No description available.

Ce travail est consacré à la synthèse et à la caractérisation de composés chalcogénures. Pour la plupart nouveaux, ces composés ont la particularité de présenter des structures complexes ou dont le désordre amène une certaine complexité. La première partie de ce manuscrit est consacré à l’étude du nouveau composé monocristallin Ba0,5Cr5Se8 et de la solution solide polycristalline BaxCr5Se8 (0,5 ≤ x ≤ 0,55). Ce composé fait partie de la famille des pseudo-hollandites. Sa structure cristalline a été déterminée par diffraction des rayons X sur monocristal, un abaissement de la symétrie est observé par rapport aux pseudo-hollandites usuelles. Ces composés sont antiferromagnétiques avec une température de transition unique à 58 K, la structure magnétique du composé a été déterminée par diffraction des neutrons sur échantillon polycristallin, et sa maille magnétique correspond à une maille cristalline doublée selon b et c. Les propriétés thermoélectriques des composés sont étudiées, Ba0.5Cr5Se8 présente une ZT de 0,12 à 800 K. La deuxième partie s’est d’abord focalisée sur une structure similaire à la précédente, TlIn5Se8. Toutefois trop résistif, les structures de deux nouveaux composés ont été étudiées : TlIn4,8Cr0,2Se8 et Tl0,98In13,12Se16,3Te2,7. Ce dernier présente sur certains sites un désordre considéré statique. Finalement, le dernier chapitre a permis de mettre en avant des composés de la famille de composé lamellaire MnPSe3, ayant la particularité de présenter une paire P2. La structure du nouveau composé In2Ge2Te6 est résolue et les propriétés thermoélectriques des composés InSiTe3, Cr2Si2Te6, Cr2Ge2Te6 et In2Ge2Te6 sont étudiées. Des défauts d’empilement ont été mis en lumière et expliquent l’impact sur le libre parcours moyen des phonons. L’ensemble des composés dont les propriétés thermoélectriques ont été étudiées présentent des conductivités thermiques faibles, bien en deçà du W.m-1.K-1 dans de nombreux cas. Des ZTs de 0,18 à 673 K et 0,43 à 773 K sont trouvées pour In2Ge2Te6 et Cr2Ge2Te6. / This work has been focused on synthetizing and characterising chalcogenide compounds. Most new, those compounds show complex structures or where disorder bring complexity. The first part of this manuscript is dedicated to the study of the new single-cristalline Ba0.5Cr5Se8 and of the related polycristalline solid-solution BaxCr5Se8 (0.5 ≤ x ≤ 0.55). This compound is part of the pseudo-hollandite family. Its cristalline structure has been resolved by means of single-crystal X-ray diffraction, a lowering of symetryis observed compared to usual pseudo-hollandites. All antiferromagnetic, the compounds exhibit a transition at 58 K, the magnetic structure has been resolved using neutron diffraction on polycrystal and is twice the cristalline one along b and c. Thermoelectric properties of the compounds have been studied and a maximum ZT of 0.12 is observed at 800 K for Ba0.5Cr5Se8. The second section has first focused on a similar structure to the previous one, TlIn5Se8. Although too resistive to be interesting, two new compounds have been studied: TlIn4.8Cr0.2Se8 and Tl0.98In13.12Se16.3Te2.7. The latter quaternary exhibits static disorder on specific crystallographic sites. The last chapter highlights compounds from the lamellar compound MnPSe3 family, with the particularity to possess P2 pairs. The structure of the new In2Ge2Te6 has been resolved and thermoelectric properties of the InSiTe3, Cr2Si2Te6, Cr2Ge2Te6 and In2Ge2Te6 have been studied. Stacking faults were observed in In2Ge2Te6 and explain the impact on the phonon mean free path. All the compounds whose thermoelectric properties have been studied exhibit low thermal conductivity, below 1 W.m-1.K-1 for most of them. ZTs of 0.18 at 673 K and 0.43 at 773 K were found for In2Ge2Te6 and Cr2Ge2Te6.

The electromagnetic diffraction problem is formulated in terms of either the electric or magnetic Hertz potential. This approach is equivalent to traditional methods based on the vector form of Green's theorem, but it is less widely known. The components of the Hertz potentials are independent, and each satisfies a scalar wave equation. The formal solutions for these components are therefore given by two equations referred to as the Rayleigh formulas, which are familiar from scalar diffraction theory. A physical interpretation of the Rayleigh solution shows that the diffracted wave may be thought of as a superposition of elementary, electromagnetic Huygens wavelets. Depending on the type of Green's function that is chosen, these wavelets have the same form as fields radiated by dipoles of different orientations (D-theory) or by special types of quadrupoles (Q-theory). Using techniques which are well known from scalar theory, it is shown that the diffracted wave can be represented as an angular spectrum of electromagnetic plane waves, and that this description is equivalent to the Q-theory approach. The use of approximate, Kirchhoff-type boundary conditions in the Hertz potential formalism is investigated. When these boundary conditions are used in the D-theory, the diffracted wave is found to be identical with the results of more traditional theories that apply the boundary conditions directly to the fields in the aperture. Using these boundary conditions in the Q-theory yields different results, because they are applied to the Hertz potentials rather than to the fields themselves. The differences between the two approaches are most apparent when the aperture is small in comparison with the wavelength. To determine which theory is more appropriate for Kirchhoff-type boundary conditions, an experiment to measure the diffraction from subwavelength-diameter pinholes is performed. The Q-theory shows better agreement with the results. It is also determined that the best agreement is obtained when the magnetic rather than electric Hertz potential is used.

No description available.

La technique de diffraction de monocristaux est la plus utilisée pour déterminer une structure tridimensionnelle de protéine, permettant ainsi la compréhension de sa fonction biologique.Cependant, cette technique nécessite l'obtention d'un monocristal.La détermination d'une structure par diffraction de poudre ne requiert que l'obtention d'un précipité cristallin, souvent obtenu lors de la recherche d'une condition de cristallisation.Nous présentons dans cette thèse plusieurs protéines étudiées par diffraction de poudre. Le développement de nouvelles méthodes pour la préparation des échantillons et l'acquisition des données sont présentées, étant donnée leur importance cruciale dans ces études.Nous avons étudié le polymorphisme de l'urate oxidase par la détermination des différentes phases cristallines résultant des modifications des conditions de cristallisation. Cette étude a débouché sur l'identification d'une forme cristalline nouvelle d'intérêt pharmaceutique. Une des phases d'urate oxidase à permis l'obtention d'un cliché de diffraction de qualité suffisante à la redétermination et l'affinement de sa structure.Un protocole pour le refroidissement cryogénique de poudre de protéineest présenté, offrant une durée de vie accrue de l'échantillon lors de l'acquisition de données.Ce protocole a permis l'affinement de deux structures d'insuline humaine. Nous présentons également la détermination d'une structure préliminaire du domaine macro du virus Mayaro, basé uniquement sur des données acquises sur un unique échantillon polycristallin en forme d'oursin. Une étude de la matrice de protection de deux baculovirus illustre les limites auxquelles se heurte actuellement la technique de diffraction de poudre de protéines.En annexes, les étapes nécessaires pour la préparation et l'analyse des données sont présentées. / Knowledge of the structure of proteins helps in understanding theirbiological function.The main technique used, single crystal diffraction, requires thelimiting step of growing a single crystal.On the other hand, powder diffraction requires only a crystallineprecipitate made of many microcrystals such as those often discardedduring the search for suitable single crystal growth conditions.We present in this thesis different studies of proteins by powder diffraction.Development of new methods for sample preparation and data acquisitionare also presented, as they have been crucial steps to obtain highquality diffraction data.We studied the polymorphism of Urate oxidase by observing thedifferent crystallographic phases resulting from the changes in thecrystallisationconditions.A crystallographic phase of pharmaceutical interest has been identified.Also one phase of urate oxidase complexed with its inhibitor gave apowder pattern sufficient to re-determine and refine its structure.A protocol for cryocooling protein powder samples has been found,extending the lifespan of the sample in the intense X-ray beam.This allowed the refinement from powder data of two forms ofcryocooled human insulin.We present also the determination of a preliminary structure of themayaro virus macro domain, based on a powder diffraction patternobtained on a single urchin-like bundle of needles.A study of the protective protein matrix of two baculoviruses ispresented, showing some current limits of the method.In annexes, the steps for preparing and analysing protein powders are described.

Analysis of scattered, or diffraction energy (the seismic response of small-scale objects) in the seismic data from Canterbury Basin, New Zealand reveals additional geological information about depositional patterns in sedimentary deposits. Diffrac- tion images from the seismic response for Canterbury Basin provide complementary interpretation tools to the conventional specular reflection images. To image diffrac- tions for a dataset from Canterbury Basin, I take the following steps: First, I attenuate multiples using a surface multiple prediction algorithm to predict multiples and apply regularized nonstationary regression to adaptively subtract the predicted multiples. Next, I separate diffractions using the plane-wave destruction method. The plane- wave destruction method removes conventional reflected energy in order to enhance the diffracted energy. I then apply a velocity continuation method on diffraction data to estimate migration velocities and then migrate the data using Kirchhoff migration in the dip-angle-gather domain. The resultant conventional and diffraction images are improved images suitable for geological interpretation of prograding sediment drifts. / text

Made available in DSpace on 2014-10-09T12:30:58Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:18Z (GMT). No. of bitstreams: 1 01359.pdf: 2828846 bytes, checksum: 96fc94fc037258801bfe26fea35e7fea (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:30:21Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:18Z (GMT). No. of bitstreams: 1 01188.pdf: 1509042 bytes, checksum: 43ff4895dd33d76cc9210d2ba77fcfd2 (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:47:46Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:26Z (GMT). No. of bitstreams: 1 08349.pdf: 3194587 bytes, checksum: 65eb4db04988a87107998b9237835cdd (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:46:56Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:09:47Z (GMT). No. of bitstreams: 1 09060.pdf: 8685574 bytes, checksum: 4cca556c554e4dce4f2f896a6cd6f9fd (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP