Dans le contexte actuel, les ressources en énergie fossiles diminuent et deviennent de plus en plus couteuses, se pose aussi le problème de l’environnement. Dans ce cadre, les piles à combustible à oxydes solides (Solid Oxide Fuel Cell en anglais, SOFC) sont une source d’énergie propre et alternative très prometteuse. Utilisé de façon réversible, ce système peut également permettre le stockage de l’électricité produite de façon intermittente via l’électrolyse de l’eau. Néanmoins, plusieurs verrous technologiques restent encore à lever en matière de performances et de durabilité des matériaux actuellement utilisés, notamment pour ce qui concernent les matériaux d’électrode. Dans ce travail de thèse de doctorat, notre contribution a porté sur deux matériaux de cathode de SOFC, Ba2Co9O14 et Ca3Co4O9+δ, et des composés dérivés de La4Ti2O10 pouvant présenter un intérêt comme matériau d’anode. Nous nous sommes intéressés plus particulièrement à la compréhension des mécanismes physico-chimiques intervenant au sein de ces matériaux en faisant appel à la spectroscopie d’impédance. Pour les cobaltites, cette étude a permis de mettre en évidence les paramètres limitants les performances électrochimiques. Elle aidera à l’optimisation de futures cellules complètes plus performantes. Pour les phases dérivées de La4Ti2O10, une étude par diffusion des neutrons a permis de confirmer les mécanismes de diffusion de l’oxygène au sein de ces matériaux. Leurs conductivités et propriétés catalytiques restent néanmoins insuffisantes pour pouvoir espérer les utiliser comme matériau d’anode, au contraire d’autres titanates de lanthane de structure perovskite lamellaire. / In the current context, fossil energy resources decrease and become more expensive, in addition to environmental concern. In this frame, solid oxide fuel cells (SOFC) are a promising green alternative energy source. Reversibly used, this system can also allow storage of electricity produced intermittently through the electrolysis of water. However, several bottlenecks still remain in terms of performances and stability of materials currently used to improve their lifetime and decrease their working temperature. In this doctoral thesis, our contribution focused on two cathode materials for SOFCs, Ba2Co9O14 and Ca3Co4O9+δ, and compounds derived from La4Ti2O10 which may be relevant as anode material. Our study mainly focused on the understanding of the physicochemical mechanisms involved in these materials by using impedance spectroscopy. For cobaltites, this study has led to the identification of the limiting parameters and will help the future optimization of complete stacks with better performances. For the La4Ti2O10 derived phases with the cuspidine structure, a neutron scattering study confirmed the oxygen diffusion mechanisms in these materials. However, their conductivity and catalytic properties remain insufficient to hope to use these compounds as SOFC’s anode, unlike other lanthanum titanates which display a layered perovskite structure.

Dans le contexte énergétique actuel, les piles à combustible à oxyde solide sont très prometteuses comme source d’énergie alternative pour la production d’électricité. Quelques verrous restent cependant à lever pour améliorer leur durabilité, notamment en termes de matériaux d’électrode. Ce travail de thèse s’est intéressé à la caractérisation de nouveaux matériaux d’anode et de cathode. La substitution partielle du titane par du vanadium dans le titanate de lanthane La4Ti2O10 de structure cuspidine a permis de conduire à des matériaux d’anode prometteurs. Des résistances spécifiques surfaciques (ASR, Area Specific Resistance) de l’ordre de 0,2 W.cm2 ont été obtenues à 750°C sous hydrogène. Au niveau de la cathode, nos recherches ont porté sur deux types de cobaltites : une pérovskite de formulation Ba1-xCo0,9Fe0,2Nb0,1O3-d avec x = 0 et 0,1 et un matériau innovant Ba2Co9O14. Dans les deux cas, après optimisation de la microstructure des électrodes, les ASR sont inférieure à 0,1 W.cm2 à 700°C. / In the current energy context, solid oxide fuel cells hold great promise as an alternative energy source for electricity generation. However, bottlenecks remain to improve their sustainability, particularly in terms of electrode materials. This work focused on the characterization of new anode and cathode materials. The partial substitution of titanium by vanadium in the lanthanum titanate La4Ti2O10 of cuspidine structure has led to promising anode materials with Aera Specific Resistance (ASR) of the order of 0.2 W.cm2 at 750 ° C under hydrogen. At the cathode, our research has focused on two types of cobaltites: a perovskite Ba1-xCo0,9Fe0,2Nb0,1O3-d with x = 0 and 0.1 and an innovative material Ba2Co9O14. In either case, after optimization of the microstructure of the electrodes, ASR less than 0.1 W.cm2 at 700 ° C were obtained.

Mould powders are synthetic slags that contain mixtures of silica (SiO2), lime (CaO), sodium oxide (Na2O), fluorspar (CaF2), and carbon (C). When heated to elevated temperatures these powders liquefy and float on the liquid steel in the mould. Mould oscillation helps the liquid flux to penetrate the tiny gap between the mould and the newly formed solid steel shell. In this position the liquid flux partially solidifies against the water cooled mould, while a small portion of the flux remains liquid next to the steel shell to provide lubrication between the moving parts. Effective horizontal heat transfer in the mould is critical for solidifying the liquid steel inthe mould. This process is largely influenced by the thickness and the nature of the flux layer that infiltrates the mould/shell gap. When casting titanium stabilised stainless steels the alloying element reacts with the molten flux, ultimately changing the behaviour of the flux. During the casting process, titanium from the liquid steel reacts with the molten flux producing solids at high temperatures known as perovskite (CaTiO3). Research has shown that perovskite reduces the lubrication capabilities of casting fluxes leading to detrimental effects on product quality while posing a serious threat of machine damage (breakout). The focus of this study is to investigate the effect of titanium pickup on the solidification nature of mould flux and the consequences on horizontal heat transfer. To achieve this, an experimental setup was constructed to simulate the behaviour of mould flux during continuous casting. Analyses of the test flux indicated that the liquid flux closest to the cold side (mould) instantly froze to produce a glassy solid structure. Closer to the hot side (steel shell), solid particles such as perovskite, cuspidine (Ca4Si2O7F2), olivine (Ca,Mg,Mn)2SiO4 and nepheline (Na2O.Al2O3.(SiO2)2) could be identified. Similar solid particles were also found in a slag rim sample taken during the industrial casting of 321- titanium stabilised stainless steel using SPH-KA1 mould powder. Further investigations of the crystalline flux layers showed the entrapment of many tiny gas bubbles during solidification. This porous structure acted as a thermal heat barrier limiting horizontal heat transfer. Experimental testing on 3.0 and 6.0mm flux thickness revealed that the overall thermal conductivity of mould flux decreased as the flux porosity increased. Larger amounts of gas entrapment (in the solid flux structure) resulted in higher thermal resistances which ultimately reduced the heat transfer capabilities of the flux. A second heat barrier, which has a far more dominating effect on the overall heat transfer, is created on mould surface during flux solidification. This thermal contact resistance is also found to be the result of entrapped gas bubbles. Experimental results concluded that the effect of titanium pickup on heat transfer is primarily overshadowed by the larger effect of the thermal contact resistance that is formed during mould flux solidification. The contact resistance in combination with gas entrapment in the solid crystalline structure is considered to be the key factors preventing horizontal heat transfer during continuous casting. / Dissertation (MEng (Metallurgical Engineering))--University of Pretoria, 2006. / Materials Science and Metallurgical Engineering / MEng / unrestricted