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The Uitkomst Complex is a mineralized, layered basic to ultrabasic intrusion, hosted by sedimentary rocks of the lower part of the Transvaal Supergroup. It is situated on the farms Uitkomst 541JT and Slaaihoek 540JT, about 25 km north of Badplaas and 50 km east of the eastern limb of the Bushveld Complex in the Mpumalanga province of South Africa. The intrusion plunges between 8 to 10º to the northwest with an established length of 12 km and a total thickness of 850 m. It is divided into seven lithological Units (from base to top), the Basal Gabbro (BGAB), Lower Harzburgite (LHZBG), Chromitiferous Harzburgite (PCR), Main Harzburgite (MHZBG), Pyroxenite (PXT), Gabbronorite (GN) and Upper Gabbro units (UGAB). A detailed petrographic and geochemical investigation of borehole core SH176, which provided a complete intersection of the Uitkomst Complex was carried out. The study shows that the Complex may have crystallized in a dynamic magma conduit setting. The whole rock geochemical trends indicate that there is a reversed fractionation in the basal portion of the Complex and a lack of fractionation in much of the MHZBG. Trace and REE variations show a decrease in concentration with height, contrary to what is expected of a progressively differentiating magma in a close system. Further, the platinum-group element concentration of the four basal units show no depletion with increasing height, suggesting that the individual units are not related to each other by means of in situ fractionation. Instead, a model whereby the individual units crystallized from distinct pulses of magma best explains the data. By comparing Nd isotopes and ratios of highly incompatible trace elements like [Th/La]n and [Sm/Ta]n from the Uitkomst Complex and Bushveld Complex it is seen that the Uitkomst magmas are of a similar lineage as the B1 magma of the Bushveld Complex, supporting a genetic link between the two complexes. The upper portion of the Uitkomst Complex shows values more akin to B3 magmas indicating the possible presence of more than one type of magma. Based on the available S isotope and trace element data, the sulphides of the Complex appear to have formed within the Complex, probably in response to contamination of the magma with dolomite. Entrainment of sulphides from depth is considered unlikely. The relatively low Cu/Ni ratios of the sulphides in the LHZBG, PCR and MHZBG (Cu/Ni 0.03 to 0.8) may be modelled by sulphide segregation from B1 magma and not from fractionation of sulphides that were later entrained in the streaming magma. / Dissertation (MSc)--University of Pretoria, 2006. / Geography, Geoinformatics and Meteorology / Unrestricted

La possibilité d’obtenir une émission laser efficace sur une large bande spectrale autour de 1.05 µm a été démontrée récemment en utilisant des monocristaux CaF2 and SrF2 dopés Nd3+. Cette émission, éteinte du fait de la relaxation croisée entre ions dans les matériaux de type fluorite, peut être exaltée avec l’insertion d’ions “tampons” comme Y3+ ou Lu3+. Une émission laser accordable sur une large bande spectrale et la génération d’impulsions ultracourtes sont donc possibles. De plus, ce type de matériau est particulièrement intéressant pour des amplificateurs de forte puissance pompés par diodes. Une étude complète des propriétés spectrales et thermomécaniques de cristaux de CaF2:Nd3+ co-dopés avec des concentrations variables de Lu3+ a été menée en collaboration avec le CEA CESTA au sein du projet LASCAN pour de futurs développements au sein du Laser MégaJoule (LMJ) avec pour but l’amélioration des performances des amplificateurs pilotes. L’effet d’élimination des clusters de Nd3+ par le co-dopage avec le Lu3+ et l’apparition de deux sites actifs différents a été mise en évidence et caractérisée en détail. Ce travail présente ainsi une spectroscopie complète des centres actifs dans CaF2:Nd3+,Lu3+, une étude des propriétés thermomécaniques, ainsi que des propriétés d’amplification optique des matériaux étudiés. / It was recently demonstrated that efficient and broadband laser emission was possible with Nd-doped CaF2 and SrF2 single crystals around 1.05 µm. Such laser emission, known as completely quenched because of cross-relaxation in the singly doped fluorites, increases spectacularly by co-doping with non-optically active “buffer” ions like Y3+ or Lu3+. Broadband laser emission and ultra-short laser operation are therefore possible. The material is particularly appealing for large scale high peak power diode-pumped amplifiers. A deep investigation of the spectral properties of CaF2:Nd3+ crystals co-doped with various amounts of Lu3+ was performed. The cluster breaking effect of Lu3+ codoping has as a side-effect the appearance of two different contributions, identified as two different active sites, which is in agreement with recent observations. In this work, we investigate in depth the different centres’ spectroscopic properties and operational parameters for laser applications,their evolution as the lutetium concentration increases, and the thermomechanical properties of said samples. A preliminary investigation on the amplification properties and laser operation of said materials is performed as well.

L’objectif de cette thèse est de déterminer une reconstruction de l’altération continentale dans le bassin du Nil depuis 100.000 ans, afin de mieux comprendre l’impact des variations climatiques sur les sols, les apports à la Méditerranée et le cycle du carbone. Ce travail repose sur une étude géochimique fine des argiles extraites d’archives sédimentaires du delta du Nil sur une échelle de temps de 100.000 ans. Il repose sur une approche inédite du couplage d’un traceur de source (isotopes du néodyme) et de traceurs d’altérations (isotopes du lithium). Les résultats de cette étude mettent en évidence une réponse rapide de l’altération continentale aux variations hydro-climatique en Afrique du Nord. De plus, les changements climatiques en Atlantique Nord et du ralentissement de l’AMOC ont eu une influence importante sur la diminution de l’intensité d’altération continentale dans le bassin du Nil. A l’actuel, les taux d’altération, et la consommation de CO2 associée, des trapps d’Ethiopie sont relativement faibles par rapport aux autres régions basaltiques. Nos résultats montrent cependant que durant l’African Humid Period, la consommation de CO2 dans cette région était 2 à 3 fois plus importante qu’aujourd’hui. Cela indique que les trapps d’Ethiopie ont pu jouer un rôle non négligeable dans le cycle du CO2, et en particulier lors des périodes de fort runoff. Enfin, des développements analytiques ont été réalisés afin de pouvoir exploiter les compositions isotopiques en lithium des carbonates biogéniques marins, comme nouveaux traceurs des apports en eau douce du Nil. Les résultats obtenus suggèrent une influence des effets dits « vitaux » et des processus de diagénèse. / This thesis presents a reconstruction of the chemical weathering in the Nile basin since 100.000 years. His objective is to better understand the impact of climatic variations on chemical weathering, to better. This work is based on the geochemistry study on marine core recorded in the Nile delta, on a time scale of 100.000 years. It use a novel approach with the coupling of à source tracer (εNd) and chemical weathering tracers (δ7Li and elementary ratios) on the fine fraction (< 2µm). In addition, it was analyzed samples of each actual Nil sources and a core sample from Tana Lack (Ethiopie). The results of this studies have enabled to reconstruct the chemical weathering variations in the Nile basin since 100.000 years. It show a rapid respond of chemical weathering to climate variations. This was also observed by important impact of North Atlantic climate variations on the decrease of chemical weathering in the Nile basin. At present, the chemical weathering flux and the CO2 consumption of the Ethiopian traps are low comparted to the other basaltic regions, as the Deccan. However, our results show that during the most humid periods (African Humid Period) the CO2 consumption was 2 to 3 time higher than today. This indicates that the Ethiopian traps could be have played a non-negligible role in the global CO2 cycle during the Cenozoic, and principally during the most humid periods in North Africa. Finally, analytical developments have been realized to be able to exploit the lithium isotopes on biogenic carbonates as a new tracer of Nile water flood. The results suggest an influence of “vital” effect and diagenetic process.

The US navy has a critical need for air independent advanced electric power sources to replace batteries in unmanned undersea vehicles (UUVs). Solid oxide fuel cells (SOFCs) are being considered as one potential replacement option. However, SOFCs typically operate using atmospheric air as their oxidant which is not an option for this underwater application. For this application, pure pressurized oxygen would be used as the oxidant which motivates the search for a cathode material which would be optimal for a high oxygen partial pressure environments. Specifically, this research focuses on cathode materials which can exploit the unique operating conditions required for UUVs. The operation in 100% oxygen atmosphere rather than air provides a significant opportunity. This is because oxygen surface exchange and bulk transport through the cathode is mediated through point defects whose concentrations are sensitive to the partial pressure of oxygen in the atmosphere surrounding the cathode. Oxygen bulk transport along with oxygen surface exchange are the rate controlling steps in oxygen reduction and incorporation at the cathode. The focus of this research is to examine the relationship between oxygen partial pressure and its effect on SOFC cathode performance for two different families of cathode materials, namely strontium doped lanthanum manganite, and a relatively new class of cathode materials, rare-earth nickelates. The experimentally measured relationship between cathode polarization and oxygen partial pressure will be correlated with the underlying transport and surface exchange processes in both families of materials.

Depuis le début des années 2000, les performances des diodes électroluminescentes (LED) ne cessent de s’améliorer alors que leur prix connait une diminution spectaculaire grâce à une production à grande échelle liée au marché de l'éclairage. Ainsi, les LED deviennent une source de lumière intéressante pour le pompage de lasers solides, intermédiaire entre les lampes flash et les diodes laser. C’est pourquoi, nous proposons dans cette thèse, de revisiter le pompage laser par LED, 40 ans après la première démonstration. Nous avons démontré le premier système laser Nd:YVO4 pompé directement par LED. La brillance des LEDs limitant fortement les performances, nous nous sommes intéressé au concept de concentrateur luminescent (en Ce:YAG) pompé par LED. Nous avons ainsi développé une nouvelle source d’éclairage haute brillance, améliorant les performances des LEDs d’un facteur 20 pour aboutir à des éclairements comparables à ceux des diodes laser (de l’ordre de plusieurs kW/cm²). Le pompage laser par cette nouvelle source de pompage a été validé pour la première fois sur les cristaux laser de Nd:YVO4 (3 mJ obtenus avec un profil monomode et 6 mJ en multimode) ainsi que sur des cristaux de Nd:YAG. Dans ce dernier cas, un déclenchement passif à l’aide d’absorbants saturables a permis d'obtenir ainsi des performances encore jamais atteintes pour un laser pompé par LED. Ainsi, les concentrateurs pompés par LED ouvrent de nouvelles possibilités pour le pompage de matériaux laser nécessitant de forte brillance de pompage. Les premiers essais sur le saphir dopé au titane montrent qu'il est possible d'obtenir du gain sur ce matériau en pompage par LED. / Since the early 2000s, the lighting market is constantly growing up, pulling the Light-Emitting Diodes (LED) performance forward and pushing their cost down. LED is becoming an interesting source of light for laser pumping, between flashlamp and laser diodes. Thus, 40 years after the first demonstration, we suggest to revisit laser LED pumping. In this work, we demonstrated for the first time a Nd:YVO4 laser directly LED-pumped. LED radiance being limited, we took interest in LED-pumped luminescent concentrators. By developing Ce:YAG concentrator, we were able to overcome the LEDs irradiance by a factor of 20, leading to output irradiances similar to the laser diode ones (of the order of multi-kW/cm²). We validated the concept by pumping for the first time a Nd:YVO4 crystal and a Nd:YAG crystal with luminescent concentrators. Output energies of several mJ were obtained. In addition, we succeeded to get a passively Q-switched regime for the Nd:YAG laser by using saturable absorbers leading to unpreceded performance for a LED-pumped laser. Finally, LED-pumped concentrators pave the way for new possibilities for high-radiance source pumped media. Our first tests on titanium doped sapphire show that a laser gain with a LED pumping is achievable.

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Of all the Q-switching methods employed to operate a laser in giant pulse mode one of the simplest and most regularly used methods involves a rotating Porro prism. In this Thesis, experimental results are reported which show good agreement with predictions based on a rate equation model. The results indicate that it is possible to design a rotating prism Q-switched laser on the basis of those rate equations, and that the design when realized, should perform close to expectations. / Thesis / Doctor of Philosophy (PhD)

<p> Detailed Neodymium ( Nd ) and Lead ( Pb ) isotopic mapping was performed on gray gneisses from the Lac St. Jean region of Quebec, in the Central Grenville Province. The Nd model ages determined were based upon the Depleted Mantle Model of DePaolo ( 1981c ). The use of this model is justified by a Sm-Nd whole-rock isochron as well as common Pb-Pb whole-rock dating. </p> <p> The field area was divided up into three sections: Western, Central, and Eastern. The boundaries of these divisions corresponded to abrupt changes in Nd model ages. The Western section was located in the Parautochthonous Belt of Rivers et al., ( 1989 ) and almost exclusively consisted of tonalitic gray gneisses with Archean Nd model ages. Whole-rock Pb isotopic analyses produced a Transposed Palaeoisochron, implying that the rocks of the Western section were significantly affected by the Grenville event approximately 1.1 Ga ago. Major and trace element analyses indicate that the Western section represents an arc and may be the exhumed basement of the Abitibi Volcanic Belt to the north, consistent with previous work by Ciesielski ( 1992 ).</p> <p> In contrast to the Western section, the Central section which is separated from the Western section by the Allochthon Boundary Thrust of Rivers et al., ( 1989 ) has a very wide range of Nd model ages from 1.65 Ga to 2.35 Ga. The temporal and spatial range of Nd model ages, coupled with major and trace element analyses, indicates that the Central section represents an Andean style ensialic continental margin arc. The diapirs that reworked these rocks contain varying amounts of Archean material implied by the Early-Proterozoic Nd model ages of some samples, particularly in regions close to the Allochthon Boundary Thrust. Whole-rock Pb isotopic analyses produce a Transposed Palaeoisochron indicating significant U depletion caused by the Grenville orogeny.</p> <p> The Eastern section is composed almost exclusively of gneisses with Nd model ages of ca. 1.5 Ga. The boundary between the Central and Eastern sections is based solely on lithological differences and an isotopic age break form the variable Nd model ages of the Central section, to the consistent model ages of the Eastern section. A Sm-Nd isochron for all samples with ca. 1.5 Ga Nd model ages produces an age of 1.50 +/- 0.07 Ga, in close agreement with previous work ( Dickin and Higgins, 1992 ). The consistency of model ages ( > 100,000 Km^2 when combined with data from Dickin and Higgins, 1992 ) coupled with major and trace element analyses, indicates the presence of an island arc which formed at ca. 1.5 Ga and was sutured on to the Laurentian craton within 100 Ma of its formation.</p> <p> Whole-rock Pb isotope analyses indicate that the Eastern section was not affected by the Grenville event as much as the Central or Western sections were.</p> <p> Pb-Pb zircon dating for samples from the Central and Eastern sections failed to place a tight constraint between crystallization ages and Nd model ages because of excessive Pb loss.</p> / Thesis / Master of Science (MSc)