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Modelling the Effects of Element Doping and Temperature Cycling on the Fracture Toughness of β-NiAl / α-Al2O3 Interfaces in Gas Turbine EnginesTyler, Samson January 2013 (has links)
This document describes work performed related to the determination of how elemental additions
affect the interfacial fracture toughness of thermal barrier coatings at the bond coat/thermally grown oxide interface in gas turbines. These turbines are exposed to cyclical thermal loading, therefore a simulation was designed to model this interface in a temperature cycle between 200 K and 1000 K that included oxide growth between 2 μm and 27 μm. The fracture toughness of this interface was then determined to elucidate the function of elemental additions. It was shown that minimal concentrations of atomic species, such as hafnium and yttrium cause notable increases in the toughness of the bond coat/thermally grown oxide interface, while other species, such as sulphur, can dramatically reduce the toughness. Furthermore, it was shown that, contrary to some empirical results, the addition of platinum has a negligible effect on the fracture toughness of this interface.
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Transestérification des acrylates par catalyse basique hétérogène / Transesterification of acrylates by heterogeneous basic catalysisMaldonado Barrios, Adriana 05 July 2013 (has links)
Dans ce travail, nous présentons une étude originale de l'utilisation des catalyseurs basiques solides dans la réaction de transestérification des acrylates. La réaction de l'acrylate d'éthyle avec le n-hexanol a été choisie comme réaction modèle. Les catalyseurs employés, à base d'alumines modifiées par des ions alcalins, alcalino-terreux ou fluorures, se sont avérés être actifs et sélectifs dans la réaction de transestérification, réalisée en conditions douces, sans solvant, en utilisant un rapport stoéchiométrique des réactifs. Les réactions secondaires ont été identifiées comme étant des réactions d'addition de Michael. Nous avons mis en évidence que la réaction de transestérification se produit sur des sites basiques faibles, le catalyseur Ca(NO3)2/ γ-Al2O3 ayant montré la sélectivité la plus élevée en acrylate d'hexyle (> 90%) pour une conversion supérieure à 60%. L'étude du recyclage du catalyseur nous a permis de déterminer les facteurs les plus influents tels que le contact du catalyseur avec le CO2 et l'eau ainsi que la teneur en fer de l'alumine employée comme support. Ces facteurs sont déterminants pour le recyclage du catalyseur, qui peut alors être recyclé jusqu'à 4 fois dans la réaction de transesterification de l'acrylate d'éthyle par le n-hexanol sans observer de changements significatifs de la conversion et de la sélectivité / We present an original study of the use of solid basic catalysts in the transesterification reaction of acrylates. The reaction of ethyl acrylate with n-hexanol was chosen as model reaction. The catalysts employed, based on alumina modified with alkalin, alkalin earth, and fluoride ions were shown to be active and selective for the reaction of transesterification reaction carried out under mild conditions, without solvent, using a stoechiometric amount of reactants . The secondary reactions were identified as Michael addition reactions. We demonstrated that the transesterification reaction occurs on weak basic sites, the catalyst Ca (NO3)2 /γ-Al2O3 has shown the highest selectivity in the hexyl acrylate (> 90%) for conversion greater than 60%. The study of the catalyst recycling allowed to determine the most influential factors such as the catalysts contact between CO2 and water as well as the iron content of the alumina support. These factors are critical to the success of the catalyst recycling, which was done four times in the reaction of transesterification of ethyl acrylate with n-hexanol without observing significant changes in the conversion and selectivity
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Aqueous Fabrication of Pristine and Oxide Coated ZnSe NanoparticlesVan Zandt, Nicholas L. 11 June 2021 (has links)
No description available.
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Žárovzdorné ostřivo se zvýšeným obsahem mullitu / Mullite Refractory GrogZemánek, David January 2019 (has links)
Refractory aggregate manufactured from common clays, claystones and shales in Czech Republic are mostly classified as fireclay. For specific applications are these grogs not suitable and there is a need to use grogs with higher content of alumina oxide. Theoretical part of this thesis is focused on the mineral mullite, which is one of the basic minerals in Al2O3 - SiO2 system. Research is focused on methods of mullite production, manufacture of recfractory grog and new possibilities in modification of current raw materials. In experimental part is carried out a verification of possible production of grogs with increased alumina content according to the designed composition.
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Šamotové ostřivo se zvýšeným obsahem oxidu hlinitého / Fireclay Grog with a High Alumina ContentMezulianík, Tomáš January 2020 (has links)
Special refractory grog with increased alumina content are not currently produced in the Czech Republic. The price of these grogs produced abroad is high, so there is an effort to produce grogs using domestic waste fractions of claystones, which have been stored for decades. The theoretical part of the thesis describes the current results and experience with the processing of fine waste parts of claystone W super and BVP. Suitable raw materials for the preparation of grog with an increased content of alumina are characterized. In the experimental part of the thesis is verified the possibility of production of grogs with increased content of Al2O3 according to the proposed prescriptions.
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A cementitious binder from high-alumina slag generated in the steelmaking processAdesanya, E. D. (Elijah D.) 03 December 2019 (has links)
Abstract
About 4 Mt of ladle slag is generated in steelmaking processes in Europe per year, a large proportion of which (80%) is placed in landfills or stored. This pattern is expected to continue without further research for their valorisation due to increasing demand for quality steel products worldwide. Ladle slag (LS) produced in Finland possesses large amounts of calcium and aluminium and mineralogical phases which can exhibit cementitious capabilities and can be utilized in applications where expensive commercial cements are currently being used. The aim of this thesis is to investigate the properties of ladle slag in different activation pathways, including alkali activation and use as a hydraulic binder with gypsum.
The results showed that ladle slag can be used alone as a precursor in alkali activation or as the sole binder or a co-binder with gypsum in hydraulic binding. Depending on the activation pathway, compressive strength between 35–92 MPa can be achieved after 28 days. The reaction properties of alkali activated ladle slag are characterized, and it is confirmed through X-ray diffraction (XRD) that the reaction product after alkali activation is mainly an x-ray amorphous (calcium aluminate silicate hydrate-like) phase. Characterization techniques (SEM, XRD, TGA and NMR) used to analyze the LS paste binder with just water showed the hydration products of ladle slag to be dicalcium aluminate octahydrate (C₂AH₈), tricalcium aluminate hexahydrate (C₃AH₆), gibbsite (AH₃) and stratlingite (C₂ASH₈) was also identified after a prolonged period of hydration. Furthermore, it was found that to minimize the conversion, the ideal water-to-binder ratio is 0.35. The conversion mechanism is reduced at this ratio and the strength is slightly affected. Another pathway that can be used to annul the conversion of calcium aluminate hydrates formed in LS paste is through the addition of gypsum to the LS paste system to produce an ettringite-rich binder (C₆A\(\bar{S}\)₃H₃₂). When ettringite is formed in place of calcium aluminate hydrates the strength increases, frost resistance is improved, and drying shrinkage is enhanced.
Lastly, a potential application of ladle slag as a refractory material was also investigated. / Tiivistelmä
Euroopassa syntyy vuosittain noin 4 Mt terästeollisuden sivutuotetta, JV-kuonaa, josta 80 % läjitetään tai kaatopaikoitetaan. Maailmanlaajuisesti syntyvän kuonan määrä tulee todennäköisesti kasvamaan laadukkaiden terästuotteiden ennustetun kysynnän kanssa. Tämän vuoksi kuonalle tulisi löytää hyötökäyttökohde, jota vältyttäisiin läjitykseltä. JV-kuona sisältääkin suuria määriä kalsiumia ja alumiinia sekä mineralogisia faaseja, joilla on sementtimäisiä ominaisuuksia. Näin kuonaa voitaisiin käyttää sovelluksissa, joissa tällä hetkellä käytetään kalliita kaupallisia sementtejä. Tämän väitöskirjan tarkoituksena oli tutkia JV-kuonan ominaisuuksia sementtimäisenä sideaineena alkali-aktivoinnissa sekä hydraulisena sideaineena yksinään että kipsin kanssa sekoitettuna.
Väitöskirjan tulokset osoittivat, että JV-kuonaa voidaan käyttää prekursorina alkali-aktivoinnissa tai hydraulisena sideaineena pelkästään veden kanssa tai yhdessä kipsin ja veden kanssa. Saavutetut puristuslujuuset vaihtelivat 35 ja 92 MPa:n välillä, jotka vastaavat normaalin ja erityislujan betonin lujuuksia. JV-kuonan reaktiotuotteet alkali-aktivonnin jälkeen analysoitiin XRD- ja FTIR-analyyseillä. Tuloksista nähtiin, että alkali-aktivoinnin jälkeen reaktiotuote on sementin kaltainen kalsium-aluminatti-silikaati-hydraati (C-A-S-H) -tyyppinen faasi. XRD-, SEM-, TGA- ja NMR-analyysit osoittivat JV-kuonan hydrataatiotuotteiden olevan erilaisia kalsium-aluminaattihydraatteja (C₂AH₈, C₃AH₆, AH₃ ja C₂ASH₈). Tämän vuoksi työssä tutkittiin eri vesi–kuona-suhteita, ja havaittiin, että kun käytetään alhaista kuona-vesi –suhdetta (0,35), reaktiotuoteiden muutos vähenee ja lujuus paranee. Toinen tapa, jolla voidaan estää reaktiotuotteiden muuttuminen, on kipsin lisäys: lisäämällä kipsiä tuotetaan runsaasti ettringiittiä (C₆A\(\bar{S}\)₃H₃₂). Kun ettringiittiä muodostuu kalsium-aluminaattihydraattien sijaan, lujuus kasvaa, pakkaskestävyys paranee ja kuivumiskutistuma paranee.
Väitöskirjan viimeisessä osiossa tutkittiin JV-kuonan mahdollista käyttöä tulenkestävänä materiaalina ja huomattiin, että sen tulenkestävyysominaisuudet vaihtelevat käytetyn aktivointityypin mukaan.
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Molecular filtration : the study of adsorbentsTwumasi, Ebenezer January 2011 (has links)
Adsorbent materials for gas purification have been studied and developed for application in many areas. It is known that a single adsorbent may not adequately control multiple contaminants. Therefore, the development of adsorbent materials has accelerated over the past two decades, and is today an area attracting a lot of attention. In view of the global environmental movement for clean air, the development of improved sorbents will help address new challenges that cannot efficiently be met with the generic sorbents that are presently commercially available. On the other hand, the utilization of these new sorbents for specific applications within the area of molecular filtration remains largely unexplored. This thesis presents a synthesis of new sorbent materials, and the characterization and application of these materials for molecular filtration. Commercial adsorbents have been used for benchmarking for the pore properties, the applicability, and the performance of these new adsorbents. A double metal-silica adsorbent has been synthesized. The preparation procedure is based on the use of sodium silicate coagulated with various ratios of magnesium and calcium salts which yields micro-meso porous structures in the resulting material. The results show that molar ratios of Mg/Ca influence the pore parameters as well as the structure and morphology. The bimodal pore size can be tailored by controlling the Mg/Ca ratio. The effect of thermal treatment on pore parameters of these adsorbents has been investigated. The results show that heat treatment had a notable effect on the pore parameters, and that the pore structure was thermally stable even at 600°C. A synthesis method has also been developed for the preparation of carbon-silica composites. The method involves a number of routes, which can be summarised as addition of activated carbon particles to (I) the paste, (II) the salt solution, or (III) with the sodium silicate solution. In route II and III the activated carbon is present also before coagulation. The routes presented here leads to carbon-silica composites possessing high micro porosity, meso porosity as well as large surface areas. The increase in micro porosity and surface areas was linear with carbon content. The results shows further that pore size distribution may be tailored based on the route of addition of the carbon particles. Following route I and III a wide pore size (1-30nm) was obtained where as by route II a narrow pore size (1-4nm) was observed. KOH or KMnO4 modified MgCa adsorbent varieties were also prepared. The impregnationwas performed by either a direct synthesis or post-synthesis procedure. Potassium hydroxide and potassium permanganate have been chosen as impregnate chemicals. Results revealed that theimpregnate amount significantly affected both the structural and the gas adsorption characteristics of the impregnated MgCa adsorbents. The properties of double- metal adsorbents, impregnated adsorbents and carbon-silica composites were characterized by various methods (X-ray diffraction, scanning electron microscopy, thermo gravimetric analysis, and nitrogen adsorption at 77K) to study the material structure and morphology, thermal stability, ignition temperature and porous parameters with regard to surface area, pore size, pore size distribution and porosity volume, which is important for optimizing their use in many practical application. The up-take performance of adsorbents for dynamic adsorption of SO2, H2S and toluene was performed in a system similar to the setup usedin ASHRAE 145.1. Finally the applicability and performance of the impregnated modified MgCa-silica adsorbents and composites have been evaluated for H2S, SO2 and toluene adsorption and compared to some commercial adsorbent materials. Results revealed that a potassium permanganate modified MgCa-adsorbent has a H2S adsorption capacity in the range of 0.08-3.19 wt % at 50% efficiency, and that the uptake capacity was relative to the amount of potassiumpermanganate loading. Moreover, KOH modified MgCa-adsorbent shows highest SO2 adsorption capacity (1.7 wt %) which is 3.47 times higher than commercial alumina impregnate with potassium permanganate (0.49 wt %). Carbon-silica composites on the other hand shows adsorption of toluene and high adsorption capacity was obtained when carbon content was 45 wt %. The results further shows that a composite with 45 wt % carbon and obtained via route I present the highest toluene adsorption capacity ( 27.6 wt % relative to carbon content) at 0% efficiency. The large uptake capacity of this composite was attributed to the presence of high microporosity volume and a wide (1-30nm) bimodal pore system consisting of extensive mesopore channels (2-30nm) as well as large surface area. These capacity values of carbon-silica composites are competitive to results obtained for commercial coconut based carbon (31 wt %), and better than commercial alumina-carbon composite. / QC 20110405
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Ionic transport of α-alumina below 1000°C : an in-situ impedance spectrosocpy studyÖijerholm, Johan January 2004 (has links)
Ionic conductivity of metal oxides is critical for the function of a broad range of different components, such as electrolytes in solid oxide fuel cells and alloys designed for high temperature applications. In both cases the ionic conductivity can be studied by in situ impedance spectroscopy, which is also able to reveal information on the dielectric properties of the metal oxides, and in some cases the influence of their microstructure. The focus of this thesis is on impedance spectroscopy measurements of α-alumina in the temperature range 400-1000 °C. This metal oxide has found extensive use as the protective scale on heat resistant alloys. Some unpublished work on oxygen ion conductivity of yttria-stabilized zirconia is also included. The low electrical conductivity of α-alumina can be a source for errors and misinterpretations during impedance spectroscopy measurements. A major disturbance originates from leakage currents that appear in the experimental setup. These leakage currents are due to conduction through the gas phase around the sample, conduction on the sample surface, or poor insulation in the sample holder. It was shown that below 700 °C, conduction on the sample surface could severely distort the measurement. The magnitude of the distortions appeared to be sensitive to the type of electrodes used. The use of a so-called guard electrode was shown to effectively block the surface conduction in the measurements. Conductivity of metal oxides is known to be dependent on their microstructure. Generally it is believed that ionic conductivity is favoured along grain boundaries and dislocations. The influence of microstructure on conductivity was studied for α-alumina in the temperature range 400-1000 °C. The conductivity of a series of highly pure and dense samples with narrow grain size distributions was measured by impedance spectroscopy. It appeared that the activation energy for conduction increased with decreasing grain size. Results based purely on impendence spectroscopy have some inherently weaknesses. For instance no information on the nature of the charge carrier can be found. Therefore the charge transport in single crystalline α-alumina was simulated by the molecular dynamics method. The results from the simulation were then compared to results from impedance measurements on single crystalline α-alumina. From the simulation it turned out that diffusion of aluminium ions had lower activation energy than diffusion of oxygen. The activation energy of oxygen was close to the measured activation energy, and the mobility of oxygen was higher than for aluminium. Therefore the dominating charge carrier was suggested to be oxygen ions.
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Thin Film Deposition on Powder Substrates using ALD and its Characterization using XPS, TEM, and SEShah, Dhruv 28 April 2020 (has links)
The major part of my dissertation consists of thin films deposited using atomic layer deposition on flat and powder substrates. It details the various optimization experiments for process parameters like dose time, purge time, temperature, and pressure on silicon shards and powder substrates. Spectroscopic ellipsometry (SE) was used to characterize these films over a wide wavelength range (191-1688 nm). An optical model with a BEMA (Bruggeman effective medium approximation) layer was used to fit the ellipsometric data to investigate the optical properties of the alumina surface. The optimized process parameters on the flat surfaces were used for coating powder substrates. I propose a set of experiments to optimize the conditions for coating of powders and high aspect ratio structures by atomic layer deposition (ALD). The coated powders were analyzed by surface analytical techniques like X-ray photoelectron spectroscopy, spectroscopic ellipsometry, transmission electron microscopy, energy X-ray dispersive spectroscopy (EDAX), and BET. The first chapter introduces the technique of atomic layer deposition, and details its advantages and limitations over conventional thin film deposition techniques like chemical vapor deposition and physical vapor deposition. The second chapter details the initial deposition experiments performed on flat surfaces and characterization of thin films using surface analytical tools. I conducted multi-sample analysis on eleven different thin films for calculation of optical constants of alumina. The third chapter introduces thin film deposition experiments performed on powder substrates, several challenges associated with achieving conformal thin films and characterization. The fourth chapter details the experiments to achieve unilateral ALD achieved on one side of the substrates. The fifth chapter details various unconventional materials including liquid water, Coca-Cola, a coffee bean, nitrogen gas, human tooth, and printed office paper, which were analyzed by near ambient pressure XPS (NAP-XPS). This dissertation contains appendices of other tutorial articles I wrote on obtaining optical constants liquid samples using spectroscopic ellipsometry, and good experimental techniques for maintenance of vacuum equipment.
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Thin Film Deposition on Powder Substrates using ALD and its Characterization using XPS, TEM, and SEShah, Dhruv 28 April 2020 (has links)
The major part of my dissertation consists of thin films deposited using atomic layer deposition on flat and powder substrates. It details the various optimization experiments for process parameters like dose time, purge time, temperature, and pressure on silicon shards and powder substrates. Spectroscopic ellipsometry (SE) was used to characterize these films over a wide wavelength range (191-1688 nm). An optical model with a BEMA (Bruggeman effective medium approximation) layer was used to fit the ellipsometric data to investigate the optical properties of the alumina surface. The optimized process parameters on the flat surfaces were used for coating powder substrates. I propose a set of experiments to optimize the conditions for coating of powders and high aspect ratio structures by atomic layer deposition (ALD). The coated powders were analyzed by surface analytical techniques like X-ray photoelectron spectroscopy, spectroscopic ellipsometry, transmission electron microscopy, energy X-ray dispersive spectroscopy (EDAX), and BET. The first chapter introduces the technique of atomic layer deposition, and details its advantages and limitations over conventional thin film deposition techniques like chemical vapor deposition and physical vapor deposition. The second chapter details the initial deposition experiments performed on flat surfaces and characterization of thin films using surface analytical tools. I conducted multi-sample analysis on eleven different thin films for calculation of optical constants of alumina. The third chapter introduces thin film deposition experiments performed on powder substrates, several challenges associated with achieving conformal thin films and characterization. The fourth chapter details the experiments to achieve unilateral ALD achieved on one side of the substrates. The fifth chapter details various unconventional materials including liquid water, Coca-Cola, a coffee bean, nitrogen gas, human tooth, and printed office paper, which were analyzed by near ambient pressure XPS (NAP-XPS). This dissertation contains appendices of other tutorial articles I wrote on obtaining optical constants liquid samples using spectroscopic ellipsometry, and good experimental techniques for maintenance of vacuum equipment.
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