Sample records for trevor houser rhodium

  1. Retirement Benefits Jeff Houser

    E-Print Network [OSTI]

    Vacant Retirement Benefits Specialist Jeff Houser Director, Recruiting & Staffing Services for Early Education Kimberly Abel Director, Professional Development Heather Wainer Information Baker Retirement Administration Manager Lisa Vaccaro Compensation Manager Jeff Houser Interim

  2. Agnes Houser | Y-12 National Security Complex

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Agnes Houser Agnes Houser Oral History Videos Speakers INTRODUCTION Ed Bailey Jim Bailey Kay Bailey Ken Bernander Willard Brock Wilma Brooks Elmer Brummitt Naomi Brummitt Blake...

  3. December 2001 Trevor Hastie, Stanford Statistics 1 Support Vector Machines,

    E-Print Network [OSTI]

    Hastie, Trevor

    December 2001 Trevor Hastie, Stanford Statistics 1 Support Vector Machines, Kernel Logistic in Optimization and Computational Algorithms (NTOC2001) December 9-13, 2001, Kyodai-Kaikan, Kyoto, Japan http://www-stat.stanford.edu/hastie/Papers/ivmtalk.pdf #12;December 2001 Trevor Hastie, Stanford Statistics 2 Outline · Optimal separating hyperplanes

  4. Complexity of the Ritchken-Trevor-Cakici-Topyan GARCH Option Pricing Algorithm

    E-Print Network [OSTI]

    Lyuu, Yuh-Dauh

    Complexity of the Ritchken-Trevor-Cakici-Topyan GARCH Option Pricing Algorithm Yuh-Dauh Lyuu, Taiwan Abstract The trinomial-tree GARCH option pricing algo- rithm of Ritchken and Trevor (1999, exceeds a typically small number determined by the GARCH parameters. Worse, when explo- sion happens

  5. Rhodium Mossbauer Superradiance of Observable Gravitational Effect

    E-Print Network [OSTI]

    Cheng, Yao

    2007-01-01T23:59:59.000Z

    We report the direct observations of the entangled superradiance from rhodium nuclei oriented along the long edge of the polycrystalline sample. The long-lived rhodium Mossbauer effect is sensitive to the earth gravity, which opens up novel approaches of detecting the gravitational waves. Superradiance and exciton diffusion are enhanced by liquid-nitrogen cooling. Gravitational effect attributed to multipolar nuclear transition of the atto-eV natural linewidth is manifested by emissions from different sample orientations corresponding to the earth gravity. The long-range gamma coupling across grain boundaries despite the temperature variation inside sample is manifested by the observed dependence on macroscopic sample size.

  6. Rhodium Mossbauer Superradiance of Observable Gravitational Effect

    E-Print Network [OSTI]

    Yao Cheng; Bing Xia

    2007-11-18T23:59:59.000Z

    We summarize the experimental observations of three case studies on the long-lived rhodium Mossbauer Effect. Extraordinary observations reported in this work manifest the open-up of photonic band gap in analogy to the superconducting gap. Observable gravitational effect is manifested by the superradiance of different sample orientations corresponding to the earth gravity. These observations are of potential importance for detecting gravitational waves and development of the two-photon gamma laser.

  7. Resonant Propagation of Entangled Rhodium Mossbauer Gammas

    E-Print Network [OSTI]

    Yao Cheng; Zhongming Wang

    2006-10-19T23:59:59.000Z

    We report the resonant propagation of the long-lived Mossbauer gamma in the time-resolved Mossbauer spectroscopy. Recently, three entangled gammas emitted from the E3 rhodium Mossbauer transition has been proposed to interpret the extraordinary observations in the previous report. Further observation reported here is the dynamic beat of these entangled gammas at room temperature and 77K. Apparent beat anisotropy reveals their long-distance resonant propagation, which leads to suppressed Doppler shift of entangled photon transport in the Borrmann channel.

  8. Resonant Propagation of Entangled Rhodium Mossbauer Gammas

    E-Print Network [OSTI]

    Cheng, Y; Cheng, Yao; Wang, Zhongming

    2006-01-01T23:59:59.000Z

    We report the resonant propagation of the long-lived Mossbauer gamma in the time-resolved Mossbauer spectroscopy. Recently, three entangled gammas emitted from the E3 rhodium Mossbauer transition has been proposed to interpret the extraordinary observations in the previous report. Further observation reported here is the dynamic beat of these entangled gammas at room temperature and 77K. Apparent beat anisotropy reveals their long-distance resonant propagation, which leads to suppressed Doppler shift of entangled photon transport in the Borrmann channel.

  9. Implementing Six Sigma in Challenging Times: A Case Jose Hernandez, Trevor Turner,

    E-Print Network [OSTI]

    Paris-Sud XI, Université de

    Implementing Six Sigma in Challenging Times: A Case Study Jose Hernandez, Trevor Turner, DMEM by introducing Six Sigma. The paper discusses the effects that the current economic climate has had in the business and presents the findings of a Six Sigma project implementation. Keywords: Six Sigma, SMES, Cost

  10. Earth Observations for rapid response to large earthquakes Supervisors: Dr Zhenhong Li and Prof Trevor Hoey

    E-Print Network [OSTI]

    Guo, Zaoyang

    Earth Observations for rapid response to large earthquakes Supervisors: Dr Zhenhong Li and Prof Trevor Hoey School of Geographical and Earth Sciences, University of Glasgow, UK Earthquakes, together of the earth system; they are messengers of the fundamental processes that shape the surface of the Earth

  11. Functional Analysis of Human Motion Data Dirk Ormoneit y , Trevor Hastie y , and Michael Black z

    E-Print Network [OSTI]

    Ormoneit, Dirk

    of applications. For example, they provide an input for the animation of virtual characters in computer graphicsFunctional Analysis of Human Motion Data #3; Dirk Ormoneit y , Trevor Hastie y , and Michael Black@parc.xerox.com, http://www.parc.xerox.com/black/ Abstract We present a method for the modeling of 3D human motion data

  12. Lego Robotics Engineering Camps at the UC Irvine, Claire Trevor School of the Arts

    E-Print Network [OSTI]

    Loudon, Catherine

    Soccer for the young mind! Lego Robotics Engineering Camps at the UC Irvine, Claire Trevor static structures used in robotics by applying the fundamentals of art, design, math and science concepts. Robot Cadets will build strong and stable structures, explore simple machines, and program

  13. PLATINUM-GROUP METALS (Platinum, palladium, rhodium, ruthenium, iridium, osmium)

    E-Print Network [OSTI]

    and demand. With a short supply, the price of rhodium surged to a 5-year high. An increase in diesel car. Catalysts for air pollution abatement continued to be the leading demand sector for PGMs. In the United in 2004, palladium prices fell in 2005 because of weak demand and oversupply. Meanwhile, the platinum

  14. Enantioselective Rhodium-Catalyzed Allylation of Cyclic Imines with Potassium Allyltrifluoroborates

    E-Print Network [OSTI]

    Hepburn, Hamish B.; Chotsaeng, Nawasit; Luo, Yunfei; Lam, Hon Wai

    2013-01-01T23:59:59.000Z

    This Article presents further examples of the enantioselective rhodium-catalyzed addition of potassium allyltrifluoroborates to cyclic imines. A wide range of substituted allyltrifluoroborates are compatible with this ...

  15. Direct Ethanol Fuel Cells: Platinum/Rhodium Anode

    E-Print Network [OSTI]

    Petta, Jason

    Direct Ethanol Fuel Cells: Platinum/Rhodium Anode Catalysis Ken Ellis-Guardiola PCCM REU 2010 #12 EtOH+3H2O 12H+ +2CO2+ 12e- Pt C 4H+ + 4e- + O2 2H2O O2 Anode Cathode The Direct Ethanol Fuel Cell #12 Fuel Cell Test ~ 1.5 mg Pt loading. 1.0 M Ethanol flowing at 1 ml/min. O2 flowing at 100 ml/min. Cells

  16. Possible Stimulated Emission of Entangled Rhodium Mossbauer Gammas

    E-Print Network [OSTI]

    Yao Cheng; Zhongming Wang

    2006-11-02T23:59:59.000Z

    Observation of possible stimulated emission of Mossbauer gamma is reported by liquid-nitrogen quenching of rhodium sample from room temperature to 77K in the time-resolved Mossbauer spectroscopy. Recently, we have demonstrated the anomalous emission of three entangled gammas of the E3 Mossbauer transition generated by bremsstrahlung irradiation. In this work, we further report the high-speed decay of excited state. We conjecture that cooling shrinkage, gravitational redshift and crystal lattice collimate entangled gammas in a linear cavity. This opens up a new approach towards gamma lasing, if the stimulated emission occurs at this obtained low excitation density.

  17. Possible Stimulated Emission of Entangled Rhodium Mossbauer Gammas

    E-Print Network [OSTI]

    Cheng, Y; Cheng, Yao; Wang, Zhongming

    2006-01-01T23:59:59.000Z

    Observation of possible stimulated emission of Mossbauer gamma is reported by liquid-nitrogen quenching of rhodium sample from room temperature to 77K in the time-resolved Mossbauer spectroscopy. Recently, we have demonstrated the anomalous emission of three entangled gammas of the E3 Mossbauer transition generated by bremsstrahlung irradiation. In this work, we further report the high-speed decay of excited state. We conjecture that cooling shrinkage, gravitational redshift and crystal lattice collimate entangled gammas in a linear cavity. This opens up a new approach towards gamma lasing, if the stimulated emission occurs at this obtained low excitation density.

  18. Role of Si/Al Ratio on Immobilization and Stability of Rhodium Complexes on ZSM-5

    E-Print Network [OSTI]

    Long, Brandon

    2009-01-01T23:59:59.000Z

    The effect of zeolite ZSM-5 Si/Al ratio on adsorption of CO to rhodium is investigated using three different rhodium precursors. Typical dicarbonyl ligands (Rh1+(CO)2) are present in all cases, but tricarbonyl and tetracarbonyl ligands on Rh(I) are also... are two peaks both assigned to dicarbonyls, Rh1+(CO)2. With frequencies of 2116 and 2049 cm-1, they are the symmetric and antisymmetric vibrations of CO; in literature rhodium dicarbonyls are the most stable and prevalent species and so...

  19. Rhodium-catalyzed epoxide-opening cascades toward brevisin and hemibrevetoxin B

    E-Print Network [OSTI]

    Armbrust, Kurt W. (Kurt Willes)

    2014-01-01T23:59:59.000Z

    CHAPTER I. Rhodium-Catalyzed Epoxide-Opening Cascades: Formal Synthesis of (-)-Brevisin [chemical formula inserted] [Rh(CO)?Cl]? was found to be an effective catalyst for endo-selective cyclizations and cascades of ...

  20. Enantioselective Rhodium-Catalyzed Addition of Potassium Alkenyltrifluoroborates to Cyclic Imines

    E-Print Network [OSTI]

    Luo, Yunfei; Carnell, Andrew J.; Lam, Hon Wai

    2012-07-02T23:59:59.000Z

    Cyclic imines, in which the C[DOUBLE BOND]N bond is constrained in the Z?geometry, have been identified as highly effective substrates for enantioselective rhodium-catalyzed additions of potassium alkenyltrifluoroborates. Not only is the alkene...

  1. Enantioselective Rhodium-Catalyzed Nucleophilic Allylation of Cyclic Imines with Allylboron Reagents

    E-Print Network [OSTI]

    Luo, Yunfei; Hepburn, Hamish B.; Chotsaeng, Nawasit; Lam, Hon Wai

    The highly diastereo- and enantioselective title reaction of a range of cyclic imines with various potassium allyltrifluoroborates most likely proceeds via allylrhodium(I) intermediates, and represents the first rhodium-catalyzed ...

  2. Rhodium Mossbauer Supperadiance Induced by Liquid-Nitrogen Cooling

    E-Print Network [OSTI]

    Yao Cheng; Bing Xia; Zhongming Wang

    2007-06-18T23:59:59.000Z

    In the previous report, we have demonstrated cascade branching channels of the multipolar E3 transition of rhodium Mossbauer gamma via the time- and energy-resolved spectroscopy. Moreover, superradiance in the Borrmann channel from inverted nuclei gives gamma entanglement. In this letter, we report further four observations of superradiance and its associated gamma entanglement at the liquid-nitrogen temperature, i.e. (i) speed-up decay, (ii) immediate recovery of the speed-up decay after quenching, (iii) simultaneous suppression of gamma and K lines, and (iv) enhanced multiple ionizations. Anisotropic superradiant channels open by quenching and recover back immediately after quenching. Enhanced K satellites and K hypersatellites induced by cooling are attributed to the inelastic scattering of more than three entangled gammas.

  3. Rhodium Mossbauer Supperadiance Induced by Liquid-Nitrogen Cooling

    E-Print Network [OSTI]

    Cheng, Yao; Wang, Zhongming

    2007-01-01T23:59:59.000Z

    In the previous report, we have demonstrated cascade branching channels of the multipolar E3 transition of rhodium Mossbauer gamma via the time- and energy-resolved spectroscopy. Moreover, superradiance in the Borrmann channel from inverted nuclei gives gamma entanglement. In this letter, we report further four observations of superradiance and its associated gamma entanglement at the liquid-nitrogen temperature, i.e. (i) speed-up decay, (ii) immediate recovery of the speed-up decay after quenching, (iii) simultaneous suppression of gamma and K lines, and (iv) enhanced multiple ionizations. Anisotropic superradiant channels open by quenching and recover back immediately after quenching. Enhanced K satellites and K hypersatellites induced by cooling are attributed to the inelastic scattering of more than three entangled gammas.

  4. Rhodium mediated bond activation: from synthesis to catalysis

    SciTech Connect (OSTI)

    Ho, Hung-An

    2012-03-06T23:59:59.000Z

    Recently, our lab has developed monoanionic tridentate ligand, To{sup R}, showing the corresponding coordination chemistry and catalyst reactivity of magnesium, zirconium, zinc and iridium complexes. This thesis details synthetic chemistry, structural study and catalytic reactivity of the To{sup R}-supported rhodium compounds. Tl[To{sup R}] has been proved to be a superior ligand transfer agent for synthesizing rhodium complexes. The salt metathesis route of Tl[To{sup M}] with [Rh({mu}-Cl)(CO)]{sub 2} and [Rh({mu}- Cl)(COE)]{sub 2} gives To{sup M}Rh(CO){sub 2} (2.2) and To{sup M}RhH({eta}{sup 3}-C{sub 8}H{sub 13}) (3.1) respectively while Tl[To{sup P}] with [Rh({mu}-Cl)(CO)]{sub 2} affords To{sup P}Rh(CO){sub 2} (2.3). 2.2 reacts with both strong and weak electrophiles, resulting in the oxazoline N-attacked and the metal center-attacked compounds correspondingly. Using one of the metal center-attacked electrophiles, 2.3 was demonstrated to give high diastereoselectivity. Parallel to COE allylic C-H activation complex 3.1, the propene and allylbenzene allylic C-H activation products have also been synthesized. The subsequent functionalization attempts have been examined by treating with Brnsted acids, Lewis acids, electrophiles, nucleophiles, 1,3-dipolar reagents and reagents containing multiple bonds able to be inserted. Various related complexes have been obtained under these conditions, in which one of the azide insertion compounds reductively eliminates to give an allylic functionalization product stoichiometrically. 3.1 reacts with various primary alcohols to give the decarbonylation dihydride complex To{sup M}Rh(H){sub 2}CO (4.1). 4.1 shows catalytic reactivity for primary alcohol decarbonylation under a photolytic condition. Meanwhile, 2.2 has been found to be more reactive than 4.1 for catalytic alcohol decarbonylation under the same condition. Various complexes and primary alcohols have been investigated as well. The proposed mechanism is based on the stochiometric reactions of the possible metal and organic intermediates. Primary amines, hypothesized to undergo a similar reaction pathway, have been verified to give dehydrogenative coupling product, imines. In the end, the well-developed neutral tridentate Tpm coordinates to the rhodium bis(ethylene) dimer in the presence of TlPF{sub 6} to give the cationic complex, [TpmRh(C{sub 2}H{sub 4}){sub 2}][PF{sub 6}] (5.1). 5.1 serves as the first example of explicit determination of the solid state hapticity, evidenced by X-ray structure, among all the cationic Tpm{sup R}M(C{sub 2}H{sub 4}){sub 2}{sup +} (Tpm{sup R} = Tpm, Tpm*, M = Rh, Ir) derivatives. The substitution chemistry of this compound has been studied by treating with soft and hard donors. The trimethylphosphine-sbustituted complex activates molecular hydrogen to give the dihydride compound.

  5. Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

    SciTech Connect (OSTI)

    Coble, Inger M

    2008-08-15T23:59:59.000Z

    Model heterogeneous catalysts have been synthesized and studied to better understand how the surface structure of noble metal nanoparticles affects catalytic performance. In this project, monodisperse rhodium and platinum nanoparticles of controlled size and shape have been synthesized by solution phase polyol reduction, stabilized by polyvinylpyrrolidone (PVP). Model catalysts have been developed using these nanoparticles by two methods: synthesis of mesoporous silica (SBA-15) in the presence of nanoparticles (nanoparticle encapsulation, NE) to form a composite of metal nanoparticles supported on SBA-15 and by deposition of the particles onto a silicon wafer using Langmuir-Blodgett (LB) monolayer deposition. The particle shapes were analyzed by transmission electron microscopy (TEM) and high resolution TEM (HRTEM) and the sizes were determined by TEM, X-ray diffraction (XRD), and in the case of NE samples, room temperature H2 and CO adsorption isotherms. Catalytic studies were carried out in homebuilt gas-phase reactors. For the nanoparticles supported on SBA-15, the catalysts are in powder form and were studied using the homebuilt systems as plug-flow reactors. In the case of nanoparticles deposited on silicon wafers, the same systems were operated as batch reactors. This dissertation has focused on the synthesis, characterization, and reaction studies of model noble metal heterogeneous catalysts. Careful control of particle size and shape has been accomplished though solution phase synthesis of Pt and Rh nanoparticles in order to elucidate further structure-reactivity relationships in noble metal catalysis.

  6. Synthesis, structure and spectroscopic investigations of luminescent heterobimetallic gold(I)-Rhodium(I) species

    E-Print Network [OSTI]

    Dempsey, Jillian Lee

    2005-01-01T23:59:59.000Z

    A novel, three-coordinate gold(I) dimer, Au2(tfepm)3Cl2 (la, lb), was synthesized and structurally characterized. Four gold(I)-rhodium(I) heterobimetallic complexes, AuIRh'(tBuNC)2(-dppm)2C12 (2), Au'Rh'(tBuNC)2(u-dmpm)2Cl2 ...

  7. HYDROGENATION OF CO AND CO ON CLEAN RHODIUM AND IRON FOILS. CORRELATIONS OF REACTIVITIES AND SURFACE COMPOSITIONS

    E-Print Network [OSTI]

    Dwyer, D.

    2011-01-01T23:59:59.000Z

    8)"1, .i\\RY ,c\\ND DOC:UlvlENTS SECTION HYDROGENATION OF CO,AND CO ON CLEAN' RHODIUM AND iRONFOILS. CO~LA.TroNS OF REACTIVITIES AND smu:ACECCM'OSITrONS,

  8. Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

    SciTech Connect (OSTI)

    Sobolevskiy, Anatoly (Orlando, FL); Rossin, Joseph A. (Columbus, OH); Knapke, Michael J. (Columbus, OH)

    2011-07-12T23:59:59.000Z

    A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

  9. Phase Transition of Trapped Nuclear Exciton of Long-lived Rhodium Mossbauer States

    E-Print Network [OSTI]

    Xia, Bing

    2007-01-01T23:59:59.000Z

    We report two experimental observations from the long-lived rhodium Mossbauer emissions by means of the time- and energy-resolved spectroscopy. Firstly, phase transitions in time evolution indicated by characteristic spectral profiles reveal the aggregate exciton orderings of inverted nuclei at room temperature. Depending on the exciton density in polycrystal, six different phases featured by multiple ionizations are identified. Secondly, broad-band background emissions are discovered and are believed to be ascribed to branching channels of gamma radiation. More than half gamma radiation goes to these anisotropic channels. Cascade scheme to catalyze the E3 multipolar nuclear transition is thus suggested.

  10. Long-Term Testing of Rhodium-Based Catalysts for Mixed Alcohol Synthesis 2013 Progress Report

    SciTech Connect (OSTI)

    Gerber, Mark A.; Gray, Michel J.; Thompson, Becky L.

    2013-09-23T23:59:59.000Z

    The U.S. Department of Energys Pacific Northwest National Laboratory has been conducting research since 2005 to develop a catalyst for the conversion of synthesis gas (carbon monoxide and hydrogen) into mixed alcohols for use in liquid transportation fuels. Initially, research involved screening possible catalysts based on a review of the literature, because at that time, there were no commercial catalysts available. The screening effort resulted in a decision to focus on catalysts containing rhodium and manganese. Subsequent research identified iridium as a key promoter for this catalyst system. Since then, research has continued to improve rhodium/manganese/iridium-based catalysts, optimizing the relative and total concentrations of the three metals, examining baseline catalysts on alternative supports, and examining effects of additional promoters. Testing was continued in FY 2013 to evaluate the performance and long-term stability of the best catalysts tested to date. Three tests were conducted. A long-term test of over 2300 hr duration at a single set of operating conditions was conducted with the best carbon-supported catalyst. A second test of about 650 hr duration at a single set of operating conditions was performed for comparison using the same catalyst formulation on an alternative carbon support. A third test of about 680 hr duration at a single set of operating conditions was performed using the best silica-supported catalyst tested to date.

  11. Towards a Benign and Viable Rhodium Catalyzed Hydroformylation of Higher Olefins: Economic and Environmental Impact Analyses, Solvent Effects and Membrane-based Catalyst Separation

    E-Print Network [OSTI]

    Fang, Jing

    2009-04-28T23:59:59.000Z

    rhodium catalyst based on economic and environmental assessments. The specific objectives of the current work are therefore to: 8 Exploit CO 2 -expanded liquids as environmentally green solvents for hydroformylation of higher olefins and benchmark...

  12. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis 2012 Progress Report

    SciTech Connect (OSTI)

    Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O.; Thompson, Becky L.

    2012-11-01T23:59:59.000Z

    Pacific Northwest National Laboratory has been conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). In recent years, this research has primarily involved the further development of catalysts containing rhodium and manganese based on the results of earlier catalyst screening tests. Testing continued in FY 2012 to further improve the Ir-promoted RhMn catalysts on both silica and carbon supports for producing mixed oxygenates from synthesis gas. This testing re-examined selected alternative silica and carbon supports to follow up on some uncertainties in the results with previous test results. Additional tests were conducted to further optimize the total and relative concentrations of Rh, Mn, and Ir, and to examine selected promoters and promoter combinations based on earlier results. To establish optimum operating conditions, the effects of the process pressure and the feed gas composition also were evaluated.

  13. Phase Transition of Trapped Nuclear Exciton of Long-lived Rhodium Mossbauer States

    E-Print Network [OSTI]

    Yao Cheng; Bing Xia

    2007-07-11T23:59:59.000Z

    We report experimental observations of the long-lived rhodium Mossbauer emissions by the time- and energy-resolved spectroscopy. The extraordinary observations manifest the open-up of photonic band gap in analogy to the superconducting gap of remarkable symmetry breakings at transition point. These observations are of potential importance for detecting gravitational waves and development of the two-photon gamma laser. Firstly, phase transitions shown by spectral evolution of characteristic emissions reveal the different aggregate exciton orderings at room temperature. Six different phases are identified by spectra profiles emitted from the color centers. Secondly, the cascade branching of the multipolar nuclear transition is discovered being the spontaneous cascade down-conversion to generate entangled gammas. The macroscopic angular distribution of entangled gammas from the polycrystalline sample manifests a global photon-nucleus-photon bound state across the grain boundaries. Thirdly, the gamma-energy distributions depending on exciton phases reveal the photonic band gap typically on the order of several hundred eV.

  14. Shrinking Trees Trevor Hastie

    E-Print Network [OSTI]

    Hastie, Trevor

    of an automobile, weight, length, and engine size (displace), affect its gasoline consumption (mpg). The tree, called the root, to a terminal node, called a leaf, according to the rules, called splits

  15. JOURNAL DE PHYSIQUE Colloque C I , supplkment au no 2-3, Tome 32, Fkvrier-Mars 1971,page C 1 -863 MOSSBAUER EFFECT IN RHODIUM IRON ALLOYS

    E-Print Network [OSTI]

    Boyer, Edmond

    MOSSBAUER EFFECT IN RHODIUM IRON ALLOYS B. WINDOW, G. LONGWORTH and C. E. JOHNSON Materials Physics Division, A. E. R. E., Harwell, Berks., UK Rbsumb. - On a mesurk les spectres Mossbauer du 5 7Fe dans des attribuer a la compensation Kondo. Abstract. - Mossbauer spectra of 57Fe in RhFe alloys containing up to 25

  16. Mixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions

    SciTech Connect (OSTI)

    Xu, Songchen [Ames Laboratory; Manna, Kuntal [Ames Laboratory; Ellern, Arkady [Ames Laboratory; Sadow, Aaron D [Ames Laboratory

    2014-12-08T23:59:59.000Z

    In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbenebis(oxazolinyl)phenylborate proligands have been synthesized and reacted with organometallic precursors. Two proligands, PhB(OxMe2)2(ImtBuH) (H[1]; OxMe2 = 4,4-dimethyl-2-oxazoline; ImtBuH = 1-tert-butylimidazole) and PhB(OxMe2)2(ImMesH) (H[2]; ImMesH = 1-mesitylimidazole), are deprotonated with potassium benzyl to generate K[1] and K[2], and these potassium compounds serve as reagents for the synthesis of a series of rhodium and iridium complexes. Cyclooctadiene and dicarbonyl compounds {PhB(OxMe2)2ImtBu}Rh(?4-C8H12) (3), {PhB(OxMe2)2ImMes}Rh(?4-C8H12) (4), {PhB(OxMe2)2ImMes}Rh(CO)2 (5), {PhB(OxMe2)2ImMes}Ir(?4-C8H12) (6), and {PhB(OxMe2)2ImMes}Ir(CO)2 (7) are synthesized along with ToMM(?4-C8H12) (M = Rh (8); M = Ir (9); ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The spectroscopic and structural properties and reactivity of this series of compounds show electronic and steric effects of substituents on the imidazole (tert-butyl vs mesityl), effects of replacing an oxazoline in ToM with a carbene donor, and the influence of the donor ligand (CO vs C8H12). The reactions of K[2] and [M(?-Cl)(?2-C8H14)2]2 (M = Rh, Ir) provide {?4-PhB(OxMe2)2ImMes?CH2}Rh(?-H)(?-Cl)Rh(?2-C8H14)2 (10) and {PhB(OxMe2)2ImMes}IrH(?3-C8H13) (11). In the former compound, a spontaneous oxidative addition of a mesityl ortho-methyl to give a mixed-valent dirhodium species is observed, while the iridium compound forms a monometallic allyl hydride. Photochemical reactions of dicarbonyl compounds 5 and 7 result in CH bond oxidative addition providing the compounds {?4-PhB(OxMe2)2ImMes?CH2}RhH(CO) (12) and {PhB(OxMe2)2ImMes}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis-[Ir](H)(Ph) complex. Alternatively, the rhodium carbonyl 5 or iridium isocyanide {PhB(OxMe2)2ImMes}Ir(CO)CNtBu (15) reacts with PhSiH3 in the dark to form the silyl compound {PhB(OxMe2)2ImMes}RhH(SiH2Ph)CO (14) or {PhB(OxMe2)2ImMes}IrH(SiH2Ph)CNtBu (17). These examples demonstrate the enhanced thermal reactivity of {PhB(OxMe2)2ImMes}-supported iridium and rhodium carbonyl compounds in comparison to tris(oxazolinyl)borate, tris(pyrazolyl)borate, and cyclopentadienyl-supported compounds.

  17. Adsorption of Ruthenium, Rhodium and Palladium from Simulated High-Level Liquid Waste by Highly Functional Xerogel - 13286

    SciTech Connect (OSTI)

    Onishi, Takashi [Fukushima Fuels and Materials Department O-arai Research and Development Center Japan Atomic Energy Agency, Narita-cho 4002, O-arai-machi, Ibaraki, 311-1393 (Japan)] [Fukushima Fuels and Materials Department O-arai Research and Development Center Japan Atomic Energy Agency, Narita-cho 4002, O-arai-machi, Ibaraki, 311-1393 (Japan); Koyama, Shin-ichi [Fukushima Fuels and Materials Department O-arai Research and Development Center Japan Atomic Energy Agency, Narita-cho 4002, O-arai-machi, Ibaraki, 311-1393 (Japan)] [Fukushima Fuels and Materials Department O-arai Research and Development Center Japan Atomic Energy Agency, Narita-cho 4002, O-arai-machi, Ibaraki, 311-1393 (Japan); Mimura, Hitoshi [Dept. of Quantum Science and Energy Engineering, Graduate School of Engineering, Tohoku University Aramaki-Aza-Aoba 6-6-01-2,Aoba-ku, Sendai-shi, Miyagi-ken, 980-8579 (Japan)] [Dept. of Quantum Science and Energy Engineering, Graduate School of Engineering, Tohoku University Aramaki-Aza-Aoba 6-6-01-2,Aoba-ku, Sendai-shi, Miyagi-ken, 980-8579 (Japan)

    2013-07-01T23:59:59.000Z

    Fission products are generated by fission reactions in nuclear fuel. Platinum group (Pt-G) elements, such as palladium (Pd), rhodium (Rh) and ruthenium (Ru), are also produced. Generally, Pt-G elements play important roles in chemical and electrical industries. Highly functional xerogels have been developed for recovery of these useful Pt-G elements from high - level radioactive liquid waste (HLLW). An adsorption experiment from simulated HLLW was done by the column method to study the selective adsorption of Pt-G elements, and it was found that not only Pd, Rh and Ru, but also nickel, zirconium and tellurium were adsorbed. All other elements were not adsorbed. Adsorbed Pd was recovered by washing the xerogel-packed column with thiourea solution and thiourea - nitric acid mixed solution in an elution experiment. Thiourea can be a poison for automotive exhaust emission system catalysts, so it is necessary to consider its removal. Thermal decomposition and an acid digestion treatment were conducted to remove sulfur in the recovered Pd fraction. The relative content of sulfur to Pd was decreased from 858 to 0.02 after the treatment. These results will contribute to design of the Pt-G element separation system. (authors)

  18. Poly(pyridine)ruthenium(II)-photoinduced redox reactions of bipyridinium cations, poly(pyridine)rhodium complexes, and osmium ammines

    SciTech Connect (OSTI)

    Creutz, C.; Keller, A.D.; Sutin, N.; Zipp, A.P.

    1982-06-30T23:59:59.000Z

    The quenching of *RuL/sub 3//sup 2 +/ (L is a 2,2'-bipyridine or 1,10-phenanthroline derivative) emissions by three classes of oxidants Q has been examined. The results are discussed in terms of the Marcus electron-transfer model recast in a preequilibrium formalism. Substituted bipyridinium cations (methyl viologen and related compounds) undergo thermodynamically favorable reduction with a driving force ranging from 0.1 to 0.7 eV and rate constants in the range (0.4-2.0) x 10/sup 9/ M/sup -1/s/sup -1/, consistent with a diffusion rate constant of 2.0 x 10/sup 9/ M/sup -1/s/sup -1/ and an exchange rate constant of approx.10/sup 6/ M/sup -1/s/sup -1/ for the Q-Q couples. The yields of the separated redox products RuL/sub 3//sup 3 +/ and Q/sup -/ (typically 0.1 mol einstein/sup -1/ per quenching act) require K/sub 30/, the ''intramolecular'' back-reaction rate constant (to re-form ground-state RuL/sub 3//sup 2 +/ and Q), to be (2-4) x 10/sup 10/ s/sup -1/. Since K/sub 30/ increases weakly with driving force in this series, there is no evidence for inverted behavior despite the fact the ..delta..G/sup 0//sub 30/ is approx.-2 eV. With Q = Rh(4,4'-(CH/sub 3/)/sub 2/bpy)/sub 3//sup 3 +/, the quenching rate constants, k/sub q/ = (0.001-1.0) x 10/sup 9/ M/sup -1/s/sup -1/, exhibit a great sensitivity to the reducing power of *RuL/sub 3//sup 2 +/ and have been fitted to k/sub 11/ approx. = 2 x 10/sup 9/ M/sup -1/s/sup -1/ and E/sup 0//sub Q,Q/sup -// = -0.97 V for the RhL/sub 3//sup 3 +/-RhL/sub 3//sup 2 +/ couple. This E/sup 0/ value is strikingly similar to that (-0.9 V vs. aqueous SCE) obtained via cyclic voltammetry in acetonitrile. The cyclic voltammetry of the RhL/sub 3//sup 3 +/ complexes in water has been reexamined, and it is concluded that the irreversibility observed is due to ligand loss from rhodium(I).

  19. Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

    SciTech Connect (OSTI)

    Colby, Denise; Bergman, Robert; Ellman, Jonathan

    2010-05-13T23:59:59.000Z

    Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach that has seen widespread success involves the use of a proximal heteroatom that serves as a directing group for the selective functionalization of a specific C-H bond. In a survey of examples of heteroatom-directed Rh catalysis, two mechanistically distinct reaction pathways are revealed. In one case, the heteroatom acts as a chelator to bind the Rh catalyst, facilitating reactivity at a proximal site. In this case, the formation of a five-membered metallacycle provides a favorable driving force in inducing reactivity at the desired location. In the other case, the heteroatom initially coordinates the Rh catalyst and then acts to stabilize the formation of a metal-carbon bond at a proximal site. A true test of the utility of a synthetic method is in its application to the synthesis of natural products or complex molecules. Several groups have demonstrated the applicability of C-H bond functionalization reactions towards complex molecule synthesis. Target-oriented synthesis provides a platform to test the effectiveness of a method in unique chemical and steric environments. In this respect, Rh-catalyzed methods for C-H bond functionalization stand out, with several syntheses being described in the literature that utilize C-H bond functionalization in a key step. These syntheses are highlighted following the discussion of the method they employ.

  20. Journal: Trevor Downey: Ecuador June 27, 2007

    E-Print Network [OSTI]

    Farritor, Shane

    to leave Baos, and those of us trying to enter, through the muddy remains of the pass. River-Rafting Rain atmosphere. Even upon driving into Baos from Quito, around a four- hour bus drive from mountain pass to mountain pass, visitors began to sense its unstable character. My friends and I were not to begin, let

  1. Springer Series in Statistics Trevor Hastie

    E-Print Network [OSTI]

    Tibshirani, Robeert

    of Statistical Learning Data Mining,Inference,and Prediction Second Edition #12;This is page v Printer: Opaque. Additive Models, Trees, and Related Methods 10. Boosting and Additive Trees New example from ecology; some

  2. Claire Trevor School of the Arts Minor Requirements

    E-Print Network [OSTI]

    Rose, Michael R.

    to the Internet Studio Art 100 (when topic is related to digital arts) Studio Art 106: Interactive Digital Media courses: Arts 1A: Arts Core Arts 11: Digital Media: History & Foundations (formerly Arts 1D) Arts 12: Digital Media: Current Directions (formerly Arts 1E)

  3. Claire Trevor School of the Arts Digital Arts Minor Requirements

    E-Print Network [OSTI]

    Rose, Michael R.

    12A (Art, Design and Electronic Culture) _______ Art 12B (Digital Media from Steam to Steampunk) _______ Art 50A (Matter and Media) _______ Art 50B (Interaction and Experience) _______ Art 50C (Digital Media: Interaction Design) _______ II. Elective*: Choose two of the following: _______ _______ Arts 75 (Digital Media

  4. Claire Trevor School of the Arts Digital Arts Minor Requirements

    E-Print Network [OSTI]

    Rose, Michael R.

    A (Arts Core) _______ Arts 11 (Digital Media: History and Foundations) _______ Arts 12 (Digital Media: Current Directions) _______ Arts 50 (Digital Media: Experience and Content) _______ Arts 60 (Digital Media: Video/Audio for the Web) _______ Arts 70 (Digital Media: Interaction Design) _______ Arts

  5. Neutron Deficient Isotopes of Rhodium and Palladium

    E-Print Network [OSTI]

    Perlman, I.

    2010-01-01T23:59:59.000Z

    r' Contract l~o. W-7405-eng-48 To be published as a letterLaboratory Contract No. W-7405-eng-48 NEUTRON DEFICIEI\\lT I

  6. Highly Enantioselective Cycloisomerization of Enynes Catalyzed by Rhodium for the

    E-Print Network [OSTI]

    Zhang, Xumu

    raw materials, intermediates, and active ingredients in pharmaceuticals, agrochemicals, food additives

  7. PLATINUM-GROUP METALS (Platinum, palladium, rhodium, ruthenium, iridium, osmium)

    E-Print Network [OSTI]

    Africa, 59%; United Kingdom,14%; Russia, 9%; Germany, 5%; and other, 13%. Palladium: Russia, 48%; South the ore body, about 18,500 feet from the portal entrance, by the end of 1999. A second TBM also began

  8. PLATINUM-GROUP METALS (Platinum, palladium, rhodium, ruthenium, iridium, osmium)

    E-Print Network [OSTI]

    to convert hydrogen and oxygen to electricity. Palladium will also likely play a role in the fuel cell on gasoline-engine vehicles in favor of palladium. The sales of platinum jewelry are expected to drop

  9. Mechanism of Rhodium-Catalyzed Carbene Formation from Diazo

    E-Print Network [OSTI]

    Wang, Jianbo

    . J. Angew. Chem., Int. Ed. Engl. 1994, 33, 1797-1815. (d) Padwa, A.; Krumpe, K. E. Tetrahedron 1992

  10. Direct Deposition of Trivalent Rhodium Hydroxide Nanoparticles onto a

    E-Print Network [OSTI]

    pho- tocatalyst was prepared by exfoliation and intercalation of proton-exchanged KCa2Nb3O10 (see Supporting Information for details). HCa2Nb3O10 (0.13 g) was exfoliated by shaking in 50 mL of aqueous tetra % loading of Rh, 20 mM aqueous RhCl3 (0.632 mL) was added to 50 mL of the exfoliated TBAOH/Ca2Nb3O10

  11. Material synthesis and hydrogen storage of palladium-rhodium alloy.

    SciTech Connect (OSTI)

    Lavernia, Enrique J. (University of California, Davis); Yang, Nancy Y. C.; Ong, Markus D. (Whithworth University, Spokane, WA)

    2011-08-01T23:59:59.000Z

    Pd and Pd alloys are candidate material systems for Tr or H storage. We have actively engaged in material synthesis and studied the material science of hydrogen storage for Pd-Rh alloys. In collaboration with UC Davis, we successfully developed/optimized a supersonic gas atomization system, including its processing parameters, for Pd-Rh-based alloy powders. This optimized system and processing enable us to produce {le} 50-{mu}m powders with suitable metallurgical properties for H-storage R&D. In addition, we studied hydrogen absorption-desorption pressure-composition-temperature (PCT) behavior using these gas-atomized Pd-Rh alloy powders. The study shows that the pressure-composition-temperature (PCT) behavior of Pd-Rh alloys is strongly influenced by its metallurgy. The plateau pressure, slope, and H/metal capacity are highly dependent on alloy composition and its chemical distribution. For the gas-atomized Pd-10 wt% Rh, the absorption plateau pressure is relatively high and consistent. However, the absorption-desorption PCT exhibits a significant hysteresis loop that is not seen from the 30-nm nanopowders produced by chemical precipitation. In addition, we observed that the presence of hydrogen introduces strong lattice strain, plastic deformation, and dislocation networking that lead to material hardening, lattice distortions, and volume expansion. The above observations suggest that the H-induced dislocation networking is responsible for the hysteresis loop seen in the current atomized Pd-10 wt% Rh powders. This conclusion is consistent with the hypothesis suggested by Flanagan and others (Ref 1) that plastic deformation or dislocations control the hysteresis loop.

  12. Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

    E-Print Network [OSTI]

    Coble, Inger M

    2008-01-01T23:59:59.000Z

    He, H 2 , and O 2 (UHP, Praxair, used as-received) and anAirGas, CP grade), hydrogen (Praxair, UHP, 99.999%)and helium (Praxair, UHP, 99.999%) were used as received.

  13. PLATINUM-GROUP METALS (Platinum, palladium, rhodium, ruthenium, iridium, osmium)

    E-Print Network [OSTI]

    and private effort to develop fuel cell technology. Platinum is the catalyst used in fuel cells to convert for air-pollution abatement in both light- and heavy-duty vehicles. PGMs are also used in the chemical. The desire for an alternative fuel, both for automobiles and to power homes, has led to a large global public

  14. PLATINUM-GROUP METALS (Platinum, palladium, rhodium, ruthenium, iridium, osmium)

    E-Print Network [OSTI]

    public and private effort to develop fuel cell technology. Platinum is the catalyst used by fuel cells Events, Trends, and Issues: The desire for an alternative fuel for automobiles has led to a large global platinum loadings on catalysts, especially in light-duty diesel vehicles, as particulate matter emissions

  15. PLATINUM-GROUP METALS (Platinum, palladium, rhodium, ruthenium, iridium, osmium)

    E-Print Network [OSTI]

    and processors to form the Palladium Council (PdC). PdC is a nonprofit research foundation organized for the purpose of conducting research and promoting the use of palladium. PdC research and development

  16. Location Estimation with a Differential Update Ali Rahimi and Trevor Darrell

    E-Print Network [OSTI]

    Darrell, Trevor

    algorithm by cal- culating globally consistent trajectories of a robot as it navigates along a 2D trajectory. To update a trajectory of length t, the update takes O(t). When all conditional distributions are linear to recover the trajectory of a robot given noisy measurements of its movement between points in its

  17. C280 Computer VisionC280, Computer Vision Prof. Trevor Darrell

    E-Print Network [OSTI]

    Darrell, Trevor

    a house, trees, sky Theoretically I might say there were 327sky. Theoretically I might say there were 327 brightnesses and nuances of colour. Do I have "327"? No. I have sky, house, and trees.No. I have sky, house Images and its Application to Evaluating Segmentation Algorithms and Measuring Ecological Statistics

  18. Flexible Graph Layout for the Web Trevor Hansen, Kim Marriott & Bernd Meyer

    E-Print Network [OSTI]

    Marriott, Kimbal

    and is manifest in almost all web standards from the HTML/CSS [1] combination to XML/XSL [6, 23]. Recent graphics bandwidth has meant that graphics has become increasingly important on the web. Graph-based dia- grams are one of the most important types of structured graphical information. Here we demonstrate how XML can

  19. JIMAR ANNUAL REPORT FOR FY 2011 P.I. NAME: Kevin Weng, Trevor A. Branch

    E-Print Network [OSTI]

    Hawai'i at Manoa, University of

    the primary technical contact): PIFSC NOAA SPONSOR NAME: Sam Pooley PROJECT PROPOSAL TITLE: Biological IMAGES AND CAPTIONS: We will also be includ

  20. Trevor J McDougall Royal Society of Tasmania, 4th November 2014

    E-Print Network [OSTI]

    Blennerhassett, Peter

    ). Share of energy from renewable sources in 2012 (%) #12;Back to the Ocean #12;Energy content changes;#12;The vertical ocean circulation #12;The layered nature of the ocean #12;Vertical mixing by internal by internal wave breaking (the Standard Model) #12;Cabbeling and Thermobaricity This is a "parcel view

  1. Dear Friends and Patrons, Welcome to the 20112012 season of UC Irvine's Claire Trevor School

    E-Print Network [OSTI]

    Barrett, Jeffrey A.

    of new initiatives focused on sharing the excellence of our students, faculty and facilities with our and witty ensembles, Gian- Car

  2. Parallel and Scalable Architectures for Video Encoding

    E-Print Network [OSTI]

    Zhao, Zhuo

    2010-01-01T23:59:59.000Z

    vs QP . . . . . . . . . . . . . Luminance PSNR curve for Foreman . . . . . . . . . . . . . . .Luminance PSNR curveTrevor . . . . . . . . . . . . . Luminance PSNR curve for

  3. Green University Planning Committee Page 1/2 Agenda May 20, 2011

    E-Print Network [OSTI]

    Owens, Philip

    , Director, Facilities Management Trevor Fuson, CUPE Regrets: Doug Carter, Capital Projects Manager Gail

  4. UCI Names Claire Trevor Professors in Drama and Dance "These two highly regarded artists and professors add

    E-Print Network [OSTI]

    Loudon, Catherine

    , page 2) Nov. 15-16, 8pm Nov. 17, 2pm & 8pm NEW SLATE Exciting new works choreographed by UCI graduate. 15 New Slate and join us for Gallery Night before or after the performance. A RTSWEEK 2001, UCI, New Slate dance concert will offer exciting new works by UCI graduate choreographers. Robert Cohen

  5. Claire Trevor School of the Arts MAB 200 Office of the Dean Irvine, CA 92697-2775

    E-Print Network [OSTI]

    Barrett, Jeffrey A.

    faculty members this year: Diane Diefenderfer (Dance ­ Ballet/Pilates), Joel Veenstra (Drama ­ Theatre

  6. Atmospheric Boundary Layer Research Rocket Ulises Espinoza, Braeden Moore, Scott Schoen, Trevor Seguin, Jordan Van Dyke, Greg Woolston

    E-Print Network [OSTI]

    Provancher, William

    micro SD card for analysis. - Compact chassis designed to increases overall rocket stability. Flight launch. Project Description Develop an efficient, cost effective alternative to gathering data of low to validate FEA material model. Testing Wind Tunnel - 1:6 scale rocket tested in wind tunnel to determine

  7. Inversion of multi-channel data with rotated kernels M. Andy Kass, Trevor Irons, and Yaoguo Li

    E-Print Network [OSTI]

    content into numerical interpretation, so must statistically rotated data include the rotation operator), seismic de-noising (Jackson et al., 1991; Jones and Levy, 1987), blind source separation for transient content, amplitude, etc.). If interpretation is to include numerical inversion, these effects must

  8. Rhodium-Catalyzed Activation and Functionalization of the C-C Bond of Biphenylene

    E-Print Network [OSTI]

    Jones, William D.

    temperature, displacing the chelating phosphine. A new five-coordinate complex, (PPh3)2Rh(2,2-biphenyl)Cl (3 that block double-bond migration yield the cleanest product ratios. Introduction The activation of C-C bonds of these projects is to understand factors that govern this transformation and use this knowledge to selectively

  9. Rhodium Catalyzed C-H Bond Functionalization: Development of Methods and Applications in Organic Synthesis

    E-Print Network [OSTI]

    Tsai, Andy Siu-Chun

    2011-01-01T23:59:59.000Z

    Interestingly, use of allyl acetate as the coupling partnermg, 0.25 mmol, 1 equiv), allyl acetate (75 mg, 0.75 mmol, 3

  10. Ab initio simulation of the two-dimensional vibrational spectrum of dicarbonylacetylacetonato rhodium,,I...

    E-Print Network [OSTI]

    Mukamel, Shaul

    to several model systems such as small peptides, acetone, and acetonitrile.4,5 As in NMR, the power. DOI: 10.1063/1.1528605 I. INTRODUCTION The structure of molecules is the primary basis for un of multipulse nuclear magnetic resonance NMR techniques have been estab- lished and used for structure

  11. Characterization and Reaction Studies of Silica Supported Platinum and Rhodium Model Catalysts

    E-Print Network [OSTI]

    Lundwall, Matthew James

    2012-02-14T23:59:59.000Z

    onto a SiO2/Mo(112) surface and characterized using various surface analytical methods. CO chemisorption is utilized as a surface probe to estimate the concentration of various sites on the nanoparticles through thermal desorption spectroscopy (TDS...

  12. Evaluation of Polymer-Supported Rhodium Catalysts in 1-Octene Hydroformylation in Supercritical Carbon Dioxide

    E-Print Network [OSTI]

    Abdou, Hanan E.

    Carbon Dioxide Zulema K. Lopez-Castillo, Roberto Flores, Ibrahim Kani,, John P. Fackler Jr., and Aydin employed in homogeneous cataly- sis. The most common benign solvent is supercritical carbon dioxide (scCO2). It is nonflammable, inert, and inexpensive, is readily available at high purity, and has low critical properties

  13. Acetic Acid from the Carbonylation of Chloride Methane Over Rhodium Based Catalysts

    E-Print Network [OSTI]

    Bao, Xinhe

    on an indirect route via synthesis gas (syngas), i.e., methane is first con- verted to syngas before it is further transformed into other useful products [6]. However, the production of syngas from methane) 130:286290 DOI 10.1007/s10562-009-0017-9 #12;[12], which is produced from syngas feedstock with Cu

  14. Greener Hydroformylation with Nanofilterable Rhodium Catalysts in A Stirred Membrane Reactor

    E-Print Network [OSTI]

    Xie, Zhuanzhuan

    2013-05-31T23:59:59.000Z

    show that CXLs provide a way of increasing (i.e., tuning) H2/CO ratio in the liquid phase at fixed syngas feed composition, low syngas partial pressures (i.e. avoiding syngas inhibition) and mild conditions (40-60 C, tens of bars). A novel process...

  15. Thermodynamic Studies and Hydride Transfer Reactions from a Rhodium Complex to BX3 Compounds

    SciTech Connect (OSTI)

    Mock, Michael T.; Potter, Robert G.; Camaioni, Donald M.; Li, Jun; Dougherty, William G.; Kassel, W. S.; Twamley, Brendan; DuBois, Daniel L.

    2009-10-14T23:59:59.000Z

    This study examines the use of transition-metal hydride complexes that can be generated by the heterolytic cleavage of H2 gas to form BH bonds. Specifically, these studies are focused on providing a reliable and quantitative method for determining when hydride transfer from transition-metal hydrides to three-coordinate BX3 compounds will be favorable. This involves both experimental and theoretical determinations of hydride transfer abilities. Thermodynamic hydride donor abilities (?GH-) were determined for HRh(dmpe)2 and HRh(depe)2, where dmpe = 1,2-bis(dimethylphosphinoethane) and depe = 1,2-bis(diethylphosphinoethane), on a previously established scale in acetonitrile. This hydride donor ability was used to determine the hydride donor ability of [HBEt3]? on this scale. Isodesmic reactions between [HBEt3]? and various BX3 complexes to form BEt3 and [HBX3]? were examined computationally to determine the relative hydride affinities of various BX3 compounds. The use of these scales of hydride donor abilities and hydride affinities for transition-metal hydrides and BX3 compounds is illustrated with a few selected reactions relevant to the regeneration of ammonia borane. Our findings indicate that it is possible to form B?H bonds from B?X bonds, and the extent to which BX3 compounds are reduced by transition-metal hydride complexes forming species containing multiple B?H bonds depends on the heterolytic B?X bond energy. An example is the reduction of B(SPh)3 using HRh(dmpe)2 in the presence of triethylamine to form Et3N-BH3 in high yields. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  16. New Tandem Catalytic Cycles take to the Rhod(ium) | The Ames Laboratory

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative1 First Use of Energy for All Purposes (Fuel and Nonfuel), 2002; Level:Energy: Grid Integration Redefining What's Possible for Renewable Energy:Nanowire Solar541,9337, 2011R -Electrodes NewStaff

  17. Rational Design of Rhodium Complexes Featuring κ4-N,N,N,N- and

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative1 First Use of Energy for All Purposes (Fuel and Nonfuel), 2002; Level: National5Sales for4,645U.S. DOE Office of Science (SC)IntegratedSpeedingTechnicalPurchase, Delivery,AssistanceRare

  18. Making Art, Creating Infrastructure: deviantART and the Production of the Web

    E-Print Network [OSTI]

    Perkel, Daniel

    2011-01-01T23:59:59.000Z

    new Oudshoorn and Pinch argue, Users and technology are tooUsers and Technology, ed. Nelly Oudshoorn and Trevor Pinch,Users and Technology, ed. Nelly Oudshoorn and Trevor Pinch.

  19. The Ghost of the Bomb : the Bravo Medical Program, scientific uncertainty, and the legacy of U.S. Cold War science, 1954-2005

    E-Print Network [OSTI]

    Harkewicz, Laura J.

    2010-01-01T23:59:59.000Z

    and Pinch, Handbook of Science and Technology Studies, 393 and Trevor Pinch, eds. Handbook of Science and Technology

  20. E-Print Network 3.0 - ap site incision Sample Search Results

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    at Urbana-Champaign Collection: Engineering 72 Assessing the Hydroecological Effects of Stream Restoration CHRISTOPHER TREVOR HAMMERSMARK Summary: ......

  1. E-Print Network 3.0 - arvensis bromus japonicus Sample Search...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Environmental Sciences and Ecology 40 Assessing the Hydroecological Effects of Stream Restoration CHRISTOPHER TREVOR HAMMERSMARK Summary: brevissimus, Carex nebrascensis...

  2. Foundations and Trends R Information Retrieval

    E-Print Network [OSTI]

    Juola, Patrick

    such as Hugh Trevor-Roper, the author of the 1983 Hitler Diaries was Hitler himself, despite the later

  3. REAL-TIME BUILDING ENERGY SIMULATION USING ENERGYPLUS AND THE BUILDING CONTROLS VIRTUAL TEST BED

    E-Print Network [OSTI]

    Xiufeng Pang1 , Prajesh Bhattacharya1 , Zheng O'Neill2 , Philip Haves1 , Michael Wetter1 , and Trevor

  4. NUTRIA MANAGEMENT IN THE PACIFIC NORTHWEST MEETING: PRESENTATION SUMMARIES

    E-Print Network [OSTI]

    habitats Trevor Sheffels, Mark Sytsma, Jacoby Carter, and Jimmy Taylor Trevor Sheffels, PhD Jimmy Taylor Research Center Contact info already provided 541-737-1353 jimmy.d.taylor@aphis.usda.gov We deployed radio damage prevention methods for urban areas Trevor Sheffels, Mark Sytsma, Jacoby Carter, and Jimmy Taylor

  5. Insertion of SO2 into the Metal-Carbon Bonds of Rhodium and Iridium Compounds, and Reactivity of the

    E-Print Network [OSTI]

    Jones, William D.

    diverse coordination properties and its role in acid rain production. In this paper, we present two new. The sulfinate ligand can be removed with a strong acid such as HCl, generating free sulfinic acid. Acids with weakly coordinating anions protonate the sulfinate oxygen, but the sulfinic acid remains bound

  6. Publications by number 1. Synthesis of rhodium (II) pyrazolate complexes. Crystal structure of tetra--3,5-

    E-Print Network [OSTI]

    Alvarez, Pedro J.

    (dimethylphosphino)ethane. X- ray crystal structure of trans-[CrIVCl(NEt)(dmpe)2]CF3SO3, trans- [CrIV(N=CHMe)2(dimpe)2](BPh4

  7. Carboxylato compounds of chromium, copper, rhodium and molybdenum and new advances in the chemistry of V2(NXN)4

    E-Print Network [OSTI]

    Hillard, Elizabeth Anne

    2004-09-30T23:59:59.000Z

    This dissertation comprises the investigation of two subjects in the field of dimetal paddlewheel-type compounds containing metal-metal bonds: unsolvated transition metal carboxylates and triply bonded divanadium compounds. ...

  8. Rhodium Catalysts in the Oxidation of CO by O2 and NO: Shape, Composition, and Hot Electron Generation

    E-Print Network [OSTI]

    Renzas, James Russell

    2010-01-01T23:59:59.000Z

    N2O decomposition. Applied Catalysis B-Environmental Zhang,silica catalysts. Applied Catalysis A: General 1992, 92 (1),Pd/[alpha]-Al2O3. Applied Catalysis B: Environmental 1999,

  9. Rhodium Catalysts in the Oxidation of CO by O2 and NO: Shape, Composition, and Hot Electron Generation

    SciTech Connect (OSTI)

    Renzas, James R.

    2010-03-08T23:59:59.000Z

    It is well known that the activity, selectivity, and deactivation behavior of heterogeneous catalysts are strongly affected by a wide variety of parameters, including but not limited to nanoparticle size, shape, composition, support, pretreatment conditions, oxidation state, and electronic state. Enormous effort has been expended in an attempt to understand the role of these factors on catalytic behavior, but much still remains to be discovered. In this work, we have focused on deepening the present understanding of the role of nanoparticle shape, nanoparticle composition, and hot electrons on heterogeneous catalysis in the oxidation of carbon monoxide by molecular oxygen and nitric oxide. These reactions were chosen because they are important for environmental applications, such as in the catalytic converter, and because there is a wide range of experimental and theoretical insight from previous single crystal work as well as experimental data on nanoparticles obtained using new state-of-the-art techniques that aid greatly in the interpretation of results on complex nanoparticle systems. In particular, the studies presented in this work involve three types of samples: {approx} 6.5 nm Rh nanoparticles of different shapes, {approx} 15 nm Rh1-xPdx core-shell bimetallic polyhedra nanoparticles, and Rh ultra-thin film ({approx} 5 nm) catalytic nanodiodes. The colloidal nanoparticle samples were synthesized using a co-reduction of metal salts in alcohol and supported on silicon wafers using the Langmuir-Blodgett technique. This synthetic strategy enables tremendous control of nanoparticle size, shape, and composition. Nanoparticle shape was controlled through the use of different organic polymer capping layers. Bimetallic core-shell nanoparticles were synthesized by careful choice of metal salt precursors. Rh/TiO{sub x} and Rh/GaN catalytic nanodiodes were fabricated using a variety of thin film device fabrication techniques, including reactive DC magnetron sputtering, electron beam evaporation, and rapid thermal annealing. The combination of these techniques enabled control of catalytic nanodiode morphology, geometry, and electrical properties.

  10. Faraday Discuss. Chem. SOC.,1989, 87, 337-344 Butane Hydrogenolysis over Single-crystal Rhodium Catalysts

    E-Print Network [OSTI]

    Goodman, Wayne

    >propane. The hydrogenolysis reaction exhibits a good fit to Arrhenius behaviour for reaction temperatures surface coverage of hydrogen. The `roll over' affects product distribution, yielding more complete

  11. Seedless Polyol Synthesis and CO Oxidation Activity of Monodisperse (111) and (100)-Oriented Rhodium Nanocrystals in Sub-10 nm Sizes

    E-Print Network [OSTI]

    Zhang, Yawen

    2011-01-01T23:59:59.000Z

    the manifold was filled with 40 Torr CO (Praxair, UHP), 100Torr O 2 (Praxair, UHP), and abalance of He (Praxair, UHP) initially at atmospheric

  12. Rhodium Catalysts in the Oxidation of CO by O2 and NO: Shape, Composition, and Hot Electron Generation

    E-Print Network [OSTI]

    Renzas, James R.

    2010-01-01T23:59:59.000Z

    the manifold was filled with 40 Torr CO (Praxair, UHP), 100Torr O 2 (Praxair, UHP), and abalance of He (Praxair, UHP) initially at atmospheric

  13. Seedless Polyol Synthesis and CO Oxidation Activity of Monodisperse (111) and (100)-Oriented Rhodium Nanocrystals in Sub-10 nm Sizes

    SciTech Connect (OSTI)

    Zhang, Yawen; Grass, Michael E.; Huang, Wenyu; Somorjai, Gabor A.

    2010-03-15T23:59:59.000Z

    Monodisperse sub-10 nm (6.5 nm) sized Rh nanocrystals with (111) and (100) surface structures were synthesized by a seedless polyol reduction in ethylene glycol, with poly(vinylpyrrolidone) as a capping ligand. When using [Rh(Ac){sub 2}]{sub 2} as the metal precursor, (111)-oriented Rh nanopolyhedra containing 76% (111)-twined hexagons (in 2D projection) were obtained; whereas, when employing RhCl{sub 3} as the metal precursor in the presence of alkylammonium bromide, such as tetramethylammonium bromide and trimethyl(tetradecyl)ammonium bromide, (100)-oriented Rh nanocubes were obtained with 85% selectivity. The {l_brace}100{r_brace} faces of the Rh nanocrystals are stabilized by chemically adsorbed Br{sup -} ions from alkylammonium bromides, which led to (100)-oriented nanocubes. Monolayer films of the (111)-oriented Rh nanopolyhedra and (100)-oriented Rh nanocubes were deposited on silicon wafers in a Langmuir-Blodgett trough to make model 2D nanoarray catalysts. These nanocatalysts were active for CO oxidation by O{sub 2}, and the turnover frequency was independent of nanoparticle shape, consistent with that previously observed for Rh(111) and Rh(100) single crystals.

  14. HYDROGENATION OF CO AND CO ON CLEAN RHODIUM AND IRON FOILS. CORRELATIONS OF REACTIVITIES AND SURFACE COMPOSITIONS

    E-Print Network [OSTI]

    Dwyer, D.

    2011-01-01T23:59:59.000Z

    R. B. Anderson, The Fischer- Tropsch and Related Syntheses (carbons are called the Fischer-Tropsch reaction named afterwere produced by the Fischer-Tropsch reaction because of the

  15. CO HYDROGENATION OVER CLEAN AND OXIDIZED RHODIUM FOIL AND SINGLE CRYSTAL CATALYSTS. CORRELATIONS OF CATALYST ACTIVITY, SELECTIVITY AND SURFACE COMPOSITION

    E-Print Network [OSTI]

    Castner, D.G.

    2012-01-01T23:59:59.000Z

    Angeles, Calif. ) Div. Petrol. Chern. Preprints 1, 616 (be published. Calif') Div. Petrol. Chern. Preprints 1,521 (

  16. HYDROGENATION OF CO AND CO ON CLEAN RHODIUM AND IRON FOILS. CORRELATIONS OF REACTIVITIES AND SURFACE COMPOSITIONS

    E-Print Network [OSTI]

    Dwyer, D.

    2011-01-01T23:59:59.000Z

    l) As a result of coal gasification (coal + H 0 + CO + H )dynamic data for the coal gasification and water shift

  17. Carboxylato compounds of chromium, copper, rhodium and molybdenum and new advances in the chemistry of V2(NXN)4

    E-Print Network [OSTI]

    Hillard, Elizabeth Anne

    2004-09-30T23:59:59.000Z

    mature; dichromium tetraacetate was first synthesized in 1844, and hundreds of dimetal tetracarboxylates have been structurally characterized to date. A general question concerning the complexes of the type M2L4-Xn (where n = 0 to 2) is the extent...

  18. Trends in On-Road Vehicle Emissions of Ammonia , D. Littlejohn2

    E-Print Network [OSTI]

    energy of certain heterogeneous reactions on rare earth metals (e.g., palladium, platinum, and rhodium

  19. On the last mile : the effects of telecommunications regulation and deregulation in the rural western United States and Canada

    E-Print Network [OSTI]

    Kozak, Nadine Irne

    2010-01-01T23:59:59.000Z

    Sociologists of technology Trevor Pinch and Wiebe E. Bijkerand technology studies approch views technological systems as both culturally constructed and interpreted. In their research, Pinch and

  20. SmartGardenWatering: Experiences of using a garden

    E-Print Network [OSTI]

    Pearce, Jon

    discussion What are we doing now? Overview 2 2 #12;The `what': to save water in Melbourne domestic gardens want to be water efficient,Trevor? Garden Gurus, Episode 7,Autumn 2009 4 4 #12;"You've got,Trevor? 17 #12;Creating an online community: save, load & share garden models search for others Instilling

  1. *Staff Member Last Update: 9/17/13 Art Education, Studio Foundations AEF

    E-Print Network [OSTI]

    Arnold, Jonathan

    *Staff Member Last Update: 9/17/13 KEY: Art Education, Studio Foundations AEF Art History AH;Last Updated 9/17/13 COMPUTER COMMITTEE/ VISUAL RESOURCE CTR Committee Elects Chair Thom Houser, Chair Geha Nell Andrew Alex Murawski #12;Last Updated 9/17/13 PORTFOLIO REVIEW Appointed by Area Chairs Asen

  2. Sarah D. Brooks Assistant Professor Tel: (979) 845-5522

    E-Print Network [OSTI]

    and physical processes. Warm cloud and ice cloud nucleation. Urban and rural air quality. Air-sea interactions: "Hydrologic and Biogeochemical Fluxes in a Tropical Montane Cloud Forest" (PI Chris Houser, funded 2010 Career Award in Science and Engineering (awarded by the White House, nominated through USDA) National

  3. Faculty Senate Meeting January 28, 2010

    E-Print Network [OSTI]

    Gering, Jon C.

    Johnson, Stephen Hadwiger, David Gillette, Scott Olsen, Chet Breed, Jeremy Houser, Tom Zoumaras, AmandaFaculty Senate Meeting January 28, 2010 approved 2/25/10 SUB 3200 Activities Room Present: Tom TWO VOTES Carrying two votes: Stephen Hadwiger and Ray Barrow Alternates: 2 Votes at the table: 22

  4. CRN Course Title Days Time Location Instructor Core/Elective Undergraduate Courses

    E-Print Network [OSTI]

    Staff EB Core W = Wednesday 80233 305A FINANCIAL ACCOUNTING MWF 12:00-12:50 BE 243 Dozoretz EB Elective R = Thursday 82810 310 ENVIRONMENTAL ECONOMICS MW 6:00 - 7:15 GC 265 Worley EB Elective F = Friday 82811 320 ECONOMICS AND TECHNOLOGY TR 12:30 - 1:45 GC 265 Houser 80238 325 OPERATIONS RESEARCH TR 9

  5. New Directions for Cancer Drug Research of Ruthenium and Rhodium Compounds: Investigation of Cytotoxicities, Mechanisms of Cancer Cell Death, and Cellular Targets

    E-Print Network [OSTI]

    Pena Maceda, Bruno

    2014-07-02T23:59:59.000Z

    compounds were synthesized and fully characterized. The first class of complexes is based on Ru(II) coordination compounds of general formula [Ru(N^N)_(2)(N^O^())][PF_(6)], where N^N is a bidentate polypyridyl ligand (bpy = 2,2-bipyridine; phen = 1,10...

  6. Photoelectron spectra and molecular orbital calculations of dicarbonyl- and dinitrosyl-bridged cobalt, rhodium and iridium cyclopentadienyl dimers and of disulfido- and diselenido-nonacarbonyltriosmium

    E-Print Network [OSTI]

    Griewe, Greg Lewis

    1987-01-01T23:59:59.000Z

    ). The spectra are similar to that reported for Fe3(CO)9(s3-S)2, but with increased band definition. The HOMO, a 3c-2e (Os-Os-Os) bond, is dominated by the e -like orbitals of the Os(CO)3 fragment and contains most of the net metal-metal overlap population.... Ionization from this orbital occurs at lower energy than the remaining ionizations. The t2 -like orbitals on the Os(CO)3 fragments make little or no net contribution to Os-X or to Os-Os bonding. The e -like and g to a lesser extent the a -like orbitals...

  7. C-H vs C-C Bond Activation of Acetonitrile and Benzonitrile via Oxidative Addition: Rhodium vs Nickel and Cp* vs Tp

    E-Print Network [OSTI]

    Jones, William D.

    Nickel and Cp* vs Tp (Tp ) Hydrotris(3,5-dimethylpyrazol-1-yl)borate, Cp* ) 5 of acetonitrile on nickel(II) using potassium tert- butoxide.6 In contrast, the fragment [Tp

  8. One-pot synthesis of alcohols from olefins catalyzed by rhodium and ruthenium Joseph Zakzeski, Hae Ryun Lee, Yi Ling Leung, Alexis T. Bell *

    E-Print Network [OSTI]

    Bell, Alexis

    of alkenes obtained as products of FischerTropsch synthesis. Since the hydroformylation of propene to n

  9. Tridentate Phosphine Linkers for Immobilized Catalysts: Development and Characterization of Immobilized Rhodium Complexes and Solid-State NMR Studies of Polymers

    E-Print Network [OSTI]

    Guenther, Johannes 1983-

    2012-08-16T23:59:59.000Z

    decay (NMR), flame ionization detector FRPSG fluorous reversed phase silica gel xxiv GC gas chromatography h hour HRMAS high-resolution magic angle spinning HR-MS high-resolution mass spectrometry Hz Hertz i iso J scalar coupling...

  10. Universal informatics : building cyberinfrastructure, interoperating the geosciences

    E-Print Network [OSTI]

    Ribes, David

    2006-01-01T23:59:59.000Z

    users and technologies, Nelly Oudshoorn and Trevor Pinch (Pinch and Bijker emphasize the interpretive flexibility of a technologyPinch (2003). How Users Matter: The Co-Construction of Users and Technology.

  11. Drawing the straight line : social movements and hierarchies of evidence in sexual reorientation therapy debates

    E-Print Network [OSTI]

    Waidzunas, Thomas John

    2010-01-01T23:59:59.000Z

    Pinch and Bijkers SCOT (social construction of technology)Pinch 2003) of numerous understandings of sexual subjectivity along with technologiesand technologies. Ed. by Nelly Oudshoorn and Trevor Pinch.

  12. Fulfilling the promise of the personal computer : the development of accessible computer technologies, 1970-1998

    E-Print Network [OSTI]

    Petrick, Elizabeth

    2012-01-01T23:59:59.000Z

    Pinch's edited volume, How Users Matter: The Co-construction of Users and Technology.Pinch, eds. How Users Matter: The Co-Construction of Users and Technology.and Technology, eds. Nelly Oudshoorn and Trevor Pinch (

  13. Jailal Nicholas G Ablack Yohannes Abreham Mebrahtu

    E-Print Network [OSTI]

    Sinnamon, Gordon J.

    Broomfield Katrina Lin Brown Melissa Suzanne Brown Stephanie Anne Brown Trevor Cormac Vincent Bruen Luanne Donald Cameron Mark Wickus Camp Dawn Doreen Campbell Kathryn Campbell Maureen Margaret Carey Nikola

  14. Portsmouth/Paducah Project Office

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    , 2012 Robert.Smith@lex.doe.gov Eco Fair Blends Fun and Facts for Paducah Area Middle Schoolers PADUCAH, KY - Lone Oak Middle School student Trevor Tilley was impressed with a 3 rd...

  15. Electrifying the BC Vehicle Fleet Opportunities and Challenges for

    E-Print Network [OSTI]

    Pedersen, Tom

    Electrifying the BC Vehicle Fleet Opportunities and Challenges for Plug-in Hybrid, Extended Range & Pure Electric Vehicles Liam Kelly, Trevor Williams, Brett Kerrigan and Curran Crawford Institute ................................................................................. 13 3.1 BC Hydro and Vehicle

  16. The Materials Preparation Center - Making Rare Earth Metals - Part 3

    ScienceCinema (OSTI)

    Riedemann, Trevor

    2013-03-01T23:59:59.000Z

    Trevor Riedeman, manager of the MPC Rare Earth Materials Section, gives a presentation on the importance of rare earth metals and how they are made at Ames Laboratory. Part 3 of 4.

  17. The Materials Preparation Center - Making Rare Earth Metals - Part 1

    ScienceCinema (OSTI)

    Riedemann, Trevor

    2013-03-01T23:59:59.000Z

    Trevor Riedeman, manager of the MPC Rare Earth Materials Section, gives a presentation on the importance of rare earth metals and how they are made at Ames Laboratory. Part 1 of 4.

  18. BIOINFORMATICS Vol. 17 no. 6 2001

    E-Print Network [OSTI]

    Botstein, David

    microarrays Olga Troyanskaya1, Michael Cantor1, Gavin Sherlock2, Pat Brown3, Trevor Hastie4, Robert Tibshirani: The software is available at http://smi-web. stanford.edu/projects/helix/pubs/impute/ Contact: russ

  19. Probability Theory: The Logic of Science by E.T. Jaynes

    E-Print Network [OSTI]

    Franklin, James

    : Data Mining, Inference and Prediction by Trevor Hastie, Robert Tibshirani and Jerome Friedman NEW YORK, the combinatorics of dice and coins are recommended; the energetic youth who invest heavily in the calculation

  20. Use of Optical Mapping to Aid in Assembly and Finishing of Human Microbiome Genome Projects

    SciTech Connect (OSTI)

    Wagner, Trevor [OpGen, Inc

    2010-06-03T23:59:59.000Z

    Trevor Wagner of OpGen, Inc. discusses the use of optical mapping to validate the assembly of HMP genomes on June 3, 2010 at the "Sequencing, Finishing, Analysis in the Future" meeting in Santa Fe, NM

  1. A Dash of Salt

    E-Print Network [OSTI]

    Supercinski, Danielle

    2006-01-01T23:59:59.000Z

    and Agricultural Engineering; Vanessa Kelly, Jeremy Rice, Nick Russo III and Kati Stoddard, Water Management and Hydrologic Sciences; Trevor Knight, Department of Wildlife and Fisheries Sciences; Meredith Langille, Oke Nwaneshiudu and Sucheta Parkhi...

  2. The Materials Preparation Center - Making Rare Earth Metals - Part 4

    ScienceCinema (OSTI)

    Riedemann, Trevor

    2013-03-01T23:59:59.000Z

    Trevor Riedeman, manager of the MPC Rare Earth Materials Section, gives a presentation on the importance of rare earth metals and how they are made at Ames Laboratory. Part 4 of 4.

  3. Name Department Abarca, Gary Anthropology [?] abarcag@uci.edu

    E-Print Network [OSTI]

    Barrett, Jeffrey A.

    Name Department Phone Room Email Abarca, Gary Anthropology [?] abarcag@uci.edu Adams, Britni Leia Economics [?] daljutai@uci.edu Allen, Trevor J Political Science [?] trevorja@uci.edu Allison, Blake

  4. The Legacy of Oil Spills

    E-Print Network [OSTI]

    Trevors, J. T.; Saier, M. H.

    2010-01-01T23:59:59.000Z

    010-0527-5 The Legacy of Oil Spills J. T. Trevors & M. H.workers were killed, and oil has been gushing out everday. It is now June, and oil continues to spew forth into

  5. The Materials Preparation Center - Making Rare Earth Metals - Part 3

    SciTech Connect (OSTI)

    Riedemann, Trevor

    2011-01-01T23:59:59.000Z

    Trevor Riedeman, manager of the MPC Rare Earth Materials Section, gives a presentation on the importance of rare earth metals and how they are made at Ames Laboratory. Part 3 of 4.

  6. The Materials Preparation Center - Making Rare Earth Metals - Part 1

    SciTech Connect (OSTI)

    Riedemann, Trevor

    2011-01-01T23:59:59.000Z

    Trevor Riedeman, manager of the MPC Rare Earth Materials Section, gives a presentation on the importance of rare earth metals and how they are made at Ames Laboratory. Part 1 of 4.

  7. The Materials Preparation Center - Making Rare Earth Metals - Part 4

    SciTech Connect (OSTI)

    Riedemann, Trevor

    2011-01-01T23:59:59.000Z

    Trevor Riedeman, manager of the MPC Rare Earth Materials Section, gives a presentation on the importance of rare earth metals and how they are made at Ames Laboratory. Part 4 of 4.

  8. The Materials Preparation Center - Making Rare Earth Metals - Part 2

    SciTech Connect (OSTI)

    Riedemann, Trevor

    2011-01-01T23:59:59.000Z

    Trevor Riedeman, manager of the MPC Rare Earth Materials Section, gives a presentation on the importance of rare earth metals and how they are made at Ames Laboratory. Part 2 of 4.

  9. Nov. 22, 2008 n Saturday, Nov. 22, 2008,

    E-Print Network [OSTI]

    Dyer, Bill

    and constructing a bacteriophage. Fu- ture MSU Science Saturdays will cover magnetism, energy and other topics Trevor Douglas gets down and dirty with a virus cage model; C. Chemistry students wow'ed the crowd

  10. The Materials Preparation Center - Making Rare Earth Metals - Part 2

    ScienceCinema (OSTI)

    Riedemann, Trevor

    2013-03-01T23:59:59.000Z

    Trevor Riedeman, manager of the MPC Rare Earth Materials Section, gives a presentation on the importance of rare earth metals and how they are made at Ames Laboratory. Part 2 of 4.

  11. Updated as of October 16, 2011 Asterisked speakers are invited but not yet confirmed

    E-Print Network [OSTI]

    Barthelat, Francois

    Engineering) (Athens) #12;Paul Mifsud Aviation Consultant; former Vice President, government and legalGill University (Montreal) Trevor Soames - Shearman & Sterling (Brussels) 12:30 13:30 LUNCH 13:30 15

  12. Mapping your data: Integrating data into a GIS

    E-Print Network [OSTI]

    Houser, Rhonda

    2006-12-12T23:59:59.000Z

    handouts to be copied: o GIS Investigation sheet (p. 7 ? 17); note see answers p. 6 o Definitions (p. 18) o Appendix A: TIGER 2000 CFCC Codes (p. 19 ? 20) o Student Answer sheet (p. 21) Standards & Objectives National Geography Standards (Adapted from... Values? ? Change the ?Value Field? to ?CFCC? ? Click the ?Add All Values? button ArcLessons Template, Copyright ? 2005 ESRI. All rights reserved. Mapping Your Data, Copyright ? 2006 Rhonda Houser. 10 Mapping Your Data ? Read the descriptions...

  13. KU Libraries Digital Data Services Strategy

    E-Print Network [OSTI]

    McEathron, Scott R.

    2013-01-16T23:59:59.000Z

    The University of Kansas KU Libraries Digital Data Services Strategy Scott McEathron Rhonda Houser Geoffrey Husic Michele Lubbers Julie Petr Jennifer Roach Mickey Waxman Xanthippe Wedel 1/8/2013 KU Libraries Digital Data... ............................................................................................................... 8 KU Libraries Digital Data Services Strategy January 8, 2013 2 Introduction As part of the University of Kansas (KU) Libraries strategic planning process, two teams have been tasked to implement actions supporting the strategy...

  14. Search for: All records | DOE PAGES

    Office of Scientific and Technical Information (OSTI)

    ngstrom imaging of reversible and irreversible conformations in rhodium catalysts and graphene Kisielowski, Christian ; Wang, Lin-Wang ; Specht, Petra ; Calderon, Hector A. ;...

  15. Real-time sub- ngstrom imaging of reversible and irreversible...

    Office of Scientific and Technical Information (OSTI)

    ngstrom imaging of reversible and irreversible conformations in rhodium catalysts and graphene Citation Details Title: Real-time sub- ngstrom imaging of reversible and...

  16. azomethine ylide cycloaddition: Topics by E-print Network

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    environmental and reactivity qualities of organocatalysts are contributing to (more) Biggs, Robyn A. 2014-01-01 35 The enantioseletive rhodium catalyzed 2+2+2 cycloaddition of...

  17. Electronic structures of transition metal to hydrogen bonds: oxidative addition of dihydrogen to a square planar rhodium complex and quantum mechanical prediction of the geometry of a metal hydride

    E-Print Network [OSTI]

    Halpin, Carolyn F.

    1986-01-01T23:59:59.000Z

    and applications is dihydrogen or molecular hydrogen. Both the Heber process, in which nitrogen is converted to ammonia on an iron catalyst, and the Fischer-Tropsch synthesis, in which carbon monoxide is converted to hydrocarbons over iron and cobalt catalysts... systems containing hydride ligands. This work presents a computational method for examining the energetics and structures of two systems. The reaction RhC1(CO)(PHs)z + Hz ~ (H)zRhC1(CO)(PHs)z was examined to a~plain why the oxidation of RhCI(CO...

  18. This article appeared in a journal published by Elsevier. The attached copy is furnished to the author for internal non-commercial research

    E-Print Network [OSTI]

    Goodman, Wayne

    journal homepage: www.elsevier.com/locate/cattod Silica-supported rhodium-cobalt catalysts for FischerTropsch: Cobalt catalyst Bimetallic catalyst Gold Rhodium Silver Silica FischerTropsch Temperature catalyst on the FischerTropsch (FT) syn- thesis were studied. Both Au and Rh showed a promoting effect

  19. Post-Industrial Engineering: Computer Science and the Organization of White-Collar Work, 1945-1975

    E-Print Network [OSTI]

    Mamo, Andrew Benedict

    2011-01-01T23:59:59.000Z

    technologies added a new dimension to this venerable tradition. For example, see Trevor Pinch andPinch, eds. The Social Construction of Technological Systems: New Directions in the Sociology and History of Technology.Pinch, eds. , The Social Construction of Technological Systems: New Directions in the Sociology and History of Technology (

  20. Formal Type Soundness for Cyclone's Region System Dan Grossman

    E-Print Network [OSTI]

    Hicks, Michael

    collector. To support separate compilation, Cyclone requires programmers to write some explicit regionFormal Type Soundness for Cyclone's Region System Dan Grossman Greg Morrisett Trevor Jim Mike Hicks Yanling Wang James Cheney November 2001 Abstract Cyclone is a polymorphic, type-safe programming language

  1. Advance Refundings of Municipal Bonds Columbia Business School

    E-Print Network [OSTI]

    Sadeh, Norman M.

    Advance Refundings of Municipal Bonds Andrew Ang Columbia Business School and NBER Richard C. Green of Vineer Bhansali, Trevor Harris, Tal Heppenstall, Andrew Kalotay, Kemp Lewis, Paul Luhmann, Matt of colleagues, especially Jennifer Carpenter, Dan Li, Norman Sch¨urhoff, and Chester Spatt, along with seminar

  2. Ames Lab 101: Lanthanum Decanting

    ScienceCinema (OSTI)

    Riedemann, Trevor

    2012-08-29T23:59:59.000Z

    Ames Laboratory scientist Trevor Riedemann explains the process that allows Ames Laboratory to produce some of the purest lanthanum in the world. This and other high-purity rare-earth elements are used to create alloys used in various research projects and play a crucial role in the Planck satellite mission.

  3. DEAN'S LIST HONORABLE MENTION Fall Semester 2011

    E-Print Network [OSTI]

    Wong, Pak Kin

    , Trevor Ippolito, Vincent James Ireson, Thomas C. Jacob, Gregory Benjamin Jang, Dong Min Johnson, Casey A. Delacruz, Samuel Devine, Nathan D. Ding, Nan Douglas, Amy C. Driscoll, Samuel Robert Duarte Millstone, Daniel Brucker Mukusheva, Aigerim Myers, Thomas Hamilton Nerenberg, Samuel L. Neuenfeldt

  4. Ecological Studies of Wolves on Isle Royale Annual Report 20002001*

    E-Print Network [OSTI]

    ,GregWright,and leaders Justin Gude and Patty Hernandez Team 2 David Marsalis,Ari Perlman,DavidVeinot,and leaders Justin,three wolves in unsuccessful chase of cow-calf pair,Carolyn and Trevor Peterson negotiate a beaver dam crossing ground-based fieldwork, aided by Greg Burkhart, Cynthia D. Carter, Philip DeWitt, Justin Gude, Patty

  5. Molecular Cell, Volume 37 Supplemental Information

    E-Print Network [OSTI]

    Bulyk, Martha L.

    Inputs Luca Giorgetti, Trevor Siggers, Guido Tiana, Greta Caprara, Samuele Notarbartolo, Teresa Corona-kB nuclear concentration. (B) Mean Pol II occupancy on the core promoter as a function of NF-kB nuclear 1, while site 0 represents the core promoter where Pol II exchanges), its occupancy is given by 1

  6. Solar storm Risk to the north American electric grid

    E-Print Network [OSTI]

    Schrijver, Karel

    Solar storm Risk to the north American electric grid #12;Key Contacts Trevor Maynard Exposure reserved #12;Solar storm risk to the north American electric grid 3 Contents 1 EXECUTIVE SUMMARY 4 2 REFERENCES 19 #12;Solar storm risk to the north American electric grid 4 1 Executive Summary A Carrington

  7. BioOne sees sustainable scholarly publishing as an inherently collaborative enterprise connecting authors, nonprofit publishers, academic institutions, research libraries, and research funders in the common goal of maximizing access to

    E-Print Network [OSTI]

    : Winter Distribution and Migration Routes of Breeding Populations Author(s): Cheri Gratto-Trevor, R. I Connectivity of Semipalmated Sandpipers: Winter Distribution and Migration Routes of Breeding Populations CHERI4L 1G6, Canada 6 Suriname Forest Service, P.O. Box 436, Paramaribo, Suriname 7 Current Address

  8. JOURNAL OF INFORMATION SCIENCE AND ENGINEERING 28, 689-704 (2012) The Complexity of GARCH Option Pricing Models

    E-Print Network [OSTI]

    Lyuu, Yuh-Dauh

    2012-01-01T23:59:59.000Z

    JOURNAL OF INFORMATION SCIENCE AND ENGINEERING 28, 689-704 (2012) 689 The Complexity of GARCH computational over- head. In fact, raising n makes the popular Ritchken-Trevor tree under non-linear GARCH that LGARCH, AGARCH, GJR-GARCH, TS-GARCH and TGARCH share the same properties as NGARCH. The theoretical

  9. W. K. Edwards et al.: An Extensible Set-Top Box Platform for Home Media Applications Contributed Paper

    E-Print Network [OSTI]

    Edwards, Keith

    of this platform is that it can dynamically exchange code with other devices on the home network, allowing that allows control over a variety of home devices.1 Index Terms -- set-top box, home network, mobile code@cc.gatech.edu). He was previously at the Palo Alto Research Center (PARC). Mark W. Newman and Trevor Smith

  10. Talk to the Virtual Hands: Self-Animated Avatars Improve Communication in Head-Mounted Display Virtual

    E-Print Network [OSTI]

    Talk to the Virtual Hands: Self-Animated Avatars Improve Communication in Head-Mounted Display Virtual Environments Trevor J. Dodds1 *, Betty J. Mohler1 , Heinrich H. Bu lthoff1,2 1 Human Perceptionlthoff HH (2011) Talk to the Virtual Hands: Self-Animated Avatars Improve Communication in Head

  11. Evidence for periodic, Holocene loess deposition in kettles in a sandy, interlobate landscape, Michigan, USA

    E-Print Network [OSTI]

    Schaetzl, Randall

    , Michigan, USA Trevor Hobbs, Randall J. Schaetzl , Michael D. Luehmann Department of Geography, Michigan-continental North America, but are rare in Michigan, and most loess found in this region is of last-glacial age. We kettled, interlobate upland in southern Michigan, which we named the Evart Upland, for its location near

  12. Ann Arbor, Michigan May 29, 2010 Book cover for "Builder's

    E-Print Network [OSTI]

    Hoffman, Andrew J.

    Ann Arbor, Michigan May 29, 2010 Book cover for "Builder's Apprentice," published by Huron River and author of "Builders Apprentice," confronted that suspicion in the mid-1980s while mulling grad school's Apprentice" Andy Hoffman reflects on crafting a custom-built life By Domenica Trevor May 29, 2010 #12;And

  13. SOME PERSPECTIVES OF SPARSE STATISTICAL MODELING A DISSERTATION

    E-Print Network [OSTI]

    Hastie, Trevor

    SOME PERSPECTIVES OF SPARSE STATISTICAL MODELING A DISSERTATION SUBMITTED TO THE DEPARTMENT Reserved ii #12;I certify that I have read this dissertation and that, in my opinion, it is fully adequate in scope and quality as a dissertation for the degree of Doctor of Philosophy. Trevor Hastie Principal

  14. August 2007 NW Michigan Regional Fruit Grower Newsletter CALENDAR OF EVENTS

    E-Print Network [OSTI]

    /31 Pesticide Container Recycling Ends 9/24 Trevor Nichols Field Day Fennville, MI 9/27 Clean Sweep Collection and the outstanding natural resources we have in northern Michigan led me to pursue a B.S. in Resource Ecology

  15. Annual Report Budget Advisory Committee

    E-Print Network [OSTI]

    Hitchcock, Adam P.

    Annual Report of the Budget Advisory Committee McMaster University Faculty Association June 14, 2010 #12;Budget Advisory Committee, 2009/10 Virginia Aksan (Chair) History Trevor Chamberlain FinanceMaster Pension Plan MUFA Budget Advisory Committee June 14, 2010 Introduction Pensions have been all over

  16. Preparation of high specific activity technetium-96

    DOE Patents [OSTI]

    Mausner, Leonard F. (Stony Brook, NY); Srivastava, Suresh C. (Setauket, NY); Prach, Thomas (Port Jefferson, NY)

    1992-01-01T23:59:59.000Z

    The present invention relates to a method of producing Tc-96 from the proton irradiation of a rhodium target and a technique for isolating under remote hot cell conditions the Tc-96 from the proton irradiated target.

  17. Development of novel metal-catalysed methods for the transformation of Ynamides

    E-Print Network [OSTI]

    Smith, Donna Lee

    2013-11-28T23:59:59.000Z

    I. Rhodium-Catalysed Carbometalation of Ynamides using Organoboron Reagents. As an expansion of existing procedures for the carbometalation of ynamides, it was discovered that [Rh(cod)(MeCN)2]BF4 successfully promotes the ...

  18. Alcohol homologation

    DOE Patents [OSTI]

    Wegman, Richard W. (South Charleston, WV); Moloy, Kenneth G. (Charleston, WV)

    1988-01-01T23:59:59.000Z

    A process for the homologation of an alkanol by reaction with synthesis gas in contact with a system containing rhodium atom, ruthenium atom, iodine atom and a bis(diorganophosphino) alkane to selectivity produce the next higher homologue.

  19. Alcohol homologation

    DOE Patents [OSTI]

    Wegman, R.W.; Moloy, K.G.

    1988-02-23T23:59:59.000Z

    A process is described for the homologation of an alkanol by reaction with synthesis gas in contact with a system containing rhodium atom, ruthenium atom, iodine atom and a bis(diorganophosphino) alkane to selectivity produce the next higher homologue.

  20. Production of hydrogen from alcohols

    DOE Patents [OSTI]

    Deluga, Gregg A. (St. Paul, MN); Schmidt, Lanny D. (Minneapolis, MN)

    2007-08-14T23:59:59.000Z

    A process for producing hydrogen from ethanol or other alcohols. The alcohol, optionally in combination with water, is contacted with a catalyst comprising rhodium. The overall process is preferably carried out under autothermal conditions.

  1. Synthesis of oxygen-containing heterocyclic compounds based on the intramolecular OH insertion and Wolff rearrangement

    E-Print Network [OSTI]

    Wang, Jianbo

    of tetrahydrofuran derivatives.2 Palladium- catalyzed cyclization of allylic 2-alkynoates has been utilized to build of rhodium (II) acetate, with the expectation that Rh(II)-carbene intra- molecular O­H insertion should occur

  2. Journal of Catalysis 225 (2004) 116127 www.elsevier.com/locate/jcat

    E-Print Network [OSTI]

    Iglesia, Enrique

    2004-01-01T23:59:59.000Z

    and reaction pathways in methane activation and chemical conversion catalyzed by rhodium Junmei Wei and Enrique and petrochemicals. Several hundred studies have doc- umented scientific and technological progress over the past few

  3. Bifunctional chelates of RH-105 and AU199 as potential radiotherapeutic agents

    SciTech Connect (OSTI)

    Droege, P.

    1997-03-01T23:59:59.000Z

    Research is presented on new bifunctional chelating ligand systems with stability on the macroscopic and radiochemical levels. The synthesis of the following complexes are described: rhodium 105, palladium 109, and gold 198.

  4. Cyclobutane amino acids and peptidomimetics, parallel catalyst screening for aziridination

    E-Print Network [OSTI]

    Li, Shih-ming

    1996-01-01T23:59:59.000Z

    for syntheses of biologically important compounds, such as amino acids, efforts to discover a catalytic system for aziridination are desirable. Copper and rhodium catalyzed asymmetric aziridination of olefins had previously been reported by others. High yields...

  5. Shuttling P(3) [P subscript 3] from Niobium to Rhodium: The Synthesis and Use of Ph(3)SnP(3)(C(6)H(8)) [Ph subscript 3 Sn P subscript 3 (C subscript 6 H subscript 8)] as a P(3) (-) [P subscript 3 superscript 1-] Synthon

    E-Print Network [OSTI]

    Cossairt, Brandi M.

    Anatomy of a P3? [P subscript 3 superscript -] synthon: The Ph3SnP3(C6H8) [Ph subscript 3 Sn P subscript 3 (C subscript 6 H subscript 8)] molecule (see picture; Sn?red, P?orange) has been synthesized by triphosphorus ...

  6. Friday, May 9th, 2014 11:00--1:00 p.m.

    E-Print Network [OSTI]

    Massachusetts at Amherst, University of

    Olivia Brown Spencer Kuchle Trent Masiki Justin McCarthy Jacinta Saffold For the Ph.D. Donald GeeslingFriday, May 9th, 2014 11:00--1:00 p.m. S h i r l e y G r a h a m D u B o i s R e a d i n g R o o m Nielsen Jacinta Saffold For the Minor Kasi Amaral, Shawn Campbell Trevor Frederick, Carrie Howard

  7. Blurring boundaries: shifting perceptions of femininity in the context of the English Civil War

    E-Print Network [OSTI]

    Scamardo, Tara Marie

    2009-06-02T23:59:59.000Z

    of the 3 monarch and debated the nature of legitimate rule within England. King Charles challenged the members' perceptions of themselves and their roles within the country and forced men to question the very nature of a... fruitless. Diplomatic debates led to the dramatic conclusion of bloodshed and regicide. Many historians have provided analyses of the social issues of the English Civil War. Hugh Trevor-Roper and Anthony Fletcher found the religious environment...

  8. Evidence for SMAD3 as a modifier of breast cancer risk in BRCA2 mutation carriers

    E-Print Network [OSTI]

    Walker, Logan C; Fredericksen, Zachary S; Wang, Xianshu; Tarrell, Robert; Pankratz, Vernon Shane; Lindor, Noralane M; Beesley, Jonathan; Healey, Sue; Chen, Xiaoqing; (kConFab), Kathleen Cuningham Foundation Consortium for Research; Stoppa-Lyonnet, Dominique; Tirapo, Carole; Giraud, Sophie; Mazoyer, Sylvie; Muller, Daniele; Fricker, Jean-Pierre; Delnatte, Capucine; (gemo), Groupe Genetique et Cancer; Schmutzler, Rita K; Wappenschmidt, Barbara; Engel, Christoph; Schonbuchner, Ines; Deissler, Helmut; Meindl, Alfons; Hogervorst, Frans B; Verheus, Martijn; Hooning, Maartje J; van den Ouweland, Ans M W; Nelen, Marcel R; Ausems, Margreet G E M; Aalfs, Cora M; van Asperen, Christi J; Devilee, Peter; Gerrits, Monique M; Waisfisz, Quinten; (hebon), Hereditary Breast and Ovarian Cancer Research Group Netherlands; Szabo, Csilla I; ModSQuaD, The; Easton, Douglas F; Peock, Susan; Cook, Margaret; Oliver, Clare T; Frost, Debra; Harrington, Patricia; Evans, D Gareth; Lalloo, Fiona; Eeles, Rosalind; Izatt, Louise; Chu, Carol; Davidson, Rosemarie; Eccles, Diana; Ong, Kai-Ren; Cook, Jackie; Embrace, The; Rebbeck, Timothy R; Nathanson, Katherine L; Domchek, Susan M; Singer, Christian F; Gschwantler-Kaulich, Daphne; Dressler, Anne-Catharina; Pfeiler, Georg; Godwin, Andrew K; Heikkinen, Tuomas; Nevanlinna, Heli; Agnarsson, Bjarni A; Caligo, Maria Adelaide; Olsson, Hakan; Kristoffersson, Ulf; Liljegren, Annelie; Arver, Brita; Karlsson, Per; Melin, Beatrice; (swe-brca), Swedish Breast Cancer Study; Sinilnikova, Olga M; McGuffog, Lesley; Antoniou, Antonis C; Chenevix-Trench, Georgia; Spurdle, Amanda B; Couch, Fergus J

    2010-11-29T23:59:59.000Z

    RESEARCH ARTICLE Open Access Evidence for SMAD3 as a modifier of breast cancer risk in BRCA2 mutation carriers Logan C Walker1, Zachary S Fredericksen2, Xianshu Wang2, Robert Tarrell2, Vernon S Pankratz2, Noralane M Lindor2, Jonathan Beesley1, Sue... Service, Birmingham (Trevor Cole, Carole McKeown, Kai-Ren Ong, Laura Boyes); South West Regional Genetics Service, Bristol (Alan Donaldson); East Anglian Regional Genetics Service, Cambridge (Joan Paterson); Medical Genetics Services for Wales, Cardiff...

  9. Inelastic Scatterings of Entangled Mossbauer Gammas

    E-Print Network [OSTI]

    Yao Cheng; Zhongming Wang

    2006-10-12T23:59:59.000Z

    We report the observation of the temperature-dependent inelastic scattering of three entangled Mossbauer gammas in the time-resolved Mossbauer spectroscopy. Recently, the long-lived E3 Mossbauer transition of rhodium generated by bremsstrahlung irradiation has been reported. Two kinds of X-rays with the fast decay are attributed to the tri-photon effect. They are tri-photon pile-up of rhodium K X-rays and the high-Z impurity K X-rays. Energy of the particular K emission is higher than the sum energy of two Mossbauer gammas. This letter reports new discoveries by cooling down the sample using liquid nitrogen, namely the collective anomalous emission of entangled Mossbauer gammas. The enhancement of inelastic scatterings at low temperature such as rhodium K satellites is attributed to this entanglement.

  10. Inelastic Scatterings of Entangled Mossbauer Gammas

    E-Print Network [OSTI]

    Cheng, Y; Cheng, Yao; Wang, Zhongming

    2006-01-01T23:59:59.000Z

    We report the observation of the temperature-dependent inelastic scattering of three entangled Mossbauer gammas in the time-resolved Mossbauer spectroscopy. Recently, the long-lived E3 Mossbauer transition of rhodium generated by bremsstrahlung irradiation has been reported. Two kinds of x rays with the fast decay are attributed to the tri-photon effect. They are tri-photon pile-up of rhodium K x rays and the high-Z impurity K x rays. Energy of the particular K emission is greater than the sum energy of two Mossbauer gammas. This letter reports new discoveries by cooling down the sample using liquid nitrogen, namely the collective anomalous emission of entangled Mossbauer gammas. The enhancement of inelastic scatterings at low temperature such as rhodium K satellites is attributed to this entanglement.

  11. Thin film solar energy collector

    DOE Patents [OSTI]

    Aykan, Kamran (Monmouth Beach, NJ); Farrauto, Robert J. (Westfield, NJ); Jefferson, Clinton F. (Millburn, NJ); Lanam, Richard D. (Westfield, NJ)

    1983-11-22T23:59:59.000Z

    A multi-layer solar energy collector of improved stability comprising: (1) a substrate of quartz, silicate glass, stainless steel or aluminum-containing ferritic alloy; (2) a solar absorptive layer comprising silver, copper oxide, rhodium/rhodium oxide and 0-15% by weight of platinum; (3) an interlayer comprising silver or silver/platinum; and (4) an optional external anti-reflective coating, plus a method for preparing a thermally stable multi-layered solar collector, in which the absorptive layer is undercoated with a thin film of silver or silver/platinum to obtain an improved conductor-dielectric tandem.

  12. Vapor deposition of thin films

    DOE Patents [OSTI]

    Smith, David C. (Los Alamos, NM); Pattillo, Stevan G. (Los Alamos, NM); Laia, Jr., Joseph R. (Los Alamos, NM); Sattelberger, Alfred P. (Los Alamos, NM)

    1992-01-01T23:59:59.000Z

    A highly pure thin metal film having a nanocrystalline structure and a process of preparing such highly pure thin metal films of, e.g., rhodium, iridium, molybdenum, tungsten, rhenium, platinum, or palladium by plasma assisted chemical vapor deposition of, e.g., rhodium(allyl).sub.3, iridium(allyl).sub.3, molybdenum(allyl).sub.4, tungsten(allyl).sub.4, rhenium(allyl).sub.4, platinum(allyl).sub.2, or palladium(allyl).sub.2 are disclosed. Additionally, a general process of reducing the carbon content of a metallic film prepared from one or more organometallic precursor compounds by plasma assisted chemical vapor deposition is disclosed.

  13. Analog and digital dynamic compensation techniques for delayed self-powered neutron detectors

    SciTech Connect (OSTI)

    Yusuf, S.O.; Wehe, D.K. (Univ. of Michigan, Dept. of Nuclear Engineering, Ann Arbor, MI (US))

    1990-12-01T23:59:59.000Z

    This paper reports on analog and digital methods developed to compensate for the time delay associated with rhodium self-powered neutron detector signals. This delay is caused by the decay of the neutron-activated rhodium and results in a current signal with unfavorable time response characteristics. The compensating analog method is based on the use of lead-lag networks to eliminate undesirable poles and zeros. The digital method takes digitized signals and numerically solves the inverse kinetics equation that relates reactor flux to the detector current at all earlier times. These methods were tested in a realistic reactor environment, and the results illustrate the accuracy achieved using each method.

  14. Synthesis, chemical bonding and physical properties of RERhB{sub 4} (RE=Y, Dy-Lu)

    SciTech Connect (OSTI)

    Veremchuk, I. [Max-Planck-Institut fuer Chemische Physik fester Stoffe, Noethnitzer Str. 40, 01187 Dresden (Germany); Mori, T. [Max-Planck-Institut fuer Chemische Physik fester Stoffe, Noethnitzer Str. 40, 01187 Dresden (Germany); National Institute for Materials Science, Namiki 1-1, Tsukuba 305-0044 (Japan); Prots, Yu.; Schnelle, W.; Leithe-Jasper, A.; Kohout, M. [Max-Planck-Institut fuer Chemische Physik fester Stoffe, Noethnitzer Str. 40, 01187 Dresden (Germany); Grin, Yu. [Max-Planck-Institut fuer Chemische Physik fester Stoffe, Noethnitzer Str. 40, 01187 Dresden (Germany)], E-mail: grin@cpfs.mpg.de

    2008-08-15T23:59:59.000Z

    The compounds of rare-earth metals with rhodium and boron RERhB{sub 4} (RE=Y, Dy-Lu) crystallize with the orthorhombic structure type YCrB{sub 4} (space group Pbam, Pearson symbol oP24). The crystal structures of the compounds with RE=Y, Er, Tm and Yb were refined by using single-crystal diffraction data. Analysis of chemical bonding for YRhB{sub 4} and YbRhB{sub 4} was performed by electron localizability indicator and by calculation of quantum chemical charges (quantum theory of atoms in molecules). Boron and rhodium form the 3-D polyanion containing planar nets of three-bonded boron atoms interconnected by rhodium along [001]. The interaction of the RE species with the rhodium-boron polyanion is predominantly ionic. Magnetic susceptibility data of TmRhB{sub 4} and YbRhB{sub 4} showed that the RE species are in 4f{sup 12} (Tm) and 4f{sup 13} (Yb) electronic states, respectively. In the low-temperature region, the specific heat revealed a Schottky anomaly for TmRhB{sub 4} while an antiferromagnetic transition is observed at 3.5 K for YbRhB{sub 4}. X-ray absorption measurement at the Yb L{sub III} edge for YbRhB{sub 4} reveals the 4f{sup 13} state of ytterbium. - Graphical abstract: The compounds of rare-earth metals with rhodium and boron RERhB{sub 4} (RE=Y, Dy-Lu) crystallize with the orthorhombic structure type YCrB{sub 4}. Analysis of chemical bonding for YRhB{sub 4} and YbRhB{sub 4} was performed by electron localizability indicator and by calculation of quantum chemical charges (quantum theory of atoms in molecules). Boron and rhodium form the 3-D polyanion containing planar nets of three-bonded boron atoms interconnected by rhodium along [001]. The interaction of the RE species with the rhodium-boron polyanion is predominantly ionic.

  15. Heterodifunctional ligands derived from monooxidized Bis(phosphino)amines. Synthesis and transition metal (Molybdenum(0), Tungsten(0), Rhodium(I), Palladium(II), and Platinum(II)) complexes of (Diphenylphosphino)(diphenylphosphinothioyl)- and (Diphenylphosphino) (diphenylphosphinoselenoyl)phenylamine, Ph[sub 2]PN(Ph)P(E)PH[sub 2] (E = S, Se). Crystal and molecular structure of the Pt(II) Complex [Cl[sub 2]P[ovr tPPh[sub 2]N(Ph)P(S)]Ph[sub 2

    SciTech Connect (OSTI)

    Balakrishna, M.S.; Klein, R.; Uhlenbrock, S.; Pinkerton, A.A.; Cavell, R.G. (Univ. of Toledo, OH (United States))

    1993-12-08T23:59:59.000Z

    Bis(diphenylphosphino)phenylamine can be selectivity oxidized by S or Se in toluene or hexane solvents to the monooxidized thioyl or selenoyl products Ph[sub 2]PN(PH)PPh[sub 2]=E, (E = S, Se). These compounds act as bidentate chelate ligands toward metal complexes forming (CO)[sub 4]M(LL) (M = Mo, W), CO(Cl)Rh(LL), and Cl[sub 2]M(LL), (M = Pt, Pd) where (LL) is the thioyl or selenoyl derivative of the aminobis(phosphine). IR and NMR data are given for all complexes. The carbonyl infrared stretching frequencies show that the chelates form with the phosphine cis to any CO which is present. The [sup 31]P NMR of all complexes of two doublets except for the Rh complexes wherein the Rh spin also couples to phosphorous to produce two doublets of doublets. The [sup 2]J[sub PP] values range from 56 to 112 Hz. [sup 1]J[sub PSe] coupling provide valuable assistance for the assignment of the phosphorus resonances which range widely from 55 to 126 ppm for P[sup III] and from 60 to 80 ppm for the P[sup v] case. Assignment of P[sup III] and P[sup V] signals, which invert relative shift positions on occasion, is aided by the analysis of appropriate spin satellites arising from the substituents. It is concluded that coordination shifts for P[sup III] are always positive, ranging from 22 ppm for Pt[sup II] complexes to 70 ppm for Rh[sup I] complexes. Coordination shifts for P[sup V] centers are much smaller, e.g. 0.12 ppm, and in some cases the coordination shifts for the P[sup V] centers are negative versus the free ligand.

  16. Homologation process making higher alcohols

    DOE Patents [OSTI]

    Leung, Tak W. (Charleston, WV); Dombek, Bernard D. (Charleston, WV)

    1990-01-01T23:59:59.000Z

    A liquid phase process for the manufacture of C.sub.2+ alkanols by the reaction of hydrogen with carbon monoxide in the presence of a catalyst containing ruthenium, cobalt, a halide-containing compound, and an aromatic compound substituted in adjacent ring positions by nitrogen atoms. The process embraces the use of rhodium as an additive to the catalyst system.

  17. PLATINUM-GROUP METALS By Robert G. Reese

    E-Print Network [OSTI]

    petroleum-refining industries. They are also used in the of scrap. Because of their high value, PGM, chemical catalysts, industries. Of the six metals, platinum and palladium are the automobile catalysts1 PLATINUM-GROUP METALS By Robert G. Reese Six metals--platinum, palladium, rhodium, iridium

  18. Overview of ALD Precursors and Reaction Mechanisms Roy G. Gordon

    E-Print Network [OSTI]

    -flammable, non-corrosive, non-toxic, simple and non-hazardous to make and inexpensive. Presenting Author: Roy GXe YttriumY 4 CopperCu DysprosiumDy ErbiumEr LithiumLi LutetiumLu MagnesiumMg RhodiumRh RutheniumRu Sulfur

  19. CO Oxidation on Pt-Group Metals from Ultrahigh Vacuum to Near Atmospheric Pressures. F. Gao, Y. Cai, K. K. Gath, Y. Wang, M. S. Chen, Q. L. Guo, and D. W. Goodman*

    E-Print Network [OSTI]

    Goodman, Wayne

    CO Oxidation on Pt-Group Metals from Ultrahigh Vacuum to Near Atmospheric Pressures. 1. Rhodium FVised Manuscript ReceiVed: NoVember 3, 2008 The CO oxidation reaction on Rh(111) was studied both at low pressures reactor at various gaseous reactant compositions. Surface CO and O coverages were determined using

  20. Chemistry of bimetallic linked cyclopentadienyl complexes: Progress report, 1 December 1986--30 November 1989

    SciTech Connect (OSTI)

    Schrock, R.R.

    1986-12-01T23:59:59.000Z

    Research continued on the chemistry and preparation of bimetallic cyclopentadienyl complexes containing up to two tungsten or one tungsten and a cobalt, rhodium, or ruthenium. The general method for preparation and analysis of polyenes is also discussed. 7 figs., 2 tabs. (CBS)

  1. PLATINUM-GROUP METALS--2000 59.1 PLATINUMGROUP METALS

    E-Print Network [OSTI]

    , on the other hand, continued to grow and has become one of platinum's largest applications. Demand for platinum disks caused demand in electrical-electronics applications to increase substantially. Growth in consumer for platinum and rhodium can be attributed to increased demand, mainly from the automobile sector. Palladium

  2. Vol 440|16 March 2006 Photocatalystreleasinghydrogenfromwater

    E-Print Network [OSTI]

    Cai, Long

    . For now, our results demonstrate the feasibility of using photocatalysts and solar energy to produce micrograph image (for details, see supplementary information). Energy-dispersive X-ray analysis confirmed that these nanoparticles contained both rhodium and chromium. This photocatalyst modification markedly

  3. Tandem Catalysis A Highly Efficient and Rapid Approach to Synthetic Elaboration

    E-Print Network [OSTI]

    Stoltz, Brian M.

    diiodide catalyzed Mukaiyama Michael-aldol reactions C.) Zirconium catalyzed synthesis of !-cyanohydrins D and rhodium catalyzed annulation. B.) Cobalt catalyzed annulation and cycloaddition C.) Rapid synthesis of pyrroles and furans D.) Organocatalytic / Lewis acid tandem catalysis 5.) Conclusions Tandem catalysis

  4. PLATINUM-GROUP METALS--1999 58.1 PLATINUM-GROUP METALS

    E-Print Network [OSTI]

    in the United States was down by more than 8%. The automotive industry continued to be the major consumer of PGM, and rhodium, mainly from the automotive sector, led to deficits in supplies for these metals in 1999. Of the three metals, palladium had the largest deficit owing to increased demand from the automotive sector

  5. Autothermal reforming catalyst and process

    SciTech Connect (OSTI)

    Setzer, H. J.; Karavolis, S.; Lesieur, R. R.; Wnuck, W. G.

    1984-09-25T23:59:59.000Z

    High activity steam reforming catalysts are described particularly adapted for use in autothermal reforming processes. A rhodium catalyst on a calcium oxide impregnated alumina substrate allow the autothermal reforming process to take place with substantially no carbon plugging at oxygen to carbon ratios below what had been considered critical for avoiding carbon plugging of the catalyst in the past.

  6. Strong Bond Activation with Late Transition-Metal Pincer Complexes as a Foundation for Potential Catalysis

    E-Print Network [OSTI]

    Zhu, Yanjun

    2012-07-16T23:59:59.000Z

    introduction for pincer ligands ................................................ 1 1.2 Synthesis of pincer ligated transition metal complexes ........................ 3 1.3 Structural preference for group 9/10 metal complexes (4d and 5d) ...... 9 1... ..................................................................................... 126 V SYNTHESIS, CHARACTERIZATION, AND REACTIVITY OF A RHODIUM DIFLUOROCARBENE COMPLEX SUPPORTED BY PNP PINCER LIGAND ........................................................................................ 144 5.1 Introduction...

  7. Asymmetric hydrogenations of aryl alkenes using imidazol-2-ylidene iridium complexes

    E-Print Network [OSTI]

    Cui, Xiuhua

    2005-08-29T23:59:59.000Z

    Catalysts.......................32 1.4 Lanthanide-based Chiral Catalysts....................................................36 1.5 Rhodium- and Ruthenium-based Systems ........................................38 1.6 Conclusions..........................................................................................43 2.2 Synthesis of Oxazoline Library 60....................................................47 2.3 Synthesis of Imidazole Library 59 ....................................................48 2.4 Synthesis of Ligand Precursors 57...

  8. TheACSJournalof SurfacesandColloids MicrocontactPrintingofPalladium

    E-Print Network [OSTI]

    Prentiss, Mara

    :Micron-ScalePatterningby ElectrolessDepositionofGoppel PirminG.Hidber,WolfgangHelbig,EnochKim,and GeorgeM.Whitesides Departmentof Electrolessdepositionof metalssuchascopper,silver, gold,nickel,rhodium,and cobaltis a processwidely used the surfacefor selectiveelectroless metal deposition. Pailadiumis important asa catalystfor the electroless

  9. Model catalytic studies of single crystal, polycrystalline metal, and supported catalysts

    E-Print Network [OSTI]

    Yan, Zhen

    2009-05-15T23:59:59.000Z

    supported Pd/Al2 O3 catalysts, a Pd(100) single crystal, as well as polycrystalline metals of rhodium, palladium, and platinum. A hyperactive state, corresponding to an oxygen covered surface, was observed at high O 2/CO ratios at elevated pressures...

  10. Syngas Chemistry DOI: 10.1002/anie.201100735

    E-Print Network [OSTI]

    Li, Weixue

    Syngas Chemistry DOI: 10.1002/anie.201100735 Carbon Chain Growth by Formyl Insertion on Rhodium and Cobalt Catalysts in Syngas Conversion** Yong-Hui Zhao, Keju Sun, Xiufang Ma, Jinxun Liu, Dapeng Sun, Hai-Yan Su, and Wei-Xue Li* Syngas (CO/H2) produced from coal, natural gas, or biomass has attracted much

  11. Metal articles having ultrafine particles dispersed therein

    SciTech Connect (OSTI)

    Alexander, G.B.; Nadkarni, R.A.

    1992-07-28T23:59:59.000Z

    This patent describes a metal article of manufacture. It comprises: a metal selected from the group consisting of copper, silver, gold, lead, tin, nickel, zinc, cobalt, antimony, bismuth, iron, cadmium, chromium, germanium, gallium, selenium, tellurium, mercury, tungsten arsenic, manganese, iridium, indium, ruthenium, rhenium, rhodium, molybdenum, palladium, osmium and platinum; and a plurality of ultrafine particles.

  12. Selective Gaseous Extraction: Research, Development and Training for Isotope Production, Final Technical Report

    SciTech Connect (OSTI)

    Bertch, Timothy C, [General Atomics

    2014-03-31T23:59:59.000Z

    General Atomics and the University of Missouri Research Reactor (MURR) completed research and development of selective gaseous extraction of fission products from irradiated fuel, which included training and education of MURR students. The process used porous fuel and after irradiation flowed product gases through the fuel to selectively removed desired fission products with the primary goal of demonstrating the removal of rhodium 105. High removal rates for the ruthenium/rhodium (Ru/Rh), tellurium/iodine (Te/I) and molybdenum/technetium (Mo/Tc) series were demonstrated. The success of this research provides for the reuse of the target for further production, significantly reducing the production of actinide wastes relative to processes that dissolve the target. This effort was conducted under DOE funding (DE-SC0007772). General Atomics objective of the project was to conduct R&D on alternative methods to produce a number of radioactive isotopes currently needed for medical and industry applications to include rhodium-105 and other useful isotopes. Selective gaseous extraction was shown to be effective at removing radioisotopes of the ruthenium/rhodium, tellurium/iodine and molybdenum/technetium decay chains while having trace to no quantities of other fission products or actinides. This adds a new, credible method to the area of certain commercial isotope production beyond current techniques, while providing significant potential reduction of process wastes. Waste reduction, along with reduced processing time/cost provides for superior economic feasibility which may allow domestic production under full cost recovery practices. This provides the potential for improved access to domestically produced isotopes for medical diagnostics and treatment at reduced cost, providing for the public good.

  13. Formation of thin-film resistors on silicon substrates

    DOE Patents [OSTI]

    Schnable, George L. (Montgomery County, PA); Wu, Chung P. (Hamilton Township, Mercer County, NJ)

    1988-11-01T23:59:59.000Z

    The formation of thin-film resistors by the ion implantation of a metallic conductive layer in the surface of a layer of phosphosilicate glass or borophosphosilicate glass which is deposited on a silicon substrate. The metallic conductive layer materials comprise one of the group consisting of tantalum, ruthenium, rhodium, platinum and chromium silicide. The resistor is formed and annealed prior to deposition of metal, e.g. aluminum, on the substrate.

  14. Synthesis of Densely Functionalized Cyclopropanes via Diastereoselective Nucleophilic Additions to in Situ Generated Cyclopropenes

    E-Print Network [OSTI]

    Ryabchuk, Pavel

    2013-12-31T23:59:59.000Z

    .; Babkov, I.; Rubina, M.; Rubin, M. J. Org. Chem., 2013, 78, 7601. 3. Dual Control of the Selectivity in the Formal Nucleophilic Substitution of Bromocyclo- propanes en route to Densely Functionalized, Chirally-Rich Cyclopropyl Derivatives, Ryabchuk, P... Dirhodium tetrakis((R)-(N-dodecylbenzenesulfonyl)prolinate) catalyst Rh2[(R)-DOSP]4 was used by Davies et al.31 to cyclopropanate aromatic nitrogen and oxygen heterocycles. Rhodium catalyst is used to induce the decomposition of aryldiazoacetates...

  15. Steam reforming utilizing high activity catalyst

    SciTech Connect (OSTI)

    Setzer, H. J.

    1985-03-05T23:59:59.000Z

    High activity, sulfur tolerant steam reforming catalysts are described comprising rhodium or nickel supported on lanthanum stabilized alumina or magnesium promoted lanthanum stabilized alumina. The catalysts have improved activity over conventionally used catalysts in the presence of sulfur containing hydrocarbon fuel (such as No. 2 fuel oil) in a steam reforming environment. The material has particular utility in autothermal, tubular, cyclic and adiabatic steam reforming processes.

  16. Studies of Immobilized Homogeneous Metal Catalysts on Silica Supports

    SciTech Connect (OSTI)

    Keith James Stanger

    2003-05-31T23:59:59.000Z

    The tethered, chiral, chelating diphosphine rhodium complex, which catalyzes the enantioselective hydrogenation of methyl-{alpha}-acetamidocinnamate (MAC), has the illustrated structure as established by {sup 31}P NMR and IR studies. Spectral and catalytic investigations also suggest that the mechanism of action of the tethered complex is the same as that of the untethered complex in solution. The rhodium complexes, [Rh(COD)H]{sub 4}, [Rh(COD){sub 2}]{sup +}BF{sub 4}{sup -}, [Rh(COD)Cl]{sub 2}, and RhCl{sub 3} {center_dot} 3H{sub 2}O, adsorbed on SiO{sub 2} are optimally activated for toluene hydrogenation by pretreatment with H{sub 2} at 200 C. The same complexes on Pd-SiO{sub 2} are equally active without pretreatments. The active species in all cases is rhodium metal. The catalysts were characterized by XPS, TEM, DRIFTS, and mercury poisoning experiments. Rhodium on silica catalyzes the hydrogenation of fluorobenzene to produce predominantly fluorocyclohexane in heptane and 1,2-dichloroethane solvents. In heptane/methanol and heptane/water solvents, hydrodefluorination to benzene and subsequent hydrogenation to cyclohexane occurs exclusively. Benzene inhibits the hydrodefluorination of fluorobenzene. In DCE or heptane solvents, fluorocyclohexane reacts with hydrogen fluoride to form cyclohexene. Reaction conditions can be chosen to selectively yield fluorocyclohexane, cyclohexene, benzene, or cyclohexane. The oxorhenium(V) dithiolate catalyst [-S(CH{sub 2}){sub 3}s-]Re(O)(Me)(PPh{sub 3}) was modified by linking it to a tether that could be attached to a silica support. Spectroscopic investigation and catalytic oxidation reactivity showed the heterogenized catalyst's structure and reactivity to be similar to its homogeneous analog. However, the immobilized catalyst offered additional advantages of recyclability, extended stability, and increased resistance to deactivation.

  17. Photochemical reaction dynamics

    SciTech Connect (OSTI)

    Moore, B.C. [Lawrence Berkeley Laboratory, Livermore, CA (United States)

    1993-12-01T23:59:59.000Z

    The purpose of the program is to develop a fundamental understanding of unimolecular and bimolecular reaction dynamics with application in combustion and energy systems. The energy dependence in ketene isomerization, ketene dissociation dynamics, and carbonyl substitution on organometallic rhodium complexes in liquid xenon have been studied. Future studies concerning unimolecular processes in ketene as well as energy transfer and kinetic studies of methylene radicals are discussed.

  18. Bimetallic Ni-Rh catalysts with low amounts of Rh for the steam and autothermal reforming of n-butane for fuel-cell applications.

    SciTech Connect (OSTI)

    Ferrandon, M.; Kropf, A. J.; Krause, T.; Chemical Sciences and Engineering Division

    2010-05-15T23:59:59.000Z

    Mono-metallic nickel and rhodium catalysts and bimetallic Ni-Rh catalysts supported on La-Al{sub 2}O{sub 3}, CeZrO{sub 2} and CeMgOx were prepared and evaluated for catalyzing the steam and autothermal reforming of n-butane. The binary Ni-Rh supported on La-Al{sub 2}O{sub 3} catalysts with low weight loading of rhodium exhibited higher H{sub 2} yields than Ni or Rh alone. The Ni-Rh/CeZrO{sub 2} catalyst exhibited higher performance and no coke formation, compared to the same metals on other supports. A NiAl{sub 2}O{sub 4} spinel phase was obtained on all Ni and Ni-Rh catalysts supported on La-Al{sub 2}O{sub 3}. The presence of rhodium stabilized the spinel phase as well as NiOx species upon reforming while Ni alone was mostly reduced into metallic species. Extended X-ray absorption fine-structure analysis showed evidence of Ni-Rh alloy during preparation and even further after an accelerated aging at 900C in a H{sub 2}/H{sub 2}O atmosphere.

  19. Synthesis, characterization, and catalytic activity of Rh-based lanthanum zirconate pyrochlores for higher alcohol synthesis

    SciTech Connect (OSTI)

    Abdelsayed, Victor; Shekhawat, Dushyant; Poston, James A., Jr.; Spivey, James J.

    2013-05-01T23:59:59.000Z

    Two lanthanum zirconate pyrochlores (La{sub 2}Zr{sub 2}O{sub 7}; LZ) were prepared by Pechini method and tested for higher alcohols selectivity. In one, Rh was substituted into the pyrochlore lattice (LRZ, 1.7 wt%) while for the second, Rh was supported on an unsubstituted La{sub 2}Zr{sub 2}O{sub 7} (R/LZ, 1.8 wt%). X-ray photoelectron spectroscopy (XPS) and temperature programmed reduction (TPR) results show that the surface reducibility depends on whether the Rh is in (or supported on) the LZ pyrochlore. Rhodium in the LRZ is more reducible than rhodium supported on the R/LZ pyrochlore, likely due to the presence of a perovskite phase (LaRhO{sub 3}; identified by XRD), in which rhodium is more reducible. The formation of the perovskite accompanies that of the pyrochlore. CO hydrogenation results show higher ethanol selectivity for R/LZ than LRZ, possibly due to the strong interaction between Rh and LZ on the R/LZ, forming atomically close Rh{sup +}/Rh{sup 0} sites, which have been suggested to favor ethanol production.

  20. Catalytic partial oxidation of hydrocarbons

    DOE Patents [OSTI]

    Schmidt, Lanny D. (Minneapolis, MN); Krummenacher, Jakob J. (Minneapolis, MN); West, Kevin N. (Minneapolis, MN)

    2009-05-19T23:59:59.000Z

    A process for the production of a reaction product including a carbon containing compound. The process includes providing a film of a fuel source including at least one organic compound on a wall of a reactor, contacting the fuel source with a source of oxygen, forming a vaporized mixture of fuel and oxygen, and contacting the vaporized mixture of fuel and oxygen with a catalyst under conditions effective to produce a reaction product including a carbon containing compound. Preferred products include .alpha.-olefins and synthesis gas. A preferred catalyst is a supported metal catalyst, preferably including rhodium, platinum, and mixtures thereof.

  1. Method for forming gold-containing catalyst with porous structure

    DOE Patents [OSTI]

    Biener, Juergen; Hamza, Alex V; Baeumer, Marcus; Schulz, Christian; Jurgens, Birte; Biener, Monika M.

    2014-07-22T23:59:59.000Z

    A method for forming a gold-containing catalyst with porous structure according to one embodiment of the present invention includes producing a starting alloy by melting together of gold and at least one less noble metal that is selected from the group consisting of silver, copper, rhodium, palladium, and platinum; and a dealloying step comprising at least partial removal of the less noble metal by dissolving the at least one less noble metal out of the starting alloy. Additional methods and products thereof are also presented.

  2. Method and system for ethanol production

    DOE Patents [OSTI]

    Feder, Harold M. (Darien, IL); Chen, Michael J. (Darien, IL)

    1983-01-01T23:59:59.000Z

    A transition metal carbonyl and a tertiary amine are employed as a homogeneous catalytic system in methanol or a less volatile solvent to react methanol with carbon monoxide and hydrogen gas producing ethanol and carbon dioxide. The gas contains a high carbon monoxide to hydrogen ratio as is present in a typical gasifier product. The reaction has potential for anhydrous ethanol production as carbon dioxide rather than water is produced. Selected transition metal carbonyls include those of iron, rhodium ruthenium, manganese in combination with iron and possibly osmium. Selected amines include trimethylamine, N-Methylpyrrolidine, 2,4-diazabicyclooctane, dimethylneopentylamine, N-methylpiperidine and derivatives of N-methylpiperidine.

  3. Light induced electron transfer reactions of metal complexes

    SciTech Connect (OSTI)

    Sutin, N.; Creutz, C.

    1980-01-01T23:59:59.000Z

    Properties of the excited states of tris(2,2'-bipyridine) and tris(1,10-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding ground states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine complexes to effect the light decomposition of water into hydrogen and oxygen is reviewed.

  4. Catalytic partial oxidation of hydrocarbons

    DOE Patents [OSTI]

    Schmidt, Lanny D.; Krummenacher, Jakob J.; West, Kevin N.

    2007-08-28T23:59:59.000Z

    A process for the production of a reaction product including a carbon containing compound. The process includes providing a film of a fuel source including at least one organic compound on a wall of a reactor, contacting the fuel source with a source of oxygen, forming a vaporized mixture of fuel and oxygen, and contacting the vaporized mixture of fuel and oxygen with a catalyst under conditions effective to produce a reaction product including a carbon containing compound. Preferred products include .alpha.-olefins and synthesis gas. A preferred catalyst is a supported metal catalyst, preferably including rhodium, platinum, and mixtures thereof.

  5. Solid fuel volatilization to produce synthesis gas

    DOE Patents [OSTI]

    Schmidt, Lanny D.; Dauenhauer, Paul J.; Degenstein, Nick J.; Dreyer, Brandon J.; Colby, Joshua L.

    2014-07-29T23:59:59.000Z

    A method comprising contacting a carbon and hydrogen-containing solid fuel and a metal-based catalyst in the presence of oxygen to produce hydrogen gas and carbon monoxide gas, wherein the contacting occurs at a temperature sufficiently high to prevent char formation in an amount capable of stopping production of the hydrogen gas and the carbon monoxide gas is provided. In one embodiment, the metal-based catalyst comprises a rhodium-cerium catalyst. Embodiments further include a system for producing syngas. The systems and methods described herein provide shorter residence time and high selectivity for hydrogen and carbon monoxide.

  6. Carbon aerogel electrodes for direct energy conversion

    DOE Patents [OSTI]

    Mayer, Steven T. (San Leandro, CA); Kaschmitter, James L. (Pleasanton, CA); Pekala, Richard W. (Pleasant Hill, CA)

    1997-01-01T23:59:59.000Z

    A direct energy conversion device, such as a fuel cell, using carbon aerogel electrodes, wherein the carbon aerogel is loaded with a noble catalyst, such as platinum or rhodium and soaked with phosphoric acid, for example. A separator is located between the electrodes, which are placed in a cylinder having plate current collectors positioned adjacent the electrodes and connected to a power supply, and a pair of gas manifolds, containing hydrogen and oxygen positioned adjacent the current collectors. Due to the high surface area and excellent electrical conductivity of carbon aerogels, the problems relative to high polarization resistance of carbon composite electrodes conventionally used in fuel cells are overcome.

  7. Carbon aerogel electrodes for direct energy conversion

    DOE Patents [OSTI]

    Mayer, S.T.; Kaschmitter, J.L.; Pekala, R.W.

    1997-02-11T23:59:59.000Z

    A direct energy conversion device, such as a fuel cell, using carbon aerogel electrodes is described, wherein the carbon aerogel is loaded with a noble catalyst, such as platinum or rhodium and soaked with phosphoric acid, for example. A separator is located between the electrodes, which are placed in a cylinder having plate current collectors positioned adjacent the electrodes and connected to a power supply, and a pair of gas manifolds, containing hydrogen and oxygen positioned adjacent the current collectors. Due to the high surface area and excellent electrical conductivity of carbon aerogels, the problems relative to high polarization resistance of carbon composite electrodes conventionally used in fuel cells are overcome. 1 fig.

  8. Pollution prevention and waste minimization in metal finishing

    SciTech Connect (OSTI)

    Stimetz, C.J.

    1994-12-01T23:59:59.000Z

    This study was done to identify pollution prevention and waste minimization opportunities in the general plating department and the printed circuit board processing department. Recommendations for certain recycle and recovery technologies were mad in order to reduce usage of acids and the volume of heavy metal sludge that is formed at the industrial Wastewater Pretreatment Facility (IWPF). Some of these technologies discussed were acid purification, electrowinning, and ion exchange. Specific technologies are prescribed for specific processes. Those plating processes where the metals can be recovered are copper, nickel, gold, cadmium, tin, lead, and rhodium.

  9. Ternary lithium stannides Li{sub x}T{sub 3}Sn{sub 7-x} (T=Rh, Ir)

    SciTech Connect (OSTI)

    Sreeraj, Puravankara [Institut fuer Anorganische und Analytische Chemie, NRW Graduate School of Chemistry, and Sonderforschungsbereich 458, Universitaet Muenster, Corrensstrasse 30, 48149 Muenster (Germany); Kurowski, Daniel [Institut fuer Anorganische und Analytische Chemie, NRW Graduate School of Chemistry, and Sonderforschungsbereich 458, Universitaet Muenster, Corrensstrasse 30, 48149 Muenster (Germany); Hoffmann, Rolf-Dieter [Institut fuer Anorganische und Analytische Chemie, NRW Graduate School of Chemistry, and Sonderforschungsbereich 458, Universitaet Muenster, Corrensstrasse 30, 48149 Muenster (Germany); Wu Zhiyun [Institut fuer Anorganische und Analytische Chemie, NRW Graduate School of Chemistry, and Sonderforschungsbereich 458, Universitaet Muenster, Corrensstrasse 30, 48149 Muenster (Germany); Poettgen, Rainer [Institut fuer Anorganische und Analytische Chemie, NRW Graduate School of Chemistry, and Sonderforschungsbereich 458, Universitaet Muenster, Corrensstrasse 30, 48149 Muenster (Germany)]. E-mail: pottgen@uni-muenster.de

    2005-11-15T23:59:59.000Z

    The ternary stannides Li{sub x}Rh{sub 3}Sn{sub 7-x} (x=0.45, 0.64, 0.80) and Li{sub x}Ir{sub 3}Sn{sub 7-x} (x=0.62 and 0.66) were synthesized from the elements in sealed tantalum tubes in a water-cooled sample chamber of an induction furnace. The samples were characterized by X-ray diffraction on powders and single crystals. The stannides adopt the cubic Ir{sub 3}Ge{sub 7}-type structure (space group Im3-bar m, Z=4). In this structure type the tin atoms occupy the Wyckoff positions 12d and 16f and form two interpenetrating frameworks consisting of cubes and square antiprisms. The rhodium and iridium atoms center the square antiprisms and are arranged in pairs. With increasing lithium substitution the lattice parameter of Ir{sub 3}Sn{sub 7} (936.7) decreases via 932.2pm (x=0.62) to 931.2pm (x=0.66), while the Ir-Ir distance remains almost the same (290pm). A similar trend is observed for the rhodium compounds. The lithium atoms substitute Sn on both framework sites. However, the 16f site shows a substantially larger preference for Li occupation. This is in contrast to the isotypic magnesium based compounds.

  10. A RhxSy/C Catalyst for the Hydrogen Oxidation and Hydrogen Evolution Reactions in HBr

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Masud, Jahangir [Univ. of Kansas, Lawrence, KS (United States); Nguyena, Trung V. [Univ. of Kansas, Lawrence, KS (United States); Singh, Nirala [Univ. of California, Santa Barbara, CA (United States); McFarland, Eric [Univ. of California, Santa Barbara, CA (United States); Ikenberry, Myles [Kansas State Univ., Manhattan, KS (United States); Hohn, Keith [Kansas State Univ., Manhattan, KS (United States); Pan, Chun-Jern [National Taiwan University of Science & Technology, Tapei (Taiwan); Hwang, Bing-Joe [National Taiwan University of Science & Technology, Tapei (Taiwan)

    2015-01-01T23:59:59.000Z

    Rhodium sulfide (Rh2S3) on carbon support was synthesized by refluxing rhodium chloride with ammonium thiosulfate. Thermal treatment of Rh2S3 at high temperatures (600C to 850C) in presence of argon resulted in the transformation of Rh2S3 into Rh3S4, Rh17S15 and Rh which were characterized by TGA/DTA, XRD, EDX, and deconvolved XPS analyses. The catalyst particle size distribution ranged from 3 to 12 nm. Cyclic voltammetry and rotating disk electrode measurements were used to evaluate the catalytic activity for hydrogen oxidation and evolution reactions in H2SO4 and HBr solutions. The thermally treated catalysts show high activity for the hydrogen reactions. The exchange current densities (io) of the synthesized RhxSy catalysts in H2-saturated 1M H2SO4 and 1M HBr for HER and HOR were 0.9 mA/cm2 to 1.0 mA/cm2 and 0.8 to 0.9 mA/cm2, respectively. The lower io values obtained in 1M HBr solution compared to in H2SO4 might be due to the adsorption of Br- on the active surface. Stable electrochemical active surface area (ECSA) of RhxSy catalyst was obtained for CV scan limits between 0 V and 0.65 V vs. RHE. Scans with upper voltage limit beyond 0.65 V led to decreased and unreproducible ECSA measurements.

  11. Chemical Hydrogen Storage Using Polyhedral Borane Anions and Aluminum-Ammonia-Borane Complexes

    SciTech Connect (OSTI)

    Hawthorne, M. Frederick; Jalisatgi, Satish S.; Safronov, Alexander V.; Lee, Han Beak; Wu, Jianguo

    2010-10-01T23:59:59.000Z

    Phase 1. Hydrolysis of borohydride compounds offer the potential for significant hydrogen storage capacity, but most work to date has focused on one particular anion, BH4-, which requires high pH for stability. Other borohydride compounds, in particular polyhedral borane anions offer comparable hydrogen storage capacity without requiring high pH media and their long term thermal and hydrolytic stability coupled with non-toxic nature make them a very attractive alternative to NaBH4. The University of Missouri project provided the overall program focal point for the investigation of catalytic hydrolysis of polyhedral borane anions for hydrogen release. Due to their inherent stability, a transition metal catalyst was necessary for the hydrolysis of polyhedral borane anions. Transition metal ions such as cobalt, nickel, palladium and rhodium were investigated for their catalytic activity in the hydrolysis of nido-KB11H14, closo-K2B10H10, and closo-K2B12H12. The rate of hydrolysis follows first-order kinetics with respect to the concentration of the polyhedral borane anion and surface area of the rhodium catalyst. The rate of hydrolysis depends upon a) choice of polyhedral borane anion, c) concentration of polyhedral borane anion, d) surface area of the rhodium catalyst and e) temperature of the reaction. In all cases the yield of hydrogen was 100% which corresponds to ~7 wt% of hydrogen (based on material wt%). Phase 2. The phase 2 of program at the University of Missouri was focused upon developing aluminum ammonia-boranes (Al-AB) as chemical hydrogen storage materials, specifically their synthesis and studies of their dehydrogenation. The ammonia borane molecule (AB) is a demonstrated source of chemically stored hydrogen (19.6 wt%) which meets DOE performance parameters except for its regeneration from spent AB and elemental hydrogen. The presence of an aluminum center bonded to multiple AB residues might combine the efficiency of AB dehydrogenation with an aluminum mediated hydrogenation process leading to reversibility. The Al-AB complexes have comparable hydrogen capacity with other M-AB and have potential to meet DOEs 2010 and 2015 targets for system wt%.

  12. High temperature coatings for gas turbines

    DOE Patents [OSTI]

    Zheng, Xiaoci Maggie

    2003-10-21T23:59:59.000Z

    Coating for high temperature gas turbine components that include a MCrAlX phase, and an aluminum-rich phase, significantly increase oxidation and cracking resistance of the components, thereby increasing their useful life and reducing operating costs. The aluminum-rich phase includes aluminum at a higher concentration than aluminum concentration in the MCrAlX alloy, and an aluminum diffusion-retarding composition, which may include cobalt, nickel, yttrium, zirconium, niobium, molybdenum, rhodium, cadmium, indium, cerium, iron, chromium, tantalum, silicon, boron, carbon, titanium, tungsten, rhenium, platinum, and combinations thereof, and particularly nickel and/or rhenium. The aluminum-rich phase may be derived from a particulate aluminum composite that has a core comprising aluminum and a shell comprising the aluminum diffusion-retarding composition.

  13. Colloid Science of Metal Nanoparticle Catalysts in 2D and 3D Structures. Challenges of Nucleation, Growth, Composition, Particle Shape, Size Control and their Influence on Activity and Selectivity

    SciTech Connect (OSTI)

    Somorjai, Gabor A.; Park, Jeong Y.

    2008-02-13T23:59:59.000Z

    Recent breakthroughs in synthesis in nanosciences have achieved control of size and shapes of nanoparticles that are relevant for catalyst design. In this article, we review the advance of synthesis of nanoparticles, fabrication of two and three dimensional model catalyst system, characterization, and studies of activity and selectivity. The ability to synthesize monodispersed platinum and rhodium nanoparticles in the 1-10 nm range permitted us to study the influence of composition, structure, and dynamic properties of monodispersed metal nanoparticle on chemical reactivity and selectivity. We review the importance of size and shape of nanoparticles to determine the reaction selectivity in multi-path reactions. The influence of metal-support interaction has been studied by probing the hot electron flows through the metal-oxide interface in catalytic nanodiodes. Novel designs of nanoparticle catalytic systems are discussed.

  14. Refractory electrodes for joule heating and methods of using same

    SciTech Connect (OSTI)

    Lamar, David A. (West Richland, WA); Chapman, Chris C. (Richland, WA); Elliott, Michael L. (Kennewick, WA)

    1998-01-01T23:59:59.000Z

    A certain group of electrically conductive refractory materials presently known for use in high temperature applications as throat constructions, melter sidewalls, forehearth, stacks, port sills, hot face lining for slagging coal gasifiers, slag runners, and linings for nuclear waste encapsulation furnaces may be used as electrodes permitting joule heating at temperatures in excess of 1200 C. in excess of about 4400 hours even in the presence of transition group element(s). More specifically, the invention is an electrode for melting earthen materials, wherein the electrode is made from an electrically conductive refractory material, specifically at least one metal oxide wherein the metal is selected from the group consisting of chrome, ruthenium, rhodium, tin and combinations thereof.

  15. Refractory electrodes for joule heating and methods of using same

    DOE Patents [OSTI]

    Lamar, D.A.; Chapman, C.C.; Elliott, M.L.

    1998-05-12T23:59:59.000Z

    A certain group of electrically conductive refractory materials presently known for use in high temperature applications as throat constructions, melter sidewalls, forehearth, stacks, port sills, hot face lining for slagging coal gasifiers, slag runners, and linings for nuclear waste encapsulation furnaces may be used as electrodes permitting joule heating at temperatures in excess of 1,200 C in excess of about 4400 hours even in the presence of transition group element(s). More specifically, the invention is an electrode for melting earthen materials, wherein the electrode is made from an electrically conductive refractory material, specifically at least one metal oxide wherein the metal is selected from the group consisting of chrome, ruthenium, rhodium, tin and combinations thereof. 2 figs.

  16. Baseline milestone HWVP-87-V110202F: Preliminary evaluation of noble metal behavior in the Hanford waste vitrification plant reference glass HW-39

    SciTech Connect (OSTI)

    Geldart, R.W.; Bates, S.O.; Jette, S.J.

    1996-03-01T23:59:59.000Z

    The precipitation and aggregation of ruthenium (Ru), rhodium (RLh) and palladium (Pd) in the Hanford Waste Vitrification Plant (HWVP) low chromium reference glass HLW-39 were investigated to determine if there is a potential for formation of a noble metal sludge in the HWVP ceramic melter. Significant noble metal accumulations on the floor of the melter will result in the electrical shorting of the electrodes and premature failure of the melter. The purpose of this study was to obtain preliminary information on the characteristics of noble metals in a simulated HWVP glass. Following a preliminary literature view to obtain information concerning the noble metals behavior, a number of variability studies were initiated. The effects of glass redox conditions, melt temperature, melting time and noble metal concentration on the phase characteristics of these noble metals were examined.

  17. Engineering and manufacturing of ITER first mirror mock-ups

    SciTech Connect (OSTI)

    Joanny, M.; Travere, J. M.; Salasca, S.; Corre, Y. [CEA, IRFM, F-13108 Saint-Paul-lez-Durance (France); Marot, L. [Department of Physics, University of Basel, Klingelbergstrasse 82, CH-4056 Basel (Switzerland); Thellier, C.; Gallay, G.; Cammarata, C.; Passier, B.; Ferme, J. J. [SESO, 305 Rue Louis Armand CS 30504, 13593 Aix-en-Provence Cedex 3 (France)

    2010-10-15T23:59:59.000Z

    Most of the ITER optical diagnostics aiming at viewing and monitoring plasma facing components will use in-vessel metallic mirrors. These mirrors will be exposed to a severe plasma environment and lead to an important tradeoff on their design and manufacturing. As a consequence, investigations are carried out on diagnostic mirrors toward the development of optimal and reliable solutions. The goals are to assess the manufacturing feasibility of the mirror coatings, evaluate the manufacturing capability and associated performances for the mirrors cooling and polishing, and finally determine the costs and delivery time of the first prototypes with a diameter of 200 and 500 mm. Three kinds of ITER candidate mock-ups are being designed and manufactured: rhodium films on stainless steel substrate, molybdenum on TZM substrate, and silver films on stainless steel substrate. The status of the project is presented in this paper.

  18. Method for the catalytic conversion of organic materials into a product gas

    DOE Patents [OSTI]

    Elliott, Douglas C. (Richland, WA); Sealock, Jr., L. John (Richland, WA); Baker, Eddie G. (Richland, WA)

    1997-01-01T23:59:59.000Z

    A method for converting organic material into a product gas includes: a) providing a liquid reactant mixture containing liquid water and liquid organic material within a pressure reactor; b) providing an effective amount of a reduced metal catalyst selected from the group consisting of ruthenium, rhodium, osmium and iridium or mixtures thereof within the pressure reactor; and c) maintaining the liquid reactant mixture and effective amount of reduced metal catalyst in the pressure reactor at temperature and pressure conditions of from about 300.degree. C. to about 450.degree. C.; and at least 130 atmospheres for a period of time, the temperature and pressure conditions being effective to maintain the reactant mixture substantially as liquid, the effective amount of reduced metal catalyst and the period of time being sufficient to catalyze a reaction of the liquid organic material to produce a product gas composed primarily of methane, carbon dioxide and hydrogen.

  19. Method for fabricating beryllium-based multilayer structures

    DOE Patents [OSTI]

    Skulina, Kenneth M. (Livermore, CA); Bionta, Richard M. (Livermore, CA); Makowiecki, Daniel M. (Livermore, CA); Alford, Craig S. (Tracy, CA)

    2003-02-18T23:59:59.000Z

    Beryllium-based multilayer structures and a process for fabricating beryllium-based multilayer mirrors, useful in the wavelength region greater than the beryllium K-edge (111 .ANG. or 11.1 nm). The process includes alternating sputter deposition of beryllium and a metal, typically from the fifth row of the periodic table, such as niobium (Nb), molybdenum (Mo), ruthenium (Ru), and rhodium (Rh). The process includes not only the method of sputtering the materials, but the industrial hygiene controls for safe handling of beryllium. The mirrors made in accordance with the process may be utilized in soft x-ray and extreme-ultraviolet projection lithography, which requires mirrors of high reflectivity (>60%) for x-rays in the range of 60-140 .ANG. (60-14.0 nm).

  20. Lightweight, durable lead-acid batteries

    SciTech Connect (OSTI)

    Lara-Curzio, Edgar (Lenoir City, TN); An, Ke (Knoxville, TX); Kiggans, Jr., James O. (Oak Ridge, TN); Dudney, Nancy J. (Knoxville, TN); Contescu, Cristian I. (Knoxville, TN); Baker, Frederick S. (Oak Ridge, TN); Armstrong, Beth L. (Clinton, TN)

    2011-09-13T23:59:59.000Z

    A lightweight, durable lead-acid battery is disclosed. Alternative electrode materials and configurations are used to reduce weight, to increase material utilization and to extend service life. The electrode can include a current collector having a buffer layer in contact with the current collector and an electrochemically active material in contact with the buffer layer. In one form, the buffer layer includes a carbide, and the current collector includes carbon fibers having the buffer layer. The buffer layer can include a carbide and/or a noble metal selected from of gold, silver, tantalum, platinum, palladium and rhodium. When the electrode is to be used in a lead-acid battery, the electrochemically active material is selected from metallic lead (for a negative electrode) or lead peroxide (for a positive electrode).

  1. Lightweight, durable lead-acid batteries

    SciTech Connect (OSTI)

    Lara-Curzio, Edgar; An, Ke; Kiggans, Jr., James O; Dudney, Nancy J; Contescu, Cristian I; Baker, Frederick S; Armstrong, Beth L

    2013-05-21T23:59:59.000Z

    A lightweight, durable lead-acid battery is disclosed. Alternative electrode materials and configurations are used to reduce weight, to increase material utilization and to extend service life. The electrode can include a current collector having a buffer layer in contact with the current collector and an electrochemically active material in contact with the buffer layer. In one form, the buffer layer includes a carbide, and the current collector includes carbon fibers having the buffer layer. The buffer layer can include a carbide and/or a noble metal selected from of gold, silver, tantalum, platinum, palladium and rhodium. When the electrode is to be used in a lead-acid battery, the electrochemically active material is selected from metallic lead (for a negative electrode) or lead peroxide (for a positive electrode).

  2. The CAESAR project: Experimental and modeling investigations of methane reforming in a CAtalytically Enhanced Solar Absorption Receiver on a parabolic dish

    SciTech Connect (OSTI)

    Muir, J.F.; Hogan, R.E. Jr.; Skocypec, R.D. [Sandia National Labs., Albuquerque, NM (US); Buck, R. [Deutsche Forschungsanstalt fuer Luft- und Raumfahrt, Stuttgart (DE). Inst. of Technical Thermodynamics

    1993-07-01T23:59:59.000Z

    A joint US/Federal Republic of Germany (FRG) project has successfully tested a unique solar-driven chemical reactor in the CAtalytically Enhanced Solar Absorption Receiver (CAESAR) experiment. The CAESAR test was a {open_quotes}proof-of-concept{close_quotes} demonstration of carbon-dioxide reforming of methane in a commercial-scale, solar, volumetric receiver/reactor on a parabolic dish concentrator. The CAESAR design; test facility and instrumentation; thermal and chemical tests; and analysis of test results are presented in detail. Numerical models for the absorber and the receiver are developed and predicted performance is compared with test data. Post test analyses to assess the structural condition of the absorber and the effectiveness of the rhodium catalyst are presented. Unresolved technical issues are identified and future development efforts are recommended.

  3. X-ray source for mammography

    DOE Patents [OSTI]

    Logan, Clinton M. (Pleasanton, CA)

    1994-01-01T23:59:59.000Z

    An x-ray source utilizing anode material which shifts the output spectrum to higher energy and thereby obtains higher penetrating ability for screening mammography application, than the currently utilized anode material. The currently used anode material (molybdenum) produces an energy x-ray spectrum of 17.5/19.6 keV, which using the anode material of this invention (e.g. silver, rhodium, and tungsten) the x-ray spectrum would be in the 20-35 keV region. Thus, the anode material of this invention provides for imaging of breasts with higher than average x-ray opacity without increase of the radiation dose, and thus reduces the risk of induced breast cancer due to the radiation dose administered for mammograms.

  4. Pico- and nanosecond laser ablation of mixed tungsten / aluminium films

    E-Print Network [OSTI]

    Wisse, M; Steiner, R; Mathys, D; Stumpp, A; Joanny, M; Travere, J M; Meyer, E

    2014-01-01T23:59:59.000Z

    In order to extend the investigation of laser-assisted cleaning of ITER-relevant first mirror materials to the picosecond regime, a commercial laser system delivering 10 picosecond pulses at 355 nm at a frequency of up to 1 MHz has been used to investigate the ablation of mixed aluminium (oxide) / tungsten (oxide) layers deposited on poly- and nanocrystalline molybdenum as well as nanocrystalline rhodium mirrors. Characterization before and after cleaning using scanning electron microscopy (SEM) and spectrophotometry shows heavy dust formation, resulting in a degradation of the reflectivity. Cleaning using a 5 nanosecond pulses at 350 and 532 nm, on the other hand, proved very promising. The structure of the film remnants suggests that in this case buckling was the underlying removal mechanism rather than ablation. Repeated coating and cleaning using nanosecond pulses is demonstrated.

  5. Development of a remote bushing for actinide vitrification

    SciTech Connect (OSTI)

    Schumacher, R.F.; Ramsey, W.G.; Johnson, F.M. [and others

    1996-12-31T23:59:59.000Z

    The Savannah River Site (SRS) and the Savannah River Technology Center (SRTC) are combining their existing experience in handling highly radioactive, special nuclear materials with commercial glass fiberization technology in order to assemble a small vitrification system for radioactive actinide solutions. The vitrification system or {open_quotes}brushing{close_quotes}, is fabricated from platinum-rhodium alloy and is based on early marble remelt fiberization technology. Advantages of this unique system include its relatively small size, reliable operation, geometrical safety (nuclear criticality), and high temperature capability. The bushing design should be capable of vitrifying a number of the actinide nuclear materials, including solutions of americium/curium, neptunium, and possibly plutonium. State of the art, mathematical and oil model studies are being combined with basic engineering evaluations to verify and improve the thermal and mechanical design concepts.

  6. Electrochemical detection of organic acids for anaerobic-digestor control and identification of biocorrosion inception on ferrous substrates. Final report, January 1-December 31, 1990

    SciTech Connect (OSTI)

    Cook, R.L.; Patel, J.; Sammells, A.F.

    1991-01-01T23:59:59.000Z

    The program was directed towards developing in situ techniques for the detection of organic acids present in both anaerobic digestors and as a result of microbial induced corrosion (MIC). The investigation was extneded to include investigating microprobes for pH and chloride ion detection as a strategy for gaining insight into the mechanism of MIC. Experimental work identified a reversible fiber optic chemical sensor for acetate detection in aqueous solution based upon the use of rhodium octaethylporphine immobilized as a molecular host on a fiber optic substrate. Data obtained from systematically performed electrochemical measurements on gas pipeline steel in simulated bacterial metabolite mixtures were analyzed using multivariante statistical analysis; however, no definitive conclusions could be made as to the relative influence of factors aggrevating MIC induced corrosion processes. Fabrication of microelectrodes compatible for monitoring of chloride and pH in MIC corrosion pits was achieved and initial testing performed.

  7. Activity and structure of perovskites as diesel reforming catalysts for solid oxide fuel cells.

    SciTech Connect (OSTI)

    Liu, D.-J.; Krumpelt, M.; Chemical Engineering

    2005-01-01T23:59:59.000Z

    Recent progress in developing perovskite materials as more cost-effective catalysts in autothermal reforming (ATR) of diesel fuel to hydrogen-rich reformate for solid oxide fuel cell (SOFC) application is reported. Perovskite-type metal oxides with B sites partially exchanged by ruthenium were prepared and evaluated under ATR reaction conditions. The hydrogen yield, reforming efficiency, and CO{sub x} selectivity of these catalysts were investigated using diesel surrogate fuel with 50 ppm sulfur. The catalyst performances have approached or exceeded a benchmark, high-cost rhodium-based material. In parallel with the reactivity study, we also investigated the physical properties of B-site doped perovskites and their impact on the reforming performance using various characterization techniques such as BET, X-ray powder diffraction, temperature programmable reduction, scanning electron microscopy, and synchrotron X-ray absorption spectroscopy. We found that ruthenium is highly dispersed into perovskite lattice and its redox behavior is directly associated with reforming activity.

  8. Method for the catalytic conversion of organic materials into a product gas

    DOE Patents [OSTI]

    Elliott, D.C.; Sealock, L.J. Jr.; Baker, E.G.

    1997-04-01T23:59:59.000Z

    A method for converting organic material into a product gas includes: (a) providing a liquid reactant mixture containing liquid water and liquid organic material within a pressure reactor; (b) providing an effective amount of a reduced metal catalyst selected from the group consisting of ruthenium, rhodium, osmium and iridium or mixtures thereof within the pressure reactor; and (c) maintaining the liquid reactant mixture and effective amount of reduced metal catalyst in the pressure reactor at temperature and pressure conditions of from about 300 C to about 450 C; and at least 130 atmospheres for a period of time, the temperature and pressure conditions being effective to maintain the reactant mixture substantially as liquid, the effective amount of reduced metal catalyst and the period of time being sufficient to catalyze a reaction of the liquid organic material to produce a product gas composed primarily of methane, carbon dioxide and hydrogen. 5 figs.

  9. Enantioselective synthesis of L-(-)-4- boronophenylalanine (L-BPA)

    DOE Patents [OSTI]

    Samsel, Edward G. (Baton Rouge, LA)

    1992-01-01T23:59:59.000Z

    A method of making substantially pure L-BPA is disclosed. The method includes the steps of reacting 4-bromobenzaldehyde with ethylene glycol to form 4-bromobenzaldehyde ethylene glycol acetal, sequentially reacting 4-bromobenzaldehyde ethyleneglycol acetal with Mg to produce the Grignard reagent and thereafter reacting with tributyl borate and then converting to an acid environment to form 4-boronobenzaldehyde, reacting 4-boronobenzaldehyde with diethanol amine to form 4-boronobenzaldehyde diethanolamine ester, condensing the 4-boronobenzaldehyde diethanolamine ester with 2-phenyl-2-oxazolin-5-one to form an azlactone, reacting the azlactone with an alkali metal hydroxide to form z-.alpha.-benzoylamino-4-boronocinnamic acid, asymmetrically hydrogenating the z-.alpha.-benzoylamino-4-boronocinnamic acid in the presence of a catalyst of a cheltate complex of rhodium (I) with chiral bisphosphines to form L-(+)-N-benzoyl-4-boronophenylalanine, and thereafter acidifying the L-(+)-N-benzoyl-4-boronophenylalanine in an organic medium to produce L-BPA.

  10. Enantioselective synthesis of L-(-)-4- boronophenylalanine (L-BPA)

    DOE Patents [OSTI]

    Samsel, E.G.

    1992-10-20T23:59:59.000Z

    A method of making substantially pure L-BPA is disclosed. The method includes the steps of reacting 4-bromobenzaldehyde with ethylene glycol to form 4-bromobenzaldehyde ethylene glycol acetal, sequentially reacting 4-bromobenzaldehyde ethyleneglycol acetal with Mg to produce the Grignard reagent and thereafter reacting with tributyl borate and then converting to an acid environment to form 4-boronobenzaldehyde, reacting 4-boronobenzaldehyde with diethanol amine to form 4-boronobenzaldehyde diethanolamine ester, condensing the 4-boronobenzaldehyde diethanolamine ester with 2-phenyl-2-oxazolin-5-one to form an azlactone, reacting the azlactone with an alkali metal hydroxide to form z-[alpha]-benzoylamino-4boronocinnamic acid, asymmetrically hydrogenating the z-[alpha]-benzoylamino-4-boronocinnamic acid in the presence of a catalyst of a cheltate complex of rhodium (I) with chiral bisphosphines to form L-(+)-N-benzoyl-4-boronophenylalanine, and thereafter acidifying the L-(+)-N-benzoyl-4-boronophenylalanine in an organic medium to produce L-BPA. 3 figs.

  11. Ray tracing flux calculation for the small and wide angle x-ray scattering diffraction station at the SESAME synchrotron radiation facility

    SciTech Connect (OSTI)

    Salah, Wa'el [Synchrotron-light for Experimental Science and Application in the Middle East (SESAME), P.O. Box 7, Allan 19252 (Jordan); Department of Physics, The Hashemite University, Zarqa 13115 (Jordan); Sanchez del Rio, M. [European Synchrotron Radiation Facility, Bp 220, 38043 Grenoble Cedex (France); Hoorani, H. [Synchrotron-light for Experimental Science and Application in the Middle East (SESAME), P.O. Box 7, Allan 19252 (Jordan)

    2009-09-15T23:59:59.000Z

    The calculation for the optics of the synchrotron radiation small and wide angle x-ray scattering beamline, currently under construction at SESAME is described. This beamline is based on a cylindrically bent germanium (111) single crystal with an asymmetric cut of 10.5 deg., followed by a 1.2 m long rhodium coated plane mirror bent into a cylindrical form. The focusing properties of bent asymmetrically cut crystals have not yet been studied in depth. The present paper is devoted to study of a particular application of a bent asymmetrically cut crystal using ray tracing simulations with the SHADOW code. These simulations show that photon fluxes of order of 1.09x10{sup 11} photons/s will be available at the experimental focus at 8.79 keV. The focused beam dimensions will be 2.2 mm horizontal full width at half maximum (FWHM) by 0.12 mm vertical (FWHM).

  12. Significance of M2 and E3 transitions for $4p^54d^{N+1}$ and $4p^64d^{N-1}4f$ configuration metastable level lifetimes

    E-Print Network [OSTI]

    Karpukien?, R; Kisielius, R

    2015-01-01T23:59:59.000Z

    Magnetic quadrupole and electric octupole transitions from the configurations $4p^54d^{N+1}$ and $4p^64d^{N-1}4f$ were calculated along with magnetic dipole, electric dipole and electric quadrupole radiative transitions in quasirelativistic Hartree-Fock approximation. Their significance in determining the metastable level radiative lifetimes was investigated along several isoelectronic sequences for the ions from $Z=50$ to $Z=92$. Strontium-like ions, zirconium-like ions, molybdenum-like ions and rhodium-like ions were studied comprehensively. Remaining isoelectronic sequences with the ground configuration $4d^{N}$ ($N=1,3,5,7,8,10$) were also reviewed albeit in less detail. A systematic trends of determined total radiative lifetimes were studied. The importance of magnetic quadrupole and electric octupole transitions from metastable levels of ions from these isoelectronic sequences was investigated and discussed. Inclusion of such transitions of higher multipole order can change theoretical radiative lifetim...

  13. X-ray source for mammography

    DOE Patents [OSTI]

    Logan, C.M.

    1994-12-20T23:59:59.000Z

    An x-ray source is described utilizing anode material which shifts the output spectrum to higher energy and thereby obtains higher penetrating ability for screening mammography application, than the currently utilized anode material. The currently used anode material (molybdenum) produces an energy x-ray spectrum of 17.5/19.6 keV, which using the anode material of this invention (e.g. silver, rhodium, and tungsten) the x-ray spectrum would be in the 20-35 keV region. Thus, the anode material of this invention provides for imaging of breasts with higher than average x-ray opacity without increase of the radiation dose, and thus reduces the risk of induced breast cancer due to the radiation dose administered for mammograms. 6 figures.

  14. Long term materials test program. Quarterly report, April-June 1983

    SciTech Connect (OSTI)

    Not Available

    1984-01-01T23:59:59.000Z

    Corrosion and erosion/corrosion testing of gas turbine materials in the effluent from a pressurized fluidized bed coal combustor continues under the Long Term Materials Test program. Two 1000-hour erosion/corrosion screening tests of twelve candidate gas turbine vane and blade base alloys and a variety of protective coating systems have been completed. Test conditions included 1350/sup 0/F, 800 to 900 ft/s and particulate loadings of 30 to 90 ppM. Erosion/corrosion degradation rates of 1 to 4 mils/1000 hours were observed with corrosion predominant in areas of particle impaction. FeCrAlY, CoCrAlY and rhodium aluminide coatings show significantly better resistance to degradation than unprotected base alloys, aluminide or platinum-aluminide diffusion coatings.

  15. A RhxSy/C Catalyst for the Hydrogen Oxidation and Hydrogen Evolution Reactions in HBr

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Masud, Jahangir; Nguyena, Trung V.; Singh, Nirala; McFarland, Eric; Ikenberry, Myles; Hohn, Keith; Pan, Chun-Jern; Hwang, Bing-Joe

    2015-01-01T23:59:59.000Z

    Rhodium sulfide (Rh2S3) on carbon support was synthesized by refluxing rhodium chloride with ammonium thiosulfate. Thermal treatment of Rh2S3 at high temperatures (600C to 850C) in presence of argon resulted in the transformation of Rh2S3 into Rh3S4, Rh17S15 and Rh which were characterized by TGA/DTA, XRD, EDX, and deconvolved XPS analyses. The catalyst particle size distribution ranged from 3 to 12 nm. Cyclic voltammetry and rotating disk electrode measurements were used to evaluate the catalytic activity for hydrogen oxidation and evolution reactions in H2SO4 and HBr solutions. The thermally treated catalysts show high activity for the hydrogen reactions. The exchangemorecurrent densities (io) of the synthesized RhxSy catalysts in H2-saturated 1M H2SO4 and 1M HBr for HER and HOR were 0.9 mA/cm2 to 1.0 mA/cm2 and 0.8 to 0.9 mA/cm2, respectively. The lower io values obtained in 1M HBr solution compared to in H2SO4 might be due to the adsorption of Br- on the active surface. Stable electrochemical active surface area (ECSA) of RhxSy catalyst was obtained for CV scan limits between 0 V and 0.65 V vs. RHE. Scans with upper voltage limit beyond 0.65 V led to decreased and unreproducible ECSA measurements.less

  16. Separation of metallic residues from the dissolution of a high-burnup BWR fuel using nitrogen trifluoride

    SciTech Connect (OSTI)

    McNamara, Bruce K.; Buck, Edgar C.; Soderquist, Chuck Z.; Smith, Frances N.; Mausolf, Edward J.; Scheele, Randall D.

    2014-02-10T23:59:59.000Z

    Nitrogen trifluoride (NF3) was used to fluorinate the metallic residue from the dissolution of a high burnup, boiling water reactor fuel (?70 MWd/kgU). The metallic residue included the noble metal phase (containing ruthenium, rhodium, palladium, technetium, and molybdenum), and smaller amounts of zirconium, selenium, tellurium, and silver. Exposing the noble metal phase to 10% NF3 in argon between 400 and 550?C, removed molybdenum and technetium near 400?C as their volatile fluorides, and ruthenium near 500?C as its volatile fluoride. The events were thermally and temporally distinct and the conditions specified are a recipe to separate these transition metals from each other and from the noble metal phase nonvolatile residue. Depletion of the volatile fluorides resulted in substantial exothermicity. Thermal excursion behavior was recorded under non-adiabatic, isothermal conditions that typically minimize heat release. Physical characterization of the metallic noble phase and its thermal behavior are consistent with high kinetic velocity reactions encouraged by the nanoparticulate phase or perhaps catalytic influences of the mixed platinum metals with nearly pure phase structure. Post-fluorination, only two phases were present in the residual nonvolatile fraction. These were identified as a nano-crystalline, metallic palladium cubic phase and a hexagonal rhodium trifluoride (RhF3) phase. The two phases were distinct as the sub-m crystallites of metallic palladium were in contrast to the RhF3 phase, which grew from the parent nano-crystalline noble-metal phase during fluorination, to acicular crystals exceeding 20-m in length.

  17. Outlooks of HLW Partitioning Technologies Usage for Recovering of Platinum Metals from Spent Fuel

    SciTech Connect (OSTI)

    Pokhitonov, Y. A.; Estimantovskiy, V.; Romanovski, v.; Zatsev, B.; Todd, T.

    2003-02-24T23:59:59.000Z

    The existing practice of management of high level waste (HLW) generated by NPPs, call for a task of selective separation of the most dangerous long-lived radionuclides with the purpose of their subsequent immobilization and disposal. HLW partitioning allows to reduce substantially the cost of vitrified product storage owing to isolation of the most dangerous radionuclides, such as transplutonium elements (TPE) into separate fractions of small volumes, intended for ultimate storage. By now numerous investigations on partitioning of HLW of various composition have been carried out in many countries and a lot of processes permitting to recover cesium, strontium, TPE and rare earth elements (REE) have been already tested. Apart from enumerated radionuclides, a fair quantity of palladium and rhodium presents in spent fuel, but the problem of these elements recovery has not yet been decided at the operating radiochemical plants. A negative effect of platinum group metals (PGM) occurrence is determined by the formation of separate metal phase, which not only worsens the conditions of glass-melting but also shortens considerably the service life of the equipment. At the same time, the exhaustion of PGMs natural resources may finally lead to such a growth of their costs that the spent nuclear fuel would became a substituting source of these elements industrial production. Allowing above mentioned, it is of interest to develop the technique for ''reactor'' palladium and rhodium recovery process which would be compatible with HLW partitioning and could be realized using the same facilities. In the report the data on platinum metals distribution in spent fuel reprocessing products and the several flowsheets for palladium separation from HLW are presented.

  18. A RhxSy/C Catalyst for the Hydrogen Oxidation and Hydrogen Evolution Reactions in HBr

    SciTech Connect (OSTI)

    Masud, Jahangir [Univ. of Kansas, Lawrence, KS (United States); Nguyena, Trung V. [Univ. of Kansas, Lawrence, KS (United States); Singh, Nirala [Univ. of California, Santa Barbara, CA (United States); McFarland, Eric [Univ. of California, Santa Barbara, CA (United States); Ikenberry, Myles [Kansas State Univ., Manhattan, KS (United States); Hohn, Keith [Kansas State Univ., Manhattan, KS (United States); Pan, Chun-Jern [National Taiwan University of Science & Technology, Tapei (Taiwan); Hwang, Bing-Joe [National Taiwan University of Science & Technology, Tapei (Taiwan)

    2015-01-01T23:59:59.000Z

    Rhodium sulfide (Rh2S3) on carbon support was synthesized by refluxing rhodium chloride with ammonium thiosulfate. Thermal treatment of Rh2S3 at high temperatures (600C to 850C) in presence of argon resulted in the transformation of Rh2S3 into Rh3S4, Rh17S15 and Rh which were characterized by TGA/DTA, XRD, EDX, and deconvolved XPS analyses. The catalyst particle size distribution ranged from 3 to 12 nm. Cyclic voltammetry and rotating disk electrode measurements were used to evaluate the catalytic activity for hydrogen oxidation and evolution reactions in H2SO4 and HBr solutions. The thermally treated catalysts show high activity for the hydrogen reactions. The exchange current densities (io) of the synthesized RhxSy catalysts in H2-saturated 1M H2SO4 and 1M HBr for HER and HOR were 0.9 mA/cm2 to 1.0 mA/cm2 and 0.8 to 0.9 mA/cm2, respectively. The lower io values obtained in 1M HBr solution compared to in H2SO4 might be due to the adsorption of Br- on the active surface. Stable electrochemical active surface area (ECSA) of RhxSy catalyst was obtained for CV scan limits between 0 V and 0.65 V vs. RHE. Scans with upper voltage limit beyond 0.65 V led to decreased and unreproducible ECSA measurements.

  19. Final Technical Report "Catalytic Hydrogenation of Carbon Monoxide and Olefin Oxidation" Grant number : DE-FG02-86ER13615

    SciTech Connect (OSTI)

    Wayland, B.B.

    2009-08-31T23:59:59.000Z

    Title: Catalytic Hydrogenation of Carbon Monoxide and Olefin Oxidation Grant No. DE-FG02-86ER13615 PI: Wayland, B. B. (wayland@sas.upenn.edu) Abstract Development of new mechanistic strategies and catalyst materials for activation of CO, H2, CH4, C2H4, O2, and related substrates relevant to the conversion of carbon monoxide, alkanes, and alkenes to organic oxygenates are central objectives encompassed by this program. Design and synthesis of metal complexes that manifest reactivity patterns associated with potential pathways for the hydrogenation of carbon monoxide through metallo-formyl (M-CHO), dimetal ketone (M-C(O)-M), and dimetal dionyl (M-C(O)-C(O)-M) species is one major focus. Hydrocarbon oxidation using molecular oxygen is a central goal for methane activation and functionalization as well as regioselective oxidation of olefins. Discovery of new reactivity patterns and control of selectivity are pursued through designing new metal complexes and adjusting reaction conditions. Variation of reaction media promotes distinct reaction pathways that control both reaction rates and selectivities. Dimetalloradical diporphyrin complexes preorganize transition states for substrate reactions that involve two metal centers and manifest large rate increases over mono-metalloradical reactions of hydrogen, methane, and other small molecule substrates. Another broad goal and recurring theme of this program is to contribute to the thermodynamic database for a wide scope of organo-metal transformations in a range of reaction media. One of the most complete descriptions of equilibrium thermodynamics for organometallic reactions in water and methanol is emerging from the study of rhodium porphyrin substrate reactions in aqueous and alcoholic media. Water soluble group nine metalloporphyrins manifest remarkably versatile substrate reactivity in aqueous and alcoholic media which includes producing rhodium formyl (Rh-CHO) and hydroxy methyl (Rh-CH2OH) species. Exploratory directions for this program include expending new strategies for anti-Markovnikov addition of water, alcohols, and amines with olefins, developing catalytic reactions of CO to give formamides and formic esters, and evaluating the potential for coupling reactions of CO to produce organic building blocks.

  20. Catalyst and process development for hydrogen preparation from future fuel cell feedstocks. Quarterly progress report, January 1, 1980-March 31, 1980. [Pt/Rh, Pd, Pt, Rh, Ni/Rh, Rh/Re, Ni

    SciTech Connect (OSTI)

    Yarrington, R M; Feins, I R; Hwang, H S

    1980-04-01T23:59:59.000Z

    Catalysts are being screened to steam reform hydrocarbons in an autothermal reformer (STR). Twenty-one samples have been screened in a 1-in.-diam (ATR) reactor using No. 2 oil as the hydrocarbon feed. A series of platinum-rhodium catalysts were evaluated to study the effect of varying compositions. A sample containing 1.7% Pt/0.3% Rh was most active but the difference among the samples was within the range of test variability. Development of a more realistic test has been started. The effect of O/sub 2//C level on the gas composition leaving the catalytic partial oxidation section has been determined. The amount of unreacted oil increases as O/sub 2//C level decreases. The unreacted oil is more aromatic than the feedstock. The gas composition contains considerably more olefins as the O/sub 2//C level decreases. Post-run catalyst characterization indicates that the catalyst carrier does not deteriorate in the ATR test. A drastic decrease in CO chemisorption is noted on the Pt/Rh samples. This decline in CO chemisorption could either be due to metal sintering or to carbon deposition on the metal. Other analysis are required to determine which is causing the decline in CO chemisorption. Very low coke levels were found on Pt, Rh, and Pt/Rh samples. Addition of Rh to nickel reduces the coke level over that observed for nickel catalysts.

  1. Long term materials test program. Quarterly report, October-December 1983

    SciTech Connect (OSTI)

    Not Available

    1984-01-01T23:59:59.000Z

    The long-term exposure of gas turbine vane and blade base alloys and a variety of protective coating systems to the effluent from a pressurized fluidized bed coal combustor has reached 4398 hours. After 4053 hours, FeCrAlY overlay coatings and platinum/rhodium-aluminide pack diffusion coatings show excellent resistance to corrosion attack at 1500/sup 0/F. Cobalt-base coatings are somewhat more susceptible to hot corrosion, and the unprotected nickel and cobalt-base alloys are most susceptible to corrosion, although corrosion rates have decreased to less than 1 mil/1000 hours for all materials at 1500/sup 0/F; i.e., corrosion penetration data is evolving parabolically. The three-stage cyclone cleanup system became severely distorted after approximately 5600 hours total service life. Distortion of the cyclones contributed to an increased dust loading to the material test sections, 110 to 250 ppM versus normal loadings of 30 to 90 ppM, for a period of about 75 hours. This increase in dust loading caused severe erosion of the airfoils in the high-velocity test section. Metal recession ranged 4 to 18 mils of leading edge loss on the impulse airfoils, and 11 to 27 mils of leading edge loss on the reaction airfoils. A new three-stage cyclone system was installed and dust loadings now range from 15 to 45 ppM.

  2. Characterization of Tank 23H Supernate Per Saltstone Waste Acceptance Criteria Analysis Requirements-2005

    SciTech Connect (OSTI)

    Oji, L

    2005-06-01T23:59:59.000Z

    Variable depth Tank 23H samples (22-inch sample [HTF-014] and 185-inch sample [HTF-013]) were pulled from Tank 23H in February, 2005 for characterization. The characterization of the Tank 23H low activity waste is part of the overall liquid waste processing activities. This characterization examined the species identified in the Saltstone Waste Acceptance Criteria (WAC) for the transfer of waste into the Salt-Feed Tank (SFT). The samples were delivered to the Savannah River National Laboratory (SRNL) and analyzed. Apart from radium-226 with an average measured detection limit of < 2.64E+03 pCi/mL, which is about the same order of magnitude as the WAC limit (< 8.73E+03 pCi/mL), none of the species analyzed was found to approach the limits provided in the Saltstone WAC. The concentration of most of the species analyzed for the Tank 23H samples were 2-5 orders of magnitude lower than the WAC limits. The achievable detection limits for a number of the analytes were several orders of magnitude lower than the WAC limits, but one or two orders of magnitude higher than the requested detection limits. Analytes which fell into this category included plutonium-241, europium-154/155, antimony-125, tin-126, ruthenium/rhodium-106, selenium-79, nickel-59/63, ammonium ion, copper, total nickel, manganese and total organic carbon.

  3. Characterization of Tank 23H Supernate Per Saltstone Waste Acceptance Criteria Analysis Requirements -2005

    SciTech Connect (OSTI)

    Oji, L

    2005-05-05T23:59:59.000Z

    Variable depth Tank 23H samples (22-inch sample [HTF-014] and 185-inch sample [HTF-013]) were pulled from Tank 23H in February, 2005 for characterization. The characterization of the Tank 23H low activity waste is part of the overall liquid waste processing activities. This characterization examined the species identified in the Saltstone Waste Acceptance Criteria (WAC) for the transfer of waste into the Salt-Feed Tank (SFT). The samples were delivered to the Savannah River National Laboratory (SRNL) and analyzed. Apart from radium-226 with an average measured detection limit of < 2.64E+03 pCi/mL, which is about the same order of magnitude as the WAC limit (< 8.73E+03 pCi/mL), none of the species analyzed was found to approach the limits provided in the Saltstone WAC. The concentration of most of the species analyzed for the Tank 23H samples were 2-5 orders of magnitude lower than the WAC limits. The achievable detection limits for a number of the analytes were several orders of magnitude lower than the WAC limits, but one or two orders of magnitude higher than the requested detection limits. Analytes which fell into this category included plutonium-241, europium-154/155, antimony-125, tin-126, ruthenium/rhodium-106, selenium-79, nickel-59/63, ammonium ion, copper, total nickel, manganese and total organic carbon.

  4. Process for functionalizing alkanes

    DOE Patents [OSTI]

    Bergman, Robert G. (Kensington, CA); Janowicz, Andrew H. (Wilmington, DE); Periana, Roy A. (Berkeley, CA)

    1988-01-01T23:59:59.000Z

    Process for functionalizing saturated hydrocarbons comprising: (a) reacting said saturated hydrocarbons of the formula: R.sub.1 H wherein H represents a hydrogen atom; and R.sub.1 represents a saturated hydrocarbon radical, with a metal complex of the formula: CpRh[P(R.sub.2).sub.3 ]H.sub.2 wherein Cp represents a cyclopentadienyl or alkylcyclopentadienyl radical; Rh represents a rhodium atom; P represents a phosphorus atom; R.sub.2 represents a hydrocarbon radical; H represents a hydrogen atom, in the presence of ultraviolet radiation to form a hydridoalkyl complex of the formula: CpRh[P(R.sub.2).sub.3 ](R.sub.1)H (b) reacting said hydridoalkyl complex with an organic halogenating agent such as a tetrahalomethane or a haloform of the formulas: CX'X''X'''X'''' or CHX'X''X''' wherein X', X'', X'", X"" represent halogens selected from bromine, iodine or chlorine atom, at a temperature in the range of about -60.degree. to -17.degree. C. to form the corresponding haloalkyl complex of step (a) having the formula: CpRhPMe.sub.3 RX; and, (c) reacting said haloalkyl complex formed in (b) with halogen (X.sub.2) at a temperature in the range of about -60.degree. to 25.degree. C. (i.e., ambient) to form a functional haloalkyl compound.

  5. Method for the preparation of metal colloids in inverse micelles and product preferred by the method

    DOE Patents [OSTI]

    Wilcoxon, Jess P. (Albuquerque, NM)

    1992-01-01T23:59:59.000Z

    A method is provided for preparing catalytic elemental metal colloidal particles (e.g. gold, palladium, silver, rhodium, iridium, nickel, iron, platinum, molybdenum) or colloidal alloy particles (silver/iridium or platinum/gold). A homogeneous inverse micelle solution of a metal salt is first formed in a metal-salt solvent comprised of a surfactant (e.g. a nonionic or cationic surfactant) and an organic solvent. The size and number of inverse micelles is controlled by the proportions of the surfactant and the solvent. Then, the metal salt is reduced (by chemical reduction or by a pulsed or continuous wave UV laser) to colloidal particles of elemental metal. After their formation, the colloidal metal particles can be stabilized by reaction with materials that permanently add surface stabilizing groups to the surface of the colloidal metal particles. The sizes of the colloidal elemental metal particles and their size distribution is determined by the size and number of the inverse micelles. A second salt can be added with further reduction to form the colloidal alloy particles. After the colloidal elemental metal particles are formed, the homogeneous solution distributes to two phases, one phase rich in colloidal elemental metal particles and the other phase rich in surfactant. The colloidal elemental metal particles from one phase can be dried to form a powder useful as a catalyst. Surfactant can be recovered and recycled from the phase rich in surfactant.

  6. On the Use of Thermal NF3 as the Fluorination and Oxidation Agent in Treatment of Used Nuclear Fuels

    SciTech Connect (OSTI)

    Scheele, Randall D.; McNamara, Bruce K.; Casella, Andrew M.; Kozelisky, Anne E.

    2012-05-01T23:59:59.000Z

    This paper presents results of our investigation on the use of nitrogen trifluoride as the fluorination or fluorination/oxidation agent for use in a process for separating valuable constituents from used nuclear fuels by employing the volatility of many transition metal and actinide fluorides. Nitrogen trifluoride is less chemically and reactively hazardous than the hazardous and aggressive fluorinating agents used to prepare uranium hexafluoride and considered for fluoride volatility based nuclear fuels reprocessing. In addition, nitrogen trifluorides less aggressive character may be used to separate the volatile fluorides from used fuel and from themselves based on the fluorination reactions temperature sensitivity (thermal tunability) rather than relying on differences in sublimation/boiling temperature and sorbents. Our thermodynamic calculations found that nitrogen trifluoride has the potential to produce volatile fission product and actinide fluorides from candidate oxides and metals. Our simultaneous thermogravimetric and differential thermal analyses found that the oxides of lanthanum, cerium, rhodium, and plutonium fluorinated but did not form volatile fluorides and that depending on temperature volatile fluorides formed from the oxides of niobium, molybdenum, ruthenium, tellurium, uranium, and neptunium. We also demonstrated near-quantitative removal of uranium from plutonium in a mixed oxide.

  7. Process for removal of mineral particulates from coal-derived liquids

    DOE Patents [OSTI]

    McDowell, William J. (Knoxville, TN)

    1980-01-01T23:59:59.000Z

    Suspended mineral solids are separated from a coal-derived liquid containing the solids by a process comprising the steps of: (a) contacting said coal-derived liquid containing solids with a molten additive having a melting point of 100.degree.-500.degree. C. in an amount of up to 50 wt. % with respect to said coal-derived liquid containing solids, said solids present in an amount effective to increase the particle size of said mineral solids and comprising material or mixtures of material selected from the group of alkali metal hydroxides and inorganic salts having antimony, tin, lithium, sodium, potassium, magnesium, calcium, beryllium, aluminum, zinc, molybdenum, cobalt, nickel, ruthenium, rhodium or iron cations and chloride, iodide, bromide, sulfate, phosphate, borate, carbonate, sulfite, or silicate anions; and (b) maintaining said coal-derived liquid in contact with said molten additive for sufficient time to permit said mineral matter to agglomerate, thereby increasing the mean particle size of said mineral solids; and (c) recovering a coal-derived liquid product having reduced mineral solids content. The process can be carried out with less than 5 wt. % additive and in the absence of hydrogen pressure.

  8. Irradiation testing of a niobium-molybdenum developmental thermocouple

    SciTech Connect (OSTI)

    Knight, R.C.; Greenslade, D.L.

    1991-10-01T23:59:59.000Z

    A need exists for a radiation-resistant thermocouple capable of monitoring temperatures in excess of the limits of the chromel/alumel system. Tungsten/rhenium and platinum/rhodium thermocouples have sufficient temperature capability but have proven to be unstable because of irradiation-induced decalibration. The niobium/molybdenum system is believed to hold great potential for nuclear applications at temperatures up to 2000 K. However, the fragility of pure niobium and fabrication problems with niobium/molybdenum alloys have limited development of this system. Utilizing the Fast Flux Test Facility, a developmental thermocouple with a thermoelement pair consisting of a pure molybdenum and a niobium-1%zirconium alloy wire was irradiated fro 7200 hours at a temperature of 1070 K. The thermocouple performed flawlessly for the duration of the experiment and exhibited stability comparable to a companion chromel/alumel unit. A second thermocouple, operating at 1375 K, is currently being employed to monitor a fusion materials experiment in the Fast Flux Test Facility. This experiment, also scheduled for 7200 hours, will serve to further evaluate the potential of the niobium-1%zirconium/molybdenum thermoelement system. 7 refs., 7 figs.

  9. Method for bonding thin film thermocouples to ceramics

    DOE Patents [OSTI]

    Kreider, Kenneth G. (Potomac, MD)

    1993-01-01T23:59:59.000Z

    A method is provided for adhering a thin film metal thermocouple to a ceramic substrate used in an environment up to 700 degrees Centigrade, such as at a cylinder of an internal combustion engine. The method includes the steps of: depositing a thin layer of a reactive metal on a clean ceramic substrate; and depositing thin layers of platinum and a platinum-10% rhodium alloy forming the respective legs of the thermocouple on the reactive metal layer. The reactive metal layer serves as a bond coat between the thin noble metal thermocouple layers and the ceramic substrate. The thin layers of noble metal are in the range of 1-4 micrometers thick. Preferably, the ceramic substrate is selected from the group consisting of alumina and partially stabilized zirconia. Preferably, the thin layer of reactive metal is in the range of 0.015-0.030 micrometers (15-30 nanometers) thick. The preferred reactive metal is chromium. Other reactive metals may be titanium or zirconium. The thin layer of reactive metal may be deposited by sputtering in ultra high purity argon in a vacuum of approximately 2 milliTorr (0.3 Pascals).

  10. Method of generating hydrogen by catalytic decomposition of water

    DOE Patents [OSTI]

    Balachandran, Uthamalingam (Hinsdale, IL); Dorris, Stephen E. (LaGrange Park, IL); Bose, Arun C. (Pittsburgh, PA); Stiegel, Gary J. (Library, PA); Lee, Tae-Hyun (Naperville, IL)

    2002-01-01T23:59:59.000Z

    A method for producing hydrogen includes providing a feed stream comprising water; contacting at least one proton conducting membrane adapted to interact with the feed stream; splitting the water into hydrogen and oxygen at a predetermined temperature; and separating the hydrogen from the oxygen. Preferably the proton conducting membrane comprises a proton conductor and a second phase material. Preferable proton conductors suitable for use in a proton conducting membrane include a lanthanide element, a Group VIA element and a Group IA or Group IIA element such as barium, strontium, or combinations of these elements. More preferred proton conductors include yttrium. Preferable second phase materials include platinum, palladium, nickel, cobalt, chromium, manganese, vanadium, silver, gold, copper, rhodium, ruthenium, niobium, zirconium, tantalum, and combinations of these. More preferably second phase materials suitable for use in a proton conducting membrane include nickel, palladium, and combinations of these. The method for generating hydrogen is preferably preformed in the range between about 600.degree. C. and 1,700.degree. C.

  11. Catalysts for the hydrodenitrogenation of organic materials and process for the preparation of the catalysts

    DOE Patents [OSTI]

    Laine, R.M.; Hirschon, A.S.; Wilson, R.B. Jr.

    1987-12-29T23:59:59.000Z

    A process is described for the preparation of a multimetallic catalyst for the hydrodenitrogenation of an organic feedstock, which process comprises: (a) forming a precatalyst itself comprising: (1) a first metal compound selected from compounds of nickel, cobalt or mixtures thereof; (2) a second metal compound selected from compounds of chromium, molybdenum, tungsten, or mixtures thereof; and (3) an inorganic support; (b) heating the precatalyst of step (a) with a source of sulfide in a first non-oxidizing gas at a temperature and for a time effective to presulfide the precatalyst; (c) adding in a second non-oxidizing gas to the sulfided precatalyst of step (b) an organometallic transition metal moiety selected from compounds of iridium, rhodium, iron, ruthenium, tungsten or mixtures thereof for a time and at a temperature effective to chemically combine the metal components; and (d) optionally heating the chemically combined catalyst of step (b) in vacuum at a temperature and for a time effective to remove residual volatile organic materials. 12 figs.

  12. Sol-gel processed silica-alumina materials for diesel engine emission reduction catalysts

    SciTech Connect (OSTI)

    Narula, C.K.; Rokosz, M.; Allard, L.F.; Kudla, R.J.; Chattha, M.S.

    2000-04-18T23:59:59.000Z

    The incorporation of >30% silica in alumina prior to platinum impregnation improves the NOx conversion efficiency in the 200--300 C range from 45 to 57% and reduces light-off temperature. Further increase in the amount of silica to 50% is detrimental to NOx conversion efficiency. The {sup 1}H and {sup 29}Si NMR of the materials suggest that this trend is probably related to the surface acidity. The analyses of these materials by X-ray powder diffraction and electron microscopy do not reveal significant differences. Additional NOx conversion in the 350--450 C range with a maximum of 30% at 400 C can be achieved if a rhodium-impregnated 30% silica-alumina, Rh-30% SiO{sub 2}-Al{sub 2}O{sub 3}, is placed upstream of Pt-30% SiO{sub 2}-Al{sub 2}O{sub 3}. It is important to note that mixing Pt-30% SiO{sub 2}-Al{sub 2}O{sub 3} with Rh-30% SiO{sub 2}-Al{sub 2}O{sub 3} does not enhance conversion efficiency or effective temperature range.

  13. Low Cost Autothermal Diesel Reforming Catalyst Development

    SciTech Connect (OSTI)

    Shihadeh, J.; Liu, D.

    2004-01-01T23:59:59.000Z

    Catalytic autothermal reforming (ATR) represents an important step of converting fossil fuel to hydrogen rich reformate for use in solid oxide fuel cell (SOFC) stacks. The state-of-the-art reforming catalyst, at present, is a Rh based material which is effective but costly. The objective of our current research is to reduce the catalyst cost by finding an efficient ATR catalyst containing no rhodium. A group of perovskite based catalysts have been synthesized and evaluated under the reforming condition of a diesel surrogate fuel. Hydrogen yield, reforming efficiency, and conversion selectivity to carbon oxides of the catalyst ATR reaction are calculated and compared with the benchmark Rh based material. Several catalyst synthesis improvements were carried out including: 1) selectively doping metals on the A-site and B-site of the perovskite structure, 2) changing the support from perovskite to alumina, 3) altering the method of metal addition, and 4) using transition metals instead of noble metals. It was found that the catalytic activity changed little with modification of the A-site metal, while it displayed considerable dependence on the B-site metal. Perovskite supports performed much better than alumina based supports.

  14. A Cobalt-based Catalyst for CO2 Hydrogenation Under Ambient Conditions

    SciTech Connect (OSTI)

    Jeletic, Matthew S.; Mock, Michael T.; Appel, Aaron M.; Linehan, John C.

    2013-08-07T23:59:59.000Z

    Due to the continually rising levels of CO2 in the atmosphere, research into conversion of CO2 into fuels using carbon-neutral energy is currently an important topic in catalysis. Recent research on molecular catalysts has led to improved rates of CO2 conversion to formate, but unfortunately the resulting catalysts are based on precious metals such as iridium, ruthenium and rhodium and require high temperatures and high pressures for catalytic reactivity. Using established thermodynamic properties, a cobalt-based catalyst system has been designed for the catalytic production of formate from CO2 and H2, even at room temperature and one atmosphere of pressure. Using Co(dmpe)2H (dmpe is bis(dimethylphosphino)ethane) as a catalyst in tetrahydrofuran, room temperature turnover frequencies of 3,400 h-1 at 1 atm of 1:1 CO2:H2 and 74,000 h-1 at 20 atm were obtained. These results highlight the value of basic thermodynamic properties in the rational design of catalysts. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.

  15. With no Color and Scent (part III): Architecture of metal shells grown on templates by pulse current electrodeposition

    E-Print Network [OSTI]

    Strukova, Galina; Egorov, Sergey

    2012-01-01T23:59:59.000Z

    A method of growing mushroom or shell like nanostructured metal convex concave models has been worked out. Silver,copper,nickel,rhodium and Pd-Ni,Pd-Co alloy structures are reproduced as a result of self-assembly of nanowires growing on porous membranes in the course of pulse current electrodeposition. It is shown that the method allows to model not only the shell shape but also the hierarchical structure at the nano, micro and mesolevels. A 1,2 mm sized shell was grown from Pd-Ni alloy. The architecture of the models was studied by fragmentation and chemical etching. The images were obtained using SUPRA 50 VP and JEOL scanning electron microscopes. The metal shell is a bowl-shaped frame, its walls composed of densely packed nanoelements. Each nanoelement is a conical bundle of nanowires grown as a supported wine glass. The shell inner surface is a weave of nanowires with a vegetation pattern with bottom up directed lines. The inner surface exhibits also well pronounced transverse rings formed by the bottom u...

  16. Separation of gas mixtures by supported complexes. Final report, 1 October 1982-30 September 1984

    SciTech Connect (OSTI)

    Nelson, D.A.; Hallen, R.T.; Lilga, M.A.

    1985-01-01T23:59:59.000Z

    This final report covers research performed to identify and demonstrate advantageous procedures for the chemical separation of gases, such as CO, CO/sub 2/, and H/sub 2/, from medium-Btu gas mixtures by use of supported complexes. Three complexes were chosen for rapid gas uptake and selectivity at 25/sup 0/C from among a group of 22 coordination complexes synthesized during this program. The three complexes showed considerable selectivity toward individual gases. For instance, Pd/sub 2/(dpm)/sub 2/Cl/sub 2/ or bis-..mu..-(bisdiphenylphosphinomethane)-dichlorodipalladium (Pd-Pd), rapidly bound carbon monoxide from solution. This complex could be regenerated, with the carbon monoxide reversibly removed, by warming to 40/sup 0/C. The presence of other gases, such as carbon dioxide, oxygen, nitrogen, hydrogen, ethylene, or acetylene, had no effect upon the rapid uptake of carbon monoxide or its removal. Such selectivity was also noted with Ru(CO)/sub 2/(PPh/sub 3/)/sub 3/, biscarbonyltris(triphenylphosphine)ruthenium. Although this complex bound hydrogen, carbon monoxide, and oxygen in solution, the hydrogen was taken up twice as fast as carbon monoxide and seven times faster than oxygen. These gases could be removed from the complex with mild heat or decreased pressure. Crystalline Rh(OH)(CO)(PPh/sub 3/)/sub 2/, hydroxocarbonylbis(triphenylphosphine)rhodium, rapidly bound carbon dioxide; the complex was regenerated at 50/sup 0/C under reduced pressure. The rapid uptake of carbon dioxide by this complex was not changed in the presence of oxygen. In general the three selected crystalline or solvent dissolved complexes performed well in the absence of polymeric support. The stability and favorable kinetics of the three complexes suggest that they could be utilized in a solution system for gas separation (Conceptual Analyses and Preliminary Economics). Further, these complexes appear to be superb candidates as transport agents for facilitated-transport, membrane systems. 69 references, 21 figures.

  17. Task 4.9 -- Value-added products from syngas. Semi-annual report, July 1--December 31, 1996

    SciTech Connect (OSTI)

    Olson, E.S.; Sharma, R.K.

    1997-08-01T23:59:59.000Z

    The work on advanced fuel forms in 1996 focused on the synthesis of higher alcohols from mixtures of hydrogen and carbon dioxide (syngas) from coal gasification. Initial work in this project utilized a novel molybdenum sulfide catalyst previously shown to be active for hydrodesulfurization reactions of coal liquids. A pressurized fixed-bed flow-through reactor was constructed, and the MoS{sub 2} catalysts were tested with syngas under a variety of conditions. Unfortunately, the catalysts, even with higher molybdenum loading and addition of promoters, failed to give alcohol products. A batch reactor test of the catalyst was also conducted, but did not produce alcohol products. Group VIII metals have been used previously in catalysts for syngas reactions. Ruthenium and rhodium catalysts were prepared by impregnation of a hydrotalcite support. Tests with these catalysts in flow-through reactors also did not produce the desired alcohol products. The formation of higher alcohols from smaller ones, such as methanol and ethanol, could be commercially important if high selectivity could be achieved. The methanol and ethanol would be derived from syngas and fermentation, respectively. Based on previous work in other laboratories, it was hypothesized that the hydrotalcite-supported MoS{sub 2} or Ru or Rh catalysts could catalyze the formation of butyl alcohols. Although the desired 1-butanol was obtained in batch reactions with the promoted ruthenium catalyst, the reaction was not as selective as desired. Product suitable for a lower-vapor-pressure gasoline oxygenate additive was obtained, but it may not be economical to market such products in competition with methyl tertiary-butyl ether (MTBE). Flow-through catalytic bed reactions were not successful.

  18. The Behavior and Effects of the Noble Metals in the DWPF Melter System

    SciTech Connect (OSTI)

    Smith, M.E. [Westinghouse Savannah River Company, AIKEN, SC (United States); Bickford, D.F.

    1997-11-30T23:59:59.000Z

    Governments worldwide have committed to stabilization of high-level nuclear waste (HLW) by vitrification to a durable glass form for permanent disposal. All of these nuclear wastes contain the fission-product noble metals: ruthenium, rhodium, and palladium. SRS wastes also contain natural silver from iodine scrubbers. Closely associated with the noble metals are the fission products selenium and tellurium which are chemical analogs of sulfur and which combine with noble metals to influence their behavior and properties. Experience has shown that these melt insoluble metals and their compounds tend to settle to the floor of Joule-heated ceramic melters. In fact, almost all of the major research and production facilities have experienced some operational problem which can be associated with the presence of dense accumulations of these relatively conductive metals and/or their compounds. In most cases, these deposits have led to a loss of production capability, in some cases, to the point that melter operation could not continue. HLW nuclear waste vitrification facilities in the United States are the Department of Energy`s Defense Waste Processing Facility (DWPF) at the Savannah River Site, the planned Hanford Waste Vitrification Plant (HWVP) at the Hanford Site and the operating West Valley Demonstration Project (WVDP) at West Valley, NY. The Integrated DWPF Melter System (IDMS) is a vitrification test facility at the Savannah River Technology Center (SRTC). It was designed and constructed to provide an engineering-scale representation of the DWPF melter and its associated feed preparation and off-gas treatment systems. An extensive noble metals testing program was begun in 1990. The objectives of this task were to explore the effects of the noble metals on the DWPF melter feed preparation and waste vitrification processes. This report focuses on the vitrification portion of the test program.

  19. Evaluation of alternative chemical additives for high-level waste vitrification feed preparation processing

    SciTech Connect (OSTI)

    Seymour, R.G.

    1995-06-07T23:59:59.000Z

    During the development of the feed processing flowsheet for the Defense Waste Processing Facility (DWPF) at the Savannah River Site (SRS), research had shown that use of formic acid (HCOOH) could accomplish several processing objectives with one chemical addition. These objectives included the decomposition of tetraphenylborate, chemical reduction of mercury, production of acceptable rheological properties in the feed slurry, and controlling the oxidation state of the glass melt pool. However, the DEPF research had not shown that some vitrification slurry feeds had a tendency to evolve hydrogen (H{sub 2}) and ammonia (NH{sub 3}) as the result of catalytic decomposition of CHOOH with noble metals (rhodium, ruthenium, palladium) in the feed. Testing conducted at Pacific Northwest Laboratory and later at the Savannah River Technical Center showed that the H{sub 2} and NH{sub 3} could evolve at appreciable rates and quantities. The explosive nature of H{sub 2} and NH{sub 3} (as ammonium nitrate) warranted significant mitigation control and redesign of both facilities. At the time the explosive gas evolution was discovered, the DWPF was already under construction and an immediate hardware fix in tandem with flowsheet changes was necessary. However, the Hanford Waste Vitrification Plant (HWVP) was in the design phase and could afford to take time to investigate flowsheet manipulations that could solve the problem, rather than a hardware fix. Thus, the HWVP began to investigate alternatives to using HCOOH in the vitrification process. This document describes the selection, evaluation criteria, and strategy used to evaluate the performance of the alternative chemical additives to CHOOH. The status of the evaluation is also discussed.

  20. Fission-chamber-compensated self-powered detector for in-core flux measurement and reactor control

    SciTech Connect (OSTI)

    Neissel, J.P.

    1986-04-15T23:59:59.000Z

    An apparatus is described for in-core flux measurement and nuclear reactor control consisting of: a self-powered rhodium neutron detector for producing an output signal corresponding to reactor power level; first amplifier means having an input for receiving the neutron detector output signal, and the first amplifier means producing a corresponding first amplifier output signal (V/sub 1/); a fission chamber for producing an output signal corresponding to reactor power level; second amplifier means having an input for receiving the fission chamber output signal, the second amplifier means producing a corresponding second amplifier output signal; first differentiating means coupled to the output of the second amplifier means including a resistor and a capacitor coupled to provide a time constant T/sub 1//1n 2 where T/sub 1/ is the half-life of the ground state of Rh/sup 104/; third amplifier means having an input for receiving the second amplifier means output signal, the third amplifier means having a voltage gain of (1-c)/c; second differentiating means coupled to the output of the third amplifying means and including a capacitor and resistor providing a time constant T/sub 2//1n 2 where T/sub 2/ is the half-life of the isomeric state of Rh/sup 104/; and fourth amplifier means including corresponding inputs for receiving the output of the first amplifier means, a processed output from the first differentiating circuit, and a processed output from the second differentiating circuit, and for producing a corresponding summed output signal.

  1. Fate of Noble Metals during the Pyroprocessing of Spent Nuclear Fuel

    SciTech Connect (OSTI)

    B.R. Westphal; D. Vaden; S.X. Li; G.L. Fredrickson; R.D. Mariani

    2009-09-01T23:59:59.000Z

    During the pyroprocessing of spent nuclear fuel by electrochemical techniques, fission products are separated as the fuel is oxidized at the anode and refined uranium is deposited at the cathode. Those fission products that are oxidized into the molten salt electrolyte are considered active metals while those that do not react are considered noble metals. The primary noble metals encountered during pyroprocessing are molybdenum, zirconium, ruthenium, rhodium, palladium, and technetium. Pyroprocessing of spent fuel to date has involved two distinctly different electrorefiner designs, in particular the anode to cathode configuration. For one electrorefiner, the anode and cathode collector are horizontally displaced such that uranium is transported across the electrolyte medium. As expected, the noble metal removal from the uranium during refining is very high, typically in excess of 99%. For the other electrorefiner, the anode and cathode collector are vertically collocated to maximize uranium throughput. This arrangement results in significantly less noble metals removal from the uranium during refining, typically no better than 20%. In addition to electrorefiner design, operating parameters can also influence the retention of noble metals, albeit at the cost of uranium recovery. Experiments performed to date have shown that as much as 100% of the noble metals can be retained by the cladding hulls while affecting the uranium recovery by only 6%. However, it is likely that commercial pyroprocessing of spent fuel will require the uranium recovery to be much closer to 100%. The above mentioned design and operational issues will likely be driven by the effects of noble metal contamination on fuel fabrication and performance. These effects will be presented in terms of thermal properties (expansion, conductivity, and fusion) and radioactivity considerations. Ultimately, the incorporation of minor amounts of noble metals from pyroprocessing into fast reactor metallic fuel will be shown to be of no consequence to reactor performance.

  2. Macroscopic x-ray fluorescence capability for large-scale elemental mapping

    SciTech Connect (OSTI)

    Volz, Heather M [Los Alamos National Laboratory; Havrilla, George J [Los Alamos National Laboratory; Aikin, Jr., Robert M [Los Alamos National Laboratory; Montoya, Velma M [Los Alamos National Laboratory

    2010-01-01T23:59:59.000Z

    A non-destructive method of determining segregation of constituent elements over large length-scales is desired. Compositional information to moderate resolution over centimeters will be powerful not only to validate casting models but also to understand large-scale phenomena during solidification. To this end, they have rebuilt their XRF capability in conjunction with IXRF Systems, Inc. (Houston, TX) to accommodate samples that are much larger than those that typically fit into an XRF instrument chamber (up to 70 cm x 70 cm x 25 cm). This system uses a rhodium tube with maximum power of 35 kV and 100 {mu}A, the detector is a liquid nitrogen cooled lithium drifted silicon detector, and the smallest spot size is approximately 0.4 mm. Reference standard specimens will enable quantitative elemental mapping and analysis. Challenges to modifying the equipment are described. Non-uniformities in the Inconel 718 system will be shown and discussed. As another example, segregation of niobium or molybdenum in depleted uranium (DU) castings has been known to occur based on wet chemical anslysis (ICP-MS), but this destructive and time-consuming measurement is not practical for routine inspection of ingots. The U-Nb system is complicated due to overlap of the Nb K-alpha line with the U L-beta. Preliminary quantitative results are included on the distribution of Nb across slices from DU castings with different cooling rates. They foresee this macro-XRF elemental mapping capability to prove invaluable to many in the materials processing industry.

  3. Final Report: Investigation of Catalytic Pathways for Lignin Breakdown into Monomers and Fuels

    SciTech Connect (OSTI)

    Gluckstein, Jeffrey A [ORNL; Hu, Michael Z. [ORNL; Kidder, Michelle [ORNL; McFarlane, Joanna [ORNL; Narula, Chaitanya Kumar [ORNL; Sturgeon, Matthew R [ORNL

    2010-12-01T23:59:59.000Z

    Lignin is a biopolymer that comprises up to 35% of woody biomass by dry weight. It is currently underutilized compared to cellulose and hemicellulose, the other two primary components of woody biomass. Lignin has an irregular structure of methoxylated aromatic groups linked by a suite of ether and alkyl bonds which makes it difficult to degrade selectively. However, the aromatic components of lignin also make it promising as a base material for the production of aromatic fuel additives and cyclic chemical feed stocks such as styrene, benzene, and cyclohexanol. Our laboratory research focused on three methods to selectively cleave and deoxygenate purified lignin under mild conditions: acidolysis, hydrogenation and electrocatalysis. (1) Acidolysis was undertaken in CH2Cl2 at room temperature. (2) Hydrogenation was carried out by dissolving lignin and a rhodium catalyst in 1:1 water:methoxyethanol under a 1 atm H2 environment. (3) Electrocatalysis of lignin involved reacting electrically generated hydrogen atoms at a catalytic palladium cathode with lignin dissolved in a solution of aqueous methanol. In all of the experiments, the lignin degradation products were identified and quantified by gas chromatography mass spectroscopy and flame ionization detection. Yields were low, but this may have reflected the difficulty in recovering the various fractions after conversion. The homogeneous hydrogenation of lignin showed fragmentation into monomers, while the electrocatalytic hydrogenation showed production of polyaromatic hydrocarbons and substituted benzenes. In addition to the experiments, promising pathways for the conversion of lignin were assessed. Three conversion methods were compared based on their material and energy inputs and proposed improvements using better catalyst and process technology. A variety of areas were noted as needing further experimental and theoretical effort to increase the feasibility of lignin conversion to fuels.

  4. Optimum catalytic process for alcohol fuels from syngas: Second quarterly technical progress report

    SciTech Connect (OSTI)

    Not Available

    1987-07-30T23:59:59.000Z

    A base case process for economic studies of making fuel alcohols from syngas has been developed. It uses existing technologies which have been demonstrated to be feasible or have already been commercialized. The process consists of the following steps: coal or natural gas (reforming or partial oxidation) to syngas; syngas to methanol by ICI technology; methanol to light olefins by proprietary UCC technology using molecular sieves; olefins to alcohols by hydroformylation (with a homogeneous rhodium catalyst) followed by hydrogenation. Process economics for the two natural gas-based routes have been developed. With insights gained from this, an optimized and integrated multi-step process has been conceptualized which allows estimation of the lowest cost at which fuel alcohols can be produced. A 60% methanol and 40% higher alcohol mix was assumed to be a suitable fuel alcohol blend for gasoline. At a natural gas price of $2/MMBTU, the cost of producing this, by either partial oxidation or reforming, is $1.12/gal. An integrated process with autothermal reforming at 750 psia and methanol synthesis at 700 psia allows incorporation of the best features of reforming and partial oxidation as well as elimination of syngas compression. The production cost of fuel alcohols by this process is estimated to be $0.90/gal. This is, therefore, the lowest cost at which fuel alcohols can be produced by an integrated, multi-step process. An ''ideal'' process has also been conceptualized which establishes a target production cost that new technology should strive for to be competitive. This process incorporates autothermal reforming for producing syngas followed by conversion to fuel alcohols using emerging technologies. The target production cost is estimated to be $0.65/gal. 16 figs., 10 tabs.

  5. Analytical Results of DWPF Glass Sample Taken During Pouring of Canister S01913

    SciTech Connect (OSTI)

    Bannochie, C

    2005-10-01T23:59:59.000Z

    The Defense Waste Processing Facility (DWPF) began processing Sludge Batch 2 (SB2) (Macrobatch 3) in December 2001 as part of Sludge Receipt and Adjustment Tank (SRAT) Batch 208. Macrobatch 3 consists of the contents of Tank 40 and Tank 8 in approximately equal proportions. A glass sample was obtained while pouring Canister S01913 and was sent to the Savannah River National Laboratory (SRNL) Shielded Cells for characterization. This report contains observations of the glass sample, results for the density, the chemical composition, the Product Consistency Test (PCT) and the radionuclide results needed for the Production Record for Canister S01913. The following conclusions are drawn from this work: (1) The glass sample taken during the filling of canister S01913 received at SRNL weighed 33.04 grams and was dark and reflective with no obvious inclusions indicating the glass was homogeneous. (2) The results of the composition for glass sample S01913 are in good agreement ({+-} 15%) with the DWPF SME results for Batch Number 254, the SME Batch that was being fed to the melter when the sample was collected. (3) The calculated WDF was 2.58. (4) Acid dissolution of the glass samples may not have completely dissolved the noble metals rhodium and ruthenium. (5) The PCT results for the glass (normalized boron release of 1.18 g/L) indicate that it is greater than seven standard deviations more durable than the EA glass; thus, the glass meets the waste acceptance criterion for durability. (6) The measured density of the glass was 2.56 {+-} 0.03 g/cm{sup 3}.

  6. Nuclear Fuel Reprocessing

    SciTech Connect (OSTI)

    Harold F. McFarlane; Terry Todd

    2013-11-01T23:59:59.000Z

    Reprocessing is essential to closing nuclear fuel cycle. Natural uranium contains only 0.7 percent 235U, the fissile (see glossary for technical terms) isotope that produces most of the fission energy in a nuclear power plant. Prior to being used in commercial nuclear fuel, uranium is typically enriched to 35% in 235U. If the enrichment process discards depleted uranium at 0.2 percent 235U, it takes more than seven tonnes of uranium feed to produce one tonne of 4%-enriched uranium. Nuclear fuel discharged at the end of its economic lifetime contains less one percent 235U, but still more than the natural ore. Less than one percent of the uranium that enters the fuel cycle is actually used in a single pass through the reactor. The other naturally occurring isotope, 238U, directly contributes in a minor way to power generation. However, its main role is to transmute into plutoniumby neutron capture and subsequent radioactive decay of unstable uraniumand neptuniumisotopes. 239Pu and 241Pu are fissile isotopes that produce more than 40% of the fission energy in commercially deployed reactors. It is recovery of the plutonium (and to a lesser extent the uranium) for use in recycled nuclear fuel that has been the primary focus of commercial reprocessing. Uraniumtargets irradiated in special purpose reactors are also reprocessed to obtain the fission product 99Mo, the parent isotope of technetium, which is widely used inmedical procedures. Among the fission products, recovery of such expensive metals as platinum and rhodium is technically achievable, but not economically viable in current market and regulatory conditions. During the past 60 years, many different techniques for reprocessing used nuclear fuel have been proposed and tested in the laboratory. However, commercial reprocessing has been implemented along a single line of aqueous solvent extraction technology called plutonium uranium reduction extraction process (PUREX). Similarly, hundreds of types of reactor fuels have been irradiated for different purposes, but the vast majority of commercial fuel is uranium oxide clad in zirconium alloy tubing. As a result, commercial reprocessing plants have relatively narrow technical requirements for used nuclear that is accepted for processing.

  7. Process for alkane group dehydrogenation with organometallic catalyst

    DOE Patents [OSTI]

    Kaska, W.C.; Jensen, C.M.

    1998-07-14T23:59:59.000Z

    An improved process is described for the catalytic dehydrogenation of organic molecules having a ##STR1## group to produce a ##STR2## group. The organic molecules are: ##STR3## wherein: A.sup.1, A.sup.2, A.sup.3, and A.sup.4 are each independently P, As or N: E.sup.2 is independently C or N; E.sup.3 is independently C, Si or Ge; E.sup.4 is independently C, Si, or Ge; and E.sup.5 is independently C, Si or Ge; M.sup.1, M.sup.2, M.sup.3, and M.sup.4 each is a metal atom independently selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum; Q.sup.1, Q.sup.2, Q.sup.3, and Q.sup.4 are each independently a direct bond, --CH.sub.2 --, --CH.sub.2 CH.sub.2 --, or CH.dbd.CH--; in structure I, structure II or structure IV, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently selected from alkyl, alkenyl, cycloalkyl, and aryl, or R.sup.1 and R.sup.2 together and R.sup.3 and R.sup.4 together form a ring structure having from 4 to 10 carbon atoms, or in structure III, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are each independently selected from alkyl, alkenyl, cycloalkyl, and aryl, or R.sup.5 and R.sup.6 together and R.sup.7 and R.sup.8 together form a ring structure having from 4 to 10 carbon atoms, at a temperature of between about 100.degree. and 250.degree. C. for between about 1 hr and 300 days in the absence of N.sub.2. The surprisingly stable catalyst is a complex of an organic ligand comprising H, C, Si, N, P atoms, and a platinum group metal. The dehydrogenation is performed between about 100 to 200.degree. C., and has increased turnover.

  8. Process for alkane group dehydrogenation with organometallic catalyst

    DOE Patents [OSTI]

    Kaska, William C. (Goleta, CA); Jensen, Craig M. (Kailua, HI)

    1998-01-01T23:59:59.000Z

    An improved process is described for the catalytic dehydrogenation of organic molecules having a ##STR1## group to produce a ##STR2## group. The organic molecules are: ##STR3## wherein: A.sup.1, A.sup.2, A.sup.3, and A.sup.4 are each independently P, As or N: E.sup.2 is independently C or N; E.sup.3 is independently C, Si or Ge; E.sup.4 is independently C, Si, or Ge; and E.sup.5 is independently C, Si or Ge; M.sup.1, M.sup.2, M.sup.3, and M.sup.4 each is a metal atom independently selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum; Q.sup.1, Q.sup.2, Q.sup.3, and Q.sup.4 are each independently a direct bond, --CH.sub.2 --, --CH.sub.2 CH.sub.2 --, or CH.dbd.CH--; in structure I, structure II or structure IV, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently selected from alkyl, alkenyl, cycloalkyl, and aryl, or R.sup.1 and R.sup.2 together and R.sup.3 and R.sup.4 together form a ring structure having from 4 to 10 carbon atoms, or in structure III, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are each independently selected from alkyl, alkenyl, cycloalkyl, and aryl, or R.sup.5 and R.sup.6 together and R.sup.7 and R.sup.8 together form a ring structure having from 4 to 10 carbon atoms, at a temperature of between about 100.degree. and 250.degree. C. for between about 1 hr and 300 days in the absence of N.sub.2. The surprisingly stable catalyst is a complex of an organic ligand comprising H, C, Si, N, P atoms, and a platinum group metal. The dehydrogenation is performed between about 100 to 200.degree. C., and has increased turnover.

  9. TEMPERATURE MONITORING OPTIONS AVAILABLE AT THE IDAHO NATIONAL LABORATORY ADVANCED TEST REACTOR

    SciTech Connect (OSTI)

    J.E. Daw; J.L. Rempe; D.L. Knudson; T. Unruh; B.M. Chase; K.L Davis

    2012-03-01T23:59:59.000Z

    As part of the Advanced Test Reactor National Scientific User Facility (ATR NSUF) program, the Idaho National Laboratory (INL) has developed in-house capabilities to fabricate, test, and qualify new and enhanced sensors for irradiation testing. To meet recent customer requests, an array of temperature monitoring options is now available to ATR users. The method selected is determined by test requirements and budget. Melt wires are the simplest and least expensive option for monitoring temperature. INL has recently verified the melting temperature of a collection of materials with melt temperatures ranging from 100 to 1000 C with a differential scanning calorimeter installed at INLs High Temperature Test Laboratory (HTTL). INL encapsulates these melt wires in quartz or metal tubes. In the case of quartz tubes, multiple wires can be encapsulated in a single 1.6 mm diameter tube. The second option available to ATR users is a silicon carbide temperature monitor. The benefit of this option is that a single small monitor (typically 1 mm x 1 mm x 10 mm or 1 mm diameter x 10 mm length) can be used to detect peak irradiation temperatures ranging from 200 to 800 C. Equipment has been installed at INLs HTTL to complete post-irradiation resistivity measurements on SiC monitors, a technique that has been found to yield the most accurate temperatures from these monitors. For instrumented tests, thermocouples may be used. In addition to Type-K and Type-N thermocouples, a High Temperature Irradiation Resistant ThermoCouple (HTIR-TC) was developed at the HTTL that contains commercially-available doped molybdenum paired with a niobium alloy thermoelements. Long duration high temperature tests, in furnaces and in the ATR and other MTRs, demonstrate that the HTIR-TC is accurate up to 1800 C and insensitive to thermal neutron interactions. Thus, degradation observed at temperatures above 1100 C with Type K and N thermocouples and decalibration due to transmutation with tungsten-rhenium and platinum rhodium thermocouples can be avoided. INL is also developing an Ultrasonic Thermometry (UT) capability. In addition to small size, UTs offer several potential advantages over other temperature sensors. Measurements may be made near the melting point of the sensor material, potentially allowing monitoring of temperatures up to 3000 C. In addition, because no electrical insulation is required, shunting effects are avoided. Most attractive, however, is the ability to introduce acoustic discontinuities to the sensor, as this enables temperature measurements at several points along the sensor length. As discussed in this paper, the suite of temperature monitors offered by INL is not only available to ATR users, but also to users at other MTRs.

  10. Evaluation of Alternate Materials for Coated Particle Fuels for the Gas-Cooled Fast Reactor. Laboratory Directed Research and Development Program FY 2006 Final Report

    SciTech Connect (OSTI)

    Paul A. Demkowicz; Karen Wright; Jian Gan; David Petti; Todd Allen; Jake Blanchard

    2006-09-01T23:59:59.000Z

    Candidate ceramic materials were studied to determine their suitability as Gas-Cooled Fast Reactor particle fuel coatings. The ceramics examined in this work were: TiC, TiN, ZrC, ZrN, AlN, and SiC. The studies focused on (i) chemical reactivity of the ceramics with fission products palladium and rhodium, (ii) the thermomechanical stresses that develop in the fuel coatings from a variety of causes during burnup, and (iii) the radiation resiliency of the materials. The chemical reactivity of TiC, TiN, ZrC, and ZrN with Pd and Rh were all found to be much lower than that of SiC. A number of important chemical behaviors were observed at the ceramic-metal interfaces, including the formation of specific intermetallic phases and a variation in reaction rates for the different ceramics investigated. Based on the data collected in this work, the nitride ceramics (TiN and ZrN) exhibit chemical behavior that is characterized by lower reaction rates with Pd and Rh than the carbides TiC and ZrC. The thermomechanical stresses in spherical fuel particle ceramic coatings were modeled using finite element analysis, and included contributions from differential thermal expansion, fission gas pressure, fuel kernel swelling, and thermal creep. In general the tangential stresses in the coatings during full reactor operation are tensile, with ZrC showing the lowest values among TiC, ZrC, and SiC (TiN and ZrN were excluded from the comprehensive calculations due to a lack of available materials data). The work has highlighted the fact that thermal creep plays a critical role in the development of the stress state of the coatings by relaxing many of the stresses at high temperatures. To perform ion irradiations of sample materials, an irradiation beamline and high-temperature sample irradiation stage was constructed at the University of Wisconsins 1.7MV Tandem Accelerator Facility. This facility is now capable of irradiating of materials to high dose while controlling sample temperature up to 800C.

  11. Analysis Of The Sludge Batch 7b (Macrobatch 9) DWPF Pour Stream Glass Sample

    SciTech Connect (OSTI)

    Johnson, F. C.; Crawford, C. L.; Pareizs, J. M.

    2013-11-18T23:59:59.000Z

    The Defense Waste Processing Facility (DWPF) began processing Sludge Batch 7b (SB7b), also referred to as Macrobatch 9 (MB9), in January 2012. SB7b is a blend of the heel of Tank 40 from Sludge Batch 7a (SB7a) and the SB7b material that was transferred to Tank 40 from Tank 51. SB7b was processed using Frit 418. During processing of each sludge batch, the DWPF is required to take at least one glass sample to meet the objectives of the Glass Product Control Program (GPCP), which is governed by the DWPF Waste Form Compliance Plan, and to complete the necessary Production Records so that the final glass product may be disposed of at a Federal Repository. Two pour stream glass samples were collected while processing SB7b. The samples were transferred to the Savannah River National Laboratory (SRNL) where one was analyzed and the other was archived. The following conclusions were drawn from the analytical results provided in this report: The sum of oxides for the official SB7b pour stream glass is within the Product Composition Control System (PCCS) limits (95-105 wt%); The average calculated Waste Dilution Factor (WDF) for SB7b is 2.3. In general, the measured radionuclide content of the official SB7b pour stream glass is in good agreement with the calculated values from the Tank 40 dried sludge results from the SB7b Waste Acceptance Program Specification (WAPS) sample; As in previous pour stream samples, ruthenium and rhodium inclusions were detected by Scanning Electron Microscopy-Electron Dispersive Spectroscopy (SEM-EDS) in the SB7b pour stream sample; The Product Consistency Test (PCT) results indicate that the official SB7b pour stream glass meets the waste acceptance criteria for durability with a normalized boron release of 0.8 g/L, which is an order of magnitude less than the Environmental Assessment (EA) glass; The measured density of the SB7b pour stream glass was 2.70 g/cm{sup 3}; The Fe{sup 2+}/?Fe ratio of the SB7b pour stream samples was 0.07.

  12. Colloidally Synthesized Monodisperse Rh Nanoparticles Supported on SBA-15 for Size- and Pretreatment-Dependent Studies of CO Oxidation

    SciTech Connect (OSTI)

    Grass, Michael E.; Joo, Sang Hoon; Somorjai, Gabor A.

    2009-02-12T23:59:59.000Z

    A particle size dependence for CO oxidation over rhodium nanoparticles of 1.9-11.3 nm has been investigated and determined to be modified by the existence of the capping agent poly(vinylpyrrolidone) (PVP). The particles were prepared using a polyol reduction procedure with PVP as the capping agent. The Rh nanoparticles were subsequently supported on SBA-15 during hydrothermal synthesis to produce Rh/SBA-15 supported catalysts for size-dependent catalytic studies. CO oxidation by O{sub 2} at 40 Torr CO and 100 Torr O{sub 2} was investigated over two series of Rh/SBA-15 catalysts: as-synthesized Rh/SBA-15 covering the full range of Rh sizes and the same set of catalysts after high temperature calcination and reduction. The turnover frequency at 443 K increases from 0.4 to 1.7 s{sup -1} as the particle size decreases from 11.3 to 1.9 nm for the as-synthesized catalysts. After calcination and reduction, the turnover frequency is between 0.1 and 0.4 s{sup -1} with no particle size dependence. The apparent activation energy for all catalysts is {approx}30 kcal mol{sup -1} and is independent of particle size and thermal treatment. Infrared spectroscopy of CO on the Rh nanoparticles indicates that the heat treatments used influence the mode of CO adsorption. As a result, the particle size dependence for CO oxidation is altered after calcination and reduction of the catalysts. CO adsorbs at two distinct bridge sites on as-synthesized Rh/SBA-15, attributable to metallic Rh(0) and oxidized Rh(I) bridge sites. After calcination and reduction, however, CO adsorbs only at Rh(0) atop sites. The change in adsorption geometry and oxidation activity may be attributable to the interaction between PVP and the Rh surface. This capping agent affect may open new possibilities for the tailoring of metal catalysts using solution nanoparticle synthesis methods.

  13. ANALYSIS OF DWPF SLUDGE BATCH 7A (MACROBATCH 8) POUR STREAM SAMPLES

    SciTech Connect (OSTI)

    Johnson, F.

    2012-05-01T23:59:59.000Z

    The Defense Waste Processing Facility (DWPF) began processing Sludge Batch 7a (SB7a), also referred to as Macrobatch 8 (MB8), in June 2011. SB7a is a blend of the heel of Tank 40 from Sludge Batch 6 (SB6) and the SB7a material that was transferred to Tank 40 from Tank 51. SB7a was processed using Frit 418. During processing of each sludge batch, the DWPF is required to take at least one glass sample to meet the objectives of the Glass Product Control Program (GPCP), which is governed by the DWPF Waste Compliance Plan, and to complete the necessary Production Records so that the final glass product may be disposed of at a Federal Repository. Three pour stream glass samples and two Melter Feed Tank (MFT) slurry samples were collected while processing SB7a. These additional samples were taken during SB7a to understand the impact of antifoam and the melter bubblers on glass redox chemistry. The samples were transferred to the Savannah River National Laboratory (SRNL) where they were analyzed. The following conclusions were drawn from the analytical results provided in this report: (1) The sum of oxides for the official SB7a pour stream glass is within the Product Composition Control System (PCCS) limits (95-105 wt%). (2) The average calculated Waste Dilution Factor (WDF) for SB7a is 2.3. In general, the measured radionuclide content of the official SB7a pour stream glass is in good agreement with the calculated values from the Tank 40 dried sludge results from the SB7a Waste Acceptance Program Specification (WAPS) sample. (3) As in previous pour stream samples, ruthenium and rhodium inclusions were detected by Scanning Electron Microscopy-Electron Dispersive Spectroscopy (SEM-EDS) in the official SB7a pour stream sample. (4) The Product Consistency Test (PCT) results indicate that the official SB7a pour stream glass meets the waste acceptance criteria for durability with a normalized boron release of 0.64 g/L, which is an order of magnitude less than the Environmental Assessment (EA) glass. (5) The measured density of the SB7a pour stream glass was 2.7 g/cm{sup 3}. (6) The Fe{sup 2+}/{Sigma}Fe ratios of the SB7a pour stream samples were in the range of 0.04-0.13, while the MFT sample glasses prepared by SRNL were in the range of 0.02-0.04.

  14. Elimination Of Catalytic Hydrogen Generation In Defense Waste Processing Facility Slurries

    SciTech Connect (OSTI)

    Koopman, D. C.

    2013-01-22T23:59:59.000Z

    Based on lab-scale simulations of Defense Waste Processing Facility (DWPF) slurry chemistry, the addition of sodium nitrite and sodium hydroxide to waste slurries at concentrations sufficient to take the aqueous phase into the alkaline region (pH > 7) with approximately 500 mg nitrite ion/kg slurry (assuming <25 wt% total solids, or equivalently 2,000 mg nitrite/kg total solids) is sufficient to effectively deactivate the noble metal catalysts at temperatures between room temperature and boiling. This is a potential strategy for eliminating catalytic hydrogen generation from the list of concerns for sludge carried over into the DWPF Slurry Mix Evaporator Condensate Tank (SMECT) or Recycle Collection Tank (RCT). These conclusions are drawn in large part from the various phases of the DWPF catalytic hydrogen generation program conducted between 2005 and 2009. The findings could apply to various situations, including a solids carry-over from either the Sludge Receipt and Adjustment Tank (SRAT) or Slurry Mix Evaporator (SME) into the SMECT with subsequent transfer to the RCT, as well as a spill of formic acid into the sump system and transfer into an RCT that already contains sludge solids. There are other potential mitigating factors for the SMECT and RCT, since these vessels are typically operated at temperatures close to the minimum temperatures that catalytic hydrogen has been observed to occur in either the SRAT or SME (pure slurry case), and these vessels are also likely to be considerably more dilute in both noble metals and formate ion (the two essential components to catalytic hydrogen generation) than the two primary process vessels. Rhodium certainly, and ruthenium likely, are present as metal-ligand complexes that are favored under certain concentrations of the surrounding species. Therefore, in the SMECT or RCT, where a small volume of SRAT or SME material would be significantly diluted, conditions would be less optimal for forming or sustaining the catalytic ligand species. Such conditions are likely to adversely impact the ability of the transferred mass to produce hydrogen at the same rate (per unit mass SRAT or SME slurry) as in the SRAT or SME vessels.

  15. Integrated superhard and metallic coatings for MEMS : LDRD 57300 final report.

    SciTech Connect (OSTI)

    de Boer, Maarten Pieter; Maboudian, Roya (University of California at Berkeley, Berkeley, CA.)

    2004-12-01T23:59:59.000Z

    Two major research areas pertinent to microelectromechanical systems (MEMS) materials and material surfaces were explored and developed in this 5-year PECASE LDRD project carried out by Professor Roya Maboudian and her collaborators at the University of California at Berkeley. In the first research area, polycrystalline silicon carbide (poly-SiC) was developed as a structural material for MEMS. This material is potentially interesting for MEMS because compared to polycrystalline silicon (polysilicon), the structural material in Sandia National Laboratories' SUMMiTV process, it may exhibit high wear resistance, high temperature operation and a high Young's modulus to density ratio. Each of these characteristics may extend the usefulness of MEMS in Sandia National Laboratories' applications. For example, using polycrystalline silicon, wear is an important issue in microengines, temperature degradation is of concern in thermal actuators and the characteristics of resonators can be extended with the same lithography technology. Two methods of depositing poly-SiC from a 1,3-disilabutane source at 650 C to 800 C by low-pressure chemical vapor deposition (LPCVD) were demonstrated. These include a blanket method in which the material is made entirely out of poly-SiC and a method to coat previously released and fabricated polysilicon MEMS. This deposition method is much simpler to use than previous methods such as high temperature LPCVD and atmospheric CVD. Other major processing issues that were surmounted in this LDRD with the poly-SiC film include etching, doping, and residual strain control. SiC is inert and as such is notoriously difficult to etch. Here, an HBr-based chemistry was demonstrated for the first time to make highly selective etching of SiC at high etch rates. Nitrogen was incorporated from an NH3 gas source, resulting in high conductivity films. Residual strain and strain gradient were shown to depend on deposition parameters, and can be made negative or positive. The tribology of poly-SiC was also investigated. Much improved release stiction and in-use stiction performance relative to polysilicon MEMS was found. Furthermore, wear of poly-SiC-coated MEMS was much reduced relative to uncoated polysilicon MEMS. A prototype baseline process flow now exists to produce poly-SiC in the Berkeley Sensor and Actuator (BSAC) facility. In the second project, galvanic deposition of metals onto polysilicon surfaces has been developed. The possible applications include reflective and optical coatings for optical MEMS, microswitches and microrelays for radio frequency MEMS and catalytic surfaces for microchemical reactors. In contrast to electroless deposition, galvanic displacement deposition requires no prior activation of the surface and is truly selective to silicon surfaces. This approach was used to deposit copper, gold and rhodium onto polysilicon MEMS. A method to study the adhesion of these metals to polysilicon was developed. It was also shown that the surfaces could be rendered hydrophobic by applying thiol-based self-assembled monolayers. This procedure also lowered their surface energy to {approx}3 {micro}J/m{sup 2}, consistent with monolayer-coated polysilicon MEMS.

  16. Critical experiments at Sandia National Laboratories : technical meeting on low-power critical facilities and small reactors.

    SciTech Connect (OSTI)

    Harms, Gary A.; Ford, John T.; Barber, Allison Delo

    2010-11-01T23:59:59.000Z

    Sandia National Laboratories (SNL) has conducted radiation effects testing for the Department of Energy (DOE) and other contractors supporting the DOE since the 1960's. Over this period, the research reactor facilities at Sandia have had a primary mission to provide appropriate nuclear radiation environments for radiation testing and qualification of electronic components and other devices. The current generation of reactors includes the Annular Core Research Reactor (ACRR), a water-moderated pool-type reactor, fueled by elements constructed from UO2-BeO ceramic fuel pellets, and the Sandia Pulse Reactor III (SPR-III), a bare metal fast burst reactor utilizing a uranium-molybdenum alloy fuel. The SPR-III is currently defueled. The SPR Facility (SPRF) has hosted a series of critical experiments. A purpose-built critical experiment was first operated at the SPRF in the late 1980's. This experiment, called the Space Nuclear Thermal Propulsion Critical Experiment (CX), was designed to explore the reactor physics of a nuclear thermal rocket motor. This experiment was fueled with highly-enriched uranium carbide fuel in annular water-moderated fuel elements. The experiment program was completed and the fuel for the experiment was moved off-site. A second critical experiment, the Burnup Credit Critical Experiment (BUCCX) was operated at Sandia in 2002. The critical assembly for this experiment was based on the assembly used in the CX modified to accommodate low-enriched pin-type fuel in water moderator. This experiment was designed as a platform in which the reactivity effects of specific fission product poisons could be measured. Experiments were carried out on rhodium, an important fission product poison. The fuel and assembly hardware for the BUCCX remains at Sandia and is available for future experimentation. The critical experiment currently in operation at the SPRF is the Seven Percent Critical Experiment (7uPCX). This experiment is designed to provide benchmark reactor physics data to support validation of the reactor physics codes used to design commercial reactor fuel elements in an enrichment range above the current 5% enrichment cap. A first set of critical experiments in the 7uPCX has been completed. More experiments are planned in the 7uPCX series. The critical experiments at Sandia National Laboratories are currently funded by the US Department of Energy Nuclear Criticality Safety Program (NCSP). The NCSP has committed to maintain the critical experiment capability at Sandia and to support the development of a critical experiments training course at the facility. The training course is intended to provide hands-on experiment experience for the training of new and re-training of practicing Nuclear Criticality Safety Engineers. The current plans are for the development of the course to continue through the first part of fiscal year 2011 with the development culminating is the delivery of a prototype of the course in the latter part of the fiscal year. The course will be available in fiscal year 2012.

  17. Small, Inexpensive Combined NOx Sensor and O2 Sensor

    SciTech Connect (OSTI)

    W. N. Lawless; C. F. Clark, Jr.

    2008-09-08T23:59:59.000Z

    It has been successfully demonstrated in this program that a zirconia multilayer structure with rhodium-based porous electrodes performs well as an amperometric NOx sensor. The sensitivity of the sensor bodies operating at 650 to 700 C is large, with demonstrated current outputs of 14 mA at 500 ppm NOx from sensors with 30 layers. The sensor bodies are small (4.5 x 4.2 x 3.1 mm), rugged, and inexpensive. It is projected the sensor bodies will cost $5 - $10 in production. This program has built on another successful development program for an oxygen sensor based on the same principles and sponsored by DOE. This oxygen sensor is not sensitive to NOx. A significant technical hurdle has been identified and solved. It was found that the 100% Rh electrodes oxidize rapidly at the preferred operating temperatures of 650 - 700 C, and this oxidation is accompanied by a volume change which delaminates the sensors. The problem was solved by using alloys of Rh and Pt. It was found that a 10%/90% Rh/Pt alloy dropped the oxidation rate of the electrodes by orders of magnitude without degrading the NOx sensitivity of the sensors, allowing long-term stable operation at the preferred operating temperatures. Degradation in the sensor output caused by temperature cycling was identified as a change in resistance at the junction between the sensor body and the external leads attached to the sensor body. The degradation was eliminated by providing strong mechanical anchors for the wire and processing the junctions to obtain good electrical bonds. The NOx sensors also detect oxygen and therefore the fully-packaged sensor needs to be enclosed with an oxygen sensor in a small, heated zirconia chamber exposed to test gas through a diffusion plug which limits the flow of gas from the outside. Oxygen is pumped from the interior of the chamber to lower the oxygen content and the combination of measurements from the NOx and oxygen sensors yields the NOx content of the gas. Two types of electronic control units were designed and built. One control unit provides independent constant voltages to the NOx and oxygen sensors and reads the current from them (that is, detects the amount of test gas present). The second controller holds the fully-assembled sensor at the desired operating temperature and controllably pumps excess oxygen from the test chamber. While the development of the sensor body was a complete success, the development of the packaging was only partially successful. All of the basic principles were demonstrated, but the packaging was too complex to optimize the operation within the resources of the program. Thus, no fully-assembled sensors were sent to outside labs for testing of cross-sensitivities, response times, etc. Near the end of the program, Sensata Technologies of Attleboro, MA tested the sensor bodies and confirmed the CeramPhysics measurements as indicated in the following attached letter. Sensata was in the process of designing their own packaging for the sensor and performing cross-sensitivity tests when they stopped all sensor development work due to the automotive industry downturn. Recently Ceramatec Inc. of Salt Lake City has expressed an interest in testing the sensor, and other licensing opportunities are being pursued.

  18. Small, Inexpensive Combined NOx and O2 Sensor

    SciTech Connect (OSTI)

    W. Lawless; C. Clark

    2008-09-01T23:59:59.000Z

    It has been successfully demonstrated in this program that a zirconia multilayer structure with rhodium-based porous electrodes performs well as an amperometric NO{sub x} sensor. The sensitivity of the sensor bodies operating at 650 to 700 C is large, with demonstrated current outputs of 14 mA at 500 ppm NO{sub x} from sensors with 30 layers. The sensor bodies are small (4.5 x 4.2 x 3.1 mm), rugged, and inexpensive. It is projected the sensor bodies will cost $5-$10 in production. This program has built on another successful development program for an oxygen sensor based on the same principles and sponsored by DOE. This oxygen sensor is not sensitive to NO{sub x}. A significant technical hurdle has been identified and solved. It was found that the 100% Rh electrodes oxidize rapidly at the preferred operating temperatures of 650-700 C, and this oxidation is accompanied by a volume change which delaminates the sensors. The problem was solved by using alloys of Rh and Pt. It was found that a 10%/90% Rh/Pt alloy dropped the oxidation rate of the electrodes by orders of magnitude without degrading the NO{sub x} sensitivity of the sensors, allowing long-term stable operation at the preferred operating temperatures. Degradation in the sensor output caused by temperature cycling was identified as a change in resistance at the junction between the sensor body and the external leads attached to the sensor body. The degradation was eliminated by providing strong mechanical anchors for the wire and processing the junctions to obtain good electrical bonds. The NO{sub x} sensors also detect oxygen and therefore the fully-packaged sensor needs to be enclosed with an oxygen sensor in a small, heated zirconia chamber exposed to test gas through a diffusion plug which limits the flow of gas from the outside. Oxygen is pumped from the interior of the chamber to lower the oxygen content and the combination of measurements from the NO{sub x} and oxygen sensors yields the NO{sub x} content of the gas. Two types of electronic control units were designed and built. One control unit provides independent constant voltages to the NOx and oxygen sensors and reads the current from them (that is, detects the amount of test gas present). The second controller holds the fully-assembled sensor at the desired operating temperature and controllably pumps excess oxygen from the test chamber. While the development of the sensor body was a complete success, the development of the packaging was only partially successful. All of the basic principles were demonstrated, but the packaging was too complex to optimize the operation within the resources of the program. Thus, no fully-assembled sensors were sent to outside labs for testing of cross-sensitivities, response times, etc. Near the end of the program, Sensata Technologies of Attleboro, MA tested the sensor bodies and confirmed the CeramPhysics measurements as indicated in the following attached letter. Sensata was in the process of designing their own packaging for the sensor and performing cross-sensitivity tests when they stopped all sensor development work due to the automotive industry downturn. Recently Ceramatec Inc. of Salt Lake City has expressed an interest in testing the sensor, and other licensing opportunities are being pursued.

  19. DWPF CATALYTIC HYDROGEN GENERATION PROGRAM - REVIEW OF CURRENT STATUS

    SciTech Connect (OSTI)

    Koopman, D.

    2009-07-10T23:59:59.000Z

    Significant progress has been made in the past two years in improving the understanding of acid consumption and catalytic hydrogen generation during the Defense Waste Processing Facility (DWPF) processing of waste sludges in the Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME). This report reviews issues listed in prior internal reviews, describes progress with respect to the recommendations made by the December 2006 external review panel, and presents a summary of the current understanding of catalytic hydrogen generation in the DWPF Chemical Process Cell (CPC). Noble metals, such as Pd, Rh, and Ru, are historically known catalysts for the conversion of formic acid into hydrogen and carbon dioxide. Rh, Ru, and Pd are present in the DWPF SRAT feed as by-products of thermal neutron fission of {sup 235}U in the original waste. Rhodium appears to become most active for hydrogen as the nitrite ion concentration becomes low (within a factor of ten of the Rh concentration). Prior to hydrogen generation, Rh is definitely active for nitrite destruction to N{sub 2}O and potentially active for nitrite to NO formation. These reactions are all consistent with the presence of a nitro-Rh complex catalyst, although definite proof for the existence of this complex during Savannah River Site (SRS) waste processing does not exist. Ruthenium does not appear to become active for hydrogen generation until nitrite destruction is nearly complete (perhaps less nitrite than Ru in the system). Catalytic activity of Ru during nitrite destruction is significantly lower than that of either Rh or Pd. Ru appears to start activating as Rh is deactivating from its maximum catalytic activity for hydrogen generation. The slow activation of the Ru, as inferred from the slow rate of increase in hydrogen generation that occurs after initiation, may imply that some species (perhaps Ru itself) has some bound nitrite on it. Ru, rather than Rh, is primarily responsible for the hydrogen generation in the SME cycle when the hydrogen levels are high enough to be noteworthy. Mercury has a role in catalytic hydrogen generation. Two potentially distinct roles have been identified. The most dramatic effect of Hg on hydrogen generation occurs between runs with and without any Hg. When a small amount of Hg is present, it has a major inhibiting effect on Rh-catalyzed H{sub 2} generation. The Rh-Ru-Hg matrix study showed that increasing mercury from 0.5 to 2.5 wt% in the SRAT receipt total solids did not improve the inhibiting effect significantly. The next most readily identified role for Hg is the impact it has on accelerating NO production from nitrite ion. This reaction shifts the time that the ideal concentration of nitrite relative to Rh occurs, and consequently causes the most active nitro-Rh species to form sooner. The potential consequences of this shift in timing are expected to be a function of other factors such as amount of excess acid, Rh concentration, etc. Graphical data from the Rh-Ru-Hg study suggested that Hg might also be responsible for partially inhibiting Ru-catalysis initially, but that the inhibition was not sustained through the SRAT and SME cycles. Continued processing led to a subsequent increase in hydrogen generation that was often abrupt and that frequently more than doubled the hydrogen generation rate. This phenomenon may have been a function of the extent of Hg stripping versus the initial Ru concentration in these tests. Palladium is an active catalyst, and activates during (or prior to) nitrite destruction to promote N{sub 2}O formation followed by a very small amount of hydrogen. Pd then appears to deactivate. Data to date indicate that Pd should not be a species of primary concern relative to Rh and Ru for hydrogen generation. Pd was a very mild catalyst for hydrogen generation compared to Rh and Ru in the simulated waste system. Pd was comparable to Rh in enhancing N{sub 2}O production when present at equal concentration. Pd, however, is almost always present at less than a quarter of the Rh concentration in S

  20. Transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates: Catalysts for asymmetric olefin hydroamination and acceptorless alcohol decarbonylation

    SciTech Connect (OSTI)

    Manna, Kuntal [Ames Laboratory

    2012-12-17T23:59:59.000Z

    The research presented and discussed in this dissertation involves the synthesis of transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates, and their application in catalytic enantioselective olefin hydroamination and acceptorless alcohol decarbonylation. Neutral oxazolinylboranes are excellent synthetic intermediates for preparing new borate ligands and also developing organometallic complexes. Achiral and optically active bis(oxazolinyl)phenylboranes are synthesized by reaction of 2-lithio-2-oxazolide and 0.50 equiv of dichlorophenylborane. These bis(oxazolinyl)phenylboranes are oligomeric species in solid state resulting from the coordination of an oxazoline to the boron center of another borane monomer. The treatment of chiral bis(oxazolinyl)phenylboranes with sodium cyclopentadienide provide optically active cyclopentadienyl-bis(oxazolinyl)borates H[PhB(C{sub 5}H{sub 5})(Ox{sup R}){sub 2}] [Ox{sup R} = Ox{sup 4S-iPr,Me2}, Ox{sup 4R-iPr,Me2}, Ox{sup 4S-tBu]}. These optically active proligands react with an equivalent of M(NMe{sub 2}){sub 4} (M = Ti, Zr, Hf) to afford corresponding cyclopentadienyl-bis(oxazolinyl)borato group 4 complexes {PhB(C{sub 5}H{sub 4})(Ox{sup R}){sub 2}}M(NMe{sub 2}){sub 2} in high yields. These group 4 compounds catalyze cyclization of aminoalkenes at room temperature or below, providing pyrrolidine, piperidine, and azepane with enantiomeric excesses up to 99%. Our mechanistic investigations suggest a non-insertive mechanism involving concerted C?N/C?H bond formation in the turnover limiting step of the catalytic cycle. Among cyclopentadienyl-bis(oxazolinyl)borato group 4 catalysts, the zirconium complex {PhB(C{sub 5}H{sub 4})(Ox{sup 4S-iPr,Me2}){sub 2}}Zr(NMe{sub 2}){sub 2} ({S-2}Zr(NMe{sub 2}){sub 2}) displays highest activity and enantioselectivity. Interestingly, {S-2}Zr(NMe{sub 2}){sub 2} also desymmetrizes olefin moieties of achiral non-conjugated aminodienes and aminodiynes during cyclization. The cyclization of aminodienes catalyzed by {S-2}Zr(NMe{sub 2}){sub 2} affords diastereomeric mixture of cis and trans cylic amines with high diasteromeric ratios and excellent enantiomeric excesses. Similarly, the desymmetrization of alkyne moieties in {S-2}Zr(NMe{sub 2}){sub 2}-catalyzed cyclization of aminodiynes provides corresponding cyclic imines bearing quaternary stereocenters with enantiomeric excesses up to 93%. These stereoselective desymmetrization reactions are significantly affected by concentration of the substrate, temperature, and the presence of a noncyclizable primary amine. In addition, both the diastereomeric ratios and enantiomeric excesses of the products are markedly enhanced by N-deuteration of the substrates. Notably, the cationic zirconium-monoamide complex [{S-2}Zr(NMe{sub 2})][B(C{sub 6}F{sub 5}){sub 4}] obtained from neutral {S-2}Zr(NMe{sub 2}){sub 2} cyclizes primary aminopentenes providing pyrrolidines with S-configuration; whereas {S-2}Zr(NMe{sub 2}){sub 2} provides R-configured pyrrolidines. The yttrium complex {S-2}YCH{sub 2}SiMe{sub 3} also affords S-configured pyrrolidines by cyclization of aminopentenes, however the enantiomeric excesses of products are low. An alternative optically active yttrium complex {PhB(C{sub 5}H{sub 4})(Ox{sup 4S-tBu}){sub 2}}YCH{sub 2}SiMe{sub 3} ({S-3}YCH{sub 2}SiMe{sub 3}) is synthesized, which displays highly enantioselective in the cyclization of aminoalkenes at room temperature affording S-configured cyclic amines with enantiomeric excesses up to 96%. A noninsertive mechanism involving a six-membered transition state by a concerted C?N bond formation and N?H bond cleavage is proposed for {S-3}YCH{sub 2}SiMe{sub 3} system based on the kinetic, spectroscopic, and stereochemical features. In the end, a series of bis- and tris(oxazolinyl)borato iridium and rhodium complexes are synthesized with bis(oxazolinyl)phenylborane [PhB(Ox{sup Me2}){sub 2}]{sub n}, tris(oxazolinyl)borane [B(Ox{sup Me2}){sub 3}]n, and tris(4,4-dimethyl-2-oxazolinyl)phenylborate [To{sup M}]{sup ?}. All these new an