Rock fractures play an important role in flow and contaminant transport in fractured aquifers, production of oil from petroleum reservoirs, and steam generation from geothermal reservoirs. In this dissertation, phenomenological aspects of flow in unsaturated fractures were studied in visualization experiments conducted on a transparent replica of a natural, rough-walled rock fracture for inlet conditions of constant pressure and flow rate over a range of angles of inclination. The experiments demonstrated that infiltrating liquid proceeds through unsaturated rock fractures along non-uniform, localized preferential flow paths. Even in the presence of constant boundary conditions, intermittent flow was a persistent flow feature observed, where portions of the flow channel underwent cycles of snapping and reforming. Two modes of intermittent flow were observed, the pulsating blob mode and the rivulet snapping mode. A conceptual model for the rivulet snapping mode was proposed and examined using idealized, variable-aperture fractures. The frequency of intermittent flow events was measured in several experiments and related to the capillary and Bond numbers to characterize this flow behavior.

The deuteron elastic structure functions, A(Q{sup 2}) and B(Q{sup 2}), have been extracted from cross section measurements of elastic electron-deuteron scattering in coincidence using the Continuous Electron Beam Accelerator and Hall A Facilities of Jefferson Laboratory. Incident electrons were scattered off a high-power cryogenic deuterium target. Scattered electrons and recoil deuterons were detected in the two High Resolution Spectrometers of Hall A. A(Q{sup 2}) was extracted from forward angle cross section measurements in the squared four-momentum transfer range 0.684 ≤ Q{sup 2} ≤ 5.90 (GeV/c){sup 2}. B(Q{sup 2}) was determined by means of a Rosenbluth separation in the range 0.684 ≤ Q{sup 2} ≤ 1.325 (GeV/c){sup 2}. The data are compared to theoretical models based on the impulse approximation with the inclusion of meson-exchange currents and to predictions of quark dimensional scaling and perturbative quantum chromodynamics. The results are expected to provide insights into the transition from meson-nucleon to quark-gluon descriptions of the nuclear two-body system.

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 …

Gas phase chromatography using The Heavy Element Volatility Instrument (HEVI) and the On Line Gas Apparatus (OLGA III) was used to determine volatilities of ZrBr{sub 4}, HfBr{sub 4}, RfBr{sub 4}, NbBr{sub 5}, TaOBr{sub 3}, HaCl{sub 5}, WBr{sub 6}, FrBr, and BiBr{sub 3}. Short-lived isotopes of Zr, Hf, Rf, Nb, Ta, Ha, W, and Bi were produced via compound nucleus reactions at the 88-Inch Cyclotron at Lawrence Berkeley National Laboratory and transported to the experimental apparatus using a He gas transport system. The isotopes were halogenated, separated from the other reaction products, and their volatilities determined by isothermal gas phase chromatography. Adsorption Enthalpy ({Delta}H{sub a}) values for these compounds were calculated using a Monte Carlo simulation program modeling the gas phase chromatography column. All bromides showed lower volatility than molecules of similar molecular structures formed as chlorides, but followed similar trends by central element. Tantalum was observed to form the oxybromide, analogous to the formation of the oxychloride under the same conditions. For the group 4 elements, the following order in volatility and {Delta}H{sub a} was observed: RfBr{sub 4} > ZrBr{sub 4} > HfBr{sub 4}. The {Delta}H{sub a} values determined for the group 4, 5, and 6 halides are in general …

Two processes are currently under consideration for the disposition of 35 MT of surplus plutonium through its conversion into fuel for power production. These processes are the ARIES process, by which plutonium metal is converted into a powdered oxide form, and MOX fuel fabrication, where the oxide powder is combined with uranium oxide powder to form ceramic fuel. This study was undertaken to determine the optimal size for both facilities, whereby the 35 MT of plutonium metal will be converted into fuel and burned for power. The bounding conditions used were a plutonium concentration of 3--7%, a burnup of 20,000--40,000 MWd/MTHM, a core fraction of 0.1 to 0.4, and the number of reactors ranging from 2--6. Using these boundary conditions, the optimal cost was found with a plutonium concentration of 7%. This resulted in an optimal throughput ranging from 2,000 to 5,000 kg Pu/year. The data showed minimal costs, resulting from throughputs in this range, at 3,840, 2,779, and 3,497 kg Pu/year, which results in a facility lifetime of 9.1, 12.6, and 10.0 years, respectively.

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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 …

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.

A main research interest is the characterization of monolayers formed by the spontaneous adsorption of organosulfur compounds at gold. This dissertation describes the development and application of long optical pathlength thin-layer spectroelectrochemistry in an attempt to address key issues regarding the reactivity of surface-immobilized molecules. The first section of this introductory chapter briefly describes the general approach to the preparation and characterization of these films. The last section provides an overview of the main principles and advantages of thin-layer spectroelectrochemistry for studying surface-adsorbed species. The body of this dissertation is divided into four chapters. Chapter 2 consists of a paper describing the design, construction, and characterization of a cuvette-based LOPTLC. Chapter 3 is a paper which examines the reductive desorption process using thin-layer spectroelectrochemistry to monitor and identify the desorption product. Chapter 4 is a paper describing the characterization of monolayers functionalized with a catechol terminal group which serves as a redox transformable coordination site for metal ion binding. Chapter 5 discusses the application of thin-layer spectroelectrochemistry to acid-base reactivity studies of surface-immobilized molecules. The final section provides some general conclusions and a prospectus for future studies. These chapters have been processed separately for inclusion on the data base. This …

Microscale separation and detection methods for real-time monitoring of dynamic cellular processes (e.g., secretion) by capillary electrophoresis (CE) and microscopic imaging were developed. Ultraviolet laser-induced native fluorescence (LINF) provides simple, sensitive and direct detection of neurotransmitters and proteins without any derivatization. An on-column CE-LINF protocol for quantification of the release from single cell was demonstrated. Quantitative measurements of both the amount of insulin released from and the amount remaining in the cell ({beta}TC3) were achieved simultaneously. Secretion of catecholamines (norepinephrine (NE) and epinephrine (E)) from individual bovine adrenal chromaffin cells was determined using the on-column CE-LINF. Direct visualization of the secretion process of individual bovine adrenal chromaffin cells was achieved by LINF imaging microscopy with high temporal and spatial resolution. The secretion of serotonin from individual leech Retzius neurons was directly characterized by LINF microscopy with high spatial resolution.

This work describes the continued development of a new separation technique, electrochemically-modulated liquid chromatography (EMLC), from column design, retention mechanisms to pharmaceutical applications. The introduction section provides a literature review of the technique as well as a brief overview of the research in each of the chapters. This section is followed by four chapters which investigate the issues of EMLC column design, the retention mechanism of monosubstituted aromatic compounds, and the EMLC-based applications to two important classes of pharmaceutical compounds (i.e., corticosteroids and benzodiazepines). These four sections have been removed to process separately for inclusion on the database. The dissertation concludes with a general summary, a prospectus, and a list of references cited in the General Introduction. 32 refs.

The author`s group has previously shown that isocyanides are readily adsorbed from solutions to Au powder and bind to the Au surface in an end-on fashion through the terminal carbon. Later work demonstrated that the equilibrium constants for the reversible adsorption of electronically inequivalent isocyanides could be obtained using the Langmuir isotherm technique. This dissertation describes two projects completed which complement the initial findings of this group. Initially, several alkylisocyanides were synthesized to examine the effect of tail length on Au powder adsorption. It was observed that the length of the alkyl chain affected not only the Au surface binding affinity, but also the rate of surface saturation and saturation coverage values. Direct competition studies were also studied using a {sup 13}C-labeled isocyanide. These studies demonstrated the stabilization afforded by substrate-substrate packing forces in SAM`s formed by the longer chain isocyanides. In a second study, di and triisocyanides were synthesized to determine the effect that the length of the connecting link and the number of isocyanide groups (as points of attachment) have on Au adsorption stability. The work in this area describes the binding modes, relative binding affinities and surface coverage values for a series of flexible alkyl and xylyldiisocyanides …

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. …

The successful development of deformation-processed metal-metal composites (DMMC) offers the potential for ductile, high-strength structural materials with high-temperature stability. An infiltration casting process was used to permeate steel wool preforms with molten magnesium-lithium (Mg-Li) alloys. The selected matrix alloys were hexagonal close packed (HCP) Mg-4wt%Li or body centered cubic (BCC) Mg-12wt%Li; the low carbon steel wool fibers were predominantly BCC ferrite. These cast HCP/BCC and BCC/BCC composites were deformed by rolling or by extrusion and swaging. Mechanical properties, microstructure, and texture development of the composites were characterized at various levels of deformation. The HCP/BCC composites had limited formability at temperatures up to 400 C while the BCC/BCC composites had excellent formability during sheet rolling at room temperature but limited formability during swaging at room temperature. The tensile strengths of these HCP/BCC and BCC/BCC composite materials increased moderately with deformation, though less than predicted from rule of mixtures (ROM) calculations. The microstructure was characterized to correlate the filament size to the deformation strain and mechanical properties of the composite material. Stereological measurements of the filament size were used to adjust ROM calculations to reflect the actual deformation strain in the fibers. However, the experimental strengths of these composite materials were still …

This report discusses the following topics on superconductivity: nonlinearities in hard superconductors such as surface impedance of a type II superconductimg half space and harmonic generation and intermodulation due to alternating transport currents; and nonlinearities in superconducting weak links such as harmonic generation by a long Josephson Junction in a superconducting slab.

Solving the global illumination problem is equivalent to determining the intensity of every wavelength of light in all directions at every point in a given scene. The complexity of the problem has led researchers to use approximation methods for solving the problem on serial computers. Rather than using an approximation method, such as backward ray tracing or radiosity, the authors have chosen to solve the Rendering Equation by direct simulation of light transport from the light sources. This paper presents an algorithm that solves the Rendering Equation to any desired accuracy, and can be run in parallel on distributed memory or shared memory computer systems with excellent scaling properties. It appears superior in both speed and physical correctness to recent published methods involving bidirectional ray tracing or hybrid treatments of diffuse and specular surfaces. Like progressive radiosity methods, it dynamically refines the geometry decomposition where required, but does so without the excessive storage requirements for ray histories. The algorithm, called Photon, produces a scene which converges to the global illumination solution. This amounts to a huge task for a 1997-vintage serial computer, but using the power of a parallel supercomputer significantly reduces the time required to generate a solution. Currently, …

Capillary electrophoresis (CE) is an effective method for separating ionic species according to differences in their electrophoretic mobilities. CE separations of amino acids by direct detection are difficult due to their similar electrophoretic mobilities and low absorbances. However, native amino acids can be separated by CE as cations at a low pH by adding an alkanesulfonic acid to the electrolyte carrier which imparts selectivity to the system. Derivatization is unnecessary when direct UV detection is used at 185 nm. Simultaneous speciation of metal cations such as vanadium (IV) and vanadium (V) can easily be performed without complexation prior to analysis. An indirect UV detection scheme for acidic conditions was also developed using guanidine as the background carrier electrolyte (BCE) for the indirect detection of metal cations. Three chapters have been removed for separate processing. This report contains introductory material, references, and general conclusions. 80 refs.

Using high-accuracy numerical methods the author investigates the dynamics of independent electrons in both ideal and realistic superlattices subject to arbitrary ac and/or dc electric fields. For a variety of superlattice potentials, optically excited initial wave packets, and combinations of ac and dc electric fields, he numerically solves the time-dependent Schroedinger equation. In the case of ideal periodic superlattice potentials, he investigates a long list of dynamical phenomena involving multiple miniband transitions and time-dependent electric fields. These include acceleration effects associated with interminiband transitions in strong fields, Zener resonances between minibands, dynamic localization with ac fields, increased single-miniband transport with an auxiliary resonant ac field, and enhanced or suppressed interminiband probability exchange using an auxiliary ac field. For all of the cases studied, the resulting time-dependent wave function is analyzed by projecting the data onto convenient orthonormal bases. This allows a detailed comparison with approximately analytic treatments. In an effort to explain the rapid decay of experimentally measured Bloch oscillation (BO) signals the author incorporates a one-dimensional representation of interface roughness (IR) into their superlattice potential. He shows that as a result of IR, the electron dynamics can be characterized in terms of many discrete, incommensurate frequencies near the Block …

The primary objective of this research was to investigate the synthesis and characterization of Ni(OH){sub 2} powders by homogeneous precipitation. Previous research of the same method showed conflicting results and complete characterization of the particle morphology was not carried out. This study has produced precipitates having a composition of 2Ni(OH){sub 2}{center_dot}Ni(HCO{sub 3}){sub 1.85}(NO{sub 3}){sub 0.15}. The XRD patterns showed peaks commonly observed for {alpha}-Ni(OH){sub 2}. The precipitates produced from low and high cation concentration solutions showed that the mean particle size and specific surface area increased with aging time. The high specific surface area measured suggested that the particle growth occurred through the aggregation of nanosized crystallites. The TEM micrographs confirmed that the particles were actually aggregates of thin films or sheets that were crumpled and intertwined together. This work also investigated the effect of dispersant on the particle morphology. The addition of dispersants did not alter the density of the particles implying that the dispersants were not incorporated into the solid phase. A general decrease in mean particle size at each aging time was observed resulting in an increase in specific surface area. The use of dispersants provided steric hindrance for the particles in the solution to aggregate, thus …

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 …

Often a crystallographer obtains an electron density map which shows only part of the structure. In such cases, the phasing of the trial model is poor enough that the electron density map may show peaks in some of the atomic positions, but other atomic positions are not visible. There may also be extraneous peaks present which are not due to atomic positions. A method for determination of crystal structures that have resisted solution through normal crystallographic methods has been developed. PHASER is a series of FORTRAN programs which aids in the structure solution of poorly phased electron density maps by refining the crystallographic phases. It facilitates the refinement of such poorly phased electron density maps for difficult structures which might otherwise not be solvable. The trial model, which serves as the starting point for the phase refinement, may be acquired by several routes such as direct methods or Patterson methods. Modifications are made to the reverse transform process based on several assumptions. First, the starting electron density map is modified based on the fact that physically the electron density map must be non-negative at all points. In practice a small positive cutoff is used. A reverse Fourier transform is computed …

The equilibrium motion of vortices in two- and three-dimensional superconductors has been studied with a dc Superconducting QUantum Interference Device (SQUID). This technique has the advantage of probing the system in a non-invasive manner as well as providing dynamic information over many decades in frequency. Through measurements of the spectral density of magnetic flux noise, S{sub {Phi}}({omega}), as a function of temperature and applied magnetic field, the effects of proton and heavy ion irradiation on flux noise in crystals of YBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}} have been measured and compared with the effects on the critical current, J{sub c}. Both proton and heavy ion irradiation proved effective at reducing S{sub {Phi}}({omega}), with proton irradiation having a larger effect. Measurement of S{sub {Phi}}({omega}) due to the equilibrium Kosterlitz-Thouless-Berezinskii transition in two-dimensional Josephson Junction Arrays (JJAs) was studied as a function of temperature for three different arrays and using three different sensors. S{sub {Phi}} is shown to obey dynamic scaling over as many as five decades in frequency, and estimates are made for the dynamic critical exponent z. An analytic theory for the high- and low-frequency behavior of S{sub {Phi}}({omega}) is presented and compared to the measured data, with the result that the …

Research into new semiconductor materials for measurement of electromagnetic radiation over a wide range of energies has been an active field for several decades. There is a strong desire to identify and develop new materials which can lead to improved detectors. Such devices are expected to solve problems that cannot be solved using the semiconductor materials and device structures which have been traditionally used for radiation detection. In order for a detector which is subjected to some type of irradiation to respond, the radiation must undergo an interaction with the detector. The net result of the radiation interaction in a broad category of detectors is the generation of mobile electric charge carriers (electrons and/or holes) within the detector active volume. This charge is collected at the detector contacts and it forms the basic electrical signal. Typically, the collection of the charge is accomplished through the imposition of an electric field within the detector which causes the positive and/or negative charges created by the radiation to flow in opposite directions to the contacts. For the material to serve as a good radiation detector, a large fraction (preferably 100%) of all carriers created by the interacting incident radiation must be collected. Charge …

Various hydrogenation reactions on transition metals are important commercially whereas certain hydrogenolysis reactions are useful from fundamental point of view. Understanding the hydrogen mobility and kinetics of adsorption-desorption of hydrogen is important in understanding the mechanisms of such reactions involving hydrogen. The kinetics of hydrogen chemisorption was studied by means of selective excitation NMR on silica supported Pt, Rh and Pt-Rh catalysts. The activation energy of hydrogen desorption was found to be lower on silica supported Pt catalysts as compared to Rh and Pt-Rh catalysts. It was found that the rates of hydrogen adsorption and desorption on Pt-Rh catalyst were similar to those on Rh catalyst and much higher as compared to Pt catalyst. The Ru-Ag bimetallic system is much simpler to study than the Pt-Rh system and serves as a model system to characterize more complicated systems such as the K/Ru system. Ag was found to decrease the amounts of adsorbed hydrogen and the hydrogen-to-ruthenium stoichiometry. Ag reduced the populations of states with low and intermediate binding energies of hydrogen on silica supported Ru catalyst. The rates of hydrogen adsorption and desorption were also lower on silica supported Ru-Ag catalyst as compared to Ru catalyst. This report contains introductory …