Dissertations / Theses on the topic 'Gibbsite'

This thesis documents the development and application of a computer model for gibbsite, an aluminium tri-hydroxide polymorph. In particular, the work has emphasized the idea of computer modelling techniques combining with ex- observations to provide greater insight than either could separately. Chapter One provides an overview and introduction to the fields of solid state chemistry, crystallization and computer modelling. These ideas are extended in Chapter Two to include a more detailed discussion of the theoretical principles behind the modelling in this project. The development of transferable oxalate and hydroxide potential models, intended primarily for sodium oxalate and gibbsite, is described in Chapter Three. Both ab initio hypersurface fitting and lattice fitting techniques were utilized, with an average structural fitting error of under two percent. In addition, the potentials were used to successfully reproduce several (related) crystal structures, thus establishing the quality of the model. In Chapter Four, the model for gibbsite was employed in generating equilibrium and growth morphologies. The equilibrium morphology was found to give excellent agreement with experiment, with all observed faces present. However, the importance of the prismatic planes is underestimated. Also discussed in the chapter is a method for predicting the phenomenon of crystalline twinning. This technique was successfully applied to a number of systems, including gibbsite and sodium oxalate. In Chapter Five, the equilibrium morphology calculations performed earlier were extended by probing the effects of cation incorporation on the habit of gibbsite. This study was conducted in order to provide a first step in estimating the role of the crystallizing solution. Calculations of the change in surface energy caused by the replacement of a surface proton with a cation from solution ++
were made. Different crystal habits were constructed by applying a range of defect surface coverage values to each of the faces appearing in the morphology. The resulting defect morphologies were in excellent agreement with crystal habits commonly observed by experimentalists. Also, the work provided an explanation for the earlier underestimation of the prismatic faces. Chapter Six documents molecular simulations of solutions containing the major species known to be present in industrial and experimental Bayer liquors. The structuring in two solutions, one containing sodium hydroxide and the other potassium hydroxide, was probed by constructing graphs of the radial distribution functions. These plots indicated that a significant degree of ion pairing was occurring between the alkali metal cations (Na+ and K+) and the aluminate monomer ([Al(OH)4(subscript)]-). Furthermore, these cations were found to be acting as 'bridges' which stabilize multiple aluminate monomers, allowing them to form clusters. This data was used to assist in explaining vibrational spectra, and to postulate that clustering may be the origin of the fine particle suspensions noted during the induction period.

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.

Includes bibliographical references (leaves 45-49).
The current Bayer precipitation of gibbsite is notoriously slow and is considered to be the rate limiting step of the Bayer process. The present industrial reactor configuration involves precipitating gibbsite inside a series of large stainless steel agitated vessels due to the slow precipitation kinetics of gibbsite from pregnant Bayer liquor. The scope of this study is to investigate the effectiveness of using water as an antisolvent to increase the overall gibbsite yield and the associated particle behaviours under isothermal conditions. The experiments were performed in a series of batch experiments which were divided into two subsets. Firstly, the effect of different caustic concentrations present in the anti solvent on gibbsite yield was tested. Secondly, the effect of different seed loading (50 and 100 grams seeds per liter of synthetic liquor) on aggregation and fines formation were investigated. All batch experiments were conducted isothermally at 80°C under a closed system using a baffled stainless steel 316 agitated vessel. The experimental results indicated water to be a feasible medium for the isothermal antisolvent crystallisation of gibbsite from synthetic pregnant Bayer liquor. It was found that the extent of overall gibbsite yield exhibits a power law correlation to the change in the antisolvent caustic concentration with R2 ～1 (R2 = 0.99974). This finding is important as the regressed curve will be used to correlate gibbsite yield as a function of anti solvent purity. From the seed loading experiments, an Increase In seed loading under constant temperature and initial liquor supersaturation resulted in an overall decrease in product particle size due to a rise in inter-particulate attrition. However, crystal growth was not dominant during any period of the experiments with aggregation being more prominent for the system with the lower seed load. Gibbsite morphology determination from SEM revealed hexagonal solids which, in the presence of a higher seed loading indicated signs of fracture due to attrition. Quantitative evidence of this mechanism is shown USIng the discretised population balance method by Bramley et al. (1996) with the aid of the computational technique developed by Hounslow (2005) in Mathematica. Results generated using this method show decreasing aggregation with liquor de supersaturation and increased seed loading. The overall particle behaviours from the current investigation are validated by results obtained from previous gibbsite studies under very similar conditions. Although the gibbsite yield can be increased drastically in the presence of an anti solvent, the average particle size generated from this study is still too small to be commercially feasible due to the increase in initial supersaturation. Thus it is recommended that further particle size optimisation may be conducted inside a fluidised bed reactor where particles generally experience lower shear than inside a conventional agitated vessel.

Le procédé Bayer est la première des deux étapes majeures dans la production de l'aluminium. Il permet la cristallisation sous forme de gibbsite ([alpha]-Al(OH)[indice inférieur 3]) des oxydes et hydroxydes d'aluminium contenus dans la bauxite. Ce procédé, mis au point en 1888, a lieu en milieu alcalin, puisque la bauxite est dissoute jusqu'à sursaturation dans une solution d'hydroxyde de sodium concentrée pour donner ce qui est communément appelé la"liqueur Bayer". Les travaux présentés dans ce mémoire font partie d'une étude importante menée par de nombreux membres de l'équipe de recherche du laboratoire. Lors de la phase de refroidissement de la liqueur Bayer, un phénomène d'entartrage apparaît dans les échangeurs de chaleur du fait de la sursaturation en gibbsite. Ce phénomène d'entartrage occasionne alors d'importantes pertes, tant énergétiques qu'économiques, de par la diminution d'efficacité des appareillages. II faut alors procéder à différents traitements, physiques ou chimiques, pour éliminer le dépôt de tartre de gibbsite, ce qui entraîne également des coûts du fait du temps d'immobilisation des conduites concernées et des méthodes utilisées. L'une des voies explorées pour remédier à ce problème est l'adsorption de molécules organiques ou inorganiques pour empêcher, ou tout du moins ralentir la formation du tartre de gibbsite. L'adsorption des molécules utilisées sur les supports modèles a été étudiée par le biais d'une technique faisant appel à la chromatographie liquide. La mesure de constantes de Henry permet une comparaison des forces d'adsorption à faible concentration de molécules pouvant présenter un caractère inhibiteur face à la formation du tartre de gibbsite. Les matériaux utilisés sont l'acier et la gibbsite, afin de comprendre les phénomènes d'entartrage pouvant avoir lieu dans le procédé Bayer. Les molécules choisies possèdent toutes un cycle aromatique portant un groupement alcool et un halogénure en position ortho. Les mesures d'isothermes d'adsorption montrent une tendance de la force d'adsorption en fonction de la nature du substituant. Une étude comparative d'entartrage sur l'acier doux en présence ou en absence d'inhibiteurs a été menée, afin de mieux comprendre l'influence de ces molécules. De plus, des études de précipitation ont complété ces travaux afin de s'assurer que les molécules prévenant l'entartrage n'influencent pas de manière négative les rendements de précipitation de la gibbsite.

L'@amélioration de la solidité de l'alumine utilisée pour la production d'aluminium et la réductionde la génération de particules fines qui résulte des chocs lors de la calcination et des transports sont des points essentiels pour les producteurs des usines Bayer. Le but de cette étude est de montrer les liens qui existent entre les conditions opératoires de précipitation de la gibbsite et sa morphologie, et de vérifier leur impact sur la solidité de l'alumine. Des analyses sur produits industriels et sur produits élaborés en laboratoire ont été effectuées. Nous avons focalisé notre attention sur le rôle de l'étape d'agglomération. La procédure expérimentale a été choisie pour respecter au mieux les conditions industrielles. La morphologie des cristaux de gibbsite a été quantifiée en utilisant trois modes de visualisation (microscope optique avec des liquides d'immersion, microscope électronique à balayage sur poudre et sur section polie) et un ensemble de paramètres de forme. Cinq paramètres de forme ont été utilisés pour décrire la forme bidimensionnelle des cristaux du point de vue de leur rugosité, de leur allongement et de leur tortuosité. L’analyse en composantes principales a permis de synthétiser l'information pour une meilleure précision des résultats et une interprétation plus fine. Le microscope électronique à balayage permet de visualiser les facettes des cristaux. Des paramètres pseudo-tridimensionnels ont été calculés pour décrire le réseau de facettes. Sur section polie, le contour des cristaux est bien défini et permet de calculer des tàilles de côtés assimilées aux tailles des facettes. La solidité de l'alumine a été évaluée à l'aide d'un lit fluidisé standardisé et de deux indices. !. . :indice d'attrition mesure la proportion de particules de taille inférieure à 45 ~m créées lors du test. !. . :indice de brisure quantifie l'évolution globale de la distribution de taille après le passage en lit fluidisé
The@improvement of the solidity of alumina which is produced for aluminium refinery and the reduction of fine particles generation which result of shocks during calcination and transport are essential points for the Bayer producers. The aim of this study is to link the gibbsite precipitation conditions to the morphology of the crystals and to verity their impact on alumina solidity. Analysis on industrial and lab-made products was done. We have focused our attention on the role of the agglomeration step. The experimental procedure was chosen to be as close as possible to the industrial process. Gibbsite morphology was quantified by using three visualization methods (optical microscopy with different immersion liquids, scanning electron microscopy on free powder and on polished section) and a setof different shape parameters. Five shape parameters quantify the two-dimensional shape of the crystals from the point of view of their roughness, elongation and concavity. Principal component analysis have enabled an information simplification for a better precision of the results and a better interpretation. The scanning electron microscope on free powder enables the tacet network visualization. Pseudo three dimensional parameters were calculated to describe the tacet network. On polished section, the crystal frames are weil defined and enable the sizing of the crystal sides related to the tacet sides. Alumina solidity was evaluated with a standardized fluidized bed and two indices. The attrition index quantifies the proportion of particles of size less than 45 1-1m which have been created du ring the test. The breakage index quantifies the evolution of the size distribution after the test

Although the precipitation of aluminium trihydroxide as gibbsite, via the Bayer process has been widely studied, the mechanism of crystal growth is poorly understood. This work focus on the morphology of gibbsite and the relative growth rates of individual crystal faces.Initial work was carried out to characterize aluminium trihydroxide and it was found that bayerite, another polymorph, precipitated at temperatures below 50 [degrees] C and its morphology depended on the method of precipitation. Gibbsite however, precipitated above this temperature and its morphology depended on the type of alkali aluminate solutions used. The method of precipitation does not affect the morphology, only the size of the precipitate formed. The morphology of gibbsite can be altered by the addition of organic compounds which are known to inhibit gibbsite precipitation. Some of these compounds were found to selectively inhibit the growth of individual crystal faces, thus altering the overall morphology of gibbsite. Boehmite, a polymorph of aluminium hydroxide, can be produced by partial dehydration of gibbsite at 300T. The morphology of boehmite consisted of diamond shaped crystals.The influence of cation incorporation on the morphology of gibbsite was studied experimentally and computationally (molecular modelling). These studies showed that there is a linear relationship between the amount of cation incorporated and atomic radii and between the amount of cation incorporated and the defect energy calculated. The equilibrium morphology of gibbsite predicted in the absence of media matched the morphology of gibbsite grown slowly from sodium aluminate, implying that the amount of sodium incorporation is low in these crystals.The growth rates of individual crystal faces were measured in situ, and found to be a function of supersaturation squared for the prismatic faces, possibly indicating ++
that E growth occurs by spiral growth mechanism. The growth of the basal face was found to follow the spiral growth mechanism below a relative supersaturation of 0.815 and the birth and spread mechanism above this level. The activation energies and kinetic coefficients for the individual prismatic faces were also determined.Growth rate dispersion was observed in these microscopic studies, but the question of size dependency remains unanswered.The overall growth rates of gibbsite crystal, determined using rapid dynamic light scattering, was found to be an exponential function of supersaturation indicative of a birth and spread growth mechanism.

Anomalously high concentrations of arsenic and phosphate are found in the sediments of the Saguenay Fjord in comparison to those of the Gulf and St. Lawrence Estuary. The source of arsenic is unclear. It could be supplied to the Fjord by the marine waters which enter from the St. Lawrence Estuary or may have accumulated as a result of historically high levels of effluent input.
The waters of the Saguenay Fjord are also characterized by anomalously high particulate aluminum concentrations (i.e., [Al]tot/[Al] diss > 1), introduced as a result of the aluminum refining activity along the shores of its tributaries. Gibbsite (Al(OH)3), a by-product of this activity, is known to strongly adsorb phosphate and arsenate from low ionic strength aqueous solutions, and may act as a vector for these two elements to sediments of the Saguenay Fjord.
The small amount of arsenate and phosphate adsorbed onto gibbsite from seawater indicates that their adsorption to particulate aluminum in the water column cannot account for the elevated levels of arsenic and phosphate in the sediments of the Saguenay Fjord. (Abstract shortened by UMI.)

Precipitation of gibbsite from supersaturated caustic aluminate solutions has been investigated extensively due to its central role in the commercial Bayer plant, for extracting the alumina compound from bauxite. The primary focus of Bayer process simulation and optimisation is to help maximise the product recovery and the production of a product crystal size distribution (CSD) that meets the product specification and improves downstream process performance. The product CSD is essentially determined by the nucleation, growth and agglomeration kinetics, which occur simultaneously during the precipitation process. These processes are still poorly understood, owing to the high complexity of their mechanisms and of the structure of the caustic aluminate solutions. This research focuses on the modelling and kinetics estimation aspects of simulating gibbsite precipitation. Population balance theory was used to derive different laboratory gibbsite precipitator models, and the discretised population balance models of Hounslow, Ryall & Marshall (1988) and Litster, Smit & Hounslow (1995) were employed to solve the resulting partial integro-differential equations. Gibbsite kinetics rates were determined from literature correlation models and also estimated from the CSD data using the, so-called, differential method. Modelling of nonstationary gibbsite precipitation systems showed that error propagated with the precipitation time scale. The main contribution to the observed error was found to be from the uncertainties in the kinetic parameter estimates, which are estimated from experimental data and used in the simulation. This result showed that care is required when simulating the CSD of non-stationary precipitators over longer time scales, and methods that produce precise estimates of the kinetics rates from the experimental data need to be used.
Kinetics estimation study from repeated batch gibbsite precipitation data showed that the uncertainty in the experimental data coupled with the error incurred from the kinetic parameter estimation procedure used, resulted in large uncertainties in the kinetics estimates. The influences of the experimental design and the kinetics estimation technique on the accuracy and precision of estimates of the nucleation, growth and agglomeration kinetics for the gibbsite precipitation system were investigated. It was found that the operating conditions have a greater impact on the uncertainties in the estimated kinetics than does the precipitator configuration. The kinetics estimates from the integral method, i.e. non-linear parameter optimisation method, describe the gibbsite precipitation data better than those obtained by the differential method. However, both kinetics estimation techniques incurred significant uncertainties in the kinetics estimates, particularly toward the end of the precipitation runs where the kinetics rates are slow. The uncertainties in the kinetics estimates are strongly correlated to the magnitude of kinetics values and are dependent on the change in total crystal numbers and total crystal volume. Batch gibbsite precipitation data from an inhomogeneously-mixed precipitator were compared to a well-mixed precipitation system operated under the same operating conditions, i.e. supersaturation, seed charge, seed type, mean shear rate and temperature.
It was found that the gibbsite agglomeration kinetic estimates were significantly different, and hence, the product CSD, but the gibbsite growth rates were similar. It was also found that a compartmental model approach cannot fully account for the differences in suspension hydrodynamics, and resulted in unsatisfactorily CSD predictions of the inhomogeneously-mixed precipitator. This is attributed to the coupled effects of local energy dissipation rate and solids phase mixing on agglomeration process.

Le procédé Bayer est cyclique et il permet d'extraire les hydrates d'alumine, contenu dans le minerai de bauxite. L'alumine est la matière première nécessaire pour la production de l'aluminium métallique par le procédé d'électrolyse. La solubilisation des hydrates d'alumine est effectuée dans une solution d'hydroxyde de sodium concentrée, liqueur Bayer, à haute température et pression. Il existe deux types de procédé : un procédé dit à basse température (150ÀC) et un procédé dit haute température (250ÀC). Selon la température utilisée, certaines impuretés présentes dans la bauxite vont être solubilisées comme par exemple la silice, le fer ou le titane. Comme le procédé est basé sur la solubilisation puis sur la précipitation des hydrates d'alumine, la solution est chauffée puis refroidie par une série d'échangeurs de chaleur. Ces changements de température impliquent des variations dans les conditions de saturation et sursaturation ce qui va conséquemment causer la formation de tartre dans le procédé. Selon la température du procédé utilisé, la composition chimique du tartre formé peut être différente. Dans le but d'inhiber partiellement ou totalement la cristallisation de la gibbsite, ou hydrate d'alumine, sur les surfaces métalliques, la compréhension des paramètres influençant sa formation est nécessaire. L'un des moyens de réduire ou d'inhiber la formation du tartre est de modifier les énergies de surface entre les surfaces métalliques et la solution de liqueur Bayer. Pour ce faire, des métaux ayant des propriétés différentes seront étudiés en entartrage et des composés organiques seront ajoutées à la solution d'hydroxyde de sodium afin de modifier l'interface entre ces métaux et la solution. L'influence des hydrates d'alumine et des différents composés organiques sur les métaux sera déterminer [i.e. déterminée] par des mesures d'isothermes d'adsorption, de potentiels zêta et d'angles de contact, dans le but d'établir une corrélation entre l'interface métal/solution et les temps de nucléation mesurés en entartrage. Un deuxième volet consiste en la fabrication d'un montage en laboratoire permettant d'effectuer la formation reproductible du tartre de freudenbergite. La freudenbergite est un tartre à base de titane qui se forme dans le procédé à haute température. Cette étude démontre que la formation du tartre dans le procédé Bayer est un phénomène de formation de cristaux de gibbsite en solution qui vont adhérer aux défauts de surfaces des surfaces métalliques. En ce sens, la rugosité de surface des métaux est le facteur déterminant pour la formation du tartre dans le procédé Bayer. Des tests d'entartrage réalisés au laboratoire sur cinq métaux différents démontrent une corrélation évidente entre la rugosité de surface, mesurée par microscope à force atomique, et les temps de nucléation obtenus en entartrage. Les mesures d'interactions interfaciales des aluminates de sodium sur les métaux étudiés, en présence ou non de composés organiques, ne permettent pas d'établir de corrélation avec les temps de nucléation obtenus en entartrage. Par contre, l'allongement de l'entartrage en présence de gluconate et de tartrate de sodium, des composés inhibiteurs de croissance des cristaux de gibbsite, confirme le phénomène de formation du tartre par des cristaux formés en solution. La croissance des cristaux de tartre étant partiellement inhibée, les temps de nucléation vont être allongés lors des tests d'entartrage. À l'inverse, l'EDTA favorise la formation de plusieurs cristaux en solution, ce qui diminue significativement la vitesse d'entartrage lorsqu'elle est ajoutée dans la liqueur Bayer. Afin de confirmer que la rugosité de surface est le facteur prédominant dans la formation du tartre dans le procédé Bayer, dans nos conditions de laboratoire, des tests d'entartrage sont effectués sur une surface d'or recouverte d'une monocouche d'alcane thiols. Ces tests démontrent que le changement de nature de la surface d'or ne permet pas de changer significativement le temps de nucléation de l'or dans nos conditions d'entartrage. Un montage expérimental comportant un four et quatre autoclaves, contrôlé par un système informatique a permis d'effectuer la formation de tartre de freudenbergite de façon reproductible au laboratoire.

In der vorgelegten Arbeit werden sowohl effiziente als auch einfache Modifikationsansätze zur funktionalen Polymerumhüllung von Gibbsit-Plättchen präsentiert. Die plättchen-förmige Morphologie bleibt dabei nach der Polymerumhüllung erhalten. Im ersten Teil wird ein einfacher Ansatz zur Synthese von anisotropen, plättchen-förmigen Gibbsit-Polydopamin (G-PDA) Partikeln vorgestellt. Au NPs von kontrollierbarer Größe wurden auf der G-PDA Partikeloberfläche gebildet. Diese zeigten katalytische Aktivität zur Reduktion von 4-Nitrophenol und Rhodamin B (RhB) mittels Borhydrid. Die Partikel können durch ihre große, plättchen-förmige Kontaktfläche und der stark adhäsiven Eigenschaften der PDA Hülle einfach mittels Spin-Coating auf Siliziumsubstrate aufgebracht werden. Der so präparierte Nanokatalysator kann nun einfach wiederaufbereitet werden und zeigt hervorragende Wiederverwendbarkeit. Im zweiten Teil wurden anisotrope, hybride Kern-Schale Mikrogele mit wohldefinierter Struktur synthetisiert. Dabei bilden die Gibbsit Nanoplättchen den Kern und vernetztes, thermosensitives Poly(N-isopropylacylamid) die Hülle. Depolarisierte dynamische Lichtstreuung zeigte, dass die hybriden Mikrogele im kollabierten Zustand durch die plättchen-förmigen Kerne eine anisotrope Form annehmen. Der dritte Teil der Arbeit befasst sich mit der Herstellung von hochdispergierbaren, mesoporösen und stickstoffhaltighohle Kohlenstoff-Nanoplättchen. Diese neuartige Kohlenstoff-Nanostruktur wurde mittels sogenannter Silika-Nanocasting Technik unter Veswendung von hexagonalen Gibbsit-Templat und Dopamin als Kohlenstoffquelle synthetisiert. Solche hohlen Kohlenstoff-Nanostrukturen weisen exzellente, kolloidale Stabilität in wässrigen Medien vor und können direkt als Elektrodenmaterial für Superkondensatoren verwendet werden. Außerdem können sie in polyionischen Flüssigkeiten hohe Kapazitäten erzielen, wobei gleichzeitig eine hervorragende elektrochemische Stabilität gewährleistet wird.
In the present thesis, efficient and simple modification approaches have been developed to coat gibbsite platelets with a controllable thickness of functional polymer shell, which preserves the plate-like morphology after the polymer coating. In the first part, a facile approach has been presented for the synthesis of anisotropic plate-like gibbsite-polydopamine (G-PDA) particles. Au NPs with tunable size have been formed on the G-PDA particle surface, which show efficient catalytic activity for the reduction of 4-nitrophenol and Rodamine B (RhB) in the presence of borohydride. Such nanocatalysts can be easily deposited on silicon substrate by spin coating due to the large contact area of the plate-like G-PDA particles and the strong adhesive behavior of the PDA layer. The substrate-deposited nanocatalyst can be easily recycled, which shows excellent reusability. Secondly, anisotropic hybrid core-shell microgels with well-defined structures have been synthesized using gibbsite nanoplate as core and crosslinked thermosensitive poly(N-isopropylacrylamide) as shell. The analysis by depolarized dynamic light scattering shows that the hybrid microgels have an anisotropic shape in the collapsed state, caused by the anisotropy of the plate-like core. In the third part, highly dispersible mesoporous nitrogen-doped hollow carbon nanoplates have been synthesized as a new carbon nanostructure via silica nanocasting technique using dopamine as carbon precursor and hexagonal-shaped gibbsite as template. Such hollow carbon nanoplates show excellent colloidal stability in aqueous media and can be directly applied as electrode materials in supercapacitors, which offer high capacitance and excellent electrochemical stability when using poly(ionic liquid) nanoparticles as binder.

L'aluminium est produit par électrolyse de l'alumine extraite de la bauxite. Le procédé d'extraction, appelé procédé Bayer, permet de dissoudre l'alumine (Al[indice inférieur 2]O[indice inférieur 3]) présente dans le minerai sous forme de gibbsite (Al(OH)[indice inférieur 3]) dans une solution d'hydroxyde de sodium (NaOH) concentrée à une température de 150 [degrés Celsius]. La solution obtenue est saturée en gibbsite. Afin de permettre la précipitation de cette dernière, la température de la liqueur est abaissée à 65 [degrés Celsius] grâce à des échangeurs de chaleurs. La gibbsite recueillie est ensuite calcinée en alumine (Al[indice inférieur 2]O[indice inférieur 3]) disponible pour l'électrolyse. Les importantes variations de température à l'intérieur du procédé provoquent une sursaturation de la solution en gibbsite. Cette sursaturation entraîne la formation de tartre de gibbsite dans les conduites et les échangeurs de chaleur, ce qui est une problématique importante au sein du procédé d'extraction. Afin de bien comprendre le phénomène d'entartrage au sein du procédé Bayer, il est nécessaire d'étudier les paramètres qui influencent la cristallisation de la gibbsite pour pouvoir ensuite l'inhiber.L'approche utilisée dans ce travail consiste à étudier la formation des cristaux de gibbsite sur différentes surfaces et de vérifier l'influence de la température sur l'entartrage. Ainsi, différents échantillons d'acier et d'or ont été entartrés dans de la liqueur Bayer synthétique et caractérisés pour déterminer la taille et la structure des noyaux cristallins. Le deuxième volet étudié consiste à examiner l'adsorption de molécules organiques sur le fer qui, en formant une couche inhibante adsorbée à la surface de la tuyauterie, préviendrait l'entartrage. Pour cela, des mesures d'isothermes d'adsorption utilisant un HPLC ont été réalisées. Cette étude démontre que les premiers noyaux cristallins de gibbsite sont formés dans les premières 24 heures d'entartrage, et que la température influence grandement la forme et la vitesse de croissance des cristaux. De plus, le tartre adhère non seulement à la surface d'acier, mais également à la surface de métaux nobles comme l'or. Dans l'étude de l'adsorption, une méthode a été développée pour mettre en évidence rapidement des molécules qui sont susceptibles de former une couche protectrice adsorbée à la surface de l'acier. Pour celles présentant un potentiel intéressant, des isothermes d'adsorption ont été mesurées.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
On the Guarapuava Plateau/Palmas, in a low slope hillside of superficial covering from basaltic origins, on the right bank of the Rio das Pombas, Paraná state, processes of tunnel erosion (pipes) were identified. These are subsuperficial erosion processes with typical features, such as subsidence of the tunnel roof and rebate structures, which tend to evolve to superficial features. The emerging of this erosive process depends on a set of factors, being the main one, the properties of the superficial covering, such as: texture, macroporosity, granulometric composition (chemical matter make-up), density, porosity e chemical elements that make up the matter, those concerning the hydrological conditions and the topography of the hillside. In order to recognize and characterize the superficial covering in the sector of low hillside, sieve analysis was used, as well as real and apparent density, total porosity verified; toposequences were made and X-ray scattering techniques performed. The results showed that the matter which covers the low hillside sector, where the tunnels are, have a sandy texture due to the properties of microagregation generated by clay mineral, gibbsite; leaving the matter with a high porosity level, thus favoring the flowing of water through subsurfaces. The generated flows tend to be exfiltrated to a ditch wall-like surface, which causes the removal of small particles of matter (seepage). With the opening of small gullies through subsurface, the flow tend to become concentrated (tunnel scour) and consequently enlarge the subsuperficial channels by the mechanical action of the water. In a sequence of factors that can be used for the analysis of the process generation, which causes: alteration in basalt rocks, microaggregation of the matter, macroporosity and increase of water flow through subsurface. Therefore, the hydrology conditions in the hillside contributed for erosion mechanisms to emerge in subsurface, development of erosion process, formation of subsuperficial erosion and, ultimately, superficial erosion process development. These both chemical and physical features found in such field of study, show that the superficial covering is a determining factor for the subsuperficial tunnel erosion to originate in the hillside.
No Planalto de Guarapuava/Palmas, em encosta de baixa declividade e cobertura superficial de origem basáltica, à margem direita do Rio das Pombas em Guarapuava (Paraná), foram identificados processos de erosão em túneis (pipes). Trata-se de processos subsuperficiais de erosão que apresentam feições típicas, tais como, subsidência do teto do túnel e estruturas de abatimento, que tendem a evoluir para feições superficiais. A instalação desse processo erosivo depende de um conjunto de fatores, destacando-se como condicionantes, as propriedades da cobertura superficial como: textura, macroporosidade, composição granulométrica, densidade, porosidade e constituintes químicos dos materiais, e aqueles relativos às condições hidrológicas e à topografia da encosta. Buscando-se reconhecer e caracterizar a cobertura superficial do setor de baixa encosta, foram realizadas análises granulométricas, de densidade aparente, real e porosidade total, construção de topossequências e análises químicas de difração de raios-X. Os resultados indicaram que o material que recobre o setor de baixa encosta, onde aparecem os túneis, apresenta textura arenosa devido às propriedades de microagregação gerada pelo argilomineral gibbsita, deixando o material com porosidade alta, favorecendo assim a circulação de água em subsuperficie. Os fluxos gerados tendem a ser exfiltrados para uma superfície de exposição, o que provoca a remoção de pequenas partículas de material (seepage). Com a abertura de pequenos canais em subsuperfície, os fluxos tendem a se concentrar (tunnel scour) e consequentemente ampliar os canais subsuperficiais pela ação mecânica da água. Numa sequência de fatores que possam ser postos para análise da geração do processo, têm-se: alteração da rocha basáltica, microagregação do material, macroporosidade e aumento da circulação de água em subsuperfície. Assume-se que as condições hidrológicas da encosta propiciaram a instalação de mecanismos de erosão em subsuperfície, evolução do processo erosivo, formação de feições erosivas subsuperficiais e, por fim, instalação de feições erosivas superficiais. Essas características físicas e químicas encontradas na área de estudo, demonstram que a cobertura superficial é determinante para a instalação da erosão subsuperficial em túneis na encosta.

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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.

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.

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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...
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.

Gibbsite scale growth in pipe fittings is a major problem for an alumina refinery. A recent investigation into the scale growth mechanism at an alumina refinery found almost 60 % more scale growth in a reducer when compared with the connecting straight pipe sections for similar flow conditions. Scale growth occurs where liquor (supersaturated solutions) come in contact with solid surfaces and it is affected by the liquor flow velocity besides other physical and chemical parameters. The present work is dedicated to study the hydro-dynamical aspects of the mechanism of scale growth. In particular, the role of the phenomenon of turbulent bursting, stream wise and cross stream fluctuating velocity components (Ux and Uy) was investigated as the flow moves through the reducer. Particle Image Velocimetry (PIV) technique was used to get a full view of the reducer and the readings close-to-the-wall of the reducer at Reynolds number of 27,000 and 44,000 upstream which corresponds to Reynolds number of 41,500 and 66,000 downstream of the reducer respectively. The results showed an increase in cross stream and a decrease in magnitude of stream wise fluctuating velocity components, whereby we presume that the increased cross stream fluctuating velocity component increases the frequency of impacts of the scaling particles on the wall thus initiating excessive scale growth in the reducer when compared with the connecting straight pipe sections, for similar flow conditions.

Les hydroxydes d'aluminium ont été préparés à partir des solutions sursaturées d'aluminate de sodium, obtenues en attaquant l'aluminium métallique dans une solution de soude. Ces conditions évitent l'intervention, dans le mécanisme de croissance, d'autres ligands que ceux issus de l'eau, tant que la dissolution du CO₂ atmosphérique est négligeable. Les expériences de préparation de bayerite et de gibbsite menées ici sont en bon accord avec les données thermodynamiques et autres données de la littérature. Les spectres infrarouges des hydroxydes d'aluminium obtenus montrent une absorption vers 3465 cm-¹ qui ne peut pas être attribuée complètement aux hydroxyles en volume des polytypes présents dans l'échantillon, ces derniers étant identifiés à l'aide d'autres bandes vOH. Même si une partie de cette absorption correspond à la gibbsite, le reste doit être assigné à une autre famille d'hydroxyles. L'absence de spectre Raman correspondant n'est pas en faveur de particules amorphes ou de fautes d'empilement, mais plutôt d'hydroxyles exceptionnellement polaires à la surface des cristallites, bien que la fraction de ces hydroxyles superficiels sur ceux qui se situent en volume puisse être inférieure à 10-³. La comparaison de l'intensité de l'absorption à 3465 cm-¹ et de l'aire spécifique de l'échantillon montre un certain parallélisme de ces grandeurs, sans vérifier une corrélation linéaire rigoureuse. Mais des différences notables apparaissent dans les isothermes d'adsorption du krypton où, dans certains cas, on peut différencier des surfaces basales et latérales. Dans d'autres cas, la surface est beaucoup plus hétérogène et la distinction serait arbitraire. Les micrographies au MEB confirment de grandes différences de morphologies entre les échantillons et suggèrent plutôt une corrélation entre l'absorption à 3465 cm-¹ et l'aire spécifique latérale. L'interprétation proposée attribuerait cette absorption aux hydroxyles monocoordinés dont une moitié doit être protonée dans un échantillon électriquement neutre, à l'air. La possibilité de différencier les hydroxyles de surface et de volume a permis de revisiter l'interprétation des spectres infrarouges et Raman des élongations des hydroxyles en volume, dans la gibbsite ou dans la bayerite. La réactivité des molécules organiques aux interfaces des hydroxydes en milieu aqueux et l'étude de la couche de passivation d'une poudre d'aluminium métallique sont les deux points d'application qui ont été développés.

Ce travail a pour objectif de caractériser la fragmentation ultrafine. L’étude est réalisée avec un broyeur à jets d'air dans lequel les particules mises en mouvement par insufflation d'air comprimé entrent violemment en collision. Le matériau réalisé, de la gibbsite Al(OH)3 obtenue industriellement à partir de la bauxite, se présente sous la forme de grains polycristallins complexes de taille moyenne égale à 100 microns. Une méthode d'étude originale basée sur l'analyse des courbes granulométriques couplée à l'analyse morphologique a permis de montrer que la fragmentation s'opère selon trois mécanismes: l'éclatement, l'écaillage et l'attrition. Il en résulte trois populations granulométriques dont les tailles moyennes sont 75, 20 et 7 microns composés par quatre types morphologiques, les blocs compacts, les éclats, les écailles et les fines. En comparant les résultats obtenus dans un broyeur à jets d'air à ceux obtenus par compression dans un broyeur annulaire et par compression-cisaillement dans un broyeur vibroinertiel, on constate que les produits ont une morphologie identique bien que les répartitions pondérales varient avec le type de broyage. On conclut que la structure du matériau joue un rôle déterminant dans la fragmentation

L'aluminium est produit par électrolyse de l'alumine extraite de la bauxite. Tout d'abord, l'alumine (Al[indice inférieur 2]O[indice inférieur 3]) est extraite de la bauxite par le procédé Bayer. Par ce procédé, la gibbsite (Al(OH)[indice inférieur 3]) présente dans la bauxite est dissoute dans une solution concentrée d'hydroxyde de sodium (NaOH) à une température de 143 [degrés Celsius] pour une usine dite à basse température. La solution obtenue, appelée liqueur Bayer, est saturée en gibbsite. Celle-ci va être précipitée en abaissant la température de la liqueur à 65[degrés Celsius] grâce à des échangeurs de chaleurs. La gibbsite recueillie est ensuite calcinée en alumine (Al[indice inférieur 2]O[indice inférieur 3]) pour l'électrolyse.L'importante variation de température dans le procédé entraîne une sursaturation de la solution en gibbsite. Cette sursaturation provoque l'entartrage qui est une problématique importante au sein du procédé Bayer. Dans le procédé Bayer, l'entartrage est défini comme l'adhérence de composés solides à la paroi métallique de l'équipement : réservoirs, conduites, échangeurs de chaleur, etc. La composition chimique du tartre varie selon la composition de la solution ainsi que la température. Les composés les plus fréquents qui forment le tartre dans le procédé Bayer sont : la gibbsite, la sodalite Bayer, l'oxalate de sodium et le titanate de sodium ou de calcium.L'étude de l'entartrage de l'acier doux par la gibbsite dans le procédé Bayer nécessite la compréhension des paramètres qui influencent la cristallisation de la gibbsite afin de pouvoir l'inhiber.L'un des moyens pour empêcher la formation de tartre est la modification des surfaces métalliques des conduites et échangeurs de chaleur. Les trois volets examinés lors de ce travail sont la modification des surfaces métalliques par des traitements appliqués directement sur l'acier ou leur recouvrement par des revêtements polymériques formés par voie électrochimique, la caractérisation des surfaces métalliques et des polymères, et l'évaluation de l'influence des modifications apportées à l'acier doux par des tests d'entartrage dans la liqueur Bayer. La combinaison des tests d'entartrage avec les différentes techniques de caractérisation physico-chimiques des échantillons, telles que la microscopie électronique à balayage, la microscopie à force atomique, la spectrométrie X par dispersion en énergie, la spectroscopie de photoélectrons, la diffraction des rayons X et la spectroscopie infrarouge à transformée de Fourier, a permis de cibler les paramètres qui influencent l'entartrage de l'acier doux par la gibbsite. La présence de défauts, d'une grande rugosité et d'oxydes à la surface de l'acier doux favorise l'entartrage. De plus, des revêtements polymériques épais, non uniformes, poreux et contenant des groupements hydroxydes favorisent aussi l'entartrage. Par ailleurs, l'entartrage va se produire plus facilement sur l'acier que sur les polymères. Une bonne corrélation a été démontrée entre les résultats des tests d'entartrage obtenus en laboratoire et en usine. En effet, tous les traitements appliqués directement sur l'acier ont permis d'augmenter les temps de nucléation de la gibbsite. De plus, les revêtements polymériques épais, non uniformes et poreux ont des temps de nucléation plus courts alors que revêtements polymériques plus uniformes ont permis d'augmenter les temps de nucléation. Une partie des résultats présentés dans ce mémoire concernant les tests d'entartrage a été incluse dans un compte-rendu de conférence et dans la présentation orale associée:"Dynamic adsorption isotherm measurements applied to known organic precipitation inhibitors and scale control studies.", A. BRISACH-WITTMEYER, I. FONTAINE, É. ST-JEAN, A. VACHON, H. MÉNARD, N.A. BOUCHARD et R. BREAULT, Proceedings of the 8th International Alumina Quality Workshop, Darwin, Australie 2008.

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.

Anomalously high concentrations of arsenic and phosphate are found in the sediments of the Saguenay Fjord relative to those of the Gulf and St. Lawrence Estuary. Whereas the source of phosphate is likely anthropogenic, arsenic appears to be scavenged from the bottom marine waters by settling detrital and authigenic particles. The surface waters of the Saguenay Fjord show a particulate aluminum anomaly ([Al]tot/[Al]diss > 1) that decreases downstream or with increasing salinity. The mineralogy of the aluminum particulate matter may be akin to gibbsite given the refining activities in the region. The adsorption of phosphate and arsenic to various mineral oxides is well established but the scavenging capacity of gibbsite in this estuarine environment is not known.
In order to simulate the behavior of the adsorbent/adsorbate relationship during estuarine mixing, the adsorption capacity of gibbsite for arsenate and phosphate was measured in pure water; 0.67 M NaCl; 10 mM CaCl2; 10 mM CaCl2 + 0.64 M NaCl and in seawater in the absence and presence of the fluoride ion.

Les sols des planezes de tahiti sont, aux basses altitudes, des oxydisols ferrotitaniferes et, au-dessus de 1 100 m, des podzols a gibbsite et anatase. Les oxydisols sont des sols desalcalinises et desilicifies, depourvus de mineraux argileux, riches en titane herite, pour l'essentiel, de la titanomagnetite. Ces caracteristiques conditionnent l'ensemble de leurs proprietes. Les podzols sont tres differents des autres podzols tropicaux. L'horizon e est constitue de gibbsite primaire et secondaire, d'anatase et de rutile provenant pour l'essentiel du recyclage biologique. On observe plusieurs phases successives de podzolisation : a 20 000 bp, 1 200 bp et peut-etre 400 bp, la pedogenese actuelle n'etant pas podzolisante. L'activation de la podzolisation semble etre, a tahiti, en relation directe avec des periodes de refroidissement climatique.

Les travaux présentés dans cette thèse démontrent que l'adsorption des molécules organiques est une des causes de cette diminution de rendement de la précipitation. Ils mettent en évidence que tous les inhibiteurs de précipitation de la gibbsite sont adsorbés sur la surface de la gibbsite. Il est prouvé qu'une modification des propriétés d'adsorption des molécules organiques inhibitrices de précipitation modifie par le fait même les propriétés d'inhibition. L'adsorption des molécules organiques sur les différents supports a été mesurée à l'aide d'une technique dynamique faisant appel à la chromatographie. La détermination des constantes de Henry, k H , par la mesure d'isotherme d'adsorption a permis de mesurer les pouvoirs d'adsorption des supports choisis. Les matériaux étudiés sont principalement ceux retrouvés au sein du procédé Bayer, soit la gibbsite, la boehmite et l'alumine. Les résultats présentés dans Canadian Journal of Chemistry 81 (2003) suggèrent que l'adsorption en milieu aqueux est influencée par la taille des particules et non par la surface accessible déterminée par l'isotherme de Brunauer-Emmett-Teller. Les résultats présentés dans Light Metals (2005) établissent une relation entre l'adsorption de molécules organiques sur la gibbsite et l'influence sur la précipitation. L'inhibition de la précipitation par ces molécules organiques adsorbées a été mesurée par titrage potentiométrique. Le rendement de précipitation et la mesure de l'inhibition ont été déterminés en quantifiant les espèces présentes dans les solutions d'aluminate de sodium avant et après la précipitation de la gibbsite dans des solutions ne contenant pas de molécules organiques et dans des solutions contenant différentes concentrations de molécules adsorbées. Les résultats démontrent que l'adsorption de molécules organiques n'entraîne pas nécessairement l'inhibition de la précipitation suggérant que l'adsorption doit être spécifique à certains sites actifs de la gibbsite. De plus, nos travaux démontrent que l'efficacité d'un catalyseur en hydrogénation électrocatalytique dépend de l'adsorption de la molécule insaturée sur le support catalytique. Dans les articles publiés dans Langmuir 20 (2004) et Langmuir 22 (2006), les isothermes d'adsorption de la cyclohexanone et du phénol sont déterminés sur les catalyseurs utilisés pour l'hydrogénation électrocatalytique. Les résultats obtenus sur des catalyseurs de silice modifiée ex-situ par des groupements organiques montrent que plus l'adsorption est élevée, moins l'hydrogénation est efficace. Cependant, les résultats obtenus sur les catalyseurs d'alumine modifiée in-situ par des acides carboxyliques montrent qu'une augmentation de l'adsorption est favorable à la réaction d'hydrogénation. Les résultats des deux articles ne sont pas en contradiction car les ordres de grandeur de l'adsorption sur la silice et celle sur l'alumine ne sont pas les mêmes. Les mesures des isothermes d'adsorption semblent toutes se diriger vers une plage de valeurs où l'adsorption est idéale pour réaliser l'hydrogénation électrocatalytique. Pour compléter cette thèse, deux techniques électrochimiques, l'hydrogénation électrocatalytique et l'électro-oxydation, sont utilisées afin de modifier sélectivement un inhibiteur de précipitation adsorbé, le 1,2-dihydrobenzène (le catéchol). Cette molécule a été choisie comme molécule modèle car on la retrouve dans les produits de dégradation de la lignine qui est une des principales sources de molécules organiques dans le procédé Bayer. Les deux procédés électrochimiques choisis pourront ainsi être proposés comme technique de contrôles des inhibiteurs de précipitation de la gibbsite dans le procédé Bayer. Le cyclohexanediol, produit de l'hydrogénation électrocatalytique du catéchol, ne démontre aucun effet inhibiteur. Les résultats publiés dans Journal of Applied Electrochemistry 37 (2007) démontrent que l'hydrogénation électrocatalytique du catéchol est possible dans un milieu basique, sur un catalyseur de Rh/Al 2 O 3 . Cependant, la présence de l'ion aluminate diminue l'efficacité de la réaction d'hydrogénation. La présence des deux isomères du cyclohexanediol, retrouvés lors du procédé d'hydrogénation électrocatalytique, est expliquée dans Canadian Journal of Chemistry 84 (2006) par l'existence de deux intermédiaires de réaction qui sont hydrogénés plus rapidement dans le milieu basique que la molécule de départ, le catéchol. En conclusion, l'adsorption est le centre de cette thèse. Son implication dans les phénomènes d'inhibition ainsi que dans les deux réactions électrochimiques proposées en font un atout majeur pour ouvrir une nouvelle voie sélective de contrôle des molécules organiques inhibitrices de précipitation de la gibbsite dans le procédé Bayer. L'hydrogénation électrocatalytique et l'électro-oxydation sur des électrodes appropriées ont démontré un potentiel réel d'utilisation pour solutionner le problème industriel d'inhibition de précipitation et ainsi augmenter la rentabilité des usines utilisant le procédé Bayer."--Résumé abrégé par UMI.

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

Le broyage est une opération importante en technologie des poudres où des progrès sont encore possibles pour améliorer le fonctionnement des appareils existants ou concevoir de nouveaux systèmes. Pour mieux connaître les phénomènes se produisant dans les chambres de broyage l'approche classique reposant sur l'étude des cinétiques granulométriques a été combinée à une prise en compte des cinétiques morphologiques établies grâce à l'analyse d'images des fragments observés par microscopie électronique à balayage. La morphologie des particules est caractérisée à partir d'un ensemble de sept paramètres : six pour la morphologie bi-dimensionnelle et un pour la morphologie pseudo tri-dimensionnelle. En complément des outils statistiques (tests de comparaison, analyse en composantes principales) ont été utilisés pour une meilleure précision et une interprétation plus fine des résultats. Des expériences de broyage de matériaux possédant une morphologie initiale contrôlée (hydrargillites obtenues par cristallisation) ou non (roches naturelles) ont été conduites dans un broyeur à billes agité en faisant varier la concentration en solide, le diamètre et taux de remplissage en corps broyants. Après une étude préalable des particules avant broyage, l'analyse des phénomènes de réduction de taille à partir des seules évolutions des distributions granulométriques a montré ses limites. La méthode finalement proposée est basée sur un examen de l'évolution des paramètres de forme en complément de celui des distributions granulométriques et a aidé à une meilleure compréhension de ces mécanismes. Si la maîtrise des mécanismes de fragmentation peut aider au contrôle de la qualité du produit final, la pollution possible par des fragments de corps broyants doit aussi être envisagée. Une méthode basée sur l'analyse de la surface des corps broyants observés par microscopie électronique à balayage permet d'en suivre l'évolution
Comminution is an important process in powder technology, in which progress can still be made, to improve the operation of existing equipments or to design new systems. To understand better the phenomena taking place in the grinding chambers, the classical approach based on the examination of size distributions has been combined with the distributions of the shape of the fragments, observed by scanning electron microscopy and characterised by image analysis. The particle morphology has been assessed through the use of a set of seven parameters, six of them describing the 2D shape and one the pseudo 3D shape. In complement statistical tools (tests, principal component analysis) have been used. Comminution experiments have been run with different materials exhibiting either welldefined initial morphology (gibbsites obtained by crystallisation) or not (natural rocks) in a stirred bead-mill with different suspension concentrations, and beads diameters and filling rates. After a preliminary study of the particles before grinding, the analysis of the size reduction phenomena from the size distributions only has shawn its limits. The method finally proposed is based on a joint analysis of the shape and size parameters. If a better understanding of the phenomena can help to control the product quality, a possible pollution by fines produced by wear of the grinding bodies should be taken into account. A method based on the analysis of their surface by scanning electron microscopy is proposed to monitor this wear

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.

Deux systèmes à pouvoir d'oxydoréduction et de sorption de surface sont étudiés : l'oxydation de pyrite (FeS2) par du chrome (VI) et l'adsorption d'espèces 2,4-dinitrobenzoate sur gibbsite (γ-Al(OH)3). L'enjeu du premier système est d'appréhender le processus d'oxydation de la pyrite en utilisant une sonde métallique, le chrome (VI). L'analyse de la solution par spectroscopie UV-visible et la caractérisation de la phase solide par spectrométries Raman confocal, XPS, EXAFS et XANES permettent de proposer un modèle de mécanisme d'oxydation/dissolution. L'objectif de la seconde étude est de mettre en évidence une différence de réactivité de surface entre deux types de face cristalline de la gibbsite à l'aide d'une sonde organique en utilisant la spectroscopie optique en champ proche (SNOM). Les corrélations faces cristallines/spectres en champ proche indiquent une réactivité différente entre les hydroxyles mono et bi-coordonnées de la phase minérale. Un modèle de sorption est présenté
Two systems characterised by oxydoreduction and sorption of surface reactions are studied: the pyrite oxidation (FeS2) by chromium (VI) and the sorption of dinitro-2,4 benzoic species on gibbsite (γ-Al(OH)3). The aim of the first system is to study the pyrite oxidation processes of the pyrite by using chromium (VI) like a metal probe. The solution analysis by UV-visible spectroscopy and the solid phase characterisation by confocal Raman spectrometry, XPS, EXAFS and XANES allow to suggest a mechanism model of oxidation/dissolution. The objective of the second study is to display a specific chemical reactivity between two crystalline face types of the gibbsite by using an organic probe with the help of sub-wavelength spectroscopy (SNOM). Correlations between crystalline faces and near field spectra show difference reactivity between mono and bi coordinated OH groups from the mineral phase. A model of sorption is presented

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

Organic ligand complexation reactions at the mineral-water interface play an important role in several environmental and geochemical processes such as adsorption, dissolution, precipitation, pollutant transport, nutrient cycling, and colloidal stability. Although organic ligand surface complexation reactions have been extensively studied, a molecular level understanding regarding the mechanisms underlying the adsorption of such compounds is still limited. The purpose of the current study was to investigate the interactions between some common naturally occurring organic ligands and a common aluminosilicate clay mineral, kaolinite, using a combination of macroscopic and microscopic experimental methods. Molecular level information regarding the structure and binding mode of adsorbed species was obtained using in situ MIR-FTIR spectroscopy. Other experimental techniques including adsorption experiments, surface titrations, and surface complexation modelling were also employed in order to quantify and describe the macroscopic adsorption properties of the organic ligands examined. Three low molecular weight organic acids (oxalic, salicylic, and phthalic acid) and humic acid were chosen as representative organic ligands. Spectroscopic evidence revealed that low molecular weight organic acids are able to form both inner and outer sphere complexes on kaolinite, and the relative concentrations of these surface complexes varies with solution chemistry. Inner sphere coordination modes inferred are a mononuclear bidentate for oxalate (five-membered chelate ring) and phthalate (seven-membered chelate ring); and a mononuclear monodenate (six-membered pseudochelate ring) for salicylic acid. Similar coordination modes were shown to form on simpler mineral (hyrd)oxides. Elucidation of the coordination chemistry of these ligands can provide insights into the dissolution mechanisms of silicate minerals In contrast to low molecular weight organic acids, there was no evidence of inner sphere complexation by humic acid acids on kaolinite or gibbsite. The combined spectroscopic and macroscopic adsorption results suggest that cation bridging and van der Waals interactions are the two most probable mechanisms for the adsorption of humic acid by these mineral substrates. This finding casts doubts over the use of low molecular weight organic acids as humic acid analogs.

L'altération chimique des roches primaires et des minéraux dans les systèmes naturels a un impact majeur sur la formation des sols et leur composition. L'altération chimique est largement pilotée par la dissolution des minéraux. Les éléments chimiques libérés dans les eaux souterraines par la dissolution des minéraux réagissent facilement pour former des minéraux secondaires comme les argiles, zéolites et carbonates. Les carbonates se forment par réaction des cations divalents (Ca, Fe et Mg) avec CO2 dissous tandis que la formation des kaolins et de la gibbsite est attribuée à l'altération des minéraux riches en aluminium, le plus souvent les feldspaths. Le projet Carbfix à Hellisheiði (sud-ouest de l'Islande) a pour but d'utiliser les processus d'altération naturelle pour former des minéraux carbonatés par réinjection dans les roches basaltiques environnantes de CO2 provenant d'une centrale géothermique. Ce processus trouve son origine dans la dissolution des roches basaltiques riches en cations divalents (Ca, Fe et Mg) qui se combinent au CO2 injecté pour former des minéraux carbonatés. Cette thèse est centrée sur la dissolution du basalte cristallin de Stapafell qui est composé essentiellement de trois phases minérales (plagioclase, pyroxène et olivine) et qui est riche en cations divalents. La vitesse de libération des éléments du basalte à l'état stationnaire et loin de l'équilibre a été mesurée dans des réacteurs à circulation à des pH de 2 à 12 et des températures de 5 à 75°C. Les vitesses de libération de Si et Ca à l'état stationnaire présentent une variation en fonction du pH en forme de U avec une diminution des vitesses lorsque le pH augmente en conditions acides et une augmentation avec le pH en conditions alcalines. Les vitesses de libération du silicium par le basalte cristallin sont comparables à celles par le verre basaltique de même composition chimique aux faibles pH et aux températures = 25°C mais elles sont plus lentes aux pH alcalins et aux températures = 50°C. Par contre, les vitesses de libération de Mg et Fe diminuent de manière monotone avec l'accroissement du pH à toutes les températures. Ce comportement a pour cause les variations contrastées, en fonction du pH, des vitesses de dissolution des trois minéraux constitutifs du basalte: plagioclase, olivine et pyroxène. Les vitesses de libération des éléments déduites de la somme des vitesses de dissolution du plagioclase, pyroxène et olivine normalisées à la fraction volumique de ces minéraux sont, à un ordre de grandeur près, les mêmes que celles mesurées dans cette étude. En outre, les résultats expérimentaux montrent que, durant l'injection d'eaux chargées en CO2 de pH proche de 3. 6, le basalte cristallin libère préférentiellement Mg et Fe en solution par rapport à Ca. L'injection de fluides acides chargés en CO2 dans des roches cristallines basaltiques peut donc favoriser la formation de carbonates de Mg et Fe aux dépends de la calcite aux conditions de pH acides à neutres. Le plagioclase, qui est la phase la plus abondante du basalte, influence fortement la réactivité de ce dernier. La vitesse de dissolution du plagioclase, basée sur la libération de la silice, présente une variation en forme de U en fonction du pH, diminuant lorsque le pH augmente aux conditions acides mais augmentant avec le pH aux conditions alcalines. En accord avec les données de la littérature, la vitesse de dissolution du plagioclase à pH constant, en conditions acides, augmente avec sa teneur en anorthite. L'interprétation et le fit des données obtenues suggèrent que la vitesse de dissolution du plagioclase est contrôlée par la décomposition d'un complexe activé riche en silice, formé par le départ de Al de la structure du minéral. Le plus remarquable, par comparaison aux hypothèses antérieures, est que la vitesse de dissolution du plagioclase en conditions alcalines est indépendante de sa teneur en anorthite - e. G. Les vitesses de dissolution des plagioclases riches en anorthite augmentent avec le pH aux conditions alcalines. A ces conditions, il est probable que la vitesse de dissolution rapide du plagioclase domine, en raison de sa forte teneur en Ca, la libération vers la phase fluide des cations divalents du basalte cristallin. La gibbsite est généralement le premier minéral qui précipite lors de la dissolution du plagioclase. C'est un hydroxyde d'aluminium que l'on trouve dans divers sols et qui est aussi la phase principale des minerais de bauxite. Les vitesses de précipitation de la gibbsite ont été mesurées dans des réacteurs fermés, en conditions alcalines à 25 et 80°C, en fonction de l'état de saturation du fluide. Les analyses des solides après réaction ont démontré que la précipitation de gibbsite s'est produite dans toutes les expériences. L'interprétation de l'évolution dans le temps de la chimie du fluide réactif fournit des vitesses de précipitation de la gibbsite qui sont près des vitesses de dissolution du plagioclase. En plus, des vitesses de précipitation de la gibbsite diminuent plus rapidement que des vitesses de dissolution du plagioclase quand le pH descende. Ceci suggère que l'étape limitant de l'altération du plagioclase sur la surface de la terre est plutôt la consommation d'Al par formation de la gibbsite que la dissolution même du plagioclase. La kaolinite est en général le second minéral formé après la gibbsite lors de la dissolution du plagioclase à basse température. Les vitesses de précipitation de la kaolinite ont été mesurées dans des réacteurs à circulation à pH = 4 et t = 25°C, en fonction de l'état de saturation du fluide. Au total, 8 expériences de précipitation de longues durées ont été réalisées dans des fluides légèrement supersaturés par rapport à la kaolinite, en utilisant comme germes pour la précipitation une quantité connue de de kaolinite de Géorgie (KGa-1b) contenant peu de défauts et préalablement nettoyée. Les vitesses de précipitation de kaolinite mesurées sont relativement lentes comparées aux vitesses de dissolution du plagioclase. Cette observation suggère que la formation de kaolinite lors de l'altération est limitée par sa vitesse de précipitation plutôt que par que la disponibilité en Al et Si issus de la dissolution du plagioclase. L'ensemble des résultats de cette étude fournit un certain nombre de principes scientifiques de base nécessaires à la prédiction des vitesses et des conséquences de la dissolution du basalte cristallin et du plagioclase à la surface de la Terre et lors de l'injection du CO2 à proximité de la surface dans le cadre des efforts de stockage du carbone. Les résultats obtenus indiquent, bien que les vitesses de précipitation de la gibbsite soient relativement rapides, que la vitesse de précipitation relativement lente de la kaolinite peut être le processus contrôlant la formation de ce minéral à la surface de la Terre. Cette observation souligne la nécessité de poursuivre la quantification de la précipitation de ce minéral secondaire aux conditions typiques de la surface de la Terre. En outre, comme les proportions des différents métaux divalents libérés par les basaltes cristallins varient sensiblement avec le pH, la carbonatation des basaltes doit produire un changement systématique de l'identité des minéraux carbonatés et des zéolites précipités en fonction de la distance au puits d'injection. Cette dernière conclusion pourra être directement testée dans le cadre du projet CarbFix actuellement conduit à Hellisheiði en Islande
The chemical weathering of primary rocks and minerals in natural systems has a major impact on soil development and its composition. Chemical weathering is driven to a large extent by mineral dissolution. Through mineral dissolution, elements are released into groundwater and can readily react to precipitate secondary minerals such as clays, zeolites, and carbonates. Carbonates form from divalent cations (e. G. Ca, Fe and Mg) and CO2, and kaolin clay and gibbsite formation is attributed to the weathering of aluminium- rich minerals, most notably the feldspars. The CarbFix Project in Hellisheiði SW-Iceland aims to use natural weathering processes to form carbonate minerals by the re-injection of CO2 from a geothermal power plant back into surrounding basaltic rocks. This process is driven by the dissolution of basaltic rocks, rich in divalent cations, which can combine with injected CO2 to form and precipitate carbonates. This thesis focuses on the dissolution behaviour of Stapafell crystalline basalt, which consists of three major phases (plagioclase, pyroxene, and olivine) and is rich in divalent cations. Steady-state element release rates from crystalline basalt at far-from-equilibrium conditions were measured at pH from 2 to 11 and temperatures from 5° to 75° C in mixed-flow reactors. Steady-state Si and Ca release rates exhibit a U-shaped variation with pH, where rates decrease with increasing pH at acid condition but increase with increasing pH at alkaline conditions. Silicon release rates from crystalline basalt are comparable to Si release rates from basaltic glass of the same chemical composition at low pH and temperatures =25°C but slower at alkaline pH and temperatures =50°C. In contrast, Mg and Fe release rates decrease continuously with increasing pH at all temperatures. This behaviour is interpreted to stem from the contrasting dissolution behaviours of the three major minerals comprising the basalt: plagioclase, pyroxene, and olivine. Element release rates estimated from the sum of the volume fraction normalized dissolution rates of plagioclase, pyroxene, and olivine are within one order of magnitude of those measured in this study. In addition, these experimental results show that during injection of CO2-charged waters with pH close to 3. 6, crystalline basalt preferentially releases Mg and Fe relative to Ca to the fluid phase. The injection of acidic CO2-charged fluids into crystalline basaltic rocks may therefore favour the formation of Mg and Fe carbonates rather than calcite at acidic to neutral conditions. Plagioclase is the most abundant phase in crystalline basalts and thus influences strongly its reactivity. Plagioclase dissolution rates based on Si release show a common U-shaped behaviour as a function of pH where rates decrease with increasing pH at acid condition but increase with increasing pH at alkaline conditions. Constant pH plagioclase dissolution rates increase with increasing anorthite content at acid conditions, in agreement with literature findings. Interpretation and data fitting suggests that plagioclase dissolution rates are consistent with their control by the detachment of Si-rich activated complexes formed by the removal of Al from the mineral framework. Most notably, compared with previous assumptions, plagioclase dissolution rates are independent of plagioclase composition at alkaline conditions, e. G. Anorthite-rich plagioclase dissolution rates increase with increasing pH at alkaline conditions. At such conditions rapid plagioclase dissolution rates likely dominate divalent metal release from crystalline basalts to the fluids phase due to its high Ca content. Gibbsite is commonly the first mineral formed during low temperature dissolution of plagioclase. Gibbsite is an aluminium-hydroxide that is found in various soils as well as the dominant phase in many bauxite ores. Gibbsite precipitation rates were measured in closed system reactors at alkaline condition, both at 25 °C and 80 °C as a function of fluid saturation state. Analyses of the solids demonstrate that gibbsite precipitation occurred in all experiments. The comparison of gibbsite precipitation to the dissolution rates of plagioclase at pH 11 shows that the rates are close to equal. The precipitation rates of gibbsite, however, decrease faster with decreasing pH than plagioclase dissolution rates. As such it seem likely that plagioclase dissolution is faster than gibbsite precipitation at near to neutral pH, and the relatively slow rate of gibbsite precipitation influences plagioclase weathering in many Earth surface systems. Kaolinite is commonly the second secondary mineral formed during low temperature dissolution of plagioclase. Kaolinite precipitation rates were measured in mixed flow reactors as a function of fluid saturation state at pH=4 and 25 °C. In total eight long-term precipitation experiments were performed in fluids mildly supersaturated with respect to kaolinite, together with a known quantity of cleaned low defect Georgia Kaolinite as seeds. Measured kaolinite precipitation rates are relatively slow compared with plagioclase dissolution rates. This observation suggests that kaolinite formation during weathering is limited by its precipitation rates rather than by the availability of aqueous species sourced from plagioclase dissolution. Taken together the results of this study provide some of the fundamental scientific basic for predicting the rates and consequences of crystalline basalt and plagioclase dissolution at both the Earth's surface and during the near surface injection of CO2 as part of carbon storage efforts. Results indicate that although gibbsite precipitation rates are relatively rapid, the relatively slow precipitation rates of kaolinite may be the process controlling the formation of this mineral at the Earth's surface. This observation highlights the need to further quantify this secondary mineral precipitation rates at conditions typical at the Earth's surface. Moreover, as the composition of divalent metals released from crystalline basalts varies significantly with pH, CO2 carbonation in basalt should yield a systematic variation in the identity of carbonate and zeolite minerals precipitated with distance from the injection site. This latter conclusion can be tested directly as part of the currently on-going CarbFix project in Hellisheiði, Iceland

Les études concernant l'évolution chimique et structurale d'espèces d'aluminium en présence de salicylate ont été menées en combinant plusieurs méthodes d'analyses telles que l'électrophorèse, les spectroscopies infrarouges et RMN, les méthodes thermiques et de diffusion de rayonnement. Dans les cas étudiés, les agrégats d'Al13, la gibbsite et la montmorillonite intercalée par l'Al13, ces méthodes nous ont permis de mettre en évidence des changements structuraux important, du à la dissolution de l'aluminium en fonction de la concentration en ligand organique. L’interaction entre les espèces d'aluminium hydrolyse et le salicylate révèle deux phénomènes: la complexation et la dissolution. L’étude de la complexation nous a permis de mettre en évidence la nature et le type de complexation entre l'aluminium et le salicylate. Aux faibles concentrations en ligand, la complexation se fait sur les sites les plus réactifs, les sites charges Al-OH2+. Elle a pour effet de neutraliser le système et donc de condenser la structure des agrégats. Aux fortes concentrations en ligand, la complexation se poursuit sur les sites neutres, ce qui provoque la rupture des liaisons Al-O. La nature du complexe entre l'aluminium et le salicylate est un bidentate impliquant les oxygènes du groupement carboxyl. Ce complexe observé par IR est identique pour les agrégats et pour la gibbsite. La complexation entre le salicylate et l'aluminium a pour conséquence la dissolution des espèces étudiées. La caractéristique la plus marquante, observée pour les trois cas étudiés, est le fait que la dissolution ne commence que lorsque l'on apporte un excès de charge dans le système. La dissolution provoque des modifications structurales à plusieurs échelles sur les agrégats et la montmorillonite-Al13 mais pas sur la gibbsite: échelle locale, semi-locale et à grande distance. La cinétique de dissolution est quant à elle très différente selon la nature et l'environnement de l'aluminium

There are descriptions of various processes which can promote the elimination of the heavy metal ions present on aqueous waste. Most of those processes relays on the use of precipitating agents, such as hydroxides or sulfides. However these methods are open to criticism since they generated by themselves more solid wastes and there is no such thing as a totally insoluble salt. Other methods employ solid phases that can retain the ions trough adsorption or ion exchange mechanisms. There are, for instance, various reports describing the use of zeolites, aluminosilicates etc., on those retention processes with very significant results. Herein we report the study of the retention of the ion chrome by alumina, gibbsite, a commercial molecular sieves and kaolinite, an aluminosilicate found on the nature, using different conditions of concentration chromium in solution, temperature and contact time, complemented with studies on the discharge of the ion from these materials. Though the inner nature of the retention processes needs further experiments to be clarified, molecular sieves and gibbsite proved to be the most successful phase for the retention of the ion chrome due the almost absolutely ratio of the retention theirselves and their high resistance against leaching processes.
Encontram-se na literatura diferentes processos envolvendo tratamento de soluções contendo metais pesados na sua forma iônica. O método mais empregado para a remoção de metais pesados de efluentes baseia-se na precipitação dos cátions metálicos, em solução, pela adição de agentes precipitantes. Estes agentes podem ser soluções de hidróxidos ou de sulfetos, pois estas geram precipitados de baixa solubilidade. No entanto, apesar de muito eficiente, a precipitação é um método de tratamento sujeito a críticas porque gera um resíduo sólido e, portanto, não soluciona totalmente o problema. Assim, além dos métodos baseados em precipitação, existem os baseados em adsorção e troca iônica. Diversos estudos de retenção de metais pesados por adsorventes e trocadores iônicos têm sido relatados na literatura. Dentre eles, destacam-se os aluminossilicatos e, especificamente, as zeólitas. Neste trabalho, relatamos o estudo da retenção do íon cromo por alumina, gibbsita, uma peneira molecular comercial e caulinita, um aluminossilicato natural, em diferentes condições de concentração de cromo em solução, temperatura e tempo de contato entre as soluções e as fases estacionárias, paralelamente com estudos de lixiviação do íon cromo retido nesses materiais. Embora sejam necessários experimentos complementares para elucidar a natureza intrínseca do processo de retenção, verificou-se que a peneira molecular e a gibbsita são as fases mais eficientes para a retenção do íon cromo, ambas com capacidade de retenção quase total e alta resistência a processos de lixiviação.

L'objet de cette these est l'etude de certaines proprietes des mesures de gibbs sur un reseau et principalement la disparition de l'une d'entre elles, la quasilocalite, lorsque l'on applique a ces mesures des transformations dites du groupe de renormalisation, tres courantes en physique theorique. Nous decrivons aussi diverses tentatives de restauration du formalisme gibbsien, qui, a travers une definition affaiblie de la gibbsiannite, permettent d'obtenir une conservation de ce concept sous l'action de transformations du groupe de renormalisation. Alors que le chapitre 2 est consacre a une etude generale des mesures de gibbs, nous decrivons certaines pathologies des mesures images par le groupe de renormalisation dans le chapitre 3 et nous consacrons le chapitre 4 a la description de trois restaurations existant a l'heure actuelle, la presque quasilocalite, la gibbsiannite faible et la quasilocalite fractale. Nous donnons ensuite divers axes de recherches dans le chapitre 5 et une caracterisation des mesures de gibbs invariantes par translation, dite approche variationnelle, est decrite en annexe.

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A alumina é um dos óxidos mais importantes na indústria cerâmica, sendo utilizado principalmente na forma de alumina calcinada ou fundida sendo aplicada, dentre outras formas, como material adsorvente. Neste trabalho desenvolveu-se um método de produção de alumina de transição a partir da mistura de gibbsita, proveniente do processo Bayer, e hidróxido de alumínio gel, proveniente de reação de sulfato de alumínio e hidróxido de amônio visando a aplicação como material adsorvente para remoção de Cu 2+ em solução aquosa. Foram investigadas as condições de adsorção incluindo tempo de contato e pH. Os ensaios foram realizados a 30 oC e 50 ºC, nos quais 1 g de alumina produzida foi submetida a contato com 100 ml de uma solução aquosa contendo Cu2+. As concentrações das soluções aquosas empregadas foram de 100, 200, 400, 800, 1600 e 2000 ppm de solução de sulfato de cobre. A caracterização das soluções de sulfato de cobre foi realizada em espectrofotometria UV e a caracterização do material produzido foi realizada através de DRX, EDX e área superficial BET. Avaliou-se o tempo de contato para o alcance do equilíbrio de adsorção sendo este tempo otimizado em 15 min. O efeito do pH sobre a adsorção mostrou que aumentando a temperatura de adsorção há um aumento do valor de pH em relação ao pH da solução inicial de sulfato de cobre. As isotermas de Langmuir e Freundlich apresentaram resultados satisfatórios para adsorção, sendo a isoterma de Langmuir a que melhor se ajustou aos dados de adsorção. Através das isotermas de equilíbrio verificou-se que o material produzido tem boa capacidade de adsorção para o íon Cu2+.
Alumina is one of the most important oxides in the ceramic industry, being used mainly in the form of calcined alumina or fused applied, among other ways, as adsorbent material. In this work is a transition alumina production method from a mixture of gibbsite, from the Bayer process, gel and aluminum hydroxide, from the reaction of aluminum sulfate and ammonium hydroxide targeting the application as an adsorbent material for removing Cu2 + in aqueous solution. Adsorption conditions including contact time and pH were investigated. Assays were carried out at 30 ° C and 50 ° C, in which 1 g of alumina produced was subjected to contact with 100 ml of an aqueous solution containing Cu2 +. The concentrations of the aqueous solutions employed were 100, 200, 400, 800, 1600 and 2000 ppm copper sulphate solution. The characterization of copper sulfate solutions was performed in UV spectrophotometry and characterization of the material produced was carried out by XRD, EDX and BET surface area. Evaluated the contact time to achieve the adsorption equilibrium which is optimized time 15 min. The effect of pH on the adsorption shows that the adsorption temperature increases there is an increased pH compared with the pH of the initial solution of copper sulfate. The isotherms of Langmuir and Freundlich had satisfactory results for adsorption, and the Langmuir isotherm that better fits the adsorption data. Through the equilibrium isotherms it was found that the material produced has adsorption capacity for Cu2 + ion.

L'altération chimique des roches primaires et des minéraux dans les systèmes naturels a un impact majeur sur la formation des sols et leur composition. L'altération chimique est largement pilotée par la dissolution des minéraux. Les éléments chimiques libérés dans les eaux souterraines par la dissolution des minéraux réagissent facilement pour former des minéraux secondaires comme les argiles, zéolites et carbonates. Les carbonates se forment par réaction des cations divalents (Ca, Fe et Mg) avec CO2 dissous tandis que la formation des kaolins et de la gibbsite est attribuée à l'altération des minéraux riches en aluminium, le plus souvent les feldspaths. Le projet Carbfix à Hellisheiði (sud-ouest de l'Islande) a pour but d'utiliser les processus d'altération naturelle pour former des minéraux carbonatés par réinjection dans les roches basaltiques environnantes de CO2 provenant d'une centrale géothermique. Ce processus trouve son origine dans la dissolution des roches basaltiques riches en cations divalents (Ca, Fe et Mg) qui se combinent au CO2 injecté pour former des minéraux carbonatés. Cette thèse est centrée sur la dissolution du basalte cristallin de Stapafell qui est composé essentiellement de trois phases minérales (plagioclase, pyroxène et olivine) et qui est riche en cations divalents. La vitesse de libération des éléments du basalte à l'état stationnaire et loin de l'équilibre a été mesurée dans des réacteurs à circulation à des pH de 2 à 12 et des températures de 5 à 75°C. Les vitesses de libération de Si et Ca à l'état stationnaire présentent une variation en fonction du pH en forme de U avec une diminution des vitesses lorsque le pH augmente en conditions acides et une augmentation avec le pH en conditions alcalines. Les vitesses de libération du silicium par le basalte cristallin sont comparables à celles par le verre basaltique de même composition chimique aux faibles pH et aux températures ≥ 25°C mais elles sont plus lentes aux pH alcalins et aux températures ≥ 50°C. Par contre, les vitesses de libération de Mg et Fe diminuent de manière monotone avec l'accroissement du pH à toutes les températures. Ce comportement a pour cause les variations contrastées, en fonction du pH, des vitesses de dissolution des trois minéraux constitutifs du basalte: plagioclase, olivine et pyroxène. Les vitesses de libération des éléments déduites de la somme des vitesses de dissolution du plagioclase, pyroxène et olivine normalisées à la fraction volumique de ces minéraux sont, à un ordre de grandeur près, les mêmes que celles mesurées dans cette étude. En outre, les résultats expérimentaux montrent que, durant l'injection d'eaux chargées en CO2 de pH proche de 3.6, le basalte cristallin libère préférentiellement Mg et Fe en solution par rapport à Ca. L'injection de fluides acides chargés en CO2 dans des roches cristallines basaltiques peut donc favoriser la formation de carbonates de Mg et Fe aux dépends de la calcite aux conditions de pH acides à neutres. Le plagioclase, qui est la phase la plus abondante du basalte, influence fortement la réactivité de ce dernier. La vitesse de dissolution du plagioclase, basée sur la libération de la silice, présente une variation en forme de U en fonction du pH, diminuant lorsque le pH augmente aux conditions acides mais augmentant avec le pH aux conditions alcalines. En accord avec les données de la littérature, la vitesse de dissolution du plagioclase à pH constant, en conditions acides, augmente avec sa teneur en anorthite. L'interprétation et le fit des données obtenues suggèrent que la vitesse de dissolution du plagioclase est contrôlée par la décomposition d'un complexe activé riche en silice, formé par le départ de Al de la structure du minéral. Le plus remarquable, par comparaison aux hypothèses antérieures, est que la vitesse de dissolution du plagioclase en conditions alcalines est indépendante de sa teneur en anorthite - e.g. les vitesses de dissolution des plagioclases riches en anorthite augmentent avec le pH aux conditions alcalines. A ces conditions, il est probable que la vitesse de dissolution rapide du plagioclase domine, en raison de sa forte teneur en Ca, la libération vers la phase fluide des cations divalents du basalte cristallin. La gibbsite est généralement le premier minéral qui précipite lors de la dissolution du plagioclase. C'est un hydroxyde d'aluminium que l'on trouve dans divers sols et qui est aussi la phase principale des minerais de bauxite. Les vitesses de précipitation de la gibbsite ont été mesurées dans des réacteurs fermés, en conditions alcalines à 25 et 80°C, en fonction de l'état de saturation du fluide. Les analyses des solides après réaction ont démontré que la précipitation de gibbsite s'est produite dans toutes les expériences. L'interprétation de l'évolution dans le temps de la chimie du fluide réactif fournit des vitesses de précipitation de la gibbsite qui sont près des vitesses de dissolution du plagioclase. En plus, des vitesses de précipitation de la gibbsite diminuent plus rapidement que des vitesses de dissolution du plagioclase quand le pH descende. Ceci suggère que l'étape limitant de l'altération du plagioclase sur la surface de la terre est plutôt la consommation d'Al par formation de la gibbsite que la dissolution même du plagioclase. La kaolinite est en général le second minéral formé après la gibbsite lors de la dissolution du plagioclase à basse température. Les vitesses de précipitation de la kaolinite ont été mesurées dans des réacteurs à circulation à pH = 4 et t = 25°C, en fonction de l'état de saturation du fluide. Au total, 8 expériences de précipitation de longues durées ont été réalisées dans des fluides légèrement supersaturés par rapport à la kaolinite, en utilisant comme germes pour la précipitation une quantité connue de de kaolinite de Géorgie (KGa-1b) contenant peu de défauts et préalablement nettoyée. Les vitesses de précipitation de kaolinite mesurées sont relativement lentes comparées aux vitesses de dissolution du plagioclase. Cette observation suggère que la formation de kaolinite lors de l'altération est limitée par sa vitesse de précipitation plutôt que par que la disponibilité en Al et Si issus de la dissolution du plagioclase. L'ensemble des résultats de cette étude fournit un certain nombre de principes scientifiques de base nécessaires à la prédiction des vitesses et des conséquences de la dissolution du basalte cristallin et du plagioclase à la surface de la Terre et lors de l'injection du CO2 à proximité de la surface dans le cadre des efforts de stockage du carbone. Les résultats obtenus indiquent, bien que les vitesses de précipitation de la gibbsite soient relativement rapides, que la vitesse de précipitation relativement lente de la kaolinite peut être le processus contrôlant la formation de ce minéral à la surface de la Terre. Cette observation souligne la nécessité de poursuivre la quantification de la précipitation de ce minéral secondaire aux conditions typiques de la surface de la Terre. En outre, comme les proportions des différents métaux divalents libérés par les basaltes cristallins varient sensiblement avec le pH, la carbonatation des basaltes doit produire un changement systématique de l'identité des minéraux carbonatés et des zéolites précipités en fonction de la distance au puits d'injection. Cette dernière conclusion pourra être directement testée dans le cadre du projet CarbFix actuellement conduit à Hellisheiði en Islande.

Dissertação (mestrado)—Universidade de Brasília, Instituto de Geociências Aplicadas, 2013.
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O objetivo do presente estudo foi verificar a influência da correção atmosférica e de crosstalk a espacialização da relação Caulinita/(Caulinita+Gibbsita) em solos dos municípios de Niquelândia e de São João d’Aliança – GO, por meio da aplicação do índice espectral RCGb scale, desenvolvido por Baptista (2001), em imagens ASTER SWIR L1A e L1B, e em produtos sob demanda AST_07 e AST_07XT. Nesse estudo foram utilizados os módulos FLAASH e QUAC, para a correção atmosférica e o software CRSTX 30, para a correção do efeito crosstalk. A câmara SWIR do ASTER é afetada por um problema de “vazamento” de sinal, o crosstalk que ocorre nos detectores da banda 4 sobre os detectores das bandas vizinhas, ou seja, nas bandas 5 e 9, afetando o sinal detectado. Com isso, os espectros dos dados ASTER-SWIR apresentam um deslocamento das feições de absorção da caulinita, e essa, juntamente com a gibbsita são utilizadas para a determinação do grau de intemperismo os solos tropicais. De acordo com os resultados das imagens conclui-se que, para o município São João d’Aliança, para a investigação da relação mineralógica em solos, o produto sob demanda ASTER AST-07 – imagem de reflectância sem correção crosstalk e com correção atmosférica, a imagem L1B convertida para reflectância, com correção crosstalk, por meio do software CRSTK30 e com correção atmosférica, por meio da aplicação do algoritmo QUAC; a imagem de radiância L1B (radiância no nível do sensor) sem correção crosstalk e sem correção atmosférica; a imagem L1B convertida para reflectância, por meio do módulo Flat Field, sem correção crosstalk e sem correção atmosférica; a imagem L1B convertida para reflectância, por meio do módulo Flat Field, com correção crosstalk e sem correção atmosférica e produto sob demanda ASTER AST- 07XT – imagem de reflectância com correção crosstalk e com correção atmosférica são as mais adequadas. No caso de Niquelândia, a imagem de radiância L1B (radiância no nível do sensor) sem correção crosstalk e sem correção atmosférica; a imagem L1B convertida para reflectância, por meio do módulo Flat Field, sem correção crosstalk e sem correção atmosférica; a imagem L1B convertida para reflectância, por meio do módulo Flat Field, com correção crosstalk e sem correção atmosférica; a imagem L1B convertida para reflectância, com correção crosstalk, por meio do software CRSTK30 e com correção atmosférica por meio da aplicação do algoritmo FLAASH e a imagem de radiância L1A convertida para reflectância, sem correção crosstalk e com correção atmosférica por meio da aplicação do algoritmo QUAC, são as mais adequadas para a investigação da espacialização da relação Caulinita/(Caulinita+Gibbsita). Desse modo, os valores obtidos por meio da aplicação do RCGb scale , índice proporcional ao valor Ki dos solos, apresentaram proximidade aos valores referentes às amostras de campo na maioria dos processamento realizados tanto para Niquelândia como para São João d’Aliança, confirmando, assim a potencialidade desse índice sobre os dados ASTER. ______________________________________________________________________________ ABSTRACT
The aim of this study was to investigate the influence of atmospheric correction and crosstalk of the spatial relationship of kaolinite/(kaolinite + gibbsite) in soils of São João d’Aliança.- GO, by applying the spectral index RCGb scale, developed by Baptista (2001), ASTER images in L1A and L1B-SWIR, and AST_07 AST_07XT on-demand products. The area of study is located in São João d’Aliança-GO, that is cut by Serra Geral do Parana and has part of its area in Vale do Parana, which has flattened topography, with slopes less than 3% . For this paper FLAASH and QUAC modules were used for the atmospheric correction software, and CRSTX 30, to correct the crosstalk effect. The SWIR ASTER camera is affected by a problem of "leakage" signal, the crosstalk that occurs in the band 4 detectors on auto neighboring bands, ie, bands 5 and 9, affecting the signal detected. Considering that, the ASTER-SWIR spectra shows a shift of absorption features of kaolinite, and this, together with gibbsite are used for determining the degree of weathering of tropical soils. According to the results of the images we conclude that, for the county of São João d’Aliança, for mineralogical investigation of the relationship, the ASTER AST-07 product demand - image reflectance without crosstalk correction and with atmospheric correction, the L1B converted to reflectance image with crosstalk correction, through CRSTK30 software and atmospheric correction by applying the QUAC's algorithm, L1B radiance image (radiance at sensor level) without crosstalk correction and without atmospheric correction, the L1B image converted to reflectance through the Flat Field module, without crosstalk correction and atmospheric correction, the L1B image converted to reflectance through the Flat Field module, with crosstalk correction and without atmospheric correction ASTER AST-07XT product demand - reflectance image with rosstalk correction and atmospheric correction are the most appropriate. Where Niquelândia, the image of L1B radiance (radiance at sensor level) without crosstalk correction and without atmospheric correction, the image L1B converted to reflectance through the Flat Field module without crosstalk correction and without atmospheric correction, the image L1B converted to reflectance through the module Flat Field correction crosstalk with and without atmospheric correction, the image L1B converted to reflectance, with crosstalk correction, through software CRSTK30 and atmospheric correction by applying the algorithm and the image of radiance FLAASH L1A converted to reflectance, no crosstalk correction and atmospheric correction by applying the algorithm QUAC, are best suited for the investigation of the spatial relationship of kaolinite/(kaolinite+gibbsite). Thereby, the values obtained by applying the RCGb scale , Ki proportional index to the land value, presents proximity to the field samples figures in most processing done to Niquelândia and São João d’Aliança., thus confirming the potential of this index on ASTER data.

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
Planalto Ocidental Paulista (POP) é uma das principais áreas de cultivo de citros do país, representando cerca de 80% da produção nacional, tendo ainda grande participação na produção de açúcar e álcool. A caracterização e quantificação mineralógica dos solos desta região torna-se importante para melhor entendimento dos processos pedogênicos do solo, e uso de melhores práticas de manejo. Por meio de ferramentas como a geoestatística é possível entender a relação entre a mineralogia do solo e as formas da paisagem, indicando a variabilidade espacial dos dados e a dependência entre os atributos pedogênicos e os geomórficos da região. Assim, o presente trabalho teve como objetivos: a) caracterizar os teores e a cristalinidade da caulinita (Ct) e gibbsita (Gb), e suas relações com os diferentes compartimentos geológicos e geomorfológicos do POP; b) e avaliar o potencial de diferentes metodologias aplicadas às curvas espectrais, dada pela técnica de espectroscopia de reflectância difusa (ERD), para estimativa da razão entre Ct e Gb, e caracterizar a variabilidade espacial da razão para o POP. Foram coletadas 600 amostras de solo georreferenciadas, próximas às principais rodovias do estado de São Paulo. Para quantificação dos teores e cristalinidade da Ct e Gb foi utilizada a técnica de difratometria de raios X (DRX) e a metodologia de Rietveld. A quantificação não convencional pela técnica de ERD, foi feita por três metodologias aplicadas às curvas espectrais: contínuo removível, relação direta do vale e regressão mínima por quadrados parciais. Os dados foram submetidos a análises de estatística descritiva, análise de regressão (para comparativo entre as técnicas) e análises geoestatísticas, pela krigagem simples. Os compartimentos geológicos e geomorfológicos influenciam na distribuição dos teores de Ct e Gb, e na formação cristalográfica destes. Ambientes de geologia Arenítica apresentam maiores teores de Ct, menos cristalinas, e ambientes de Basalto maiores teores de Gb de maior cristalinidade. A ERD mostrou-se como uma técnica eficiente para a estimativa não convencional dos minerais, tendo a metodologia do contínuo removível apresentado os melhores parâmetros estatísticos, entre a comparação de valores dados pela DRX e pela ERD. A variabilidade espacial da razão entre Ct e Gb, apresentou padrões semelhantes entre os mapas de dados da DRX e ERD, para ambas as metodologias.
The Ouest Paulista Plateau (POP) is one of the main areas of citrus cultivation in the country, accounting for about 80% of the national production, with a large share of sugar and alcohol production. The characterization and mineralogical quantification of the soils of this region becomes important for a better understanding of the soil pedogenic processes, and the use of better management practices. Through tools such as geostatistics, it is possible to understand the relationship between soil mineralogy and landscape forms, indicating the spatial variability of the data and the dependence between the pedogenic and geomorphic attributes of the region. Thus, the present work had as objectives: a) to characterize the contents and crystallinity of kaolinite (Kt) and gibbsite (Gb), and its relations with the different geological and geomorphological compartments of POP; B) and to evaluate the potential of different methodologies applied to the spectral curves, given by the diffuse reflectance spectroscopy (DRS) technique, to estimate the ratio between Ct and Gb, and to characterize the spatial variability of the ratio for the POP. A total of 600 georeferenced soil samples were collected near the main highways in the state of São Paulo. The X-ray diffraction (XRD) technique and the Rietveld methodology were used to quantify the Ct and Gb contents and crystallinity. The unconventional quantification by the DRS technique was done by three methodologies applied to the spectral curves: removable continuous, direct ratio of the valley and minimum regression by partial squares. Data were submitted to descriptive statistics analysis, regression analysis (for comparison between the techniques) and geostatistical analysis, by simple kriging. The geological and geomorphological compartments influence the distribution of Kt and Gb contents and their crystallographic formation. Environments of sandstone geology have higher levels of Ct, less crystalline, and environments of basalt greater Gb levels of greater crystallinity. DRS proved to be an efficient technique for the unconventional estimation of minerals, and the methodology of the removable continuum presented the best statistical parameters between the comparison of values given by the XRD and the DRS. The spatial variability of the ratio between Kt and Gb presented similar patterns between the XRD and DRS data maps for both methodologies.
FAPESP: 2015/20692-0

Orientador: José Marques Júnior
Coorientador: Angélica Santos Rabelo de Souza Bahia
Banca: Adriana Aparecida Ribon
Banca: Newton La Scala Junior
Resumo: Planalto Ocidental Paulista (POP) é uma das principais áreas de cultivo de citros do país, representando cerca de 80% da produção nacional, tendo ainda grande participação na produção de açúcar e álcool. A caracterização e quantificação mineralógica dos solos desta região torna-se importante para melhor entendimento dos processos pedogênicos do solo, e uso de melhores práticas de manejo. Por meio de ferramentas como a geoestatística é possível entender a relação entre a mineralogia do solo e as formas da paisagem, indicando a variabilidade espacial dos dados e a dependência entre os atributos pedogênicos e os geomórficos da região. Assim, o presente trabalho teve como objetivos: a) caracterizar os teores e a cristalinidade da caulinita (Ct) e gibbsita (Gb), e suas relações com os diferentes compartimentos geológicos e geomorfológicos do POP; b) e avaliar o potencial de diferentes metodologias aplicadas às curvas espectrais, dada pela técnica de espectroscopia de reflectância difusa (ERD), para estimativa da razão entre Ct e Gb, e caracterizar a variabilidade espacial da razão para o POP. Foram coletadas 600 amostras de solo georreferenciadas, próximas às principais rodovias do estado de São Paulo. Para quantificação dos teores e cristalinidade da Ct e Gb foi utilizada a técnica de difratometria de raios X (DRX) e a metodologia de Rietveld. A quantificação não convencional pela técnica de ERD, foi feita por três metodologias aplicadas às curvas espectrais: contínuo removível, ... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: The Ouest Paulista Plateau (POP) is one of the main areas of citrus cultivation in the country, accounting for about 80% of the national production, with a large share of sugar and alcohol production. The characterization and mineralogical quantification of the soils of this region becomes important for a better understanding of the soil pedogenic processes, and the use of better management practices. Through tools such as geostatistics, it is possible to understand the relationship between soil mineralogy and landscape forms, indicating the spatial variability of the data and the dependence between the pedogenic and geomorphic attributes of the region. Thus, the present work had as objectives: a) to characterize the contents and crystallinity of kaolinite (Kt) and gibbsite (Gb), and its relations with the different geological and geomorphological compartments of POP; B) and to evaluate the potential of different methodologies applied to the spectral curves, given by the diffuse reflectance spectroscopy (DRS) technique, to estimate the ratio between Ct and Gb, and to characterize the spatial variability of the ratio for the POP. A total of 600 georeferenced soil samples were collected near the main highways in the state of São Paulo. The X-ray diffraction (XRD) technique and the Rietveld methodology were used to quantify the Ct and Gb contents and crystallinity. The unconventional quantification by the DRS technique was done by three methodologies applied to the spectral curves: removable continuous, direct ratio of the valley and minimum regression by partial squares. Data were submitted to descriptive statistics analysis, regression analysis (for comparison between the techniques) and geostatistical analysis, by simple kriging. The geological and geomorphological compartments influence the distribution of Kt and Gb con ... (Complete abstract click electronic access below)
Mestre

碩士
中興大學
土壤環境科學系所
95
Li/Al-Layered double hydroxides (Li/Al-LDHs) can be synthesized by intercalating Li+ salt into the structure of Al(OH)3 layer. In the structure of Li/Al-LDH, Li+ ions occupy the vacant sites in the dioctahedral Al(OH)3 layers. As a result, Li/Al-LDHs have high anion exchange capacity, and have been investigated for its potential applications as anion adsorbents. Li/Al-LDHs have been synthesized with a wide variety of anions, whose physical and chemical properties may play an important role in determing the structural stability of Li/Al-LDHs. In this study, the deintercalation reactions of Li/Al-LDHs with various interlayer anions were investgated for the effects of radius, shape and hydration energy of those anions. The results showed that, in general, the larger the hydration radius, the higher the deintercalation rate. An inverse relationship between the activation energy of the reaction and the hydration radius of the interlayer anions was also found. Therefore, in addition to columbic interaction among the interlayer anions and the positively charged hydroxide layers of Li/Al-LDHs, the interaction between interlayer anions and water, and the size and shape of these anions also play an important role in determing Li+ stability in Li/Al-LDHs.

碩士
國立成功大學
地球科學系
83
High-pressure Raman spectra of gibbsite were studied up to 23.3 GPa, in diamond anvil cell at room temperature. 23 Raman- active modes were observed at ambient conditions and predominantly located in two regions: the lower-frequency region and the higher-frequency region. The wavenumber of modes in lower-frequency region (200 ~1200 cm-1) increases linearly with increasing pressure, with the slope of 0.4~7cm-1/ GPa up to 3.25 GPa. On the other hand,the OH-stetching modes show decreasing wavenumber while increasing pressure, in agreement with the general observations that OH bonds in hydrous phases become weakened under pressure, such as brucite and portlandite. Based on the observed Raman spectra under pressure region in the present study, significant variations occur at 2.7±0.5 GPa , where a phase transformation may take place for gibbsite.At pressures higher than 2.7±0.5 GPa, some Raman modes disappear and other new ones grow up with the slopes of new bands increasing to 2.5~10 cm-1/GPa. Raman spectrum of the after-compressed-sample is different from that of gibbsite, showing the new phase may have peresisted to the ambient conditions. Similar behavior in gibbsite was observed in EDXRD (Li et al., 1995), and, thus, it may indicate a reconstructive phase transformation at 2.7±0.5GPa. On the basis of the present data, no sign of dehydration occurring up to 23.3 GPa is indicated, and gibbsite sample after pressure release is likely consistent with the polymorphs of Al(OH)3 - nordstrandite.