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Étude de systèmes de matériaux évolutifs : interactions solides-gaz, propriétés catalytiques et électriques dans le cas d'hydroxycarbonates, carbonates et oxydes à base de terres rares (La, Ce, Lu)

Abstract : The present work deals with the solid gas interactions between lanthanum and cerium based phases (hydroxycarbonates LaOHCO3, CeOHCO3, carbonate La2O2CO3, and oxides La2O3, CeO2), and the gases CH4, CO and CO2. These interactions might be involved in gas sensor or catalytic applications. The main interest of these rare earth based systems resides in the fact that they are evolving materials in environmental conditions. The initial hydroxycarbonate phases are synthesized via specific precipitation sol-gel routes. The phases La2O2CO3, La2O3 and CeO2 are obtained by thermal treatment of the hydroxycarbonates. The various phases are first characterized by X-ray diffraction. Their crystal sizes and morphologies are then determined by scanning and transmission electron microscopy (SEM, TEM). The catalytic interactions of these polycrystalline solids with air-CH4 and air-CO mixtures are studied making use of Fourier Transform Infrared spectroscopy of emitted gases, at various temperatures (100 to 550°C), and as a function of time. The conversions of CH4 and CO into CO2 are observed from air - gas flows crossing through polycrystalline walls of the polycrystalline catalytic materials. The catalytic efficiency is defined as being proportional to the FTIR absorbed intensities due to the CO2 molecules. These intensities depend on time and temperature. The electrical analyses of compacted pellets are performed by electrical impedance spectrometry at various temperatures. For a given temperature, the conversions of CO and CH4 into CO2 reach a stabilized level after an initiation time. This stabilized level increases with temperature and reaches a maximum value depending on material nature and specific area. The conversion of CO is obtained at temperatures lower than the ones observed for CH4. These time dependent catalytic conversions are modeled from an elemental Avrami's approach. The carbonatation kinetics are determined first by thermal and thermogravimetry analyses, at fixed temperatures, as a function of time. Two steps in carbonatation are evidenced. Using electrical impedance spectrometry as a function of time and temperature the electrical evolutions of lanthanum and cerium based systems subjected to carbonatation and decarbonatation are analyzed. As a first step, the electrical responses associated with the phase modifications of the hydroxycarbonate phases LaOHCO3 and CeOHCO3 during thermal decomposition under air are determined. Then, the electrical signals due to carbonatation and decarbonatation processes are analyzed: the ionic mobility of CO32- ions in the carbonate solid is evaluated. The evolving series LaOHCO3-La2O2CO3 - La2O3 might be of a high interest in gas sensor systems, working at variable temperatures and sensitive to CH4, CO or CO2.
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Submitted on : Thursday, June 23, 2011 - 4:43:17 PM
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Bahcine Bakiz. Étude de systèmes de matériaux évolutifs : interactions solides-gaz, propriétés catalytiques et électriques dans le cas d'hydroxycarbonates, carbonates et oxydes à base de terres rares (La, Ce, Lu). Matériaux. Université du Sud Toulon Var, 2010. Français. ⟨tel-00602907⟩

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