In this thesis, the microstructure of organic photovoltaic APFO-3:PC61BM bulk-heterojunction blends was examined. Earlier studies have focused on the microstructure after spin coating. This thesis aims to give a better insight into microstructural degradation as the films are annealed above the glass transition temperature, Tg, and the mixture approaches thermodynamic equilibrium. Electro- and photoluminescence studies indicate that the polymer and PC61BM are intermixed on a scale shorter than the exciton diffusion length of 10 nm, even when annealed above Tg. The temperature stability of APFO-3:PC61BM was also investigated with respect to the molecular weight of the polymer. The photovoltaic performance of these blends was found to be stable up to temperatures approaching the glass transition temperature, especially if a high molecular-weight APFO-3 grade was used.   The crystallization of PC61BM was also investigated. Above Tg, PC61BM crystallization was found to commence, albeit slowly at temperatures close to Tg. At elevated temperatures instead, micrometer sized crystals were observed to form. It was also noted that illumination while annealing APFO-3:PC61BM thin films above Tg affected PC61BM crystallization, the origin of which is so far unclear although chemical degradation could be largely excluded.

Estimating the integrated volatility of high frequency realized prices is an important issue in microstructure literature. Bandi and Russell (2006) derived the optimal-sampling frequency, and Zhang et al. (2005) proposed a "two-scales estimator" to solve the problem. In this study, we propose a new estimator based on a signal to noise ratio statistic with convergence rate of Op (n^(−1/ 4) ). The method is applicable to both constant and stochastic volatility models and modi¡Âes the Op (n^(−1/ 6) ) convergence rate of Zhang et al. (2005). The proposed estimator is shown to be asymptotic e¡Ócient as the maximum likelihood estimate for the constant volatility case. Furthermore, unbiased estimators of the two elements, the variance of the microstructure noise and the fourth moment of the realized log returns, are also proposed to facilitate the estimation of integrated volatility. The asymptotic prop- erties and e®ectiveness of the proposed estimators are investigated both theoretically and via simulation study.

Aluminum alloys are widely used in many manufacturing areas due to good castability, lightness and mechanical properties. The purpose of this research is to investigate copper’s influence on an Al-Si-Mg alloy (A356). Copper in the range of 0.6 – 1.6 wt. % has been used in an A356 aluminum based alloy. In this work a simulation of three different casting processes, sand-, die- and high pressure die-casting has been employed with the help of gradient solidification equipment. The microstructure of the samples has been studied by optical and scanning electron microscopy. Materials in both as-cast and heat treated states have been investigated through tensile test bars  to get the mechanical properties of the different conditions.   Questions that have been subjected to answer are what influence does copper have on the plastic deformation and on fracture behavior and whether there is a relationship between the content of copper and increased porosity or not; and in that case explore this relationship  between the amount of copper and the mechanical behaviour.   It has been analyzed that a peak of mechanical properties is obtained with a content about 1.6 wt. % copper. The increment of copper seems to have a remarkable impact on the mechanical properties and especially after the aging process showing a large raise on the ultimate tensile strength and yield strength. Relationship between the copper content and increased porosity could not be found.

With the increased interest in bainitic steels, fundamental understanding of the bainite transformationis of major importance. Unfortunately, the research on bainite has been hampered by an oldcontroversy on its formation mechanism. Over the years two quite different theories have developedclaiming to describe the bainite transformation i.e. the diffusionless and the diffusion controlledtheory. In this thesis, attention is directed towards fundamental understanding of the bainitetransformation and both experimental and theoretical approaches are used in order to reveal its truenatureIn the first part of this thesis the symmetry in the Fe-C phase diagram is studied. It is based on ametallographic mapping of microstructures using light optical microscopy and scanning electronmicroscopy in a high carbon steel. The mapping revealed symmetries both with respect to temperatureand carbon content and an acicular eutectoid with cementite as the leading phase was found andidentified as inverse bainite. By accepting that all the eutectoid microstructures forms by diffusion ofcarbon, one may explain the existence of symmetries in the Fe-C phase diagram. Additional supportof its existence is obtained from an observation of symmetries in an alloyed steel. From the performedwork it was concluded that the existence of symmetries among the eutectoid microstructures fromaustenite supports the idea that bainite forms by a diffusion controlled transformation.In the second part the growth of bainite is considered. An experimental study using laser scanningconfocal microscopy was performed and growth rates of the transformation products from austenite ina high carbon, high chromium steel was analysed. The growth rate measurements reveals the kineticrelation between Widmanstätten cementite and the acicular eutectoid previously identified as inversebainite which confirms its existence and the conclusions drawn in the first part. In addition, in-situobservations of bainite formation below Ms provide additional support for the diffusion controlledtheory for bainite formation.The final part of the work is a study of the critical conditions for the formation of acicular ferrite.Based on experimental information found in the literature a thermodynamic analysis is performed inview of the two theories. The results demonstrate that the governing process for Fe-C alloys cannot bediffusionless but both kinds of processes can formally be used for predicting Bs temperatures for Fe-Calloys. / <p>QC 20130503</p>

Le but de cette thèse est d'approfondir les connaissances académiques sur les variations jointes des actifs financiers à haute fréquence en les analysant sous un point de vue novateur. Nous tirons profit d'une base de données de prix tick-by-tick pour mettre en lumière de nouveaux faits stylises sur la corrélation haute fréquence, et également pour tester la validité empirique de modèles multivariés. Dans le chapitre 1, nous discutons des raisons pour lesquelles la corrélation haute fréquence est d'une importance capitale pour le trading. Par ailleurs, nous passons en revue la littérature empirique et théorique sur la corrélation à de petites échelles de temps. Puis nous décrivons les principales caractéristiques du jeu de données que nous utilisons. Enfin, nous énonçons les résultats obtenus dans cette thèse. Dans le chapitre 2, nous proposons une extension du modèle de subordination au cas multivarié. Elle repose sur la définition d'un temps événementiel global qui agrège l'activité financière de tous les actifs considérés. Nous testons la capacité de notre modèle à capturer les propriétés notables de la distribution multivariée empirique des rendements et observons de convaincantes similarités. Dans le chapitre 3, nous étudions les relations lead/lag à haute fréquence en utilisant un estimateur de fonction de corrélation adapte aux données tick-by-tick. Nous illustrons sa supériorité par rapport à l'estimateur standard de corrélation pour détecter le phénomène de lead/lag. Nous établissons un parallèle entre le lead/lag et des mesures classiques de liquidité et révélons un arbitrage pour déterminer les paires optimales pour le trading de lead/lag. Enfin, nous évaluons la performance d'un indicateur basé sur le lead/lag pour prévoir l'évolution des prix à court terme. Dans le chapitre 4, nous nous intéressons au profil saisonnier de la corrélation intra-journalière. Nous estimons ce profil sur quatre univers d'actions et observons des ressemblances frappantes. Nous tentons d'incorporer ce fait stylise dans un modèle de prix tick-by-tick base sur des processus de Hawkes. Le modèle ainsi construit capture le profil de corrélation empirique assez finement, malgré sa difficulté à atteindre le niveau de corrélation absolu.

Entre l'enfournement des matières premières sur le bain liquide et le verre la sortie du four, on peut s'interroger sur les étapes par lesquelles le mélange vitrifiable passe avant d'être transformé en un liquide homogène. D'un point de vue chronologique, l'élaboration du verre peut être considérée en trois étapes : l'état initial du mélange granulaire avant réaction ; l'étape de réaction chimique entre les différents constituants ; un liquide avec ses inclusions gazeuses et solides (bulles et quartz résiduel). Chacune de ces étapes concerne un domaine spécifique, avec un fort couplage entre physique et chimie. Aborder la façon dont réagissent ces matières premières ensemble et comment la microstructure peut influencer le chemin réactionnel suivi globalement par le mélange est indispensable pour savoir a chaque moment de la transformation quels mécanismes sont mis en jeu. Cela permettrait de corriger certains problèmes liés à l'élaboration d'un verre industriel (bulles piégé es dans le liquide, grains de quartz non incorporés au liquide, hétérogénéité chimique du liquide). La variété de phénomènes possibles lors de la fusion d'un mélange vitrifiable industriel nous poussera à simplifier le système un maximum, afin d'être capable de relier l'évolution de la microstructure à celle de la chimie du matériau. C'est la raison pour laquelle nous avons décidé d'étudier le système SiO2-Na2CO3. Nous avons de plus utilisé des grains tamisés dans des tranches précises, afin de pouvoir relier la transformation chimique du mélange à la répartition spatiale initiale du mélange granulaire.

Sulfide Stress Cracking (SSC) resistance of the newly developed API-X100 High Strength Low Alloy (HSLA) steel was investigated in the NACE TM0177 "A" solution. The NACE TM0177 "A" solution is a hydrogen sulfide (H2S) saturated solution containing 5.0 wt.% sodium chloride (NaC1) and 0.5 wt.% acetic acid (CH3COOH). The aim of this thesis was to study the effect of microstructure, non-metallic inclusions and alloying elements of the X100 on H2S corrosion and SSC susceptibility. The study was conducted by means of electrochemical polarization techniques and constant load (proof ring) testing. Microstructural analysis and electrochemical polarization results for X100were compared with those for X80, an older generation HSLA steel. Uniaxial constant load SSC testing was conducted using X100 samples and the results were compared with those reported for older generation HSLA steels. Addition of H2S to the NACE TM0177 "A" solution increased the corrosion rate of X100from 51.6 to 96.7 mpy. The effect of H2S on the corrosion rate was similar for X80. The corrosion rate for X80 increased from 45.2 to 80.2 mpy when H2S was added to the test solution. Addition of H2S enhanced the anodic kinetics by forming a catalyst (FeHSads) on the metal surface and as a result, shifted the anodic polarization curve to more current densities. Moreover, the cathodic half cell potential increased due to the decrease in pH, from 2.9 to 2.7, which shifted the cathodic polarization curve to more current densities. The increase in both the anodic and cathodic currents, after H2S addition, caused the rise in the corrosion current density. In H2S saturated NACE TM-0177 "A" solution, the X100 steel corrosion rate was higher than the X80 steel by 20%. Longer phase boundaries and larger nonmetallic inclusions in the X100 microstructure generated more areas with dissimilar corrosion potentials and therefore, a stronger driving force for corrosion. Higher density of second phase regions and larger nonmetallic inclusions acted as an increased cathode area on the X100 surface which increased the cathodic current density and consequently, increased the corrosion current density. Proof ring tests on the X100 gave a threshold stress value, C5th, of 46% YS, 343.1 MPa(49.7 ksi). The main failure was caused by SSC cracking. SSC nucleated at corrosion pits on the metal surface and microcracks in the metal body and propagated perpendicular to the applied stress. Hydrogen Induced Cracking (HIC) was observed in the X100. HIC cracks nucleated at banded martensite-ferrite interfaces and propagated along the rolling direction parallel to the applied tensile stress through the softer ferrite phase. When compared to older HSLA grades, the X100 tested in this study had a high SSC susceptibility and therefore, is not be recommended for H2S service applications. The high X100 SSC susceptibility was caused by the material high corrosion rates in H2Smedia which formed corrosion pits that acted as crack initiation sites on the metal surface and provided more hydrogen that migrated into the steel. In addition, the X100 inhomogeneous microstructure provided a high density of hydrogen traps in front of the main crack tip which promoted SSC microcrack formation inside the metal. Microcracks in the metal body connected with the main crack tip that originated from corrosion pits which assisted SSC propagation.

Ce travail s'inscrit dans le contexte de la modélisation et de la prévision de la durée de vie des aubes de turbine haute pression des turbines à gaz. Ces pièces sont réalisées en superalliage monocristallin base nickel tel que le MC2, matériau principal de l'étude. En service, ces dernières sont soumises à des conditions extrêmes de température et de contrainte. Des régimes d'urgence, dits O.E.I. (.One Engine Inoperative.), peuvent aussi survenir sur un hélicoptère bi-moteur : un des deux moteurs s'arrête ce qui provoque une augmentation de la température en sortie de chambre de combustion pour le moteur restant en fonctionnement. Dans le cadre de ce travail, le comportement anisotherme en fluage et en fatigue/fluage du superalliage monocristallin a été étudié afin de déterminer les répercussions des surchauffes à 1200. sur le comportement mécanique ultérieur à 1050. Il a pu être déterminé que le temps de pré-endommagement avant la surchauffe joue un rôle capital vis-à-vis de la durée de vie post-surchauffe. Cette influence est très dépendante de l'état microstructural du matériau sur lequel est réalisée la surchauffe (morphologie des précipités γ ', contraintes de cohérence entre les phases γ et γ '). Du point de vue des mécanismes d'endommagement, il a aussi été constaté que le niveau de température a une importance majeure en modifiant les contraintes de cohérence entre les deux phases γ et γ '. L'état microstructural jouant un rôle majeur sur la durée de vie lors des essais isothermes et anisothermes, une étude de l'évolution de la microstructure γ /γ' autour des particules de phase intermétallique μ a été faite, ainsi qu'une mesure expérimentale de l'évolution de la porosité, mesurée par des analyses tomographiques grâce à des essais de fluage multi-interrompus à haute température. Ceci a permis d'aboutir à un paramètre de dommage, à la frontière entre métallurgie et mécanique, prenant en compte les évolutions microstructurales. La coalescence orientée se déroulant à haute température, connue sous le nom de mise en radeaux, a une forte influence sur le comportement et l'endommagement des superalliages monocristallins. Ainsi, un nouveau modèle de mise en radeaux, prenant en compte la vitesse de sollicitation, a été implémenté dans le modèle de plasticité cristalline couplé comportement/endommagement Polystar. Ceci a permis d'améliorer la modélisation des essais longs. D'autres modifications ont été effectuées afin d'améliorer la modélisation lors des essais cycliques et de relaxation. Ce nouveau modèle a été testé et validé sur une éprouvette bi-entaillée générant des champs mécaniques multiaxiaux pendant un essai de fluage complexe anisotherme.

Le soudage par faisceau d'électrons d'alliages à durcissement structural de la série 7xxx induit des modifications importantes de leur microstructure, et par conséquent de leur comportement mécanique. Cette étude visait à formuler une loi de comportement incluant l'endommagement de structures soudées par une approche locale de la rupture. Pour cela, la microstructure de la soudure et les propriétés mécaniques résultantes sont caractérisées. Le lien est fait entre la distribution de précipités fins et les propriétés plastiques, ainsi qu'entre la précipitation grossière et les micromécanismes d'endommagement. Le modèle aux éléments finis proposé prend en compte le comportement plastique des différentes zones et reproduit le comportement en endommagement de la zone fondue, qui constitue le maillon faible de la structure à cause de l'évaporation d'éléments d'alliages durant le soudage. Ce modèle a été validé dans une gamme étendue de sollicitations mécaniques (géométrie, entaille).

This thesis aims to improve the performance of latex-based pressure-sensitive adhesives (PSAs). PSA performance is usually evaluated by tack, peel strength and shear strength. Tack and peel strength characterize a PSA’s bonding strength to a substrate while shear strength reflects a PSA’s capability to resist shear deformation. In general, increasing shear strength leads to a decrease in tack and peel strength. While there are several commercial PSA synthesis methods, the two most important methods consist of either solvent-based or latex-based techniques. While latex-based PSAs are more environmentally compliant than solvent-based PSAs, they tend to have much lower shear strength, at similar tack and peel strength levels. Therefore, the goal in this thesis was to greatly improve the shear strength of latex-based PSAs at little to no sacrifice to tack and peel strength. In this study, controlling the polymer microstructure of latexes or their corresponding PSA films was used as the main method for improving the PSA performance. The research was sub-divided into four parts. First, the influence of chain transfer agent (CTA) and cross-linker on latex polymer microstructure was studied via seeded semi-batch emulsion polymerization of butyl acrylate (BA) and methyl methacrylate (MMA). Three techniques were used to produce the latexes: (1) adding CTA only, (2) adding cross-linker only, and (3) adding both CTA and cross-linker. It was found that using CTA and cross-linker simultaneously allows one to expand the range of latex microstructural possibilities. For example, latexes with similar gel contents but different Mc (molecular weight between cross-links) and Mw (molecular weight of sol polymers) could be produced if CTA and cross-linker concentration are both increased. However, for the corresponding PSAs with similar gel contents, the relationship between their polymer microstructure and performance was difficult to establish as almost all of the medium and high gel content PSAs showed very low tack and peel strength as well as extremely large shear strength readings. In the second part of this thesis, in order to improve the tack and peel strength of medium and high gel content PSAs, the monomer composition and emulsifier concentration were varied. It was found that changing the monomer mixture from BA/MMA to BA/acrylic acid (AA)/2-hydroxyethyl methacrylate (HEMA) while simultaneously decreasing emulsifier concentration dramatically improved the corresponding PSAs’ shear strength as well as tack and peel strength. The addition of polar groups to the PSA increased its cohesive strength due to the presence of strong hydrogen bonding; meanwhile, PSA films’ surface tension increased. In the third part, two series of BA/AA/HEMA latexes were generated by varying the amounts of CTA either in the absence or presence of cross-linker. The latexes produced in the absence of cross-linker exhibited significantly larger Mc and Mw compared to their counterparts with similar gel contents prepared with cross-linker. The PSAs with the larger Mc and Mw showed much larger shear strengths due to improved entanglements between the polymer chains. In the final part of the thesis, the performance of the BA/AA/HEMA PSAs was further improved by post-heating. Compared with original latex-based PSAs with similar gel contents, heat-treated PSAs showed not only significantly improved shear strengths, but also much larger tack and peel strengths. The different shear strengths were related to the PSAs’ gel structures, which were discrete in the original PSAs but continuous in the heat-treated PSAs. The improved tack and peel strengths were related to the PSA films’ surface smoothness. During the post-heating process, the PSA polymer flowed, resulting in much smoother surfaces than the original PSA films. In addition, the effect of post-heating was related to the polymer microstructure of the untreated PSAs. Decreasing the amount of very small or very big polymers or simultaneously increasing Mc and Mw could lead to post-treated PSAs with significantly better performance. Moreover, it was found that by optimizing the polymer microstructure of the original latex-based PSAs, it was possible to obtain a treated PSA with similar or even better performance than a solvent-based PSA with similar polymer microstructure. Our original objective was surpassed: in two cases, not only was shear strength greatly improved, but so were tack and peel strength due to the simultaneous modification of PSA bulk and surface properties.