La théorie de couplage de mode (MCT) est l'une des méthodes les plus utilisées pour étudier les transitions vitreuses dans les fluides classiques. Ses prédictions sont en général en accord semi quantitatif avec les simulations. Sa mise en oeuvre nécessite la détermination de la structure statique, généralement par résolution des équations d'Orsntein-Zernike avec une fermeture adéquate. Partant de fermetures utilisant des fonctions « bridges » déduites de la fonctionnelle de référence du mélange de sphères dures, notre travail a consisté d'abord à étudier l'influence de la qualité de cette structure statique sur les prédictions relatives aux états non ergodiques dans des mélanges binaires dissymétriques. Nous avons ensuite considéré les résultats de la théorie du couplage de modes dans sa version naïf (NMCT ) et complète, afin d'analyser les mécanismes d'arrêt, les comparer au fluide effectif et aux approches stochastiques (équations de Langevin généralisées). Enfin, nous proposons une version pragmatique de cette méthode qui fournit des prédictions en meilleur accord quantitatif avec les résultats des simulations pour une variété de potentiels d'interaction / The mode coupling theory (MCT) is one of the most widely used methods for studying the glass transition in classical fluids. Its predictions are usually in semi-quantitative agreement with simulation. Its implementation requires the determination of the static structure usually from the Ornstein-Zernike equations with a suitable closure. Starting from closures that use bridge functions deduced from the hard-sphere reference functional, our work consisted first in studying the influence of the quality of this static structure on the predictions concerning the non-ergodic states in asymmetric binary mixtures. We next considered the results of the mode coupling theory in its naive and full versions, in order to analyze the arrest mechanisms and compare them to the effective fluid and the stochastic approaches (generalized Langevin equations). Finally, we propose a pragmatic version of this method that provides predictions in better quantitative agreement with simulations for a variety of interaction potentials

Le but de ce travail de thèse consiste à étudier les propriétés physico-chimiques des verres chalcogénures afin de pouvoir les utiliser comme membranes de capteurs chimiques destinés pour le dosage des ions Hg²⁺. Dans un premier temps, les propriétés macroscopiques des systèmes vitreux AgY-As₂S₃ (Y = Br, I), HgS-GeS₂, AgI-HgS-As₂S₃ et AgI-HgS-GeS₂, telles que les densités et les températures caractéristiques (Tg et Tc) ont été mesurées et analysées selon les compositions des verres. Puis, dans un second temps, les propriétés de transport ont été étudiés à l'aide de la spectroscopie d'impédance complexe d'une part, ou d'autre part, par des mesures de la résistivité. Ces dernières montrent que les verres de chalcogénures dopés à l'halogénure d'argent présentent deux différents régimes de transports au-dessus du seuil de percolation xc ≈ 30 ppm : (i) domaine de percolation critique, et (ii) domaine contrôlé par modificateur. Vient ensuite la troisième partie, elle consiste à déchiffrer les relations composition/structure/propriété grâce à plusieurs études structurales. Des mesures par spectroscopie Raman, par diffraction de neutrons et de rayons X haute énergie, par diffusion des neutrons sous petits angles (SANS), ainsi que des modélisations RMC/DFT et AMID ont été réalisées. Enfin, la dernière partie de ce travail était une étude préliminaire des caractéristiques des nouveaux capteurs chimiques. Il a été consacré à l'étude des relations entre la composition et la sensibilité des membranes ainsi qu'aux limites de détection qui les définissent. / The aim of the thesis is to study the physicochemical properties of the silver halide doped chalcogenide glasses for the possibility to use them as chemical sensors for quantitative analysis of Hg²⁺ ions. First, the macroscopic properties of AgY-As₂S₃ (Y = Br, I), HgS-GeS₂, AgI-HgS-As₂S₃ and AgI-HgS-GeS₂ glassy systems such as the densities and the characteristic temperatures (Tg and Tc) were measured and analyzed according to the glass compositions. Second, the transport properties were studied using complex impedance and dc conductivity. Measurements show that the silver halide doped chalcogenide glasses exhibit two drastically different ion transport regimes above the percolation threshold at xc ≈ 30 ppm : (i) critical percolation, and (ii) modifier-controlled regimes. Third, to unveil the composition/structure/property relationships, various structural studies were carried out. Raman spectroscopy, high-energy X-ray diffraction, neutron diffraction and small-angle neutron scattering experiments, together with RMC/DFT and AMID modelling were employed. Finally, the last part was a preliminary study of the characteristics of new chemical sensors. It was devoted to study the relationship between the membranes' composition and sensitivity but also detection limits.

L'objectif de ce travail a consisté à identifier des polluants émergents dans des eaux usées issues de stations d'épuration ainsi que dans le milieu naturel et à proposer une méthode de remédiation et un suivi de ces polluants. Dans un premier temps, nous avons identifié les polluants organiques contenus dans les échantillons d'eaux usées et issues du milieu naturel par chromatographie en phase liquide ou gazeuse couplée à une spectrométrie de masse, chromatographie en phase gazeuse par espace de tête statique et par spectrométrie par torche à plasma couplée à une spectrométrie de masse. Différents polluants ont été trouvés tels que les phtalates, des substances médicamenteuses, le cholestérol et des éléments de traces métalliques. Dans le but de piéger ces polluants, différents polymères de cyclodextrine (CD) solubles et insolubles dans l'eau ont été synthétisés et leurs capacités d'adsorption ont été évaluées. Après adsorption sur les polymères de CD, nous avons observé une diminution de la teneur en carbone organique total (COT) de l'effluent. Ces polymères se sont révélés être des adsorbants efficaces. Dans un second temps, des verres du système pseudo-ternaire Agl-HgS-As₂S₃ ont été synthétisés en ajoutant le composé le composé Agl dans le système pseudo-binaire HgS-As₂S₃. Ces verres de chalcogénures sont des membranes ionosélectives permettant de détecter les ions Hg²⁺ dans les effluents. Tout d'abord, nous avons défini le domaine vitreux des verres à l'aide de la diffraction des rayons X, ensuite les propriétés macroscopiques des verres ont été déterminées. Ainsi, les propriétés de transport ont été étudiées à l'aide de la spectroscopie d'impédance complexe montrant que l'ajout d'Agl dans le verre pseudo-binaire HgS-As₂S₃ provoque une augmentation de la conductivité ionique. Afin de comprendre ce phénomène, diverses études structurales ont été déployées par spectroscopie Raman, diffraction de neutrons et de rayon X haute énergie. Ces techniques ont montré que l'évolution de la conductivité ionique est dépendante de la structure du verre qui forme des chemins préférentiels de conduction. Enfin, différents capteurs avec différentes compositions sont testés afin de définir la sensibilité, la limite de détection et les coefficients de sélectivité en présence d'ions interférents. / The aim of this work was to identify the emerging pollutants in the effluents of wastewater treatment plants as well as in the natural environment, and to propose a method of remediation and monitoring of these pollutants. In the first part of the thesis, we have identified the organic pollutants contained in the wastewater samples using (i) gas and/or liquid chromatography coupled with a mass spectrometry, (ii) static-headspace gas chromatography, and (iii) inductively coupled plasma atomic emission spectroscopy. Different pollutants were found such as phthalates, drugs, cholesterol, and heavy metal traces. In order to trap these pollutants, various water soluble/insoluble cyclodextrin β-CD polymers have been synthesized and their adsorption capacities were evaluated. After the analysis of the effluent samples, we observed a decrease of the Total Organic Carbon (TOC). This decrease was attributed to the adsorption of pollutant by CD polymers which have proven to be effective adsorbents. The second part of the thesis included two main sub-parts : (i) a synthesis and characterization part and (ii) an application part. In the first sub-part, chalcogenide glasses in the pseudo-ternary Agl-HgS-As₂S₃ system have been synthesized by adding silver iodide "Agl" to the quasi-binary HgS-As₂S₃ system. The vitreous domain and the macroscopic properties of glass samples were determined. Electrical conductivity of glasses was studied using both the complex impedance spectroscopy and resistivity measurements ; it was found that adding Agl to the quasi-binary HgS-As₂S₃ alloy causes an increase in the ionic conductivity. Structural studies, using various techniques as Raman spectroscopy, neutron scattering and high-energy X-ray diffraction, have been performed in order to decipher the relation between both structural and transport properties in these glasses. In the second sub-part, the obtained glasses in the ternary system were used as membranes in chemical sensors dedicated to mercury detection in aqueous solution. As a result, various sensors with different compositions were tested to determine their corresponding sensitivity, detection limit and selectivity coefficients in the presence of interfering ions.

Estudos sistemáticos utilizando a técnica de SAXS foram realizados no síncrotom do LURE (Orsay) com feixe intenso de geometria pontua:, para descrever a cinética e as estruturas obtidas durante as etapas de transformação sol -> gel úmido -> gel seco -> vidros de sílica . As análises foram feitas em termos de uma lei de potência I = q-? cujo expoente está relacionado a dimensão fractal de massa ou de superfície das estruturas. Devido a polidispersividade das unidades espalhadoras as dimensões fractais verificadas podem ser resultados de dimensões reais encobertas por uma distribuição de tamanhos. As curvas obtidas para a cinética de gelificação e envelhecimento dos géis úmidos mostram expoentes que indicam fractalidade de massa e, posteriormente, de superfície. Uma microestrutura composta, que pode resultar de uma agregação limitada por difusão (DLA) seguido de agregação de agregados (C-C) foi observado nas soluções básicas. Por outro lado, os agregados ácidos parecem surgir do crescimento contínuo de cadeias até atingir a interligação com outros agregados com uma cinética que pode ser descrita pelo modelo DLA. No estado de aerogeis outras técnicas como picnometria de mercúrio e hélio, microscopia eletrônica de transmissão e adsorção de gás de nitrogênio, foram também aproveitadas. Nestes materiais encontramos em uma faixa estreita de escala, um expoente indicando fractalidade de massa, embora com superfície lisa. Os resultados estão de acordo com um modelo de estrutura que tem uma matriz de SiO2 densa. A estrutura fractal desaparece durante o tratamento térmico de densificação devido ao rearranjo estrutural. / Systematic SAXS studies have been performed at the LURE synchrotron (Orsay) using an intense beam of point-like cross-section to describe the kinetic and the structure obtained during the sol-> humid gel -> dry gel ->silica glass. The analysis were done in terms of a power law, I = q-? , whose exponent is related to mass and surface fractal dimensions of the structures. Due to polidispersity of the scattering units the found fractal dimensions can be \"smeared\" dimensions that result from a size distribution. All the kinetic and aging humids curves showed evidenced of fractal structures. A composed microstructure that can be originated by clustering of clusters (C-C) of primary units grown by diffusion limited-aggregation (DLA), was observed for basic gels. By other hand, the acidic cluster seems to grow continuously reaching gelation through crosslinking of the clusters. The DLA model seems to describe this process. In the aerogels study others techniques like density measurements using Hg and He, TEM and adsorption of N2 gas were done along with SAXS measurements. Here we could find a narrow range in which the system is a mass fractal, although its surface has been already smoothened. The results agree with a dense SiO2 matrix model. During the densification no fractal structure was verified due to structural rearrangements at high temperature.

Made available in DSpace on 2017-07-21T19:25:45Z (GMT). No. of bitstreams: 1 Ivan Mathias.pdf: 11996423 bytes, checksum: f3bdcfad9b494e72052f6a36c4a749d4 (MD5) Previous issue date: 2015-04-01 / Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico do Paraná / In this work two vitreous systems are studied, the lithium disilicate (LS2) and sodiumcalcium-silica with stoichiometry 2Na2O.CaO.3SiO2 (2N1C3S) and the glassceramics formed from these by heat treatment. Several properties were determined for the two systems as a function of crystallized volume fraction, from glass to fully crystallization (100%), highlighting the fracture toughness and the brittle-ductile transition, with the last two determined only for the LS2 glass-ceramic. Hardness and elastic modulus were obtained for the two glass-ceramics and their values increase with the crystallized volume fraction in the glass ceramic, with the exception of hardness of 2N1C3S, which has its maximum for the crystallized volume fraction of 9%. Thermal expansion coefficients were determined and are larger in the LS2 glassy phase and in the 2N1C3S crystalline phase, thereby generating mean residual stresses obtained by Selsing model of -76 MPa for the LS2 (compression in the crystal) and 232 MPa for the 2N1C3S (traction in the crystal). The indentation fracture toughness was also determined for the two systems using the Anstis' and Niihara's models. The results show an increase of indentation fracture toughness with the crystalline volume fraction for LS2 glass-ceramic and also a dependence with indentation load. As for the 2N1C3S glass-ceramic, indentation fracture toughness are reduced at intermediate crystalline fractions, which is attributed to residual stresses arising from the difference between the thermal expansion mismatch between the glass and the crystalline phases. LS2 glass-ceramic flexural strength increases with the crystalline fraction, from 103 ± 3 MPa for the glass to 260 ± 20 MPa for the fully crystallized sample. Without the removal of the crystallization surface layer, this value rises to 290 ± 20 MPa. The increase in flexural strength in the first 20% of the crystallized fraction is more pronounced. As the size of the precipitates was kept constant, this increase can be related only to the increase in the crystallized fraction. The residual stress in the matrix, the critical radius of spontaneous cracking of the crystals and the crack mean free path between the precipitates were considered in the analysis of the increase in flexural strength. The existence of pores in the samples was a factor that limited its resistance. The fracture toughness (KDTIC) a function of the crystallized fraction was determined for LS2 glassceramics using the double torsion technique. It was found that KDTIC increases with the crystallized fraction, from 0.75 MPa.m1/2 for the glass to about 3.50 ± 0.05 MPa.m1/2 for the fully crystallized sample, a significant increase of approximately five times. Several factors were analyzed as possible causes of the increase in KDTIC. The experimental data are better adjusted with a recently proposed model with one adjustable parameter that relates the ratio of the crystal and glass areas to the crystallized volume fraction. The brittle-ductile transition (BDT) of LS2 glass and glass-ceramic samples (39% crystallized volume fraction) were determined for three different strain rates. BDT temperatures were determined for each strain rate.Activation energies of BDT for the glass and glass-ceramic were obtained, which were 5.2 ± 0.2 eV and 7 ± 2 eV. It was found that BDT activation energy in glass resembles the activation energy of the LS2 viscous flow, thus concluding the BDT in LS2 is governed by viscous flow of the glass matrix. Finally, the fact of the activation energy of the glass ceramic be larger than the glass was attributed to the fact that the viscosity of the vitreous matrix is "hindered" by the presence of crystalline precipitates. A viscosity model of a rigid spheres composite was used as an analogy to explain this observation. / No presente trabalho são estudados dois sistemas vítreos, o dissilicato de lítio (LS2) e o soda-cal-sílica de estequiometria 2Na2O.CaO.3SiO2 (2N1C3S), bem como os vitrocerâmicos formados a partir destes através de tratamentos térmicos. Diversas propriedades foram determinadas para os dois sistemas em função da fração cristalizada, desde vidro até os 100%, com destaque para a tenacidade à fratura e a transição frágil-dúctil, sendo estas últimas determinadas somente para o LS2. Dureza e módulo de elasticidade foram obtidos para os dois sistemas e seus valores aumentam com a fração volumétrica cristalizada no vitrocerâmico, com exceção da dureza no 2N1C3S, que tem seu máximo para a fração cristalizada de 9%. Os coeficientes de expansão térmica foram determinados e são maiores na fase vítrea do LS2 e na fase cristalina do 2N1C3S, gerando assim tensões residuais médias obtidas pelo modelo de Selsing de -76 MPa para o LS2 (compressiva no cristal) e 232 MPa para o 2N1C3S (trativa no cristal). A tenacidade à fratura por indentação (KC) foi determinada também para os dois sistemas, sendo utilizados os modelos de Anstis e Niihara. Os resultados mostram um aumento com a fração cristalina para o LS2 e também uma dependência com a carga utilizada no teste. Já para o 2N1C3S, os valores de KC sofrem uma redução em frações cristalinas intermediárias, comportamento atribuído às tensões residuais oriundas da diferença entre os coeficientes de expansão térmica e anisotropias elásticas do material. Os ensaios de resistência à flexão mostraram que para o LS2 a resistência aumenta com a fração cristalina, passando de 103 ± 3 MPa para o vidro para 260 ± 20 MPa para a amostra totalmente cristalizada. Se não removermos a camada de cristalização superficial, este valor sobe para 290 ± 20 MPa. O aumento da resistência à flexão nos primeiros 20% da fração cristalizada é mais pronunciado. Como o tamanho dos precipitados foi mantido constante, esse aumento pode ser relacionado apenas ao aumento na fração cristalizada. A tensão residual na matriz, o raio crítico dos cristais para trincamento espontâneo e o livre caminho médio da trinca entre os precipitados foram considerados na análise do aumento da resistência à flexão. A existência de poros nas amostras foi um fator que limitou a sua resistência. Caso amostras sem poros fossem feitas, um aumento em torno de 20 a 30% da resistência seria obtido. A tenacidade à fratura (KDTIC) foi determinada para o LS2 pela técnica de torção dupla em função da fração cristalizada. Foi verificado que KDTIC aumenta com a fração cristalizada, passando de 0,75 MPa.m1/2 para o vidro para cerca de 3,50 ±0,05 MPa.m1/2 para a amostra totalmente cristalizada, um aumento significativo de aproximadamente cinco vezes. Diversos fatores foram apontados como possíveis causas do aumento da tenacidade e foi verificado que os fatores considerados de forma isolada não são suficientes para descrever completamente o aumento na tenacidade. Os dados experimentais são melhor ajustados com um modelo de um parâmetro de ajuste recentemente proposto que relaciona a razão entre as áreas dos cristais e do vidro na superfície de fratura com a fração cristalizada. A transição frágil-dúctil (TFD) de amostras vítreas e vitrocerâmica (39% fração cristalizada) de LS2 foram determinadas para três taxas de deformação. Foram determinadas as temperaturas de TFD para cada uma das taxas e foi verificada uma dependência com a taxa de deformação. Foram calculadas as energias de ativação para a TFD no vidro e vitrocerâmico, sendo elas de 5,2 ± 0,2 eV e 7 ± 2 eV. Verificou-se que a energia de ativação da TFD no vidro se assemelha a energia de ativação do escoamento viscoso do LS2, concluindo assim que a TFD no LS2 é governada pelo escoamento viscoso da matriz vítrea. Por fim, o fato da energia de ativação do vitrocerâmico ser maior que do vidro foi atribuída ao fato de que a viscosidade da matriz vítrea seria "dificultada" pela presença dos precipitados cristalinos. Um modelo de viscosidade de um compósito com esferas rígidas foi utilizado como analogia para explicar essa observação.

Dans la présente thèse de doctorat je présente des résultats concernant des modèles désordonnés et frustrés venant de la physique statistique et de l'optimisation combinatoire. Comme application de la théorie des verres de spins, j'étudie le modèle de Blume, Emery et Griffiths désordonné et frustré. Ce modèle est traité dans l'approximation de champ moyen dans le cadre de la méthode des répliques A l'aide de l'Ansatz symétrique dans les répliques je présente une solution numérique complète puis je discute des effets de brisure de cette symétrie La stabilité de la solution symétrique a été Rudik et les régions instables identifiées Le diagramme de phase exhibe des transitions de premier et de second ordre. Le point tricritique persiste dans le modèle frustré, Ce qui est en accord avec des travaux antérieurs une version du modèle BEG avec un potentiel chimique désordonné a également été étudiée. les calculs confirment que le point tricritique apparaît à plus basse température quand il y a du désordre. Ensuite je considère le problème de la bipartition d'un graphe. Ce problème correspond du point de vue de la physique statistique h un verre de spins soumis h une contrainte d'aimantation totale nulle. je considère les propriétés statistiques des solutions de faible énergie engendrées par des algorithmes heuristiques. de tels algorithme sont en général conçus pour résoudre des problèmes d'optimisation combinatoire qui sont NP- difficiles. Plusieurs heuristiques ont 60 implémentées pour le problème de la bipartition de graphe. des lois d'échelle ont été obtenues : en particulier la moyenne et la variance du coût obéissent A une loi linéaire en N. Par conséquent le coût obtenu par des heuristiques est une quantité auto-moyennante. je suggère que cette propriété est générale valable aussi pour les solutions aléatoires pour les solutions quasi-optimales et pour les solutions optimales. En outre je propose une procédure pour comparer des algorithmes heuristiques. Cette procédure tient compte de la qualité de la solution aussi bien que du temps de calcul utilisé. Dans la troisième partie de ma thèse j'ai étudié en détail les propriétés h température nulle des verres de spins sur des graphes aléatoires lacunaires avec une coordination fixe. les verres de spins sur de tels graphes peuvent être considérés comme une approximation aux vrais verres de spins qui est plus réaliste que le modèle de Sherrington et Kirkpatrick. J'ai conçu un nouvel algorithme pour trouver les états fondamentaux. Aussi je teste numériquement une conjecture de Banavar, Sherrington et Sourlas qui donne la densité d'énergie du fondamental dans la limite de grande taille en fonction de la coordination. La distribution du paramètre d'ordre se révèle être non triviale et les données présentent une forte indication de la présence d'ultramétricité pour toutes les valeur de la coordination. Ces résultats confirment que les propriétés particulières des verres de spin, déduites an niveau de l'approximation de champ moyen dans le cadre du modèle de Sherrington et Kirkpatrick, sont aussi présentes pour des modèles plus réalistes comme les verres de spins sur des graphes aléatoires lacunaires avec une coordination fixe.

Bulk metallic glasses (BMGs) are a new class of structural materials and exhibit unique combinations of mechanical properties. As a result, their mechanical behavior has been an active area of scientific pursuit in the recent past and considerable emphasis has been paid to understand plastic deformation in them. It is now well accepted that shear transformation zones (STZs), aided by free volume, are the fundamental carriers of plasticity. At a microscopic level, deformation at low temperatures and high stresses tends to localize into shear bands. Most BMGs posses high fracture toughness despite high yield strengths and poor global ductility. However, the micro-mechanisms of fracture and fatigue in this new class of materials are not fully understood yet. The overall objective of this study is to provide insights into the fracture and fatigue response of amorphous alloys, which is important both from scientific and technological perspectives. The key questions we seek to answer through this study are the following. Do amorphous alloys undergo a ductile-brittle transition (DBT), and if so what are the reasons for it? What are the parameters that influence fatigue crack initiation in amorphous alloys and whether fatigue life can be improved by surface treatments? A related question is whether the BMGs are susceptible to deformation-induced crystallization (DIC). A Zr-based BMG, Zr41.2Ti13.75Cu12.5Ni10Be22.5 was utilized to conduct this study. By comparing the fracture and fatigue behaviors in the as-cast and annealed states {annealing was carried out below the glass transition temperature (Tg) because of established embrittlement effects}, we seek to provide answers for the questions posed above. We begin by examining the influence of temperature on the toughness of BMGs. Impact toughness measurements show that the annealed samples, which are brittle at room temperature, recover the lost toughness beyond a critical temperature (TDB) and exhibit a sharp DBT. However, the hardness remains unaffected across the TDB. Fractography reveals nano-scale patterning and cleavage fracture in the brittle state, while the formation of thick vein-patterns and shear fracture are characteristics of the ductile state of the annealed samples. We explore various micro-mechanistic possibilities for explaining the features of this transition, including a critical Poisson’s ratio-toughness correlation. Next, to understand the origins of fatigue crack initiation, we study the un-notched fatigue response of as-cast and sub-Tg annealed Zr-based BMG specimens. Because of embrittlement and nano-crystallization at the crack initiation region, the annealed specimens exhibit a lower fatigue life than the as-cast specimens. Shot-peening of the as-cast specimens did not exhibit significant improvement in their fatigue performance because of competing effects between the compressive residual stress field (CRSF) and deformation-induced softening. To further investigate surface and repeated loading effects, the tribological response of the as-cast Zr-based BMG was compared with specimens annealed above and below the Tg. A good correlation between the hardness (increasing as a function of the annealing temperature) and wear rate was obtained. The formation and peeling of the oxide layer formed during testing was the primary wear mechanism in all the specimens. Lastly, crystallization was observed within the deformed region of the as-cast Zr-based BMG repeatedly scratched with a sharp diamond indenter. But, transmission electron microscopy (TEM) does not reveal any evidence of crystallization within the indents formed within an electron transparent film formed by laser deposition of the as-cast Zr-based BMG. Absence of crystallization in deformed regions obtained by designing critical experiments, which avoid artifacts generated during sample preparation, suggests that the occasional observation of DIC might be an exception rather than the rule in BMGs.

The thesis describes the study of slow dynamics of confined polymers and soft colloids. We study the finite size effect on the dynamics of glassy polymers using newly developed interfacial microrheology technique. Systematic measurement have been performed to address the issue of reduction of glass transition under confinements. Slow and heterogeneous dynamics are the underlined observed behavior for dynamics in confined glassy polymers. The slow relaxation dynamics and dynamical heterogeneity in polymer grafted nanoparticles (PGNPs) systems were studied using advanced X - ray photon correlation spectroscopy (XPCS) techniques. Our studies presented in this thesis on dynamics of polymer grafted nanoparticle systems in melts and solution are the first attempt to study them experimentally. Thus our work shed the light about new technique to study confined system more accurately and explore new soft colloidal system to study fascinating dynamics and interesting phase behavior. In Chapter 1, we provide the theoretical background along with brief review of the literature for understanding the results presented in this thesis. The details of the experimental set up and their operating principle along with the details of the experimental conditions are provided in Chapter 2. In Chapter 3 we present our newly developed technique (interfacial microrhelogy) and its consequences to study the complex fluids at interface. Chapter 4 discusses the concentration and temperature dependent glassy dynamics in confined glassy polymers. In Chapter 5 we provide the structural and dynamical study of polymer grafted nanoparticles in melts and solutions. We provide the summary of our result and the future prospective of the work in Chapter 6. Chapter-1 provides the ground work and theoretical aspects for understanding the results presented in this thesis. It starts with the discussion about the slow dynamics of complex fluids and transit to dynamic behavior of polymer in confinement, glassy dynamics in confinements . This also discusses the basic aspects of studying viscoelastic properties using rheology, interface rheology, microrheology, interface microrheology techinques. In continuation it discusses structure and dynamics of different soft colloids investigated for last decade and then theoretical aspects of XPCS is discussed. Towards the end of this Chapter, we discuss the procedure to explain and understand systems dynamical heterogeneity near glass like phase transition. Chapter-2 contains the details of the experimental techniques which has been used for the study of confined polymers and soft colloids. Brief introduction to basic principles of the measurements followed by details of the material and methods have been provided. Chapter-3 we discuss the interafacial microrheology of different complex fluids and advantages of the techniques is discussed in Chapter 3. This includes discussion about the technique sensitivity at the surface using quantum dots (QDs) as a probe and about the configuration of the QDs at/on monolayer. Later on establishment of the technique has been demonstrated through easurements on arachidic acid, poly(methylmethacrylate) (PMMA), poly(vinylacetate) (PVAc), poly(methylacrylate) (PMA) monolayers. The extracted subdiffusive nature of QDs in on monolayers through mean square displacement has been explained using fractional Brownian motion model. Towards the end of the chapter we discuss about the extraction of real and imaginary elastic modulus from mean square displacement data using generalized Stokes-Einstein relation for the quasi two dimensional systems and explains about the possible viscoelastic transition in the different monolayers. The concentration and temperature dependent glassy dynamics of confined polymers (PMMA) are discussed in Chapter-4. We demonstrate the microscopic nature of spatio-temporal variation of dynamics of glassy polymers confined to a monolayer of 2 3 nm thickness as a function of surface density and temperature. It illustrates the systems dynamical heterogeneity and explain the observed large reduction of glass transition temperature in confined system through finite size effect. In Chapter 5 we discuss the result based on systematic studies of dynamics of PGNPs in melts and solutions. In addition it also illustrates the structural anisotropy and anomalous dynamical transitions in binary mixture of PGNPs and homopolymers in good solvent condition. It provides temperature and wave vector dependent XPCS measurements on polymer grafted nanoparticles with the variation of functionality. The functionality ( f ) dependent nonmonotonic relaxation in melts of PGNPs and solvent quality dependent non monotonic relaxation of PGNPs system have been elaborated in the continuation. We present possible phase behavior of PGNPs system in good solvent with addition of homopolymer of two different molecular weight. Chapter 6 contains the summary and the future perspective of the work presented.

Στα πλαίσια της παρούσας διδακτορικής διατριβής έγινε προσπάθεια να μελετηθούν μέσω φασματοσκοπίας Raman τα δομικά και τα δυναμικά χαρακτηριστικά διαφόρων ανόργανων υγρών και γυαλιών σε μεγάλο θερμοκρασιακό εύρος. Αναπτύχθηκαν μέθοδοι, με τις οποίες επιτεύχθηκε η φασματοσκοπική μελέτη υλικών υψηλής καθαρότητας σε θερμοκρασίες έως και 2000oC. Τα φασματοσκοπικά δεδομένα Raman διαφόρων γυαλιών και υγρών περιορίζονται σε θερμοκρασίες έως 1000oC λόγω διαφόρων πειραματικών δυσκολιών που παρουσιάζονται σε μετρήσεις δονητικής φασματοσκοπίας σε υψηλές θερμοκρασίες. Η κυριότερη δυσκολία είναι η πολύ ισχυρή ακτινοβολία μέλανος σώματος, η οποία υπερκαλύπτει το ασθενές σήμα Raman μην επιτρέποντας από κάποιο σημείο και πέρα τη λήψη των φασμάτων. Προκειμένου να ξεπεραστούν οι πειραματικές δυσκολίες αναπτύχθηκε στα πλαίσια της παρούσας διδακτορικής διατριβής ένα σύστημα Raman που συνδυάζει τις «τεχνικές ελλείψεως δοχείου» (“containerless techniques”) και τη χρήση ενός laser υπερύθρου (CO2-laser) ως θερμαντική πηγή, επιτρέποντας τη λήψη φασμάτων για πρώτη φορά σε θερμοκρασίες έως και 2000oC. Οι «τεχνικές ελλείψεως δοχείου» χωρίζονται σε δύο κατηγορίες, την «τεχνική αιώρησης» του δείγματος (“levitation technique”) όπου το υλικό αιωρείται υπό μορφή υγρής σταγόνας σε κατάλληλης γεωμετρίας ακροφύσιο με χρήση προωθητικού αερίου και την «τεχνική αυτοϋποστήριξης» του δείγματος (“self-support technique”) όπου το υγρό υποστηρίζεται από τη στερεά φάση του ίδιου υλικού. Το βασικότερο πλεονεκτήμα του συνδυασμού της φασματοσκοπίας Raman, των «τεχνικών ελλείψεως δοχείου» και της θέρμανσης με χρήση ενός laser υπερύθρου είναι ο σημαντικός περιορισμός της θερμικής εκπομπής, αφού απουσιάζει η ισχυρή θερμική εκπομπή του φούρνου, δίνοντας τη δυνατότητα μελέτης υψηλότηκτων υλικών αποφεύγοντας μολύνσεις, ετερογενή πυρηνοποίηση, αντιδράσεις μεταξύ υλικών και δοχείων σε υψηλές θερμοκρασίες επιτρέποντας την εφαρμογή της επιθυμητής ατμόσφαιρας στο υπό εξέταση υλικό. Μελετήθηκαν με δονητική φασματοσκοπία Raman μη-οξυγονούχες (ZnCl2, ZnBr2, xZnCl2-(1-x)AlCl3) και οξυγονούχες (SiO2, K2Si4O9, xCaO-(1-x)SiO2, xCaO-(1-x)Al2O3) ενώσεις με ενδογενείς πειραματικές δυσκολίες, όπως πολύ υψηλά σημεία τήξης (~2000oC για την περίπτωση των οξειδίων), υψηλή υγροσκοπικότητα, μεγάλες τάσεις ατμών κ.α. ξεπερνώντας τους διαφόρους πειραματικούς περιορισμούς και πραγματοποιήθηκε προσπάθεια σύνδεσης ανάμεσα στο δομικό και δυναμικό χαρακτήρα τους λαμβάνοντας φάσματα Raman σε θερμοκρασιακό εύρος που περιλαμβάνει την κρυσταλλική, υαλώδη, υπέρψυκτη και υγρή κατάσταση. Από τις πληροφορίες που λαμβάνονται για τα τοπικά πολύεδρα συναρμογής σε μικρής κλίμακας τάξη μέσω φασματοσκοπίας Raman γίνεται προσπάθεια να διασαφηνιστεί ο ρόλος των «τροποποιητών του δικτύου» (“network modifiers”) κατά την εισαγωγή τους σε υλικά με πλήρως πολυμερισμένες, τρισδιάστατες, δικτυακές τετραεδρικές δομές (“network formers”). Η δομή σε ενδιάμεσης κλίμακας τάξη (φάσμα Raman χαμηλών συχνοτήτων), η κορυφή Boson, η ημιελαστική κορυφή και χαρακτηριστικά όπως ο εύθραυστος/ισχυρός χαρακτήρας και η μη-εκθετική/εκθετική συμπεριφορά των υπό μελέτη υλικών προσδιορίστηκαν συναρτήσει της θερμοκρασίας και τα αποτελέσματα αναλύονται στα πλαίσια θεωρητικών και φαινομενολογικών μοντέλων που αφορούν την υαλώδη μετάβαση. / e present the Raman spectroscopic results concerning the structure and the dynamics of several inorganic melts and glasses in a broad temperature range. The development of pioneering methods appropriate for high temperature material research and their combination with Raman spectroscopy provided spectroscopic results of high-purity materials at temperatures up to 2000oC. High-temperature Raman data are limited at temperatures below 1000oC due to several experimental difficulties concerning high-temperature vibrational measurements. The main difficulty is the intensive black body radiation, which overwhelms the weak Raman signal and consequently no spectrum can be recorded. In order to overcome the experimental difficulties, we developed a Raman setup, which combines the “containerless techniques” with the use of an infrared laser (CO2-laser) as a heating source permitting the recording of Raman spectra at temperatures up to 2000oC. The “containerless techniques” are divided in two main categories. The “levitation technique”, where the liquid sample is levitated using a nozzle with the appropriate geometry and a supporting gas and the “self-support technique”, where the liquid sample is supported from the solid part of the same material. The main advantage of the Raman spectroscopy-containerlees techniques-laser heating combination is the effective limitation of the black body radiation giving the opportunity to use the desirable atmosphere on the sample and study high-melting materials preventing contamination, heterogeneous nucleation, reactions between materials and containers at high temperatures. We studied several non-oxide (ZnCl2, ZnBr2, xZnCl2-(1-x)AlCl3) and oxide (SiO2, K2Si4O9, xCaO-(1-x)SiO2, xCaO-(1-x)Al2O3) systems with intrinsic experimental difficulties, such as high melting points (~2000oC), hygroscopic nature, high vapor pressures etc. We recorded Raman spectra in extensive temperature range covering the crystalline, the glassy, the supercooled and the molten state in order to elucidate the structure and the involved dynamics of these materials. Information concerning the local coordination polyhedra in short range order have been used for clarifying the role of “network modifiers” inside the fully polymerized threedimensional tetrahedral networks (“network formers”). The structure in medium range order (low-frequency Raman spectrum), the Boson peak, the Quasi-Elastic line and characteristics such as the fragile/strong character and the non-exponential/exponential behavior of these materials have been put under focus and the results are discussed in the framework of the current phenomenological status of the field.

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