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

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

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

A study of aluminum recovery from power plant fly ash by high temperature chlorination was undertaken to demonstrate that fly ash could be a potential source of aluminum, iron and possibly silicon. Magnetic separation of the iron oxide served as a first step to alleviate the iron contamination problem. However, the agglomeration of some iron oxide with alumina and silica made it difficult to completely separate the iron from the fly ash. Further iron separation was achieved by chlorinating the nonmagnetic ash fraction at 550/sup 0/C for 30 minutes. This reduced the iron oxide content to less than 4 percent by weight. Chlorine flow rates affected the reaction rate much more drastically than temperatures. This suggested that diffusion was the major rate-controlling step. Besides Fe/sub 2/O/sub 3/, Al/sub 2/O/sub 3/ and SiO/sub 2/, other oxides such as CaO, K/sub 2/O, Na/sub 2/O and MgO might have complicated the alumina recovery by forming individual chlorides or complexes. Investigating methods for separating more Fe/sub 2/O/sub 3/, and possibly CaO, K/sub 2/O, Na/sub 2/O and MgO from the nonmagnetic ash fraction before chlorinating it is highly recommended.

Remarkable advances have been made since rapid solidification was first introduced to the field of materials science and technology. New types of materials such as amorphous alloys and nanostructure materials have been developed as a result of rapid solidification techniques. While these advances are, in many respects, ground breaking, much remains to be discerned concerning the fundamental relationships that exist between a liquid and a rapidly solidified solid. The scope of the current dissertation involves an extensive set of experimental, analytical, and computational studies designed to increase the overall understanding of morphological selection, phase competition, and structural hierarchy that occurs under far-from equilibrium conditions. High pressure gas atomization and Cu-block melt-spinning are the two different rapid solidification techniques applied in this study. The research is mainly focused on Al-Si and Al-Sm alloy systems. Silicon and samarium produce different, yet favorable, systems for exploration when alloyed with aluminum under far-from equilibrium conditions. One of the main differences comes from the positions of their respective T{sub 0} curves, which makes Al-Si a good candidate for solubility extension while the plunging T{sub 0} line in Al-Sm promotes glass formation. The rapidly solidified gas-atomized Al-Si powders within a composition range of 15 to 50 …

Abstract: And investigation of the interactions between 300-Mev neutrons and xenon was made by means of a cloud chamber in a pulsed magnetic field of 21,700 gauss placed in the neutron beam of the 184-inch Berkeley cyclotron. Eighty-seven negative pion events and 257 other stars were analyzed. In addition an experimental check was made on the energy of the incoming neutrons. Classification, identification, and angular and energy distributions of prongs associated with all events are presented. Interpretations of results are given.

An investigation of the interactions between 300-Mev neutrons and xenon was made by means of a cloud chamber in a pulsed magnetic field of 21,700 gauss placed in the neutron beam of the 184-inch Berkeley cyclotron. Eighty-seven negative pion events and 257 other stars were analyzed. In addition an experimental check was made on the energy of the incoming neutrons. Classification, identification, and angular and energy distributions of prongs associated with all events are presented. Interpretations of results are given.

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

Single Particle Aerosol Mass Spectrometry (SPAMS) was evaluated as a real-time detection technique for single particles of high explosives. Dual-polarity time-of-flight mass spectra were obtained for samples of 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitro-1,3,5-triazinane (RDX), and pentaerythritol tetranitrate (PETN); peaks indicative of each compound were identified. Composite explosives, Comp B, Semtex 1A, and Semtex 1H were also analyzed, and peaks due to the explosive components of each sample were present in each spectrum. Mass spectral variability with laser fluence is discussed. The ability of the SPAMS system to identify explosive components in a single complex explosive particle ({approx}1 pg) without the need for consumables is demonstrated. SPAMS was also applied to the detection of Chemical Warfare Agent (CWA) simulants in the liquid and vapor phases. Liquid simulants for sarin, cyclosarin, tabun, and VX were analyzed; peaks indicative of each simulant were identified. Vapor phase CWA simulants were adsorbed onto alumina, silica, Zeolite, activated carbon, and metal powders which were directly analyzed using SPAMS. The use of metal powders as adsorbent materials was especially useful in the analysis of triethyl phosphate (TEP), a VX stimulant, which was undetectable using SPAMS in the liquid phase. The capability of SPAMS to detect high explosives and CWA …

Evaporated films of La, Ce, Yb, Y, Ag--Mn(5 percent), KCl, MnF$sub 2$, CsCl and LaF$sub 3$ were studied using the soft x-ray appearance potential spectroscopy (SXAPS) technique. Studies were also made of bulk polycrystalline samples of Y, Zr, Nb, and Mo. The results are discussed in terms of existing SXAPS theories. Several similarities between soft x-ray absorption (SXA) data and the SXAPS results are discussed, and it is shown that the SXA data can aid in the interpretation of SXAPS spectra when using the well-known self-convolution model. In this approximation the absorption coefficient, $alpha$(E), is substituted for the density of states, N(E-E/sub c/) $Yields$ $alpha$(E). For more localized excitations, a convolution of $alpha$(E) with bremsstrahlung isochromat data, based on Wendin's two density of states formalism is used to predict SNAPS results. (auth)

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.

Various single-molecule techniques were utilized for ultra-sensitive early diagnosis of viral DNA and antigen and basic mechanism study of enzymatic reactions. DNA of human papilloma virus (HPV) served as the screening target in a flow system. Alexa Fluor 532 (AF532) labeled single-stranded DNA probes were hybridized to the target HPV-16 DNA in solution. The individual hybridized molecules were imaged with an intensified charge-coupled device (ICCD) in two ways. In the single-color mode, target molecules were detected via fluorescence from hybridized probes only. This system could detect HPV-16 DNA in the presence of human genomic DNA down to 0.7 copy/cell and had a linear dynamic range of over 6 orders of magnitude. In the dual-color mode, fluorescence resonance energy transfer (FRET) was employed to achieve zero false-positive count. We also showed that DNA extracts from Pap test specimens did not interfere with the system. A surface-based method was used to improve the throughput of the flow system. HPV-16 DNA was hybridized to probes on a glass surface and detected with a total internal reflection fluorescence (TIRF) microscope. In the single-probe mode, the whole genome and target DNA were fluorescently labeled before hybridization, and the detection limit is similar to the flow …

This report addresses the design and performance of the atom probe field ion microscope.

Authenticated two-party Diffie-Hellman key exchange allows two principals A and B, communicating over a public network, and each holding a pair of matching public/private keys to agree on a session key. Protocols designed to deal with this problem ensure A (B resp.)that no other principals aside from B (A resp.) can learn any information about this value. These protocols additionally often ensure A and B that their respective partner has actually computed the shared secret value. A natural extension to the above cryptographic protocol problem is to consider a pool of principals agreeing on a session key. Over the years several papers have extended the two-party Diffie-Hellman key exchange to the multi-party setting but no formal treatments were carried out till recently. In light of recent developments in the formalization of the authenticated two-party Diffie-Hellman key exchange we have in this thesis laid out the authenticated group Diffie-Hellman key exchange on firmer foundations.

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A search for neutral supersymmetric Higgs bosons and work relating to the improvement of the b-tagging and trigger capabilities at the D0 detector during Run II of the Fermilab Tevatron collider is presented. The search for evidence of the Higgs sector in the Standard Model (SM) and supersymmetric extensions of the SM are a high priority for the D0 collaboration, and b-tagging and good triggers are a vital component of these searches. The development and commissioning of the first triggers at D0 which use b-tagging is outlined, along with the development of a new secondary vertex b-tagging tool for use in the Level 3 trigger. Upgrades to the Level 3 trigger hit finding code, which have led to significant improvements in the quality and efficiency of the tracking code, and by extension the b-tagging tools, are also presented. An offline Neural Network (NN) b-tagging tool was developed, trained on Monte Carlo and extensively tested and measured on data. The new b-tagging tool significantly improves the b-tagging performance at D0, for a fixed fake rate relative improvements in signal efficiency range from {approx} 40% to {approx} 15%. Fake rates, for a fixed signal efficiency, are typically reduced to between a quarter …

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

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Theoretical methods for designing sequences of radio frequency (rf) radiation pulses for broadband excitation of spin systems in nuclear magnetic resonance (NMR) are described. The sequences excite spins uniformly over large ranges of resonant frequencies arising from static magnetic field inhomogeneity, chemical shift differences, or spin couplings, or over large ranges of rf field amplitudes. Specific sequences for creating a population inversion or transverse magnetization are derived and demonstrated experimentally in liquid and solid state NMR. One approach to broadband excitation is based on principles of coherent averaging theory. A general formalism for deriving pulse sequences is given, along with computational methods for specific cases. This approach leads to sequences that produce strictly constant transformations of a spin system. The importance of this feature in NMR applications is discussed. A second approach to broadband excitation makes use of iterative schemes, i.e. sets of operations that are applied repetitively to a given initial pulse sequences, generating a series of increasingly complex sequences with increasingly desirable properties. A general mathematical framework for analyzing iterative schemes is developed. An iterative scheme is treated as a function that acts on a space of operators corresponding to the transformations produced by all possible pulse sequences. …

From abstract: "A study of factors affecting the vapor handling capacity of perforated plate liquid-vapor contacting columns. Vapor phase pressure drop across plates, liquid entrainment upward from plate to plate, and plate stability were investigated as functions of operational and geometric column parameters."

Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu{sub 2}O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu{sub 2}O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu{sub 2}O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N{sub 2} and CO{sub 2}. At the end of each reaction, the catalyst was found to be Cu{sub 2}O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

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This document contains information about the characterization and application of microearthquake clusters and fault zone dynamics. Topics discussed include: Seismological studies; fault-zone dynamics; periodic recurrence; scaling of microearthquakes to large earthquakes; implications of fault mechanics and seismic hazards; and wave propagation and temporal changes.

The interaction between carbide coating formation rates and dissolution kinetics in the tantalum-carbon system was investigated. The research was driven by the need to characterize carbide coating formation rates. The characterization of the carbide coating formation rates was required to engineer an optimum processing scheme for the fabrication of the ultracorrosion-resistant composite, carbon-saturated tantalum. A packed-bed carburization process was successfully engineered and employed. The packed-bed carburization process produced consistent, predictable, and repeatable carbide coatings. A digital imaging analysis measurement process for accurate and consistent measurement of carbide coating thicknesses was developed. A process for removing the chemically stable and extremely hard tantalum-carbide coatings was also developed in this work.