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Nanoscale chemical and mechanical characterization of thin films:sum frequency generation (SFG) vibrational spectroscopy at buriedinterfaces

Description: Sum frequency generation (SFG) surface vibrational spectroscopy was used to characterize interfaces pertinent to current surface engineering applications, such as thin film polymers and novel catalysts. An array of advanced surface science techniques like scanning probe microscopy (SPM), x-ray photoelectron spectroscopy (XPS), gas chromatography (GC) and electron microscopy were used to obtain experimental measurements complementary to SFG data elucidating polymer and catalyst surface composition, surface structure, and surface mechanical behavior. Experiments reported in this dissertation concentrate on three fundamental questions: (1) How does the interfacial molecular structure differ from that of the bulk in real world applications? (2) How do differences in chemical environment affect interface composition or conformation? (3) How do these changes correlate to properties such as mechanical or catalytic performance? The density, surface energy and bonding at a solid interface dramatically alter the polymer configuration, physics and mechanical properties such as surface glass transition, adhesion and hardness. The enhanced sensitivity of SFG at the buried interface is applied to three systems: a series of acrylates under compression, the compositions and segregation behavior of binary polymer polyolefin blends, and the changes in surface structure of a hydrogel as a function of hydration. In addition, a catalytically active thin film of polymer coated nanoparticles is investigated to evaluate the efficacy of SFG to provide in situ information for catalytic reactions involving small mass adsorption and/or product development. Through the use of SFG, in situ total internal reflection (TIR) was used to increase the sensitivity of SFG and provide the necessary specificity to investigate interfaces of thin polymer films and nanostructures previously considered unfeasible. The dynamic nature of thin film surfaces is examined and it is found that the non-equilibrium states contribute to practical applications of acrylates, blends and hydrogels. Lastly, nanoparticle surfaces and the catalytic activity and selectivity of ...
Date: May 19, 2006
Creator: Kweskin, S.J.
Partner: UNT Libraries Government Documents Department

Synthesis and Manipulation of Semiconductor Nanocrystals inMicrofluidic Reactors

Description: Microfluidic reactors are investigated as a mechanism tocontrol the growth of semiconductor nanocrystals and characterize thestructural evolution of colloidal quantum dots. Due to their shortdiffusion lengths, low thermal masses, and predictable fluid dynamics,microfluidic devices can be used to quickly and reproducibly alterreaction conditions such as concentration, temperature, and reactiontime, while allowing for rapid reagent mixing and productcharacterization. These features are particularly useful for colloidalnanocrystal reactions, which scale poorly and are difficult to controland characterize in bulk fluids. To demonstrate the capabilities ofnanoparticle microreactors, a size series of spherical CdSe nanocrystalswas synthesized at high temperature in a continuous-flow, microfabricatedglass reactor. Nanocrystal diameters are reproducibly controlled bysystematically altering reaction parameters such as the temperature,concentration, and reaction time. Microreactors with finer control overtemperature and reagent mixing were designed to synthesize nanoparticlesof different shapes, such as rods, tetrapods, and hollow shells. The twomajor challenges observed with continuous flow reactors are thedeposition of particles on channel walls and the broad distribution ofresidence times that result from laminar flow. To alleviate theseproblems, I designed and fabricated liquid-liquid segmented flowmicroreactors in which the reaction precursors are encapsulated inflowing droplets suspended in an immiscible carrier fluid. The synthesisof CdSe nanocrystals in such microreactors exhibited reduced depositionand residence time distributions while enabling the rapid screening aseries of samples isolated in nL droplets. Microfluidic reactors werealso designed to modify the composition of existing nanocrystals andcharacterize the kinetics of such reactions. The millisecond kinetics ofthe CdSe-to-Ag2Se nanocrystal cation exchange reaction are measured insitu with micro-X-ray Absorption Spectroscopy in silicon microreactorsspecifically designed for rapid mixing and time-resolved X-rayspectroscopy. These results demonstrate that microreactors are valuablefor controlling and characterizing a wide range of reactions in nLvolumes even when nanoscale particles, high temperatures, causticreagents, and rapid time scales are involved. These experiments providethe foundation for future microfluidic investigations into the mechanismsof nanocrystal growth, crystal ...
Date: December 19, 2006
Creator: Chan, Emory Ming-Yue
Partner: UNT Libraries Government Documents Department

High-Pressure Catalytic Reactions of C6 Hydrocarbons on PlatinumSingle-Crystals and nanoparticles: A Sum Frequency Generation VibrationalSpectroscopic and Kinetic Study

Description: Catalytic reactions of cyclohexene, benzene, n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene on platinum catalysts were monitored in situ via sum frequency generation (SFG) vibrational spectroscopy and gas chromatography (GC). SFG is a surface specific vibrational spectroscopic tool capable of monitoring submonolayer coverages under reaction conditions without gas-phase interference. SFG was used to identify the surface intermediates present during catalytic processes on Pt(111) and Pt(100) single-crystals and on cubic and cuboctahedra Pt nanoparticles in the Torr pressure regime and at high temperatures (300K-450K). At low pressures (<10{sup -6} Torr), cyclohexene hydrogenated and dehydrogenates to form cyclohexyl (C{sub 6}H{sub 11}) and {pi}-allyl C{sub 6}H{sub 9}, respectively, on Pt(100). Increasing pressures to 1.5 Torr form cyclohexyl, {pi}-allyl C{sub 6}H{sub 9}, and 1,4-cyclohexadiene, illustrating the necessity to investigate catalytic reactions at high-pressures. Simultaneously, GC was used to acquire turnover rates that were correlated to reactive intermediates observed spectroscopically. Benzene hydrogenation on Pt(111) and Pt(100) illustrated structure sensitivity via both vibrational spectroscopy and kinetics. Both cyclohexane and cyclohexene were produced on Pt(111), while only cyclohexane was formed on Pt(100). Additionally, {pi}-allyl c-C{sub 6}H{sub 9} was found only on Pt(100), indicating that cyclohexene rapidly dehydrogenates on the (100) surface. The structure insensitive production of cyclohexane was found to exhibit a compensation effect and was analyzed using the selective energy transfer (SET) model. The SET model suggests that the Pt-H system donates energy to the E{sub 2u} mode of free benzene, which leads to catalysis. Linear C{sub 6} (n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene) hydrocarbons were also investigated in the presence and absence of excess hydrogen on Pt(100). Based on spectroscopic signatures, mechanisms for catalytic isomerization and dehydrocyclization of n-hexane were identified. The structure sensitivity of benzene hydrogenation on shape controlled platinum nanoparticles was also studied. The nanoparticles showed similar selectivities to those found for Pt(111) and Pt(100) single-crystals. ...
Date: December 19, 2007
Creator: Bratlie, Kaitlin
Partner: UNT Libraries Government Documents Department

Sum Frequency Generation Vibrational Spectroscopy Studies on ModelPeptide Adsorption at the Hydrophobic Solid-Water and HydrophilicSolid-Water Interfaces

Description: Sum frequency generation (SFG) vibrational spectroscopy has been used to study the interfacial structure of several polypeptides and amino acids adsorbed to hydrophobic and hydrophilic surfaces under a variety of experimental conditions. Peptide sequence, peptide chain length, peptide hydrophobicity, peptide side-chain type, surface hydrophobicity, and solution ionic strength all affect an adsorbed peptide's interfacial structure. Herein, it is demonstrated that with the choice of simple, model peptides and amino acids, surface specific SFG vibrational spectroscopy can be a powerful tool to elucidate the interfacial structure of these adsorbates. Herein, four experiments are described. In one, a series of isosequential amphiphilic peptides are synthesized and studied when adsorbed to both hydrophobic and hydrophilic surfaces. On hydrophobic surfaces of deuterated polystyrene, it was determined that the hydrophobic part of the peptide is ordered at the solid-liquid interface, while the hydrophilic part of the peptide appears to have a random orientation at this interface. On a hydrophilic surface of silica, it was determined that an ordered peptide was only observed if a peptide had stable secondary structure in solution. In another experiment, the interfacial structure of a model amphiphilic peptide was studied as a function of the ionic strength of the solution, a parameter that could change the peptide's secondary structure in solution. It was determined that on a hydrophobic surface, the peptide's interfacial structure was independent of its structure in solution. This was in contrast to the adsorbed structure on a hydrophilic surface, where the peptide's interfacial structure showed a strong dependence on its solution secondary structure. In a third experiment, the SFG spectra of lysine and proline amino acids on both hydrophobic and hydrophilic surfaces were obtained by using a different experimental geometry that increases the SFG signal. Upon comparison of these spectra to the SFG spectra of interfacial polylysine and ...
Date: December 19, 2007
Creator: York, Roger L.
Partner: UNT Libraries Government Documents Department

Search for Large Extra Dimensions Based on Observations of Neutron Stars with the Fermi-LAT

Description: Large extra dimensions (LED) have been proposed to account for the apparent weakness of gravitation. These theories also indicate that the postulated massive Kaluza-Klein (KK) gravitons may be produced by nucleon-nucleon bremsstrahlung in the course of core collapse of supernovae. Hannestad and Raffelt have predicted energy spectra of gamma ray emission from the decay of KK gravitons trapped by the gravity of the remnant neutron stars (NS). These and other authors have used EGRET data on NS to obtain stringent limits on LED. Fermi-LAT is observing radio pulsar positions obtained from radio and x-ray catalogs. NS with certain characteristics are unlikely emitter of gamma rays, and emit in radio and perhaps x-rays. This talk will focus on the blind analysis we plan to perform, which has been developed using the 1st 2 months of all sky data and Monte Carlo simulations, to obtain limits on LED based on about 1 year of Fermi-LAT data. Preliminary limits from this analysis using these first 2 months of data will be also be discussed.
Date: September 19, 2012
Creator: Berenji, Bijan & /Stanford U., Appl. Phys. Dept. /SLAC
Partner: UNT Libraries Government Documents Department

Energy Spread Reduction of Electron Beams Produced via Laser Wake

Description: Laser wakefield acceleration of electrons holds great promise for producing ultra-compact stages of GeV scale, high quality electron beams for applications such as x-ray free electron lasers and high energy colliders. Ultra-high intensity laser pulses can be self-guided by relativistic plasma waves over tens of vacuum diffraction lengths, to give >1 GeV energy in cm-scale low density plasma using ionization-induced injection to inject charge into the wake at low densities. This thesis describes a series of experiments which investigates the physics of LWFA in the self-guided blowout regime. Beginning with high density gas jet experiments the scaling of the LWFA-produced electron beam energy with plasma electron density is found to be in excellent agreement with both phenomenological theory and with 3-D PIC simulations. It is also determined that self-trapping of background electrons into the wake exhibits a threshold as a function of the electron density, and at the densities required to produce electron beams with energies exceeding 1 GeV a different mechanism is required to trap charge into low density wakes. By introducing small concentrations of high-Z gas to the nominal He background the ionization-induced injection mechanism is enabled. Electron trapping is observed at densities as low as 1.3 x 10{sup 18} cm{sup -3} in a gas cell target, and 1.45 GeV electrons are demonstrated for the first time from LWFA. This is currently the highest electron energy ever produced from LWFA. The ionization-induced trapping mechanism is also shown to generate quasi-continuous electron beam energies, which is undesirable for accelerator applications. By limiting the region over which ionization-induced trapping occurs, the energy spread of the electron beams can be controlled. The development of a novel two-stage gas cell target provides the capability to tailor the gas composition in the longitudinal direction, and confine the trapping process to occur only in ...
Date: March 19, 2012
Creator: Pollock, B
Partner: UNT Libraries Government Documents Department

An Enquiry Concerning Charmless Semileptonic Decays of Bottom Mesons

Description: The branching fractions for the decays B {yields} P{ell}{nu}{sub {ell}}, where P are the pseudoscalar charmless mesons {pi}{sup {+-}}, {pi}{sup 0}, {eta} and {eta}{prime} and {ell} is an electron or muon, are measured with B{sup 0} and B{sup {+-}} mesons found in the recoil of a second B meson decaying as B {yields} D{ell}{nu}{sub {ell}} or B {yields} D*{ell}{nu}{sub {ell}}. The measurements are based on a data set of 348 fb{sup -1} of e{sup +}e{sup -} collisions at {radical}s = 10.58 GeV recorded with the BABAR detector. Assuming isospin symmetry, measured pionic branching fractions are combined into {Beta}(B{sup 0} {yields} {pi}{sup -}{ell}{sup +}{nu}{sub {ell}}) = (1.54 {+-} 0.17{sub (stat)} {+-} 0.09{sub (syst)}) x 10{sup -4}. First evidence of the B{sup +} {yields} {eta}{ell}{sup +}{nu}{sub {ell}} decay is seen; its branching fraction is measured to be {Beta}(B{sup +} {yields} {eta}{ell}{sup +}{nu}{sub {ell}}) = (0.64 {+-} 0.20{sub (stat)} {+-} 0.03{sub (syst)}) x 10{sup -4}. It is determined that {Beta}(B{sup +} {yields} {eta}{prime}{ell}{sup +}{nu}{sub {ell}}) < 0.47 x 10{sup -4} to 90% confidence. Partial branching fractions for the pionic decays in ranges of the momentum transfer and various published calculations of the B {yields} {pi} hadronic form factor are used to obtain values of the magnitude of the Cabibbo-Kobayashi-Maskawa matrix element V{sub ub} between 3.61 and 4.07 x 10{sup -3}.
Date: September 19, 2008
Creator: Chaisanguanthum, Kris Somboon & /SLAC, /Harvard U.
Partner: UNT Libraries Government Documents Department

Inclusive Rates and Spectra of the Lambda, Cascade, and Omega Hyperons atBaBar

Description: We employ Runs 1-4 off-peak data sample (about 21.5 fb{sup -1}) to produce the current world-best spectra and production rates measurements for three strangely-flavored baryons: the {Lambda} hyperon, the cascade hyperon, and the {Omega} hyperon. These improved measurements shall enable theoretical and phenomelogical workers to generate more realistic models for the hadronization process, currently one of the unresolved problem areas in the standard model of particle physics. This analysis was conducted using codes from release 16 series. We report the production rate at 10.54 GeV for the {Lambda} as 0.0900 {+-} 0.0006(stat.) {+-} 0.0039(sys.) per hadronic event. Our measured production rate at the same energy for the cascade hyperon is 0.00562 {+-} 0.00013(stat.) {+-} 0.00045(sys.) per hadronic event, while that for the {Omega} hyperon is 0.00027 {+-} 0.00004(stat.) {+-} 0.0008(sys.) per hadronic event. The spectral measurements for the respective particles also constitute current world-best measurements.
Date: May 19, 2008
Creator: Chien, Andrew L.
Partner: UNT Libraries Government Documents Department

Considering value of information when using CFD in design

Description: This thesis presents an approach to find lower resolution CFD models that can accurately lead a designer to a correct decision at a lower computational cost. High-fidelity CFD models often contain too much information and come at a higher computational cost, limiting the designs a designer can test and how much optimization can be performed on the design. Lower model resolution is commonly used to reduce computational time. However there are no clear guidelines on how much model accuracy is required. Instead experience and intuition are used to select an appropriate lower resolution model. This thesis presents an alternative to this ad hoc method by considering the added value of the addition information provided by increasing accurate and more computationally expensive models.
Date: December 19, 2009
Creator: Misra, John Satprim
Partner: UNT Libraries Government Documents Department

X-ray resonant magnetic scattering investigations of hexagonal multiferroics RMnO3 (R = Dy, Ho, Er)

Description: Electricity and magnetism were unified into a common subject by James Clerk Maxwell in the nineteenth century yielding the electromagnetic theory. Four equations govern the dynamics of electric charges and magnetic fields, commonly known as Maxwell's equations. Maxwell's equations demonstrate that an accelerated charged particle can produce magnetic fields and a time varying magnetic field can induce a voltage - thereby linking the two phenomena. However, in solids, electric and magnetic ordering are most often considered separately and usually with good reason: the electric charges of electrons and ions are responsible for the charge effects, whereas the electron spin governs magnetic properties.
Date: December 19, 2009
Creator: Nandi, Shibabrata
Partner: UNT Libraries Government Documents Department

Direct analysis of samples by mass spectrometry: From elements to bio-molecules using laser ablation inductively couple plasma mass spectrometry and laser desorption/ionization mass spectrometry

Description: Mass spectrometric methods that are able to analyze solid samples or biological materials with little or no sample preparation are invaluable to science as well as society. Fundamental research that has discovered experimental and instrumental parameters that inhibit fractionation effects that occur during the quantification of elemental species in solid samples by laser ablation inductively coupled plasma mass spectrometry is described. Research that determines the effectiveness of novel laser desorption/ionization mass spectrometric methods for the molecular analysis of biological tissues at atmospheric pressure and at high spatial resolution is also described. A spatial resolution is achieved that is able to analyze samples at the single cell level.
Date: August 19, 2009
Creator: Perdian, David C.
Partner: UNT Libraries Government Documents Department

Evaluation of bisphenol E cyanate ester for the resin-injection repair of advanced composites

Description: This thesis is a compilation of a general introduction and literature review that ties together the subsequent chapters which consist of two journal articles that have yet to be submitted for publication. The overall topic relates to the evaluation and application of a new class of cyanate ester resin with unique properties that lend it applicable to use as a resin for injection repair of high glass transition temperature polymer matrix composites. The first article (Chapter 2) details the evaluation and optimization of adhesive properties of this cyanate ester and alumina nanocomposites under different conditions. The second article (Chapter 3) describes the development and evaluation of an injection repair system for repairing delaminations in polymer matrix composites.
Date: December 19, 2009
Creator: Lio, Wilber Yaote
Partner: UNT Libraries Government Documents Department

Search for the Production of Gluinos and Squarks with the CDF II Experiment at the Tevatron Collider

Description: This thesis reports on two searches for the production of squarks and gluinos, supersymmetric partners of the Standard Model (SM) quarks and gluons, using the CDF detector at the Tevatron √s = 1.96 TeV p$\bar{p}$ collider. An inclusive search for squarks and gluinos pair production is performed in events with large E<sub>T</sub> and multiple jets in the final state, based on 2 fb<sup>-1</sup> of CDF Run II data. The analysis is performed within the framework of minimal supergravity (mSUGRA) and assumes R-parity conservation where sparticles are produced in pairs. The expected signal is characterized by the production of multiple jets of hadrons from the cascade decays of squarks and gluinos and large missing transverse energy E<sub>T</sub> from the lightest supersymmetric particles (LSP). The measurements are in good agreement with SM predictions for backgrounds. The results are translated into 95% confidence level (CL) upper limits on production cross sections and squark and gluino masses in a given mSUGRA scenario. An upper limit on the production cross section is placed in the range between 1 pb and 0.1 pb, depending on the gluino and squark masses considered. The result of the search is negative for gluino and squark masses up to 392 GeV/c<sup>2</sup> in the region where gluino and squark masses are close to each other, gluino masses up to 280 GeV/c<sup>2</sup> regardless of the squark mass, and gluino masses up to 423 GeV=c<sup>2</sup> for squark masses below 378 GeV/c<sup>2</sup>. These results are compatible with the latest limits on squark/gluino production obtained by the D0 Collaboration and considerably improve the previous exclusion limits from direct and indirect searches at LEP and the Tevatron. The inclusive search is then extended to a scenario where the pair production of sbottom squarks is dominant. The new search is performed in a generic MSSM scenario with ...
Date: May 19, 2010
Creator: De Lorenzo, Gianluca
Partner: UNT Libraries Government Documents Department

Ultrafast Magnetization Dynamics of SrRuO3 Thin Films

Description: Itinerant ferromagnet SrRuO3 has drawn interest from physicists due to its unusual transport and magnetic properties as well as from engineers due to its low resistivity and good lattice-matching to other oxide materials. The exact electronic structure remains a mystery, as well as details of the interactions between magnetic and electron transport properties. This thesis describes the use of time-resolved magneto-optical Kerr spectroscopy to study the ferromagnetic resonance of SrRuO3 thin films, where the ferromagnetic resonance is initiated by a sudden change in the easy axis direction in response to a pump pulse. The rotation of the easy axis is induced by laser heating, taking advantage of a temperature-dependent easy axis direction in SrRuO3 thin films. By measuring the change in temperature of the magnetic system in response to the laser pulse, we find that the specific heat is dominated by magnons up to unusually high temperature, ~;;100 K, and thermal diffusion is limited by a boundary resistance between the film and the substrate that is not consistent with standard phonon reflection and scattering models. We observe a high FMR frequency, 250 GHz, and large Gilbert damping parameter, alpha ~;; 1, consistent with strong spin-orbit coupling. We observe a time-dependent change in the easy axis direction on a ps time-scale, and we find that parameters associated with the change in easy axis, as well as the damping parameter, have a non-monotonic temperature dependence similar to that observed in anomalous Hall measurements.
Date: May 19, 2009
Creator: Langner, Matthew C.
Partner: UNT Libraries Government Documents Department

Steric and electronic effects of 1,3-disubstituted cyclopentadienyl ligands on metallocene derivatives of Cerium, Titanium, Manganese, and Iron

Description: Sterically demanding 1,3-disubstituted cyclopentadienyl ligands were used to modify the physical properties of the corresponding metallocenes. Sterically demanding ligands provided kinetic stabilization for trivalent cerium compounds. Tris(di-t-butylcyclopentadienyl)cerium was prepared and anion competition between halides and cyclopentadienyl groups which had complicated synthesis of the tris(cyclopentadienyl)compound was qualitatively examined. Bis(di-t-butylcyclopentadienyl)cerium methyl was prepared and its rate of decomposition, by ligand redistribution, to tris(di-t-butylcyclopentadienyl)cerium was shown to be slower than the corresponding rate for less sterically demanding ligands. Asymmetrically substituted ligands provided a symmetry label for examination of chemical exchange processes. Tris[trimethylsilyl(t-butyl)cyclopentadienyl]cerium was prepared and the rate of interconversion between the C1 and C3 isomers was examined. The enthalpy difference between the two distereomers is 7.0 kJ/mol. The sterically demanding cyclopentadienyl ligands ansa-di-t-butylcyclopentadiene (Me2Si[(Me3C)2C5H3]2), ansa-bis(trimethylsilyl)cyclopentadiene (Me2Si[(Me3Si)2C5H3]2) and tetra-t-butylfulvalene and metallocene derivatives of the ligands were prepared and their structures were examined by single crystal X-ray crystallography. The effect that substituents on the cyclopentadienyl ring have on the pi-electron system of the ligand was examined through interaction between ligand and metal orbitals. A series of 1,3-disubstituted manganocenes was prepared and their electronic states were determined by solid-state magnetic susceptibility, electron paramagnetic resonance, X-ray crystallography, and variable temperature UV-vis spectroscopy. Spin-equilibria in [(Me3C)2C5H3]2Mn and [(Me3C)(Me3Si)C5H3]2Mn were examined and indicate an enthalpy difference of 15 kJ/mol between the high-spin and low-spin forms. Cyclopentadienyl groups resistant to intramolecular oxidative addition allowed isolation of compounds susceptible to intramolecular decomposition. A kinetically stable, base-free titanocene was prepared using di-t-butylcyclopentadienyl ligands and the reactivity of the compound toward small molecules was investigated. The titanocene reacts reversibly with hydrogen to form the titanocene dihydride and the equilibrium in solution between titanocene dihydride, and titanocene and hydrogen, was examined.
Date: May 19, 2000
Creator: Sofield, C.D.
Partner: UNT Libraries Government Documents Department

Magnetization studies of oxides related to the high temperature cuprate superconductors

Description: The magnetic properties related to the following high temperature superconductors were measured utilizing a Faraday magnetometer: BaCuO{sub 2+x}, La{sub 2} CuO{sub 4}, Sr{sub 2} RhO{sub 4}, Sr{sub 2} VO{sub 4}, and Sr{sub 2} CuO{sub 3}. Neutron diffraction, magnetic susceptibility, and heat capacity measurements are discussed.
Date: June 19, 1995
Creator: Wang, Z.
Partner: UNT Libraries Government Documents Department

Sub-micron scale conduction processes on clean surfaces

Description: Electrical conductance has been measured in-situ in two dimensions in the Ag/Si(111) system as a function of incident adatom flux rate with a 4-probe method. A conductance study in a 3-D conical structure was also made using field emission. For the 2-D study, the origin of conduction is still unclear, as transport by percolating Ag clusters and conduction through the substrate lvia electrons from the film have both been suggested. Experiments varying the flux rate were conducted to decide between the two. Smoother films are expected at lower growth rates which would result in faster drops in the 4-probe voltage; however the 4-probe voltage vs deposition time for various flux rates collapse into a universal curve which indicates that the morphology is not relevant and supports through the substrate. In the 3-D conductance study, a single, lateral micromachined W protrusion on a silica substrate is examined to identify the factors controlling emission in micromachined structures. The I-V characteristics and emission pattern indicate that miniprotrusions of a few hundred Angstroms, much smaller than the nominal radius of the tip, exist on the tip and are responsible for the emission. Adsorption-desorption events from the background environment are the cause of large fluctuations in the emitting current. Comparison of the emission of a single tip to gated arrays suggest that only a fraction of the tips in the array are emitting.
Date: June 19, 1995
Creator: Kimberlin, K.
Partner: UNT Libraries Government Documents Department

Oxidation and creep behavior of Mo*5*Si*3* based materials

Description: Mo{sub 5}Si{sub 3} shows promise as a high temperature creep resistant material. The high temperature oxidation resistance of Mo{sub 5}Si{sub 3} has been found to be poor, however, limiting its use in oxidizing atmospheres. Undoped Mo{sub 5}Si{sub 3} exhibits mass loss in the temperature range 800{degrees}-1200{degrees}C due to volatilization of molybdenum oxide, indicating that the silica scale does not provide a passivating layer. The addition of boron results in protective scale formation and parabolic oxidation kinetics in the temperature range of 1050{degrees}-1300{degrees}C. The oxidation rate of Mo{sub 5}Si{sub 3} was decreased by 5 orders of magnitude at 1200{degrees}C by doping with less than two weight percent boron. Boron doping eliminates catastrophic {open_quote}pest{close_quote} oxidation at 800{degrees}C. The mechanism for improved oxidation resistance of boron doped Mo{sub 5}Si{sub 3} is due to scale modification by boron.
Date: June 19, 1995
Creator: Meyer, M.
Partner: UNT Libraries Government Documents Department

New electrolyte systems for capillary zone electrophoresis of metal cations and non-ionic organic compounds

Description: Excellent separations of metal ions can be obtained very quickly by capillary electrophoresis provided a weak complexing reagent is incorporated into the electrolyte to alter the effective mobilities of the sample ions. Indirect photometric detection is possible by also adding a UV-sensitive ion to the electrolyte. Separations are described using phthalate, tartrate, lactate or hydroxyisobutyrate as the complexing reagent. A separation of twenty-seven metal ions was achieved in only 6 min using a lactate system. A mechanism for the separation of lanthanides is proposed for the hydroxyisobutyrate system.
Date: June 19, 1995
Creator: Shi, Y.
Partner: UNT Libraries Government Documents Department

Synthesis and study of novel silicon-based unsaturated polymers

Description: Novel unsaturated polymers have been synthesized and studied as precursors to silicon carbide and third order nonlinear optical materials. X ray structures were obtained. Kinetic and mechanistic studies of the unique thermal isomerization of dimethylenedisilacyclobutane to a carbene were conducted.
Date: June 19, 1995
Creator: Lin, J.
Partner: UNT Libraries Government Documents Department

Development of Chiral LC-MS Methods for small Molecules and Their Applications in the Analysis of Enantiomeric Composition and Pharmacokinetic Studies

Description: The purpose of this research was to develop sensitive LC-MS methods for enantiomeric separation and detection, and then apply these methods for determination of enantiomeric composition and for the study of pharmacokinetic and pharmacodynamic properties of a chiral nutraceutical. Our first study, evaluated the use of reverse phase and polar organic mode for chiral LC-API/MS method development. Reverse phase methods containing high water were found to decrease ionization efficiency in electrospray, while polar organic methods offered good compatibility and low limits of detection with ESI. The use of lower flow rates dramatically increased the sensitivity by an order of magnitude. Additionally, for rapid chiral screening, the coupled Chirobiotic column afforded great applicability for LC-MS method development. Our second study, continued with chiral LC-MS method development in this case for the normal phase mode. Ethoxynonafluorobutane, a fluorocarbon with low flammability and no flashpoint, was used as a substitute solvent for hexane/heptane mobile phases for LC-APCI/MS. Comparable chromatographic resolutions and selectivities were found using ENFB substituted mobile phase systems, although, peak efficiencies were significantly diminished. Limits of detection were either comparable or better for ENFB-MS over heptane-PDA detection. The miscibility of ENFB with a variety of commonly used organic modifiers provided for flexibility in method development. For APCI, lower flow rates did not increase sensitivity as significantly as was previously found for ESI-MS detection. The chiral analysis of native amino acids was evaluated using both APCI and ESI sources. For free amino acids and small peptides, APCI was found to have better sensitivities over ESI at high flow rates. For larger peptides, however, sensitivity was greatly improved with the use of electrospray. Additionally, sensitivity was enhanced with the use of non-volatile additives, This optimized method was then used to simultaneously separate all 19 native amino acids enantiomerically in less than 20 minutes, ...
Date: December 19, 2004
Creator: Desai, Meera Jay
Partner: UNT Libraries Government Documents Department

Microstructural Development in Al-Si Powder During Rapid Solidification

Description: Powder metallurgy has become an increasingly important form of metal processing because of its ability to produce materials with superior mechanical properties. These properties are due in part to the unique and often desirable microstructures which arise as a result of the extreme levels of undercooling achieved, especially in the finest size powder, and the subsequent rapid solidification which occurs. A better understanding of the fundamental processes of nucleation and growth is required to further exploit the potential of rapid solidification processing. Aluminum-silicon, an alloy of significant industrial importance, was chosen as a model for simple eutectic systems displaying an unfaceted/faceted interface and skewed coupled eutectic growth zone, Al-Si powder produced by high pressure gas atomization was studied to determine the relationship between microstructure and alloy composition as a function of powder size and atomization gas. Critical experimental measurements of hypereutectic (Si-rich) compositions were used to determine undercooling and interface velocity, based on the theoretical models which are available. Solidification conditions were analyzed as a function of particle diameter and distance from nucleation site. A revised microstructural map is proposed which allows the prediction of particle morphology based on temperature and composition. It is hoped that this work, by providing enhanced understanding of the processes which govern the development of the solidification morphology of gas atomized powder, will eventually allow for better control of processing conditions so that particle microstructures can be optimized for specific applications.
Date: December 19, 2004
Creator: Genau, Amber Lynn
Partner: UNT Libraries Government Documents Department

Mesoporous Silica Nanomaterials for Applications in Catalysis, Sensing, Drug Delivery and Gene Transfection

Description: The central theme of this dissertation is represented by the versatility of mesoporous silica nanomaterials in various applications such as catalysis and bio-applications, with main focus on biological applications of Mesoporous Silica Nanospheres (MSN). The metamorphosis that we impose to these materials from catalysis to sensing and to drug and gene delivery is detailed in this dissertation. First, we developed a synthetic method that can fine tune the amount of chemically accessible organic functional groups on the pores surface of MSN by exploiting electrostatic and size matching between the cationic alkylammonium head group of the cetyltrimethylammonium bromide (CTAB) surfactant and various anionic organoalkoxysilane precursors at the micelle-water interface in a base-catalyzed condensation reaction of silicate. Aiming nature imitation, we demonstrated the catalytic abilities of the MSNs, We utilized an ethylenediamine functional group for chelating Cu{sup 2+} as a catalytic functional group anchored inside the mesopores. Thus, a polyalkynylene-based conducting polymer (molecular wire) was synthesized within the Cu-functionalized MSNs silica catalyst. For sensing applications, we have synthesized a poly(lactic acid) coated mesoporous silica nanosphere (PLA-MSN) material that serves as a fluorescence sensor system for detection of amino-containing neurotransmitters in neutral aqueous buffer. We exploited the mesoporosity of MSNs for encapsulating pharmaceutical drugs. We examined bio-friendly capping molecules such as polyamidoamine dendrimers of generations G2 to G4, to prevent the drug leaching. Next, the drug delivery system employed MSNs loaded with Doxorubicin, an anticancer drug. The results demonstrated that these nano-Trojan horses have ability to deliver Doxorubicin to cancer cells and induce their death. Finally, to demonstrate the potential of MSN as an universal cellular transmembrane nanovehicle, we anchored positively charged dendrimers on the surface of MSN and utilize them to complex cationic DNA. The p-EGFP-CI gene-coated MSN nanocomposite was able to transfect cancer cell lines, such as human HeLa and CHO ...
Date: December 19, 2005
Creator: Radu, Daniela Rodica
Partner: UNT Libraries Government Documents Department

Quantum Chemistry, and Eclectic Mix: From Silicon Carbide to Size Consistency

Description: Chemistry is a field of great breadth and variety. It is this diversity that makes for both an interesting and challenging field. My interests have spanned three major areas of theoretical chemistry: applications, method development, and method evaluation. The topics presented in this thesis are as follows: (1) a multi-reference study of the geometries and relative energies of four atom silicon carbide clusters in the gas phase; (2) the reaction of acetylene on the Si(100)-(2x1) surface; (3) an improvement to the Effective Fragment Potential (EFP) solvent model to enable the study of reactions in both aqueous and nonaqueous solution; and (4) an evaluation of the size consistency of Multireference Perturbation Theory (MRPT). In the following section, the author briefly discusses two topics central to, and present throughout, this thesis: Multi-reference methods and Quantum Mechanics/Molecular Mechanics (QM/MM) methods.
Date: December 19, 2004
Creator: Rintelman, Jamie Marie
Partner: UNT Libraries Government Documents Department