This thesis presents the derivation of the theory leading to the determination of the governing equations of chemically reacting flows under local thermodynamic equilibrium, which rigorously takes into account effects of elemental (de)mixing. As a result, new transport coefficients appear in the equations allowing a quantitative predictions and helping to gain deeper insight into the physics of chemically reacting flows at and near local equilibrium. These transport coefficients have been computed for both air and carbon dioxide mixtures allowing the application of this theory to both Earth and Mars entry problems in the framework of the methodology for the determination of the catalytic activity of Thermal Protections Systems (TPS) materials. Firstly, we analyze the influence of elemental fraction variations on the computation of thermochemical equilibrium flows for both air and carbon dioxide mixtures. To this end, the equilibrium computations are compared with several chemical regimes to better analyze the influence of chemistry on wall heat flux and to observe the elemental fractions behavior along a stagnation line. The results of several computations are presented to highlight the effects of elemental demixing on the stagnation point heat flux and chemical equilibrium composition for air and carbon dioxide mixtures. Moreover, in the chemical nonequilibrium computations, the characteristic time of chemistry is artificially decreased and in the limit the chemical equilibrium regime, with variable elemental fractions, is achieved. Then, we apply the closed form of the equations governing the behavior of local thermodynamic equilibrium flows, accounting for the variation in local elemental concentrations in a rigorous manner, to simulate heat and mass transfer in CO2/N2 mixtures. This allows for the analysis of the boundary layer near the stagnation point of a hypersonic vehicle entering the true Martian atmosphere. The results obtained using this formulation are compared with those obtained using a previous form of the equations where the diffusive fluxes of elements are computed as a linear combination of the species diffusive fluxes. This not only validates the new formulation but also highlights its advantages with respect to the previous one : by using and analyzing the full set of equilibrium transport coefficients we arrive at a deep understanding of the mass and heat transfer for a CO2/N2 mixture. Secondly, we present and analyze detailed numerical simulations of high-pressure inductively coupled air plasma flows both in the torch and in the test chamber using two different mathematical formulations: an extended chemical non-equilibrium formalism including finite rate chemistry and a form of the equations valid in the limit of local thermodynamic equilibrium and accounting for the demixing of chemical elements. Simulations at various operating pressures indicate that significant demixing of oxygen and nitrogen occurs, regardless of the degree of nonequilibrium in the plasma. As the operating pressure is increased, chemistry becomes increasingly fast and the nonequilibrium results correctly approach the results obtained assuming local thermodynamic equilibrium, supporting the validity of the proposed local equilibrium formulation. A similar analysis is conducted for CO2 plasma flows, showing the importance of elemental diffusion on the plasma behavior in the VKI plasmatron torch. Thirdly, the extension of numerical tools developed at the von Karman Institute, required within the methodology for the determination of catalycity properties for thermal protection system materials, has been completed for CO2 flows. Non equilibrium stagnation line computations have been performed for several outer edge conditions in order to analyze the influence of the chemical models for bulk reactions. Moreover, wall surface reactions have been examined, and the importance of several recombination processes has been discussed. This analysis has revealed the limits of the model currently used, leading to the proposal of an alternative approach for the description of the flow-surface interaction. Finally the effects of outer edge elemental fractions on the heat flux map is analyzed, showing the need to add them to the list of parameters of the methodology currently used to determine catalycity properties of thermal protection materials.

The effects of polymer concentration and solvents on cocrystal morphology of low solubility drugs were investigated, both of which had an impact. The melting temperatures also decreased with increasing polymer concentration. Placing the binding agent, benzene, at different interfaces induced morphological changes, such as formation of porous cocrystals. Previously liquid-liquid phase separation (LLPS) has been reported as a hindrance in the crystallisation process impeding further development. A phase diagram was constructed, and different phases were categorised into 4 types. After separation of the highly concentrated amorphous Oil Phase II, it was prone to gradual crystallisation. Crystallisation took place over 30-60 minutes; this allowed the in-situ monitoring. A novel cocrystallisation technique was developed; from (LLPS). Cocrystals of indomethacin with saccharin and nicotinamide were obtained by mixing Oil Phase II with the coformers. In-situ monitoring by spectroscopic had gradual changes in spectra; characteristic peaks increased in height and area with the formation of crystals until the reaction was complete. With crystal formation, the XRD spectra gradually had a sharper baseline due to a decrease in the amorphous indomethacin. The photoluminescence (PL) spectra displayed several peaks coupling into one large hump together with increasing intensity as the sample crystallised. There was a shift in the peak absorbance of the pure drug crystals obtained from LLPS and the indomethacin:saccharin cocrystal obtained from LLPS. Amorphous stabilisation was achieved by mixing polymer (PVP) with Oil Phase II. There were no changes to the XRD diffractogram as the sample did not undergo crystallisation.

Hollow fiber membranes offer the opportunity to dramatically reduce the energy required to perform gas separations in the chemical industry. The membranes are fabricated from highly non-Newtonian precursor materials, including concentrated polymer solutions that sometimes also contain dispersed particles. These materials are susceptible to shear-induced microstructural changes during processing, which can affect the characteristics of the resulting membrane. This thesis explores several shear-related effects using materials and flow conditions that are relevant for fiber spinning. The findings are discussed as they relate to membrane processing, and also from the standpoint of enhancing our fundamental understanding of the underlying phenomena. First, the effect of shear on polymeric dope solutions was investigated. Shear-induced demixing—a phenomenon not previously studied in membrane materials—was found to occur in membrane dopes. Phase separation experiments also showed that shear-induced demixing promotes macrovoid formation. The demixing process was found to depend not only on the instantaneous shear conditions, but also on the shear history of the solution. This suggests that low-shear flow processes that occur in the upstream tubing and channels used for fiber spinning can affect macrovoid formation. The effect of viscoelastic media on dispersed particles was also explored. Shear-small-angle light scattering results showed that particles suspended in membrane dope solutions formed aggregated, vorticity-oriented structures when shear rates in the shear-thinning regime of the polymer solution were applied. Shear rates well below the shear-thinning regime did not produce any structure. In fact, the application of a Newtonian shear rate to a sample already containing the vorticity structure caused the sample to return to isotropy. Measurements using a highly elastic, constant-viscosity Boger fluid showed that strong normal forces alone are not sufficient to form the vorticity structures, but that shear thinning is also required. Lastly, a study was conducted examining cross-stream migration of particles dispersed in viscoelastic media. Fluids exhibiting varying degrees of shear thinning and normal forces were found to have different effects on the particle distribution along the shear gradient axis in Poiseuille flow. Shear thinning was found to promote migration toward the channel center, while normal stresses tended to cause migration toward the channel walls. In addition to hollow fiber spinning, many other industrially relevant applications involve polymer solutions and suspensions of particles in viscoelastic media. Often, the properties and performance of the material depend strongly on the internal microstructure. The results from the research described in this thesis can be used to guide the design of materials and processing conditions, so that the desired microstructural characteristics can be achieved.

Cette thèse décrit comment la morphologie et le polymorphisme de membranes en fluorure de poly(vinylidène) (PVDF) préparées par séparation de phase induite par la vapeur d'eau (VIPS) et par un non-solvant liquide peuvent être ajustés par la température à laquelle le PVDF est dissous (Tdis) pour former la solution de coulée. Les résultats montrent que Tdis présente une transition, notée comme la température de dissolution critique (Tcri), à partir de laquelle la morphologie et le polymorphisme des membranes changent radicalement. Ce phénomène observé pour les trois solvants, N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), and N,M-dimethylformamide (DMF), et les non-solvants (eau et une série d'alcools) utilisés dans cette étude peut être considéré comme général. La cristallisation a lieu avant la démixtion L-L quelle que soit Tdis. Pour une Tdis supérieure à Tcri, les membranes se présentent sous forme de nodules (cristallite forme beta) dont la taille décroît lorsque Tdis diminue. Ce domaine a été dénommé "à grossissement libre" car les chaînes de polymère peuvent cristalliser librement pendant la séparation de phase. Pour une Tdis inférieure à Tcri, des membranes avec une structure bi-continue (cristallite forme alpha) sont obtenues. Ce domaine a été appelé "à grossissement empêché" dans la mesure où la séparation de phase s'accompagne d'une gélification. Nous avons démontré que la morphologie et le polymorphisme cristallin des membranes de PVDF peuvent ainsi être contrôlés par la Tdis et la vitesse d'échange avec le non-solvant. Ces résultats sont interprétés en termes d'auto germination et de compétition entre gélification, cristallisation et démixtion L-L. / This dissertation shows how the morphology and polymorphism of poly(vinylidene fluoride) (PVDF) membranes prepared by using vapor-induced phase separation (VIPS) and liquid-induced phase separation (LIPS) were tuned by varying the dissolution temperature at which PVDF was dissolved (Tdis) to form the casting solution. We observed a transition temperature denoted by critical dissolution temperature, Tcri, across which the morphology and polymorphism of membranes (obtained by VIPS) drastically changed. The phenomenon was considered as general, as a Tcri was observed for all the three solvents N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF) and the non-solvents, water and a series of alcohols, used in the present study. No matter which Tdis we used, polymer crystallization occurred prior to the L-L demixing. With Tdis above Tcri, the prepared membranes were composed of nodules (mainly in beta crystalline form) and the size of polymer domains decreased as the Tdis decreased. Because the polymer chains could freely coarsen to a large domain during the phase separation, we called the system free coarsening. With Tdis below Tcri, membranes with lacy (bi-continuous) structure (mainly in alpha crystalline form) were obtained. Because the polymer solution gelled during the phase separation, we called the system hindered coarsening. It was proven that PVDF membrane morphology and crystalline polymorphs can be monitored by Tdis and the solvent-nonsolvent exchange rate. These results were discussed in terms of self-seeding effect and competition between the gelation, crystallisation and L-L demixing.

No description available.

In this thesis, we consider two models from physics, which are characterized by the interplay of thermodynamical and fluid mechanical phenomena: demixing (spinodal decomposition) and Rayleigh--Bénard convection. In both models, we investigate the dependencies of certain intrinsic quantities on the system parameters. The first model describes a thermodynamically driven demixing process of a binary viscous fluid. During the evolution, the two components of the mixture separate into two domains of the different equilibrium volume fractions. One observes a clear tendency: Larger domains grow at the expense of smaller ones, and thus, the average domain sizes increases --- a phenomenon called coarsening. It turns out that two mechanisms are relevant for the coarsening process. At an early stage of the evolution, material transport is essentially mediated by diffusion; at a later stage, when the typical domain size exceeds a certain value, due to the viscosity of the mixture, a fluid flow sets in and becomes the relevant transport mechanism. In both regimes, the growth rates of the typical domain size obey certain power laws. In this thesis, we rigorously establish one-sided bounds on these growth rates via a priori estimates. The second model, Rayleigh--Bénard convection, describes the behavior of a fluid between two rigid horizontal plates that is heated from below and cooled from above. There are two competing heat transfer mechanisms in the system: On the one hand, thermodynamics favors a state in which temperature variations are locally minimized. Thus, in our model, the thermodynamical equilibrium state is realized by a temperature with a linearly decreasing profile, corresponding to pure conduction. On the other hand, due to differences in the densities of hot and cold fluid parcels, buoyancy forces act on the fluid. This results in an upward motion of hot parcels and a downward motion of cold parcels. We study the dependence of the average upward heat flux, measured in the so-called Nusselt number, on the temperature forcing encoded by the container height. It turns out that the efficiency of the heat transport is independent of the height of the container, and thus, the Nusselt number is a constant function of height. Using a priori estimates, we prove an upper bound on the Nusselt number that displays this dependency --- up to logarithmic errors. Further investigations on the flow pattern in Rayleigh--Bénard convection show a clear separation of length scales: Along the horizontal top and bottom plates one observes thin boundary layers in which heat is essentially conducted, whereas the large bulk is characterized by a convective heat flow. We give first rigorous results in favor of linear temperature profiles in the boundary layers, which indicate that heat is indeed essentially conducted close to the boundaries.

This thesis presents the derivation of the theory leading to the determination of the governing equations of chemically reacting flows under local thermodynamic equilibrium, which rigorously takes into account effects of elemental (de)mixing. As a result, new transport coefficients appear in the equations allowing a quantitative predictions and helping to gain deeper insight into the physics of chemically reacting flows at and near local equilibrium. These transport coefficients have been computed for both air and carbon dioxide mixtures allowing the application of this theory to both Earth and Mars entry problems in the framework of the methodology for the determination of the catalytic activity of Thermal Protections Systems (TPS) materials.<p>Firstly, we analyze the influence of elemental fraction variations on the computation of thermochemical equilibrium flows for both air and carbon dioxide mixtures. To this end, the equilibrium computations are compared with several chemical regimes to better analyze the influence of chemistry on wall heat flux and to observe the elemental fractions behavior along a stagnation line. The results of several computations are presented to highlight the effects of elemental demixing on the stagnation point heat flux and chemical equilibrium composition for air and carbon dioxide mixtures. Moreover, in the chemical nonequilibrium computations, the characteristic time of chemistry is artificially decreased and in the limit the chemical equilibrium regime, with variable elemental fractions, is achieved. Then, we apply the closed form of the equations governing the behavior of local thermodynamic equilibrium flows, accounting for the variation in local elemental concentrations in a rigorous manner, to simulate heat and mass transfer in CO2/N2 mixtures. This allows for the analysis of the boundary layer near the stagnation point of a hypersonic vehicle entering the true Martian atmosphere. The results obtained using this formulation are compared with those obtained using a previous form of the equations where the diffusive fluxes of elements are computed as a linear combination of the species diffusive fluxes. This not only validates the new formulation but also highlights its advantages with respect to the previous one :by using and analyzing the full set of equilibrium transport coefficients we arrive at a deep understanding of the mass and heat transfer for a CO2/N2 mixture.<p>Secondly, we present and analyze detailed numerical simulations of high-pressure inductively coupled air plasma flows both in the torch and in the test chamber using two different mathematical formulations: an extended chemical non-equilibrium formalism including finite rate chemistry and a form of the equations valid in the limit of local thermodynamic equilibrium and accounting for the demixing of chemical elements. Simulations at various operating pressures indicate that significant demixing of oxygen and nitrogen occurs, regardless of the degree of nonequilibrium in the plasma. As the operating pressure is increased, chemistry becomes increasingly fast and the nonequilibrium results correctly approach the results obtained assuming local thermodynamic equilibrium, supporting the validity of the proposed local equilibrium formulation. A similar analysis is conducted for CO2 plasma flows, showing the importance of elemental diffusion on the plasma behavior in the VKI plasmatron torch.<p>Thirdly, the extension of numerical tools developed at the von Karman Institute, required within the methodology for the determination of catalycity properties for thermal protection system materials, has been completed for CO2 flows. Non equilibrium stagnation line computations have been performed for several outer edge conditions in order to analyze the influence of the chemical models for bulk reactions. Moreover, wall surface reactions have been examined, and the importance of several recombination processes has been discussed. This analysis has revealed the limits of the model currently used, leading to the proposal of an alternative approach for the description of the flow-surface interaction. Finally the effects of outer edge elemental fractions on the heat flux map is analyzed, showing the need to add them to the list of parameters of the methodology currently used to determine catalycity properties of thermal protection materials. / Doctorat en sciences appliquées / info:eu-repo/semantics/nonPublished

L’objectif de cette thèse est l’étude thermodynamique des systèmes {amine – eau} et {CO2 – amine – eau}. Les amines étudiées sont des amines démixantes qui ont la particularité de présenter une séparation de phase liquide-liquide en solution aqueuse en fonction de la température et du taux de charge en CO2. Ces composés sont considérés comme de nouveaux solvants potentiels pour le captage du CO2. Les séparations de phase liquide- liquide des systèmes {amine – eau} ont été mises en évidence par calorimétrie et par une technique visuelle en utilisant un microcalorimètre (microDSCIII, Setaram) et une cellule d’équilibre de phase (SPM20, Thar Technologies). Pour permettre la représentation thermodynamique des systèmes {amine – eau}, les volumes molaires d’excès, les enthalpies molaires d’excès et les capacités calorifiques spécifiques ont été mesurés. Les enthalpies de mélange ont été déterminées avec une technique calorimétrique à écoulement. Le calorimètre employé est un BT2.15 de chez Setaram équipé avec une cellule de mélange développée au laboratoire. Les volumes molaires d’excès on été déterminés à partir des mesures des masses volumiques obtenues avec un densimètre à tube vibrant. Les capacités calorifiques spécifiques ont été déterminées avec le microcalorimètre microDSCIII. Les enthalpies d’absorption du CO2 dans les solutions aqueuses et les limites de solubilité ont été étudiées pour les amines présentant un intérêt pour le captage du CO2 avec une technique calorimétrique à écoulement utilisant un C80 de chez Setaram. La dernière partie de ce travail concerne le développement de modèle thermodynamique pour corréler les données mesurées. Les énergies de Gibbs des systèmes {amine – eau} sont calculées en utilisant soit le modèle étendu UNIQUAC soit le modèle NRTL. Cependant, deux sets de paramètres ont été obtenus pour décrire d’une part les équilibres liquide-liquide et d’autre part, les enthalpies molaires d’excès et les capacités calorifique spécifiques. Pour les systèmes {CO2 – amine – eau}, un modèle gamma-phi a été utilisé. Les paramètres d’interaction ont été ajustés à partir de données d’équilibre liquide vapeur et permettent de prédire les enthalpies de solutions, les limites de solubilités et la spéciation du système en fonction du taux de charge. / The aim of this Ph.D. thesis is the thermodynamic study of {amine – water} and {CO2 – amine – water} systems. The amines are demixing amines, which have the singularity to exhibit a liquid-liquid phase separation in aqueous solutions as a function of temperature, composition and CO2 loading charge. These compounds can be considerate as new absorbents for CO2 capture. The liquid-liquid phase separations for {amine – water} systems were detected by calorimetry and visual techniques using a microcalorimeter (microDSCIII, Setaram) and an equilibrium cell (SPM20, Thar Technologies). In order to help in the thermodynamic representation of {amine – water} systems, excess molar volumes, excess molar enthalpies and specific heat capacities were measured. The enthalpies of mixing were determined using a flow calorimetric technique. The calorimeter was a BT2.15 from Setaram equipped with a homemade mixing cell. Excess molar volumes were determined from densities measurement performed with a vibrating tube densitometer. The enthalpies of solution of CO2 with absorbent and limits of gas solubility were studied for selected systems of interest for CO2 capture using a flow calorimetric technique. Last part of this work concerns the development of thermodynamic models to correlate the experimental data. The Gibbs energies of studied {amine – water} systems were calculating using both extended UNIQUAC and NRTL models. However, two sets of parameters were necessary to describe on one side the liquid-liquid equilibrium of mixtures and on the other side excess molar enthalpies and specific heat capacities. For {CO2 – amine – water} systems, a gamma-phi model was used. Interactions parameters were adjusted with vapor-liquid data and are able to predict the enthalpy of solution of CO2 in aqueous amine solutions, solubility limits of gas and speciation of the system as a function of loading charge.

No description available.

Le procédé de séparation de phase est importante car elle détermine la structure des matériaux finaux. Il existe de nombreux systèmes qui ont plus d'une phase tels que des mousses et des gels. Les mousses sont des dispersions aqueuses de bulles de gaz dans une phase aqueuse et gels apparaissent lorsque certains microscopique unité de base commence à se rassembler formant un grand réseau solide qui enjambe l'espace macroscopique. Ils ont de nombreuses applications dans l'industrie et la vie quotidienne. Dans cette thèse, tout d'abord, je me concentre sur l'étude de différents types de séparation de phase. Deuxièmement, je étudié les effets spécifiques d'ions sur l'agrégation des particules colloïdales et tensioactif, le but est de faire des mousses stables. Dans la lacune de miscibilité il existe deux types de séparation de phase: la croissance nucléation et la décomposition spinodale, ils ont différents mécanismes et de la cinétique de croissance. Par conséquent, mon premier projet est d'étudier le processus d'évolution d'eux et de leurs effets sur la structure finale du matériau. Les gels peuvent être préparés par l'ajout de sel à la dispersion de particules colloïdales, ils ont un grand nombre d'applications telles que dans les aliments et la science des matériaux. Dans cette thèse, nous utilisons différents types de sels de comparer les propriétés de gel à partir de deux aspects macroscopiques et microscopiques. Obtenir des mousses stables est significatif dans la vue de leur beaucoup d'applications, mais les moyens de les faire sont pour la plupart compliqué. Dans cette thèse, nous pouvons obtenir des mousses stables par l'intermédiaire de deux façons. On est tout simplement en ajoutant des sels de solutions de tensioactifs, à travers lequel nous pouvons faire la mousse ultra-stable. Une autre façon est d'utiliser la phase de gel, nous avons étudié en tant que phase continue dans les mousses à arrêter le vieillissement de la mousse. / Phase separation process is important as it determines the structure of the final materials. There are many systems that have more than one phase such as foams and gels. Aqueous foams are dispersions of gas bubbles in a water phase and gels appear when some basic microscopic unit starts to aggregate forming a large solid network that spans macroscopic space. They have many applications in industry and daily life. In the present thesis, firstly, I focus on studying different types of phase separation. Secondly, I studied the ion specific effects on the aggregation of colloidal particles and surfactant, the purpose is to make stable foams. In the miscibility gap there are two types of phase separation: Nucleation growth and spinodal decomposition, they have different growth mechanisms and kinetics. Therefore, my first p project is to investigate the evolution process of them and their effects to the final structure of material. Gels can be made by adding salt to the dispersion of colloidal particles, they have a large number of applications such as in food and material science. In this dissertation, we use different types of salts to compare gel properties from both macroscopic and microscopic aspects. Obtaining stable foams is significant in the view of their plenty of applications, but the ways to make them are mostly complicated. In this thesis, we can obtain stable foams via two ways. One is simply by adding salts to surfactant solutions, through which we can make ultrastable foam. Another way is using the gel phase we have studied as the continuous phase in foams to arrest the foam aging.