Experimentation validated a simple moisture conditioning scheme to prepare Gr/Ep composite parts for precision applications by measuring dimensional changes over 90 days. It was shown that an elevated temperature moisture conditioning scheme produced a dimensionally stable part from which precision structures could be built/machined without significant moisture induced dimensional changes after fabrication. Conversely, that unconditioned Gr/Ep composite panels exhibited unacceptably large dimensional changes (i.e., greater than 125 ppM). It was also shown that time required to produce stable parts was shorter, by more than an order of magnitude, employing the conditioning scheme than using no conditioning scheme (46 days versus 1000+ days). Two final use environments were chosen for the experiments: 50% RH/21C and 0% RH/21C. Fiberite 3034K was chosen for its widespread use in aerospace applications. Two typical lay-ups were chosen, one with low sensitivity to hygrothermal distortions and the other high sensitivity: [0, {plus_minus} 45, 90]s, [0, {plus_minus} 15, 0]s. By employing an elevated temperature, constant humidity conditioning scheme, test panels achieved an equilibrium moisture content in less time, by more than an order of magnitude, than panels exposed to the same humidity environment and ambient temperature. Dimensional changes, over 90 days, were up to 4 times lower …

High-pressure, high-temperature scanning tunneling microscopy (HPHTSTM) was used to study adsorbate structures and reactions on single crystal model catalytic systems. Studies of the automobile catalytic converter reaction [CO + NO {yields} 1/2 N{sub 2} + CO{sub 2}] on Rh(111) and ethylene hydrogenation [C{sub 2}H{sub 4} + H{sub 2} {yields} C{sub 2}H{sub 6}] on Rh(111) and Pt(111) elucidated information on adsorbate structures in equilibrium with high-pressure gas and the relationship of atomic and molecular mobility to chemistry. STM studies of NO on Rh(111) showed that adsorbed NO forms two high-pressure structures, with the phase transformation from the (2 x 2) structure to the (3 x 3) structure occurring at 0.03 Torr. The (3 x 3) structure only exists when the surface is in equilibrium with the gas phase. The heat of adsorption of this new structure was determined by measuring the pressures and temperatures at which both (2 x 2) and (3 x 3) structures coexisted. The energy barrier between the two structures was calculated by observing the time necessary for the phase transformation to take place. High-pressure STM studies of the coadsorption of CO and NO on Rh(111) showed that CO and NO form a mixed (2 x 2) structure …

This research has shown that epilayers with residual impurity concentrations of 5 x 10{sup 13} cm{sup {minus}3} can be grown by producing the purest Pb available in the world. These epilayers have extremely low minority acceptor concentrations, which is ideal for fabrication of IR absorbing layers. The Pb LPE growth of Ge also has the advantageous property of gettering Cu from the epilayer and the substrate. Epilayers have been grown with intentional Sb doping for IR absorption on lightly doped substrates. This research has proven that properly working Ge BIB detectors can be fabricated from the liquid phase as long as pure enough solvents are available. The detectors have responded at proper wavelengths when reversed biased even though the response did not quite reach minimum wavenumbers. Optimization of the Sb doping concentration should further decrease the photoionization energy of these detectors. Ge BIB detectors have been fabricated that respond to 60 cm{sup {minus}1} with low responsivity. Through reduction of the minority residual impurities, detector performance has reached responsivities of 1 A/W. These detectors have exhibited quantum efficiency and NEP values that rival conventional photoconductors and are expected to provide a much more sensitive tool for new scientific discoveries in a …

This thesis determines what, if any, measurements of aerosol properties made at the Earth surface are representative of those within the entire air column. Data from the Atmospheric Radiation Measurement site at the Southern Great Plains, the only location in the world where ground-based and in situ airborne measurements are routinely made. Flight legs during the one-year period from March 2000 were categorized as either within or above the atmospheric boundary layer (ABL) by use of an objective mixing height determination technique. Correlations between aerosol properties measured at the surface and those within and above the ABL were computed. Aerosol extensive and intensive properties measured at the surface were found representative of values within the ABL, but not of within the free atmosphere.

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Backup shutdown systems proposed for future LMRs may employ discreet absorber particles to provide the negative reactivity insertion. When actuated, these systems release a dense packing of particles from an out-of-core region to settle into an in-core region. The multiple particle settling behavior is analyzed by the method of continuity waves. This method provides predictions of the dynamic response of the system including the average particle velocity and volume fraction of particles vs. time. Although hindered settling problems have been previously analyzed using continuity wave theory, this application represents an extension of the theory to conditions of unrestrained settling. Typical cases are analyzed and numerical results are calculated based on a semi-empirical drift-flux model. For 1/4-inch diameter boron-carbide particles in hot liquid sodium, the unrestrained settling problem assumes a steady-state solution when the average volume fraction of particles is 0.295 and the average particle velocity is 26.0 cm/s.

This thesis presents measurements of the oscillations of muon antineutrinos in the atmospheric sector, where world knowledge of antineutrino oscillations lags well behind the knowledge of neutrinos, as well as a search for {nu}{sub {mu}} {yields} {bar {nu}}{sub {mu}} transitions. Differences between neutrino and antineutrino oscillations could be a sign of physics beyond the Standard Model, including non-standard matter interactions or the violation of CPT symmetry. These measurements leverage the sign-selecting capabilities of the magnetized steel-scintillator MINOS detectors to analyze antineutrinos from the NuMI beam, both when it is in neutrino-mode and when it is in antineutrino-mode. Antineutrino oscillations are observed at |{Delta}{bar m}{sub atm}{sup 2}| = (3.36{sub -0.40}{sup +0.46}(stat) {+-} 0.06(syst)) x 10{sup -3} eV{sup 2} and sin{sup 2}(2{bar {theta}}{sub 23}) = 0.860{sub -0.12}{sup +0.11}(stat) {+-} 0.01(syst). The oscillation parameters measured for antineutrinos and those measured by MINOS for neutrinos differ by a large enough margin that the chance of obtaining two values as discrepant as those observed is only 2%, assuming the two measurements arise from the same underlying mechanism, with the same parameter values. No evidence is seen for neutrino-to-antineutrino transitions.

The authors consider polymers, modeled as self-avoiding walks with interactions on a hexagonal lattice, and examine the applicability of certain Monte Carlo methods for estimating their mean properties at equilibrium. Specifically, the authors use the pivoting algorithm of Madras and Sokal and Metroplis rejection to locate the phase transition, which is known to occur at {beta}{sub crit} {approx} 0.99, and to recalculate the known value of the critical exponent {nu} {approx} 0.58 of the system for {beta} = {beta}{sub crit}. Although the pivoting-Metropolis algorithm works well for short walks (N < 300), for larger N the Metropolis criterion combined with the self-avoidance constraint lead to an unacceptably small acceptance fraction. In addition, the algorithm becomes effectively non-ergodic, getting trapped in valleys whose centers are local energy minima in phase space, leading to convergence towards different values of {nu}. The authors use a variety of tools, e.g. entropy estimation and histograms, to improve the results for large N, but they are only of limited effectiveness. Their estimate of {beta}{sub crit} using smaller values of N is 1.01 {+-} 0.01, and the estimate for {nu} at this value of {beta} is 0.59 {+-} 0.005. They conclude that even a seemingly simple system …

One of the key engineered barriers in the design of the proposed Yucca Mountain repository is the waste canister that encapsulates the spent fuel elements. Current candidate metals for the canisters to be emplaced at Yucca Mountain include cast iron, carbon steel, Incoloy 825 and titanium code-12. This project was designed to evaluate passive electrochemical noise techniques for measuring pitting and corrosion characteristics of candidate materials under prototypical repository conditions. Experimental techniques were also developed and optimized for measurements in a radiation environment. These techniques provide a new method for understanding material response to environmental effects (i.e., gamma radiation, temperature, solution chemistry) through the measurement of electrochemical noise generated during the corrosion of the metal surface. In addition, because of the passive nature of the measurement the technique could offer a means of in-situ monitoring of barrier performance.

The utility of microearthquake data for characterizing the Northwest Geysers geothermal field and the Long Valley Caldera (LVC) was investigated. Three-dimensional (3-D) P- and S-wave seismic velocity models were estimated for the Coldwater Creek Steam Field (CCSF) in the Northwest Geysers region. Hypocenters relocated using these 3-D models appear to be associated with the steam producing zone, with a deeper cluster of hypocenters beneath an active injection well. Spatial and temporal patterns of seismicity exhibit strong correlation with geothermal exploitation. A 3-D differential attenuation model was also developed for the CCSF from spectral ratios corrected for strong site effects. High-velocity anomalies and low attenuation in the near surface correspond to Franciscan metagraywacke and greenstone units. Microearthquakes recorded at seismographic stations located near the metagraywacke unit exhibit high corner frequencies. Low-velocity anomalies and higher attenuation in the near surface are associated with sections of Franciscan melange. Near-surface high attenuation and high Vp/Vs are interpreted to indicate liquid-saturated regions affected by meteoric recharge. High attenuation and low Vp/Vs marks the steam producing zone, suggesting undersaturation of the reservoir rocks. The extent of the high attenuation and low Vp/Vs anomalies suggest that the CCSF steam reservoir may extend northwestward beyond the known producing …

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Some applications of flavor symmetry are examined. Approximate flavor symmetries and their consequences in the MSSM (Minimal Supersymmetric Standard Model) are considered, and found to give natural values for the possible B- and L-violating couplings that are empirically acceptable, except for the case of proton decay. The coupling constants of SU(3) are calculated and used to parameterize the decays of the D mesons in broken flavor SU(3). The resulting couplings are used to estimate the long-distance contributions to D-meson mixing.

Although we know that many supernovae are aspherical, the exact nature of their geometry is undetermined. Because all the supernovae we observe are too distant to be resolved, the ejecta structure can't be directly imaged, and asymmetry must be inferred from signatures in the spectral features and polarization of the supernova light. The empirical interpretation of this data, however, is rather limited--to learn more about the detailed supernova geometry, theoretical modeling must been undertaken. One expects the geometry to be closely tied to the explosion mechanism and the progenitor star system, both of which are still under debate. Studying the 3-dimensional structure of supernovae should therefore provide new break throughs in our understanding. The goal of this thesis is to advance new techniques for calculating radiative transfer in 3-dimensional expanding atmospheres, and use them to study the flux and polarization signatures of aspherical supernovae. We develop a 3-D Monte Carlo transfer code and use it to directly fit recent spectropolarimetric observations, as well as calculate the observable properties of detailed multi-dimensional hydrodynamical explosion simulations. While previous theoretical efforts have been restricted to ellipsoidal models, we study several more complicated configurations that are tied to specific physical scenarios. We explore clumpy …

Melanie Waltman's dissertation to be presented on March 24, 2010.

Methyltrioxorhenium (MTO) catalyzes the desulfurization of thiiranes by triphenylphosphine. Enormous enhancement in rate is observed when the catalyst is pretreated with hydrogen sulfide prior to the reaction. Using 2-mercaptomethylthiophenol as a ligand, the author synthesized several model complexes to study the mechanism of this reaction. With suitable model systems, they were able to show that the active catalyst is a Re(V) species. The reactions are highly stereospecific and very tolerant to functional groups. As part of the studies, he synthesized and crystallographically characterized the first examples of neutral terminal and bridging Re(V)sulfidocomplexes. Some of these complexes undergo fast oxygen atom transfer reactions with organic and inorganic oxidants. Studies on these model complexes led them to the discovery that MTO catalyzes the selective oxidation of thiols to disulfides. This report contains the Introduction; ``Chapter 6: Isomerization of Propargylic Alcohols to Enones and Enals Catalyzed by Methylrhenium Trioxide``; and Conclusions.

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Our approach involves on-axis illumination of the compounds inside the capillary detection region and is applied to absorbance and fluorescence detection. Absorbance measurements were made by focussing an incident laser beam into one capillary end; by using signals collected over the entire length of analyte band, this enhances the analytical path length of conventional absorbance detection 60x. This instrument offers a 15x improvement in detection limits. Three fluorescence detection experiments are discussed, all of which involve insertion of an optical fiber into capillary. The first uses a high refractive index liquid phase to obtain total internal reflectance along capillary axis, this reducing light scatter. The second uses a charge-coupled device camera for simultaneous imaging of a capillary array (this may be useful in genome sequencing, etc.). The third is a study of fluid motion inside the capillary under pressure-driven and electroosmotic flow. The thesis is divided into four parts. Figs, tabs.

The author discusses the photodissociation of light elements due to the radiative decay of a massive particle, and he has shown how to constrain the model parameters from the observed light-element abundances. He adopted two quasar absorption system (QAS) D/H values, as well as solar system data for D/H and {sup 3}He/H. For each of these, he used two {sup 4}He values. He presents his results in terms of the confidence level at which each theoretical parameter set (i.e., the set of properties of a radiatively decaying particle) is excluded by the observed abundances. His algorithm for computing the confidence level is consistent and general enough to apply not only to the scenarios investigated in this work, but also to many other non-standard theories of BBN.

The synthesis of magnetic nanoparticles has long been an area of active research. Magnetic nanoparticles can be used in a wide variety of applications such as magnetic inks, magnetic memory devices, drug delivery, magnetic resonance imaging (MRI) contrast agents, and pathogen detection in foods. In applications such as MRI, particle uniformity is particularly crucial, as is the magnetic response of the particles. Uniform magnetic particles with good magnetic properties are therefore required. One particularly effective technique for synthesizing nanoparticles involves biomineralization, which is a naturally occurring process that can produce highly complex nanostructures. Also, the technique involves mild conditions (ambient temperature and close to neutral pH) that make this approach suitable for a wide variety of materials. The term 'bioinspired' is important because biomineralization research is inspired by the naturally occurring process, which occurs in certain microorganisms called 'magnetotactic bacteria'. Magnetotactic bacteria use biomineralization proteins to produce magnetite crystals having very good uniformity in size and morphology. The bacteria use these magnetic particles to navigate according to external magnetic fields. Because these bacteria synthesize high quality crystals, research has focused on imitating aspects of this biomineralization in vitro. In particular, a biomineralization iron-binding protein found in a certain species of …

The research presented and discussed within involves the development of novel biological applications of mesoporous silica nanoparticles (MSN) and an investigation of mesoporous material by transmission electron microscopy (TEM). Mesoporous silica nanoparticles organically functionalized shown to undergo endocytosis in cancer cells and drug release from the pores was controlled intracellularly and intercellularly. Transmission electron microscopy investigations demonstrated the variety of morphologies produced in this field of mesoporous silica nanomaterial synthesis. A series of room-temperature ionic liquid (RTIL) containing mesoporous silica nanoparticle (MSN) materials with various particle morphologies, including spheres, ellipsoids, rods, and tubes, were synthesized. By changing the RTIL template, the pore morphology was tuned from the MCM-41 type of hexagonal mesopores to rotational moire type of helical channels, and to wormhole-like porous structures. These materials were used as controlled release delivery nanodevices to deliver antibacterial ionic liquids against Escherichia coli K12. The involvement of a specific organosiloxane function group, covalently attached to the exterior of fluorescein doped mesoporous silica nanoparticles (FITC-MSN), on the degree and kinetics of endocytosis in cancer and plant cells was investigated. The kinetics of endocystosis of TEG coated FITC-MSN is significantly quicker than FITC-MSN as determined by flow cytometry experiments. The fluorescence confocal microscopy investigation …

Over the past ten years, methods have been developed to construct discrete nanostructures using nanocrystals and biomolecules. While these frequently consist of gold nanocrystals and DNA, semiconductor nanocrystals as well as antibodies and enzymes have also been used. One example of discrete nanostructures is dimers of gold nanocrystals linked together with complementary DNA. This type of nanostructure is also known as a nanocrystal molecule. Discrete nanostructures of this kind have a number of potential applications, from highly parallel self-assembly of electronics components and rapid read-out of DNA computations to biological imaging and a variety of bioassays. My research focused in three main areas. The first area, the refinement of electrophoresis as a purification and characterization method, included application of agarose gel electrophoresis to the purification of discrete gold nanocrystal/DNA conjugates and nanocrystal molecules, as well as development of a more detailed understanding of the hydrodynamic behavior of these materials in gels. The second area, the development of methods for quantitative analysis of transmission electron microscope data, used computer programs written to find pair correlations as well as higher order correlations. With these programs, it is possible to reliably locate and measure nanocrystal molecules in TEM images. The final area of …

The Neel temperatures, T{sub N}, of Tb{sub x}Er{sub 1-x}Ni{sub 2}B{sub 2}C samples have been determined from the temperature dependence of magnetization measurements. A breakdown of the de Gennes scaling of T{sub N} with a clear turning point around x = 0.45 has been observed. The T{sub N} values of Tb{sub x}Er{sub 1-x}Ni{sub 2}B{sub 2}C do not change much within the range of O &lt; x &lt; 0.45 and then, for larger x they increase almost linearly with concentration until T{sub N} = 14.9K is reached for x = 1, TbNi{sub 2}B{sub 2}C. The clear change in the x-dependence of T{sub N} around x = 0.45 can be linked to a change in the local moment ordering direction from transverse to longitudinal, a change which is consistent with recent resonant X-ray scattering data. These features in T{sub N}(x) can be explained using a mean field model.

Results of this thesis show that STM measurements can provide information about the surfaces and their adsorbates. Stability of Pt(110) under high pressures of H2, O2, and CO was studied (Chap. 4). In situ UHV and high vacuum experiments were carried out for sulfur on Pt(111) (Chap.5). STM studies of CO/S/Pt(111) in high CO pressures showed that the Pt substrate undergoes a stacking-fault-domain reconstruction involving periodic transitions from fcc to hcp stacking of top-layer atoms (Chap.6). In Chap.7, the stability of propylene on Pt(111) and the decomposition products were studied in situ with the HPSTM. Finally, in Chap.8, results are presented which show how the Pt tip of the HPSTM was used to locally rehydrogenate and oxidize carbonaceous clusters deposited on the Pt(111) surface; the Pt tip acted as a catalyst after activation by short voltage pulses.