The characterization of diffusion of lead and other trace elements in certain mineral phases has great significance in reconstructing the thermal history of the earth's crust. Such studies permit better interpretation of ages'' obtained from isotopic dating. This study uses ion implantation to introduce lead into the minerals apatite and zircon. Diffusion profiles are obtained using Rutherford backscattering (RBS) and the results fit with a model to determine D. Results for apatite over the temperature range 600--900{degree}C show agreement with earlier results obtained traditional geologic techniques. This suggests that radiation damage induced by ion implantation has little effect on diffusion in this case. This approach is both simple and useful in studying diffusion over a temperature range of geologic interest without inordinate annealing times. 17 refs., 5 figs.

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.

The electrocatalytic activities were compared for pure and chloride-doped beta-PbO{sub 2} (Cl-PbO{sub 2}) films on gold and platinum substrates. Rate constants were increased significantly for oxidations of Mn{sup 2+}, toluene, benzyl alcohol, dimethylsulphoxide (DMSO) and benzaldehyde in acidic media by the incorporation of Cl{sup {minus}} into the oxide films. These reactions are concluded to occur by the electrocatalytic transfer of oxygen from H{sub 2}O to the reaction products. Results of x-ray diffraction studies indicate the Cl-PbO{sub 2} film continues to have the slightly distorted rutile structure of pure beta-PbO{sub 2}. The observed electrocatalytic phenomena are concluded to be the beneficial consequence of surface defects generated when Cl{sup {minus}} serves for charge compensation within the surface matrix and, thereby, increases the number of surface sites capable of adsorbing hydroxyl radicals which are transferred in the electrocatalytic O-transfer reactions. 91 refs., 44 figs., 10 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 purpose of this investigation is to study the mechanisms of sulfur capture when burning coal-water-limestone mixtures (CWLM) in fluidized beds. Special care is taken to make comparisons with to dry coal and sorbent under comparable experimental conditions. A series of experiments were performed in an eight-inch diameter bubbling fluidized bed combustor to address this problem. 33 refs., 17 figs., 5 tabs.

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.

The precipitation of jarosite compounds to remove Na, K, Fe, and SO{sub 4}{sup 2{minus}} impurities from spent acid solutions from a chemical coal cleaning process was studied. Simple heating of model solutions containing Fe{sub 2}(SO{sub 4}){sub 3}, Na{sub 2}SO{sub 4}, and K{sub 2}SO{sub 4} caused jarosite (KFe{sub 3}(SO{sub 4}){sub 2}(OH){sub 6}) to form preferentially to natrojarosite (NaFe{sub 3}(SO{sub 4}){sub 2}(OH){sub 6}). Virtually all of the K, about 90% of the Fe, and about 30% of the SO{sub 4}{sup 2{minus}} could be precipitated from those solutions at 95{degree}C, while little or no Na was removed. However, simple heating of model solutions containing only Fe{sub 2}(SO{sub 4}){sub 3} and Na{sub 2}SO{sub 4} up to 95{degree}C for {le}12 hours produced low yields of jarosite compounds, and the Fe concentration in the solution had to be increased to avoid the formation of undesirable Fe compounds. Precipitate yields could be increased dramatically in model solutions of Na{sub 2}SO{sub 4}/Fe{sub 2}(SO{sub 4}){sub 3} containing excess Fe by using either CaCO{sub 3}, Ca(OH){sub 2}, or ZnO to neutralize H{sub 2}SO{sub 4} released during hydrolysis of the Fe{sub 2}(SO{sub 4}){sub 3} and during the precipitation reactions. Results obtained from the studies with model solutions were applied to spent …

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).

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 …

The objective of this study was to investigate the role of oceanic carbon chemistry in modulating the atmospheric levels of CO[sub 2]. It is well known that the oceans are the primary sink of the excess carbon pumped into the atmosphere since the beginning of the industrial period. The suspended particulate and the dissolved organic matters in the deep ocean play important roles as carriers of carbon and other elements critical to the fate of CO[sub 2]. In addition, the suspended particulate matter provides sites for oxidation-reduction reactions and microbial activities. The problem is of an intricate system with complex chemical, physical and biological processes. This report describes a methodology to describe the interconversions of different forms of the organic and inorganic nutrients, that may be incorporated in the ocean circulation models. Our approach includes the driving force behind the transfers in addition to balancing the elements. Such thermodynamic considerations of describing the imbalance in the chemical potentials is a new and unique feature of our approach.

The quenching and stability behavior of forced-flow helium-cooled, cable-in-conduit conductors (CICC) has been analyzed using a new computer program. This computer analysis code was developed for performing general, transient, thermal analyses on CICCs. The program includes the necessary details for the physical properties of all the constituent materials of such conductors, and accurately models the thermo- and fluid-dynamic behavior of the helium coolant starting from a wide range of initial conditions. It has been applied to a study of the stability and quench behavior of several large-scale conductor options being considered for use in the magnet systems of the International Thermonuclear Experimental Reactor (ITER), and the results will be reported here. 3 refs., 14 figs.

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.

The EMP consists of a Compliance Monitoring Sampling Program and a Supplemental monitoring Sampling Program. The Compliance Monitoring Sampling Program will be conducted during a summer and a winter Baseline periods during the Pre-Construction/Construction phases of the Project and during a summer and a winter period following the successful Startup and Operational phase of the completed Project. compliance monitoring consist of conducting all the sampling and observation programs associated with existing required Federal, State, and Local Regulations, Permits and Orders. These include air, water, and waste monitoring and OSHA and NESHAP monitoring. The Supplemental Monitoring Program will also be conducted during a summer and a winter Baseline periods during the Pre-Construction/Construction phases of the Demonstration Facility and during a summer and a winter period following the successful startup and Operational phase of the completed Facility. Supplemental Monitoring includes sampling of 27 additional streams that are important to measure operational or environmental performance and impacts of the installation of the new COG treatment facilities.

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 …

The purpose of the DOE limestone injection multistage burner (LIMB) Demonstration Project Extension is to extend the data base on LIMB technology and to expand DOE's list of Clean Coal Technologies by demonstrating the Coolside process as part of the project. The main objectives of this project are: to demonstrate the general applicability of LIMB technology by testing 3 coals and 4 sorbents (total of 12 coal/sorbent combinations) at the Ohio Edison Edgewater plant; and to demonstrate that Coolside is a viable technology for improving precipitator performance and reducing sulfur dioxide emissions while acceptable operability is maintained. Progress is reported. 3 figs.

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 …

In August 1987, a routine Ames test on soot from the Lawrence Livermore National Laboratory (LLNL) 4-in. gun showed that the soot was mutagenic to Salmonella bacteria. Subsequent liquid chromatography on the soot showed that, out of hundreds of ultravoilet-absorbing compounds found in the residue, only three or four were mutagenic. When a sample large enough to weigh was collected, it was found that No environmentally identified complex mixture has ever been reported with as much Ames/Salmonella activity per gram as the gun residues.'' Since then, Ames tests of hundreds of samples have verified that the residues from our gun tanks may be hazardous to health. The actual degree of the hazard and the identity of the offending chemicals are still unknown. 2 refs.

The Fusion ENgineering International eXperimental (FENIX) Test Facility which is nearing completion at Lawrence Livermore National Laboratory, is a 76-t set of superconducting magnets housed in a 4-m-diameter cryostat. It represents a significant step toward meeting the testing needs for the development of superconductors appropriate for large-scale magnet applications such as the International Thermonuclear Experimental Reactor (ITER). The magnet set is configured to allow radial access to the 0.4-m-diameter high-field region where maximum fields up to 14 T will be provided. The facility is fitted with a thermally isolated test well with a port to the high-field region that allows insertion and removal of test conductors without disturbing the cryogenic environment of the magnets. It is expected that the facility will be made available to magnet developers internationally, and this paper discusses its general design features, its construction, and its capabilities.

This task evaluated the materials compatibility of LaNi[sub 5-x]Al[sub x] (x= 0.3, 0.75) hydrides and palladium coated kieselguhr with austenitic stainless steel in hydrogen and tritium process environments. Based on observations of retired prototype hydride storage beds and materials exposure testing samples designed for this study, no materials compatibility problem was indicated. Scanning electron microscopy observations of features on stainless steel surfaces after exposure to hydrides are also commonly found on as-received materials before hydriding. These features are caused by either normal heat treating and acid cleaning of stainless steel or reflect the final machining operation.

The growth, structure, and thermal stability of ultra-thin metal films (Rh on Ag(100); Au on Pd(110) and Pt on Pd(110)) is investigated using surface sensitive techniques. The three systems studied present a variety of differing characteristics which can contribute to the growth mode, two-dimensional structure, and thermal stability of the films. The main factors contributing to the differing properties of the three systems presented here are: (1) the different substrate morphologies; (2) the differences in surface free energies between the overlayer and the substrate; (3) the degree of lattice mismatch for a particular system; and (4) the extent of miscibility of the two metals. 200 refs., 38 figs.

A modification to the proportional chamber design makes it possible to achieve 5{mu}m spatial resolution in particle tracking. Achieving this requires knowing exactly what the electric field is in the chamber, and simple approximations to the field are not accurate enough. The operation of the chamber and techniques which accurately evaluate the electric field are discussed.