Experimentalmente, a transição entre as fases gel e gel-líquida de bicamadas fosfolipídicas pode ser mensurada por técnicas de anisotropia de fluorescência. A partir de uma sonda interna à membrana, a diferença entre as radiações absorvida e emitida, causada pela rotação da sonda no intervalo de fluorescência, relaciona-se com a fluidez da membrana. Com esta técnica aplicada à sondas DPH, foi encontrada influência do líquido iônico (LI) C14MImCl na temperatura de transição de fase de fosfolipídios carregados (DPPG), mas não nos casos neutros (DPPC e DMPC). A temperatura de transição para DPPG apresenta queda de 45oC, em estado puro, para 26oC com concentração de 30%mol de LI. Neste estudo, simulações de dinâmica molecular foram conduzidas de forma a descrever as interações de LI com os fosfolipídios de bicamadas em dois casos, DPPC e DPPG, e de analisar o comportamento dinâmico da sonda. Diferentes condições iniciais de mistura entre lipídios e LI foram consideradas nas simulações. Os resultados indicam que, quando misturadas aleatoriamente, ambos os lipídios apresentam agregação espontânea, evoluindo para forma lamelar com LI distribuído uniformemente. Quando uniformemente distribuído, o LI diminuí a interação entre lipídios e outras moléculas do sistema nos dois casos, porém com maior intensidade em DPPG devido à repulsão dos contra íons catiônicos (Na+) do lipídio, enquanto que em DPPC os contra íons aniônicos provenientes do LI (Cl-) mantém-se perto da interface. O comportamento da sonda foi qualitativamente reproduzido e visto ser altamente correlacionado com a fluidez das caudas, medida por meio do parâmetro de ordem deutérica. Por conta da equivalência das caudas entre DPPC e DPPG, encontrou-se omportamento similar nos dois sistemas. / The gel-liquid phase transition of phospholipid bilayers can be experimentally measured via fluorescence anisotropy techniques. Using a fluorescent probe within the membrane, the difference between absorbed and emitted radiation due to rotational movement can be related to the bilayer fluidity. The use of the fluorescent probe DPH shows the influence of the ionic liquid (IL) C14MImCl on the phase transition temperature of charged lipids (DPPG) but not neutral ones (DPPC and DMPC). The phase transition temperature for DPPG bilayers dropped from 45oC, in pure state, to 26oC, with 30%mol concentration of IL. In this study, molecular dynamics (MD) simulations were performed in order to describe the IL interactions with the phospholipids in the membranes for two cases, DPPG and DPPC, and to analyze the dynamical behavior of the probe. Different initial conditions of the mixture between IL and lipids were considered in the simulations. The results indicate that in random initial conditions, both lipids spontaneously aggregates with the IL into a bilayer shape with IL uniformly distributed across it. The uniform distribution of IL in the membranes decreased the total interaction of the lipids and the other molecules in the system for both cases, but with higher influence in DPPG due to repulsion of cationic counter ions from the lipids (Na+), whereas in DPPC the anionic counter ions from IL (Cl-) remained closer to the bilayer interface. The probe behavior was qualitatively verified and found to be highly correlated with the lipid tails fluidity, through the calculated Deuter order parameter. Because of tails equivalence between the DPPG and DPPC, it was found a similar behavior of the probe in both systems.

La tectonique actuelle et récente (~40 Ma) de la région Egée-Anatolie en fait un laboratoire naturel privilégié pour l'étude de la déformation continentale. L'analyse de la structure détaillée et de la déformation du manteau de cette zone de collision continentale immature constitue une étape indispensable pour comprendre les relations entre la cinématique de surface et la dynamique du manteau. La structure du manteau supérieur a été étudiée à l'échelle de la région en réalisant un modèle 3-D de la vitesse des ondes S par tomographie télésismique en ondes de surface. Les résolutions latérale (~100-200 km) et verticale (~50 km) des images obtenues, grâce à l'utilisation d'un réseau sismologique large bande composé de ~150 stations (permanentes et temporaires (expérience SIMBAAD), apporte de nouvelles contraintes sur la structure du manteau de la Grèce continentale à l'Anatolie centrale. Cette tomographie révèle notamment des corrélations verticales claires entre les géométries des déchirures affectant le slab Hellénique et celles des zones de cisaillement trans-tensives qui accommodent le mouvement rapide du bloc Egéen vers le SW. Le slab Chypriote est clairement imagé dans le modèle 3-D comme plissé et déchiré en plusieurs segments sous l'Anatolie. L'analyse de l'anisotropie azimutale par méthode de réseau sur les ondes de Rayleigh a permis de proposer l'existence de deux couches anisotropes dans le manteau supérieur. L'étude de variations latérales de l'anisotropie sous la région suggère que la déformation des slabs et la cinématique de surface sont contrôlées par des flux mantelliques toroïdaux de différentes échelles. / The last ~40 M.y. tectonics of the Aegean-Anatolia region has shaped a natural laboratory ideal to study the continental deformation processes. The detailed analysis of the mantle structure and deformation of this non-mature continental collision zone constitutes an essential step to investigate the contribution of mantle dynamics to surface kinematics. The upper mantle structure is investigated over the entire region through a new 3-D S-wave velocity model from surface-wave tomography. The model reveals remarkable vertical correlations between geometries of the Hellenic slab tears and geometries of shear zones which accommodate the rapid SW movement of the Aegean bloc. The Cyprus slab is clearly identified in the 3-D model as fold and torn in tree segments beneath Anatolia. The observed azimuthal anisotropy from Rayleigh-wave array analysis suggests the existence of two anisotropic layers in the upper mantle. The lateral variations of anisotropy beneath the region are interpreted as the indication of toroidal mantle flows at different scales governing the slabs deformation and the surface kinematics.

Nenhuma / In this work, the strong correlation between the structural and magnetic properties in systems of reduced dimensionality is explored. Particularly, the magnetic properties of epitaxially grown ultrathin films and coupled layers, as a function of their constitution, thickness, structure and temperature, are studied. The investigated systems illustrate that perpendicular magnetic anisotropy in thin films can be achieved via tetragonal distortion or perpendicular exchange coupling. Specifically, Fe films grown on Rh(001) are examined, with emphasis both on their spin reorientation transition and on a complex magnetic structure existing at the first Fe monolayer. Contrasted to Fe/Rh(001), Ni films grown on Rh(001) and on Pd(001) are studied, highlighting the reverse spin reorientation transition and the perpendicular magnetic anisotropy originating from the large tetragonally distorted structure created by epitaxy. Concurrently, the indication of induced moments in the Pd(001) substrate in this system is also considered. Additionally, Ni films grown on Pd(001) covered with CoO antiferromagnetic layers are explored, emphasizing the effect of exchange coupling on their magnetic perpendicular anisotropy. Finally, the system consisting of a CoO single layer grown directly on Pd(001) is investigated, highlighting the indication of a ferromagnet under-layer, induced in the Pd(001) substrate by the CoO antiferromagnetic layer. / Neste trabalho, a forte correlação entre a estrutura e as propriedades magnéticas de sistemas de dimensionalidade reduzida, é explorada. Em particular, as propriedades magnéticas de filmes e camadas acopladas epitaxiais, em função de sua constituição, espessura, estrutura e temperatura são investigadas. Os sistemas investigados exemplificam que a anisotropia magnética perpendicular em filmes finos pode ser alcançada via distorção tetragonal ou pelo acoplamento de troca perpendicular. Especificamente, filmes de Fe crescidos em Rh(001) são investigados com ênfase em sua transição de reorientação de spin e em uma estrutura magnética complexa presente na primeira monocamada de Fe. Em contraste com Fe/Rh(001), filmes de Ni crescidos em Rh(001) e em Pd(001) são estudados destacando-se a transição de reorientação de spin reversa e a anisotropia magnética perpendicular, com origem na estrutura tetragonal distorcida criada por epitaxia. Concorrentemente, a indicação de momentos magnéticos induzidos no substrato de Pd(001) nesse sistema também é considerada. Além disso, filmes de Ni crescidos em Pd(001), cobertos com camadas de CoO antiferromagnéticas, são exploradas dando ênfase no efeito de acoplamento de troca em sua anisotropia magnética perpendicular. Por fim, o sistema constituído de uma camada de CoO, crescida diretamente em Pd(001), é investigado, destacando-se a indicação de uma camada ferromagnética induzida no substrato de Pd(001) pela camada antiferromagnética de CoO.

O conhecimento das propriedades dielétricas do osso tem se mostrado importante na medicina ortopédica para aplicações em diagnóstico e tratamento da osteoporose, de fraturas, controle da osteonecrose e, também, na área de cerâmicas industriais (porcelana de osso). Neste trabalho, apresenta-se uma metodologia de avaliação das permissividades complexas de osso cortical de fêmur bovino desidratado, utilizando-se o método de impedância em uma linha de transmissão. Esta se constitui de um condutor coaxial, do tipo N, de uma porta, e um terminal aberto, que é conectado a um analisador de impedância. A faixa de freqüência considerada está compreendida entre 100 Hz e 1 MHz. Em particular, apresenta-se uma metodologia de caracterização dielétrica de osso, com ênfase nas avaliações das suas características anisotrópicas. Alguns resultados das propriedades dielétricas são comparados com os valores experimentais e teóricos disponíveis na literatura. Este procedimento é justificado, haja vista que os valores experimentais encontrados na literatura são esparsos e pontuais, quando se considera toda a faixa do espectro eletromagnético avaliado. Ressalta-se que não existe um consenso entre especialistas da área sobre a precisão e metodologia de obtenção destes. O mesmo ocorre com relação aos protocolos de medição propostos nas normas internacionais, em particular, quando se buscam padrões de avaliações de materiais biológicos sólidos. Os valores da permissividade obtidos com as medidas realizadas entre 100 Hz e 1 MHz evidenciam a presença de uma anisotropia efetiva, sendo esta característica ressaltada em freqüências da ordem de algumas dezenas de kHz. Embora o fenômeno de anisotropia não se manifeste nas faixas superiores à anteriormente mencionada, algumas medidas foram realizadas, também, numa faixa de freqüências superiores, entre 50 MHz e 3 GHz. Utilizou-se um analisador de redes conectado a um dispositivo coaxial de duas portas, visando avaliar a adequabilidade dos procedimentos de preparação do tecido ósseo na avaliação das características de materiais biológicos em altas freqüências, já que se dispunha da instrumentação necessária e de alguns resultados, obtidos na literatura, para sua validação. / The knowledge of the dielectric properties of bones has become important to orthopedic therapy, for applications in the diagnosis and treatment of osteoporosis, fractures, and osteonecrosis, as well as is the industrial ceramics field (bone china). This work proposes a methodology for the evaluation of the complex permittivity of a dehydrated cortical bone of bovine femur, using an impedance method in a transmission line. The transmission line is composed by an one-port open-ended N-type coaxial conductor, connected to an impedance analyzer. The frequency range studied was 100 Hz - 1 MHz. The methodology proposed is proper for the dielectric characterization of bone and this work emphasizes the evaluation of its anisotropic characteristics. Some dielectric properties experimentally found in this work are compared to the experimental and theoretical results available in literature, which are sparse and punctual in the considered electromagnetic spectrum. It is pointed out that there is no agreement among the experts when the subject is the proper measuring methodology and its precision. The same occurs when the subject is the measuring protocols proposed by the international standards, especially for solid biological materials. The permittivity results obtained in frequencies between 100 Hz and 1 MHz evince an effective anisotropy, which stands out in frequencies of a few tens of kHz. Although the anisotropy phenomenon does not occur in a frequency range higher than the one previously mentioned, some measures were taken in the 50 MHz - 3 GHz range for validation, based on results from literature. A network analyzer and a two-port coaxial device were then used in such measures, which aimed the evaluation of the adequacy of the procedure used in the preparation of the bone tissue in high-frequency measurements.

The Middle-Upper Jurassic sedimentary rocks (i.e., the Entrada Sandstone, Wanakah Formation, and Morrison Formation) in western Colorado were mostly deposited in the Paradox Basin and form part of the modern-day Colorado Plateau in the Cordilleran foreland region. These rocks were deposited in the Mesozoic during periods of active tectonic processes in western and eastern Laurentia due to the Cordilleran magmatism and continued rifting of Pangaea, respectively. The Middle-Late Jurassic sedimentary record in the Paradox Basin shows rapid transition in depositional environments, pulses in sedimentation, post-depositional alteration, and changes in provenance. This dissertation project utilizes three main scientific tools to address pertinent geologic questions regarding the stratigraphic evolution of these units in the Paradox Basin. U-Pb detrital zircon geochronology of sandstones from these units show local and distal provenance sources. The anisotropy of magnetic susceptibility (AMS) of sediments and rock magnetism attribute the post-depositional alteration to percolation of ferruginous fluids driven by an adjacent regional uplift. Multi-geochemical proxies in paleosols suggest variable redox conditions, and a sub-humid to humid paleoclimate with seasonal precipitation during sedimentary hiatus in the Paradox Basin.

Válvulas de Spin têm sido utilizadas na fabricação de sensores magnéticos e memórias de acesso randômico, sendo muito importantes do ponto de vista tecnológico. Neste trabalho, foram exploradas as análises das curvas de reversão de primeira ordem da magnetorresistência (MR-FORC), bem como ajustes das curvas de histereses da magnetização e magnetorresistência, para estudar o fenômeno de exchange-bias, anisotropia magnética e propriedades magnetorresistivas. As válvulas de spin estudadas foram do tipo NiFe/Cu/NiFe/IrMn, tendo camadas semente e de cobertura de Ta, preparadas por sputtering. Um modelo fenomenológico de parede de domínios no material antiferromagnético (AFM) foi utilizado, levando em conta as anisotropias magnéticas e interações entre as camadas. Também foram consideradas certas dispersões da anisotropia dos grãos ferromagnéticos (FM) e antiferromagnéticos (com distribuições Gaussianas) em torno dos respectivos eixos de anisotropia uniaxiais. Para o ajuste da magnetização para algumas amostras, foi necessário utilizar uma rotação no plano de um ângulo nos eixos de anisotropia uniaxiais do FM e AFM, em relação à direção do campo magnético aplicado durante a deposição dos filmes. Bons ajustes das curvas de histereses das magnetizações foram obtidos nas direções medidas do campo magnético aplicado. Um método baseado em medidas de variações angulares da magnetorresistência em campos constantes foi proposto para extrair este ângulo para cada amostra. Foram obtidas razoáveis concordâncias entre estes ângulos e os correspondentes extraídos dos ajustes das curvas de magnetização. Através da análise dos diagramas da MR-FORC e de simulações indicados dos resultados dos ajustes das histereses da magnetização, foi encontrada uma relação direta entre os campos de interação (e suas incertezas) com os campos de exchange-bias (HEB) dos grãos da distribuição (extraídos das simulações, usando a largura da distribuição obtida do ajuste). Resumindo, esta análise mostrou que esta técnica permite extrair informações comparativas sobre a dispersão dos eixos de anisotropia dos grãos FM e AFM em torno do eixo de anisotropia uniaxial, o que pode ser importante na caracterização dos sensores magnetorresistivos. Além disso, análise dos diagramas MR-FORC indicaram início da presença de descontinuidade na camada de NiFe presa em 27, com um aumento acentuado (acima do previsto) para a amostra com 25. Este aumento acima do previsto corrobora com nossa hipótese. As simulações das curvas de histerese da magnetorresistência não foram muito bons, indicando que melhorias devem ser introduzidas no modelo utilizado para a simulação da histerese da magnetorresistência, obtidos a partir dos ângulos das camadas ferromagnéticas livre e presa. A questão referente a presença em algumas das amostras de um desalinhamento entre os eixos fácéis do FM e do AFM ainda é uma questão em aberta, mas neste trabalho foi encontrado que este ângulo é igual a 2. / Spin Valves have been employed as magnetic sensors and used in random access memories, showing they are very important in terms of technological point of view. In this work, analyses of the magnetoresistance first order reversal curves (MR-FORC) have been used, as well as fittings of the magnetization and magnetoresistance hysteresis, to study the exchange-bias phenomena, magnetic anisotropies and magnetoresistance in spin valves. Sputtering has been used to the deposition of NiFe/Cu/NiFe/IrMn, and Ta has been deposited as seed and buffer layers. A domain wall model (in the antiferromagnetic layer) taking into account the magnetic anisotropies and the interactions between the layers has been employed to fit the magnetization hysteresis. Some textures have been also introduced to take into account the ferromagnetic (FM) and antiferromagnetic (AFM) grains dispersion (with Gaussian distributions) centered around the respective uniaxial anisotropy axes. However, to obtain good fits for some samples, it has been necessary to include an in-plane rotation of an angle of the both FM and AFM easy axes in relation to the field direction applied during the growing of the films. Good fits of the magnetization hysteresis have been obtained for all measured directions of the applied field. A new method based on the angular variation of the magnetoresistance to constant fields has been proposed to extract directly these angles. Reasonable agreements have been obtained between these angles and the corresponding ones extracted from the fits of the magnetization loops. Through the analyses of the MR-FORC and from the simulations indicated by the parameters (obtained from the fittings of magnetization loops), a direct relation between the interaction fields (and its uncertainties) and the exchange-bias fields of the grains of the distribution (extracted from the simulations, using the width of the distribution obtained from the magnetization fittings) has been identified. In summary, this analysis has showed that this technique allows to extract comparative information about the dispersion of the anisotropy axes of the FM and AFM grains around the uniaxial axis, which can be very import to the characterization of spin-valve based sensors. Besides, MR-FORC analyses have also indicated the presence of a threshold of discontinuity of the pinned NiFe layer at 27, showing a huge increase (above of the expected) to the sample at 25, and this unexpected increasing has corroborated with our hypothese. Simulations of the magnetoresistance loops have not been good, indicating that improvements should be included in the model employed to simulate these curves, obtained from the pinned and free angles of the NiFe layers. Concerning the case of the presence of misalignments of FM and AFM for some samples, it is still an open question, but in this work, we have found that this angle () is equal to 2.

Thesis. 1977. Sc.D.--Massachusetts Institute of Technology. Dept. of Civil Engineering. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING. / Vita. / Bibliography: leaves 381-386. / Sc.D.

Ceramic materials are natural or synthetic, inorganic, non-metallic materials incorporating ionic and covalent bonding. Most ceramics in use are polycrystalline materials where grains are connected by a network of solid-solid interfaces called grain boundaries. The structure of the grain boundaries and their arrangement play a key role in determining materials properties. Developing a fundamental understanding of the formation, structure, migration and methods of control grain boundaries have drawn the interest of scientists for over a century.<br> While grain boundaries were initially treated as isotropic, advances in materials science has expanded to include energetically anisotropic boundaries. The orientation and structure of a grain boundary, determined by this anisotropy, controls the mobility of a grain boundary. The mobility is the controlling factor during grain growth impacting the microstructural evolution of a material.<br> This thesis covers fundamental research to model how a materials’ equilibrium crystal shape can be used as a grain growth control mechanism. First an overview of ceramic processing and microstructural development is presented with a focus on the role of grain boundaries in determining the properties of a material. The role of anisotropy and related recent work is highlighted setting the foundation for the link between the equilibrium crystal shape and grain growth. A discussion on the selection of the NiO-MgO system for all experimental work is included.<br> A novel production and processing route for NiO-MgO was developed. Mechanical alloying and milling resulted in significant impurity contamination therefore a chemical production route was used. A modified amorphous citrate process was developed where metal salts containing Ni and Mg were mixed with a polyfunctional organic acid. Rapid dehydration and calcination at 500°C resulted in chemically homogeneous powders. The amorphous citrate production route produced powder with crystallites ranging from 244-393 nm and agglomerates ranging from 20-300 μm with plate-like morphology.<br> NiO-MgO powders produced via the amorphous citrate method were sintered using various techniques. Conventional sintering was unable to produce fully dense samples peaking with relative densities from 95-96%. The introduction of pressure through spark plasma sintering and hot pressing improved the relative sample density to 97-100%. It was discovered that exposure to the vacuum required for spark plasma sintering and hot pressing resulted in the reduction of NiO. Spark plasma sintering created oxygen depleted regions and hot pressing further reduced NiO to pure nickel metal which precipitated out at the grain boundaries.<br> Due to the poor sintering behavior of NiO-MgO grain growth experiments were carried out on the large agglomerates formed during the amorphous citrate process. Agglomerates with more than 50 grains with a thickness of at least 1 μm were selected. Grain growth was measured across five compositions with Ni:Mg ratios of 100:0, 75:25, 50:50, 25:75, 0:100. The average grain size and growth rate increased with increasing nickel content with a significant jump between 50% and 75%. Increasing nickel content was also observed to correspond with a higher number of grains exhibiting surface faceting.<br> The NiO-MgO equilibrium crystal shape as a function of composition was measured previously. To make the equilibrium crystal shape a more viable control for grain growth a quantitative microstructural characterization technique was developed to measure a materials equilibrium crystal shape. Topographic surface information (surface facets measured by atomic force microscopy, AFM) and grain crystallographic orientation (measured by electron back-scattered diffraction, EBSD) were combined to produce the crystallographic topography of a sample surface. Surface crystallographic topography was used to identify the faceting behavior of grains with a range of orientations. Using the combined data, facet stability maps (n diagrams) for NiO-MgO were developed.<br> Controlling grain growth via the equilibrium crystal shape offers the potential to produce microstructures with a high frequency of desirable grain boundaries (grain boundary engineering) and therefore properties. The combination of using AFM and EBSD to create crystallographic topographical surface data and n-diagrams has been demonstrated. N-diagrams for most materials do not exist, but the technique used here can be applied to a wide range of materials and will expand the ability to control microstructures of ceramic materials.<br><br>

Les progrès de l'imagerie sismique ces trente dernières années ont permis de révéler la structure complexe de la graine : une anisotropie cylindrique de quelques pourcents dont la structure fine présente des variations radiales et latérales. Ce travail de thèse s’est concentré sur les différentes dynamiques susceptibles de provoquer une telle structure. [Il y a autre chose dans cette structure]Nous avons revisité la dynamique induite par la force de Lorentz, discutant les conditions aux limites, la croissance de la graine et la stratification en densité. La déformation n’est raisonnablement suffisante que pour des viscosités inférieures à 1012 Pa.s, dans la fourchette basse des estimations. Les modèles d'écoulements globaux dans la graine peuvent se classer en deux grandes catégories. Pour un profil de densité stable, seul un forçage extérieur, tel que la force de Lorentz, peut induire un écoulement. Dans le cas instable, la dynamique est contrôlée principalement par des instabilités de convection. Les nouvelles estimations de la diffusion thermique limitent les instabilités thermiques à des âges de graine de l'ordre de la centaine de millions d'années. En se focalisant sur deux paramètres, la viscosité et l'âge de la graine, nous avons construit un diagramme de régime qui compare quantitativement les différents modèles proposés dans la littérature. En croisant amplitude du taux de déformation et géométrie attendues, on peut raisonnablement restreindre les domaines qui pourraient engendrer la structure observée. Pourtant, aucun modèle n'est pour l'instant capable d'expliquer à la fois l'amplitude et la géométrie de l'anisotropie sismique et encore moins la dichotomie Est-Ouest. La couche F est une anomalie dans le noyau externe : d’une épaisseur de 200 km environ, à la base du noyau externe, elle présente des vitesses d’ondes sismiques plus faibles que celles prédites pour un noyau liquide parfaitement mélangé. Elle est interprétée comme une zone chimiquement appauvrie, en contradiction avec la cristallisation de la graine qui libère des éléments légers à la surface même de la graine. Nous étudions la possibilité d’une cristallisation en volume dans cette couche. Les particules de fer solides sédimentent en croissant dans un liquide de plus en plus appauvri en éléments légers. Cette neige de fer est stable sous certaines conditions, étudiées ici. / In the past thirty years, our understanding of the inner core structure has increased with the number of seismic studies. Observations reveal a global anisotropy with a cylindrical symmetry and radial and lateral heterogeneities. In this work, I have studied different hypothesis on the dynamics of the inner core to explain these observations. Revisiting the dynamics induced by the Lorentz force, we studied the effect of new boundary conditions, the effect of stratification and growth rate. However, the obtained flow is not strong enough to deform the media for viscosities larger than 1012 Pa.s, in the lower bound of the published inner core estimates. Deformation mechanisms can be subdivided between natural convection (arising from unstable thermal or compositional gradients) and externally forced flows, like the one induced by the Lorentz force. Recent estimates of the thermal diffusivity of iron at high pressure limit the possibility of thermal convection to an age of the inner core lower than a hundred of millions years. Two key parameters emerge for the inner core dynamics: the sign and strength of the density stratification and the viscosity of the inner core. We construct a regime diagram for the Earth’s inner core dynamics that compares the different published models in term of maximum instantaneous deformation rate. This diagram allows us to compare both expected strain rate and deformation geometry with the seismic observations. However, we find that no published model can explain all the seismic observations. The inner core anisotropy and the hemispherical dichotomy are especially difficult to reconcile with these models. The F-Layer is a 200km anomalous layer at the bottom of the outer that presents low P-Wave velocities compared to well-Mixed model. It has been interpreted as a layer depleted in light elements, whereas we usually consider that light elements are expelled at the surface of the inner core by freezing of the outer core alloy. We study the hypothesis of freezing in the bulk of the layer, with iron particles growing and settling in an increasingly depleted liquid.

Cette thèse a porté sur l'étude des propriétés structurales et électroniques d'une série de complexes cubiques A-FeCo représentant des modèles moléculaires des CoFe-PBA. Ces cubes hétérobimétalliques neutres de formule A{Fe4Co4(CN)12} reproduisent une série d'unités cubiques uniques excisées du composé inorganique de type " bleu de prusse ". Le composé moléculaire octamétallique est composé de 4 ions FeIIBS, 3 ions CoIIIBS et 1 ion CoIIHS reliés par des ponts cyanures. Un monocation est hébergée à l'intérieur du cube. Les ions métalliques situés au coin du cube sont liés par des ligand tridentés de type scorpionate (Tp pour Fe et pzTp pour Co). La présence d'un ion Co (II) non équivalent induit un abaissement de la symétrie du Td à C3v. La DRX sur monocristaux a permis de déterminer avec précision l'emplacement du cation inséré dans le cube. En raison de la présence d'une charge négative formelle dans l'un des coins de la cage (celle accueillant l'ion Co (II)), deux types d'interactions entre le cation et le cube ont été postulés. L'une est une interaction électrostatique, et l'autre est l'interaction entre le cation (acide de Lewis) et les systèmes de cyanure (base de Lewis). Au sein de la famille des cubes contenant des ions alcalins, le Cs + interagit avec les 12 ponts cyanures alors que le K + n'interagit qu'avec trois d'entre eux. La spectroscopie RMN 133Cs a permis de confirmer une interaction chimique entre le césium (invité) et la cage (hôte). Ces cubes ont montré une remarquable capacité d'encapsuler différentes monocations de tailles et de nature différentes. / This thesis has focused on the investigation of the structural and electronic properties of a series of A-FeCo cubic complexes representing molecular models of the CoFe-PBAs. These neutral heterobimetallic cubes of abbreviated formula A-{Fe4Co4(CN)12} reproduce a series of single cubic units excised from the Prussian Blue type framework. The octametallic anionic core is composed by 4xFeIILS, 3xCoIIILS and 1xCoIIHS connected via bridging cyanides. A monocation is encapsulated inside the cube. The metal ions situated at the corner of the cube are facially capped by tridentate “scorpionate ligand” (Tp for Fe and pzTp for Co). The occurrence of one non-equivalent Co(II) ion induces a lowering of the symmetry from Td to C3v. Single crystal XRD allowed determining precisely the location of the inserted cation in the cube. Because of the presence of a formal negative charge in one of the corner of the cage (that accommodating the Co(II) ion), two types of interactions between the cation and the cube have been postulated. One is an electrostatic interaction, and the other one is the interaction between the cation (Lewis acid) and the cyanide systems (Lewis base). Within the family of alkali ion containing cubes, the Cs+ interacts with the 12 cyanide bridges whereas the K+ interacts with only three of them. The 133Cs-NMR spectroscopy allowed confirming a through bond interaction between the guest caesium and the host cage.