The research carried out in this thesis has concentrated on the application of numerical solutions to geotechnical penetration problems in offshore engineering. Several important issues closely relevant to deep-water oil and gas developments were investigated, covering installation of suction caisson foundations, interpretation of fullflow penetrometers and shallow penetration of a cylindrical object (submarine pipeline or T-bar), all in clayey sediments such as are often encountered in deep-water sites. These problems are commonly characterised by large vertical movements of structural elements relative to the seabed. A large deformation finite element method was adopted and further developed to simulate these challenging problems, referred to as Remeshing and Interpolation Technique with Small Strain. In this approach, a sequence of small strain Lagrangian increments, remeshing and interpolation of stresses and material properties are repeated until the required displacement has been reached. This technique is able to model relative motion between the penetrating objects and the soil, which is critical for evaluating soil heave inside the caissons, the effect of penetration-induced remoulding on the resistance of full-flow penetrometers, and influence of soil surface heave on the embedment of pipelines. '...' Simple expressions were presented allowing the resistance factors for the T-bar and ball penetrometers to be expressed as a function of the rate and strain-softening parameters. By considering average strength conditions during penetration and extraction of these full-flow penetrometers, an approximate expression was derived that allowed estimation of the hypothetical resistance factor with no strain-softening, and hence an initial estimate of the stain-rate dependency of the soil. Further simulations of cyclic penetration tests showed that a cyclic range of three diameters of the penetrometers was sufficient to avoid overlap of the failure mechanism at the extremes and mid-point of the cyclic range. The ball had higher resistance factors compared with the T-bar, but with similar cyclic resistance degradation curves, which could be fitted accurately by simple expressions consistent with the strain-softening soil model adopted. Based on the curve fitting, more accurate equations were proposed to deduce the resistance factor with no strain-softening, compared with that suggested previously based on the resistances measured in the first cycle of penetration and extraction. The strain-rate dependency was similar in intact or post-cyclic soil for a given rate parameter. The resistance factor for the post-cyclic condition was higher than that for the initial conditions, to some degree depending upon soil sensitivity and brittleness parameter. For the shallow penetration of a cylindrical object, the penetration resistance profile observed from centrifuge model tests was very well captured by the numerical simulation. The mechanism of shear band shedding was reproduced by the numerical technique, although the frequency of the shear band generation and the exact shape of the heave profile were not correctly captured, which were limited by the simple strainsoftening soil model adopted.

Understanding the bearing response of the footings on layered soils has always been a challenge for researchers. Due to the limitations of analytical and empirical solutions it had been difficult to understand the true bearing behavior. Some researchers have tried solving this problem by numerical analysis and have found some success. In this study the numerical analysis approach has been applied using a commercial tool FLAC (Fast Lagrangian Analysis of Continua) to study the bearing response of surface footings on layered clays. First, small deformation analyses were taken up to study the undrained bearing response of strip and circular footings resting on a horizontally layered strong over a soft clay foundation, and then over soft over strong clay foundation. In the end application of large strain mode of FLAC was explored to investigate the large deformation behavior of the strip footing resting on the surface of a strong over soft clay foundation. All models were run by applying velocity loading and a elastic-perfectly plastic Tresca yield criterion has been used. The results are compared with published Finite Element Method (FEM) results, and with analytical, empirical and semi-empirical solutions. It was found that bearing capacity results from the present small-strain FLAC analyses agree well with the FEM results. However, these results in most of the cases tend to differ (as much as 49% for certain layered clay foundations) from those predicted with analytical, empirical and semi-empirical solutions, mainly due to the assumptions made in these solutions. Since no such assumptions are made in the present FLAC analyses, the results and the methodology of this thesis can be applied to predict the bearing capacity of the practical problems. Application of the large-strain mode of FLAC to study the large deformation of shallow foundations has pointed out a limitation of FLAC in completing such analyses. However, it is observed from the early trends of these analyses that whereas the small deformation analysis may under estimate the ultimate bearing capacity for certain cases of layered foundations where the upper clay is moderately stiffer than the lower clay layer, it might also over predict the ultimate bearing capacity for other cases when the upper clay is very stiff in comparison to the lower clay layer. / February 2007

Las esmectitas como hectorita o saponita, son silicatos laminares. Tienen múltiples aplicaciones (catálisis, nanocomposites, adsorbentes) e interesa tener un material reproducible y sin impurezas. Los métodos convencionales de síntesis comportan tratamientos largos o a altas temperaturas. La introducción del microondas puede disminuir ambos. El objetivo de esta tesis es estudiar la síntesis de hectorita y saponita con microondas y su aplicación como soportes catalíticos de Ni en la hidrogenación de óxido de estireno para la obtención de 2-feniletanol (componente principal de la esencia de rosas) y en la preparación de composites con poliuretano. Se obtienen hectoritas y saponitas reproducibles. Cuando se emplean como soportes de catalizadores de Ni se obtienen conversión y selectividad total hacia el 2-feniletanol. Cuando se utilizan las arcillas obtenidas en preparación de composites sus propiedades son comparables a los de la bibliografía. / Smectites like hectorite or saponite, are phyllosilicates. They can be applied for many purposes (catalysis, nanocomposites, adsorbents) but a reproducible, pure material is necessary. Classical methods of synthesis involve long synthesis times at high temperatures. The use of microwaves can be an interesting alternative. The scope of this thesis is to study the synthesis of hectorites and saponites with microwaves and their application as supports of Ni catalysts in the hydrogenation of styrene oxide to obtain 2-phenylethanol (main component of rose oil) and in the preparation of composites with polyurethane. We obtained reproducible hectorites and saponites. When used as supports of Ni catalysts we obtained total conversion and selectivity to 2-phenyethanol. When obtained clays were used in the preparation of polyurethane composites, their properties were comparables to those of the bibliography

Understanding the bearing response of the footings on layered soils has always been a challenge for researchers. Due to the limitations of analytical and empirical solutions it had been difficult to understand the true bearing behavior. Some researchers have tried solving this problem by numerical analysis and have found some success. In this study the numerical analysis approach has been applied using a commercial tool FLAC (Fast Lagrangian Analysis of Continua) to study the bearing response of surface footings on layered clays. First, small deformation analyses were taken up to study the undrained bearing response of strip and circular footings resting on a horizontally layered strong over a soft clay foundation, and then over soft over strong clay foundation. In the end application of large strain mode of FLAC was explored to investigate the large deformation behavior of the strip footing resting on the surface of a strong over soft clay foundation. All models were run by applying velocity loading and a elastic-perfectly plastic Tresca yield criterion has been used. The results are compared with published Finite Element Method (FEM) results, and with analytical, empirical and semi-empirical solutions. It was found that bearing capacity results from the present small-strain FLAC analyses agree well with the FEM results. However, these results in most of the cases tend to differ (as much as 49% for certain layered clay foundations) from those predicted with analytical, empirical and semi-empirical solutions, mainly due to the assumptions made in these solutions. Since no such assumptions are made in the present FLAC analyses, the results and the methodology of this thesis can be applied to predict the bearing capacity of the practical problems. Application of the large-strain mode of FLAC to study the large deformation of shallow foundations has pointed out a limitation of FLAC in completing such analyses. However, it is observed from the early trends of these analyses that whereas the small deformation analysis may under estimate the ultimate bearing capacity for certain cases of layered foundations where the upper clay is moderately stiffer than the lower clay layer, it might also over predict the ultimate bearing capacity for other cases when the upper clay is very stiff in comparison to the lower clay layer.

Organic-inorganic nanostructured composites are nowadays integrated in the field of material science and technology. They are used as advanced materials directly or as precursors to novel composites with potential applications in optics, mechanics, energy, catalysis and medicine. Many properties of these complex materials depend on conformational rearrangements in their inherently dynamic organic parts. The focus of this thesis is on the study of the molecular mobility in ordered nanostructured composites and lyotropic mesophases and also on the development of relevant solid-state NMR methodologies. In this work, a number of new experimental approaches were proposed for dipolar NMR spectroscopy for characterizing molecular dynamics with atomic-level resolution in complex solids and liquids. A new acquisition scheme for two-dimensional dipolar spectroscopy has been developed in order to expand the spectral window in the indirect dimension while using limited radio-frequency power. Selective decoupling of spin-1 nuclei for sign-sensitive determination of the heteronuclear dipolar coupling has been described. A new dipolar recoupling technique for rotating samples has been developed to achieve high dipolar resolution in a wide range of dipolar coupling strength. The experimental techniques developed herein are capable of delivering detailed model-independent information on molecular motional parameters that can be directly compared in different composites and their bulk analogs. Solid-state NMR has been applied to study the local molecular dynamics of surfactant molecules in nanostructured organic-inorganic composites of different morphologies. On the basis of the experimental profiles of local order parameters, physical motional models for the confined surfactant molecules were put forward. In layered materials, a number of motional modes of surfactant molecules were observed depending on sample composition. These modes ranged from essentially immobilized rigid states to highly flexible and anisotropically tumbling states. In ordered hexagonal silica, highly dynamic conformationally disordered chains with restricted motion of the segments close to the head group have been found. The results presented in this thesis provide a step towards the comprehensive characterization of the molecular states and understanding the great variability of the molecular assemblies in advanced nanostructured organic−inorganic composite materials. / <p>QC 20150225</p>

Understanding the bearing response of the footings on layered soils has always been a challenge for researchers. Due to the limitations of analytical and empirical solutions it had been difficult to understand the true bearing behavior. Some researchers have tried solving this problem by numerical analysis and have found some success. In this study the numerical analysis approach has been applied using a commercial tool FLAC (Fast Lagrangian Analysis of Continua) to study the bearing response of surface footings on layered clays. First, small deformation analyses were taken up to study the undrained bearing response of strip and circular footings resting on a horizontally layered strong over a soft clay foundation, and then over soft over strong clay foundation. In the end application of large strain mode of FLAC was explored to investigate the large deformation behavior of the strip footing resting on the surface of a strong over soft clay foundation. All models were run by applying velocity loading and a elastic-perfectly plastic Tresca yield criterion has been used. The results are compared with published Finite Element Method (FEM) results, and with analytical, empirical and semi-empirical solutions. It was found that bearing capacity results from the present small-strain FLAC analyses agree well with the FEM results. However, these results in most of the cases tend to differ (as much as 49% for certain layered clay foundations) from those predicted with analytical, empirical and semi-empirical solutions, mainly due to the assumptions made in these solutions. Since no such assumptions are made in the present FLAC analyses, the results and the methodology of this thesis can be applied to predict the bearing capacity of the practical problems. Application of the large-strain mode of FLAC to study the large deformation of shallow foundations has pointed out a limitation of FLAC in completing such analyses. However, it is observed from the early trends of these analyses that whereas the small deformation analysis may under estimate the ultimate bearing capacity for certain cases of layered foundations where the upper clay is moderately stiffer than the lower clay layer, it might also over predict the ultimate bearing capacity for other cases when the upper clay is very stiff in comparison to the lower clay layer.

Some normally consolidated soft soils manifest strength sensitivity, ie these soil manifest strain softening when shear in an undrained mode. These soils, referred to as sensitive soft soils, have the typical features of strain hardening in drained shearing and strain softening in undrained shearing. The consolidation lines of these soils are also curved (concave upwards) in the semi-log space. However, under high consolidation stress or upon large shearing, these soils re-gain the features of re-constituted soil. Ground improvement methods like stone columns were reported as not effective when installed in the sensitive soft clays. But mechanism of the un-effectiveness of the stone columns remains unknown because of lack of a suitable and simple model for simulating the stress-strain behaviours of sensitive soft soils. Although these soils have a meta-stable micro-structure, models that developed for simulating structured firm soils are not suitable for simulating sensitive soft soil features. Thus, a new model was formulated. The new model can degenerate back to a Modified Cam Clay model. The ability of new model in simulating a range of behaviour was verified by using the finite difference (FD) method in solving the partial differential equations of the soil model for a range of tri-axial test conditions. The model was further implemented in coupled analysis formulation and coded into FEM program AFENA. Various cases with different soil parameters were then simulated and compared with the FD solutions for various triaxial tests so as to check the stability of the FEM code. The coupled FEA was then used to simulate the performance of geosynthetic-encased stone columns. A new stone column element and a geo-encasement element were developed and coded into AFENA. The stone column simulations were then done for both non-sensitive soils (represented by Modified Cam Clay model) and sensitive soft soil (represented by the new model). Parametric study was conducted to examine the performance of the geo-encased stone columns in both types of soils. Furthermore, two different installation methods: wished-in installation and full displacement installation were studied numerically. Cross comparison was done to investigate how the sensitive soft soil features interact with the installation method in affecting the performance of the geo-encased stone columns. A range of factors that influence the geosynthetic-encased stone columns performance installed in soft soils were also made clear.

[Truncated abstract] Three-legged mobile jack-up rigs supported on spudcan foundations are used to perform most offshore drilling in shallow to moderate water depths, and are now capable of operating in water depths up to 130 m. With the gradual move towards heavier rigs in deeper water, and continuing high accident rates during preloading of the spudcan foundations, appraisal of the performance and safety of jack-up rigs has become increasingly important. A crucial aspect of this is to improve understanding of the mechanisms of soil flow around spudcan foundations undergoing continuous large penetration, and to provide accurate estimates of spudcan penetration resistance, avoiding excessive conservatism. Spudcan foundations undergo progressive penetration during preloading, contrasting with onshore practice where a footing is placed at the base of a pre-excavated hole or trench. However, spudcan penetration is generally assessed within the framework used for onshore foundations, considering the bearing resistance of spudcans pre-placed at different depths within the soil profile. The lack of accurate design approaches that take proper account of the nature of spudcan continuous penetration, which is particularly important in layered soil profiles, is an important factor in the high rate of accidents. ... It was found that when a spudcan penetrated into single layer clay, there were three distinct penetration mechanisms: during initial penetration, soil flow extended upwards to the surface leading to surface heave and formation of a cavity above the spudcan; with further penetration, soil began to flow back gradually onto the top of the spudcan; during deep penetration, soil back-flow continued to occur while the initial cavity remained unchanged. For spudcan penetration in stiff-over-soft clay, four interesting aspects of the soil flow mechanisms were identified: (a) vertically downward motion of the soil and consequent deformation of the layer interface; (b) trapping of the stronger material beneath the spudcan, with this material being carried down into the underlying soft layer; (c) delayed back-flow of soil around the spudcan into the cavity formed above the spudcan; (d) eventual localised flow around the embedded spudcan, surrounded by strong soil. At some stage during continuous spudcan penetration, the soil starts to flow back into the cavity above the spudcan. The resulting back-flow provides a seal above the penetrating spudcan and limits the cavity depth. It was shown that the current offshore design guidelines are based on the wrong criterion for when back-flow occurs. New design charts with robust expressions were developed to estimate the point of back-flow and hence the cavity depth above the installed spudcan. Load-penetration responses were presented in terms of normalised soil properties and geometry factors for both single layer and two-layer clay profiles, taking full account of the observed flow mechanisms. Further, guidelines were suggested to evaluate the likelihood and severity of spudcan punch-through failure in layered clays. Finally, the effect of strain-rate and strain-softening was examined, in an attempt to model real soil behaviour more closely. Adjustment factors were proposed to modify the design approaches developed on the basis of ideal elastic-perfectly plastic soil behaviour.

Neste trabalho, fracionou-se e tratou-se a argila Brasgel. Esta argila foi pilarizada em vários estágios de facionamento e/ou tratamento com 5 meq de Al / g de argila: (i) Al-PILC, a argila passou por todos os estágios de fracionamento e tratamento (ARG), (ii) Al-PILCFe, a argila não passou pela etapa de retirada de Fe livre (ARGFe) e (iii) Al-PILCFe/silte, a argila não passou pelas etapas de retirada de silte e Fe livre (ARGFE/silte). Em análise por DRX observou-se que as Al-PILCs apresentaram uma distância basal maior que as argilas de partida. A análise textural indicou que as argilas Al-PILCs e ARGs são materiais mesoporosos, com poros do tipo fenda estreita e do tipo fenda, respectivamente. Além disso, as Al-PILCs apresentaram área superficial razoavelmente maior que as ARGs correspondentes. Outras análises feitas nas argilas foram: teor de Si, Fe e Al; CTC; FTIR; TGA e TGD. As argilas Brasgel pilarizadas foram usadas como catalisador na reação de isomerização do óxido de estireno em hexano sob refluxo. A reação foi seletiva na formação de fenilacetaldeído. As argilas Al-PILCFe e Al-PILCFe/silte apresentaram melhor desempenho catalítico (100 % de conversão em 20 min de reação). Assim, as argilas Brasgel pilarizadas se apresentaram como uma Tecnologia Limpa na reação de isomerização do óxido de estireno ao fenilacetaldeído. Palavras-chave: Desenvolvimento Sustentável. Tecnologia Limpa. Química Verde. Argilas Pilarizadas. Isomerização de Epóxidos. / This work, the Brasgel clay was fractionated and treated. The clay was pillared in several stages of fractionation and / or treatment with Al 5 meq / g of clay: (i) Al- PILC, the clay has passed through all stages of treatment and fractionation (ARG), (ii) Al-PILCFe, the clay would not pass the step of removal of free Fe (ARGFe) and (iii) Al-PILCFe/silt, clay has not gone through the steps of removing silt and free Fe (ARGFE/silt). XRD analysis showed that the Al-PILCs showed a basal spacing greater than the starting clays. The textural analysis indicated that the Al-PILCs and ARGs are mesoporous materials, with pore narrow slit type and slit type, respectively. Moreover, the Al-PILCs showed reasonable surface area greater than the corresponding ARGs. Other analyzes were made on clays: the content of Si, Fe and Al; CEC, FTIR, TGA and TGD. Brasgel pillared clays have been used as catalyst in the isomerization reaction of the styrene oxide in refluxing. The reaction was selective for the formation of phenylacetaldehyde. Al-PILCFe and Al-PILCFe/silt clays showed better catalytic performance (100% conversion in 20 min of reaction). Thus, the pillared clays Brasgel presented as a Clean Technology in the isomerization reaction of styrene oxide to phenylacetaldehyde. Keywords: Sustainable Development. Clean Technology. Green Chemistry. Pillared Clays. Isomerization of Epoxides.

Made available in DSpace on 2014-12-17T14:07:03Z (GMT). No. of bitstreams: 1 LeonardoFM.pdf: 4456392 bytes, checksum: 36e6d8718ecd158955c24006e7afca9a (MD5) Previous issue date: 2009-10-30 / The mining industry is responsible for the generation of waste from their natural process of extraction. The mining impacts in urban areas are of special importance due to the high urban occupation, which are exacerbated due to the proximity of the mined areas and populated areas. Some solutions to wastedisposal have the potential to significantly reduce the environmental risks and liabilities, but represent higher costs in the stages of deployment and operation. The addition of mining waste as raw material in the development of commercial products reduces the environmental impacts, transforming the waste into a positive element in the generation of employment and income. This thesis studies the incorporation of waste iron ore in two clays, one from the ceramic industry of the City of Natal and the other from the ceramic industry of the Serid? Region, both in the State of Rio Grande do Norte, Brazil. Percentages of iron ore waste of 5%, 10% , 15%, 20%, 25% and 30% were used in the tested ceramic matrix. The two clays and the iron ore waste used as part of this investigation were characterized by X-ray diffraction tests, X-ray fluorescence tests, differential thermal analysis, thermogravimetric analysis and dilatometric analysis. The samples were sintered under temperatures of 850 ?C, 950 ?C and 1050?C at a heating rate of 5 ?C/min with isotherms of two hours. The following tests were performed with the samples: linear shrinkage, water absorption, apparent porosity, apparent density, mass loss in fire and bending resistance in order to obtain their physical and mechanical properties. An amount of 5% of waste iron ore in the matrix clay at a temperature of 850 0C resulted in na increase of about 65% in the tensile strength of the clay samples from the Natal ceramic industry. A linear shrinkage of only 0.12% was observed for the samples, which indicates that the physical properties of the final product were not influenced by the addition of the waste / A ind?stria extrativa mineral ? respons?vel pela gera??o de res?duos provenientes do seu processo natural de extra??o. Os impactos da minera??o em ?rea urbana revestem-se de especial import?ncia devido ao alto grau de ocupa??o urbana, que s?o agravados face ? proximidade entre as ?reas mineradas e as ?reas habitadas. Algumas solu??es de disposi??o de res?duos t?m potencial de reduzir significativamente os riscos e o passivo ambiental, por?m representam custos elevados nas etapas de implanta??o e de opera??o. A adi??o de res?duos de min?rio de ferro como mat?ria-prima na elabora??o de produtos que s?o utilizados comercialmente tem como objetivo diminuir os impactos ambientais, transformando esses res?duos em elementos positivos na gera??o de trabalho e renda. O presente trabalho estuda a incorpora??o de res?duo de min?rio de ferro em duas argilas, uma do p?lo cer?mico da Grande Natal e outra do p?lo cer?mico da Regi?o do Serid?, ambas do Estado do Rio Grande do Norte, em percentuais de 5%, 10%, 15%, 20%, 25% e 30%, com o intuito de verificar a potencialidade da incorpora??o do res?duo em matriz cer?mica. As mat?rias-primas foram caracterizadas atrav?s dos ensaios de difra??o de raios X, fluoresc?ncia de raios X, an?lise t?rmica diferencial, an?lise termogravim?trica e an?lise dilatom?trica. Os corpos-de-prova foram conformados e em seguida sinterizados nas temperaturas de 850 ?C, 950 ?C e 1050 ?C, ? taxa de aquecimento de 5 ?C/min, com iso terma de duas horas. Foram realizados os ensaios tecnol?gicos de retra??o linear de queima, absor??o de ?gua, porosidade aparente, massa espec?fica aparente, perda demassa ao fogo e tens?o de ruptura ? flex?o, com o intuito de se obter suas propriedades f?sicas e mec?nica. A argila do p?lo cer?mico da Grande Natal apresentou um aumento em torno de 65% na tens?o de ruptura ? flex?o, com um percentual ?nfimo de 0,12% na sua retra??o linear de queima, quando adicionados 5% de res?duo de min?rio de ferro na matriz de argila ? temperatura de 850 ?C, n?o comprometendo assim as p ropriedades f?sicas do produto final