The capacitance of the edge plane of pyrolytic graphite electrodes, in acetonitrile solutions, is measured by recording the current response to an applied triangular voltage sweep; TVS, and then fitting the current response with an appropriate function, (via a set of adjustable parameters). The pretreatment of the electrodes, the supporting electrolyte concentration used, and the frequency of the input TVS, were all found to affect the measured capacitance. In these experiments, a background current was also seen and the shape of the current output for the TVS; the charging/discharging curve, is shown to correlate with the magnitude of this background current. In addition, the size of the background current was found to have some dependence on the type of electrode pretreatment procedure used. 60 refs., 49 figs., 3 tabs.

An SFM has been constructed capable of operating at 143 K. Two contributions to SFM technology are described: a new method of fabricating tips, and new designs of SFM springs that significantly lower the noise level. The SFM has been used to image several biological samples (including collagen, ferritin, RNA, purple membrane) at 143 K and room temperature. No improvement in resolution resulted from 143 K operation; several possible reasons for this are discussed. Possibly sharper tips may help. The 143 K SFM will allow the study of new categories of samples, such as those prepared by freeze-frame, single molecules (temperature dependence of mechanical properties), etc. The SFM was used to cut single collagen molecules into segments with a precision of {le} 10 nm.

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.

This (<100 {Angstrom}) silica-alumina layers were tested as potential model heterogeneous acid catalysts for combined surface science and catalysis studies. Three preparation methods were used: oxidation of r3 {times} r3 R30 Al/Si(111) structure in UHV; deposition on Si(lll) from aqueous solution; and argon ion beam sputter deposition in UHV. The homogeneous thin layers are amorphous, and the chemical environment of surface atoms is similar to that of Si, Al and oxygen atoms on high surface area acid catalysts. Since the ion beam-deposited thin layer of silica-alumina has the same composition as the target zeolite this deposition method is a promising tool to prepare model catalysts using practical catalyst targets. The silica-alumina layers are active in cumene cracking, a typical acid catalyzed reaction. In order to clearly distinguish background reactions and the acid catalyzed reaction at least 20 cm{sup 2} catalyst surface area is needed. Two series of model platinum-alumina catalysts were prepared in a combined UHV -- high pressure reactor cell apparatus by depositing alumina on polycrystalline Pt foil and by vapor depositing Pt on a thin alumina layer on Au. Both model surfaces have been prepared with and without chlorine. AES, CO desorption as well as methyl cyclopentane (MCP) …

This thesis details measurements of electrostatic turbulence and transport in the Madison Symmetric Torus reversed field pinch. The electrostatic fluctuation levels are found to be large, with {tilde n}{sub e}/n{sub e} {approximately} 30%--55% and {tilde T}{sub e}/T{sub e} {approximately} 15%--40%. The frequency and wavenumber spectra are broad, with {Delta}n {approximately} 70--150 and {Delta}m {approximately} 3--6, and differ from measured magnetic fluctuation spectra. The transport inferred from coherence measurements indicates that electrostatic fluctuations can account for most of the observed particle losses, but contribute only {approximately}20% to the observed electron energy loss.

Electrostatic turbulence and transport measurements are performed on the Tokapole-II tokamak at the University of Wisconsin-Madison, as the safety-factor and the edge equilibrium gradients and varied substantially. Tokapole-II is a poloidal divertor tokamak capable of operating at a wide range of safety factors due to its unique magnetic limiter configuration. It also has retractable material limiters in a large scrape-off region, which permits the study of edge boundary conditions like density and temperature gradients. The turbulence is independent of safety factor, but strongly sensitive to the local density gradient, which itself depends upon the limiter configuration. When a material limiter is inserted in a high <qa> discharge, the density gradient is increased locally together with a local increase of the turbulence. On the other hand, limiter insertion in low <qa> discharges did not increase the density gradient as much and the turbulence properties are unchanged with respect to the magnetic limiter case. It is conducted then, that electrostatic turbulence is caused by the density gradient. Although the electrostatic fluctuation driven transport is enhanced in the large density gradient case, it is in all cases to small to explain the observed energy confinement times. To explore instabilities with small wavelengths, a …

MHD computations demonstrate that feedback can sustain reversal and reduce loop voltage in resistive-shell reversed field pinch (RFP) plasmas. In the absence of a close-fitting conducting shell, feedback with conducting coils {approximately}2R/a tearing modes resonant near axis is found to restore plasma parameters to nearly their levels with a close-fitting conducting shell. When original dynamo modes are stabilized, neighboring tearing modes grow to maintain the RFP dynamo more efficiently. This suggests that experimentally observed limits on RFP pulselengths to the order of the shell time can be overcome by applying feedback to a few helical modes. Feedback with resistive coils yields information on requirements for more physically realistic feedback systems and on the potentiality of improvement of resistive-shell plasma parameters beyond the conducting-shell case. Plasma response to shell rotation is investigated, and issues relevant to mode locking and feedback rotation of individual modes are discussed.

The objective of this study was to examine the hypothesis that select functional groups of bacteria from pristine sites have an innate ability to degrade synthetic aromatics that often contaminate groundwater environments,due to exposure to naturally occurring recalcitrant aromatics in their environment. This study demonstrates that subsurface microbial communities are capable of utilizing lignin and humic acid breakdown products. Utilizers of these compounds were found to be present in most all the wells tested. Even the deepest aquifer tested had utilizers present for all six of the aromatics tested. Highest counts for the aromatics tested were observed with the naturally occurring breakdown products of either lignin or humic acid. Carboxylic acids were found to be an important sole carbon source for groundwater bacteria possibly explained by the fact that they are produced by the oxidative cleavage of aromatic ring structures. The carbohydrate sole carbon sources that demonstrated the greatest densities were ones commonly associated with humics. This study indicates that utilization of naturally occurring aromatic compounds in the subsurface is an important nutritional source for groundwater bacteria. In addition, it suggests that adaptation to naturally occurring recalcitrant substrates is the origin of degradative pathways for xenobiotic compounds with analogous structure. …

The decay of hot nuclei formed in the reactions {sup 139}La + {sup 27}Al, {sup 51}V, {sup nat}Cu, and {sup 139}La were studied by the coincident detection of up to four complex fragments (Z > 3) emitted in these reactions. Fragments were characterized as to their atomic number, energy and in- and out-of-plane angles. The probability of the decay by an event of a given complex fragment multiplicity as a function of excitation energy per nucleon of the source is nearly independent of the system studied. Additionally, there is no large increase in the proportion of multiple fragment events as the excitation energy of the source increases past 5 MeV/nucleon. This is at odds with many prompt multifragmentation models of nuclear decay. The reactions {sup 139}La + {sup 27}Al, {sup 51}V, {sup nat}Cu were also studied by combining a dynamical model calculation that simulates the early stages of nuclear reactions with a statistical model calculation for the latter stages of the reactions. For the reaction {sup 139}La + {sup 27}Al, these calculations reproduced many of the experimental features, but other features were not reproduced. For the reaction {sup 139}La + {sup 51}V, the calculation failed to reproduce somewhat more of …

The analysis of light-cone wavefunctions seems the most promising theoretical approach to a detailed understanding of the structure of relativistic bound states, particularly hadrons. However, there are numerous complications in this approach. Most importantly, the light-cone approach sacrifices manifest rotational invariance in exchange for the elimination of negative-energy states. The requirement of rotational invariance of the full theory places important constraints on proposed light-cone wavefunctions, whether they are modelled or extracted from some numerical procedure. A formulation of the consequences of the hidden rotational symmetry has been sought for some time; it is presented in Chapter 2. In lattice gauge theory or heavy-quark effective theory, much of the focus is on the extraction of numerical values of operators which are related to the hadronic wavefunction. These operators are to some extent interdependent, with relations induced by fundamental constraints on the underlying wavefunction. The consequences of the requirement of unitarity are explored in Chapter 3, and are found to have startling phenomenological relevance. To test model light-cone wavefunctions, experimental predictions must be made. The reliability of perturbative QCD as a tool for making such predictions has been questioned. In Chapter 4, the author presents a computation of the rates for nucleon-antinucleon …

Oxide superconductors with high critical temperature {Tc} make sensitive thermometers for several types of infrared bolometers. The authors built composite bolometers with YBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}} thermometers on sapphire substrates which have higher sensitivity than competing thermal detectors which operate at temperatures above 77 K. A 1 x 1 mm bolometer with gold black serving as the radiation absorber has useful sensitivity for wavelengths 20--100 {mu}m. A 3 x 3 mm bolometer with a bismuth film as the absorber operates from 20--100 {mu}m. High-{Tc} bolometers which are fabricated with micromachining techniques on membranes of Si or Si{sub 3}N{sub 4} have potential application to large-format arrays which are used for infrared imaging. A nonisothermal high-{Tc} bolometer can be fabricated on a membrane of yttria-stabilized zirconia (YSZ) which is in thermal contact with the heat sink along the perimeter of the membrane. A thermal analysis indicates that the YSZ membrane bolometer can have improved sensitivity compared to the sapphire bolometer for spectrometer applications. The quasiparticle tunneling current in a superconductor-insulator-superconductor (SIS) junction is highly nonlinear in the applied voltage. The authors have made the first measurement of the linear response of the quasiparticle current in a Nb/AlO{sub x}/Nb junction over a broad …

Limestone can be used more effectively as a sorbent for H{sub 2}S in high-temperature gas-cleaning applications if it is prevented from undergoing calcination. Sorption of H{sub 2}S by limestone is impeded by sintering of the product CaS layer. Sintering of CaS is catalyzed by CO{sub 2}, but is not affected by N{sub 2} or H{sub 2}. The kinetics of CaS sintering was determined for the temperature range 750--900{degrees}C. When hydrogen sulfide is heated above 600{degrees}C in the presence of carbon dioxide elemental sulfur is formed. The rate-limiting step of elemental sulfur formation is thermal decomposition of H{sub 2}S. Part of the hydrogen thereby produced reacts with CO{sub 2}, forming CO via the water-gas-shift reaction. The equilibrium of H{sub 2}S decomposition is therefore shifted to favor the formation of elemental sulfur. The main byproduct is COS, formed by a reaction between CO{sub 2} and H{sub 2}S that is analogous to the water-gas-shift reaction. Smaller amounts of SO{sub 2} and CS{sub 2} also form. Molybdenum disulfide is a strong catalyst for H{sub 2}S decomposition in the presence of CO{sub 2}. A process for recovery of sulfur from H{sub 2}S using this chemistry is as follows: Hydrogen sulfide is heated in a high-temperature …

A process for the deposition of sol-gel derived thin films on porous substrates has been developed; such films should be useful for solid oxide fuel cells and related applications. Yttria-stabilized zirconia films have been formed from metal alkoxide starting solutions. Dense films have been deposited on metal substrates and ceramic substrates, both dense and porous, through dip-coating and spin-coating techniques, followed by a heat treatment in air. X-ray diffraction has been used to determine the crystalline phases formed and the extent of reactions with various substrates which may be encountered in gas/gas devices. Surface coatings have been successfully applied to porous substrates through the control of substrate pore size and deposition parameters. Wetting of the substrate pores by the coating solution is discussed, and conditions are defined for which films can be deposited over the pores without filling the interiors of the pores. Shrinkage cracking was encountered in films thicker than a critical value, which depended on the sol-gel process parameters and on the substrate characteristics. Local discontinuities were also observed in films which were thinner than a critical value which depended on the substrate pore size. A theoretical discussion of cracking mechanisms is presented for both types of cracking, …

The vortex method is a numerical scheme for solving the vorticity transport equation. Chorin introduced modern vortex methods. The vortex method is a Lagrangian, grid free method which has less intrinsic diffusion than many grid schemes. It is adaptive in the sense that elements are needed only where the vorticity is non-zero. Our description of vortex methods begins with the point vortex method of Rosenhead for two dimensional inviscid flow, and builds upon it to eventually cover the case of three dimensional slightly viscous flow with boundaries. This section gives an introduction to the fundamentals of the vortex method. This is done in order to give a basic impression of the previous work and its line of development, as well as develop some notation and concepts which will be used later. The purpose here is not to give a full review of vortex methods or the contributions made by all the researchers in the field. Please refer to the excellent review papers in Sethian and Gustafson, chapters 1 Sethian, 2 Hald, 3 Sethian, 8 Chorin provide a solid introduction to vortex methods, including convergence theory, application in two dimensions and connection to statistical mechanics and polymers. Much of the information …

Procedures required for minimizing structural defects generated during ion beam synthesis of SiGe alloy layers were studied. Synthesis of 200 mm SiGe alloy layers by implantation of 120-keV Ge ions into <100> oriented Si wafers yielded various Ge peak concentrations after the following doses, 2{times}10{sup 16}cm{sup {minus}2}, 3{times}10{sup 16}cm{sup {minus}2} (mid), and 5{times}10{sup 16}cm{sup {minus}2} (high). Following implantation, solid phase epitaxial (SPE) annealing in ambient N2 at 800C for 1 hr. resulted in only slight redistribution of the Ge. Two kinds of extended defects were observed in alloy layers over 3{times}l0{sup 16}cm{sup {minus}2}cm dose at room temperature (RT): end-of-range (EOR) dislocation loops and strain-induced stacking faults. Density of EOR dislocation loops was much lower in alloys produced by 77K implantation than by RT implantation. Decreasing the dose to obtain 5 at% peak Ge concentration prevents strain relaxation, while those SPE layers with more than 7 at% Ge peak show high densities of misfit- induced stacking faults. Sequential implantation of C following high dose Ge implantation (12 at% Ge peak concentration in layer) brought about a remarkable decrease in density of misfit-induced stacking faults. For peak implanted C > 0.55 at%, stacking fault generation in the epitaxial layer was suppressed, owing …

Gas-phase isothermal chromatogaphy is a method by which volatile compounds of different chemical elements can be separated according to their volatilities. The technique, coupled with theoretical modeling of the processes occurring in the chromatogaphy column, provides accurate determination of thermodynamic properties (e.g., adsorption enthalpies) for compounds of elements, such as the transactinides, which can only be produced on an atom-at-a-time basis. In addition, the chemical selectivity of the isothermal chromatogaphy technique provides the decontamination from interfering activities necessary for the determination of the nuclear decay properties of isotopes of the transactinide elements. Volatility measurements were performed on chloride species of Rf and its group 4 homologs, Zr and Hf, as well as Ha and its group 5 homologs, Nb and Ta. Adsorption enthalpies were calculated for all species using a Monte Carlo code simulation based on a microscopic model for gas thermochromatography in open columns with laminar flow of the carrier gas. Preliminary results are presented for Zr- and Nb-bromides.

The rotational distributions of CO products from the dissociation of ketene at photolysis energies 10 cm{sup {minus}1} below, 56, 110, 200, 325, 425, 1,107, 1,435, 1,720, and 2,500 cm{sup {minus}1} above the singlet threshold, are measured in a supersonic free jet of ketene. The CO(v{double_prime} = 0) rotational distributions at 56, 110, 200, 325, and 425 cm{sup {minus}1} are bimodal. The peaks at low J`s, which are due to CO from the singlet channel, show that the product rotational distribution of CO product from ketene dissociation on the singlet surface is well described by phase space theory (PST). For CO(v{double_prime} = 0) rotational distributions at higher excess energies, the singlet and triplet contributions are not clearly resolved, and the singlet/triplet branching ratios are estimated by assuming that PST accurately predicts the CO rotational distribution from the singlet channel and that the distribution from the triplet channel changes little from that at 10 cm{sup {minus}1} below the singlet threshold. At 2,500 cm{sup {minus}1} excess energy, the CO(v{double_prime} = 1) rotational distribution is obtained, and the ratio of CO(v{double_prime} = 1) to CO(v{double_prime} = 0) products for the singlet channel is close to the variational RRKM calculation, 0.038, and the separate statistical …

This study investigates the sulfidation of limestone at high temperatures (700--900{degree}C) as the first step in the design of a High-Temperature Coal-Gas Clean-Up system using millimeter-size limestone particles. Several workers have found that the rate of this reaction significantly decreases after an initial 10 to 15% conversion of CaCO{sub 3} to CaS. The present work attempts to explain this feature. It is first established that millimeter-size limestone particles do not sinter at temperatures up to the CaCO{sub 3} calcination point (899{degree}C at 1.03 bar CO{sub 2} partial pressure). It is then shown that CaS sinters rapidly at 750 to 900{degree}C if CO{sub 2} is present in the gas phase. Scanning Electron Microscope (SEM) photographs and Electron Dispersive Spectroscopy (EDS) data reveal that the CaS product layer sinters and forms a quasi-impermeable coating around the CaCO{sub 3} grains that greatly hinders more H{sub 2}S from reaching the still unreacted parts of the stone. Moreover, most of the pores initially present within the limestone structure begin to disappear or, at least, are significantly reduced in size. From then on, subsequent conversion is limited by diffusion of H{sub 2}S through the CaS layer, possibly by S{sup 2{minus}} ionic diffusion. The kinetics is then …

The relation of structure to lack of superconductivity in Pr-Ba-Cu-O was systematically investigated. First, the phase equilibria of this system was studied to find the processing parameters which maximize the cation-site ordering between Pr and Ba ions. Second, a comparative study between superconducting Nd-Ba-Cu-0 and non- superconducting Pr-Ba-Cu-0 was performed by forming solid-solution Nd- Pr-Ba-Cu-0. The relation between structure and superconductivity in Nd{sub 1{minus}x}Pr{sub x}Ba{sub 2}Cu{sub 3}O{sub 7{minus}{delta}} is investigated. {Tc} decreases monotonically with increasing {times} and superconductivity disappears at around x=0.3-0.4. {Tc} is enhanced by 10K when the sample is processed at an oxygen partial pressure (PO{sub 2}) of 0.01 atm, followed by oxygenation at 450C. Depression of {Tc} as a function of {times} and PO {sub 2} is explained in terms of a charge-transfer model. It is suggested that destruction of superconductivity in the RE{sub 1{minus}x}Pr{sub x}Ba{sub 2}CU{sub 3}O{sub 7{minus}{delta}} (RE=rare-earth) system can be viewed as disruption of four-fold planar coordinated Cu ions in the chain-site due to permanent occupation of extra Pr ions on Ba sites.

Visible and Fourier transform infrared (FTIR) absorption spectroscopies are used to observe protein conformational changes occuring during the bacteriorhodopsin photocycle. Spectroscopic measurements which define the conditions under which bacteriorhodopsin can be isolated and trapped in two distinct substates of the m intermediate of the photocycle, M{sub 1}, and M{sub 2}, are described. A protocol that can be used for high-resolution electron diffraction studies is presented that will trap glucose-embedded purple membrane in the M{sub 1}and M{sub 2} substates at greater than 90% concentration. It was discovered that glucose alone does not provide a fully hydrated environment for bacteriorhodopsin. Equilibration of glucose-embedded samples at high humidity can result in a physical state that is demonstrably closer to the native, fully hydrated state. An extension of the C-T Model of bacteriorhodopsin functionality (Fodor et al., 1988; Mathies et al., 1991) is proposed based on FTIR results and guided by published spectra from resonance Raman and FTIR work. 105 refs.

A new diagnostic device, the Omegatron Probe, has been developed to investigate relative impurity levels and impurity charge state distribution in the Alcator C-Mod Tokamak edge plasma. The Omegatron probe consists of two principal components, a ``front-end`` of independently biased grids, arranged in a gridded energy analyzer fashion and a large collection cavity. Particles enter the probe in a thin ``ribbon`` through a knife-edge slit. The grids provide a means to measure and control the parallel energy distribution of the ions. In the collection cavity, an oscillating electric field is applied perpendicularly to the ambient magnetic field. Ions whose cyclotron frequencies are resonant with this electric field oscillation will gain perpendicular energy and be collected. In this way, the probe can be operated in two modes: first, by fixing the potentials on the grids and sweeping frequencies to obtain a `` Z/m spectrum`` of ion species and second, by fixing the frequency and sweeping the grid potentials to obtain the distribution function of an individual impurity species. The Omegatron probe performed successfully in tests on a Hollow Cathode Discharge (HCD) linear plasma column. It obtained measurements of T{sub e} {approx} 5 eV, T{sub i} (H{sup +}) {approx} 2.0 {plus_minus} 0.2 …

Kinetic data for elimination of silylene supports formation of a ``tighter`` transition state, indicating a silacyclopropene intermediate. This extends the silacyclopropene mechanism to the cyclicdialkyne system and validates the consistency of the mechanism for silylakynes, in general. Investigation into the other possible silacyclopropene product established the instability of the product. The work with silylketenes proved that an inherent difference exists between reactivity of monosilyl-substituted ketenes and polysilyl-substituted ketenes. Although the mechanism for thermal decomposition of bis(silyl)ketenes can be modified to account for the unexpected silylene elimination products, reasons for the difference are limited to speculation. The photochemistry of silylketenes has not been previously studied, so a model system does not exist for comparison with our polysilylketene work. The photochemical experimentation suggests that the photochemistry and thermochemistry of polysilylketenes is not the same. A more extensive study of the mechanism of the systems covered in this research as well as with monosilyl-substituted systems is needed.

Mechanisms and associated energetics for adatom diffusion on the (100) and (110) surfaces of Ni, Cu, Rh, Pd, and Ag are investigated. Self-diffusion was studied on (100) and (I 10) surfaces of Ni, Cu, Pd and Ag using corrected effective medium method (CEM) and approximation to CEM used for molecular dynamics and Monte Carlo studies (MD/MC-CEM). Self-diffusion on Pd(100), Ag(100), Ni(110), Cu(110), Pd(110), and Ag(110) is accomplished by classical diffusion: the adatom hops from its equilibrium adsorption site over an intervening bridge site to an adjacent equilibrium site. Self-diffusion on Ni(100) and Cu(100) proceeds by atomic-exchange diffusion: the adatom on the surface displaces an atom in the first surface layer. Aside from explicit inclusion of the kinetic-exchange-correlation energy, it is critical to include enough movable atoms in the calculation to insure correct energetics. Distortions induced by these diffusion mechanisms, especially atomic exchange, are long ranged in surface plane, owing to small distortions of many atoms being energetically favored over large distortions of few atoms. Energetics and rates of heterogeneous adatom diffusion on the (100) surfaces of Ni, Cu, Rh, Pd, and Ag show that the final state energies differ due to variation of metallic bonding with coordination for different types …

Effects of resonant tunneling between bound quantum states of a current-biased Josephson tunnel junction is studied both theoretically and experimentally. Several effects are predicted to arise from resonant tunneling, including a series of voltage peaks along the supercurrent branch of the current-voltage characteristic, and enhanced rate of escape from zero voltage state to voltage state at particular values of bias current. A model is developed to estimate magnitude and duration of voltage peaks, and to estimate enhancement of the escape rate, which appears as peaks in the rate as a function of bias current. An experimental investigation was carried out in an attempt to observe these predicted peaks in the escape rate distribution in a current-biased DC SQUID, which is shown to be dynamically equivalent to a Josephson junction with adjustable critical current. Electrical contact to each SQUID (fabricated from aluminium) was made through high resistance thin film leads located on the substrate. These resistors provided a high impedance at the plasma frequency which is for the isolation of the SQUID from its electromagnetic environment. Measurements were carried out on a dilution refrigerator at temperatures as low as 19 mK. No evidence was found for resonant tunneling; this is attributed …