La matière dense et tiède (WDM pour Warm Dense Matter) est caractérisée par des températures proches de celle de Fermi et des densités proches du solide. Cette thèse présente des études expérimentales de la WDM éventuellement hors équilibre électron-ion, à l'aide de la spectroscopie d'absorption X près des seuils (XANES) résolue en temps. Nous avons développé un dispositif expérimental de XANES résolu en temps, basé sur un spectromètre à deux cristaux de Bragg, qui permet d'obtenir d'une part le signal émis par la source X utilisée, et d'autre part le signal transmis à travers un échantillon fin d'aluminium. La comparaison de ces deux grandeurs permet de mesurer l'absorption absolue de l'échantillon. L'échantillon est excité par un faisceau laser ultra-bref afin d'atteindre les conditions thermodynamiques attendues.Le dépôt laser étant réalisé sur les électrons de l'échantillon, les ions restent froids pendant l'interaction. L'équilibration thermique qui suit a une durée attendue de l'ordre de quelques picosecondes. Lors d'une première expérience, nous avons étudié la dynamique des transitions de phase subies par une feuille d'aluminium de 100 nm d'épaisseur, chauffée par un laser de 120 fs, avec un flux relativement élevé (6 J/cm²). La transition solide-liquide a lieu sur une échelle de temps plus faible que la résolution (environ 3 ps). La transition liquide-vapeur atomique a lieu après une vingtaine de picosecondes, en accord avec des simulations hydrodynamiques. Afin d'observer plus précisément la transition solide-liquide, nous avons réalisé une seconde expérience avec des flux plus faibles (< 1J/cm²). La feuille d'aluminium reste dans un état localement structuré aux temps longs. L'observation de la diminution progressive des modulations XANES, correspondant à une perte partielle d'ordre local, permet de déterminer la dynamique de l'augmentation de la température ionique. La comparaison des résultats expérimentaux avec des simulations hydrodynamiques, et de dynamique moléculaire quantique, a montré que le XANES est un diagnostic pertinent de la température ionique pendant et au delà de la fusion, permettant de suivre l'équilibration thermique électrons-ions. Nous avons constaté un temps caractéristique de l'équilibration significativement plus long qu'attendu, ce qui questionne la détermination du taux de collisions électrons-ions dans le régime dense et tiède. Ce même diagnostic a été exploité lors de deux expériences où nous avons étudié la silice comprimée par un choc laser jusqu'à des densités atteignant plus de deux fois celle du solide. Nous avons ainsi pu suivre l'évolution des structures électronique et ionique de la silice. Pour obtenir une meilleure résolution temporelle, nous avons réalisé deux autres expériences en utilisant une source X bêtatron et un laser X à électrons libres. La faisabilité d'expériences de XANES avec des résolutions femtosecondes a ainsi été démontrée. / Warm Dense Matter (WDM) is characterized by temperatures near the Fermi one and densities close to the solid. Experimental studies of WDM eventually out of electron-ion equilibrium are presented in this thesis with the help of time-resolved X-ray Absorption Near Edge Spectroscopy(XANES).We have developed a time-resolved XANES set-up, based on a two-Bragg-crystals spectrometer, allowing to record in one hand the X-ray source emitted signal, and in the other hand the transmitted one through a thin aluminum sample. The absolute absorption of the sample is measured comparing these two signals. The aluminum sample is heated by an ultrafast laser beam in order to reach the required thermodynamical conditions. Note that the energy is deposited on the electrons, whereas the ions keep cold during the interaction. The thermal equilibration follows with an expected picosecond time scale. We performed a first experiment with the aim of studying the phase transitions undergone by a 100 nm depth aluminum foil, heated with a 120fs laser with a high fluence (6 J/cm²). The solid-liquid transition occurs on a time-scale shorter than the experimental resolution (about 3 ps). Le liquid-vapor transition occurs after about 20 ps, consistent with hydrodynamical simulations. In order to study more precisely the solid-liquid transition, we performed a second experiment with the same set-up but lower laser fluences (< 1 J/cm²). The aluminum foil stays in a locally-structured state even after long delays. The dynamics of the ionic temperature increase can be followed watching the progressive lessening of XANES modulations, corresponding to a partial decrease of the local order. Then one can reach the thermal electron-ion equilibration dynamics. The comparison of experimental data with hydrodynamics and quantum molecular dynamics simulations have revealed the relevance of XANES measurements in order to follow the ionic temperature during and above melting. The precision of the measurements allow to notice a significantly longer equilibration time-scale than expected, questioning the electron-ion collision rate determination in the warm dense regime. The same diagnostic has been operated during two experiments in order to study laser-shock compressed silica up to densities doubling the solid one. We have been able to follow the evolution of the electronic and ionic structures of silica. In order to reach a shorter time resolution, we performed experiments with two other X-ray sources : betatron and a X-ray free electron laser. The feasibility of femtosecond time-resolved XANES experiments have been demonstrated.

Phosphorus (P) one of the essential elements to plants and animals, is a non-renewable resource and accuatlly high demanded in agriculture. The World\'s population growth and future estimatives on food demands raises the question about the sustainability of the current agriculture systems, speccially concerns about the low P use efficiency in agroecosystems. Brazilian agriculture requires high P inputs and many researches has been developed to increase the crops yield and, consequently, food production efficiency. However, this development was achieved at the high costs of mineral fertilisers (specially P) and long-term perspectives about the costs of the intensification in the tropical agriculture is accuattly in debate. In this conxtext, in the present thesis chapter two we evaluated the evolution of the Brazilian cropland basis and P demands, quantifying the Brazil P Legacy and, based on scenarios involving the cropland area and yield expansion, we estimated the future (up to 2050) Legacy P and P fertilisers demand. We also estimated the potential aleviation that could be achieved in the mineral fertilizers consumption by utilisation and improvements on manure P recycling. Alternatively, considering the systems intensification and its effects on P availability, we proposed alternative scenarios to promote the Legacy P utilisation in Brazil\'s improved agriculture systems to grant the agriculture expansion without huge increments on the national P fertilisers consumption. A worldwide recognized advance in Brazilian agriculture is the Cerrado, where large cropland areas accually are cultivated twice a year, improving the food and fiber production without any additional disturbance of natural ecossystems. In this context, no-tillage (NT) agriculture has been widely used and, as consequence, soil fertility has been improved, which could be also farorable to the P availability, when rotation with crop species with P mobilization mechanisms are introduced, such as cover crops utilisation. However, the effects of these improved rotated systems on P bioavailability in long-term in tropical soils remains uncert in the literature and was our objective in the chapter three, where is described a study envolving the evaluation of long-term changes on P fractions in tropical Oxisols, from two long-term field trials involving tillage systems (NT and conventional tillage, CT) and cover crops (millet, brachiaria, maize and control, fallow). The long-term cultivation generated large amounts of legacy P in the soil and with the brachiaria introduction as cover crop, more P was recycled in the topsoil and labile P and all the organic P fractions increased. Based on the cover crop effects, we proposed that the bioavailability of the legacy P could be represented by the P extracted by the labile fractions + moderately labile P fractions. In the chapter four, we used other techniques actually widely applied to P speciation, and we applied in tropical soils affected by the native Cerrado conversion into NT and CT agriculture. A multiple approach to identify and quantify the P forms in tropical soils were proposed by the utilisation of Hedley\'s fractionation togheter with P K-edge XANES for P-bindings into inorganic soil matrix and liquid 31P-NMR spectroscopy to complement the organic P species in tropical soils. / Fósforo (P), um dos elementos essenciais às plantas e animais, é um recurso não-renovável e altamente demandado na agricultura atualmente. O crescimento da população mundial e as estimativas futuras da demanda de alimentos aumentam os questionamentos sobre a sustentabilidade dos sistemas agrícolas atuais, especialmente no que se refere a baixa eficiência no uso do P na agricultura. A agricultura brasileira requer altas quantidades de P e muitas pesquisas tem sido desenvolvidas para aumentar a produtividades das culturas e, conseequentemente, a eficiencia da produção de alimentos. Entretanto, este desenvolvimento tem sido alcançado a altos custos com uso de fertilizantes minerais (sobretudo P) e as perspectivas de longo prazo sobre os custos da intensificação da agricultura tropical estão atualmente em debate. Nesse contexto, no capítulo dois da presente tese avaliamos a evolução da área cultivada no Brasil e das demandas de P, quantificando o legado do P no Brasil e, baseado em cenários envolvendo a expansão da área cultivada e da produtividade, estimamos o futuro (até 2050) legado de P e as demandas por fertilizantes fosfatados. Ainda estimamos a potencial redução no consumo de fertilizantes fosfatados que pode ser alcançada pela utilização e melhorias na reciclagem do P oriundo de dejetos. Alternativamente, considerando a intensificação dos sistemas e seus efeitos na disponibilidade de P, propusemos cenários alternativos visando a utilização do \"Legacy P\" em sistemas agrícolas melhorados para garantir a expansão agrícola sem drásticos incrementos no consumo nacional de fertilizantes fosfatados. Um avanço internacionalmente reconhecido na agricultura Brasileira é o Cerrado, onde extensas áreas agrícolas são cultivadas duas vezes ao ano, incrementando assim a produção de alimentos e fibras sem qualquer custo aos ecossistemas naturais. Nesse contexto, a agricultura sob plantio direto (PD) tem sido amplamente difundida e, como consequencia, a fertilidade dos solos tem-se elevado, o que pode também favorecer a disponibilidade de P, quando são introduzidas rotações com espécies de plantas que apresentam mecanismos de mobilização do P, como o uso de plantas de cobertura. Entretanto, os efeitos desses sistemas melhorados de rotação na biodisponibilidade de P em solos tropicais no longo prazo permanecem incertos na literatura e foram objeto de estudo no capítulo três, onde está descrito um estudo envolvendo a avaliação das mudanças de longo-prazo nas frações de P em Latossolos, oriundos de dois experimentos de campo de longa duração no Cerrado, envolvendo a avaliação de sistemas de preparo (PD e preparo convencional, PC) e plantas de cobertura (milheto, braquiária milho e um controle, apenas pousio). O cultivo por longo tempo resultou em grandes quantididades de \"Legacy P\" acumulado no solo e, com o uso de braquiária como cultura de cobertura, maior quantidade de P foi reciclado para as camadas superiores do solo e as frações de P lábil e todas as frações organicas aumentaram. Baseado nos efeitos das plantas de cobertura, sugerimos que a biodisponibilidade do \"Legacy P\" pode ser representada pelo P extraído nas frações lábeis + o P de frações moderadamente lábeis. No capítulo quatro, utilizamos outras técincas atualmente difundidas para a especiação de P, aplicando-as em solos tropicais influenciados pela conversão do Cerrado nativo em agricultura sob PD e PC. Uma abordagem múltipla para identificação e quantificação de formas de P em solos tropicais foi proposta através da utilização do fracionamento de P proposto por Hedley em conjunto com a especiação de P por XANES da borda K do P para identificação de ligação do P a matrix inorgânica do solo, e espectroscopia de ressonância magnética nuclear (NMR) para complementação da identificação de espécies orgânicas de P em solos tropicais.

Phosphorus (P) one of the essential elements to plants and animals, is a non-renewable resource and accuatlly high demanded in agriculture. The World\'s population growth and future estimatives on food demands raises the question about the sustainability of the current agriculture systems, speccially concerns about the low P use efficiency in agroecosystems. Brazilian agriculture requires high P inputs and many researches has been developed to increase the crops yield and, consequently, food production efficiency. However, this development was achieved at the high costs of mineral fertilisers (specially P) and long-term perspectives about the costs of the intensification in the tropical agriculture is accuattly in debate. In this conxtext, in the present thesis chapter two we evaluated the evolution of the Brazilian cropland basis and P demands, quantifying the Brazil P Legacy and, based on scenarios involving the cropland area and yield expansion, we estimated the future (up to 2050) Legacy P and P fertilisers demand. We also estimated the potential aleviation that could be achieved in the mineral fertilizers consumption by utilisation and improvements on manure P recycling. Alternatively, considering the systems intensification and its effects on P availability, we proposed alternative scenarios to promote the Legacy P utilisation in Brazil\'s improved agriculture systems to grant the agriculture expansion without huge increments on the national P fertilisers consumption. A worldwide recognized advance in Brazilian agriculture is the Cerrado, where large cropland areas accually are cultivated twice a year, improving the food and fiber production without any additional disturbance of natural ecossystems. In this context, no-tillage (NT) agriculture has been widely used and, as consequence, soil fertility has been improved, which could be also farorable to the P availability, when rotation with crop species with P mobilization mechanisms are introduced, such as cover crops utilisation. However, the effects of these improved rotated systems on P bioavailability in long-term in tropical soils remains uncert in the literature and was our objective in the chapter three, where is described a study envolving the evaluation of long-term changes on P fractions in tropical Oxisols, from two long-term field trials involving tillage systems (NT and conventional tillage, CT) and cover crops (millet, brachiaria, maize and control, fallow). The long-term cultivation generated large amounts of legacy P in the soil and with the brachiaria introduction as cover crop, more P was recycled in the topsoil and labile P and all the organic P fractions increased. Based on the cover crop effects, we proposed that the bioavailability of the legacy P could be represented by the P extracted by the labile fractions + moderately labile P fractions. In the chapter four, we used other techniques actually widely applied to P speciation, and we applied in tropical soils affected by the native Cerrado conversion into NT and CT agriculture. A multiple approach to identify and quantify the P forms in tropical soils were proposed by the utilisation of Hedley\'s fractionation togheter with P K-edge XANES for P-bindings into inorganic soil matrix and liquid 31P-NMR spectroscopy to complement the organic P species in tropical soils. / Fósforo (P), um dos elementos essenciais às plantas e animais, é um recurso não-renovável e altamente demandado na agricultura atualmente. O crescimento da população mundial e as estimativas futuras da demanda de alimentos aumentam os questionamentos sobre a sustentabilidade dos sistemas agrícolas atuais, especialmente no que se refere a baixa eficiência no uso do P na agricultura. A agricultura brasileira requer altas quantidades de P e muitas pesquisas tem sido desenvolvidas para aumentar a produtividades das culturas e, conseequentemente, a eficiencia da produção de alimentos. Entretanto, este desenvolvimento tem sido alcançado a altos custos com uso de fertilizantes minerais (sobretudo P) e as perspectivas de longo prazo sobre os custos da intensificação da agricultura tropical estão atualmente em debate. Nesse contexto, no capítulo dois da presente tese avaliamos a evolução da área cultivada no Brasil e das demandas de P, quantificando o legado do P no Brasil e, baseado em cenários envolvendo a expansão da área cultivada e da produtividade, estimamos o futuro (até 2050) legado de P e as demandas por fertilizantes fosfatados. Ainda estimamos a potencial redução no consumo de fertilizantes fosfatados que pode ser alcançada pela utilização e melhorias na reciclagem do P oriundo de dejetos. Alternativamente, considerando a intensificação dos sistemas e seus efeitos na disponibilidade de P, propusemos cenários alternativos visando a utilização do \"Legacy P\" em sistemas agrícolas melhorados para garantir a expansão agrícola sem drásticos incrementos no consumo nacional de fertilizantes fosfatados. Um avanço internacionalmente reconhecido na agricultura Brasileira é o Cerrado, onde extensas áreas agrícolas são cultivadas duas vezes ao ano, incrementando assim a produção de alimentos e fibras sem qualquer custo aos ecossistemas naturais. Nesse contexto, a agricultura sob plantio direto (PD) tem sido amplamente difundida e, como consequencia, a fertilidade dos solos tem-se elevado, o que pode também favorecer a disponibilidade de P, quando são introduzidas rotações com espécies de plantas que apresentam mecanismos de mobilização do P, como o uso de plantas de cobertura. Entretanto, os efeitos desses sistemas melhorados de rotação na biodisponibilidade de P em solos tropicais no longo prazo permanecem incertos na literatura e foram objeto de estudo no capítulo três, onde está descrito um estudo envolvendo a avaliação das mudanças de longo-prazo nas frações de P em Latossolos, oriundos de dois experimentos de campo de longa duração no Cerrado, envolvendo a avaliação de sistemas de preparo (PD e preparo convencional, PC) e plantas de cobertura (milheto, braquiária milho e um controle, apenas pousio). O cultivo por longo tempo resultou em grandes quantididades de \"Legacy P\" acumulado no solo e, com o uso de braquiária como cultura de cobertura, maior quantidade de P foi reciclado para as camadas superiores do solo e as frações de P lábil e todas as frações organicas aumentaram. Baseado nos efeitos das plantas de cobertura, sugerimos que a biodisponibilidade do \"Legacy P\" pode ser representada pelo P extraído nas frações lábeis + o P de frações moderadamente lábeis. No capítulo quatro, utilizamos outras técincas atualmente difundidas para a especiação de P, aplicando-as em solos tropicais influenciados pela conversão do Cerrado nativo em agricultura sob PD e PC. Uma abordagem múltipla para identificação e quantificação de formas de P em solos tropicais foi proposta através da utilização do fracionamento de P proposto por Hedley em conjunto com a especiação de P por XANES da borda K do P para identificação de ligação do P a matrix inorgânica do solo, e espectroscopia de ressonância magnética nuclear (NMR) para complementação da identificação de espécies orgânicas de P em solos tropicais.

Um einen besseren Zugang zum Verständnis struktureller Eigenschaften von den ternären Verbindungen des Systems Yb–Pd–Ga zu bekommen, wurden zunächst die Ordnungs- und Unordnungsbeziehungen sowie die chemische Bindung in den Kristallstrukturen binärer Pd–Ga- bzw. Yb–Ga-Verbindungen analysiert. Im Rahmen der phasenanalytischen Untersuchungen des binären Systems Yb–Ga konnte eine neue Verbindung charakterisiert werden (Ytterbiumpentagallid). Für den galliumreichen Teil des ternären Phasendiagramms Yb–Pd–Ga wurde ein isothermer Schnitt bei 600 °C erstellt (&amp;gt; 50 At.-% Ga). Die Homogenitätsbereiche der untersuchten Verbindungen wurden metallographisch bzw. röntgenographisch bestimmt. Die Kristallstrukturen wurden aus Röntgen-Einkristalldaten bestimmt. In den Kristallstrukturen wurden drei unterschiedliche Arten von Unordnung beobachtet (Substitutionsunordnung, Symmetrie-Brechung, Positionsunordnung). Für eine Reihe von Verbindungen des Systems Yb–Pd–Ga wurde der elektronische Zustand von Yb bestimmt. Dies gelang mit Hilfe von Messungen der magnetischen Suszeptibilität bzw. mit der Röntgen-Absorptionsnahkantenspektroskopie.

Verbindungen mit Spinellstruktur im quasiternären System &amp;quot;LiO0.5-MnOx-FeOx&amp;quot; finden industriell als keramische Werkstoffe in der Elektrotechnik und Elektronik Verwendung. So werden Lithium-Mangan-Spinelloxide der Form Li1+xMn2-xO4 (x =&amp;gt; 0) als Kathodenmaterial für wiederaufladbare Lithiumbatterien untersucht. Sowohl Lithium- als auch Manganferrit finden Einsatz als steuerbare Komponenten in der Mikrowellentechnik und Manganferrite als Leistungsüberträger in Spulen und Transformatoren der Hochfrequenztechnik. Für einen solchen technischen Einsatz sind die Kenntnisse der Bedingungen für die Synthese phasenreiner Spinelle und deren Struktur unerlässlich. Die Darstellung der Spinelle erfolgte im Rahmen dieser Arbeit aus gefriergetrockneten Lithium-Mangan-Eisenformiaten. Diese Precursoren zeichnen sich durch hohe Reaktivität und exakte Metallionenstöchiometrie aus. Der Zersetzungsablauf von gefriergetrockneten Li-Mn(II)-Fe(III)-Formiaten unter Argon wurde mittels thermischer Analyse, gekoppelt mit der Massenspektroskopie, sowie durch Röntgenpulveraufnahmen der Zwischenprodukte untersucht. Aus den vorzersetzten Precursoren gewünschter Zusammensetzung wurden unter kontrollierten Temperatur- und Sauerstoffpartialdruckbedingungen einphasige Spinelloxide dargestellt. Die so erhaltenen Verbindungen mit Spinellstruktur wurden mittels Röntgenbeugung und Strukturverfeinerung sowie XANES- und Mößbauerspektroskopie und magnetischen Messungen untersucht. Aus der Kombination dieser Methoden konnten Schlussfolgerungen bezüglich der Struktur, Kationenverteilung und Eigenschaften der jeweiligen Spinelle gewonnen werden. Im Mittelpunkt der Arbeit steht die in der Literatur nicht beschriebene Mischkristallreihe LixMn1+xFe2?2xO4, die Mn(II) und Mn(III) oder Mn(III) und Mn(IV) für x &amp;lt; 0.5 oder x &amp;gt; 0.5 enthält. Mit zunehmendem x-Wert vergrößert sich der Anteil von Lithiumionen auf Tetraeder-plätzen. Bei einem Wert x = 4/7 erreicht dieser Anteil 100%. Unter Einbeziehung der Ergebnisse der Mößbaueruntersuchungen ergeben sich für die Spinellverbindungen mit x = 2/7, 3/7 und 4/7 die folgenden Kationenverteilungen: (Li1.04Mn2+2.81-[delta]Fe3+3.15Mn3+[delta])A[Li0.96Fe3+6.85Mn3+6-[delta]Mn2+0.19+[delta]]BO28 (Li2.37Mn2+1.0-*Fe3+2.98Mn3+0.65+*)A[Li0.63Fe3+5.02Mn3+8.35-*Mn2+*]BO28 (Li4.0Fe3+2.37Mn3+0.63)A[Fe3+3.63Mn3+9.37Mn4+1.0]BO28. Eine theoretisch vorhersehbare Zunahme der Sättigungsmagnetisierung bei kleinen x-Werten wird durch Abnahme der kooperativen Kopplungseffekte mit Abnahme des Eisengehaltes nicht beobachtet. Zusammenfassend kann festgehalten werden, dass die Darstellung phasenreiner Spinelloxide aus den vorzersetzten gefriergetrockneten Li-Mn-Fe-Formiaten im gesamten Bereich zwischen den bekannten quasibinären Spinellverbindungen MnFe2O4, Li0.5Fe2.5O4, LiMn2O4 und Li4/3Mn5/3O4 im quaternären System Li-Mn-Fe-O unter jeweils definierten pO2/T-Bedingungen möglich ist. Die Synthesetemperaturen sind teilweise um 100°C bis 200°C niedriger als bei vergleichbaren Proben aus den Festkörpereaktionen. Manganreiche Spinelle außerhalb dieses Bereiches konnten nicht synthetisiert werden.

No description available.

Dans le domaine des couches minces (épaisseur~Å) associant un métal magnétique (Fe, Co, Ni) et un élément non magnétique (essentiellement métallique ou isolant), de remarquables propriétés physiques (aimantation, transport) nécessitent des caractérisations structurales fines. En particulier, citons le cas de jonctions tunnel (métal/isolant/métal) à aimantation perpendiculaire qui sont en cours d'étude au laboratoire Spintec (UMR8191 (CEA/CNRS/UJF). Ces nanomatériaux sont déposés par voie physique (pulvérisation cathodique) au sein de ce laboratoire. Ces nanostructures sont également sondées par diffraction aux rayons X au sein de l'Institut Néel (UPR 2940) via une collaboration entre Spintec et une équipe de cet Institut (Surface, interfaces et nanostructures du Département MCMF, Matière Condensée, Matériaux, et Fonctions). Ces mesures de réflectivité X constituent la sonde privilégiée de choix dans la cadre de cette thèse. D'autres voies sont également exploitées: à l'aide des moyens de rayonnement synchrotron tels que la spectroscopie d'absorption de rayons X : EXAFS, XANES et XMCD. La thèse aura pour but d'étudier expérimentalement ces phénomènes en couches continues sur ces empilements à jonction tunnel avec aimantation perpendiculaire. Plus précisément, le travail de thèse permettra de comprendre les mesures magnétiques (effectuées à l'institut Néel notamment par magnétométrie SQUID et HALL à basse température) grâce à une batterie de mesures structurales (diffraction aux rayons X, rasant, figures de pôles, réflectivité, absorption X …). Notamment, l'influence des paramètres de dépôt (types de couches, épaisseurs, recuits) du matériau sont étudiées via la collaboration entre les différents groupes de recherche précédemment cités. Cette thématique s'inscrit d'une part dans le cadre de travaux menés à Spintec et dédiés à la recherche de nouveaux matériaux à forte valeur ajoutée industrielle (sur le stockage d'information à ultrahaute densité sur media discrets par exemple). Elle s'inscrit d'autre part dans le renforcement de liens entre recherches fondamentales (laboratoire propre du CNRS comme l'institut Néel) et appliquées (CEA), avec un recours aux solides compétences en caractérisations structurales et magnétiques de l'Institut Néel. / In the domain of thin film (thickness ~ Å) combining a magnetic metal (Fe, Co, Ni) and a non-magnetic (largely metal or insulator), remarkable physical properties (magnetization, transport) require fine structural characterization. In particular, include the case of tunnel junctions (metal / insulator / metal) with perpendicular magnetization which are being studied in the laboratory Spintec (UMR8191 (CEA / CNRS / UJF). These nanomaterials are deposited by physical (sputtering) in this laboratory. These nanostructures are probed by X-ray diffraction in the Neel Institute (UPR 2940) via collaboration between Spintec and a team of the Institute (Surface, Interfaces and Nanostructures Department MCFP, Condensed Matter Materials and Functions). These reflectivity measurements X are the preferred sensor of choice in the context of this thesis. Other routes are also used: using means such as synchrotron radiation absorption spectroscopy X-ray: EXAFS, XANES and XMCD. The thesis will aim to study these phenomena experimentally in continuous layers on the tunnel junction stacks with perpendicular magnetization. Specifically, the thesis will include the magnetic measurements (performed at the Institut Néel SQUID magnetometry including HALL and low temperature) through a battery of structural. This theme is part of a share in the context of work carried Spintec and dedicated to research of new materials with high added value industries (information storage on ultra-high density of discrete media for example). It registers on the other hand in strengthening links between basic research (CNRS own laboratories as Neel Institute) and applied (ECA), with strong skills in use of structural and magnetic characterization of the Institute Neel.

La Terre contient une quantité significative d’eau et son manteau est très oxydé par rapport aux conditions canoniques de la nébuleuse solaire, ce qui est contradictoire avec l’existence de son noyau métallique et sa position dans le Système solaire. Ceci implique que l’état rédox de la Terre ait augmenté au début de son histoire. Aujourd’hui, de nombreuses études suggèrent que cette évolution se soit faite à travers une accrétion hétérogène. Ainsi les premières briques élémentaires de notre planète seraient constituées de matériel très réduit et une grande partie de la différenciation précoce (extraction du noyau et différenciation silicatée) se seraient donc déroulées en conditions très réductrices (entre IW-5.5 et IW-2). L’objectif de cette thèse est de mesurer l’impact de ces conditions sur le comportement des terres rares (REE) et des éléments fortement chargés (HSFE), et de modéliser leur répartition dans les différents réservoirs lors de la différenciation précoce de la Terre. Nous réalisons une soixantaine d’expériences de fusion – cristallisation à l’équilibre de matériel chondritique à basse (5 GPa) et haute (26 GPa) pression, dans une gamme de conditions rédox allant de IW (tampon fer – wüstite) à IW-8. Afin de caractériser le paramètre fO 2 dans ces conditions extrêmes, nous développons un formalisme thermodynamique adapté, basé sur l’équilibre Si-SiO 2 . En analysant les différentes phases à l’équilibre dans les différents échantillons, nous calculons et établissons la première banque de données de partage cristal (enstatite, bridgmanite = pérovskite silicatée, majorite) – liquide silicaté, métal-silicate et sulfure-silicate pour les HFSE et les REE en conditions très réductrices. Grâce aux données enstatite – liquide nous développons un proxy de la fO 2 , basé sur le rapport D(Cr)/D(V) et grâce auquel nous mesurons la fO 2 de chondres de type I comme étant similaires aux conditions canoniques de la nébuleuse (IW-7). Nos données de partage métal – silicate prouvent que l’extraction du noyau terrestre n’est pas à l’origine d’un fractionnement des terres rares. Au contraire, en mesurant pour la première fois le spectre XANES du Nb 2+ et du Ta 3+ dans des verres silicatés à des teneurs de l’ordre du ppm, nous prouvons que le comportement de Nb et Ta est contrôlé par la fO 2 . En intégrant nos données de partage à un modèle d’accrétion hétérogène nous montrons que la signature sous-chondritique en Nb/Ta de la Terre silicatée peut être le résultat de l’accrétion d’un matériel chondritique évoluant avec le temps combinée à l’extraction du noyau en conditions réductrices, ce qui réfute l’hypothèse d’une Terre se formant à partir d’un matériel oxydé. Nos expériences de haute pression montrent que le partage des REE et des HFSE dans la majorite et la bridgmanite est très sensible à la fO 2. De plus, le processus de dismutation du fer, invoqué pour expliquer l’augmentation de la fO 2 du manteau lors de la cristallisation de l’océan magmatique, ne semble pas être un mécanisme efficace en-dessous de IW. Enfin, nos données montrent que Ti, V, Cr, Mn, Nb et Ta sont chalcophiles en conditions très réductrices. L’extraction précoce d’un liquide sulfuré dans ces conditions a donc pu modifier les rapports élémentaires supposés chondritiques dans la Terre silicatée. L’extraction d’une importante quantité de FeS pourrait aussi être à l’origine d’un découplage Zr/Hf. / The Earth contains significant amounts of water and its mantle is highly oxidized compared to the solar nebula canonical conditions, which is inconsistent with the existence of its metallic core and its location in the Solar System. This implies the redox state of the Earth has increased during its early history as suggested in heterogeneous accretion models. Thus, the first building blocks of our planet would have been made of highly reduced material, and the early Earth’s differentiation (core extraction and silicate differentiation) would have taken place under highly reducing conditions (between IW-5.5 and IW-2). The aim of this thesis is to measure the impact of these conditions on rare earth elements (REE) and high field strength elements (HFSE) behavior, and model their distribution into the main reservoirs formed early in Earth’s history. We run about sixteen melting – crystallization experiments, starting from chondritic material and equilibrating it at low (5 GPa) and high (26 GPa) pressure, spanning a redox range going from IW (iron – wüstite buffer) to IW-8. In order to characterize the fO 2 parameter in these extreme conditions, we develop an adapted thermodynamic formalism, based on Si-SiO 2 equilibrium. Analyzing the various equilibrated phases within our experimental samples, we calculate and propose the first crystal (enstatite, bridgmanite = Mg-perovskite, majorite) – silicate liquid, metal – silicate, sulfide – silicate partition coefficients database for HFSE and REE under highly reducing conditions. Using our enstatite-liquid data we develop a fO 2 proxy based on D(Cr)/D(V) ratio and we measure type I chondrule fO 2 as being similar to canonical nebular conditions (IW-7). Our metal-silicate partitioning data prove that Earth core extraction is not responsible for REE fractionation. On the contrary, recording for the first time Nb 2+ and Ta 3+ XANES spectra in silicate glasses and at ppm level concentrations, we prove that Nb and Ta behavior is mainly controlled by fO 2 . Using our partitioning data in a heterogeneous accretion model, we show that sub-chondritic Nb/Ta signature of the silicate Earth (14 ± 0.3) can be the result of the accretion of chondritic material changing with time, combined with the progressive extraction of the core in reducing conditions. This refutes the hypothesis of an oxidized material building the Earth. Our high-pressure experiments show that REE and HFSE partitioning in majorite and bridgmanite is very sensitive to fO 2 . Moreover, iron dismutation process, invoked to explain mantle fO 2 increase during magma ocean crystallization, does not seem to be an efficient mechanism below IW. Finally, our data show that Ti, V, Cr, Mn, Nb and Ta are chalcophiles under highly reducing conditions. Consequently, early extraction of a sulfide melt at an early and reduced stage could have modified chondritic elementary ratios in the silicate Earth. Extraction of a substantial amount of FeS may also cause a Zr/Hf decoupling.

Verbindungen mit Spinellstruktur im quasiternären System &amp;quot;LiO0.5-MnOx-FeOx&amp;quot; finden industriell als keramische Werkstoffe in der Elektrotechnik und Elektronik Verwendung. So werden Lithium-Mangan-Spinelloxide der Form Li1+xMn2-xO4 (x =&amp;gt; 0) als Kathodenmaterial für wiederaufladbare Lithiumbatterien untersucht. Sowohl Lithium- als auch Manganferrit finden Einsatz als steuerbare Komponenten in der Mikrowellentechnik und Manganferrite als Leistungsüberträger in Spulen und Transformatoren der Hochfrequenztechnik. Für einen solchen technischen Einsatz sind die Kenntnisse der Bedingungen für die Synthese phasenreiner Spinelle und deren Struktur unerlässlich. Die Darstellung der Spinelle erfolgte im Rahmen dieser Arbeit aus gefriergetrockneten Lithium-Mangan-Eisenformiaten. Diese Precursoren zeichnen sich durch hohe Reaktivität und exakte Metallionenstöchiometrie aus. Der Zersetzungsablauf von gefriergetrockneten Li-Mn(II)-Fe(III)-Formiaten unter Argon wurde mittels thermischer Analyse, gekoppelt mit der Massenspektroskopie, sowie durch Röntgenpulveraufnahmen der Zwischenprodukte untersucht. Aus den vorzersetzten Precursoren gewünschter Zusammensetzung wurden unter kontrollierten Temperatur- und Sauerstoffpartialdruckbedingungen einphasige Spinelloxide dargestellt. Die so erhaltenen Verbindungen mit Spinellstruktur wurden mittels Röntgenbeugung und Strukturverfeinerung sowie XANES- und Mößbauerspektroskopie und magnetischen Messungen untersucht. Aus der Kombination dieser Methoden konnten Schlussfolgerungen bezüglich der Struktur, Kationenverteilung und Eigenschaften der jeweiligen Spinelle gewonnen werden. Im Mittelpunkt der Arbeit steht die in der Literatur nicht beschriebene Mischkristallreihe LixMn1+xFe2?2xO4, die Mn(II) und Mn(III) oder Mn(III) und Mn(IV) für x &amp;lt; 0.5 oder x &amp;gt; 0.5 enthält. Mit zunehmendem x-Wert vergrößert sich der Anteil von Lithiumionen auf Tetraeder-plätzen. Bei einem Wert x = 4/7 erreicht dieser Anteil 100%. Unter Einbeziehung der Ergebnisse der Mößbaueruntersuchungen ergeben sich für die Spinellverbindungen mit x = 2/7, 3/7 und 4/7 die folgenden Kationenverteilungen: (Li1.04Mn2+2.81-[delta]Fe3+3.15Mn3+[delta])A[Li0.96Fe3+6.85Mn3+6-[delta]Mn2+0.19+[delta]]BO28 (Li2.37Mn2+1.0-*Fe3+2.98Mn3+0.65+*)A[Li0.63Fe3+5.02Mn3+8.35-*Mn2+*]BO28 (Li4.0Fe3+2.37Mn3+0.63)A[Fe3+3.63Mn3+9.37Mn4+1.0]BO28. Eine theoretisch vorhersehbare Zunahme der Sättigungsmagnetisierung bei kleinen x-Werten wird durch Abnahme der kooperativen Kopplungseffekte mit Abnahme des Eisengehaltes nicht beobachtet. Zusammenfassend kann festgehalten werden, dass die Darstellung phasenreiner Spinelloxide aus den vorzersetzten gefriergetrockneten Li-Mn-Fe-Formiaten im gesamten Bereich zwischen den bekannten quasibinären Spinellverbindungen MnFe2O4, Li0.5Fe2.5O4, LiMn2O4 und Li4/3Mn5/3O4 im quaternären System Li-Mn-Fe-O unter jeweils definierten pO2/T-Bedingungen möglich ist. Die Synthesetemperaturen sind teilweise um 100°C bis 200°C niedriger als bei vergleichbaren Proben aus den Festkörpereaktionen. Manganreiche Spinelle außerhalb dieses Bereiches konnten nicht synthetisiert werden.

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 &gt; 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.