This thesis will examine the velocity structure of Austfonna, a large ice cap in the Svalbard archipelago. The remoteness of its location had previously hindered detailed observation by traditional methods, but indirect evidence suggested that it had the potential to be dynamically interesting. A recently developed remote sensing technique, SAR interferometry (inSAR), has allowed us to obtain the most detailed map of Austfonna's topography to date, plus unprecedented synoptic measurements of its velocity field. A four year time series of data acquired by the European Remote Sensing satellites ERS-1 and ERS-2 has been used to delineate active and inactive areas of the ice cap, which suggest that past ideas about Austfonna's thermal structure may need to be re-examined. It has also revealed large temporal velocity variations in one of its major drainage basins. These are difficult to classify because intermittent sampling has prevented us from determining their temporal wavelength, and also because globally the database of observed glacier velocity variations is so sparse that the range of possible variable flow scenarios is unknown. The work here demonstrates the huge potential for inSAR in helping to resolve such issues, and in providing an invaluable resource for scientists monitoring the stability of the world's ice fields.

Cette thèse concerne l’étude de phase de séparation de deux polymères thermosensibles connus-poly(N-isopropylacylamide) (PNIPAM) et poly(2-isopropyl-2-oxazoline) (PIPOZ). Parmi des études variées sur ces deux polymères, il y a encore deux parties de leurs propriétés thermiques inexplicites à être étudiées. Une partie concerne l’effet de consolvant de PNIPAM dans l’eau et un autre solvant hydromiscible. L’autre est l’effet de propriétés de groupes terminaux de chaînes sur la séparation de phase de PIPOZ. Pour ce faire, nous avons d’abord étudié l’effet de l’architecture de chaînes sur l’effet de cosolvant de PNIPAMs dans le mélange de méthanol/eau en utilisant un PNIPAM en étoile avec 4 branches et un PNIPAM cyclique comme modèles. Avec PNIPAM en étoile, l’adhérence de branches PNIPAM de à un cœur hydrophobique provoque une réduction de Tc (la température du point de turbidité) et une enthalpie plus faible de la transition de phase. En revanche, la Tc de PNIPAM en étoile dépend de la masse molaire de polymère. La coopérativité de déhydratation diminue pour PNIPAM en étoile et PNIPAM cyclique à cause de la limite topologique. Une étude sur l’influence de concentration en polymère sur l’effet de cosolvant de PNIPAM dans le mélange méthanol/eau a montré qu’une séparation de phase liquide-liquide macroscopique (MLLPS) a lieu pour une solution de PNIPAM dans le mélange méthanol/eau avec la fraction molaire de méthanol entre 0.127 et 0.421 et la concentration en PNIPAM est constante à 10 g.L-1. Après deux jours d’équilibration à température ambiante, la suspension turbide de PNIPAM dans le mélange méthanol/eau se sépare en deux phases dont une phase possède beaucoup plus de PNIPAM que l’autre. Un diagramme de phase qui montre la MLLPS pour le mélange PNIPAM/eau/méthanol a été établi à base de données expérimentales. La taille et la morphologie de gouttelettes dans la phase riche en polymère condensée dépendent de la fraction molaire de méthanol. Parce que la présence de méthanol influence la tension de surface des gouttelettes liquides, un équilibre lent de la séparation de phase pour PNIPAM/eau/méthanol système a été accéléré et une séparation de phase liquide-liquide macroscopique apparait. Afin d’étudier l’effet de groupes terminaux sur les propriétés de solution de PIPOZ, deux PIPOZs téléchéliques avec groupe perfluorodécanyle (FPIPOZ) ou groupe octadécyle (C18PIPOZ) comme extrémités de chaîne ont été synthétisés. Les valeurs de Tc des polymères téléchéliques ont beaucoup diminué par rapport à celle de PIPOZ. Des micelles stables se forment dans des solutions aqueuses de polymères téléchéliques. La micellization et la séparation de phase de ces polymères dans l’eau ont été étudiées. La séparation de phase de PIPOZs téléchéliques suit le mécanisme de MLLPS. Des différences en tailles de gouttelettes formées à l’intérieur de solutions de deux polymères ont été observées. Pour étudier profondément les différences dans le comportement d’association entre deux polymères téléchéliques, les intensités des signaux de polymères correspondants et les temps de relaxation T1, T2 ont été mesurés. Des valeurs de T2 de protons correspondants aux IPOZs sont plus hautes. / This thesis focused on the phase separation of two well-known thermoresponsive polymers, namely PNIPAM (poly(N-isopropylacrylamide)) and PIPOZ (poly(2-isopropyl-2-oxazoline). Despite various studies of the two polymers, two aspects of their thermal properties remained unclear and needed to be investigated. One is the cononsolvency effect of PNIPAM in water and a second water miscible solvent. The other is the effect of the end group properties on the phase separation of PIPOZ. With this in mind, we first studied the effect of the chain architecture on the cononsolvency of PNIPAM in water/methanol mixture, employing a 4-arm star shape PNIPAM and a cyclic PNIPAM as model. Tethering PNIPAM arms to a hydrophobic core resulted in a reduced Tc (cloud point temperature) and a lower phase transition enthalpy change. The Tc of the star shape PNIPAM was inversely dependent on the polymer molecular weight. The dehydration cooperativity was depressed for the star PNIPAM and cyclic PNIPAM due to topological constraints. A study of the effect of polymer concentration on the cononsolvency of PNIPAM in water/methanol mixture revealed a macroscopic liquid-liquid phase separation (MLLPS) for PNIPAM in water/methanol mixtures of methanol molar fraction ranging from 0.127 to 0.421 at a polymer concentration of 10 g·L-1. The turbid suspension of PNIPAM/water/methanol separated into a polymer rich phase coexisting with a polymer poor solution phase after equilibration for two days at room temperature. The phase diagram showing the MLLPS for the PNIPAM/water/methanol mixtures was constructed based on experimental data. The droplets in the condensed polymer rich phase showed a dependence on the methanol molar fraction. Methanol affects the surface tension of the liquid droplets. The slow equilibrium kinetics of PNIPAM phase separation was sped up and a macroscopic liquid-liquid phase separation realized. In order to study the effect of end groups on the solution properties of PIPOZ, two telechelic PIPOZ end capped with perfluorodecanyl groups (FPIPOZ) and octadecyl groups (C18PIPOZ), respectively, were synthesized. The Tc values of the telechelic polymers were greatly reduced after end-functionalization. Stable micelles formed in aqueous solutions of the telechelic polymers. The micellization and phase separation of the telechelic polymers in water were studied. The phase separation of the telechelic PIPOZs in water followed a liquid-liquid phase separation mechanism. Differences in the sizes of droplets formed inside of the two polymer solutions were observed. To further investigate the differences in the association behaviour between the two telechelic polymer, NMR signal intensities and T1 and T2 relaxation times were examined. Higher 1H T2 values were obtained for the IPOZ unit in FPIPOZ than that in C18PIPOZ, indicating a higher mobility of the main chain in the FPIPOZ micelles than that in the C18PIPOZ micelles. Together with the 13C NMR and 19F NMR relaxation studies, we obtained better knowledge of the association properties of the telechelic PIPOZ in water. NMR relaxation studies proved to be efficient way of probing the solution behaviour of the polymers.

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

Cette thèse présente une étude du modèle XY bidimensionnel dans des conditions réalistes, comme la présence d'imperfections (impuretés non magnétiques) ou la taille finie du réseau. Ces deux aspects sont typiques de situations expérimentales et nécessitent un questionnement théorique. Nous avons également considéré le comportement a basse température du modèle d'Heisenberg fini et avons trouve un comportement analogue a celui du modèle XY. Nous avons utilise a la fois une approche analytique et des simulations numériques pour traiter le problème. Les résultats essentiels de ce travail sont: (a) la détermination de l'exposant de décroissance algébrique de la fonction de corrélation du modèle XY dilue, analytiquement avec l'approximation d'ondes de spins et par simulations Monte Carlo a l'aide de l'algorithme de Wolff, (b) l'estimation correspondante dans le cas du modèle d'Heisenberg sur réseau fini a basse température assortie de simulations numériques également, (c) la forme de l'interaction entre les impuretés non magnétiques et les défauts topologiques dans le cadre du modèle de Villain et dans le modèle de Kosterlitz-Thouless, et l'estimation analytique de la réduction de température critique basée sur la forme de cette interaction, (d) la détermination numérique de la distribution de probabilité de l'aimantation résiduelle sur un système fini en présence de désordre. Pour l'ensemble de nos travaux, nous avons obtenu un bon accord entre les prédictions théoriques et les simulations numériques, de même qu'avec des travaux antérieurs le cas écheant. / The thesis presents a study of the two-dimensional XY model exposed to such realistic conditions as the presence of lattice imperfections (nonmagnetic impurities) and lattice finiteness. Both features are typical for experimentally accessible magnetic materials and ask for theoretical description. We also have explored the low-temperature behaviour of a finite two-dimensional Heisenberg model and found behaviour similar to that of the 2D XY model. We have used both analytical and computer experiment approaches to tackle the problem. The essential output of the work consists of: (a) estimation of the non-universal exponent of the power law decay of the pair correlation function of a diluted 2D XY model at low temperature as a function of dilution, analytically in the spin-wave approximation, and in the Monte Carlo simulations using the Wolff algorithm; (b) analytical estimation of the corresponding exponent of the 2D Heisenberg model in the low-temperature limit for the finite lattice size and its comparison to the Monte Carlo simulations; (c) evaluation of the form of interaction between nonmagnetic impurities and topological defects within the Villain model as well as in the Kosterlitz-Thouless model, and analytical prediction of the critical temperature reduction made on the basis of this interaction; (d) Monte Carlo investigation of the form of the residual magnetization probability distribution in a finite system in presence of nonmagnetic disorder (dilution). We found all our analytical predictions in quite well agreement with the Monte Carlo simulation results as well as with other researches of the similar problems.

Call number: LD2668 .R4 1967 C33

M.Sc. / Dense non-aqueous phase liquids (DNAPLs) are groups of chemicals often found beneath the water surface when chemical contamination of water occurs and they are called groundwater contaminants. Their improper storage and extensive use in industries as well as their slow degradation provide a long term source for of low level contamination of ground- and river water. Evidence from both human and animal studies suggests that volatile organic and organochlorinated compounds (specific types of DNAPLs), may increase host susceptibility to microbial infection, induce alterations in the maturation of effector immune cells and compromise immune surveillance mechanisms. These effects of DNAPLs hold special relevance for people living with HIV/AIDS. In light of this, the present study investigated the in vitro immunological effects of the two most common DNAPLs contaminants, Trichloroethylene (TCE) and Aroclor-1254 (ARO) in peripheral blood mononuclear cells (PBMCs) of immunocompromised and healthy donors. TCE and ARO were successfully dissolved in cell culture medium and added to freshly isolated PBMCs in a 1:1 ratio. Following incubation, cell functionality and cytotoxicity (or immunotoxicity) were assessed using MTT and LDH. Viability was confirmed and/or cell death analyzed by flow cytometry. Culture supernatants were used to assess NO and cytokine production as well as for quantification of viral replication. TCE and ARO induced a significant (p<0.05) decrease in cell viability/functionality in a dose-dependent manner. Flow cytometric analysis of cell death pathways indicated that TCE and ARO induced apoptosis. These chemicals also induced the secretion of both NO and proinflammatory cytokines suggesting that they may induce apoptosis via an inflammatory pathway, which may explain the mitochondrial dysfunction as determined by the MTT assay. ARO effects were more prominent than those of TCE, and both were more detrimental to HIV positive PBMCs compared to uninfected cells. The viral p24 levels increased in a dose-dependent fashion suggesting an effect for TCE and ARO on viral replication. This research concludes that DNAPL-contamination is detrimental to especially immuno-compromised systems.

Magister Educationis - MEd / Reading is one of the components of literacy that plays a crucial role in accessing knowledge. It develops the children’s mind and stimulates their understanding of the reading content and enables them to function and communicate effectively in society. Research conducted in the field of literacy suggests that there is a literacy crisis (especially in reading), around the world. Recent research indicates that South African Foundation Phase learners perform poorly in reading comprehension. Considering poor literacy results observed in South Africa, it is important to explore reading as a socio-cultural and cognitive practice and to identify the factors that contribute towards adequate acquisition of reading comprehension skills in the Foundation Phase. Thus the focus of this study is on reading comprehension in isiXhosa Home Language which is used as the main language of learning and teaching from Grade R - 3. I have used a qualitative approach as an underpinning research methodological framework for this study. Data was collected by means of interviews and classroom observations from two selected Grade three classrooms in one primary school in the Western Cape. The findings of this study illustrate the significance of learners’ prior knowledge and the use of adequate resources to enhance learners’ reading comprehension. The study concludes that reading comprehension is a cognitive process that demands innovative teaching approaches that will facilitate meaningful learning across the curriculum.

Ce travail de thèse porte sur la synthèse de carbures de molybdène sur support afin de tester leurs performances catalytiques dans des réactions d’hydrogénation. Dans ce but, la conversion d'acide succinique en phase aqueuse dans un réacteur discontinu et du dioxyde de carbone en phase gazeuse dans un réacteur à flux continu, ont été effectuées. Les catalyseurs ont été préparés par la méthode de carburation par réduction en température programmée, pendant laquelle des paramètres ont été modifiés conduisant à différents rapports molybdène/carbone. Les différents catalyseurs testés dans cette réaction étaient actifs pour la conversion de l'acide succinique en gamma-butyrolctone et, plus remarquablement, en acide butyrique, ce dernier n'était pas obtenu en quantités significatives avec des catalyseurs à base de métaux précieux. L’augmentation de la conversion d’acide succinique avec une sélectivité plus élevée en acide butyrique a été faite avec les catalyseurs contenant plus de carbone, préparés en augmentant la vitesse spatiale horaire gazeuse. Les intermédiaires ont été ensuite convertis en tétrahydrofurane, butanol, 1,4-butanediol et butane. La désactivation observée lors de recyclage du catalyseur a été principalement attribuée à une diminution de la quantité de molybdène et de carbone carbidique, démontrée par l'analyse XPS. Des essais préliminaires de ces catalyseurs dans l'hydrogénation du dioxyde de carbone ont montré qu'ils fonctionnaient principalement en tant que catalyseurs pour la réaction du gaz à l’eau inverse, et l'excès de carbone entrave l'activité catalytique d'une manière opposée à la réaction en phase aqueuse. Le support semble jouer un rôle dans la réactivité des catalyseurs, la conversion du dioxyde de carbone ainsi que la sélectivité en méthane et méthanol, qui ont augmenté dans l'ordre suivant: carbure de molybdène sur support DT51 TiO2> P25 TiO2 ˜ ZrO2 / This work focuses on the synthesis of supported molybdenum carbides and evaluating their catalytic performance in succinic acid hydrogenation reactions in aqueous phase using batch reactor and carbon dioxide hydrogenation in gas phase using continuous flow reactor. The catalysts were prepared by the temperature programmed reduction carburization method, where the parameters were modified leading to different molybdenum to carbon ratios. The different catalysts tested were active in converting succinic acid to gamma butyrolctone and more remarkably butyric acid which is not reported in significant quantities in this reaction with precious metal based catalysts. The catalysts containing more carbon contents that were prepared by increasing the gas hourly space velocity showed higher activity in converting succinic acid and higher selectivity to butyric acid. The intermediates were then converted to tetrahydrofuran, butanol, 1,4-butanediol and butane gas. The deactivation observed while recycling the catalyst was mainly attributed to a decrease in the amounts of carbidic molybdenum and carbidic carbon, as demonstrated by XPS analysis. Preliminary tests for these catalysts in carbon dioxide hydrogenation showed that they functioned mainly as reverse water gas shift catalysts, and the excess of carbon hinders the catalytic activity in an opposite manner of the reaction in aqueous phase. The support seems playing a role in the reactivity of the catalysts, carbon dioxide conversion as well as methane and methanol selectivity increased in the order: molybdenum carbide supported on DT51 TiO2 > P25 TiO2 ˜ ZrO2

A dissertation submitted to the Faculty of Engineering, University of the Witwatersrand) in partial fulfilment of the requirements for the degree of Master of Science in Engjneering Johannesburg, 1994 / Recent international investigations into new advanced materials have shown that the intennetallic compound, RuA1, possesses prormising characteristics for high-temperature use in corrosive environments. In order to optimise production of this alloy, an understanding of the Ru-A1 system is necessary. [Abbreviated Abstract. Open document to view full version]

A thesis submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, in fulfilment of the requirements for the degree of Doctor of Philosophy in Engineering (Metallurgy and Materials Engineering). Johannesburg, March 2014 / This study investigated the C-Ni-V ternary phase diagram and identification of possible abrasive-resistance alloys. Twenty-four alloys were made from the elemental components and were arc-melted under an argon atmosphere, using Ti as an oxygen-getter. These alloys were analysed in both the as-cast condition, and after annealing for 1000oC and water quenching. Microstructural characterization was carried out in a SEM with EDX, and was done to confirm the phases. The results were used to plot a solidification projection and all binary phases extended into ternary, except for ~Ni8V, ~NiV3 and ~V2C which were not found, due to the sample compositions chosen. The extensions of the binary phases were: ~Ni3V: ~15 at.% C; ~Ni2V: ~20 at.% C; σ′: ~18 at.% C; (Ni): ~27 at.% C; ~V8C7: ~2 at.% Ni; ~V6C5: ~2 at.% Ni and ~VC: ~2 at.% Ni. The liquidus surface was derived, and three ternary invariant reactions were identified. The isothermal section at 1000oC was also constructed. Hardness of the alloys was studied in both conditions. Alloys with (Ni) (188-402HV5) were found to be ductile with low hardness. Alloys containing (V), ~Ni3V and ~Ni2V were identified as hard phases (533-1052 HV5). Alloys with σ′ phase were very hard (1065-1266 HV5) extremely brittle with cracks. Fracture toughness of the C-Ni-V alloys 0.9-5.2 (MPa.m-1/2) were comparable with ceramics 0.5-5.3(MPa.m-1/2). The wear behaviour of the alloys was characterized by sliding the carbide alloys against a Cr-steel ball in a pin-on-disc configuration. There were several co-existing wear mechanisms: abrasion, adhesion and the formation of a thin tribolayers. The wear coefficients for a 10N contact load after a sliding wear path of 300m varied between 0.1 x 10-6and 7.6 x 10-6(mm3/Nm), which was not as good as WC-Co hard metals, but close. / MT2017