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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

A Scaled Final Focus Experiment for Heavy Ion Fusion

Description: A one-tenth dimensionally scaled version of a final focus sub-system design for a heavy ion fusion driver is built and tested. By properly scaling the physics parameters that relate particle energy and mass, beam current, beam emittance, and focusing field, the transverse dynamics of a driver scale final focus are replicated in a small laboratory beam. The experiment uses a 95 {micro}A beam of 160 keV Cs{sup +} ions to study the dynamics as the beam is brought to a ballistic focus in a lattice of six quadrupole magnets. Diagnostic stations along the experiment track the evolution of the transverse phase space of the beam. The measured focal spot size is consistent with calculations and the report of the design on which the experiment is based. By uniformly varying the strengths of the focusing fields in the lattice, the chromatic effect of a small energy deviation on the spot size can be reproduced. This is done for {+-}1% and {+-}2% shifts and the changes in the focus are measured. Additionally, a 400 {micro}A beam is propagated through the experiment and partially neutralized after the last magnet using electrons released from a hot tungsten filament. The increase in beam current allows for the observation of significant effects on both the size and shape of the focal spot when the electrons are added.
Date: September 19, 2000
Creator: MacLaren, Stephan, Alexander
Partner: UNT Libraries Government Documents Department

UV-Raman spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption studies of model and bulk heterogeneous catalysts

Description: X-ray photoelectron spectroscopy (XPS) and Temperature Programmed Desorption (TPD) have been used to investigate the surface structure of model heterogeneous catalysts in ultra-high vacuum (UHV). UV-Raman spectroscopy has been used to probe the structure of bulk model catalysts in ambient and reaction conditions. The structural information obtained through UV-Raman spectroscopy has been correlated with both the UHV surface analysis and reaction results. The present day propylene and ethylene polymerization catalysts (Ziegler-Natta catalysts) are prepared by deposition of TiCl{sub 4} and a Al(Et){sub 3} co-catalyst on a microporous Mg-ethoxide support that is prepared from MgCl{sub 2} and ethanol. A model thin film catalyst is prepared by depositing metallic Mg on a Au foil in a UHV chamber in a background of TiCl{sub 4} in the gas phase. XPS results indicate that the Mg is completely oxidized to MgCl{sub 2} by TiCl{sub 4} resulting in a thin film of MgCl{sub 2}/TiCl{sub x}, where x = 2, 3, and 4. To prepare an active catalyst, the thin film of MgCl{sub 2}/TiCl{sub x} on Au foil is enclosed in a high pressure cell contained within the UHV chamber and exposed to {approx}1 Torr of Al(Et){sub 3}.
Date: August 19, 2002
Creator: Tewell, Craig R.
Partner: UNT Libraries Government Documents Department

Low energy electron diffraction (LEED) and sum frequency generation (SFG) vibrational spectroscopy studies of solid-vacuum, solid-air and solid-liquid interfaces

Description: Electron based surface probing techniques can provide detailed information about surface structure or chemical composition in vacuum environments. The development of new surface techniques has made possible in situ molecular level studies of solid-gas interfaces and more recently, solid-liquid interfaces. The aim of this dissertation is two-fold. First, by using novel sample preparation, Low Energy Electron Diffraction (LEED) and other traditional ultra high vacuum (UHV) techniques are shown to provide new information on the insulator/vacuum interface. The surface structure of the classic insulator NaCl has been determined using these methods. Second, using sum frequency generation (SFG) surface specific vibrational spectroscopy studies were performed on both the biopolymer/air and electrode/electrolyte interfaces. The surface structure and composition of polyetherurethane-silicone copolymers were determined in air using SFG, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). SFG studies of the electrode (platinum, gold and copper)/electrolyte interface were performed as a function of applied potential in an electrochemical cell.
Date: August 19, 2002
Creator: Hoffer, Saskia
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

Chromatographic Separations of Enantiomers and Underivatized Oligosaccharides

Description: My graduate research has focused on separation science and bioanalytical analysis, which emphasized in method development. It includes three major areas: enantiomeric separations using high performance liquid chromatography (HPLC), Super/subcritical fluid chromatography (SFC), and capillary electrophoresis (CE); drug-protein binding behavior studies using CE; and carbohydrate analysis using liquid chromatograph-electrospray ionization mass spectrometry (LC-ESI-MS). Enantiomeric separations continue to be extremely important in the pharmaceutical industry. An in-depth evaluation of the enantiomeric separation capabilities of macrocyclic glycopeptides CSPs with SFC mobile phases was investigated using a set of over 100 chiral compounds. It was found that the macrocyclic based CSPs were able to separate enantiomers of various compounds with different polarities and functionalities. Seventy percent of all separations were achieved in less than 4 min due to the high flow rate (4.0 ml/min) that can be used in SFC. Drug-protein binding is an important process in determining the activity and fate of a drug once it enters the body. Two drug/protein systems have been studied using frontal analysis CE method. More sensitive fluorescence detection was introduced in this assay, which overcame the problem of low sensitivity that is common when using UV detection for drug-protein studies. In addition, the first usage of an argon ion laser with 257 nm beam coupled with CCD camera as a frontal analysis detection method enabled the simultaneous observation of drug fluorescence as well as the protein fluorescence. LC-ESI-MS was used for the separation and characterization of underivatized oligosaccharide mixtures. With the limits of detection as low as 50 picograms, all individual components of oligosaccharide mixtures (up to 11 glucose-units long) were baseline resolved on a Cyclobond I 2000 column and detected using ESI-MS. This system is characterized by high chromatographic resolution, high column stability, and high sensitivity. In addition, this method showed potential usefulness for the ...
Date: December 19, 2004
Creator: Liu, Ying
Partner: UNT Libraries Government Documents Department

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

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

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

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

Photoemission Study of the Rare Earth Intermetallic Compounds: RNi2Ge2 (R=Eu, Gd)

Description: EuNi{sub 2}Ge{sub 2} and GdNi{sub 2}Ge{sub 2} are two members of the RT{sub 2}X{sub 2} (R = rare earth, T = transition metal and X = Si, Ge) family of intermetallic compounds, which has been studied since the early 1980s. These ternary rare-earth intermetallic compounds with the tetragonal ThCr{sub 2}Si{sub 2} structure are known for their wide variety of magnetic properties, Extensive studies of the RT{sub 2}X{sub 2} series can be found in Refs [ 1,2,3]. The magnetic properties of the rare-earth nickel germanides RNi{sub 2}Ge{sub 2} were recently studied in more detail [4]. The purpose of this dissertation is to investigate the electronic structure (both valence band and shallow core levels) of single crystals of EuNi{sub 2}Ge{sub 2} and GdNi{sub 2}Ge{sub 2} and to check the assumptions that the f electrons are non-interacting and, consequently, the rigid-band model for these crystals would work [11], using synchrotron radiation because, to the best of our knowledge, no photoemission measurements on those have been reported. Photoemission spectroscopy has been widely used to study the detailed electronic structure of metals and alloys, and especially angle-resolved photoemission spectroscopy (ARPES) has proven to be a powerful technique for investigating Fermi surfaces (FSs) of single-crystal compounds.
Date: December 19, 2004
Creator: Park, Jongik
Partner: UNT Libraries Government Documents Department

A Performance Comparison of Tree and Ring Topologies in Distributed System

Description: A distributed system is a collection of computers that are connected via a communication network. Distributed systems have become commonplace due to the wide availability of low-cost, high performance computers and network devices. However, the management infrastructure often does not scale well when distributed systems get very large. Some of the considerations in building a distributed system are the choice of the network topology and the method used to construct the distributed system so as to optimize the scalability and reliability of the system, lower the cost of linking nodes together and minimize the message delay in transmission, and simplify system resource management. We have developed a new distributed management system that is able to handle the dynamic increase of system size, detect and recover the unexpected failure of system services, and manage system resources. The topologies used in the system are the tree-structured network and the ring-structured network. This thesis presents the research background, system components, design, implementation, experiment results and the conclusions of our work. The thesis is organized as follows: the research background is presented in chapter 1. Chapter 2 describes the system components, including the different node types and different connection types used in the system. In chapter 3, we describe the message types and message formats in the system. We discuss the system design and implementation in chapter 4. In chapter 5, we present the test environment and results, Finally, we conclude with a summary and describe our future work in chapter 6.
Date: December 19, 2005
Creator: Huang, Min
Partner: UNT Libraries Government Documents Department

Phase Transformations in Cast Duplex Stainless Steels

Description: Duplex stainless steels (DSS) constitute both ferrite and austenite as a matrix. Such a microstructure confers a high corrosion resistance with favorable mechanical properties. However, intermetallic phases such as {sigma} and {chi} can also form during casting or high-temperature processing and can degrade the properties of the DSS. This research was initiated to develop time-temperature-transformation (TTT) and continuous-cooling-transformation (CCT) diagrams of two types of cast duplex stainless steels, CD3MN (Fe-22Cr-5Ni-Mo-N) and CD3MWCuN (Fe-25Cr-7Ni-Mo-W-Cu-N), in order to understand the time and temperature ranges for intermetallic phase formation. The alloys were heat treated isothermally or under controlled cooling conditions and then characterized using conventional metallographic methods that included tint etching, and also using electron microscopy (SEM, TEM) and wavelength dispersive spectroscopy (WDS). The kinetics of intermetallic-phase ({sigma} + {chi}) formation were analyzed using the Johnson-Mehl-Avrami (MA) equation in the case of isothermal transformations and a modified form of this equation in the case of continuous cooling transformations. The rate of intermetallic-phase formation was found to be much faster in CD3MWCuN than CD3MN due mainly to differences in the major alloying contents such as Cr, Ni and Mo. To examine in more detail the effects of these elements of the phase stabilities; a series of eight steel castings was designed with the Cr, Ni and Mo contents systematically varied with respect to the nominal composition of CD3MN. The effects of varying the contents of alloying additions on the formation of intermetallic phases were also studied computationally using the commercial thermodynamic software package, Thermo-Calc. In general, {sigma} was stabilized with increasing Cr addition and {chi} by increasing Mo addition. However, a delicate balance among Ni and other minor elements such as N and Si also exists. Phase equilibria in DSS can be affected by local composition fluctuations in the cast alloy. This may cause ...
Date: December 19, 2004
Creator: Kim, Yoon-Jun
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

Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

Description: In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl{sub 2} (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh), with aromatic aldehydes or aryl ketones resulted in reductive coupling of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph){sub 2}C(Ph){sub 2}O] to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and {alpha}-hydroxy ketones to benzaldehyde and {alpha}-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of products, including mono-, bis-alkoxo, and chelating diolato complexes, depending on the identity of diols and the stoichiometry employed. It was also found that tin porphyrin complexes promoted the oxidative cleavage of vicinal diols and the oxidation ...
Date: December 19, 2004
Creator: Du, Guodong
Partner: UNT Libraries Government Documents Department

Drama in Dynamics: Boom, Splash, and Speed

Description: The full nature of chemistry and physics cannot be captured by static calculations alone. Dynamics calculations allow the simulation of time-dependent phenomena. This facilitates both comparisons with experimental data and the prediction and interpretation of details not easily obtainable from experiments. Simulations thus provide a direct link between theory and experiment, between microscopic details of a system and macroscopic observed properties. Many types of dynamics calculations exist. The most important distinction between the methods and the decision of which method to use can be described in terms of the size and type of molecule/reaction under consideration and the type and level of accuracy required in the final properties of interest. These considerations must be balanced with available computational codes and resources as simulations to mimic ''real-life'' may require many time steps. As indicated in the title, the theme of this thesis is dynamics. The goal is to utilize the best type of dynamics for the system under study while trying to perform dynamics in the most accurate way possible. As a quantum chemist, this involves some level of first principles calculations by default. Very accurate calculations of small molecules and molecular systems are now possible with relatively high-level ab initio quantum chemistry. For example, a quantum chemical potential energy surface (PES) can be developed ''on-the-fly'' with dynamic reaction path (DRP) methods. In this way a classical trajectory is developed without prior knowledge of the PES. In order to treat solvation processes and the condensed phase, large numbers of molecules are required, especially in predicting bulk behavior. The Effective Fragment Potential (EFP) method for solvation decreases the cost of a fully quantum mechanical calculation by dividing a chemical system into an ab initio region that contains the solute and an ''effective fragment'' region that contains the remaining solvent molecules. But, despite ...
Date: December 19, 2004
Creator: Netzloff, Heather Marie
Partner: UNT Libraries Government Documents Department

Hole Burning Imaging Studies of Cancerous and Analogous Normal Ovarian Tissues Utilizing Organelle Specific Dyes

Description: Presented in this dissertation is the successful demonstration that nonphotochemical hole burning (NPWB) imaging can be used to study in vitro tissue cellular systems for discerning differences in cellular ultrastructures due to cancer development. This has been accomplished with the surgically removed cancerous ovarian and analogous normal peritoneal tissues from the same patient and the application of a fluorescent mitochondrion specific dye, Molecular Probe MitoFluor Far Red 680 (MF680), commonly known as rhodamine 800, that has been proven to exhibit efficient NPHB. From the results presented in Chapters 4 and 5 , and Appendix B, the following conclusions were made: (1) fluorescence excitation spectra of MF680 and confocal microscopy images of thin sliced tissues incubated with MF680 confirm the site-specificity of the probe molecules in the cellular systems. (2) Tunneling parameters, {lambda}{sub 0} and {sigma}{sub {lambda}}, as well as the standard hole burning parameters (namely, {gamma} and S), have been determined for the tissue samples by hole growth kinetics (HGK) analyses. Unlike the preliminary cultured cell studies, these parameters have not shown the ability to distinguish tissue cellular matrices surrounding the chromophores. (3) Effects of an external electric (Stark) field on the nonphotochemical holes have been used to determine the changes in permanent dipole moment (f{Delta}{mu}) for MF680 in tissue samples when burn laser polarization is parallel to the Stark field. Differences are detected between f{Delta}{mu}s in the two tissue samples, with the cancerous tissue exhibiting a more pronounced change (1.35-fold increase) in permanent dipole moment change relative to the normal analogs. It is speculated that the difference may be related to differences in mitochondrial membrane potentials in these tissue samples. (4) In the HGK mode, hole burning imaging (HBI) of cells adhered to coverslips and cooled to liquid helium temperatures in the complete absence of cryopreservatives, shows the ability ...
Date: December 19, 2004
Creator: Matsuzaki, Satoshi
Partner: UNT Libraries Government Documents Department

Gas Sensors Based on Ceramic p-n Heterocontacts

Description: Ceramic p-n heterocontacts based on CuO/ZnO were successfully synthesized and a systematic study of their hydrogen sensitivity was conducted. The sensitivity and response rates of CuO/ZnO sensors were studied utilizing current-voltage, current-time, and impedance spectroscopy measurements. The heterocontacts showed well-defined rectifying characteristics and were observed to detect hydrogen via both dc and ac measurements. Surface coverage data were derived from current-time measurements which were then fit to a two-site Langmuir adsorption model quite satisfactorily. The fit suggested that there should be two energetically different adsorption sites in the system. The heterocontacts were doped in an attempt to increase the sensitivity and the response rate of the sensor. First, the effects of doping the p-type (CuO) on the sensor characteristics were investigated. Doping the p-type CuO with both acceptor and isovalent dopants greatly improved the hydrogen sensitivity. The sensitivity of pure heterocontact observed via I-V measurements was increased from {approx}2.3 to {approx}9.4 with Ni doping. Dopants also enhanced the rectifying characteristics of the heterocontacts. Small amounts of Li addition were shown to decrease the reverse bias (saturation) current to 0.2 mA at a bias level of -5V. No unambiguous trends were observed between the sensitivity, the conductivity, and the density of the samples. Comparing the two phase microstructure to the single phase microstructure there was no dramatic increase in the sensitivity. Kinetic studies also confirmed the improved sensor characteristics with doping. The dopants decreased the response time of the sensor by decreasing the response time of one of the adsorption sites. The n-type ZnO was doped with both acceptor and donor dopants. Li doping resulted in the degradation of the p-n junction and the response time of the sensor. However, the current-voltage behavior of Ga-doped heterocontacts showed the best rectifying characteristics with very high forward currents. Ga doped heterocontacts showed the ...
Date: December 19, 2004
Creator: Aygun, Seymen Murat
Partner: UNT Libraries Government Documents Department

Gas-Solid Displacement Reactions for Converting Silica Diatom Frustules into MgO and TiO2

Description: Technology for the microfabrication of freely moving parts began with a Bell Labs microgear spun by an air jet, and electrostatic silicon micro motors in the mid-1980s. It continued with development work on micropositioning of optics, miniature heat exchangers, small fluidic devices, and chemical reaction chambers. Recently, there has been a great deal of interest centered on the design and manufacture of devices of nanometer proportions and this speculation has spawned a new industry named, nanotechnology. Despite the technological and economic promise of this technology, current commercial micro/mesofabrication methods have largely been based upon two-dimensional processing principles which is not well suited to the low-cost mass production of three-dimensional micro devices with complex geometries and meso/nanoscale features. Diatoms are three dimensional (3D) microstructures from nature that provide a practical alternative for nanotechnology and microfabrication. Diatoms (Figure 1) are single-celled micro algae that form rigid cell walls (frustules) composed of amorphous silica. Their dimensions can range from less than 1 micron to several hundreds of microns. They are distributed throughout the world in aquatic, semi-aquatic and moist habitats, and extremely abundant in freshwater and marine ecosystems. Diatoms are thought to be responsible for up to 25% of the world's net primary production of organic carbon (by transforming of carbon dioxide and water into sugars by photosynthesis). Approximately 10{sup 5} unique diatom frustule shapes have been claimed to exist in nature. The frustules are composed of two valves that fit together like a petri-dish, connected to each other by one or more girdle bands. The frustule wall consists of a nanoporous assembly of silica nanoparticles. They absorb soluble silica from water even at extremely low concentrations and metabolize and deposit it as an external skeleton. Continued reproduction of a single parent diatom can yield large numbers of descendant diatoms, each of which ...
Date: December 19, 2004
Creator: Kalem, Tugba
Partner: UNT Libraries Government Documents Department

Oxidation Behavior and Chlorination Treatment to Improve Oxidation Resistance of Nb-Mo-Si-B Alloys

Description: This thesis is written in an alternate format. The thesis is composed of a general introduction, two original manuscripts, and a general conclusion. References cited within each chapter are given at the end of each chapter. The general introduction starts with the driving force behind this research, and gives an overview of previous work on boron doped molybdenum silicides, Nb/Nb{sub 5}Si{sub 3} composites, boron modified niobium silicides and molybdenum niobium silicides. Chapter 2 focuses on the oxidation behavior of Nb-Mo-Si-B alloys. Chapter 3 contains studies on a novel chlorination technique to improve the oxidation resistance of Nb-Mo-Si-B alloys. Chapter 4 summarizes the important results in this study.
Date: December 19, 2004
Creator: Behrani, Vikas
Partner: UNT Libraries Government Documents Department

Performance Study and Dynamic Optimization Design for Thread Pool Systems

Description: Thread pools have been widely used by many multithreaded applications. However, the determination of the pool size according to the application behavior still remains problematic. To automate this process, in this thesis we have developed a set of performance metrics for quantitatively analyzing thread pool performance. For our experiments, we built a thread pool system which provides a general framework for thread pool research. Based on this simulation environment, we studied the performance impact brought by the thread pool on different multithreaded applications. Additionally, the correlations between internal characterizations of thread pools and their throughput were also examined. We then proposed and evaluated a heuristic algorithm to dynamically determine the optimal thread pool size. The simulation results show that this approach is effective in improving overall application performance.
Date: December 19, 2004
Creator: Xu, Dongping
Partner: UNT Libraries Government Documents Department

Development of colorimetric solid Phase Extraction (C-SPE) for in-flight Monitoring of spacecraft Water Supplies

Description: Although having recently been extremely successful gathering data on the surface of Mars, robotic missions are not an effective substitute for the insight and knowledge about our solar system that can be gained though first-hand exploration. Earlier this year, President Bush presented a ''new course'' for the U.S. space program that shifts NASA's focus to the development of new manned space vehicles to the return of humans to the moon. Re-establishing the human presence on the moon will eventually lead to humans permanently living and working in space and also serve as a possible launch point for missions into deeper space. There are several obstacles to the realization of these goals, most notably the lack of life support and environmental regeneration and monitoring hardware capable of functioning on long duration spaceflight. In the case of the latter, past experience on the International Space Station (ISS), Mir, and the Space Shuttle has strongly underscored the need to develop broad spectrum in-flight chemical sensors that: (1) meet current environmental monitoring requirements on ISS as well as projected requirements for future missions, and (2) enable the in-situ acquisition and analysis of analytical data in order to further define on-orbit monitoring requirements. Additionally, systems must be designed to account for factors unique to on-orbit deployment such as crew time availability, payload restrictions, material consumption, and effective operation in microgravity. This dissertation focuses on the development, ground testing, and microgravity flight demonstration of Colorimetric Solid Phase Extraction (C-SPE) as a candidate technology to meet the near- and long-term water quality monitoring needs of NASA. The introduction will elaborate further on the operational and design requirements for on-orbit water quality monitoring systems by discussing some of the characteristics of an ''ideal'' system. A description of C-SPE and how the individual components of the platform are combined ...
Date: December 19, 2004
Creator: Gazda, Daniel Bryan
Partner: UNT Libraries Government Documents Department