A search for innovative synthetic routes to new metal-metal bonded metal-halide clusters resulted in isolation of two completely independent dimeric species. The syntheses and characterizations of Ta/sub 2/X/sub 6/(SC/sub 4/H/sub 8/)/sub 3/ (X = Cl, Br) and ((n-C/sub 3/H/sub 7/)/sub 4/N)/sub 2/(W/sub 2/Br/sub 9/) followed entirely different experimental routes, yet occasionally similar properties linked the two projects. (auth)

Experimental studies have been carried out in which the A15 phase of the Nb-Al-Ge system has been synthesized in the form of thin filaments contained in form rolled wires. A powder metallurgy approach has been used to achieve controlled porosity in compacts of sintered niobium powder. Infiltration with an aluminum-germanium eutectic alloy followed by mechanical deformation has produced small interconnected filaments embedded in the Nb matrix. Diffusion heat treatment for a short time transforms them into the A15 superconducting compound with a size range of 1-5 microns at 1300/sup 0/C and 1-9 microns at 1750/sup 0/C. The superconducting properties T/sub c/ and J/sub c/ were evaluated for samples subjected to different condition of time and temperature. The influence of certain parameters involved in the process has been investigated. The microstructure and microhardness of the Al-Ge eutectic alloy cooled at high and low cooling rates from temperatures between 900-400/sup 0/C have been evaluated. Optical and electron beam metallographic results are presented for the analysis of the different phases and relative compositions. The critical temperature measured inductively is between 16.4/sup 0/K and 18.1/sup 0/K depending on the heat treatment. The critical current density as a function of the applied magnetic field is …

The investigation of two poorly understood but technologically important physical properties of silicate glasses and related materials is described. The use of Electron Paramagnetic Resonance to investigate the nature of radiation-induced damage in glasses exposed to a variety of high-energy radiation sources is discussed first. Second, the measurement of the nonlinear index of refraction coefficient in a variety of optical materials related to the design of high-power laser systems is described. The radiation damage investigations rely heavily on the comparison of experimental results for different experimental situations. The comparison of EPR lineshapes, absolute spin densities and power saturation behavior is used to probe a variety of microscopic and macroscopic aspects of radiation damage in glasses. Comparison of radiation damage associated with exposure to gamma rays and fast neutrons (and combinations thereof) are interpreted in terms of the microscopic damage mechanisms which are expected to be associated with the specific radiations. Comparison of radiation damage behavior in different types of glasses is also interpreted in terms of the behavior expected for the specific materials. The body of data which is generated is found to be internally self-consistent and is also generally consistent with the radiation damage behavior expected for specific situations. …

A detailed interpretation is presented of E-field ratio telluric, bipole-dipole resistivity mapping, and dipole-dipole resistivity data obtained in the course of geophysical exploration of the Leach Hot Springs area of Grass Valley, Nevada. Several areas are singled out as being worthy of further investigation of their geothermal potential. Comparison of the three electrical exploration techniques indicates that: the bipole-dipole resistivity mapping method is the least useful; the dipole-dipole resistivity method can be very useful, but is, for practical purposes, exceptionally expensive and difficult to interpret; the E-field ratio telluric method can be a highly successful reconnaissance technique for delineating structures and relating the resistivities of different regions within the survey area.

Four sialon-type materials using volcanic ash as a raw material were characterized and some of their properties were determined. The M3 and M4 materials were identified as ..beta../sup 1/--Si/sub 3/N/sub 4/ sialons; their principal constituent is silicon. The M2 material was identified as a 15R-A1N polytype sialon whose principal constituent is aluminum. The M1 material is a mixture of the two types. An overview of results showing the general structural formulae and the relative order of the materials with respect to various properties as determined by the investigation is presented. It is concluded that of the materials tested, the M2 material shows the most promise as a candidate for meeting some of the current needs for high-temperature materials. It is also concluded that more research is needed in order to explain the low resistance of these materials to thermal shock since their coefficients of thermal expansion are relatively low.

The one- and two-dimensional Ginzburg-Landau equations are numerically integrated in a slab geometry, which is appropriate for comparison to experimental work done on films. When two-dimensional variations become energetically favorable, a vortex is found to nucleate and move to the center of the film with the Gibbs free energy decreasing during the process. An important process by which the energy is lowered during this nucleation procedure is found to be the savings in condensation energy arising from the shrinking size of the vortex core as it moves to the center of the film. The solutions of the Ginzburg-Landau equations are used to explain anomalies observed experimentally in the tunneling characteristics of thin films of PbIn. Excellent agreement between theory and experiment is found with the Ginzburg-Landau equations correctly predicting the field at which flux would first enter the films. We then use the Clem model of an isolated vortex to model vortex nucleation and dynamics under the influence of a transport current. The entry fields predicted by the model are found to be off by almost a factor of two but have the advantage of requiring simple computer programs for their solution, while the Ginzburg-Landau solutions require substantially more numerical …

The polarized absorption spectra for K/sub 2/PtBr/sub 4/ . 2H/sub 2/O, (N(C/sub 2/H/sub 5/)/sub 4/)/sub 2/PtBr/sub 6/, and Mo/sub 2/(O/sub 2/CCH/sub 2/NH/sub 3/)/sub 4/(SO/sub 4/)/sub 2/ . 4H/sub 2/O have been recorded at 300 and 15/sup 0/K. In K/sub 2/PtBr/sub 4/ . 2H/sub 2/O the bands at 24,000 and 27,000 cm/sup -1/ in both a- and b-polarizations appear to be vibronically induced. The energy spacing of the vibrational structure was noted to be somewhat higher at 180 cm/sup -1/ than for the analogous structure of K/sub 2/PtBr/sub 4/. The presence of a Pt/sub 2/Br/sub 6//sup 2 -/ impurity gave rise to red sections, which evidently were due to the electron transfer, Pt(IV)/reverse arrow/Pt(II), occurring in c-polarization. Very weak spin-forbidden bands were observable in all three polarizations below 23,500 cm/sup -1/. In the crystal spectra of (N(C/sub 2/H/sub 5/)/sub 4/)/sub 2/Pt/sub 2/Br/sub 6/ the transitions were defined with respect to the three molecular axes of the Pt/sub 2/Br/sub 6//sup 2 -/ ion. Excited states were assigned under the D/sub 2//sub h/ point group symmetry of the ion. The delocalization of the d electrons gave rise to strongly enhanced intensities for both spin-forbidden and spin-allowed d/reverse arrow/d transitions. The M/reverse arrow/L charge-transfer …

A method is developed to optimize the separated-pair independent particle (SPIP) wave function; it is a special case of the separated-pair theory obtained by using two-term natural expansions of the geminals. The orbitals are optimized by a theory based on the generalized Brillouin theorem and iterative configuration interaction (CI) calculations in the space of the SPIP function and its single excitations. The geminal expansion coefficients are optimized by serial 2 x 2 CI calculations. Formulas are derived for the matrix elements. An algorithm to implement the method is presented, and the work needed to evaluate the molecular integrals is discussed. (auth)

A special hydriding system was designed and constructed to satisfy conditions for hydriding niobium. This system controlled the temperature and hydrogen atmosphere surrounding the niobium while ultrasonic measurements were recorded. Ultrasonic wave velocities were determined by measurement of the times for ultrasonic pulses to transit and then echo through known dimensions of test specimens. The method which was employed is commonly known as the pulse-echo-overlap method. This study confirmed the general trends of earlier investigations. In this study C' continued to decrease and C/sub 44/ continued to increase up to 4.69 atomic percent hydrogen which is the maximum concentration which has yet been examined. In the case of the niobium-hydrogen system the Snoek effect may well be a contributory factor to the decrease of C' with increasing hydrogen concentration. However, crystallographic considerations preclude this effect from contributing a concentration dependence to C/sub 44/ or B. The observation of the present work implies that other factors must also be contributing to the overall behavior.

The development of a unique type of large superconducting solenoid magnet, characterized by very high current density windings and a two-phase helium tubular cooling system is described. The development of the magnet's conceptual design and the construction of two test solenoids are described. The successful test of the superconducting coil and its tubular cooling refrigeration system is presented. The safety, environmental and economic impacts of the test program on future developments in high energy physics are shown. Large solid angle particle detectors for colliding beam physics will analyze both charged and neutral particles. In many cases, these detectors will require neutral particles, such as gamma rays, to pass through the magnet coil with minimum interaction. The magnet coils must be as thin as possible. The use of superconducting windings allows one to minimize radiation thickness, while at the same time maximizing charged particle momentum resolution and saving substantial quantities of electrical energy. The results of the experimental measurements show that large high current density solenoid magnets can be made to operate at high stored energies. The superconducting magnet development described has a positive safety and environmental impact. The use of large high current density thin superconducting solenoids has been proposed …

The crystal and molecular structures of the following organophosphorus (OP) insecticides have been determined by three-dimensional X-ray analysis: ronnel (0,0-dimethyl 0-2,4,5 trichlorophenyl phosphorothioate), ronnel oxon (0,0-dimethyl 0-2,4,5 trichlorophenyl phosphate), bomophos (0-(4-bromo-2,5-dichlorophenyl) 0,0-dimethyl phosphorothioate), Ruelene (0-(4-tert-Butyl-2-chlorophenyl)-0-methyl-N-methyl phosphoroamidate), fospirate (0,0-dimethyl 0-3,5,6-trichloro-2-pyridyl phosphate) and chlorpyrifos (0,0-diethyl 0-3,5,6-trichloro-2-pyridyl phosphorothioate). Phosphorus to meta hydrogen distances for the respective compounds are: 5.51, 5.49, 5.42, (5.68, 5.13), 5.79 and 5.78 A. All of these distances fall well within the range of literature values cited for the intramolecular active site-separation distance for insect acetylcholinesterase (AChE), yet are well outside that for mammalian AChE. In addition the crystal structure of ronnel displays a hydrogen-sulfur intermolecular interaction in the b direction and a phosphorus which is readily accessible for phosphorylation of AChE. The structure of ronnel oxon is quite similar to that of ronnel. CNDO 11 molecular orbital calculations are presented to show the charge distribution in the compound. A likely intramolecular hydrogen bond in bromophos restricts rotation about the phenolic C-O bond. The configuration of Ruelene is substantiated by CNDO 11 molecular orbital calculations and van der Waals arguments and features a possible weak intramolecular hydrogen bond which somewhat restricts rotation about the phenolic C-O bond. Charge density information …

Results are reported from an investigation of correlations between molecular structural parameters of selected organophosphorus insecticides and their corresponding toxic effectiveness. The crystal and molecular structures of azinphos-methyl, emidithion, and tetrachlorvinphos were determined via three-dimensional x-ray analysis. Acetylcholinesterase (AChE) in nerve cells was identified as the target for organophosphorus insecticides.

Electron transfer from the excited state of sensitizing dyes to the conduction band of semiconductors has been studied through photoelectrochemical techniques. Two systems were analyzed in detail: rhodamine B on ZnO and rose bengal on TiO/sub 2/. Prior to electrochemical experimentation, the adsorption characteristics of these dyes were investigated using ZnO, ZnS, and TiO/sub 2/ single crystals as substrates. Absorbance measurements of the adsorbed dye were taken as a function of the solution concentration of the dye. Adsorption isotherms heats of adsorption were also established; they were similar to literature data reported for adsorption of these dyes on powdered substrates. Using the absorbance data, the quantum efficiency for photoinjection of electrons from rhodamine B into a ZnO electrode was determined to be 2.7 x 10/sup -2/. This value was independent of the dye surface concentration down to 50% coverage of the electrode. With the assumption that not all of the rhodamine B adsorbed on the electrode has the same rate of electron injection, a kinetic model for the time decay of the photocurrent was developed; data were analyzed according to this theory. A rate constant for photoreduction of the adsorbed dye was determined for the reducing agents. 86 references.

Commercial secondary hardening steel, VASCO MA, has been subjected to modified heat treatments to introduce mixed microstructures of martensite and lower bainite. Dilatometry, tensile testing, hardness measurements and slow-bend testing have been carried out and the mechanical properties obtained have been correlated to microstructure using scanning electron microscopy and metallography. Duplex microstructures containing small amounts of lower bainite are found to show an increased toughness (at similar strength levels) on tempering in the secondary hardening range, as compared to initially fully martensitic microstructures. As the percentage of lower bainite in the duplex microstructures is increased, the secondary hardening peak is found to attenuate. The effect of different austenitization treatments on the secondary hardening behavior, has also been studied. Thermal cycling (for grain refinement) at lower austenitization temperatures is found to reprecipitate out carbon, which has been taken into solution in earlier high temperature austenitization, thereby leading to a significant depletion in the strength of this secondary hardening steel. Alloy carbides, in the secondary hardening stage, have also been analyzed using energy dispersive analysis of x-rays.

An improved electrostatic precipitator called a space charge precipitator was tested and studied. A space charge precipitator differs from a conventional model in that the fields necessary to move the particles from the gas to the collecting surfaces are provided by a cloud of charged innocuous drops, such as glycerine or water, rather than by a charged electrode system. The flow conditions, electrical equipment, and physical dimensions of the test precipitator are typical of industrial applications. Experiments using water fog at a velocity of 10 ft/sec and a residence time of 0.6 sec, for a system charged at 25 kV, show a removal of iron oxide particles of approximately 52 percent. Theoretical calculations, assuming 2 micron particles, predict a removal of 50 percent. The results with glycerine fog are comparable. Experiments at various flowrates for both water fog and glycerine fog show a trend of decreasing particle removal for increasing flowrate. An identical trend is predicted by the space charge theory. Electron micrographs verify that only particles smaller than two microns are present in the laboratory precipitator.

Two mathematical methods are utilized (one a form of adiabatic approximation, and the other closely related to the Zener method from collision theory) in order to calculate the probability of three-photon ionization when strong counter propagating pulses are tuned very near a two-photon resonant state. In this case the inverted populations predicted by Grischkowsky and Loy for smooth laser pulses lead to larger ionization probabilities than would be obtained for a square pulse of equal peak power and energy per pulse. The line shape of the ionization probability is also quite unusual in this problem. A sharp onset in the ionization probability occurs as the lasers are tuned through the exact unperturbed two-photon resonance. Under proper conditions, the change can be from a very small value to one near unity. It occurs in a very small frequency range determined by the larger of the residual Doppler effect and the reciprocal duration of the pulse. Thus, the line shape retains a Doppler-free aspect even at power levels such that power broadening would dwarf even the full Doppler effect in the case of a square pulse of equal energy and peak power. The same mathematical methods have been used to calculate line …

The (/sup 6/Li,/sup 8/B) reaction has been investigated on targets of /sup 26/Mg, /sup 24/Mg, /sup 16/O, /sup 13/C, /sup 12/C, /sup 11/B, /sup 10/B, and /sup 9/Be at a bombarding energy of 80.0 MeV, and on targets of /sup 16/O, /sup 12/C, /sup 9/Be, /sup 7/Li, and /sup 6/Li at a bombarding energy of 93.3 MeV. Only levels consistent with direct, single-step two-proton pickup reaction mechanisms were observed to be strongly populated. On T/sub z/ = 0 targets, the spectroscopic selectivity of this reaction resembles that of the analogous (p,t) reaction. Additionally, these data demonstrate the dominance of spatially symmetric transfer of the two protons. On T/sub z/ greater than 0 targets the (/sup 6/Li,/sup 8/B) reaction was employed to locate two previously unreported levels (at 7.47 +- 0.05 MeV and 8.86 +- 0.07 MeV) in the T/sub z/ = 2 nuclide /sup 24/Ne and to establish the low-lying 1p-shell states in the T/sub z/ = /sup 3///sub 2/ nuclei /sup 11/Be, /sup 9/Li, and /sup 7/He. However, no evidence was seen for any narrow levels in the T/sub z/ = /sup 3///sub 2/ nuclide /sup 5/H nor for any narrow excited states in /sup 7/He. The angular distributions …

The proton NMR in powdered samples of H/sub 2/O(s), H/sub 2/S(s), and C/sub 6/H/sub 6/(s) have been studied by multiple pulse line narrowing techniques. The resultant spectra provide nuclear magnetic shielding tensors that are (at least approximately) axially symmetric. The anisotropy is 34.2 +- 1.0 ppM for ice, 11.1 +- 1.0 ppM for the highest-temperature phase of solid hydrogen sulfide, and -5.3 +- 0.3 for benzene. Comparisons are made with previous experimental and theoretical work.

A high-pressure liquid-phase microreactor was developed to determine the kinetics and reaction networks of catalytic hydrodesulfurization and hydrodenitrogenation of polynuclear aromatic compounds found in coal-derived liquids. This reactor permits the use of small quantities of reactants and catalyst. This reactor design is expected to be useful generally and is not limited to hydroprocessing. The microreactor was designed to operate entirely in the liquid phase. The hydrogen required for the hydrogenation reactions is dissolved into the liquid phase before entering the reactor. A high total pressure is kept on the system, and no gas phase is ever permitted. Further, the system was designed to allow either the pulse or steady-state mode of operation. The specific design criteria were: hydrogen saturation pressure 0-61 atm, total pressure 0-272 atm, reactor temperatures up to 450/sup 0/C and space velocities between 1 and 10 (1/hr). The equipment has been operated at 21 atm hydrogen pressure and 104 atm total pressure over a range of temperatures and flow rates. A four-day test was conducted at steady-state conditions. The results indicate a significant break-in period for fresh catalyst.

An experimental investigation was carried out to improve the froth flotation method of separating coal pyrite. The effect of several surface active agents on the floatability of an Iowa coal and its associated pyrite was studied in both the presence and absence of methyl isobutyl carbinol (MIBC), a commonly used frother. The effectiveness of a special method of chemical pretreatment for depressing pyrite was also investigated. The zeta potential of the same coal and pyrite was measured under the same conditions used in the flotation tests (in the absence of frother). In the absence of MIBC, the floatability of coal and pyrite was low, and appeared to depend on pH. The maximum recovery of pyrite was obtained at a pH of 4.5 with recovery being less at higher or lower pH. The addition of a small amount of MIBC significantly increased the recovery of coal and pyrite with the increase in the recovery of coal being much greater than the increase in the recovery of pyrite. Also in the presence of MIBC, the floatability of coal and pyrite seemed to be affected more by pH than in the absence of MIBC. On the other hand, several potential pyrite depressants were …

The magnetic properties of quenched and annealed powder specimens of MnPt were investigated using x-ray diffraction, magnetization measurements and neutron diffraction techniques. Thin films of MnPt were prepared by rf sputtering techniques and the films were investigated by x-ray diffraction and magnetization measurements. The powder specimens of MnPt were found to be typically antiferromagnetic in an L1/sub 0/ structure with Mn atoms occupying the (001) planes. The Mn moments were antiparallel to their nearest neighbors in the (001) planes. The atomic moment of Mn is (4.1 +- .2) ..mu../sub B/ for the annealed specimens and (3.9 +- .2) ..mu../sub B/ for the quenched specimens. Neutron data failed to determine whether or not Pt carries a moment. Assuming a moment associated with the Pt atoms, the maximum value is 0.2 ..mu../sub B/ per atom. The quenched specimens contained small ferromagnetic regions probably with a composition of 18-32 at. percent Mn. The sputtered films of MnPt were highly disordered in all but one specimen, which was amorphous. The films were ferromagnetic with the deduced Mn moment of (3.0 +- .3) ..mu../sub B/ per atom, which may not represent the true value because the films were not entirely ferromagnetic.

The polarized electronic absorption spectra for single crystals of potassium octachlorodimolybdate (II-dihydrate, potassium tetra-..mu..-sulfatodimolybdate (II)-dihydrate and potassium tetra-..mu..-sulfatodimolybdate (II,III)-3.5 hydrate have been obtained at room and liquid helium temperatures.

A method of calculating the transport coefficient in an axisymmetric toroidal plasma is presented. This method is useful in calculating the transport coefficients in a Tokamak plasma confinement device. The particle density and temperature are shown to be a constant on a magnetic flux surface. Transport equations are given for the total particle flux and total energy flux crossing a closed toroidal surface. Also transport equations are given for the toroidal magnetic flux. A computer code was written to calculate the transport coefficients for a three species plasma, electrons and two species of ions. This is useful for calculating the transport coefficients of a plasma which contains impurities. It was found that the particle and energy transport coefficients are increased by a large amount, and the transport coefficients for the toroidal magnetic field are reduced by a small amount.

In an effort to determine the details of reaction mechanisms, kinetic parameters are obtained for the following two catalytic reactions, C/sub 2/H/sub 4/ + H/sub 2/ ..-->.. C/sub 2/H/sub 6/ and C/sub 2/H/sub 6/ + H/sub 2/ ..-->.. 2 CH/sub 4/. The first reaction is carried out, for the most part, under reaction conditions (e.g. 110-200 K) which prevent complications caused by a side reaction, the surface dehydrogenation of adsorbed ethylene. The second reaction is carried out at somewhat higher temperatures (80 to 200/sup 0/C). Both reactions are studied in the pressure range 0.5 to 1000 ..mu... Extensive isotope labeling experiments are also carried out, which together with the kinetic measurements support in a self-consistent way the following mechanisms of hydrogen addition. The adsorbed species C/sub 2/H/sub 5/(a) and H(a) are found to be intermediates in both the hydrogenation and hydrogenolysis reactions. In the case of the hydrogenation reaction, the rate limiting step is found to be the irreversible addition of an adsorbed hydrogen atom to an adsorbed ethylene molecule to produce C/sub 2/H/sub 5/(a) which is further hydrogenated to produce ethane. The hydrogenolysis occurs by dissociative adsorption of ethane to produce C/sub 2/H/sub 5/(a) and H(a). In this case …