Includes bibliographical references. / 1 v. : / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / This thesis investigates the nature and origins of minerals of a group known as layer (sheet) silicates or phyllosilicates. It consists of a collection of research papers grouped into 3 categories: modulated layer silicates, clay silicates and the weathering of rocks and minerals, including the formation of clay minerals. Central to the research has been the use of X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). All three research categories were carried out simultaneously. / Thesis (D.Sc.)--University of Adelaide, Dept. of Geology and Geophysics, 1999

Includes bibliographical references. / 1 v. : / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / This thesis investigates the nature and origins of minerals of a group known as layer (sheet) silicates or phyllosilicates. It consists of a collection of research papers grouped into 3 categories: modulated layer silicates, clay silicates and the weathering of rocks and minerals, including the formation of clay minerals. Central to the research has been the use of X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). All three research categories were carried out simultaneously. / Thesis (D.Sc.)--University of Adelaide, Dept. of Geology and Geophysics, 1999

No description available.

Les suspensions minérales de particules fines sont connues pour leur comportement non-Newtonien pendant l'écoulement. Les interactions particule-particule dans de tels systèmes (c’est-à-dire, suspensions minérales) ne sont pas limitées au contact physique, e.g. collision et frottement. La capacité des minéraux de développer une charge dans l'environnement aqueux justifie des comportements différents des systèmes similaires de première vue. C’est à dire qu’étant caractérisées avec la même fraction volumétrique, composition chimique et granulométrie des solides et densité de dispersant, deux suspensions peuvent montrer un comportement rhéologique différent en raison de la chimie de la solution. Dans ce cas, la composition ionique du dispersant définira la charge des particules, et donc le degré d'agglomération/dispersion dans la suspension. Les argiles phyllosilicates sont connues pour être particulièrement problématiques dans les processus de valorisation des minéraux. L’origine de ces minéraux phyllosilicates implique leur inhomogénéité chimique spatiale, ce qui signifie que le bord et la face de la particule montrent des propriétés chimiques et physiques différentes. La présence de tels minéraux dans les dispositifs d'agitation (réservoirs d'agitation, cellules de flottation) est souvent caractérisée par la coexistence de volumes de suspension stagnants et agités, ce qui a un impact négatif sur l'efficacité de l'agitation. Dans ce travail, les suspensions aqueuses diluées de Na-bentonite ont été examinées par vélocimétrie par imagerie par résonance magnétique afin d'étudier l'influence du pH et du type d'électrolyte monovalent sur leur comportement rhéologique local. Les résultats ont montré que les suspensions contenant 0,1% de solide en volume peuvent présenter une bande de cisaillement, une localisation de cisaillement ou aucun phénomène local en fonction de la chimie du milieu de suspension. Il a été suggéré que l’existence d’une «master curve» (ou courbe d’écoulement globale) pour les suspensions diluées dépendait de l’organisation des particules de bentonite dans la suspension, cette organisation est influencée par la chimie de solution et l’historique des contraintes précédentes. Dans l'étape suivante, une seconde et troisieme phases minérales (hématite et quartz) ont été ajoutées dans la matrice de bentonite. L’intérêt dans tels systèmes est lié au comportement sous écoulement des matrices formées avec des types de contacts différents entre particules. Les types de contacts établis dans les suspensions avec une chimie différente du milieu ont été discutés, ainsi que leurs propriétés d’écoulement / Fine particle mineral slurries are known to exhibit non-Newtonian behavior under the load. The particle-particle interactions in such suspensions go beyond physical contact due to the collision and friction. An ability of minerals to gain the charge in the aqueous environment justifies different behaviors of the similar systems. Being characterized with the same volumetric fraction, chemistry and particle size distribution of solids, and specific gravity of dispersing media, two suspensions can possess different rheological behavior due to the chemistry of the solution. In this case, the ionic composition of the media defines particle charging, and thus the degree of agglomeration/dispersion in the suspension. Phyllosilicate clays are known to be particularly problematic in the mineral beneficiation processes. Their nature leads spatial chemical inhomogeneity, meaning that the particle edge and face possess different chemical and physical properties. The presence of such minerals in the stirring devices (stirring tanks, flotation cells) is often characterized with coexistence of stagnant and agitated volumes of slurry, which negatively impacts the efficiency of stirring. In this work, the dilute aqueous Na-bentonite suspensions were examined via magnetic resonance imaging velocimetry to investigate the influence of pH and type of monovalent electrolyte on their local rheological behavior. The results indicated that suspensions with 0.1 vol.% solid can exhibit shear banding, shear localization or no local phenomenon as a function of chemistry of the suspending media. It was suggested that the existence of master curve (or global flow curve) for dilute suspensions was dependent on the bentonite particle organization in the suspension, which was influenced by the chemistry of the environment and the previous flow history. In the next step, second mineral phase (hematite or quartz) was added to the bentonite matrix. The interest in examination of such systems is related to the flow behavior of matrix formed with different kinds of inter-particle contacts. For example, at pH 4 the resulting electrostatic interaction between positively charged bentonite edge and negatively charged quartz is attractive, whereas at the same pH it is repulsive with the positively charged hematite. These electrostatic interactions result in different organization of matrix particles around another mineral phase. In the system with solely repulsive interactions between all sites of all mineral phases (e.g., quartz and bentonite, pH 10) the deviation from Newtonian behavior is justified by the shear-induced particle rearrangements, collision and friction. The difference in the arrangement of bentonite particle aggregates around the hematite or quartz particles was observed using SEM. As a next step the third mineral phase was added. The types of contacts established in the suspensions with different chemistry of the media were discussed along with their flow propperties

Les latérites couvrent plus de 30% des surfaces émergées. Comprendre leur évolution future est essentiel pour prédire les changements qui affecteront le fonctionnement de la Zone Critique dans les siècles à venir. La littérature a pu montrer que les horizons indurés de ces sols comportaient plusieurs générations de minéraux secondaires qui pouvaient être reliées à différents événements paléoclimatiques. Des études isotopiques ont montré que les horizons non indurés de ces sols pouvaient aussi posséder des générations distinctes de minéraux secondaires. La datation par Résonance Paramagnétique Électronique, a été appliquée sur des kaolinites de latérites dans le but d’identifier si ce minéral possède bien plusieurs générations au sein d’un même profil et si ces dernières étaient corrélables avec des événements paléoclimatiques globaux ou régionaux. Au cours de cette thèse, deux régolithes du Plateau du Karnataka (Inde), quatre du bassin du Rio Négro (Brésil) et un de la région de Syerstone (Australie) ont été étudiés. Les résultats de ces datations ont permis de distinguer différentes générations de kaolinites au sein de chacun des profils étudiés. Ces dernières sont par ailleurs toutes corrélables avec des périodes de fortes précipitations liées aux évolutions climatiques régionales et/ou globales. Ces résultats confirment aussi l’existence du phénomène de rajeunissement profils latéritiques au cours des temps géologiques. Le travail de cette thèse corrobore l’hypothèse de l’évolution épisodique de ces sols tropicaux et souligne leur importante stabilité dans les temps géologiques. / Laterites are covering a third of the continental surfaces. Understanding their evolution through the ongoing climate change is critical to predict the future Critical Zone transformation. Laterite duricrusts can contain several generations of secondary minerals that can be correlated with distinct paleoclimatic events. Isotopic studies showed that loose laterites may also be formed by several generations of secondary minerals. The objective of this PhD was to confirm that loose laterites contain several generations of kaolinites and that they formed during regional and/or global paleoclimatic events. With this aim in view, a recent dating methodology, the Electron Paramagnetic Resonance dating of kaolinites, was used on tropical regolith profiles from three continents with distinct geodynamic histories: India (Karnataka plateau), South America (Rio Negro basin, Brazil) and Australia (Syerstone region, New South Wale). The data set of this PhD confirms that a regolith contains several generations of kaolinites. All the identified generations of the present study can be correlated with regional paleoclimatic events or with tropical weathering favourable periods initiated by global paleoclimatic trends. Kaolinite generations formed preferentially during high precipitations periods and result from the rejuvenation of laterite profiles. The results of this PhD confirm that laterites have an episodic evolution.

A thesis submitted for the degree of Doctor of Philosophy in the Faculty of Science at the University of the Witwatersrand. / The present thesis is divided into three parts. The study described in Part I arose out of a request by the Chamber of Mines Mining Research Laboratory to the National Institute for Metallurgy to undertake a preliminary study of whether it would be feasible, in Witwatersrand conglomerates, to carry out rapid delimitation of areas rich in gold and/or uranium at the rock face, a procedure which would permit areas of rich ore to be removed selectively by means of the "rock-cutter". The approach adopted in this study was essentially geochemical, while conventional mineralogical techniques (macro-auto radiographs , thin section and polished section analyses) provided a control. The samples were drawn from the Vaal Reef at Hartebeestfontein and Zandpan and from the Ventersdorp Contact Reef at Venterspost, and were analysed quantitatively for gold, silver, uranium, pyrite, muscovite, pyrophyllite, chlorite, quartz, iron, potassium, nickel, titanium, zirconium and chromium. The intensity of the interrelationships between the elements and minerals analysed for was examined statistically by means of correlation covariance and factor analysis programmes written for an IBM 360/50 digital computer. A sympathetic relationship -- defined as significant positive correlation (with a correlation coefficient r> 0. 7) -- was found to exist between gold and uranium in both the Vaal Reef and Ventersdorp Contact Reef samples. These findings suggest that gold and uranium can be removed Simultaneously by means of the rock-cutter, and that radioactivity can be used as an indicator for on-site delimitation of areas rich in gold. In the course of the study described in Part I, it became evident that little detailed mineralogical work had ever been done on the phyllosilicates occurring in the Witwatersrand System. Accordingly, certain phyllosilicates from Witwatersrand conglomerate bands and other sources were examined in detail, this study being described in Part II of the present thesis. This study called for detailed chemical, optical, X-ray crystallographic, infra-red, differential thermal and thermogravimetric analyses, the results of which are presented. The findings were examined in the light of variolls classification schemes that have bep proposed for the phyllosilicates. This investigation revealed the need for a universally acceptable system of classification for the phyllosilicates, which should preferably be drawn up under the auspices of the International Mineralogical Association to avoid the confusion that exists at present. Part III of the present thesis is devoted to a discussion and description of various analytical techniques that had to be modified or developed to meet th8 requirements of the studies described in Parts I and II. The techniques described include: (1) An X-ray diffraction method which was developed for the quantitative analysis of pyrite, muscovite, pyrophyllite, chlorite and quartz in crushed ore from Witwatersrand conglomerates. This method makes use of novacul iie as an external standard and of binary mixtures as analytical standards, and had a mean absolute error of 1. 1 %. This method may be expanded to permit analysis of an n-component mixture. (2) A whole rock pressed powder technique of X-ray fluorescence analysis which was used for the quantitative determination of iron, potassium, nickel, titanium, zirconium and chromium. This method makes use of internstional rock standards as external standards. Six computer programmes used for the computation of the analytical results and in the statistical and crystallographic calculations are also presented in Part III. / AC2017

O Pórfiro Yarumalito está localizado na parte norte do Distrito Mineiro Marmato a oeste do vale do rio Cauca-Patía, no Departamento de Antioquia. Este distrito mineiro é reconhecido pela histórica exploração das mineralizações de ouro. Os depósitos de ouro na região estão associados a veios controlados por estruturas e em stockworks, que são desenvolvidos em rochas ígneas associadas a eventos magmáticos do miocénico superior como a Formação Cômbia. Nesta dissertação foram caracterizadas rochas porfiriticas de composição andesitica, dacítica mineralizada e dacítica estéril, junto com as alterações hidrotermais que afetaram principalmente as últimas, utilizando microscopia óptica convencional (luz transmitida e refletida) e equipamentos de MEV na Universidade Federal do Rio Grande do Sul. Os resultados da petrografia permitiram distinguir no pórfiro dacítico mineralizado estágios de alteração potássica, propilítica e fílica, que indicam intensa circulação de fluidos em um amplo intervalo de temperatura, enquanto no pórfiro dacítico estéril se distinguiu só sericitização. Nestas alterações se fez uma seleção criteriosa de exemplares de mica trioctaédrica, clorita e mica dioctaédrica que foram analisados por microssonda eletrônica na Universidade de Brasilia Os resultados da química mineral sugerem a ocorrência de diversas trocas catiônicas durante o estágio magmático–hidrotermal. Estas trocas têm lugar tanto no sitio VI como no sitio IV, incluindo elementos como Si, Al, Mg, Fe, Ti e Mn. Estas trocas afetaram a composição no sítio A (intercamada) e também têm efeito na quantidade de ânions de F e Cl presentes na estrutura dos minerais analisados. Tanto as micas trioctaédricas magmáticas do pórfiro dacítico mineralizado como as da alteração potássica correspondem com biotitas magnésias, no entanto as micas trioctaédricas hidrotermais têm tendência para flogopitas, mostrando o aumento de Mg no sistema. Nas micas dioctaédricas se observa uma tendência para fengita no estágio correspondente com o pórfiro dacíto mineralizado. Para as cloritas a maior parte dos exemplares analisados corresponde com ripidiolitas. / The Yarumalito Porphyry is located in the northern part of the Mining District Marmato to west of the Cauca-Patía river valley in the Department of Antioquia. This mining district is known for historical exploration of gold mineralization. The gold deposits in the region are associated with veins controlled by structures and stockworks, which are developed in igneous rocks associated with magmatic events of the late Miocene as Combia Formation. In this thesis were characterized porphyritic rocks of andesitic and dacitic (mineralized and barren) composition and the hydrothermal alteration that affected principally the last two, using conventional optical microscopy (transmitted and reflected light) and SEM equipment at the Federal University of Rio Grande do Sul. The results of petrography allowed distinguish in the mineralized dacitic porphyry mainly stages of potassic alteration, propylitic alteration and phyllic alteration, indicating intense circulation of fluids in a wide temperature range. Meanwhile barren dacitic porphyry only has phyllic alteration. In these alteration were made a careful selection of trioctahedral mica, chlorite and dioctahedral mica that were analyzed by electron microprobe at the University of Brasilia. The results of mineral chemistry suggest the occurrence of several cationic exchanges during magmatic-hydrothermal stage. These exchanges take place both on site VI and in the site IV, including elements such as Si, Al, Mg, Fe, Ti and Mn. These changes affected the composition of A site (interlayer) and also have effect on the amount of anions of F and Cl in the structure of analyzed minerals. Both, the magmatic trioctahedral micas of mineralized dacitic porphyry and that generated in potassic alteration correspond with magnesium biotites, however hydrothermal 8 trioctahedral micas have tendency to phlogopites indicating the rise in Mg content in the system, dioctahedral micas have a tendency for phengite in stages corresponding with the mineralized dacitic porphyry. Chlorites in most analyzed samples correspond to ripidiolitas.

O Pórfiro Yarumalito está localizado na parte norte do Distrito Mineiro Marmato a oeste do vale do rio Cauca-Patía, no Departamento de Antioquia. Este distrito mineiro é reconhecido pela histórica exploração das mineralizações de ouro. Os depósitos de ouro na região estão associados a veios controlados por estruturas e em stockworks, que são desenvolvidos em rochas ígneas associadas a eventos magmáticos do miocénico superior como a Formação Cômbia. Nesta dissertação foram caracterizadas rochas porfiriticas de composição andesitica, dacítica mineralizada e dacítica estéril, junto com as alterações hidrotermais que afetaram principalmente as últimas, utilizando microscopia óptica convencional (luz transmitida e refletida) e equipamentos de MEV na Universidade Federal do Rio Grande do Sul. Os resultados da petrografia permitiram distinguir no pórfiro dacítico mineralizado estágios de alteração potássica, propilítica e fílica, que indicam intensa circulação de fluidos em um amplo intervalo de temperatura, enquanto no pórfiro dacítico estéril se distinguiu só sericitização. Nestas alterações se fez uma seleção criteriosa de exemplares de mica trioctaédrica, clorita e mica dioctaédrica que foram analisados por microssonda eletrônica na Universidade de Brasilia Os resultados da química mineral sugerem a ocorrência de diversas trocas catiônicas durante o estágio magmático–hidrotermal. Estas trocas têm lugar tanto no sitio VI como no sitio IV, incluindo elementos como Si, Al, Mg, Fe, Ti e Mn. Estas trocas afetaram a composição no sítio A (intercamada) e também têm efeito na quantidade de ânions de F e Cl presentes na estrutura dos minerais analisados. Tanto as micas trioctaédricas magmáticas do pórfiro dacítico mineralizado como as da alteração potássica correspondem com biotitas magnésias, no entanto as micas trioctaédricas hidrotermais têm tendência para flogopitas, mostrando o aumento de Mg no sistema. Nas micas dioctaédricas se observa uma tendência para fengita no estágio correspondente com o pórfiro dacíto mineralizado. Para as cloritas a maior parte dos exemplares analisados corresponde com ripidiolitas. / The Yarumalito Porphyry is located in the northern part of the Mining District Marmato to west of the Cauca-Patía river valley in the Department of Antioquia. This mining district is known for historical exploration of gold mineralization. The gold deposits in the region are associated with veins controlled by structures and stockworks, which are developed in igneous rocks associated with magmatic events of the late Miocene as Combia Formation. In this thesis were characterized porphyritic rocks of andesitic and dacitic (mineralized and barren) composition and the hydrothermal alteration that affected principally the last two, using conventional optical microscopy (transmitted and reflected light) and SEM equipment at the Federal University of Rio Grande do Sul. The results of petrography allowed distinguish in the mineralized dacitic porphyry mainly stages of potassic alteration, propylitic alteration and phyllic alteration, indicating intense circulation of fluids in a wide temperature range. Meanwhile barren dacitic porphyry only has phyllic alteration. In these alteration were made a careful selection of trioctahedral mica, chlorite and dioctahedral mica that were analyzed by electron microprobe at the University of Brasilia. The results of mineral chemistry suggest the occurrence of several cationic exchanges during magmatic-hydrothermal stage. These exchanges take place both on site VI and in the site IV, including elements such as Si, Al, Mg, Fe, Ti and Mn. These changes affected the composition of A site (interlayer) and also have effect on the amount of anions of F and Cl in the structure of analyzed minerals. Both, the magmatic trioctahedral micas of mineralized dacitic porphyry and that generated in potassic alteration correspond with magnesium biotites, however hydrothermal 8 trioctahedral micas have tendency to phlogopites indicating the rise in Mg content in the system, dioctahedral micas have a tendency for phengite in stages corresponding with the mineralized dacitic porphyry. Chlorites in most analyzed samples correspond to ripidiolitas.

Orientador: Claudio Airoldi / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-17T19:54:52Z (GMT). No. of bitstreams: 1 Badshah_Syed_D.pdf: 4398020 bytes, checksum: 41352eaf93af6ab6efa1bf20fb83ffd9 (MD5) Previous issue date: 2011 / Resumo: No presente trabalho, híbridos inorgânico-orgânicos nanoestruturados de sílica mesoporosa e de filossilicatos de magnésio lamelares com estrutura similar ao talco foram sintetizados e caracterizados. A máxima capacidade sorptiva de cátions dos híbridos e as características energéticas das interações dos cátions com centros básicos, na interface sólido/líquido, foram também estudadas. A sílica mesoporosa análoga aos materiais SBA-15 tem sido sintetizada por meio do tribloco co-polímero EO20-PO70 -EO20 (P123 - Pluronic®), que atua como um agente direcionador estrutural. Os materiais SBA-15 sintetizados foram funcionalizados com vários agentes sililantes, os quais apresentam os seguintes grupos funcionais: amida, nitrila e marfolina ou base de Schiff do anel tiofênico. Os agentes sililantes com os grupos funcionais mencionados acima foram sintetizados por meio de reações de adição de Michael do aceptor de Michael a,b - insaturado (acrilamida, acrilonitrila e 4- acriloilmarfolina), ou por meio da reação de base de Schiff do 2-tiofenocaboxaldeído com os agentes sililantes aminados, comercialmente disponíveis. As técnicas de espalhamento de raios X a baixa ângulo (SAXS) e de adsorção/desorção de nitrogênio para a SBA-15 pura e a SBA-15 funcionalizada mostraram um arranjo estrutural hexagonal bem-ordenado nos materiais. Os filossilicatos lamelares híbridos com diferentes porções orgânicas presentes dentro dos nanoespaços lamelares foram sintetizados por meio de reações sol-gel de uma única etapa. Com esse intuito, os agentes sililantes com vários grupos funcionais (tiopropanamida, tiocarbamato, nitrila e base de Schiff ou anel tiofênico) foram sintetizados e reagiram com uma solução metanólica de nitrato de magnésio, sob condições básicas. A difratometria de raios X indicou distâncias basais maiores de que 1 nm para os filossilicatos híbridos sintéticos. A técnica de difração de raios X também mostrou que a estrutura inorgânica dos filossilicatos híbridos era similar àquela do talco natural. A estrutura inorgânica do filossilicato híbrido é composta de camadas octaédricas ocupadas pelo átomo de magnésio hexacoordenado presentes entre duas camadas tetraédricas silícicas, em que a porção orgânica está covalentemente ligada à camada tetraédrica da estrutura em camadas. A integridade das porções orgânicas ligadas à rede inorgânica da sílica mesoporosa ou dos filossilicatos foi confirmada por meio da Espectroscopia no Infravermelho com transformada de Fourier e por meio da técnica de Ressonância Magnética no estado sólido para os núcleos Si e C. A máxima incorporação de porções orgânicas foi determinada por meio da análise elementar. As porções orgânicas ligadas aos materiais híbridos contêm: nitrogênio, oxigênio e enxofre, os quais correspondem aos sítios básicos disponíveis para a remoção de espécies como: Pb, Cu, Cd e Ni. As capacidades sorptivas máximas dos materiais híbridos para tais cátions foram obtidas por meio de Isotermas de adsorção de Langmuir. Os resultados revelam que os filossilicatos lamelares híbridos apresentam elevada capacidade para remoção de cátions em comparação com os materiais SBA-15, devido ao elevado grau de funcionalização. A energética das interações entre os cátions e os centros básicos ao longo da interface sólido/líquido foram determinadas através da microcalorimetria. As variações negativas da energia de Gibbs, de entalpia e os valores positivos de variação entrópica indicam interações espontâneas e favoráveis entre os sólidos e os íons metálicos. Esses resultados favoráveis indicam que os híbridos sintetizados podem ser úteis na remoção de cátions tóxicos de soluções aquosas, auxiliando na despoluição de ecossistemas / Abstract: In the present work, nanostructured inorganic-organic hybrids based on mesoporous silica and lamellar magnesium phyllosilicates with talc-like structure were synthesized and characterized. The maximum cations sorption capacity of the hybrids and energetic features from cation- basic center interactions at the solid liquid interface were also studied. The mesoporous silica analogous to SBA-15 materials has been synthesized through the triblock co-polymer EO20-PO70 -EO20 (P123 ¿ Pluronic®) as a structured directing agent. The synthesized SBA-15 materials were functionalized with various silylating agents having organic functional groups of amide, nitrile, and marpholine or Schiff base of thiophenic ring. The silylating agents with the aforementioned functional groups were synthesized either by the Michael addition reactions of a,b-unsaturated Michael acceptor (acrylamide, acrylonitrile and 4-acryloylmarpholine) or by the Schiff base reaction of 2-thiophenecaboxaldehyde with commercially available aminated silylating agents. Small angle X-ray scattering (SAXS) and nitrogen adsorption/desorption experiments for both SBA-15 and functionalized SBA-15 showed well-ordered hexagonal array structure. The lamellar phyllosilicates hybrids with different organic moieties inside the lamellar nanospaces were synthesized through a single step sol-gel reaction. For this purpose, silylating agents with various functional groups (thiopropanamide, thiocarbamate, nitrile and Schiff base of thiophenic ring) were synthesized and reacted with methanolic solution of magnesium nitrate under basic conditions. The X-ray diffraction showed basal distances of more than 1 nanometer for the synthetic hybrid phyllosilicates. The XRD also showed that the inorganic structure of the hybrid phyllosilicates was similar to that of natural talc. The inorganic network of the hybrid phyllosilicate is composed of octahedral sheet occupied by hexacoordinated magnesium atom sandwiched between two tetrahedral silicic sheets, and the organic moiety is covalently bonded to the tetrahedral sheet of the layered structure. The integrity of organic moieties attached to the inorganic network of mesoporous silica or phyllosilicates was confirmed by the Fourier transform infrared spectroscopy and nuclear magnetic resonance in the solid-state for the Si and C nuclei. The maximum incorporation of organic moieties was determined through elemental analysis. The attached organic moieties of the hybrid materials contain nitrogen, oxygen or sulfur basic centers available for divalent lead, copper, cadmium and nickel cation removal. The maximum sorption capacities of the hybrids for such cations were obtained through Langmuir adsorption isotherms. The results reveal that the lamellar magnesium phyllosilicate hybrids present high capacity for cations removal as compared to functionalized SBA-15 materials, due to a high degree of functionalization. The energetic of cation-basic centers interactions at the solid/liquid interface were determined through microcalorimetry. The negative Gibbs energy, exothermic enthalpy and positive entropic values indicate spontaneous and favorable interactions between the solids and metal ions. These favorable results indicated that the synthesized hybrids can be useful for removal of toxic cations from aqueous solutions for the improvement of ecosystem / Doutorado / Quimica Inorganica / Doutor em Ciências

Orientador: Claudio Airoldi / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T14:21:13Z (GMT). No. of bitstreams: 1 Moscofian_AndreaSalesdeOliveira_D.pdf: 1968679 bytes, checksum: b66014bf3fdc4c05b9755eac5d6d6ef0 (MD5) Previous issue date: 2009 / Resumo: Filossilicatos de magnésio e sílicas mesoporosas, com grupos orgânicos ligados às estruturas poliméricas inorgânicas, foram estudados na remoção de corantes. Para a síntese dos materiais nanoestruturados organofuncionalizados foram empregados agentes sililantes, (H3CO)3Si-R1, em que R1 é a cadeia carbônica contendo grupos funcionais: 3-aminopropiltrimetoxissilano, cloreto de octadecildimetil(3-trimetoxissilil-propil)amônio, 3-mercaptopropiltrimetoxissilano, 3-etilenodiaminopropiltrimetoxissilano e 3-dietilenotriaminopropiltrimetoxissilano. Através do processo sol-gel foram obtidos filossilicatos com estruturas inorgânicas similares àquelas dos silicatos lamelares naturais e sílicas mesoporosas empregando-se o surfatante CTAB como direcionador da estrutura inorgânica. As moléculas pendentes nos poros dos novos materiais com cargas positivas ou protonadas interagiram com as cargas negativas dos corantes utilizados na indústria têxtil: amarelo reativo GR, vermelho reativo RB e azul reativo RN. O estudo de adsorção mostrou que o filossilicato contendo cloreto de octadecildimetil(3-trimetoxissilil-propil)amônio, Fil-COTA, foi o material que apresentou a maior capacidade de adsorção, 1343 mg gpara o corante amarelo GR, 1286 mg g para o azul reativo RN e 344 mg gpara o vermelho reativo RB. Também foram realizados testes em amostras reais de efluente têxtil. Os resultados mostraram que não é necessário ajustar o pH inicial, a saturação do material ocorre após 3 h, sendo necessária uma massa mínima de 2,5 g dm de Fil-COTA. Portanto, este material é promissor no tratamento de efluentes têxteis reais. / Abstract: Magnesium phyllosilicates and mesoporous silicas, with organic groups anchored onto an inorganic polymeric backbones were studied for dye removal. In the synthesis of the organofunctionalized nanostructured materials, the silylanting agents, (H3CO)3Si-R1, where R1 represents carbonic chain containing functional groups: 3-aminopropyltrimethoxysilane, octadecyl (3-trimethoxysylilpropyl)ammonium chloride, 3 ¿ mercaptopropyltri-methoxysilane, 3-ethylenediaminetrymethoxysilane and 3-diethy-lenetriaminetrymethoxysilane were employed. The sol-gel process was used and phyllosilicates with inorganic lamellar structures similar to those of natural silicate and mesoporous silicas were obtained using the surfactant CTAB as template to direct inorganic structure in the latter case. The pendent molecules in pores of the new material with positive charge interact with the negative charge of the dyes used in the textile industry: reactive yellow GR, reactive red RB and reactive blue RN. The adsorption study showed that the phyllosilicate containing octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, Fil-COTA, presented the highest adsorption capacity, 1343 mg g for reactive yellow GR, 1286 mg g for reactive blue RN and 344 mg g for reactive red RB. Real samples of textile effluents were also tested. The results showed that it is not necessary to ajust the inicial pH, surface saturation occurs after 3 h and the minimum mass necessary is 2,5 g dm of Fil-COTA. Thus, this is a promising material for textile effluent treatement. / Doutorado / Quimica Inorganica / Doutor em Ciências