Molybdenum disilicide has been predominantly used for furnace heating elements, but recently there has been interest in its use for high temperature structural applications. The reason for this increased interest stems from its desirable characteristics which are a high melting point, relatively low density, good oxidation resistance, relatively good thermal conductivity and electronically conductive. The melting point of MoSi{sub 2} is approximately 2030{degrees}C as compared to a melting point of 1340{degrees}C for the Ni-based superalloys. This could potentially give MoSi{sub 2} a big advantage over the Ni-based superalloys in turbine applications because the operating temperature can be increased resulting in an increase in turbine efficiency and reduced emissions. The relatively low density (6.25g/cm{sup 3}) compared to the Ni-based superalloys (8.9 g/cm{sup 3}) is an important advantage in turbine applications because of the need for low weight. Good oxidation resistance stems from the ability of MoSi{sub 2} to form a protective SiO{sub 2} surface layer when exposed to oxygen. Another advantageous feature of MoSi{sub 2} is its thermal conductivity which is superior to Ni-based superalloys at low temperatures and comparable to the Ni-based superalloys at high temperatures. This allows heat to be dissipated at a rate better than ceramics and comparable …

This work attempts to show the feasibility of nondestructive characterization of non-ferrous alloys. Aluminum alloys have a small single crystal anisotropy which requires very precise ultrasonic velocity measurements for derivation of orientation distribution coefficients (ODCs); the precision in the ultrasonic velocity measurement required for aluminum alloys is much greater than is necessary for iron alloys or other alloys with a large single crystal anisotropy. To provide greater precision, some signal processing corrections need to be applied to account for the inherent, half-bandwidth offset in triggered pulses when using a zero-crossing technique for determining ultrasonic velocity. In addition, alloys with small single crystal anisotropy show a larger dependence on the single crystal elastic constants (SCECs) when predicting ODCs which require absolute velocity measurements. Attempts were made to independently determine these elastics constants in an effort to improve correlation between ultrasonically derived ODCs and diffraction derived ODCs. The greater precision required to accurately derive ODCs in aluminum alloys using ultrasonic nondestructive techniques is easily attainable. Ultrasonically derived ODCs show good correlation with derivations made by Bragg diffraction techniques, both neutron and X-ray. The best correlation was shown when relative velocity measurements could be used in the derivations of the ODCs. Calculation of …

The work presented here evaluates the dynamics of a beam of heavy ions propagating through a chamber filled with gas. The motivation for this research stems from the possibility of using heavy ion beams as a driver in inertial confinement fusion reactors for the purpose of generating electricity. Such a study is important in determining the constraints on the beam which limit its focus to the small radius necessary for the ignition of thermonuclear microexplosions which are the source of fusion energy. Nuclear fusion is the process of combining light nuclei to form heavier ones. One possible fusion reaction combines two isotopes of hydrogen, deuterium and tritium, to form an alpha particle and a neutron, with an accompanying release of {approximately}17.6 MeV of energy. Generating electricity from fusion requires that we create such reactions in an efficient and controlled fashion, and harness the resulting energy. In the inertial confinement fusion (ICF) approach to energy production, a small spherical target, a few millimeters in radius, of deuterium and tritium fuel is compressed so that the density and temperature of the fuel are high enough, {approximately}200 g/cm{sup 3} and {approximately}20 keV, that a substantial number of fusion reactions occur; the pellet microexplosion …

This thesis discusses characterization of two ferroelectric materials and the fabrication of bolometers. Potassium tantalate niobate (KTN) and potassium dihydrogen phosphate (KDP) are chosen because they can be optimized for operation near 100K. Chap. 2 reviews the physics underlying pyroelectric materials and its subclass of ferroelectric materials. Aspects of pyroelectric detection are discussed in Chap. 3 including measurement circuit, noise sources, and effects of materials properties on pyroelectric response. Chap. 4 discusses materials selection and specific characteristics of KTN and KDP; Chap. 5 describes materials preparation; and Chap. 6 presents detector configuration and a thermal analysis of the pyroelectric detector. Electrical techniques used to characterize the materials and devices and results are discussed in Chap. 7 followed by conclusions on feasibility of KDP and KTN pyroelectric detectors in Chap. 8.

A study was undertaken to examine permeable zones identified in boreholes open to the underlying basalt and to describe the vertical cross flows present in the boreholes. To understand the permeable zones in the boreholes detailed descriptions and measurements of three outcrops in the Snake River Plain, three cores at the Idaho Chemical Processing Plant (ICPP) at the INEL, and over fifty borehole TV logs from the INEL were carried out. Based on the observations made on the three outcrops an idealized basalt lava flow model was generated that used a set of nomenclature that would be standard for the basalt lava flows studied. An upper vesicular zone, a sometimes absent columnar zone, central zone, and lower vesicular zone make up the basalt lava flow model. The overall distinction between the different zones are based on the vesicle shape size, vesicularity, and fractures present. The results of the studies also indicated that the basalt lava flows at the INEL are distal to medial facies pahoehoe lava flows with close fitting contacts. The most permeable zones identified in these basalts are fractured vesiculated portions of the top of the lava flow, the columnar areas, and basalt-flow contacts in order of importance. …

A liquid chromatographic method for the determination of water in soil or clay samples is presented. In a separate study, the optimization of electrophoretic separation of alkylated phenolate ions was optimized by varying the pH and acetonitrile concentration of the buffer solutions.

A program is currently in progress at Argonne National Laboratory to evaluate and develop evaporator technology for concentrating radioactive waste streams. By concentrating radioactive waste streams, disposal costs can be significantly reduced. To effectively reduce the volume of waste, the evaporator must achieve high decontamination factors so that the distillate is sufficiently free of radioactive material. One technology that shows a great deal of potential for this application is being developed by LICON, Inc. In this program, Argonne plans to apply LICON`s evaporator designs to the processing of radioactive solutions. Concepts that need to be incorporated into the design of the evaporator include, criticality safety, remote operation and maintenance, and materials of construction. To design an effective process for concentrating waste streams, both solubility and vapor-liquid equilibrium data are needed. The key issue, however, is the high decontamination factors that have been demonstrated by this equipment. Two major contributions were made to this project. First, a literature survey was completed to obtain available solubility and vapor-liquid equilibrium data. Some vapor-liquid data necessary for the project but not available in the literature was obtained experimentally. Second, the decontamination factor for the evaporator was determined using neutron activation analysis (NAA).

A reproducible, high-yield synthesis of mono([8]annulene)uranium(4)dichloride (1) is reported, along with the X-ray crystal structural of the bis(pyridine) adduct. Metathesis reactions of the half-sandwich complex 1 with a variety of simple alkyl and alkoxy reagents failed to generate any isolable mono-ring complexes. Reactions of 1 with polydentate, delocalized anions did produce stable derivatives, including mono([8]annulene)uranium(4)bis(acetylacetonate) (4). An X-ray crystal structure of 4 is reported.

The syntheses of silicon-containing compounds and the studies of their rearrangements have been active research areas in the Barton research group. Previously, the addition of disilanes to acetylenes was studied in the group and an intramolecular 2S + 2A mechanism has been proposed. In this thesis, the work is focused on the addition of disilanes to cumulenes. The syntheses of the precursors are discussed and the possible mechanisms for their thermal, photochemical and catalytic rearrangements are proposed. Conjugated organic polymers have been studied in the group since 1985 because of their potential for exhibiting high electroconductivity, photoconductivity, strong non-linear optical response and intense fluorescence. In the second section of this dissertation, the synthesis and property studies of poly(phenylene vinylene) analogues are discussed.

The vibrational to translational (V{yields}T) energy transfer in collisions between large highly vibrationally excited polyatomics and rare gases was investigated by time-of-flight techniques. Two different methods, UV excitation followed by intemal conversion and infrared multiphoton excitation (IRMPE), were used to form vibrationally excited molecular beams of hexafluorobenzene and sulfur hexafluoride, respectively. The product translational energy was found to be independent of the vibrational excitation. These results indicate that the probability distribution function for V{yields}T energy transfer is peaked at zero. The collisional relaxation of large polyatomic molecules with rare gases most likely occurs through a rotationally mediated process. Photodissociation of nitrobenzene in a molecular beam was studied at 266 nm. Two primary dissociation channels were identified including simple bond rupture to produce nitrogen dioxide and phenyl radical and isomerization to form nitric oxide and phenoxy radical. The time-of-flight spectra indicate that simple bond rupture and isomerization occurs via two different mechanisms. Secondary dissociation of the phenoxy radicals to carbon monoxide and cyclopentadienyl radicals was observed as well as secondary photodissociation of phenyl radical to give H atom and benzyne. A supersonic methyl radical beam source is developed. The beam source configuration and conditions were optimized for CH{sub 3} production from …

The hydrogeologic properties of a shallow, fractured granitic rock aquifer in the foothills of the Sierra Nevada, California were investigated via the analysis of borehole geophysical logs and pumping tests. The drawdowns produced during these tests are not indicative of any simple conceptual aquifer model, and borehole logs show that the granite is intensely fractured. These observations are suggestive of a complex fracture-flow geometry which is extremely difficult to decipher. However, through the measurement of orientations of individual subsurface fractures from acoustic televiewer logs, and correlation between particular fractures and electrical resistivity and thermal-pulse flowmeter logs, it was found that the aquifer is, in general, comprised of two subhorizontal and nearly parallel zones of unloading fractures. Downhole flowmeter measurements taken in several wells provide further evidence for the inferred dual-layer structure of the aquifer, as well as yield quantitative measures of the contribution of flow from each zone. Analysis of drawdowns in pumped wells reveals that there are zones of relatively high transmissivity immediately around them. It was found that these properties, as well as a nearby zone of lower transmissivity, can account for their observed drawdowns. A numerical model was constructed to test whether these major heterogeneities could also …

This thesis describes a number of diverse experiments whose common theme is to elaborate some aspect of DNA supercoiling. The torsion elastic constant of DNA is measure as a function of superhelix density using the technique of picosecond Time Resolved Fluorescence Polarization Anisotropy (FPA) of intercalated ethidium bromide. The results agree with theories which predict that the anisotropy decay should vary with the square root of the relative viscosity. This experiment furthermore demonstrates a sensitivity of FPA to a change in torsion elastic constant of less than 10%. A number of covalently closed DNA samples, ranging in superhelix density from = {minus}0.123 to {plus}0.042, are then examined. A novel method for measuring changes in local supercoiling on a large PNA molecule which is sensitive to changes in supercoiling of regions of chromosomal DNA as short as 1 kilobase in length is presented. Study of chromosomal supercoiling regulating anaerobic gene expression in the facultative photosynthetic bacterium, Rhodobacter capsulatus showed that no stable change in chromosomal supercoiling upon a shift from aerobic respiratory growth to anaerobic photosynthetic conditions. Studies to detect transient changes in DNA supercoiling indicate that DNA downstream from heavily transcribed genes for the photosynthetic reaction center are relaxed or …

Volume rendering allows us to represent a density cloud with ideal properties (single scattering, no self-shadowing, etc.). Scientific visualization utilizes this technique by mapping an abstract variable or property in a computer simulation to a synthetic density cloud. This thesis extends volume rendering from its limitation of isotropic density clouds to anisotropic and/or noisy density clouds. Design aspects of these techniques are discussed that aid in the comprehension of scientific information. Anisotropic volume rendering is used to represent vector based quantities in scientific visualization. Velocity and vorticity in a fluid flow, electric and magnetic waves in an electromagnetic simulation, and blood flow within the body are examples of vector based information within a computer simulation or gathered from instrumentation. Understand these fields can be crucial to understanding the overall physics or physiology. Three techniques for representing three-dimensional vector fields are presented: Line Bundles, Textured Splats and Hair Splats. These techniques are aimed at providing a high-level (qualitative) overview of the flows, offering the user a substantial amount of information with a single image or animation. Non-homogenous volume rendering is used to represent multiple variables. Computer simulations can typically have over thirty variables, which describe properties whose understanding are useful to …

Mortandad Canyon is a discharge site for treated industrial effluents containing radionuclides and other chemicals at Los Alamos National Laboratory, New Mexico. This study was conducted to develop an understanding of the unsaturated hydrologic behavior below the canyon floor. The main goal of this study was to evaluate the hypothetical performance of the vadose zone above the water table. Numerical simulations of unsaturated groundwater flow at the site were conducted using the Finite Element Heat and Mass Transfer (FEHM) code. A two-dimensional cross-section along the canyon's axis was used to model flow between an alluvial groundwater system and the regional aquifer approximately 300 m below. Using recharge estimated from a water budget developed in 1967, the simulations showed waters from the perched water table reaching the regional aquifer in 13.8 years, much faster than previously thought. Additionally, simulations indicate that saturation is occurring in the Guaje pumice bed an d that the Tshirege Unit 1B is near saturation. Lithologic boundaries between the eight materials play an important role in flow and solute transport within the system. Horizontal flow is shown to occur in three thin zones above capillary barriers; however, vertical flow dominates the system. Other simulations were conducted to …

BaF{sub 2} has the advantage over other scintillators, when comparing radiation hardness, scintillation decay time, and fast scintillation yield. Since the fast BaF{sub 2} emissions have peak wavelengths of 220, 195, and 170 nm, a wavelength shifter (WLS) is needed. Organic fluors were evaluated as WLS components. Results indicate that spectral separation using WLS is possible, but not to the extent desired; other techniques must be used also. Alternative scintillators, such as CeF{sub 3}, should be investigated.

Measurements have been made of the scaled jet energies (x{sub 1}, x{sub 2}, x{sub 3}) and the Ellis-Karliner angle (cos{theta}{sub EK}), which are sensitive to the spill of the gluon, in the 3-jet hadronic events from the e{sup +}e{sup {minus}} annihilation at the Z{sup 0} resonance. The experiment is performed with the SLD detector at the Stanford Linear Accelerator Center (SLAC). The data used in this analysis was collected during the 1992 physics run, which includes 10,252 hadronic Z{sup 0} events that have CDC information written out. Only charged tracks measured in the central drift chamber are used for the measurements of the above variables. The raw data are found to be in good agreement with the Monte Carlo simulations passing the same set of track and event selection cuts. A bin-to-bin correction is done for the distributions of x{sub 1}, x{sub 2}, x{sub 3}, and cos{theta}{sub EK} to account for the effects of hadronization, detector acceptance and resolution. The corrected data is compared to the parton level distributions of x{sub 1}, x{sub 2}, x{sub 3}, and cos{theta}{sub EK} simulated from the vector QCD model and the scalar gluon model respectively. The systematic errors, calculated for all the bins in …

The research illustrated in this thesis was performed under the guidance of Professor Dennis C. Johnson beginning in March 1987. Chapter 2 concentrates on the development and electrocatalytic properties of iron-doped {beta}-PbO{sub 2} films on noble-metal substrates. Chapter 3 focuses attention on the preparation and characterization of iron-doped {beta}-PbO{sub 2} films on titanium substrates (Fe-PbO{sub 2}/Ti). Chapter 4 discusses anodic evolution of ozone at Fe-PbO{sub 2}/Ti electrodes. Chapter 5 describes electrochemical incineration of p-benzoquinone (BQ) at Fe-PbO{sub 2}/Ti electrodes. In addition, the Appendix includes another published paper which is a detailed study of {alpha}-PbO{sub 2} films deposited on various types of stainless steel substrates.

Solid-phase extraction (SPE) has grown to be one of the most widely used methods for isolation and preconcentration of a vast range of compounds from aqueous solutions. By modifying polymeric SPE resins with chelating functional groups, the selective uptake of metals was accomplished. The resin, along with adsorbed metals, was vaporized in the ICP and detection of the metals was then possible using either mass or emission spectroscopy. Drug analyses in biological fluids have received heightened attention as drug testing is on the increase both in sports and in the work environment. By using a direct-injection technique, biological fluids can be injected directly into the liquid chromatographic system with no pretreatment. A new surfactant, a sulfonated form of Brij-30 (Brij-S) is shown to prevent the uptake of serum proteins on commercial HPLC columns by forming a thin coating on the silica C18 surface. Excellent separations of eight or more drugs with a wide range of retention times were obtained. The separations had sharper peaks and lower retention times than similar separations performed with the surfactant sodium dodecylsulfate (SDS). Quantitative recovery of a number of drugs with limits of detection near 1 ppm with a 5 {micro}l injection volume were obtained. …

Analysis of the literature indicated that radon transport models significantly and consistently underpredict the advective entry into houses of soil-gas borne radon. Advective entry is the dominant mechanism resulting in high concentrations of radon indoors. The author investigated the source of the model-measurement discrepancy via carefully controlled field experiments conducted at an experimental basement located in natural soil in Ben Lomond, California. Early experiments at the structure confirmed the existence and magnitude of the model-measurement discrepancy, ensuring that it was not merely an artifact of inherently complex and poorly understood field sites. The measured soil-gas entry rate during structure depressurization was found to be an order of magnitude larger than predicted by a current three-dimensional numerical model of radon transport. The exact magnitude of the discrepancy depends on whether the arithmetic or geometric mean of the small-scale measurements of permeability is used to estimate the effective permeability of the soil. This factor is a critical empirical input to the model and was determined for the Ben Lomond site in the typical fashion using single-probe static depressurization measurements at multiple locations. The remainder of the dissertation research tests a hypothesis to explain the observed discrepancy: that soil permeability assessed using relatively …

A letter and list of candidates supported by the Gay and Lesbian Victory Fund.

Femtosecond time- and angle-resolved two-photon photoemission spectroscopy has been used to study fundamental aspects of excited electron dynamics at metal-dielectric interfaces, including layer-by-layer evolution of electronic structure and two-dimensional electron localization. On bare Ag(111), the lifetimes of image states are dominated by their position with respect to the projected bulk band structure. The n = 2 state has a shorter lifetime than the n = 1 state due to degeneracy with the bulk conduction band. As the parallel momentum of the n = 1 image electron increases, the lifetime decreases. With decreasing temperatures, the n = 1 image electrons, with zero or nonzero parallel momentum, all become longer lived. Adsorption of one to three layers of n-heptane results in an approximately exponential increase in lifetime as a function of layer thickness. This results from the formation of a tunneling barrier through which the interfacial electrons must decay, consistent with the repulsive bulk electron affinity of n-alkanes. The lifetimes of the higher quantum states indicate that the presence of the monolayer significantly reduces coupling of the image states to the bulk band structure. These results are compared with predictions of a dielectric continuum model. The study of electron lateral motion shows …

A model has been developed which describes the ablation process of frozen hydrogen pellets in an electromagnetic railgun. The model incorporates the neutral gas shielding model in which the pellet surface is heated by incident electrons from the plasma arc. The heated surface then ablates, forming a neutral cloud which attenuates the incoming electrons. The energy lost in the cloud by the electrons heats the ablatant material as it flows into the plasma arc. Under steady-state conditions, a scaling law for the ablation rate was derived as a function of plasma-arc temperature and density. In addition, flow conditions and the criteria for the existence of a steady-state solution were formulated and subsequently examined under simplifying assumptions. Comparison with experimentally observed ablation rates shows good qualitative agreement.

The {alpha}-induced thick-target {gamma}-ray yield from light elements has been measured in the energy range 5.6 MeV {le} E{sub {alpha}} {le} 10 MeV. The {gamma}-ray yield for > 2.1 MeV from thick targets of beryllium, boron nitride, sodium fluoride, magnesium, aluminum and silicon were measured using the {alpha}-particle beam from the Lawrence Berkeley Laboratories 88 in. cyclotron. The elemental yields from this experiment were used to construct the {alpha}-induced direct production {gamma}-ray spectrum from materials in the SNO detector, a large volume ultra-low background neutrino detector located in the Creighton mine near Sudbury, Canada. This background source was an order of magnitude lower than predicted by previous calculations. These measurements are in good agreement with theoretical calculations of this spectrum based on a statistical nuclear model of the reaction, with the gross high energy spectrum structure being reproduced to within a factor of two. Detailed comparison of experimental and theoretical excitation population distribution of several residual nuclei indicate the same level of agreement within experimental uncertainties.

Angle-resolved photoemission extended fine structure (ARPEFS) was used to study molecular and metallic overlayers on metal surfaces through analysis of p2mg(2{times}1)CO/Ni(110) and the p(2{times}2)K/Ni(111) adsorption. For the dense p2mg(2{times}1)CO/Ni(110) surface layer, photoemission intensities from C 1s level were measured in three directions at photoelectron kinetic energies 60-400 eV. Using multiple-scattering spherical-wave (MSSW) modeling, it was found that CO molecules are adsorbed on short-bridge sites, with adjacent CO along the [110] direction displaced alternatively in opposite directions towards the [001] azimuths to form a zigzag chain geometry. The tilt angle is 16{plus_minus}2{degree} from the surface normal for the direction linking the C atom and the center of the Ni bridge. The carbon C-Ni interatomic distance was determined to be 1.94{plus_minus}0.02{Angstrom}. The first- to second-layer spacing of Ni is 1.27{plus_minus}0.04{Angstrom}, up from 1.10{Angstrom} for the clean Ni(110) surface, but close to the 1.25{Angstrom} Ni interlayer spacing in the bulk. The C-O bond length and tilt angle were varied within small ranges (1.10--1.20{Angstrom} and 15--23{degrees}) in our MSSW simulations. Best agreement between experiment and simulations was achieved at 1.16{Angstrom} and 19{degrees}. This yields an O-O distance of 2.95{Angstrom} for the two nearest CO molecules, (van der Waals` radius {approximately} 1.5 {Angstrom} for oxygen). …