This thesis focuses on a number of aspects governing the transformation of gibbsite, via intermediate phases, to a-alumina. These aspects include the size and morphology of the gibbsite grains, the influence of additions of foreign elements, the effect of a mechanical treatment of the gibbsite prior to calcination, and combinations of these factors. The materials were characterisedb y scanninge lectron microscopy, X-ray diffraction and surfacea rea measurementsF. or someo f the calcined materials an attempt was made to sinter the powders to a dense body to investigate if any of the treatments during calcination had an effect on this process. The literature review covers the current state of understanding of the production of bulk alumina powder by the Bayer process and the phase changes seen on calcination of precursors to the stable a-alumina phase. A detailed description of the phase changes is given and the various routes and conditions necessary for the transformations to occur are considered. The transformations are examined in relation to the morphology of the crystals and the variables controlling the phase transformation route are discussed. Calcination in air showed that the size of the gibbsite grain governs the calcination route taken to reach a-alumina. The standard gibbsites used in this work show a mixed calcination sequence transforming both via the boehmite phase, followed by the y, 8 and 0 phases, and via the x and K phases. The formation of boehmite is attributed to retention of water vapour within the grainDifferences in morphology of the starting materials showed that for the range of materials seen, the morphology of the grain is less important than its size. The super fine material confirmed that a small grain size transforms via the non-boehmite route only, with the other gibbsites taking intermediate routes as for the standard gibbsites. Of the additions made prior to calcination, aluminium fluoride was found to reduce the transformation temperature to a-alumina by approximately 300°C. Other additions had little effect on the transformation temperature although a reduction in grain size was seen with aluminium chloride. It was found that good mixing of the alumina fluoride was essential to obtain reliable and reproducible results. This is due to the small amounts of additive that are needed and the sensitivity of the process to concentration variations. Mineralisation of a range of gibbsites showed that the presence of sodium in the starting material was crucial in reducing the calcination temperature. This led to the conclusion that the sodium and fluoride react to form a liquid phase. The presence of a liquid phase increases the mobility of the aluminium and oxygen atoms resulting in a reduction of the transformation temperature. Fluoride additions to the gibbsites with different morphologies showed that the presence of sodium was the governing factor in reduction of the transformation temperature. Milling of the starting materials showed that there was a small reduction in the transformation temperature between some of the phases. The energy involved in milling leads to activation of the gibbsite. This activation takes the form of a reduction in the grain size and in a reduction of the crystallinity seen in the XRD patternFluoride additions during the calcination of sapphire with a standard gibbsite powder showed preferential grain growth. It was possible to initiate growth of small plate-like crystals on the polished surface of a piece of sapphire parallel to the basal plane. Crystal growth was also seen in scratches on a polished surface perpendicular to the basal plane

Ce travail qui a été effectué au sein du groupe radiochimie de l'IPN Orsay, participe à l'enrichissement des connaissances destinées à la compréhension du comportement des radionucléides à travers l'environnement. Le comportement et l'évolution des radionucléides sont des phénomènes souvent complexes à caractériser expérimentalement qui dépendent des interactions aux interfaces eau / surface minérale, lesquelles peuvent être modélisées grâce à des méthodes théoriques. Lors de cette étude, nous avons choisi d'utiliser des méthodes de dynamique moléculaire (DM), lesquelles permettent de considérer explicitement les effets du solvant, de la température et d'étudier la dynamique de l'ion uranyle. Dans un premier temps, des méthodes de dynamique moléculaire Car-Parrinello basées sur la théorie de la fonctionnelle de la densité (DFT) ont permis de caractériser finement les structures d'équilibres de l'ion uranyle en solution et à l'interface eau/ face (001) de gibbsite. Dans le cas d'un pH faible, les complexes d'adsorption présents à l'interface eau/ face (001) de gibbsite ont été identifiés et comparées aux données expérimentales disponibles. Leurs énergies relatives et les énergies d'activations impliquées dans le processus de sorption ont également été déterminées. Dans un deuxième temps, des méthodes de dynamique moléculaire classique ont été employées afin de modéliser des systèmes de plus grande taille, donc plus réalistes, sur des échelles de temps plus longues. La comparaison des résultats DM Car-Parrinello / DM classique a montré qu'une dynamique classique utilisée avec les potentiels non polarisables de Guilbaud, CLAYFF et SPC/E, permet de modéliser le comportement de l'ion uranyle à l'interface eau/ face (001) de gibbsite. Les longs temps de simulation permettent de mettre en avant le caractère diffusif de l'ion uranyle à l'interface eau/ face (001) de la gibbsite. Enfin, L'effet d'une élévation de la température a été étudié. La rétention de l'ion uranyle diminue avec la température.

For the safety assessment of high-level nuclear waste repositories, it is mandatory to know the transportation paths of contaminants, e.g. actinyl ions, in the geological barrier. The most attention needs to be focused on the transport in aquifers, because water contamination, depending on retention and migration processes of radionuclides in the geosphere, is of primary environmental concern. The migration behavior of actinides in ground water is mainly controlled by aquatic speciations and sorption processes at water-mineral interfaces. Hence, the investigation of complexspecies in aqueous solutions and at mineral surfaces becomes essential for the safety assessment in the near and far field of nuclear repositories. For deep ground repositories, clay and clay minerals are considered as possible host rocks, because they show a low permeability and are expected to have a high retention capacity towards actinyl ions. But the complexity of naturally occurring minerals in particular their surface often hampers the unequivocal interpretation of results obtained from sorption experiments. The use of model phases only showing one particular functional group at the surfaces with a well defined surface topology is an appropriate approach for the understanding of the basic sorption processes. Aluminum oxide and hydroxides are of special interest because they represent main components in clays and clay minerals. In particular, gibbsite is widely used as a model system because it represents not only the most common crystalline aluminum hydroxide but also a ubiquitous weathering product of alumosilicates. Furthermore, the elemental structural unit of gibbsite, that is the Al(OH)6 octahedron, occurs ubiquitously as part of the structure of common clay minerals like kaolinite. In the present study, the sorption processes of U(VI) and Np(V) on gibbsite were studied under consideration of the aqueous speciation.

Este trabalho apresenta os resultados de pesquisas realizadas com rejeitos de bauxitas, provenientes da usina operada pela Companhia Brasileira de Alumínio CBA, em Itamarati de Minas, MG. O circuito industrial da CBA tem operações de escrubagem, peneiramento, deslamagem e separação de minerais pesados, através de um circuito de concentração em espirais Reichert e de separação magnética. Porém, ainda são perdidos importantes teores de alumina aproveitável na fração fina, que é atualmente considerada rejeito. A flotação reversa da sílica insolúvel presente neste rejeito, seguida de separação magnética do produto deprimido, permite recuperar gibbsita, e produzir areia para construção civil e manutenção de estradas. O concentrado magnético pode ser usado como aditivo de carga na produção de cimento Portland. Portanto, o beneficiamento desta fração, além da importância econômica, vem contribuir para a conservação dos recursos minerais. Através de ensaios em bancada e em usina piloto, este trabalho demonstra a aplicabilidade deste processo a bauxitas de Miraí, sudeste de Minas Gerais. Após a separação magnética, obtém-se um concentrado com recuperações de 28,8% em massa e 81,2% metalúrgica, com 54% de alumina aproveitável e relação Al2O3/SiO2 de 12,6. Os resultados aqui obtidos indicam viabilidade para aplicação industrial do processo desenvolvido. / This research presents the results achieved by the author in recovering gibbsite from industrial bauxite tailings. The tailings samples were provided by Companhia Brasileira de Alumínio CBA, from it´s Itamarati de Minas, MG plant. The CBA´s Itamarati de Minas plant has a complete circuit of scrubbing, desliming, and heavy minerals separation in spiral concentrators, complemented by high intensity magnetic separation, but it still loses the values contained in the fine fraction of the beneficiated ore, which currently consists of a tailing. Reverse flotation of the insoluble silica present in this tailings stream, followed by magnetic separation of the depressed product, allows to recover gibbsite, and produces silica sand, which can be used in civil construction work and road maintenance. The magnetic concentrate can be used as a charge additive to Portland cement production. Thus, the beneficiation of this fraction is important both economically and for mineral resources conservation. Through experimentation on bench and at pilot plant scale tests, this work explores the feasibility of such a process to the bauxites from Miraí, southeastern Minas Gerais state. After magnetic separation, the concentrate reached available alumina grades of 54% at pilot plant, with 28.8% mass recovery and 81.2% metallurgical recovery, with a Al2O3/SiO2 ratio of 12.6. This shows viability for industrial scale application of the process.

Este trabalho apresenta os resultados de pesquisas realizadas com rejeitos de bauxitas, provenientes da usina operada pela Companhia Brasileira de Alumínio CBA, em Itamarati de Minas, MG. O circuito industrial da CBA tem operações de escrubagem, peneiramento, deslamagem e separação de minerais pesados, através de um circuito de concentração em espirais Reichert e de separação magnética. Porém, ainda são perdidos importantes teores de alumina aproveitável na fração fina, que é atualmente considerada rejeito. A flotação reversa da sílica insolúvel presente neste rejeito, seguida de separação magnética do produto deprimido, permite recuperar gibbsita, e produzir areia para construção civil e manutenção de estradas. O concentrado magnético pode ser usado como aditivo de carga na produção de cimento Portland. Portanto, o beneficiamento desta fração, além da importância econômica, vem contribuir para a conservação dos recursos minerais. Através de ensaios em bancada e em usina piloto, este trabalho demonstra a aplicabilidade deste processo a bauxitas de Miraí, sudeste de Minas Gerais. Após a separação magnética, obtém-se um concentrado com recuperações de 28,8% em massa e 81,2% metalúrgica, com 54% de alumina aproveitável e relação Al2O3/SiO2 de 12,6. Os resultados aqui obtidos indicam viabilidade para aplicação industrial do processo desenvolvido. / This research presents the results achieved by the author in recovering gibbsite from industrial bauxite tailings. The tailings samples were provided by Companhia Brasileira de Alumínio CBA, from it´s Itamarati de Minas, MG plant. The CBA´s Itamarati de Minas plant has a complete circuit of scrubbing, desliming, and heavy minerals separation in spiral concentrators, complemented by high intensity magnetic separation, but it still loses the values contained in the fine fraction of the beneficiated ore, which currently consists of a tailing. Reverse flotation of the insoluble silica present in this tailings stream, followed by magnetic separation of the depressed product, allows to recover gibbsite, and produces silica sand, which can be used in civil construction work and road maintenance. The magnetic concentrate can be used as a charge additive to Portland cement production. Thus, the beneficiation of this fraction is important both economically and for mineral resources conservation. Through experimentation on bench and at pilot plant scale tests, this work explores the feasibility of such a process to the bauxites from Miraí, southeastern Minas Gerais state. After magnetic separation, the concentrate reached available alumina grades of 54% at pilot plant, with 28.8% mass recovery and 81.2% metallurgical recovery, with a Al2O3/SiO2 ratio of 12.6. This shows viability for industrial scale application of the process.

<p> This thesis contains an introduction to the surface chemistry of minerals in aqueous environment, and a summary of five manuscripts concerning adsorption reactions at the surfaces of nano-sized gibbsite (α-Al(OH)3), amorphous silica and kaolinite.</p><p> Nano-sized gibbsite was synthesized and thoroughly characterized using X-ray diffraction, high-resolution transmission electron microscopy, atomic force microscopy and Fourier transform infrared spectroscopy. The adsorption of protons and the development of charge at the surfaces were studied using high precision potentiometry and zeta potential measurements. The results showed that singly coordinated surface sites at the particle edges protonate/deprotonate, while ion pairs with the medium ions are formed at doubly coordinated surface sites at the basal planes. This ion pair formation is a slow reaction, requiring long equilibrium times.</p><p> The adsorption of o-phthalate, maleate, fumarate, malonate and oxalate onto gibbsite surfaces was studied using Fourier transform infrared spectroscopy, zeta potential measurements, adsorption measurements and theoretical frequency calculations. All ligands were found to form outer-sphere complexes at the basal planes. Significant amounts of inner-sphere complexes at the particle edges were found for malonate and oxalate only. The observed adsorption was described using surface complexation models.</p><p> The proton reactions at the surface of amorphous silica were described using a two-site model. XPS indicated that Na+ is accumulated in the vicinity of the surface. Proton reactions at kaolinite surfaces were explained using a nonelectrostatic model, assuming that only the aluminol and silanol sites at the particle edges are reactive. Extensive modeling provided support for this assumption. </p>

This thesis contains an introduction to the surface chemistry of minerals in aqueous environment, and a summary of five manuscripts concerning adsorption reactions at the surfaces of nano-sized gibbsite (α-Al(OH)3), amorphous silica and kaolinite. Nano-sized gibbsite was synthesized and thoroughly characterized using X-ray diffraction, high-resolution transmission electron microscopy, atomic force microscopy and Fourier transform infrared spectroscopy. The adsorption of protons and the development of charge at the surfaces were studied using high precision potentiometry and zeta potential measurements. The results showed that singly coordinated surface sites at the particle edges protonate/deprotonate, while ion pairs with the medium ions are formed at doubly coordinated surface sites at the basal planes. This ion pair formation is a slow reaction, requiring long equilibrium times. The adsorption of o-phthalate, maleate, fumarate, malonate and oxalate onto gibbsite surfaces was studied using Fourier transform infrared spectroscopy, zeta potential measurements, adsorption measurements and theoretical frequency calculations. All ligands were found to form outer-sphere complexes at the basal planes. Significant amounts of inner-sphere complexes at the particle edges were found for malonate and oxalate only. The observed adsorption was described using surface complexation models. The proton reactions at the surface of amorphous silica were described using a two-site model. XPS indicated that Na+ is accumulated in the vicinity of the surface. Proton reactions at kaolinite surfaces were explained using a nonelectrostatic model, assuming that only the aluminol and silanol sites at the particle edges are reactive. Extensive modeling provided support for this assumption.

Resumo: Os atributos mineralógicos e físicos possuem dependência espacial e a distribuição espacial destes atributos possui relação com as formas do relevo. O objeto deste trabalho foi avaliar os atributos mineralógicos da fração argila e os atributos físicos de um argissolo em curvaturas do relevo, assim como avaliar a correlação entre esses atributos. Uma malha de dimensão 100 x 100 m foi delimitada em uma área caracterizada pela forma convexa e outra pela fôrma côncava. As malhas possuem espaçamento regular de 10 x 10 m e os pontos de cruzamento deste espaçamento determinaram os pontos de coleta das amostras, num total de 121 pontos amostrais georreferenciados em cada malha. Os atributos físicos foram avaliados nas profundidades 0,0- 0,2 e 0,2-0,4 m e os atributos mineralógicos na profundidade 0,0- 0,2 m. Os atributos físicos analisados foram diâmetro médio ponderado, diâmetro médio geométrico, agregados maiores que 2 mm, agregados entre 2 e 1 mm , agregados menores que 1 mm, microporos, macroporos, volume total de poros, densidade do solo, resistência do solo à penetração e teor de água no solo, já os atributos mineralógicos da fração argila foram largura a meia altura, diâmetro médio do cristal dos óxidos de ferro, da caulinita e gibbsita, substituição isomórfica e área de superfície específica da hematita e goethita. Os teores da goethita e hematita e razão goethita/(goethita+hematita) e razão caulinita/(caulinita+gibbsita) também foram calculados. Os dados foram submetidos às análises estatísticas e geoestatísticas para avaliação da variabilidade espacial e influência das curvaturas nestes atributos. Para avaliação da relação entre os atributos da mineralogia e físicos realizaram-se as análises de correlação simples e espacial. Os atributos físicos e mineralógicos apresentaram-se dependentes das curvaturas do relevo... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The mineralogicals and physical attributes have spatial dependence and the distribution of these attributes has relation with the forms of relief. The object of this study was to evaluate the attributes of clay mineralogy and the physical attributes of an argissol in curvatures of relief, as well as assess the correlation between these attributes. A grid size of 100 x 100 meters was defined in an area characterized by the convex shape and another in an area characterized by the concave shape. The grids have regular spacing of 10 x 10 m and the spacing of the points of intersection determine the points of collection of samples, a total of 121 georeferenced sample points in each grid. The physical attributes were evaluated in depth from 0.0 - 0.2 and 0.2 -0.4 m and the mineralogical attributes in depth 0,00-0,20 m. The physical attributes were analyzed: mean weight diameter, mean geometric diameter, aggregates larger than 2 mm, aggregates between 2 and 1 mm, aggregates smaller than 1 mm, microporosity, macroporosity, total porosity, bulk density, penetration resistance and water content in soil. The attributes of minerals were: width at half height, average diameter of crystals of iron oxides and kaolinite and gibbsite and isomorphic substitution and specific surface area of hematite and goethite. The contents of goethite and hematite and ratio goethite / (goethite + hematite) [Gt / (Gt + Hm)] and ratio kaolinite / (kaolinite + gibbsite) [Ct / (Ct + Gb)] were also calculated. Data were subjected to statistical and geostatistical analysis to evaluate the spatial variability and influence of these curvatures on these attributes. To assess the relation between mineralogy and physical attributes simple and spation correlation analysis where made. The physical and mineralogical attributes and depend on the curvature of the relief. There was also the influence of crystallinity of goethite and gibbsite in soil physical. / Orientador: José Marques Júnior / Coorientador: Gener Tadeu Pereira / Banca: Marcílio Vieira Martins Filho / Banca: Zigomar Menezes de Souza / Mestre

Resumo: A agricultura de precisão implica a análise da variabilidade espacial dos fatores de produção e a aplicação dos insumos de forma localizada e em doses precisas. O presente trabalho teve por objetivo analisar a influência do relevo na variabilidade espacial dos atributos químicos e mineralógicos para aplicação de insumos em taxa variável. Duas parcelas de um hectare foram delimitadas em área côncava e convexa. Foram retiradas 121 amostras em cada área. Os teores de P disponível apresentaram-se diferenciados nas duas áreas estudadas, sendo que os menores valores médios de P se encontram na área convexa na qual estão presentes os maiores teores de gibsita. A formação dos minerais da fração argila é condicionada pelas variações do relevo, sendo que a área convexa apresentou ambiente mais favorável à formação da gibsita do que a área côncava, demonstrando que o relevo pode ser utilizado para a definição de limites de área mais homogênea. A gibsita foi o fator determinante para a maior capacidade de adsorção máxima de P e a menor disponibilidade de fósforo na área convexa. O uso da técnica de geoestatística possibilitou a precisa descrição das propriedades do solo. / Abstract: Precision agriculture implies on the analysis of the spatial variability of the production factors and the application of inputs in a localized way and on precise doses. The present work aimed to analyze the influence of the relief on the spatial variability of the chemical and mineralogical attributes for the application of inputs in variable rates. Two parcels of one hectare were bounded in concave and convex area. 121 samples were taken from each area. The levels of available P have shown to be different on the two studied areas, being the lowest mean values of P on the convex area, where the highest levels of gibbsite are present. The formation of the minerals from the clay fraction is conditioned by the relief variations, being that the convex area has presented a more favorable environment for the formation of gibbsite than the concave area, showing that relief may be used for the definition of limits in more homogenous areas. Gibbsite was the determinant factor for the higher capacity of P maximum adsorption and lower availability of phosphorous on the convex area. The use of the geostatistics technique has made possible the precise description of the soil properties. / Orientador: José Marques Júnior / Coorientador: Gener Tadeu Pereira / Banca: Luis Reynaldo Ferracciú Alleoni / Banca: Marcilio Vieira Martins Filho / Mestre

Made available in DSpace on 2014-06-11T19:28:30Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-02-28Bitstream added on 2014-06-13T20:28:03Z : No. of bitstreams: 1 barbieri_dm_me_jabo.pdf: 1564707 bytes, checksum: a8664218c7a3889aee0ba6b464711e70 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A agricultura de precisão implica a análise da variabilidade espacial dos fatores de produção e a aplicação dos insumos de forma localizada e em doses precisas. O presente trabalho teve por objetivo analisar a influência do relevo na variabilidade espacial dos atributos químicos e mineralógicos para aplicação de insumos em taxa variável. Duas parcelas de um hectare foram delimitadas em área côncava e convexa. Foram retiradas 121 amostras em cada área. Os teores de P disponível apresentaram-se diferenciados nas duas áreas estudadas, sendo que os menores valores médios de P se encontram na área convexa na qual estão presentes os maiores teores de gibsita. A formação dos minerais da fração argila é condicionada pelas variações do relevo, sendo que a área convexa apresentou ambiente mais favorável à formação da gibsita do que a área côncava, demonstrando que o relevo pode ser utilizado para a definição de limites de área mais homogênea. A gibsita foi o fator determinante para a maior capacidade de adsorção máxima de P e a menor disponibilidade de fósforo na área convexa. O uso da técnica de geoestatística possibilitou a precisa descrição das propriedades do solo. / Precision agriculture implies on the analysis of the spatial variability of the production factors and the application of inputs in a localized way and on precise doses. The present work aimed to analyze the influence of the relief on the spatial variability of the chemical and mineralogical attributes for the application of inputs in variable rates. Two parcels of one hectare were bounded in concave and convex area. 121 samples were taken from each area. The levels of available P have shown to be different on the two studied areas, being the lowest mean values of P on the convex area, where the highest levels of gibbsite are present. The formation of the minerals from the clay fraction is conditioned by the relief variations, being that the convex area has presented a more favorable environment for the formation of gibbsite than the concave area, showing that relief may be used for the definition of limits in more homogenous areas. Gibbsite was the determinant factor for the higher capacity of P maximum adsorption and lower availability of phosphorous on the convex area. The use of the geostatistics technique has made possible the precise description of the soil properties.