Foi preparado o nanocompósito de borracha natural/argila chocolate B modificada por sodificação via seca com variação no processo, utilizando silicato de sódio ao invés de carbonato de sódio e tratada com sal quaternário de amônio, cloreto hexadecil trimetil amônio. A argila no seu estado natural, após sodificação e após quaternização foi caracterizada pelas técnicas de microscopia estereoscópica, análise térmica, infravermelho, difração de raios X e microscopia eletrônica de varredura. Outras cargas orgânicas foram adicionadas, como celulose e piaçava e comparadas com cargas tradicionais, como o negro de fumo. As placas obtidas, após vulcanização, tiveram medidas as suas propriedades mecânicas e foram analisadas por DRX e MEV. Os nanocompósitos obtidos mostraram melhoria nas suas propriedades mecânicas em comparação com as placas sem a adição de argila. / The natural rubber/clay chocolate B nanocomposite modified by dry sodification process with variation processing was prepared using sodium silicate instead of sodium carbonate and treated with quaternary ammonium salt, hexadecyl trimethyl ammonium chloride. The clay in its natural state after sodification and after quaternization was characterized by the techniques of stereoscopic microscopy, thermal analysis, infrared, X-ray diffraction and scanning electron microscopy. Other organic fillers were added, such as cellulose and piaçava, and compared with traditional fillers such as carbon black. The plates obtained after vulcanization had their mechanical properties measured and were analyzed by XRD and SEM. The obtained nanocomposites showed improvement in their mechanical properties in comparison with the plates without the addition of clay.

Neste estudo, investigaram-se mudanças nas propriedades coloidais de uma esmectita pilarizada com polihidroxicátion de alumínio. A solução pilarizante foi preparada mediante gotejamento de solução NaOH 0,4 mol L-1 em solução de AlCl3.6H2O 0,2 mol L-1, a qual foi adicionada à suspensão de argila de 1% m/m. Para avaliar mudanças nas propriedades das argilas, recorreu-se às técnicas de titulação potenciométrica descontínua, análise química total, DRX, FTIR, CTC e isotermas de adsorção/dessorção de N2. Além disso, foram realizados ensaios de adsorção de Cu2+ para avaliar a capacidade de remoção do metal de soluções aquosas pelas argilas pilarizadas e gerar informações relacionadas à interação entre adsorvente e adsorbato. Naturalmente, a argila apresentou espaçamento basal de 1,26 nm, ao passo que as pilarizadas apresentaram valores de 1,78 nm (500 oC) e 1,80 nm (350 oC). Dados da análise química total mostraram se tratar de uma montmorillonita com altos teores de Fe3+, e confirmou o aumento nos teores de Al3+ na estrutura da argila após pilarização. Os valores de área superficial específica e volume de microporos foram maiores para as argilas pilarizadas, enquanto que a CTC foi maior para a argila natural. A titulação potenciométrica mostrou modificação nas curvas de titulação com o processo de pilarização, em que nas argilas pilarizadas surgiram novos sítios de reação. Dentre as equações de adsorção aplicadas, Langmuir, Freundlich e Temkin, a primeira apresentou valores de r2 das equações linearizadas maior para todas as argilas e menor desvio médio (?g%) para argila natural, ao passo que a equação de Temkin mostrou valores de ?g(%) menores para as argilas pilarizadas. Parâmetros termodinâmicos confirmaram que a reação de adsorção de Cu2+ é espontânea para todas as argilas, principalmente para as argilas pilarizadas. Além disso, cálculos baseados em equações de Dubinin-Radushkevich evidenciam que a ligação é fraca entre metal e argila, caracterizando reações de fisissorção. / In this study, an Al-pillared smectite was synthesized and changes in its colloidal properties were investigated. The pillaring solution was prepared adding dropwise adequate volume of NaOH 0,4M to AlCl3.6H2O 0,2M solution. Then, the pillaring solution was added to a 1% w/w clay slurry with constant stirring. Potentiometric titration, chemical analysis, XRD, FTIR, CEC and N2 sorption/dessoption isotherms analysis were done to characterize the changes in clay properties. Moreover, adsorption experiments were carried out in order to evaluate the capacity of the pillared clays to remove Cu2+ from aqueous solution and to characterize the interaction between adsorbent and adsorbate. The natural clay has a basal spacing of 1.26 nm whereas the pillared clays reached 1.78 nm (500 oC) and 1.80 nm (350 oC) after calcination. Chemical analysis revealed that the montmorillonite used has high content of Fe3+ and the increase in the Al3+ amount in the structure of the pillared clays after pillaring process. The surface area and micropore volume were higher for the pillared clays and the CEC was higher for the natural clay. The pillaring process changed the potentiometric titration curves, wherein the pillared clays exhibited new reactive site. Experimental data were fit to Langmuir, Freundlich and Temkin adsorption equations, being the the first one the best (highest r2 value) for all the clays and lower standard deviation (?g%) for the natural clay. On the other hand, Temkin equation exhibited ?g% value lower for the pillared clays. Thermodynamics parameters demonstrate that the Cu2+ adsorption process is spontaneous for all the clays, but with higher values for the pillared materials. In addition, application of the Dubinin-Radushkevich equation revealed that the bond between the metal and the clay are weak, characterizing a physisorption.

Estimation of effective diffusion coefficients is essential to be able to describe the diffusive transport of solutes in porous media. It has been shown in theory that in the case of uncharged porous materials the effective diffusion coefficient of solutes is a function of the pore morphology of the material and can be described by their tortuosity (tensor). To estimate the apparent diffusion coefficients, the values of tortuosity and porosity should be known first. In contrast with calculation of porosity, which can be easily obtained, estimation of tortuosity is intricate, particularly with increasing micro-geometry complexity in porous media. Moreover, many engineering materials (e.g, clays and shales) are characterized by electrical surface charges on particles of the porous material which can strongly affect the diffusive transport properties of ions. For these materials, estimation of effective diffusion coefficients have been mostly based on phenomenological equations with no link to underlying microscale properties of these charged materials although a few recent studies have used alternative methods to obtain the diffusion parameters. / In the first part of this thesis a numerical method based on a recently proposed up-scaled Poisson-Nernst-Planck type of equation (PNP) and its microscale counterpart is employed to estimate the tortuosity and thus the effective and apparent diffusion coefficients in thin charged membranes. Beside this, a new mathematical approach for estimation of tortuosity is applied and validated. This mathematical approach is also derived while upscaling of micro-scale Poisson-Nernst-Planck system of equations using the volume averaging method. A variety of different pore 2D and 3D micro-geometries together with different electrochemical conditions are studied here. To validate the new approaches, the relation between porosity and tortuosity has been obtained using a multi-scale approach and compared with published results. These include comparison with the results from a recently developed numerical method that is based on macro and micro-scale PNP equations. / Results confirm that the tortuosity value is the same for porous media with electrically uncharged and charged particles but only when using a consistent set of PNP equations. The effects of charged particles are captured by the ratio of average concentration to effective intrinsic concentration in the macroscopic PNP equations. Using this ratio allows to consistently take into account electro-chemical interactions of ions and charges on particles and so excludes any ambiguity generally encountered in phenomenological equations. / Steady-state diffusion studies dominate this thesis; however, understanding of transient ion transport in porous media is also important. The last section of this thesis briefly introduces transient diffusion through bentonite. To do so, the micro Nernst-Planck equation with electro-neutrality condition (NPE) is solved for a porous medium which consists of compacted bentonite. This system has been studied before in another research using an experimental approach and the results are available for both transient and steady-state phases. Three different conditions are assumed for NPE governing equations and then the numerical results from these three conditions are compared to the experimental values and analytical phenomenological solution. The tortuosity is treated as a fitting parameter and the effective diffusion coefficient can be calculated based on these tortuosity values. The results show that including a sorption term in the NPE equations can render similar results as the experimental values in transient and steady state phases. Also, as a fitting parameter, the tortuosity values were found varying with background concentration. This highlights the need to monitor multiple diffusing ion fluxes and membrane potential to fully characterize electro-diffusive transport from fundamental principles (which have been investigated in first part of this thesis) rather than phenomenological equations for predictive studies. / This research has lead to two different journal articles submissions, one already accepted in Computers and Geotechnics (October 22, 2009, 5-yrs Impact Factor 0.884) and the other one still under review.

The current study investigated application of natural adsorbents in brine treatment. Brines are hypersaline waters generated in power stations and mining industries rich in Mg2+, K+, Ca2+, Na+, SO4 2- , Cl- and traces of heavy metals, thus there is a need for these brines to be treated to recover potable water and remove problematic elements. Natural adsorbents have been successfully used in waste water treatment because of their high surface area and high adsorptive properties when they are conditioned with acid or base. The investigation of pH showed that natural adsorbents did not perform well at low pH of 4 and 6. The adsorbents were able to work efficiently at the natural pH of 8.52 of the brine solution. These results show that natural adsorbents hold great potential to remove cationic major components and selected heavy metal species from industrial brine wastewater. Heterogeneity of natural adsorbents samples, even when they have the same origin, could be a problem when wastewater treatment systems utilizing natural clinoptilolite and bentonite are planned to be developed. Therefore, it is very important to characterize the reserves fully in order to make them attractive in developing treatment technologies.

Thin layers with high barrier to oxygen and other gases are a key component to many packaging applications, such as flexible electronics, food, and pharmaceuticals. Vapor deposited thin films provide significant gas barrier, but are prone to cracking when flexed, require special, non-ambient processing environments, and can involve complex fabrication when layered with polymers. The addition of clay into polymers can enhance barrier properties relative to the neat polymer; however, these composites are subject to clay aggregation at high loadings, which leads to increased opacity and random platelet alignment that ultimately reduce barrier improvement. Layer-by-layer (LbL) assembly is capable of producing thin films that exhibit super gas barrier properties, while remaining flexible and completely transparent. Montmorillonite (MMT) clay and branched polyethylenimine (PEI) were deposited via LbL assembly to create gas barrier films that can be tailored by altering the pH of the PEI deposition solution or the concentration of the MMT suspension. Films grow linearly as a function of layers deposited, where increasing PEI pH increases spacing between clay layers and increasing MMT concentration increases thin film clay content. An oxygen transmission rate (OTR) below the detection limit of commercial instrumentation (< 0.005 cm3/m2•day•atm) is observed after 70 layers of 0.2 wt % MMT or 24 layers of 2 wt % MMT are deposited with pH 10 PEI onto 179 µm thick poly(ethylene terephthalate) (PET) film. Three-component films of PEI, poly(acrylic acid) (PAA), and MMT grow exponentially as a function of PEI/PAA/PEI/MMT quadlayers deposited. A transparent, ultrathin film of only four quadlayers deposited onto PET exhibits the lowest oxygen permeability ever reported for any thin film material, at only 51 nm thick. Finally, the first example of LbL assembly using large aspect ratio vermiculite (VMT) clay was performed. PEI/VMT films grow linearly as a function of layers deposited and exhibit 95 % light transmission with 97 wt % VMT. The barrier of these films is due to the highly aligned nanobrick wall structure that creates a tortuous path for permeating molecules. Coupling high flexibility, transparency, and barrier, these coatings are good candidates for a variety of packaging applications.

Coronary artery disease and chronic pain are serious health issues that cause severe discomfort and suffering in society today. Antithrombotic agents and highly potent analgesics play a critical role in improving the recovery process for patients being treated for these diseases. This thesis focuses on the design and study of pellet-based drug dosage forms which allow diffusion-controlled delivery of drugs with the aim of achieving optimal therapeutic outcomes. A wet slurry process was used to mix the drug and the polymer and/or clay precursor excipients into a paste. The pellets were then shaped via ionotropic gelation (alginate hydrogel beads/pellets), extrusion/spheronization (halloysite clay pellets) or geopolymerization. The decrease in the drug diffusion rate in the alginate beads was affected by the drug's molecular size and charge and the characteristics (such as concentration and chemical structure) of the surrounding alginate gel. The halloysite clay pellets provided sustained release of the highly potent drug fentanyl at both gastric pH 1 and intestinal pH 6.8. As expected, crushing the pellets reduced the diffusion barrier, resulting in more rapid release (dose dumping). The use of mechanically strong geopolymer gels was investigated as a potential means of preventing dose dumping as a result of crushing of the dosage form. Variations in the synthesis composition resulted in drastic changes in the microstructure morphology, the porosity, the mechanical stability and the drug release rate. Pore network modeling and finite element simulations were employed to theoretically evaluate the effects of porosity and drug solubility in the geopolymer structure on the drug release process. Fitting the model parameters to experimental data showed that increased average pore connectivity, a greater pore size distribution, and increased drug solubility in the pellet resulted in an increased drug release rate. Furthermore, incorporation of pH-sensitive organic polymers in the geopolymer structure reduced the high drug release rate from the pellets at gastric pH. These results indicate that geopolymers have potential for use in pellet form; both the release rate of the drug and the mechanical stability of the pellets can be optimized to prevent dose dumping.

En presente trabajo se estudian las condiciones de servicio, así como el proceso que ocurre al producirse la rotura del suelo en cargas rápidas sobre arcillas: a) Elaboración de un modelo elasto-plástico, en el cual se reproduzca la plastificación progresiva del material, definiendo un nuevo criterio de rotura que pueda incluir los factores más representativos del comportamiento de la arcilla, incluso la anisotropía y la heterogeneidad de la misma que no eran considerados anteriormente. b) Introducción de este modelo reológico en un nuevo modelo de elementos finitos. De entre las diferentes posibilidades se ha elegido un modelo híbrido en tensiones y deformaciones, para lo cual partiendo del principio variacional de REISSNER, se ha generalizado para estudiar la fase plástica. La discretización se ha efectuado con los elementos triangulares y cuadrangulares híbridos. c) Se aplica el modelo en una zapata en faja indefinida actuando sobre una capa de arcilla deformable sobre una base rocosa rígida con interfaz lisa, variándose todos los parámetros que en él intervienen y deducción de una serie de conclusiones sobre la influencia de los factores estudiados en el comportamiento de la arcilla. / In this paper we study the conditions of service, and the process that occurs at ground breaking in fast load on clays: a) Development of elastic-plastic model in which to play the pushover of the material, defining a new failure criterion which may include factors represent the behavior of the clay, including the anisotropy and heterogeneity of the same were not considered previously. b) Introduction of the rheological model in a new finite element model. Among the different possibilities we have chosen a hybrid model stresses and strains for which starting from the Reissner variational principle has been generalized to study the plastic phase. The discretization was made with triangular and quadrangular elements hybrids. c) Model was applied in a strip footing on indefinite acting on a layer of deformable clay on a rock hard smooth interface, by varying all the parameters involved in it and deduction of a number of conclusions about the influence of the factors studied the behavior of the clay.

The current study investigated application of natural adsorbents in brine treatment. Brines are hypersaline waters generated in power stations and mining industries rich in Mg2+, K+, Ca2+, Na+, SO4 2- , Cl- and traces of heavy metals, thus there is a need for these brines to be treated to recover potable water and remove problematic elements. Natural adsorbents have been successfully used in waste water treatment because of their high surface area and high adsorptive properties when they are conditioned with acid or base. The investigation of pH showed that natural adsorbents did not perform well at low pH of 4 and 6. The adsorbents were able to work efficiently at the natural pH of 8.52 of the brine solution. These results show that natural adsorbents hold great potential to remove cationic major components and selected heavy metal species from industrial brine wastewater. Heterogeneity of natural adsorbents samples, even when they have the same origin, could be a problem when wastewater treatment systems utilizing natural clinoptilolite and bentonite are planned to be developed. Therefore, it is very important to characterize the reserves fully in order to make them attractive in developing treatment technologies.

In this thesis, it is aimed to design lithium extraction from boron clays using statistical design of experiments and robust design methodologies. There are several factors affecting extraction of lithium from clays. The most important of these factors have been limited to a number of six which have been gypsum to clay ratio, roasting temperature, roasting time, leaching solid to liquid ratio, leaching time and limestone to clay ratio. For every factor, three levels have been chosen and an experiment has been designed. After performing three replications for each of the experimental run, signal to noise ratio transformation, ANOVA, regression analysis and response surface methodology have been applied on the results of the experiments. Optimization and confirmation experiments have been made sequentially to find factor settings that maximize lithium extraction with minimal variation. The mean of the maximum extraction has been observed as 83.81% with a standard deviation of 4.89 and the 95% prediction interval for the mean extraction is (73.729, 94.730). This result is in agreement with the studies that have been made in the literature. However / this study is unique in the sense that lithium is extracted from boron clays by using limestone directly from the nature, and gypsum as a waste product of boric acid production. Since these two materials add about 20% cost to the extraction process, the results of this study become important. Moreover, in this study it has been shown that statistical design of experiments help mining industry to reduce the need for standardization.

Os ensaios de palheta são frequentemente utilizados na estimativa da resistência não-drenada de depósitos de argilas moles devido à simplicidade do equipamento, rapidez de execução e baixo custo. A velocidade de deformação em ensaios de palheta de campo é, geralmente, de 6º/min. Contudo, os resultados destes ensaios são influenciados por vários fatores e, dentre eles, a velocidade de rotação pode ser considerada um dos mais importantes. Sob condições não-drenadas, os materiais argilosos apresentam ganho de resistência não-drenada com o aumento da velocidade de cisalhamento, resultante da viscosidade da água adsorvida nas partículas de solo. Como o ensaio de palheta tem sido cada vez mais utilizado para estimar a resistência não-drenada de outros solos de granulometria fina, como siltes, resíduos de mineração entre outros, é preciso ter cautela na interpretação dos resultados nestes materiais, pois a utilização da velocidade padrão de campo pode levar à ocorrência de drenagem parcial durante o cisalhamento e, nestes casos, os solos apresentam resistência e rigidez maiores que sob condições não-drenadas. Desta forma, o objetivo deste trabalho consiste na avaliação da influência da velocidade de rotação do ensaio de palheta na resistência dos solos. Foram realizados ensaios de palheta, utilizando palhetas de 20,2, 25,5 e 40,0 mm de diâmetro e com relação altura-diâmetro igual a 2 a velocidades de rotação de 0,68 a 10800o/min, utilizando três misturas compostas por 85% caulim e 15% bentonita com 100, 130% e 160% de umidade (argilosas), uma mistura composta por caulim puro a 50% de umidade (silte) e uma mistura composta por 60% caulim e 40% areia com 40% de umidade (silte). A partir dos resultados dos ensaios de palheta, observou-se que a resistência não-drenada aumenta com a velocidade, sob condições não-drenadas, tanto para os solos argilosos quanto para os siltosos. A resistência não-drenada também é influenciada pelo diâmetro da palheta e pelo índice de vazios do solo, e consequentemente pelo seu teor de umidade. A resposta viscosa dos ensaios de palheta ao longo de toda a faixa não-drenada pode ser descrita por uma equação potencial (para valores de velocidade adimensional maiores que 10). Os solos siltosos, especialmente a argila misturada com areia, também apresentam aumento de resistência com o aumento da velocidade, sob condições não-drenadas, mais pronunciado que para os solos argilosos. Entretanto, a pequenas velocidades, uma parcela do excesso de poro pressão gerado durante a rotação da palheta foi dissipado, ocasionando efeitos de drenagem parcial durante o cisalhamento. O torque medido durante os ensaios é influenciado pelas dimensões da palheta. Porém, não foi verificada qualquer tendência de variação na resistência normalizada (T/Tref) decorrente das dimensões da palheta. A velocidade normalizada (V) considera diretamente, além da velocidade, a geometria da palheta e o coeficiente de adensamento do solo e reflete os efeitos de permeabilidade, rigidez e velocidade de cisalhamento, fatores que também controlam a viscosidade. Desta forma, os efeitos viscosos dos ensaios de palheta são representados com precisão no espaço normalizado. Além da avaliação dos efeitos de velocidade devido a viscosidade, a normalização dos resultados no espaço T/Tref versus V possibilita também a avaliação dos efeitos de drenagem parcial. Ou seja, dois fenômenos físicos distintos podem ser identificados e interpretados utilizando a mesma abordagem. / Vane tests are frequently used to estimate the undrained shear strength of soft clays deposits because of the equipment simplicity, speed and low costs. The strain rate used in vane shear tests is generally of 6o/min. However, vane tests results are influenced by many factors and rate of shear can be considered one of the most important. Under undrained conditions, undrained shear strength of clayey soils increases with shear velocity. This increase on undrained shear strength occurs due to viscous effects. Furthermore, this method has been used to estimate the undrained shear strength of other fine-grained materials such as silts, tailings, among others. Tests results interpretation must to be careful on these materials, because partial drainage can occur during shear tests conducted at the standard field shear rate. In this cases, soil strength and stiffness are higher than under undrained conditions. Thus, this research is aimed to evaluate the influence of the vane shear velocity in soils strength. Vane tests were conducted using vanes with 20.2, 25.5 and 40.0 mm in diameter and with aspect ratio of 2, at rotation rates from 0.68 to 1800o/min using three kaolin-bentonite mixtures composed by 85% kaolin and 15% bentonite with a water content of 100, 130 and 160% (clay), a mixture composed just by kaolin with a 50% water content (silt) and a mixture composed by 60% kaolin and 40% Osório sand with a 40% water content (silt). Tests results shows that clay and silt strength increases with shear rate, under undrained conditions. Undrained shear strength is also influenced by vane diameter and soil void ratio, and consequently by water content. Viscous response on vane tests throughout the undrained range of velocities can be described by a power law (for normalized velocity values further than 10). Silty soils, especially clay-sand mixtures under undrained conditions, exhibited a greater increase on strength than the increased observed for clayey soils. Neverthless, in some tests conducted at low shear velocities, part of pore pressure excess generated during vane rotation was dissipated, occasioning partial drainage effects during shear. The measured torque has been influenced by vane blade dimensions, but any variation on normalized resistance (T/Tref) wasn’t found as a result of vane dimensions. Normalized velocity considers directly peripheral velocity, vane geometry and soil coeficient of consolidation and reflects permeability, stifness and shear rate effects, factors that also control viscous effects. Thus, viscous effects in vane tests are accurately represented on normalized space. In addiction to rate effects due to viscosity evaluation, results normalization on T/Tref versus V space enable partial drainage effects assessment. It shows that the two distinct physical phenomena can be identified and interpreted using one single approach.