Abstract Aluminum oxide was utilized as a carrier of active metals copper and manganese. Catalysts with various metal ratios and weight loadings were produced by incipient impregnation to treattoluene. From the 24 catalysts we prepared, this investigation selected the most effective catalyst, based on the conversion rate of toluene and CO2 yield. The influence of operating parameters of toluene oxidization on the conversion rate and long-term variations in catalytic activity were investigated, and the physical properties of catalysts were determined by SEM and XRD. The conversion rate for toluene and CO2 yield reached 95% when the Cu/Mn catalyst was used with a metal ratio of 1:1 and 20% loading at 350¢XC, an influent toluene concentration of 1000ppm, oxygen concentration of 21%, a space velocity of 12000 hr-1, and relative humidity of 26%. The toluene conversion rate increased as reaction temperature and influent concentration of oxygen increased, but decreased as the initial toluene concentration and space velocity increased. The long-term test proceeded for seven days at a constant influent toluene concentration of 1000ppm, constant oxygen concentration of 21%, constant space velocity of 12000hr-1 and constant relative humidity of 26%. The stability of the Cu/Mn catalyst structure was assessed. Differences between fresh and aged catalysts were analyzed using analytical instruments such as SEM, and XRD. No obvious deactivation of the catalytic surface was detected. Keywords aluminum oxide, Cu/Mn catalyst, toluene, and operational parameters

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A new materials system of a single layered Co(W) barrier/liner coupled with a Cu(Mn) alloy seed was investigated. Atom probe tomography visualized the sub-nanoscale structure of Cu(Mn)/Co(W) system, and thereby revealed Cu diffusion behavior of Co(W). Grain boundaries of Co were found to be the diffusion path, and successfully stuffed by W. Mn in Cu(Mn) also segregated to stuff the grain boundaries of Co. Combination of these two additives enabled high barrier property against Cu diffusion of Cu(Mn)/Co(W). Foreseeing tiny and high-aspect-ratio Cu interconnect features, Cu(Mn)/Co(W) was fabricated by ALD/CVD processes. To maximize the performance, minor impurities of the film incorporated from the ligand of the precursors were controlled by precursor selection. Thin, conformal, and smooth films were finally demonstrated onto a trench substrate.

<p>Long-term stability and chromium (Cr) contamination are two major concerns for application of chromium-bearing metallic materials as interconnects of solid oxide fuel cells (SOFCs) at intermediate temperature (~800°C). Copper-manganese (Cu-Mn) and cobalt-manganese (Co-Mn) spinel can be promising coating materials for the metallic interconnects as they show high electrical conductivities. The first objective of this research is to develop an economical and convenient method through which the spinel coatings can be applied to the metallic substrates. The investigations on the crystal structure of CuᵪMn₃₋ᵪO₄ spinel, e.g., structure symmetry and cation distributions, have always been controversial, which hinders the total understanding of the detailed structure of the material. In order to resolve the inconsistency, in-situ neutron and X-ray diffraction were employed to determine the structure of the spinel.</p> <p>A novel method was developed to obtain high quality manganese coating without any additives (sulphur or selenium compounds). Cu-Mn and Co-Mn spinel coatings were applied to metallic coupons by electrodeposition and subsequent annealing. The method is convenient and easy to control. The performance testing showed that the area specific resistances (ASRs) of the coated samples (0.003 Ω•cm²) are much lower than that of the uncoated UNS 430 (0.189 Ω•cm²) after oxidation at 750°C for 1500 hours. Moreover, both spinel coatings can effectively suppress the outward diffusion of Cr, which resulted in reduction of Cr contamination significantly. The oxidation studies of Cu-Mn coating revealed the transformation mechanisms of Cu-Mn coating to the spinel. In-situ neutron and X-ray diffraction analysis clarified the crystal symmetry of CuᵪMn₃₋ᵪO₄ spinel and CuMnO₂ at high temperatures. Rietveld refinement revealed the cation distribution of Cu and Mn ions on tetrahedral and octrahedral sites of CuᵪMn₃₋ᵪO₄ spinel, which was compared to values in the literatures. / Thesis / Doctor of Philosophy (PhD)

Abstract Isopropyl alcohol¡]IPA¡^and toluene are extensively used in industry as solvents. They are all highly toxic to animals and humans. Accordingly, IPA and toluene are strongly associated with problems of VOCs. In first step catalytic incineration was adopted to decompose IPA and toluene in laboratory, and the second step for a pilot-scale regenerative catalytic oxidizer ¡]RCO¡^were adopted to decompose mixture VOCs in real soil herein. The screening test of catalytic activity and the influences of the operational parameters on IPA and toluene removal efficiencies were widely discussed through catalytic incinerations of IPA and toluene in laboratory. The more effective and cheaper catalysts through above discussions of catalytic incineration were selected. And they were utilized in an pilot scale RCO as follows to investigate their performance in VOCs oxidation and RCO operations in THC removal of contamination soils. The achievements of this study are summarized as follows: ¡]1¡^Cu/Mn and Cu/Co gravel catalytic incinerations of isopropyl alcohol The results demonstrated that 10 wt% Cu0.6Co0.4 catalyst was the most effective because the CO2 yield reached 95 % under the following operating conditions; a temperature of 425oC, an inlet IPA concentration of 2500 ppm, an oxygen concentration of 21%, and a space velocity of 13500 hr-1. Additionally, the stability test results indicated that the 10 wt% Cu0.6Co0.4 catalyst exhibited excellent stability at both low and high conversion of IPA. ¡]2¡^20% Cu/Mn aluminum oxide catalytic incinerations of toluene The conversion for toluene reached 95% when the Cu/Mn catalyst was used with a metal ratio of 1:1 and 20% loading at 350¢XC, an influent toluene concentration of 1000 ppm, oxygen concentration of 21%, a space velocity of 12000 hr-1, and relative humidity of 26%. The long-term test was proceeded for seven days at a constant influent toluene concentration of 1000 ppm, constant oxygen concentration of 21%, constant space velocity of 12000 hr-1 and constant relative humidity of 26%. The SEM results indicated the Cu/Mn catalyst was quite stable at 350¢J. ¡]3¡^RCO testing for a copper/manganese catalyst of gaseous toluene The Cu/Mn (20wt%) catalyst was selected as the best one, because it converted 95% of the toluene at 400¢J. The results also indicating that the Cu/Mn catalyst was quite stable at 400¢J. (4) RTO treatment of VOCs with SVE system The conversion for VOCs reached 80% at 900¢XC, an influent VOCs concentration of 450-2000 ppm and a gas flow rate of 0.5 m3/min.The Thermal Recovery Efficiency¡]TRE¡^was approximately 86-90% in a RTO operated at 800-900¢J. (5)RCO treatment of VOCs with SVE system¡]10 wt% Cu0.6Co0.4 gravel catalyst¡^ The 10 wt% Cu0.6Co0.4 gravel catalyst was the poverty active, because it converted 65% of the VOCs by SVE system operated at 650¢J. (6)RCO treatment of VOCs with SVE system¡]20% Cu/Mn aluminum oxide catalytst¡^ The 20% Cu/Mn aluminum oxide catalytic was the best choice, because it converted 95% of the VOCs at 650¢J, an influent VOCs concentration of 450-10000 ppm and a gas flow rate of 0.5-1.5 m3/min. The SEM results indicated that the conversion of VOCs decay did not clearly vary at 650¢J, also indicating that the Cu/Mn catalyst selected was quite stable. The TRE was approximately 90% in a RCO¡]20% Cu/Mn aluminum oxide catalytic¡^operated at 650¢J. (7)RCO treatment of VOCs with SVE system¡]20% Cu/Mn gravel catalytst¡^ The 20% Cu/Mn gravel catalytst was the best selection , because it converted 95% of the VOCs at 600¢J, an influent VOCs concentration of 450-10000 ppm and a gas flow rate of 0.5-1.5 m3/min. The SEM results indicated that the conversion of VOCs decay did not clearly vary at 600¢J, also indicating that the Cu/Mn catalyst selected was quite stable. The TRE was approximately 90% in a RCO¡]20% Cu/Mn gravel catalytic¡^operated at 600¢J.

A new materials system of a single layered Co(W) barrier/liner coupled with a Cu(Mn) alloy seed was investigated. Atom probe tomography visualized the sub-nanoscale structure of Cu(Mn)/Co(W) system, and thereby revealed Cu diffusion behavior of Co(W). Grain boundaries of Co were found to be the diffusion path, and successfully stuffed by W. Mn in Cu(Mn) also segregated to stuff the grain boundaries of Co. Combination of these two additives enabled high barrier property against Cu diffusion of Cu(Mn)/Co(W). Foreseeing tiny and high-aspect-ratio Cu interconnect features, Cu(Mn)/Co(W) was fabricated by ALD/CVD processes. To maximize the performance, minor impurities of the film incorporated from the ligand of the precursors were controlled by precursor selection. Thin, conformal, and smooth films were finally demonstrated onto a trench substrate.

Cette thèse est consacrée à l'étude des structures atomiques des phases icosaédriques de type F et leurs dislocations.<br /><br />Dans cette étude nous avons d'abord construit une structure générique permettant de traiter dans un seul schéma les phases icosaédriques de type F connues. Afin de valider ce modèle nous avons synthétisé quelques compositions suggérées par ce dernier. Ces synthèses ont permis entre autres de découvrir deux nouvelles phases quasipériodiques à la stoechiométrie Al66,08Cu21,35Mn8,29Fe4,28 , l'une icosaédrique (métastable) de type F et l'autre décagonale (stable). Elles ont montré, à une composition au-delà de celles déjà étudiées dans le système (Al,Pd,Fe), l'existence d'une phase F-IQC.<br /><br /> Globalement, ces résultats expérimentaux d'études de nouvelles phases icosaédriques ont permis de montrer la fiabilité du modèle : sur les trois essais de nouvelles compositions, deux ont montré l'existence de phases icosaédriques de type F et la troisième a mis en évidence une phase décagonale en relation d'épitaxie canonique avec la phase icosaédrique brut métastable (axe 10 confondu avec un axe 5).<br /><br />Possédant un modèle fiable nous avons donc pu y introduire des dislocations. Nous avons ainsi précisé la géométrie des dislocations à l'échelle atomique, hors de la zone de cœur, dans les phases F-IQC. Dans cette structure nous avons aussi identifié les mouvements des phasons et tenté d'apporter des éléments de réponse aux mouvements de ces dislocations.