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Solute segregation to ceramic grain boundaries governs material processing and microstructure evolution, and can strongly influence material properties critical to engineering performance. Understanding the evolution and implications of grain boundary chemistry is a vital component in the greater effort to engineer ceramics with controlled microstructures. This study examines solute segregation to engineered grain boundaries in titanium-doped sapphire (Al2O3) bicrystals, and explores relationships between grain boundary structure and chemistry at the nanometer scale using spectroscopic and imaging techniques in the transmission electron microscope (TEM). Results demonstrate dramatic changes in solute segregation stemming from small fluctuations in grain boundary plane and structure. Titanium and silicon solute species exhibit strong tendencies to segregate to non-basal and basal grain boundary planes, respectively. Evidence suggests that grain boundary faceting occurs in low-angle twis t boundaries to accommodate nonequilibrium solute segregation related to slow specimen cooling rates, while faceting of tilt grain boundaries often occurs to expose special planes of the coincidence site lattice (CSL). Moreover, quantitative analysis of grain boundary chemistry indicates preferential segregation of charged defects to grain boundary dislocations. These results offer direct proof that static dislocations in ionic materials can assume a net charge, and emphasize the importance of interactions between charged …

this research has shown that it is possible to deposit coatings of gas atomized Cu{sub 47}Ti{sub 33}Zr{sub 11}Ni{sub 8}Si{sub 1} powders containing various levels of oxygen contamination using plasma arc spray methods. The structure of the coating was found to depend primarily on the spray environment, with an argon atmosphere producing the most amorphous samples for a given starting powder. The oxygen content of the coatings reflected the relative levels of the oxygen contamination in the starting powders. The analysis of the starting powders displayed oxygen contents ranging from 0.125-0.79 wt.%. It was shown that higher oxygen levels lead to more crystalline structure in the starting powders as determined by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). This trend was found to be true for both the starting powders and for the plasma sprayed coatings. Chemical composition for all starting powders was very close to the nominal alloy composition. Chemical changes in the coatings involved the loss of Cu in coatings where high levels of oxidation were found. Cavitation erosion testing of selected coatings showed a weak trend that coatings prepared by vacuum plasma spray (VPS) had lower damage rates, but there was no clear data to indicate which …

Alkali metal aluminohydrides have high potential as solid hydrogen storage materials. They have been known for their irreversible dehydrogenation process below 100 atm until Bogdanovic et al [1, 2] succeeded in the re-hydrogenation of NaAlH{sub 4} below 70 atm. They achieved 4 wt.% H{sub 2} reversible capacity by doping NaAlH{sub 4} with Ti and/or Fe organo-metalic compounds as catalysts. This suggests that other alkali and, possibly alkaline earth metal aluminohydrides can be used for reversible hydrogen storage when modified by proper dopants. In this research, Zr{sub 27}Ti{sub 9}Ni{sub 38}V{sub 5}Mn{sub 16}Cr{sub 5}, LaNi{sub 4.85}Sn{sub 0.15}, Al{sub 3}Ti, and PdCl{sub 2} were combined with LiAlH{sub 4} by ball-milling to study whether or not LiAlH{sub 4} is capable to both absorb and desorb hydrogen near ambient conditions. X-ray powder diffraction, differential thermal analysis, and scanning electron microscopy were employed for sample characterizations. All four compounds worked as catalysts in the dehydrogenation reactions of both LiAlH{sub 4} and Li{sub 3}AlH{sub 6} by inducing the decomposition at lower temperature. However, none of them was applicable as catalyst in the reverse hydrogenation reaction at low to moderate hydrogen pressure.

Fe{sub 2}VAl has recently been discovered to have a negative temperature coefficient of resistivity, moderately enhanced specific heat coefficient, and a large DOS at the Fermi level by photoemission. This triggered a round of heated research to understand the ground state of this material, both theoretically and experimentally. here they report a comprehensive characterization of Fe{sub 2}VAl. X-ray diffraction exhibited appreciable antisite disorder in all of our samples. FTIR spectroscopy measurements showed that the carrier density and scattering time had little sample-to-sample variation or temperature dependence for near-stoichiometric samples. FTIR and DC resistivity suggest that the transport properties of Fe{sub 2}VAl are influenced by both localized and delocalized carriers, with the former primarily responsible for the negative temperature coefficient of resistivity. Magnetization measurements reveal that near-stoichiometric samples have superparamagnetic clusters with at least two sizes of moments. X-ray photoemission from Fe core level showed localized magnetic moments on site-exchanged Fe. They conclude that in Fe{sub 2}VAl, antisite disorder causes significant modification to the semi-metallic band structure proposed by LDA calculations. With antisite disorder considered, they are now able to explain most of the physical properties of Fe{sub 2}VAl.

Current theories have been successful in explaining many nonlinear optical experiments in undoped semiconductors. However, these theories require a ground state which is assumed to be uncorrelated. Strongly correlated systems of current interest, such as a two dimensional electron gas in a high magnetic field, cannot be explained in this manner because the correlations in the ground state and the low energy collective excitations cause a breakdown of the conventional techniques. We perform ultrafast time-resolved four-wave mixing on $n$-modulation doped quantum wells, which contain a quasi-two dimensional electron gas, in a large magnetic field, when only a single Landau level is excited and also when two levels are excited together. We find evidence for memory effects and as strong coupling between the Landau levels induced by the electron gas. We compare our results with simulations based on a new microscopic approach capable of treating the collective effects and correlations of the doped electrons, and find a good qualitative agreement. By looking at the individual contributions to the model, we determine that the unusual correlation effects seen in the experiments are caused by the scattering of photo-excited electron-hole pairs with the electron gas, leading to new excited states which are not …

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Hydrogenated amorphous silicon germanium films (a-SiGe:H) and devices have been extensively studied because of the tunable band gap for matching the solar spectrum and mature the fabrication techniques. a-SiGe:H thin film solar cells have great potential for commercial manufacture because of very low cost and adaptability to large-scale manufacturing. Although it has been demonstrated that a-SiGe:H thin films and devices with good quality can be produced successfully, some issues regarding growth chemistry have remained yet unexplored, such as the hydrogen and inert-gas dilution, bombardment effect, and chemical annealing, to name a few. The alloying of the SiGe introduces above an order-of-magnitude higher defect density, which degrades the performance of the a-SiGe:H thin film solar cells. This degradation becomes worse when high growth-rate deposition is required. Preferential attachment of hydrogen to silicon, clustering of Ge and Si, and columnar structure and buried dihydride radicals make the film intolerably bad. The work presented here uses the Electron-Cyclotron-Resonance Plasma-Enhanced Chemical Vapor Deposition (ECR-PECVD) technique to fabricate a-SiGe:H films and devices with high growth rates. Helium gas, together with a small amount of H{sub 2}, was used as the plasma species. Thickness, optical band gap, conductivity, Urbach energy, mobility-lifetime product, I-V curve, and quantum …

Motor vehicles are a significant source of population exposure to air pollution. Focusing on California's South Coast Air Basin as a case study, the author combines ambient monitoring station data with hourly time-activity patterns to determine the population intake of motor vehicle emissions during 1996-1999. Three microenvironments are considered wherein the exposure to motor vehicle emissions is higher than in ambient air: in and near vehicles, inside a building that is near a freeway, and inside a residence with an attached garage. Total motor vehicle emissions are taken from the EMFAC model. The 15 million people in the South Coast inhale 0.0048% of primary, nonreactive compounds emitted into the basin by motor vehicles. Intake of motor vehicle emissions is 46% higher than the average ambient concentration times the average breathing rate, because of microenvironments and because of temporal and spatial correlation among breathing rates, concentrations, and population densities. Intake fraction (iF) summarizes the emissions-to-intake relationship as the ratio of population intake to total emissions. iF is a population level exposure metric that incorporates spatial, temporal, and interindividual variability in exposures. iFs can facilitate the calculation of population exposures by distilling complex emissions-transport-receptor relationships. The author demonstrates this point by predicting …

The goal of this thesis is to determine under what conditions, if any, measurements of aerosol properties made at the Earth's surface are representative of aerosol properties within the column of air above the surface. This thesis will use data from the Atmospheric Radiation Measurement (ARM) site at the Southern Great Plains (SGP) which is the only location in the world where ground-based and in situ airborne measurements are made on a routine basis. All flight legs in the one-year period from March 2000-March 2001 were categorized as either within or above the atmospheric boundary layer using an objective mixing height determination technique. The correlations between the aerosol properties measured at the surface and the measured within and above the ABL were then computed. The conclusion of this comparison is that the aerosol extensive and intensive properties measured at the surface are representative of values within the ABL, but not within the free atmosphere.

This thesis determines what, if any, measurements of aerosol properties made at the Earth surface are representative of those within the entire air column. Data from the Atmospheric Radiation Measurement site at the Southern Great Plains, the only location in the world where ground-based and in situ airborne measurements are routinely made. Flight legs during the one-year period from March 2000 were categorized as either within or above the atmospheric boundary layer (ABL) by use of an objective mixing height determination technique. Correlations between aerosol properties measured at the surface and those within and above the ABL were computed. Aerosol extensive and intensive properties measured at the surface were found representative of values within the ABL, but not of within the free atmosphere.

A laboratory investigation was undertaken to determine the effect of microbe generated gas bubbles in controlled, saturated sediment columns utilizing a novel technique involving acoustic wave propagation. Specifically, the effect of denitrifying bacteria on saturated flow conditions was evaluated in light of the stimulated production of N{sub 2} gas and the resulting plugging of the pore throats. The propagation of high frequency acoustic waves through the sediment columns was used to locate those regions in the column where gas accumulation occurred. Over a period of six weeks, regions of gas accumulation resulted in the attenuation of acoustic wave energies with the decreases in amplitude typically greater than one order of magnitude.

This research presents a study of the hardness, electrical, and thermal properties AlMgB{sub 14} containing Al{sub 2}MgO{sub 4} spinel. This research also investigated how much Al{sub 2}MgO{sub 4} spinel consistently forms with AlMgB{sub 14}, if AlMgB{sub 14} materials can be produced by hot isostatic pressing (HIP), what effects TiC and TiB{sub 2} have on this composite material, and the importance of mechanical alloying. Included also is a study of the variation in hardness measurements and how they relate to SI units. Heretofore, all ultra-hard materials (hardness > 40 GPA) have been found to be cubic in structure, electrical insulators, and expensive; the behavior of AlMgB{sub 14}, which in certain specimens and compositions can have hardness values greater than 40 GPa, is therefore quite unusual since it is non-cubic, conductive, and moderate in cost. This offers an opportunity to investigate the relationship between hardness, thermal, and electrical properties from a new perspective. The main purpose of this project was to characterize the different properties of the AlMgB{sub 14} materials and to demonstrate that this material can be made in bulk. The technologies used for this study include microhardness measurement techniques, scanning electron microscopy, energy dispersive spectroscopy, x-ray diffraction spectroscopy, x-ray diffraction …

Current trends toward miniaturization and the use of lead(Pb)-free solder in electronic packaging present new problems in the reliability of solder joints. This study was performed in order to understand the microstructure and microstructural evolution of small volumes of nominally eutectic Au-Sn solder joints (80Au-20Sn by weight), which gives insight into properties and reliability.

The partial oxidation of 1,3-butadiene has been investigated over VMoO catalysts synthesized by sol-gel techniques. Surface areas were 9-14 m{sup 2}/g, and compositions were within the solid solution regime, i.e. below 15.0 mol % MoO{sub 3}/(MoO{sub 3} + V{sub 2}O{sub 5}). Laser Raman Spectroscopy and XRD data indicated that solid solutions were formed, and pre- and post-reaction XPS data indicated that catalyst surfaces contained some V{sup +4} and were further reduced in 1,3-butadiene oxidation. A reaction pathway for 1,3-butadiene partial oxidation to maleic anhydride was shown to involve intermediates such as 3,4-epoxy-1-butene, crotonaldehyde, furan, and 2-butene-1,4-dial. The addition of water to the reaction stream substantially increased catalyst activity and improved selectivity to crotonaldehyde and furan at specific reaction temperatures. At higher water addition concentrations, furan selectivity increased from 12% to over 25%. The catalytic effects of water addition were related to competitive adsorption with various V{sub 2}O{sub 5}-based surface sites, including the vanadyl V=O, corner sharing V-O-V and edge sharing V-O oxygen. Higher levels of water addition were proposed to impose acidic character by dissociative adsorption. In addition, a novel combinatorial synthesis technique for VMoO was used to investigate the phase transitions of V{sub 2}O{sub 5}, solid solutions of Mo …

The study of the reactions between heavy ions and {sup 208}Pb, {sup 209}Bi, {sup 238}U, and {sup 248} Cm targets was performed to look at the differences between the cross sections of hot and cold fusion reactions. Experimental cross sections were compared with predictions from statistical computer codes to evaluate the effectiveness of the computer code in predicting production cross sections. Hot fusion reactions were studied with the MG system, catcher foil techniques and the Berkeley Gas-filled Separator (BGS). 3n- and 4n-exit channel production cross sections were obtained for the {sup 238}U({sup 18}O,xn){sup 256-x}Fm, {sup 238}U({sup 22}Ne,xn){sup 260-x}No, and {sup 248}Cm({sup 15}N,xn){sup 263-x}Lr reactions and are similar to previous experimental results. The experimental cross sections were accurately modeled by the predictions of the HIVAP code using the Reisdorf and Schaedel parameters and are consistent with the existing systematics of 4n exit channel reaction products. Cold fusion reactions were examined using the BGS. The {sup 208}Pb({sup 48}Ca,xn){sup 256-x}No, {sup 208}Pb({sup 50}Ti,xn){sup 258-x}Rf, {sup 208}Pb({sup 51}V,xn){sup 259-x}Db, {sup 209}Bi({sup 50}Ti,xn){sup 259-x}Db, and {sup 209}Bi({sup 51}V,xn){sup 260-x}Sg reactions were studied. The experimental production cross sections are in agreement with the results observed in previous experiments. It was necessary to slightly alter the Reisdorf …

Sample preparation has been one of the major bottlenecks for many high throughput analyses. The purpose of this research was to develop new sample preparation and integration approach for DNA sequencing, PCR based DNA analysis and combinatorial screening of homogeneous catalysis based on multiplexed capillary electrophoresis with laser induced fluorescence or imaging UV absorption detection. The author first introduced a method to integrate the front-end tasks to DNA capillary-array sequencers. protocols for directly sequencing the plasmids from a single bacterial colony in fused-silica capillaries were developed. After the colony was picked, lysis was accomplished in situ in the plastic sample tube using either a thermocycler or heating block. Upon heating, the plasmids were released while chromsomal DNA and membrane proteins were denatured and precipitated to the bottom of the tube. After adding enzyme and Sanger reagents, the resulting solution was aspirated into the reaction capillaries by a syringe pump, and cycle sequencing was initiated. No deleterious effect upon the reaction efficiency, the on-line purification system, or the capillary electrophoresis separation was observed, even though the crude lysate was used as the template. Multiplexed on-line DNA sequencing data from 8 parallel channels allowed base calling up to 620 bp with an …