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The detection of trace amounts of H and D present in Zr-2.5%Nb in the form of ZrH and ZrD, respectively, by LIBS was explored. The intended use case for this experimentation was CANada Deuterium Uranium (CANDU) nuclear reactor pressure tube inspections where hydride buildup can lessen the mechanical strength of these components. As these tubes carry coolant and house the fuel bundles, their integrity is paramount. A LIBS inspection method is of interest in the nuclear industry due to the operational flexibility it would introduce and its ability to reduce the cost, time, and radiation dose associated with inspection campaigns of pressure tubes in CANDU nuclear reactors. Using LIBS, simultaneous detection of H and D was achieved in a low-pressure air environment using a microjoule, picosecond pulsed laser and emission being captured by a high-resolution spectrometer. The emission lines of the two species were blended, however, two peaks can be seen. Experiments using a milijoule, nanosecond pulsed laser in a LIBS setup were also conducted at atmospheric pressures. These experiments failed to show D emission, however. In addition to detecting emission from H and D, a Monte Carlo algorithm was developed for estimating the error associated with a LIBS inspection of a pressure tube segment. ZrH and ZrD form heterogeneous structures in the bulk of the Zr-2.5%Nb pressure tube material, meaning that a single measurement would not be indicative of the entire tube. Using metallographs of artificially hydrided pressure tube samples, the error within a given confidence interval was found as a function of number of measurement sites and ablation diameter. Furthermore, the impacts to Zr-2.5%Nb based on intense laser-matter interactions was investigated by optical microscopy and interferometry, allowing for 3-dimensional reconstructions of ablation craters. The morphology of millijoule, nanosecond pulsed laser-matter interaction and microjoule, picosecond pulsed laser-matter interaction were the subjects of this investigation. The salient difference between the two interactions is the evidence of substantial melting and subsequent re-deposition of material in the case of nanosecond interactions, whereas picosecond ablation yielded little melting. These results support the further development of a LIBS-based inspection method for determining the concentration of H and D in Zr-2.5%Nb. It was found that a vacuum environment allows for the simultaneous detection of H and D emission. Further experimentation should explore using low-pressure buffer gas environments as a method to further distinguish emission between the two species. / Thesis / Master of Applied Science (MASc)

Land-use practices have long been associated with alterations in stream ecosystem structure and function, however, 'exurbanization' and its impact on streams is poorly understood. This study compares the ecosystem structure and function of 9 southern Appalachian streams of differing land-use (forested, exurban, agricultural). Impacts of land-use on leaf breakdown are examined in Chapter 1. Leaf breakdown rates were significantly related to land-use. Forested streams exhibited the slowest breakdown rates, followed by exurban streams, with agricultural streams having the fastest rates. Leaf breakdown was most strongly related to discharge (white oak) and some fine sediment metrics (red maple). Our results suggest that the altered hydrological regimes in agricultural streams, as well as the influx of fine sediments into streams from exurban development, can play a role in altering in-stream organic matter processing. The taxa and number of shredders present may play a role to a lesser extent. Impacts of land-use on macroinvertebrate assemblages are examined in Chapter 2. Shannon diversity, %EPT, and NCBI were significantly related to land-use regime. There were significant negative relationships between macroinvertebrate diversity and conductivity and temperature. In addition, biotic integrity had a significant negative relationship with conductivity. Canonical Correspondence Analysis (CCA) showed that agricultural streams were characterized by temperature and flow, forested streams by MPS and standing stock course particulate organic matter (SSCPOM), and two of three exurban streams by conductivity and temperature. Principal Coordinates Analysis (PCoA) revealed that while macroinvertebrate communities overlapped, some differences in community assemblage could be seen between land-use types. / Master of Science

An experimental evaluation of the breakdown characteristics of the nonuniform electric fields established between two spheres and between two points in a crossflow was conducted and the results were then compared to the breakdown characteristics in quiescent air. The aluminum spheres used in this investigation ranged in diameter from 0.635 em to 2.54 em. The points had a radius of curvature of 0.5 mm. The velocities of the crossflow ranged from 23 mls to 58 mls and the gap distances ranged from 0.5 cm to 2.0 cm. Photography was used to determine the effect of the crossflow on the luminous spark for all electrodes. The sparking voltages in the crossflow were a function of the crossflow velocity, electrode size and gap distance. It was concluded that the most significant increase of sparking voltages in a crossflow, as compared to the same configuration in quiescent air, was for the point-point gap at a distance of 2.0 cm for a 58 mls crossflow. As the electrodes were increased in size, the effect of a given crossflow decreased. For the 2.54 cm spheres with a 58 mls crossflow, there was actually a decrease in the sparking voltage as compared to its counterpart in quiescent air. The photographs showed a significant deflection of the spark in the direction of the crossflow for the point-point gap, but no significant deflection was detected for the other electrode geometries. / Master of Science

Oxide dielectric breakdown is an old problem that has been studied over decades. It causes power dissipations and irreversible damage to the electronic devices. The aggressive downscaling of the device size exponentially increases the leakage current density, which also raises the risk of dielectric breakdown. It has been proposed that point defects, current leakages, impurity diffusions, etc. all contribute to the change of oxide chemical composition and ultimately lead to the dielectric breakdown. However, the conclusive cause and a clear understanding of the entire process of dielectric breakdown are still under debate. In this research, the electronic structure at metal/oxide interfaces is studied using first-principle calculations within the framework of Density Functional Theory (DFT) to investigate any possible key signature that would trigger the dielectric breakdown. A classical band alignment method, the Van de Walle method, is applied to the case study of the Al/crystal-SiO2 (Al/c-SiO2) interface. Point defects, such as oxygen vacancy (VO) and hydrogen impurity (IH), are introduced into the Al/c-SiO2 interface to study the effects on band offset and electronic structure caused by point defects at metal/oxide interfaces. It is shown that the bonding chemistry at metal/oxide interfaces, which is mainly ionic bond, polarizes the interface. It results in many interface effects such as the interface dipole, built-in voltage, band bending, etc. Charge density analysis also indicates that the interface can localize charge due to such ionic bonding. It is also found that VO at the interface traps metal electrons which closes the open -sp3 orbital. The analysis on local potential shows that the metal potential penetrates through a few layers of oxide starting from the interface, which metalizes the interfacial region and induces unoccupied states in the oxide band gap. In addition, it is shown that higher oxygen content at metal/oxide interfaces minimizes such metal potential invasion. In addition, an oxygen vacancy is created at multiple sites through the Al/c-SiO2 and Al/a-SiO2 interface systems, separately. The oxygen local pressure is also calculated before its removal using Quantum Stress Density theory. Correlations among electronic structure, stress density, and vacancy formation energy are found, which provide informative insights into the defect generation controlling and dielectric breakdown analysis. A new band alignment approach based on the projection of plane-waves (PWs) into the space-dependent atomic orbital (LCAO) basis is presented and tested against classical band offset methods -- the Van de Walle method. It is found that the new band alignment approach can provide a quantitative and reliable band alignment and can be applied to the heterojunctions consisting of amorphous materials. The new band alignment approach reveals the real-space dependency of the electronic structure at interfaces. In addition, it includes all interface effects, such as the interface dipole, built-in voltage, virtual oxide thinning, and band deformation, which cannot be derived using classical band offset methods. This new band alignment approach is applied to the case study of both the Al/amorphous-SiO2 (Al/a-SiO2) interface and the Al/c-SiO2. We have found that at extremely low dimensions, the reduction of the insulator character due to the virtual oxide thinning is a pure quantum effect. I highlight that the quantum tunneling current leakage is more critical than the decrease of the potential barrier height on the failure of the devices. / PHD

The structure and function of stream ecosystems may be strongly influenced by land-use practices within watersheds. The magnitude of land-use impacts may depend upon the spatial arrangement of development in watersheds. This study examines the relationship between land-cover patterns and stream structure and function in 9 southern Appalachian headwater basins. Using a GIS/remote sensing approach, land-cover patterns were quantified at several spatial scales, including the entire watershed, riparian corridor, and riparian sub-corridors extending upstream in 200 m increments for 2 km. In-stream physico-chemical variables were related to land-cover patterns at different spatial scales. Dissolved constituents (e.g., TIN, alkalinity) were frequently related to physical features or land-cover patterns at the watershed scale. Conversely, mean substrate particle size and stream temperature were most strongly related to land-use practices at the entire riparian corridor scale. Finally, maximum stream temperature was best explained from land-cover patterns at the 200 m sub-corridor scale. The relationship between land-cover patterns and benthic macroinvertebrate communities is examined in Chapter 1. Macroinvertebrate assemblage structure was quantified using the slope of rank-abundance plots, and further described using standard diversity and evenness indices. Macroinvertebrate taxa richness ranged from 24 to 54 among sites, and the analysis of rank-abundance curves defined three distinct groups with high, medium, and low diversity. In general, other macroinvertebrate indices were in accord with rank-abundance groups, with richness and evenness decreasing among sites with maximum stream temperature. Macroinvertebrate indices were most strongly related to land cover patterns evaluated at the 200 m sub-corridor scale, suggesting local, streamside development effectively alters assemblage structure. The relationship between land-cover patterns and leaf breakdown is examined in Chapter 2. Breakdown rate for American sycamore (Plantanus occidentalis) leaf packs varied significantly among sites (k = 0.0051 to 0.0180 d-1), but fell within the range reported in the literature for sycamore. Leaf breakdown rate increased among sites with shredder density and biomass. Further, breakdown rate and shredder density and biomass were positively related to mean substrate particle size. Though several instream variables were related to watershed-scale features, leaf breakdown rate was not related to land cover at the watershed scale. Leaf breakdown rate was inversely related to % non-forest within riparian sub-corridors of approximately 1 km. Results suggest that the distribution of shredders is critical to leaf processing in these streams. In some streams, increased sediment inputs as a result of agricultural activity or residential development in riparian corridors may limit the distribution of shredders and thus influence leaf breakdown rates. Alternatively, near stream development may reduce the quantity and/or quality of allochthonous inputs to streams, and thus indirectly influence the distribution of shredders. / Master of Science

Eastern hemlock (Tsuga canadensis) is a prominent tree in the forests of eastern North America, where it commonly grows along headwater streams. It is experiencing widespread mortality due to infestations of an introduced insect, the hemlock woolly adelgid (Adelges tsugae). Eliminations of tree species are known to have ecosystem-level effects, and one consequence of hemlock death is a change in allochthonous inputs to headwater streams. I predicted that hemlock twigs' dendritic structure, abundance, and resistance to decay currently make them highly effective retainers of leaves in headwater streams, with consequences for nutrient uptake. To understand the role of hemlock twigs in streams and to compare their functions to those of a potential replacement species, I (1) quantified the decomposition and microbial colonization of twigs and (2) manipulated twig standing crops to quantify effects on leaf retention and nutrient uptake. Hemlock twigs provide a poor-quality substrate for microbial colonization and growth relative to birch (Betula lenta) twigs and are more resistant to breakdown than birch. Although hemlock twigs appear to be effective in retaining leaves, they do not substantially affect reach-scale uptake of ammonium, which is much more strongly influenced by the timing of leaf inputs. Although hemlock death may subtly change patterns of organic matter accumulation and breakdown, the potentially important effects of hemlock death include changes in large wood inputs, changes in hydrologic regime, and increases in rhododendron cover. / Master of Science

This dissertation summarizes the research performed towards the development, analysis, and testing of two new sample configurations used for characterizing dielectric materials over a wide band of frequencies. In the two configurations, a cylindrical cavity completely filled with a sample of the dielectric material of interest is used. The two configurations are the following: 1. The cylindrical cavity is adapted to the end of a transmission line and the reflection coefficient is measured. The complex permittivity of the dielectric sample is then derived from the measured reflection coefficient information. 2. The cylindrical cavity is placed between two transmission lines. The complex permittivity of the dielectric material can be computed from either the measured reflection coefficient or the measured transmission coefficient. The full field analysis of these configurations is carried out and the solution is obtained using the method of moments. Computer simulation experiments are performed to test the sensitivity of these techniques and predict their performance. Actual experiments on some dielectric materials with known dielectric properties are performed for verification. The first configuration is also used to characterize two thick film dielectric materials. These configurations proved to provide solutions to the many problems with the conventional configurations found in the literature. / Ph. D.

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