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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
71

Dynamique hyperfréquence d'aimantation induite par transfert de spin

Bianchini, Laurence 15 December 2010 (has links) (PDF)
Des dispositifs magnétorésistifs sont actuellement utilisés comme têtes de lecture dans les disques durs. Le contexte de la miniaturisation des capteurs magnétiques pour accommoder l'augmentation de la densité de stockage implique une augmentation du bruit magnétique d'origine thermique. L'utilisation d'une oscillation entretenue par le courant permettrait l'augmentation combinée de la sensibilité magnétique ainsi que de sa vitesse de lecture. L'étude présentée a pour but de clarifier les divers comportements des oscillations de l'aimantation induites par le transfert de spin, dans la gamme de la dizaine de gigahertz, dans des jonctions tunnel magnétiques à barrière de MgO. Nous présentons, dans une première partie, une étude détaillée des modes d'oscillations entretenues dans les différentes couches magnétiques du système. L'identification des modes permet ainsi de " lire " des données codées par domaines magnétiques d'après la mesure de la fréquence de l'oscillateur. Dans la seconde partie de cette thèse, nous présentons des mesures temporelles d ces oscillations. Nous analysons le bruit d'amplitude et de phase d'une oscillation entretenue et nous présentons une première mesure expérimentale du coefficient de nonlinéarité de la fréquence. Les temps caractéristiques extraits sont significatifs de l'agilité du dispositif et la nonlinéarité, spécifique aux oscillateurs à transfert de spin, induit un élargissement inhomogène de la raie spectrale.
72

Spindynamik in Tunnelelementen mit senkrechter magnetischer Anisotropie / Spin dynamics in tunnel junctions with perpendicular magnetic anisotropy

Zbarsky, Vladyslav 22 January 2015 (has links)
No description available.
73

Análise comparativa da composição química de aço e escória e rendimento metálico de um FEA entre parâmetros de carregamento e injeções distintos

Vieira, Deisi January 2017 (has links)
Aliar alta produtividade ao menor custo de processo é o principal desafio econômico de uma Aciaria Elétrica. Para isso, mudanças no processo almejando práticas que resultam em uma maior eficiência do FEA, com um menor custo envolvido, ocorrem constantemente. Este trabalho avalia um processo de FEA, com capacidade de 62 toneladas de aço, operando com carregamento de sucata metálica e ferro-gusa. Dois grupos de corridas de aço, pertencentes à dois cenários distintos, foram estudadas. Os cenários foram denominados Cenário I e Cenário II, sendo que, no segundo cenário ocorreram mudanças nas práticas de injeções de carbono e oxigênio, nas práticas de adição de cales no carregamento e mudanças na quantidade de Sucata Shredder no FEA. O objetivo deste trabalho foi analisar como essas mudanças influenciaram no processo. A composição química de aço e escória de dois padrões de carga (C e E) foi comparada entre os cenários. Verificou-se que a massa de escória diminuiu para os dois padrões de carga. Porém, a basicidade do padrão C foi reduzida de 2,5 para 2,1, enquanto para o padrão E manteve-se em 2,2 para os dois cenários. O MgO de saturação foi avaliado através de diagramas de saturação isotérmicos (ISD), e a maior parte das corridas do Cenário II ficaram acima da linha de saturação da escória. Houve uma redução de 30% do oxigênio injetado para os dois padrões e seus teores de fósforo no aço aumentaram significativamente. No entanto, apenas o padrão C teve uma variação nos teores de carbono no aço. A energia elétrica consumida mostrou-se dependente dos teores de FeO e MgO da escória. O padrão E apresentou um aumento significativo de 10 kWh/t. O rendimento metálico dos padrões C e E aumentou 3,59% e 2,22%, respectivamente. No Cenário II, o aumento da sucata Shredder no carregamento foi duas vezes maior. O Cenário II apresentou uma redução dos teores de cobre no aço para os dois padrões. As quantidades médias de injeção de carbono não tiveram variação significativa, por outro lado, através dos gráficos de distribuição, notou-se uma maior estabilidade nos valores de injeção. Para o padrão E observou-se uma quantidade mínima de ferro na escória para a razão global C/O de 0,75. Uma análise da razão das injeções de carbono e oxigênio durante o refino foi feita. Observou-se uma maior estabilidade das injeções ao longo do tempo de refino para o Cenário II em ambos os padrões. / Combine high productivity and lower costs is the main economical challenge of a steelmaking melt shop. Therefore, changes in the process aiming practices that result in higher efficiency of the EAF, with lower costs, occur frequently. This work evaluates an EAF process, with capacity of 62t of steel, operating with metal scrap and pig iron load. Two groups of steel heats that represents two distinct scenarios were studied. The scenarios were called Scenario I and Scenario II. In the Scenario II carbon and oxygen injection practices, limes loading practice and Shredder scrap loading amount were modified. The aim of the present work is analyze how these changes affected process parameters. The steel and slag chemical composition of two loading patterns (C and E) was compared on the scenarios. It was found that the slag mass reduces for both loading patterns. However, the basicity of the pattern C was reduced from 2.5 to 2.1 while the pattern E was maintained on 2.2 for both scenarios. The MgO saturation content of the slag is evaluated through Isothermal Solubility Diagrams. Most of the heats of the Scenario II MgO content are higher than the minimal saturation content. There was a reduction of 30% of the injected oxygen for both loading patterns and their P content increased significantly. Meanwhile, only the pattern C shows a variation on carbon content in the steel. The electric power consumption showed proportional relation to FeO and MgO content of the slag and the pattern E showed a significant increase of 10 kWh/t. The metallic yield of the patterns C and E increased 3.59 and 2.22, respectively. The scenario II showed a reduction of the Cu content in both patterns. The carbon injection amount means did not vary significantly, but, through distribution graphs, was noted a higher stability in the injection amount. For the E pattern, a minimum amount of iron in the slag was observed for the overall C/O ratio of 0,75. An analysis of the ratio of the carbon and oxygen injection during the refining period was done. It was observed a higher stability of the injections along the refining period for the Scenario II on both patterns.
74

Análise comparativa da composição química de aço e escória e rendimento metálico de um FEA entre parâmetros de carregamento e injeções distintos

Vieira, Deisi January 2017 (has links)
Aliar alta produtividade ao menor custo de processo é o principal desafio econômico de uma Aciaria Elétrica. Para isso, mudanças no processo almejando práticas que resultam em uma maior eficiência do FEA, com um menor custo envolvido, ocorrem constantemente. Este trabalho avalia um processo de FEA, com capacidade de 62 toneladas de aço, operando com carregamento de sucata metálica e ferro-gusa. Dois grupos de corridas de aço, pertencentes à dois cenários distintos, foram estudadas. Os cenários foram denominados Cenário I e Cenário II, sendo que, no segundo cenário ocorreram mudanças nas práticas de injeções de carbono e oxigênio, nas práticas de adição de cales no carregamento e mudanças na quantidade de Sucata Shredder no FEA. O objetivo deste trabalho foi analisar como essas mudanças influenciaram no processo. A composição química de aço e escória de dois padrões de carga (C e E) foi comparada entre os cenários. Verificou-se que a massa de escória diminuiu para os dois padrões de carga. Porém, a basicidade do padrão C foi reduzida de 2,5 para 2,1, enquanto para o padrão E manteve-se em 2,2 para os dois cenários. O MgO de saturação foi avaliado através de diagramas de saturação isotérmicos (ISD), e a maior parte das corridas do Cenário II ficaram acima da linha de saturação da escória. Houve uma redução de 30% do oxigênio injetado para os dois padrões e seus teores de fósforo no aço aumentaram significativamente. No entanto, apenas o padrão C teve uma variação nos teores de carbono no aço. A energia elétrica consumida mostrou-se dependente dos teores de FeO e MgO da escória. O padrão E apresentou um aumento significativo de 10 kWh/t. O rendimento metálico dos padrões C e E aumentou 3,59% e 2,22%, respectivamente. No Cenário II, o aumento da sucata Shredder no carregamento foi duas vezes maior. O Cenário II apresentou uma redução dos teores de cobre no aço para os dois padrões. As quantidades médias de injeção de carbono não tiveram variação significativa, por outro lado, através dos gráficos de distribuição, notou-se uma maior estabilidade nos valores de injeção. Para o padrão E observou-se uma quantidade mínima de ferro na escória para a razão global C/O de 0,75. Uma análise da razão das injeções de carbono e oxigênio durante o refino foi feita. Observou-se uma maior estabilidade das injeções ao longo do tempo de refino para o Cenário II em ambos os padrões. / Combine high productivity and lower costs is the main economical challenge of a steelmaking melt shop. Therefore, changes in the process aiming practices that result in higher efficiency of the EAF, with lower costs, occur frequently. This work evaluates an EAF process, with capacity of 62t of steel, operating with metal scrap and pig iron load. Two groups of steel heats that represents two distinct scenarios were studied. The scenarios were called Scenario I and Scenario II. In the Scenario II carbon and oxygen injection practices, limes loading practice and Shredder scrap loading amount were modified. The aim of the present work is analyze how these changes affected process parameters. The steel and slag chemical composition of two loading patterns (C and E) was compared on the scenarios. It was found that the slag mass reduces for both loading patterns. However, the basicity of the pattern C was reduced from 2.5 to 2.1 while the pattern E was maintained on 2.2 for both scenarios. The MgO saturation content of the slag is evaluated through Isothermal Solubility Diagrams. Most of the heats of the Scenario II MgO content are higher than the minimal saturation content. There was a reduction of 30% of the injected oxygen for both loading patterns and their P content increased significantly. Meanwhile, only the pattern C shows a variation on carbon content in the steel. The electric power consumption showed proportional relation to FeO and MgO content of the slag and the pattern E showed a significant increase of 10 kWh/t. The metallic yield of the patterns C and E increased 3.59 and 2.22, respectively. The scenario II showed a reduction of the Cu content in both patterns. The carbon injection amount means did not vary significantly, but, through distribution graphs, was noted a higher stability in the injection amount. For the E pattern, a minimum amount of iron in the slag was observed for the overall C/O ratio of 0,75. An analysis of the ratio of the carbon and oxygen injection during the refining period was done. It was observed a higher stability of the injections along the refining period for the Scenario II on both patterns.
75

Réactivité de nanoparticules d'oxydes d'orientations définies / Reactivity of oxyde nanoparticles with defined orientations

Haque, Francia 09 October 2015 (has links)
La connaissance d’un système gaz/solide requiert l’analyse de l’adsorption, du premier stade jusqu’à saturation. C’est la motivation de l’analyse des surfaces sous vide. L’approche des surfaces divisées est souvent tronquée. Pratiquée à des pressions suffisamment élevées pour être compatible avec un temps de réaction raisonnable, elle ne permet pas l'analyse de la surface nue à la monocouche. L’objectif du présent travail a été d’établir une continuité d’observation par FTIR, de l’UHV à la pression ambiante, de poudres de MgO, ZnO et ZnxMg1-xO exposées à l’eau ou à l’hydrogène. Il a été montré que les fumées de ZnO se comparent à des cristaux présentant les faces (0001), (0001̅), (101̅0), (112̅0), avec un rapport non-polaire/polaire de 75/25. Par FTIR combinée à la photoémission et à la désorption thermique, trois étapes de l’hydroxylation des fumées de MgO ont été identifiées : défauts ponctuels (10-8 mbar), marches (10-6 mbar) puis terrasses (> 10-5 mbar), avec une restructuration qui prouve que l’eau change la structure de surface de MgO. La représentation commune de la surface de MgO par une suite de facettes (100) est mise en cause. Aux faibles teneurs en zinc, l’oxyde mixte ZnxMg1-xO est formé de cristallites cubiques de même structure que MgO. Le zinc en substitution tend à ségréger vers les sites de basse coordinence où il affecte les propriétés d’adsorption d’eau et d’hydrogène. Par ailleurs, le mélange ZnO-MgO obtenu par combustion d’alliage ZnMg offre une possibilité d’application grâce aux propriétés bactéricides de ZnO et de faible toxicité de MgO. L’ensemble des résultats montre la pertinence de l’étude des poudres pratiquée dans les conditions de l’UHV. / The analysis of adsorption from the first stage to saturation is necessary to understand gas/solid interactions. This is the motivation for surface analysis under vacuum. The common approach of dispersed materials surfaces is incomplete since working pressures, that are high enough to achieve reasonable reaction times, do not allow studies of powder surfaces from bare to fully covered. The aim of the present work is to examine the successive changes of ZnO, MgO and ZnxMg1-xO nanopowders upon exposure to water or hydrogen from UHV to the ambient by FTIR. It is shown that ZnO smokes behave in a same way as a collection of single crystals which exhibit (0001), (0001̅), (101̅0) and (112̅0) faces with a non-polar/polar ratio of 75/25. Combining FTIR with XPS and TPD techniques, three stages of hydroxylation were identified on MgO smokes: point defects (10-8 mbar), steps (10-6 mbar) then terraces (> 10-5 mbar). Results indicate a reorganisation of surface structure showing that water adsorption on MgO(100) is an irreversible process. The common model of MgO as a series of (100) facets is questioned. At low concentrations of zinc, the mixed oxide ZnxMg1-xO consists of crystals with similar structure as MgO. A segregation of Zn2+ toward low coordinated surface sites is suggested to explain the changes in reactivity of the ZnxMg1-xO with respect to water and hydrogen at low coverages. Furthermore, the mixture ZnO-MgO produced by combustion of ZnMg alloy combines the antibacterial properties of ZnO and the biocompatibility of MgO, interesting for potential applications. The overall results demonstrate the relevance of the study of powders in ultra-high vacuum conditions.
76

A study on the Submerged Entry Nozzels (SEN) respecting clogging and decarburization

Memarpour, Arashk January 2010 (has links)
The submerged entry nozzle (SEN) has been used to transport the molten steel from tundish to the mould. The main purpose of the SEN usage is both to prevent oxygen and nitrogen pick-up by molten steel and to achieve the desired flow condition in the mould. Therefore, the SEN can be considered as a vital factor for a stable casting process and the steel quality. Furthermore, the steelmaking processes occur at high temperatures around 1873 K so the interaction between the refractory materials of the SEN and molten steel is unavoidable. Therefore, the knowledge of the SEN behaviors during pre-heating and casting is necessary for the design of the steelmaking processes. The internal surfaces of modern SENs are coated with a glass/silicon powder layer to prevent the SEN graphite oxidation during pre-heating. The effects of the interaction between the coating layer and the SEN base refractory materials on clogging were studied in supplement 1. The results of the study indicated the penetration of the formed alkaline-rich glaze into the Alumina/graphite base refractory during pre-heating. More specifically, the alkaline-rich glaze reacts with graphite to form carbon monoxide gas. Thereafter, dissociation of CO at the SEN/molten metal interface takes place. This leads to reoxidation of dissolved REM (Rare Earth Metal), which form the “In Situ” REM oxides at the interface between the SEN and the REM alloyed molten steel. Also, the interaction of the penetrated glaze with alumina in the SEN base refractory materials leads to a formation of a high-viscous alumina-rich glaze during the SEN pre-heating process. This in turn, creates a very uneven surface at the SEN internal surface. The “In Situ” formation of the REM oxides together with the uneven internal surface of the SEN may facilitate the accumulation of the primary inclusions. Supplement 1 revealed the disadvantages of the glass/silicon powder layer. On the other hand the carbon oxidation is a main industrial problem for un-coated Alumina/Graphite Submerged Entry Nozzles (SEN) during pre-heating. This led to the proposal of a new refractory material for the SEN. In supplement 2, the effect of ZrSi2 antioxidant and the coexistence of antioxidant additive and (4B2O3 ·BaO) glass powder on carbon oxidation were investigated at simulated non-isothermal heating conditions in a  controlled atmosphere. Also, the effect of ZrSi2 antioxidant on carbon oxidation was investigated at isothermal temperatures at 1473 K and 1773 K. The specimens’ weight losses and temperatures were plotted versus time and compared to each others. The thickness of the oxide areas were measured and also examined using XRD, FEG-SEM and EDS. The coexistence of 8 wt% ZrSi2 and 15 wt% (4B2O3 ·BaO) glass powder of the total alumina/Graphite base refractory materials, presented the most effective resistance to carbon oxidation. The 121% volume expansion due to the Zircon formation during heating and filling up the open pores by (4B2O3 ·BaO) glaze during green body sintering led to an excellent carbon oxidation resistance. In supplement 3, decarburization behaviors of Al2O3-C, ZrO2-C and MgO-C refractory materials constituting a commercial Submerged Entry Nozzle (SEN), have been investigated in different gas atmosphere consisting of CO2, O2 and Ar. The (CO2/O2) ratio values were kept the same as it is in propane combustion flue gas at Air Fuel Ratio (AFR) values equal to 1.5 and 1 for both Air-fuel and Oxygen-fuel combustions. Laboratory experiments were carried out non-isothermally in the temperature range 873 K to 1473 K at 15 K/min followed by isothermal heating at 1473 K for 60 min. The decarburization ratio (α) values of the three refractory types were determined by measuring the weight losses of the samples. The results showed that the decarburization ratio (α) values of the MgO-C refractory became 3.1 times higher for oxygen-fuel combustion compared to air-fuel combustion both at AFR equal to 1.5 in the temperature range 873 K to 1473 K. The decarburization ratio (α) values for Al2O3-C samples were the same as for the isothermal heating at 1473 K and non-isothermal heating in the temperature range 473  to 1773 K with a 15 K/min heating rate. It substantiates the SEN preheating advantage at higher temperatures for shorter holding times instead of heating at lower temperatures for longer holding times. Jander’s diffusion model was proposed for estimating the decarburization rate of Al2O3-C refractory in the SEN. The activation energy for Al2O3-C samples heated at AFR equal to 1.5, for air-fuel and oxygen-fuel combustions were found to be 84.5 KJ/mol and 95.5 KJ/mol respectively during non-isothermal heating in the temperature range 873 K to 1473 K. / QC 20101008
77

Investigation of the Magnetic- and Electron Transport Properties of Fe/MgO Superlattices

Rostom, Ali, Holmgren, David January 2022 (has links)
Anti-ferromagnetic interlayer exchange coupling between iron layers in Fe/MgO superlatices have recently been of interest among researchers for its potential application in 3D memory storage in computers (hard drives) and in the research field of spintronics. Thinfilms and bi-layers between the 10-100 ångström range in thicknesses were analyzed for its resistive properties during different conditions. Both mono-layers and superlatices were experimented with.The resistivity of the films was measured with both the four-probe method and the Van der Pauw method. Because of mechanical limitations with respect to the direction of the external magnetic field, the Van der Pauw method had to be used for the superlattice measurements. The collected data from all the measurments of the superlattice suggest that the electric current is not only passing the capping layer of the lattice but did not however show any sign of resisitive properties changing with changing magnetic profile. The resistivity of thesuperlattice was similar to that of the resistivity calculated from data when the external magnetic field was off. The results from this study show for the first time that it is possible to measure the electronic transport within an Fe/MgO superlattice which provides a basis for futher investigations.
78

Polyethylene/metal oxide nanocomposites for electrical insulation in future HVDC-cables : probing properties from nano to macro

Pallon, Love January 2016 (has links)
Nanocomposites of polyethylene and metal oxide nanoparticles have shown to be a feasible approachto the next generation of insulation in high voltage direct current cables. In order to reach an operationvoltage of 1 MV new insulation materials with reduced conductivity and increased breakdown strengthas compared to modern low-density polyethylene (LDPE) is needed.In this work polyethylene MgO nanocomposites for electrical insulation has been produced andcharacterized both from an electrical and material perspective. The MgO nanoparticles weresynthesized into polycrystalline nanoparticles with a large specific surface area (167 m2 g–1). Meltprocessing by extrusion resulted in evenly dispersed MgO nanoparticles in LDPE for the silane surfacemodified MgO as compared to the unmodified MgO. All systems showed a reduction in conductivityby up to two orders of magnitude at low loading levels (1–3 wt.%), but where the surface modifiedsystems were able to retain reduced conductivity even at loading levels of 9 wt.%. A maximuminteraction radius to influence the conductivity of the MgO nanoparticles was theoretically determinedto ca. 800 nm. The interaction radius was in turn experimentally observed around Al2O3 nanoparticlesembedded in LDPE using Intermodulation electrostatic force microscopy. By applying a voltage on theAFM-tip charge injection and extraction around the Al2O3 nanoparticles was observed, visualizing theexistence of additional localized energy states on, and around, the nanoparticles. Ptychography wasused to reveal nanometre features in 3D of electrical trees formed under DC-conditions. Thevisualization showed that the electrical tree grows by pre-step voids in front of the propagatingchannels, facilitating further growth, much in analogy to mechanical crack propagation (Griffithconcept). An electromechanical effect was attributed as possible mechanism for the formation of the voids. / Nanokompositer av polyeten och metalloxidpartiklar anses vara möjliga material att använda i morgondagens isolationshölje till högspänningskablar för likström. För att nå en transmissionsspänning på 1 MV behövs isolationsmaterial som i jämförelse med dagens polyeten har lägre elektrisk ledningsförmåga, högre styrka mot elektriskt genomslag och som kan kontrollera ansamling av rymdladdningar. De senaste årens forskning har visat att kompositer av polyeten med nanopartiklar av metalloxider har potential att nå dessa egenskaper. I det här arbetet har kompositer av polyeten och nanopartiklar av MgO för elektrisk isolation producerats och karaktäriserats. Nanopartiklar av MgO har framställts från en vattenbaserad utfällning med efterföljande calcinering, vilket resulterade i polykristallina partiklar med en mycket stor specifik ytarea (167m2 g-1). MgO-nanopartiklarna ytmodifierades i n-heptan genom att kovalent binda oktyl(trietoxi)silan och oktadekyl(trimetoxi)silan till partiklarna för att skapa en hydrofob och skyddande yta. Extrudering av de ytmodifierade MgO nanopartiklarna tillsammans med polyeten resulterade i en utmärkt dispergering med jämnt fördelad partiklar i hela kompositen, vilket ska jämföras med de omodifierade partiklarna som till stor utsträckning bildade agglomerat i polymeren. Alla kompositer med låg fyllnadsgrad (1–3 vikt% MgO) visade upp till 100 gånger lägre elektrisk konduktivitet jämfört med värdet för ofylld polyeten. Vid högre koncentrationer av omodifierade MgO förbättrades inte de isolerande egenskaperna på grund av för stor andel agglomerat, medan kompositerna med de ytmodifierade fyllmedlen som var väl dispergerade behöll en kraftig reducerad elektrisk konduktivitet upp till 9 vikt% fyllnadshalt. Den minsta interaktionsradien för MgO-nanopartiklarna för att minska den elektriska konduktiviten i kompositerna fastställdes med bildanalys och simuleringar till ca 800 nm. Den teoretiskt beräknade interaktionsradien kompletterades med observation av en experimentell interaktionsradie genom att mäta laddningsfördelningen över en Al2O3-nanopartikle i en polyetenfilm med intermodulation (frekvens-mixning) elektrostatisk kraftmikroskop (ImEFM), vilket är en ny AFM-metod för att mäta ytpotentialer. Genom att lägga på en spänning på AFM-kantilevern kunde det visualiseras hur laddningar, både injicerades och extraherades, från nanopartiklarna men inte från polyeten. Det tolkades som att extra energinivåer skapades på och runt nanopartiklarna som fungerar för att fånga in laddningar, ekvivalent med den gängse tolkningen att nanopartiklar introducera extra elektronfällor i den polymera matrisen i nanokompositer. Nanotomografi användes för att avbilda elektriska träd i tre dimensioner. Avbildningen av det elektriska trädet visade att tillväxten av trädet hade skett genom bildning av håligheter framför den framväxande trädstrukturen. Håligheterna leder till försvagning av materialet framför det propagerande trädet och förenklar på det sättet fortsatt tillväxt. Bildningen av håligheter framför trädstrukturen uppvisar en analogi till propagering av sprickor vid mekanisk belastning, i enlighet med Griffiths koncept. / <p>QC 20161006</p>
79

Novel solid base catalysts for Michael additions

Li, Zhijian 05 September 2005 (has links)
Im Gegensatz zu „festen Säuren“ sind „feste Basen“ wesentlich seltener Untersuchungsgegenstand in ihrer Anwendung als Katalysatoren in der heterogenen Katalyse. In der vorliegenden Promotionsarbeit wurden entgegen diesem Trend die Herstellung, Charakterisierung und Anwendung basischer Oxide sowie modifizierter Oxide in ihrer Eignung als feste Basen in der Katalyse untersucht. Zu diesen Katalysatoren gehören MgO, hergestellt nach unterschiedlichen Methoden, Kalium modifiziertes ZrO2, calcinierte Mg-Al Hydrotalcite und ein neuartiges Katalysatorsystem auf der Basis von Mg(O,F)-Kompositionen, die zum ersten Mal nach einem Sol-Gel-Fluorierungsverfahren hergestellt wurden. Die Katalysatoren wurden mittels N2 Adsorptions/Desorptionsuntersuchungen (BET), XRD, FTIR, XPS, TG-DTA-DTG und MAS NMR untersucht. Die Säure-Basen-Eigenschaften der Katalysatoren wurden durch TPD, FTIR Spektroskopie und Mikrokalorimetrie charakterisiert und mit den katalytischen Eigenschaften korreliert. Calcinierte Mg-Al Hydrotalcite und Mg(O,F) waren in diesem Zusammenhang am stärksten aktiv und auch selektiv wie für die Flüssigphasenreaktion der Michael-Addition von CH aciden Verbindungen mit Methylvinylketon gezeigt wurde. / In contrast to solid acid catalysts, much fewer efforts have been made to study solid base catalysts. In this thesis, preparation, characterization and application of oxides and modified oxide as solid base catalysts were studied. The catalysts include MgO prepared by different methods, potassium-modified ZrO2, calcined Mg-Al hydrotalcites, and a novel catalyst system Mg(O,F), which was prepared by sol-gel method for the first time. The catalysts were studied by N2 adsorption/desorption measurement, XRD, FTIR, XPS, TG-DTA-DTG and NMR. Acid-base properties of the catalysts were investigated by TPD, FTIR spectroscopy and microcalorimetry to correlate with the catalytic behavior. Calcined Mg-Al hydrotalcite and Mg(O,F) are found to be highly active and selective catalysts for liquid-phase Michael additions of CH-acid compounds with methyl vinyl ketone.
80

Summenfrequenzerzeugungsspektroskopie an Metallen,Oxiden und oxidgeträgerten Metallpartikeln

Aumer, Andreas 28 June 2010 (has links)
Die vorliegende Arbeit widmet sich der Untersuchung von 4 Modellsystemen der Oberflächenforschung. Die verwendeten experimentellen Methoden sind Summenfrequenzerzeugungsspekroskopie (SFG), Thermische Desorptionsspektroskopie (TDS), Beugung niederenergetischer Elektronen (LEED), Augerelektronenspektroskopie (AES), Infrarotadsorptionsspektrokopie (IRAS) und Rastertunnelmikroskopie (STM). Durch die Verwendung von SFG waren Messungen bis zu 50 mbar möglich. Die untersuchten Systeme sind: CO auf Pt(111), Wasser auf Ag(001) und MgO/Ag(001), CO auf Au/MgO/Ag(001) und CO auf Au-Pd/MgO/Ag(001). Bei den Messungen von CO auf Pt(111) tritt unter bestimmten Druck- und Temperaturbedingungen eine bisher nicht näher untersuchte Doppelpeakstruktur auf, die genauer charakterisiert wurde. Die Untersuchungen von Wasser auf MgO/Ag(001) und Ag(001) zeigen, dass sich auf MgO/Ag(001) zuerst eine Monolage Wasser mit einer darauffolgenden Multilage ausbildet, wohingegen es auf Ag(001) von Beginn an in einer Multilagenschicht wächst. Die Monolage kann unter der Multilage gemessen werden und einige Resonanzen identifiziert werden. Für Au/MgO/Ag(001) zeigte sich mittels STM eine Abhängigkeit des Au-Wachstums von der Schichtdicke, die allerdings nicht spektroskopisch in Erscheinung tritt. Bei den Messungen an gemischten Au-Pd-Teilchen auf MgO/Ag(001) zeigen sich Unterschiede im Adsorptionsverhalten zwischen reinen Metallteilchen und gemischten Teilchen, die auf eine Wechselwirkung zwischen den beiden Metallen zurückzuführen ist. Nach Heizschritten auf 600 K reichern sich die Au-Atome im Mantel des Teilchens an, das Pd bildet den Kern. Die Ergebnisse aller Messungen werden unter Berücksichtigung neuer Veröffentlichungen diskutiert. / This thesis focuses on 4 different model systems of surface science. The experimental techniques used for the measurements include sum frequency generation (SFG), thermal desorption spectroscopy (TDS), low energy electron diffraction (LEED), Auger electron spectroscopy (AES), infrared adsorption spectrosocopy (IRAS) and scanning tunneling microscopy (STM). By using SFG, measurements could be performed up to a pressure of 50 mbar. The systems under investigation were: CO on Pt(111), water on Ag(001) and on MgO/Ag(001), CO on Au/MgO/Ag(001), and CO on Au-Pd/MgO/Ag(001). The system of CO on Pt(111) exhibits a two peak-pattern under certain pressure and temperature conditions which has not been studied so far. Various experiments helped to elucidate the origin of this distinct behaviour. The measurements of water on Ag(001) and MgO/Ag(001) show that on MgO, water first adsorbs as a monolayer with a following multilayer, whereas on Ag(001) it adsorbs as a multilayer from the beginning. The monolayer can be studied below the multilayer and some resonances can be identified. For the case of Au/MgO/Ag(001), STM shows that the growth mode of Au depends on the thickness of the supporting MgO film, which can not be seen with spectroscopic methods. For mixed Au-Pd particles on MgO/Ag(001) a clear difference in the adsorption behaviour between pure metal particles and mixed particles can be seen, which is explained by an interaction between these metals. Annealing the mixed particles to 600 K leads to a segregation of the metals, where the Au atoms diffuse to the shell and the Pd atoms make up the core. The results of all these measurements are discussed in the light of recent publications.

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