La{sub 2{minus}x}Sr{sub x}CuO{sub 4} (0 {le} x {le} 0.15) can all be intercalated with oxygen by a novel electrochemical oxidation method. Bulk superconductivity is found with an onset {Tc} {approx} 40 K for the whole range 0.01 {le} x {le} 0.15; for x = 0.25 and 0.33, the electrochemical oxidation did not improve the superconducting properties. The magnetic susceptibility {chi}(T = 50--320 K) data for La{sub 2}CuO{sub 4.11} and La{sub 1.92}Sr{sub 0.08}CuO{sub 4.07} are nearly identical with those of conventionally prepared La{sub 1.85}Sr{sub 0.15}CuO{sub 4}, indicating that the hole doping level (p) in the CuO{sub 2} planes of the three compounds is nearly the same. Combined thermogravimetric analysis and iodometric titration experiments indicate that part of the intercalated oxygen has a formal valence close to {minus}1. The maximum doped-hole concentration in the CuO{sub 2} planes that can be achieved from combined Sr-doping and electrochemical oxygen doping for 0 {le} x {le} 0.15 is p {approx} 0.16 holes/formula unit. Oxygen can also intercalate into single crystal La{sub 2}CuO{sub 4} through a slow electrochemical oxidation process. The required low current and long time for the charging process reflects that the oxygen intercalation for a single crystal is limited by its small specific …

Hydrogenated amorphous silicon and related materials have been applied to radiation detectors, utilizing their good radiation resistance and the feasibility of making deposits over a large area at low cost. Effects of deposition parameters on various material properties of a-Si:H have been studied to produce a material satisfying the requirements for specific detection application. Thick(-{approximately}50 {mu}m), device quality a-Si:H p-i-n diodes for direct detection of minimum ionizing particles have been prepared with low internal stress by a combination of low temperature growth, He-dilution of silane, and post annealing. The structure of the new film contained voids and tiny crystalline inclusions and was different from the one observed in conventional a-Si:H. Deposition on patterned substrates was attempted as an alternative to controlling deposition parameters to minimize substrate bending and delamination of thick a-Si:H films. Growth on an inversed-pyramid pattern reduced the substrate bending by a factor of 3{approximately}4 for the same thickness film. Thin (0.1 {approximately} 0.2 {mu}m) films of a-Si:H and a-SiC:H have been applied to microstrip gas chambers to control gain instabilities due to charges on the substrate. Light sensitivity of the a-Si:H sheet resistance was minimized and the surface resistivity was successfully` controlled in the range of 10{sup …

Three complementary surface structure probes, x-ray photoelectron diffraction (XPD), scanning tunneling microscopy (STM), and low-energy electron diffraction (LEED) have been combined in a single instrument. This experimental system has been utilized to study the structure and growth mechanisms of iron oxide films on Pt(111); these films were formed by first depositing a single overlayer of Fe with a certain coverage in monolayers (ML`s), and then thermally oxidizing it in an oxygen atmosphere. For films up to {approximately}1 ML in thickness, a bilayer of Fe and O similar to those in FeO(111) is found to form. In agreement with prior studies, STM and LEED show this to be an incommensurate oxide film forming a lateral superlattice with short- and long-range periodicities of {approximately}3.1 {Angstrom} and {approximately}26.0 {Angstrom}. XPD in addition shows a topmost oxygen layer to be relaxed inward by -0.6 {Angstrom} compared to bulk FeO(111), and these are new structural conclusions. The oxygen stacking in the FeO(111) bilayer is dominated by one of two possible binding sites. For thicker iron oxide films from 1.25 ML to 3.0 ML, the growth mode is essentially Stranski-Krastanov: iron oxide islands form on top of the FeO(111) bilayer mentioned above. For iron oxide films …

Before experiments using actinide elements are performed, synthetic routes are tested using lanthanides of comparable ionic radii as surrogates. Compound and solid solution formation in several lanthanide-containing titanate and zircono-titanate systems have been established using X-ray diffraction (XRD) analysis, which helped to define interesting and novel experiments, some of which have been performed and are discussed, for selected actinide elements. The aqueous solubilities of several lanthanide- and actinide-containing compounds, representative of the systems studied, were tested in several leachants, including the WIPP {open_quotes}A{close_quotes} brine, following modified Materials Characterization Center procedures (MCC-3). The WIPP {open_quotes}A{close_quotes} brine is a synthetic substitute for that found in nature at the Waste Isolation Pilot Plant (WIPP) in New Mexico. The concentrations of cerium, used as a surrogate for plutonium, leached by the WIPP {open_quotes}A{close_quotes} brine from all the cerium-containing compounds and solid solutions tested were below the Inductively Coupled Plasma (ICP) atomic emission spectrometry limit of detection (10 ppm) established for cerium in this brine. The concentrations of plutonium leached from the two plutonium-containing solid solutions were less than 1 ppm as determined by gross alpha counting and alpha pulse height analysis. Concentrations of strontium leached by the WIPP brine from stable strontium containing titanate …

This dissertation describes several three-body dissociations and the photodissociation of methyl radicals studied using photofragment translational spectroscopy. The first chapter provides an introduction to three body dissociation, examines current experimental methodology, and includes a discussion on the treatment of photofragment translational spectroscopy data arising from three-body fragmentation. The ultraviolet photodissociation of azomethane into two methyl radicals and nitrogen is discussed in chapter 2. Chapter 3 describes the photodissociation of acetone at 248 nm and 193 nm. At 248 nm the translational energy release from the initial C-C bond cleavage matches the exit barrier height and a comparison with results at 266 nm suggests that <E{sub T}> is invariant to the available energy. A fraction of the nascent CH{sub 3}CO radicals spontaneously dissociate following rotational averaging. The <E{sub T}> for the second C-C bond cleavage also matches the exit barrier height. At 193 nm the experimental data can be successfully fit assuming that the dynamics are analogous to those at 248 nm. A simplified model of energy partitioning which adequately describes the experimental results is discussed. Experiments on acetyl halides provide additional evidence to support the proposed acetone dissociation mechanism. A value of 17.0{+-}1.0 kcal/mole for the barrier height, CH{sub 3}CO …

Dicyclopentadienyluranium halide dimers have been prepared and their solution behavior examined. These molecules exist as dimers in solution, and the halide ligands undergo rapid site exchange on the NMR timescale above 50 C. Analogous dicyclopentadienyluranium hydroxide dimers have also been prepared; they oxidatively eliminate hydrogen to give the corresponding oxide dimers. Mechanism of this reaction is consistent with {alpha}migration of one of the hydroxide hydrogen atoms to a uranium center followed by elimination of hydrogen. Ground state of [(Me{sub 3}Si){sub 2}C{sub 5}H{sub 3}]{sub 3}M M = Nd, U and their base adducts has been examined by variable temperature magnetic susceptibility and EPR spectroscopy. The ground state is found to be {sup 4}I{sub 9/2} with a crystal field state consisting largely of J{sub z} = 1/2 lowest, in agreement with previous studies on tris-cyclopentadienylneodymium complexes. The zirconium metallocene Cp{sub 3}Zr has been prepared, characterized crystallographically, and its reactivity studied. Its chemical behavior is controlled by presence of an electron in the non-bonding, d{sub z}2 orbital which prevents formation of base adducts Of Cp{sub 3}Zr, but allows Cp{sub 3}Zr to abstract atoms from other molecules. Electonic and EPR spectra of Cp*{sub 2}TiX complexes, where Cp* is Me{sub 5}C{sub 5} and X is …

To gain insight on the controlling mechanisms for VOC transport in porous media, the relations among sorbent properties, sorption equilibrium and intraparticle diffusion processes were studied at the level of individual sorbent particles and laboratory columns for soil and activated carbon systems. Transport and sorption of VOCs and water vapor were first elucidated within individual dry soil mineral grains. Soil properties, sorption capacity, and sorption rates were measured for 3 test soils; results suggest that the soil grains are porous, while the sorption isotherms are nonlinear and adsorption-desorption rates are slow and asymmetric. An intragranular pore diffusion model coupled with the nonlinear Freundlich isotherm was developed to describe the sorption kinetic curves. Transport of benzene and water vapor within peat was studied; partitioning and sorption kinetics were determined with an electrobalance. A dual diffusion model was developed. Transport of benzene in dry and moist soil columns was studied, followed by gaseous transport and sorption in activated carbon. The pore diffusion model provides good fits to sorption kinetics for VOCs to soil and VOC to granular activated carbon and activated carbon fibers. Results of this research indicate that: Intraparticle diffusion along with a nonlinea sorption isotherm are responsible for the slow, …

The work documented in this thesis follows the traditional order. In this chapter a general discussion of ionic conduction and of glassy materials are followed by a brief outline of the experimental techniques for the investigation of fast ionic conduction in glassy materials, including NMR and impedance spectroscopy techniques. A summary of the previous and present studies is presented in the last section of this introductory chapter. The details of the background theory and models are found in the Chapter II, followed by the description of the experimental details in Chapter III. Chapter IV of the thesis describes the experimental results and the analysis of the experimental observations followed by the conclusions in chapter V.

The dissertation, titled ''Genetic Algorithms Applied to Nonlinear and Complex Domains'', describes and then applies a new class of powerful search algorithms (GAS) to certain domains. GAS are capable of solving complex and nonlinear problems where many parameters interact to produce a ''final'' result such as the optimization of the laser pulse in the interaction of an atom with an intense laser field. GAS can very efficiently locate the global maximum by searching parameter space in problems which are unsuitable for a search using traditional methods. In particular, the dissertation contains new scientific findings in two areas. First, the dissertation examines the interaction of an ultra-intense short laser pulse with atoms. GAS are used to find the optimal frequency for stabilizing atoms in the ionization process. This leads to a new theoretical formulation, to explain what is happening during the ionization process and how the electron is responding to finite (real-life) laser pulse shapes. It is shown that the dynamics of the process can be very sensitive to the ramp of the pulse at high frequencies. The new theory which is formulated, also uses a novel concept (known as the (t,t') method) to numerically solve the time-dependent Schrodinger equation Second, …

Release rates of 15 radionuclides from waste packages expected to result from partitioning and transmutation of Light-Water Reactor (LWR) and Actinide-Burning Liquid-Metal Reactor (ALMR) spent fuel are calculated and compared to release rates from standard LWR spent fuel packages. The release rates are input to a model for radionuclide transport from the proposed geologic repository at Yucca Mountain to the water table. Discharge rates at the water table are calculated and used in a model for transport to the accessible environment, defined to be five kilometers from the repository edge. Concentrations and dose rates at the accessible environment from spent fuel and wastes from reprocessing, with partitioning and transmutation, are calculated. Partitioning and transmutation of LWR and ALMR spent fuel reduces the inventories of uranium, neptunium, plutonium, americium and curium in the high-level waste by factors of 40 to 500. However, because release rates of all of the actinides except curium are limited by solubility and are independent of package inventory, they are not reduced correspondingly. Only for curium is the repository release rate much lower for reprocessing wastes.

The interaction of superconductivity with magnetism has been one of the most interesting and important phenomena in solid state physics since the 1950`s when small amounts of magnetic impurities were incorporated in superconductors. The discovery of the magnetic superconductors RNi{sub 2}B{sub 2}C (R = rare earth, Y) offers a new system to study this interaction. The wide ranges of superconducting transition (T{sub c}) and antiferromagnetic (AF) ordering temperatures (T{sub N}) (0 K {le} T{sub c} {le} 16 K, 0 K {le} T{sub N} {le} 20 K) give a good opportunity to observe a variety of interesting phenomena. Single crystals of high quality with appropriate size and mass are crucial in examining the anisotropic intrinsic properties. Single crystals have been grown successfully by an unusual high temperature flux method and characterized thoroughly by X-ray, electrical transport, magnetization, neutron scattering, scanning electron microscopy, and other measurements.

{sup 129}Xe NMR is potentially useful for the investigation of material surfaces, but has been limited to high surface area samples in which sufficient xenon can be loaded to achieve acceptable signal to noise ratios. In Chapter 2 conventional {sup 129}Xe NMR is used to study a high surface area polymer, a catalyst, and a confined liquid crystal to determine the topology of these systems. Further information about the spatial proximity of different sites of the catalyst and liquid crystal systems is determined through two dimensional exchange NMR in Chapter 3. Lower surface area systems may be investigated with spin-polarized xenon, which may be achieved through optical pumping and spin exchange. Optically polarized xenon can be up to 10{sup 5} times more sensitive than thermally polarized xenon. In Chapter 4 highly polarized xenon is used to examine the surface of poly(acrylonitrile) and the formation of xenon clathrate hydrates. An attractive use of polarized xenon is as a magnetization source in cross polarization experiments. Cross polarization from adsorbed polarized xenon may allow detection of surface nuclei with drastic enhancements. A non-selective low field thermal mixing technique is used to enhance the {sup 13}C signal of CO{sub 2} of xenon occluded in …

Volatile organic compounds (VOCs) are suspected to contribute significantly to ``Sick Building Syndrome`` (SBS), a complex of subchronic symptoms that occurs during and in general decreases away from occupancy of the building in question. A new approach takes into account individual VOC potencies, as well as the highly correlated nature of the complex VOC mixtures found indoors. The new VOC metrics are statistically significant predictors of symptom outcomes from the California Healthy Buildings Study data. Multivariate logistic regression analyses were used to test the hypothesis that a summary measure of the VOC mixture, other risk factors, and covariates for each worker will lead to better prediction of symptom outcome. VOC metrics based on animal irritancy measures and principal component analysis had the most influence in the prediction of eye, dermal, and nasal symptoms. After adjustment, a water-based paints and solvents source was found to be associated with dermal and eye irritation. The more typical VOC exposure metrics used in prior analyses were not useful in symptom prediction in the adjusted model (total VOC (TVOC), or sum of individually identified VOCs ({Sigma}VOC{sub i})). Also not useful were three other VOC metrics that took into account potency, but did not adjust for …

The dynamics of variable-density turbulent fluids are studied by direct numerical simulation. The flow is incompressible so that acoustic waves are decoupled from the problem, and implying that density is not a thermodynamic variable. Changes in density occur due to molecular mixing. The velocity field is, in general, divergent. A pseudo-spectral numerical technique is used to solve the equations of motion. Three-dimensional simulations are performed using a grid size of 128{sup 3} grid points. Two types of problems are studied: (1) the decay of isotropic, variable-density turbulence, and (2) buoyancy-generated turbulence in a fluid with large density fluctuations (such that the Boussinesq approximation is not valid). In the case of isotropic, variable-density turbulence, the overall statistical decay behavior, for the cases studied, is relatively unaffected by the presence of density variations when the initial density and velocity fields are statistically independent. The results for this case are in quantitative agreement with previous numerical and laboratory results. In this case, the initial density field has a bimodal probability density function (pdf) which evolves in time towards a Gaussian distribution. The pdf of the density field is symmetric about its mean value throughout its evolution. If the initial velocity and density fields …

Novel unsaturated polymers have been synthesized and studied as precursors to silicon carbide and third order nonlinear optical materials. X ray structures were obtained. Kinetic and mechanistic studies of the unique thermal isomerization of dimethylenedisilacyclobutane to a carbene were conducted.

This dissertation discusses studies of the electron-hole pair dynamics of CdS{sub x}Se{sub 1-x} semiconductor alloys for the entire compositional range from x = 1 to x = 0 as examined by the ultrafast fluorescence techniques of time correlated single photon counting and fluorescence upconversion. Specifically, samples with x = 1, .75, .5, .25, and 0 were studied each at a spread of wavelengths about its respective emission maximum which varies according to {lambda} = 718nm - 210x nm. The decays of these samples were found to obey a Kohlrausch distribution, exp [(t/{tau}){sup {beta}}], with the exponent 3 in the range .5-.7 for the alloys. These results are in agreement with those expected for localization due to local potential variations resulting from the random distribution of sulfur and selenium atoms on the element VI A sub-lattice. This localization can be understood in terms of Anderson localization of the holes in states whose energy distribution tails into the forbidden energy band-gap. Because these states have energy dependent lifetimes, the carriers can decay via many parallel channels. This distribution of channels is the ultimate source of the Kohlrausch form of the fluorescence decays.

This report described the oxidation and oxidation resistance of Ti{sub 5}Si{sub 3}, along with a discussion on general material properties. Single crystal studies of Ti{sub 5}Si{sub 3}Z{sub x} are included.

This thesis has been largely concerned with defining the oxidizing power of Ag(III) and Ag(II) in anhydrous hydrogen fluoride (aHF) solution. Emphasis was on cationic species, since in a cation the electronegativity of a given oxidation state is greatest. Cationic Ag(III) solv has a short half life at ordinary temperatures, oxidizing the solvent to elemental fluorine with formation of Ag(II). Salts of such a cation have not yet been preparable, but solutions which must contain such a species have proved to be effective and powerful oxidizers. In presence of PtF{sub 6}{sup {minus}}, RuF{sub 6}{sup {minus}}, or RhF{sub 6}{sup {minus}}, Ag(III) solv effectively oxidizes the anions to release the neutral hexafluorides. Such reactivity ranks cationic Ag(III) as the most powerfully oxidizing chemical agent known as far. Unlike its trivalent relative Ag (II) solv is thermodynamically stable in acid aHF. Nevertheless, it oxidizes IrF{sub 6}{sup {minus}} to IrF{sub 6} at room temperature, placing its oxidizing potential not more than 2 eV below that of cationic Ag(III). Range of Ag{sup 2+} (MF{sub 6}{sup {minus}}){sub 2} salts attainable in aHF has been explored. An anion must be stable with respect to electron loss to Ag{sup 2+}. The anion must also be a poor F{sup …

Time resolved dynamics of high intensity laser interactions with atomic clusters have been studied with both theoretical analysis and experiment. A short-pulse Ti:sapphire laser system, which could produce 50 mJ of energy in a 50 fs pulse, was built to perform these experiments. The laser used a novel single grating stretcher and was pumped, in part, by a custom Nd:YLF laser system, including 19 mm Nd:YLF amplifiers. It was found that there is an optimal pulse width to maximize absorption for a given cluster size. This optimal pulse width ranged from 400 fs for 85 A radius xenon clusters to 1.2 ps for 205 {angstrom} radius xenon clusters. Using a pump-probe configuration, the absorption of the probe radiation was observed to reach a maximum for a particular time delay between pump and probe, dependent on the cluster size. The delay for peak absorption was 800, 1400, and 2100 fs for 85 {angstrom}, 130 {angstrom}, and 170 {angstrom} radius xenon clusters respectively. Model calculations suggest that these effects are due to resonant heating of the spherical plasma in agreement with the hydrodynamic interpretation of cluster interactions. While this simple hydrodynamic code produces reasonable agreement with data, it does not include bulk …

The magnetic properties related to the following high temperature superconductors were measured utilizing a Faraday magnetometer: BaCuO{sub 2+x}, La{sub 2} CuO{sub 4}, Sr{sub 2} RhO{sub 4}, Sr{sub 2} VO{sub 4}, and Sr{sub 2} CuO{sub 3}. Neutron diffraction, magnetic susceptibility, and heat capacity measurements are discussed.

A prototype Compton scatter camera for imaging gamma rays has been built and tested. This camera addresses unique aspects of gamma-ray imaging at nuclear industrial sites, including gamma-ray energies in the 0.5 to 3.0 MeV range and polychromatic fields. Analytic models of camera efficiency, resolution and contaminating events are developed. The response of the camera bears strong similarity to emission computed tomography devices used in nuclear medicine. A direct Fourier based algorithm is developed to reconstruct two-dimensional images of measured gamma-ray fields. Iterative ART and MLE algorithms are also investigated. The point response of the camera to gamma rays of energies from 0.5 to 2.8 MeV is measured and compared to the analytic models. The direct reconstruction algorithm is at least ten times more efficient than the iterative algorithms are also investigated. The point response of the camera to gamma rays energies from 0.5 to 2.8 MeV is measured and compared to the analytic models. The direct reconstruction algorithm is at least ten times more efficient than the iterative algorithms and produces images that are, in general, of the same quality. Measured images of several phantoms are shown. Important results include angular resolutions as low as 4.4{degrees}, reproduction of phantom …

This report discusses the following topics: Circular magnetic x-ray dichroism at the ER L{sub 3} Edge; angular dependence of circular magnetic x-ray dichroism in rare earth compounds: and circular magnetic x-ray dichroism in crystalline and amorphous GDFE{sub 2}.

The behavior of two structural clay tile infilled frames subjected to dynamic loading is investigated. The testing was performed by USACERL using a biaxial shake table machine on which two framed infills were spaced nine feet apart and connected by steel trusses and an eight inch concrete roof slab. The infills were composed of structural clay tile block which were laid with the cores horizontal. The specimen was loaded in both the out-of-plane and in-plane directions using a site specific time history record. The testing focused on determining frame and panel load-deflection behavior, acceleration amplification, and frequency degradation characteristics. The out-of-plane tests resulted in little degradation of frequency which means there was little loss of stiffness. There was no evidence of the infill {open_quotes}walking-out{close_quotes} of the steel frame; in fact the infill still had substantial stability after completion of the out-of-plane tests. As a result of the gradual increase in ground motion in the in-plane testing, the stiffness of the specimen gradually decreased. Strength and stiffness characteristics obtained from the dynamic testing were comparable to results and behavior seen in static tests. Degradation in the panel was much more rapid under the stronger ground motions which were produced during the …

The inner-shell photoionized x-ray lasing scheme is an attractive method for achieving x-ray lasing at short wavelengths, via population inversion following inner-shell photoionization (ISPI). This scheme promises both a short wavelength and a short pulse source of coherent x rays with high average power. In this dissertation a very complete study of the ISPI x-ray laser scheme is done concerning target structure, filter design and lasant medium. An investigation of the rapid rise time of x-ray emission from targets heated by an ultra-short pulse high-intensity optical laser was conducted for use as the x-ray source for ISPI x-ray lasing. Lasing by this approach in C at a wavelength of 45 {angstrom} requires a short pulse (about 50 fsec) driving optical laser with an energy of 1-5 J and traveling wave optics with an accuracy of {approximately} 15 {micro}m. The optical laser is incident on a high-Z target creating a high-density plasma which emits a broadband spectrum of x rays. This x-ray source is passed through a filter to eliminate the low-energy x rays. The remaining high-energy x rays preferentially photoionize inner-shell electrons resulting in a population inversion. Inner-shell photoionized x-ray lasing relies on the large energy of a K-{alpha} transition …