During a survey of black cotton soil zones of Karnataka, indigenously stabilized black cotton soil deposits were encountered in Belgaum, Bijapur, Bagalkot and Gadag Districts of Karnataka. These modified black cotton soils have low swelling and negligible shrinkage tendencies. Owing to their low volume change potential on moisture content changes, these soils are widely preferred in earth construction activities. The exact origin of these modified black cotton soil deposits is not known. According to anecdotal references, these soils were prepared by mixing unknown proportions of wood ash, organic matter and black cotton soil and allowing them to age for unknown periods of time. As wood-ash was apparently used in their preparation, these modified black cotton soils are referred to as ash-modified soils (AMS) in the thesis. The practice of preparing ash-modified soils is no longer pursued in black cotton soil regions of Karnataka and the available supply of this indigenously stabilized soil is being fast depleted. Also, attempts have not been made to characterize the physico-chemical and engineering properties of AMS deposits of Karnataka. Given the widespread utilization of ash-modified soils in black cotton soil areas of Karnataka, there is a need to understand their physico-chemical and engineering behaviour and the physico-chemical mechanisms responsible for their chemical modification. Swelling and shrinkage of expansive soil deposits are cyclic in nature due to periodic climatic changes. Chemically stabilized black cotton soil deposits are also expected to experience cyclic wetting and drying due to seasonal climatic changes. The impact of cyclic wetting and drying on the swelling behaviour of natural expansive soils is well-documented. However, the impact of alternate wetting and drying on the swelling behaviour of admixture stabilized expansive soils (these include natural - ash-modified soils and laboratory - lime stabilized black cotton soils) has not been examined. Such a study would be helpful to assess the long term behaviour of admixture stabilized soils in field situations. To achieve the above objectives, experiments are performed that study: 1.The physico-chemical and engineering properties of ash-modified soils from different Districts of Karnataka. The physico-chemical and engineering properties of natural black cotton soil (BCS) specimens from locations adjacent to ash-modified soil deposits are also examined to understand and evaluate the changes in the engineering characteristics of the ash-modified soils due to addition of admixtures. 2. Identify the physico-chemical mechanisms responsible for the chemical stabilizationof ash-modified soils. 3.The influence of cyclic wetting and drying on the wetting induced volume changebehaviour of admixture stabilized black cotton soils, namely, ash-modified blackcotton soils and lime stabilized black cotton soils.

Sub-surface soil pollution by various processes with high concentration of contaminants can significantly alter geotechnical properties of soils causing unexpected failures of structures founded on them. The changes can occur due to alteration in soil water interaction processes and/or by intense chemical interactions leading to mineralogical and microstructural changes. Behaviour of soil upon contamination with alkali pollutant is one of the major concerns faced by the geotechnical researchers in recent years. In the present study an attempt has been made to understand the role of mineralogical and morphological changes on the volume change (swelling and compressibility) behaviour of soils by prolonged interaction with caustic alkali pollutant. Based on the results it has been proposed to develop remedial measures to nullify and/or control the detrimental effects. A comprehensive experimental program has been planned to achieve these objectives. The experimental investigations carried out and results obtained are presented in eight chapters as follows. The broad outline of thesis is given in Chapter 1. A detailed review of literature on the type of phyllosilicate minerals present in various soils is presented in Chapter 2 with a view to select most common soils for the study. Various sources of contaminants and their effect on the properties of soils have been summarised. Present understanding on the mechanisms leading to changes in the soil properties has been elucidated. The occurrence of alkali contamination has been reviewed in this chapter which enabled to select the ranges of alkali concentration for the study. Based on the review of various methods employed to improve the soil behaviour, the use of salt solutions such as potassium chloride (KCl) and magnesium chloride (MgClB2B) and pozzolanic fly ash has been considered to counteract the alkali effects. Based on this detailed survey, the scope of the present investigation has been elaborated at the end of the chapter. Chapter 3 presents different materials used and various methods adapted in the current study. Three soils having different mineralogy have been used in this study to bring out the effect of alkali solutions on their volume change behaviour. While two soils were classified as CH, the third one was of CL. The CH soils used in this study are called Black Cotton Soils in India. One soil contained predominantly mixed layer illite-smectite mineral (BCS I) and the other contained predominantly montmorillonite mineral (BCS M). The locally available CL soil used is referred as red earth (RE) whose predominant mineral is kaolinite. Alkali solutions of concentration ranging from 1N to 4N are prepared using sodium hydroxide pellets (NaOH). Slat solutions viz. potassium chloride and magnesium chloride and pozzolanic fly ash obtained from Neyveli thermal power plant (NFA) are used as additives. Procedures to determine the geotechnical properties of the soils such as Atterberg limits, specific gravity, grain size distribution and compaction characteristics are given in this chapter. Procedures for identifying the mineral and microstructure of the soils such as X-ray diffraction (XRD) and scanning electron microscopy (SEM) are also presented in this chapter. Standard oedometer tests with fixed ring apparatus were performed to study the volume change behaviour of soils under various conditions. Volume change behaviour of soils in the presence of alkali solutions is presented in Chapter 4. In order to assess the effect of alkali solution on the volume change behaviour of soils it is necessary to study their behaviour in water. Relatively very high swell was observed in BCS M, whereas the swell in RE and BCS I soil specimens was very low and moderate respectively. Adsorption of water to form diffuse double layer near the negative surface of clay mineral particles leads to swelling in soils. The thickness of the double layer depends on the cation exchange capacity of soil. Higher cation exchange capacity leads to development of higher thickness of double layer thereby inducing swell. The higher is the swell the higher would be the compression. The effect of different concentrations (1N, 2N and 4N) of alkali solutions on volume change behaviour of three types of soil is presented in this chapter. All the three soils studied, irrespective of their mineralogical composition, exhibited high swell when contaminated with alkali solution compared to water. However, the extent and nature of swell varied both with the type of mineral present in the soil and concentration of sodium hydroxide solution. The swell in BCS I increases with increase in the concentration of the alkali solution. In 1N alkali solution the high swell occurred is due to the breaking up of interstratified mineral into constituent minerals initiated by the leaching of potassium from soil due to high pH. In 2N and 4N alkali solutions, the observed high swell occurs in two stages: the first stage of swelling is due to breaking up of interstratified mineral into constituent minerals initiated by the leaching of potassium from soil due to high pH, and the second stage of swelling is due to the formation of new minerals (Zeolite P in case of 2N NaOH and Sodalite in case of 4N NaOH). The nature of swell is influenced by the formation of minerals depending on the concentration of alkali solution. Thus the studies clearly indicate that the swelling is due to the release of potassium from soil at higher pH and due to mineralogical changes depending upon the concentration of alkali solution. Confirmative tests were conducted to support the release of potassium during first stage of swelling and mineralogical alteration after second stage of swelling. The high swell in BCS M becomes higher in 1N alkali solution. The increased swell in the soil with 1N alkali solution is due to increase in the ion exchange capacity of soil at higher pH. The swell which is very high with 1N alkali solution decreases with 2N alkali solution. With increase in concentration of alkali solution to 2N, the increase in the negative charges due to alkalinity becomes less and the swell decreases due to dominant influence of electrolyte effect. With increase in the concentration of alkali solution to 4N, both these influences become less and the amount of swell remains the same. Significant increase in the amount of swell is observed with alkali solution even in non-swelling red earth. The nature of swell as well as the formation of minerals is not altered by the change in the concentration of alkali solution. At any concentrations of alkali solution the observed swell is noticed in two stages – very small first stage of swell due to lower ion exchange capacity and considerable second stage of swell due to the formation of new mineral (Sodalite) with any concentration of alkali solution. It has been observed that the normal hyperbolic swell – compression relationship does not apply for the alkali contaminated soils. The higher swell does not result in higher compression, as the swollen soil remains fairly incompressible. Analysis of the results and detailed studies on micro-structure and mineralogy of soils bring out mechanism of alkali effects. Comparing the swell behaviour of soils with alkali solutions brings out the relative importance of various mechanisms proposed for induced heave. The effect of salt solutions used viz., potassium chloride and magnesium chloride to restrict the influence of alkali solution on the volume change behaviour of BCS I is presented in Chapter 5. These salts react with alkali solution to form partly soluble potassium hydroxide (KOH) and sparingly soluble magnesium hydroxide (Mg(OH)B2B) respectively. Presence of ionic potassium can bring out potassium linkages, by bridging potassium ion between the unit layers of expansive minerals reducing the swell. Magnesium ions can restrict swell, by replacing the monovalent exchangeable ions present in soil and/or by formation of magnesium hydroxide which is a weak cementing agent. The effect of potassium hydroxide on the volume change behaviour of soil has been studied and the results clearly indicate that fixation of potassium is facilitated by high pH of KOH solution. Addition of potassium chloride has partially controlled the alkali induced heave in soil. Of the two stages of swelling observed in soil in the presence of 4N alkali solution, only the first phase of swelling is reduced which may be due to electrolyte effect and/or due to fixation of potassium. The second phase of swelling that occurs in soil due to mineralogical changes can not be controlled with the use of potassium chloride. Addition of magnesium chloride salt solution also reduced the effect of alkali solution mostly due to suppression of thickness of diffuse double layer that develops near clay surface. The nature of reduction in the swell of alkali solution during the two stages by magnesium chloride is similar to that of potassium chloride. The partial reduction in swell of soil in the presence of salt solutions leads to reduction in the compressibility of soil. Detailed data and analysis, presented in this chapter, bring out the role of microstructure and mineralogy on soil behaviour. The abnormal volume changes due to mineralogical changes affected by high concentration of sodium hydroxide could not be controlled with salt solutions, attempts are made to utilize fly ash to control the alkali induced heave. The pozzolanic compounds produced by hydration of compounds presented and/or produced by lime silica reactions can bind the soil particles controlling the swelling. The results on the effectiveness of fly ash on BCS I soil are presented in Chapter 6. The physical and chemical properties of fly ash along with the mineralogical composition and the microstructure of the fly ash are also presented in this chapter. Before studying the effect of fly ash to control the volume change behaviour of soils in presence of alkali solutions, the effect of alkali solutions on the volume change behaviour of fly ash itself has been studied. The results showed no noticeable changes in swell and compressibility of fly ash, encouraging its use for controlling the alkali induced swell. The ability of different percentages (10%, 20% and 50%) of fly ash to control alkali induced volume changes in soil with varying concentrations of alkali solutions, viz., 1N, 2N and 4N has been studied. The results indicate that the addition of fly ash effectively reduces alkali induced swell in BCS I. The effectiveness of fly ash increases with increase in its content. The reduction in swelling of soil is partially due to replacement of soil with fly ash and mainly due to cementation of soil particles by pozzolanic compounds produced. More than 25% of fly ash is generally required to significantly reduce the swell in alkali solutions. The reduction in swell with addition of fly ash also leads to lower compressibility of soil. The role of microstructure and mineralogy in controlling the volume change behaviour are also presented in this chapter. The effectiveness of fly ash in controlling the volume changes in RE and BCS M due to alkali solutions are studied in Chapter 7. The addition of fly ash completely eliminates the swelling in both the soils. The reduction in swelling up on addition of fly ash is essentially due to efficient binding of particles by pozzolanic reaction compounds. Addition of even 10% of fly ash is sufficient in completely arresting the swelling of RE and BCS M by alkali solution. Detailed data and analysis of the results to bring out the role of microstructure and mineralogy on the behaviour of soils are presented. It is clear that relatively higher amounts of fly ash is required to control the alkali induced heave in BCS I than in other soils at higher concentrations of alkali solution. The major conclusions from the study are presented in Chapter 8. The thesis demonstrates that alkali contamination alters mineralogy and morphology of soils affecting the volume change behaviour significantly. The study also brings out that fly ash can control the undesirable swell that occurs in most types of soils by cementing the soil particles to resist swelling. Though the amount of fly ash required to control the alkali induced heave varies, 25% of fly ash is often sufficient.

L'appariement est une composante indispensable à la description des noyaux atomiques. Ses effets sur les propriétés statiques du noyau sont à présent bien connus. Dans ce mémoire, l'effet de l'appariement sur la dynamique nucléaire est étudié. Différentes théories qui incluent l'appariement sont comparées dans un cas modèle. La théorie TDHF+BCS qui apparaît comme un bon compromis entre la richesse de la physique qu'elle contient et son coût numérique est retenue pour les applications aux noyaux. L'introduction de l'appariement dans cette approximation pose de nouveaux problémes liés à (1) la brisure de la symétrie associée au nombre de particules, (2) la non-conservation de l'équation de continuité. Ces difficultés sont analysées en détail et des solutions pratiques sont proposées. Dans cette thèse, un programme TDHF+BCS en 3 dimensions permettant de simuler la dynamique des noyaux a été d'eveloppé. L'application de cette théorie aux résonances géantes a montré que l'appariement n'affecte que les états excités de basse énergie. La composante collective de haute énergie n'étant modifiée que par les conditions initiales. Une étude complète des résonances géantes quadrupolaires a été réalisée pour plus de 700 noyaux sphériques ou déformés. Un bon accord est alors trouvé avec les données expérimentales pour l'énergie collective de la résonance. Cette théorie a ensuite été appliquée à l'étude des réactions de transfert de nucléons lors des collisions noyau-noyau. Une nouvelle méthode de détermination des probabilités de transfert est proposée. Il est montré que l'appariement augmente de manière significative les probabilités de transférer deux nucléons.

In this thesis the cubic spline guidance law and its variants are derived. A detailed analysis is carried out to find the initial conditions for successful interception. The results are applied to three dimensional guidance design and for solving waypoint following problems. The basic cubic spline guidance law is derived for intercepting a stationary target at a desired impact angle in a surface-to-surface engagement scenario. The guidance law is obtained using an inverse method, from a cubic spline curve based trajectory. For overcoming the drawbacks of the basic cubic spline guidance law, it is modified by introducing an additional parameter. This modification has an interesting feature that the guidance command can be obtained using a single cubic spline polynomial even for impact angles greater than π/2, while resulting in substantial improvement in the guidance performance in terms of lateral acceleration demand and length of the trajectory. For imparting robustness to the cubic spline guidance law, in the presence of uncertainties and acceleration saturation, an explicit guidance expression is also derived. A comprehensive capturability study of the proposed guidance law is carried out. The capturability for the cubic spline guidance law is defined in terms of the set of all feasible initial conditions for successful interception. This set is analytically derived and its dependence on various factors, such as initial engagement geometry and interceptor capability, are also established. The basic cubic spline guidance and its variants are also derived for a three dimen- sional scenario. The novelty of the present work lies in the particular representation of the three dimensional cubic spline curve and the adoption of the analytical results available for two dimensional cubic spline guidance law. This enables selection of the boundary condition at launch for given terminal boundary condition and also in avoiding the singularities associated with the inverse method based guidance laws. For establishing the feasibility of the guidance laws in the real world, the rigid body dynamics of the interceptor is presented as a 6 degrees-of-freedom model. Further, using a simplified model, elementary autopilots are also designed. The successful interception of the target in the presence of the rigid body dynamics proves practical applicability of the cubic spline based guidance laws. Finally, the theory developed in the first part of the thesis is applied to solve the waypoint following problem. A smooth path is designed for transition of vehicle velocity from incoming to outgoing direction. The approach developed is similar to Dubins’ path, as it comprises line–cubic spline–line segments. The important feature of this method is that the cubic spline segments are fitted such that the path curvature is bounded by a pre-specified constrained value and the acceleration demand for following the smooth path obtained by this method, gradually increases to the maximum value and then decreases. This property is advantageous from a practical point of view. All the results obtained are verified with the help of numerical simulations which are included in the thesis. The proposed cubic spline guidance law is conceptually simple, does not use linearised kinematic equations, is independent of time-to-go es- timates, and is also computationally inexpensive.

En raison de leur complexité croissante, la solubilité des nouvelles entités chimiques en milieu aqueux est de plus en plus faible. Ainsi, le développement de beaucoup de principes actifs échoue à cause d’une hydrosolubilité insuffisante. De nombreuses technologies existent pour améliorer la solubilité et/ou solubilisation de tels composés. Cette thèse est ciblée sur la formulation de dispersions solides amorphes par extrusion à chaud. En particulier, un principe actif d’intérêt industriel sera formulé en utilisant une extrudeuse bi-vis disponible sur la plateforme Gala®. Cette technologie autorise l’utilisation d’un grand nombre de matrices, ce qui peut nécessiter un grand nombre d’essais expérimentaux. Une attention particulière est donc portée à l’utilisation de méthodes prédictives de la miscibilité entre les composants qui peuvent ainsi permettre une première sélection des matrices. Sur la base de ces résultats, une étude sur le procédé de hot melt extrusion a ensuite été réalisée. / The aqueous solubility of new chemical entities is increasingly weak, due to their complex structure, and many API fail in development due to insufficient solubility. Many technologies exist to enhance the solubility and / or dissolution of such compounds in aqueous media. Among all of these methods, this thesis is focused on the formulation of amorphous solid dispersions by hot melt extrusion. A lot of matrix can be used to formulate with this technology, so few methods to estimate miscibility between API and matrices will also be presented in this thesis. Finally, a study about the hot melt extrusion process will also be presented.

La première partie de cette thèse concerne les phases inhomogènes<br />FFLO. Celles-ci peuvent apparaître dans les supraconducteurs<br />ou les gaz d'atomes froids fermioniques en présence d'une différence<br />homogène de potentiels chimiques entre les deux états de spin.<br />Nous regardons la compétition<br />entre les différentes phases FFLO près de la transition.<br />A 2D, nous utilisons une approche de type Ginzburg-Landau <br />pour prédire une cascade de transitions entre des phases inhomogènes<br />de plus en plus complexes.<br />A 3D ou la transition FFLO est du premier ordre, <br />nous présentons une méthode numérique <br />de résolution des équations quasiclassiques d'Eilenberger <br />basée sur un développement de Fourier. <br />Nous déterminons ainsi les phases inhomogènes de plus basse énergie.<br /><br />Dans la seconde partie, nous étendons la théorie perturbative<br />de Bogoliubov aux quasicondensats dans une représentation densité-phase.<br />Nous obtenons des prédictions pour différentes observables.

Pour la description des propriétés de basse température des systèmes en physique de la matière condensée, il est souvent utile de travailler avec un espace dynamique réduit. Cette philosophie s'applique aux systèmes bicouches à effet Hall quantique comme aux systèmes d'anyons et aux systèmes magnétiques frustrés qui représentent les exemples discutés dans cette thèse. <br /><br />On introduit une classe générale d'états appariés de fermions composites. Ces fonctions d'onde sont exploitées pour analyser l'état fondamental des systèmes bicouches à effet Hall au facteur de remplissage total un. A partir d'une étude de Monte Carlo variationnel nous concluons que la transition de phase compressible à incompressible observée dans ce système est du deuxième ordre. Nous étudions également la question de l'existence d'un état apparié à demi-remplissage dans les simples couches. Ensuite nous considérons des schémas de réduction dimensionnelle de systèmes bidimensionnels sur la sphère vers des systèmes unidimensionnels sur le cercle. Un tel mapping est établi pour des systèmes libres et un candidat pour un système d'anyons généralisé est proposé. Finalement, nous analysons les systèmes de spins magnétiques sur réseaux bidimensionnels et discutons si un état de glace de spins peut exister en présence d'interactions dipolaires à longue portée.

Le concept de théorie effective, en tant que modèle s'appliquant dans une certaine gamme d'énergie et/ou pour un régime restreint de paramètres, s'est enrichi des idées du groupe de renormalisation qui peut relier deux modèles a priori bien distincts par un changement continu d'échelle. L'intuition physique resurgit, même pour des problèmes d'apparence formelle, où il s'agit bien souvent de deviner les briques élémentaire, les quasiparticules, qui vont façonner le comportement physique, par exemple à basse énergie. Dans cet exposé, je soulignerai la récurrence de ce concept dans mes recherches en atomes froids et en physique mésoscopique de ces cinq dernières années. Je débuterai par une introduction aux problèmes à trois et quatre corps dans les gaz d'atomes froids où des propriétés universelles émergent lorsque les interactions entre atomes deviennent résonantes. Je parlerai ensuite des gaz de fermions fortement déséquilibrés, étudiés par exemple dans le groupe de Christophe Salomon et Frédéric Chevy au LKB, et de la pertinence de la notion de gaz de Fermi de polarons pour décrire les profils de densités observés. Je présenterai pour poursuivre les expériences de transport dans les nanotubes de carbone, comme celles réalisées au LPA dans le groupe de Takis Kontos, et le modèle Kondo pour le couplage d'une impureté aux électrons des électrodes. Je profiterai de cette occasion pour introduire l'approche de liquide de Fermi de ce problème initiée par Nozières. Je finirai mon exposé par une discussion du circuit RC quantique, un sujet auquel je me suis beaucoup intéressé ces dernières années en lien avec une expérience remarquable réalisée au LPA dans le groupe de physique mésoscopique. Je montrerai comment le concept de liquide de Fermi permet de comprendre l'apparition de résistances universelles quantifiées pour ce circuit quantique.