Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nesta Dissertação foi utilizado um sistema catalítico Zieger-Natta à base de neodímio para avaliar a influência do agente de halogenação e da razão molar halogênio:Nd sobre a atividade catalítica, a constante de velocidade de propagação, a conversão da polimerização, a microestrutura, a massa molecular e a polidispersão do polibutadieno 1,4-cis. O sistema utilizado era constituído por versatato de neodímio (NdV), hidreto de diisobutilalumínio (DIBAH) e um agente de halogenação. Os agentes halogenantes estudados foram: cloreto de t-butila (t-BuCl), sesquicloreto de etilalumínio (EASC) e cloreto de dietilalumínio (DEAC), em valores de razão molar Cl:Nd que variaram entre 0,5:1 e 5:1 e o dietil-eterato de trifluoreto de boro (BF3.Et2O), na razão molar F:Nd = 3:1. Os polímeros foram caracterizados por espectroscopia na região do infravermelho para determinação da microestrutura e por cromatografia de exclusão por tamanho para determinação das massas moleculares. O teor de unidades 1,4-cis variou de 90 a 98%, a massa molecular numérica média ( ) permaneceu na faixa entre 0,2 e 2x105, e a massa molecular ponderal média ( ) variou de 1,4 a 4x105 / In this Dissertation a catalyst system based on neodymium was employed to evaluate the influence of halogen source and the halogen:Nd molar ratio on the catalyst activity, polymerization constant rate, polymerization conversion, molecular weight characteristics and microstructure of polybutadiene. The catalyst systems were formed by diisobutylaluminium hydride (DIBAH), neodymium versatate (NdV) and a halogen source. The halogenating agents studied were t-butyl chloride (t-BuCl), ethylaluminium sesquichloride (EASC) and diethylaluminium chloride (DEAC) in a nCl:nNd molar ratio in the range from 0,5 to 5, and boron trifluoride diethyl ether (BF3.Et2O). The polymers were characterized by infrared espectroscopy for determining the microstructure and by size exclusion chromatography to obtain the molecular mass characteristics. The cis-1,4 units contents varied from 90 to 98%, the number-average molecular mass ( ) varied from 0,2 to 2x105 and the weight-average molecular mass ( ) varied from 1,4 to 4x105

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Orientador: Leandro Russovski Tessler / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-09-11T21:07:05Z (GMT). No. of bitstreams: 1 BiggemannTejero_DanielCarlos_D.pdf: 10164089 bytes, checksum: 92ca23a6073fc8197bc0a0519b8227b1 (MD5) Previous issue date: 2005 / Resumo: Nesse trabalho apresentamos o estudo da otimização da fotoluminescência (PL) de filmes finos de a-SiNx:H<Nd> preparados pela técnica de RF co- sputtering. A PL foi estudada em função da concentração de nitrogênio e de neodímio. Foi observado que os íons são excitados através da matriz amorfa. O mecanismo de excitação é mais eficiente em amostras com gap óptico E04 aproximadamente igual ao dobro da transição 4 I 9/2 ® 3 F 3/2 , indicando um processo de excitação dos íons dominantemente via recombinações não-radiativas de elétrons da cauda de banda de condução nas dangling bonds. O modelo mais adequado para descrever a excitação dos íons Nd 3+ é o DRAE (Defect Related Auger Excitation), que foi proposto originalmente para o Er 3+ em a-Si:H. Foi feito um estudo da PL com o tratamento térmico das amostras até temperaturas de 700°C. Os resultados de medidas de micro-Raman e HRTEM (High Resolution Transmission Electron Microscopy) mostram que as mudanças na estrutura dos filmes (presença de nano-cristais de Si e/ou Si3 N4 ) aparecem quando a PL não é mais detectável. Isso implica que o tratamento térmico aumenta a PL principalmente deixando o entorno químico dos íons Nd3+ mais favorável para as transições 4f. Em amostras na geometria de guia de onda planar, fizermos medidas de ganho óptico, tempo de vida da PL em função da temperatura e da potência de excitação. Os resultados mostram ganho óptico no material somente a baixas temperaturas e sob excitações acima de 5 kW/cm 2 . A PL em função da intensidade de excitação apresenta mudança de derivada também acima de 5 kW/cm 2 . Esses resultados permitem considerar o material como promissor para aplicações em amplificadores ópticos integrados / Abstract: In this work, we report a study of the photoluminescence (PL) optimization of a-SiNx:H<Nd> thin films prepared by RF co-sputtering. The PL was investigated as a function of nitrogen and neodymium concentrations. We observed that the Nd ions are excited through the amorphous matrix. The excitation mechanism is more efficient in samples where the optical gap E04 is twice the 4 I 9/2 ® 3 F 3/2 transition of Nd ions, showing an excitation process mostly dominated by non-radiative recombinations of electrons from conduction band tails into dangling bonds. The most adequate model to describe the excitation of Nd 3+ ions is the DRAE model (Defect Related Auger Excitation), originally proposed for Er 3+ in a-Si:H. We study the PL of the samples with thermal annealing at temperatures up to 700°C. Micro Raman and HRTEM (High Resolution Transmission Electron Microscopy) measurements show that small structural changes (presence of Si and/or Si3 N4 nano crystals) appear when no more PL is detectable. This implies that the annealing enhances the PL mainly modifying the chemical neighborhood of the Nd3+ ions to be more favorable for the 4f transitions. In samples with planar waveguide geometry, we performed optical gain measurements, PL lifetime as a function of temperature and excitation power. The results showed optical gain only at low temperatures and under excitation intensities higher than 5 kW/cm 2. The behavior of the PL as a function of excitation intensity shows a change in its derivate also at an excitation power higher than 5 kW/cm 2 . These results allow us to consider this material as promising for applications in integrated optical amplifiers / Doutorado / Física da Matéria Condensada / Doutor em Ciências

O elemento químico neodímio (Nd) atualmente está em evidência pois é parte fundamental em aplicações produzidas por empresas ligadas a tecnologias limpas e de ponta. Porém, é classificado como crítico pelo departamento de energia dos EUA em função do monopólio chinês atuante em sua exploração e comercialização. Devido à crescente demanda frente à restrita disponibilidade, a recuperação deste metal está em ascensão. Uma das aplicações do neodímio é o ímã permanente de neodímio-ferro-boro, utilizado em hard disk drives (HDs) de computadores. Desta forma, este estudo visou caracterizar os ímãs provenientes de HDs de computadores e estabelecer uma rota de recuperação do neodímio por meio de processos mecânicos e hidrometalúrgicos. Por meio da pesagem dos HDs e seus ímãs obteve-se massa média de 3,04 g e 7,91 g para laptop e desktop, respectivamente, representando menos de 3% da massa total do HD. A desmagnetização foi atingida por meio de aquecimento até a temperatura de Curie, em torno de 312 °C, e a cominuição realizada em moinho de facas, onde foram obtidas três granulometrias classificadas em frações A, B e C. Qualitativamente as amostras, foram analisados por meio de difração de raios-X (DRX), onde a fase tetragonal Nd2Fe14B foi o constituinte dominante, e por meio de análise em microscópio eletrônico de varredura (MEV). Semi-quantitativamente os ímãs, seus revestimentos e o precipitado final foram avaliados por meio de espectrometria de fluorescência de raios-X (FRX). A composição média de 21,5% de neodímio e 65,1% de ferro em massa, além de outros elementos químicos, obtida por meio de espectrometria de emissão óptica com plasma (ICP-OES), mostrou teor de neodímio superior aos minérios explorados, tornando este resíduo interessante em relação à recuperação deste metal. O procedimento hidrometalúrgico adotado envolveu a lixiviação das amostras em ácido sulfúrico 2M e a variação de três parâmetros: razão sólido/líquido, temperatura e tempo, em dois níveis. Posteriormente foi realizada a precipitação seletiva por meio de NaOH, formando o duplo sal NaNd(SO4)2.nH2O. Os resultados mostraram que a lixiviação de neodímio atingiu eficiência média acima de 94%, porém todos os experimentos apresentaram material não lixiviado, majoritariamente composto por níquel e cobre. / The chemical element neodymium (Nd) currently is in evidence as it is a fundamental part in applications manufactured by clean and advanced technology companies. However, it is classified as critical by the United States Department of Energy due to Chinese monopoly in its exploration and commercialization. Due to increasing demand in contrast with scarce supply, the recovery of neodymium is growing. One of the applications of this metal is the neodymium-iron-boron permanent magnet, used in hard disk drives (HDDs) of computers. Therefore, this study aimed magnets characterizing from HDDs of computers and then establishing a recovery route for neodymium by mechanical and hydrometallurgical processes. By weighing the HDDs and their magnets it was obtained the average weight of 3.04 g and 7.91 g for laptop and desktop, respectively, representing less than 3% of the HDDs total mass. Demagnetizing was achieved by heating up to Curie temperature of around 312 °C, and the comminution in knives mill resulted in three granulometries classified into fractions A, B and C. Qualitatively, magnets were analyzed by X-ray diffraction (XRD), where the tetragonal phase Nd2Fe14B was the dominant constituent of the sample, and through analysis in a scanning electron microscope (SEM). Semi-quantitatively, the magnets, its covers, and the final precipitate were evaluated by X-ray fluorescence spectrometry (XRF). The average composition of neodymium and iron showed 21.5% and 65.1% by weight, respectively, among other chemical elements. This results were obtained by optical emission spectrometry (ICP-OES), representing a higher neodymium content compared to the ores content, which makes this waste interesting from a neodymium recovery point of view. The procedure adopted involved hydrometallurgical leaching of the samples in 2M sulfuric acid varying three parameters: liquid/solid ratio, temperature and time, each one on two levels. Subsequently, the selective precipitation by NaOH was performed to form the double salt NaNd(SO4)2.nH2O. The results showed that neodymium leaching efficiency reached above 94%, but the experiments showed as well some material left, mainly composed of nickel and copper.

Due to Earth’s efficient crustal recycling through plate tectonics, the remaining physical record of Earth’s first two billion years consists of mineral fragments and heavily metamorphosed rocks in isolated Archean cratons. Characterization of Earth’s earliest tectonic processes requires investigation of all available records; the mineral garnet has been largely overlooked. The major element chemistry and samarium-neodymium (Sm-Nd) isotope ratios preserved in fragmented detrital garnet and Archean metamorphic garnet record the timing and conditions of early tectonic events. This work presents detailed methodology for a new detrital garnet geochronometer unlocking age information from previously undateable detrital garnet surviving recycling in sediment, sedimentary rocks, and metasedimentary rocks. The new method’s utility is demonstrated by dating garnet from a Scottish sedimentary rock and nineteen individual garnet grains from a tributary to the French Broad River in the southern Appalachians. In the southern Appalachians, garnet and existing monazite ages overlap (though the mean garnet age is slightly younger) to record the most recent metamorphic event and both are younger than inherited zircon ages. Proof-of-concept testing demonstrating protocol development for blank-correction and routine analysis of samples smaller than 1 ng advances small Sm-Nd analysis. Additionally, this work applies existing Sm-Nd garnet geochronology methods to search for garnet older than 2.5 Ga and provide age constraints on the complicated metamorphic histories of two Archean cratons. A search for detrital garnet in a sample from the Jack Hills metasedimentary belt of Western Australia hosting the Earth’s oldest known terrestrial materials (ca. 4.3 Ga) failed to produce garnet. Instead, two samples collected ~4 km south of the Jack Hills belt in the Narryer Terrane were dated to confirm Narryer regional metamorphism at ca. 2.6 Ga. The Acasta gneiss of northern Canada, arguably Earth’s oldest known cohesive rock outcrop (ca. 4.0 Ga), produced one of the Earth’s oldest known garnet ages. Garnet ages of ca. 2.95 Ga constrain the timing of Archean metamorphism and the data also indicate potential for preservation of even older garnet. Finally, a compilation of published garnet ages in the literature is presented to summarize the community’s progress in the search for Earth’s oldest garnet. / 2017-12-06T00:00:00Z

Lithium and neodymium are two critical materials in our modern society, many technological solutions depend on them. Lithium is used in batteries, which are used in cars and portable electronics. Neodymium, which is a rare earth element, is mainly used in permanent magnets which are used in smartphones, hard disc drives and turbines. There are many reports regarding the availability of the metals, with different results. The available data on the reserves varies considerably, from the few sources there are. In this report, based on geological availability, forecasts are done to investigate how much the production can increase and when it will peak. The prognoses are based on historic production to which different functions, the logistic, gompertz and richards, are fitted with the least square method. The production will peak in the end of this century and in the beginning of the next century for both metals. The production of lithium does not seem to be sufficient for both producing electric and hybrid cars with only li-ion batteries along with fusion. The neodymium production will be sufficient for producing a lower percentage of direct driven wind turbines and electric cars with NiMH batteries. Lithium in seawater is sometimes considered a future source. Since the lithium concentration is low, large volumes have to be processed in order to extract a reasonable amount of lithium. Currently it is not economic to extract lithium from seawater.

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Developing renewable alternatives for energy production is one of the main methods for climate change mitigation and sustainable development. As the key component in permanent magnets, neodymium is considered as one of the most critical elements in the rare earth family in the development of modern society. It plays a significant role in increasing efficiency and reducing weight in many applications like hard disc drives, audio equipment, direct- driven gearless and conventional wind turbine design, as well as electric vehicles designs with NiMH batteries. The emerging problem of neodymium production is the peak neodymium issue, which implies a potential risk of supply in the future due to the unsustainable production pathway. Now, China is producing more than 90% of the rare earth elements with an around 40% reserves and is facing severe problems of environmental pollution, smuggling, and increasing domestic demand. This paper makes efforts to see if the risk of supply would constrain future wind power development with a special focus on the China’s dominance in production and policies. By fitting historic production data with three curve models (logistic, Gompertz, and Richards) and designing future demand based on IEA’s scenarios, the projections of future supply and demand trends of neodymium was obtained. This paper shows that though neodymium-based wind turbine construction might not be the cause for neodymium shortage, it would be confronted with material constraints in the future. Thus, more consideration should be taken in the investment of wind turbines with permanent magnet. Also, a mineral strategy, which integrates technological innovation, joint effort from different stakeholders, and better resource management, is required for a sustainable production of neodymium in the long run.

The stoichiometry of the Nd_1+xBa_2-xCu₃O_7-δ solid solution has been investigated using XRD and EPMA. At 980°C in air, an essentially continuous solid solution forms with limiting compositions x_min = 0.03(1) and x_max = 0.92(2). The solid solution limits are independent of temperature over the range 300 to 1050°C, i.e. stoichiometric Nd123 does not form. Preliminary studies show that annealing in an Ar atmosphere does not affect x_min. Three structurally distinct polymorphs of Nd123ss exist - tetragonal Nd123ss, orthorhombic Nd123ss and orthorhombic Nd123ss. The stability range of each in air has been determined. Quenched samples with 0.03 ≤ x ≤ 0.6 have the tetragonal Nd123ss structure. On oxygenation, samples with 0.03 ≤ x <˜0.2 are orthorhombic. The orthorhombic-tetragonal phase transition is second order, both with increasing temperature and increasing x. Samples with 0.7-0.9 have the orthorhombic Nd213ss structure at all oxygen contents. Tetragonal Nd123ss is isostructural with tetragonal Y123 and orthorhombic Nd123ss is isostructural with orthorhombic Y123. Orthorhombic Nd213ss has the ideal stoichiometry Nd₂BaCu₃O_7-δ and is based on a 2a x b x 2c superstructure of the Nd123ss structure. The supercell is due to ordering of the Nd and Ba atoms, which leads to ordering of the oxygen atoms. Melting temperatures decrease with x. Two distinct regions of melting behaviour are observed; the first for 0.03 ≤ x ≤ 0.6 with a thermal minimum at x˜0.4, and the second for 0.7 ≤ x ≤ 0.9. Oxygen contents increase with x. Samples with larger x values have a smaller range of oxygen contents. High pressure oxygen annealing results in a constant Cu valence state of ˜2.35 for all values of x. Average copper valence states <2 are only obtained readily for x ≤ 0.3. T_c decreases with x and samples become non-superconducting at x˜0.5. For samples annealed in 1 bar O₂, 'double plateau' behaviour is observed.