices. Nous trouvons également une écriture similaire pour les quasi- trous, les quasi-électron et la branche magnétoroton.Dans les chapitres 4 et 5, je me concentre sur l'étude des excitations de bord chirales des phases de HQF. Je présente une étude microscopique de ces états de bord dans la géométrie du cylindre, lorsque les quasi-particules peuvent passer d'un bord à l'autre par effet tunnel. J'étudie d'abord dans le chapitre 4 la phase de HQF principale dont l'état fondamental est bien décrit par la fonction d'onde de Laughlin. Pour un échelle d'énergie plus faible que le gap du volume, le théorie effective est donnée par un fluide d'électrons unidimensionnel bien particulier : un liquide de Luttinger chiral. À l'aide de diagonalisations numériques exactes, nous étudions le spectre des états de bord formé de le combinaison des deux bord contre-propageant sur chacun des cotés du cylindre. Nous montrons que les deux bords se combinent pour former un liquide de Luttinger non-chiral, où le terme de courant reflète le transfert de quasi-particules entre les bords. Cela nous permet d'estimer numériquement les paramètre de Luttinger pour un faible nombre de particules, et nous trouvons une valeur cohérente avec la théorie de X. G. Wen.J'analyse ensuite dans le chapitre 5 les modes de bord des phases de HQF au remplissage 5/2. À partir une construction basée sur la Théorie des Champs Conformes (TCC), Moore et Read (Nucl. Phys. B, 1991) ont proposé que la physique essentielle de cette phase soit décrite par un état apparié de fermion composites. Une propriété importante de cet état est que ses excitations émergentes permutent sous une statistique non-abéliène. Lorsqu'elles sont localisées sur les bords, ces excitations sont décrites par un boson chiral et un fermion de Majorana. Dans la géométrie du cylindre, nous montrons que le spectre des excitations de bord est fomé des tours conformes du modèle IsingxU(1). De plus, par une méthode Monte-Carlo, nous estimons les différentes dimensions d'échelle sur des grands systèmes (environ 50 électrons), et nous trouvons des valeurs en accord avec les prédictions de la TCC.Dans le dernier chapitre de ce manuscrit, je présente un travail que j'ai réalisé à UBC (Vancouver) en collaboration avec Marcel Franz sur les phase de Hall quantiques de spin induites dans le graphène par des adatomes. Dans ce système, les adatomes induisent un couplage spin-orbite sur les électrons des la feuille de graphène et introduisent du désordre qui est susceptible de détruire le gap spectral. Nous montrons dans ce chapitre que le gap spectral est préservé lorsque des valeurs réalistes de paramètres sont usités. De plus, au moyen de calculs analytiques à base énergie et de diagonalisations numériques exactes, nous identifions un signal caractéristique dans la densité d'états locale mettant en évidence la présence d'un gap topologique. Ce signal pourrait être observé au moyen d'un microscope à effet tunnel
I present in this thesis a study that I did in the university Paris-sud under the supervision of Thierry Jolicœur onto Fractional Quantum Hall (FQH) phases in the cylinder geometry. After a short introduction in the first chapter, I present some basic concept relative to the FQH effect in the second one and introduce some essential features relative to the cylinder geometry, useful for the chapters 3, 4, and 5. The chapter 3 is dedicated to the study of the thin cylinder limit, i.e. when the circumference of the cylinder is of the order of a few magnetic length. In this limit, it is known that the Laughlin wave function at the filling factor 1/q is reduced to a one dimensional crystal in the lowest Landau level orbitals where one every q orbitals is occupied. We Taylor expand the Hamiltonian when the circumference is small compare to the magnetic length in order to study an intermediate limit. When only the first four terms of the development are kept, it is possible to find exact representations of the ground state with "squeezing" operators or matrix products. We also find similar representations for quasiholes, quasielectrons and the magnetorton branch. These results have been published in the article Phys. Rev. B 85, 155116 (2012). In the chapter 4 and 5 I focus onto the gapless chiral edge excitations of FQH phases. I present a microscopic study of those edges states in the cylindrical geometry where quasiparticles are able to tunnel between edges. I first study the principal FQH phase at the filling fraction 1/3 whose ground state is well described by the Laughlin wave function in the chapter 4. For an energy scale lower than the bulk gap, the effective theory is given by a very peculiar one dimensional electron fluid localized at the edge: a chiral Luttinger liquid. Using numerical exact diagonalizations, we study the spectrum of edge modes formed by the two counter-propagating edges on each side of the cylinder. We show that the two edges combine to form a non-chiral Luttinger liquid, where the current term reflects the transfer of quasiparticles between edges. This allows us to estimate numerically the Luttinger parameter for a small number of particles and find it coherent with the one predicted by X. G. Wen theory. We published this work in Phys. Rev. B 86, 115214 (2012). I then analyze edge modes of the FQH phase at filling fraction 5/2 in the chapter 5. From a Conformal Field Theory (CFT) based construction, Moore and Read (Nucl. Phys. B, 1991) proposed that the essential physics of this phase is described by a paired state of composite fermions. A striking property of this state is that emergent excitations braid with non-Abelian statistics. When localized along the edge, those excitations are described through a chiral boson and a Majorana fermion. In the cylinder geometry, we show that the spectrum of edge excitations is composed of all conformal towers of the IsingxU(1) model. In addition, with a Monte Carlo method, we estimate the various scaling dimensions for large systems (about 50 electrons), and find them consistent with the CFT predictions.In the last chapter of my manuscript, I present a work that I did in UBC (Vancouver) in collaboration with Marcel Franz onto quantum spin Hall phases in graphene induced by adatoms. In this system, adatoms induce a spin orbit coupling for electrons in the graphene sheet and create some disorder which might be responsible for destruction the spectral gap. We show in this chapter and in the article [Phys. Rev. B 89, 201410(R) (2014)] that the spectral gap remains open for a realistic range of parameters. In addition, with analytical computations in the low energy approximation and numerical exact diagonalizations, we find characteristic signal in the local density of states highlighting the presence of topological gap. This signal might be observed in scanning tunneling spectroscopy experiments

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Monteiro, Filho Elias de Souza. "Equilibrio de fases de sistemas contendo polimeros sinteticos e carboidratos em meio aquoso." [s.n.], 2009. http://repositorio.unicamp.br/jspui/handle/REPOSIP/321742.

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Orientadores: Antonio Jose de Almeida Meirelles, Pedro de Alcantara Pessoa Filho
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos
Made available in DSpace on 2018-08-14T08:10:52Z (GMT). No. of bitstreams: 1 MonteiroFilho_EliasdeSouza.pdf: 12530059 bytes, checksum: 1e25eb71e0f6b6a45db80658070acd61 (MD5) Previous issue date: 2009
Resumo: A proposta do presente trabalho foi estudar o equilíbrio de fases de sistemas binários e ternários formados por um polímero sintético de óxido de propileno (PO) ou de um co-polímero bloco de óxido de etileno (EO) e PO e/ou um carboidrato de glicose dissolvidos em água. No total 25 diagramas de equilíbrio líquido-líquido (ELL) foram determinados a temperaturas entre 288,15 e 308,15 K para sistemas ternários, 4 diagramas de ELL para sistemas binários e 9 conjuntos de dados de atividade de água para soluções aquosas binárias e ternárias de diversos dos reagentes estudados. Dos diagramas de ELL ternários, 18 são diagramas cujo oligossacarídeo é polidisperso. A polidispersão influencia significativamente no comportamento do sistema. A temperatura também foi adotada como variável em alguns casos. Os resultados obtidos contribuem para elucidar o comportamento em solução aquosa de co-polímeros bloco de EO e PO com diversas massas molares e relações entre os blocos, e de glicose, maltose ou diversos polímeros de glicose em uma faixa razoável de temperaturas. Estes polímeros são bastante pesquisados para uso em sistemas bi ou mesmo polifásicos para purificação de substâncias de origem biotecnológica. Diferentes tipos de diagramas foram observados, bem como comportamentos diversos da atividade de água. A modelagem termodinâmica foi realizada com base em diversas equações propostas e de uso corrente. Incorpora, ainda, o comportamento diferenciado devido à polidispersão e à temperatura. Os resultados indicam que um bom modelo termodinâmico é capaz não apenas de fornecer informações para controle de processos, mas também sobre as interações moleculares e, com isso, predizer o comportamento de sistemas mais complexos
Abstract: This work relates phase equilibrium of binary and ternary systems formed by aqueous mixtures of EO-PO block co-polymers of five different molar masses and EO/PO ratios, and maltodextrins of three different mean molar masses studied at 298.15 K. 25 Liquid-Liquid Equilibrium (LLE) phase diagrams for ternary systems at temperatures ranging from 288,15 to 308,15 K, plus 4 LLE diagrams for binary systems and 9 water activity data sets, were determined. Of the ternary systems, 18 contain a polydisperse carbohydrate, and this polidispersity influences markedly the system's behavior. Temperature was also investigated in some cases. The results obtained contribute to elucidate the behavior of water solutions containing EO-PO block co-polymers of various molar masses and blocks ratios and glucose, maltose or several glucose polymers in a reasonable temperature range. These polymers are investigated for applications in aqueous two-phase systems. Different kinds of diagrams were observed, as well as water activity reductions. Thermodynamic modeling was performed employing current models. Also, polydispersity and temperature effects were incorporated. The results indicate that a good thermodynamic model is capable of not only provide information for process control purposes, but also about molecular interaction and predict the behavior of more complex systems
Universidade Estadual de Campi
Engenharia de Alimentos
Doutor em Engenharia de Alimentos

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Mukherjee, Manas. "Bubble Solid Interaction." Thesis, Indian Institute of Science, 2004. http://hdl.handle.net/2005/78.

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The interaction of a bubble with solid surfaces, hydrophobic and hydrophilic, was investigated. When a bubble approaches towards a solid surface, a thin liquid film forms between them. The liquid in the film drains until an instability forms and film ruptures resulting in a three phase contact (TPC). Following rupture, the TPC line spreads on the solid surface. In the present study, glycerol-water solutions with varying percentages of water were used to investigate the effect of viscosity. Experiments were carried out with varying bubble size. The rupture and TPC line movement were recorded by high-speed digital video camera. The dependence of the TPC line movement on different parameters was investigated. The experimental results were compared with the existing theories for the TPC line movement. An empirical equation was developed to predict the TPC line movement. Formation or rupturing of the intervening film in case of a hydrophilic surfaces, which were glass surface cleaned by six cleaning techniques, was investigated. It was shown that a stable film forms for acid or alkali cleaning.

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Liedtke, Anne-Kathrin. "Study of a new gas-liquid-solid three phase contact mode at millimetric scale : catalytic reactors using “slurry Taylor” flow." Thesis, Lyon 1, 2014. http://www.theses.fr/2014LYO10137/document.

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Des réacteurs avec solide en suspension (« slurry »), très répandu dans l'industrie chimique, du laboratoire à la production, offrent des bonnes capacités en transfert de matière et de chaleur. Leur flexibilité facilite le changement de la phase solide et permet une régénération en continue des catalyseurs en cas de désactivation. Cependant, ils présentent un fort rétro-mélange, et donc un désavantage pour des réactions ayant des enjeux de sélectivité et/ou de conversion poussées. L'écoulement segmenté dit de Taylor est souvent mis en œuvre dans les réacteurs micro-structurés (RMS), grâce à ses propriétés intéressantes (capacités de transfert, écoulement, piston). Cependant, l'utilisation des solides catalytiques dans ces RMS est le plus souvent résolue par immobilisation du catalyseur nuisant la flexibilité. L'écoulement « slurry Taylor » (EST) qui utilise les recirculations internes dans les segments liquides pour transporter des particules en poudre, peut potentiellement répondre à cet enjeu. L'objet de cette étude est la conception et la caractérisation de ce nouveau mode de contact gaz-liquide-solide (G-L-S) dans des tubes millimétriques horizontaux et verticaux. Des études hydrodynamiques ont révélé différents régimes d'écoulement dépendant de la vitesse et de l'orientation de l'écoulement. Pour étudier le transfert de matière L-S, une résine échangeuse d'ion a été utilisée et une première corrélation pour le nombre de Sherwood est proposée
Slurry reactors, widely encountered in chemical industry (laboratory scale up to manufactaring), offer good mass and heat transfer capacities and their high flexibility ensures the simple changeover of solid phases enables a continuous online fresh catalyst feed for fast deactivating catalysts. However slurry reactors promote a high degree of backmixing which can be a drawback for reactions with selectivity issues or when very high conversions are required. In microreaction technology, Taylor flow is often employed providing excellent heat and mass transfer and almost ideal plug flow behavior. Solid handing in these small structures is often resolved by immobilizing the solid catalyst which impinges on the flexibility. One possible solution to combine beneficial properties of Taylor flow with the operational flexibility of conventional slurry reactors is a “slurry Taylor” flow (STF) where catalyst particles are suspended and kept in motion by the internal circulations present in the liquid slugs. The focus of this work is the design and characterization of this innovative gas-liquid-solid contactor. Particles were transported in millimetric horizontal and vertical tubing without the risk of clogging. Hydrodynamic studies revealed different flow patterns depending mainly on velocity and flow orientation. Ion exchange resin particles were used to study the liquid-solid mass transfer and first correlation for the Sherwood number in STF is proposed

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24

Li, Shi-Ming. "Mean-Field Free-Energy Lattice Boltzmann Method for Liquid-Vapor Interfacial Flows." Diss., Virginia Tech, 2007. http://hdl.handle.net/10919/29621.

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This dissertation includes a theoretical and numerical development to simulate liquid-vapor flows and the applications to microchannels. First, we obtain a consistent non-local pressure equation for simulating liquid-vapor interfacial flows using mean-field free-energy theory. This new pressure equation is shown to be the general form of the classical van der Waals" square-gradient theory. The new equation is implemented in two-dimensional (2D) D2Q7, D2Q9, and three-dimensional (3D) D3Q19 lattice Boltzmann method (LBM). The three LBM models are validated successfully in a number of analytical solutions of liquid-vapor interfacial flows. Second, we have shown that the common bounceback condition in the literature leads to an unphysical velocity at the wall in the presence of surface forces. A few new consistent mass and energy conserving velocity-boundary conditions are developed for D2Q7, D2Q9, and D3Q19 LBM models, respectively. The three LBM models are shown to have the capabilities to successfully simulate different wall wettabilities, the three typical theories or laws for moving contact lines, and liquid-vapor channel flows. Third, proper scaling laws are derived to represent the physical system in the framework of the LBM. For the first time, to the best of the author's knowledge, we obtain a flow regime map for liquid-vapor channel flows with a numerical method. Our flow map is the first flow regime map so far for submicrochannel flows, and also the first iso-thermal flow regime map for CO₂ mini- and micro-channel flows. Our results show that three major flow regimes occur, including dispersed, bubble/plug, and liquid strip flow. The vapor and liquid dispersed flows happen at the two extremities of vapor quality. When vapor quality increases beyond a threshold, bubble/plug patterns appear. The bubble/plug regimes include symmetric and distorted, submerged and non-wetting, single and train bubbles/plugs, and some combination of them. When the Weber number<10, the bubble/plug flow regime turns to a liquid strip pattern at the increased vapor quality of 0.5~0.6. When the Weber number>10, the regime transition occurs around a vapor quality of 0.10~0.20. In fact, when an inertia is large enough to destroy the initial flow pattern, the transition boundary between the bubble and strip regimes depends only on vapor quality and exists between x=0.10 and 0.20. The liquid strip flow regimes include stratified strip, wavy-stratified strip, intermittent strip, liquid lump, and wispy-strip flow. We also find that the liquid-vapor interfaces become distorted at the Weber number of 500~1000, independent of vapor quality. The comparisons of our flow maps with two typical experiments show that the simulations capture the basic and important flow mechanisms for the flow regime transition from the bubble/plug regimes to the strip regimes and from the non-distorted interfaces to the distorted interfaces. Last, our available results show that the flow regimes of both 2D and 3D fall in the same three broad categories with similar subdivisions of the flow regimes, even though the 3D duct produces some specific 3D corner flow patterns. The comparison between 2D and 3D flows shows that the flow map obtained from 2D flows can be generally applied to a 3D situation, with caution, when 3D information is not available. In addition, our 3D study shows that different wettabilities generate different flow regimes. With the complete wetting wall, the flow pattern is the most stable.
Ph. D.

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Tachon, Loïc. "Développement d'outils numériques et expérimentaux dédiés à l'étude de l'évaporation en présence de ligne triple." Thesis, Aix-Marseille 1, 2011. http://www.theses.fr/2011AIX10027/document.

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Les travaux réalisés au cours de cette thèse visent à apporter une aide à la compréhension des mécanismes régissant l'évaporation des films liquides. La physique des problèmes à changement de phase avec ligne de contact est gouvernée par des mécanismes agissant au niveau de ces dernières ainsi qu'au niveau des interfaces gaz-liquide. La description géométrique des interfaces est donc un point clef dans cette étude tant d'un point de vue numérique qu'expérimental. Un outil numérique tridimensionnel de suivi d'interface infiniment fine a été créé afin d'anticiper la simulation numérique de ces problèmes. Cet algorithme repose sur une description quadratique de l'interface qui est une surface du maillage. L’ordre de convergence de cette méthode relatif à différentes caractéristiques (courbure, normale, position) de l'interface ainsi que sa qualité conservative ont été étudiés.Parallèlement à cette approche numérique, une technique expérimentale d'inversion optique a été développée. Celle-ci permet la mesure dynamique du profil d'une interface au voisinage de la ligne de contact dans le cadre de fluide très mouillant. Cette méthode, appliquée dans le cadre d'un problème de film en évaporation quasi axisymétrique a permis, dans le cadre d'une expérience simple, une première quantification des flux de chaleur et de masse échangés au niveau de la ligne de contact
The tasks fulfilled during this study aim at providing tools for understanding the mechanisms of liquid film evaporation. Evaporation in the presence of a triple lines is ruled by physical mechanisms acting on these singularities as well as on the gas liquid interfaces. Thus, the interface description, under it numerical as experimental aspects, is a key point of this study. A numerical tridimentionnal sharp interface tracking tool has been developed to be used in further numerical simulation of the evaporation problem. In this algorithm, the interface is described as a quadratic grid surface. Its convergence orders relatively to geometrical parameters of the interface (curvature, normal, position) has been studied.In the mean time, an experimental optical inversion technique has been developed and validated. It allows a dynamic measurement of the interface shape in the vicinity of the triple line of highly wetting fluid. This method has been applied to the case of a quasi axisymetric evaporating film and provides a first quantification of the heat and mass transfers generated by the triple line region

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Rivière-Cantin, Sophie. "Morphologie et propriétés élastiques de phases hexatiques dans des films monomoléculaires d'acides gras." Phd thesis, Université Pierre et Marie Curie - Paris VI, 1995. http://tel.archives-ouvertes.fr/tel-00001108.

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Cette thèse présente une étude de films monomoléculaires d'acides gras à l'interface eau-air, principalement par microscopie à l'angle de Brewster. Cette technique permet l'observation directe des coexistences de phases lors de transitions de phases du premier ordre; de plus elle est sensible à l'anisotropie optique des films. La première partie contient une étude du diagramme de phase des acides gras, qui comporte des mésophases analogues aux phases de cristaux liquides smectiques. Nous avons montré que lors des transitions de phases entre phases denses, la texture (l'arrangement moléculaire)des phases est réversible et nous avons obtenu des informations sur l'ordre des transitions. Nous avons aussi mis en évidence, dans deux phases constituées de molécules verticales, une très faible anisotropie optique due à la forme rectangulaire du réseau moléculaire. Nous avons ensuite étudié une film d'acide myristique adsorbé à la surface d'une solution aqueuse d'acide myristique. Nous avons observé des domaines d'une mésophase "inclinée" contenant des lignes de défauts d'orientationmoléculaire présentant des fluctuations thermiques. La mesure de leur amplitude a permis de déterminer la tension de ces lignes. Nous nous sommes aussi intéressés aux constantes élastiques qui gouvernent la forme et la texture à l'équilibre des domaines de mésophase. Nous avons d'une part déterminé la tension de ligne de l'interface entre une phase liquide et une mésophase "inclinée" en étudiant la forme des domaines. Celle-ci résulte de l'équilibre entre la tension de ligne, qui favorise des domaines circulaires, et les interactions répulsives à longue portée entre dipoles moléculaires, qui forment les domaines. Des mesures de potentiel de surface ont permis de calculer l'intensité des forces dipolaires. d'autre part, la texture d'autre domaines de cette mésophaseinclinée nous a renseigné sur la valeur du rapport entre l'élasticité de courbure de la direction moléculaire et l'anisotropie de la tension de ligne.

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GENDREU, PHILIPPE. "Etude des champs ultrasonores impulsionnels generes dans les liquides et les solides par des transducteurs piezocomposites. Application a la focalisation dans les solides : barrette de phase en contact." Paris 7, 1995. http://www.theses.fr/1995PA077029.

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Cette these est consacree a l'etude des champs ultrasonores impulsionnels generes dans les liquides et les solides par des transducteurs piezocomposites rectangulaires. Les deplacements transitoires a la surface d'un transducteur piezocomposite 1-3 ont ete mesures dans l'eau avec une sonde interferometrique heterodyne. Une sequence animee montrant l'etat instantane de la surface du piezocomposite a ete construite. Des mesures optiques du deplacement ont egalement ete faites sur une fine membrane au voisinage du transducteur et en champ lointain. Elles ont montre que, malgre les inhomogeneites de deplacement de surface, un transducteur piezocomposite peut etre assimile a une source fonctionnant en mode piston. Nous avons calcule des reponses impulsionnelles de diffraction qui donnent le champ de deplacement en tout point d'un liquide connaissant le deplacement de l'ouverture piston fourni par un modele de transduction unidimensionnel ou par la mesure du deplacement en champ tres proche. Nous avons ensuite construit un modele impulsionnel permettant de predire le champ ultrasonore cree dans un solide par une barrette de phase en contact. Ce modele prend en compte les proprietes elastiques intrinseques du solide et les effets de diffraction lies a la forme et a l'environnement acousto-electrique du transducteur. A partir des fonctions de green impulsionnelles nous avons etabli deux formulations pour la reponse impulsionnelle de diffraction en supposant que le transducteur vibre en mode piston (piston de contrainte). La premiere permet de calculer le deplacement dans le solide resultant de la superposition des ondes longitudinale, transversale et conique. La deuxieme totalement analytique considere que les ondes longitudinale et transversale sont decouplees, l'onde conique n'etant pas decrite. Ces deux formulations ont ete validees experimentalement grace a des mesures optiques precises du champ de deplacement. Nous avons montre que l'onde longitudinale pouvait etre focalisee efficacement pour des valeurs importantes de l'angle de deflexion

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Lopez, Claire. "Synthèse de polymères à empreintes moléculaires d'alcaloïdes Vinca pour leur extraction sur phase solide dans des extraits de plantes ou des fluides biologiques : développement du détecteur conductimétrique sans contact à couplage capacitif et de la technique de la double injection en électrophorèse capillaire." Thesis, Orléans, 2010. http://www.theses.fr/2010ORLE2078.

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Ce mémoire reporte dans une première partie les études menées sur des polymères à empreintes moléculaires (MIP) en extraction solide-liquide (SPE). La nature des interactions polymère-analyte, l’influence de la composition de la matrice de l’échantillon et la sélectivité des MIPs sont étudiés.La première application concerne l’extraction de molécules ciblées dans un extrait de plante. Deux MIPs respectivement préparés à partir de l’acide méthacrylique (MAA) et l’acide itaconique (IA) et avec respectivement la catharanthine et la vindoline comme molécule empreinte ont montré leur sélectivité sur des solutions standards puis sur un extrait de plante. Des expériences de réactivité croisée réalisées sur des molécules analogues à la molécule empreinte (alcaloïdes dimères) montrent la spécificité de reconnaissance des analytes par les MIPs. Le MIP-catharanthine est caractérisé par les isothermes de Scatchard et sa capacité est évaluée en SPE à partir de l’extrait de Catharanthus roseus. Un MIP préparé à partir de MAA avec la vinorelbine comme molécule empreinte a été appliqué à des matrices aqueuses salines pour l’extraction de la vinflunine et de son métabolite dans du plasma bovin et de l’urine. Des rendements d’extraction élevés ont été atteints grâce à une étude de l’impact des sels et au choix de solvants de lavage adaptés à la matrice. Une deuxième partie montre la simplicité d’utilisation et la sensibilité de la détection conductimétrique sans contact à couplage capacitif (C4D) lors de l’analyse du contre-ion et du principe actif dans des composés pharmaceutiques en électrophorèse capillaire (EC). La technique de la double injection a permis l’analyse simultanée des cations et des anions. La méthode EC-C4D développée est appliquée aux alcaloïdes Vinca et à différents médicaments avec des contre-ions anioniques ou cationiques
This thesis reports in a first part results obtained with molecularly imprinted polymers (MIP) during solid liquid extraction. Polymer-analyte interactions, composition of the sample matrix and selectivity of MIPs have been studied.The first application concerned the extraction of molecules in a plant extract. Two MIPs respectively prepared from the methacrylic acid (MAA) and itaconic acid ( IA) and with respectively catharanthine and vindoline as template showed their selectivity on standard solutions then on a plant extract. Experiments of cross reactivity performed with analogue of the template (dimers alkaloids) have proved the specificity of analytes recognition by the MIPs. The MIP-catharanthine is characterized by Scatchard isotherms and its capacity was estimated from the extract of Catharanthus roseus. A MIP prepared from MAA with the vinorelbine as template was applied in salt aqueous matrices for the extraction of vinflunine and its metabolite in bovine plasma and urine. High extraction recoveries were reached with a study of the impact of salts and the choice of washing solvents adapted to the matrix. The second part showed the simplicity of use and the sensibility of capacitively coupled contactless conductivity detection (C4D) for the analysis of counter-ion and active principle in pharmaceutical compounds in capillary electrophoresis (CE). The technique of double injection allowed the simultaneous analysis of cations and anions. The developed method EC-C4D was applied to Vinca alkaloids and various medicines with anionic or cationic counter-ions

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Lecoeur-Lorin, Marie. "Intérêt du détecteur à dichroïsme circulaire en chromatographie liquide et du détecteur conductimétrique à couplage capacitif en électrophorèse capillaire pour l'analyse de molécules chirales. Applications aux composés pharmaceutiques et aux pesticides." Phd thesis, Université d'Orléans, 2008. http://tel.archives-ouvertes.fr/tel-00362022.

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La séparation des énantiomères de principes actifs pharmaceutiques suscite un vif intérêt en raison des propriétés pharmacologiques, toxicologiques ou biologiques différentes qui peuvent exister entre deux isomères optiques. Le développement de méthodes d'analyse spécifiques et sensibles est donc nécessaire afin de contrôler la présence de traces de l'énantiomère inactif dans des lots de fabrication de médicaments.
L'utilisation d'un détecteur à dichroïsme circulaire en chromatographie en phase liquide a permis de déterminer simultanément les puretés optique et chimique de plusieurs principes actifs pharmaceutiques. La sensibilité de la détection dichroïque est toutefois influencée par différents facteurs (nature des chromophores de l'analyte, pH de la phase mobile, température de la cellule de détection, utilisation d'un filtre électronique). Malgré un manque de sensibilité, le détecteur à dichroïsme circulaire permet de déterminer rapidement la pureté énantiomérique de principes actifs en CPL, sans séparation préalable des énantiomères sur un support chiral.
D'autre part, l'aptitude de l'électrophorèse capillaire à séparer des énantiomères de pesticides possédant des hétéroatomes comme centres d'asymétrie a été confirmée. Ainsi, la séparation des énantiomères d'un pesticide organophosphoré et de ses deux métabolites chiraux a été réalisée. Cette méthode a été pré-validée puis appliquée à des matrices environnementales.
Enfin, la simplicité d'utilisation et la sensibilité de la détection conductimétrique sans contact à couplage capacitif sont des atouts indéniables lors de la détermination de la pureté énantiomérique d'amines dénuées de groupements chromophores en électrophorèse capillaire.

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Renault, Jean-Christophe. "Étude du mécanisme de dégradation du méthanol au contact du nickel dans le cadre d'une boucle fluide diphasique à pompage capillaire." Thesis, Pau, 2017. http://www.theses.fr/2017PAUU3017/document.

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Dans le domaine ferroviaire les contraintes pesant sur les systèmes de traction électrique sont telles que cela constitue une branche à part de l’électronique, appelée « électronique de puissance ». La nécessité du refroidissement est exacerbée par la présence de très fortes puissances électriques circulant dans ces systèmes. Une adaptation au domaine ferroviaire des boucles fluides diphasiques à pompage capillaire, initialement conçues pour des applications spatiales, pourrait constituer une réponse avantageuse à ce besoin de refroidissement. Ce sont des moyens de transfert thermique passifs, modulaires, très performants et très fiables. La vaporisation du fluide caloporteur se fait dans une mèche poreuse, engendrant une différence de pression entre la vapeur et le liquide, permettant la mise en mouvement du fluide dans tout le système. Elles fonctionnent donc sans pompe ni aucun organe mécanique de mise en mouvement du fluide.Des adaptations ont été effectuées par ALSTOM et EHP (Euro Heat Pipe) sur ces boucles conduisant à un prototype appelé « Capillary Pumped Loop for Integrated Power » (CPLIP). Dans ce contexte, l’objectif de cette thèse est d’étudier la compatibilité chimique du fluide diphasique utilisé dans la CPLIP, le méthanol, avec le matériau de la mèche poreuse de la CPLIP, du nickel fritté. Cette compatibilité sera notamment étudiée aux températures de fonctionnement qui pourraient être plus élevées qu’elles ne le sont actuellement avec l’utilisation du carbure de silicium dans l’électronique de puissance. Deux bancs d’essai ont été développés spécifiquement pour l’étude du vieillissement d’un fluide au contact d’un solide catalytique. Le premier est un réacteur batch permettant de déterminer la cinétique de réaction. Un second banc d’essais a été conçu dans le but de se rapprocher des conditions de fonctionnement des boucles fluides diphasiques. Du fait des contraintes liées à l’étude de la réaction par analyse des composés chimiques, il n’était pas possible de faire circuler le fluide par pompage capillaire. C’est donc une boucle fluide diphasique gravitaire qui a été mise au point. Le fonctionnement de ce procédé étant loin d’être trivial, une partie de ce travail est consacrée à décrire le comportement thermique de ce procédé, à l’aide de résultats expérimentaux ainsi que d’un modèle numérique simple. Les analyses sur ces deux bancs de test ont été faites à l’aide d’un micro-chromatographe en phase gazeuse. Des essais de caractérisation de la surface, au travers d’analyses de microscopie à balayage électronique, de spectrophotométrie à rayon X et des analyses BET ont permis d’avoir une idée plus précise de la surface du nickel fritté. Ces analyses ont également été effectuées après réaction, de manière à obtenir plus d’informations sur l’évolution de l’état de surface au cours de la réaction. Différents essais ont ensuite été effectués pour différentes températures et différentes granulométries qui nous ont permis de proposer un mécanisme de la dégradation du méthanol au contact du matériau constituant la mèche poreuse. Enfin, des premiers tests ont été effectués sur la boucle fluide diphasique de manière à étudier la dégradation du méthanol dans des conditions proches de celles qui seront rencontrées dans les boucles industrielles
In the railway field the constraints on electric traction systems are such that these systems constitute a separate branch of electronics, called "power electronics". Furthermore, the needs for cooling these systems are increased by the presence of very high electrical currents flowing in these systems. An adaptation to the railway field of two-phase fluid capillary pumped loops, initially designed for space applications, could be an advantageous response to this cooling need. The capillary pumped loops are passive and modular heat transfer devices, characterized by their highly efficient and highly reliable behavior. The vaporization of the heat transfer fluid takes place in a porous wick, generating a pressure difference between the vapor and the liquid phase, allowing the setting in motion of the fluid throughout the system. They therefore operate without pump or any mechanical element to set the fluid in motion. Adaptations have been made by ALSTOM and EHP (Euro Heat Pipe) on these loops, leading to a prototype called "Capillary Pumped Loop for Integrated Power" (CPLIP). The goal of this PhD, in this context, is to study the chemical compatibility of methanol, which is the fluid used in the CPLIP, with the material of the CPLIP wick based on sintered nickel. Their compatibility will be mainly studied for temperatures higher than those currently encountered in the loop, to take into account the increase of operating temperature due to the development of silicon carbide in power electronics.Two test benches have been developed specifically for the study of the aging of a couple fluid/catalytic solid in contact. The first one is a batch reactor used to determine the reaction kinetics. A second test bench has been designed with the aim to partially reproduce the operating conditions of the CPLIP. Because of the constraints related to the study of the reaction including analysis of the chemical compounds, it was not possible to generate capillary pumping to the setting in motion of the fluid. A gravitational two-phase fluid loop has therefore been developed. Since the use of this process is quite complex, a part of this work is devoted to describe its thermal behavior, using experimental results as well as a simple numerical model. On these two test benches, a gas chromatograph was used to perform chemical analyzes. Surface characterization tests, using scanning electron microscopy, X-ray spectrophotometry and BET analyzes, provided a more accurate knowledge of the surface area of the sintered nickel. Analyzes were also carried out after reaction, in order to obtain more information on the evolution of the surface state during the reaction. Various tests were then carried out for different temperatures and particle sizes which allowed us to offer a degradation mechanism of methanol in contact with the nickel of the porous wick. Finally, first tests were carried out on the gravitational two-phase fluid loop in order to study the degradation of methanol under conditions representative to those encountered in industrial loops

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Huang, Poa-Hui, and 黃寶慧. "By reverse phase high pressure liquid chromatography analysis of commercially available drugs Olanzapine drug content." Thesis, 2013. http://ndltd.ncl.edu.tw/handle/01586629970191807171.

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碩士
高雄醫學大學
醫學研究所
101
In this thesis, the high-performance liquid chromatography, a broadly used instrument for drug analysis was applied to establish a fast, accurate and efficient method for the analysis of the marketed olanzapine, a clinical drug for schizophrenia. A Vercopak C18 [250 × 4.6 mm (id)] column was used as stationary phase and the mixture of (20 mM NaH2PO4；pH = 6.8) / (methanol/acetonitrile = 1/1) = (30/70，V/V) was utilized as mobile phase. The UV detection (254 nm) and flow rate of the mobile phase (1.0 mL/min) were performed. The resulting assay exhibited a linear range of 6 ~ 16 μg/mL (r = 0.99990), a relative standard deviation of 0.4% (n = 5) for the precision of repeated injections of 10 ?慊/mL, a relative standard deviation of 0.4%(n = 18) for different days intermediate precision, a relative standard deviation of 0.2%(n = 12) for different persons, a relative standard deviation of 0.2%(n = 12) for different instruements and a recovery of 100.3% ~ 101.3%. For a robustness testing of the analytical method, flow rate ± 0.2 mL/min, pH ± 0.2 and the composition of mobile phase (± 5% were studied. From experimental results, our analytical method was proved to exhibit the advantages of accuracy, precision and specificity. Thus, the quantitative analysis of the marketed olanzapine was established.

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32

Cai, Wen-Zhang, and 蔡文章. "The influences of Ni content on the liquid phase sintering and microstructure of boron-containing powder metallurgy steels." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/t9pbn5.

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碩士
國立臺北科技大學
材料科學與工程研究所
104
Powder metallurgy (PM) steels have been widely utilized in the structural material. To further increase their mechanical properties, liquid phase sintering, which does not much increase the production cost, is a feasible way to promote densification of the PM steels. However, every alloying element in the PM steel can affect the mechanism of liquid formation and its microstructure. Therefore, the role of the various alloying element should be clearly identified. The main objective of this research was to examine the influences of nickel content (0, 1.8, 4 wt%) and adding ways (elemental powder system and prealloy system) on liquid phase sintering of boron-containing PM steel (Fe-0.5Mo-0.4B-0.5C). The result showed that the microstructure after liquid phase sintering contained continuous boride at the grain boundary. According to the electron back-scatter diffraction (EBSD) and electron probe microanalysis (EPMA) results, it can be found that the boride phase at the grain boundary is M2B structure after 1200°C sintering. Moreover, after 1250°C sintering for one hour, carbon atoms in the original graphite powder gradually diffused into the eutectic liquid and change the boride phase after sintering. The M2B structure in the steel sintered at 1200°C were replaced by an M3(B,C) borocarbide in the steel sintered at 1250°C for one hour. The results of thermal analysis and density demonstrate that nickel can lower the temperature for liquid formation and thus increase the sintered density. The increase in the sintered density of Fe-0.5Mo-0.4B-0.5C steel after sintering at 1250°C for one hour is 0.52 g/cm3. When the 4 wt% Ni additive is added into the Fe-0.5Mo-0.4B-0.5C steel, the increases in the sintered densities after sintering at 1250°C for one hour are 0.63 g/cm3and 0.65 g/cm3, for the prealloy system and elemental powder system, respectively. These findings show that increasing the nickel content in the boron-containing PM steels is beneficial for the liquid phase sintering and sintered density.

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33

HACKETT, JAMES LAWRENCE III. "AN INVESTIGATION OF THE MIDDLE PHASE MICROEMULSION TO LIQUID CRYSTAL TRANSITION IN ANIONIC SURFACTANT SYSTEMS AT LOW ALCOHOL CONTENT." Thesis, 1987. http://hdl.handle.net/1911/16062.

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Equilibrium phase behavior is reported for two anionic surfactant, alcohol, sodium chloride, water, n-decane systems, in the region where a transition occurred from microemulsion to liquid crystalline phases with decreasing alcohol content and decreasing temperature. One surfactant/co-surfactant pair studied was a commercial a -olefin sulfonate and n-butanol. The other was pure sodium dodecyl sulfate (SDS) and n-hexanol. A general, complex pattern of phase behavior was seen which included a four-phase coexistence region of brine, microemulsion, lamellar liquid crystal, and oil and two three-phase regions containing both microemulsion and liquid crystal. Compositional analysis of selected formulations in the four-phase region of the SDS system showed the liquid crystals to be oil-rich, making them different from lamellar phases in aqueous surfactant systems that contain over 90% water. In much of the four-phase region, complete separation of the phases did not occur even after yearlong equilibration at constant temperature. Instead, oil and brine were found to coexist with stable birefringent dispersions which, at least at some compositions, apparently contained three phases: microemulsion, liquid crystal, and oil. The dispersions in the SDS system exhibited non-Newtonian behavior with apparent viscosities ranging from 50 to 100 mPa s at a shear rate of 10 sec$\sp{-1}$. Microemulsion viscosities in the same system were an order of magnitude lower. Preliminary experiments suggest these dispersions are capable of displacing oil from a model porous medium when flowed at typical reservoir rates. They are thus of potential interest for enhanced oil recovery. Other investigations concerned the phase behavior of an ethoxylated, propoxylated sulfate system and two Zwitterionic surfactants in brine. The former study revealed a pattern of phase behavior similar to that reported for anionic surfactants with increasing salinity. However, with respect to temperature, these species behaved like nonionic surfactants. The Zwitterionic ammoniopropane sulfonates are unusual in that they display enhanced solubility in brine over that in pure water. As a result, a pattern of phase behavior reversed from that found in most anionic systems was observed with increasing salinity. A tentative explanation was given in terms of changes in surfactant molecular configuration with salinity, as suggested by others.

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34

Cui, Zhongkai. "Novel non phospholipid liposomes with high sterol content : development and characterization." Thèse, 2012. http://hdl.handle.net/1866/9157.

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Les liposomes sont des nanovecteurs polyvalents et prometteurs quant à leur utilisation dans plusieurs domaines. Il y a une décennie, un nouveau type de liposome constitué d’amphiphiles monoalkylés et de stérols est né fortuitement dans notre groupe. Ils sont nommés Stérosomes puisqu’ils contiennent une grande proportion de stérols, entre 50 et 70 mol %. Les objectifs de cette thèse sont de développer de nouvelles formulations de Stérosomes ayant des caractéristiques spécifiques et d’acquérir une compréhension plus profonde des règles physicochimiques qui dictent leur comportement de phase. Nous avons spécifiquement examiné le rôle de motifs moléculaires des stérols, de la charge interfaciale et de la capacité à former des liaisons H dans les interactions intermoléculaires menant à l’autoassemblage. Le comportement de phase a été caractérisé par calorimétrie différentielle à balayage (DSC), par spectroscopie infrarouge (IR) et par spectroscopie de résonance magnétique nucléaire du deutérium (²H NMR). Premièrement, nous avons établi certaines corrélations entre la structure des stérols, leur tendance à former des bicouches fluides en présence d'amphiphile monoalkylé et la perméabilité des grandes vésicules unilamellaires (LUV) formées. La nature des stérols module les propriétés de mélange avec de l’acide palmitique (PA). Les stérols portant une chaîne volumineuse en position C17 sont moins aptes à induire des bicouches fluides que ceux qui ont une chaîne plus simple, comme celle du cholestérol. Un grand ordre de la chaîne alkyle de PA est un effet commun à tous les stérols investigués. Il a été démontré que la perméabilité des LUV peut être contrôlée en utilisant des stérols différents. Cependant, ces stérols n’ont aucun impact significatif sur la sensibilité des Stérosomes au pH. Afin de créer des liposomes qui sont sensibles au pH et qui ont une charge positive à la surface, des Stérosomes composés de stéarylamine et de cholestérol (Chol) ont été conçus et caractérisés. Il a été conclu que l’état de protonation de l’amine, dans ce travail, ou du groupe carboxylique, dans un travail précédent, confère une sensibilité au pH et détermine la charge à la surface du liposome. Les premiers Stérosomes complètement neutres ont été fabriqués en utilisant un réseau de fortes liaisons H intermoléculaires. Le groupe sulfoxyde est capable de former de fortes liaisons H avec le cholestérol et les molécules d’eau. Une bicouche fluide métastable a été obtenue, à la température de la pièce, à partir d'un mélange équimolaire d’octadécyl méthyl sulfoxyde (OMSO) et de Chol. Ce comportement distinct a permis d’extruder le mélange pour former des LUV à la température de la pièce. Après 30 h, le temps de vie de la phase métastable, des Stérosomes stables et imperméables existaient toujours sous une forme solide. Un diagramme de température-composition a été proposé afin de résumer le comportement de phase des mélanges d’OMSO/Chol. Finalement, nous avons élaboré des Stérosomes furtifs en incorporant du polyéthylène glycol (PEG) avec une ancre de cholestérol (PEG-Chol) à l’interface de Stérosomes de PA/Chol. Jusqu’à 20 mol % de PEG-Chol peut être introduit sans perturber la structure de la bicouche. La présence du PEG-Chol n’a aucun impact significatif sur la perméabilité de la LUV. L'encapsulation active de la doxorubicine, un médicament contre le cancer, a été réalisée malgré la faible perméabilité de ces LUV et la présence du PEG à l’interface. L’inclusion de PEG a modifié considérablement les propriétés de l’interface et a diminué la libération induite par la variation de pH observée avec des LUV nues de PA/Chol. Cette formulation inédite est potentiellement utile pour l’administration intraveineuse de médicaments.
Liposomes are promising and versatile nanocarriers suitable for potential applications in many fields. A decade ago, a new type of liposomes formed from monoalkylated amphiphiles and sterols was born somehow fortuitously in our group. They are referred to as Sterosomes, because they contain a large proportion of sterols, between 50 and 70 mol %. The objectives of the present thesis are to develop novel Sterosome formulations with specific features, and to gain a deeper understanding of the physicochemical rules that dictate their phase behavior. We have specifically examined the role of the molecular features of sterols, of the interfacial charges and of the H-bond capacity in the intermolecular interactions leading to the self-assembly. The phase behavior was characterized by differential scanning calorimetry (DSC), infrared spectroscopy (IR), and nuclear magnetic resonance spectroscopy of deuterium (2H NMR). First, we have established some correlations between the structure of the sterols, the propensity to form fluid bilayers, and the permeability of the resulting large unilamellar vesicles (LUVs). The nature of the sterol modulates the properties of the mixture with palmitic acid (PA). Sterols bearing a bulky tail chain at C17 are less capable to induce fluid bilayers than those with a non-bulky tail chain, like that of cholesterol. A large ordering of the alkyl chain of PA is an effect exhibited by all of the investigated sterols. It is shown that the permeability of the LUVs can be controlled using different sterols. However, these sterols have no significant impact on the pH-sensitivity of Sterosomes. In order to create liposomes that are pH-sensitive and that have a positive surface charge, Sterosomes composed of stearylamine and cholesterol (Chol) were designed and characterized. It is concluded that the protonation/deprotonation state of the amine (in this work) and carboxylic acid (in previous work) groups confers the pH-sensitivity and determines the surface charge of the liposomes. The first completely neutral Sterosomes were crafted based on the creation of strong intermolecular hydrogen bond networks. The sulfoxide group was capable of forming strong hydrogen bonds with cholesterol and water molecules. In an equimolar octadecyl methyl sulfoxide (OMSO)/Chol mixture, a metastable fluid bilayer was obtained at room temperature. This distinct phase behavior allowed extruding the mixtures to form LUVs at room temperature. After 30 h, the life-time of the metastable phase, stable and impermeable Sterosomes still existed in the solid form. A temperature–composition diagram was proposed to summarize the phase behavior of OMSO/Chol mixtures. Finally, a further step was made to prepare “stealth” Sterosomes by incorporating polyethylene glycol (PEG) with a cholesterol anchor (PEG-Chol) at the interface of PA/Chol Sterosomes. Up to 20 mol % PEG-Chol can be introduced without disturbing the bilayer structure. The presence of PEG-Chol had no significant impact on the permeability of the resulting LUVs. Active-loading of an anti-cancer drug, doxorubicin, can be achieved despite the low permeability of these LUVs and the presence of the PEG at the interface. The inclusion of PEG modified considerably the interface properties and decreased significantly the pH-triggered release observed with naked PA/Chol LUVs. This novel formulation is potentially useful for the application of intravenous administration in the drug delivery field.

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35

DiGiovanni, Anthony A. "Quasi-ductile mechanisms in porous liquid phase sintered alumina induced by Hertzian contact /." Diss., 1999. http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqdiss&rft_dat=xri:pqdiss:9935157.

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36

"Studies of Capsaicinoids Contents of Locally Grown and Commercial Chilies Using Reversed-Phase High Performance Liquid Chromatography." East Tennessee State University, 2009. http://etd-submit.etsu.edu/etd/theses/available/etd-0705109-224929/.

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37

Capt, William Michael. "Experimental measurement and finite element modeling of bioheat transfer with phase changes of molten metal in contact with porcine skin." 2003. http://wwwlib.umi.com/cr/utexas/fullcit?p3110740.

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38

Shabani, Roxana. "Three-phase contact line phenomena in droplets on solid and liquid surfaces: electrocapillary, pinning, wetting line velocity effect, and free liquid surface deformation." Doctoral diss., 2013. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/6180.

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In this dissertation, physical phenomena relevant to (i) an interface formed between two fluids and a solid phase (wetting line) and (ii) an interface between three fluids (triple contact line) were investigated. In the former case, the wetting line (WL) phenomena, which encompass the wetting line energy (WLE), the wetting line velocity (WLV), and the contact angle hysteresis, were studied using a micropump based on electrowetting on dielectric (EWOD). In the latter case, the air film lubrication effect and the liquid free surface deformation were taken into account to explain the dual equilibrium states of water droplets on liquid free surfaces. A micropump based on droplet/meniscus pressure gradient generated by EWOD was designed and fabricated. By altering the contact angle between liquid and solid using an electric field a pressure gradient was induced and a small droplet was pumped into the channel. The flow rate in the channel was found to be constant in spite of the changes in the droplet's radius. The WL phenomena were studied to unravel the physical concept behind the micropump constant flow rate. The observation and measurement reveal that the shrinking input droplet changes its shape in two modes in time sequence: (i) its contact angle decreases, while its wetting area remains constant, and (ii) its WL starts to move while its contact angle changes. Contact angles were measured for the advancing and receding WLs at different velocities to capture a full picture of contact angle behavior. The effects of the WLE on the static contact angle and the WLV on the dynamic contact angle in the pump operation were investigated. Also the effect of EWOD voltage on the magnitude and uniformity of the micropump flow rate was studied. Dynamic contact angles were used to accurately calculate the pressure gradient between the droplet and the meniscus, and estimate the flow rate. It was shown that neglecting either of these effects not only results in a considerable gap between the predicted and the measured flow rates but also in an unphysical instability in the flow rate analysis. However, when the WLE and WLV effects were fully taken into account, an excellent agreement between the predicted and the experimental flow rates was obtained. For the study of the TCL between three fluids, aqueous droplets were formed at oil-air interface and two stable configurations of (i) non-coalescent droplet and (ii) cap/bead droplet were observed. General solutions for energy and force analysis were obtained and were shown to be in good agreement with the experimental observations. Further the energy barrier obtained for transition from configuration (i) to (ii) was correlated to the droplet release height and the probability of non-coalescent droplet formation. Droplets formed on the solid surfaces and on the free surface of immiscible liquids have various applications in droplet-based microfluidic devices. This research provides an insight into their formation and manipulation.
Ph.D.
Doctorate
Mechanical and Aerospace Engineering
Engineering and Computer Science
Mechanical Engineering

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39

Yang, Nai-Hsuan, and 楊乃璇. "The Effect on the Interfacial Mass Transfer of a Gas-Liquid Contact Device by Adding a Low Surface Tension Solvent into the Gas or Liquid Phase." Thesis, 2007. http://ndltd.ncl.edu.tw/handle/72918923126438852442.

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碩士
中原大學
化學工程研究所
95
Adding a low surface tension volatile organic solvent into the surface of working solution of lithium chloride in a dehumidification system, the surface tension gradient will be occurred in the gas-liquid interface and formed the interfacial turbulence, which is called the force Marangoni convention. When the system has this phenomenon, it will increase the degree of interfacial turbulence and dominate the mass transfer performance between the gas-liquid interface. This theory will be applied in a gas-liquid contact device to find the effect of interfacial turbulence and dehumidification efficiency by adding a low surface tension solvent into the gas or liquid phase. The operating parameters include inlet humidity, lithium chloride concentration, etc. The experiments will find out the differences of the dehumidification efficiency in different conditions of with adding alcohols in gas or liquid phases and without adding alcohols.

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Cheng, Chun-Ping, and 陳俊彬. "Determination the catechins and caffeine contents of tea drinks by using ODS-solid-phase extraction on-line to high performance liquid chromatography." Thesis, 2008. http://ndltd.ncl.edu.tw/handle/12643924389008394587.

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碩士
高雄師範大學
化學系
97
This research tries to use the Octadecylsilane(ODS) for packing solid phase extraction (SPE) to have the concentration effect and then the SPE connects with the high performance liquid chromatography(HPLC) to detect the trace catechins in the tea drinks. By using the physical absorption nature of ODS to absorb the catechins and caffeine, the on-line SPE first concentrates the analytes. Then the analytes are desorbed by the gradient elution of mobile phase and analysed by HPLC. The experimental results show that it is effective to separate the catechins and the caffeine (GC, C, EGC, Caf, EC, EGCG, GCG, ECG, CG) by using the on-line SPE-HPLC. The linear correlation coefficient is above 0.998. The detection limits are below 5 μg/L, one tenth of the detection limits with the direct HPLC analysis method. The ODS-solid-phase extraction has the enrichment factors of 49.48, 80.57, 92.87, 81.58, 67.82, 64.79, 104.59, 43.05, and 75.55 correspond to GC, C, EGC, Caf, EC, EGCG, GCG, ECG, and CG, respectively. Finally, we try to determinate the catechins and caffeine content of the real tea drinks by using the on-line SPE-HPLC. The result shows that the recoveries of the real tea drinks are between 100% ± 20% ( except GC, C). So the on-line SPE-HPLC has the advantages for reducing the sample loss, reducing pre-process and having automation for detecting the catechins and caffeine content. It is able to achieve the goal of the lowering the detection limits by the SPE concentration effect.

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Vavrouš, Adam. "Rychlé metody analýzy migrantů z materiálů ve styku s potravinami." Doctoral thesis, 2020. http://www.nusl.cz/ntk/nusl-415366.

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(AJ) Food contact materials pose a risk to human health due to a variety of contaminants which they can release into food. These compounds, migrants, include aromatic hydrocarbons, dialkyl phthalates, bisphenols, printing ink photoinitiators, and perfluoroalkyl compounds. The determination of all these substances can be expensive and time-consuming since universally applicable analytical approaches are not available nowadays. This work attempted to develop methods for the simultaneous determination of migrants from all of the mentioned groups in paper-based food contact materials and fatty food. A total of 68 contaminants were studied in paper products using liquid chromatography and gas chromatography coupled with tandem mass spectrometry detection. All analytes were isolated simultaneously using the modified "QuEChERS" method. This method demonstrated acceptable recovery and repeatability for most analytes in the validation study; LOQs ranged from 1.3 to 220 µg/kg. Analysis of 132 real paper products confirmed the occurrence of almost all studied analytes, which were often present in complex mixtures and at concentrations up to 628 mg/kg. A total of 41 potential contaminants were monitored in fatty foods by liquid chromatography with tandem mass detection. Contamination of the mobile phase by...

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Santos, Ângelo Emanuel Neves dos. "Design and simulation of a smart bottle with fill-level sensing based on oxide TFT technology." Master's thesis, 2016. http://hdl.handle.net/10362/19593.

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Packaging is an important element responsible for brand growth and one of the main rea-sons for producers to gain competitive advantages through technological innovation. In this re-gard, the aim of this work is to design a fully autonomous electronic system for a smart bottle packaging, being integrated in a European project named ROLL-OUT. The desired application for the smart bottle is to act as a fill-level sensor system in order to determine the liquid content level that exists inside an opaque bottle, so the consumer can exactly know the remaining quantity of the product inside. An in-house amorphous indium–gallium–zinc oxide thin-film transistor (a-IGZO TFT) model, previously developed, was used for circuit designing purposes. This model was based in an artificial neural network (ANN) equivalent circuit approach. Taking into account that only n-type oxide TFTs were used, plenty of electronic building-blocks have been designed: clock generator, non-overlapping phase generator, a capacitance-to-voltage converter and a comparator. As it was demonstrated by electrical simulations, it has been achieved good functionality for each block, having a final system with a power dissipation of 2.3 mW (VDD=10 V) not considering the clock generator. Four printed circuit boards (PCBs) have been also designed in order to help in the testing phase. Mask layouts were already designed and are currently in fabrication, foreseeing a suc-cessful circuit fabrication, and a major step towards the design and integration of complex trans-ducer systems using oxide TFTs technology.

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Dissertations / Theses on the topic 'Liquid phase content'

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