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 National Ignition Facility (NIF) will use the world's largest laser to compress and heat BB-sized capsules of fusion fuel to thermo-nuclear ignition. NIF experiments will produce temperatures and densities like those in the Sun or in an exploding nuclear weapon. The experiments will help scientists sustain confidence in the nuclear weapon stockpile without nuclear tests as a unique element of the DOE'S Stockpile Stewardship Program and will produce additional benefits in basic science and fusion energy.

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.

An experimental investigation of soft x-ray production resulting from the interaction of intense near infra-red laser radiation with gases is presented in this thesis. Specifically, soft x-ray generation through high order harmonic generation or exploiting intense inverse bremsstrahlung heating is examined. Most of these studies are conducted with femtosecond, terawatt class Cr:LiSrAlF{sub 6} (LiSAF) laser, though results derived from studies with other laser systems are presented as well. The majority of this work is devoted to experimental investigations, however, theoretical and computational models are developed to interpret the data. These studies are motivated by the possibility of utilizing the physics of intense laser/matter interactions as a potential compact source of bright x-rays. Consequently, the thrust of many of the experiments conducted is aimed at characterizing the x-rays produced for possible use in applications. In general, the studies of this manuscript fall into three categories. First, a unique 130 fs, 8 TW laser that is based on chirped pulse amplification, is described, and its performance is evaluated. The generation of x-rays through high order harmonics is then discussed with emphasis on characterizing and optimizing harmonic generation. Finally, the generation of strong, incoherent x-ray radiation by the intense irradiation of large (>1,000 …

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. …

Capillary electrophoresis has been widely accepted as a fast separation technique in DNA analysis. In this dissertation, a new sieving matrix is described for DNA analysis, especially DNA sequencing, genetic typing and mutation detection. A high-throughput 96 capillary array electrophoresis system was also demonstrated for simultaneous multiple genotyping. The authors first evaluated the influence of different capillary coatings on the performance of DNA sequencing. A bare capillary was compared with a DB-wax, an FC-coated and a polyvinylpyrrolidone dynamically coated capillary with PEO as sieving matrix. It was found that covalently-coated capillaries had no better performance than bare capillaries while PVP coating provided excellent and reproducible results. The authors also developed a new sieving Matrix for DNA separation based on commercially available poly(vinylpyrrolidone) (PVP). This sieving matrix has a very low viscosity and an excellent self-coating effect. Successful separations were achieved in uncoated capillaries. Sequencing of M13mp18 showed good resolution up to 500 bases in treated PVP solution. Temperature gradient capillary electrophoresis and PVP solution was applied to mutation detection. A heteroduplex sample and a homoduplex reference were injected during a pair of continuous runs. A temperature gradient of 10 C with a ramp of 0.7 C/min was swept throughout the …

This thesis comprises three parts: Electrocatalysis of anodic oxygen-transfer reactions: aliphatic amines at mixed Ag-Pb oxide thin-film electrodes; oxidation of ammonia at anodized Ag-Pb eutectic alloy electrodes; and temperature effects on oxidation of ethylamine, alanine, and aquated ammonia.

An ocean model with adaptive mesh refinement (AMR) capability is presented for simulating ocean circulation on decade time scales. The model closely resembles the LLNL ocean general circulation model with some components incorporated from other well known ocean models when appropriate. Spatial components are discretized using finite differences on a staggered grid where tracer and pressure variables are defined at cell centers and velocities at cell vertices (B-grid). Horizontal motion is modeled explicitly with leapfrog and Euler forward-backward time integration, and vertical motion is modeled semi-implicitly. New AMR strategies are presented for horizontal refinement on a B-grid, leapfrog time integration, and time integration of coupled systems with unequal time steps. These AMR capabilities are added to the LLNL software package SAMRAI (Structured Adaptive Mesh Refinement Application Infrastructure) and validated with standard benchmark tests. The ocean model is built on top of the amended SAMRAI library. The resulting model has the capability to dynamically increase resolution in localized areas of the domain. Limited basin tests are conducted using various refinement criteria and produce convergence trends in the model solution as refinement is increased. Carbon sequestration simulations are performed on decade time scales in domains the size of the North Atlantic and …

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 …

The kinetics of the reactions of C{sub 2}H{sub 5} radical with Co(NH{sub 3}){sub 5}X{sup 2+}, Ru(NH{sub 3}){sub 5}X{sup 2+}, and Co(dmgH){sub 2} (X) (Y) (X = Br, Cl, N{sub 3}, SCN; Y = H{sub 2}O, CH{sub 3}CN) complexes were studied using laser flash photolysis of ethylcobalt complexes. The kinetics were obtained by the kinetic probe method. Some relative rate constants were also determined by a competition method based on ethyl halide product ratios. The kinetics of colligation reactions of a series of alkyl radicals with {beta}-Ni(cyclam){sup 2+} were studied using flaser flash photolysis of alkylcobalt complexes. Again, the kinetics were obtained by employing the kinetic probe competition method. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H{sub 2}O{sup 2+} were studied. Activation parameters were obtained for the unimolecular homolysis of C{sub 2}H{sub 5}Ni(cyclam)H{sub 2}O{sup 2+}. Kinetic and thermodynamic data obtained from these reactions were compared with those for the {sigma}-bonded organometallic complexes. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H{sub 2}O{sup 2+} complexes were studied by monitoring the formation of the oxygen insertion product RO{sub 2}Ni(cyclam)H{sub 2}O{sup 2+}. The higher rate constants for the reactions of alkyl radicals with oxygen in solution, as compared with …

It was hypothesized that the variations in time to solution are driven by the competing mechanisms of exploration and exploitation.This thesis explores this hypothesis by examining two contrasting problems that embody the hypothesized tradeoff between exploration and exploitation. Plus one recall store (PORS) is an optimization problem based on the idea of a simple calculator with four buttons: plus, one, store, and recall. Integer addition and store are classified as operations, and one and memory recall are classified as terminals. The goal is to arrange a fixed number of keystrokes in a way that maximizes the numerical result. PORS 15 (15 keystrokes) represents the subset of difficult PORS problems and PORS 16 (16 keystrokes) represents the subset of PORS problems that are easiest to optimize. The goal of this work is to examine the tradeoff between exploitation and exploration in graph based evolutionary algorithm (GBEA) optimization. To do this, computational experiments are used to examine how solutions evolve in PORS 15 and 16 problems when solved using GBEAs. The experiment is comprised of three components; the graphs and the population, the evolutionary algorithm rule set, and the example problems. The complete, hypercube, and cycle graphs were used for this experiment. …

This study investigates the neutronics design aspects of a hybrid fusion-fission energy system called the Laser Fusion-Fission Hybrid (LFFH). A LFFH combines current Laser Inertial Confinement fusion technology with that of advanced fission reactor technology to produce a system that eliminates many of the negative aspects of pure fusion or pure fission systems. When examining the LFFH energy mission, a significant portion of the United States and world energy production could be supplied by LFFH plants. The LFFH engine described utilizes a central fusion chamber surrounded by multiple layers of multiplying and moderating media. These layers, or blankets, include coolant plenums, a beryllium (Be) multiplier layer, a fertile fission blanket and a graphite-pebble reflector. Each layer is separated by perforated oxide dispersion strengthened (ODS) ferritic steel walls. The central fusion chamber is surrounded by an ODS ferritic steel first wall. The first wall is coated with 250-500 {micro}m of tungsten to mitigate x-ray damage. The first wall is cooled by Li{sub 17}Pb{sub 83} eutectic, chosen for its neutron multiplication and good heat transfer properties. The {sub 17}Pb{sub 83} flows in a jacket around the first wall to an extraction plenum. The main coolant injection plenum is immediately behind the Li{sub …

Ultrasonic techniques have recently been applied to the texture characterization in polycrystalline aggregates of hexagonal crystals. The basis of this application lies in the relations between the elastic constants {bar C}{sub ij} of the aggregates, which can be inferred from ultrasonic wave velocity measurements, and the orientation distribution coefficients. This communication present such relations for aggregates which possess orthotopic material symmetry and hexagonal crystal symmetry for Voigt, Reuss, and Hill averaging methods in a unified and concise representation.

A variety of experimental techniques were utilized to examine the high temperature phase equilibria in the Bi-Sr-Ca-Cu-O-Ag system. Quenching studies were used to determine the liquid solubility of Ag in the Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} (Bi2212) melt and the details of the peritectic decomposition pathway of Bi2212 as a function on Ag content and oxygen partial pressure (PO{sub 2}). A liquid immiscibility region between oxide and Ag liquids in the 8--98 at% range was found above 900 C. Two eutectics were found in the Bi2212-Ag pseudobinary. On the oxide rich side, a eutectic exists at approximately 4 at% Ag. On the Ag rich side, a eutectic exists at approximately 98 at% Ag at a temperature of 15 C below the melting point of pure Ag. Six distinct solid phases were found to be in equilibrium with the partial melt within the Ag content and PO{sub 2} range studied. The stability of these solid phases were found to be highly sensitive to PO{sub 2}, and to a much lesser extent Ag content. High temperature x-ray diffraction (HTXRD) studies of this system are in conflict with these results. It is suggested that these discrepancies are due to experimental artifacts caused by …

Generalized Parton Distributions (GPDs) are universal functions which provide a comprehensive description of hadron properties in terms of quarks and gluons. Deeply Virtual Compton Scattering (DVCS) is the simplest hard exclusive process involving GPDs. In particular, the DVCS on the neutron is mostly sensitive to E, the less constrained GPD, wich allows to access to the quark angular momentum. The first dedicated DVCS experiment on the neutron ran in the Hall A of Jefferson Lab in fall 2004. The high luminosity of the experiment and the resulting background rate recquired specific devices which are decribed in this document. The analysis methods and the experiment results, leading to preliminary constraints on the GPD E, are presented.

The processing of materials with unique electronic, mechanical, optical and thermal properties plays a crucial role in modern technology. The quality of these materials depend strongly on the microstructure and the solute/dopant fields in the solid product, that are strongly influenced by the intricate coupling of heat and mass transfer and melt flow in the growth systems. An integrated research program is developed that include precisely characterized experiments and detailed physical and numerical modeling of the complex transport and dynamical processes. Direct numerical simulation of the solidification process is carried out that takes into account the unsteady thermo-solutal convection in the vertical Bridgman crystal growth system, and accurately models the thermal interaction between the furnace and the ampoule by appropriately using experimentally measured thermal profiles. The flow instabilities and transitions and the nonlinear evolution following the transitions are investigated by time series and flow pattern analysis. A range of complex dynamical behavior is predicted with increasing thermal Rayleigh number. The route to chaos appears as: steady convection {r_arrow} transient mono-periodic {r_arrow} transient bi-periodic {r_arrow} transient quasi-periodic {r_arrow} transient intermittent oscillation-relaxation {r_arrow} stable intermittent oscillation-relaxation attractor. The spatio-temporal dynamics of the melt flow is found to be directly related to the …

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.

Chapter 1 of this thesis describes the various stages of tumor development and a multitude of diagnostic techniques used to detect cancer. Chapter 2 gives an overview of the aspects of hole burning spectroscopy important for its application to the study of cellular systems. Chapter 3 gives general descriptions of cellular organelles, structures, and physical properties that can serve as possible markers for the differentiation of normal and cancerous cells. Also described in Chapter 3 are the principles of cryobiology important for low temperature spectroscopy of cells, characterization of MCF-10F (normal) and MCF-7 (cancer) cells lines which will serve as model systems, and cellular characteristics of aluminum phthalocyanine tetrasulfonate (APT), which was used as the test probe. Chapters 4 and 5 are previously published papers by the author pertaining to the results obtained from the application of hole burning to the study of cellular systems. Chapter 4 presents the first results obtained by spectral hole burning of cellular systems and Chapter 5 gives results for the differentiation of MCF-10F and MCF-7 cells stained with APT by an external applied electric (Stark) field. A general conclusion is presented in Chapter 6. Appendices A and B provide additional characterization of the cell/probe …

Suppression of mass spectral peaks due to matrix problem is a major hurdle to overcome during identification work. So far, preliminary studies have been done in investigating solutions containing various percentages of nitric and hydrochloric acid. Since other anions would also be present in real samples, also needed to be examined is how the extent of suppression of metal complexes by Cl{sup {minus}} compares with suppression by other anions such as PO{sub 4}{sup 3{minus}} or SO{sub 4}{sup 2{minus}}. If suppression of other anions is as severe as that of the chloride ion, then it would be virtually impossible to analyze unknown samples containing large amount of such anions by direct infusion electrospray mass spectrometry. It seems like a separation step is needed to separate these matrix anions from the metal complexes prior to putting the solution through the electrospray. However, separation of inorganic complexes can be difficult and has not been studied thoroughly as LC separation of bioorganic compounds. Both zinc and copper chloro complexes have been observed to be more tolerant to higher amount of chloride ion present in a solution compared to the group I and II metal chloro complexes. Other transition metals including the lanthanide complexes need …

This study of the RAgSb{sub 2} series of compounds arose as part of an investigation of rare earth intermetallic compounds containing antimony with the rare earth in a position with tetragonal point symmetry. Materials with the rare earth in a position with tetragonal point symmetry frequently manifest strong anisotropies and rich complexity in the magnetic properties, and yet are simple enough to analyze. Antimony containing intermetallic compounds commonly possess low carrier densities and have only recently been the subject of study. Large single grain crystals were grown of the RAgSb{sub 2} (R=Y, La-Nd, Sm, Gd-Tm) series of compounds out of a high temperature solution. This method of crystal growth, commonly known as flux growth is a versatile method which takes advantage of the decreasing solubility of the target compound with decreasing temperature. Overall, the results of the crystal growth were impressive with the synthesis of single crystals of LaAgSb{sub 2} approaching one gram. However, the sample yield diminishes as the rare earth elements become smaller and heavier. Consequently, no crystals could be grown with R=Yb or Lu. Furthermore, EuAgSb{sub 2} could not be synthesized, likely due to the divalency of the Eu ion. For most of the RAgSb{sub 2} compounds, …

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 …

In today's environment, computers and networks are increasing exposed to a number of software vulnerabilities. Information about these vulnerabilities is collected and disseminated via various large publicly available databases such as BugTraq, OSVDB and ICAT. Each of these databases, individually, do not cover all aspects of a vulnerability and lack a standard format among them, making it difficult for end-users to easily compare various vulnerabilities. A central database of vulnerabilities has not been available until today for a number of reasons, such as the non-uniform methods by which current vulnerability database providers receive information, disagreement over which features of a particular vulnerability are important and how best to present them, and the non-utility of the information presented in many databases. The goal of this software vulnerability taxonomy consolidation project is to address the need for a universally accepted vulnerability taxonomy that classifies vulnerabilities in an unambiguous manner. A consolidated vulnerability database (CVDB) was implemented that coalesces and organizes vulnerability data from disparate data sources. Based on the work done in this paper, there is strong evidence that a consolidated taxonomy encompassing and organizing all relevant data can be achieved. However, three primary obstacles remain: lack of referencing a common ''primary …

It is well known that the activity, selectivity, and deactivation behavior of heterogeneous catalysts are strongly affected by a wide variety of parameters, including but not limited to nanoparticle size, shape, composition, support, pretreatment conditions, oxidation state, and electronic state. Enormous effort has been expended in an attempt to understand the role of these factors on catalytic behavior, but much still remains to be discovered. In this work, we have focused on deepening the present understanding of the role of nanoparticle shape, nanoparticle composition, and hot electrons on heterogeneous catalysis in the oxidation of carbon monoxide by molecular oxygen and nitric oxide. These reactions were chosen because they are important for environmental applications, such as in the catalytic converter, and because there is a wide range of experimental and theoretical insight from previous single crystal work as well as experimental data on nanoparticles obtained using new state-of-the-art techniques that aid greatly in the interpretation of results on complex nanoparticle systems. In particular, the studies presented in this work involve three types of samples: ~ 6.5 nm Rh nanoparticles of different shapes, ~ 15 nm Rh_1-xPd_x core-shell bimetallic polyhedra nanoparticles, and Rh ultra-thin film (~ 5 nm) catalytic nanodiodes. The colloidal …

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 …