Perovskite based materials have great potentials for various energy applications and the search for new materials for uses in SOFCs has largely been concentrated to this class of compounds. In this search, we have studied perovskite phases in the system La2Co1+z(Ti1-xMgx)1-zO6, with 0  x 0.9 and z = 0.0, 0.2, 0.4, 0.6. Crystal structures were characterized by XRD and, for selected compositions, also by NPD and SAED. They exhibit with increasing x, as well as increasing z, a progressive increase in symmetry from monoclinic to orthorhombic to rhombohedral. The main focus in this work has been on the investigation of structure-property relations for compositions with 0.0 x 0.5 and z = 0. The nominal oxidation state of Co increases for these with increasing x, from Co2+ for x = 0 to Co3+ for x = 0.5. Magnetic measurements and XANES studies showed that the average spin state of Co changes linearly with increasing x, up to x = 0.5, in accordance with varying proportions of Co with two fixed oxidation states, i.e. Co2+ and Co3+. The data suggests that the Co3+ ions have an IS spin state or a mixture of LS and HS spin states for all compositions with nominally only Co2+ and Co3+ ions, possibly with the exception of the composition with x = 0.1, 0.2 and z = 0, for which the data indicate that the spin state might be HS. The XANES data indicate furthermore that for the perovskite phases with z = 0 and x > 0.5, which in the absence of O atom vacancies contain formally Co4+, the highest oxidation state of Co is Co3+, implying that the substitution of Ti4+ by Mg2+ for x ³ 0.5 effects an oxidation of O2- ions rather than an oxidation of Co3+ ions. The thermal expansion was found to increase nearly linearly with increasing oxidation state of Co. This agrees well with findings in previous studies and is attributable to an increase in the ionic radius of Co3+ ions with increasing temperature, due to a thermal excitation from a LS to IS or LS/HS spin states. High temperature electronic conductivity measurements indicate that the electronic conductivity increases with an increase of both relative and absolute amount of Co3+. The latter can be attributed to an increase in the number of Co-O-Co connections. Additional high temperature magnetic measurements for selected samples, whose susceptibilities did not follow a Curie law behaviour up to room temperature, showed effective magnetic moments that did approach plateaus even at high temperatures (900 K). Interpretations of these data are, however, hindered by the samples losing oxygen during the applied heating-cooling cycle. The present study has shown that the investigated system is suitable for further studies, of more fundamental character, which could provide further insight of the structure-property relationships that depend on the oxidation state of Co. / Studies of cobalt based perovskites for cathode materials in solid oxide fuel cells.

[ES] Los avances tecnológicos se encuentran, en algunas ocasiones, limitados debido a la imposibilidad de combinar las excelentes prestaciones de los materiales conocidos con algunas funcionalidades críticas necesarias para desarrollar nuevas aplicaciones tecnológicas. Estos nuevos materiales con un diseño a la carta resultan extremadamente interesantes ya que permiten combinar propiedades y funcionalidades actualmente inalcanzables. La circona, u oxido de zirconio (ZrO2), es un sólido cristalino blanco con enlaces iónicos altamente estables que es principalmente obtenido en forma de polvo para aplicaciones tecnológicas. Debido a sus propiedades física y químicas, la circona es un material cerámico que posee una serie de características excepcionales, que incluyen una dureza, tenacidad y fractura relativamente altas en comparación con otros materiales cerámicos, bajo coeficiente de fricción y alto punto de fusión. Además, es un material relativamente no reactivo cuando se expone a ambientes húmedos y corrosivos en comparación con otros materiales como metales y polímeros, con buena resistencia a altas temperaturas y abrasión. Todas estas propiedades posicionan a la circona como un material muy versátil con un amplio espectro de aplicaciones que abarca intercambiadores de calor, celdas de combustible, componentes de turbinas para sistemas aeronáuticos y generación de electricidad, así como para medicina, odontología y otras aplicaciones. El propósito de esta tesis doctoral es la obtención de materiales base circona que puedan ser empleados en la fabricación de nuevos composites con funcionalidades a la carta en sectores tecnológicos como el transporte, energía, medicina, etc. Para ello se utilizarán técnicas de sinterización no-convencionales: Microondas (MW) y Spark Plasma Sintering (SPS). Para este trabajo se plantea el estudio de distintos composites base circona: circona reforzada con óxido de niobio (Nb2O5), Titania (TiO2) y composites de circona reforzados con manganita de lantano dopada con estroncio (LSM). El resultado final de esta investigación permitirá determinar si las técnicas rápidas de sinterización no-convencional, permiten mejoran las propiedades mecánicas, eléctricas y magnéticas de los materiales obtenidos en comparación con la sinterización por métodos convencionales. / [CA] Els avenços tecnològics són, en algunes ocasions, limitats per la impossibilitat de combinar l'excel·lent comportament dels materials coneguts amb algunes funcionalitats crítiques necessàries per desenvolupar noves aplicacions tecnològiques. Aquests nous materials amb disseny a la carta resulten summament interessants ja que permeten combinar propietats i funcionalitats actualment inabastables. La circonia, o òxid de zirconi (ZrO2), és un sòlid cristal·lí blanc amb enllaços iònics altament estables que s'obté principalment en forma de pols per a aplicacions tecnològiques. A causa de les seves propietats físiques i químiques, la zircònia és un material ceràmic que posseeix una sèrie de característiques excepcionals, que inclouen duresa, tenacitat i fractura relativament altes en comparació amb altres materials ceràmics, baix coeficient de fricció i alt punt de fusió. A més, és un material relativament no reactiu quan s'exposa a ambients humits i corrosius en comparació amb altres materials com metalls i polímers, amb bona resistència a altes temperatures i abrasió. Totes aquestes propietats posicionen a la zircònia com un material molt versàtil amb un ampli espectre d'aplicacions que inclou intercanviadors de calor, piles de combustible, components de turbines per a sistemes aeronàutics i generació d'electricitat, així com per a medicina, odontologia i altres aplicacions. L'objectiu d'aquesta tesi doctoral és l'obtenció de materials base de zircònia que puguin ser utilitzats en la fabricació de nous compòsits amb funcionalitats sota demanda en sectors tecnològics com transport, energia, medicina, etc. Per a això, s'utilitzaran tècniques de sinterització no convencionals utilitzat: microones (MW) i sinterització per plasma d'espurna (SPS) Per a aquest treball es proposa l'estudi de diferents composites a força de zircònia: zircònia reforçada amb òxid de niobi (Nb2O5), titanat (TiO2) i composites de zircònia reforçats amb manganita de lantani dopat amb estronci (LSM). El resultat final d'aquesta investigació permetrà determinar si les tècniques de sinterització ràpida no convencional permeten millorar les propietats mecàniques, elèctriques i magnètiques dels materials obtinguts en comparació amb la sinterització per mètodes convencionals. / [EN] Technological advances are, on some occasions, limited due to the impossibility of combining the excellent performance of known materials with some critical functionalities necessary to develop new technological applications. These new materials of great design are extremely interesting since they allow combining properties and functionalities currently unattainable. Zirconia, or zirconium oxide (ZrO2), is a white crystalline solid with highly stable ionic bonds that is mainly obtained in powder form for technological applications. Due to its physical and chemical properties, zirconia is a ceramic material that possesses several exceptional characteristics, including relatively high hardness, toughness and fracture compared to other ceramic materials, low coefficient of friction, and high melting point. Furthermore, it is a relatively non-reactive material when exposed to humid and corrosive environments compared to other materials such as metals and polymers, with good resistance to high temperatures and abrasion. All these properties position zirconia as a very versatile material with a wide spectrum of applications that includes heat exchangers, fuel cells, turbine components for aeronautical systems and electricity generation, as well as for medicine, dentistry, and other applications. The purpose of this doctoral thesis is to obtain zirconia base materials that can be used in the manufacture of new composites with on-demand functionalities in technological sectors such as transport, energy, medicine, etc. For this, non-conventional sintering techniques will be used: Microwaves (MW) and Spark Plasma Sintering (SPS) For this work, the study of different zirconia-based composites is proposed: zirconia reinforced with niobium oxide (Nb2O5), titania (TiO2) and zirconia composites reinforced with strontium-doped lanthanum manganite (LSM). The result of this research will make it possible to determine whether rapid non-conventional sintering techniques allow the mechanical, electrical, and magnetic properties of the materials obtained to be improved compared to sintering by conventional methods. / El autor agradece a la Generalitat Valenciana por la ayuda económica recibida para la beca del programa Santiago Grisolía (GRISOLIAP/2018/168) / Guillén Pineda, RM. (2021). Desarrollo de materiales cerámicos base circona sinterizados mediante técnicas rápidas no convencionales [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/180231 / TESIS

Anorthite is crystalline phase in the ceramic body. Is acquired on burning a mixture of calcium ceramic raw material. This work deals with the influence on the resulting properties of anorthite ceramic body, especially flexural strength, porosity, shrinkage, thermal expansion coefficient. And the influence of different CaO sources on the properties. As a source of CaO was used calcium carbonate, calcium hydroxide and fluid fly ash.

Les signatures de l’existence des phonons sont omniprésentes dans les propriétés des matériaux. En première approximation, on peut scinder l'effet des phonons sur la structure électronique en deux contributions. D’une part, l'interaction électron-phonon capture la réponse électronique aux vibrations des noyaux du cristal, et d’autre, l'énergie libre de la population de phonons modifie le volume cristallin à l’équilibre. En plus d'être responsables de la dépendance en température de la structure électronique, ces deux mécanismes affectent les niveaux d'énergie à température nulle, à travers le mouvement du point zéro et l'énergie du point zéro. Cette thèse analyse l’apport de ces deux mécanismes à la renormalisation du point zéro (ZPR) de l'énergie de la bande interdite des semi-conducteurs. Une généralisation du modèle de Fröhlich prenant en compte l'anisotropie et les dégénérescences présentes dans les matériaux réels révèle que l'interaction non adiabatique entre les électrons et les noyaux domine le ZPR dans les matériaux polaires. La prise en compte de ce mécanisme dans l'évaluation de l'interaction électron-phonon est déterminante pour reproduire adéquatement les données expérimentales. L'approche développée par Grüneisen, qui néglige communément les effets du point zéro, reproduit la dilatation du point zéro du réseau (ZPLE) et sa contribution au ZPR obtenues avec la méthode standard basée sur la minimisation de l'énergie libre à moindre coût numérique, y compris pour les matériaux anisotropes. La contribution du ZPLE au ZPR total, qui a reçu peu d'attention dans la littérature, peut atteindre de 20% à plus de 80% de la contribution de l'interaction électron-phonon, y compris dans des matériaux constitués de noyaux légers. Elle domine même le ZPR du GaAs dans le contexte de la DFT semi-locale. Il est donc essentiel de traiter les deux contributions sur le même pied d'égalité pour modéliser le ZPR avec précision. L'inclusion du couplage spin-orbite (SOC) diminue le ZPR d'un ensemble substantiel de matériaux cubiques de structure zinc-blende, diamant et rock-salt. L'essentiel de cette variation tire son origine de l'effet du SOC sur les énergies électroniques statiques, qui provient en grande partie de la variation des masses effectives des bandes de valence au point \(\Gamma\). La réduction du ZPR peut être estimée à partir d'un modèle de Fröhlich généralisé auquel on a introduit le SOC. Les subtilités numériques liées au traitement de la séparation de Dresselhaus dans les matériaux non centrosymétriques sont discutées. On démontre enfin comment l'effet combiné de l'interaction électron-phonon et de la dilatation thermique affecte le diagramme de phase topologique du BiTeI. L'augmentation de la température repousse l'apparition de la phase d'isolant topologique \(\mathbb{Z}_2\) vers des pressions plus élevées et élargit la plage de pressions correspondant à la phase intermédiaire de type semi-métal de Weyl. Le caractère orbital dominant des extrema de bande influence significativement leur sensibilité à la pression et au changement de topologie. Pour guider la recherche expérimentale de phases topologiquement non triviales dans les matériaux de façon adéquate, les études numériques doivent donc considérer l'effet de la température. / Phonon signatures are ubiquitous in material properties. At first order, the effect of phonons on the electronic structure can be split into two contributions. On the one hand, the electron-phonon interaction captures the electronic response to the vibrations of the nuclei. On the other hand, the free energy of the phonon population modifies the crystalline volume at equilibrium. In addition to driving the temperature dependence of the electronic structure, these two mechanisms affect the energy levels at zero temperature through zero-point motion and zero-point energy. This thesis investigates the contribution of these two mechanisms to the zero point renormalization (ZPR) of the band gap energy of semiconductors. A generalized Fröhlich model taking into account the anisotropy and degeneracies occurring in real materials reveals that the non-adiabatic interaction between electrons and nuclei dominates the ZPR in polar materials. Taking this mechanism into account when evaluating the electron-phonon interaction is crucial to reproduce experimental data adequately. The Grüneisen formalism, which commonly neglects zero-point effects, reproduces the zero-point lattice expansion (ZPLE) and its contribution to the ZPR obtained from the standard method based on free energy minimization at lower numerical cost, including for anisotropic materials. The ZPLE contribution to the total ZPR, which has received little attention in the literature, can reach from 20% to more than 80% of the contribution of the electron-phonon interaction, including in materials containing light atoms. It even dominates the ZPR of GaAs within semilocal DFT. Therefore, both contributions should be treated on an equal footing to model the ZPR accurately. The inclusion of spin-orbit coupling (SOC) decreases the ZPR of a substantial set of cubic materials of zincblende, diamond and rocksalt structure. This variation originates mostly from the effect of SOC on the static electronic eigenvalues, which comes largely from the variation of the effective masses of the valence bands at the \(\Gamma\) point. The reduction of the ZPR can be estimated from a generalized Fröhlich model in which SOC has been introduced. Numerical subtleties related to the treatment of Dresselhaus separation in non-centrosymmetric materials are discussed. We finally show how the combination of electron-phonon interaction and thermal expansion affects the topological phase diagram of BiTeI. An increase in temperature pushes the \(\mathbb{Z}_2\) topological insulator phase towards higher pressures and widens the pressure range corresponding to the Weyl semi-metal intermediate phase. The leading orbital character of the band extrema significantly influences their sensitivity to variations in pressure and topology. To adequately guide the experimental search for topologically non-trivial phases in materials, numerical studies must therefore consider the effect of temperature.

Diese Arbeit präsentiert eine umfassende in-situ Studie zur thermischen Ausdehnung von β-Ga2O3 im Temperaturbereich von Raumtemperatur (RT) bis 1200 K sowie zum Wachstum dünner Ga2O3 Schichten durch plasmaunterstützte Molekularstrahlepitaxie (MBE). Hierfür kamen synchrotron-basierte hochauflösende Röntgenbeugung (HRXRD) sowie die Beugung hochenergetischer Elektronen bei Reflexion (RHEED) zum Einsatz. Die dadurch erhaltenen Resultate gestatten detaillierte quantitative Aussagen zu den Ausdehnungskoeffizienten (CTE) von β-Ga2O3 und ein tieferes Verständnis des Wachstumsprozesses von Ga2O3 sowohl im Rahmen der Homo- als auch der Heteroepitaxie. / This thesis presents a comprehensive in-situ study on the thermal expansion of beta-Ga2O3 from room temperature (RT) to 1200 K, and the thin film growth of Ga2O3 as carried out by oxygen plasma assisted molecular beam epitaxy (MBE) using synchrotron-based high-resolution x-ray diffraction (HRXRD) and reflection high-energy electron diffraction (RHEED). The obtained results provide a quantitative analysis on the coefficients of thermal expansion (CTE) of beta-Ga2O3, and a deeper understanding in the growth process of Ga2O3 in both homoepitaxy and heteroepitaxy.

Much study has been carried out to determine the properties of Lamellar Graphite Iron (LGI) or grey iron and their relations to factors such as the cooling rate, the dendrite morphology, the pouring temperature, and so on. However, there hasn’t been much comprehensive study on the properties of LGI outside the generally used and accepted composition, with 1 to 3% Silicon. The scope of this study is to measure and evaluate the thermal conductivity and tensile strength of LGI, for a higher concentration of  Si and different carbon contents. The concentration of Si aimed for was 4% but the concentration obtained after spectroscopy was between 4.1% to 4.15%. There are two hypereutectic, one near-eutectic and three hypoeutectic samples considered and these six chemical compositions were cast under different cooling conditions . The cooling time has been varied by providing different molds of 30mm, 55mm, and 80mm diameter cylinders respectively, for all the six sample compositions. The microstructure analysis carried out studies the segregation of Si, the graphite morphology, primary austenite morphology. These factors are then compared to the thermal and tensile behavior measured in this study. It can be observed that the thermal conductivity studied in the present work has a direct correlation for a higher Si content and tends to be greater than the thermal conductivity values observed from other studies with lower content Of Si. However, the conductivity shows an inverse relation with the cooling rate and is maximum for the samples with the lowest cooling rate. The tensile strength, on the other hand, seems to have a lower value than that observed in previous studies for LGI with 1 to 3% Si, but shows a direct correlation with the cooling rate. The mean area fraction of dendrites obtained and the mean interdendritic hydraulic diameter is also measured and their influence on the properties are also studied. The addition of more Si has greatly favored the thermal behavior positively but has also reduced the tensile strength.

In den letzten Jahren intensivierten sich die Bemühungen, anisotropes Verhalten von Gesteinen in numerischen Modellen abzubilden. Für ein tiefgreifendes Verständnis dieser Prozesse sind numerische Modelle gut geeignet, da hier die Rand- und Anfangsbedingungen sehr exakt vorgegeben werden können, um das Verhalten eines pkysikalischen Systems unter vollständig kontrollierbaren Bedingungen zu studieren. Am Beispiel von Gneis wird ein numerisches Modell für die Modellierung einaxialer Druck- und Spaltzugversuche vorgestellt. Dieses nutzt den Diskreten-Element-Code 3DEC der Fa. Itasca Consulting Group, Inc. um gekoppeltes nichtlinear-anisotropes thermo-mechanisches Materialverhalten zu simulieren. In dieser Arbeit wird sowohl der Modellaufbau anhand eines GBM gezeigt, als auch ein Stoffgesetz zur Simulation eines nichtlinearen orthotropen thermischen Expansionsverhaltens entwickelt. Die dafür benötigten Modellparameter werden anhand von durchgeführten Laborversuchen kalibriert. Das entwickelte Modell wird dann angewendet, um die Modellierung einaxialer Druck- und Spaltzugversuchen für ein anisotropes Material (Gneis) durchzuführen, um das Modell zu validieren. Am Ende der Arbeit wird eine praktische Anwendung des Modells in Form eines Schneidversuchs gezeigt. / In recent years, efforts have intensified to simulate the anisotropic behavior of rocks in numerical models. Numerical models are well suited for a profound understanding of these processes, since the boundary and initial conditions can be specified very precisely in order to study the behavior of a physical system under fully controllable conditions. Using the example of gneiss, a numerical model is presented for the modeling of uniaxial compression and Brazilian tensile tests. The discrete element code 3DEC from the company Itasca Consulting Group, Inc. is used to simulate coupled nonlinear- anisotropic thermo-mechanical material behavior. In this thesis the model generation is shown using Grain-Based Models and a material law for the simulation of a nonlinear orthotropic thermal expansion behavior is developed. The model parameters required for this are calibrated based on performed laboratory tests. The developed model is then applied to perform modeling of uniaxial compression and Brazilian tensile tests for an anisotropic material (gneiss) to validate the model. Lastly, a practical application of the model is shown in the form of a cutting test.

International Telemetering Conference Proceedings / October 28-31, 1996 / Town and Country Hotel and Convention Center, San Diego, California / Eutectic (63% tin-37% lead) or near-eutectic (40% tin-60% lead) tin-lead solder is widely used for creating electrical interconnections between the printed wiring board (PWB) and the components mounted on the board surface. For components mounted directly on the PWB mounting pads, that is, surface mounted components, the tin-lead solder also constitutes the mechanical interconnection. Eutectic solder has a melting point of 183°C (361°F). It is important to realize that its homologous temperature, defined as the temperature in degrees Kelvin over its melting point temperature (T(m)), also in degrees Kelvin, is defined as T/T(m). At room temperature (25°C = 298K), eutectic solder's homologous temperature is 0.65. It is widely acknowledged that materials having a homologous temperature ≥ 0.5 are readily subject to creep, and the solder joints of printed wiring assemblies are routinely exposed to temperatures above room temperature. Hence, solder joints tend to be subject to both thermal fatigue and creep. This can lead to premature failures during service conditions. The geometry, that is, the lead configuration, of the joints can also affect failure. Various geometries are better suited to withstand failure than others. The purpose of this paper is to explore solder joint failures of dual in-line (DIP) integrated circuit components, leadless ceramic chip carriers (LCCCs), and gull wing and J-lead surface mount components mounted on PWBs.

Depuis le début des années 1990 on suit l'évolution globale du niveau de la mer grâce aux satellites altimétriques. Ils observent une hausse du niveau moyen global de la mer (GMSL) de 3.4 ± 0.4 mm/an sur la période 1993-2016 (ce qui représente le double de ce qui a été observé au cours du 20ème siècle par les marégraphes, hausse à 1.7 mm/an entre 1900 et 1990). Le GMSL présente aussi des fluctuations interannuelles qui peuvent atteindre quelques millimètres, surtout pendant les épisodes ENSO. Cette hausse n'est pas régionalement uniforme : elle a été 3 fois plus rapide que la hausse moyenne globale dans certaines zones entre 1993 et 2016. Au cours du 21ème siècle, on s'attend à une hausse accrue du GMSL pouvant aller jusqu'à 1 m à l'horizon 2100, avec une forte variabilité régionale. Il est donc important de comprendre l'évolution actuelle du niveau des océans qui constitue une menace sérieuse pour de nombreuses régions côtières basses souvent très peuplées. Cette thèse s'inscrit dans le contexte du projet niveau de la mer CCI (Climate Change Initiative) de l'Agence Spatiale Européenne (ESA) ayant pour objectif de fournir de meilleurs produits du niveau de la mer combinant les missions Topex/Poseidon, Jason-1/2, ERS-1/2 et Envisat. L'objectif premier de cette thèse est de valider ces produits SL_CCI du niveau de la mer en utilisant différentes approches, en particulier par l'étude du bilan (comparaison du GMSL observé avec la somme des différentes contributions : composante stérique, fonte des glaces continentales et transferts d'eau depuis les terres émergées). Un autre objectif est d'estimer les composantes du niveau de la mer mal connues, et tout particulièrement le contenu thermique de l'océan profond non mesurable par le système Argo, et la contribution du stock d'eau sur les continents. Ces travaux ont montré que la contribution de l'océan profond en dessous de 2000m est faible sur la période 2005-2013 et contenue dans la barre d'incertitudes des données (erreurs qui proviennent essentiellement, (1) des produits niveau de la mer altimétriques et des lacunes de la couverture géographique des données Argo dans la région Indonésienne pour la tendance et (2) des produits GRACE et Argo pour la variabilité interannuelle). Nos résultats et la méthode utilisée montrent que le niveau de la mer et ses composantes sont encore entachés d'erreurs importantes. Dans la deuxième partie, nous avons analysé l'influence du phénomène ENSO (El Niño et La Niña) sur les variations interannuelles du GMSL. Nous montrons que lors des évènements La Niña comme celui de 2010-2011, le déficit de précipitations sur l'océan (et l'excès sur les continents) conduit à une baisse temporaire de la masse de l'océan global et donc du niveau de la mer. C'est essentiellement la variation de masse de l'océan qui explique la variabilité interannuelle du niveau de la mer lors des évènements ENSO, et le déficit (La Niña) ou excès (El Niño) de masse se trouve confiné dans l'océan Pacifique tropical Nord. Pour finir, nous analysons l'évolution de la température moyenne de l'air et de l'océan en surface sur la période du "hiatus" (2003-2013). Nous montrons que ce hiatus, c'est à dire le ralentissement récent de la hausse de la température moyenne globale de la Terre est un phénomène quasi global, même si le Pacifique tropical Est s'est fortement refroidi. Cette "supposée" pause récente s'explique par la variabilité naturelle interne du climat. La Terre est toujours en état de déséquilibre énergétique dû à l'accumulation de gaz à effet de serre. Nous mettons en évidence le rôle de la variabilité naturelle à court terme sur les changements à plus long terme associés au réchauffement climatique anthropique. / Since the early 1990s sea level is routinely measured using high-precision altimeter satellites. These observe a rise in global mean sea level (GMSL) of 3.4 ± 0.4 mm/yr over the 1993-2016 period (which is twice what has been observed during the 20th century by the tide gauges, with a rise of 1.7 +/- 0.3 mm/yr). The interannual variability in the GMSL can reach several millimeters, especially during ENSO events. The rate of sea level rise is not regionally uniform. During the altimetry era, it was three times faster than the global mean in some areas. During the 21st century, we expect a greater rise of the GMSL than today, up to 1 m in 2100, with strong regional variability. It is therefore important to understand the current evolution of the sea level, since it represents a serious threat to many low coastal areas, often densely populated of the planet. My thesis research deals with the Sea Level CCI (Climate Change Initiative) project of the European Space Agency (ESA) which objective is to provide improved sea level products combining several altimetry missions, including Topex/Poseidon, Jason-1/2, ERS-1/2 and Envisat. The primary objective of my thesis was to validate the CCI sea level products using different approaches, in particular the sea level budget approach. It consists of comparing the observed GMSL with the sum of different contributions : the steric component, melting of continental ice and transfers of water between the land surface and oceans. Another objective was to estimate the poorly known components to sea level rise, in particular the heat content of the deep ocean not measurable by Argo, and the contribution of water storage on the land. My work has shown that the contribution of the deep ocean below 2000m to the rising sea level is small over the 2005-2013 periods and not significant compared to the data uncertainties. The main uncertainties come from: (1) -in terms of trend- the altimetry sea level products and gaps in the geographical coverage of Argo data in the Indonesian region, and (2) -in terms of interannual variability- the GRACE and Argo products. My results and the method used show that the sea level and its components are still affected by important errors. In the second part, I analyzed the influence of ENSO (El Niño and La Niña) on the interannual variations of the GMSL. I showed that during La Niña events, like that of 2010-2011, the rainfall deficit over the ocean (and excess over the continents) leads to a temporary decrease in the global ocean mass and therefore in the GMSL. This is essentially the ocean mass variation that explains the interannual variability of the GMSL during ENSO events. Furthermore, the deficit (La Niña) or excess (El Niño) ocean mass is confined in the north tropical Pacific Ocean. Finally, I analyzed the evolution of the average temperature of air and ocean surface over the period of the "hiatus" (2003-2013). I showed that this hiatus, i.e. the recent slowdown in the rise of the global mean Earth's temperature is an almost global phenomenon, though cooling of the tropical eastern Pacific has slightly contributed. This recent pause is attributable to natural internal climate variability. The Earth is indeed still in a state of energetic imbalance due to the accumulation of greenhouse gases. I highlighted the role of the natural variability that is superimposed to the anthropogenic global warming.

Increasing interest in an effciency enhancement of existing energy sources led to an extended research in the field of thermoelectrics. Especially skutterudites with their high power factor (electric conductivity times Seebeck coefficient squared) are suitable thermoelectric materials. However, a further improvement of their thermoelectric properties is necessary. The relatively high thermal conductivity can be decreased by introducing loosely bound guest ions, whereas atom substitution or nanostructuring (as thin films) could yield an increased power factor. The present work proves the feasibility to deposit single phase skutterudite thin films by MBE technique. In this regard CoSby and FeSby film series were deposited with three different methods: i) codeposition at elevated temperatures, ii) codeposition at room temperature followed by post-annealing, and iii) modulated elemental reactant method. The structural and thermoelectric properties of these films were investigated by taking the thermal stability of the film and the substrate properties into account. Compared to the stoichiometric Sb content of skutterudites of 75 at.%, a small excess of Sb is necessary for achieving single phase skutterudite films. It was found, that the deposited single phase CoSb3 films reveal bipolar conduction (and therefore a low Seebeck coefficient), whereas FeSb3 films show p-type conduction and very promising power factors at room temperature. The need of substrates with a low thermal conductivity and a suitable thermal expansion coefficient is also demonstrated. A high thermal conductivity influences the measurements of the Seebeck coefficient and the obtained values will be underestimated by thermal shortening of the film by the substrate. If the thermal expansion coefficient of film and substrate differ strongly from each other, crack formation at the film surface was observed. Furthermore, the realization of controlled doping by substitution as well as the incorporation of guest ions was successfully shown. Hence, this work is a good starting point for designing skutterudite based thin film structures. Two successful examples for such structures are given: i) a thickness series, where a strong decrease of the resistivity was observed for films with a thickness lower than 10nm, and ii) a FexCo1-xSb3 gradient film, for which the gradient was maintained even at an annealing temperature of 400°C.:Contents 1 Introduction 2 Nanostructured thermoelectric materials 2.1 Thermoelectric materials and ZT 2.2 Recent developments in improving ZT in thin films 3 Thermoelectric transport theory 3.1 Electronic transport coefficients 3.2 Lattice thermal conductivity 4 Skutterudites as promising thermoelectric material 4.1 CoSb3 4.1.1 Structural properties of skutterudites 4.1.2 Band structure of CoSb3 and density of states 4.1.3 Thermoelectric properties of CoSb3 4.1.4 Synthesis of CoSb3 thin films 4.2 FeSb3 4.2.1 Structural and thermoelectric properties of FeSb3 thin films 4.2.2 Synthesis of FeSb3 thin films 5 Experimental methods 5.1 Basic methods for structural characterization 5.2 Electric characterization: Resistivity and Hall measurements using van der Pauw geometry 5.3 Thermoelectric characterization (Seebeck coefficient) 5.4 Thermal characterization methods 6 Deposition of skutterudite thin films 6.1 Deposition chamber and deposition parameters 6.2 Deposition methods 6.3 Composition control of skutterudite films 7 Control of structural properties by the used deposition method 7.1 Structural properties of CoSb3 thin films 7.1.1 Crystallization characteristics of CoSb3 films 7.1.2 Comparison of films deposited with different deposition methods 7.1.3 Influence of different deposition parameters on the film properties 7.2 Structural properties of FeSb3 thin films 7.2.1 Crystallization behaviour 7.2.2 Structural properties of post-annealed Fe-Sb films prepared by codeposition 7.2.3 Influence of the heating rate on the film properties 8 CoSb3 and FeSb3 composition series 8.1 CoSby composition series 8.1.1 Films deposited at elevated temperatures 8.1.2 Annealed films 8.2 FeSby composition series 9 Influence of various substrates on the film properties 9.1 Substrate influence on the film morphology 9.2 Substrate influence on thermoelectric properties and measurements 10 FexCo1-xSb3 - controlled doping by substitution of Co with Fe 10.1 Properties of codeposited FexCo1-xSb3 films 10.2 Properties of FexCo1-xSb3 films deposited via MERM 11 Filled CoSb3 thin films 12 Examples for nanostructured thin film approaches 12.1 CoSb3 thickness series 12.2 FexCo1-xSb3 gradient films 13 Summary and Outlook