Made available in DSpace on 2014-12-17T14:58:25Z (GMT). No. of bitstreams: 1 GustavoAB.pdf: 2461248 bytes, checksum: 0536be02b6961005820ca67a7e2765de (MD5) Previous issue date: 2007-01-19 / Fillers are often added in composites to enhance performance and/or to reduce cost. Fiberglass pipes must meet performance requirements and industrial sand is frequently added for the pipe to be cost competitive. The sand is added to increase pipe wall thickness, thus increase pipe stiffness. The main goal of the present work is to conduct an experimental investigation between pipes fabricated with and without de addition of sand, to be used in the petroleum industry. Pipes were built using E-glass fibers, polyester resin and siliceous sand. The fabrication process used hand lay up and filament winding and was divided in two different parts: the liner and the structural wall. All tested pipes had the same liner, but different structural wall composition, which is the layer where siliceous sand may be added or not. The comparative investigation was developed considering the results of longitudinal tensile tests, hoop tensile tests, hydrostatic pressure leak tests and parallel-plate loading stiffness tests. SEM was used to analyze if the sand caused any damage to the glass fibers, during the fabrication process, because of the fiber-sand contact. The procedure was also used to verify the composite conditions after the hydrostatic pressure leak test. The results proved that the addition of siliceous sand reduced the leak pressure in about 17 %. In the other hand, this loss in pressure was compensated by a stiffness increment of more than 380 %. MEV analyses show that it is possible to find damage on the fiber-sand contact, but on a very small amount. On most cases, the contact occurs without damage evidences. In summary, the addition of sand filler represented a 27.8 % of cost reduction, when compared to a pipe designed with glass fiber and resin only. This cost reduction combined to the good mechanical tests results make siliceous sand filler suitable for fiberglass pressure pipes / Cargas de adi??o s?o utilizadas com freq??ncia, em materiais comp?sitos, para atingir propriedades mec?nicas requeridas por normas e para redu??o de custos. As tubula??es em pl?stico refor?ado com fibras de vidro (PRFV), utilizadas para aplica??es com altas press?es, devem atender a requisitos m?nimos de projeto estabelecidos em normas. Para tanto, a areia vem sendo utilizada como carga de adi??o, no sentido de manter os tubos em PRFV competitivos no mercado. A areia ? adicionada para aumentar a espessura da parede, aumentando com isso a rigidez. Este trabalho teve como principal objetivo analisar a influ?ncia da areia nas propriedades mec?nicas de tubula??es de PRFV, visando sua aplica??o na ind?stria do petr?leo e do g?s, atrav?s de ensaios comparativos entre tubos com e sem a adi??o de areia. Os tubos foram fabricados com fibras de vidro tipo E na forma de fios cont?nuos e manta, resina poli?ster ortoft?lica e areia quartzosa. A fabrica??o foi realizada em duas etapas distintas, sendo a primeira camada do tubo denominada de barreira qu?mica (processo de lamina??o manual) e a segunda camada denominada estrutura (fabricada pelo processo de filamento cont?nuo). A areia ? adicionada no tubo juntamente com as camadas de filamento cont?nuo e, portanto, ? um constituinte da estrutura do tubo. A an?lise comparativa foi conduzida atrav?s de ensaios de tra??o axial e ircunferencial, press?o hidrost?tica e rigidez, al?m de an?lises com microsc?pio eletr?nico de varredura (MEV). Foram avaliadas as for?as resultantes de ruptura e o m?dulo de elasticidade circunferencial, al?m da rigidez. As an?lises com MEV foram conduzidas para verificar a presen?a de danos causados as fibras, durante o processo de fabrica??o, e para verificar as condi??es do laminado ap?s os ensaios de press?o hidrost?tica. Os resultados mostraram que a adi??o de areia causou uma redu??o na press?o de ruptura do tubo de 17 %. Por?m esta perda foi compensada pelo grande acr?scimo na rigidez que foi da ordem de 380 % . As an?lises no MEV mostraram que ocorrem danos durante o processo de fabrica??o, mas em quantidades muito pequenas. Na maioria dos casos o contato areia/fibras ocorre sem evid?ncias de danos. Em resumo, a areia representa uma redu??o de 27,8 % no custo final do tubo, que somado aos bons resultados obtidos nos ensaios mec?nicos, faz deste material uma excelente op??o de carga de adi??o para tubula??es de PRFV utilizadas com altas press?es

Title: Palladium catalysts deposited over novel siliceous supports Author: Pavlína Křečková Department: Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague Supervisor: prof. RNDr. Petr Štěpnička, Ph.D. Supervisor's e-mail address: stepnic@natur.cuni.cz Advisor: prof. Ing. Jiří Čejka, DrSc. Advisor's e-mail address: jiri.cejka@jh-inst.cas.cz Abstract Keywords: palladium; deposited catalysts; siliceous supports; C-C coupling reaction. The aim of this work was to prepare a deposited palladium catalyst from Pd2+ and twodimensional zeolite ITQ-2 bearing ≡SiCH2CH2CH2NHCH2CH2NEt2 groups at the surface. This catalys has been evaluated in the Heck reaction between n-butyl-acrylate and brombenzene to give n-butyl-cinnamate. Influence of the reaction temperature, the solvent, base and hydrate water on the progress of the Heck reaction was investigated. This work also deals with the possibility of recycling the catalyst and, due to its nature, with the quantity of leached palladium into the reaction mixture. Furthermore, the work describes differences in morphology between the fresh and a recycled catalyst.

In the Colossal Cave area, Pima County, Arizona, massive blocks of Paleozoic sedimentary rocks have been thrust from a southerly direction over an irregular surface of Rincon Valley granite of Laramide age. The Paleozoic rocks involved in the thrusting are the Bolsa quartzite, Abrigo formation, Martin limestone, Escabrosa limestone, Horquilla limestone, and Andrada formation. The Pantano formation (Miocene ?) is also present under the thrust sheet. The thrusting is of an imbricate nature with slip-page mainly teaking place along incompetent rock units. Large folds occur in the Escabrosa limestone and Horquilla lime-stone. A siliceous breccia is associated with thrust planes in the area. The competent units of the Paleozoic sediments were fractured and brecciated along the thrust planes. Solutions dissolved part of the silica and hematite from the Bolsa quartzite and deposited it in the fractured and brecciated zones.

Ce travail de recherche analyse l'influence de différentes natures de granulats sur le comportement thermo-hydro-mécanique du béton soumis à une température élevée. Dans la première partie, trois granulats (calcaire, silico-calcaire et siliceux) subissent des cycles de chauffage/refroidissement à 150°C, 300°C, 450°C, 600°C et 750°C. Les évolutions physico-chimiques, minéralogiques et microstructurales de ces granulats soumis à une température élevée sont analysées pour comprendre le processus d'instabilité. La deuxième partie est consacrée aux bétons réalisés avec les trois granulats analysés précédemment soumis à une température élevée. Nous déterminons l'évolution de la fissuration, des propriétés thermiques, physiques et mécaniques du béton en fonction des températures subies. Le comportement mécanique résiduel du béton varie selon la nature des granulats et l'influence de granulat dépend aussi de la compacité de la pâte cimentaire. La partie relative à la simulation d'un incendie dans un tunnel avec un bicouche roche/béton fabriqué au laboratoire permet d'analyser le comportement du béton et de la roche en s'intéressant aux transferts de chaleur dans les 2 matériaux au cours de l'exposition à une température élevée. / This research analyses the influence of different types of aggregates on the thermo-hydro-mechanical behavior of concrete subjected to high temperature. In the first part, three aggregates (calcareous, silico-calcareous and siliceous) undergo the heating/cooling cycles at a rate of 1°C/min to 150°C, 300°C, 450°C, 600°C and 750°C. The physico-chemical, mineralogical and microstructural evolutions of these aggregates subjected to high temperature are analysed to understand the instability's process. The second part of the experimental study is devoted to concrete made with three aggregates discussed above. We determine the evolution of the cracking, the thermal properties, the physical and mechanical properties of the concrete with the temperatures experienced. The residual mechanical behavior of concrete varies with the nature of aggregates and the influence of aggregate depends also on the compactness of the cement paste. The part relating to a simulation of a tunnel fire with a rock/concrete bilayer manufactured in the laboratory permits to analyse the behavior of concrete and rock by focusing on the heat transfer in the two materials during the exposure to high temperature.

This thesis describes a numerical investigation of shallow circular foundations resting on various types of soil, mainly siliceous and calcareous sands. An elasto-plastic constitutive model, namely the MIT-S1 model (Pestana, 1994), which can predict the rate independent behaviour of different types of soils ranging through uncemented sands, silts and clays, is used to simulating the compression, drained triaxial shear and shallow circular foundation responses. It is found that this model provides a reasonable fit to measured behaviour, particularly for highly compressible calcareous sands, because of the superior modelling of the volumetric compression. The features of the MIT-S1 model have been used to investigate the effects of density, stress level (or foundation size), inherent anisotropy and material type on the response of shallow foundations. It was found that the MIT-S1 model is able to distinguish responses on dilatant siliceous and compressible calcareous sands by relatively minor adjustment of the model parameters. Kinematic mechanisms extracted from finite element calculations show different deformation patterns typical for these sands, with a bulb of compressed material and punching shear for calcareous sand, and a classical rupture failure pattern accompanied by surface heave for siliceous sand. Moreover, it was observed that the classical failure pattern transforms gradually to a punching shear failure pattern as the foundation size increases. From this evidence, a dimensional transition between these failure mechanisms can be defined, referred to as the critical size. The critical size is also the limiting foundation size to apply conventional bearing capacity analyses. Alternative approaches are needed, focusing mainly on the soil compressibility, for shallow foundations greater than the critical size. Two approaches, 1-D compression and bearing modulus analyses, have been proposed for those foundation conditions. From the validations, the former is applicable for extremely large foundations, very loose soil conditions and highly compressible calcareous materials, while the latter is suitable for moderate levels of compressibility or foundation size. It is suggested that appropriate assessment of compression features is of great importance for shallow foundation analysis on sand.

M.Sc. / This thesis involves a study ofthe geology surrounding the —530 Ma to —519 Ma Venetia kimberlite pipes situated between AIldays and Messina (now renamed Musina) in the Beit Bridge Terrane of the Limpopo Belt, South Africa. The Limpopo Belt is an eastnortheast trending high grade metamorphic terrane thought until recently to be the result ofa collisional event between the Kaapv_aal and Zimbabwe Cratons between 2.7 and 2.65 Ga. However, recent studies have challenged this concept and suggest that the assembly was more complex and took place over an extended period of time ending at —2.04 Ga. This study involved surface mapping of the Farms Rugen (south) and Ostrolenca, providing additional information to help with mine planning, grade control and exploration. It forms a portion of a project initiated between Venetia Mine, the Venetia- Limpopo Nature Reserve and Professor Jay Barton of RAU to geologically map in detail the area around the pipes (scale < 1:10 000) and to study various aspects of the regional geology. The rock types into which the Venetia kimberlite pipes intruded belong to the Venetia klippe, an east-west trending synclinal structure with the axial plane dipping steeply northwards. Lithologically, the Venetia klippe comprises four layered units in which interlayered granitic or arkosic quartzofeldspathic gneisses, with and without biotite and garnet, and para and ortho-amphibolite, quartzite and meta-carbonate rocks (marble and limestone), banded iron formation and calc-silicate rock occur. Geochemical analysis (SEM and electron microprobe) of the meta-carbonates (re-crystallised magnesian limestone, coarse-grained marble and fine-grained foliated marble), indicate the precursors to be magnesian limestone, dolomite and limestone. Several events have been identified during the structural evolution of the area. They include: formation of gneissic metamorphic layering, tectonic suturing between different lithologies, formation of a syncline and east-west strike-slip faulting, north-south trending folds and northeast-southwest dextral strike-slip faulting, tourmaline bearing pegmatite emplacement, dolerite intrusion, tourmaline absent pegmatite emplacement, kimberlite emplacement and reactivation of pre-existing structures. Depositional structures only in the fine-grained foliated marble are preserved, e.g. graded bedding, cross-bedding, rip-up clasts and channels. These structures suggest deposition of the carbonates in two main depositional environments; peritidal (channels and rip-up clasts) and subtidal shelf (graded bedding and cross-bedding). A study of pegmatites in the area shows two main pegmatite types: tourmaline bearing and tormaline absent, each locally displaying a zonation. Mineralogically, the pegmaties are rich in quartz and albite and lack K-feldspar so they are classified as sodic-rich or plagio-pegmatites. Step heating 40Ar/39Ar analyses of muscovite from undeformed pegmatite yields an age of —2.0 Ga, which is interpreted to represent the time of pegmatite emplacement into the Venetia klippe rocks. Structurally, the pegmatites are sheet-like bodies cross-cutting compositional layering, joints, faults, folds and the dolerite, except for the older tourmaline bearing pegmatite that has intruded along east-west faults, but not northeast-southwest trending faults. By applying the principles of a dike propagation model, the source of the Venetia pegmatites should be greater than 5X5X5 km in volume and a maximum of 10km away. An appropriate granitic source has been recognized on the farm Gotha to the south of the mine by Martina Barnett. Leucocratic granodiorite, tonalite and granite with minor xenoliths of amphibolite, quartzite and magnetite quartzite define the Gotha Granitic Complex and pegmatite decreases in abundance away from it to the north and east. Deposition of Unit 3 lithologies into a rifted basin and an ancient epeiric sea is possible. However, there is more evidence (peritidal and shelf environments of the metacarbonates) and clean mature quartzites to suggest deposition into a passive continental margin or epeiric sea similar to the Malmani dolomites of the Transvaal Supergroup.