The electrochemistry of the heterobimetallic complexes (fulvalene)WFe(CO){sub 5} (30) and (fulvalene)WRu(CO){sub 5} (31) has been investigated. Compound 30 is reduced in two one-electron processes, and this behavior was exploited synthetically to prepare a tetranuclear dimer by selective metal reduction. Complex 31 displayed a distinction between the metals upon reoxidation of the dianion, allowing the formation of a dimer by selective metal anion oxidation. The redox behavior of 30 led to an investigation of the use of electrocatalysis to effect metal-specific ligand substitution. It was found that reduction of 30 with a catalytic amount of CpFe(C{sub 6}Me{sub 6}) (97) in the presence of excess P(OMe){sub 3} or PMe{sub 3} led to the formation of the zwitterions (fulvalene)[W(CO){sub 3}{sup {minus}}][Fe(CO)PR{sub 3}{sup +}] (107, R = P(OMe){sub 3}; 108, R = PMe{sub 3}). Compound 31 also displayed unique behavior with different reducing agents, as the monosubstituted zwitterion (fulvalene)[W(CO){sub 3}{sup {minus}}][Ru(CO){sub 2}(PMe{sub 3}){sup +}] was obtained when 97 was used while the disubstituted complex (fulvalene) [W(CO){sub 3}{sup {minus}}] [Ru(CO)(PMe{sub 3}){sub 2}{sup +}] was produced when Cp*Fe(C{sub 6}Me{sub 6}) was the catalyst. Potential synthetic routes to quatercyclopentadienyl complexes were also explored. Various attempts to couple heterobimetallic fulvalene compounds proved to be unsuccessful. 138 refs.

This dissertation describes nuclear magnetic resonance experiments and theory which have been developed to study quadrupolar nuclei (those nuclei with spin greater than one-half) in the solid state. Primarily, the technique of dynamic-angle spinning (DAS) is extensively reviewed and expanded upon in this thesis. Specifically, the improvement in both the resolution (two-dimensional pure-absorptive phase methods and DAS angle choice) and sensitivity (pulse-sequence development), along with effective spinning speed enhancement (again through choice of DAS conditions or alternative multiple pulse schemes) of dynamic-angle spinning experiment was realized with both theory and experimental examples. The application of DAS to new types of nuclei (specifically the {sup 87}Rb and {sup 85}Rb nuclear spins) and materials (specifically amorphous solids) has also greatly expanded the possibilities of the use of DAS to study a larger range of materials. This dissertation is meant to demonstrate both recent advances and applications of the DAS technique, and by no means represents a comprehensive study of any particular chemical problem.

This study investigates effects of aging in air and argon at 170 C on Cu coupons which were pretinned with 75Sn-25Pb, 8Sn-92Pb, and 5Sn-95Pb solders. Coatings were applied using electroplating or hot dipping techniques. The coating thickness was controlled between 3 to 3{mu}m and the specimens were aged for 0 hours, 2 hours, 24 hours and 2 weeks. Wetting balance tests were used to evaluate the wettability of the test specimens. Microstructural development was evaluated using X-ray diffraction, energy dispersive X-ray and Auger spectroscopy, as well as optical and scanning electron microscopy. The wetting behavior of the test specimens is interpreted with respect to observed microstructural changes and as a function of aging time, solder composition, and processing conditions.

Radioactive metal waste makes up a significant portion of the waste currently being sent for disposal. Recovery of this metal as a valuable resource is possible through the use of decontamination technologies. Through the development and use of expert systems a comparison can be made of laser decontamination, a technology currently under development at Ames Laboratory, with currently available decontamination technologies for applicability to the types of metal waste being generated and the effectiveness of these versus simply disposing of the waste. These technologies can be technically and economically evaluated by the use of expert systems techniques to provide a waste management decision making tool that generates, given an identified metal waste, waste management recommendations. The user enters waste characteristic information as input and the system then recommends decontamination technologies, determines residual contamination levels and possible waste management strategies, carries out a cost analysis and then ranks, according to cost, the possibilities for management of the waste. The expert system was developed using information from literature and personnel experienced in the use of decontamination technologies and requires validation by human experts and assignment of confidence factors to the knowledge represented within.

Since an amorphous solid is often defined as that which lacks long-range order, the atomic structure is typically characterized in terms of the high-degree of short-range order. Most descriptions of vapor-deposited amorphous alloys focus on characterizing this order, while assuming that the material is chemically homogeneous beyond a few near neighbors. By coupling traditional small-angle x-ray scattering which probes spatial variations of the electron density with anomalous dispersion which creates a species-specific contrast, one can discern cracks and voids from chemical inhomogeneity. In particular, one finds that the chemical inhomogeneities which have been previously reported in amorphous Fe{sub x}Ge{sub 1-x} and Mo{sub x}Ge{sub 1-x} are quite anisotropic, depending significantly on the direction of film growth. With the addition of small amounts of metal atoms (x<0.2), no films appear isotropic nor homogeneous through the metal/insulator transition. The results indicate that fluctuations in the growth direction play a pivotal role in preventing simple growth models of a columnar structure or one that evolves systematically as it grows. The anomalous scattering measurements identify the metal atoms (Fe or Mo) as the source of the anisotropy, with the Ge atoms distributed homogeneously. The author has developed a method for using these measurements to determine …

This dissertation addresses the issue of composition modulation in sputtered amorphous metal-germanium thin films with the aim of understanding the intermediate range structure of these films as a function of composition. The investigative tool used in this work is anomalous small-angle X-ray scattering (ASAXS). The primary focus of this investigation is the amorphous iron-germanium (a-Fe{sub x}Ge{sub 100-x}) system with particular emphasis on the semiconductor-rich regime. Brief excursions are made into the amorphous tungsten-germanium (a-W{sub x}Ge{sub 100-x}) and the amorphous molybdenum-germanium (a-Mo{sub x}Ge{sub 100-x}) systems. All three systems exhibit an amorphous structure over a broad composition range extending from pure amorphous germanium to approximately 70 atomic percent metal when prepared as sputtered films. Across this composition range the structures change from the open, covalently bonded, tetrahedral network of pure a-Ge to densely packed metals. The structural changes are accompanied by a semiconductor-metal transition in all three systems as well as a ferromagnetic transition in the a-Fe{sub x}Ge{sub 100-x} system and a superconducting transition in the a-Mo{sub x}Ge{sub 100-x} system. A long standing question, particularly in the a-Fe{sub x}Ge{sub 100-x} and the a-Mo{sub x}Ge{sub 100-x} systems, has been whether the structural changes (and therefore the accompanying electrical and magnetic transitions) are accomplished …

The EQCM was used to study the deposition and composition of electrodeposited pure PbO{sub 2} and Bi-doped PbO{sub 2} active toward anodic oxygen-transfer reactions. Within the doped films, Bi is incorporated as Bi{sup +5} in the form of BiO{sub 2}A, where A is ClO{sub 4}{sup {minus}} or NO{sub 3}{sup {minus}}. For deposition of these 2 materials, changes in hydration between the Au oxide and the depositing film resulted in higher mass-to-charge ratios. XRD and XPS were used to study the films; the rutile structure of PbO{sub 2} is retained even with the Bi doping. The EQCM was also used to study the formation and dissolution of Au oxide and preoxide structures formed on the Au substrate electrodes in acidic media. The preoxide structures were AuOH and increased the surface mass. For the formation of stable Au films on quartz wafers, Ti interlayers between Au and quartz was found to be very effective.

This work is concerned with the development of approximate methods to describe relatively large chemical systems. This effort has been divided into two primary directions: First, we have extended and applied a semiclassical transition state theory (SCTST) originally proposed by Miller to obtain microcanonical and canonical (thermal) rates for chemical reactions described by a nonseparable Hamiltonian, i.e. most reactions. Second, we have developed a method to describe the fluctuations of decay rates of individual energy states from the average RRKM rate in systems where the direct calculation of individual rates would be impossible. Combined with the semiclassical theory this latter effort has provided a direct comparison to the experimental results of Moore and coworkers. In SCTST, the Hamiltonian is expanded about the barrier and the ``good`` action-angle variables are obtained perturbatively; a WKB analysis of the effectively one-dimensional reactive direction then provides the transmission probabilities. The advantages of this local approximate treatment are that it includes tunneling effects and anharmonicity, and it systematically provides a multi-dimensional dividing surface in phase space. The SCTST thermal rate expression has been reformulated providing increased numerical efficiency (as compared to a naive Boltzmann average), an appealing link to conventional transition state theory (involving a …

The main goal of the work presented in this thesis is produce highly spin-polarized xenon to create much greater signal intensities (up to 54,000 times greater) so as to allow studies to be made on systems with low surface area and long spin-lattice relaxation times. The spin-exchange optical pumping technique used to create high nuclear spin polarization is described in detail in chapter two. This technique is initially applied to some multiple-pulse optically detected NMR experiments in low magnetic field (50G) that allow the study of quadrupoler interactions with a surface of only a few square centimeters. In chapter three the apparatus used to allow high field {sup 129}Xe NMR studies to be performed with extremely high sensitivity is described and applied to experiments on diamagnetic susceptibility effects in thin ({approximately}2000 layers) films of frozen xenon. Preliminary surface investigations of laser polarized {sup 129}Xe adsorbed an a variety of materials (salts, molecular crystals, amorphous carbon, graphite) are then discussed. A full detailed study of the surface of a particular polymer, poly(acrylic acid), is presented in chapter four which shows the kind of detailed information that can be obtained from this technique. Along with preliminary results for several similar polymers, a …

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

The perturbed particle transport coefficients were determined for a range of plasma conditions in the Alcator C tokamak, a component of the Microwave Tokamak Experiment (MTX), from analysis of density perturbations created in gas modulation experiments. Density measurements from a 15 chord far-infrared interferometer were sufficiently detailed to allow radial profiles of the transport coefficients to be resolved. Gas modulation experiments were carried out on plasmas over a range of relatively low currents and a wide variety of line-averaged densities, including values near the Greenwald density limit. With this technique the perturbed diffusion coefficient D and the perturbed convection velocity V can be determined simultaneously. Measured profiles of D rise toward the outside of the plasma column in a manner generally similar to those determined previously for {chi}{sub e,HP} from sawtooth heat pulse propagation. Values of D are typically smaller than those of {chi}{sub e,HP} given for the same line-averaged densities by a factor of 2-5. Diffusion coefficients from a series of discharges at constant current showed little variation with density through most of the saturated ohmic confinement regime. At the Greenwald density limit threshold a dramatic increase occurred in both the perturbed convective and diffusive transport coefficients in the …

As the field of computational fluid dynamics (CFD) continues to mature, algorithms are required to exploit the most recent advances in approximation theory, numerical mathematics, computing architectures, and hardware. Meeting this requirement is particularly challenging in incompressible fluid mechanics, where primitive-variable CFD formulations that are robust, while also accurate and efficient in three dimensions, remain an elusive goal. This dissertation asserts that one key to accomplishing this goal is recognition of the dual role assumed by the pressure, i.e., a mechanism for instantaneously enforcing conservation of mass and a force in the mechanical balance law for conservation of momentum. Proving this assertion has motivated the development of a new, primitive-variable, incompressible, CFD algorithm called the Continuity Constraint Method (CCM). The theoretical basis for the CCM consists of a finite-element spatial semi-discretization of a Galerkin weak statement, equal-order interpolation for all state-variables, a 0-implicit time-integration scheme, and a quasi-Newton iterative procedure extended by a Taylor Weak Statement (TWS) formulation for dispersion error control. Original contributions to algorithmic theory include: (a) formulation of the unsteady evolution of the divergence error, (b) investigation of the role of non-smoothness in the discretized continuity-constraint function, (c) development of a uniformly H{sup 1} Galerkin weak statement …

In this dissertation the possibility that chaos and simple determinism are governing the dynamics of reversed field pinch (RFP) plasmas is investigated. To properly assess this possibility, data from both numerical simulations and experiment are analyzed. A large repertoire of nonlinear analysis techniques is used to identify low dimensional chaos in the data. These tools include phase portraits and Poincare sections, correlation dimension, the spectrum of Lyapunov exponents and short term predictability. In addition, nonlinear noise reduction techniques are applied to the experimental data in an attempt to extract any underlying deterministic dynamics. Two model systems are used to simulate the plasma dynamics. These are the DEBS code, which models global RFP dynamics, and the dissipative trapped electron mode (DTEM) model, which models drift wave turbulence. Data from both simulations show strong indications of low dimensional chaos and simple determinism. Experimental date were obtained from the Madison Symmetric Torus RFP and consist of a wide array of both global and local diagnostic signals. None of the signals shows any indication of low dimensional chaos or low simple determinism. Moreover, most of the analysis tools indicate the experimental system is very high dimensional with properties similar to noise. Nonlinear noise reduction …

This report discusses the problems of a large positive sodium void reactivity effect in liquid metal reactors which have received increased attention following the accident at Chernobyl, a light water reactor with a positive coolant void coefficient. While the probability of voiding sodium is small, a large positive sodium void reactivity effect is, in many minds, unacceptable. Analyses were performed on models of an advanced liquid metal reactors to determine the effects fuel type have on the sodium void reactivity effect. Three fuel types were considered; metal, oxide, and nitride. Calculations were performed using three-dimensional, multigroup diffusion theory. Two programs were developed to aid the analyses. One calculated the capture-to-fission ratio and the other calculated reaction rates of selected materials. A one-group equation was derived to determine a theoretical basis for the sodium void reactivity effect. An option was presented for a shortened core having a near-zero sodium-void worth. The effect on the sodium void reactivity effect of using actinides as fuel is also considered.

It proved possible to produce consistent, high-quality nanocrystalline ZnS powders with grain sizes as small as 8 nm. These powders are nano-porous and are readily impregnated with GaP precursor, although inconsistently. Both crystal structure and small grain size of the ZnS can be maintained through the use of GaP. Heat treatment of the impregnated powders results in a ZnS-GaP composite structure where the grain sizes of the phases are on the order of 10--20 nm. Conventional powder processing should be able to produce optically dense ceramic compacts with improved mechanical properties and suitable IR transmission.

The development of a versatile picosecond ultraviolet/vacuum ultraviolet temporal spectrometer and its potential use for measuring internal energy redistribution in isolated molecules are described in detail. A detailed description of the double-pass Nd:YAG amplifier and the dye amplifiers is given with the pulse energies achieved in the visible, ultraviolet, and vacuum ultraviolet. The amplified visible pulses are shown to be of sub-picosecond duration and near transform limited. The instrument`s temporal response ({le}10 ps) is derived from an instrument limited measurement of the dissociation lifetime of methyl iodide at 266 nm. The methyl iodide experiment is used to discuss the various sources of noise and background signals that are intrinsic to this type of experiment. Non-time-resolved experiments measuring the branching ratio and kinetic energy distributions of products from the 193 nm photodissociation of cyclopentadiene and thiophene are presented. These studies were done using the molecular beam Photofragment Translational Spectroscopy (PTS) technique. The results from the cyclopentadiene experiment confirm that H atom elimination to yield the cyclopentadienyl radical is the dominant dissociation channel. A barrier of {ge}5 kcal/mol can be understood in terms of the delocalization of the radical electron of the cyclopentadienyl fragment. A concerted elimination yielding cyclopropene and acetylene was …

This thesis is divided into 4 parts: a review, ion chromatography of metal cations on carboxylic resins, separation of hydrophilic organic acids and small polar compounds on macroporous resin columns, and use of eluent modifiers for liquid chromatographic separation of carboxylic acids using conductivity detection.

Polystyrene divinylbenzene was modified by acetyl, sulfonic acid, and quaternary ammonium groups. A resin functionalized with an acetyl group was impregnated in a PTFE membrane and used to extract and concentrate phenolic compounds from aqueous samples. The acetyl group created a surface easily wetted, making it an efficient adsorbent for polar compounds in water. The membrane stabilized the resin bed. Partially sulfonated high surface area resins are used to extract and group separate an aqueous mixture of neutral and basic organics; the bases are adsorbed electrostatically to the sulfonic acid groups, while the neutraons are adsorbed hydrophobically. A two-step elution is then used to separate the two fractions. A partially functionalized anion exchange resin is used to separate organic acids and phenols from neutrals in a similar way. Carboxylic acids are analyzed by HPLC and phenols by GC.

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 purpose of this study is to find aluminum alloys that are effective for use as wire vacuum seals in the 800MeV particle accelerator located at the Louis Anderson Meson Physics Facility (LAMPF) in Los Alamos, NM. Three alloys, Al 1100, Al 3003, and Al 6061, are investigated under uniaxial compression to determine stresses for a given height reduction from 0 to 70 percent, and to find plastic flow and surface interaction effects. Right-circular cylindrical specimens are compressed on-end (cylindrically) and radially (for modeling as compressed wire). Aluminum 1100 and 3003 alloys are compared for length to diameter ratios of 1 and 2 for both compression types, and are then compared to results of radial compression of annealed small diameter Al 1100 wire currently used at LAMPE. The specimens are also compressed between three different platen surfaces, polished steel, etched steel, and aluminum 6061-T6, to determine effects of friction. The Al 3003 alloy exhibits 20 to 25% lower stresses at all height reductions than Al 1100 for both cylindrical and radial compression.

This report neutron radiography measuring methods and the neutron radiography model.

The characteristics of martensitic transformations in solids are largely determined by the elastic strain that develops as martensite particles grow and interact. To study the development of microstructure, a finite-element computer simulation model was constructed to mimic the transformation process. The transformation is athermal and simulated at each incremental step by transforming the cell which maximizes the decrease in the free energy. To determine the free energy change, the elastic energy developed during martensite growth is calculated from the theory of linear elasticity for elastically homogeneous media, and updated as the transformation proceeds.

In this thesis the fundamental concepts of moderately coupled plasmas, for which 2{approx_lt}ln{Lambda}{sub b}{approx_lt}10, are, for the first time, presented. This investigation is motivated because neither the conventional Fokker-Planck approximation [for weakly coupled plasmas (ln{Lambda}{sub b}{approx_lt}10)] nor the theory of dielectric response with correlations for strongly coupled plasmas (ln{Lambda}{sub b}{approx_lt}1) has satisfactorily addressed this regime. Specifically, herein the standard Fokker-Planck operator for Coulomb collisions has been modified to include hitherto neglected terms that are directly associated with large-angle scattering. In addition a reduced electron-ion collision operator has been calculated that, for the first time, manifests 1/ln{Lambda}{sub b} corrections. Precise calculations of some relaxation rates and crude calculations of electron transport coefficients have been made. As one of major applications of the modified Fokker-Planck equation, the stopping powers and {rho}R have been calculated for charged fusion products ({alpha}`s, {sup 3}H, {sup 3}He) and hot electrons interacting with plasmas relevant to inertial confinement fusion. In the second major topic of this thesis, advances made in the area of laboratory x-ray sources are presented. First, and most importantly, through the use a Cockcroft-Walton linear accelerator, a charged particle induced x-ray emission (PIXE) source has been developed. Intense line x radiation (including K-, L-, …

Results are presented here from several two dimensional numerical calculations of events in Type II supernovae. A new 2-D hydrodynamics and neutrino transport code has been used to compute the effect on the supernova explosion mechanism of convection between the neutrinosphere and the shock. This convection is referred to as exterior convection to distinguish it from convection beneath the neutrinosphere. The model equations and initial and boundary conditions are presented along with the simulation results. The 2-D code was used to compute an exterior convective velocity to compare with the convective model of the Mayle and Wilson 1-D code. Results are presented from several runs with varying sizes of initial perturbation, as well as a case with no initial perturbation but including the effects of rotation. The M&W code does not produce an explosion using the 2-D convective velocity. Exterior convection enhances the outward propagation of the shock, but not enough to ensure a successful explosion. Analytic estimates of the growth rate of the neutron finger instability axe presented. It is shown that this instability can occur beneath the neutrinosphere of the proto-neutron star in a supernova explosion with a growth time of {approximately} 3 microseconds. The behavior of the …