[pt] O escoamento de emulsões é encontrado em diversos processos de recuperação e produção de petróleo. O escoamento de emulsões em meios porosos depende de diversos parâmetros como a relação do tamanho das gotas ao tamanho dos poros, a razão de viscosidades, a vazão volumétrica e o efeito destes parâmetros ainda não é bem compreendido. Uma análise detalhada na escala microscópica dos fenômenos envolvidos se faz essencial para a melhora do entendimento completo do escoamento de emulsões em um reservatório. Isto permitiria o desenvolvimento de melhores modelos de simulação para o escoamento multifísico em meios porosos. Neste trabalho, o escoamento de emulsões óleo-água através de um capilar com garganta foi estudado através de experimentos e teoria. A análise experimental consistiu da visualização sob um microscópio do escoamento e da medição da queda de pressão em função da vazão para diferentes emulsões. A análise teórica englobou o estudo do escoamento em regime permanente de uma gota de óleo imersa em água através de um capilar e o estudo do escoamento transiente da mesma gota através de um capilar com uma garganta. Os resultados mostram que os modelos de escoamento de emulsões em meios porosos não devem ser baseados em propriedades macroscópicas da emulsão quando o tamanho das gotas da fase dispersa for da mesma ordem de grandeza do tamanho dos poros. Neste caso, a queda de pressão é função da tensão interfacial, a razão de viscosidades, a vazão e a razão entre o tamanho das gotas e o diâmetro do poro. Os resultados apresentados neste trabalho podem ser usados no projeto de emulsões apropriadas para controle de mobilidade em operações de recuperação avançada através de injeção de emulsões. / [en] Flow of emulsions is found in many petroleum recovery and production processes and it is often referred to in the context of tertiary oil recovery. The characteristics of emulsion flow in porous media depend on several parameters such as medium drop size to pore size ratio, viscosity ratio, flow rate and the effect of these parameters is far from being entirely understood. A detailed analysis at a microscopic scale of the flow is essential to improve the understanding of flow of an emulsion in a reservoir. This would lead to the development of better simulation models, henceforth increasing the predictability capability of reservoir simulators for enhanced oil recovery applications. In this work, flow of oil-water emulsions through constricted capillaries, used as model for the geometry inside a porous media, is studied experimentally and theoretically. The experimental approach consisted of measuring pressure drop response as a function of flow rate for different emulsions and visualizing the flow under an optical microscope to understand the phenomena involved. The theoretical approach is divided in two parts. First, the immiscible steady flow of a infinite single drop suspended in an less viscous fluid through a capillary was analyzed by solving the Navier- Stokes equations with the appropriate boundary conditions for free-surface flow. The second part of the theoretical analysis consisted of solving the transient flow of a drop suspended in a less viscous fluid through a capillary with a constriction. It is shown the effect of capillary number and viscosity ratio over the main responses of the flow. The results show that models of emulsion flow in a porous media cannot be based on the macroscopic properties of the emulsion when the drop diameter is of the same order of magnitude as the pore throat diameter. In this case flow rate-pressure drop is a strong function of the interfacial tension, viscosity ratio, flow rate and drop to pore size ratio. The results can be used to design appropriate emulsions to control the water mobility during EOR operations by emulsion injection.

Cette thèse concerne la modélisation, l'étude mathématique et la simulation numérique des problèmes d'écoulements diphasique (liquide et gaz) multi-composant (principalement eau et hydrogène) en milieu poreux. Le domaine d'application typique concerne le stockage des déchets radioactifs de moyenne et haute activité à vie longue. Ce type d'étude est motivé, entre autre, par une augmentation de la pression au sein du stockage due à un dégagement d'hydrogène au niveau des colis, pouvant ainsi fracturer la roche environnante et donc faciliter la migration des radionucléides. En supposant que le transfert de masse entre l'hydrogène gazeux et l'hydrogène dissous est donné par la loi de Henry un premier modèle est étudié. Une preuve d'existence de solutions faibles pour ce modèle a été réalisée sans hypothèse de petites données et en traitant le modèle complet en considérant que la densité de chaque composant dépend de sa propre pression. Ensuite,nous avons fait évoluer le modèle vers un modèle à transfert de masse dynamique. On établit l'existence de solutions faibles pour ce deuxième modèle avec un principe du maximum sur la saturation liquide et sur la fraction massique d'hydrogène dissous. Parallèlement, un code numérique en 1D a été développé afin de comparer les solutions numériques obtenues entre le premier modèle et le second modèle lorsque la cinétique de changement de phase devient instantanée. Des accords probant ont été obtenus sur différents cas tests dont un issu des cas tests du GNR MOMAS diphasique. Enfin, un schéma numérique de type volumes finis avec un décentrage phase par phase pour la simulation des écoulements diphasiques eau-gaz sous l'hypothèse que la densité de chaque phase dépend de sa propre pression a été proposé. On établit la convergence de ce schéma numérique. Ce schéma a été validé sur un maillage 2D non structuré.

Made available in DSpace on 2014-12-17T14:06:47Z (GMT). No. of bitstreams: 1 JoseFSJ_DISSERT_2008.pdf: 20908474 bytes, checksum: 6066ac5af7bd753501dc151675ed9175 (MD5) Previous issue date: 2008-03-17 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Ta-Cu bulk composites combine high mechanical resistance of the Ta with high electrical and thermal conductivity of the Cu. These are important characteristics to electrical contacts, microwave absorber and heat skinks. However, the low wettability of Ta under Cu liquid and insolubility mutual these elements come hard sintering this composite. High-energy milling (HEM) produces composite powders with high homogeneity and refines the grain size. This work focus to study Ta-20wt%Cu composite powders prepared by mechanical mixture and HEM with two different conditions of milling in a planetary ball mill and then their sintering using hydrogen plasma furnace and a resistive vacuum furnace. After milling, the powders were pressed in a steel dye at a pressure of 200 MPa. The cylindrical samples pressed were sintered by resistive vacuum furnace at 10-4torr with a sintering temperature at 1100?C / 60 minutes and with heat rate at 10?C/min and were sintered by plasma furnace with sintering temperatures at 550, 660 and 800?C without isotherm under hydrogen atmosphere with heat rate at 80?C/min. The characterizations of the powders produced were analyzed by scanning electron microscopy (SEM), x-ray diffraction (XRD) and laser granulometry. After the sintering the samples were analyzed by SEM, XRD and density and mass loss tests. The results had shown that to high intense milling condition produced composite particles with shorter milling time and amorphization of both phases after 50 hours of milling. The composite particles can produce denser structure than mixed powders, if heated above the Cu melting point. After the Cu to arrive in the melting point, liquid copper leaves the composite particles and fills the pores / O comp?sito Ta-Cu alia a alta resist?ncia mec?nica do Ta com a alta condutividade t?rmica e el?trica do Cu. Estas s?o caracter?sticas importantes para contatos el?tricos, absorvedores de microondas ou dissipadores de calor. Todavia, a baixa molhabilidade do Cu l?quido no Ta s?lido e a m?tua insolubilidade desses elementos tornam dif?cil a densifica??o deste material. A moagem de alta energia (MAE) produz p?s comp?sitos com alta homogeneidade e refina o tamanho de gr?o. Este trabalho faz um estudo sobre p?s comp?sitos Ta-20%Cu preparados por mistura mec?nica e moagem de alta energia com duas condi??es distintas de moagem em um moinho do tipo planet?rio e sua posterior sinteriza??o em um forno a plasma de hidrog?nio e em um forno resistivo sob v?cuo. Amostras cil?ndricas foram obtidas usando uma press?o de 200 MPa. Elas foram sinterizadas em forno resistivo a 1100?C por 60 minutos sob um v?cuo de 10-4torr com uma taxa de aquecimento de 10?C/min e em um forno a plasma de H2 a 550, 660 e 800?C sem tempo de isoterma de sinteriza??o com uma taxa de aquecimento de 80?C/min. Para caracteriza??o dos p?s produzidos foram realizadas microscopia eletr?nica de varredura (MEV), difra??es de raios x (DRX) e granulometria a laser. Ap?s a sinteriza??o as amostras foram analisadas atrav?s de MEV, DRX, densidade e perda m?ssica. Os resultados mostram que para condi??o de moagem mais intensa part?culas comp?sitas s?o produzidas com poucas horas de moagem e h? uma amorfiza??o do t?ntalo e do cobre ap?s 50 horas de moagem. A MAE produz part?culas comp?sitas com uma densidade estrutural maior do que os p?s misturados, se as amostras forem aquecidas acima do ponto de fus?o do cobre. Ap?s o cobre atingir o ponto de fus?o, o cobre l?quido deixa as part?culas comp?sitas e preenche os poros

Transmissions are an essential part of a vehicle powertrain. An optimally designed powertrain can result in energy savings, reduced environmental impact and increased comfort and reliability. Along with other components of the powertrain, efficiency is also a major concern in the design of transmissions. The churning power losses associated with the motion of gears through the oil represent a significant portion of the total power losses in a transmission and therefore need to be estimated. A lack of reliable empirical models for the prediction of these losses has led to the emergence of CFD (Computational Fluid Dynamics) as a means to (i) predict these losses and (ii) promote a deeper understanding of the physical phenomena responsible for theselosses in order to improve existing models. The commercial CFD solver STAR-CCM+ is used to investigate the oil distribution and the churning power losses inside two gearbox configurations namely an FZG (Technical Institute for the Study of Gears and Drive Mechanisms) gearbox and a planetary gearbox. A comparison of two motion handling techniques in STARCCM+ namely MRF (Moving Reference Frame) and RBM (Rigid Body Motion) models is made in terms of the accuracy of results and the computational requirements using the FZG gearbox. A sensitivity analysis on how the size of gap between the meshing gear teeth affects the flow and the computational requirements is also done using the FZG gearbox. Different modelling alternatives are investigated for the planetary gearbox and the best choices have been determined. The numerical simulations are solved in an unsteady framework where the VOF (Volume Of Fluid) multiphase model is used to track the interface between the immiscible phases. The overset meshing technique has been used to reconfigure the mesh at each time step. The results from the CFD simulations are presented and discussed in terms of the modelling choices made and their effect on the accuracy of the results. The MRF method is a cheaper alternative compared to the RBM model however, the former model does not accurately simulate the transient start-up and instead provides just a regime solution of the unsteady problem. As expected, the accuracy of the results suffers from having a large gap between the meshing gear teeth. The use of compressible ideal gas model for the air phase with a pressure boundary condition gives the optimum performance for the planetary gearbox. The outcomes can be used toeffectively study transmission flows using CFD and thereby improve the design of future transmissions for improved efficiency.

Ce travail présente une contribution à la modélisation numérique des systèmes de suspensions dans le cadre de la théorie cinétique. Cette description continue des systèmes de suspensions permet de prendre en compte l'influence de la structure à l'échelle microscopique sur la cinétique de l'écoulement macroscopique. Cependant elle présente l'inconvénient majeur d'être définie sur un espace à haute dimension et rend alors difficile la résolution de ces modèles avec des approches déterministes classiques. Afin de s'affranchir, ou du moins d'alléger, le poids du caractère micro-macro des approches en théorie cinétique, plusieurs techniques de réduction dimensionnelle s'appuyant sur l'utilisation de la Décomposition Généralisée en modes Propres (PGD) sont présentées. Une étude de différents algorithmes PGD est conduite, et dont l'efficacité en termes de vitesse de convergence et d'optimalité de la solution est illustrée. La simulation de mélanges de fluides immiscibles est conduite à l'aide du Tenseur d'aire qui est un puissant outil de caractérisation du mélange. Cependant celui-ci nécessite l'introduction d'une relation de fermeture dont l'impact est évalué avec le modèle de théorie cinétique équivalent et exact. Finalement, la simulation de systèmes de suspensions colloïdales décrits par l'équation de Smoluchowski présente une approche originale de la modélisation des suspensions solides. Cette approche permet de s'affranchir avantageusement du bruit statistique inhérent aux simulations stochastiques traditionnellement mises en œuvre. / This work is a contribution to the numerical modeling of suspension system in the kinetic theory framework. This continuum description of suspension system allows to account for the microstructure impact on the kinetic of the macroscopic flow. However, its main drawback is related to the high dimensional spaces in which kinetic theory models are defined and makes difficult for classical deterministic approaches to solve such systems. One possibility for circumventing, or at least alleviate, the weight of the micro-macro kinetic theory approaches lies in the use of separated representations strategies based on the Proper Generalized Decomposition (PGD). A study of different PGD algorithms is driven, illustrating the efficiency of these algorithms in terms of convergence speed and optimality of the solution obtained. The immiscible fluids blends modeling is driven using the area tensor which is a powerful numerical tool for characterizing blends. However it needs the introduction of closure relation of which impact is measured using equivalent and exact kinetic theory model. Finally, the numerical modeling of colloidal suspension system described by the Smoluchowski equation presents an original approach of the modeling of solid suspension system. This description allows to circumvent the statistical noise inherent to the stochastic approaches commonly used.

[pt] A compreensão dos mecanismos e fenômenos de transporte relacionados ao fluxo multifásico em meios porosos é de grande relevância para diversas aplicações práticas como captura e sequestro de dióxido de carbono, transporte em células de combustível e recuperação avançada de reservatórios de hidrocarbonetos. A geometria do espaço poroso e as interações dos fluidos com sua parte sólida determinam propriedades macroscópicas como porosidade, permeabilidades relativas e pressão capilar. Porém, a visão em escala microscópica fornece uma melhor descrição e entendimento dos processos físicos e químicos do escoamento de fluidos no espaço poroso. Neste trabalho desenvolvemos um simulador de rede de poros para análise do escoamento bifásico de fluidos imiscíveis tanto para o processo de drenagem quanto para o de embebição. O modelo de rede 240×40 tem capilares com raios médios na ordem de 52.35 micrometro com constrição. Os padrões de escoamento e eficiências de deslocamento foram obtidos para diferentes razões de viscosidade e números de capilaridade. Os resultados encontrados, considerando deslocamento pistão, foram similares a de experimentos realizados previamente, injetando água no meio saturado de óleo. Na drenagem, a saturação residual de óleo cai com o aumento do número de capilaridade. O padrão de escoamento observado é de fingerings viscosos e, a frente de deslocamento torna-se mais estável com o aumento da razão de viscosidade. Na embebição, para números de capilaridade mais baixos, o escoamento foi dominado por fingers capilares. Para números de capilaridade altos, fingers viscosos foram predominantes e, com o aumento da razão de viscosidade, a frente apresentou maior estabilidade. / [en] Understanding the mechanisms and transport phenomena of multiphase flow in porous media has great relevance in several practical applications, such as capture and sequestration of carbon dioxide, transport in fuel cells and enhancement hydrocarbon recovery. The geometry of pore space and the fluid interactions with the solid determine macroscopic properties such as porosity, relative permeabilities and capillary pressure. However, microscopic analysis provides a better description and comprehension of physical and chemical processes of fluid flow in the pore space. In this work, we developed a pore-network simulator to analyze immiscible two-phase flow for both drainage and imbibition processes. The 240×40 pore-network model has constricted capillary channels with radius on the order of 52.35 micrometer. Flow patterns and displacement efficiencies evaluation were obtained at different viscosity ratios and capillary numbers. The results, considering piston-like displacement, were similar to experiments realized previously, injecting water in an oil saturated medium. In the drainage process, the oil saturation reduces with increasing capillary number. The observed flow pattern is viscous fingerings and the front is stable with the higher viscosity ratio. In imbibition, the flow was dominated by capillary fingers at low capillary numbers. At high capillary numbers, viscous fingers were predominant and, with increasing viscosity ratio, the front presented higher stability.

Dans cette thèse, on a étudié l’évolution de l’interface par électro-osmose entre deux couches de fluides dans un canal microfluidique. Les applications de ce problème concernent le mélange et le transport, sans contact avec des actionneurs, de fluides en micro-canal. De nombreuses questions restent toutefois posées lorsque le champ est oscillant en temps, notamment vis à vis de la stabilité de l'interface entre les deux fluides. Une analyse de stabilité linéaire basée sur une perturbation à l’interface a été réalisée pour un film mince d'électrolyte sous des champs électriques continus (constants) et alternatifs (dépendant du temps). Une analyse asymptotique avec une hypothèse de grande longueur d’onde des équations d'Orr-Sommerfeld a été appliquée afin de déterminer les seuils de stabilité paramétriques d'un film mince aqueux. L’accent a été mis sur les effets de la tension de surface, de la pression de disjonction pour l'interaction gaz-liquide-substrat, de l'amplitude et de la fréquence du champ électrique appliqué, ainsi que du potentiel zêta du substrat et de la surface libre. Une analyse comparative des profils de vitesse de l’état de base avec et sans contraintes de Maxwell à l’interface, a montré que les gradients de vitesse étaient importants à l'interface liquide-liquide avec les contraintes de Maxwell. De tels gradients sont essentiels à l'instabilité interfaciale sous l’action d’un champ électrique périodique car ils peuvent atténuer ou amplifier les ondes à l’interface. Parallèlement, un dispositif expérimental a été conçu et monté afin de caractériser l’écoulement électroosmotique dans un micro-canal rectangulaire. Avec l'aide d'une analyse PTV (« Particle Tracking Velocimetry »), les distributions de vitesse ont été obtenues et comparées aux prédictions théoriques. Cette comparaison a permis d’estimer le potentiel zêta du PDMS utilisé, valeur conforme à la valeur indiquée dans la littérature. / Since the past decade, use of electro-osmotic flow (EOF) as an alternative flow mechanism in microdevices is becoming more popular due to its less bulky and low maintenance system design. However, one of the biggest shortcomings for its usage in mainstream applications is that it requires the concerned liquid to be electrically conductive. One idea can be to use the flow of conductive fluids to transport non-conductive liquids passively via interfacial shear transfer. Such an idea can has numerous applications in a wide range of fields like bio-chemical processing (e.g. lab-on-a-chip reactors, mixers, etc.), to oil extraction from porous rock formations. One of the significant characteristics of micro-scale flows is high surface to volume ratio, which significantly highlights the role of multi-phase interfaces in such dynamics. The presence of a fluid-fluid interface in an EOF necessitates the characterization of the parameters responsible for hydrodynamic instability of such systems. The present work focuses on the role of steady and time-dependent electric stress (Maxwell stress), capillary force and disjoining pressure on fluid-fluid interfacial instability. A linear stability analysis of interfacial perturbation was performed for a thin film of electrolyte under DC and AC electric fields. Through long wave asymptotic analysis of the Orr-Sommerfeld equations, parametric stability thresholds of a thin aqueous film explored. Further, a set of experiments were performed in order to characterize the EOF in a rectangular microchannel. With the help of a Particle Tracking Velocimetry analysis, velocity distributions were obtained which agreed well to the theoretical values. This was further used to estimate PDMS zeta potential, which was found to be within the reported values in the existing literature. Liquid-liquid interfacial deformation was also explored under a time-periodic EOF and a wide range of the magnitudes of capillary force, and diffusive and convective transport.

Controlling conformation of macromolecules, both in solution and solid state, has remained an exciting challenge till date as it confronts the entropy driven random coil conformation. Folded forms of biomacromolecules, like proteins and nucleic acids, have served as role-models to the scientists in terms of designing synthetic foldamers. The folded functional forms of proteins and nucleic acids have been shown to rely heavily on various factors, like directional hydrogen bonding, intrinsic conformational preferences of the backbone, solvation (e.g. hydrophobic effects), coulombic interactions, charge-transfer interactions, metal-ion complexation, etc. Chapter-1 discusses various designs of synthetic polymers explored by research groups world-over to emulate the exquisite conformational control exercised by biomacromolecular systems. Our laboratory has been extensively involved since 2004 in designing charge-transfer complexation induced folding of flexible donor-acceptor (DA) polymeric systems, such as those shown in Scheme 1. It was observed that such polymers adopt a folded conformation in polar solvents, like methanol, in the presence of an excess of an appropriate alkali metal ion. To explore folding in the solid state, Jonas and co-workers recently showed that a polyethylene-like polyester with long alkylene segments containing periodically located pendant propyl group forms a semicrystalline morphology with alternating crystalline and amorphous regions primarily because of the periodic folding of the backbone due to the steric exclusion of the propyl branches from the crystalline domains. In order to explore immiscibility-driven folding of polyethylene-like polyesters, Roy et al. designed a periodically grafted amphiphilic copolymer (PGAC) containing long alkylene segments (mimicking polyethylene) and pendant oligoethyleneglycol chains at periodic intervals (Scheme 2). Scheme 2: Proposed folding of a periodically grafted amphiphilic copolymer It was demonstrated that immiscibility between the hydrocarbon backbone and pendant PEG segments drives the polymer to adopt a folded zigzag conformation as shown in Scheme 2. The above synthetic strategy, however, does not permit easy structural variation of the side chain segments because the side-chain segment is covalently linked to the malonate monomer. In Chapter-2, a more general strategy to prepare periodically grafted copolymers has been described. In an effort to do so, we designed a series of clickable polyesters carrying propargyl/allyl functionality at regular intervals along the polymer backbone, as shown in Scheme 3. Scheme 3: Periodically clickable polyesters for the preparation of periodically grafted copolymers The polyesters were prepared by reacting either 2-propargyl-1,3-propanediol, 2,2-dipropargyl-1,3-propanediol or 2-allyl-2-propargyl-1,3-propanediol with an alkylene diacid chloride, namely 1,20-eicosanedioic acid chloride, under solution polycondensation conditions. Since these polyesters carry either, one propargyl, two propargyls or one propargyl and one allyl group on every repeat unit, it provides us an opportunity to synthesise exact graft copolymers with one side chain, two side chains or even two dissimilar side chains per repeat unit. In Chapter-3, the periodically clickable polyesters were reacted with MPEG-350 (PEG 350 monomethyl ether) azides using Cu(I) catalyzed azide-yne click reaction to generate periodically grafted amphiphilic copolymers (PGAC) carrying crystallizable hydrophobic backbone and pendant hydrophilic MPEG-350 side-chains (Scheme 4). Since the PGACs carry either one or two pendant MPEG-350 chains on every repeat unit, it allowed us to examine the effect of steric crowding on the crystallization propensity of the central alkylene segment. Scheme 4: Functionalization of periodically clickable polyesters with MPEG 350 azide by azide-yne click reaction From DSC studies, it was observed that increase in steric crowding at junctions resulting from increased side-chain volume hinders effective packing of the hydrocarbon backbone. As a result, both transition temperatures and the enthalpies associated with these transitions decreases. SAXS and AFM studies revealed the formation of lamellar morphology with alternate domains of PEG and hydrocarbon. Based on these observations, we proposed that self-segregation between hydrophobic backbone and hydrophilic side-chains induce the backbone to adopt a folded zigzag conformation (Scheme 5). Scheme 5: Schematic depiction of self-segregation induced folding of PGAC and their assembly on mica surface (AFM image) In order to study the effect of solvent polarity on conformational evolution of the periodically grafted amphiphilic copolymers, we randomly incorporated pyrene in the backbone of the polymer by reacting a small fraction (~ 5 mole %) of the propargyl groups with pyrene azide. Fluorescence study of the pyrene labelled polymer showed that increase in solvent polarity increases the intensity of the excimer band dramatically; this suggests the possible collapse of the polymer chain to the folded zigzag form. In an extension of this work, the PGAC was further used as template to synthesise layered silicates that appears to replicate the lamellar periodicity seen in the polymer. In order to study the effect of reversing the amphiphilicity on self-segregation, in Chapter-4, we synthesised a series of clickable polyesters carrying PEG segments of varying lengths, namely PEG 300, PEG 600 and PEG 1000, along the polymer backbone. The polymers were prepared by trans-esterification of 2-propargyl dihexylmalonate with different PEG-diols. These polyesters were then clicked with docosyl (C22) azide using Cu(I) catalyzed azide-yne click reaction to generate the desired periodically grafted amphiphilic polymers carrying crystallizable hydrophobic pendant chains at periodic intervals; the periodicity in this case was governed by the length of the PEG diols (Scheme 6). Scheme 6: PGACs carrying hydrophilic PEG backbone and crystallizable hydrophobic pendant docosyl chains Varying the average periodicity of grafting provided an opportunity to examine its consequences on the self-segregation behavior. Given the strong tendency of the pendant docosyl segments to crystallize, DSC studies proved useful to analyse the self-segregation; DOCOPEG 300 clearly exhibited the most effective self-segregation, whereas both DOCOPEG 600 and DOCOPEG 1000 showed weaker segregation. Based on the observations from DSC studies, we proposed that the PEG backbone adopts a hairpin like conformation (Scheme 7). Scheme 7: Proposed self-segregation through hairpin like conformation of backbone PEG segments In order to confirm the bulk morphology, we carried out small angle X-ray scattering (SAXS) and atomic force microscopic (AFM) studies. The SAXS profiles confirmed the observations from DSC studies, and only DOCOPEG 300 exhibited well-defined lamellar ordering. Thus, it is clear that the length of the backbone PEG segment (volume-fraction) strongly influences the morphology of the PGACs. Based on the inter-lamellar spacing from SAXS and the height measurements from AFM studies (Scheme 8), we proposed that these polymers form lamellar morphology through inter-digitation of the pendant docosyl side-chains. The observations from Chapters 3 and 4 suggested that the crystallization of the backbone has a dramatic effect on the conformation of the polymer backbone. In order to explore the possibility of independent crystallization of both backbone and pendant side-chains, the periodically clickable polyesters, described in Chapter-2, were quantitatively reacted with a fluoroalkyl azide, namely CF3(CF2)7CH2CH2N3 using Cu(I) catalyzed azide-yne click reaction; Chapter-5 describes these polyesters carrying long chain alkylene segments along the backbone and either one or two perfluoroalkyl segments located at periodic intervals along the polymer chain (Scheme 9). DSC thermograms of two of the samples showed two distinct endotherms associated with the melting of the individual domains, while the WAXS patterns confirm the existence of two separate peaks corresponding to the inter-chain distances within the crystalline lattices of the hydrocarbon (HC) and fluorocarbon (FC) domains; this confirmed the occurrence of independent crystallization of both the backbone and side chains. Scheme 10: Left-variation of SAXS profile of all three polymers as a function of temperature, Right- molecular modelling of representative FC-HC-FC triblock structures. Interestingly, a smectic-type liquid crystalline phase was observed at temperatures between the two melting transitions. SAXS data, on the other hand, revealed the formation of an extended lamellar morphology with alternating domains of HC and FC (Scheme 10). The inter-lamellar spacing calculated from SAXS matches reasonably well with those estimated from TEM images. Based on these observations, we proposed that the FC modified polymers adopt a folded zigzag conformation whereby the backbone alkylene (HC) segment becomes colocated at the center and is flanked by the perfluoroalkyl (FC) groups on either side, as depicted in Scheme 11. Melting of alternate HC domains first leads to the formation of a smectic-type liquid crystalline mesophase, wherein the crystalline FC domains retain the smectic ordering; this was confirmed by polarizing light microscopic observations. Scheme 11: Schematic presentation of self-segregation induced folding of polymer chains; and hence crystallization assisted assembly of these singly folded chains to form lamellar structure One interesting challenge would be to create unsymmetrical folded structures, wherein the top and bottom segments of the zigzag folded form would be occupied by two different segments, such as PEG and FC, whereas the backbone alkylene segment would form the central domain; this would lead to the possible formation of consecutive domains of PEG, HC and FC through immiscibility driven self-segregation process. In Chapter-6, several approaches to access such systems have been described; one such design that could have resulted in the successful synthesis of a periodically clickable polymer carrying orthogonally clickable propargyl and allyl groups along the backbone in an alternating fashion is depicted in (Scheme 12). The parent polyester was successfully synthesized and the propargyl group was first clicked with the FC-azide to yield the FC-clicked polyester; however, several attempts to click MPEG-SH onto the allyl groups using thiol-ene click reaction failed. Scheme 12: Scheme for the synthesis of alternating orthogonally clickable polymer In order to accomplish our final objective, we chose to first prepare the FC-clicked diacid chloride and polymerize it with an azide-alkyne clickable macro-diol, as depicted in Scheme 13; this approach was successful and yielded the desired clickable polyester bearing the FC segments at every alternate location. This polymer was then clicked with PEG-750 azide to yield the final targeted polymer that carries mutually immiscible FC and PEG-750 segments at alternating positions along the polymer backbone. The occurrence of self-segregation of FC, PEG-750 and the alkylene backbone (HC) was first examined by DSC studies, which appeared to suggest the presence of three peaks, although these were not very well-resolved. Scheme 13: Schematic for the synthesis of the polymer carrying FC and PEG 750 alternatingly along the backbone A schematic depiction of the anticipated organization of such unsymmetric folded macromolecules is shown in Scheme 15; it is evident that because of mutual immiscibility, the layers will be organized such that the FC domains of adjacent layers will be together and similarly the PEG domains of adjacent layers will also be together. Such an organization would lead to an estimated spacing that would correspond to a bilayer of the folded structures. Interestingly, SAXS study (Scheme 14) reveals the formation of lamellar morphology with a d-spacing of 14.6 nm. Scheme 14: Figure 6.10: SAXS profile of the polymer PE-FC-PEG 750 In order to gain an estimate of the expected inter-lamellar spacing, the end-to-end distance of a model repeat-unit was computed to be ~ 9.4 nm. It is, therefore, evident that the inter-lamellar spacing of 14.6 nm seen in the SAXS is significantly larger and must represent a bilayer type organization (Scheme 15). In this regard it is important to say that the organization of these alternatingly functionalized folded chains should give a variety of d-spacings. Because of highest electron density contrast of FC among PEG, HC and FC, we proposed that the d-spacing calculated from the SAXS profile corresponds to ‘d4’ in Scheme 15. This first demonstration of the formation of zigzag folded unsymmetric entities bearing dissimilar segments on either side of the folded chain holds exciting potential for a variety of different applications and beckons further investigations. Scheme 15: Schematic for the proposed self-assembly of the singly folded polymer chains

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The present thesis deals with synthesis of free alloy nanoparticles in immiscible alloy systems by the process of laser ablation under a liquid. In this process the alloy target is submerged in a liquid and the plume formed by the laser beam interaction with the target is confined in the liquid. The nanoparticles formed inside this plume and get quenched by the surrounding liquid yielding suspension of nanoparticles in the liquid. By the addition of suitable surfactants, these nanoparticles can be protected from other reactions and their size can be controlled by preventing further growth. We have selected immiscible alloys for the present study. These alloys tend to phase separate in melt as well as in solid depending on the value of the positive heat of mixing. We have used two binary alloys for the present study. These are alloys in Ag-Cu system and Fe-Cu system. In both these systems, there are reports of formation of extended solid solution due to kinetic factors during nonequilibrium processing like rapid solidification and mechanical alloying. In the present thesis we report synthesis of alloy nanoparticles of different compositions and sizes in these two systems and explore the nature of the phases that form in the small (nano) particles and their evolutionary pathways leading to the final microstructure. Microscopic techniques, especially transmission electron microscope, were used for characterization of these nanoparticles. The phase evolution was further studied using in situ microscopic techniques. After introducing the thesis in the Chapter 1, we describe briefly the relevant literatures in Chapter 2. The experimental details, in particular the experimental set up for laser ablation with targets under liquid are described in chapter 3. This chapter also includes the experimental details of the characterization. Transmission electron microscopy was used as primary characterization tool in the present study. The Chapter 4 presents the result of our study of alloy nanoparticles in Fe-Cu system. This system exhibits a submerged liquid miscibility gap. Although we have studied alloy targets of different compositions, the results of alloy nanoparticles obtained from targets with compositions Cu-40at.%Fe and Cu-60at.%Fe were primarily presented in this chapter. The nanoparticles that were synthesized had a size range of approximately 40nm to more than 100 nm. These particles have spherical morphology. The measurements of local compositions of different locations in the particle indicate the presence of a layer of Fe3O4 oxide at the spherical surface. This layer is devoid of copper. Most of the copper exist in the core of the particle. Fe rich spherical particles of much smaller size (~15 nm) are found to be embedded in the copper rich core. The copper formed solid solution with Fe and a copper concentration gradient exists in the particle below oxide layer due to oxidation of Fe. In contrast the nanoparticles obtained from alloy target with composition Fe-40at.% Cu have a spherical morphology. These have a composite structure with a Fe core in addition to Fe3O4 oxide layer at the surface. We have attempted to explain the phase evolution taking into account under cooling of the melt condensate that forms in the plume and their subsequent solidification through submerged miscibility gap. The chapters 5-7 deals with alloys of Ag-Cu system. In Chapter 5, we have carried out a detailed study of morphological evolution of the nanoparticles of Ag-Cu system. After optimizing the ablation parameters using pure Ag and Cu targets, we have synthesized alloy nanoparticles using different target compositions over the entire range of compositions with sizes having a mode of 25 nm. The evolution of the two phase structure is shown to be composition dependent with particles near equiatomic composition exhibit solid solution with uniformly distributed segregations of composition (Cu & Ag rich) while copper rich alloys exhibit a core shell structure with outer layer being Ag rich. The isothermal experiments again reveal emergence of core-shell morphology at intermediate time for particles with equiatomic composition. In order to compare the results of Ag-Cu nanoparticles with particles produced by other techniques we have synthesized Ag-Cu nanoparticles of near equiatomic composition by chemical route using nitrate salts and NaBH4 as reducing agent. PVP was used as capping agent. The results are presented in chapter 6. Depending on time of reaction, it is possible to synthesis free alloy particles from 2-3 nm to a network of chains. The nanoparticles contain Ag rich and Ag deficient region with Ag tends to segregate near surface. We have also presented mechanism for the formation of chain structure with prolonged reaction. The thermodynamic basis of phase formation in the immiscible system and evolution of phases under nonequilibrium situation have been discussed in chapter 7. This also includes a model to estimate size dependent surface energy. The analysis presented allows a discussion of possible pathways for phase evolution observed in the present work. The thesis ends with a final chapter that discussed the critical issues remains to be addressed and possible future work.