Les membranes à transport d’oxygène (OTM) sont des membranes céramiques denses qui sont capables de transporter l’oxygène de manière totalement sélective à travers un gradient de pression partielle d’oxygène. Elles peuvent être utilisées pour diminuer les émissions de gaz à effet de serre dans le cadre de la capture et du stockage du CO2 ou pour augmenter l’efficacité de l’oxydation partielle du méthane. La semi-perméabilité de l’oxygène est proportionnelle à la conductivité ambipolaire du matériau. Cependant, les OTM avec des conductivités ambipolaires élevées sont plus susceptibles de se dégrader rapidement dans les conditions d’utilisation. Pour être compétitives, les OTMs doivent donc remplir plusieurs critères, notamment avoir un flux élevé mais être aussi stables chimiquement, thermiquement, mécaniquement et être peu chères. CaTi0.9Fe0.1O3−δ (CTF) a été récemment présenté comme étant un matériau prometteur pouvant remplir ces critères et mérite d’être étudié plus en détail.Cette thèse se focalise sur les performances (mesurées par le flux d’oxygène) et la stabilité chimique et thermique du CTF. Pour améliorer les performances d’une membrane, il est nécessaire de savoir si la semi-perméation est limitée par les réactions en surface ou par la diffusion en volume. Les premiers résultats de ces travaux détaillent les étapes limitantes du transport de l’oxygène dans le CTF. En particulier, grâce à un montage expérimental spécifique et des expériences complémentaires, il a été montré que le CTF est limité à la fois par la diffusion en volume et les réactions de surfaces pour T < 750°C mais est majoritairement limité par la diffusion en volume à plus haute température. Les chapitres suivant détaillent la diffusion dans le volume et la conductivité électrique en fonction de la pression partielle d’oxygène et de la température, au vu de la chimie des défauts du CTF. Dans les conditions de fonctionnement, le CTF doit être considéré comme étant un conducteur mixte, avec une conductivité ionique qui devient prédominante pour des températures supérieures à 800°C.La seconde partie est consacrée à l’étude de la stabilité du CTF sous des atmosphères réactives, spécifiques aux OTM, qui sont connues comme provoquant des dégradations pour certains matériaux. Des tests de vieillissement sous atmosphères de CO2, CO, H2 n’ont montré aucune dégradation du flux de semi-perméation sur plusieurs centaines d’heures. Seulement une légère diminution du flux (- 25%) a été observée en présence de CO2 et de vapeur d’eau mais après cent heures sous hélium, le flux initial a été retrouvé. Des analyses DRX, MEB et Raman post-mortem n’ont révélé aucun signe notable de dégradation en surface et dans le volume. Un test sous CH4 a également été effectué, et la formation de CO, CO2, H2 et H2O a été suivie pendant des centaines d’heures. Malgré la présence de ces gaz réactifs, la même valeur du flux de semi-perméation a été retrouvée après 1000 heures de test sous méthane, témoignant d’une très bonne stabilité du CTF dans ces conditions réductrices. En conséquence, malgré des valeurs de flux relativement faibles (5×10-3 mL.min-1.cm-1 à 900°C), ce matériau est plein de promesse et son excellente stabilité sous méthane notamment peut être très intéressante pour certaines applications. / Oxygen transport membranes (OTM) are dense ceramic membranes that allow oxygen diffusion along a chemical potential gradient. OTMs can increase the efficiency of oxycombustion processes or partial oxidation of methane, resulting in lower CO2 emissions overall. The oxygen transport is proportional to the ambipolar conductivity of the OTM material. However, OTM materials with the highest ambipolar conductivity are more prone to fast degradation under operation conditions. To be competitive, OTMs must associate high oxygen transport properties but also must be chemically, thermally, and mechanically stable, and preferably not expensive. CaTi0.9Fe0.1O3−δ (CTF) has recently been shown to match these demands, appearing as a promising OTM material that is worth studying in further detail.This PhD is therefore dedicated to study the performance and stability of CTF in typical operation conditions of an OTM. To improve the performance of a membrane, it is necessary to determine if the semi-permeation is limited by surface exchange reactions or by bulk diffusion. The first results of this work will detail the nature of the limiting reaction step for oxygen transport in CTF. Specifically, CTF is co-limited by bulk diffusion and surface exchange reactions at T < 750 °C, but is mainly limited by bulk diffusion at higher temperatures. The following chapter details the bulk diffusion process and electrical conductivity in light of the defect chemistry of CTF, as a function of oxygen partial pressure and temperature. Under typical operation conditions, CTF must be regarded as a mixed ionic and electronic conductor, with increasing predominance of ionic conductivity at T > 800°C. The second part is dedicated to the stability of the CTF under atmospheric compositions typically found in standard operating conditions, known to degrade the performance of usual membrane materials. The oxygen transport of CTF is shown to remain extremely stable under CO2, CO, and H2 atmospheres over several hundred hours. Some degradation (- 25% of oxygen semi permeation flux) was observed when exposed to humidified CO2, but returning to initial values when exposed to dry helium for a hundred hour. Post-mortem XRD, SEM and Raman analyses did not show any obvious signs of surface or bulk degradation. CTF was tested for CH4 oxidation for a thousand hours and the formation of CO, CO2 and H2O was followed. Despite this reactive environment, the oxygen transport CTF membrane fully regenerates upon returning to helium atmosphere. Therefore, despite relatively low performance (5×10-3 mL.min-1.cm-1 at 900°C), this material is full of promises and especially its outstanding stability under methane can be very interesting for some applications.

Increasing the rate of orthodontic tooth movement (OTM) can reduce risks such as periodontal disease and caries. This study investigated whether light emitting diode (LED) phototherapy could accelerate the rate of OTM. Orthodontic patients with bilaterally symmetric extraction of premolars were recruited. During space closure, LED phototherapy was applied to one side of the dental arch for a specified time and the contralateral side acted as the control. Space closure was measured immediately prior to, during and later in space closure. All 11 patients were compliant with LED application. The results revealed no significant changes in the rate of OTM with LED phototherapy over 3 months of extraction space closure. The findings were contrary to previous findings with laser phototherapy and could be related to the dosage or method of LED phototherapy delivery. Further investigations are needed to determine whether LED phototherapy application can influence the rate of OTM.

Increasing the rate of orthodontic tooth movement (OTM) can reduce risks such as periodontal disease and caries. This study investigated whether light emitting diode (LED) phototherapy could accelerate the rate of OTM. Orthodontic patients with bilaterally symmetric extraction of premolars were recruited. During space closure, LED phototherapy was applied to one side of the dental arch for a specified time and the contralateral side acted as the control. Space closure was measured immediately prior to, during and later in space closure. All 11 patients were compliant with LED application. The results revealed no significant changes in the rate of OTM with LED phototherapy over 3 months of extraction space closure. The findings were contrary to previous findings with laser phototherapy and could be related to the dosage or method of LED phototherapy delivery. Further investigations are needed to determine whether LED phototherapy application can influence the rate of OTM.

The following study aims to examine the success of using option-implied volatility to forecast realized volatility in derivative markets as the preferred market practice. The approach adopted by this study was to compare realized volatility against the monthly average forecast over the period 2005 to 2010. The data selection spanned across currency and commodities markets; short and long-term horizons; before and after the global financial crisis; as well as developed and developing (emerging) markets. To test the success of the forecasting technique, the study used the T-test to test the sample means for any statistical differences between the means of the forecast variable (optionimplied volatility) and the realized variable. The data for the study was obtained from BloombergTM. The findings across all research question showed that this forecasting technique has performed poorly in general for various reasons. There are different arguments in literature as to which forecasting method works best and under what conditions, some practitioners prefer using historical data methods others prefer more technical methods such as the GARCH 1.1. The use of financial derivatives to mitigate financial risk has become a common practice for organizations with a global presence; however market volatility poses a great risk to the financial stability of these organizations. Forecasting volatility continues to be a challenge for market practitioners. / Dissertation (MBA)--University of Pretoria, 2013. / Gordon Institute of Business Science (GIBS) / unrestricted