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Large-eddy simulation of turbulent flow using the finite element method

Description: The equations of motion describing turbulent flows (in both the low and high Reynolds-number regimes) are well established. However, present day computers cannot meet the enormous computational requirement for numerically solving the governing equations for common engineering flows in the high Reynolds number turbulent regime. The characteristics that make turbulent, high Reynolds number flows difficult to simulate is the extreme range of time and space scales of motion. Most current engineering calculations are performed using semi-empirical equations, developed in terms of the flow mean (average) properties. These turbulence{open_quote} models{close_quote} (semi-empirical/analytical approximations) do not explicitly account for the eddy structures and thus, the temporal and spatial flow fluctuations are not resolved. In these averaging approaches, it is necessary to approximate all the turbulent structures using semi-empirical relations, and as a result, the turbulence models must be tailored for specific flow conditions and geometries with parameters obtained (usually) from physical experiments. The motivation for this research is the development of a finite element turbulence modeling approach which will ultimately be used to predict the wind flow around buildings. Accurate turbulence models of building flow are needed to predict the dispersion of airborne pollutants. The building flow turbulence models used today are not capable of predicting the three-dimensional separating and reattaching flows without the manipulation of many empirical parameters. These empirical parameters must be set by experimental data and they may vary unpredictably with building geometry, building orientation, and upstream flow conditions.
Date: February 15, 1995
Creator: McCallen, R. C.
Partner: UNT Libraries Government Documents Department

Historical Exposures to Chemicals at the Rocky Flats Nuclear Weapons Plant: A Pilot Retrospective Exposure Assessment

Description: In a mortality study of white males who had worked at the Rocky Flats Nuclear Weapons Plant between 1952 and 1979, an increased number of deaths from benign and unspecified intracranial neoplasms was found. A case-control study nested within this cohort investigated the hypothesis that an association existed between brain tumor death and exposure to either internally deposited plutonium or external ionizing radiation. There was no statistically significant association found between estimated radiation exposure from internally deposited plutonium and the development of brain tumors. Exposure by job or work area showed no significant difference between the cohort and the control groups. An update of the study found elevated risk estimates for (1) all lymphopoietic neoplasms, and (2) all causes of death in employees with body burdens greater than or equal to two nanocuries of plutonium. There was an excess of brain tumors for the entire cohort. Similar cohort studies conducted on worker populations from other plutonium handling facilities have not yet shown any elevated risks for brain tumors. Historically, the Rocky Flats Nuclear Weapons Plant used large quantities of chemicals in their production operations. The use of solvents, particularly carbon tetrachloride, was unique to Rocky Flats. No investigation of the possible confounding effects of chemical exposures was done in the initial studies. The objectives of the present study are to (1) investigate the history of chemical use at the Rocky Flats facility; (2) locate and analyze chemical monitoring information in order to assess employee exposure to the chemicals that were used in the highest volume; and (3) determine the feasibility of establishing a chemical exposure assessment model that could be used in future epidemiology studies.
Date: February 1, 1999
Creator: Robertson, Janeen Denise
Partner: UNT Libraries Government Documents Department

Development of a high-resolution soft x-ray (30--1500 eV) beamline at the Advanced Light Source and its use for the study of angle-resolved photoemission extended fine structure

Description: ALS Bending magnet beamline 9.3.2 is for high resolution spectroscopy, with circularly polarized light. Fixed included-angle SGM uses three gratings for 30--1500 eV photons; circular polarization is produced by an aperture for selecting the beam above or below the horizontal plane. Photocurrent from upper and lower jaws of entrance slit sets a piezoelectric drive feedback loop on the vertically deflecting mirror for stable beam. End station has a movable platform. With photomeission data from Stanford, structure of c(2{times}2)P/Fe(100) was determined using angle-resolved photoemission extended fine structure (ARPEFS). Multiple-scattering spherical-wave (MSSW) calculations indicate that P atoms adsorb in fourfold hollow sites 1.02A above the first Fe layer. Self-consistent-field X{alpha} scattered wave calculation confirm that the Fe{sub 1}-Fe{sub 2} space is contracted for S/Fe but not for P/Fe; comparison is made to atomic N and O on Fe(100). Final-state effects on ARPEFS curves used literature data from the S 1s and 2p core levels of c(2{times}2)S/Ni(001); a generalized Ramsauer-Townsend splitting is present in the 1s but not 2p data. An approximate method for analyzing ARPEFS data from a non-s initial state using only the higher-{ell} partial wave was tested successfully. ARPEFS data from clean surfaces were collected normal to Ni(111) (3p core levels) and 5{degree} off-normal from Cu(111)(3s, 3p). Fourier transforms (FT) resemble adsorbate systems, showing backscattering signals from atoms up to 4 layers below emitters. 3p FTs show scattering from 6 nearest neighbors in the same crystal layer as the emitters. MSSW calulation indicate that Cu 3p photoemission is mostly d-wave. FTs also indicate double-scattering and single-scattering from laterally distant atoms; calculations indicate that the signal is dominated by photoemission from the first 2 crystal layers.
Date: February 1, 1996
Creator: Huff, W. R. A.
Partner: UNT Libraries Government Documents Department

Surface structures of Al-Pd-Mn and Al-Cu-Fe icosahedral quasicrystals

Description: In this dissertation, the author reports on the surface structure of i-Al-Pd-Mn twofold, threefold, fivefold and i-Al-Cu-Fe fivefold surfaces. The LEED studies indicate the existence of two distinct stages in the regrowth of all four surfaces after Ar{sup +} sputtering. In the first stage, upon annealing at relatively low temperature: 500K--800K (depending on different surfaces), a cubic phase appears. The cubic LEED patterns transform irreversibly to unreconstructed quasicrystalline patterns upon annealing to higher temperatures, indicating that the cubic overlayers are metastable. Based upon the data for three chemically-identical, but symmetrically-inequivalent surfaces, a model is developed for the relation between the cubic overlayers and the quasicrystalline substrate. The model is based upon the related symmetries of cubic close-packed and icosahedral-packed materials. These results may be general among Al-rich, icosahedral materials. STM study of Al-Pd-Mn fivefold surface shows that terrace-step-kink structures start to form on the surface after annealing above 700K. Large, atomic ally-flat terraces were formed after annealing at 900K. Fine structures with fivefold icosahedral symmetry were found on those terraces. Data analysis and comparison of the STM images and structure model of icosahedral Al-Pd-Mn suggest that the fine structures in the STM images may be the pseudo Mackay (PMI) clusters which are the structure units of the structure model. Based upon his results, he can conclude that quasicrystalline structures are the stable structures of quasicrystal surfaces. In other words, quasicrystalline structures extend from the bulk to the surface. As a result of the effort reported in this dissertation, he believes that he has increased his understanding of the surface structure of icosahedral quasicrystals to a new level.
Date: February 12, 1999
Creator: Shen, Z.
Partner: UNT Libraries Government Documents Department

Gas atomization processing of tin and silicon modified LaNi{sub 5} for nickel-metal hydride battery applications

Description: Numerous researchers have studied the relevant material properties of so-called AB{sub 5} alloys for battery applications. These studies involved LaNi{sub 5} substituted alloys which were prepared using conventional cast and crush alloying techniques. While valuable to the understanding of metal hydride effects, the previous work nearly ignored the potential for alternative direct powder production methods, like high pressure gas atomization (HPGA). Thus, there is a need to understand the relationship between gas atomization processes, powder particle solidification phases, and hydrogen absorption properties of ultra fine (< 25 {micro}m) atomized powders with high surface area for enhanced battery performance. Concurrently, development of a gas atomization nozzle that is more efficient than all current designs is needed to increase the yield of ultrafine AB{sub 5} alloy powder for further processing advantage. Gas atomization processing of the AB{sub 5} alloys was demonstrated to be effective in producing ultrafine spherical powders that were resilient to hydrogen cycling for the benefit of improving corrosion resistance in battery application. These ultrafine powders benefited from the rapid solidification process by having refined solute segregation in the microstructure of the gas atomized powders which enabled a rapid anneal treatment of the powders. The author has demonstrated the ability to produce high yields of ultrafine powder efficiently and cost effectively, using the new HPGA-III technology. Thus, the potential benefits of processing AB{sub 5} alloys using the new HPGA technology could reduce manufacturing cost of nickel-metal hydride powder. In the near future, the manufacture of AB{sub 5} alloy powders could become a continuous and rapid production process. The economic benefit of an improved AB{sub 5} production process may thereby encourage the use of nickel-metal hydride rechargeable batteries in electrical vehicle applications in the foreseeable future.
Date: February 12, 1999
Creator: Ting, J.
Partner: UNT Libraries Government Documents Department

The analysis of aqueous mixtures using liquid chromatography-electrospray mass spectrometry

Description: The focus of this dissertation is the use of chromatographic methods coupled with electrospray mass spectrometry (ES-MS) for the determination of both organic and inorganic compounds in aqueous solutions. The combination of liquid chromatography (LC) methods and ES-MS offers one of the foremost methods for determining compounds in complex aqueous solutions. In this work, LC-ES-MS methods are devised using ion exclusion chromatography, reversed phase chromatography, and ion exchange chromatography, as well as capillary electrophoresis (CE). For an aqueous sample, these LC-ES-MS and CE-ES-MS techniques require no sample preparation or analyte derivatization, which makes it possible to observe a wide variety of analytes as they exist in solution. The majority of this work focuses on the use of LC-ES-MS for the determination of unknown products and intermediates formed during electrochemical incineration (ECI), an experimental waste remediation process. This report contains a general introduction to the project and the general conclusions. Four chapters have been removed for separate processing. Titles are: Chapter 2: Determination of small carboxylic acids by ion exclusion chromatography with electrospray mass spectrometry; Chapter 3: Electrochemical incineration of benzoquinone in aqueous media using a quaternary metal oxide electrode in the absence of a soluble supporting electrolyte; Chapter 4: The determination of electrochemical incineration products of 4-chlorophenol by liquid chromatography-electrospray mass spectrometry; and Chapter 5: Determination of small carboxylic acids by capillary electrophoresis with electrospray mass spectrometry.
Date: February 12, 1999
Creator: Johnson, S.
Partner: UNT Libraries Government Documents Department

Calibration of laser ablation inductively coupled plasma mass spectrometry using dried solution aerosols for the quantitative analysis of solid samples

Description: Inductively coupled plasma mass spectrometry (ICP-MS) has become the method of choice for elemental and isotopic analysis. Several factors contribute to its success. Modern instruments are capable of routine analysis at part per trillion levels with relative detection limits in part per quadrillion levels. Sensitivities in these instruments can be as high as 200 million counts per second per part per million with linear dynamic ranges up to eight orders of magnitude. With standards for only a few elements, rapid semiquantitative analysis of over 70 elements in an individual sample can be performed. Less than 20 years after its inception ICP-MS has shown to be applicable to several areas of science. These include geochemistry, the nuclear industry, environmental chemistry, clinical chemistry, the semiconductor industry, and forensic chemistry. In this introduction, the general attributes of ICP-MS will be discussed in terms of instrumentation and sample introduction. The advantages and disadvantages of current systems are presented. A detailed description of one method of sample introduction, laser ablation, is given. The paper also gives conclusions and suggestions for future work. Chapter 2, Quantitative analysis of solids by laser ablation inductively coupled plasma mass spectrometry using dried solution aerosols for calibration, has been removed for separate processing.
Date: February 12, 1999
Creator: Leach, J.
Partner: UNT Libraries Government Documents Department

Chiral separation of pharmaceutical compounds using electrochemically modulated liquid chromatography (EMLC)

Description: This research explores the application of a new technique, termed electrochemically modulated liquid chromatography (EMLC), to the chiral separations of pharmaceutical compounds. The introduction section provides a literature review of the technique and its applications, as well as brief overview of the research described in each of the next two chapters. Chapter 2 investigates the EMLC-based enantiomeric separation of a group of chiral benzodiazepines with {beta}-cyclodextrin as a chiral mobile phase additive. Chapter 3 demonstrates the effects of several experimental parameters on the separation efficiency of drug enantiomers. The author concludes with a general summary and possible directions for future studies. Chapters 2 and 3 are processed separately.
Date: February 12, 1999
Creator: Wang, S.
Partner: UNT Libraries Government Documents Department

Structure sensitive adsorption of hydrogen on ruthenium and ruthenium-silver catalysts supported on silica

Description: Supported metal catalysts typically consist of particles with sizes less than 10 nm, and because of the small crystallite size, low coordination number sites (edges and corners) represent a significant fraction of all surface sites. Furthermore, it has been demonstrated that adsorption rates can be much greater at these low coordination sites than on basal plane sites. What has not been generally appreciated, however, is that preferential adsorption at edge and corner sites may explain the mechanism by which a promoter, or the addition of a second metal to form a bimetallic, can alter the selectivity and rate of reaction. For example, the measurements of hydrogen adsorption onto supported Ru-Ag catalysts show marked decreases in the amount of hydrogen adsorbed relative to the amount adsorbed on Ru catalysts. Although it is known that Ag does not dissociatively adsorb hydrogen, this decrease cannot be explained by a simple one-to-one site blocking mechanism unless Ag preferentially populates edges and corners, thereby reducing the number of Ru edge sites. Indeed, Monte Carlo simulations of Ru-Group IB metal catalysts predict that Group IB metal atoms preferentially populate corner and edge sites of ruthenium crystals. This evidence, taken together, suggests that adsorption occurs preferentially at Ru corner and edge sites, which act as portals onto basal planes. A model based on this portal theory for hydrogen adsorption onto supported ruthenium bimetallic catalysts has been developed using a rate equation approach. Specifically, the model accounts for the following features: (1) preferential adsorption through portals, (2) basal plane site-energy multiplicity, and (3) hydrogen spillover onto the support. A comparison of model predictions with experiment is presented for different concentration of Ag in Ru-Ag catalysts. The portal model of hydrogen adsorption can explain the observed decreased in the amount of hydrogen adsorbed on Ru-Ag catalysts. The model can ...
Date: February 12, 1999
Creator: Kumar, N.
Partner: UNT Libraries Government Documents Department

Collision-induced dissociation reactions and pulsed field ionization photoelectron

Description: This report summarized the four parts of the research study and describes the general conclusions. Individual chapters have been removed for separate processing. The chapter titles are: A study of the dissociation of CH{sub 3}SH{sup +} by collisional activation: Observation of non-statistical behavior; High resolution vacuum ultraviolet pulsed field ionization photoelectron band for OCS{sup +}(X{sup 2}{Pi}): An experimental and theoretical study; Rotationally resolved pulsed field ionization photoelectron bands of H{sub 2}{sup +} ({Chi}{sup 2}{Sigma}{sup +}{sub g}, v{sup +} = 0--18); and Rotationally resolved pulsed field ionization photoelectron bands of HD{sup +} ({Chi}{sup 2}{Sigma}{sup +}, v{sup +} = 0--21).
Date: February 12, 1999
Creator: Stimson, S.
Partner: UNT Libraries Government Documents Department

Solid phase epitaxial regrowth of (100)GaAs

Description: This thesis showed that low temperature (250 C) SPE of stoichiometrically balanced ion implanted GaAs layers can yield good epitaxial recovery for doses near the amorphization threshold. For 250 C anneals, most of the regrowth occurred in the first 10 min. HRTEM revealed much lower stacking fault density in the co-implanted sample than in the As-only and Ga-only samples with comparable doses. After low temp annealing, the nonstoichiometric samples had a large number of residual defects. For higher dose implants, very high temperatures (700 C) were needed to remove residual defects for all samples. The stoichiometrically balanced layer did not regrow better than the Ga-only and As-only samples. The co-implanted sample exhibited a thinner amorphous layer and a room temperature (RT) annealing effect. The amorphous layer regrew about 5 nm, suggesting that stoichiometrically balanced amorphous layers can regrow even at RT. Mechanisms for solid phase crystallization in (100)GasAs is discussed: nucleation and growth of randomly oriented crystallites and SPE. These two mechanisms compete in compound semiconductors at much lower temperatures than in Si. For the low dose As-only and Ga-only samples with low-temp anneals, both mechanisms are active. For this amorphization threshold dose, crystallites remain in the amorphous layer for all as-implants. 250 C annealing showed recrystallization from the surface and bulk for these samples; for the co-implant, the mechanism is not evident.
Date: February 1, 1996
Creator: Almonte, M. I.
Partner: UNT Libraries Government Documents Department

Computational modeling of neoclassical and resistive MHD tearing modes in tokamaks

Description: Numerical studies of the linear and nonlinear evolution of magnetic tearing type modes in three-dimensional toroidal geometry are presented. In addition to traditional resistive MHD effects, where the parameter {Delta}{prime} determines the stability properties, neoclassical effects have been included for the first time in such models. The inclusion of neoclassical physics introduces and additional free-energy source for the nonlinear formation of magnetic islands through the effects of a bootstrap current in Ohm`s law. The neoclassical tearing mode is demonstrated to be destabilized in plasmas which are otherwise {Delta}{prime} stable, albeit once an island width threshold is exceeded. The simulations are based on a set of neoclassical reduced magnetohydrodynamic (MHD) equations in three-dimensional toroidal geometry derived from the two-fluid equations in the limit of small inverse aspect ratio {epsilon} and low plasma pressure {beta} with neoclassical closures for the viscous force {del} {center_dot} {leftrightarrow}{pi}. The poloidal magnetic flux {psi}, the toroidal vorticity {omega}{sup {zeta}}, and the plasma pressure p are time advanced using the parallel projection of Ohm`s law, the toroidal projection of the curl of the momentum equation, and a pressure evolution equation with anisotropic pressure transport parallel to and across magnetic field lines. The equations are implemented in an initial value code which Fourier decomposes equilibrium and perturbation quantities in the poloidal and toroidal directions, and finite differences them radially based on a equilibrium straight magnetic field line representation. An implicit algorithm is used to advance the linear terms; the nonlinear terms are advanced explicitly. The simulations are benchmarked linearly and nonlinearly against single and multiple helicity {Delta}{prime} tearing modes in toroidal geometry in the absence of neo-classical effects.
Date: February 1, 1996
Creator: Gianakon, T.A.
Partner: UNT Libraries Government Documents Department

Optically detected magnetic resonance studies on {pi}-conjugate polymers and novel carbon allotropes

Description: This report describes the following: introduction to photoluminescence detected magnetic resonance (PLDMR); introduction to {pi}-conjugated systems; PLDMR measurements on poly(p-phenylene)-type ladder polymers; PLMDR measurements on poly(p-phenylene ethylene); and PLDMR measurements on C{sub 70}, polythiophene, poly(p-phenylene vinylene) and Dan-40. Appendices to this report describe: Operation of ODMR (optically detected magnetic resonance) spectrometer; ODMR system parameters; and Special purpose circuitry.
Date: February 12, 1999
Creator: Partee, J.
Partner: UNT Libraries Government Documents Department

Neutron scattering studies of the RENi{sub 2}B{sub 2}C (RE = Lu, Y, Ho, Er): Lattice dynamics

Description: The first chapter gives a brief overview of the system discussed in this dissertation. Chapters 2--5 and Appendix B of this dissertation consist of papers that are published, or have been submitted, which show experimental data regarding the phonon softening of LuNi{sub 2}B{sub 2}C. These papers have been removed and processed separately. Chapter 6 will contain a summary of the conclusions up to date. Appendix A will consist of a brief derivation of {chi}(q) which is talked about in the introduction of the dissertation. Appendix B will contain a Born-von Karman model fit to the experimental LuNi{sub 2}B{sub 2}C data and a comparison with experimental data. Appendix C will contain a brief summary of the work done on LuNi{sub 2}B{sub 2}C as well as a complete listing of experimental data taken on the crystals which may be needed later for theoretical models of this system. Appendix D will outline a brief introduction covering some of the field theory used in the theoretical work for this thesis.
Date: February 23, 1998
Creator: Bullock, M.
Partner: UNT Libraries Government Documents Department

Single- and multi-photon ionization studies of organosulfur species

Description: Accurate ionization energies (IE`s) for molecular species are used for prediction of chemical reactivity and are of fundamental importance to chemists. The IE of a gaseous molecule can be determined routinely in a photoionization or a photoelectron experiment. IE determinations made in conventional photoionization and photoelectron studies have uncertainties in the range of 3--100 meV (25--250 cm{sup {minus}1}). In the past decade, the most exciting development in the field of photoionization and photoelectron spectroscopy has been the availability of high resolution, tunable ultraviolet (UV) and vacuum ultraviolet (VUV) laser sources. The laser pulsed field ionization photoelectron (PFI-PE) scheme is currently the state-of-the-art photoelectron spectroscopic technique and is capable of providing photoelectron energy resolution close to the optical resolution. The author has focused attention on the photoionization processes of some sulfur-containing species. The studies of the photoionization and photodissociation on sulfur-containing compounds [such as CS{sub 2}, CH{sub 3}SH, CH{sub 3}SSCH{sub 3}, CH{sub 3}CH{sub 2}SCH{sub 2}CH{sub 3}, HSCH{sub 2}CH{sub 2}SH and C{sub 4}H{sub 4}S (thiophene) and sulfur-containing radicals, such as HS, CS, CH{sub 3}S, CH{sub 3}CH{sub 2}S and CH{sub 3}SS], have been the major subjects in the group because sulfur is an important species contributing to air pollution in the atmosphere. The modeling of the combustion and oxidation of sulfur compounds represents important steps for the control of both the production and the elimination of sulfur-containing pollutants. Chapter 1 is a general introduction of the thesis. Chapters 2 and 6 contain five papers published in, or accepted for publication in, academic periodicals. In Chapter 7, the progress of the construction in the laboratory of a new vacuum ultraviolet laser system equipped with a reflectron mass spectrometer is presented. Chapters 2 through 7 have been removed for separate processing. A general conclusion of these studies are given in Chapter 8 followed by an ...
Date: February 12, 1999
Creator: Cheung, Y.S.
Partner: UNT Libraries Government Documents Department

Syntheses and studies of organosilicon compounds

Description: The syntheses of polycarbosilanes and polysilanes as silicon carbide ceramic precursors have been active research areas in the Barton Research Group. In this thesis, the work is focused on the preparation of polycarbosilanes and polysilanes as stoichiometric silicon carbide precursor polymers. The syntheses of the precursor polymers are discussed and the conversions of these precursors to silicon carbide via pyrolysis are reported. The XRD pattern and elemental analyses of the resulting silicon carbide ceramics are presented. Silicon monoxide is an important intermediate in the production of silicon metal. The existence of silicon monoxide in gap phase has been widely accepted. In the second part of this thesis, the generation of gaseous silicon monoxide in four different reactors and the reactions of gaseous silicon monoxide towards organic compounds are discussed.
Date: February 12, 1999
Creator: Xie, R.
Partner: UNT Libraries Government Documents Department

Decomposition of chlorinated ethylenes and ethanes in an electron beam generated plasma reactor

Description: An electron beam generated plasma reactor (EBGPR) is used to determine the plasma chemistry kinetics, energetics and decomposition pathways of six chlorinated ethylenes and ethanes: 1,1,1-trichloroethane, 1,1-dichloroethane, ethyl chloride, trichloroethylene, 1,1-dichloroethylene, and vinyl chloride. A traditional chemical kinetic and chemical engineering analysis of the data from the EBGPR is performed, and the following hypothesis was verified: The specific energy required for chlorinated VOC decomposition in the electron beam generated plasma reactor is determined by the electron attachment coefficient of the VOC and the susceptibility of the molecule to radical attack. The technology was demonstrated at the Hanford Reservation to remove VOCs from soils.
Date: February 1, 1996
Creator: Vitale, S.A.
Partner: UNT Libraries Government Documents Department

Capillary electrophoretic study of individual exocytotic events in single mast cells

Description: The peak profile of individual degranulation events from the on-column release of serotonin from single rat peritoneal mast cells (RPMCs) was monitored using capillary electrophoresis with laser-induced native fluorescence detection (CE-LINF). Serotonin, an important biogenic amine, is contained in granules (0.25 fL) within RPMCs and is extruded by a process termed exocytosis. The secretagogue, Polymyxin B sulfate, was used as the CE running buffer after injection of a single RPMC into the separation capillary to stimulate the release of the granules. Because the release process occurs on a ms time scale, monitoring individual exocytotic events is possible with the coupling of high-speed CE and LINF detection.
Date: February 12, 1999
Creator: Ho, A.M.W.
Partner: UNT Libraries Government Documents Department

LiV{sub 2}O{sub 4}: A heavy fermion transition metal oxide

Description: The format of this dissertation is as follows. In the remainder of Chapter 1, brief introductions and reviews are given to the topics of frustration, heavy fermions and spinels including the precedent work of LiV{sub 2}O{sub 4}. In Chapter 2, as a general overview of this work the important publication in Physical Review Letters by the author of this dissertation and collaborators regarding the discovery of the heavy fermion behavior in LiV{sub 2}O{sub 4} is introduced [removed for separate processing]. The preparation methods employed by the author for nine LiV{sub 2}O{sub 4} and two Li{sub 1+x}Ti{sub 2{minus}x}O{sub 4} (x = 0 and 1/3) polycrystalline samples are introduced in Chapter 3. The subsequent structural characterization of the LiV{sub 2}O{sub 4} and Li{sub 1+x}Ti{sub 2{minus}x}O{sub 4} samples was done by the author using thermogravimetric analysis (TGA), x-ray diffraction measurements and their structural refinements by the Rietveld analysis. The results of the characterization are detailed in Chapter 3. In Chapter 4 magnetization measurements carried out by the author are detailed. In Chapter 5, after briefly discussing the resistivity measurement results including the single-crystal work by Rogers et al., for the purpose of clear characterization of LiV{sub 2}O{sub 4} it is of great importance to introduce in the following chapters the experiments and subsequent data analyses done by his collaborators. Heat capacity measurements (Chapter 6) were carried out and analyzed by Dr. C.A. Swenson, and modeled theoretically by Dr. D.C. Johnston. In Chapter 7 a thermal expansion study using neutron diffraction by Dr. O. Chmaissem et al. and capacitance dilatometry measurements by Dr. C.A. Swenson are introduced. The data analyses for the thermal expansion study were mainly done by Dr. O. Chmaissem (for neutron diffraction) and Dr. C.A. Swendon (for dilatometry), with assistances by Dr. J.D. Jorgensen, Dr. D.C. Johnston, and S. Kondo the ...
Date: February 12, 1999
Creator: Kondo, Shinichiro
Partner: UNT Libraries Government Documents Department

Synthesis and characterization of novel group VI metal (Mo, W) nitride and oxide compounds

Description: Investigations into the preparation of tungsten nitrides have involved the synthesis of molecular precursors, and their conversion to tungsten nitrides at relatively low temperatures. Two interesting molecular precursors, [WNCl{sub 3}{center_dot}NCCH{sub 3}]{sub 4} and WN(N{sub 3}){sub 3}{center_dot}xNCCH{sub 3}, have been prepared and characterized. The molecular structure of the first consists of a W{sub 4}N{sub 4} tetrameric core with multiple and single W-N bonds arranged in an alternating fashion. Three new solid state phases, amorphous W{sub 3}N{sub 5}, cubic WN, and W{sub 2}N{sub 2}(C{sub 2}N{sub 2}), have been discovered by solid state and chemical vapor transport reactions. The structures have been investigated. A systematic study in the Ln{sub 2}O{sub 3}-MoO{sub 3}-Mo (Ln = La, Ce, Pr, Nd, Sm) system has been explored to better understand LnMo{sub 8}O{sub 14}. The study has shown that the sizes of the rare-earth cations affect the formation of these phases. Larger cations (La, Ce, and Pr) aid in the formation of trans-Mo{sub 8} bicapped octahedra, and the smaller cations (Nd, Sm) only stabilize the cis-Mo{sub 8} bicapped octahedra. Magnetic susceptibility measurements have indicated that no effective moment contribution arises from the Mo{sub 8} metal clusters, even though the cis-Mo{sub 8} cluster in LnMo{sub 8}O{sub 14}, containing all cis-Mo{sub 8} octahedra, apparently contains an odd number of electrons (23). Electrical resistivity measurements and electronic structure calculations have shown that the LnMo{sub 8}O{sub 14} compounds containing cis-Mo{sub 8} clusters are metallic, and the LnMo{sub 8}O{sub 14} compounds containing a 1:1 ratio of cis- to trans-Mo{sub 8} clusters are semiconducting.
Date: February 23, 1998
Creator: Zhang, Z.
Partner: UNT Libraries Government Documents Department

Photodissociation dynamics of polyatomic molecules

Description: This report consists of five studies as follows: A laser photofragmentation time-of-flight mass spectrometric study of acetophenone at 193 and 248 nm; A 193 nm laser photofragmentation time-of-flight mass spectrometric study of dimethylsulfoxide; 193 nm laser photofragmentation time-of-flight mass spectrometric study of HSCH{sub 2}CH{sub 2}SH; Thiophene biradical decay of the primary laser photofragmentation product at 193 nm; and Scattering cross sections for O({sup 3}P)[SO(X,{sup 3}{Sigma}{sup {minus}})] + He[Ne, Ar, Kr]. Chapters are included for the introduction and general conclusions.
Date: February 23, 1998
Creator: Zhao, H.
Partner: UNT Libraries Government Documents Department

Synthesis, characterization, and structure of reduced tungsten chalcogenide cluster complexes

Description: Over the previous twenty years, ternary molybdenum chalcogenides of the general formula M{sub x}Mo{sub 6}Y{sub 8} (M = ternary metal cation; Y = chalcogenide), known as Chevrel phases, have been extensively studied. Many of these compounds have been found to have superconductivity, catalytic activity and ionic conductivity. The rich chemistry of the Chevrel phases raises considerable interest in finding the tungsten analogues of these phases. However, no such analogue has ever been synthesized, although the Chevrel phases are usually prepared directly from elements at high temperatures above 1000{degrees}C. The absence of the tungsten analogues may be caused by their thermodynamic instability at such high temperatures. Thus it might be necessary to avoid high-temperature synthetic procedures in order to establish the ternary and binary tungsten chalcogenides. A major focus of the McCarley research group has been on the preparation of M{sub 6}Y{sub 8}L{sub 6} (M = Mo, W; Y = S, Se, Te) cluster complexes as low temperature pathways to the Chevrel phases.
Date: February 1, 1997
Creator: Xiaobing, Xie
Partner: UNT Libraries Government Documents Department

Inductively coupled plasma mass spectrometry with a twin quadrupole instrument using laser ablation sample introduction and monodisperse dried microparticulate injection

Description: The focus of this dissertation is the use of a twin quadrupole inductively coupled plasma mass spectrometer (ICP-MS) for the simultaneous detection of two m/z values. The twin quadrupole ICP-MS is used with laser ablation sample introduction in both the steady state (10 Hz) and single pulse modes. Steady state signals are highly correlated and the majority of flicker noise cancels when the ratio is calculated. Using a copper sample, the isotope ratio {sup 63}Cu{sup +}/{sup 65}Cu{sup +} is measured with a relative standard deviation (RSD) of 0.26%. Transient signals for single laser pulses are also obtained. Copper isotope ratio measurements for several laser pulses are measured with an RSD of 0.85%. Laser ablation (LA) is used with steel samples to assess the ability of the twin quadrupole ICP-MS to eliminate flicker noise of minor components of steel samples. Isotopic and internal standard ratios are measured in the first part of this work. The isotope ratio {sup 52}Cr{sup +}/{sup 53}Cr{sup +} (Cr present at 1.31 %) can be measured with an RSD of 0.06 % to 0.1 %. For internal standard elements, RSDs improve from 1.9 % in the Cr{sup +} signal to 0.12% for the ratio of {sup 51}V{sup +} to {sup 52}Cr{sup +}. In the second part of this work, one mass spectrometer is scanned while the second channel measures an individual m/z value. When the ratio of these two signals is calculated, the peak shapes in the mass spectrum are improved significantly. Pulses of analyte and matrix ions from individual drops are measured simultaneously using the twin quadrupole ICP-MS with monodisperse dried microparticulate injection (MDMI). At modest Pb concentrations (500 ppm), a shoulder on the leading edge of the Li{sup +} signal becomes apparent. Space charge effects are consistent with the disturbances seen.
Date: February 1, 1997
Creator: Allen, L.A.
Partner: UNT Libraries Government Documents Department

Capillary electrophoresis separation of neutral organic compounds, pharmaceutical drugs, proteins and peptides, enantiomers, and anions

Description: Addition of a novel anionic surfactant, namely lauryl polyoxyethylene sulfate, to an aqueous-acetonitrile electrolyte makes it possible to separate nonionic organic compounds by capillary electrophoresis. Separation is based on differences in the association between analytes and the surfactant. Highly hydrophobic compounds such as polyaromatic hydrocarbons are well separated by this new surfactant. Migration times of analytes can be readily changed over an unusually large range by varying the additive concentration and the proportion of acetonitrile in the electrolyte. Several examples are given, including the separation of four methylbenz[a]anthracene isomers and the separation of normal and deuterated acetophenone. The effect of adding this new surfactant to the acidic electrolyte was also investigated. Incorporation of cetyltrimethylammonium bromide in the electrolyte is shown to dynamically coat the capillary and reverse electroosmotic flow. Chiral recognition mechanism is studied using novel synthetic surfactants as chiral selectors, which are made from amino acids reacting with alkyl chloroformates. A satisfactory separation of both inorganic and organic anions is obtained using electrolyte solutions as high as 5 M sodium chloride using direct photometric detection. The effect of various salts on electrophoretic and electroosmotic mobility is further discussed. Several examples are given under high-salt conditions.
Date: February 12, 1999
Creator: Ding, W.L.
Partner: UNT Libraries Government Documents Department