With the recent discovery of the giant magnetocaloric effect and the beginning of extensive research on the properties of Gd{sub 5}(Si{sub x}Ge{sub 1-x}){sub 4}, a necessity has developed for a better understanding of the microstructure and crystal structure of this family of rare earth compounds with startling phenomenological properties. The aim of this research is to characterize the microstructure of the Gd{sub 5}(Si{sub x}Ge{sub 1-x}){sub 4}, with X {approx_equal} 2 and its phase change by using both transmission and electron microscopes. A brief history of past work on Gd{sub 5}(Si{sub x}Ge{sub 1-x}){sub 4} is necessary to understand this research in its proper context.

Submitted to Univ. of Tennessee, Knoxville. The fast neutron-induced fission cross section of U/sup 234/ was measured from threshold to 4-Mev neutron energy. A maximum of 1.26 barns was found at 850 kev followed by a minimum of 1.10 barns at 8050 kev. The angular ani-sotropy of the fragment distribution was measured for neutron energies from 400 kev to 4 Mev. Extrema in the ratio sigma /sub f//( sigma /sub f(90 deg ) were found at 500, 850, and 1050 kev; the distribution at 500 kev showing a maximum in the direction normal to the beam (side-wise peaking) while that at 850 kev showed a maximum along the beam direction. The distribution at 8050 kev showed forward peaking but to a lesser extent than for energies immediately higher or lower. The behavior was analyzed according to the theories of Bohr and Wheeler. The dip in cross section between 850 and 1050 kev is consistent with the suggestion of Wheeler that neutron competition in the decay of the compound nucleus enters with increased strength in this area. Vibration-rotational levels in U/sup 234/ beginning at 790 kev are known to exist and inelastic neutron scattering to these levels serves to depress the …

The research in this thesis explores the separation capabilities of a new technique termed electrochemically-modulated liquid chromatography (EMLC). The thesis begins with a general introduction section which provides a literature review of this technique as well as a brief background discussion of the two research projects in each of the next two chapters. The two papers which follow investigate the application of EMLC to the separation of a mixture of aromatic amino acids and of a mixture of polycyclic aromatic hydrocarbons (PAHs). The last section presents general conclusions and summarizes the thesis. References are compiled in the reference section of each chapter. The two papers have been removed for separate processing.

Capillary electrophoresis (CE) and high-performance liquid chromatography (HPLC) are widely used analytical separation techniques with many applications in chemical, biochemical, and biomedical sciences. Conventional analyte identification in these techniques is based on retention/migration times of standards; requiring a high degree of reproducibility, availability of reliable standards, and absence of coelution. From this, several new information-rich detection methods (also known as hyphenated techniques) are being explored that would be capable of providing unambiguous on-line identification of separating analytes in CE and HPLC. As further discussed, a number of such on-line detection methods have shown considerable success, including Raman, nuclear magnetic resonance (NMR), mass spectrometry (MS), and fluorescence line-narrowing spectroscopy (FLNS). In this thesis, the feasibility and potential of combining the highly sensitive and selective laser-based detection method of FLNS with analytical separation techniques are discussed and presented. A summary of previously demonstrated FLNS detection interfaced with chromatography and electrophoresis is given, and recent results from on-line FLNS detection in CE (CE-FLNS), and the new combination of HPLC-FLNS, are shown.

Senior colloquium written by a student in the UNT Honors College discussing Greek sculpture and architecture as filtered through the Fauve, Constructivist, Dada, and Pop artistic movements. The author takes examples of Grecian sculpture, recreates them in each of the other styles, and discusses the results.

Over the last ten years, photonic band gap (PBG) theory and technology have become an important area of research because of the numerous possible applications ranging from high-efficiency laser diodes to optical circuitry. This research concentrates on reducing the length scale in the fabrication of layered photonic band gap structures and developing procedures to improve processing consistency. Various procedures and materials have been used in the fabrication of layered PBG structures. This research focused on an economical micro transfer molding approach to create the final PBG structure. A poly dimethylsiloxane (PDMS) rubber mold was created from a silicon substrate. It was filled with epoxy and built layer-by-layer to create a 3-D epoxy structure. This structure was infiltrated with nanoparticle titania or a titania sol-gel, then fired to remove the polymer mold, leaving a monolithic ceramic inverse of the epoxy structure. The final result was a lattice of titania rolds that resembles a face-centered tetragonal structure. The original intent of this research was to miniaturize this process to a bar size small enough to create a photonic band gap for wavelengths of visible electro-magnetic radiation. The factor limiting progress was the absence of a silicon master mold of small enough dimensions. …

Throughout this thesis, the fundamental aspects involved in the electrocatalysis of anodic O-transfer reactions and cathodic H-transfer reactions have been studied. The investigation into anodic O-transfer reactions at undoped and Fe(III)[doped MnO{sub 2} films] revealed that MnO{sub 2} film electrodes prepared by a cycling voltammetry deposition show improved response for DMSO oxidation at the film electrodes vs. the Au substrate. Doping of the MnO{sub 2} films with Fe(III) further enhanced electrode activity. Reasons for this increase are believed to involve the adsorption of DMSO by the Fe(III) sites. The investigation into anodic O-transfer reactions at undoped and Fe(III)-doped RuO{sub 2} films showed that the Fe(III)-doped RuO{sub 2}-film electrodes are applicable for anodic detection of sulfur compounds. The Fe(III) sites in the Fe-RuO{sub 2} films are speculated to act as adsorption sites for the sulfur species while the Ru(IV) sites function for anodic discharge of H{sub 2}O to generate the adsorbed OH species. The investigation into cathodic H-transfer reactions, specifically nitrate reduction, at various pure metals and their alloys demonstrated that the incorporation of metals into alloy materials can create a material that exhibits bifunctional properties for the various steps involved in the overall nitrate reduction reaction. The Sb{sub 10}Sn{sub 20}Ti{sub …

The underlying theme of this thesis is the use of polymeric materials in bioapplications. Chapters 2-5 either develop a fundamental understanding of current materials used for bioapplications or establish protocols and procedures used in characterizing and synthesizing novel materials. In chapters 6 and 7 these principles and procedures are applied to the development of materials to be used for gene therapy and drug delivery. Chapter one is an introduction to the ideas that will be necessary to understand the subsequent chapters, as well as a literature review of these topics. Chapter two is a paper that has been published in the ''Journal of Controlled Release'' that examines the mechanism of drug release from a polymer gel, as well as experimental design suggestions for the evaluation of water soluble drug delivery systems. Chapter three is a paper that has been published in the ''Journal of Pharmaceutical Sciences'' that discusses the effect ionic salts have on properties of the polymer systems examined in chapter two. Chapter four is a paper published in the Materials Research Society Fall 2000 Symposium Series dealing with the design and synthesis of a pH-sensitive polymeric drug delivery device. Chapter five is a paper that has been published …

This dissertation includes three different topics: general introduction of capillary electrophoresis (CE); gradient in CE and CE in biological separations; and capillary gel electrophoresis (CGE) for DNA separation. Factors such as temperature, viscosity, pH, and the surface of capillary walls affecting the separation performance are demonstrated. A pH gradient between 3.0 and 5.2 is useful to improve the resolution among eight different organic acids. A flow gradient due to the change in the concentration of surfactant, which is able to coat to the capillary wall to change the flow rate and its direction, is also shown as a good way to improve the resolution for organic compounds. A temperature gradient caused by joule heat is shown by voltage programming to enhance the resolution and shorten the separation time for several phenolic compounds. The author also shows that self-regulating dynamic control of electroosmotic flow in CE by simply running separation in different concentrations of surfactant has less matrix effect on the separation performance. One of the most important demonstrations in this dissertation is that the author proposes on-column reaction which gives several advantages including the use of a small amount of sample, low risk of contamination, and time saving and kinetic …

This dissertation focuses on techniques for (1) increasing ethanol yields from saccharification and fermentation of cellulose using immobilized cellulase, and (2) the characterization and classification of lignocellulosic feedstocks, and quantification of useful parameters such as the syringyl/guaiacyl (S/G) lignin monomer content using 1064 nm dispersive multichannel Raman spectroscopy and chemometrics.

It is possible to produce alumina-zirconia ceramic samples through existing solidification techniques. The resulting microstructures typically consist of rods of zirconia in an alumina matrix, although a lamellar structure has been noted in some cases. In nearly all cases, colony growth was present which may possibly result from grain size, repeated nucleation events, and lamellar oscillations. In the same vein, it appears that the amount of impurities within the system might be the underlying cause for the colony growth. Colony growth was diminished through impurity control as the higher purity samples exhibited colony free behavior. In addition to colony formations, faceted alumina dendrites or nonfaceted zirconia dendrites may result in the ceramic if the sample is solidified out of the coupled zone. In all cases, for larger-sized Bridgman samples, a lower limit in the eutectic spacing was noted. The solidification model which includes the kinetic effect has been developed, although the effect appears to be negligible under present experimental conditions. A spacing limit might also occur due to the result of heat flow problems. Heat flow out of the ceramic is difficult to control, often causing radial and not axial growth. This behavior is exaggerated in the presence of impurities. …

The N-body problem is to simulate the motion of N particles under the influence of mutual force fields based on an inverse square law. The problem has applications in several domains including astrophysics, molecular dynamics, fluid dynamics, radiosity methods in computer graphics and numerical complex analysis. Research efforts have focused on reducing the O(N{sup 2}) time per iteration required by the naive algorithm of computing each pairwise interaction. Widely respected among these are the Barnes-Hut and Greengard methods. Greengard claims his algorithm reduces the complexity to O(N) time per iteration. Throughout this thesis, we concentrate on rigorous, distribution-independent, worst-case analysis of the N-body methods. We show that Greengard`s algorithm is not O(N), as claimed. Both Barnes-Hut and Greengard`s methods depend on the same data structure, which we show is distribution-dependent. For the distribution that results in the smallest running time, we show that Greengard`s algorithm is {Omega}(N log{sup 2} N) in two dimensions and {Omega}(N log{sup 4} N) in three dimensions. We have designed a hierarchical data structure whose size depends entirely upon the number of particles and is independent of the distribution of the particles. We show that both Greengard`s and Barnes-Hut algorithms can be used in conjunction with …

This thesis contains the results of organometallic studies of thiophene and selenophene coordination in transition metal complexes. Chromium tricarbonyl complexes of thiophene, selenophene, and their alkyl-substituted derivatives were prepared and variable-temperature {sup 13}C NMR spectra of these complexes were recorded in dimethyl ether. Bandshape analyses of these spectra yielded activation parameters for restricted rotation of the thiophene and selenophene ligands in these complexes. Extended Hueckel molecular orbital calculations (EHMO) of the free thiophene and selenophene ligands and selected chromium tricarbonyl thiophene complexes were performed to better explain the activation barriers of these complexes. The structure of Cr(CO){sub 3}({eta}{sup 5}-2,5-dimethylthiophene) was established by a single crystal X-ray diffraction study.

In core-collapse supernovae, strong blast waves drive interfaces susceptible to Rayleigh-Taylor (RT), Richtmyer-Meshkov (RM), and Kelvin-Helmholtz (KH) instabilities. In addition, perturbation growth can result from material expansion in large-scale velocity gradients behind the shock front. Laser-driven experiments are designed to produce a strongly shocked interface whose evolution is a scaled version of the unstable hydrogen-helium interface in core-collapse supernovae such as SN 1987A. The ultimate goal of this research is to develop an understanding of the effect of hydrodynamic instabilities and the resulting transition to turbulence on supernovae observables that remain as yet unexplained. In this dissertation, we present a computational study of unstable systems driven by high Mach number shock and blast waves. Using multi-physics radiation hydrodynamics codes and theoretical models, we consider the late nonlinear instability evolution of single mode, few mode, and multimode interfaces. We rely primarily on 2D calculations but present recent 3D results as well. For planar multimode systems, we show that compressibility effects preclude the emergence of a regime of self-similar instability growth independent of the initial conditions (IC's) by allowing for memory of the initial conditions to be retained in the mix-width at all times. The loss of transverse spectral information is demonstrated, …

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 …

The focus of this thesis was first to characterize and improve the applicability of Fe(III) and Bi(V) doped PbO{sub 2} film electrodes for use in anodic O-transfer reactions of toxic and waste organic compounds, e.g. phenol, aniline, benzene, and naphthalene. Further, they investigated the use of alternative solution/electrode interfacial excitation techniques to enhance the performance of these electrodes for remediation and electrosynthetic applications. Finally, they have attempted to identify a less toxic metal oxide film that may hold promise for future studies in the electrocatalysis and photoelectrocatalysis of O-transfer reactions using metal oxide film electrodes.

The properties of both carbon and gold substrates are easily affected by the judicious choice of a surface modification protocol. Several such processes for altering surface composition have been published in literature. The research presented in this thesis primarily focuses on the development of on-column methods to modify carbon stationary phases used in electrochemically modulated liquid chromatography (EMLC). To this end, both porous graphitic carbon (PGC) and glassy carbon (GC) particles have been modified on-column by the electroreduction of arenediazonium salts and the oxidation of arylacetate anions (the Kolbe reaction). Once modified, the carbon stationary phases show enhanced chromatographic performance both in conventional liquid chromatographic columns and EMLC columns. Additionally, one may also exploit the creation of aryl films to by electroreduction of arenediazonium salts in the creation of nanostructured materials. The formation of mercaptobenzene film on the surface of a GC electrode provides a linking platform for the chemisorption of gold nanoparticles. After deposition of nanoparticles, the surface chemistry of the gold can be further altered by self-assembled monolayer (SAM) formation via the chemisorption of a second thiol species. Finally, the properties of gold films can be altered such that they display carbon-like behavior through the formation of benzenehexathiol …

This dissertation describes a variety of studies meant to improve the analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation (LA) ICP-MS. The emission behavior of individual droplets and LA generated particles in an ICP is studied using a high-speed, high frame rate digital camera. Phenomena are observed during the ablation of silicate glass that would cause elemental fractionation during analysis by ICP-MS. Preliminary work for ICP torch developments specifically tailored for the improvement of LA sample introduction are presented. An abnormal scarcity of metal-argon polyatomic ions (MAr{sup +}) is observed during ICP-MS analysis. Evidence shows that MAr{sup +} ions are dissociated by collisions with background gas in a shockwave near the tip of the skimmer cone. Method development towards the improvement of LA-ICP-MS for environmental monitoring is described. A method is developed to trap small particles in a collodion matrix and analyze each particle individually by LA-ICP-MS.

This thesis investigated the biology and importance of the corn flea beetle vector and its role in the Stewart's disease of corn pathosystem. This was accomplished by determining the number of corn flea beetle generations that occur in Iowa and by quantifying the proportions of those populations found to be infested with the causal agent of Stewart's disease, pantoea stewartii. In addition, a preliminary study was conducted to determine how soil temperature was influenced by air temperature and how this may be applied to forecasting for Stewart's disease of corn. Research using yellow sticky cards and sweep netting demonstrated that there are overwintering, first, and second field generations of the corn flea beetle in Iowa. It was also observed that there was a period during June of both 1999 and 2000 when corn flea beetles were not found, which is important new management information. This research has also demonstrated that the incidence of P. stewartii-infested corn flea beetles can be monitored by ELISA testing and that the incidence fluctuates greatly throughout the corn growing season. The initial level of inoculum (P. stewartii-infested corn flea beetles in the adult overwintering generation) does not remain static during the spring as was previously …

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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 …

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 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-metallic 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.

A new technique for in situ imaging and screening heterogeneous catalysts by using multiplexed capillary electrophoresis with absorption detection was developed. By bundling the inlets of a large number of capillaries, an imaging probe can be created that can be used to sample products formed directly from a catalytic surface with high spatial resolution. In this work, they used surfaces made of platinum, iron or gold wires as model catalytic surfaces for imaging. Various shapes were recorded including squares and triangles. Model catalytic surfaces consisting of both iron and platinum wires in the shape of a cross were also imaged successfully. Each of the two wires produced a different electrochemical product that was separated by capillary electrophoresis. Based on the collected data they were able to distinguish the products from each wire in the reconstructed image.

The goal of this thesis is to develop a new Channel Interface device for the MPICH Implementation of the MPI (Message Passing Interface) standard using MP{_}Lite. MP{_}Lite is a lightweight message-passing library that is not a full MPI implementation, but offers high performance MPICH (Message Passing Interface CHameleon) is a full implementation of the MPI standard that has the p4 library as the underlying communication device for TCP/IP networks. By integrating MP{_}Lite as a Channel Interface device in MPICH, a parallel programmer can utilize the full MPI implementation of MPICH as well as the high bandwidth offered by MP{_}Lite. There are several layers in the MPICH library where one can tie a new device. The Channel Interface is the lowest layer that requires very few functions to add a new device. By attaching MP{_}Lite to MPICH at the lowest level, the Channel Interface, almost all of the performance of the MP{_}Lite library can be delivered to the applications using MPICH. MP{_}Lite can be implemented either as a blocking or a non-blocking Channel Interface device. The performance was measured on two separate test clusters, the PC and the Alpha miniclusters, having Gigabit Ethernet connections. The PC cluster has two 1.8 GHz …