ABSTRACT In jet problems the conserved quantity plays a central role in the solution process. The conserved quantities for laminar jets have been established either from physical arguments or by integrating Prandtl's momentum boundary layer equation across the jet and using the boundary conditions and the continuity equation. This method of deriving conserved quantities is not entirely systematic and in problems such as the wall jet requires considerable mathematical and physical insight. A systematic way to derive the conserved quantities for jet °ows using conservation laws is presented in this dissertation. Two-dimensional, ra- dial and axisymmetric °ows are considered and conserved quantities for liquid, free and wall jets for each type of °ow are derived. The jet °ows are described by Prandtl's momentum boundary layer equation and the continuity equation. The stream function transforms Prandtl's momentum boundary layer equation and the continuity equation into a single third- order partial di®erential equation for the stream function. The multiplier approach is used to derive conserved vectors for the system as well as for the third-order partial di®erential equation for the stream function for each jet °ow. The liquid jet, the free jet and the wall jet satisfy the same partial di®erential equations but the boundary conditions for each jet are di®erent. The conserved vectors depend only on the partial di®erential equations. The derivation of the conserved quantity depends on the boundary conditions as well as on the di®erential equations. The boundary condi- tions therefore determine which conserved vector is associated with which jet. By integrating the corresponding conservation laws across the jet and imposing the boundary conditions, conserved quantities are derived. This approach gives a uni¯ed treatment to the derivation of conserved quantities for jet °ows and may lead to a new classi¯cation of jets through conserved vectors. The conservation laws for second order scalar partial di®erential equations and systems of partial di®erential equations which occur in °uid mechanics are constructed using di®erent approaches. The direct method, Noether's theorem, the characteristic method, the variational derivative method (mul- tiplier approach) for arbitrary functions as well as on the solution space, symmetry conditions on the conserved quantities, the direct construction formula approach, the partial Noether approach and the Noether approach for the equation and its adjoint are discussed and explained with the help of an illustrative example. The conservation laws for the non-linear di®usion equa- tion for the spreading of an axisymmetric thin liquid drop, the system of two partial di®erential equations governing °ow in the laminar two-dimensional jet and the system of two partial di®erential equations governing °ow in the laminar radial jet are discussed via these approaches. The group invariant solutions for the system of equations governing °ow in two-dimensional and radial free jets are derived. It is shown that the group invariant solution and similarity solution are the same. The similarity solution to Prandtl's boundary layer equations for two- dimensional and radial °ows with vanishing or constant mainstream velocity gives rise to a third-order ordinary di®erential equation which depends on a parameter. For speci¯c values of the parameter the symmetry solutions for the third-order ordinary di®erential equation are constructed. The invariant solutions of the third-order ordinary di®erential equation are also derived.

L’utilisation de séquences RMN de diffusion permet d’étudier les échanges dynamiques du PEO en tant que petite molécule qui diffuse à travers les parois de nanocapsules creuses de PMMA afin de maîtriser son relargage en fonction du milieu. Ces objets nanostructurés étant élaborés via la formation de stéréocomplexe entre les PMMA isotactique et syndiotactique dans l’acétonitrile, une étude préliminaire a été consacrée à l’influence d’interactions PMMA/PEO sur la morphologie des nanocapsules creuses.Dans un premier temps, nous avons étudié les interactions stéréospécifiques au sein des systèmes binaires PMMA stéréorégulier/PEO dans le chloroforme, solvant non complexant, puis dans l’acétonitrile. L’utilisation de la méthode RMN DOSY nous a donc permis de mettre en évidence la formation d’une double distribution de nanoagrégats de tailles et de composition contrôlés. Le PEO étant présent dans une des populations de nanoagrégats, sa présence induit et stabilise les agrégats de PMMA. Les interactions PMMA/PEO dépendantes de la tacticité du PMMA sont responsables de ces nanostructures. Elles sont non seulement contrôlées par la tacticité du PMMA mais également par la concentration et la masse molaire du PEO. Dans le chloroforme, un modèle d’interaction en trois étapes en fonction de la concentration en PEO, en a été déduit soulignant l’effet prépondérant de la conformation des polymères sur ces interactions. De plus, une généralisation dans plusieurs solvants de ce modèle d’interactions stéréospécifiques a permis de mettre en évidence la corrélation entre la longueur des séquences isotactiques ou syndiotactiques, leurs conformations et la masse molaire du PEO. Dans un second temps, nous avons pu en déduire une corrélation avec la diminution du phénomène de stéréocomplexation dans les systèmes stéréocomplexe du PMMA/PEO/CD3CN sur la base des interactions observées entre les deux polymères en solution dans l’acétonitrile. Le PEO perturbe en partie la formation du stéréocomplexe, permettant ainsi de mettre en évidence l’influence de la présence de PEO sur la structure des nanocapsules creuses de PMMA et son effet désintégrant.Ces études ont montré que les mécanismes de diffusion à travers les parois utilisés dans les systèmes à relargage contrôlé ne peuvent faire l’impasse sur l’analyse préalable des interactions potentielles entre les molécules sondes et la structure des parois polymériques. En effet, ces interactions peuvent fortement modifiés la structure de ces containers et les mécanismes de diffusion doivent prendre quantitativement en compte ces effets pour être efficients.Ces travaux laissent entrevoir la démarche scientifique à suivre pour le développement de modèle de libération contrôlée de molécules actives à travers les membranes des nanocapsules, elles-mêmes incluses dans des systèmes polymériques. / Use of NMR pulse sequences to measure diffusion permits to study the dynamic exchange of PEO as a small molecule that diffuses through hollow PMMA nanocapsules walls in order to control its release according to the environment. These nanostructured objects being composed of stereocomplex between isotactic and syndiotactic PMMA in acetonitrile, a preliminary study was devoted to the influence of PMMA/PEO interactions on the morphology of hollow nanocapsules.Firstly, we studied stereospecific interactions in binary systems stereoregular PMMA/PEO in chloroform, non-complexing solvent, and acetonitrile. The use of the DOSY NMR method allowed us to demonstrate the formation of a double distribution of nanoaggregates of controlled size and composition. PEO is present in a population of nanoaggregates inducing and stabilizing the PMMA aggregates. PMMA/PEO interactions dependent of tacticity PMMA are responsible for these nanostructures. They are not only controlled by PMMA tacticity but also by concentration and molecular weight of PEO. In chloroform, an interaction model in three stages depending on PEO concentration has been deducted highlighting predominant effect of polymer conformation on these interactions. In addition, a generalization of this stereospecific interactions model in several solvents has highlighted the correlation between the length of isotactic or syndiotactic sequences, their conformations and PEO molecular weight. In a second step, we were able to deduce a correlation with the decrease of stereocomplexation phenomenon in the systems PMMA stereocomplex/PEO/CD3CN based on interactions observed between the two polymers in solution in acetonitrile. PEO partly disrupts stereocomplex formation, thus highlighting the influence of PEO presence on hollow PMMA nanocapsules structure and its disintegrating effect. These studies have shown that diffusion mechanisms through the walls used in controlled release systems cannot ignore preliminary analysis of potential interactions between probe molecules and polymer walls structure. Indeed, these interactions can significantly change the structure of these containers and delivery mechanisms must take these effects into account quantitatively to be efficient.These studies suggest scientific approach to follow the development of controlled release model of active molecules through nanocapsules membranes, which are included in polymeric systems.

abstract: The marketing and development of solutions has become an increasingly important concept in both marketing practice and theory. Recent conceptual work has defined solutions as sets of products and services that allow customers to achieve customized outcomes. Although the definition of a solution is becoming clearer, the process through which solution value is generated is still opaque. The purpose of this study was to add clarity to both marketing theory and practice by examining the solution value co-creation process in depth. Service-dominant logic, the relational view, service value co-creation, and theories of organizational learning and knowledge were the basis for this examination. Social capital was also examined to determine how these important relational concepts are involved in solution development. The study was conducted in four separate phases using a multi-method approach of quantitative surveys, qualitative surveys, and depth interviews. A large, multinational educational firm provided the context for the study which included access to their solution sales force and customer base. Quantitative data was collected from 97 key informants across 182 different customer opportunities for both new and existing solution engagements. Qualitative data was also collected from 71 respondents to provide a mixed-method triangulation of how solution value is created. Overall, the study provided strong support to the idea that knowledge sharing between solution providers and their customers plays a pivotal role in the co-creation of solution value. / Dissertation/Thesis / Ph.D. Business Administration 2011

Cette étude a été menée afin d’identifier les paramètres qui permettent de contrôler la réaction de géopolymérisation et les propriétés d’usage des matériaux finaux. Différentes sources aluminosilicates et solutions alcalines ont donc été sélectionnées afin d’évaluer leur réactivité. Ensuite, une étude de faisabilité des matériaux consolidés a été initiée pour identifier les zones d’existence des matériaux géopolymères dans le diagramme ternaire Si/Al/M/O. L’évolution des échantillons au cours de la formation a été suivie par analyses thermiques (ATD-ATG), pour quantifier l’énergie nécessaire à la formation des oligomères, et par spectroscopies infrarouge et résonance magnétique nucléaire afin de déterminer la nature des réseaux formés et le taux de la réaction. Une forte corrélation a été mise en évidence entre la réactivité des précurseurs, la structure locale et poreuse et les propriétés mécaniques. Ces données ont été exploitées pour valoriser d’une part une argile tunisienne de faible réactivité et d’autre part pour recycler un déchet géopolymère dans des nouvelles formulations. / This study was undertaken to identify the parameters that control the geopolymerization reaction and the working properties of the final materials. To do this, various aluminosilicate sources and alkaline solutions have been studied to exacerbate their reactivity. Then a feasibility study of the consolidated materials was conducted to identify the geopolymer existence domain in Si-Al-M / O ternary diagram. The evolution of samples during formation was monitored by thermal analysis (DTA-TGA), to quantify the required energy for oligomer formation, and infrared and nuclear magnetic resonance spectroscopies to determine the nature of formed networks and the reaction rate. A strong correlation was evidenced between the precursors reactivity, the local and porous structure and the mechanical properties. The obtained results have been exploited to use poorly reactive Tunisian clay as alternative aluminosilicate source and also to reuse geopolymer waste in new formulations.

Ce travail est basé sur l’étude la qualité de matières premières argileuses utilisées dans la production de briques en terre cuite ainsi que sur la valorisation de ces matières premières dans les liants géopolymères. Une première étape a consisté à caractériser par des techniques de caractérisations physico-chimiques, structurales, et thermiques plus de 30 matières premières. Ceci a permis de réaliser des abaques à partir des corrélations issues des aptitudes favorables ou mauvaises dans la production de brique. Parallèlement, des investigations sur la présence de fer et de kaolinite / muscovite ont été menées et ont permis d’évaluer la localisation du fer dans ces différents prélèvements. Dans un second temps, une étude associée à la valorisation de ce mélange de production dans les liants géopolymère a été mis en œuvre. Différentes sources aluminosilicates, de température de calcination différente, ont été utilisées. La caractérisation lors de la consolidation par spectroscopie IRTF a alors mis en évidence des réactions de polycondensation et la formation de liaisons Si-O-Ca. La synthèse de liant géopolymère avec addition de calcium dans un mélange de production a alors révélé des interactions différentes selon le type de cation alcalin (sodium, potassium) de la solution de silicate. La revalorisation de ces matières premières dans de nouveaux produits innovants, substituant les agrégats d’argile expansée, a été réalisée. / This study is based on the investigation of the brick clay quality and on their valorization in a geopolymer binder. First, numerous clay samples were analyzed by physical, chemical, structural and thermal characterizations, which led to abacus plots, allowing to distinguish an efficient or a non-suitable clay for the bricks production. Simultaneously, the iron interaction with the clay minerals was established. An experimental protocol was determined for the company to determine the clay quality for a brick production. Then, a feasibility study of the valorization of these clay minerals in a geopolymer binder was conducted. The FTIR study highlighted a polycondensation reaction and a reaction with the calcium, which was more or less important according to the alkali cation type of the silicate solution. An alternative to the lightweight expanded clay aggregates was evidenced, with the revalorization of brick clay materials in a lightweight geopolymer product.

La préservation statique à froid (SCS) est l’étalon-or de la préservation des organes après une greffe. En raison de la pénurie d’organes et de l’augmentation du nombre de patients figurant sur la liste d’attente, le recours aux organes provenant des donneurs à critères élargis, lesquels sont très sensibles au syndrome d’ischémie-reperfusion (IRS), ce qui entraîne une non-fonction primaire (PNF) ou un dysfonctionnement précoce (EAD), est de plus en plus fréquent.Cette recherche avait pour but d’étudier et d’identifier de nouvelles stratégies pour améliorer la qualité de la préservation des organes - d'atténuer les séquelles de l'IRS en utilisant la machine de perfusion hépatique à différentes températures et à différentes périodes d'utilisation après le prélèvement de l'organe ou en ajoutant une hémoglobine extracellulaire en tant que transporteur d'oxygène pendant le SCS.Deux modèles différents ex-vivo ont été analysés : L’un chez le petit animal avec des foies de rats normaux et stéatosiques, pour la perfusion hypothermique (HMP) et SCS avec le transporteur d'oxygène et au niveau préclinique, des foies humains stéatosiques récusés, pour la perfusion normothermique (NMP).Les résultats ont confirmé de manière significative l'intérêt de l’HMP dans la phase pré-ischémique du SCS et celui de l'utilisation de l'hémoglobine extracellulaire en améliorant la fonction hépatique, le maintien de l'anatomie des hépatocytes et en réduisant des marqueurs du stress oxydatif, de l'apoptose et de l'inflammation. Egalement, l'utilisation de NMP a permis d'analyser les foies sévèrement stéatosiques pouvant être récupérés pour une transplantation dans un avenir très proche.Cette recherche met en évidence de nouvelles approches en matière de préservation d'organes susceptibles d'augmenter le pool d'organes et d'améliorer les résultats en transplantation hépatique.Mots-clés : greffe de foie, stockage froid dans le froid, perfusion dans une machine à foie, lésion de reperfusion par ischémie, transporteur d'oxygène. / Static cold storage (SCS) is the gold standard of organ preservation after being procured for transplantation. Due to the organ shortage and the increase of number of patients in the waiting list have pushed the use organs from extended criteria donors which are very susceptible to the ischemia reperfusion syndrome (IRS) leading to primary non-function (PNF) or to early allograft dysfunction (EAD).This research was aimed to study and identify new strategies to improve the quality of organ preservation -liver, to attenuate the IRS sequels by using the liver perfusion machine (LPM) at different temperatures and times of usage after the organ procurement or by adding an extracellular hemoglobin as an oxygen carrier during SCS.Two different ex-vivo models were analyzed: small animal -normal and steatotic rat livers, for hypothermic perfusion (HMP) and SCS with the oxygen carrier and preclinical -steatotic discarded human livers, for normothermic perfusion (NMP).The results significantly confirmed the benefit of the HMP in the preischemic phase of SCS and that of the use of the extracellular hemoglobin by improving the liver function, maintenance of the hepatocytes anatomy and by a reduction of the oxidative stress, apoptosis and inflammation markers. Also, the use of NMP permitted to analyze the severely steatotic livers that can be rescued for transplantation in the very near future.This investigation unveils new approaches in organ preservation that could increase the pool of organs and improve the results in liver transplantation. Key words: liver transplantation, static cold storage, liver machine perfusion, ischemia reperfusion injury, oxygen carrier.

Orientador: Rafael Zadorosny / Resumo: Os materiais supercondutores são extremamente promissores a novas aplicações. Podemos encontrar diversos estudos sobre o supercondutor YBCO, porém o tratamento térmico para a formação da fase YBa2Cu3O7-δ (Y123) na forma de nanofibras ainda não é bem definido na literatura. Para estudar de forma sistemática essa questão, e definir uma boa rota de tratamento térmico, fios com diâmetros em torno de 300 nm foram obtidos por Solution Blow Spinning (SBS) a partir de uma solução contendo acetatos metálicos de ítrio, bário e cobre, polímero PVP (polivinilpirrolidona), ácidos acético e propiônico, e metanol. Os fios poliméricos foram submetidos a um tratamento térmico para obtenção da fase Y123. Este tratamento foi dividido em duas partes, a primeira variando a temperatura máxima de sinterização (850°C, 875°C, 900°C e 925°C) por 1 hora. E a segunda variando o tempo em que as fibras ficaram submetidas à temperatura de 925°C (10 min, 30 min, 1h, 3h e 6h). Para analisar a influência da temperatura e do tempo de sinterização foram utilizados Microscopia Eletrônica de Varredura (MEV), Difração de raios-X (DRX) e Magnetometria AC. As análises de DRX indicaram a presença do YBa2Cu3O7-δ em todas as amostras, porém, com fases secundárias. As medidas de susceptibilidade magnética revelaram influência da temperatura de sinterização na blindagem magnética da amostra, indicando que as amostras tratadas a 925°C/1h obtiveram a melhor resposta magnética. Sendo assim, o melhor tratamento térmico foi o... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Although the production of YBa2Cu3O7-δ (Y123) has been extensively reported in the literature, there is still a lack of information concerning the ideal heat-treatment routes applied to Y123 nanowires. Thus, wires with diameters around 300 nm were prepared by Solution Blow Spinning (SBS) from a solution containing yttrium, barium and copper metal acetates, PVP polymer (polyvinylpyrrolidone), acetic and propionic acids, and methanol. The resulting polymer wires were heat-treated to obtain the Y123 ceramic phase. Those treatments were divided into two parts: in the first one, which lasted 1 hour, the maximum sintering temperature was changed (850°C, 875°C, 900°C, and 925°C); in the second one, the time of the plateau at 925°C was altered (10 min, 30 min, 1h, 3h, and 6h). The structural characterization was carried out by Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), and AC Magnetometry. SEM images revealed that all samples yielded wires with an average diameter ranging from 241 nm to 376 nm. XRD analysis indicated the presence of the secondary phase BaCuO2 in all samples, as well as the phase Y123. Magnetic measurements corroborate the other characterizations, and indicate the sample sintered at 925 °C/1h as the one giving the highest magnetic response. / Mestre

京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第20455号 / 人博第805号 / 新制||人||194(附属図書館) / 28||人博||805(吉田南総合図書館) / 京都大学大学院人間・環境学研究科共生人間学専攻 / (主査)教授 清水 扇丈, 教授 足立 匡義, 准教授 木坂 正史, 教授 森本 芳則 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

Throughout the past 70 years, a great deal of research conducted on defining and testing problem-solving skills has led towards solution-focused practices and philosophies. As a result, some literature exists illustrating the efficacy of solution-focused practices. However, no published research exists on the factors that contribute to solution building. This study tested for components of solution building while creating a solution building inventory. Factor analysis failed to find specific factors within solution building. The results indicated that solution building is a unidimensional concept. Implications for using the solution building inventory are discussed. / Ph. D.

Log K values, valid at zero ionic strength are reported for the interaction in aqueous solution of CN- with Ni2+ and Hg2+ at 10°, 25° and 40°C, and with Pd2+ at 25°C. ∆H° and ∆S° values valid at zero ionic strength and 25°C are also reported for the interaction of CN- with Hg2+ and for the reaction Pd(CN)42- + CN- = Pd(CN)53-. In connection with the study of Pd2+ - CN- interaction, log K values for the hydrolysis of Pd2+ to give PqOH+ and Pd(OH)2 and an E° value for the reaction Pd(s) = Pd2+ + 2e- are reported. A least squares computational method is developed for the calculation of the equilibrium constants, enthalpy changes and entropy changes for metal-ligand interactions from a single thermometric titration curve (Entropy Titration). This method has been tested by determining log K, ∆H° and ∆S° values for the interaction of Ag+ and Cu2+ with pyridine, Hg(CN)2 with CN- and HgCl2 with Cl-. The results indicate that both the computational method and entropy titration technique are applicable to the determination of the thermodynamics of interaction of metal-ligand systems. Log K, ∆H° and ∆S° values have been determined for the interaction of SO42+ with H+ and thirty +1, +2 and +3 metal ions. The results are compared to electrostatic predictions and deviations from electrostatic predictions are attributed to specific solvent interactions. Log K, ∆H° and ∆S° values are reported for the interaction of Hg(CN)2 with thiourea in water-ethanol solvent mixtures. The results indicate that there is a significant change in the solvolysis of the species in solution at approximately 20 mole per-cent ethanol.