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Molecular genetic and molecular evolutionary studies on the bacteriochlorophyll synthesis genes of Rhodobacter capsulatus

Description: Rhodobacter capsulatus, purple bacterium capable of either aerobic or photosynthetic growth, has proven to be very useful in genetic studies of photosynthesis. Forty-four genes clustered together within a 46 kilobase region are required to establish photosynthetic ability in R. capsulatus. Approximately twenty of these genes are involved in bacteriochlorophyll synthesis of which eight ``bch`` genes are the subject of this thesis. Six of these genes were found to code for the two ring reductases. The first converts protochlorophyllide (PChlide) into a chlorin, the immediate precursor to chlorophyll a, and then into a bacteriochlorin. Each reductase is shown to be made up of three subunits. PChlide reductase is coded by the genes bchN, bchB, and bchL. Proteins with amino acid sequences markedly similar to those of bchN and bchL have been shown in other organisms to be required for chlorophyll synthesis; hence, their designation as chlN and chlB. A third chloroplast-encoded gene of heretofore unknown function shares amino acid identities with bchB and is probably the third subunit of the plant PChlide reductase. The bchA locus, which encodes the chlorin reductase, is found to be made up of three separate, translationally coupled genes, referred to as bchX, bchY, and bchZ. Amino acid similarities between bchX, bchL, and the nitrogenase reductase protein nifH suggest that all three classes of proteins share certain three-dimensional structural features, including elements that are central to the enzymatic mechanism of nifH. PChlide reductase and chlorin reductase are clearly derived from a common ancestor. Several lines of analysis suggests the ancestor of both enzyme systems reduced PChlide twice to produce bacteriochlorophyll supporting the concept bacteriochlorophyll as the ancestral reaction center pigment.
Date: August 1, 1992
Creator: Burke-Agueero, D. H.

Oxygen electrode reaction in molten carbonate fuel cells. Final report, September 15, 1987--September 14, 1990

Description: Molten carbonate fuel cell system is a leading candidate for the utility power generation because of its high efficiency for fuel to AC power conversion, capability for an internal reforming, and a very low environmental impact. However, the performance of the molten carbonate fuel cell is limited by the oxygen reduction reaction and the cell life time is limited by the stability of the cathode material. An elucidation of oxygen reduction reaction in molten alkali carbonate is essential because overpotential losses in the molten carbonate fuel cell are considerably greater at the oxygen cathode than at the fuel anode. Oxygen reduction on a fully-immersed gold electrode in a lithium carbonate melt was investigated by electrochemical impedance spectroscopy and cyclic voltammetry to determine electrode kinetic and mass transfer parameters. The dependences of electrode kinetic and mass transfer parameters on gas composition and temperature were examined to determine the reaction orders and the activation energies. The results showed that oxygen reduction in a pure lithium carbonate melt occurs via the peroxide mechanism. A mass transfer parameter, D{sub O}{sup 1/2}C{sub O}, estimated by the cyclic voltammetry concurred with that calculated by the EIS technique. The temperature dependence of the exchange current density and the product D{sub O}{sup 1/2}C{sub O} were examined and the apparent activation energies were determined to be about 122 and 175 kJ/ mol, respectively.
Date: July 7, 1992
Creator: Appleby, A. J. & White, R. E.

Development and application of a high speed digital data acquisition technique to study steam bubble collapse using particle image velocimetry

Description: The use of a Particle Image Velocimetry (PIV) method, which uses digital cameras for data acquisition, for studying high speed fluid flows is usually limited by the digital camera`s frame acquisition rate. The velocity of the fluid under study has to be limited to insure that the tracer seeds suspended in the fluid remain in the camera`s focal plane for at least two consecutive images. However, the use of digital cameras for data acquisition is desirable to simplify and expedite the data analysis process. A technique was developed which will measure fluid velocities with PIV techniques using two successive digital images and two different framing rates simultaneously. The first part of the method will measure changes which occur to the flow field at the relatively slow framing rate of 53.8 ms. The second part will measure changes to the same flow field at the relatively fast framing rate of 100 to 320 {mu}s. The effectiveness of this technique was tested by studying the collapse of steam bubbles in a subcooled tank of water, a relatively high speed phenomena. The tracer particles were recorded and velocity vectors for the fluid were obtained far from the steam bubble collapse.
Date: August 1, 1992
Creator: Schmidl, W. D.

A kinetic study of methanol synthesis in a slurry reactor using a CuO/ZnO/Al{sub 2}O{sub 3} catalyst

Description: A kinetic model that describes the methanol production rate over a CuO/ZnO/AI{sub 2}0{sub 3} catalyst (United Catalyst L-951) at typical industrial operating conditions is developed using a slurry reactor. Different experiments are conducted in which the H{sub 2}/(CO+CO{sub 2}) ratio is equal to 2, 1, and 0.5, respectively, while the CO/CO{sub 2} ratio is held constant at 9. At each H{sub 2}/(CO+CO{sub 2}) ratio the space velocity is set at four different values in the range of 3000-13,000 1/hr kg{sub cat}. The effect of H{sub 2}/(CO+CO{sub 2}) ratio and space velocity on methanol production rate, conversions, and product composition is further investigated. The results indicate that the highest methanol production rate can be achieved at H{sub 2}/(CO+CO{sub 2}) ratio of 1 followed by H{sub 2}/(CO+CO{sub 2}) ratio of 0.5 and 2 respectively. The hydrogen and carbon monoxide conversions decrease with increasing space velocity for all H{sub 2}/(CO+CO{sub 2}) ratios tested. Carbon monoxide hydrogenation appears to be the main route to methanol at H{sub 2}/(CO+CO{sub 2}) ratio of 0.5 and 2. On the other hand, carbon dioxide hydrogenation appears to be the main route to methanol at H{sub 2}/(CO+CO{sub 2}) ratio of 1. At all H{sub 2}/(CO+CO{sub 2}) ratios, the extent of the reverse water gas shift reaction decreases with increasing space velocity. The effect of temperature on the kinetics is examined by using the same experimental approach at 508 K. It is found that a different reaction sequence takes place at each temperature. Also, a time on stream study is conducted simultaneously in order to investigate the characteristic of catalyst deactivation with time on stream. During the first 150 hours of time on stream, the catalyst loses approximately 2/3 of its initial activity before reaching a steady state activity.
Date: May 1, 1992
Creator: Al-Adwani, H. A.

Measurement of current density fluctuations and ambipolar particle flux due to magnetic fluctuations in MST

Description: Studies of magnetic fluctuation induced particle transport on Reversed Field Pinch plasmas were done on the Madison Symmetric Torus. Plasma current density and current density fluctuations were measured using a multi-coil magnetic probes. The low frequency (f<50 kHz) current density fluctuations are consistent with the global resistive tearing instabilities predicted by 3-D MHD simulations. At frequencies above 50 kHz, the magnetic fluctuations were detected to be localized with a radial correlation length of about 1--2 cm. These modes are locally resonant modes since the measured dominant mode number spectra match the local safety factor q. The net charged particle flux induced by magnetic fluctuations was obtained by measuring the correlation term <{tilde j}{sub {parallel}} {tilde B}{sub r}>. The result of zero net charged particle loss was obtained, meaning the flux is ambipolar. The ambipolarity of low frequency global tearing modes is satisfied through the phase relations determined by tearing instabilities. The ambipolarity of high frequency localized modes could be partially explained by the simple model of Waltz based on the radial average of small scale turbulence.
Date: August 1, 1992
Creator: Shen, Weimin

Synthesis of higher alcohols from carbon monoxide and hydrogen in a slurry reactor

Description: Higher, i.e. C{sub 2{sup +}}, alcohols are desired as gasoline additives, feedstocks for producing ethers and as alternative fuels for automobiles. In all cases, the backbone branching of an alcohol improves octane rating, which is essential for good engine performance. These types of branched, higher alcohols are the desired products for a process converting synthesis gas, a CO and H{sub 2} mixture, often generated from coal gasification. Based on this premise, promoted ZnCr oxide catalysts appear to be as one of the best avenues for further investigation. Once this investigation is complete, a natural extension is to replace the Cr in the ZnCr oxide catalyst with Mo and W, both in the same elemental triad with Cr. Mo has already been shown as an active HAS catalyst, both on a SiO{sub 2} support and in the MoS{sub 2} form. The three catalyst combinations, ZnMo, ZnW, and MnCr oxides will be tested in the stirred autoclave system. However, if none of the three indicate any comparable activity and/or selectivity toward higher alcohols as compared with other HAS catalysts, then an investigation of the effects of Cs promotion on the ZnCr oxide methanol catalysts will be executed.
Date: August 28, 1992
Creator: McCutchen, M. S.

Seismic wave propagation in thinly-layered media with steep reflectors

Description: Seismic waves reflected from steep reflectors in the earth`s subsurface spend a significant amount of time travelling more or less horizontally. Therefore, accurate imaging of steep geologic structure requires knowledge of the behavior of these horizontally propagating waves. In particular, the effect of tunneling on seismic waves propagating in thinly-layered media must be understood. I describe a method for modeling seismic waves traveling in thinly-layered media. This method, a frequency-wavenumber finite-difference scheme coupled with the Born approximation, is useful in studying seismic waves reflected from steep geologic structures.
Date: May 1, 1992
Creator: Deng, H. L.

A dip-dependent divergence correction

Description: A divergence correction is conventionally applied to zero-offset data in an effort to preserved amplitude information. The conventional divergence correction compensates for the geometrical spreading of a point source in a horizontally layered medium where velocity varies with depth only. The dip-dependent divergence correction extends the conventional correction for improved amplitude processing of dipping beds. The dip-dependent divergence correction is computed by dynamic ray tracing, and applied to stacked data using a dip decomposition technique. This correction decreases amplitudes relative to the conventional correction for steep dips and late times. In a data example from the Gulf of Mexico, the conventional correction over- amplified the reflection off a salt dome flank by a factor of 1.6. High amplitudes near salt flanks are also associated with the presence of hydrocarbons. Applying the dip-dependent divergence correction ensures that ``bright spots`` are not due to over-amplification of steep dips by the conventional correction. In areas like the Gulf of Mexico, where the velocity function varies primarily with depth, and steep beds are commonplace, the dip-dependent divergence correction is an inexpensive way to improve the amplitude information in seismic images.
Date: July 1, 1992
Creator: Fazzari, Franscesca

Solid-polymer-electrolyte fuel cells

Description: A transport model for polymer electrolytes is presented, based on concentrated solution theory and irreversible thermodynamics. Thermodynamic driving forces are developed, transport properties are identified and experiments devised. Transport number of water in Nafion 117 membrane is determined using a concentration cell. It is 1.4 for a membrane equilibrated with saturated water vapor at 25{degrees}C, decreases slowly as the membrane is dehydrated, and falls sharply toward zero as the water content approaches zero. The relation between transference number, transport number, and electroosmotic drag coefficient is presented, and their relevance to water-management is discussed. A mathematical model of transport in a solid-polymer-electrolyte fuel cell is presented. A two-dimensional membrane-electrode assembly is considered. Water management, thermal management, and utilization of fuel are examined in detail. The membrane separators of these fuel cells require sorbed water to maintain conductivity; therefore it is necessary to manage the water content in membranes to ensure efficient operation. Water and thermal management are interrelated. Rate of heat removal is shown to be a critical parameter in the operation of these fuel cells. Current-voltage curves are presented for operation on air and reformed methanol. Equations for convective diffusion to a rotating disk are solved numerically for a consolute point between the bulk concentration and the surface. A singular-perturbation expansion is presented for the condition where the bulk concentration is nearly equal to the consolute-point composition. Results are compared to Levich`s solution and analysis.
Date: July 1, 1992
Creator: Fuller, T. F.

Surface structure determinations of ordered sulfur overlayers on Mo(100) and Re(0001) by low-energy electron diffraction intensity analysis

Description: A newly developed method for surface structure determination, tensor LEED, combined with automated search was used to analyze the structures. The ordered structures of S on Mo(100) which were studied formed a c(2 {times} 2), c(4 {times} 2), and p(2 {times} l) periodicities at coverages of 0.5, 0.75, 1.0 ML (monolayers, of one sulfur atom per one molybdenum atom) respectively. A MO{sub 2}S-like overlayer, which formed at coverages greater than 1.0 ML, is also discussed. Calculations for the c(2 {times} 2) structure gave a best fit geometry with S adsorbed in a four-fold symmetric hollow site and the second layer buckled by 0.09{Angstrom}. The S-Mo bond length is 2.45{Angstrom} and the Pendry R-factor is 0.21. Preliminary calculations for the c(4 {times} 2) structure did not yield an acceptable fit. The three models tried are discussed. Calculations for p(2 {times} l) data did not yield an acceptable geometry either. The types of models that were tried are discussed. Implications of this analysis are discussed along with results of a scanning tunneling microscopy (STM) investigation. The ordered structures on the RE(0001) surface studied have p(2 {times} 2) and (2{radical}3 {times} 2{radical}3)R30{degree} periodicities and occurred at S coverages of 0.25 and 0.5 ML respectively. Best fit structure for p(2 {times} 2) structure has S adsorbed in a three-fold hollow hcp site and exhibits a buckling of the first and second Re layers. The first layer is buckled by 0.05{Angstrom} and the second layer is buckled by 0.06{Angstrom}. Re-S bond length is 2.32{Angstrom} and Pendry R-factor is 0.21. Preliminary results of dynamical LEED investigation of (2{radical}3 {times} 2{radical}3)R30{degree} structure show reasonable agreement with a model with a 6-S atom basis.
Date: November 1, 1992
Creator: Jentz, D. W.

The synthesis and structural characterization of novel transition metal fluorides

Description: High purity KMF{sub 6} and K{sub 2}MF{sub 6} salts (M = Mo,Re, Ru, Os, Ir, Pt) are obtained from reduction hexafluorides. A rhombohedral unit cell is observed for KReF{sub 6}. Fluoride ion capture by Lewis acids from the hexafluorometallate (IV) salts affords high purity tetrafluorides for M = Mo, Re, Ru, Os, and Pd. The structure of RuF{sub 4} is determined from X-ray synchrotron and neutron powder data. Unit cells based on theorthorhombic PdF{sub 4} type cell are derived from X-ray powder data for ReF{sub 4} and OsF{sub 4}. Fluoride ion capture from KAgF{sub 4} provides the thermally unstable trifluoride as a bright, red, diamagnetic solid. The structure solution of AgF{sub 3} and redetermination of the AuF{sub 3} structure from X-ray synchrotron and neutron powder data demonstrate that the two are isostnictural. Thermal decomposition product of AgF{sub 3} is the mixed valence compound Ag{sup II}Ag{sub 2}{sup III}F{sub 8}. Several new salts containing the (Ag - F){sub n}{sup n+} chain cation are prepared. The first linear (Ag - F){sub n}{sup n+} chain is observed in AgF{sup +}BF{sub 4 {sup {minus}}} which crystallizes in a tetragonal unit. AgFAuF{sub 4} has a triclinic unit cell and is isostructural with CuFAuF{sub 4}. AgFAuF{sub 6} has an orthorhombic unit cell and appears to be isostructural with AgFAsF{sub 6}. A second mixed valence silver fluoride, Ag{sup II}Ag{sup III}F{sub 5}, is prepared, which magnetic measurements indicate is probably an AgF{sup +} salt. Magnetic data for all of the AgF{sup +} salts exhibit low magnitude, temperature independent paramagnetism characteristic of metallic systems. Cationic AG(II) in acidic AHF solutions is a powerful oxidizer, capable of oxidizing Xe to Xe(II) and O{sub 2} to O{sub 2}{sup +}. Reactions with C{sub 6}F{sub 6} and C{sub 3}F{sub 6} suggest an electron capture mechanism for cationic AG(II) oxidations.
Date: September 1, 1992
Creator: Casteel, W. J. Jr.

Temperature history and microstructure of alumina

Description: A simple process for the attainment of fully dense and improved microstructure for Al{sub 2}O{sub 3} ceramics has been developed. Pure, narrow size distribution, submicron powder is used. Homogenization heat treatment of Al{sub 2}O{sub 3} powder compacts at 800{degree}C for 50 hours produces more uniform pore structure and higher green strength. Pore size distribution becomes narrower. Near fully dense, fine-grained (< 1.2{mu}m) and uniform grain size-distribution, undoped Al{sub 2}O{sub 3} ceramics can be produced using a high quality powder, a high-pressure cold isostatic forming method, and a two-step sintering technique. Improvements in the microstructure of Al{sub 2}O{sub 3} ceramics homogenized at 800{degree}C/50 h include a smaller pore size and a more uniform pore size distribution. Prevention of differential densification in the early stages and delay of pore channel closure to the later stages of sintering are believed to be the primary mechanisms for the microstructure improvement in two-step sintering. Two-step sintering is an alternate way to improve the microstructure of Al{sub 2}O{sub 3} ceramics compared to fast firing or MgO doping. When a homogenization heat treatment and the fast firing are combined, the final density is higher than from fast firing alone. However, the two-step sintering technique is simple and there is no size limit. Generalization of two-step sintering to more systems is needed. For 250 ppM MgO-doped Al{sub 2}O{sub 3} ceramics, homogenization of powder compacts at 800{degree}C for 50 hours produces 0.80{mu}m. This improvement is explained by the distribution of MgO becoming more uniform during the homogenization heat treatment, which enhances the effectiveness of MgO doping.
Date: May 1, 1992
Creator: Lin, Jiang Tsair

Electronic excited states as a probe of surface adsorbate structure and dynamics in liquid xenon

Description: A combination of second harmonic generation (SHG) and a simple dipole-dipole interaction model is presented as a new technique for determining adsorbate geometries on surfaces. The polarization dependence of SHG is used to define possible geometries of the adsorbate about the surface normal. Absorption band shifts using geometry constraints imposed by SHG data are derived for a dimer constructed from two arbitrarily placed monomers on the surface using the dipole-dipole interaction potential. These formulae can be used to determine the orientation of the two monomers relative to each other. A simplified version of this formalism is used to interpret absorption band shifts for rhodamine B adsorbed on fused silica. A brief history of the exciton is given with particular detail to Xe. Data are presented for transient absorption at RT in liquid xenon on the picosecond time scale. These are observations of both tunneling through the barrier that separates the free and trapped exciton states and the subsequent trapping of the exciton. In high densities both of these processes are found to occur within 2 to 6 picoseconds in agreement with theories of Kmiecik and Schreiber and of Martin. A threshold density is observed that separates relaxation via single binary collisions and relaxation that proceeds via Martin`s resonant energy transfer hopping mechanism.
Date: August 1, 1992
Creator: Peterson, E. S.

The effect of low Au concentrations on the properties of eutectic Sn/Pb

Description: This study was of the effects moderately low Au concentrations ({le} 10 wt%) have on the mechanical properties and microstructure of an eutectic Sn/Pb alloy. Vibration (60--90 Hz swept sine wave for 30 hours) and thermal cycling (0--110C for 1450 cycles) reliability tests were performed on fine pitch leaded chip carriers using eutectic Sn/Pb solder on PCBs (printed circuit boards) with 0, 5, 10, 20, and 50{mu}in nominal Au thicknesses. Testing was also performed on double shear creep specimens consisting of arrays of regular pitch joints. There was a dramatic increase in the number of joints containing voids with increasing Au concentration, an effect more pronounced in the creep joints than in the reliability joints. These voids tended to coalesce and grow during rework simulation of the reliability joints. AuSn{sub 4} intermetallics present in toe of 4.8 wt% (50 {mu}in) Au vibration joints rotated from initial vertical perpendicular to surface of PCB metallization, solidification positions to roughly horizontal (parallel to plating surface) orientations during rework simulation and during aging of the parts. The AuSn{sub 4} intermetallics in the toe of the 4.8 wt% (50{mu}in) Au reflowed joints also rotated after vibration testing. No joint failures were observed in either vibration tested or thermally cycled specimens. Cracks formed in some of the vibration tested specimen joints under the heel of the gull-wing lead at Pb-rich phases. Thermally cycled specimens showed eutectic microstructure and intermetallic coarsening without crack formation. Creep tests showed loss of the superplasticity in eutectic Sn/Pb alloys with even the lowest Au concentration tested of 0.2 wt% Au. Intermetallic rotation was not a factor in crack propagation, but void presence was. Cracks tended to form in joints containing voids before forming in void-free joints. Crack propagation followed Sn/Sn grain boundaries and Sn/Pb phase boundaries from Pb-rich phase to Pb-rich ...
Date: May 1, 1992
Creator: Kramer, P. A.

The electrical conductivity of sodium polysulfide melts

Description: The sodium polysulfide melt has been described by a macroscopic model. This model considers the melt to be composed of sodium cations, monosulfide anions, and neutral sulfur solvent. The transport equations of concentrated-solution theory are used to derived the governing equations for this binaryelectrolyte melt model. These equations relate measurable transport properties to fundamental transport parameters. The focus of this research is to measure the electrical conductivity of sodium polysulfide melts and calculate one of fundamental transport parameters from the experimental data. The conductance cells used in the conductivity measurements are axisymmetric cylindrical cells with a microelectrode. The electrode effects, including double-layer capacity, charge transfer resistance, and concentration overpotential, were minimized by the use of the alternating current at an adequately high frequency. The high cell constants of the conductance cells not only enhanced the experimental accuracy but also made the electrode effects negligible. The electrical conductivities of sodium polysulfide Na{sub 2}S{sub 4} and Na{sub 2}S{sub 5} were measured as a function of temperature (range: 300 to 360{degree}C). Variations between experiments were only up to 2%. The values of the Arrhenius activation energy derived from the experimental data are about 33 kJ/mol. The fundamental transport parameter which quantifies the interaction within sodium cations and monosulfide anions are of interest and expected to be positive. Values of it were calculated from the experimental conductivity data and most of them are positive. Some negative values were obtained probably due to the experimental errors of transference number, diffusion coefficient, density or conductivity data.
Date: June 1, 1992
Creator: Wang, Meihui

Development and application of the quasi-potential transformation

Description: The quasi-potential transformation, based on the Kirchhoff transformation, reduces the equations governing mass-transfer in a steady-state, nonconvective electrolytic system into two independent parts. The geometry-specific part involves the solution of Laplace`s equation subject to the relevant boundary conditions. The system-specific part involves the solution of a set of coupled first-order, nonlinear, ordinary differential equations. We develop a theoretical basis for the quasi-potential transformation using potential theory. The major assumption on which the quasi-potential transformation is based is that the concentrations can be written as single-valued functions of the electrostatic potential. We see how the system-specific part of the calculation is developed. Boundary conditions are outlined, and the geometry-specific calculations for the disk and hemisphere electrodes are developed. We combine the system-specific calculations for the binary and acidic copper sulfate solutions with these geometry-specific calculations to obtain complete concentration profiles, potential distributions, and current density distributions for these systems. We also investigate the effect of migration on limiting currents.
Date: August 1, 1992
Creator: Pillay, B.

Reaction dynamics and photochemistry of divalent systems

Description: Results are presented of molecular beam studies of bimolecular and unimolecular reactions of Ba. Chapter 1 discusses the reaction Ba + NO{sub 2}. Formation of the dominant BaO({sup 1}{Sigma}) + NO products resulted primarily from decay of long-lived Ba{sup +}NO{sub 2}{sup {minus}} collision complexes. Secondary mechanisms led to formation of forward scattered, internally excited BaO, and BaNO + O. D{sub o}(Ba-NO) = 65{plus_minus}20 kcal/mol. Reactions of ground state and electronically excited Ba with water and alcohols are examined in Chapter 2. Reaction of Ba({sup 1}S) + H{sup 2}O led to BaO + H{sub 2}, whereas excited state Ba({sup 1}D) + H{sub 2}O reacted to form BaOH + H. Collisions between Ba and CH{sub 3}OH led to BaOCH{sub 3} + H. Radical channels involve H-atom migration and are promoted by excitation of the incident Ba atom. In Chapter 3, reactions of Ba({sup 1}S) with ClO{sub 2}2 and O{sub 3} are discussed. Again, direct and complex mechanisms were observed. Formation of BaCl + O{sub 2} from decomposition of Ba{sup +}ClO{sub 2}{sup {minus}} accounted for 10% of total reaction crass section. Although Ba + O{sub 3} {yields} BaO + 0{sub 2} occurs primarily by direct reaction mechanisms, the secondary channel Ba + 0{sub 3} {yields} BaO{sub 2} + 0 involved decay of long lived Ba{sup +}O{sub 3}{sup {minus}} intermediates. D{sub o}(Ba{minus}O{sub 2}) = 120 {plus_minus}20 kcal/mol. Photodissociation dynamics of NO{sub 3} is explored in chapter 4. Visible excitation leads to formation of NO + 0{sub 2} and NO{sub 2} + O. Wavelength dependence of branching ratios is investigated. D{sub o}(O-NO{sub 2}) = 48.55 kcal/mole ;and calculate {Delta}H{sub f}(NO{sub 3}) = 17.75 kcal/mole (298K). Chapter 5 discusses the photodissociation of OClO in a molecular beam. Although ClO({sup 2}II) + O({sup 3}P) is dominant, Cl({sup 2}P) + O{sub 2} also forms, with a max yield ...
Date: May 1, 1992
Creator: Davis, H. F.

The processing and potential applications of porous silicon

Description: Stability of a cylindrical pore under the influence of surface energy is important for porous silicon (PS) processing in the integrated circuit industry. Once the zig-zag cylindrical pores of porous silicon or oxidized porous silicon (OPS) are unstable and breakup into rows of isolated spherical pores, oxidation of PS and densification/nitridation of OPS become difficult. Swing to difficulty transport of reactant gas (O{sub 2}, NH{sub 3}) or the trapped gas (for densification of OPS). A first order analysis of the stability of a cylindrical pore or cylinder is considered first. Growth of small sinusoidal perturbations by viscous flow or evaporation/condensation result in dependence of perturbation growth rate on perturbation wavelength. Rapid thermal oxidation (RTO) of porous silicon is proposed as an alternative for the tedious two-step 300 and 800C oxidation process. Transmission electron microscopy, energy dispersive spectroscopy ESCA are used for quality control. Also, rapid thermal nitridation of oxidized porous silicon in ammonia is proposed to enhance OPS resistance to HF solution. Pores breakup of OPS results in a trapped gas problem during densification. Wet helium is proposed as OPS densification ambient gas to shorten densification time. Finally, PS is proposed to be an extrinsic gettering center in silicon wafers. The suppression of oxidation-induced stacking faults is used to demonstrate the gettering ability. Possible mechanism is discussed.
Date: July 1, 1992
Creator: Shieh, Syyuan

Nucleation and growth in electrodeposition of thin copper films on pyrolytic graphite

Description: Electrodeposition of Cu on graphite electrodes was studied, with emphasis on nucleation. Various ex-situ and in-situ methods were investigated for determining the number density of nuclei. Two direct methods were studied (scanning electron microscopy and scanning tunneling microscopy); indirect determinations included Raman spectroscopy and analysis of potentiostatic current transients. Though some of the techniques correctly predicted the nucleation densities under special conditions, SEM was the most reliable tool. The large scatter in the data necessitated steps to minimize this effect. To electrodeposit Cu on graphite, a nucleation overpotential of 250 mV was measured with cyclic voltammetry; such a large overpotential does not occur on a Pt or on a Cu-covered graphite electrode. The deposition potential is the dominant parameter governing nucleation density. There is a sharp increase in the nucleation density with applied potential. Cu can be deposited on highly oriented pyrolytic graphite only between the nucleation overpotential and the hydrogen evolution potential. To increase the Cu nucleation density, while avoiding excessive H evolution, a double pulse potential technique was used; nucleation densities on the order of 10{sup 10} nuclei/cm{sup 2} were achieved. The use of inhibitors (PVA, benzotriazole) was also investigated. Deposition on conducting polymer electrodes was also studied; initial results with polyaniline show promise. 57 figs, 6 tabs, refs. (DLC)
Date: May 1, 1992
Creator: Kinaci, F. S. & Muller, R. H.

Separation of compounds with multiple -OH groups from dilute aqueous solutions via complexation with organoboronate

Description: The complexing extractant agent investigated in this work is 3-nitrophenylboronic acid (NPBA) in its anionic form (NPB). NPBA and Aliquat 336 (quaternary amine) is dissolved in 2-ethyl-l-hexanol, and the extractant is contacted with aq. NaOH. Solutes investigated were 1,2-propanediol, glycerol, fructose, sorbitol and lactic acid. Batch extraction experiments were performed at 25{degree}C. Partition coefficients, distribution ratios and loadings are reported for varying concentrations of solute and NPB. All solutes complexed with NPB{sup {minus}}, with all complexes containing only one NPB{sup {minus}} per complex. The 1:1 complexation constants for the solutes glycerol, fructose and sorbitol follow trends similar to complexation with B(OH){sub 4}{sup {minus}} (aq.), i.e. the complexation constants increase with increasing number of {minus}OH groups available for complexation. Assumption of 1:1 complex is not valid for 1, 2-propanediol, which showed overloading (more than one mole of solute complexed to one mole NPB{sup {minus}}) at higher concentrations. The {minus}OH group on the NPB{sup {minus}} which is left uncomplexed after one solute molecule had bound to the other two {minus}OH groups may be responsible for the overloading. Overloading is also observed in extraction of tactic acid, but through a different mechanism. It was found that TOMA{sup +} can extract lactic acid to an extent comparable to the uptake of lactic acid by NPB{sup {minus}}. The complexation is probably through formation of an acid-base ion pair. Losses of NPBA into the aqueous phase could lead to problems, poor economics in industrial separation processes. One way of overcoming this problem would be to incorporate the NPBA onto a solid support.
Date: May 1, 1992
Creator: Chow, Tina Kuo Fung

Chemistry of radiation damage to wire chambers

Description: Proportional counters are used to study aspects of radiation damage to wire chambers (wire aging). Principles of low-pressure, rf plasma chemistry are used to predict the plasma chemistry in electron avalanches (1 atm, dc). (1) Aging is studied in CF{sub 4}/iC{sub 4}H{sub 10} gas mixtures. Wire deposits are analyzed by Auger electron spectroscopy. An apparent cathode aging process resulting in loss of gain rather than in a self-sustained current is observed in CF{sub 4}-rich gases. A four-part model considering plasma polymerization of the hydrocarbon, etching of wire deposits by CF{sub 4}, acceleration of deposition processes in strongly etching environments, and reactivity of the wire surface is developed to understand anode wire aging in CF{sub 4}/iC{sub 4}H{sub 10} gases. Practical guidelines suggested by the model are discussed. (2) Data are presented to suggest that trace amounts of Freons do not affect aging rates in either dimethyl ether or Ar/C{sub 2}H{sub 6}. Apparent loss of gain is explained by attachment of primary electrons to a continuously increasing concentration of Freon 11 (CCl{sub 3}F) in the counter gas. An increase in the concentration of Freon 11 in dimethyl ether is caused by a distillation process in the gas supply bottle and is a natural consequence of the unequal volatilities of the two compounds.
Date: August 1, 1992
Creator: Wise, J.

An analysis of multiple particle settling for LMR backup shutdown systems

Description: Backup shutdown systems proposed for future LMRs may employ discreet absorber particles to provide the negative reactivity insertion. When actuated, these systems release a dense packing of particles from an out-of-core region to settle into an in-core region. The multiple particle settling behavior is analyzed by the method of continuity waves. This method provides predictions of the dynamic response of the system including the average particle velocity and volume fraction of particles vs. time. Although hindered settling problems have been previously analyzed using continuity wave theory, this application represents an extension of the theory to conditions of unrestrained settling. Typical cases are analyzed and numerical results are calculated based on a semi-empirical drift-flux model. For 1/4-inch diameter boron-carbide particles in hot liquid sodium, the unrestrained settling problem assumes a steady-state solution when the average volume fraction of particles is 0.295 and the average particle velocity is 26.0 cm/s.
Date: May 1, 1992
Creator: Brock, R. W.

Radiative heat transfer in porous uranium dioxide

Description: Due to low thermal conductivity and high emissivity of UO{sub 2}, it has been suggested that radiative heat transfer may play a significant role in heat transfer through pores of UO{sub 2} fuel. This possibility was computationally investigated and contribution of radiative heat transfer within pores to overall heat transport in porous UO{sub 2} quantified. A repeating unit cell was developed to model approximately a porous UO{sub 2} fuel system, and the heat transfer through unit cells representing a wide variety of fuel conditions was calculated using a finite element computer program. Conduction through solid fuel matrix as wekk as pore gas, and radiative exchange at pore surface was incorporated. A variety of pore compositions were investigated: porosity, pore size, shape and orientation, temperature, and temperature gradient. Calculations were made in which pore surface radiation was both modeled and neglected. The difference between yielding the integral contribution of radiative heat transfer mechanism to overall heat transport. Results indicate that radiative component of heat transfer within pores is small for conditions representative of light water reactor fuel, typically less than 1% of total heat transport. It is much larger, however, for conditions present in liquid metal fast breeder reactor fuel; during restructuring of this fuel type early in life, the radiative heat transfer mode was shown to contribute as much as 10-20% of total heat transport in hottest regions of fuel.
Date: December 1, 1992
Creator: Hayes, S. L.

The fabrication and performance of YBa{sub 2}Cu{sub 3}O{sub 7-x} SQUID magnetometers

Description: To enhance the SQUID`s field sensitivity, it is coupled to a flux transformer, a closed superconducting circuit consisting of a pickup loop, to which a signal is applied, connected in series to an input coil, which is inductively coupled to the SQUID. To fabricate an optimal flux transformer, one must use more than one superconducting thin-film layer, each of which is patterned into narrow strips or wires. Some wires from different layers cross, yet remain electrically isolated, to form crossovers, while in other places there must be superconducting contact between wires from different layers. Together, the superconducting wire, superconducting-superconducting contact and the superconducting crossover constitute a superconducting interconnect or multilayer wiring technology. We discuss the development of an interconnect technology involving the high transition temperature ({Tc}) superconductor YBa{sub 2}Cu{sub 3}O{sub 7-x} (YBCO). Because of the need for epitaxial growth there are limits on materials for the insulating layer separating the YBCO films in multilayer structures, and on deposition and patterning techniques. We discuss the use of pulsed laser deposition in conjunction with patterning by shadow masks and later by photolithography to produce interconnects, multiturn input coils, and flux transformers. We also discuss the performance of SQUID magnetometers, in which a flux transformer fabricated on one substrate is coupled to a SQUID fabricated on another. The first magnetometers were hybrids -- high {Tc} transformers coupled to low {Tc} SQUIDS, while later ones had both high {Tc} transformers and SQUIDs and could operate immersed in liquid nitrogen. We report on a magnetometer with a magnetic field sensitivity at lHz of about 2pTHz{minus}{sup 1/2} at 77K, that was successfully used to perform magnetocardiograms on human subjects.
Date: July 1, 1992
Creator: Kingston, J. J.