Modeling the competition between drying and curing processes in polymerizing films is of great importance to many existing and developing materials synthesis processes. These processes involve multiple length and time scales ranging from molecular to macroscopic, and are challenging to fully model in situations where the polymerization is non-ideal, such as sol-gel silica thin film formation. A comprehensive model of sol-gel silica film formation should link macroscopic flow and drying (controlled by process parameters) to film microstructure (which dictates the properties of the films). This dissertation describes a multiscale model in which dynamic Monte Carlo (DMC) polymerization simulations are coupled to a continuum model of drying. Unlike statistical methods, DMC simulations track the entire molecular structure distribution to allow the calculation not only of molecular weight but also of cycle ranks and topological indices related to molecular size and shape. The entire DMC simulation (containing 106 monomers) is treated as a particle of sol whose position and composition are tracked in the continuum mass transport model of drying. The validity of the multiscale model is verified by the good agreement of the conversion evolution of DMC and continuum simulations for ideal polycondensation and first shell substitution effect (FSSE) cases. Because our model allows cyclic and cage-like siloxanes to form, it is better able to predict the silica gelation conversion than other reported kinetic models. By studying the competition between molecular growth and cyclization, and the competition between mass transfer (drying) and reaction (gelation) on the drying process of the sol-gel silica film, we observe that cyclization delays gelation, shrinks the molecular size, increases the likelihood of skin formation, and leads to a molecular structure gradient inside the film. We also find that compared with a model with only 3-membered rings, the molecular structure is more complicated and the structure gradients in the films are larger with 4- membered rings. We expect that our simulation will allow better prediction of the formation of structure gradients in sol-gel derived ceramics and other nonideal multifunctional polycondensation products, and that this will help in developing procedures to reduce coating defects.

Ce travail concerne l’étude et la modélisation du phénomène de multifissuration transversedes fils dans les CMC tissés. Sa connaissance est fondamentale pour déterminer soneffet sur les champs de contraintes, la progression des endommagements et la durée de viedu matériau.À partir d’observations sur des coupes de CMC, des matériaux virtuels sont développéset des essais virtuels réalisés. Différentes séquences de fissuration transverse sont simuléessur diverses microstructures de CMC. Ces simulations se substituent à des observations expérimentalesimpossibles à réaliser.Un modèle statistique de multifissuration est développé sur la base du principe dumaillon faible appliqué à une distribution ponctuelle de Poisson. Les singularités micostructurellessont représentées par des défauts dans un milieu homogène équivalent (MHE).Les modifications des fonctions de distribution au cours de la multifissuration sont modélisées.Le modèle statistique permet de réaliser un changement d’échelle à la suite duquel lamultifissuration transverse est simulée dans le MHE avec une réduction des temps de calculde l’ordre de 90%. / This work deals with the study and modeling of multiple crakcing of tows in wovenCMCs. Its understanding is fundamental to determine the effect on stress fields, the evolutionof damage and the lifetime of material.From observations on real CMC pieces, virtual materials are developed and multiplecracking virtual testing is achieved. Different scenarii are simulated on various CMC microstructures.These simulations are a substitute for impossible experimental observations.A statistical model for multiple cracking based on the weakest link principle applied to adistribution of Poisson is developed. Micostructural singularities are represented by defectsin a homogeneous medium equivalent (EHM). Modifications of distribution functions duringthe multicracking are modeled.The statistical model realizes a scale changing : transverse multicracking is simulated inthe EHM with a reduction of almost 90% for computational time.

L'industrie de la microélectronique est en perpétuelle évolution, surtout concernant la diminution des dimensions des composants. Ainsi, pour les nouvelles générations de mémoires non volatiles Flash, le poly-silicium de la grille flottante pourrait être remplacé par des nanoplots discrets de silicium. L'élaboration de ces nanoplots par LPCVD (Low Pressure Chemical Vapor Deposition) à partir de silane SiH4 sur un substrat amorphe SiO2 demeure l'une des voies privilégiées par l'industrie. Le fonctionnement de ce type de mémoires est fortement dépendant des conditions de synthèse des nanoplots de silicium. Ce travail de cette thèse visait donc à améliorer la compréhension des mécanismes de nucléation et de croissance en jeu. Nous avons étudié les premiers instants de la nucléation en chimie quantique, grâce à l'utilisation de la théorie DFT, en considérant l'oxyde de silicium comme surface de dépôt. Des lois cinétiques intrinsèques ont été tirées de ces résultats DFT et elles ont été implémentées dans un modèle de simulation à l'échelle du procédé industriel, sur la base du code de CFD Fluent. Pour la nucléation, il est apparu que seul le silylène, SiH2, peut se chimisorber à la surface du substrat. De plus, sa faible concentration et la première désorption de H2, qui est très lente, expliquent le temps d'incubation. Pour la croissance, le caractère auto-catalytique des dépôts a été expliqué par la contribution très forte du silane au dépôt dès la seconde chimisorption. L'étape limitant la croissance est clairement la désorption de H2. La réalisation d'essais expérimentaux et la comparaison avec le modèle multi-échelles issu de notre travail a permis d'expliquer pourquoi les cinétiques classiques de la littérature surestiment la vitesse de dépôt des nanoplots. Il est aussi apparu que la vitesse de dépôt du silicium sur des nanoplots en croissance est plus forte que celle d'un film de silicium continu « épais ». La prise en compte des sites de chimisorption lors des premiers instants et la description détaillée de la désorption de H2 sont des paramètres clés pour rendre compte du comportement des dépôts de nanoplots de silicium. / The need of high integrated systems of the everyday life involves a permanent evolution of the microelectronic industry. Integrated circuits involving non volatile Flash memories are good examples of these trends. In this technology, the poly-silicon floating gate could be replaced by a discrete trap floating gate in which discrete traps are made up of silicon nanodots. The synthesis of nanodots by LPCVD (Low Pressure Chemical Vapor Deposition) from silane SiH4 on SiO2 surfaces remains one of the most promising ways of industrial synthesis. Despite a huge experimental effort, fundamental understanding of the key mechanisms of nanodots nucleation and growth remains elusive. Here we find the main objectives of the thesis. For nucleation, our main results reveal that only silylene SiH2 is involved in the very first steps of nucleation. The incubation time experimentally observed can be explained by the low SiH2 concentration and the first slow H2 desorption process. For growth, silane is the main responsible for deposition, which explains the autocatalytic behaviour of silicon deposition. The growth limiting step is clearly the H2 desorption process. Comparisons between experimental and multiscale modelling allow to explain why classical kinetics of the literature overestimate nanodots deposition rate. We have found that the silicon deposition rate is higher on nanometer silicon dots than on a continuous silicon film. Key parameters to conveniently model nanodots deposition are good descriptions of the first chemisorption sites and of the H2 desorption process.

Le travail exposé dans ce mémoire propose un examen, selon une approche multiéchelle, de la relation entre l’évolution de l’endommagement et la perte de conductibilité thermique de Compositesà Matrice Céramique. Les recherches sont menées à la fois sur le plan expérimental et sur le plan théorique. La démarche mise en oeuvre consiste à examiner deux échelles significatives (Microet Meso) auxquelles agissent des mécanismes d’endommagement différents et à évaluer pardes techniques d’homogénéisation l’effet sur les propriétés thermiques effectives.Une attention particulière a été donnée à l’élaboration d’une démarche expérimentale approfondieassociant des moyens de caractérisation mécanique, thermique et microstructurale. Aux deuxéchelles étudiées, un banc expérimental a été conçu pour réaliser des mesures thermiques sur des CMC sollicités mécaniquement. La diffusivité thermique longitudinale du mini composite est estimée par thermographie à détection synchrone. Des variantes de la méthode flash en face arrière sont mises en oeuvre pour l’étude du composite tissé. Par ailleurs, la progression de l’endommagementest déduite de l’enregistrement des signaux acoustiques et d’observations microstructurales post-mortem. Les résultats expérimentaux sont systématiquement comparés à des simulations. A l’échelle Micro, un modèle micromécanique est proposé afin de simuler la perte de conductivité thermique d’un mini composite en traction. A l’échelle Méso, une stratégie multiéchelle de calcul numérique de l’effet de l’endommagement sur les propriétés thermiques d’un CMC tissé est présentée. / In this work the relationship between the evolution of damage and the loss of thermal propertiesof Ceramic Matrix Composites is investigated by a multiscale approach. Research are conductedboth experimentally and theoretically. The implemented approach is to consider two significantscales (micro and meso) where different damage mechanisms are operating and then assess theeffect on the effective thermal properties by homogenization techniques.Particular attention has been given to the development of a thorough experimental work combiningvarious characterization tools (mechanical, thermal and microstructural). At the two aforementionedscales, an experimental setup was designed to perform thermal measurements onCMC under tensile test. Thermal diffusivity of minicomposites is estimated using Lock-in thermography.Also, tranverse diffusivity mapping as well as global in-plane diffusivity of woven CMCare determined by suitable rear face flash methods. The evolution of damage is then derived fromacoustic emission activity along with postmortem microstructural observations. Experimental resultsare systematically compared to simulations. At microscale, a micromechanical-based modelis used to simulate the loss of thermal conductivity of a minicomposite under tensile test. At mesoscale,a multiscale Finite ElementModel is proposed to compute the effect of damage on thermalproperties of woven CMC.

Variability in neural activity has historically been treated as noise, in favour of deriving estimates based on central tendency (e.g., mean). Recently, researchers have shown that variability and mean confer different sources of information and that increased variability in neural activity is associated with superior behavioural performance and that it decreases during late-life. Although mounting evidence suggests that neural variability is beneficial, it is less clear whether these findings are driven by within- or between-person factors and whether they are apparent during higher-order cognitive tasks. Further, variability can be derived in several different ways, drawing into question its congruence across operationalizations. The present investigation sought to separate within- and between-person sources of variance in order to ascertain what was driving any observable effects in three operationalizations of cerebral oxygenation, computed based on central tendency (mean), variability (standard deviation) and signal complexity (multivariate multiscale entropy). 25 older adults (71-81 years of age) completed two tasks of executive functions while undergoing assessment using functional near infrared spectroscopy. Time-varying covariation models were employed to estimate the effects of cerebral oxygenation on behavioural performance, as well as the moderating effects of age and fall status. Findings suggest that mean and variability are differentially associated with behavioural performance and are increased in older adults at greater fall risk. Whereas mean based computations were positively associated with more accurate and faster responding, variability based computations were primarily associated with faster responding only and occurred in non-overlapping regions of prefrontal cortex. Future studies of neural variability may consider examining within- and between-person factors and operationalizing signal complexity in cerebral oxygenation over longer time periods to examine its effects over multiple time scales. / Graduate / drewh@uvic.ca

Thermally induced phase transformation in NiTi shape memory alloys (SMA) shows strong size and shape, collectively termed length scale effects, at the nano to micrometer scales, and that has important implications for the design and use of devices and structures at such scales. This paper, based on a recently developed multiscale model that utilizes molecular dynamics (MD) simulations at small scales and MD-verified phase field (PhF) simulations at larger scales, reports results on specific length scale effects, i.e. length scale effects in martensite phase fraction evolution, transformation temperatures (martensite and austenite start and finish) and in the thermally cyclic transformation between austenitic and martensitic phase. The multiscale study identifies saturation points for length scale effects and studies, for the first time, the length scale effect on the kinetics (i.e. developed internal strains) in the B19 phase during phase transformation. The major part of the work addresses small scale single crystals in specific orientations. However, the multiscale method is used in a unique and novel way to indirectly study length scale and grain size effects on evolution kinetics in polycrystalline NiTi, and to compare the simulation results to experiments. The interplay of the grain size and the length scale effect on the thermally induced martensite phase fraction (MPF) evolution is also shown in this present study. Finally, the multiscale coupling results are employed to improve phenomenological material models for NiTi SMA.

Martensitic phase transformation in NiTi shape memory alloys (SMA) occurs over a hierarchy of spatial scales, as evidenced from observed multiscale patterns of the martensitic phase fraction, which depend on the material microstructure and on the size of the SMA specimen. This paper presents a methodology for the multiscale tracking of the thermally induced martensitic phase transformation process in NiTi SMA. Fine scale stochastic phase field simulations are coupled to macroscale experimental measurements through the compound wavelet matrix method (CWM). A novel process for obtaining CWM fine scale wavelet coefficients is used that enhances the effectiveness of the method in transferring uncertainties from fine to coarse scales, and also ensures the preservation of spatial correlations in the phase fraction pattern. Size effects, well-documented in the literature, play an important role in designing the multiscale tracking methodology. Molecular dynamics (MD) simulations are employed to verify the phase field simulations in terms of different statistical measures and to demonstrate size effects at the nanometer scale. The effects of thermally induced martensite phase fraction uncertainties on the constitutive response of NiTi SMA is demonstrated.

Ces travaux portent sur le développement d’un matériau virtuel pour la simulation et l’optimisation des matériaux à microstructure hétérogène, en particulier des composites à matrice céramique de nouvelle génération. Pour ce faire une modélisation du fil est mise en place, au travers d’une démarche intégrée qui prend en compte la complexité de la microstructure et de sa variabilité issues du procédé de fabrication. La démarche proposée repose sur deux étapes : i) la construction d’une morphologie synthétique du fil, basée sur l’étude de micrographies et ii) une méthode de simulation multiéchelle inspirée de la méthode des éléments finis généralisée. L’originalité de cette dernière provient de l’utilisation de motifs, sorte de situations physiques ou topologiques élémentaires, pour décrire à la fois la microstructure et la cinématique locale. La démarche est validée et appliquée à diverses sections de fil synthétiques 2D, pour lesquelles le choix des motifs est discuté. L’extension au traitement de tronçon 3D du fil, ainsi qu’à la simulation de la fissuration à l’aide d’une méthode discrète est discutée et des premiers éléments de réponse sont apportés. / The thesis work focus on the development of a virtual material for heterogeneous materials simulation and optimization, especially in the case of now generation of ceramic-matrix composites. To do that, a model at the scale of the yarn is built up, by using an integrated approach that account for the complexity of the microstructure and its variability arising from the manufacturing process. This approach is made of two steps: i) the construction of a synthetic yarn, using micrographics studies and ii) a multiscale approach based on the generalized finites elements method. The originality of that method come from the use of pattern, sort of typical physical or topological situation, that describe both the local structure and kinematic. The approach is validated and applied to various 2D cross-sections of synthetic yarns, for which the choice of patterns is discussed. Extension to 3D section of the yarn, together with the simulation of the fracture in a discrete manner, is discussed and first elements of answer are proposed.

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