Dissertation (Ph.D.)--Auburn University, 2006. / Abstract. Vita. Includes bibliographic references.

The sintering behavior to form TiC-Ni-Mo cermet using a nano-size TiC powders was investigated in flowing Argon gas at 1500°C. Nano-sized titanium carbide powders with high purity, high surface area, and low cost were synthesized from carbon coated Ti containing precursors utilizing a patented process. The sintering studies showed that an increase in theoretical density (TD) with increasing molybdenum content. TiC based cermets were characterized using X-ray diffraction (XRD), Vickers hardness, and scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS). Mechanical properties, electrical conductivity and oxidation resistance results shows potential applications as interconnect for Low/Intermediate Temperature Solid Oxide Fuel Cells (SOFC) and machining tool tips.

Wide cracks in land-based Ni- or Co-base superalloy turbine components are difficult to repair successfully using conventional welding or brazing techniques. This project examined the feasibility of liquid phase diffusion brazing using novel Ni- and Co-base braze alloys containing Hf or Zr as melt point depressant for the repair of wide cracks in turbine components. An optimized braze cycle was developed and the joints were evaluated using various metallographic techniques and mechanical tests (elevated temperature tensile tests, creep rupture tests and low cycle fatigue tests). Microstructural examination revealed the presence of Hf- or Zr-rich intermetallic phases (most likely Ni7Hf2 or Ni5Zr) in Ni-base braze joints. These intermetallic compounds were, however, observed to be significantly softer than the boride phases routinely found in commercially available braze alloys with boron as melt point depressant. As a result, the novel wide gap brazed joints displayed excellent mechanical properties (ranging from 80% to 100% of the base metal’s properties). The low cycle fatigue properties of wide gap braze joints performed using a combination of MarM247 superalloy powder and Ni-Cr-Hf or Ni-Cr-Zr braze filler metals were found to be superior to those of the widely used Ni-Cr-B braze filler metals. Wide gap braze repair of FSX-414 Co-base superalloy using novel MarM509/MarM509B and MarM509/Co-Hf braze alloys resulted in high temperature tensile properties equivalent to those of weld repairs in the same parent material (using Nozzalloy filler metal). The creep rupture and low cycle fatigue (LCF) properties of the braze joints were superior to those of welds performed using MarM918 filler metal. / Thesis (PhD)--University of Pretoria, 2008. / Materials Science and Metallurgical Engineering / unrestricted

Using photochemical and emulsion pro­cedures, a study has been made of the liquid-phase oxida­tion of p-cymene with respect to the nature of the result­ing hydroperoxides and their decomposition products, and the relative extent of oxidative attack at the methyl and iso­propyl groups. Hydroperoxide decomposition was negligible in the photochemical oxidations at 60C, and the product was shown to consist of 20% primary and 80% tertiary hydroper­oxide by reduction of the total product and fractionation of the resulting alcohols. The following compounds were shown to be present in the emulsion oxidation product in addition to the above mentioned hydroperoxides: dimethyl-p-tolylcarbinol, p-methylacetophenone, p-isopropylphenylcarbinol, cumic acid, p-acetobenzoic acid, p-A-hydroperoxyisopropyl, benzoic acid, and p-(I-hydroxyisopropyl) benzoic acid. By chromatographic separation of the acids and reduction of the other products, the relative extent of attack at the two positions was shown to be 1:4, identical with that of the photochemical oxidation. Pure tertiary hydroperoxide has been obtained for the first time. / Thesis / Master of Science (MS)

<p> A diffusion cell of the "shearing type" was used to diminish the effect of convection which is always present when two liquid phases are brought into contact with each other in a diffusion cell. Also a special optical arrangement was used to photograph the refractive index distribution of the system. For those systems with refractive index changing linearly with concentration, the concentration profiles were obtained and diffusion coefficients were calculated at different concentrations. </p> <p> This optical method gave only fair reproducibility- the deviation among diffusivities found for systems investigated varying from 3 to 10%- however, it permitted rapid analysis and on this basis is recommended for situations where speed is essential and high accuracy is not required. </p> / Thesis / Master of Engineering (ME)

No description available.

Yes / Diffusion brazing has gained much popularity as a technique capable of joining dissimilar lightweight metal alloys and has the potential for a wide range of applications in aerospace and transportation industries, where microstructural changes that will determine the mechanical and chemical properties of the final joint must be controlled. This study explores the effect of Al2O3 nanoparticles on the mechanical and microstructural properties of diffusion brazed magnesium (AZ31) and aluminium (Al-1100) joints. The results showed that the addition of Al2O3 nanoparticle to the electrodeposited Cu coating increased the volume of eutectic liquid formed at the interface which caused a change to the bonding mechanism and accelerated the bonding process. When the Cu/Al2O3 nanocomposite coatings were used as the interlayer, a maximum bond strength of 46 MPa was achieved after 2 min bonding time while samples bonded using pure-Cu interlayers achieved maximum strength after 10 min bonding time. Chemical analysis of the bond region confirmed that when short bonding times are used, the intermetallic compounds formed at the interface are limited to the compounds consumed in the eutectic reaction.

L'objectif de ce travail était de comprendre les mécanismes menant à la formation de SiC-3C sur substrats de SiC hexagonaux lors de la croissance par mécanisme Vapeur-Liquide-Solide (VLS) à partir d'une phase liquide Si-Ge. Notre étude s'est concentrée sur les premiers instants de l'interaction liquide/SiC, c'est-a-dire sans ajout de phase gazeuse réactive (propane). Nous avons montré qu'il se formait très rapidement des îlots de SiC-3C à la surface des germes. L'étude en fonction de divers paramètres (température et durée de plateau, vitesse de chauffage, nature du germe) a permis de mettre en évidence l'influence prononcée du creuset en graphite dans lequel est confinée la réaction. Les observations expérimentales associées à des calculs thermodynamiques ont permis de montrer que l'étape prépondérante, pour la formation du 3C, est sans doute la réaction transitoire entre un liquide très riche en germanium et le germe de SiC. Des considérations d'ordre cinétiques sont cependant à prendre en compte pour expliquer le caractère hors équilibre de la réaction / The aim of this work was to understand the mechanisms that lead to the 3C-SiC formation on hexagonal SiC substrates during the Vapor-Liquid-Solid (VLS) growth from a Si-Ge liquid phase. Our study focused on the early stages of the liquid/SiC interaction, i.e. without reactive gaseous phase (propane) addition. We have shown that 3C-SiC islands were very rapidly formed upon seeds surface. The study of several parameters (such as temperature and duration of the plateau, heating rate, nature of the seed) evidenced the huge influence of the graphite crucible that contains the reaction. Experimental observations combined with thermodynamic calculations show that the most important step for the 3C formation, is the transient reaction between a germanium very rich liquid and the SiC seed. Kinetic effects have to be taken into account to explain the out-of-equilibrium nature of the reaction.

No description available.

Atualmente, a malária é considerada a principal infecção parasitária existente e apresenta distribuição mundial. Dentre as alternativas terapêuticas utilizadas, destacam-se cloroquina (CQ), mefloquina (MQ) e, recentemente, arteméter (ART). Segundo a literatura, estudos farmacocinéticos destes fármacos têm sido dificultados pela ausência de métodos adequados de análise em fluidos biológicos e, no caso dos fármacos quirais (CQ e MQ), com capacidade de determinar os enantiômeros individualmente. Com isso, o objetivo deste trabalho foi avaliar o emprego da microextração em fase líquida (LPME) na preparação de amostras para a determinação destes três fármacos antimaláricos e respectivos metabólitos em plasma. O método para análise enantiosseletiva de CQ e metabólitos teve a LPME como técnica de preparação de amostras, a qual apresentou valores de recuperação no intervalo de 28-66%. Estes analitos foram separados na coluna Chirobiotic V em fase polar-orgânica, com posterior detecção por espectrometria de massas (MS), com interface de eletronebulização (ESI) no modo positivo. O método desenvolvido foi linear no intervalo de 5-500 ng mL-1 para todos os analitos avaliados. A disposição cinética de CQ e do principal metabólito monodesetilcloroquina (DCQ) em ratos sugere enantiosseletividade após administração do fármaco na forma racêmica, com maiores concentrações de (+)-(S)-CQ e (-)-(R)-DCQ. O método para análise dos enantiômeros de MQ e do metabólito aquiral carboximefloquina (CMQ) também foi desenvolvido empregando LPME na preparação das amostras. A extração destes analitos foi realizada em duas etapas para eficaz recuperação dos mesmos (valores entre 35-38%). Os analitos foram separados na coluna Chirobiotic T em fase polarorgânica, com detecção por absorção no ultravioleta em 285 nm. O método apresentou linearidade no intervalo de 50-1500 e 50-3000 ng mL-1 para os enantiômeros de MQ e CMQ, respectivamente. A disposição cinética de MQ em ratos indica enantiosseletividade com maiores concentrações de (+)-(RS)- MQ após administração do fármaco na forma racêmica. A separação cromatográfica em fase reversa de ART e metabólito diidroartemisinina (DHA) foi alcançada utilizando-se coluna contendo Si-Zr-PMTDS como fase estacionária e a detecção destes analitos foi realizada empregando-se MS no modo ESI positivo. O procedimento otimizado de LPME em duas fases para extração de ART e DHA em plasma resultou em valores de recuperação de 32 e 25%, respectivamente. O método desenvolvido foi linear no intervalo de 5- 1000 ng mL-1 para ambos os analitos. O estudo piloto de disposição cinética em ratos evidenciou maiores concentrações de DHA. Os resultados obtidos confirmam a viabilidade da LPME para extração destes antimaláricos e respectivos metabólitos em plasma. / Currently, malaria is the main parasitic infection and shows worldwide distribution. Among therapeutic options used, chloroquine (CQ), mefloquine (MQ) and, more recently, artemether (ART) have been standing out. According to the literature, pharmacokinetic studies of these drugs have been hampered by the lack of proper methods of analysis in biological fluids and, regarding the chiral drugs (CQ and MQ), with the ability to determine the individual enantiomers. Therefore, the aim of this work was to evaluate the utilization of liquid-phase microextraction as the sample preparation technique for the determination of these antimalarial drugs and their metabolites in plasma. The enantioselective analysis of CQ and its metabolites was carried out using LPME as technique of sample preparation, which yielded recovery rates within 28- 66%. These analytes were resolved on a Chirobiotic V column in the polarorganic mode and further detected using mass spectrometry (MS) with electrospray interface (ESI) in the positive mode. The developed method was linear in the range of 5-500 ng mL-1 for all analytes studied. The kinetic disposition of CQ and its main metabolite monodesethylchloroquine (DCQ) in rats suggests enantioselectivity following the administration of the racemic drug, with higher concentrations of (+)-(S)-CQ and (-)-(R)-DCQ. The method for the analysis of the enantiomers of MQ and its achiral metabolite carboxymefloquine (CMQ) also had LPME as technique of sample preparation. The extraction of these analytes was carried out in two-steps to obtain efficient recovery rates (values within 35-38%). The analytes were resolved on a Chirobiotic T column in polar-organic mode and ultraviolet detection was performed at 285 nm. The method was linear in the range of 50-1500 and 50-3000 ng mL-1 for the enantiomers of MQ and CMQ, respectively. The kinetic disposition of MQ in rats indicates enantioselectivity with higher concentrations of (+)-(RS)-MQ following the administration of the racemic drug. The chromatographic resolution of ART and its metabolite dihydroartemisinin (DHA) in the reversed mode was achieved utilizing a column containing Si-Zr-PMTDS as stationary phase and their detection was conducted employing MS in the positive ESI mode. The optimized two-phase LPME procedure for the extraction of ART and DHA from plasma showed recovery values of 32 and 25%, respectively. The developed method was linear over the range of 5-1000 ng mL-1 for both analytes. The pilot study of kinetic disposition in rats showed higher concentrations of DHA. The obtained results confirm the feasibility of LPME for the extraction of these antimalarial drugs and their metabolites from plasma.