The formation constants for the reactions PuO{sub 2}{sup +} + H{sub 2}O = PuO{sub 2}(OH) + H{sup +} and PuO{sub 2}{sup +} + CO{sub 3}{sup 2} = PuO{sub 2}(CO{sub 3}){sup {minus}} were determined in aqueous sodium perchlorate solutions by laser-induced photoacoustic spectroscopy. The molar absorptivity of the PuO{sub 2}{sup +} band at 569 nm decreased with increasing hydroxide concentration. Similarly, spectral changes occurred between 540 and 580 nm as the carbonate concentration was increased. The absorption data were analyzed by the non-linear least-squares program SQUAD to yield complexation constants. Using the specific ion interaction theory, both complexation constants were extrapolated to zero ionic strength. These thermodynamic complexation constants were combined with the oxidation-reduction potentials of Pu to obtain Eh versus pH diagrams. 120 refs., 35 figs., 12 tabs.

Leaky faults provide a flow path for fluids to move underground. It is very important to characterize such faults in various engineering projects. The purpose of this work is to develop mathematical solutions for this characterization. The flow of water in an aquifer system and the flow of air in the unsaturated fault-rock system were studied. If the leaky fault cuts through two aquifers, characterization of the fault can be achieved by pumping water from one of the aquifers, which are assumed to be horizontal and of uniform thickness. Analytical solutions have been developed for two cases of either a negligibly small or a significantly large drawdown in the unpumped aquifer. Some practical methods for using these solutions are presented. 45 refs., 72 figs., 11 tabs.

No present light water reactor accident analysis code employs both high state of the art neutronics and thermal-hydraulics computational algorithms. Adding a modern three-dimensional neutron kinetics model to the present TRAC-PFI/MOD2 code would create a fully up to date pressurized water reactor accident evaluation code. After reviewing several options, it was decided that the Nodal Expansion Method would best provide the basis for this multidimensional transient neutronic analysis capability. Steady-state and transient versions of the Nodal Expansion Method were coded in both three-dimensional Cartesian and cylindrical geometries. In stand-alone form this method of solving the few group neutron diffusion equations was shown to yield efficient and accurate results for a variety of steady-state and transient benchmark problems. The Nodal Expansion Method was then incorporated into TRAC-PFl/MOD2. The combined NEM/TRAC code results agreed well with the EPRI-ARROTTA core-only transient analysis code when modelling a severe PWR control rod ejection accident.

A comprehensive theoretical study has been carried out on the flow behavior of both single and multiple phase non-Newtonian fluids in porous media. This work is divided into three parts: (1) development of numerical and analytical solutions; (2) theoretical studies of transient flow of non-Newtonian fluids in porous media; and (3) applications of well test analysis and displacement efficiency evaluation to field problems. A fully implicit, integral finite difference model has been developed for simulation of non-Newtonian and Newtonian fluid flow through porous media. Several commonly-used rheological models of power-law and Bingham plastic non-Newtonian fluids have been incorporated in the simulator. A Buckley-Leverett type analytical solution for one-dimensional, immiscible displacement involving non-Newtonian fluids in porous media has been developed. Based on this solution, a graphic approach for evaluating non-Newtonian displacement efficiency has been developed. The Buckley-Leverett-Welge theory is extended to flow problems with non-Newtonian fluids. An integral method is also presented for the study of transient flow of Bingham fluids in porous media. In addition, two well test analysis methods have been developed for analyzing pressure transient tests of power-law and Bingham fluids, respectively. Applications are included to demonstrate this new technology. The physical mechanisms involved in immiscible displacement with …

Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO{sub 2} and H{sub 2}S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, SUCCiOlC acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility …

Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO{sub 2} and H{sub 2}S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, succinic acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility …

As a continuation of the research on bcc Gd-Mg alloy system by Herchenroeder and Gschneidner, the metastable bcc Gd-Cd alloys were studied with the emphasis on their metallurgical and magnetic properties. An essentially single phase alloy could be retained for Cd concentrations from 15 at. % Cd to 19 at. % Cd, which is in the vicinity of the eutectoid composition of {beta}Gd in the Gd-Cd system. The lattice constants obtained for these alloys were used to determine the lattice constant of pure bcc Gd by extrapolation to 0 at. % Cd. Good agreement between this extrapolated value and that obtained from Gd-Mg alloys by using the same method suggested the validity of such extrapolation method. Thermal stability of these metastable bcc Gd-Cd alloys was examined by using differential thermal analysis (DTA).

Resistivity measurements have been performed for electric characterization of the compounds Ba{sub 5}Sb{sub 3} and Ba{sub 5}Sb{sub 3}Cl, both with the Mn{sub 5}Si{sub 3} structure type, along with Ca{sub 5}Bi{sub 3} and Ca{sub 5}Bi{sub 3}F, both with the {beta}-Yb{sub 5}Sb{sub 3} structure type. These measurements were taken as a function of temperature using the four probe method on pressed polycrystalline pellets of the compounds. A sealed apparatus was developed for containing these air-sensitive compounds throughout the experiments. By a simple electron count, one extra electron in both Ba{sub 5}Sb{sub 3} and Ca{sub 5}Bi{sub 3} should occupy a conduction band, giving these compounds a metallic character. In the cases of Ba{sub 5}Sb{sub 3}Cl and Ca{sub 5}Bi{sub 3}F, the extra electron should bond to the halide, both filling the valence band and giving rise to semiconducting character. Ca{sub 5}Bi{sub 3}, Ca{sub 5}Bi{sub 3}F, and Ba{sub 5}Sb{sub 3}Cl were found to comply with the electron count prediction. Ba{sub 5}Sb{sub 3}, however, was found to be a semiconductor (E{sub g} = 0.30 eV) with a larger band gap than its corresponding chloride (E{sub g} = 0.09 eV).

An angle-resolved photoemission study of the normal and superconducting states in Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} was performed. Measurements in the normal state show bands dispersing through the Fermi level from at least 350 meV below E{sub F}. The Fermi level crossings are consistant with local-density band calculation, including a point calculated to be of Bi-O character. Additional measurements were made where bands crossed the Fermi level between 100 and 250K, along with measurements on an adjacent Pt foil. The Fermi edges of both materials agree to within the noise. Below the Fermi level, the spectra show correlation effects on the form of an increased effective mass. The shape of the spectra can be explained by a lifetime-broadened photohole and secondary electrons. The effective inverse photohole lifetime is linear in energy. A superconducting gap has been measured at a number of points where there is density at the Fermi level in the normal state. By proper modeling, a gap of 24 meV was obtained for all these points, including points of Cu-O and Bi-O character respectively, according to band calculation. The lack of gap anisotropy in the basal plane suggests that pinning in this material is not d-wave pairing.

This thesis encompasses two separate research projects. The first project, described in Chapter 2 was a project investigating the fatigue behavior of thermoset Fiber Composite (FC) sandwich wall ties. The second research project detailed in this thesis was a project studying the bond and tensile properties of FC rod and FC fibers.

The reactive o-quinodimethanes, 1,2-dimethylene-1,2-dihydronaphthalene (9) and o-xylylene (1) were observed by flow {sup 1}H NMR spectroscopy at room temperature. The {sup 1}H NMR spectrum of 9 was obtained in the absence of precursor and dimers. However, the {sup 1}H NMR spectrum of the more reactive 1, generated in a similar manner from (o-((trimethylsilyl)methyl)benzyl)trimethylammonium iodide (5.) could be obtained only in the presence of its stable (4 + 2) and (4 + 4) dimers. The dimerization kinetics of 3-methyl- (5{prime}), 3,6-dimethyl- (11), 3-isopropyl- (12), and 3,6-diisoproply-1,2-xylylene (13) in acetonitrile (CH{sub 3}CN) were studied by stopped-flow UV-visible spectroscopy. Fluoride ion induced 1,2-elimination from 2-elimination from 2-trimethylsilylbenzocyclobutenyl-1 mesylate (26) was used to generate the reactive molecule benzocyclobutadiene (1{prime}) in CD{sub 3}CN, which was observed by flow {sup 1}H NMR spectroscopy at room temperature. The {sup 1}H NMR spectrum (in CD{sub 3}CN) of 1,2-dimethylene-1,2-dihydrothiophene (1{double prime}), obtained by fluoride ion induced 1,4-elimination from 3-(trimethylammoniummethyl)-2-(trimethylsilylmethyl)thiophene iodine was observed by flow {sup 1}H NMR spectroscopy at room temperature. The dimerization rate of 1{double prime} in CH{sub 3}CN, generated in the same manner, was measured by UV-visible spectroscopy. 166 refs., 7 figs., 7 tabs.

Measurements of the normal state magnetic susceptibility {chi}(T) of YBa{sub 2}Cu{sub 3}O{sub 7}, Bi{sub 1.8}Pb{sub 0.2}Sr{sub 2}CaCu{sub 2}O{sub 8+{delta}}, and Bi{sub 2{minus}x}Pb{sub x}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10+{delta}} (x = 0.2 and 0.25) were carried out. All {chi}(T) data show negative curvature below {approximately}2{Tc}. The data for YBa{sub 2}Cu{sub 3}O{sub 7} are in excellent agreement with a new calculation of the superconducting fluctuation diamagnetism. From the analysis, we infer s-wave pairing and microscopic parameters are obtained. For {chi}(T) of YBa{sub 2}Cu{sub 3}O{sub 7}, part of the negative curvature is inferred to arise from the normal state background. We find a strong temperature dependent anisotropy {delta}{chi} {equivalent to} {chi}{sub c} {minus} {chi}{sub ab} and estimate the normal state spin contributions to {chi}(T). The heat capacity C(T) of YBa{sub 2}Cu{sub 3}O{sub 7} is reported for 0.4 K < T < 400 K in zero and 70 kG magnetic fields. In addition to the feature associated with the onset of the superconductivity at {Tc}, two anomalies in C(T) were observed near 74 K and 330 K, with another possible anomaly near 102 K; the temperatures at which they occur correlate with anomalies in {chi}(T) and ultransonic measurements. The occurrence of the anomaly at {approx …

The first part of this thesis will search for the thermal isomerization of olefins to carbenes which is predicted to be a high energy process by calculations and has only been observed in a few strained olefins. The possibility of thermal isomerization of simple olefins to carbenes will be explored. Substitution of a silyl group on the double bond of an olefin allows a potential intermediate which has a {beta}-radical to the silyl group during the cis-trans isomerization. The effects of a trimethylsilyl group on this isomerization are the subject of this study. The second part of this thesis will include the generation and chemistry of intermediates containing a silicon-nitrogen double bond. The isomerization of parent silanimine to the aminosilylene was calculated to be a high energy process. New approaches to the silicon-nitrogen double bond will also be presented. 92 refs., 12 figs., 11 tabs.

A method for determining the location and possible existence of symmetry elements in Patterson superposition maps has been developed. A comparison of the original superposition map and a superposition map operated on by the symmetry element gives possible translations to the location of the symmetry element. A reciprocal space approach using structure factor-like quantities obtained from the Fourier transform of the superposition function is then used to determine the best'' location of the symmetry element. Constraints based upon the space group requirements are also used as a check on the locations. The locations of the symmetry elements are used to modify the Fourier transform coefficients of the superposition function to give an approximation of the structure factors, which are then refined using the EG relation. The analysis of several compounds using this method is presented. Reciprocal space techniques for locating multiple images in the superposition function are also presented, along with methods to remove the effect of multiple images in the Fourier transform coefficients of the superposition map. In addition, crystallographic studies of the extended chain structure of (NHC{sub 5}H{sub 5})SbI{sub 4} and of the twinning method of the orthorhombic form of the high-{Tc} superconductor YBa{sub 2}Cu{sub 3}O{sub 7-x} are …

Optical properties and electronic structures of disordered Ag{sub 1- x}In{sub x}(x = 0.0, 0.04, 0.08, 0.12) and Ni{sub 1-x}Cu{sub x} (x = 0.0, 0.1, 0.3, 0.4) alloys and ordered AuGa{sub 2}, PtGa{sub 2}, {beta}{prime}-NiAl, {beta}{prime}-CoAl, CeSn{sub 3}, and LaSn{sub 3} have been studied. The complex dielectric functions have been determined for Ag{sub 1-x}In{sub x}, Ni{sub 1-x}Cu{sub x}, AuGa{sub 2}, and PtGa{sub 2} in the 1.2--5.5 eV region and for CeSn{sub 3} and LaSn{sub 3} in the 1.5--4.5 eV region using spectroscopic ellipsometry. Self-consistent relativistic band calculations using the linearized-augmented-plane-wave method have been performed for AuGa{sub 2}, PtGa{sub 2}, {beta}{prime}-NiAl, {beta}{prime}-CoAl, CeSn{sub 3}, and LaSn{sub 3} to interpret the experimental optical spectra.

There has been much recent interest in the photochemistry and photophysics of transition metal polypyridine complexes due to the possibility of their use in solar energy conversion systems. The excited state of these compounds are known to undergo useful electron transfer and energy transfer reactions. This work attempts to elucidate the mechanism of the quenching of *CrL{sub 3}{sup 3+} (where L = 2,2{prime}-bipyridine, 4,4{prime}-dimethyl-2,2{prime}-bipyridine, 1,10-phenanthroline, 5-chloro-1,10-phenanthroline, 5-methyl-1,10-phenanthroline) by oxalate ions in neutral pH. Evidence suggests an ion-pairing pre-equilibrium followed by rate limiting electron transfer to produce CrL{sub 3}{sup 2+} and CO{sub 2}{sup {minus}} can then react with ground state chromium(III) species to produce another mole of the reduced product or it can produce a secondary transient as in the case of phenanthroline and substituted phenanthroline complexes. The secondary transient reacts to produce CrL{sub 3}{sup 2+} in a subsequent reaction. 85 refs., 24 figs., 7 tabs.

Proton magnetic resonance spectroscopy, or nuclear magnetic resonance (NMR) of hydrogen, has been applied to investigate silica-supported Group VIII monometallic and Group VIII-Group IB bimetallic catalysts and alumina- and silica-supported platinum-rhenium bimetallic catalysts. Two adsorbed states of hydrogen, i.e., irreversible and reversible hydrogen, on the surfaces of monometallic Ru, Pt, and Cu particles and bimetallic Ru-Group Ib, Pt-Group Ib, and Pt-Re particles were observed directly via proton NMR. The same amounts of the irreversible hydrogen adsorbed on pure Ru catalysts were measured by both proton NMR and the volumetric technique. The electronic environments on surfaces of monometallic catalysts are sensitive to changes in metal dispersion, state of adsorbed hydrogen, and residual chlorine. Surface compositions for the Ru--Cu and Pt--Cu bimetallic catalysts were determined by NMR of adsorbed hydrogen. 297 refs., 96 figs., 19 tabs.

The electrocatalysis of oxygen-transfer reactions is discussed in two parts. In Part I, the reduction of iodate (IO{sub 3}{sup {minus}}) is examined as an example of cathodic oxygen transfer. On oxide-covered Pt electrodes (PtO), a large cathodic current is observed in the presence of IO{sub 3}{sup {minus}} to coincide with the reduction of PtO. The total cathodic charge exceeds the amount required for reduction of PtO and IO{sub 3}{sup {minus}} to produce an adsorbed product. An electrocatalytic link between reduction of IO{sub 3}{sup {minus}} and reduction of PtO is indicated. In addition, on oxide-free Pt electrodes, the reduction of IO{sub 3}{sup {minus}} is determined to be sensitive to surface treatment. The electrocatalytic oxidation of CN{sup {minus}} is presented as an example of anodic oxygen transfer in Part II. The voltametric response of CN{sup {minus}} is virtually nonexistent at PbO{sub 2} electrodes. The response is significantly improved by doping PbO{sub 2} with Cu. Cyanide is also oxidized effectively at CuO-film electrodes. Copper is concluded to serve as an adsorption site for CN{sup {minus}}. It is proposed that an oxygen tunneling mechanism comparable to electron tunneling does not occur at the electrode-solution interface. The adsorption of CN{sup {minus}} is therefore considered to …

This thesis is divided into two sections, which describe portions of the data acquisition system and online software for the Cherenkov Ring Imaging Detector (CRID) for the SLD, and analyses of several low cross section strangeonium channels in data from the LASS spectrometer. The CRID section includes a description of the data acquisition system, determination of the preamplifier gain, and development of an online pulse finding algorithm based on deconvolution. Deconvolution uses knowledge of the preamplifier impulse response to aid in pulse finding. The algorithm is fast and shows good single pulse resolution and excellent double pulse resolution in preliminary tests. The strangeonium analyses are based on data from a 4.1 event/nanobarn exposure of the LASS spectrometer in K{sup {minus}}p interactions at 11 GeV/c, and include studies of {Lambda}{eta}{pi}{sup {plus}}{pi}{sup {minus}}, {Lambda}{Kappa}*{Kappa}*, and {Lambda}{phi}{phi}.

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.

Results covering burn intensities in the nW to {mu}W/cm{sup 2} range, of dispersive hole growth kinetics are reported for Oxazine 720 in glycerol glasses and polyvinyl alcohol polymer films and their deuterated analogues. A theoretical model which employs a distribution function for the hole burning rate constant based upon a Gaussian distribution for the tunnel parameter is shown to accurately describe the kinetic data. This model incorporates the linear electron-phonon coupling. A method for calculating the nonphotochemical quantum yield is presented which utilizes the Gaussian distribution of tunnel parameters. The quantum yield calculation can be extended to determine a quantum yield as a function of hole depth. The effect of spontaneous hole filling is shown to be insignificant over the burn intensity range studied. Average relaxation rates for hole burning are {approximately}8 orders of magnitude greater than for hole filling. The dispersive kinetics of hole burning are observed to be independent over the temperature range of these experiments, 1.6 to 7.0 K. 6 refs., 20 figs., 1 tab.

We have studied the interactions of water and perfluorodiethyl ether on Ru(100) in order to model the effects of surface structure and humidity on the bonding and decomposition of perfluoroalkyl ether lubricants with metal surfaces. In order to understand the interactions on Ru(100), we have first investigated the interactions of each of these adsorbates alone on the clean surface. The interactions of water with Ru(100) have been studied using both thermal desorption spectroscopy (TDS) and electron energy loss spectroscopy (EELS). From these studies we conclude that a small amount of water dissociates on this surface (5--10% of a monolayer), but water is adsorbed in a predominantly molecular form on this surface with an increasing degree of hydrogen-bonding with increasing coverage. The effects of hydrogen and oxygen coadsorption on the interactions of water with this surface have also been studied using TDS. Finally, the interactions of coadsorbed water and perfluorodiethyl ether on Ru(100) have been investigated using TDS.

The data engineers and scientists use to determine if the groundwater supply is contaminated are derived from analysis of samples taken largely from monitoring wells. For these data to be reliable several factors must be considered. One factor is the integrity of the monitoring well. In this project, emphasis has been placed on the potential impact on water quality caused by diffusion across the threaded joints of PVC pipe. In this study, the diffusion of trichloroethylene across several common types of threaded joints (i.e., square flush, modified ACME, modified ACME stub, and ACME) has been measured. Samples were obtained from the water inside the pipe sections and analyzed for trichloroethylene by gas chromatography. Breakthrough occurs within days of the samples being placed in the baths. The softened PVC joints of the pipes in the pure trichloroethylene split before the first sample interval of 1.5 weeks. The data show great variability in casting joints from the same manufacturer, and indicate a need for increased precision in the manufacturing of the PVC pipe joints. A one-dimensional diffusion model is used to determine an equivalent gap size through which the diffusion occurs. Flow rates through the threaded joints are calculated by using the …

Data are presented for the first time on exclusive Pomeron-Pomeron interactions which produce a neutral strange and neutral antistrange particle pair in a central system X. In this paper, the system, X, is identified as one of the following neutral combinations; K{sub s}{sup 0}K{sub s}{sup 0}, K{sub s}{sup 0}K{sup {plus minus}}{pi}{sup {minus plus}}, {Lambda}{sup 0}{bar {Lambda}}{sup 0}, {Lambda}{sup 0}{bar {Lambda}}{sup 0}*. These data were obtained in proton-proton collisions at {radical}s = 62 GeV at the CERN ISR. The triggering systems used to obtain these data are described, followed by a description of the data. The central system mass distributions are presented along with differential mass cross section estimates. A broad enhancement is seen in the K{sub s}{sup 0}K{sub s}{sup 0} system at a mass of 1.2 GeV, and is likely to have the quantum numbers J{sup PC} = 0{sup ++}. Total cross section estimates of 1.3 {plus minus} .64 {mu}b in the K{sub 2}{sup 0}K{sub s}{sup 0} system, . 44 {plus minus} .14 {mu}b in the K{sub s}{sup 0}K{sup {plus minus}}{pi}{sup {minus plus}} system, .20 {plus minus} .14 {mu}b in the {Lambda}{sup 0}{bar {Lambda}}{sup 0} system, and .13 {plus minus} .06 {mu}b in the {Lambda}{sup 0}{bar {Lambda}}{sup 0}* system are …