Dans le contexte actuel, l’approvisionnement en terres rares est un enjeu capital, et le recyclage des déchets produits par les sociétés industrialisées apparaît comme une solution extrêmement pertinente d’un point de vue écologique. Dans ce travail, nous nous sommes intéressés aux aimants permanents Nd-Fe-B, car ils constituent un gisement potentiel important pour le néodyme, mais aussi pour le dysprosium et le praséodyme, éléments également critiques. Plus précisément, les aimants présents au sein des disques durs d’ordinateur ont été étudiés en vue de leur recyclage. L’intérêt est donc de mettre en place des solutions permettant le retraitement et la valorisation de ces aimants, présentant non seulement un impact environnemental faible, mais également un coût bas. Nous avons décidé de nous intéresser au traitement hydrothermal des aimants permanents Nd-Fe-B en vue de leur recyclage. L’étude du traitement thermique des aimants Nd-Fe-B en présence d’une solution saline pour des températures avoisinant les 225°C, permet la mise en évidence d’une dégradation complète du matériau. La poudre récupérée à l’issue du procédé est donc constituée de cristaux octaédriques, correspondant à la magnétite, et de cristaux aciculaires correspondant aux hydroxydes de néodyme, mais également aux différentes terres rares présentes en tant que dopants dans la phase intergranulaire. A l’issue du traitement hydrothermal, les fragments de revêtement peuvent être retirés par tamisage, en raison de leur dimension millimétrique, et les ocydes de fer séparés des hydroxydes de terres rares par séparation magnétique. Afin de valoriser les aimants Nd-Fe-B comme matière première magnétique permettant la fabrication de nouveaux aimants permanents, le broyage a également été envisagé. Des échantillons d’alliage Nd2Fe14B ont été broyés à haute énergie sous atmosphère protectrice, et nous avons réalisé l’étude microstructurale et magnétique de ces poudres. Les échantillons ont été analysés par magnétométrie SQUID, par spectrométrie Mössbauer, ainsi que par Sonde Atomique Tomographique. Ainsi, nous avons pu mettre en évidence un phénomène couplé de décomposition et de nanostructuration à l’échelle moléculaire de la phase Nd2Fe14B. L’ensemble de ce travail a donc permis d’étudier le comportement et les transformations des aimants Nd-Fe-B au cours de deux procédés très différents : le traitement hydrothermal et le broyage mécanique. Les résultats obtenus lors du traitement hydrothermal sont très prometteurs en vue du recyclage des terres rares à grande échelle. / Rare earth supplying is a very current topic, linked to the rare earth crisis of 2010. « Urban mining » is a promising path for recycling rare earths included in waste daily generated by industralized countries. In this work, we focus on recycling Nd-Fe-B permanent magnets, because they are a very interesting deposit for Neodymium, but also for Dysprosium and Praseodymium. More precisely, permanent magnets included in hard disks drives have been considered. The objective of this work is to set up environmentally friendly and low cost recycling processes for rare earths. First, we investigated hydrothermal treatment of Nd-Fe-B permanent magnets, We developed a new and environmentally friendly approach for recycling Ni−Cu coated Nd-Fe−B permanent magnets included in computer hard disk drives. In a closed reactor, the coated magnets are heated at 250 °C in water mixed with sodium chloride for up to 18 h. First, the hydrothermal treatment induces the removal of the metallic coating that can be recovered by sieving. Then, the Nd-rich phase reacts with water, leading to the formation of Nd(OH)3. Atomic hydrogen is absorbed by the Nd2Fe14B phase, leading to the formation of Nd2Fe14BHx. The volume expansion of the intergranular phase, in relation to the formation of Nd(OH)3, together with the lattice expansion of the Nd2Fe14BHx phase causes the disintegration of the magnets. Finally, Nd2Fe14BHx is oxidized by water into Fe3O4 and Nd(OH)3. The Nd(OH)3 crystals can be isolated from the Fe3O4 crystals by magnetic separation. This process is thus an easy way to extract rare earths from permanent magnets found in WEEE. It uses green chemistry design principles and can be applied to large amounts of magnetic wastes. Mechanical milling of Nd-Fe-B permanent magnets has also been investigated, and, in the study presented here, the milling effect on the magnetic properties of the Nd2Fe14B intermetallic was investigated using SQUID measurements, Mössbauer spectrometry and atom probe tomography (APT). Mechanical milling of the Nd2Fe14B alloy leads to its decomposition and its nanostructuration. This transformation induces first the formation of an amorphous, disordered phase Nd-Fe-B, with an enrichment in Neodymium; then to the formation of a mixture of -Fe and Nd-rich regions. The corresponding microstructure is very characteristic, with the formation of pure iron particles, with a hundred of nanometers in size, surrounded by an amorphous shell enriched in Neodymium and in Boron. Finally, intermixing of these phases is observed. Thanks to this work, we determine the behavior and the transformations of Nd-Fe-B permanent magnets during two very different processes: hydrothermal treatment and mechanical milling. Results obtained with hydrothermal treatment are very promising for recycling rare earths at the industrial scale.

On a global scale, the deployment of wind power plants is soaring. However, the availability of their construction materials could be a potential bottleneck, a problem rarely discussed in literature so far. Rare earth elements represent the most critical materials in terms of high economic importance, supply risk and environmental risk. This study therefore provides a market analysis of rare earths, ascertaining that geological scarcity is not the main problem. Instead, four kinds of market failure are identified: market power, co-production, by-production and negative externalities. Altogether, the market for rare earth metals is in a state of severe disequilibrium. Subsequently, an estimate of future rare earth demand patterns based on the wind power industry by 2050 reveals that the current level of supply is unlikely to be sufficient in the long run. To allow for a more elaborate analysis, two options of including a rare earth side condition in an integrated assessment model are finally suggested.

The subject of this thesis are channel waveguide lasers in epitaxial garnet films grown by liquid phase epitaxy. Results of this thesis include: The feasibility of a waveguide laser with erbium-doped YIG as the active material is discussed. Nonlinear rate equations that describe the behavior of this laser are formulated and solved numerically. The material parameters that are needed as the input are taken from literature. The simulations reveal that the performance of the laser depends critically on the magnitude of the upconversion parameter W22. A thorough analysis shows, however, that the values of W22 that are found in literature are most likely too small. The other parameter of importance is the background loss of the waveguide. Our results indicate that, unless the absorption losses of the LPE grown iron garnet films can be significantly reduced, the chances to realize such a device are only minimal. The mechanisms behind the absorption losses in LPE grown YIG films are investigated. During the LPE growth process, lead, platinum and other non-trivalent impurities are incorporated into the films in high concentrations. While platinum is tetravalent only, lead can be both di- and tetravalent. Depending on the ratio of the lead and the platinum concentrations, the near infrared absorption can be caused by three entirely different mechanisms. In case the tetravalent impurities are the majority, charge compensation is achieved by the formation of Fe2+ and the absorption is caused by crystal field transitions between the 5E and the 5T2 states of the Fe2+-ion. If the divalent impurities are in the majority, the absorption is due to crystal field transitions between the 5T2 and the 5E states of the Fe4-ion. In LPE-grown iron garnets, however, the impurity with the highest concentration is usually lead. We prove that lead performs self-compensation as it is incorporated in Pb2+/4+ pairs on neighboring lattice sites, and that the optical absorption is caused entirely by a charge transfer transition between the two neighboring lead ions. The electrical conductivity is measured in a temperature range from 300 to 800 K. It is demonstrated that in this temperature range the so-called impurity conduction is the predominant conduction mechanism in all types of films. Around room temperature, the conductivity shows an abnormal temperature behavior as the measured Bohr radius of the impurity ions almost doubles between 295 and 370 K. This can be explained by the fact that film and substrate have different temperature expansion coefficients. As the temperature increases, the stress in the film changes from tensile to compressive. When that happens, the {Pb2+} and the [Pb4+] ions counteract the strain in that they interchange their lattice sites. Also, Fe4+, if present, switches from the tetrahedral to the octahedral site which reduces the lattice constant of the film. This interpretation finds support in the results on the optical absorption, in the lattice mismatch, and in MCD spectra that were previously measured by Milani and Paroli. Based on the above findings, an easy way to eliminate the growth induced absorption in LPE iron garnet films is presented. By co-doping the films with other di- and tetravalent ions like Mg and Ge in high concentrations, the concentration of absorbing Pb2+/Pb4+ centers is greatly reduced due to the formation of non-absorbing Pb2+/Ge4+ and Ca2+/Pb4+ centers. As a result, absorption losses as low as 0.05 cm-1 at 1.3 µm wavelength have been achieved. In the second part of this thesis the fabrication of a channel waveguide laser in epitaxial Nd:GGG films is described. The films are grown by LPE on [111] oriented GGG substrates from a PbO/B2O3 flux. To increase the index contrast between film and substrate, Bi is added to the melt. Initially, the films showed strong brown discoloration and a high defect density. Luminescence lifetime measurements revealed severe quenching problems. The chemical analysis of the films by EPMA shows that platinum from the crucible enters the films but no lead from the flux. It is found that the platinum in GGG, similar to the lead in YIG, forms Pt2+/Pt4+ centers in order to achieve charge compensation. The quenching is caused by the charge transfer transition between the two platinum ions. To eliminate the quenching, MgO is added to the melt. As a result, the brown discoloration, the quenching and the growth defects disappear. From the planar film rib waveguides are fabricated using ion beam etching. The unclad waveguides are cut and the endfaces are polished to couple light in and out. Both endfaces are perpendicular to the waveguide within 0.1°. The losses are derived from the Fabry-Perot interferences. Losses as low as 0.2 dB/cm are achieved for both TE and TM modes. Laser oscillation starts at a launched pump power of 5 mW. The resonator is formed by the polished endfaces of the waveguide, no dielectric mirrors have been applied. Thus, the facet reflectivity is only about 10%. The launched pump power is measured precisely using a novel technique at which the luminescence intensity emitted through the surface is spatially resolved with a beam profile analyzer. Coupling efficiencies of over 90% are measured. The slope efficiency is found to be 48%.

Cette thèse de doctorat se fixe tout particulièrement pour objectif d’apporter un éclairage sur la problématique de la production des éléments de terres rares aux États-Unis. Ces minéraux, aux qualités nucléaire très particulières, constituent des intrants cruciaux dans certaines technologies et industries stratégiques : technologies « vertes », technologies d’information et de communication, ainsi que dans les technologies militaires. Ces minéraux stratégiques constituent aujourd’hui un enjeu géoéconomique mais aussi géopolitique et environnemental majeur. En 2011, 97 % des éléments de terres rares dans le monde proviennent de la Chine (qui dispose donc d’un monopole), selon l’United States Geological Survey. Cette position de la Chine a soulevé des inquiétudes chez les responsables américains concernant l’accès à ces ressources minérales, de manière évidente depuis 2010. Cette recherche questionne le rôle crucial joué par les acteurs au sein des agences étatsuniennes dans l’objectif d’élaborer une politique solide pour faire face au risque géopolitique lié à la vulnérabilité des États-Unis face au risque de ruptures d’approvisionnement de ces minéraux stratégiques. Ces minéraux sont donc une source de conflit international, surtout en raison de la montée de la Chine comme un nouveau joueur sur la scène internationale, dotée d’un quasi monopole sur les terres rares. Situé à la croisée des préoccupations géoéconomiques et géopolitiques et environnementales, il a semblé nécessaire de comprendre quels enjeux essentiels soulèvent ces minéraux stratégiques : enjeux géoéconomiques, défis géopolitique ou danger écologique ? C’est donc en ces termes que nous examinerons la question des minéraux de terres rares par les États-Unis. / This doctoral dissertation particularly aims at shedding light on the issue of U.S. rare earth production, a group of minerals with very special qualities nuclear, which are vital inputs in certain strategic industries and technologies: green technologies, information and communication technologies, as well as in military technologies. These strategic minerals constitute nowadays one of the major challenges associated with geo-economic, geopolitical and environmental issues. In 2011, China has provided approximately 97 percent of the world’s rare earth minerals (near-monopoly) according to U.S. Geological Survey data. This position of China has raised concerns about access to these mineral resources among American officials, obviously since 2010. This research discuss the crucial role played by actors within the U.S. Agencies to develop a robust policy to deal with the geopolitical risks about U.S. vulnerability to a supply disruption of these critical strategic minerals, as part of a source of international conflict, especially with the rise of China as a new player on the international stage. Located at the crossroads of geo-economic, geopolitical, and environmental concerns, it seems necessary to understand what key impasses constitute rare earths strategic minerals, economic power or geopolitical challenges or ecological danger? It is in these terms that we will deal with the issue of rare earths as considered by the United States.

This thesis studies different Eu optical centers in MgS:Eu and CaS:Eu thin films produced by Chemically Controlled Pulse Laser Deposition (CCPLD) and evaluates their suitability for the development of spectral storage devices of the future. The produced thin films consist of one or more optically active layer(s), MgS:Eu, CaS:Eu or a similar material, and a corresponding ZnS capping layer that functions as a protecting barrier for the other layers and preserves their composition and integrity. Given that the synthesis of the materials used to produce the multilayer structures in this work proved a great challenge, careful attention was given to the optimization of all fabrication parameters. Mass Spectrometry was used during the deposition of the thin films and the data obtained resulted on improvements and optimization of the deposition process. Scanning electron microscopy studies of these thin films were conducted to study degradation upon long-term storage. Microscopy results show that the morphology of the produced thin films is correlated to the growth environment during deposition and deterioration of the deposited materials could be initiated by nano-gaps and cracks in the capping layer of the thin films. In addition to optical centers in MgS:Eu and CaS:Eu, new centers were created by changing the thin film growth environment inside a hi-vacuum chamber, modifying the composition of the ablation target material, or both. For example, introducing O2, or alternatively HCl, inside the CCPLD chamber while producing MgS:Eu thin films results in the formation of impurity associated centers across lattice sites throughout the deposited structures. In another method of impurity doping studied, Cl- and Na+ were introduced into the MgS:Eu and CaS:Eu lattices by mixing trace amounts of the impurity ions into these materials in polycrystalline form and making this mixture a deposition target by hi-pressure cold compression technique. The introduction of these impurity ions will alter the crystal field environment around the Eu ions thus creating new optical centers with a shift in energy of their characteristic Zero Phonon Line. After extensive characterization of the optical properties of the thin films produced, laser-induced fluorescence spectroscopy and absorption spectroscopy measurements confirm that they are suitable candidates to be used in conjunction with power-gated spectral holeburning technique and could potentially provide ultrahigh, terabits per square inch, storage densities. / Physics

Characteristic L-shell x rays of the five rare earths Pr, Sm, Eu, Gd, and Dy were studied in this work. The x rays were produced by ionization from 0.3 to 2.0 MeV protons from the 2.0 MV Van de Graaff at North Texas State University. Total L-shell ionization and x-ray production cross sections were measured for Sm and compared to the BEA, CBEA and PWBA theories. Total L-shell ionization cross sections were measured for Pr, Eu, Gd, and Dy and compared to the BEA, CBEA, and PWBA. The CBEA and PWBA fit the samarium data well for both ionization and x-ray production cross sections. The BEA was generally 40 per cent lower than the data. The CBEA and the PWBA also fit the ionization cross section data for Pr, Eu, Gd and Dy, while the BEA was generally 40 per cent lower than the data.

O método cerâmico é a rota de síntese mais utilizada na produção de materiais luminescentes no estado sólido dopados com íons terras raras. Porém, as altas temperaturas necessárias para a formação dos compostos somada ao longo tempo de síntese levantam questões sobre a viabilidade energética desse método. Nos dias atuais, há grande interesse em buscar alternativas mais sustentáveis que gastem menos energia, e produtos com performances cada vez melhores. Nesse cenário, foi proposta a síntese dos materiais com luminescência persistente em forno de micro-ondas doméstico, por se tratar de um equipamento relativamente barato, que gasta muito menos energia que um forno tubular convencional, e tem um tempo de síntese muito menor. Os materiais SrS:Eu2+,TR3+ (TR = Ce, Nd, Sm, Dy, Er e Yb) foram produzidos pelo método de síntese no estado sólido assistida por micro-ondas, e para validação e comparação do método, os materiais SrS:TR (TR = Eu2+, Ce3+, Sm3+ e Yb2+/3+) foram preparados por ambos os métodos cerâmico e assistido por micro-ondas. Estudos de estrutura e morfologia dos materiais preparados foram realizados com medidas de DRX em pó e XANES na borda-LIII dos íons terras raras e na borda-K do enxofre. As propriedades luminescentes dos materiais foram investigadas com medidas de termoluminescência, luminância, espectroscopia UVVisível, espectroscopia UV-Vácuo e XEOL. Todos os materiais dopados com Eu2+ têm uma banda larga de emissão centrada em 620 nm atribuída à transição 4f65d1→4f7 com forte efeito nefelauxético. Além do Eu2+, foram observadas transições 5d→4f para o Ce3+ e o Yb2+. Estudos de luminescência persistente mostraram que a co-dopagem do SrS:Eu2+ com íons TR3+ aumentaram a duração do tempo de emissão de luz dos materiais após cessada a fonte de irradiação em mais de 400 %. Além disso, não se observou diferença na duração do fenômeno para os diferentes íons co-dopantes, mostrando que o mecanismo de luminescência persistes nesse material é governado pelo armadilhamento de elétrons em defeitos pontuais na matriz. Um novo fenômeno foi observado com a intensa luminescência persistente gerada após irradiação com raios X. Por fim, foram realizados testes de aplicação dos materiais com luminescência persistente em iluminação no estado sólido para geração de luz branca, mostrando que eles podem ser utilizados em LEDs persistentes. / Hitherto, the ceramic method is the most employed synthesis route on the production of solid-state luminescent materials doped with rare-earth ions. However, the high temperatures required for the compounds formation added up to the long synthesis time give rise to questions about the energetic viability of this method. Nowadays there is a great interest in finding more sustainable alternatives which demands less energy and provides products with better performances. Is this scenario, the synthesis of the persistent luminescence materials in a domestic microwave oven was proposed, because it is a relatively cheap equipment that spends much less energy than a conventional tubular furnace and has a shorter synthesis time. Thus, the materials SrS:Eu2+,TR3+ (TR = Ce, Nd, Sm, Dy, Er e Yb) were prepared via the microwaveassisted solid-state synthesis, and, for validation and comparison between methods, the materials SrS:TR (TR = Eu2+, Ce3+, Sm3+ and Yb2+/3+) were prepared via both the ceramic and microwave-assisted methods. Studies of structure and morphology of the prepared materials were undertaken with XRD and XANES at LIII-edge of rare-earth ions and K-edge of sulfur measurements. The luminescent properties of the materials were explored with thermoluminescence, luminance, UV-Vis spectroscopy, VUV spectroscopy and XEOL measurements. All the Eu2+-doped materials have a large emission band centered at 620 nm assigned to the 4f65d1→4f7 transition with strong nephelauxetic effect. Besides Eu2+, 5d→4f transitions were observed for Ce3+ and Yb2+ as well. Persistent luminescence studies showed that co-doping SrS:Eu2+ with TR3+ have improved the light emission timespan in over 400 % after removing the irradiation source. Moreover, no difference was detected on the emission timespan for the different co-dopant ions, showing that the persistent luminescence mechanism for this material is governed by electron trapping on the matrix point defects. A new phenomenon with high-intensity persistent luminescence was observed in these materials after irradiation with X-ray. At last, tests of application of the persistent luminescent materials with solid-state white-lighting were made, showing that they can be used in persistent LEDs.

Estruturas fotônicas à base de silício têm despertado grande interesse por permitirem uma perfeita integração entre processos ópticos e eletrônicos em um único chip. Além de compatíveis com a atual indústria microeletrônica, acredita-se, que tais estruturas possam aumentar consideravelmente a velocidade de processamento de informações. Uma microcavidade óptica é um exemplo de estrutura fotônica simples. Feita à base de silício, e dopada com íons terra-rara, tal microcavidade pode intensificar a emissão gerada pelo íon e resultar em um dispositivo de importância tecnológica. O projeto-construção deste tipo de microcavidade deve considerar a sua região de funcionamento e os materiais a serem utilizados. Deve contemplar, ainda, algumas condições externas que, eventualmente, possam alterar o seu funcionamento. Uma dessas condições é descrita pelo chamado coeficiente termo-óptico que indica a dependência do índice de refração com a temperatura. Dentro desse contexto a presente Tese de Doutorado foi dedicada ao estudo de microcavidades ópticas com janelas de transmissão em 650 nm e em 1550 nm – correspondendo às regiões de menores perdas de fibras ópticas de plástico e de sílica. As microcavidades compreenderam espelhos de Bragg [camadas alternadas de silício amorfo (a-Si) e nitreto de silício amorfo (a-SiN)], um filme de a-SiN como espaçador, e foram depositadas sobre substratos de sílica pela técnica de sputtering. As cavidades MC-Er e MC-ErYb tiveram como espaçadores filmes de a-SiN dopados com Er e Er + Yb, respectivamente. Medidas de fotoluminescência da MC-ErYb na região do infravermelho próximo indicaram um aumento de 48 vezes na emissão dos íons Er3+ (em ~1535 nm) comparado a um filme de a-SiN dopado com érbio devido: (1) a presença do itérbio e, (2) às múltiplas reflexões sofridas pela luz nos espelhos de Bragg. As microcavidades cujos espaçadores eram a-SiN puro foram submetidas a medidas de transmissão óptica em função da temperatura de medida. O deslocamento da janela de transmissão devido às variações de temperatura permitiu determinar o valor do TOC do a-SiN como: (6.2±0.1)×10-5 ºC-1 (em ~ 620 nm) e, (4.7±0.1)×10-5 ºC -1 (em ~ 1510 nm). Até onde sabemos, o TOC do a-SiN no VIS foi determinado pela primeira vez neste trabalho. / Silicon photonic based structures have attracted great interest for allowing a perfect integration between optical and electronic process in a single chip. Besides being compatible with the actual microelectronic industry, it is believed that such structures can considerably increase the information processing speed. An optical microcavity is an example of a simple photonic structure. Made based on silicon, and doped with rare-earth ions, such microcavity may enhance the emission generated by the ion and become a device of technological importance. The project-construction of this kind of microcavity has to consider the operation region and the materials used. It still has to take into account external conditions that may, eventually, change its operation. One of these conditions is described by the thermo-optic coefficient (TOC) that shows the dependence of the refractive index with the temperature. Within this context the present PhD thesis was dedicated to the study of optical microcavities with transmission windows at 650 nm and at 1550 nm – corresponding to the low losses regions of the plastic and silica optical fibers. The microcavities comprised Bragg mirrors [alternated layers of amorphous silicon (a-Si) and amorphous silicon nitride (a-SiN)], one film of a-SiN as spacer, and were deposited on silica substrates by the sputtering technique. The MC-Er and MC-ErYb cavities had Er and Er+Yb-doped a-SiN films as spacers, respectively. Photoluminescence measurements of the MC-ErYb in the near infrared showed an enhancement of 48 times in the emission of the Er3+ ions (at ~ 1535 nm) compared with an Er-doped a-SiN film owing to: (1) the presence of ytterbium and, (2) the multiple reflections experienced by the light at the Bragg mirrors. The microcavities whose spacers were pure a-SiN were submitted to optical transmission measurements as a function of the measurement temperature. The shift of the transmission window due to variations in the temperature allowed determining the a-SiN TOC: (6.2±0.1)×10-5 ºC-1 (at ~ 620 nm) and, (4.7±0.1)×10-5 ºC -1 (at ~ 1510 nm). To the best of our knowledge, the a-SiN TOC in the visible was determined for the first time in this work.

Os estudos visando o aproveitamento dos minerais de interesse econômico associados ao Granito Madeira, Pitinga, AM, foram subdivididos em três etapas. A primeira etapa compreendeu a realização de estudos de caracterização tecnológica, com um detalhado estudo mineralógico enfocando a forma de ocorrência e granulometria de liberação dos minerais de interesse. Foi identificado pela primeira vez a presença de criolita, mineral raro, cujo valor agregado supera o conjunto de todos os demais minerais de interesse econômico. Verificou-se que a granulometria de liberação dos minerais pesados era muito distinta; valores de 80% são observados para a zirconita acumulada abaixo de 0,595 mm, para a cassiterita abaixo de 0,297 mm e para os minerais de nióbio abaixo de 0,149 mm. A segunda etapa compreendeu, essencialmente, a realização de estudos de desenvolvimento de processo de concentração dos minerais pesados, incluindo ensaios de concentração densitária e separações eletrostática e magnética. Foram estabelecidas as características dos concentrados passíveis de serem obtidos e suas respectivas recuperações metalúrgicas, bem como definido um fluxograma de beneficiamento a ser confirmado em escala piloto. A terceira etapa teve por enfoque principal o desenvolvimento de uma rota de processo para a concentração da criolita, a qual, embora ainda não otimizada, é sumariada a seguir: - deslamagem dos rejeitos da concentração densitária, seguido de flotação aniônica direta, mediante a utilização de \"tal oil\" como coletor e amido de milho e como processor; - remoagem do concentrado \"rougher\" a menos 0,074 mm, em circuito fechado com classificação, seguido de flotação reversa do concentrado \"rougher\" remoído, com coletor catiônico, Armacflote MIC-66 (marca Akzo); - descoleta do concentrado da flotação catiônica, seguido de flotação aniônica com sulfonato de petróleo, Aero 840 (marca Cyanamid), para a separação entre a criolita e os demais minerais de flúor portadores de cálcio; - separação magnética de alta intensidade via úmida, \"WHIMS\", do concentrado da última etapa de flotação (com 0,5% a 0,7% de Fe203), visando minimizar os teores de ferro; - lixiviação clorídrica do produto não-magnético, com a redução suplementar dos teores de ferro, atingindo valores de 0,16 a 0,20% de Fe203. / Studies at the Pitinga primary ore envolved three stages. The first one consisted of detailed mineralogical studies emphasizing the occurrence patterns and the degree of liberation of the minerals in the granitic ground ore. Cryolite in the Pitinga ore was then identified for the first time. The liberation sizes for heavy minerals are quite distinct; a liberation degree of 80% was observed for zircon accumulated under 0,595 mm for cassiterite under 0,297 mm and for niobium minerals under 0,149 mm. The second stage comprised essentially mineral dressing studies to concentrate the heavy minerals. Discontinuous gravity concentration, electrostatic and magnetic separation tests were performed to establish the characteristics of the mineral concentrates and their recoveries, as well as to define a plant flowsheet to be confirmed in continuous pilot plant tests. The definition of a mineral processing route for cryolite concentration was the main object of the last stage. The following sequence of procedures, to be further investigated, was established: - disliming of gravity concentration taillings, followed by direct anionic flotation of fluorine minerals, using tall oil as collector and starch as depressant; - regrinding of the rougher concentrate to minus 0,074 mm, in a closed circuit with classification, followed by reverse cationic flotation to remove silicates, with Armacflote MIC-66 (Akzo trade mark); - remotion of the cationic collector and subsequence anionic flotation with petroleum sulfonate as collector (Aero 840, Cyanamid trade mark), to separate cryolite from the other fluorine minerals and small amounts of silicates; - wet high intensity magnetic separation (WHIMS) on the obtained flotation concentrate; - dilute hydrochloric acid leaching of the non-magnetic product from WHIMS to reduce the iron contamination levels to around 0,16% to 0,25% Fe203.

Os complexos [TR2(L)3⋅x(H2O)]y(H2O) (Eu3+, Gd3+ e Tb3+) com os ligantes dicarboxilatos alifáticos OXA, MAL, SUC, GLU, ADP, PIM, SUB, AZL, SEB, UND e DOD foram preparados pelo método de precipitação. Estes compostos de coordenação foram sintetizados em solução aquosa e com aquecimento (~ 80 ºC) e apresentaram-se na forma de pós brancos, cristalinos, não higroscópicos e insolúveis em solventes polares e apolares. A análise elementar (CHN) indicou a proporção molar M:L de 2:3 e o número de moléculas de H2O dos complexos, que foi confi rmado pelos dados de análise térmica (TG/DTG). A temperatura final de saída das moléculas de H2O dos complexos apresentou um padrão em ziguezague em função do tamanho da cadeia carbônica dos ligantes, levando ao chamado efeito odd-even. As análises de espectroscopia de absorção no infravermelho (FTIR) confirmaram a efetiva coordenação dos ligantes já desprotonados aos íons TR3+ via modo misto de coordenação ponte-quelato, exceto no caso dos complexos [TR2(OXA) 3⋅6(H2O)]4(H2O)4(H2O) que ocorre via ponte bidentada. Os difratogramas de raios-X pelo método do pó (XPD) indicam que os complexos apresentam elevada cristalinidade, pertencendo ao sistema cristalino monoclínico e que os complexos com o mesmo ligante e diferentes íons TR3+ são isomórficos. As imagens de microscopia eletrônica de varredura (MEV) mostram que os compostos apresentam diferentes morfologias tais como bastão, placas ou um misto de placas e cubos, como no caso dos complexos de Eu3+ com os ligantes OXA, SUC e DOD respectivamente. A investigação por espectroscopia de absorção dos sais sódicos dos ligantes (Na2L) e a reflectância difusa, bem como o estudo fotoluminescente (espectros de excitação e emissão) dos complexos de Eu3+, Gd3+ e Tb3+ foi realizada e discutida. O comportamento fotoluminescente dos complexos baseados nos tempos de vida (t) do nível emissor 5D0 do íon Eu3+, rendimento quântico intrínseco (QLnLn), taxas de decaimento radiativo (Arad) e não-radiativo (Anrad) foram determinadas. Ademais, foi realizado o estudo sistemático teórico e experimental para calcular os parâmetros de intensidade Ω2 e Ω4. Os espectros de fosforescência resolvidos no tempo dos complexos de Gd3+ apresentaram bandas largas oriundas dos níveis tripleto (T1) dos ligantes ~ 22950 cm-1, mais próximos do nível emissor 5D4 (Tb3+) do que do nível 5D0 (Eu3+), sugerindo que a alta intensidade luminescente exibida pelos complexos de Tb3+ comparados com os complexos análogos de Eu3+ é devida à transferência de energia intramolecular mais eficiente. Os espectros de reflectância difusa confirmam a presença de bandas 4f8→4f75d1 e LMCT nos complexos de Tb3+ e Eu3+, respectivamente. Os espectros de emissão dos íons Tb3+ e Eu3+ apresentaram bandas finas referentes a transições intraconfiguracionais 4f, sendo que as transições 5D4→7F5 (~ 545 nm) e 5D0→7F2 (~ 611 nm) foram as mais intensas, respectivamente. Os valores de rendimento quântico intrínseco QLnLn dos complexos variaram entre 13 e 28%, dentro dos quais o composto [Eu2 (SUC) 3⋅2(H2O)]H2O apresentou o maior valor. Este comportamento espectroscópico mostra que as moléculas de H2O atuam como um eficiente canal de supressão de luminescência. Os valores dos parâmetros de intensidade experimentais e teóricos (Ω2 e Ω4) apresentaram excelente concordância e mostraram o comportamento em ziguezague. Isto sugere que o íon Eu3+ atua como uma poderosa sonda espectroscópica para o efeito odd-even. Os complexos de Gd3+, Eu3+ e Tb3+ apresentaram cores de emissão azul, vermelha e verde, respectivamente, sugerindo que podem ser utilizados como dispositivos moleculares conversores de luz (DMCLs). / The [RE2(L)3⋅x(H2O)]y(H2O) complexes (RE3+: Eu3+, Gd3+ and Tb3+) with the aliphatic dicarboxylates ligands OXA, MAL, SUC, GLU, ADP, PIM, SUB, AZL, SEB, UND e DOD have been prepared by the precipitation method. These coordination compounds were synthesized in aqueous solution and heating (~ 80 °C) and presented as white crystalline powder, non-hygroscopic and insoluble in both polar and nonpolar solvents. The elemental analysis (CHN) indicated the M:L molar ratio of 2:3 and the number of water molecules of the complexes, which were confirmed by thermal analysis (TG/DTG) data. The final evaporating temperature of the H2O molecules of the complexes presented a zigzag pattern as a function of the carbon chain size of the ligands, leading to the so-called odd-even effect. The infrared absorption spectroscopy (FTIR) confirmed the effective coordination of the already deprotonated ligands to the RE3+ ions via the mixed mode of bridge-chelate coordination, except for the [RE2 (OXA)3⋅6(H2O)]4(H2O) complexes that occur via bidentate bridge mode. The X-ray powder diffraction (XPD) patterns indicate that the complexes present high crystallinity and the compounds with the same ligand and different RE3+ ions present isomorphic character. Scanning electron microscopy (SEM) images showed that the Eu3+ complexes with OXA, SUC and DOD ligands exhibited different morphologies such as rods, sheets or a mixture of sheets and cubes, respectively. The absorption spectroscopy investigation of the ligand sodium salts (Na2L) and the diffuse reflectance as well as the luminescence study (excitation and emission spectra) for the Eu3+, Gd3+ and Tb3+ complexes have been performed and discussed. The photoluminescent behavior of the complexes based on the lifetime (t) of the 5D0 emitting level of the Eu3+ ion, intrinsic quantum yield (QLnLn), radiative (Arad) and nonradiative (Anrad) were determined. In addition, the theoretical and experimental systematic study was carried out to calculate the intensity parameters Ω2 and Ω4. The time resolved phosphorescence spectra of the Gd3+ complexes showed broad emission bands assigned to the triplet (T1) states of the ligands at ~ 22950 cm-1, closer to the 5D4 emitting level (Tb3+) than to the 5D0 level (Eu3+), suggesting that the higher luminescent intensity exhibited by the Tb3+ complexes compared to the Eu3+ analog complexes are due to a more efficient L—RE3+ intramolecular energy transfer. The diffuse reflectance data confirmed the presence of 4f8→4f75d1 and LMCT absorption bands in the Tb3+ and Eu3+ complexes, respectively. The emission spectra of the Tb3+ and Eu3+ ions showed narrow bands due to the intraconfigurational 4f transitions, among them the 5D4→7F5 (~ 545 nm) and 5D0→7F2 (~ 611 nm) transitions were the most intense, respectively. The values of intrinsic quantum yield QLnLn of the complexes ranged from 13 to 28%, in which the [Eu2 (SUC)3⋅2(H2O)]H2O complex presented the highest value due to its lower number of H2O molecules. This optical behavior shows that the H2O molecules act as an efficient luminescence quenching channel. The values of experimental and theoretical intensity parameters (Ω2 and Ω4) presented excellent agreement which showed the zigzag behavior. These indicate that the Eu3+ ion acts as a powerful spectroscopic probe for the odd-even effect. The Gd3+, Eu3+ and Tb3+ complexes showed blue, red and green emission colors, respectively, suggesting that can be applied as light-converting molecular devices.