451 |
The effect of applied and magnetic fields on the crystallisation of hydrocarbonsRodericks, Michele Melanie January 2003 (has links)
This thesis provides a background on the effects of applied and magnetic fields on crystallisation, and summarises the analytical techniques employed for characterisation and analysis. The study of applied fields was carried out on the crystallisation of one main system-solid nonadecane. This was then studied further to establish the effects of a solvent and a mixed solid system on the crystallisation of nonadecane. The systems studied were the crystallisations of: static and dynamic nonadecane, static and dynamic nonadecane in heptane, static and dynamic nonadecane and heneicosane, static and dynamic nonadecane and heneicosane in heptane and static and dynamic nonadecane and crude oil. The results of these studies showed that the magnetic and applied fields can affect electrostatic forces in molecular solids. It also showed that even the weakest of these forces, Van der Waals forces are affected by applied and magnetic fields.
|
452 |
Texture determination from ultrasound for HCP and cubic materialsLan, Bo January 2014 (has links)
Crystallographic texture in polycrystalline HCP and cubic materials, often developed during thermomechanical deformations, has profound effects on properties at the macroscopic or component level. Given the respective natures of current detection techniques, a non-destructive, three-dimensional bulk texture detection method for these materials has not yet been developed. This thesis aims to achieve this goal through systematic studies on the relationship between ultrasonic wave velocity and texture. The feasibility of such development is firstly reviewed via the combination of computational and experimental studies on exemplary HCP materials. Numerical results obtained via a representative volume element (RVE) methodology reveal that the wave speed varies progressively and significantly with changing texture, and experimental ultrasound studies combined with EBSD characterisation demonstrate distinguished velocity profiles for samples with different textures. Thus the possibility of the development is demonstrated from these combined results. A novel convolution theorem is then presented, which couples the single crystal wave speed (the kernel function) with polycrystal orientation distribution function to give the resultant polycrystal wave speed function. Firstly developed on HCP and then successfully extended to general anisotropic materials, the theorem expresses the three functions as harmonic expansions thus enabling the calculation of any one of them when the other two are known. Hence, the forward problem of determination of polycrystal wave speed is solved for all crystal systems with verifications on varying textures showing near-perfect representation of the sensitivity of wave speed to texture as well as quantitative predictions of polycrystal wave speed. More importantly, the theorem also presents a solution to the long-standing inverse problem for HCP and cubic materials, with proof of principle established where groups of HCP and cubic textures are recovered solely from polycrystal wave velocities through the theorem and the results show good agreements with the original textures. Therefore the theorem opens up the possibility of developing a powerful technique for bulk texture measurement and wave propagation studies in HCP, cubic materials and beyond.
|
453 |
X-ray and synchrotron topography of twinned diamonds and diamonds from BrazilMachado, Walmer Guedes January 1984 (has links)
X-ray diffraction topography, using both conventional and synchrotron sources, has been employd t reveal, to a resoltuoon of 1um, internal structural imperfections in diamonds from Brazil. Many of these diamonds were found to be twinned; and X-ray studies have been made of twinned diamonds from Brazil and elsewhere, in order to elucidate the mechanisms of twinning in diamond. Numerous X-ray topographs have been taken of contact twins (mcles), interpenetrant cubes and mulitple twins. The well collimated beam of synchrotron radiation at the SERV Daresbury Laboratory has proved most useful in revealing, in the forward reflexion Laue photographers, small twinned regions of diamons: the presence of which would have been mised by conventioanl methods.
|
454 |
Controlling reactive materials by crystallisation and hostingMartin, Alan January 2014 (has links)
The research herein presents an approach to stabilising reactive materials by engineering and designing strategies for forming multi-component materials containing the reactive molecules by use of their non-covalent intermolecular interactions. These interactions may be utilised as part of a design approach to create new materials of more beneficial physical and chemical properties for the desired application. The reactive materials focussed on in this research are organic peroxyacids, in particular peroxyacetic acid, meta-chloroperbenzoic acid and 6-phthalimidoperoxyhexanoic acid. The stabilities of these target materials under different conditions are probed to find a suitable environment for crystallisation experiments. Crystal structures of the materials were isolated and characterised and the peroxyacids were subsequently cocrystallised with materials chosen to interact with the target molecules to form new molecular complexes, including carboxylic acids, π stacking materials and metal salts. A hosting approach was also employed to form multi-component systems containing these materials, crystallising them with larger, stable, structure-generating compounds with the aim of intercalating the reactive molecules in their stable structure. To this end, urea based compounds, cyclodextrins and Montmorillonite clay were investigated as hosting materials. Candidate multi-component materials were synthesised which successfully retain peroxyacid reactivity. A second set of materials studied was agrichemicals, which also frequently have reactive character, in which a change in physical properties was pursued by the method of forming new crystalline complexes. Five new crystalline agrochemical molecular complexes were synthesised and tested for thermal stability in comparison to the original materials to assess for changes in properties of the multi-component materials.
|
455 |
Bubbles propagation in undoped and Titanium (Ti3+)-doped sapphire crystals grown by Czochralski (Cz) technique / Propagation des bulles dans le saphir non dopé et dopé titane (Ti3+) cristallisé par la technique Czochralski (Cz)Li, Hui 08 December 2014 (has links)
En dépit de leurs simplicités chimiques, de leurs fusion congruente, de leurs performances mécaniques et de leurs propriétés optiques, les monocristaux de saphir contiennent comme défauts des bulles aussi connus sous le nom de micro-vides. Quelle que soit la technologie de croissance, les cristaux obtenus sont caractérisés par la présence de micro-et macro-bulles qui affectent leurs qualités optiques et mécaniques limitant ainsi leurs applications. Ces bulles dégradent les propriétés optiques et l'efficacité des lasers produits par une réduction de la transparence des saphirs; elles induisent également des défauts de surface pendant le processus de polissage. Afin d'améliorer la qualité des cristaux, il est important d'éliminer les bulles, de connaître la raison de leurs formations, les causes de leurs propagations, de leurs constitutions, et de leurs diffusions dans le cristal. Nous avons étudié la distribution des bulles et leurs tailles dans les cristaux de saphir non dopés et dopés titane obtenus par la technique Czochralski (Cz). Les données expérimentales recueillies ont permis de connaître l'effet de différents paramètres de croissance sur la distribution, la densité et la taille des bulles. La propagation des bulles et leurs distributions dans les cristaux ne sont pas influencées par le type de germe. Si les vitesses de tirages augmentent, le diamètre des bulles diminuent et leurs densités augmentent. Les bulles formées dans le cristal de saphir sont influencées par la matière formant la charge de départ. L’utilisation de saphirs craquelés comme charge de départ pourrait être une bonne façon de minimiser la création de bulles et de limiter leurs propagations. Les résultats obtenus dans le cadre de cette thèse décrivent l'ensemble des phénomènes impliqués lors de l'incorporation de bulles dans les cristaux de saphir non dopés et dopés titane / In spite of the chemical simplicity, the congruent melt behaviour and it’s performed mechanical and optical properties sapphire single crystals contain bubbles defects also known as micro-voids. Whatever the growth technology, the grown crystals are characterized by the presence of micro and macro bubbles which affect the optical and mechanical quality of the crystal limiting their application. They degrade the optical properties and the laser efficiency by reduction of the transparency; they also induce surface defects during substrate polishing process. In order to improve the crystal quality, it is important to eliminate bubbles defects and know the reason of their formation, the causes of their propagation, their incorporation and their distribution in the crystal. We have studied bubbles distribution and their size in undoped and Ti-doped sapphire crystals grown by Czochralski (Cz) technique. The collected experimental data made it possible to know the effect of several growth parameters on the distribution, the density and the size of the bubbles. The bubbles propagation and distribution in the crystal are not influenced by the seed type. If the pulling rate increases, the diameter of bubbles decreases and their density increases. The bubbles formed in sapphire crystal are influenced by the starting charge material. Using sapphire crackle as starting charge could be a good way to minimise bubbles creation and limited their propagation. The obtained results in the frame of this thesis describe the whole phenomena involved during bubbles incorporation in undoped and Ti-doped sapphire crystals
|
456 |
Effect of guest uptake and high pressure on Zn- and Zr- metal-organic frameworksHobday, Claire Louise January 2017 (has links)
Porous materials are essential to our everyday lives, for example as an effective catalyst in the cracking of crude oil, or as water softeners in washing powder. When developing novel functional porous materials, it is necessary to fully understand their structure-property relationships to maximise their ability to be used in industrially relevant settings. This thesis aims to understand the mechanical and adsorption properties of a class of porous solids metal-organic frameworks (or MOFs), which have many potential applications owing to their tuneable structures. Due to the inherent 3-D crystalline structure of MOFs, a wide range crystallographic techniques were used to determine structure-property relationships. To achieve maximum in-depth structural knowledge, both classical and quantum theoretical approaches were also applied to complement the understanding of both the energetics and structural details. Chapters One and Two begin with an overview of the state of the art studies carried out on MOFs, focusing on the use of high-pressure crystallography to understand their properties. In addition, there is emphasise on the importance of complementary computational methods that are used in the characterisation of MOFs. In Chapter Three, an isostructural series of MOFs (zeolitic imidazolate frameworks, or ZIFs) were studied for methanol adsorption by employing both experimental and molecular simulation techniques. These frameworks are gating materials, where the imidazole linker rotates upon adsorption of guest, and it was found that through ligand substitution the gate opening angle and onset pressure to gating could be tuned. By using high-pressure Xray crystallography the structure of the ZIFs were studied upon the uptake of guest and the degree of ring rotation quantified. In combination with periodic DFT and grand canonical Monte Carlo simulations the energy barrier to rotation and energies of adsorption could be calculated, respectively. Chapter Four focuses on one ZIF in particular, ZIF-8 ((Zn6(MeIm)12, MeIm = 2- methylimidazole) and details the adsorption of a selection of gases into the pores. The experimental method of cryogenic gas loading into a diamond anvil cell in this chapter is novel to MOFs. This method, in combination with molecular crystallography, is used to determine the structural response of the framework to guest-uptake as well as the crystallographic positions of the adsorption sites. In combination with in silico methods, the adsorption energies of guest-sites could be calculated, detailing which interactions drive the gating behaviour. The method of cryogenic loading highlighted how extreme conditions can be used to extract useful information about structural behaviour of MOFs on uptake of gas molecules into the pores, and when used in combination with computational methods, we have a powerful tool to analyse both positions and energies of adsorption sites. With this information, progress can be made in developing MOFs to maximize favourable interactions and lead to the development of MOFs with better selective gas storage properties. Chapter Five focuses on the synthesis and characterisation of the physical properties of a series of Zr-containing MOFs, called UiO-MOFs. The high valency of Zr(IV) and 12-fold coordination of the metal cluster in these materials, are associated with high shear and bulk moduli, which surpass those of other MOFs. A combination of single-crystal nano-indentation, high-pressure X-ray diffraction studies, density functional theory (DFT) calculations, and first-principles molecular dynamics (MD) simulations were used to determine the compressibility, elasticity and hardness of these materials, whose mechanical robustness was correlated to their different structural features, in-particular, how using non-linear linkers between the metal clusters stabilises the framework to compression. Chapter Six expands upon the series of Zr-MOFs in Chapter Five, and looks at how the mechanical properties of these MOFs are affected upon increasing the linker length. The experimentally determined elastics modulus of one of the frameworks, UiO-sdc (Zr6O4(OH)4(sdc)6 where sdc =4,4’-stillbene dicarboxylate), was found to lie above those of other highly porous MOFs. In addition, the elastic modulus was found to decrease linearly as a function of increasing the linker length, extending the structure-property relationships determined in Chapter Five.
|
457 |
Etude du récepteur nucléaire stéroïdien ERR en complexe avec ADN et ligands par une approche de biologie structurale intégrative / Study of the steroid nuclear receptor ERR in complex with DNA and ligands by an integrative structural biology approachTazibt, Karima 28 November 2016 (has links)
Les récepteurs nucléaires régulent l’expression des gènes importants pour le développement et l’homéostasie des cellules eucaryotes. Si certains d’entre eux sont activés par la liaison d’un ligand naturel, d’autres, comme le récepteur ERR, sont orphelins et ne possèdent pas de ligand naturel connu à ce jour. ERR se lie via son domaine DBD sur un élément de réponse ERRE au niveau des régions promotrices des gènes et son activité peut être modulée par la liaison de ligands synthétiques antagonistes. Par une approche de biologie structurale intégrative combinant biochimie, biophysique et cristallographie aux rayons-X, mon travail de thèse consistait en l’étude de l’organisation structurale d’ERR pour comprendre les mécanismes d’antagonisme induits par le ligand agoniste inverse XCT-790, et la topologie qu’il adopte en interagissant avec l’ADN. Mon projet était axé sur l’étude des domaines modulaires DBD et LBD en complexe avec ADN et ligand transposée à l’étude fonctionnelle du récepteur entier. Par un important travail biochimique, j’ai mis en place les protocoles de purification de ces protéines et caractérisé biophysiquement la stabilité et la stœchiométrie des complexes avec ADN et ligand. J’ai mis en évidence que le ligand XCT-790 se lie sur chacun des monomères de LBD avec une forte affinité et que le DBD interagit avec un ERRE sous la forme d’un monomère. De multiples essais de cristallisation ont abouti à l’obtention de cristaux pour les complexes avec le LBD et le DBD ayant diffracté respectivement jusqu’à 3,5 Å et 7 Å de résolution sans néanmoins pouvoir en déterminer les structures. L’ensemble de ces résultats permettent de conclure que le DBD est monomérique sur les ERRE et IR3 et semble être dimérique sur l’élément de réponse combiné ERRE/ERE. La topologie qu’adopte ERR sur l’ADN est dictée par la liaison de ligand et serait la conséquence d’une communication allostérique entre les domaines modulaires. Ces connaissances acquises faciliteront la détermination structurale d’ERR entier par cristallographie aux rayons-X ou par cryo-microscopie électronique. / Nuclear receptors regulate expression of important genes involved in development and homeostasis in eukaryotic cells. While some of them are regulated by the binding of a natural ligand, others, like ERR, are orphan and don’t have any natural ligand identified up to now. ERR binds to ERRE response elements through its DBD on promoter regions of genes and its activity can be modulated by the binding of synthetic antagonist ligands. By an integrative structural biology approach, my thesis work consisted in the study of the structural organization of ERR to understand the antagonism mechanisms induced by the inverse agonist XCT-790, and the adopted topology upon binding to DNA. My project focused on the study of the modular domains DBD and LBD complexes with DNA and ligand and extended to the functional study of the whole receptor. Thanks to significant biochemical work, I set up the purification protocols for these proteins and characterized by biophysics the stability and stoichiometry of the DNA and ligand complexes. This work revealed that XCT-790 binds on each LBD monomer with high affinity and that the DBD interacts to an ERRE as a monomer. Many crystallization trials led to crystals for the LBD and DBD complexes that diffracted respectively up to 3.5 Å and 7 Å of resolution but no structure could be determined. These results allow to conclude that the DBD is monomeric on the ERRE and IR3 and appears to be dimeric on the combined response element ERRE/ERE. The topology adopted by ERR on DNA is guided by the ligand binding and might be the consequence for an allosteric communication between the modular domains. These results provide the basis for a future structure determination of the full ERR by X-ray crystallography and cryo electron microscopy.
|
458 |
Multimodal sensing and imaging technology by integrated scanning electron, force, and near-field microwave microscopy and its application to submicrometer studies / Technologie de détection et d'imagerie multimodale par microscopie intégrée à balayage électronique, à force et à micro-ondes en champ proche, et son application aux études submicrométriquesHaenssler, Olaf Christian 22 February 2018 (has links)
La combinaison de plusieurs procédés d’imagerie et de mesure permet d’obtenir des ensembles de données complémentaires et parfois uniques. A l’aide d’une technique hybride de microscopie présentant des modalités de mesure différentes et des enregistrements synchrones, on peut recueillir des informations complémentaires sur des échantillons à l’échelle nanométrique. De plus, l’intégration de procédés nanorobotiques et de logiciels open-source permet une approche technologique pour la recherche sur les semi-conducteurs et les sciences des matériaux. Ce travail démontre le potentiel d’une telle technologie. Ce démonstrateur fonctionne dans la chambre d‘un MEB et sert de plateforme technologique dans laquelle sont intégrés différentes modalités, technologies et procédés. Un AFM basé sur un interféromètre optique compact permet l’imagerie de la topographie de surface tandis qu’un microscope à micro-ondes à balayage enregistre les caractéristiques électromagnétiques dans la gamme de fréquence des micro-ondes, le tout opérant dans le même MEB. L’engin est contrôlé par un ensemble de logiciels qui est optimisé pour la nanorobotique basée sur l‘imagerie. Ce démonstrateur technologique permet d’observer en direct la région d’intérêt à l’aide du microscope électronique tandis qu’est effectuée en champ proche la caractérisation de la surface de l’échantillon par intermédiaire des micro-ondes évanescentes et des forces intermoléculaires. Ensuite, est présenté un standard multimodal de test et qui valide la fonctionnalité de l’instrument démonstrateur. Le présent travail est complété par une analyse électrique de capacités MOS ainsi que leur approximation destinée au calibrage. / Various disciplines of micro- and nanotechnology requires combinatorial tools for the investigation, manipulation and transport of materials in the submicrometer range. The coupling of multiple sensing and imaging techniques allows for obtaining complementary and often unique datasets of samples under test. By means of an integrated microscopy technique with different modalities, it is possible to gain multiple information about nanoscale samples by recording at the same time. The expansion with nanorobotics and an open-source software framework, leads to a technology approach for semiconductor research and material science. This work shows the potential of such a multimodal technology approach by focusing on a demonstrator setup. It operates under high-vacuum conditions inside the chamber of a Scanning Electron Microscope and serves as a technology platform by fusing various microscopy modalities, techniques and processes. An Atomic Force Microscope based on a compact, optical interferometer performs imaging of surface topography, and a Scanning Microwave Microscope records electromagnetic properties in the microwave frequency domain, both operating inside an SEM. A software framework controls the instrument. The setup allows for observing with SEM, while imaging and characterizing with interacting evanescent microwaves and intermolecular forces simultaneously. In addition, a multimodal test standard is introduced and subsequently confirms the functionality of the demonstrator. Within this context, the work also includes an electrical analysis of micro-scale MOS capacitors, including an approximation for use in the calibration.
|
459 |
Evolución geoquímica de cuencas evaporíticas terciarias: implicaciones en la composición isotópica disuelto en el océano durante el terciarioCendón Sevilla, Dionisio Ignacio 05 March 1999 (has links)
Esta memoria trata de la evolución geoquímica de cuencas evaporíticas terciarias y de su utilidad en la reconstrucción de la evolución isotópica (delta(34)S y delta(18)O) del sulfato disuelto en el océano durante el Terciario. Para ello se ha dividido el texto en tres partes principales:
Parte 1. Se tratan los aspectos metodológicos y se describen las técnicas empleadas. El microanálisis de inclusiones fluidas mediante Cryo-SEM-EDS, permite el análisis cuantitativo de los solutos en inclusiones fluidas congeladas de tamaños de hasta 15 delta m. Los electrolitos analizados son los componentes mayoritarios presentes en las salmueras atrapadas. Na, K. Mg, Ca, Cl y SO(4). La precisión del método varia según los casos, pero es inferior al 6% para todos ellos salvo para el Cl (<15%). Con el objeto de ampliar el número de elementos analizados a minoritarios y traza, se han realizado análisis mediante otra técnica, LA-ICP-MS, demostrándose que ambas técnicas son complementarias.
También se describe la metodología empleada en el análisis isotópico, en especial el funcionamiento de las líneas de extracción de gases y la manipulación de las muestras. Otra parte fundamental es la descripción del funcionamiento de las simulaciones numéricas y sus fundamentos teóricos. Todos los datos analíticos obtenidos de forma sistemática a lo largo de las secuencias evaporíticas son comparados con simulaciones numéricas en diferentes escenarios. Estas comparaciones permiten refinar un modelo de evolución de las cuencas evaporiticas durante la precipitación de las evaporitas, en especial de las halitas. De esta forma se obtienen los parámetros fundamentales en la evolución hidrológica de la cuenca: el índice de restricción, que indica lo abierta o cerrada que está la cuenca a los aportes externos, y las proporciones de recarga, que son las proporciones aproximadas de los distintos tipos de aguas que llegan a la cuenca (continentales, marinas, reciclajes, etc.).
Las composiciones isotópicas también están introducidas en los modelos, de forma que una vez determinados el índice de restricción y las proporciones de recarga puede ajustarse la evolución isotópica de las unidades evaporíticas. Al establecerse el carácter marino de la totalidad o de parte de las unidades, éstas pueden ser utilizadas para deducir la composición isotópica de las salmueras y del océano original del que proceden. Los datos de composición isotópica del mar, obtenidos a partir de estas unidades están corregidos de los fraccionamientos provocados por cristalización o por variaciones en el índice de restricción de la cuenca. Por otra parte pueden detectarse otros fenómenos que modifican la composición isotópica, tales como la sulfato-reducción bacteriana o el reciclaje de evaporitas previamente formadas. En el caso del reciclaje puede llegar a cuantificarse de forma aproximada.
Parte II. En esta parte se aplica la metodología descrita a diferentes cuencas evaporíticas.
a) Cuenca surpirenaica (subcuenca navarra). En este caso ya existen trabajos anteriores en los que se aplica la metodología descrita y en los que se muestra el carácter marino de la unidad halítica inferior (UHI) y el carácter continental de la unidad halítica superior (UHS). En esta memoria se aplica de forma complementaria el estudio de inclusiones fluidas al estudio de las zonas estériles en los yacimientos de silvita de Subiza (Navarra). Se determina el carácter primario de la silvita y el origen sinsedimentario de las zonas estériles.
b) Cuenca surpirenaica (subcuenca catalana). Ésta tiene apones fundamentalmente marinos, si bien se pone de manifiesto la importante influencia del reciclaje de los yesos marginales durante la precipitación de la halita. Esta influencia queda registrada en las composiciones isotópicas más pesadas de la subcuenca catalana respecto de la navarra. Ambas subcuencas siguen una evolución paralela, aunque la mayor influencia continental en la subcuenca catalana parece sugerir una menor conexión entre ambas subcuencas. Para ambas subcuencas se deduce la composición isotópica del mar durante el Eoceno superior.
c) Fosa Renana (Cuenca de Mulhouse. Alsacia). La evolución de esta cuenca durante la precipitación de la Sal IV es fundamentalmente continental como indican la evolución de solutos en las inclusiones fluidas, composiciones isotópicas y determinaciones (87)Sr/(86)Sr. Es posible la existencia de una influencia marina en la base de la Sal IV, cerca de la llamada zona fosilífera, si bien no se preserva según evoluciona el medio. En esta cuenca se ponen de manifiesto procesos de mezclas de aguas de diferentes orígenes y en proporciones variables en el tiempo. También se identifican procesos redox con
reequilibración del oxígeno del sulfato con el oxígeno disuelto en la salmuera. Eslos procesos provocan el enriquecimiento de la delta(18)O hasta valores de +/- 22º/ºº y parecen estar relacionados a una mayor actividad bacteriana en la cuenca. Los datos obtenidos no permiten deducir la composición isotópica del mar durante el Oligoceno.
d) Cuenca Precarpática. Se pone de manifiesto la importancia del reciclaje durante la precipitación de toda la unidad halitica. La fuente de solutos es mayoritariamente marina, al principio de la precipitación de halita, y se pone de manifiesto un incremento notable del reciclaje de evaporitas. La composición isotópica de los sulfatos intercalados entre halita y de los yesos marginales es muy semejante. Se plantea el reciclaje de los sulfatos precipitados en el margen activo de la cuenca como posible fuente de solutos. A partir de los datos obtenidos y una vez determinada la influencia del reciclaje, se deduce una composición isotópica para el mar durante el Badeniense.
e) Cuenca de Lorca. Las conclusiones de los estudios preexistentes sobre inclusiones fluidas se ven confirmadas por los nuevos datos isotópicos obtenidos. Se diferencia en la unidad salina un tramo inferior de origen marino, con variaciones en el índice de restricción y apones continentales puntuales que provocan ligeras variaciones isotópicas. Por encima se distingue un tramo superior, de origen continental, con una evolución isotópica que se interpreta por el reciclaje de diferentes proporciones de sulfatos de la propia cuenca y sulfatos de origen Triásico. A partir de los datos de la unidad salina (tramo inferior) se deduce la composición isotópica del mar messiniense.
f) Cuenca de Caltanissetta. Los datos de inclusiones fluidas preexistentes y los realizados para esta memoria diferencian un tramo halltico inferior, de origen marino, y un tramo superior, separado por sulfatos de K y Mg, que muestra su carácter marino, pero con influencias del reciclaje de evaporitas de la propia cuenca. Se ha determinado la evolución isotópica de dos sondeos diferentes, siendo los resultados iguales para ambos, y en concordancia con los resultados de las inclusiones fluidas. A partir del tramo marino se obtiene un rango para la composición isotópica delta(34)S del océano messiniense que coincide con la deducida en la cuenca de Lorca. Las delta(18)O obtenidas son aproximadamente +3 º/ºº más pesadas e incompatibles con las deducidas en Lorca. Se propone la existencia de procesos redox generalizados de forma semejante a como sucede en medios actuales de origen marino.
Parte III. En esta parte se realizan diversas consideraciones sobre la evolución del sulfato disuelto en el océano. A partir de los datos obtenidos en diferentes cuencas evaporíticas, se concluye que el déficit de sulfato (respecto a la evaporación del mar actual), común a muchas cuencas evaporíticas, no se debe a cambios globales en la composición del océano sino a variaciones locales dentro de las propias cuencas evaporíticas. Procesos de dolomitización o la entrada de salmueras ricas en Ca son las responsables del descenso en la concentración de sulfato. Una de las consecuencias directas del déficit de sulfato es la precipitación de silvita como mineral primario a partir de la evaporación de agua marina. En cuanto a la composición isotópica., se insiste en la necesidad de conocer con exactitud el origen marino de las evaporitas empleadas para deducir la evolución isotópica del sulfato disuelto en el océano. La metodología empleada en trabajos anteriores en la que se utilizan evaporitas de orígenes diversos, y en ocasiones desconocidos, provocan la imprecisión de las curvas de evolución isotópica deducidas. La metodología presentada en esta memoria permite el refinamiento de dichas curvas y la obtención de datos precisos sobre la composición isotópica del sulfato disuelto en el océano. / The subject of this thesis is the geochemical evolution of tertiary evaporitic basins and their use in reconstructing the isotopic evolution (delta(34)S y delta(18)O) of sulphate dissolved in the ocean during the Tertiary.
Part 1: The methodology is discussed and the techniques employed are described. Microanalysis using Cryo-SEM-EDS allows the quantitative analysis of frozen fluid inclusions up lo 15 mili-micres in size. The major solutes analysed from the trapped brine are Na. K, Mg, Ca, CI and SO. To analyse minor and trace elements, diverse analyses have been carried out using another technique, LA-ICP-MS. Thus demonstrating that, these techniques complement each other.
The methodology used in isotopic analysis and numerical simulations, how they work and their theoretical bases are also described. The analytical data are compared with numerical simulations that reproduce different scenarios. Thus a model of the evaporitic basins evolution during precipitation can be refined. From these models fundamental parameters in the basins hydrological evolution have been obtained: restriction index and recharge proportions.
The isotopic compositions are also introduced into the models so the isotopic evolution of the evaporitic units can be adjusted. Once the marine origin has been established, the model is used to deduce the brine's isotopic composition and that of the original ocean.
Part II: In this section the methodology discussed above is applied to various evaporitic basins.
- Southpyrenean basin (Navarran sub-basin, Spain)
- Southpyrenean basin (Catalonian sub-basin, Spain)
- Rhine Graben (Mulhouse basin, Alsace, France)
- pre-Carpathian basin (Poland)
- Lorca basin (Murcia, Spain)
- Caltanissetta basin (Sicily, ltaly)
Part III: According to the data obtained from different evaporitic basins it is concluded that the sulphate deficit - in respect to the evaporation of today's seawater - common in many evaporitic basins is not due to global changes in the oceans composition but rather lo local variations within the evaporitic basins. Regarding the isotopic compositions, it is important lo assure the exact marine origin of the evaporates that are used to deduce the isotopic evolution of sulphate dissolved in the ocean. The methodology presented in this thesis allows isotopic curves to be refined.
|
460 |
Microstructuration of nonlinear optical materials: methodologies, characterization, and applicationsGolconda, Raj Kumar 23 October 2012 (has links)
One and two dimensional microstructures were fabricated by ultrafast laser ablation on KTiOPO4 and RbTiOPO4, and by selective chemical etching on LiNbO3 single crystals to investigate the diffractive properties associated to the nonlinear optical properties of these materials. Asymmetric diffraction patterns were obtained for the second harmonic generated by the samples after illumination with an IR laser beam. We also explored a possible application for these structures as it is the development of RGBY laser phosphor displays. To do that, we embedded luminescent nanoparticles doped with lanthanide ions, and synthesized by the sol-gel Pechini method, into the micrometer holes inscribed on the surface of KTiOPO4 and RbTiOPO4. In this way, multicolor light emissions can be controlled spatially at the micrometer scale. The RGBY colors were generated by using different up-conversion mechanisms by pumping in the infrared, with several advantages to the current laser phosphor display technology pumped in the UV. / En esta tesis hemos fabricado micro estructuras uni- y bidimensionales mediante ablación laser ultrarápida sobre monocristales de KTiOPO4 y RbTiOPO4, y mediante ataque químico selectivo sobre monocristales de LiNbO3, para investigar la difracción asociada a las propiedades de óptica no lineal de estos materiales, observando la formación de patrones de difracción asimétricos para el segundo harmónico generado por las muestras al iluminarlas con un láser IR. También hemos explorado una posible aplicación para estas estructuras: pantallas RGBY de fósforos excitados mediante láser. Para ello, hemos incorporado partículas luminiscentes dopadas con iones lantánidos dentro de los poros inscritos sobre KTiOPO4 y RbTiOPO4. De esta forma, las emisiones multicolor, generadas mediante diferentes mecanismos de up-conversion por excitación en el IR, con ventajas respecto a la tecnología actual que utiliza láseres en el UV, pueden ser controladas espacialmente a escala micrométrica
|
Page generated in 0.0167 seconds