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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
61

Droplet-Based Approaches to Probe Complex Behavior in Colloidal Fluids with High Composition Resolution

Bleier, Blake J. 01 May 2018 (has links)
In this work, microfluidic and millifluidic droplets are utilized to study and control complex fluid behavior with high composition resolution. Different techniques are used on two length scales to create unique approaches towards the same goal of merging droplet-based experiments with classical colloidal characterization experiments. First, a microfluidic dehydrating droplet device is characterized and a procedure established by concentrating a phase separating organic-inorganic system on chip and using geometric calculations to determine composition. The device is then expanded to a more complex, particle-polymer system to investigate suspension stability and interparticle behavior. A model system containing silica particles and PEO polymer is found to transition from a bridging flocculation mechanism to polymer-coated particle jamming based on the mass ratio of polymer to particle. Lastly, a phase separating particle-polymer system consisting of polystyrene particles and hydroxyethyl cellulose is concentrated on-chip. Interparticle interactions are controlled by varying particle size, polymer size, and polymer type and the effects on phase behavior are examined. Droplet experiments are scaled-up to millifluidic droplets and concentration gradients are used to produce high composition resolution in place of time, used in the dehydrating microfluidic experiments. A novel, millifluidic containment device is created to study aggregation and sedimentation in droplets containing carbon black and OLOA surfactant suspended in dodecane. A slow increase in stabilization behavior is observed as opposed to the previously observed sharp “on-off” effect. The droplet production technique is then improved to achieve more complex composition paths and the device is expanded for a small angle neutron scattering (SANS) application. SANS is performed on flowing droplets with varying concentration to map interparticle interactions and phase behavior of complex particulate systems. Feasibility of device is demonstrated and preliminary model systems of silica particles and polymer, salt, and surfactant are analyzed and characterized.
62

Amorphous phase separation and crystallization in the BaO-TiO2-SiO2 system: experimental approach and thermodynamic study / Séparation de phase amorphe et cristallisation dans le système BaO-TiO2-SiO2: une approche expérimentale et une étude thermodynamique.

Boulay, Emilie 13 February 2015 (has links)
Glass-ceramics are of growing interest due to their enhanced properties compared to the base glasses. More specifically, the control of microstructures is a major challenge as the properties of glass-ceramics are the direct consequences of microstructures. Microstructures can be modified by forming specific crystal phases or by using a prior amorphous phase separation before crystallization. The PhD thesis objectives are to demonstrate that the properties of silicate glasses can be enhanced by controlling their microstructure genesis with composition and thermal process parameters. More specifically, two systems were studied and compared: the BaO-TiO2-SiO2 system and the soda-lime silica Na2O-CaO-SiO2 used industrially. Both systems exhibit a large zone of immiscibility allowing the study of the influence of phase separation on crystallization.<p>The first system BaO-TiO2-SiO2 has gathered interest from the interesting properties of fresnoite (Ba2TiSi2O8): piezo and pyroelectricity, second harmonic generation and blue/white photoluminescence. Many studies on the stoichiometric composition were conducted to understand and improve those promising properties. However, it was recently suggested that the photoluminescence can be improved with composition exhibiting phase separation. This indicates that the photoluminescence intensity can be improved through a microstructural control. The possible role of a prior amorphous phase separation on the subsequent crystallization has been however the topic of vigorous debates over the last decades and has not yet been clarified, especially regarding the role of the interfaces created by the phase separation. In this PhD, the effect of phase separation on fresnoite crystallization was studied. This had to pass through the calculation of the liquid-liquid immiscibility in the phase diagram in order to select suitable compositions to compare in a systematic study. The systematic study concludes to a surface crystallization mechanism for all non- stoichiometric compositions and shows no influence between amorphous droplets and matrix crystallization. This study was also completed with the investigation of the effect of composition (i.e. SiO2-excess), annealing temperature and prior heat treatment, i.e. heating rate, cooling rate or a prior isothermal step before annealing. It is shown that specific microstructures are obtained depending on the process parameters. Finally, selected compositions and heat treatment show how photoluminescence intensity can be improved by a microstructural control. The highest intensity is obtained with a high crystallization fraction and a maximization of the number of interfaces.<p>The results obtained in the study of the BaO-TiO2-SiO2 system are extended to the soda-lime-silica system in order to study the effect of phase separation on crystallization. It is shown that cristobalite forma- tion from the surface cannot be avoided and that the involved composition shift inhibits phase separation. It is consequently difficult to observe an interplay. Those studies lead to a general discussion about the criteria allowing to observe an interplay between phase separation and crystallization in oxide glasses. / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished
63

The Morphology and Equilibration of Levitated Secondary Organic Particles Under Controlled Conditions

Gorkowski, Kyle J. 01 September 2017 (has links)
I advanced the understanding of particle morphology and its implications for the behavior and effects of atmospheric aerosol particles. I have developed new experimental methods for the Aerosol Optical Tweezers (AOT) system and expanded the AOT’s application into studying realistic secondary organic aerosol (SOA) particle phases. The AOT is a highly accurate system developed to study individual particles in real-time for prolonged periods of time. While previous AOT studies have focused on binary or ternary chemical systems, I have investigated complex SOA, and how they interact with other chemical phases, and the surrounding gas-phase. This work has led to new insights into liquid-liquid phase separation and the resulting particle morphology, the surface tension, solubility, and volatility of SOA, and diffusion coefficients of SOA phases. I designed a new aerosol optical tweezers chamber for delivering a uniformly mixed aerosol flow to the trapped droplet’s position. I used this chamber to determine the phase-separation morphology and resulting properties of complex mixed droplets. A series of experiments using simple compounds are presented to establish my ability to use the cavity enhanced Raman spectra to distinguish between homogenous single-phase, and phase-separated core-shell or partially-engulfed morphologies. I have developed a new algorithm for the analysis of whispering gallery modes (WGMs) present in the cavity enhanced Raman spectra retrieved from droplets trapped in the AOT. My algorithm improves the computational scaling when analyzing core-shell droplets (i.e. phase-separated or biphasic droplets) in the AOT, making it computationally practical to analyze spectra collected over many hours at a few Hz. I then demonstrate for the first time the capture and analysis of SOA on a droplet suspended in an AOT. I examined three initial chemical systems of aqueous NaCl, aqueous glycerol, and squalane at ~ 75% relative humidity. For each system I added α-pinene SOA – generated directly in the AOT chamber – to the trapped droplet. The resulting morphology was always observed to be a core of the initial droplet surrounded by a shell of the added SOA. By combining my AOT observations of particle morphology with results from SOA smog chamber experiments, I conclude that the α-pinene SOA shell creates no major diffusion limitations for water, glycerol, and squalane under humid conditions. My AOT experiments highlight the prominence of phase-separated core-shell morphologies for secondary organic aerosols interacting with a range of other chemical phases. The unique analytical capabilities of the aerosol optical tweezers provide a new approach for advancing the understanding of the chemical and physical evolution of complex atmospheric particulate matter, and the important environmental impacts of aerosols on atmospheric chemistry, air quality, human health, and climate change.
64

Hybrid polymer/liquid vesicles as new particles for drug delivery and cell mimics / Vésicules hybrides lipide/polymères comme nouveaux systèmes de vectorisation et modèles de membranes cellulaires

Dao, Thi Phuong Tuyen 16 December 2016 (has links)
Les vésicules hybrides polymère/lipides sont des structures récemment développées dans la littérature. Idéalement, celles-ci peuvent présenter la biocompatibilité et la biofonctionnalité des liposomes, ainsi que la robustesse, la faible perméabilité et la versatilité de fonctionnalisation chimique conférées par les chaînes de copolymères. Cependant, à ce jour, les facteurs régissant la séparation des phases dans ces membranes hybrides ne sont pas bien compris. Dans ce travail, nous avons étudié en détail la formation et la séparation de phases dans les membranes de vésicules géantes (GHUVs) et de taille nanométriques(100nm) (LHUVs) constituées de phospholipides en phase fluide ou gel et de copolymères à base de poly (diméthylsiloxane) et de poly (éthylène glycol). Différentes architectures(greffée, tribloc) et masses molaires ont été utilisées. La séparation de phase a été étudiée sur les vésicules géantes à l’échelle micrométrique et nanométrique respectivement par microscopie confocale et imagerie de fluorescence résolue en temps (FLIM), tandis que pour les LHUVs, différentes techniques comme la diffusion de neutrons, la Cryo-microscopie et la spectroscopie de fluorescence résolue dans le temps ont été combinées. Nous avons pu montrer que la fraction lipide/polymère, l'état physique du lipide et la tension de la ligne aux interfaces lipide/polymère modulable par la masse molaire et l'architecture du copolymère sont les facteurs importants régissant la formation et la structuration des vésicules hybrides. Enfin, nous avons montré que les propriétés élastiques de la membrane peuvent être modulées via la composition polymère lipide. / Hybrid copolymer/lipid vesicle are recently developed self-assembled structures that could present biocompatibility and biofunctionality of liposomes, as well as robustness, low permeability and functionality variability conferred by the copolymer chains. However, to date, physical and molecular parameters governing copolymer/lipid phase separation in these hybrid membranes are not well understood. In this work, we studied in detail the formation and phase separation in the membranes of both Giant Unilamellar Hybrid Vesicles(GHUVs) and Large Unilamellar Hybrid Vesicles (LHUVs) obtained from the mixture of phospholipids in the fluid (liquid disordered) or gel state (solid ordered) with various copolymers based on poly(dimethylsiloxane) (PDMS) and poly(ethylene glycol) (PEO) with different architectures (grafted, triblock) and molar masses. For GHUVs, phase separation at the micron scale and nanoscale was evaluated through confocal microscopy, and Fluorescence lifetime imaging microscopy technique (FLIM) respectively, where as acombination of Small angle neutron scattering (SANS), Cryo-transmission electron microscopy (Cryo-TEM) and Time-resolved Förster resonance energy transfer (TR-FRET) techniques was used for LHUVs. We demonstrate that the lipid/polymer fraction, lipid physical state, and the line tension at lipid polymer/lipid boundaries which can be finely modulated by the molar mass and architecture of the copolymer are important factors that govern the formation and structuration of hybrid vesicles. We also evidence that elasticity ofthe hybrid membrane can be modulated via the lipid polymer composition, through the use of micropipettes techniques.
65

Micro-tomographie d’un borosilicate de baryum démixé : du mûrissement à la fragmentation / Micro-tomography of the coarsening of a phase-separated barium borosilicate glass

Bouttes, David 08 October 2014 (has links)
On utilise un verre de borosilicate de baryum comme système modèle pour étudier la séparation de phase dans les liquides. Plus spécifiquement, on considère le mûrissement dans le régime hydrodynamique visqueux, où la taille caractéristique des domaines évolue linéairement en temps : ∼ (γ/η)t, avec η la viscosité et γ la tension de surface. Le système est initialement bicontinu, ce qui est nécessaire pour ce régime de croissance.La morphologie des domaines est obtenue grâce à des expériences de microtomographie à rayons X in situ sur la ligne ID19 du synchrotron ESRF (European Synchrotron Radiation Facility). Des outils d’analyse d’image 3D spécialement développés pour l’étude permettent d’extraire des grandeurs d’intérêt. On a ainsi mesuré les volumes et les surfaces des domaines, les distributions de tailles de cordes, la caractéristique d’Euler et les courbures moyennes et gaussiennes locales. Ces grandeurs sont étudiées à travers le prisme de la loi d’échelle dynamique, qui prédit une croissance auto-similaire.Le système se sépare en deux phases ayant un contraste de viscosité très marqué (plusieurs ordres de grandeur). Le paramètre de contrôle essentiel est la fraction volumique de la phase la moins visqueuse. Lorsque cette phase moins visqueuse est minoritaire, elle se fragmente progressivement, jusqu’à arrêter la croissance. Cette fragmentation présente un caractère auto-similaire en raison de son couplage avec le mûrissement, ce qui génère des distributions de tailles de domaines larges, qu’on prédit sous la forme d’une loi puissance. Plus généralement, le mûrissement de la structure suit la loi d’échelle dynamique tant que la fragmentation reste marginale.On utilise un verre de borosilicate de baryum comme système modèle pour étudier la séparation de phase dans les liquides. Plus spécifiquement, on considère le mûrissement dans le régime hydrodynamique visqueux, où la taille caractéristique des domaines évolue linéairement en temps : ∼ (γ/η)t, avec η la viscosité et γ la tension de surface. Le système est initialement bicontinu, ce qui est nécessaire pour ce régime de croissance. La morphologie des domaines est obtenue grâce à des expériences de microtomographie à rayons X in situ sur la ligne ID19 du synchrotron ESRF (European Synchrotron Radiation Facility). Des outils d’analyse d’image 3D spécialement développés pour l’étude permettent d’extraire des grandeurs d’intérêt. On a ainsi mesuré les volumes et les surfaces des domaines, les distributions de tailles de cordes, la caractéristique d’Euler et les courbures moyennes et gaussiennes locales. Ces grandeurs sont étudiées à travers le prisme de la loi d’échelle dynamique, qui prédit une croissance auto-similaire.Le système se sépare en deux phases ayant un contraste de viscosité très marqué (plusieurs ordres de grandeur). Le paramètre de contrôle essentiel est la fraction volumique de la phase la moins visqueuse. Lorsque cette phase moins visqueuse est minoritaire, elle se fragmente progressivement, jusqu’à arrêter la croissance. Cette fragmentation présente un caractère auto-similaire en raison de son couplage avec le mûrissement, ce qui génère des distributions de tailles de domaines larges, qu’on prédit sous la forme d’une loi puissance. Plus généralement, le mûrissement de la structure suit la loi d’échelle dynamique tant que la fragmentation reste marginale. / We use a barium borosilicate glass as a model system to study phase separation in liquids. We consider here the coarsening process in the viscous hydrodynamical regime, where the characteristic length scale grows linearly with time : ∼ (γ/η)t, with η the viscosity and γ the interfacial tension. The system is initially bicontinuous, which is mandatory for this growth regime.X-ray microtomography experiments are performed in situ at the ID19 beamline of the European Synchrotron Radiation Facility (ESRF) in order to obtain the morphology of the domains. We developed dedicated image processing routines for the analysis of the 3D images. We computed the volumes and surface areas of the domains, chord-length distributions, the Euler characteristic as well as local mean and Gaussian curvatures. Dynamic scaling hypothesis predicts a self-similar growth, which served as a basis for the discussion of these measurements. The glass separates in two phases with a very high viscosity contrast (several orders of magnitude). The main control parameter in our experiments is then the volume fraction of the less viscous phase. When this low-viscosity phase is the minority one, it undergoes a gradual fragmentation that eventually stops the coarsening. This fragmentation process bears self-similar features, which result in a wide distribution of domains sizes. We indeed predict a power-law distribution. More generally, we observed that the coarsening process follows the dynamic scaling hypothesis as long as fragmentation remains insignificant.
66

Étude des mécanismes interdépendants d’élaboration d’une membrane polymère sans solvant organique par une méthode originale de séparation de phase (TIPS-LCST), à partir d’un polymère biosourcé : l’hydroxypropylcellulose / Study of interdependent mechanisms of a new polymeric membrane elaboration without organic solvent by phase separation process (TIPS-LCST) from hydroxypropylcellulose

Hanafia, Amira 15 May 2014 (has links)
La séparation de phase au sein d'un système polymère/solvant est la méthode la plus couramment utilisée pour élaborer une membrane polymère poreuse. Les principales méthodes d'inversion de phase nécessitent l'usage de solvants organiques qui génèrent des problèmes environnementaux (traitement des bains de coagulation) et sanitaires (sécurité des installations industrielles). Cette étude porte sur le développement d'une nouvelle membrane polymère poreuse à partir d'un polymère biosourcé et hydrosoluble, l'hydroxypropylcellulose (HPC), permettant de s'affranchir de l'usage de solvants organiques. La propriété de thermosensibilité de l'HPC, caractérisé par une température critique basse en solution dans l'eau (LCST) de l'ordre de 40 °C, a par ailleurs permis de développer un procédé original d'élaboration de membranes HPC par séparation de phase induite par augmentation de la température au-delà de la LCST. Ce travail vise un triple objectif : (i) déterminer la formulation idoine permettant de former une membrane poreuse insoluble dans l'eau à partir d'HPC, (ii) appréhender et comprendre les mécanismes de structuration de la matrice polymère à travers l'interaction des mécanismes interdépendants de séparation de phase par décomposition spinodale, de réticulation chimique et d'extraction du solvant par évaporation et enfin (iii) caractériser l'aptitude des membranes à la filtration d'une solution aqueuse sous pression. Le suivi en ligne de la dynamique de séparation de phase d'un système HPC/eau/réticulant ± porogène (PEG200) par microscopie optique en contraste de phase, de la réticulation par rhéologie et de l'évaporation de l'eau par thermogravimétrie a ainsi permis de mettre en évidence l'impact de la formulation et des paramètres de conduite du procédé d'inversion de phase sur les propriétés morphologiques et d'usage des membranes. La porosité membranaire et le caractère symétrique de la morphologie ont notamment été corrélés à la vitesse des phénomènes concomitants de réticulation et d'évaporation de l'eau, donc à la vitesse de montée en température du procédé TIPS-LCST. La caractérisation de la perméabilité à l'eau des membranes HPC a confirmé l'efficacité de la réticulation et la résistance structurale des membranes au cours de plusieurs filtrations continues à l'eau. En raison du caractère thermosensible de l'HPC, ces membranes ont montré une aptitude remarquable à la filtration de solutions aqueuses à température élevée (60 °C). Par ailleurs, il a été montré que la perméabilité des membranes pouvait être en partie contrôlée par la température et la pression transmembranaire appliquée. / Phase separation of polyer/solvent system is the most widespread industrial process to manufacture membranes. Large solvent quantity is usually used whatever the process, hence leading to environmental (coagulation and washing baths treatment) and health (industrial and plant safety) problems.This study focuses on the development of new porous membranes made from hydroxypropylcellulose (HPC), a water soluble polymer, avoiding the use of any organic solvent. Moreover, the thermo-sensitive character of this polymer, characterized by a Lower Critical Solution Temperature (LCST) in water of about 40 °C, enabled to design an original thermally induced phase separation process by temperature increase above the LCST. This study aims (i) to find the ideal polymer solution composition to produce insoluble HPC membrane, (ii) to approach and understand the link between phase separation mechanism by spinodal decomposition, crosslinkig reaction and water extraction by evaporation, (iii) characterize pure water permeability under pressure. On-line monitoring of phase sepration dynamics by phase contrast optical microscopy, crosslinking reaction by rheology and water evaporation by thermogravimetric analysis of the system HPC/water/cross-linking agent ± porogen (PEG200) allowed an understanding of simultaneous and related mechanisms occurring during elaboration (phase separation / cross-linking / water evaporation) and a correlation with HPC membrane morphologies and characteristics in relation with phase separation process parametres. Pure water permeability characterization demonstrated the efficiency of cross-linking and structural strength during several filtration cycles. Furthermore, it has been shown that water permeability of HPC membranes could be controlled in part by the temperature and the applied pressure.
67

Mechanistic Understanding of Dissolution of Amorphous Solid Dispersions

Sugandha Saboo (8766711) 27 April 2020 (has links)
<p>As amorphous solid dispersions (ASDs) are more widely employed as a formulation strategy for poorly water-soluble drugs, there is a pressing need to increase the drug loading in these formulations. The drug loading is typically kept low to obtain the desired drug release rate, but often results in large or even multiple dosage units, which is undesirable from a patient compliance perspective. We have identified the cause of this conundrum to be the drug loading dependent dissolution mechanism of ASDs. At low drug loadings, the dissolution rate of ASDs is polymer-controlled, while at high drug loadings, the dissolution rate is drug-controlled and considerably slower. This phenomenon is most pronounced for ASDs with hydrophilic polymers, such as poly (vinylpyrrolidone-co-vinyl acetate) (PVPVA) and the change in dissolution mechanism from being polymer-controlled to drug-controlled has been attributed to water-induced amorphous-amorphous phase separation (AAPS) in higher drug loading ASD matrices of hydrophilic polymers. The drug loading limit for this switch has been found to be dependent on drug properties as well as drug-polymer interactions. Interestingly, drug-polymer hydrogen bonding interaction has been found to be detrimental and decrease the drug loading limit for polymer-controlled release while drug log P did not have any impact on this limit. Variable dissolution temperature studies indicated a detrimental impact on the polymer-controlled drug loading limit when the drug-rich phase (of phase separated ASD matrix) exists in a glassy state. ASDs with relatively hydrophobic polymers, such as hypromellose acetate succinate (HPMCAS), have been found to be polymer-controlled up to higher drug loadings. The mechanistic understanding obtained in this body of work can thus be adopted to develop strategies enabling ASD formulations with optimized performance and improved drug loading.</p>
68

Study of Thermally Responsive Ionic Liquids for Novel Water Desalination and Energy Conversion Applications

Zhong, Yujiang 04 1900 (has links)
The rapidly expanding of the global population in the 21st-century forces people facing two serious problems: water scarcity and energy shortage. Enormous continuous studies focus on providing enough fresh water and energy in a sustainable way. This thesis aims at exploring novel membrane processes based on thermally responsive ionic liquids with the upper critical solution temperature (UCST ILs) for water desalination and energy conversion from low-grade heat energy to electricity. A UCST IL protonated betaine bis(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]) was first experimentally studied as a novel draw solute in a thermal forward osmosis (FO). A 3.2 M [Hbet][Tf2N] solution can be obtained via spontaneous phase separation from an IL and water mixture at room temperature. By heating and maintaining the temperature above 56°C, this solution can draw water from high-salinity solution up to 3.0 M, 5 times salty as the sea water. The IL draw solution can be easily regenerated by phase separation. Conducting the FO process at higher temperatures can also increase the water flux. According to the different choices of the freshwater polishing step, the electric energy consumption in this novel process was estimated as 26.3% to 64.2% of conventional one-step sea water reverse osmosis. Two UCST ILs with better performance, [Hbet][Tf2N] and choline bis(trifluoromethylsulfonyl)imide ([Choline][Tf2N]), were selected as the agents in a novel closed-loop thermally responsive IL osmotic heat engine (TRIL-OHE) to convert low-grade thermal energy to electricity. The specific energies of the [Hbet][Tf2N] system and the [Choline][Tf2N] system are 2500 kJ/t and 3700 kJ/t, which are 2.7 and 4.0 times of the seawater and river water system, respectively. The maximum power density measured from a commercial FO membrane is 1.5 W/m2 for the [Hbet][Tf2N] system and 2.3 W/m2 for the [Choline][Tf2N] system, leaving a big room to improve if highly permeable membranes are used. Another notable advantage of the TRIL-OHE is the heat released from the cooling stage can be largely recovered. A rigorous energy balance showed with a 70% heat recovery, the energy efficiency could be increased from around 20% to 70% of the Carnot efficiency in both UCST ILs systems.
69

Effects of fat particles on the stability of complex food systems / 食品混合系の安定性に与える脂肪球の影響

Hanazawa, Tomohito 25 March 2019 (has links)
京都大学 / 0048 / 新制・論文博士 / 博士(農学) / 乙第13247号 / 論農博第2872号 / 新制||農||1070(附属図書館) / 学位論文||H31||N5171(農学部図書室) / (主査)教授 松村 康生, 教授 丸山 伸之, 教授 谷 史人 / 学位規則第4条第2項該当 / Doctor of Agricultural Science / Kyoto University / DFAM
70

Preparation of Low-Valence Metal Oxide Monoliths with Three-Dimensionally Interconnected Macropores / 三次元マクロ孔をもつ低原子価金属酸化物モノリスの作製

Lu, Xuanming 23 March 2020 (has links)
京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第22277号 / 理博第4591号 / 新制||理||1659(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 竹腰 清乃理, 教授 吉村 一良 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

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