Cette thèse a pour objectif principal de développer un outil numérique capable de prédire la ductilité des matériaux polycristallins. Cet outil est basé sur le couplage de l’approche multi-échelles autocohérente à deux critères d’instabilités plastiques : la théorie de bifurcation et l’approche d’imperfection initiale. Le schéma autocohérent est utilisé pour déterminer le comportement d’un agrégat polycristallin (supposé représentatif du matériau étudié) à partir du comportement des monocristaux constitutifs. Le comportement à l’échelle monocristalline est formulé dans le cadre des grandes déformations élastoplastiques. Deux différentes versions du critère de Schmid sont successivement utilisées pour modéliser l’écoulement plastique monocristallin : la version classique et une version régularisée. Pour intégrer numériquement les équations constitutives à l’échelle monocristalline, deux algorithmes ont été développés : un algorithme de type évolutif et un algorithme de type retour radial. Les équations gouvernant le schéma autocohérent ont été revisitées. Pour résoudre ces équations, un nouvel algorithme numérique a été proposé, qui est montré être plus efficace que les algorithmes existants communément basés sur la méthode du point fixe. De plus, une approche numérique robuste a été développée, qui permet de coupler le modèle autocohérent à l’approche d’imperfection initiale. La performance ainsi que la robustesse des différents algorithmes et schémas numériques développés ont été mis en évidence à travers plusieurs résultats de simulation. L’effet de plusieurs paramètres et choix de modélisation sur la prédiction de formabilité des tôles métalliques a été extensivement analysé. / The main objective of this PhD thesis is to develop a numerical tool capable of predicting the ductility of polycrystalline materials. This tool is based on the coupling of the self-consistent multiscale approach with two plastic instability criteria: the bifurcation theory and the initial imperfection approach. The self-consistent scheme is used to derive the mechanical behavior of a polycrystalline aggregate (assumed to be representative of the studied material) from that of its microscopic constituents (the single crystals). The constitutive framework at the single crystal scale follows a finite strain rate-independent formulation. Two different versions of the Schmid law are successively used to model the plastic flow: the classical version and a regularized one. To solve the constitutive equations at the single crystal scale, two numerical algorithms have been developed: one is based on the usual return-mapping scheme and the other on the so-called ultimate scheme. The equations governing the self-consistent approach have been revisited. To solve these equations, a new numerical scheme has been developed, which is shown to be more efficient than the existing schemes commonly based on the fixed point method. Also, a robust numerical approach has been developed to couple the self-consistent model to the initial imperfection approach. The performance and the robustness of the different numerical schemes and algorithms developed have been highlighted through several simulation results. The impact of various parameters and modeling choices on the formability prediction of sheet metals has been extensively analyzed.

Cette thèse s'intéresse à la rationalisation du mécanisme de transfert d'excitation dans des polyphénylènes éthynylènes (PPE). Une étude statique approfondie a été réalisée en utilisant la TDDFT, permettant de confirmer la localisation des états excités de méta-PPE sur des fragments para, ainsi que la hiérarchie des interactions régissant les propriétés photochimiques des PPE. Des intersections coniques ont été identifiées, de même que les principales composantes de l'espace de branchement. Leur étude a soutenu l'hypothèse d'un transfert d'énergie par conversion interne entre états excités localisés sur des fragments para.D'autre part, nous avons proposé un modèle vibronique multiéchelles pour l'énergie des états électroniques. En particulier, nous avons exprimé les énergies des orbitales frontières de PPE en fonction des énergies des orbitales frontières du benzène et de l'acetylène via un Hamiltonien effectif de type Hückel. Un travail de mapping et d'optimisation nous a permis d'aboutir à une expression pour l'énergie de transition électronique en fonction d'un nombre réduit de coordonnées nucléaires locales. / The present work is focused on the rationalization of the excitation transfer mechanism in polyphenylene ethynylenes (PPEs). A static study was performed using TDDFT, allowing to confirm both the localization of the excited states of meta-PPEs on para building blocks and the hierarchy in the interactions governing the photochemical properties of PPEs. Conical intersections were identified, along with few components of their branching spaces. Studying those supported the assumption of an energy transfer proceeding through internal conversion between excited states localized on different building blocks.In addition, we proposed a multiscale vibronic model for the energy of the eletronic states. In particular, we expressed the energies of the frontier orbitals of PPEs in terms of the energies of the frontier orbitals of benzene and acetylene, using an effective Hückel-type Hamiltonian. Perfoming different optimizations, we achieved to propose an expression for the energy of the electronic transition in terms of a reduced number of local nuclear coordinates.

Orientador: Eduardo Cardoso de Abreu / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Matemática Estatística e Computação Científica / Made available in DSpace on 2018-08-26T22:28:13Z (GMT). No. of bitstreams: 1 Ferraz_PaolaCunha_M.pdf: 6535346 bytes, checksum: 5f9c9ba53cd3e63fc60c09c90ad2c625 (MD5) Previous issue date: 2015 / Resumo: O foco deste trabalho é aproximação numérica de problemas envolvendo equações diferenciais parciais (EDPs), de natureza elíptica, no contexto de aplicações em dinâmica de fluidos em meios porosos. Especificamente, a dissertação pretende contribuir com uma implementação de um algoritmo multiescala e multigrid, recentemente introduzido na literatura, para resolução aproximada de sistemas de equações lineares de grande porte e mal condicionados, proveniente dessa classe de EDPs, tipicamente associada a problemas de Poisson de pressão-velocidade com condições de contornos típicas de fluxo em meios porosos. O problema concreto de Poisson discutido neste trabalho será desacoplado do sistema de transporte de EDPs de convecção-difusão, com convecção dominante, e linearizado por meio do emprego de uma técnica de decomposição de operadores. A metodologia para a discretização do problema elíptico de Poisson é elementos finitos mistos híbridos. A resolução numérica do sistema linear resultante deste procedimento será realizado via um método do tipo Gradientes Conjugados com Pré-condicionamento (PCG) multiescala e multigrid. Combinamos as metodologias multi-escala e multigrid de modo a capturar os distintos comprimentos de onda associados aos diferentes comprimentos de onda do operador diferencial auto-adjunto de Poisson, fortemente influenciado pela heterogeneidade das propriedades geológicas do meio poroso, em particular da permeabilidade absoluta, que pode exibir flutuações em várias ordens de grandeza. Experimentos computacionais em aplicações de problemas de dinâmica de fluidos em meios porosos são apresentados e discutidos para verificação dos resultados obtidos / Abstract: The focus of this work is the numerical approximation of differential problems involving partial differential equations (PDE's) of elliptic nature, in the context of modelling and simulation in fluid dynamics in porous media. The dissertation aims to contribute with an implementation of a multiscale multigrid algorithm, recently introduced in the literature, designed for solving ill-conditioned large linear systems of equations derived from those classes of PDE's, typically associated with Poisson problems of pressure-velocity with boundary conditions typical of flow in porous media. The Poisson problem discussed here is identified from the coupled convection-diffusion transport system counterpart of PDE's, with dominated convection, and by a linearization by means the use of an operator splitting approach. The methodology used for the discretization of the Poisson elliptic problem is by mixed hybrid finite elements. The numerical solution of the resulting linear system will be addressed by a multiscale multigrid preconditioned conjugate gradient (PCG) method. We combine both methodologies in order to capture the distinct wavelengths associated with the different wavelengths from the assosiated self-adjoint Poisson operator, strongly influenced by the heterogeneity of the geological properties of the porous media, in particular to the absolute permeability tensor, which in turn might exhibit very large fluctuations of orders of magnitude. Numerical experiments in applications of fluid dynamics problems in porous media are presented and discussed for a verification of the results obtained by direct numerical simulations with the multiscale multigrid algorithm under consideration / Mestrado / Matematica Aplicada / Mestra em Matemática Aplicada

The exceptional properties of nanocrystals (NCs) are strongly influenced by many different characteristics, such as their size and shape, but also by characteristics on the atomic scale, such as their crystal structure, their surface structure, as well as by potential microstructure defects. While the size and shape of NCs are frequently determined in a statistical manner, atomic-scale characteristics are usually quantified only for a small number of individual NCs and thus with limited statistical relevance. Within this work, a characterization workflow was established that is capable of determining relevant NC characteristics simultaneously in a sufficiently detailed and statistically relevant manner. The workflow is based on transmission electron microscopy, networked by a correlative multiscale approach that combines atomic-scale information on NCs obtained from high-resolution imaging with statistical information on NCs obtained from low-resolution imaging, assisted by a semi-automatic segmentation routine. The approach is complemented by other characterization techniques, such as X-ray diffraction, UV-vis spectroscopy, dynamic light scattering, or alternating gradient magnetometry. The general applicability of the developed workflow is illustrated on several examples, i.e., on the classification of Au NCs with different structures, on the statistical determination of the facet configurations of Au nanorods, on the study of the hierarchical structure of multi-core iron oxide nanoflowers and its influence on their magnetic properties, and on the evaluation of the interplay between size, morphology, microstructure defects, and optoelectronic properties of CdSe NCs.:List of abbreviations and symbols 1 Introduction 1.1 Types of nanocrystals 1.2 Characterization of nanocrystals 1.3 Motivation and outline of this thesis 2 Materials and methods 2.1 Nanocrystal synthesis 2.1.1 Au nanocrystals 2.1.2 Au nanorods 2.1.3 Multi-core iron oxide nanoparticles 2.1.4 CdSe nanocrystals 2.2 Nanocrystal characterization 2.2.1 Transmission electron microscopy 2.2.2 X-ray diffraction 2.2.3 UV-vis spectroscopy 2.2.3.1 Au nanocrystals 2.2.3.2 Au nanorods 2.2.3.3 CdSe nanocrystals 2.2.4 Dynamic light scattering 2.2.5 Alternating gradient magnetometry 2.3 Methodical development 2.3.1 Correlative multiscale approach – Statistical information beyond size and shape 2.3.2 Semi-automatic segmentation routine 3 Classification of Au nanocrystals with comparable size but different morphology and defect structure 3.1 Introduction 3.1.1 Morphologies and structures of Au nanocrystals 3.1.2 Localized surface plasmon resonance of Au nanocrystals 3.1.3 Motivation and outline 3.2 Results 3.2.1 Microstructural characteristics of the Au nanocrystals 3.2.2 Insufficiency of two-dimensional size and shape for an unambiguous classification of the Au nanocrystals 3.2.3 Statistical classification of the Au nanocrystals 3.2.4 Advantage of a multidimensional characterization of the Au nanocrystals 3.2.5 Estimation of the density of planar defects in the Au nanoplates 3.3 Discussion 3.4 Conclusions 4 Statistical determination of the facet configurations of Au nanorods 4.1 Introduction 4.1.1 Growth mechanism and facet formation of Au nanorods 4.1.2 Localized surface plasmon resonance of Au nanorods 4.1.3 Catalytic activity of Au nanorods 4.1.4 Motivation and outline 4.2 Results 4.2.1 Statistical determination of the size and shape of the Au nanorods 4.2.2 Microstructural characteristics and facet configurations of the Au nanorods 4.2.3 Statistical determination of the facet configurations of the Au nanorods 4.3 Discussion 4.4 Conclusions 5 Influence of the hierarchical architecture of multi-core iron oxide nanoflowers on their magnetic properties 5.1 Introduction 5.1.1 Phase composition and phase distribution in iron oxide nanoparticles 5.1.2 Magnetic properties of iron oxide nanoparticles 5.1.3 Mono-core vs. multi-core iron oxide nanoparticles 5.1.4 Motivation and outline 5.2 Results 5.2.1 Phase composition, vacancy ordering, and antiphase boundaries 5.2.2 Arrangement and coherence of individual cores within the iron oxide nanoflowers 5.2.3 Statistical determination of particle, core, and shell size 5.2.4 Influence of the coherence of the cores on the magnetic properties 5.3 Discussion 5.4 Conclusions 6 Interplay between size, morphology, microstructure defects, and optoelectronic properties of CdSe nanocrystals 6.1 Introduction 6.1.1 Polymorphism in CdSe nanocrystals 6.1.2 Optoelectronic properties of CdSe nanocrystals 6.1.3 Nucleation, growth, and coarsening of CdSe nanocrystals 6.1.4 Motivation and outline 6.2 Results 6.2.1 Influence of the synthesis temperature on the optoelectronic properties of the CdSe nanocrystals 6.2.2 Microstructural characteristics of the CdSe nanocrystals 6.2.3 Statistical determination of size, shape, and amount of oriented attachment of the CdSe nanocrystals 6.3 Discussion 6.4 Conclusions 7 Summary and outlook References Publications

Metall-Schaumstoff-Verbundelemente werden aufgrund ihrer sehr guten Flammschutzwirkung, selbsttragenden Eigenschaften bei geringem Gewicht und der kostengünstigen Montagemöglichkeit zunehmend in der Baubranche zur effizienten Wärmedämmung eingesetzt. Die Verbundelemente bestehen aus zwei flächigen, linierten oder profilierten, außen liegenden metallischen Deckschichten geringer Dicke, in denen der Zwischenraum (Kernschicht) mit einer wärmedämmenden Hartschaumschicht aus z. B. Polyisocyanurat ausgefüllt ist. Bedingt durch den (kontinuierlichen) Fertigungsprozess entstehen im Schaumkern material- und strukturbedingte Inhomogenitäten, wodurch dessen Materialeigenschaften über der Schaumdicke variieren. Diese Inhomogenitäten können die mechanischen Eigenschaften der Verbundelemente negativ beeinflussen und zu einem frühzeitigen Versagen führen. Aus diesem Grund ist das Verständnis bzw. die Berücksichtigung der lokalen Effekte im Schaum sowohl für die Auslegung der Verbundelemente als auch zur Schöpfung möglicher Potenziale zur Verbesserung der Produktqualität essenziell. Da die Betrachtung der lokalen Einflussfaktoren experimentell und analytisch nur begrenzt isoliert möglich ist, wird in dieser Arbeit ein numerischer Multiskalen-Ansatz unter Verwendung der Finite-Elemente-Methode vorgestellt, welcher in der Lage ist, die mechanischen Eigenschaften der lokalen mesoskaligen Schaumstrukturen mittels Homogenisierung in einem makroskaligen Simulationsmodell eines kompletten Verbundelementes zu berücksichtigen. Für die Validierung und Bewertung des Modells werden kommerziell erhältliche Verbundelemente verwendet. Im ersten Schritt werden die lokalen (höhenaufgelösten) Schaumeigenschaften dieser Verbundelemente experimentell charakterisiert. Besonderes Augenmerk liegt auf der Analyse des Schaumbasismaterials und der Zellstruktur. Basierend auf den experimentellen Daten wird ein mesoskaliges Simulationsmodell eines Repräsentativen Volumenelements erstellt und validiert, welches eine Vorhersage der mechanischen Eigenschaften anisotroper Schaumstrukturen mit unterschiedlichen Aspektverhältnissen und Orientierungen der individuellen Zellen auf Basis definierter Ellipsoidpackungen und einer anisotropen Mosaik-Methode ermöglicht. Neben der Vorhersage der lokalen Schaumeigenschaften bietet das mesoskalige Modell die Möglichkeit, Auswirkungen einzelner Einflussfaktoren auf die Schaumeigenschaften isoliert zu betrachten. Ein Vergleich zwischen experimentellen und numerischen Ergebnissen aus einem zuvor definierten Bereich zeigt, dass sowohl im Experiment, als auch in der mesoskaligen Simulation die Strukturen ein stark anisotropes Verhalten aufweisen, wobei der Grad der Anisotropie in der Simulation tendenziell leicht unterschätzt wird. Trotz kleiner Abweichungen stimmen die Simulationsergebnisse gut mit den experimentellen Daten überein. Demnach ist das mesoskalige Simulationsmodell geeignet, um die lokalen, anisotropen mechanischen Schaumeigenschaften nachzubilden. Darauf aufbauend werden die lokalen Materialeigenschaften eines ausgewählten Verbundelementes numerisch bestimmt und auf das makroskopische Modell übertragen. Im Zuge dessen werden sowohl geeignete Methoden zur Implementierung der Schaumeigenschaften vorgestellt, als auch eine Sensitivitätsanalyse zum Einfluss der Auflösung der lokalen mesoskaligen Schaumstruktur auf die makroskopischen Eigenschaften der Verbundelemente durchgeführt. Die Qualität des makroskopischen Simulationsmodells wird über den Vergleich der simulativen Ergebnisse mit bauteil-typischen Messungen analysiert. Vergleichbar zur mesoskaligen Validierung können die makroskaligen Bauteileigenschaften mit kleineren Abweichungen gut wiedergegeben werden. Voraussetzung ist jedoch, dass die im Vergleich zur (nahezu) homogenen Schaum-Kernschicht äußeren, inhomogenen Randschichten separat modelliert werden. Diese Erkenntnisse lassen sich auch auf andere Verbundelemente mit unterschiedlichen Dicken übertragen, da aus den experimentellen Untersuchungen bekannt ist, dass die Verbundelemente qualitativ vergleichbare Eigenschaftsverteilungen aufweisen. Aufgrund des hohen Rechen- und Modellierungsaufwands wird abschließend bewertet, inwiefern die komplexen mesomechanischen Eigenschaften anisotroper Schaumstrukturen in zukünftigen Multiskalen-Simulationen effizienter berücksichtigt werden können. Hierzu wird ein Künstliches Neuronales Netz verwendet, wobei der Fokus aufgrund der benötigten Dauer zur Erstellung einer geeigneten Datenbasis auf der Vorhersage des orthotropen Steifigkeitstensors liegt. Die Ergebnisse zeigen, dass bei einer geeigneten Netzwerkstruktur und einer ausreichenden Datenbasis die mechanischen Eigenschaften komplexer Zellstrukturen mittels eines Neuronalen Netzes innerhalb von Sekunden sehr gut reproduziert werden können. In einer abschließenden Studie wird der Einfluss der Datenbankgröße auf die Vorhersagegenauigkeit untersucht. Es kann festgestellt werden, dass mindestens 500 Trainingsdatenpunkte erforderlich sind, um eine ausreichende Genauigkeit zu erreichen. / Metal-foam composite elements are used increasingly for efficient thermal insulation in the construction industry due to their very good flame-retardancy, self-supporting properties combined with low weight, and low-cost assembly options. The composite elements consist of two thin, flat, lined, or profiled external metallic cover layers, in which the interspace (core layer) is filled with a thermally insulating low-density layer of rigid foam, e.g. polyisocyanurate. Due to the (continuous) manufacturing process, material- and structure-related inhomogeneities occur in the foam core, causing its material properties to vary over the core thickness. These inhomogeneities can negatively affect the mechanical properties of the composite elements and lead to premature failure. For this reason, understanding and considering the local effects is essential both for the design of the composite elements and for creating possible potentials to improve the product quality. Since the consideration of local influencing factors is limited experimentally and analytically in isolation, this work presents a numerical multiscale approach using the finite element method, which can consider the mechanical properties of the local mesoscale foam structures using homogenization in a macroscale simulation model of a complete composite element. For the validation and evaluation of the model, commercially available composite elements are used. In a first step, the local (height-resolved) foam properties of these composite elements are characterized experimentally. Particular attention is paid to the analysis of foam base material, foam density, and cell structure. Based on the experimental data, a mesoscale simulation model of a representative volume element is created and validated, which allows a prediction of mechanical properties of anisotropic foam structures with different aspect ratios and orientations of the individual cells based on defined ellipsoid packings and an anisotropic tessellation method. In addition to predicting local foam properties, this mesoscale model offers the possibility to consider effects of individual influencing factors on foam performance in isolation. A comparison between experimental and numerical results from a previously defined area shows that in both the experiment and the mesoscale simulation, the structures exhibit strongly anisotropic behavior, although the degree of anisotropy tends to be slightly underestimated in the simulation. Despite small deviations, simulation results agree well with experimental data. Accordingly, this mesoscale simulation model is suitable to reproduce local anisotropic mechanical foam properties. Based on this, local material properties of a selected composite element are determined numerically and transferred to the macroscopic model. In the course of this, suitable methods for implementing foam properties are presented as well as a sensitivity analysis on the influence of resolution of the local mesoscale foam structure on macroscopic properties of composite elements. The quality of the macroscopic simulation model is again analyzed via a comparison of simulative results with component-typical measurements. Comparable to the mesoscale validation, macroscale component properties can be reproduced well with minor deviations. A prerequisite, however, is that outer, inhomogeneous layers are modeled separately compared to (nearly) homogeneous foam core layer. These findings can also be applied to other composite elements with different thicknesses since it is known from experimental investigations that composite elements exhibit qualitatively comparable property distributions. Finally, due to the high computational and modeling effort, it is evaluated to what extent the complex mesomechanical properties of anisotropic foam structures can be considered more efficiently in future multiscale simulations. For this purpose, an Artificial Neural Network is used, focusing on the prediction of orthotropic stiffness tensor due to the required duration to generate a suitable database. Results from this study show that with a suitable network structure and a sufficient database, the mechanical properties of complex foam structures can be reproduced very well via the Artificial Neural Network within seconds. In a final study, the effect of the database size on the prediction accuracy was examined. It could be observed that at least 500 training datapoints are required to obtain sufficient accuracy.