As condições de geração e migração de magmas na crosta continental foram investigadas a partir de estudos de detalhe em dois afloramentos de granitos anatéticos tipo Nazaré Paulista (Nappe Socorro Guaxupé, região de Atibaia, SP), utilizando como ferramentas principais a geoquímica de elementos maiores e traços em rochas e minerais e a isotopia Sr-Nd. O granito Nazaré Paulista tem uma ampla variedade composicional, sendo as duas variedades principais um granada leucogranito e um granada-biotita granito cinza com uma rede de vênulas de leucogranito (~625 Ma, U-Pb monazita). Ambos os tipos formam corpos sub-concordantes de dimensões decamétricas nos dois afloramentos; as relações de contato quando observadas indicam a intrusão posterior dos granada leucogranitos. Dois tipos de leucossomas foram reconhecidos em paragnaisses migmatíticos associados aos granitos Nazaré Paulista: (1) granada-biotita tonalito com baixa razão Rb/Sr (0,3), padrões de ETR pouco fracionados ((La/Yb)N = 4-5) e com anomalia negativa de Eu e assinatura isotópica Sr-Nd idêntica à do mesossoma; (2) granada leucogranito, com razão Rb/Sr de ~0,56, padrões de ETR pouco fracionados ((La/Yb)N = 5), com anomalia positiva de Eu e eNd(t) idêntico ao do mesossoma, mas com 87Sr/86Sr(t) mais baixa. Ambos os tipos de leucossomas são distintos dos granitos e foram interpretados como produtos da fusão em presença de água do paragnaisse, respectivamente antes e depois da geração de feldspato potássico no protolito. Alguns contrastes geoquímicos relevantes são observados entre os granitos cinza e os leucogranitos: os primeiros apresentam maior mg# e Zr e padrões de ETR mais fracionados; as razões Rb-Sr de ambos os tipos são semelhantes (0,4-0,7). A assinatura isotópica Sr-Nd dos granitos mostra importante variação (eNd(t) = -16 a -13 e 87Sr/86Sr(t) = 0,716-0,728); apenas duas amostras de leucogranito têm assinatura coincidente com o campo dos paragnaisses regionais. Assumindo os paragnaisses como fonte única dos granitos Nazaré Paulista, é necessário que a fusão tenha ocorrido em desequílibrio e em presença de água. A química de elementos traços em granada foi fundamental para a identificação dos diversos processos de diferenciação que respondem pela variedade de granitos observada. Parte dos granitos cinza carrega um componente restítico, representado por granadas com núcleos ricos em ETRP+Y semelhantes às granadas dos paragnaisses encaixantes. As vênulas de granada leucogranito que cortam o granito cinza são formadas provavelmente pela ?refusão? do mush original durante a rápida ascensão e exibem granadas pobres em ETRP, cujos teores aumentam para a borda, definindo um padrão tipicamente magmático. Os leucogranitos que formam corpos isolados podem em parte corresponder a diferenciados do granito cinza, conforme indicado pelas relações de campo e pela geoquímica de rocha. No entanto os leucogranitos com alta 87Sr/86Sr(t) apresentam granadas com núcleos ricos em ETRP+Y e monazita com composição similar a dos paragnaisses, reforçando a hipótese de serem estes produtos da fusão direta de paragnaisses. / The conditions of melt generation and migration in the continental crust were investigated through a detailed study of two outcrops of the anatectic Nazaré Paulista granites (Socorro-Guaxupé, Nappe, Atibaia region, SE Brazil), using as main tools the rock and mineral major and trace-element geochemistry and Sr-Nd isotopy. The Nazaré Paulista granite shows a wide compositional variation, and can be grouped into two main types: a garnet leucogranite and a veined grey garnet-biotite granite, the latter dated at ~625 Ma (monazite U-Pb ID-TIMS). These types occur as subconcordant bodies 10-50 m wide and are present in both outcrops; where observed, the contact relationships show that the garnet leucogranites intruded after the grey granites. Two types of leucosome were recognized in migmatitic paragneisses associated to the Nazaré Paulista granites: (1) garnet-biotite tonalite with low Rb/Sr (0.3 ), slightly fractionated REE patterns ((La/Yb)N = 4-5) with negative Eu anomalies and Sr-Nd isotope signature identical to that of the mesosome; and (2) garnet leucogranite, with Rb/Sr ~0.56, slightly fractionated REE patterns ((La/Yb)N ~ 5) with positive Eu anomalies, eNd(t) identical to that of the mesosome, but lower 87Sr/86Sr(t). Both leucosomes are different from the granites, and were interpreted as the products of water-present melting of the paragneiss, respectively before and after the crystallization of K-feldspar in the protolith. Some relevant geochemical contrasts are observed between the two types of Nazaré Paulista granites: compared to the leucogranites, the gray granites show greater mg# and Zr and more fractionated REE patterns; the Rb/Sr ratios of both are low (0.4-0.7). The Sr-Nd isotope signature has important variations (eNd(t) = -16 to -13 and 87Sr/86Sr(t) = 0.716-0.728); only two leucogranite samples have signatures that are coincident with the field of the regional paragneisses. Assuming the paragneisses as the only source of the Nazaré Paulista granites would require that melting occurred under disequilibrium and water-present conditions. The trace-element chemistry of garnet was important to identify the differentiation processes that respond for the observed variety of anatectic granites. Part of the gray granites carries a restitic component, represented by ETRP+Y-rich garnet cores that are similar to the garnets from the country-rock paragneisses. The garnet leucogranite veins that cut the gray granite were probably formed by \"partial remelting\" of the original mush during rapid ascent, their idiomorphic garnet crystals have a distinctive composition (low HREE in the cores, increasing slightly to the rims), interpreted as magmatic. Some of the leucogranites forming isolated bodies may have been generated by fractionation from the gray granite, as indicated by field relations and rock geochemistry. On the other hand, the leucogranite with high 87Sr/86Sr(t) has ETRP+Y-rich garnet cores and its monazite is compositionally similar to that of the paragneisses, features indicative that they were probably produced by direct melting of these rocks.

Catalytic combustion is an environmentally friendlytechnique to combust fuels in e.g. gas turbines. Introducing acatalyst into the combustion chamber of a gas turbine allowscombustion outside the normal flammability limits. Hence, theadiabatic flame temperature may be lowered below the thresholdtemperature for thermal NOXformation while maintaining a stable combustion.However, several challenges are connected to the application ofcatalytic combustion in gas turbines. The first part of thisthesis reviews the use of catalytic combustion in gas turbines.The influence of the fuel has been studied and compared overdifferent catalyst materials. The material section is divided into two parts. The firstconcerns bimetallic palladium catalysts. These catalysts showeda more stable activity compared to their pure palladiumcounterparts for methane combustion. This was verified both byusing an annular reactor at ambient pressure and a pilot-scalereactor at elevated pressures and flows closely resembling theones found in a gas turbine combustor. The second part concerns high-temperature materials, whichmay be used either as active or washcoat materials. A novelgroup of materials for catalysis, i.e. garnets, has beensynthesised and tested in combustion of methane, a low-heatingvalue gas and diesel fuel. The garnets showed some interestingabilities especially for combustion of low-heating value, LHV,gas. Two other materials were also studied, i.e. spinels andhexaaluminates, both showed very promising thermal stabilityand the substituted hexaaluminates also showed a good catalyticactivity. Finally, deactivation of the catalyst materials was studied.In this part the sulphur poisoning of palladium, platinum andthe above-mentioned complex metal oxides has been studied forcombustion of a LHV gas. Platinum and surprisingly the garnetwere least deactivated. Palladium was severely affected formethane combustion while the other washcoat materials were mostaffected for carbon monoxide and hydrogen. <b>Keywords:</b>catalytic combustion, catalyst materials,palladium, platinum, bimetallic, garnet, spinel, hexaaluminate,deactivation, sulphur, poisoning, diesel, methane,hydrocarbons

A series of crustal-scale shear zones demarcates the northern and eastern margins of the North Caribou greenstone belt (NCGB), proximal to a Mesoarchean terrane boundary in the core of the western Superior Province of Canada. The dominant deformation produced a pervasive steeply dipping fabric that trends broadly parallel to the doubly arcuate shape of the belt and was responsible for tight folding the banded iron formation host to Goldcorp’s prolific gold deposit at Musselwhite mine. The shear zones in the North Caribou greenstone belt are of particular interest because of their ability to channel hydrothermal fluids with the potential to bear ore and cause alteration of the middle to shallow crust. Shear zones are commonly reactivated during subsequent tectonism, but exhibit a consistent and dominant dextral shear sense across the belt; fabric-forming micas and chlorite are generally Mg-rich. Although garnets samples from within the shear zones are dominantly almandine, they possess variable geochemical trends (HREEs of >2 orders of magnitude) and can be syn-, intra-, or post-tectonic in origin. In situ geochronological analysis of zircon (U-Pb) and monazite (total-Pb) in high strain rocks in and around the NCGB, interpreted in light of in situ geochemical analysis of garnet and fabric-forming micas and chlorite, reveals four relatively discrete events that span 400 million years. Metamorphism of the mid-crust was coeval with magmatism during docking of the Island Lake domain at c. 2.86 Ga and subsequent terrane accretion at the north and south margins of the North Caribou Superterrane from c. 2.75 to 2.71 Ga. Transpressive shear at c. 2.60 to 2.56 Ga and late re-activation of shear zones at c. 2.44 Ga produced a steeply-dipping pervasive fabric, and channeled fluids for late crystallization of garnet and monazite recorded in the Markop Lake deformation zone. These observations implicate a horizontal tectonic model similar to the modern eastern Pacific plate margin. Further, this study highlights the caution that should be exercised when using traditional rock forming metamorphic minerals (mica, chlorite, garnet) when attempting to vector into zones of hydrothermal alteration within midcrustal rocks.

Due to the fast expansion and development in the optical communication industry, the demand for the broad-band laser light source as used to the optical transmission network system has correspondingly increased. Cr4+ doped YAG crystal fibers, with its broad-band spectral property, is thus becoming more and more indispensable to the growth of the industry. However, the Cr4+:YAG crystal fiber in its own repetitive growth process brings with itself one problem: after each re-growth, the concentration of Cr2O3 and Cr4+ ions would reduce appreciatively. Hence, finding sound solutions for effectively raising the concentration of Cr4+ is now becoming an essential issue in the field. The thesis mainly focuses on the development of using Cr4+:YAG as the laser gain medium. Thin layers of CaO, MgO, and Cr2O3 was coated on the circumference of the Cr:YAG crystal fiber. The LHPG method was then employed to re-grow the coated samples, during which the doped concentration of CaO, MgO and Cr2O3 can in-diffuse. And the effect of charge compensation would go further to simultaneously raise the concentration of Cr4+ ions. Now we have successfully enhance the concentration of Cr4+ ions to 4.86x10-3 wt.%. This study, with the use of the E-Gun coating machine and the IAD (ion-beam assisted deposition) system, also probes the technical side of how to better improve the quality of the crystal fiber laser. Both end faces of the Cr4+:YAG crystal fiber were coated with optical thin films by TiO2 and SiO2 targets. In addition to raise the quality of the thin films, the IAD system also functions to create a laser cavity in which both the anti-reflectance (AR) effect (for pumping the light source) and the high reflectance (HR) effect (for stimulating the light source) are achieved. The accompanied benefits would be the reduction of transmission loss, the increased laser efficiency, and thus a more successful and more stable crystal fiber laser.

Abstract During the last decade, the fast-growing communication need has promoted the development of the wavelength of 1.3 mm~1.6 mm laser light source. The Cr4+ doped YAG solid-state laser has potential to meet this super wideband demand. In addition, solid state laser has the merits of high laser beam quality, long lifetime, compact, and simple structure. In this thesis, crystal fiber was used as the laser gain medium, and coated with optical thin film at its end facets as the laser cavity. Using this configuration, the volume and cost of the laser can be appreciatively reduced, and the heat dissipation can be improved. The laser-heated-pedestal-growth method was used to grow crystal fiber, which can obtain small diameter at very fast rate and accurate control. High quality Cr4+:YAG crystal fiber with the smallest diameter of 50 mm was grown. A glass-packaged technique clothes the crystal fiber with a core diameter as small as 11 mm. Outside the glass clad Cr4+:YAG crystal fiber, Al-Cu alloy was employed as the heat sink to improve heat dissipation. After grinding, polishing, and coating of this device, the Cr4+:YAG crystal fiber laser was fabricated. Some characteristics of Cr4+:YAG crystal fiber, such as the distribution of Cr2O3 and CaO doping concentration, fluorescence intensity, refraction index, propagation loss, and absorption coefficient were measured and analyzed. In the meanwhile, some simulations of the laser output power depending on the absorption coefficient, propagation loss, output coupling, crystal fiber diameter, and crystal boundary temperature were discussed.

During last decade, the fast-growing communication need has promoted the development of 1.3 £gm~1.6 £gm laser light source. The Cr4+ doped YAG solid-state laser has potential to meet this broadband demand. In addition, diode-laser-pumped solid state laser has the merits of high laser beam quality, long lifetime, compact, and simple structure. In this thesis, crystal fiber was used as the laser gain medium, and coated with optical thin film at its end facets as the laser cavity. Using this configuration, the volume and cost of the laser can be appreciatively reduced, and the heat dissipation can be improved. The laser-heated-pedestal-growth method was used to grow crystal fiber, which can obtain small diameter at very fast rate. Outside the glass clad Cr4+:YAG crystal fiber, Al-Cu alloy was employed as the heat sink to improve heat dissipation. After grinding, polishing, and coating of this device, the Cr4+:YAG crystal fiber laser was fabricated. Some characteristics of Cr4+:YAG crystal fiber, such as the distribution of Cr2O3 and CaO doping concentration, fluorescence intensity, refraction index, propagation loss, and absorption coefficient were measured and analyzed. A record-low threshold of 0.75 mW was achieved. It is more than 500 times lower than any previously reported Cr4+:YAG lasers, and a slope efficiency of 6.9% was obtained. The ultralow-threshold lasing is made possible by the low propagation loss of 0.08 dB/cm and the high pump intensity of the core. Such a low-threshold operation makes the double-clad crystal fiber laser be compatible to present optical communication systems. In the meanwhile, some simulations of the laser output power have been developed to predict the experimental results.

<p>Catalytic combustion is an environmentally friendlytechnique to combust fuels in e.g. gas turbines. Introducing acatalyst into the combustion chamber of a gas turbine allowscombustion outside the normal flammability limits. Hence, theadiabatic flame temperature may be lowered below the thresholdtemperature for thermal NO_Xformation while maintaining a stable combustion.However, several challenges are connected to the application ofcatalytic combustion in gas turbines. The first part of thisthesis reviews the use of catalytic combustion in gas turbines.The influence of the fuel has been studied and compared overdifferent catalyst materials.</p><p>The material section is divided into two parts. The firstconcerns bimetallic palladium catalysts. These catalysts showeda more stable activity compared to their pure palladiumcounterparts for methane combustion. This was verified both byusing an annular reactor at ambient pressure and a pilot-scalereactor at elevated pressures and flows closely resembling theones found in a gas turbine combustor.</p><p>The second part concerns high-temperature materials, whichmay be used either as active or washcoat materials. A novelgroup of materials for catalysis, i.e. garnets, has beensynthesised and tested in combustion of methane, a low-heatingvalue gas and diesel fuel. The garnets showed some interestingabilities especially for combustion of low-heating value, LHV,gas. Two other materials were also studied, i.e. spinels andhexaaluminates, both showed very promising thermal stabilityand the substituted hexaaluminates also showed a good catalyticactivity.</p><p>Finally, deactivation of the catalyst materials was studied.In this part the sulphur poisoning of palladium, platinum andthe above-mentioned complex metal oxides has been studied forcombustion of a LHV gas. Platinum and surprisingly the garnetwere least deactivated. Palladium was severely affected formethane combustion while the other washcoat materials were mostaffected for carbon monoxide and hydrogen.</p><p><b>Keywords:</b>catalytic combustion, catalyst materials,palladium, platinum, bimetallic, garnet, spinel, hexaaluminate,deactivation, sulphur, poisoning, diesel, methane,hydrocarbons</p>

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published_or_final_version / abstract / toc / Earth Sciences / Doctoral / Doctor of Philosophy

No description available.