La prédiction du clivage des aciers ferritiques a été largement étudiée à l’aide de l’approchelocale de la rupture, et des modèles macroscopiques identifiés phénoménologiquement comme celui de Beremin. Cette prédiction reste cependant difficile dans le domaine de transition ductilefragile. Cela a conduit à des études micromécaniques par les approches polycristallines afin de décrire l’évolution de la contrainte de clivage en fonction de la température pour les aciers bainitiques. Dans cette étude, on utilise une approche polycristalline, puis on développe un modèle macroscopique de prédiction du clivage d’un acier de microstructure plus simple, un acier sphéroïdisé. De nombreux résultats de la littérature indiquent que leur rupture est due à la microfissuration des carbures. Le comportement mécanique et la rupture d'un acier sphéroïdisé C35R sont obtenus par des essais de traction simple et de ténacité dans une gamme de température entre -196 et 20°C. Les analyses microstructurales sont effectuées pour déterminer la distribution de taille des grains et des carbures. Des modélisations simplifiées de la microstructure de l’acier sont proposées. L’aspect polycristallin du matériau est pris en compte. Une étude paramétrique concernant la distribution des contraintes dans les carbures est réalisée. On montre que les paramètres du modèle polycristallin n’influencent pas cette distribution à la condition de représenter le même comportement global en traction. La prédiction de la rupture par clivage est basée sur une approche probabiliste, considérant la dispersion des contraintes dans les carbures due à l'hétérogénéité des champs mécaniques issue de la modélisation polycristalline. La probabilité élémentaire de rupture des carbures est ainsi obtenue. Différents modèles de rupture macroscopiques sont alors développés, basés sur des critères en germination et propagation des microfissures. Ils sont appliqués à une éprouvette SENT afin de prédire la ténacité dans le bas de la transition ductile-fragile. La comparaison avec les résultats expérimentaux montre que l’on doit prendre en compte l’évolution de la densité volumique des microfissures avec le chargement, l’extension des microfissures de taille variable ou leur émoussement. L’importance des différents critères dépend de la température. / The cleavage fracture prediction of the ferritic steels has been widely studied using the localapproach to fracture and macroscopic phenomenological models like Beremin. This prediction remains difficult in the ductile-brittle transition domain. Therefore, micromechanical studies have been carried out using polycrystalline approaches to describe the evolution of the cleavage stress in function of temperature for the bainitic steels. In this study, a macroscopic model using a polycrystalline approach is developed to predict the cleavage of one steel with a simple microstructure: a spheroidized steel. Many results in the literature indicate that its fracture is due to carbide microcracking. The mechanical and fracture behavior of a spheroidized steel C35R are obtained by tensile and toughness tests in a temperature range between -196°C and 20°C. The microstructural analyses are performed to determine the grain and carbide size distribution. Simplified microstructure models of the steel are proposed. The polycrystalline aspect of the material is taken into account. A parametric study on the carbide stress distribution is carried out. It is shown that the parameters of the polycrystalline model do not influence the carbide stress distribution if the same global tensile behavior is represented. The cleavage fracture prediction is based on the probabilistic approach, considering the stress scatter in the carbides due to the mechanical fields’ heterogeneity related to the polycrystalline modelling. Thus, the elementary fracture probability function is obtained. Different macroscopic fracture models are then developed based on the criteria based on nucleation and propagation of microcracks. The models are applied to a SENT specimen to predict the toughness in the bottom of the ductile-brittle transition domain. The comparison with experimental results shows that the evolution of the microcracks volume density with the loading, the extension of the microcracks with various sizes or their blunting, must be taken into account. The importance of the different criterions depends on the temperature.

O objetivo deste trabalho foi o estudo do íon Fe3+ em monocristais e fibras monocristalinas de LiNbO3, através da técnica espectroscópica da Ressonância Paramagnética Eletrônica (RPE), nas freqüências de 10 e 34GHz, à temperatura ambiente. O Hamiltoniano de Spin para o íon Fe3+ ocupando um sítio de simetria trigonal (C3v) é dado por: H = \'beta\' \'VET.H\' \'VET.g\' \'VET.S\' + \'B20O20+B40O40 . Foram analisadas três amostras de LiNbO3, com diferentes concentrações de Fe3+ e os parâmetros de campo cristalino e fator-g encontrados são: fibra (0.3 mol% de Fe3+) g = 1.9908 \'+OU-\' 0.0002, \'B. SUP. 0 INF. 2\' = 5.4\'+OU-\'0.2x10-2 cm-1 , \'B. SUP. 0 INF. 4\' = -7.7\'+OU-\'1.5x10-5cm-1, monocristal 90 (0.22 mol%) g = 2.0043\'+OU-\'0.0002, \'B. SUP. 0 INF. 2\' = 5.35\'+OU-\'0.25x10-2 cm-1, \'B. SUP. 0 INF. 4\'= - 4.03\'+OU-\'1.4x10-5cm-1, monocristal 99 (0.02 mol%) g = 2.0026\'+OU-\'0.0004, \'B. SUP. 0 INF. 2\' = 5.4\'+OU-\'0.3x10-2 cm-1, \'B. SUP. 0 INF. 4\' = - 8.33\'+OU-\'1.6x10-5cm-1. Foi medida e analisada a dependência angular da largura das linhas nas duas bandas de freqüências. Através de modelos teóricos (Watanabe, Orbach-Das-Sharma, Spinspin, Spin-spin Spin-órbita) calculamos o parâmetro de desdobramento a campo zero, \'B. SUP. 0 INF. 2\', do estado fundamental do íon Fe3+, para determinar qual o sítio que este íon ocupa no LiNbO3. / We report EPR measurements of Fe3+ ion in bulk LiNbO3 single crystals and in the form of fibers. Spin Hamiltonian for the Fe3+ ion in a trigonal symmetry (C3v) site is given by: H = \'beta\' \'VET.H\' \'VET.g\' \'VET.S\' + \'B20O20+B40O40. Measurements were performed at room temperature and two frequency bands, 10 and 34GHz, using three samples of LiNbO3 with different concentrations of Fe3+ g-factor and the crystal field parameters were found to be: for fiber (0.3 mol% of Fe3+) g = 1.9908 \'+OU-\' 0.0002, \'B. SUP. 0 INF. 2\' = 5.4\'+OU-\'0.2x10-2 cm-1 , \'B. SUP. 0 INF. 4\' = -7.7\'+OU-\'1.5x10-5cm-1, for the single crystal 90 (0.22 mol%) g = 2.0043\'+OU-\'0.0002, \'B. SUP. 0 INF. 2\' = 5.35\'+OU \'0.25x10-2 cm-1, \'B. SUP. 0 INF. 4\'= - 4.03\'+OU-\'1.4x10-5 cm-1, and for the single crystal 99 (0.02 mol%) g = 2.0026\'+OU-\'0.0004, \'B. SUP. 0 INF. 2\' = 5.4\'+OU-\'0.3x10-2 cm-1, \'B. SUP. 0 INF. 4\' = - 8.33\'+OU-\'1.6x10-5cm-1. The angular dependence of the line width were also measured and compared with theoretical model. To determine the substitutional site of Fe3+ ion in the LiNbO3 lattice, we calculated the zero field splitting parameter \'B. SUP. 0 INF. 2\' of the ground state, using many theoretical models (Watanabe, Orbach-Das-Sharma, Spin-spin, Spin-Spin Spinorbita).

O processo de interferência de RNA refere-se ao silenciamento pós transcricional seqüência-específico de genes em animais e plantas capaz de ser promovido por dsRNA homólogo à seqüência do gene silenciado. Este processo pode ser aplicado como terapia, que apresenta como vantagens a especificidade pelos alvos escolhidos, a possibilidade de tratar uma enorme gama de doenças genéticas, além do fato de ser muito potente e eficaz. Contudo, o principal desafio consiste em manter a estabilidade dos siRNAs nos fluidos biológicos, visto que estes são bastante susceptíveis à excreção renal e a degradação por RNAses. Com isso, reforça-se a necessidade de sistemas de liberação adequados, que sejam capazes de manter a estabilidade dos siRNAs por tempo suficiente para que atinjam os órgãos alvo da terapia e promover sua liberação sustentada. De particular interesse são determinadas proteínas e peptídeos de transdução (PTDs) que podem ser ligados a fármacos hidrofílicos e assim tornam possível com que estes atravessem membranas. Neste sentido, muitos sistemas carreadores não-virais tem sido estudados para a veiculação de siRNA, sendo de cunho inovador o desenvolvimento de sistemas de liberação nanoestruturados baseados em cristais líquidos funcionalizados com peptídeos de transdução de membrana para a veiculação tópica de siRNAs. Desta forma, nanopartículas de cristais líquidos de fase hexagonal contendo ou não os aditivos catiônicos polietileimina (PEI) e oleilamina (OAM) foram funcionalizadas com peptídeos de transdução de membranas TAT (TAT) ou penetratin (PNT). Os sistemas obtidos foram complexados com siRNA por interação eletrostática e caracterizados através de medidas de tamanho de partícula/ polidispersividade, potencial zeta e eficiência de complexação. A citotoxicidade dos sistemas foi avaliada em fibroblastos L929 pelo ensaio do MTT e por citometria de fluxo e a avaliação da transfecção in vitro foi realizada por citometria de fluxo e por microscopia de fluorescência. Os sistemas contendo PEI ou OAM apresentavam potencial zeta positivo e foram capazes de complexar o siRNA adicionado na concentração de 10 ?M. Os estudos em culturas celulares demonstraram que os sistemas contendo ácido oleico (AO) foram mais eficientes quanto à transfecção em células de fibroblastos L929 e esta eficiência de transfecção foi aumentada com a funcionalização com o peptídeo TAT. A partir daí, os sistemas selecionados foram avaliados quanto a penetração cutânea in vivo. Os sistemas nanodispersos formados por MO/AO/PEI proporcionaram uma maior liberação de siRNA na pele e a eficiência de supressão de TNF-alfa em modelo animal de inflamação cutânea foram maiores que formulações controle. Com isso, demonstrou-se que os sistemas desenvolvidos são promissores para a futura aplicação na terapia gênica tópica de doenças cutâneas inflamatórias. / The RNA interference process refers to the sequence-specific posttranscriptional silencing of genes in animals and plants capable of being promoted by dsRNA that are homologous to the sequence of the silenced gene. This process can be applied as therapy, which presents advantages such as the specificity to the chosen targets, the possibility to treat a variety of genetic diseases, besides being very potent and efficacious. However, the major hurdle consists in keeping the siRNAs stability in the biological fluids, because they are susceptible to renal clearance and degradation by RNAses. Thus, there is the need for suitable delivery systems, capable of maintaining the stability of siRNAs for sufficient time so they can reach the target organ in the therapy and promote sustained release. Of particular interest are certain proteins and peptides transduction domains (PTDs) that can be connected to hydrophilic drugs and thus make it possible to cross cell membranes. Within this context, many non-viral vectors have been studied for siRNA vehiculation which makes innovative the present study because it aims at the development of nanostructured delivery systems based on liquid crystals functionalyzed with membrane transduction peptides for the topical vehiculation of siRNAs. Thus, hexagonal phase liquid crystal nanoparticles containing or not the cationinc polyethylenimine (PEI) and oleylamine (OAM) were functionalyzed with membrane transduction peptides TAT (TAT) or penetratin (PNT). The obtained systems were complexed with siRNA by eletrostatic interaction and characterized for particle size, polidispersity, zeta potential and complexation efficiency. The cytotoxicity of the formulations was performed with L929 fibroblasts by MTT assay and flow cytometry and the in vitro transfection was evaluated by flow cytometry and fluorescence microscopy. The systems containing PEI or OAM presented positive zeta potential and could complex siRNA at the concentration of 10 ?M. The cell culture studies demonstrated that the systems containing oleic acid (OA) were the most efficient to transfect L929 cells and the transfection efficiency was enhanced with the functionalization with the TAT peptide. Thereafter, the selected systems were evaluated for the in vivo skin penetration. The nanosdispersed systems composed of MO/OA/PEI functionalyzed with TAT resulted in a higher siRNA penetration and release in the skin, promoting higher TNF alfa supression in animal model of cutaneous inflammation, compared to the control formulations. Hence, we demonstrated that the developed systems are promising for the treatment of inflammatory skin diseases.

Dans une approche de dimensionnement en fatigue basée sur un critère multiaxial, les paramètres d’entrée ducritère (contraintes, déformations, termes énergétiques) sont généralement calculés sur un état stabilisé. Dans lesmétaux, il s’agit souvent du premier cycle, en supposant que le matériau se comporte élastiquement ou présente desprocessus de plasticité très localisés. Dans les matériaux viscoélastiques comme les polymères, l’évolutionsignificative de la raideur en début de cyclage soulève la question de la stabilisation du cycle sur lequel lesparamètres mécaniques devraient être calculés. Un enjeu majeur est donc de définir et prédire cet état stabilisé, c’està dire non seulement l’évolution de la déformation moyenne qui accompagne le cyclage mais aussi la bouclestabilisée elle-même et les contributions énergétiques pertinentes. Pour être applicable à des structures, le modèledoit conserver un formalisme aussi maniable que possible.Dans cette étude, réalisée sur les 1000 premiers cycles de la vie d’un polyéthylène, il est montré, par des essaisde recouvrance, que la contribution viscoélastique à l’évolution de la déformation moyenne est majoritaire. Unintérêt particulier est donc porté à la caractérisation expérimentale et à la modélisation macroscopique de cet aspectdu comportement.La première partie du travail est menée dans un cadre purement mécanique. L’accumulation cyclique estétudiée expérimentalement au cours des premiers 1000 cycles à force contrôlée et faible fréquence, à la températureambiante. L’influence de la fréquence et du rapport de charge sur la réponse viscoélastique est étudiée. Lacomparaison d’essais de traction et de cisaillement de type Iosipescu permet de discuter les parts volumique etdéviatorique. Un modèle viscoélastique non linéaire isotherme en petites déformations est proposé dans le cadre dela Thermodynamique des Processus Irréversibles.Dans la deuxième partie, l’étude expérimentale et théorique est étendue au cadre thermo-mécanique. Latempérature est en effet intrinsèquement couplée à la viscoélasticité dans les polymères ; cet effet peut conduire àdes auto-échauffements importants. Les mêmes essais de traction et cisaillement sont réalisés par le LMGC deMontpellier avec une métrologie différente : la mesure de champs de température et déformation au cours de l’essaipermet de calculer les différents termes de l’équation de diffusion de la chaleur et d’accéder aux sources de chaleur.Ces résultats expérimentaux sont analysés et confrontés à une extension du modèle thermo-viscoélastique dumodèle dans laquelle le couplage est introduit via la thermo-élasticité (par la déformation volumique) et via ladissipation visqueuse (sur la base du principe d’équivalence temps-température). / Fatigue design approaches based on fatigue life criteria require as an input mechanical parameters (stress orstrain components or equivalent measurements, energetic terms) usually calculated over the first cycle, assumingthat the material behaves elastically or exhibits highly localized plasticity processes. In viscous materials likepolymers, such approaches raise the question of the stabilization of the cycle over which the mechanical parametersshould be computed. The challenge is not only to predict the ratcheting strain but also the stabilized loop itself andthe relevant energetic contributions, within a formalism as simple as possible to be used for structure simulations.In this study conducted in polyethylene, a special interest is paid on the viscoelastic contribution, expected tohighly contribute in the low stress range of high-cycle fatigue. A challenge is to accurately capture two time scales,i.e. the long term scale of strain ratcheting and the short term scale of the cycle itself.In the first part, cyclic accommodation is experimentally investigated over the first thousand cycles of forcecontrolledtests at room temperature. Viscoelasticity tackles in a specific way the frequency and mean stresssensitivity which are both varied in the experiments. Viscoelasticity also questions the volume / deviator partition:tension and shear tests are compared to highlight this point.After establishing from recovery tests that viscoelasticity mainly contributes to the ratcheting strain in bothexperiments series, a small-strain non-linear viscoelastic model is proposed in the framework of Thermodynamicsof Irreversible Processes. The aim is to capture the ratcheting strain evolution and recovery kinetics, as well as thestabilized loop area and dynamic modulus. The mean strain kinetics and non-recoverable term appearunderestimated, due to the fact that inelastic strain parts are not taken into account in the model. On the other hand,the loop area and rigidity are reasonably predicted.Volume / deviatoric contributions are on two counts an open issue, because of their different contribution tothermoelastic coupling. Thermo-mechanical coupling is examined in the last part of the presentation, by couplingthe above described model to temperature and analyzing the resulting heat sources evolution.

L’objet de cette thèse est de démontrer que pour certaines représentations p : GK −! GLn(Fp) continues de GK, il existe un relèvement r : GK −! Gln (Zp) de p en une représentation cristalline. C’est un problème purement local, tout comme les méthodes utilisées pour le résoudre. / In this thesis, we prove that certain representations of the absolute Galois group of a finite extension of Qp with coefficients in Fp lift to crystalline representation with coefficients in Zp.

The research work presented in this thesis comprises a detailed investigation of conductivity mechanism in crystalline polymer electrolytes and development of a new class of ceramic-polymer composite electrolytes for Li-ion batteries. Firstly, a robust methodology for the synthesis of monodispersed poly(ethylene oxides) has been established and a series of dimethyl-protected homologues with 13, 15, 17, 28, 29, 30 ethylene oxide repeat units was prepared. The approach is based on reiterative cycles of chain extension and deprotection, followed by end-capping of the oligomeric chain ends with methyl groups. The poly(ethylene oxide) homologues show a superior level of monodispersity to previous work and were subsequently used to prepare crystalline PEO6:LiPF6 polymer electrolytes. A correlation between the number of ether oxygens in the polymer chain and the ionic conductivity of crystalline polymer electrolytes has been established. The structure and dynamics of the monodispersed complexes were studied using solid-state NMR spectroscopy for the first time. The results are in agreement with the proposed mechanism of ionic conductivity in crystalline polymer electrolytes. A new class of composite solid electrolytes for all-solid-state batteries with a lithium metal anode is reported. The composite material consists of a 3D interpenetrating network of a ceramic electrolyte, Li₁.₄Al₀.₄Ge₁.₆(PO₄)₃, and an inert polymer (polypropylene), providing continuous pathways for the ionic transport and excellent mechanical properties. 3D connectivity of this novel composite was confirmed using X-ray microtomography and AC impedance spectroscopy.

The experiments to be described here were undertaken for the purpose of determining, if possible, by NMR techniques whether or not the hydroxyl protons in mica are bound in a regular crystalline array, and, if so, whether or not the hydroxyl protons occur in reasonably isolated pairs as in waters of hydration.

>Magister Scientiae - MSc / Crystalline basement aquifers are an important source of water supply in sub-Saharan Africa for various purposes. These aquifers are characterized by fractured rock networks which form pathways for groundwater recharge, flow, and discharge in subterranean groundwater areas. The fractured rock networks in these areas form fractured rock aquifers which in some cases are protected or reserved. In South Africa, various aquifers with these characteristics have been declared as subterranean groundwater control areas. The physical characteristics of these hydrogeological settings remains crucial in sustaining ecosystems and supporting socio-economic practices such as irrigation, among others. However, the role of fracture connectivity in crystalline basement aquifers remains poorly understood despite the well-established knowledge about the hydrogeological characteristics of such areas. / 2022

Semicrystalline polymers constitute the majority of the commercially manufactured polymers, mostly known as commodities with low modulus and inferior properties. A robust approach used in tailoring such commodity’s properties for more advanced applications is through the incorporation of inorganic nanoparticles (NPs). Over the past half century, polymer nanocomposites (PNCs) have attracted extensive interest in fundamental research and technological applications. However, NPs have been found to result in complicated alterations in the semicrystalline polymer crystallization kinetics, and their crystalline morphology, which could either synergistically or adversely affect the final composite properties. A comprehensive understanding of this topic is still lacking, which with one could tune the final polymer properties for various cutting-edge applications. In this dissertation, we focus on the crystallization kinetics of semicrystalline PNCs and the connection between the morphology and the mechanical (and rheological) properties of such hybrid systems. First, we control the NP dispersion and self-assembly in a semicrystalline poly(ethylene oxide) (PEO) matrix using both bare and polymer-grafted NPs. We show that bare NPs (with different sizes) and unimodal poly(methyl methacrylate) (PMMA)-g-SiO2 NPs uniformly disperse in a PEO matrix because of the favorable interaction between the matrix and the NP surface (or the PMMA brush). Grafting the latter NPs with a short dense polystyrene brush that is immiscible with PEO while varying the PMMA grafting parameters induces self-assembly and leads to various NP structures: well-dispersed, connected sheets, strings, and large aggregates. Next, we systematically investigate the role of bare and self-assembled grafted NPs on the spherulitic growth kinetics of semicrystalline polymers. In all cases, the incorporation of spherical NPs suppresses the polymer growth kinetics. Using rheological measurements, we show that the reduction in growth is mainly attributed to the NPs increasing the melt viscosity; whereas, they minimally alter the secondary nucleation process. Surprisingly, the PNC growth kinetics is suppressed in two apparently universal manners when plotted as a function of confinement: NP dominated and brush-controlled regimes. Bare NPs and large aggregates of polymer-grafted NPs appear to nearly follow the same dependence for the role of additives on polymer viscosity, weakly suppressing the growth kinetics. On the other hand, all the other self-assembled NP structures showed much stronger growth reductions because of the larger increase in the melt viscosity by the chemically bonded brush. Given our prior knowledge of the PNC growth kinetics, we then draw generalized trends for the role of bare and grafted NPs in nucleating semicrystalline polymers. This is achieved by comparing the polymer crystallization kinetics in the presence of large, asymmetric, immobile fillers (selected from the well-established literature) to those smaller, spherical, mobile NPs (examined throughout this thesis). Generally, NPs serve as heterogenous nucleation sites when incorporated at smaller amounts, leading to accelerated crystallization kinetics. At larger filler contents, NPs confine the polymer chains into smaller domains and become more susceptible to aggregation, which results in antinucleating effects and suppressing the crystallization rate. Such competing effects result in a maximum nucleation efficiency at moderate filler contents. It is also worth noting that the degree of nucleation enhancement and subsequent suppression depends on the system and is controlled by NP dispersion, geometry, and surface chemistry. For example, one- and two-dimensional NPs usually result in a higher nucleation power compared to spherical NPs. Another major difference between mobile and immobile fillers is that when slowly crystallizing from the melt, the smaller diffusive NPs can be segregated and ordered into hierarchal structures (interlamellar sheets and interfibrillar and interspherulitic aggregates). This provides a much richer class of materials with a kinetics route in controlling NP assemblies. Finally, we create robustly toughened semicrystalline polymers by confining the PEO crystallization using a densely grafted PMMA brush (i.e., PMMA-g-SiO₂) with different molecular weights. For comparison, we prepare linear PMMA/PEO blends with equivalent PMMA molecular weights and volume fractions to those of the nanocomposites. We show that PMMA-g¬-SiO₂ NPs surpass linear PMMA homopolymers in terms of toughening the PEO matrix, with the grafted system experiencing relatively higher connectivity and lower crystallinity. At moderate confinement, the nanocomposite sustains a maximum modulus increase of 42%, with around a 200-fold increase in the PEO toughness. This provides a novel route for toughening semicrystalline polymers using noncrystallizable polymer-grafted NPs.

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