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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

Nanostructured Solid Oxide Fuel Cell Electrodes

Description: The ability of Solid Oxide Fuel Cells (SOFC) to directly and efficiently convert the chemical energy in hydrocarbon fuels to electricity places the technology in a unique and exciting position to play a significant role in the clean energy revolution. In order to make SOFC technology cost competitive with existing technologies, the operating temperatures have been decreased to the range where costly ceramic components may be substituted with inexpensive metal components within the cell and stack design. However, a number of issues have arisen due to this decrease in temperature: decreased electrolyte ionic conductivity, cathode reaction rate limitations, and a decrease in anode contaminant tolerance. While the decrease in electrolyte ionic conductivities has been countered by decreasing the electrolyte thickness, the electrode limitations have remained a more difficult problem. Nanostructuring SOFC electrodes addresses the major electrode issues. The infiltration method used in this dissertation to produce nanostructure SOFC electrodes creates a connected network of nanoparticles; since the method allows for the incorporation of the nanoparticles after electrode backbone formation, previously incompatible advanced electrocatalysts can be infiltrated providing electronic conductivity and electrocatalysis within well-formed electrolyte backbones. Furthermore, the method is used to significantly enhance the conventional electrode design by adding secondary electrocatalysts. Performance enhancement and improved anode contamination tolerance are demonstrated in each of the electrodes. Additionally, cell processing and the infiltration method developed in conjunction with this dissertation are reviewed.
Date: December 15, 2007
Creator: Sholklapper, Tal Zvi
Partner: UNT Libraries Government Documents Department

Control of Laser Plasma Based Accelerators up to 1 GeV

Description: This dissertation documents the development of a broadband electron spectrometer (ESM) for GeV class Laser Wakefield Accelerators (LWFA), the production of high quality GeV electron beams (e-beams) for the first time in a LWFA by using a capillary discharge guide (CDG), and a statistical analysis of CDG-LWFAs. An ESM specialized for CDG-LWFAs with an unprecedented wide momentum acceptance, from 0.01 to 1.1 GeV in a single shot, has been developed. Simultaneous measurement of e-beam spectra and output laser properties as well as a large angular acceptance (> {+-} 10 mrad) were realized by employing a slitless scheme. A scintillating screen (LANEX Fast back, LANEX-FB)--camera system allowed faster than 1 Hz operation and evaluation of the spatial properties of e-beams. The design provided sufficient resolution for the whole range of the ESM (below 5% for beams with 2 mrad divergence). The calibration between light yield from LANEX-FB and total charge, and a study on the electron energy dependence (0.071 to 1.23 GeV) of LANEX-FB were performed at the Advanced light source (ALS), Lawrence Berkeley National Laboratory (LBNL). Using this calibration data, the developed ESM provided a charge measurement as well. The production of high quality electron beams up to 1 GeV from a centimeter-scale accelerator was demonstrated. The experiment used a 310 {micro}m diameter gas-filled capillary discharge waveguide that channeled relativistically-intense laser pulses (42 TW, 4.5 x 10{sup 18} W/cm{sup 2}) over 3.3 centimeters of sufficiently low density ({approx_equal} 4.3 x 10{sup 18}/cm{sup 3}) plasma. Also demonstrated was stable self-injection and acceleration at a beam energy of {approx_equal} 0.5 GeV by using a 225 {micro}m diameter capillary. Relativistically-intense laser pulses (12 TW, 1.3 x 10{sup 18}W/cm{sup 2}) were guided over 3.3 centimeters of low density ({approx_equal} 3.5 x 10{sup 18}/cm{sup 3}) plasma in this experiment. A statistical analysis of the CDG-LWFAs ...
Date: December 3, 2007
Creator: Nakamura, Kei
Partner: UNT Libraries Government Documents Department

M5Si3(M=Ti, Nb, Mo) Based Transition-Metal Silicides for High Temperature Applications

Description: Transition metal silicides are being considered for future engine turbine components at temperatures up to 1600 C. Although significant improvement in high temperature strength, room temperature fracture toughness has been realized in the past decade, further improvement in oxidation resistance is needed. Oxidation mechanism of Ti{sub 5}Si{sub 3}-based alloys was investigated. Oxidation behavior of Ti{sub 5}Si{sub 3}-based alloy strongly depends on the atmosphere. Presence of Nitrogen alters the oxidation behavior of Ti{sub 5}Si{sub 3} by nucleation and growth of nitride subscale. Ti{sub 5}Si{sub 3.2} and Ti{sub 5}Si{sub 3}C{sub 0.5} alloys exhibited an excellent oxidation resistance in nitrogen bearing atmosphere due to limited dissolution of nitrogen and increased Si/Ti activity ratio. MoSi{sub 2} coating developed by pack cementation to protect Mo-based Mo-Si-B composites was found to be effective up to 1500 C. Shifting coating composition to T1+T2+Mo{sub 3}Si region showed the possibility to extend the coating lifetime above 1500 C by more than ten times via formation of slow growing Mo{sub 3}Si or T2 interlayer without sacrificing the oxidation resistance of the coating. The phase equilibria in the Nb-rich portion of Nb-B system has been evaluated experimentally using metallographic analysis and differential thermal analyzer (DTA). It was shown that Nb{sub ss} (solid solution) and NbB are the only two primary phases in the 0-40 at.% B composition range, and the eutectic reaction L {leftrightarrow} Nb{sub SS} + NbB was determined to occur at 2104 {+-} 5 C by DTA.
Date: December 1, 2007
Creator: Tang, Zhihong
Partner: UNT Libraries Government Documents Department

A Search for the Higgs Boson in its Associated Production with a W Vector Boson in p anti-p Collisions at s**(1/2) = 1.96-TeV

Description: We present the results of a search for the Standard Model Higgs boson in its associated production with a W vector boson in p{bar p} collisions at {radical}s = 1.96 TeV using the complete Run IIA dataset with an integrated luminosity of 1.04 fb{sup -1} collected by the D0 experiment. The salient features of this analysis are the extended geometric acceptance by including the pseudorapidity covered by the end cap calorimeter, optimization in b-tagging and event selection criteria. We observe very good agreement in the data compared to the expectation form the modeling of Standard Model background for the WH signal. No excess events in data are observed over the predicted background. We establish that the evidence for observing the Higgs boson in this channel is inconclusive and proceed to set upper cross section limits on the associated WH production at 95% confidence level. We derive the cross section upper limits for the Higgs mass (m{sub H}) ranging from 105 GeV/c{sup 2} to 145 GeV/c{sup 2}. For m{sub H} = 115 GeV/c{sup 2}, the observed (expected) upper limit is 0.8 (0.9) pb compared to the Standard Model expectation of 0.13 pb.
Date: December 1, 2007
Creator: Kaushik, Venkatesh S. & /Texas U., Arlington
Partner: UNT Libraries Government Documents Department

Bayesian based design of real-time sensor systems for high-risk indoor contaminants

Description: The sudden release of toxic contaminants that reach indoor spaces can be hazardousto building occupants. To respond effectively, the contaminant release must be quicklydetected and characterized to determine unobserved parameters, such as release locationand strength. Characterizing the release requires solving an inverse problem. Designinga robust real-time sensor system that solves the inverse problem is challenging becausethe fate and transport of contaminants is complex, sensor information is limited andimperfect, and real-time estimation is computationally constrained.This dissertation uses a system-level approach, based on a Bayes Monte Carloframework, to develop sensor-system design concepts and methods. I describe threeinvestigations that explore complex relationships among sensors, network architecture,interpretation algorithms, and system performance. The investigations use data obtainedfrom tracer gas experiments conducted in a real building. The influence of individual sensor characteristics on the sensor-system performance for binary-type contaminant sensors is analyzed. Performance tradeoffs among sensor accuracy, threshold level and response time are identified; these attributes could not be inferred without a system-level analysis. For example, more accurate but slower sensors are found to outperform less accurate but faster sensors. Secondly, I investigate how the sensor-system performance can be understood in terms of contaminant transport processes and the model representation that is used to solve the inverse problem. The determination of release location and mass are shown to be related to and constrained by transport and mixing time scales. These time scales explain performance differences among different sensor networks. For example, the effect of longer sensor response times is comparably less for releases with longer mixing time scales. The third investigation explores how information fusion from heterogeneous sensors may improve the sensor-system performance and offset the need for more contaminant sensors. Physics- and algorithm-based frameworks are presented for selecting and fusing information from noncontaminant sensors. The frameworks are demonstrated with door-position sensors, which are found to ...
Date: December 1, 2007
Creator: Sreedharan, Priya & Sreedharan, Priya
Partner: UNT Libraries Government Documents Department

Analysis of Protein-RNA and Protein-Peptide Interactions in Equine Infectious Anemia

Description: Macromolecular interactions are essential for virtually all cellular functions including signal transduction processes, metabolic processes, regulation of gene expression and immune responses. This dissertation focuses on the characterization of two important macromolecular interactions involved in the relationship between Equine Infectious Anemia Virus (EIAV) and its host cell in horse: (1) the interaction between the EIAV Rev protein and its binding site, the Rev-responsive element (RRE) and (2) interactions between equine MHC class I molecules and epitope peptides derived from EIAV proteins. EIAV, one of the most divergent members of the lentivirus family, has a single-stranded RNA genome and carries several regulatory and structural proteins within its viral particle. Rev is an essential EIAV regulatory encoded protein that interacts with the viral RRE, a specific binding site in the viral mRNA. Using a combination of experimental and computational methods, the interactions between EIAV Rev and RRE were characterized in detail. EIAV Rev was shown to have a bipartite RNA binding domain contain two arginine rich motifs (ARMs). The RRE secondary structure was determined and specific structural motifs that act as cis-regulatory elements for EIAV Rev-RRE interaction were identified. Interestingly, a structural motif located in the high affinity Rev binding site is well conserved in several diverse lentiviral genoes, including HIV-1. Macromolecular interactions involved in the immune response of the horse to EIAV infection were investigated by analyzing complexes between MHC class I proteins and epitope peptides derived from EIAV Rev, Env and Gag proteins. Computational modeling results provided a mechanistic explanation for the experimental finding that a single amino acid change in the peptide binding domain of the quine MHC class I molecule differentially affectes the recognitino of specific epitopes by EIAV-specific CTL. Together, the findings in this dissertation provide novel insights into the strategy used by EIAV to replicate itself, ...
Date: December 1, 2007
Creator: Lee, Jae-Hyung
Partner: UNT Libraries Government Documents Department

Controlled Dissolution of Surface Layers for Elemental Analysis by Inductively Coupled Plasma-Mass Spectrometry

Description: Determining the composition of thin layers is increasingly important for a variety of industrial materials such as adhesives, coatings and microelectronics. Secondary ion mass spectrometry (SIMS), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), glow discharge optical emission spectroscopy (GDOES), glow discharge mass spectrometry (GDMS), and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) are some of the techniques that are currently employed for the direct analysis of the sample surface. Although these techniques do not suffer from the contamination problems that often plague sample dissolution studies, they do require matrix matched standards for quantification. Often, these standards are not readily available. Despite the costs of clean hoods, Teflon pipette tips and bottles, and pure acids, partial sample dissolution is the primary method used in the semiconductor industry to quantify surface impurities. Specifically, vapor phase decomposition (VPD) coupled to ICP-MS or total reflection x-ray fluorescence (TXRF) provides elemental information from the top most surface layers at detection sensitivities in the 10{sup 7}-10{sup 10}atoms/cm{sup 2} range. The ability to quantify with standard solutions is a main advantage of these techniques. Li and Houk applied a VPD-like technique to steel. The signal ratio of trace element to matrix element was used for quantification. Although controlled dissolution concentrations determined for some of the dissolved elements agreed with the certified values, concentrations determined for refractory elements (Ti, Nb and Ta) were too low. LA-ICP-MS and scanning electron microscopy (SEM) measurements indicated that carbide grains distributed throughout the matrix were high in these refractory elements. These elements dissolved at a slower rate than the matrix element, Fe. If the analyte element is not removed at a rate similar to the matrix element a true representation of the sample layer cannot be realized. Specifically, the ratio of analyte signal to matrix element signal does not equal the actual ...
Date: December 1, 2007
Creator: Lorge, Susan Elizabeth
Partner: UNT Libraries Government Documents Department

Improving Hardness and Toughness of Boride Composites Based on AIMgB14

Description: The search for new super-hard materials has usually focused on strongly bonded, highly symmetric crystal structures similar to diamond. The two hardest single-phase materials, diamond and cubic boron nitride (cBN), are metastable, and both must be produced at high temperatures and pressures, which makes their production costly. In 2000, a superhard composite based on a low-symmetry, boron-rich compound was reported. Since then, many advances have been made in the study of this AlMgB{sub 14}-TiB{sub 2} composite. The composite has been shown to exhibit hardness greater than either of its constituent phases, relying on its sub-micron microstructure to provide hardening and strengthening mechanisms. With possible hardness around 40 GPa, an AlMgB{sub 14} - 60 vol% TiB{sub 2} approaches the hardness of cBN, yet is amenable to processing under ambient pressure conditions. There are interesting aspects of both the AlMgB{sub 14} and TiB{sub 2} phases. AlMgB{sub 14} is comprised of a framework of boron, mostly in icosahedral arrangements. It is part of a family of 12 known compounds with the same boron lattice, with the metal atoms replaced by Li, Na, Y or a number of Lanthanides. Another peculiar trait of this family of compounds is that every one contains a certain amount of intrinsic vacancies on one or both of the metal sites. These vacancies are significant, ranging from 3 to 43% of sites depending on the composition. TiB{sub 2} is a popular specialty ceramic material due to its high hardness, moderate toughness, good corrosion resistance, and high thermal and electrical conductivity. The major drawback is the difficulty of densification of pure TiB2 ceramics. A combination of sintering aids, pressure, and temperatures of 1800 C are often required to achieve near full density articles. The AlMgB{sub 14} - TiB{sub 2} composites can achieve 99% density from hot-pressing at 1400 C. This ...
Date: December 1, 2007
Creator: Peters, Justin Steven
Partner: UNT Libraries Government Documents Department

The Study of Electromagnetic Wave Propogation in Photonic Crystals Via Planewave Based Transfer (Scattering) Matrix Method with Active Gain Material Applications

Description: In this dissertation, a set of numerical simulation tools are developed under previous work to efficiently and accurately study one-dimensional (1D), two-dimensional(2D), 2D slab and three-dimensional (3D) photonic crystal structures and their defects effects by means of spectrum (transmission, reflection, absorption), band structure (dispersion relation), and electric and/or magnetic fields distribution (mode profiles). Furthermore, the lasing property and spontaneous emission behaviors are studied when active gain materials are presented in the photonic crystal structures. Various physical properties such as resonant cavity quality factor, waveguide loss, propagation group velocity of electromagnetic wave and light-current curve (for lasing devices) can be obtained from the developed software package.
Date: December 1, 2007
Creator: LI, Ming
Partner: UNT Libraries Government Documents Department

Thermosetting Polymer-Matrix Composites for Strucutral Repair Applications

Description: Several classes of thermosetting polymer matrix composites were evaluated for use in structural repair applications. Initial work involved the characterization and evaluation of woven carbon fiber/epoxy matrix composites for structural pipeline repair. Cyanate ester resins were evaluated as a replacement for epoxy in composites for high-temperature pipe repair applications, and as the basis for adhesives for resin infusion repair of high-temperature composite materials. Carbon fiber/cyanate ester matrix composites and fumed silica/cyanate ester nanocomposites were evaluated for their thermal, mechanical, viscoelastic, and rheological properties as they relate to their structure, chemistry, and processing characteristics. The bisphenol E cyanate ester under investigation possesses a high glass transition temperature, excellent mechanical properties, and unique ambient temperature processability. The incorporate of fumed silica served to enhance the mechanical and rheological properties of the polymer and reduce thermal expansion without sacrificing glass transition or drastically altering curing kinetics. Characterization of the composites included dynamic mechanical analysis, thermomechanical analysis, differential scanning calorimetry, thermogravimetric analysis, rheological and rheokinetic evaluation, and transmission electron microscopy.
Date: December 1, 2007
Creator: Goertzen, William Kirby
Partner: UNT Libraries Government Documents Department

Mechanisms Associated with Rumpling of Pt-Modified Beta-NiAl Coatings

Description: The formation of surface undulations (i.e. rumpling) at the bond coat/thermally grown oxide (TGO) interface has been shown to cause failure by spallation of the ceramic top coat in aero-turbine systems. Many mechanisms have been proposed concerning the cause of these surface distortions; however, there is little agreement on what may be the dominating cause of the rumpling behavior. Of there mechanisms, the reversible phase transformation from a cubic {beta}-NiAl structure to a face centered tetragonal (FCT) martensitic phase was of particular interest because of its ability to form surface rumpling in Pt-modified {beta} bulk alloys. However, the bulk alloys used in obtaining that result were simple ternary systems and not relevant to actual coating compositions as other alloying elements enter the coating due to coating/substrate interdiffusion at high temperature. In the current study, the depletion behavior of a commercial coating was studied. Compositions from the depletion path were determined and bulk alloys representing these coating compositions were prepared. The martensitic phase transformation was then characterized using DSC and XRD. The martensitic start temperature on cooling, Ms, was consistently found to be significantly lower than previously reported values (e.g. 530 C vs 100 C). Because of the low Ms temperature, the formation of the martensitic phase was concluded to be unnecessary for the occurrence of rumpling. However, cyclic exposure treatments at low temperature ({approx} 400 C) of bulk alloys and commercial coatings did show the detrimental effects of the phase transformation in the form of crack formation and propagation leading to eventual failure of the alloys. The current work also infers that the differences in coefficient of thermal expansion (CTE) mismatch between the coating and substrate are the dominating factor leading to rumpling. Dilatometry measurements were made on bulk alloys representing depleted coatings and the superalloy substrate to determine CTE ...
Date: December 1, 2007
Creator: Henderkott, Joseph Peter
Partner: UNT Libraries Government Documents Department

NMR Studies of the Vanadium Spin Dynamics and Spin Structure in LiV2O4, CaV2O4, and (LixV1-x)3BO5 (x is almost equal to 0.33, 0.40)

Description: Strong electron correlation is believed to be an essential and unifying factor in diverse properties of condensed matter systems. Ground states that can arise due to electron correlation effects include Mott insulators, heavy fermion, ferromagnetism and antiferromagnetism, spin glasses, and high-temperature superconductivity. The electronic systems in transition metal oxide compounds are often highly correlated. In this thesis, the author presents experimental studies on three strongly correlated vanadium oxide compounds: LiV{sub 2}O{sub 4}, (Li{sub x}V{sub 1-x}){sub 3}BO{sub 5}, and CaV{sub 2}O{sub 4}, which have completely different ground states.
Date: December 1, 2007
Creator: Zong, Xiaopeng
Partner: UNT Libraries Government Documents Department

Pattern Formation and Growth Kinetics in Eutectic Systems

Description: Growth patterns during liquid/solid phase transformation are governed by simultaneous effects of heat and mass transfer mechanisms, creation of new interfaces, jump of the crystallization units from liquid to solid and their rearrangement in the solid matrix. To examine how the above processes influence the scale of microstructure, two eutectic systems are chosen for the study: a polymeric system polyethylene glycol-p-dibromobenzene (PEG-DBBZ) and a simple molecular system succinonitrile (SCN)-camphor. The scaling law for SCN-camphor system is found to follow the classical Jackson-Hunt model of circular rod eutectic, where the diffusion in the liquid and the interface energy are the main physics governing the two-phase pattern. In contrast, a significantly different scaling law is observed for the polymer system. The interface kinetics of PEG phase and its solute concentration dependence thus have been critically investigated for the first time by directional solidification technique. A model is then proposed that shows that the two-phase pattern in polymers is governed by the interface diffusion and the interface kinetics. In SCN-camphor system, a new branch of eutectic, elliptical shape rodl, is found in thin samples where only one layer of camphor rods is present. It is found that the orientation of the ellipse can change from the major axis in the direction of the thickness to the direction of the width as the velocity and/or the sample thickness is decreased. A theoretical model is developed that predicts the spacing and orientation of the elliptical rods in a thin sample. The single phase growth patterns of SCN-camphor system were also examined with emphasis on the three-dimensional single cell and cell/dendrite transition. For the 3D single cell in a capillary tube, the entire cell shape ahead of the eutectic front can be described by the Saffmann-Taylor finger only at extremely low growth rate. A 3D directional ...
Date: December 1, 2007
Creator: Teng, Jing
Partner: UNT Libraries Government Documents Department

Processing and Protection of Rare Earth Permanent Magnet Particulate for Bonded Magnet Applications

Description: Rapid solidification of novel mixed rare earth-iron-boron, MRE{sub 2}Fe{sub 14}B (MRE = Nd, Y, Dy; currently), magnet alloys via high pressure gas atomization (HPGA) have produced similar properties and structures as closely related alloys produced by melt spinning (MS) at low wheel speeds. Recent additions of titanium carbide and zirconium to the permanent magnet (PM) alloy design in HPGA powder (using He atomization gas) have made it possible to achieve highly refined microstructures with magnetic properties approaching melt spun particulate at cooling rates of 10{sup 5}-10{sup 6}K/s. By producing HPGA powders with the desirable qualities of melt spun ribbon, the need for crushing ribbon was eliminated in bonded magnet fabrication. The spherical geometry of HPGA powders is more ideal for processing of bonded permanent magnets since higher loading fractions can be obtained during compression and injection molding. This increased volume loading of spherical PM powder can be predicted to yield a higher maximum energy product (BH){sub max} for bonded magnets in high performance applications. Passivation of RE-containing powder is warranted for the large-scale manufacturing of bonded magnets in applications with increased temperature and exposure to humidity. Irreversible magnetic losses due to oxidation and corrosion of particulates is a known drawback of RE-Fe-B based alloys during further processing, e.g. injection molding, as well as during use as a bonded magnet. To counteract these effects, a modified gas atomization chamber allowed for a novel approach to in situ passivation of solidified particle surfaces through injection of a reactive gas, nitrogen trifluoride (NF{sub 3}). The ability to control surface chemistry during atomization processing of fine spherical RE-Fe-B powders produced advantages over current processing methodologies. In particular, the capability to coat particles while 'in flight' may eliminate the need for post atomization treatment, otherwise a necessary step for oxidation and corrosion resistance. Stability of ...
Date: December 1, 2007
Creator: Sokolowski, Peter Kelly
Partner: UNT Libraries Government Documents Department

The Development and Optimization of Techniques for Monitoring Water Quality on-Board Spacecraft Using Colorimetric Solid-Phase Extraction (C-SPE)

Description: The main focus of this dissertation is the design, development, and ground and microgravity validation of methods for monitoring drinking water quality on-board NASA spacecraft using clorimetric-solid phase extraction (C-SPE). The Introduction will overview the need for in-flight water quality analysis and will detail some of the challenges associated with operations in the absence of gravity. The ability of C-SPE methods to meet these challenges will then be discussed, followed by a literature review on existing applications of C-SPE and similar techniques. Finally, a brief discussion of diffuse reflectance spectroscopy theory, which provides a means for analyte identification and quantification in C-SPE analyses, is presented. Following the Introduction, four research chapters are presented as separate manuscripts. Chapter 1 reports the results from microgravity testing of existing C-SPE methods and procedures aboard NASA's C-9 microgravity simulator. Chapter 2 discusses the development of a C-SPE method for determining the total concentration of biocidal silver (i.e., in both dissolved and colloidal forms) in water samples. Chapter 3 presents the first application of the C-SPE technique to the determination of an organic analyte (i.e., formaldehyde). Chapter 4, which is a departure from the main focus of the thesis, details the results of an investigation into the effect of substrate rotation on the kinetics involved in the antigen and labeling steps in sandwich immunoassays. These research chapters are followed by general conclusions and a prospectus section.
Date: December 1, 2007
Creator: Hill, April
Partner: UNT Libraries Government Documents Department

Development of Carbon Based optically Transparent Electrodes from Pyrolyzed Photoresist for the Investigation of Phenomena at Electrified Carbon-Solution Interfaces

Description: The work presented herein describes a fundamental investigations of carbon as electrode material by using the pyrolysis of photoresist to create an optically transparent material. The development of these carbon-based optically transparent electrodes (C-OTEs) enables investigations of molecular interactions within the electrical double layer, processes that are central to a wide range of important phenomena, including the impact of changes in the surface charge density on adsorption. The electrochemical importance of carbon cannot be understated, having relevance to separations and detection by providing a wide potential window and low background current in addition to being low cost and light weight. The interactions that govern the processes at the carbon electrode surface has been studied extensively. A variety of publications from the laboratories of McCreery and Kinoshita provide in depth summaries about carbon and its many applications in electrochemistry. These studies reveal that defects, impurities, oxidation, and a variety of functional groups create adsorption sites on carbon surfaces with different characteristics. The interest in C-OTEs was sparked by the desire to study and understand the behavior of individual molecules at electrified interfaces. It draws on the earlier development of Electrochemically Modulated Liquid Chromatography (EMLC), which uses carbon as the stationary phase. EMLC takes advantage of changing the applied potential to the carbon electrode to influence the retention behavior of analytes. However, perspectives gained from, for example, chromatographic measurements reflect the integrated response of a large ensemble of potentially diverse interactions between the adsorbates and the carbon electrode. Considering the chemically and physically heterogeneous surface of electrode materials such as glassy carbon, the integrated response provides little insight into the interactions at a single molecule level. To investigate individual processes, they have developed C-OTEs in order to couple electrochemistry with single molecule spectroscopy (SMS). Like EMLC, the novel merger of SMS with ...
Date: December 1, 2007
Creator: Donner, Sebastian
Partner: UNT Libraries Government Documents Department

Developments and Applications of Electrophoresis and Small Molecule Laser Desorption Ionization Mass Spectrometry

Description: Ultra-sensitive native fluorescence detection of proteins with miniaturized one- and two-dimensional polyacrylamide gel electrophoresis was achieved with laser side-entry excitation, which provides both high excitation power and low background level. The detection limit for R-phycoerythrin protein spots in 1-D SDS-PAGE was as low as 15 fg, which corresponds to 40 thousand molecules only. The average detection limit of six standard native proteins was 5 pg per band and the dynamic range spanned more than 3 orders of magnitude. Approximately 150 protein spots from 30 ng of total Escherichia coli extraction were detected on a 0.8 cm x 1 cm gel in two-dimensional separation. Estrogen-DNA adducts as 4-OHE{sub 1}(E{sub 2})-1-N3Ade and 4-OHEI(E2)-2-NacCys were hypothesized as early risk assessment of prostate and breast cancers. Capillary electrophoresis, luminescence/absorption spectroscopy and LC-MS were used to characterize and detect these adducts. Monoclonal antibodies against each individual adduct were developed and used to enrich such compounds from urine samples of prostate and breast cancer patients as well as healthy people. Adduct 4-OHE{sub 1}-1-N3Ade was detected at much higher level in urine from subjects with prostate cancer patients compared to healthy males. The same adduct and 4-OHEI-2-NacCys were also detected at a much higher level in urine from a woman with breast carcinoma than samples from healthy controls. These two DNA adducts may serve as novel biomarkers for early diagnostic of cancers. The adsorption properties of R-phycoerythrin (RPE), on the fused-silica surface were studied using capillary electrophoresis (CE) and single molecule spectroscopy. The band shapes and migration times were measured in CE. Adsorption and desorption events were recorded at the single-molecule level by imaging of the evanescent-field layer using total internal reflection. The adsorbed RPE molecules on the fused-silica prism surface were counted with confidence based on Imagej software. The capacity factor and desorption rate were estimated ...
Date: December 1, 2007
Creator: Zhang, Hui
Partner: UNT Libraries Government Documents Department

Electrospray Ionization Mass Spectrometry: From Cluster Ions to Toxic metal Ions in Biology

Description: This dissertation focused on using electrospray ionization mass spectrometry to study cluster ions and toxic metal ions in biology. In Chapter 2, it was shown that primary, secondary and quarternary amines exhibit different clustering characteristics under identical instrument conditions. Carbon chain length also played a role in cluster ion formation. In Chapters 3 and 4, the effects of solvent types/ratios and various instrumental parameters on cluster ion formation were examined. It was found that instrument interface design also plays a critical role in the cluster ion distribution seen in the mass spectrum. In Chapter 5, ESI-MS was used to investigate toxic metal binding to the [Gln{sup 11}]-amyloid {beta}-protein fragment (1-16). Pb and Cd bound stronger than Zn, even in the presence of excess Zn. Hg bound weaker than Zn. There are endless options for future work on cluster ions. Any molecule that is poorly ionized in positive ion mode can potentially show an increase in ionization efficiency if an appropriate anion is used to produce a net negative charge. It is possible that drug protein or drug/DNA complexes can also be stabilized by adding counter-ions. This would preserve the solution characteristics of the complex in the gas phase. Once in the gas phase, CID could determine the drug binding location on the biomolecule. There are many research projects regarding toxic metals in biology that have yet to be investigated or even discovered. This is an area of research with an almost endless future because of the changing dynamics of biological systems. What is deemed safe today may show toxic effects in the future. Evolutionary changes in protein structures may render them more susceptible to toxic metal binding. As the understanding of toxicity evolves, so does the demand for new toxic metal research. New instrumentation designs and software make it possible ...
Date: December 1, 2007
Creator: Lentz, Nicholas B.
Partner: UNT Libraries Government Documents Department

High Temperature Oxidation Behavior of gamma-Ni+gamma'-Ni3Al Alloys and Coatings Modified with Pt and Reactive Elements

Description: Materials for high-pressure turbine blades must be able to operate in the high-temperature gases (above 1000 C) emerging from the combustion chamber. Accordingly, the development of nickel-based superalloys has been constantly motivated by the need to have improved engine efficiency, reliability and service lifetime under the harsh conditions imposed by the turbine environment. However, the melting point of nickel (1455 C) provides a natural ceiling for the temperature capability of nickel-based superalloys. Thus, surface-engineered turbine components with modified diffusion coatings and overlay coatings are used. Theses coatings are capable of forming a compact and adherent oxide scale, which greatly impedes the further transport of reactants between the high-temperature gases and the underlying metal and thus reducing attack by the atmosphere. Typically, these coatings contain {beta}-NiAl as a principal constituent phase in order to have sufficient aluminum content to form an Al{sub 2}O{sub 3} scale at elevated temperatures. The drawbacks to the currently-used {beta}-based coatings, such as phase instabilities, associated stresses induced by such phase instabilities, and extensive coating/substrate interdiffusion, are major motivations in this study to seek next-generation coatings. The high-temperature oxidation resistance of novel Pt + Hf-modified {gamma}-Ni + {gamma}-Ni{sub 3}Al-based alloys and coatings were investigated in this study. Both early-stage and 4-days isothermal oxidation behavior of single-phase {gamma}-Ni and {gamma}{prime}-Ni{sub 3}Al alloys were assessed by examining the weight changes, oxide-scale structures, and elemental concentration profiles through the scales and subsurface alloy regions. It was found that Pt promotes Al{sub 2}O{sub 3} formation by suppressing the NiO growth on both {gamma}-Ni and {gamma}{prime}Ni{sub 3}Al single-phase alloys. This effect increases with increasing Pt content. Moreover, Pt exhibits this effect even at lower temperatures ({approx}970 C) in the very early stage of oxidation. It was also inferred that Pt enhances the diffusive flux of aluminum from the substrate to the scale/alloy ...
Date: December 1, 2007
Creator: Mu, Nan
Partner: UNT Libraries Government Documents Department