Composites based on binary polymer blends of polystyrene (PS)/poly(ethylene-co-vinyl alcohol) (EVOH) (70/30 wt%) containing natural Montmorillonite, Na-MMTs (Nanomer PGW or Cloisite Na+) and organically modified Montmorillonite clays, OMMTs (Nanomer I.30T, Cloisite 30B or Cloisite 10A) were prepared via melt compounding. The interactions between the polymers and clays were studied using flow micro-calorimetry (FMC). Data obtained from FMC indicated that the probe molecule mimicking EVOH (butan-2-ol) interacted with the MMTs and OMMTs much more strongly than PS. Scanning electron microscopy (SEM) revealed that composites based on binary blends had dispersed/continuous morphologies, in which EVOH was dispersed in a PS matrix. The size of the EVOH droplets in the PS matrix increased with increasing clay loading. Transmission electron microscopy (TEM) and wide angle X-ray diffraction (WAXD) were used to determine the extent of dispersion and location of clay in the PS/EVOH/clay composites. These techniques confirmed the formation of intercalated clay structures. As predicted by FMC, the clay platelets were selectively located in the EVOH phase, independent of the blending sequence and the type of organic modifier in the OMMT. Composites containing OMMTs showed better dispersion of platelets within the EVOH phase than those containing Na-MMTs. Differential scanning calorimetry (DSC); showed the crystallisation behaviour of EVOH to depend on the clay loading and the nature of the organic modifier in the OMMT. Nanomer PGW, Cloisite Na+ and Cloisite 30B acted as weak nucleating agents. In contrast, Nanomer I.30T and Cloisite 10A significantly hindered the crystallisation of EVOH in the blends due to the restriction of chain segment mobility. Dynamic mechanical thermal analysis (DMTA) confirmed that the presence of clay increases the storage modulus of the composites compared to an unfilled blend. In addition, the improvement in storage modulus reflected the dispersion state of the different clays and their interaction with the polymers of the blend. Ternary-blend based composites were formed by adding poly(styrene-co-acrylonitrile) (SAN) to the composites based on binary PS/EVOH blends. This resulted in a finer dispersion of the EVOH phase and the development of a core-shell morphology, in which SAN encapsulated and formed shells around EVOH droplets. In contrast to binary blend composites, the clay platelets were found at the interface between SAN and EVOH in the ternary blends.

Various porous media were tested with biosurfactant solutions (rhamnolipid or Emulsan) at concentrations ranging from 0 ppm to 1000 ppm. The biosurfactant solutions in the presence of porous media often showed substantial gas hydrate catalyzation, localization on selected surfaces, and/or specific hydrate form (massive, stratified, dispersed.) At 1000-ppm concentrations of rhamnolipid, all porous media surfaces exhibited the same hydrate formation rate increase of 187% over the control. The curves generated for rhamnolipid or Emulsan concentration versus peak hydrate formation rate resembled certain classical adsorption curves. Bentonite and aragonite showed hydrate catalyzation properties with or without biosurfactants. The preference for hydrate formation on porous media surfaces (no surfactant) was: Bentonite/nontronite > aragonite/stainless steel > Ottawa sand/kaolinite. Porous media/biosurfactant concentration combinations play marked roles in the types of gas hydrates formed: massive, dendritic, or needle-like. The research helps to explain the vast occurrence of gas hydrates in ocean sediments.

As argilas da região de Uberaba, MG, foram estudadas tendo como objetivo contribuir para o conhecimento de sua gênese, mineralogia e aplicações tecnológicas em cerâmica de materiais refratários. Inicialmente foram identificadas duas áreas de argilas refratárias, uma com maior, e a outra com menor teor de alumina. Em função da análise de documentos, tais como pedidos de licença de lavra junto ao DNPM, planos de mineração e respectivos mapas e croquis das empresas que se utilizam dessas argilas, de informações fornecidas pelos mineradores de argilas refratárias, e de observações no campo das ocorrências, coletaram-se amostras de três bacias denominadas: Boa Esperança, Caraço e Tijuco. As amostras foram estudadas por meio de análises granulométricas, microscopia óptica dos resíduos leves e pesados, difração de raios X, análises térmicas: diferencial e termogravimétrica, análises químicas, microscopia eletrônica de varredura da fração argila e ensaios cerâmicos: módulo de ruptura à flexão, absorção de água, porosidade aparente, em corpos de prova prensados, cone pirométrico, e consumo de defloculante. Os resultados das análises granulométricas sugerem que nas três bacias predominou um ambiente de baixa energia, com regime de sedimentação em águas calmas, provavelmente produto de planícies de inundação. Os sedimentos são constituídos basicamente pelos minerais caulinita, gibbsita, quartzo, mais raramente micas. A presença de quartzo com baixo grau de arredondamento e esfericidade sugere a possibilidade da contribuição de rochas próximas. Os minerais pesados, zircão, turmalina e rutilo, com elevado grau de esfericidade e arredondamento, parecem indicar que as argilas teriam se originado pelo retrabalhamento de rochas sedimentares. Já a presença de cianita (majoritário), estaurolita e sillimanita, com baixo grau de esfericidade e arredondamento, evidenciam a contribuição de rochas metamórficas. Do ponto de vista cerâmico, os materiais estudados podem ser classificados como argilas refratárias. As mais aluminosas são indicadas para a fabricação de chamotes para refratários sílicoaluminosos a aluminosos, ocorrem preferencialmente na região de Caraço e Tijuco. As menos aluminosas podem ser utilizadas como argilas ligantes para chamotas ou como componentes de massas para cerâmica branca, típicas da área de Boa Esperança. Estas podem ser utilizadas, quando o teor de gibbsita na composição não exceder a 14%, por processos via úmida (colagem). As mais aluminosas, além do consumo elevado do defloculante, tem comportamento tixotrópico em suspensão aquosa, não sendo recomendadas para produção de materiais refratários por colagem. / The main goal of the study of the clays from Uberaba, Minas Gerais State, Brazil, was to contribute to the knowledge of their origin, their mineralogical constitution and their technological applications in refractory products. First two different areas containing refractory clays were identified, one presenting a higher alumina content and the other one presenting a lower alumina content. From the analysis of different document sources such as licensing requests for mining from DNPM; mining plans with maps and croquis from the companies which use these clays; information provided by miners of refractory clays and field investigations, samples were collected in the three basins named Boa Esperança, Caraço and Tijuco. The samples were studied by means of grain sized analyses, optic microscopy of the light and heavy residues, X rays diffraction analysis, differential and thermogravimetric thermal analysis, scanning electron microscopic, chemical analysis and ceramic tests, including flexural strength, water absorption, apparent porosity, in pressed bodies of test, and pyrometric cones and deffloculant consumption. The results of the grain sized analyses suggest, for the three basins, an environment of low energy, with a sedimentation regimen of calm waters, probably flooding plain. The sediments are constituted mainly by caulinita, gibbsite, quartz and more rare mica. The presence of quartz, with low degree of rounding and sphericity suggest the contribution of nearby rocks. The heavy minerals, zircon, tourmaline and rutile, with high degree of sphericity and rounding, seems to indicate that the refractories clays were originated from reworked sedimentary rocks. On the other hand, cyanite (majority), estaurolite and sillimanite, with low degree of sphericity and rounding, evidenciate contribution from metamorphic rocks. From a ceramic point of view, the studied materials may be classified as refractory clays. The ones with higher contents of alumina are indicated for the production of chamottes for silica-alumina and alumina refractory products and are found preferably in the Caraço and Tijuco area. The less aluminous ones may be used as binding clays for chamottes or as components of sanitaryware slip, and are typical in the Boa Esperança area. They may be used in wet processes (slip casting) when the gibbsite content is lower than 14%. The ones with higher contents of alumina, besides the high deffloculant consumption, present a thixotropic behavior in aqueous suspensions. Thus, its use is not recommended for the making of refractory products by slip casting.

As argilas da região de Uberaba, MG, foram estudadas tendo como objetivo contribuir para o conhecimento de sua gênese, mineralogia e aplicações tecnológicas em cerâmica de materiais refratários. Inicialmente foram identificadas duas áreas de argilas refratárias, uma com maior, e a outra com menor teor de alumina. Em função da análise de documentos, tais como pedidos de licença de lavra junto ao DNPM, planos de mineração e respectivos mapas e croquis das empresas que se utilizam dessas argilas, de informações fornecidas pelos mineradores de argilas refratárias, e de observações no campo das ocorrências, coletaram-se amostras de três bacias denominadas: Boa Esperança, Caraço e Tijuco. As amostras foram estudadas por meio de análises granulométricas, microscopia óptica dos resíduos leves e pesados, difração de raios X, análises térmicas: diferencial e termogravimétrica, análises químicas, microscopia eletrônica de varredura da fração argila e ensaios cerâmicos: módulo de ruptura à flexão, absorção de água, porosidade aparente, em corpos de prova prensados, cone pirométrico, e consumo de defloculante. Os resultados das análises granulométricas sugerem que nas três bacias predominou um ambiente de baixa energia, com regime de sedimentação em águas calmas, provavelmente produto de planícies de inundação. Os sedimentos são constituídos basicamente pelos minerais caulinita, gibbsita, quartzo, mais raramente micas. A presença de quartzo com baixo grau de arredondamento e esfericidade sugere a possibilidade da contribuição de rochas próximas. Os minerais pesados, zircão, turmalina e rutilo, com elevado grau de esfericidade e arredondamento, parecem indicar que as argilas teriam se originado pelo retrabalhamento de rochas sedimentares. Já a presença de cianita (majoritário), estaurolita e sillimanita, com baixo grau de esfericidade e arredondamento, evidenciam a contribuição de rochas metamórficas. Do ponto de vista cerâmico, os materiais estudados podem ser classificados como argilas refratárias. As mais aluminosas são indicadas para a fabricação de chamotes para refratários sílicoaluminosos a aluminosos, ocorrem preferencialmente na região de Caraço e Tijuco. As menos aluminosas podem ser utilizadas como argilas ligantes para chamotas ou como componentes de massas para cerâmica branca, típicas da área de Boa Esperança. Estas podem ser utilizadas, quando o teor de gibbsita na composição não exceder a 14%, por processos via úmida (colagem). As mais aluminosas, além do consumo elevado do defloculante, tem comportamento tixotrópico em suspensão aquosa, não sendo recomendadas para produção de materiais refratários por colagem. / The main goal of the study of the clays from Uberaba, Minas Gerais State, Brazil, was to contribute to the knowledge of their origin, their mineralogical constitution and their technological applications in refractory products. First two different areas containing refractory clays were identified, one presenting a higher alumina content and the other one presenting a lower alumina content. From the analysis of different document sources such as licensing requests for mining from DNPM; mining plans with maps and croquis from the companies which use these clays; information provided by miners of refractory clays and field investigations, samples were collected in the three basins named Boa Esperança, Caraço and Tijuco. The samples were studied by means of grain sized analyses, optic microscopy of the light and heavy residues, X rays diffraction analysis, differential and thermogravimetric thermal analysis, scanning electron microscopic, chemical analysis and ceramic tests, including flexural strength, water absorption, apparent porosity, in pressed bodies of test, and pyrometric cones and deffloculant consumption. The results of the grain sized analyses suggest, for the three basins, an environment of low energy, with a sedimentation regimen of calm waters, probably flooding plain. The sediments are constituted mainly by caulinita, gibbsite, quartz and more rare mica. The presence of quartz, with low degree of rounding and sphericity suggest the contribution of nearby rocks. The heavy minerals, zircon, tourmaline and rutile, with high degree of sphericity and rounding, seems to indicate that the refractories clays were originated from reworked sedimentary rocks. On the other hand, cyanite (majority), estaurolite and sillimanite, with low degree of sphericity and rounding, evidenciate contribution from metamorphic rocks. From a ceramic point of view, the studied materials may be classified as refractory clays. The ones with higher contents of alumina are indicated for the production of chamottes for silica-alumina and alumina refractory products and are found preferably in the Caraço and Tijuco area. The less aluminous ones may be used as binding clays for chamottes or as components of sanitaryware slip, and are typical in the Boa Esperança area. They may be used in wet processes (slip casting) when the gibbsite content is lower than 14%. The ones with higher contents of alumina, besides the high deffloculant consumption, present a thixotropic behavior in aqueous suspensions. Thus, its use is not recommended for the making of refractory products by slip casting.

Clays are used for long for the control of soil and water pollution as they are inexpensive natural materials with a high adsorption capacity for a wide range of pollutants. However their use as components in engineered waste containment systems is often limited when it comes to the control of organic contaminants as the clays are organophobic in nature. Organic modification of the natural clays, by replacing the exchangeable inorganic cations of clay with organic cations, can facilitate to overcome this limitation. On modification the clays become organophilic which can enhance their sorption capacities for organic contaminants. There are several ways by which natural clays can be modified with organic cations. The type of clay, the type of modifier, and the extent of modification play an important role in enhancing the organic sorption capacity. Sorption of organics by the organo clays depends on a large extent on the specific interactions that occur between modified clay and the organic contaminants. The interaction between the clay and the contaminants depend on the physico-chemical properties of modified clay and nature of organic contaminants. Since the properties of natural clays are likely to be altered by the modification a detailed study has been taken up to understand the physico chemical characteristics of organo clays which essentially control their organic sorption efficiency. Apart from bentonite which is widely used as a component of barrier systems, the characteristics of other types of clays on organic modification also needs to be assessed as they can also form part of the containment system frequently. Further the modification of clays is bound to bring in significant changes on their geotechnical properties which may affect their performance when used as barrier material. Only limited research has been conducted in the past on the geotechnical characteristics of organo clay. Therefore extensive studies have been carried out on the evaluation of the geotechnical characteristics of organo clays and the effect of organic modification on important geotechnical properties. Since very often inorganic and organic contaminants can occur simultaneously, admixtures of bentonite and organically modified clays needs to be employed as a part of clay barrier system. Moreover clay alone is very rarely used as component of barrier systems and significant portion of barrier material usually include non clay fraction. Hence studies have been carried out on mixtures containing different proportions of organo clay and bentonite and sand – organo clay / bentonite to evaluate their geotechnical behavior. Important geotechnical properties considered for detailed studies are swelling, compressibility and permeability. Detailed studies on the organic sorption capacities of different organically modified and unmodified clays, mixtures of bentonite and organo clays have also been conducted. The results of studies conducted are presented in 9 chapters. The organization of the thesis is as follows: Chapter 1 gives detailed background information on the sources and hazards of organic contaminants, inadequacy of conventional barriers to contain organic contaminants, the need for modification of natural clays, and the methods for organic modification of clays. Extensive review of literature has highlighted the need to study the effect of organic modification on the physico chemical and geotechnical properties of clay in different pore fluids. Organo clays were prepared using a wide range of clays viz., two types of bentonites of different regions, black cotton clay and commercially available kaolinite with a long chain organic cation. The extent of organic modification was varied by varying the amount of organic cation exchanged as function of total cation exchange capacity of the clays. Detailed physico chemical characterization of these modified and unmodified clays has been carried out with the help of different state of art techniques. The Chapter 2 brings out the effect of modification, role of type of clay and type of modifiers on the characteristics of organo clays by comparing the physico chemical characteristics of different modified and unmodified clays. The organic modification of montmorillonitc clays with long chain organic cation is found to increase their lattice spacing with the amount of modification whereas no such increase was observed on modification of kaolinitic clays even when all the exchangeable inorganic cations were replaced with the organic cations. The XRD studies revealed that the intercalated organic cations of the modified montmorillonite clays assumed mono, bi, or pseudo tri layer depending on the extent of organic modification. Irrespective of the type of clay modified or the modifier used all the organo clays tend to become e hydrophobic, and the surface area of the clays was found to decrease. A comparison of the characteristics of clays modified in laboratory with organo clay obtained commercially revealed that the organic modification was more effective for the organo clay prepared in the laboratory. As the index properties of all clays are generally correlated with their geotechnical characteristics, the effect of organic modification on the index properties of clays was studied. Chapter 3 presents the effect of organic modification on the plasticity and free swell behavior of clays. The index properties of commercially available organo clay and the unmodified clay used for its preparation were evaluated with pore fluids of different dielectric constants. Fluids of varied dielectric constants were chosen as it is one of the important characteristics to understand the behavior of clays. It was observed that the organic modification of clays reduced the plasticity of the clays in water and increased the plasticity in less polar liquids like ethanol. As the organo clays are more hydrophobic, the water holding capacity and plasticity in water is decreased to a large extent. The free swell behavior of clays in different pore fluids were assessed in terms of the modified free swell index. It was found that trend of variation of free swell index with dielectric constant for modified and unmodified clays, as in the case of plasticity is quite opposite. The swell volume of the modified clays was observed to be controlled more by surface solvation than by the development of the inter particle repulsive forces and diffused double layer. The effect of incorporating unmodified bentonite with organically modified clay on the index properties of bentonite has also been studied. The results suggested that the effect of organo clay addition to bentonite was always to reduce its plasticity and free swell in water. However in pore fluids of lower dielectric an increase in the plasticity and free swell was observed with increasing organo clay content in the mixture. This owes to the fact that organo clays can interact strongly with organic fluids, changing its fabric arrangement. As reported from literature it is well established that the swell of clays has conflicting role on the stability and permeability of clay barriers. Swelling of clays is liable to cause a reduction in hydraulic conductivity, enhance the retention times of contaminants and attribute self healing capacity to the liners. Even though extensive studies have been carried out on the swell behaviour and mechanism of swell of unmodified clays, no systematic research is reported on the effect of organic modification on swell behavior of clays especially in the presence of different pore fluids. Chapter 4 describes the results of oedometer swell tests carried out on compacted samples of modified, unmodified clays and organo clay –bentonite mixture in the presence of different pore fluids such as water, ethanol, and their mixture and carbon tetra chloride. Swelling ability of the unmodified clays was not completely suppressed even in the presence of low polar miscible organic liquids as they were molded at water contents corresponding to the optimum moisture content (OMC). The order of the swelling for the unmodified bentonites was in the order of the polarity of the pore fluids used, while the order is reversed upon organic modification of clays. The mechanism of swell in the case of organo clays in organic liquids was related to the solvation of the organic liquid by the intercalated organic cations. And unlike in the case of unmodified clays, the organo clays showed “solvent induced swelling”. Both organic modification and addition of organo clay to bentonite resulted in the suppression of the swelling of clays in water irrespective of the type of modifier or the extent of organic modification. The Chapter 5 gives a detailed account of the compressibility behavior of organically modified clays and its mixtures with bentonite when the samples were molded with water at their respective OMC and later inundated with different fluids. Significant differences were observed on the compressibility of modified and unmodified clay in different fluids. Organic modification of clays reduced their affinity to water and resulted in lowering the compressibility. However there was an increased compressibility for the organo clays when the samples were inundated with non polar liquids and the compression of the organo clay in non polar fluid was not influenced by the nature of clay nor by the type of modifier. The compressibility of the mixtures of organo clay and bentonite in non polar liquids was generally controlled by the organo clay component of the mixture. Organo clays can be recommended as additives in bentonite slurries for construction of slurry walls in order to improve the containment of organics. But the amendment should not compromise the stability and integrity of the slurry walls. Moreover the influence of addition of sorptive material like organo clay on the compressibility behavior of bentonite slurry has received little attention and needs serious consideration as the studies in the previous chapter has brought out that the compressibility of compacted bentonite reduced significantly on organic modification as well as on addition of orgno clay. The Chapter 6 deals with the compressibility behavior of slurries of unmodified bentonite, organo clay, and their mixtures molded with respective liquid limits with water and later inundated with fluids of different dielectric constants as the slurries frequently get in contact with fluids other than water during their operational life. However it was observed that the effect of polarity of the inundating liquid is masked in all the cases by the presence of large amount of initial molding water as the possible specific chemical interactions between organo clay and non polar fluids were restricted in the presence of large amount of molding water. But the slurry samples molded and inundated with non polar carbon tetra chloride showed that the organo clay samples are more compressible when molded with carbon tetrachloride. The chapter also gives a brief discussion on the effect of initial molding water content on the compressibility of organo clays and its mixtures. The compression was found to increase with increase in initial water content irrespective of the type of inundating fluid in agreement with the behavior observed in the case of unmodified clays. However the effect was less pronounced at higher applied pressures. The Chapter 7 brings out the volume change behavior of organo clay amended sand bentonite mixtures (SOB) which form potential barrier to prevent and /or remove contaminants. The compaction behavior of mixtures showed that the degree of compaction achieved was controlled mainly by the sand content and proportion of organo clay in the total fine fraction. The volume change behavior of the SOB mixtures were assessed with the help of oedometer tests conducted on mixtures compacted at OMC conditions and inundated with different fluids same as those used for the swell tests. The samples with higher sand content showed no observable swell when inundated with liquids viz., water, ethanol and their mixture as all the swollen finer particles were accommodated in the voids created by sand particles. However a high swell percentage was measured when samples with high organo clay content were inundated with carbon tetrachloride. Moreover with increased amounts of organo clay in the mix the swelling of bentonite was suppressed and the same trend continued even when the pore fluids were changed to liquids of medium polarity. The organo clays are capable of interacting strongly with non polar liquids like carbon tetra chloride, and hence an appreciable swell was noted when inundated with them especially in the case of mixtures with high organo clay content. The swell behavior of SOB mixtures with lower sand contents were controlled mostly by the interaction of the pore fluid with bentonite and organo clay, interactions between organo clay and bentonite and the polarity of the pore fluid. As the pore fluid polarity was decreased the influence of organo clay component of the mixture was more pronounced. The Chapter 8 explains the hydraulic performance of modified and unmodified clays along with that of the mixtures of organo clay with bentonite and SOB. The coefficient of permeability was calculated from the consolidation data obtained on sample molded at OMC. The permeability variations observed on changing the pore fluids were studied at each applied pressure. The hydraulic conductivity showed a decreasing trend with the increase in applied pressure for all the clays. The specific interactions of the organo clay with the pore fluids and the clay content were found to play a role in controlling the permeability. Limited tests were carried out to simulate a condition where a SOB liner is proposed as a secondary liner below a punctured geo membrane and its hydraulic performance was evaluated with diesel and water as pore fluids. The permeability coefficients with diesel as permeant were observed to decrease with increase in organo clay content of the mixture irrespective of the applied pressure where as the reverse was true when permeated with water. Thus the use of SOB as secondary liner below storage tanks so as to control the transport of contaminants leaking containments systems is established. The organic sorption efficiency of the modified and unmodified clays and the mixture were evaluated in terms of removal of total organic carbon (TOC) and reduction in chemical oxygen demand (COD) of the different leachates including municipal solid waste (MSW) leachate when treated with different types of modified and unmodified clays. All the modified clays irrespective of the type of clay or the type of modifier used showed improved organic sorption capacity. The sorption of TOC was found to follow a linear sorption mechanism in the case of organo clays and the organic contaminants were partitioned on to the organic phase attached to the organo clays. The composition, age and type of leacahte played a major role in controlling the organic sorption efficiency of organo clays in the case of MSW leachates. The studies done with different mixtures of organo clay and bentonite and SOB mixtures clearly proved that the addition of organo clay always enhanced the organic sorption efficiency of the mixtures. The results are discussed in Chapter 9. The Chapter 10 highlights the major conclusions drawn from the study. The study, apart from satisfying the research zeal on understanding the behavior of organo clays, has generated important information useful for the geo environmental engineer to arrive at appropriate design of barrier systems incorporating organically modified clay, based on the characteristics of pore fluid.

São propostas modificações em um modelo hipoplástico buscando representar o comportamento mecânico de argilas sobreadensadas. São introduzidos no modelo a razão de sobreadensamento, o intercepto de coesão e índices que representam características do trecho sobreadensado, resultando em parâmetros com claro sentido físico e de fácil determinação. A equação constitutiva é então calibrada com parâmetros de solos sobreadensados e a capacidade dos modelos de representar o comportamento de dois solos em particular é verificada, confrontando as previsões teóricas com resultados experimentais em diversas situações de carregamento e para uma larga faixa de razões de sobreadensamento. Verifica-se que as modificações introduzidas no modelo hipoplástico contemplam avanços significativos na representação dos efeitos do sobreadensamento, como a curvatura da envoltória de resistência no trecho sobreadensado, o aumento do módulo de deformabilidade com o grau de sobreadensamento, diferente rigidez no carregamento e no recarregamento, o aumento das tensões desviadoras de ruptura em solos sobreadensados, a diminuição da tendência à contração volumétrica com o aumento da razão de sobreadensamento, chegando à expansão volumétrica, e, nas solicitações não-drenadas, pressão neutra negativa quando o solo encontra-se fortemente sobreadensado. / Modifications in a hypoplastic model are proposed intending to represent the mechanical behavior of overconsolidated clays. The overconsolidation ratio, the cohesion intercept and indices that represent overconsolidation characteristics are introduced in the model, resulting in parameters with a clear physical meaning and of easy to determine. The constitutive equation is then calibrated with parameters of overconsolidated soils and the capacity of the models of representing the behavior of two soils in particular is checked, confronting the theoretical predictions with experimental results in several loading situations and in a wide overconsolidation ratio range. It is verified that the modifications introduced into hypoplastic model contemplates significant advances in the representation of the effects of overconsolidation, like the curvature of the strength envelope in the overconsolidation region, the increase of the deformability modulus with the overconsolitadion ratio, different stiffness in loading and reloading, the increase of the deviator stress at failure in overconsolidated soils, presenting peak deviator stress, a decrease of the tendency to volumetric contraction with the increase of the overconsolidation ratio, including to the volumetric expansion, and, in undrained tests, negative pore pressure when the soil is heavily overconsolidated.

Orientador: Antenor Zanardo / Banca: Jorge Silva Bettencourt / Banca: Roberto Peres Xavier / Banca: Sebastião Gomes de Carvalho / Banca: Maria Margarita Torres Moreno / Resumo: A Mina Granusso está situada nas proximidades de Cordeirópolis/SP e constitui uma fonte importante de matéria-prima para o Pólo Cerâmico de Santa Getrudes. No local aflora uma sucessão de rochas da Formação Corumbataí (Permiano Superior) constituída na base por lamitos maciços que gradam para ritmitos siltosos, passando para um horizonte psamo-pelítico e culminando em uma seqüência de ritmitos siltoarenosos. Uma feição particular é a presença de zonas de alteração hidrotermal, associadas a veios quartzo-carbonáticos e fraturas, que impuseram às rochas alterações químicas, mineralógicas e texturais. Estudos petrográficos, químicos e de DRX indicam que após a compactação mecânica houve injeção de fluidos diagenéticos em um sistema de fraturas originando veios de quartzo de baixa cristalinidade e enriquecimento de sílica de horizontes silto-arenosos. Uma nova injeção fluidal impulsionada pela ação do magmatismo basáltico acelerou a formação de albitas e deu origem a veios com calcita, quartzo, clorita e pirita. Os dados de d18O e d13C mostram que os carbonatos se precipitaram de um fluido isotopicamente homogêneo sem variações drásticas de temperatura. Valores de d13C entre -8,1 a -4,5 (PDB) indicam uma fonte profunda para o CO2 que deu origem a calcita enquanto que valores de d18O entre +18,9 e +24,1 (SMOW) sugere interações sucessivas do fluido com a rocha hospedeira e abaixamento de temperatura. / Abstract: The Granusso mine is located near the Corderopolis city and constitutes an important source of raw material to the Santa Gertrudes Ceramic Cluster. Late Permian sedimentary rocks of the Corumbataí Formation outcrops in the area. The litological succession comprises a sequence of massif, banded to laminate siltstone topped by carbonate to sandy siltstone. Hydrothermal alteration is an important feature generally associated with host rock whitening. A large basaltic sill intruded the sequence and affected the evolution of the diagenetic and hydrothermal process. Petrographic, chemical and XRD dates suggest that after the mechanical compaction a fluid injection caused the precipitation of low-cristalinity quartz and silica enrichment of sandy-siltstone horizons. A new fluid injection driven by the Serra Geral magmatism triggered albite formation and gave rise to the pyrite-chlorite-quartzcalcite veins. Carbon and oxygen isotope studies of the host rocks and veins show that carbonate precipitated from a homogeneous fluid without strong changes in temperatures along hydrothermal conducts. d13C values of -4,5 to -8,1 (PDB) indicate a CO2 deep-source while d18O of +18,4 to +24,1 (SMOW) and the positive correlarion beetween d18O and d13C values suggest a temperature-dependent trend accompanied by a progressively increasing of fluid/rock interaction. / Doutor

São propostas modificações em um modelo hipoplástico buscando representar o comportamento mecânico de argilas sobreadensadas. São introduzidos no modelo a razão de sobreadensamento, o intercepto de coesão e índices que representam características do trecho sobreadensado, resultando em parâmetros com claro sentido físico e de fácil determinação. A equação constitutiva é então calibrada com parâmetros de solos sobreadensados e a capacidade dos modelos de representar o comportamento de dois solos em particular é verificada, confrontando as previsões teóricas com resultados experimentais em diversas situações de carregamento e para uma larga faixa de razões de sobreadensamento. Verifica-se que as modificações introduzidas no modelo hipoplástico contemplam avanços significativos na representação dos efeitos do sobreadensamento, como a curvatura da envoltória de resistência no trecho sobreadensado, o aumento do módulo de deformabilidade com o grau de sobreadensamento, diferente rigidez no carregamento e no recarregamento, o aumento das tensões desviadoras de ruptura em solos sobreadensados, a diminuição da tendência à contração volumétrica com o aumento da razão de sobreadensamento, chegando à expansão volumétrica, e, nas solicitações não-drenadas, pressão neutra negativa quando o solo encontra-se fortemente sobreadensado. / Modifications in a hypoplastic model are proposed intending to represent the mechanical behavior of overconsolidated clays. The overconsolidation ratio, the cohesion intercept and indices that represent overconsolidation characteristics are introduced in the model, resulting in parameters with a clear physical meaning and of easy to determine. The constitutive equation is then calibrated with parameters of overconsolidated soils and the capacity of the models of representing the behavior of two soils in particular is checked, confronting the theoretical predictions with experimental results in several loading situations and in a wide overconsolidation ratio range. It is verified that the modifications introduced into hypoplastic model contemplates significant advances in the representation of the effects of overconsolidation, like the curvature of the strength envelope in the overconsolidation region, the increase of the deformability modulus with the overconsolitadion ratio, different stiffness in loading and reloading, the increase of the deviator stress at failure in overconsolidated soils, presenting peak deviator stress, a decrease of the tendency to volumetric contraction with the increase of the overconsolidation ratio, including to the volumetric expansion, and, in undrained tests, negative pore pressure when the soil is heavily overconsolidated.

A incorporação de nanocargas minerais e vegetais em matriz polimérica tem sido estudada, principalmente, com o objetivo de melhorar as propriedades de desempenho mecânico dos polímeros para aplicações industriais diversas. As argilas organofilizadas e as fibras vegetais estão entre os materiais que se destacam como cargas adicionadas ao polímero para a formação de nanocompósitos. Essa área de estudo tem despertado interesse também devido à obtenção de melhorias de propriedades físicas, químicas e mecânicas desses materiais quando comparadas às dos materiais compósitos tradicionais. O objetivo da pesquisa foi estudar algumas dessas propriedades em nanocompósitos produzidos com polipropileno, argila esmectítica brasileira e fibra do ouriço da castanha-do-brasil, com ênfase na melhora das propriedades mecânicas. Inicialmente, os materiais componentes foram caracterizados por diversos ensaios, tais como, difração de raios X, granulometria, infravermelho, microscopia eletrônica de varredura, temperatura de degradação térmica, além de ensaios específicos para medir características individuais da argila, como, viscosidade Fann, inchamento de Foster, limite de plasticidade, fluorescência de raios X, entre outros. Posteriormente, o polipropileno graftizado com anidrido maleico (PP-g-MA) foi incorporado ao PP puro (PP), em extrusora dupla rosca, nas proporções de 5%, 10% e 20% em peso e injetados os corpos de prova para os ensaios de tração e impacto. A partir dos resultados das propriedades mecânicas definiu-se o uso de 5% de PP-g-MA para preparação dos nanocompósitos definitivos. Finalmente, variou-se a quantidade de fibra na composição. Foram obtidos nanocompósitos de polipropileno (PP) e 5% PPg- MA reforçado com 5% em peso da argila organofilizada e fibra do ouriço da castanha-do-brasil em três proporções 5%, 10% e 15% em peso. As amostras foram caracterizadas por diferentes técnicas (DRX, MEV, FTIR, TG/DSC) e medidas as resistências mecânicas à tração, flexão e impacto. Todos os nanocompósitos apresentaram aumento na resistência mecânica quando comparados ao polímero sem argila e fibra. / The incorporation of vegetable and mineral nanofillers in polymer matrix has been studied mainly in order to improve the mechanical performance properties of polymers for various industrial applications. The organoclays and vegetable fibers are among the materials that stand out as fillers added to polymer for the formation of nanocomposites. This study has also attracted interest owing to achieve improvements in various properties when compared to other traditional composite materials. This study aims to investigate the effects of adding organophilic clay and brazilian nut fibers on the some physical, chemical and mechanical properties of polypropylene nanocomposite. Initially, The component materials were characterized by tests, such as X-ray diffraction, particle size, infrared, scanning electron microscopy, thermal degradation, as well as specific assays for measuring individual characteristics and properties of the clay, for example, viscosity Fann, Foster swelling, plasticity limit, X-ray fluorescence, among others. In the second step, the graftizado polypropylene with maleic anhydride (PP-g-MA) was incorporated into the pure PP, extruded in proportions of 5 weight%, 10 weight% and 20 weight% and injected the samples for tensile and impact tests. From the results of mechanical properties was defined using 5 weight% of PP-g-Ma for the incorporation into pure PP. Finally, samples were prepared containing only polymer, graftizado polymer/clay, graftizado polymer/clay/ fiber. The addition of clay was 5 weight% and the fiber was added to 5 weight%, 10 weight% and 15% by weight, respectively. The nanocomposites were prepared double-screw extruder and the samples injection molded, then, they were characterized by X-ray diffraction, scanning electron microscope (SEM), thermal analysis (TG/DSC), infrared spectroscopy and mechanical strength, flexural and impact test. All the nanocomposites increased mechanical properties as compared to polymer without clay and fibers.

Made available in DSpace on 2014-06-11T19:23:28Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-08-13Bitstream added on 2014-06-13T18:50:38Z : No. of bitstreams: 1 tavares_ll_me_sjrp.pdf: 1771695 bytes, checksum: ae4d9f94fd6915f2e3ae8fda69b172e0 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O propósito deste estudo foi verificar alterações na estrutura e em algumas propriedades funcionais de biofilmes produzidos com zeína adicionados de argilas modificadas. As argilas modificadas Cloisite® 15A e Cloisite® 30B foram adicionadas na solução filmogênica sob agitação nas proporções de 1, 2 e 4% em relação à massa de zeína e os filmes formados pelo método “casting”. Ácido oléico e glicerol foram utilizados como agentes plasticizantes. Para a caracterização da microestrutura dos biofilmes foram realizadas as análises de Microscopia Eletrônica de Varredura (MEV), Ótica (MO) e Espectroscopia no Infravermelho (FTIR) e as propriedades funcionais avaliadas foram Opacidade, Solubilidade e Permeabilidade ao Vapor d’Água. Por meio das imagens obtidas na MEV observou-se que os acréscimos de argilas nos filmes resultaram na formação de uma microestrutura heterogênea, ou seja, estrutura de fase separada chamada de microcompósito ou tactóide, uma vez que as argilas não dispersaram no filme, o que proporcionou a formação de agregados. No entanto, por meio das imagens obtidas com a MO, observou-se uma distribuição uniforme dos glóbulos de lipídeos na matriz protéica, para todos os filmes. Em concordância com a característica da microestrutura dos filmes elaborados identificados na MEV, o FTIR foi capaz de identificar número de onda referente às argilas, indicando que a mesma não estabeleceu estruturação com a proteína, confirmando a formação de uma estrutura de fase separada tipo tactoide. Todos os filmes elaborados apresentaram maior opacidade quando comparados com o polietileno em razão da presença de pigmentos carotenóides. Pequenas diferenças na espessura das amostras e a quantidade de argila adicionada não influenciaram na transparência dos materiais. Os testes... / The purpose of this study was to evaluate changes in the structure and some functional properties of zein edible films added with modified clays. The modified clays Cloisite® 15A and Cloisite® 30B were added in the solution under agitation in the proportions of 1, 2 and 4% based on the weigh of zein. The films were formed pouring the solution on a surface to dry by casting method. Oleic acid and glycerol were used as plasticizer agents. Analyses of Scanning Electron Microscopy (SEM), Optical Microscopy (MO) and Infrared Spectroscopy (FTIR) were performed to characterize the microstructure of biofilms. The functional properties evaluated were opacity, solubility and permeability of water vapor. SEM images showed that the additions of clays in the films resulted in the formation of a heterogeneous microstructure, i.e. the phase separated structure called microcomposite or tactoids, since the clays were not dispersed in the film, which forms points of aggregates. However, the images obtained with MO showed an even distribution of lipids globules in the protein matrix, for all films. In agreement with the characteristic of the microstructure of the films showed by SEM, FTIR analyses pointed out the absence of wave number related to the clays, indicating that it was not established a really binding of the clays with the protein molecule. This confirms the formation of a material with phase separated, tactoid type. All the films prepared showed higher opacity when compared with polyethylene because of the presence of carotenoid pigments. Little differences in thickness of the samples and the amount of clay added did not influence the transparency of materials. Statistical mean tests of water solubility of the samples showed no differences among those films added with clay and the control. Water... (Complete abstract click electronic access below)