L’extraction d’éléments d’intérêt (terres rares, métaux lourds, métaux de transition, radionucléides) de de minerais conventionnels ou non conventionnels (mines urbaines) et d’effluents industriel ou nucléaire est un enjeu majeure dans les procédés d’extraction, de recyclage et/ou de décontamination.Un grand nombre de solides organiques et inorganiques, chélatants ou échangeurs d’ions, ont été développés pour un tri ionique sélectif par procédé solide/liquide.L’introduction covalente de ligands spécifiques dans le squelette de la résine permet d’augmenter la sélectivité vis-à-vis d’une cible métallique par la nature des agents de complexation, leurs sites de chélation et leur rigidité.L’objectif de cette thèse recouvre d’une part la synthèse de systèmes chélatant réactifs, leur polymérisation pour la préparation des résines « super »chélatantes et d’autre part, l’évaluation des polymères pour l’extraction/séparation d’ions, les terres rares étant plus particulièrement ciblées.A partir de résines formo-phénolique incorporant du catéchol et la 8-hydroxyquinoléine qui sont des précurseurs phénoliques, nous avons pu montrer que la récupération sélective du germanium été possible vis-à-vis du silicium ou du zinc en fonction de leur proportion dans la matrice polymérique.La synthèse des précurseurs phénoliques intégrant des ligands comme l’acide diglycolamique et les diglycolamides a permis la mise en œuvre de résine pour la récupération des terres rares. Une étude sur la compréhension de la synthèse des résines ainsi que leurs performances d’extraction a ainsi été réalisée et a pu mettre en évidence le potentiel de ces résines pour la récupération et valorisation des terres rares.Une ouverture vers d’autres possibilités de synthèses de ce type de résines (matériaux poreux, sous forme de mousse…) est également proposée pour permettre d’augmenter les surfaces de contacts lors des extractions solide-liquide et ainsi augmenter les performances de ces matériaux. / Extraction of specific targeted species (rare earth, heavy metals, transition metals, radionuclides) from industrial (mining deposit and urban mining) and nuclear effluents is an important issue in the recycling and / or decontamination processes. A large number of organic and inorganic solids, chelating or ion-exchanging materials, have been developed for selective ionic separation by solid / liquid process. Metal-specific ligands incorporate in the structure of the resin itself is an interesting way to perform ion separation taking the advantage of the selectivity of chelating agents. The aims of this project are firstly the synthesis of chelating original systems and then prepare specific ion exchange resins.From formo-phenolic resins incorporating catechol and 8-hydroxyquinoline, we have been able to show that the selective recovery of germanium from silicon or zinc was possible, , depending on their proportion of each phenolic precursors in the polymeric matrix.The synthesis of the phenolic precursors integrating ligands such as diglycolamic acid and diglycolamides allowed the use of resin for the recovery of rare earths elemnets. A study on the understanding of the synthesis of resins as well as their performance of extraction was thus realized and was able to highlight the potential of these resins for the recovery and valorization of the rare earths elements.An opening towards other possibilities of synthesis of this type of resins (porous materials, in the form of foam, etc.) is also proposed in order to increase the contact surfaces during solid-liquid extractions and thus increase the performance of these materials.

In this work, we have investigated the thermal properties (diffusivity (D), conductivity (K), temperature coefficient of the optical path length change (ds/dT), etc) and loss processes owing to the ion-ion interactions, in Nd3+ doped laser materials, specifically YAG ceramic and CGGG crystal. Since the fluorescence quantum efficiency, , is directly related to these mechanisms that lead to luminescence quenching, the studies were carried out mainly observing the effects of these processes on . To this goal we used mainly the thermal lens technique and conventional spectroscopy. In Nd:YAG ceramic, we have investigated the losses due to down-conversion or, as they are well known, concentration quenching that are basically cross relaxation (CR) and energy migration (EM). From these results, it was concluded that the main source of luminescence quenching is CR and that the small ds/dT value together with the high optimum concentration put this material as candidate for several applications. In Nd:CGGG crystal, we have studied the loss processes owing to upconversion or, as is better known, upconversion Auger (UA) or energy transfer upconversion, which are important in laser systems of high. / Fundação de Amparo a Pesquisa do Estado de Alagoas / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho investigamos as propriedades térmicas (difusividade (D), condutividade (K), variação do caminho óptico com a temperatura (ds/dT), etc) e processos de perdas devido a interações entre íons, em materiais lasers dopados com Nd3+, especificamente cerâmica de YAG e cristal CGGG. Desde que a eficiência quântica de fluorescência, , está diretamente relacionada com esses mecanismos que levam a supressão da luminescência, os estudos foram realizados principalmente observando os efeitos desses agentes sobre . Para esse propósito, usamos principalmente a técnica de lente térmica e espectroscopia convencional. Na cerâmica de Nd:YAG investigamos as perdas por down-conversion ou, como é melhor conhecidas, quenching de concentração que são basicamente relaxação cruzada (RC) e migração de energia (ME). Nesses resultados concluímos que a principal fonte de supressão da luminescência é RC e que o valor de ds/dT baixo juntamente com a concentração ótima alta apresentam esse material com boas perspectivas de aplicações. No cristal Nd:CGGG estudamos os processos de perdas por upconversion ou, como é melhor conhecido, conversão ascendente Auger (CAA) ou conversão ascendente por transferência de energia, os quais são importantes em sistemas lasers de alta potência e/ou altas concentrações de íons dopantes. Com a presença dos processos de CAA é adicionado mais um canal de decaimento não radiativo. E como resultado foi observado uma diminuição de η e consequentemente um aumento da carga térmica (φ). O conhecimento dos processos investigados nesta dissertação é de importância fundamental para a engenharia e caracterização de matérias lasers.

Ce travail a porté sur la synthèse et caractérisations structurales, optiques et électriques des films d’oxyde d'étain (SnOx) dopés avec des éléments de terres rares (RE: Néodyme, Praséodyme ou Ytterbium). L’objectif est de démontrer la conversion de photons UV voire Visible en photons rouges via ces films RE :SnOx, tout en conservant leurs propriétés d’oxydes transparents conducteurs. Les films ont été produits par des méthodes chimiques (sol-gel, précipitation) ou physiques (pulvérisation cathodique). Grâce à des analyses fines, nous avons pu corréler les propriétés structurales et de composition des couches RE :SnOx avec leurs propriétés d’émission de photons. Nous avons pu établir les conditions optimales de conversion photonique dans des systèmes à une seule ou double terre rare. Les mécanismes régissant le transfert dans ces films ont été avancés. Enfin, nous avons appliqué ces couches minces RE :SnOx optimisés sur des cellules solaires en silicium et en CIGS et nous avons montré une amélioration des paramètres photovoltaïques du dispositif ainsi qu’un net gain dans la réponse spectrale de la cellule dans l’UV. / Spectral conversion using lanthanide doped materials with excellent performances is a great challenging topic and of particular interest for photovoltaic. This work aims at functionalizing transparent conductive oxide materials with rare earth elements for photons conversion purpose without affecting transparency and transport properties of the TCO. The spectral conversion targeted in this thesis is of type “down”, in other words, we aim at converting high energy UV photons into low energy visible or NIR photons useful to solar cells. For this purpose we investigated the doping process of SnO2 as a host material with different rare earths such as Nd, Tb, Pr, and Yb. To understand the insertion process and the optical activation of the rare earth, RE-doped SnO2 nanoparticles (powders) have been synthesised by two chemical methods: co-precipitation and sol-gel. The results have shown an efficient insertion of the RE into the SnO2 structure with excellent emission properties. In view of application of RE-doped SnOx thin films to solar cells, studies concerning NIR emitting RE have been conducted (Nd, Yb, and co-doping with Yb and Nd) using sputtering. Several deposition parameters and post deposition treatments have been done in order to find the best chemical environment favourable to the RE emission. We have precisely identified the region of the UV light converted into NIR photons and proposed several energy transfer mechanisms occurring between the host SnOx and the REs. In case of co-doping, a second spectral conversion process has been identified; visible photons can be efficiently converted into NIR photons through energy transfer from Nd3+ to Yb3+ ions. Finally, application of these conversion layers to solar cells such as CIGS and Si based have shown an improvement of the cells characteristics, among others the Field factor, the cell efficiency and the increase of the spectral response of the cell in the UV region, thanks to the conversion of the UV photons into NIR photons. The good electrical properties of the RE-doped SnOx layers have been highlighted as well. We believe that these conversion layers will provide a step ahead towards better solar cells performances.

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Die 17 Elemente der Seltenen Erden sind Bestandteil vieler Hochtechnologieprodukte, wie Elektromotoren, Spezialgläsern oder Katalysatoren, dennoch liegt die Recyclingrate aus End-of-Life-Produkten derzeit unter 1 %. Mit der Feststoffchlorierung wurde im Rahmen dieser Arbeit eine chemikalien- und kostensparende Methode für den Aufschluss Seltener Erden aus Leuchtstoff- und Magnetabfällen untersucht. Dabei wurden die gemahlenen Edukte mit NH4Cl vermischt und anschließend im Drehrohrofen erhitzt. Durch thermische Zersetzung des NH4Cl wird HCl- und NH3-Gas freigesetzt. Ersteres überführt die Seltenen Erden in die wasserlöslichen Metallchloride, während der NH3 im Prozess als Lösung in 5N-Reinheit anfiel. Die Seltenerdausbeuten lagen je nach Ausgangsstoff zwischen 83,9 und 99,9 %. Die Optimierung der Feststoffchlorierung erfolgte anhand statistischer Versuchspläne, wodurch neue, überraschende Erkenntnisse im Hinblick auf Reaktionsverläufe, Selektivitäten und Prozessführung gewonnen werden konnten.