Orientador: Liliane Maria Ferrareso Lona / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-19T15:02:05Z (GMT). No. of bitstreams: 1 MacedoNeto_JoseCostade_D.pdf: 15337503 bytes, checksum: 2d35593a90de41c2e7333e60488e1bf0 (MD5) Previous issue date: 2011 / Resumo: Materiais nanocompósitos poliméricos utilizando argilas naturais como reforço tem sido bastante estudados por apresentar propriedades melhoradas em relação ao polímero sem reforço. Este trabalho tem como objetivo produzir e caracterizar materiais nanocompósitos polimérico com matriz de poliestireno por meio da polimerização in situ em emulsão utilizando com nanopartícula a caulinita amazônica. Os resultados obtidos mostraram que a caulinita utilizada como reforço neste trabalho apresentou alta razão de aspecto, foi possível ser intercalada por moléculas orgânicas de dimetilsulfóxido (DMSO) e acetato de potássio (AcK). Nesta tese foram produzidos nanocompósitos com 1, 3 e 5% de caulinita modificada com DMSO e outros com 1, 3 e 5% de argila modificada com AcK. A estabilidade do látex produzido pela polimerização foi medida por dynamic light scattering (DLS). O látex com 3% de argila modificada com DMSO apresentou melhor estabilidade em relação ao com 1% de argila e ao do poliestireno puro. As análises por difração de raios X (DRX) e microscopia eletrônica de varredura de alta resolução (HRSEM) revelaram que a utilização das quantidades 1 e 3% de argila modificada com DMSO são as ideais para a obtenção de nanocompósitos. A análise termogravimétrica (TGA) dos nanocompósitos com 1 e 3% apresentou melhores propriedades térmicas em relação ao polímero sem reforço. A análise por calorimetria exploratória diferencial (DSC) mostrou que a adição de 1 e 3% de argila não alterou a temperatura de transição vítrea em relação ao polímero sem reforço. A análise térmica dinâmico-mecânica (TDMA) mostrou que o módulo de armazenamento (E') foi maior para o poliestireno puro em relação aos nanocompósitos com 1 e 3% de argila durante o aquecimento. A TDMA também mostrou que a adição de 1 e 3% de argila não influenciou a temperatura de transição vítrea (Tg). O ensaio de inflamabilidade horizontal mostrou que a taxa de queima foi menor para o nanocompósito com 3% de argila em relação ao PS e 1%. Sendo assim, foi possível produzir nanocompósitos com a caulinita. O látex obtido com 3% de argila foi o mais estável. Os nanocompósitos com quantidades de1 e 3% de argila obtiveram melhores propriedades térmicas em relação ao poliestireno sem argila. O PS puro apresentou maior E' as quantidades de 1 e 3% de argila não influenciou a Tg. O nanocompósito com 3% de argila obteve menor taxa de queima / Abstract: Polymer nanocomposites materials using natural clays as reinforcement has been extensively studied by presenting improved properties compared to unreinforced polymer. The goal of This work is to produce and characterize a polymer nanocomposites materials with matrix od polystyrene and nanoparticle by kaolinite through in situ emulsion polymerization. The kaolinite used as reinforcement in this study had a high aspect ratio, could be intercalated by organic molecules of dimethylsulfoxide (DMSO) and potassium acetate (ACK). In this thesis were produced nanocomposites with 1, 3 and 5% kaolinite modified with DMSO and others with 1, 3 and 5% clay modified with AcK. The stability of the latex produced by polymerization was measured by dynamic light scattering (DLS). Latex with 3% clay modified with DMSO showed better stability compared with the 1% clay and the pure polystyrene. Analyses by X-ray diffraction (XRD) and scanning electron microscopy, high resolution (HRSEM) revealed that use of the quantities 1 and 3% clay modified with DMSO are ideal for obtaining nanocomposites. The thermogravimetric analysis (TGA) of the nanocomposites with 1 and 3% showed better thermal properties compared to unreinforced polymer. Analysis by differential scanning calorimetry (DSC) showed that the addition of 1 and 3% clay did not change the glass transition temperature compared to the unreinforced polymer. The dynamic mechanical thermal analysis (TDMA) showed that the storage modulus (E') was higher for the pure polystyrene compared to nanocomposites with 1 and 3% clay during heating. TDMA also showed that the addition of 1 and 3% clay did not influence the glass transition temperature (Tg). The horizontal flammability test showed that the burn rate was lower for the nanocomposite with 3% clay compared to PS and 1%. Therefore, it was possible to produce nanocomposites with kaolinite. The latex obtained with 3% clay was the most stable. Nanocomposites with quantities of 1 and 3% clay had better thermal properties compared to polystyrene clay. The pure PS had a higher E' quantities of 1 and 3% clay did not affect the Tg. The nanocomposite with 3% clay had lower burn rate / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

Abstract The Surma basin is a part of the Bengal Basin situated in northeastern Bangladesh. The presence of eight gas fields and one oil field makes this an area that is interesting both economically and geologically. In spite of detailed geological and geophysical investigations, information available on palynostratigraphy and geochemistry for the area is scanty. The aim of the present work was to investigate the palynological assemblages, mineralogy and geochemistry of the Surma Group (SG) sequences in Surma Basin, Bangladesh. Core samples (n = 188) were gathered from the wells following: Patharia well-5, Rashidpur well-1, Atgram well-IX, Habiganj well-1, Kailastila well-1 and Fenchuganj well-2. They were provided by BAPEX (Bangladesh Petroleum Exploration Company). X-ray Fluorescence (XRF), Atomic Absorption Spectrometry (AAS), Loss of Ignition (LOI), X-ray diffraction (XRD), Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) were used for geochemical and mineralogical study of shale samples. In the palynological study, the distributions of pollens and spores were determined. For data analysis, SPSS computer programme was used. Palynological assemblages of the Surma Group of sedimentary sequence of Bangladesh include taxa range in age from the lower Miocene to the Upper Miocene which can be potentially used in dating and correlation. The Lower Miocene interval is correlated with the Simsang Palynological Zone IV of Meghalaya, India and the Bengal Palynological Zone (BPZ) V. The Upper Miocene is correlated with the Simsang Palynological Zone IV of Meghalaya, India and the BPZ Zone V of Bengal. They were deposited in two types of paleoenvironments ranging from the brackish type to shallow marine to brackish. The sequence contains reworked palynomorphs of BPZ IV and III namely Meyeripollies naharkotensis, Polypodiesporites Oligocenecus, Palmepollenities Eocencus and ornamented Tricolpate pollen of the Eocene-Oligocene age which are mainly encountered in the lower Miocene sediments indicative of increased tectonic activity in the area. Geochemical ratios (SiO2/ Al2O3, Cu/Zn, Maturity = K2O+ Al2O3/Na2O+MgO, Rb/K2O, K2O/Na2O, Cr/Rb, Zr/Rb, V/Rb, Th/U etc.) were useful for determining grain size, maturity, tectonics and environment of deposition. High Ba enrichment was detected in the Patharia well-5 and showed high surface water productivity and diagenetic mobilisation. Tectonic descrimination was achieved using SiO2 and K2O/Na2O ratio. XRD analysis revealed the minerals kaolinite, illite, chlorite, illite/smectite (I/S) and kaolinite/smectite (K/S) mixed layers. Kaolinite/Smectite here reported for the first time in Bangladesh. Clay mineral analyses provided evidence for diagenesis. Smectite diagenesis and dehydration have contributed to the generation of overpressure in the Bhuban Formation in the Patharia well -5. Geochemical ratios of the present study from the Surma Basin is undoubtedly a powerful technique and can be applied to any sedimentary basin analysis to infer the palaeoenvironment, palaeoclimate and palaeotectonics.

No description available.

Accurate prediction of long-term moisture expansion in fired clay ceramics requires finding a relationship between the reactivity of a ceramic material with moisture and time. Recently a (time)1/4 law has been proposed which provides a precise relationship between moisture expansion and mass gain in fired clay ceramics and time. However, mass gain studies rather than expansive strain studies provide a more accurate and fundamental measure of the reactivity of fired clay ceramics with moisture. The possibility of using the (time)1/4 law to describe rate of mass gain and consequently to predict moisture expansion in fired clay ceramics with time requires study of the effect of chemical composition and firing temperature on the linear dependence of mass gain on (time)1/4. Pure kaolinite as well as kaolinite mixed with controlled additions of alkali and alkaline-earth metals were employed in this study. These materials were fired at temperatures between 800°C and 1200°C. Mass gain due to the chemical combination of the fired materials with moisture was measured using a recording microbalance under tightly controlled environmental conditions of temperature and relative humidity. The mass gain results show that the (time)1/4 law can be used to obtain an accurate linear relationship between long-term mass gain and time at almost all firing temperatures and at all different compositions. The presence of alkali metals was found to strongly affect the chemical combination of fired clay ceramics with moisture and hence affect the rate of mass gain. On the other hand, alkaline earth metals were found to produce similar reaction kinetics to kaolinite alone. BET surface area and X-ray diffraction results confirm that there is a correlation between the reactivity with moisture and both the specific surface area and crystallinity of fired clay ceramics.

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.

CSÁKI, Štefan: Thermophysical and electrical properties of illite-based ceramics. [Doctoral thesis]. Constantine the Philosopher University in Nitra. Faculty of Natural Sciences. Charles University. Faculty of Mathematics and Physics. Supervisor: prof. RNDr. Libor Vozár, CSc. (Constantine the Philosopher University in Nitra), doc. Ing. Patrik Dobroň, PhD. (Charles University). Nitra & Prague, 2018. 107 p. Illitic clays are of special importance in the ceramic industry. Therefore, a deep knowledge of the thermophysical processes, as well as the electric properties, is of special importance. The illitic clay originated in Northeastern Hungary was used in this thesis. The reactions, occurring during firing, were studied using thermal analyses (Differential thermal analysis, Thermogravimetry, Thermodilatometry) and special attention was paid to the measurement of the electrical conductivity (both DC and AC). Up to 250 řC, where the removal of the physically bond water (PBW) takes place, the dominant charge carriers were the H+ and OH- ions. After the PBW was removed, Na+ and K+ ions became the dominant charge carriers. During dehydroxylation (450 - 750 řC) H+ and OH- ions were freed from the illite structure, which supported the electrical conduction in the samples. At ~ 970 řC glassy phase appeared...

Rare earth elements (REEs) are critically important for high-tech, renewable energy and defense industries. However, rare earth minerals (REMs) are stable compounds, requiring aggressive conditions to decompose them for their extraction and use. One exception is the ion-adsorption clays (IACs) that are mined in South China. They were formed in nature via the adsorption of the REE ions on clay minerals; therefore, they can be readily extracted into solution under mild conditions using the ion-exchange leaching process using (NH4)2SO4 as lixiviant. It also happens that IACs are the largest source of the heavy rare earth elements (HREEs) that are critical, especially for the defense industry. At present, more than 80% of the HREEs are produced commercially from the IACs mined in Southeast Asia. The objective of the present research was to study the fundamental mechanisms involved in the formation and processing of IACs using the ion-change leaching process. The first part of the project was the synthesis of IACs by contacting kaolinite samples with known concentrations of rare earth chloride (REECl3) solutions at different pHs and analyzing the synthetic IACs for XPS studies. It was found that the REE adsorption on kaolinite stays constant in acidic pHs. At pH 7 and above, adsorption density increases sharply, possibly due to the formation of REE(OH)3 and/or REE(OOH). The IACs formed under these conditions responded well to the ion-exchange leaching process by reducing the pH to below 7. In the second part of the study, the effect of iron (Fe3+) species co-adsorbing with REEs on the kaolinite surface was studied. Unlike the colloidal phases of IACs formed at pH > 7, the synthetic IACs formed in the presence of iron did not respond to the ion-exchange leaching process using (NH4)2SO4 as lixiviant. This problem has been solved by subjecting the synthetic IACs to a reducing condition to convert the Fe3+ to soluble Fe2+ species at pH < 7. The driving force for the standard exchange leaching process is the large differences between the hydration enthalpies of the Ln3+ ions that are in the range of -3,400 kJ/mole and that of the NH4+ ions (-320 kJ/mole). In the present work, alkylammonium ions (CnH2nNH4+) of varying chain lengths were used as novel lixiviants and obtained excellent results. Since these are surface active species, their concentrations in the vicinity of the clay minerals that are negatively charged would be substantially higher than in the bulk. As a result, it was possible to achieve the same level of leaching efficiencies as obtained using ammonium sulfate at approximately ten times lower reagent dosages. One of the problems associated with extracting REEs from coal-based clays is that the REE concentrations are typically in the range of 300 to 600 ppm, which makes it difficult to extract the critical materials economically using ion-exchange leaching and other processes. As a means to overcome this issue, the REE-bearing particles, including IACs and REMs, were liberated by blunging and subsequently upgraded using the hydrophobic-hydrophilic separation (HHS) process. The results showed that blunging outperformed grinding in liberating the REE-bearing particles from the clayey materials in coal. It was shown that one can improve blunging by increasing the disjoining in the thin liquid films present between clay and other minerals by controlling the double-layer (EDL) forces. These findings should enhance our understanding of the fundamental mechanisms involved in upgrading critical materials and thereby increase the economic viability of REE recovery from coal-based materials. / Doctor of Philosophy / Rare earth elements (REEs) play a vital role in numerous modern industries, advanced technological applications, and defense industries. The United States accounts for about 15 % of the global demand for REEs. However, the country heavily relies on imported Chinese raw materials, creating vulnerability in the U.S. supply chain. REEs are rarely found in concentrations suitable for mining, and in certain cases, extracting and processing conventional REE deposits come with significant environmental hazards. The limited availability of rare earth elements (REEs) raises concerns regarding their production despite their critical role in high-tech industries. Consequently, various federal agencies and private enterprises have recently attempted to identify promising alternative resources due to these complex challenges. REEs have been found in several major coal basins and are evidenced to be associated with coal byproducts such as kaolinite clays–one of the major host materials of IACs. This research investigates the recovery of rare earth elements (REEs) from clayey materials through various processes. Emphasis is placed on the synthesis of ion-adsorption clays from kaolinite, and the factors influencing the ion-exchange leaching process are being studied. Furthermore, the impact of iron co-adsorption on REE binding to kaolinite is being examined, and reductive leaching is being evaluated as a means to overcome the hindrance caused by iron passivating layers. Novel lixiviants are being tested as alternatives to conventional lixiviant ((NH4)2SO4) for REE extraction. The application of hydrophobic-hydrophilic separation techniques for extracting REE-bearing particles from coal clay samples is also being explored, with a comparison made between grinding and blunging processes. Overall, valuable insights into the efficient recovery of REEs from clay minerals are being obtained, contributing to the development of cost-effective and novel approaches for their extraction.

No description available.

An integrated program has been developed to explore the reactivity of 2:1 phyllosilicates (biotite and the clays montmorillonite, hectorite, and nontronite) with respect to acid dissolution using in situ atomic force microscopy (AFM). Three techniques are described which make it possible to fix these minerals and other small particles to a suitable substrate for examination in the fluid cell of the atomic force microscope. A suite of macros has also been developed for the Image SXM image analysis environment which make possible the accurate and consistent measurement of the dimensions of clay particles in a series of AFM images, so that dissolution rates can be measured during a fluid cell experiment. Particles of biotite and montmorillonite were dissolved, and their dissolution rates normalized to their reactive surface area, which corresponds to the area of their edge surfaces (A_e). The A_e-normalized rates for these minerals between pH 1-2 are all ~10E^-8 mol/m²*s, and compare very well to other A_e-normalized dissolution rates in the literature. Differences between the A_e-normalized rates for biotite and the BET-normalized rates (derived from solution chemical studies) found in the literature can be easily explained in terms of the proportion of edge surface area and the formation of leached layers. However, the differences between the A_e-normalized montmorillonite rates and the literature values cannot be explained the same way. Rather, it is demonstrated that rates derived from solution studies of montmorillonite dissolution have been affected by the colloidal behavior of the mineral particles. Finally, the dissolution behavior of hectorite (a trioctahedral smectite) and nontronite ( a dioctahedral smectite) were compared. Based on the differential reactivity of their crystal faces, a model of their surface atomic structures is formulated using Hartman-Perdock crystal growth theory, which explains the observed data if it is assumed that the rate-determining step of the dissolution mechanism is the breaking of connecting bonds between the octahedral and tetrahedral sheets of the mineral structure. / Ph. D.

X-ray photoelectron spectroscopy (XPS) has been used to study the bonding of adsorbed metal cations to clay minerals. Binding energy differences of the adsorbed metal cations can be related to changes in the electron density or charge on the atom of interest. Adsorption experiments were carried out in aqueous solution at controlled pH's of 2, 4, 6, 8, and 10 for Ba²⁺, Co²⁺, Cr³⁺, adsroption on the clays kaolinite and ripidolite. Solution processes were monitored by measuring the solution concentrations of dissolved silica and the metal ions Fe³⁺, Mg²⁺, K⁺, Al³⁺, Cr³⁺, and Co²⁺ at the beginning and the end of the experiment. Atomic absorption spectroscopy was used to determine the metal ion concentrations and dissolved silica was determined spectrophotometrically as a molybdate complex. Examination of the adsorbed cation species on the clay surface by XPS indicated that the clays behaved as nucleation centers at or near the pH of precipitation of the cations. Further it was found that high spin Co²⁺ in solution became low spin Co²⁺ or formed a highly covalent bond when adsorbed on kaolinite at pH's 4, 6, and 7 and on ripidolite at pH 2 and 4. Finally, if the clay has a negatively charged surface which donates some of its charge to the positive cation, then the barium XPS data indicated that ripidolite has a greater negative surface charge than kaolinite. This idea was supported by calculations of the surface charge density from CEC and surface area data. / Master of Science