Respirable coal mine dust (RCMD) has long been recognized as an occupational health hazard. In addition to coal, RCMD can contain minerals such as crystalline silica (i.e., most often present as quartz). There has been a resurgence of lung diseases among US coal miners since the late-1990s which has emphasized the need for better quartz monitoring, and better dust characterization in general. Quartz monitoring in coal mines has traditionally used infrared (IR) spectroscopy-based analytical methods such as the MSHA Method P7 that require significant sample preparation and must be performed in a centralized lab. There are generally thus days to weeks between dust sample collection and reporting of results, which can prevent the prompt mitigation efforts to better control dust and reduce exposures. Recently, a rapid analysis method for quartz has been developed by the US National Institute for Occupational Safety and Health (NIOSH) using direct-on-filter (DOF) Fourier Transform Infrared (FTIR) spectroscopy. The method has been demonstrated in a number of NIOSH-led studies using both laboratory and field samples, and the results show very good accuracy relative to the Method P7 reference. However, it has heretofore not been widely used by others or compared to results from other non-IR analytical methods. Moreover, while FTIR can allow the measurement of additional analytes, this has not yet been a focus of DOF FTIR for RCMD analysis. Analytes such as kaolinite and calcite could be of particular interest in the context of RCMD source apportionment. In this thesis, the DOF FTIR method is used to estimate silica, kaolinite, and calcite mineral fraction in RCMD samples collected in 16 coal mines, and in the laboratory using dust source materials from those same mines. The results are compared to results from other dust characterization methods such as mass-based thermogravimetric analysis (TGA) and particle-based scanning electron microscopy with energy dispersive X-ray (SEM-EDX). Results indicate the usefulness of the DOF FTIR method, and comparison suggests the presence of significant non-carbonate minerals other than silica and kaolinite in the coal mine dust. The results also show that SEM-EDX frequently indicates more mineral content (primarily other aluminosilicates), than that is predicted by either FTIR or the TGA. Additionally, by focusing mainly on calcite (generally sourced from limestone-based rock dust used in coal mines to prevent coal dust explosion), the second part of this study explores basic source apportionment by analyzing mine samples and samples of major dust source materials (such as run-of-mine coal, rock strata, and rock dust products). Results show that calcite can serve as a suitable proxy for rock dust in coal mine dust, and the results are consistent with expectations surrounding the contribution of dust from different mine locations and sample sources. Additionally, the DOF FTIR also showed good agreement with the TGA and SEM-EDX. / Master of Science / Respirable dust generated in coal mines has long been recognized as an occupational health hazard. In addition to coal, coal mine dust can contain minerals such as crystalline silica, which is particularly hazardous. Since the mid-1990s, there has been an alarming and unexpected increase in lung diseases in coal miners. Respirable crystalline silica is assumed to be a likely causal factor for this resurgence of lung diseases, and this has emphasized the need for better respirable crystalline silica monitoring and to better understand coal mine dust composition. The standard method of measurement of silica (called the MSHA Method P7) generally takes days to weeks between dust sample collection and reporting of results, which can prevent the mine from taking prompt mitigative efforts to better control dust and reduce exposures. Recently, a rapid analysis method for silica has been developed by the US National Institute for Occupational Safety and Health (NIOSH) called the DOF FTIR (direct-on-filter Fourier Transform Infrared Spectroscopy). This method has been shown to have very good accuracy relative to the standard method (MSHA P7). However, it has heretofore not been widely used by others or compared to results from other analytical methods. Moreover, DOF FTIR can also be used to estimate other minerals of interest such as kaolinite and calcite, which can be important in the context of understanding coal mine dust sources. In this thesis, the DOF FTIR method is used to estimate silica, kaolinite, and calcite mineral fraction in coal mine dust samples collected in 16 coal mines, and in the laboratory using dust source materials from those same mines. The results are compared to results from other dust analysis methods such as mass-based TGA (thermogravimetric analysis) and particle-based SEM-EDX (scanning electron microscopy with energy dispersive X-ray). Results indicate the usefulness of the DOF FTIR method, and comparison suggests the presence of significant non-carbonate minerals other than silica and kaolinite in the coal mine dust. The results also show that SEM-EDX frequently indicates more mineral content than that is predicted by either FTIR or the TGA. Additionally, by focusing mainly on calcite—which is generally sourced from limestone-based rock dust used in coal mines to prevent coal dust explosion—the second part of this study explores the sources of the dust by analysing samples collected in mines, and samples generated in lab from major dust source materials (such as the raw coal, rock strata, and rock dust products obtained from the mines). Results show that calcite can be representative of rock dust in coal mine dust, and the results are consistent with expectations surrounding the contribution of dust from different mine locations and sample sources. Additionally, the DOF FTIR also showed good agreement with the TGA and SEM-EDX.

Ce travail concerne l’étude de l’effet des impuretés sur les phénomènes physico-chimiques apparaissant durant le frittage des kaolins entre 900 et 1600 °C et les propriétés physiques qui en découlent. Le kaolin est utilisé dans le domaine des céramiques : céramique traditionnelle, porcelaine, céramiques réfractaires (mullite, chamotte), porcelaines électrotechniques, etc… Il est d’usage de contrôler la teneur et la nature des impuretés car leur présence peut limiter leurs applications.Sept kaolins ont été choisis pour les impuretés qu’ils contiennent à savoir ;• Feldspaths, quartz et oxydes de fer pour les kaolins de Tamazert (Algérie)• Matières organiques et oxyde de manganèse pour les kaolins de Djebel Debbagh (Algérie).• Matières organiques, oxydes de fer, gibbsite et anatase pour les kaolins des Charentes (France). La kaolinite ou l'halloysite, de même composition, est le minéral majeur dans chaque cas. L'ensemble des matériaux a été réduit par broyage à la taille de 63 μm. Le premier volet de l’étude consiste en une caractérisation physico-chimique des différents kaolins pour identifier et quantifier les principaux minéraux qui les composent. Le second volet concerne la compréhension des transformations thermiques qui se produisent lors du processus de deshydroxylation de la kaolinite (metakaolin) et lors de la formation de la mullite et de la cristobalite à de hautes températures (1600 °C). La microstructure, le retrait, la densification, la porosité sont les principaux paramètres étudiés dans ce volet.Le troisième volet porte sur les propriétés des kaolins lors du frittage à savoir : Les propriétés colorimétriques, mécaniques et diélectriques. L’effet des impuretés ainsi que la microstructure lors du frittage sur ces propriétés (colorimétrique, mécaniques et diélectriques) sont largement développés. Lors du frittage des différents kaolins la taille des cristallites de mullite augmente avec la température. Ces cristallites incorporent les impuretés colorantes tels que Fe2+/Fe3+, Ti4+/Ti2+ et Mn4+/Mn2+ (selon la température), ce qui résulte dans l’augmentation de la chromaticité et la diminution de la clarté à partir de 1100 °C. La transformation de la phase anatase à la phase rutile diminue le paramètre de clarté des kaolins des charentes. La présence de cristobalite dans le cas du kaolin de Djebel Debbagh riche en manganèse participe à l’augmentation de sa clarté au delà de 1400 °C. La présence de feldspath dans les kaolins de Tamazert améliore leurs propriétés diélectriques grâce à la formation de la phase vitreuse. Lors de l’augmentation de la température à1300 °C, ces propriétés augmentent, elles diminuent avec l’augmentation des fréquences (107-109Hz). Les pertes diélectriques sont plus importantes par rapport à celles rencontrées dans les matériaux céramiques (Porcelaines) utilisés dans les diélectriques qui sont en générale <10-3. Une dernière partie est consacrée à l’application d'un kaolin naturellement riche en anatase dans le domaine des porcelaines diélectriques. L’identification et la quantification des phases formées durant le frittage à 1300 °C , la porosité, la microstructure (observée par MEB) et les propriétés mécaniques et diélectriques sont déterminés. La permittivité relative théorique des porcelaines obtenues, calculée en utilisant la règle des mélanges des phases minéralogiques formées est en bon accord avec les valeurs expérimentales trouvées. / This work concerns the study of the effect of impurities on the physico-chemical phenomena occurring duringthe sintering of kaolin between 900 and 1600 °C and the resulting physical properties. Kaolin is used in the field ofceramics: traditional ceramics, porcelain, refractory ceramic (mullite, chamotte), electrotechnical porcelain, etc. ... It iscustomary to control the content and nature of impurities that may limit their applications.Seven kaolin were selected for the impurities they contain namely; Feldspar, quartz and iron oxides in kaolin of Tamazert (Algeria). Organic matters and manganese oxide for kaolin of Djebel debbagh (Algeria). Organic matter, iron oxides, gibbsite and anatase in kaolin of Charentes basin (France).Kaolinite and halloysite, with the same composition, is the major mineral in each case. All the materials werereduced by grinding to the size of 63 μm.The first part of the study consists of physico-chemical characterizations of different kaolin to identify andquantify the major minerals that compose them.The second part concerns the understanding of thermal transformations that occur during the process ofdehydroxylation of kaolinite (metakaolin) and during the formation of mullite and cristobalite at high temperatures(1600 ° C). The microstructure, shrinkage, densification, the porosity are the main parameters studied in this part.The third part deals with the properties of kaolin during sintering where colorimetric, mechanical and dielectricproperties were studied.The effect of impurities and the microstructure during sintering of these properties (color, mechanical anddielectric) are widely developed. During sintering, crystallite size of mullite of different kaolins increases withtemperature. These crystallites incorporate impurities coloring such as Fe2 +/ Fe3 +, Ti4 +/ Ti2 + and Mn4 +/ Mn 2 +(depending on temperature), resulting in the increase of the chromaticity and the decrease in brightness from 1100 ° C.The transformation of anatase to rutile phase decreases the parameter of clarity of the charente kaolin. Presence ofcristobalite in the case of kaolin of Djebel Debbagh (which is rich in manganese) participates to the increase in claritybeyond 1400 ° C. The presence of feldspar in kaolin of Tamazert improves their dielectric properties through theformation of the glassy phase. When increasing the temperature at 1300 ° C, these properties increase. Relativepermittivity of the calcined kaolin decrease with increasing frequency (107-109Hz). The dielectric losses are largercompared to those found in materials used in the dielectric which are in general <10-3.The last part is devoted to the application of kaolin naturally rich in anatase in the field of dielectric porcelain.The identification and quantification of phases formed during sintering at 1300 °C, porosity, microstructure (observedby SEM) and mechanical and dielectric properties are determined. The theoretical relative permittivity obtained bycalculation using a mixing rule of the mineralogical phases formed agrees with the experimental values.

Le développement d'un colorant naturel sensibilisateur pour les applications de cellules solaires a attiré beaucoup d'attention en raison de ses avantages inhérents, tels que son faible coût, la préparation simple, les ressources facilement disponibles et le respect de l'environnement. Toutefois, les principaux problèmes liés à la cellule solaire sensibilisée par colorant (CSSC) sont une faible photostabilité et une faible efficacité. Dans cette thèse, la bixine extrait de graines de rocou (Bixa orellana L.) a été utilisée comme sensibilisateur. Pour améliorer sa stabilité et la performance des CSSC, l’utilisation de la kaolinite activée a également été étudiée. Une CSSC à haute efficacité nécessite une photo-électrode avec une grande surface spécifique pour adsorber efficacement le colorant. Ainsi le couple TiO2/kaolinite a été préparé dans ce but. Il est considéré que la kaolinite peut confiner la lumière incidente à l'intérieur de l'électrode et peut aussi améliorer la conduction d'électrons. Dans ce système, la kaolinite a également un rôle important pour accroître la photostabilité de la bixine. Un autre facteur affectant les performances des CSSC est le rôle important de l’électrolyte. Dans ces travaux, les carbonates organiques cycliques qui ont une constante diélectrique élevée et aussi un point d’ébullition élevé (plus de 300oC) ont été évalués comme solvants de l’électrolyte. Ces travaux ont été réalisés en quatre étapes: (1) extraction, purification et caractérisation de la bixine, (2) préparation, activation et caractérisation de la kaolinite, (3) étude d’adsorption de la bixine sur la surface de la kaolinite et du TiO2, et (4) fabrication des cellules solaires sensibilisées par la bixine (CSSB). Les résultats montrent que l’extraction accélérée par solvant en utilisant un mélange de 60% de cyclohexane et 40% d’acétone peut être une méthode d’extraction efficace pour la bixine. Après purification par la chromatographie flash, la bixine est isolée avec un dégré de pureté de 99,86%. Elle est composée de 88,11% de cis-bixine et 11,75% de dicis- bixine. L’activation par l’ammoniaque de la kaolinite calcinée (la métakaolinite) est une bonne méthode pour produire la kaolinite avec une très grande surface spécifique et un rapport Si/Al élevé. L’étude d’absorption de la bixine a montré que le carbonate de diméthyle est un solvant approprié pour la bixine. Il permet à la bixine un coefficient d’absorption élevé et de bonnes caractéristiques d’adsorption sur la surface de la photo-électrode. L’adsorption de monocouche de la bixine sur la surface de TiO2 ou la surface de la kaolinite est plus favorable pour obtenir un rendement énergétique plus élevée. La présence de la métakaolinite activée dans la photo-électrode TiO2 a contribué à améliorer les performances et la stabilité de la CSSB par rapport à la CSSB fabriquée avec la photoélectrode de TiO2 pur. Ces performances sont reproductibles. L’électrolyte exerce un effet synergétique avec la métakaolinite activée en faveur de l’amélioration des paramètres électriques de la CSSB. Sous une intensité lumineuse de 200 W/m2, la CSSB comprenant une photo-électrode de TiO2 modifié par 5% de métakaolinite activée et un système électrolyte de KiI/I2 dans l’acétate de carbonate de glycérol produit un rendement énergétique de (0,050+0,006)%, ce qui est plus élevé que celui de la CSSB comprenant une photo-électrode de TiO2 pur (0,027+0,012)%. L’utilisation d’un couple redox de LiI/I2 dans l’acétate de carbonate de glycérol produit le rendement maximum (0,086+0,014)%. La fonction de stockage et de chargement d’énergie des CSSB fonctionnent bien jusqu’au troisième jour de l’analyse. A ce jour, la CSSB fabriquée en utilisant la photoélectrode de TiO2 modifiée par la métakaolinite activée est 16 fois plus stable que celle de la CSSB fabriquée en utilisant la photo-électrode de TiO2 pur. / The development of natural dye sensitizer for solar cell applications has attracted much attention because of its inherent advantages such as low cost, simple preparation, readily available resources, and low impact in the environment. However, the main problems related to dye-sensitized solar cell (DCCS) are low photostability and low efficiency. In this thesis, the bixin extracted from annatto (Bixa orellana L.) seeds was used as sensitizer. To improve its stability and the performance of the DSSC, the use of activated kaolinite was also studied. A high efficiency DSSC requires a photo-electrode with a high surface area to effectively adsorb the dye. So the couple of TiO2/kaolinite photo-electrode was prepared for this purpose. It is considered that kaolinite can confine the incident light within the electrode and can also improve the conduction of electrons. In this system, kaolinite also has an important role to increase the photostability of bixin. Another factor affecting the performance of DSSC is the important role of the electrolyte. In these studies, cyclic organic carbonates that have a high dielectric constant and also a high boiling point (above 300oC) were evaluated as solvents in the electrolyte. These works were carried out in four stages: (1) extraction, purification and characterization of bixin, (2) preparation, characterization and activation of kaolinite, (3) study of adsorption of bixin on the surface of kaolinite and TiO2, and (4) manufacturing of bixin sensitized solar cell (BSSC). The results show that the accelerated solvent extraction using a mixture of 60% cyclohexane and 40% acetone can be an effective method of extraction for bixin. After purification by flash chromatography, bixin with a degree of purity of 99.86% was isolated. It is composed of 88.11% cisbixin and 11.75% di-cis-bixin. The activation of calcined kaolinite (metakaolinite) by ammonia is a good method to produce kaolinite with very high specific surface area and a higher Si/Al ratio. The absorption study bixin has shown that the dimethyl carbonate is a suitable solvent for bixin. It allows bixin to have a high absorption coefficient and good adsorption characteristics onto the surface of the photo-electrode. The monolayer adsorption of bixin on the surface of TiO2 or kaolinite is more favorable to obtain higher energy efficiency. The presence of activated metakaolinite in the photo-electrode TiO2 has proven to improve the performance and stability of the BSSC compared to the BSSC manufactured with the pure TiO2 photo-electrode. These performances are reproducible. The electrolyte has a synergistic effect with the activated metakaolinite for improving the electrical parameters of the BSSC. Under a light intensity of 200 W/m2, the BSSC including a photo-electrode of TiO2 modified by 5% of the activated metakaolinite and KI/I2 electrolyte system in glycerol carbonate acetate produced an energy efficiency of (0.050+ 0.006)%, which is higher than that of the BSSC comprising a pure TiO2 photoelectrode (0.027+0.012)%. The use of LiI/I2 a redox couple in the glycerol carbonate acetate produces the maximum energy efficiency of (0.086+0.014)%. Its function of energy storage and loading worked well until the third day of analysis. To date, the BSSC manufactured using the photoelectrode TiO2 modified by activated metakaolinite is 16 times more stable than the BSSC manufactured using the pure TiO2 photo-electrode.

Marine clay deposits are characterized by very soft to soft consistencies (undrained strength 1-50 kPa), presence of saline pore solution and low-swelling clays. Besides, loss of metastable structure on disturbance, poor undrained strengths of soft clays is contributed by high water contents. Presence of saline pore solution and low-swelling clays (illite, chlorite, kaolinite) play an important role in developing metastable structure of soil sediments deposited in marine environment. The pore solution salinity regulates the “physico-chemical (A - R) stress” that in turn has significant bearing on development of the metastable structure. Metastable structure refers to edge-face, edge-edge associations in card-house arrangement of platy/elongate particles that develop during deposition. Loss of metastable structure of soft marine clays upon disturbance leads to excessive settlements and slope failures. Besides A - R forces, metastable structure of marine clays is contributed by cementation bonds, thixotropic hardening, ion leaching, formation or addition of dispersing agents and chemical weathering. Secondary compression also causes bonding of micro-structural units that increase stiffness and strength of the metastable structure. Review of literature brings out that majority of studies examining the role of physico-chemical factors on the engineering behavior of marine clays have focused on illite rich sediments. However, non-swelling clay, namely, kaolinite is also encountered in marine deposits (example, Pusan clay, Singapore clay, Sarapui soft clays). Kaolinites differ from illites in being 1:1 mineral (unit layer comprises of 1 silica sheet bonded to 1 gibbsite sheet) and having strong hydrogen bonding between unit layers. Consequently, kaolinite particles are thick (0.3 to 3 ìm thickness) with low surface area (10 to 20 m2/g). Also the hydrogen bonding between unit layers do not allow them to separate on hydration. Combination of very low isomorphous substitution (Al for Si 1 in 400), low cation exchange capacity (3 meq/100g), and low surface area, lead to negligible development of diffuse double layer repulsion forces between kaolinite particles. Strong positive edge (developed on broken bonds at particle edges from adsorption of hydrogen ions) negative face attraction between kaolinite particles, encourages flocculation of particles at range of water contents. It was therefore considered of interest to examine the engineering response of kaolinites to changes in pore solution salinity from leaching effects. The focus of the thesis is hence to gain better understanding of physico-chemical (pore solution salinity, A - R forces) and mechanical (secondary compression, loss of overburden) factors towards development of metastable structure of kaolinite clays deposited in synthetic seawater environments in the context of their compressibility and undrained strength characteristics. Laboratory experiments are performed with kaolinites that are slurry consolidated in conventional consolidometers in saline and synthetic seawater solutions. The metastable structure developed by consolidated specimens is relevant to alluvial marine sediments that contain kaolinite (example, Pusan clay, Singapore clay, Sarapui soft clays). The structure of the thesis is as follows: Chapter 1 gives an introduction to the thesis. Chapter 2 provides a detailed review of literature on the role of chemical factors (pore solution composition, A - R forces, osmotic suction) and mechanical processes (secondary compression and overconsolidation) in developing metastable structure of kaolinite specimens subjected to slurry consolidation and the consequent influence of metastable structure on compression, undrained strength and sensitivity characteristics of clay specimens. The Chapter also defines the scope and objectives of the study. Chapter 3 details the experimental program undertaken to bring out the role of chemical factors and mechanical processes in influencing the 1-dimensional compression and undrained strength characteristics of slurry consolidated kaolinites prepared in saline medium. Chapter 4 delineates the role of chloride salt solutions (sodium, magnesium and calcium) and synthetic seawater solution in contributing to the metastable structure developed by slurry consolidated kaolinites at various vertical effective stress (óv’) and the consequent influence of metastable structure on 1-dimensional compression, undrained strength and sensitivity characteristics of the clay. Chapter 5 examines influence of secondary compression on metastable structure developed by kaolinites that were slurry consolidated in 24.53 g/L sodium chloride and synthetic seawater solutions and the consequence of the developed metastable structure on undrained strength and sensitivity. The chapter also examines the consequences of secondary compression experienced by soft overconsolidated kaolinites on their undrained strength and sensitivity characteristics. Chapter 6 examines the relative influence of differential osmotic stress and electrochemical stress on the consolidation behaviour of kaolinite specimens that are slurry consolidated in sodium chloride solutions. The osmotic efficiencies (á) of kaolinite were obtained using the Fritz-Marine Membrane Model. Chapter 7 summarizes the major conclusions of the thesis.

Cette étude porte sur des films composites à base d'amidon de manioc plastifié au glycérol et d'une argile kaolinique, comme charge minérale. L'origine et les mécanismes des interactions argile-amidon et leur rôle sur les propriétés des films ont été examinés. Pour vaincre le caractère non-expansible de la kaolinite, l'analyse du mécanisme de son exfoliation a été effectuée par insertion du diméthylsulfoxyde suivi d'un échange en milieux acétate d'éthyle et acétate d'ammonium. Une forte déstructuration de l'édifice cristallin de la kaolinite suite à l'échange est observée. La réassociation des feuillets après échange est désordonnée et permet d'escompter une meilleure dispersion de la kaolinite intercalée au sein d'un polymère. Ceci est confirmé par les analyses comparées de microscopies et de diffraction des rayons X sur des films incorporant diverses doses d'argile brute ou intercalée. L'abaissement de la température de transition vitreuse et du module élastique, ainsi que l'accroissement des effets de barrières à la décomposition thermique, à la diffusion de vapeur d'eau et à la transmission des UV visibles confirme la dispersion meilleure de la kaolinite intercalée. L'orientation des chaînes d'amidon et la diffusion du plastifiant transporté à l'interface par l'argile sont les mécanismes qui justifient l'effet plastifiant apporté par l'argile. L'interférence des interactions amidon-argile sur les interactions chaîne-chaîne au sein de l'amidon participe à la plasticité des films en diminuant la cristallinité. Les interactions amidon-argile se sont avérées faibles du fait des répulsions électrostatiques associées à des interactions associatives de type pont hydrogène / In this study, composites films made from glycerol plasticized cassava starch and a kaolinite clay, as mineral filler, were studied. The origin and mechanisms of clay-starch interactions and their role on films properties are examined. To deal with the unexpandable nature of kaolinite, an analysis of its exfoliation mechanism was done through dimethylsulfoxide (DMSO) intercalation followed by DMSO displacement using ethyl acetate and ammonium acetate. The crystalline structure of kaolinite is deeply disordered upon DMSO displacement because of a random reassociation of the clay layers. A better dispersion of the intercalated kaolinite within a polymer matrix is then expected. This expectation was confirmed by the comparison of microscopes and X-ray diffraction analyses on films charged with various dosages of raw or DMSO intercalated kaolinite. The lowering of the glass transition temperature and the elastic modulus together with the increase of barrier effects to thermal decomposition, water vapour diffusion and visible UV transmission, confirmed that the intercalated kaolinite is better dispersed. The starch chain orientation coupled to increase starch/glycerol miscibility due to the transportation of glycerol at the interface by clay particles are the two mechanisms that better explained plasticization effect induced by the filler. The interference of starch-kaolinite interactions on starch chain-chain interactions caused a decrease of starch matrix cristallinity that contribute to increase plasticization. The starch-kaolinite interactions are found to be weak due electrostatic repulsion associated to some weak associative forces due to hydrogen bonds

Dans le contexte de stockage des déchets radioactifs en profondeur, des interactions entre le fer métal d’une part et la roche du Callovo-Oxfordien (COx), sa fraction argileuse purifiée (SCOx) ou des phases argileuses pures (kaolinite, illite, smectites) d’autre part, sont réalisées à 90°C sous atmosphère anoxique en solution chlorurée-salée. Le rôle des minéraux non argileux du COx est également étudié. L'oxydation rapide du fer métal entraine une libération d’ions fer en solution, une augmentation du pH et une diminution du Eh (réducteur). Une dissolution partielle des phases argileuses ainsi que la précipitation de serpentines ferrifères (odinite ou berthiérine, principalement) et de magnétite en faible quantité sont alors observées. En cas d’apport d'O2 au système, les serpentines ferrifères sont déstabilisées. L'exsolution du fer permet la formation d'oxydes et d’hydroxydes de fer et des particules argileuses proches des phases initiales précipitent. Lorsque du quartz est ajouté à SCOx, la dissolution partielle de ce minéral est responsable de la modification des chemins réactionnels. La formation de magnétite est alors limitée et les serpentines ferrifères sont enrichies en silice. Dans le cas de la kaolinite, DRX, MET, XPS et analyses texturales mettent en évidence la croissance des serpentines ferrifères (berthierines majoritairement) sur la surface basale des kaolinites, formant des particules kaolinite-serpentines-Fe démixées. Les techniques spectroscopiques (Mössbauer, XAS et STXM) permettent de déterminer les rapports Fe2+/Fe3+ et AlIV/AlVI jusqu'au niveau des particules élémentaires et de proposer des formules structurales pour ces serpentines ferrifères / In the context of underground disposal of high-level radioactive waste, interactions between metallic iron and Callovo-Oxfordian rock (COx), its purified clay fraction (SCOx) or pure clay phases (kaolinite, illite, smectites) were investigated at 90°C under anoxic atmosphere in chlorine solution. Role of COx non clay minerals in these reactions was also studied. Rapid metallic iron oxidation conducts to iron cations release in solution, pH increase (8-10) and Eh decrease (reducive conditions). The partial dissolution of initial clay phases and the crystallization of Fe-serpentines (odinite or berthierine mainly) and of low amount of magnetite were observed. The introduction of O2 into the system leads to Fe-serpentines destabilisation. Iron exsolution conducts to iron oxides and hydroxides formation and clay particles with composition close to the initial ones precipitate. Addition of quartz into the system leads to the partial dissolution of this mineral and to the modification of reaction pathways. Precipitation of magnetite is reduiced and Fe-serpentines are silica enriched. In the case of kaolinite-metallic iron interaction, combinated used of XRD, MET, XPS and textural analyses evidences the growth of berthierine on the basal face of kaolinites, resulting in Fe-serpentine-kaolinite demixed particles. Through the used of spectroscopic analyses (Mössbauer, XAS and STXM), we were able to determine Fe2+/Fe3+ and AlIV/AlVI ratio in elementary particles, which allows proposing structural formulae for the Fe-serpentines

Cette étude a fait l'objet de deux parties. L'une porte sur l'effet de différents types d'activation (chimique, thermique, mécanique) de kaolins (géo-matériaux riches en kaolinite) sur leurs propriétés de décoloration vis-à-vis de l'huile de riz. L'autre traite de l'effet de la taille et de la morphologie de kaolinites de synthèse sur leurs propriétés d'adsorption.Cette étude a montré que lorsque le kaolin était chauffé à plus de 100°C avant de subir une activation acide en milieu sulfurique, citrique ou oxalique, la capacité de décoloration vis-à-vis de l'huile de riz était fortement réduite. Cet effet a été directement mis en relation avec la destruction partielle ou totale de la structure de la kaolinite, associée à une forte lixiviation de l'aluminium de l'échantillon et à la précipitation de silice amorphe. Il s'est donc avéré que la préservation des sites aluminols présents sur les surfaces externes des particules de kaolinites semblait être un critère primordial à conserver en vue d'obtenir de bonne capacité de décoloration. Dans ce contexte, les meilleures capacités de décoloration (82% environ) ont été obtenues en utilisant conjointement un traitement thermique modéré (<100°C), un broyage mécanique de l'échantillon avant l'étape d'activation acide, une concentration en acide de l'ordre de 0.3 à 0.5 mol/L et un rapport (argile)/(solution acide) de l'ordre de 1/50. Notons que les plus fortes valeurs de surfaces spécifiques n'ont pas forcément été associées aux échantillons présentant les meilleures capacités de décoloration en raison de la présence de silice amorphe et de la non-préservation des sites aluminols de la kaolinite ; sites responsables de l'adsorption des pigments de molécules de chlorophylle-a.Par ailleurs, aucune étude à notre connaissance ne reliait directement les morphologies de particules de phyllosilicates à leurs propriétés d'adsorption vis-à-vis de deux cations inorganiques. Dans le cas des kaolinites naturelles, une charge permanente souvent significative et attribuable à des impuretés minéralogiques empêche toute tentative de relier directement la forme des particules à un coefficient de sélectivité entre deux cations pour des sites latéraux donnés. Des kaolinites ont donc été synthétisées par voie hydrothermale en considérant différentes conditions physico-chimiques, afin d'obtenir des morphologies variées (hexagones plus ou moins anisotropes). Pour ces échantillons synthétiques pour lesquels aucune impureté minéralogique et charge permanente n'a été détectée, des isothermes expérimentales d'adsorption entre Na+ et H+ ont été mesurées. Ces cations ont été choisis étant donné leur présence ubiquiste dans les eaux naturelles et leur fort pouvoir compétiteur par rapport aux cations traces métalliques. Grâce aux surfaces spécifiques des sites latéraux et des densités de site issues de la cristallographie des différentes faces présentes dans nos échantillons ((010), (110), (1-10)), un coefficient de sélectivité entre Na+ et H+ sur l'ensemble des sites latéraux d'une morphologie donnée a pu être estimé à l'aide d'un modèle de complexation de surface. Les résultats ont montré que le coefficient de sélectivité Na+/H+ dépendait très fortement de la morphologie de la particule, et que par conséquent les propriétés d'adsorption des kaolinites ne pouvaient pas être obtenues avec précision sans une connaissance fine de la morphologie des particules. / The dissertation consists of two main parts; the first part is devoted to the effect of physical/thermal and chemical activation of kaolin on bleaching of rice bran oil. In this study, samples were prepared from natural Ranong kaolin. This study focused on the effects of both thermal treatment (from 100 to 900°C) and chemical activation (sulfuric acid, hydrochloric acid, citric acid and oxalic acid using different acid concentrations or different clay/acid ratio) on the capacity of kaolins to bleach rice bran oil. When kaolin was treated with high temperature (>100°C) prior to reflux and with a high acid concentration during reflux, the kaolinite structure was partially or completely destroyed associated to a dramatic leaching of alumina, and amorphous silica dominated the samples. The measured maximum bleaching capacity obtained was not consistent with the highest specific surface area and pore volume; rather, it depended on the alumina contents in the samples. Thus, the partial preservation of the kaolinite structure is crucial to obtain an appropriate bleaching capacity of kaolin. This is directly related to the preservation of the aluminol sites present at the kaolinite surface. XRF analysis showed that the alumina contents of 28-34% were values to reach in order to obtain optimum bleaching capacities of kaolin, independently of the different acid used. Finally, optimum bleaching of ~83%, ~82% and ~81% were achieved by grinding the kaolin prior to reflux with low acid concentration of hydrochloric acid (0.5 M), sulfuric acid (0.3 M) and citric acid (0.5 M), respectively with clay/acid ratio of 1:50.The second part of the thesis aims to elucidate the influence of morphology of kaolinites on their sorption properties. For that, Na+/H+ sorption isotherms in water saturated conditions of synthetic kaolinites and natural well crystallized kaolinite, called KGa--1b commercialized by the Clay Mineral Society, were performed and interpreted. Kaolinites used in this study were hydrothermally synthesized from partially crystallized kaolinite as a function of different final pH (pHF) ranging from 0.8 to 8.3. Results obtained for KGa--1b were compared with data obtained in literature for this mineral, in order to fully validate this approach. This study found that cation exchange capacity, due to both isomorphic substitutions in the crystals (permanent charge), and silanol and aluminol edge sites were highly variable. Typically, CEC at pH=9 varied from ~0.8 cmolc/kg for well crystallized kaolinite (pHF 0.8) to ~33 cmolc/kg for disordered lath-shaped kaolinite (pHF 8.3). Na+/H+ sorption isotherms were obtained for all synthetic kaolinites as a function of pH ranging from pH 3 to 11. Results showed that sorption of Na+ increases dramatically with pH. Typically for all kaolinite samples except for the one synthesized at pHF=8.3, Na+ sorption is rigorously equal to zero when pH<7, indicating no permanent charge in the samples (in contrast to natural KGa--1b kaolinite), and increases when pH>7 due to sorption on edge sites. The amount of dissolved silica measured during Na+/H+ isotherm is higher for experiments performed with kaolinites synthesized in basic conditions (for pHF 7.4 and pHF 8.3) than for kaolinites synthesized in acid conditions (for pHF 0.8 and pHF 3.3). These latter results lead to conclude that sorption site density can be considered constant when pH is between 4 and 10, independently of the morphologies of particles. In this context, a thermodynamic modeling procedure using a complexation model was applied to interpret the data obtained with hexagonal- and lath-shaped particles. During this procedure, selectivity coefficient between Na+ and H+ cations were obtained considering the total edge site densities calculated from lateral specific surfaces estimated for synthetic kaolinites and crystallography data.

MENVSC / Department of Mining and Environmental Gelogy / In the present study, the physico-chemical, applications, mineralogy, geochemistry and stable isotope of Lwamondo and Zebediela kaolin is documented, in order to understand the genesis, paleoenvironmental conditions and possible utilization. Mineral identification studies were conducted using X-ray diffractometer (XRD), Fourier transform infrared spectrophotometer (FTIR) and scanning electron microscope with energy dispersive X-ray micro analysis (SEM-EDX). Major oxides were identified by X-ray Florescence (XRF) whereas trace elements were identified by Laser Ablation Inductively Coupled Plasma-Mass Spectrometer (ICP-MS). Hydrogen and oxygen isotopic composition were determined by δ18O and δD isotopic measurements. Kaolinite was dominant mineral in all the kaolin samples whereas muscovite, quartz, goethite, hematite, smectite, anatase occurred in minor to trace quantities. The chemical data show that the kaolins are composed mainly of SiO2 and Al2O3 due to the presence of quartz and kaolinite, with minor to trace amounts of other elements such as Ca, Na, Cr, K, Fe, Mn, Mg, P and Ti which affected the kaolin application negatively. Lower concentration of Ca, Na, K, Fe, Mn, Mg, and Ti show the extent of the kaolinitisation. The samples were enriched in Ni and depleted in some other trace elements. The chondrite-normalised rare earth elements patterns show enrichmnent in Heavy Rare Earth Elements (HREE) than Light Rare Earth Elements (LREE) with slight positive Eu anomaly. The Rare Earth Elements (REE) pattern and the content of other trace elements show evidence of weathering processes related to kaolinitisatioon. Kaolin genesis is explained using kaolin mineralogy, particle morphology, structural order (functional group), major and trace elements geochemical data. The data suggest that kaolin is derived from the intensive chemical weathering of intermediate to mafic rocks deposited in non-marine environment. The stable isotopes were used to determine the paleoenvironmental conditions which influenced kaolinitisation of Lwamondo and Zebediela kaolins. Stable isotopes mean values for kaolinite from both Lwamondo and Zebediela were as follows: δ18O for Lwamondo= +18.57‰ and for Zebediela = +16.67 ‰ vii and δD for Lwamondo = -65‰ and for Zebediela = -64‰. The calculated mean temperatures were 26.94 ⁰C for Lwamondo kaolin and 36 ⁰C for Zebediela kaolin. Low temperatures were inferred from stable isotope values to have been involved in the kaolinitisation wherein hydrothermal processes were eliminated. The data suggests that kaolin was formed in a weathering environment. The kaolin is found to be suitable for brick making and based on the physico-chemical, mineralogical and chemical data it was suggested that the kaolin could also be used in producing low temperature ceramics, refractory materials, pottery and stoneware

A demanda crescente por água tem feito de seu reúso planejado um tema atual e de grande importância, já citada na Agenda 21, que recomendou implementação de políticas de gestão dirigidas para o uso e reciclagem de efluentes, integrando proteção de saúde pública de grupos de risco com práticas ambientais adequadas. De acordo com as Resoluções CONAMA nº 357 e 420 os efluentes somente podem ser descartados em corpos d´água se os seus parâmetros característicos se situarem de acordo com o balizamento dado para cada classe de corpo de água. Íons metálicos podem ser removidos de soluções aquosas por diferentes processos sendo a adsorção em argilas um método que pode ser considerado efetivo e barato quando comparado aos demais. Neste estudo foi avaliada a capacidade de adsorção dos íons metálicos Cr3+, Zn2+, Cd2+, Pb2+, Cu2+ e Ni2+ em solução utilizando-se caulinita comercial com a finalidade de reúso e/ou descarte. A caracterização mineralógica e química das amostras comerciais obtidas indicou que aquela denominada caulinita C foi a que mais se adequou ao estudo visto que apresenta elevado teor de pureza mineralógica, baixos teores de elementos traço, e maior capacidade de troca catiônica. O estudo da remoção dos íons em solução indicou que o aumento razão adsorvente:adsorvato aumenta a eficiência de adsorção. O estudo da influência do pH indicou que a maior adsorção ocorre em pH levemente alcalino, pH 8. E o estudo do tempo de contato indicou que o equilíbrio de adsorção é atingido em menos de trinta minutos para todos os íons, exceto para o Ni. A análise das isotermas de adsorção indicou que a caulinita empregada neste estudo é adequada principalmente à remoção dos íons Zn (II), Cu (II) e PB (II). / The growing demand for water has made its planned reuse a current topic of great importance, as already mentioned in Agenda 21, which recommended a management policy implementation directed to the use and recycling of waste, integrating public health protection of risk groups with appropriate environmental practices. According to the 357 and 420 CONAMA Resolutions, effluents can only be dropped into water bodies if their characteristic parameters are located in accordance with the marks given for each body of water class. Metal ions can be removed from aqueous solutions by different processes being clay adsorption a method that can be considered effective and cheap when compared to others. In this study, the commercial kaolinite adsorption capacity was evaluated for the metal ions Cr3+, Zn2+, Cd2+, Pb2+, Cu2+ and Ni2+ in solution with the purpose of reuse and / or disposal. The mineralogical and chemical characterization of commercial samples obtained indicated that the one called \"kaolinite C\" was the one most suited to the study because of its high purity mineral content, low levels of trace elements, and higher cation exchange capacity. The study of ions removal in solution indicated that the increment in the dsorbent: adsorbate ratio increases the adsorption efficiency. The influence of pH indicated that most of the adsorption occurs in a slightly alkaline pH, pH 8. The study of the contact time indicates that the adsorption equilibrium is reached in less than thirty minutes for all ions except for Ni. The analysis of adsorption isotherms indicated that the kaolinite used in this study is suitable for the ion removal mainly of Zn (II), Cu (II) and Pb (II).

O processo de adsorção vem sendo utilizado como uma técnica eficaz para a remoção de íons metálicos em efluentes. Neste trabalho são apresentados os estudos para avaliar da capacidade de adsorção de cobalto em caulinita, um adsorvente de baixo custo, visando à remoção deste íon de soluções aquosas. Foi analisada a área superficial específica (S) em 25 amostras de materiais preparadas de diferentes modos: caulinita, bentonita e carvão ativado e, misturas de caulinita-bentonita e caulinita-carvão ativado. Estas misturas foram preparadas pela adição de 10, 20, 30, 40 e 50% de carvão ativado ou bentonita à caulinita. As amostras de caulinita-carvão ativado e caulinita in natura foram calcinadas a 600 e 1000 °C por 4 horas. Foi escolhida para os testes de adsorção a mistura de caulinita com 10% de carvão ativado por apresentar a melhor relação custo benefício em relação à S. Os parâmetros de adsorção investigados nesta mistura foram: tempo de contato, pH, concentração inicial de soluto, competição iônica e força iônica. Verificou-se que o tempo de contato e o pH otimizados para o propósito do trabalho foram 30 min e pH 6. Nestas condições a eficiência de remoção do íon cobalto da solução foi superior a 80%. Verificou-se que a presença de íons Cr e Zn, bem como o aumento da força iônica diminuem a capacidade de adsorção do Co na mistura adsorvente. As isotermas de Langmuir e Freundlich apresentaram R2 iguais a 0,906 e 0,597, respectivamente. Os parâmetros determinados nestas isotermas indicaram um processo espontâneo, ou seja, energeticamente favorável, para a adsorção do Co nas condições e que foram realizadas este trabalho. / The adsorption process has been used as an efficient technique for the removal of metallic ions in industrial effluent. In this work, it is presented the studies to evaluate the adsorption capacity of cobalt in kaolinite, a low cost adsorbent, aiming at the removal of this ion from aqueous solutions. The specific surface area (S) was analyzed in 25 samples prepared in different ways: kaolinite, bentonite and activated carbon and, mixtures of kaolinite-bentonite and kaolinite-activated carbon. These mixtures were prepared by adding to kaolinite 10, 20, 30, 40 or 50% of activated charcoal or bentonite. Samples of kaolinite-activated charcoal mixture and raw kaolinite were also calcined at 600 and 1000 °C for 4 hours. The adsorption parameters investigated for these adsorbents were: contact time, pH, solute initial concentration, ionic competition and ionic strength. It was found that the optimized contact time and pH, for the purpose of this work, were 30 min and pH 6. Under these conditions the cobalt ion removal efficiency was greater than 80%. It was verified that the presence of Cr and Zn ions, as well as the increase in ionic strength caused a decrease in the adsorption capacity of Co in the adsorbent mixture. The Langmuir and Freundlich isotherms presented R2 equal to 0.906 and 0.597, respectively. The parameters determined by these isotherms indicated a spontaneous process, i.e., energetically favorable, for the adsorption of Co under the conditions that this work was carried out.