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Sample records for trevor houser rhodium

  1. Soil Moisture Initialization for Climate Prediction: Characterization of Model and Observation Errors Wenge Ni-Meister (1), Jeffrey Walker(3), and Paul R. Houser (2)

    E-Print Network [OSTI]

    Walker, Jeff

    and Observation Errors Wenge Ni-Meister (1), Jeffrey Walker(3), and Paul R. Houser (2) 1. Department of Geology of the land surface soil moisture states. Passive microwave remote sensing provides quantitative information

  2. 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

  3. Photo by Trevor Marchand Mud Masons of Mali

    E-Print Network [OSTI]

    Miller, Scott

    Photo by Trevor Marchand Mud Masons of Mali opened August 31, 2013 in the Focus Gallery, ob- jects and four films made in collaboration with five masons from Djenné, Mali. Ranging in age century (http://www.mnh.si.edu/ exhibits/mud-masons/). War in northern Mali and the overthrow of the gov

  4. A review of "The Poetics of Melancholy in Early Modern England." by Douglas Trevor 

    E-Print Network [OSTI]

    Thomas P. Anderson

    2005-01-01

    . Douglas Trevor. The Poetics of Melancholy in Early Modern England. Cambridge: Cambridge University Press, 2004. xi + 252 pp. + 9 illus. $75.00. Review by THOMAS P. ANDERSON, MISSISSIPPI STATE UNIVERSITY. Douglas Trevor?s The Poetics of Melancholy... of personally felt passions? (4). In the book?s intro- ductory chapter, the author acknowledges that subjectivity was not invented 172 SEVENTEENTH-CENTURY NEWS during the early modern period, but Renaissance writers did ?invent the locus point of melancholy...

  5. Perception for the Manipulation of Socks Ping Chuan Wang, Stephen Miller, Mario Fritz, Trevor Darrell, Pieter Abbeel

    E-Print Network [OSTI]

    O'Brien, James F.

    Perception for the Manipulation of Socks Ping Chuan Wang, Stephen Miller, Mario Fritz, Trevor no easily-recognizable silhouette, Ping Chuan Wang, Stephen Miller, Trevor Darrell, and Pieter Abbeel

  6. INSTRUMENTATION TOOLS Jim Pierce \\Lambda , Michael D. Smith y , Trevor Mudge \\Lambda

    E-Print Network [OSTI]

    Mudge, Trevor

    . Section 1 describes how instrumentation tools fit into the broad range of techniques available4 INSTRUMENTATION TOOLS Jim Pierce \\Lambda , Michael D. Smith y , Trevor Mudge \\Lambda \\Lambda of Applied Sciences Harvard University, Massachusetts 1 INTRODUCTION The instrumentation of applications

  7. Rhodium-Catalyzed Asymmetric Intramolecular Hydroamination of Unactivated Alkenes

    E-Print Network [OSTI]

    Shen, Xiaoqiang

    One for the Rh(oad): The first rhodium-catalyzed asymmetric intramolecular hydroamination of unactivated olefins was developed by using dialkylbiaryl phosphine ligands (see scheme; cod=1,5-cyclooctadiene, Cy=cyclohexyl). ...

  8. DDR2 and Low Latency Variants Brian Davis, Trevor Mudge Bruce Jacob, Vinodh Cuppu

    E-Print Network [OSTI]

    Mudge, Trevor

    DDR2 and Low Latency Variants Brian Davis, Trevor Mudge Bruce Jacob, Vinodh Cuppu Electrical describes a performance examination the DDR2 DRAM architecture and the proposed cache­enhanced variants. This Task Group responsible for developing DDR2 standard. The goal the Low Latency DRAM Working Group

  9. DDR2 and Low Latency Variants Brian Davis, Trevor Mudge Bruce Jacob, Vinodh Cuppu

    E-Print Network [OSTI]

    Davis, Brian T.

    1 DDR2 and Low Latency Variants Brian Davis, Trevor Mudge Bruce Jacob, Vinodh Cuppu Electrical describes a performance examination of the DDR2 DRAM architecture and the proposed cache-enhanced variants Task Group. This Task Group is responsible for developing the DDR2 standard. The goal of the Low

  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. 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

  12. 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

  13. Population structure in a comprehensive genomic data set on human microsatellite variation Trevor J. Pemberton

    E-Print Network [OSTI]

    Rosenberg, Noah

    Population structure in a comprehensive genomic data set on human microsatellite variation Trevor J.5 Proportion of loci with 0 shared alleles identical in state (p0 ) Proportionoflociwith2shared allelesidenticalinstate(p2 ) 0.1 0.3 0.4 0 0.1 0.2 0.3 0.4 0.5 0.2 0.5 Proportion of loci with 0 shared alleles identical

  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

    2013-01-01

    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;The addition of other metals to Platinum improves its fuel cell performance Pt alone is easily

  16. Rhodium coated mirrors deposited by magnetron sputtering for fusion applications

    SciTech Connect (OSTI)

    Marot, L.; De Temmerman, G.; Oelhafen, P.; Covarel, G.; Litnovsky, A.

    2007-10-15

    Metallic mirrors will be essential components of all optical spectroscopy and imaging systems for ITER plasma diagnostics. Any change in the mirror performance, in particular, its reflectivity, due to erosion of the surface by charge exchange neutrals or deposition of impurities will influence the quality and reliability of the detected signals. Due to its high reflectivity in the visible wavelength range and its low sputtering yield, rhodium appears as an attractive material for first mirrors in ITER. However, the very high price of the raw material calls for using it in the form of a film deposited onto metallic substrates. The development of a reliable technique for the preparation of high reflectivity rhodium films is therefore of the highest importance. Rhodium layers with thicknesses of up to 2 {mu}m were produced on different substrates of interest (Mo, stainless steel, Cu) by magnetron sputtering. Produced films exhibit a low roughness and crystallite size of about 10 nm with a dense columnar structure. No impurities were detected on the surface after deposition. Scratch tests demonstrate that adhesion properties increase with substrate hardness. Detailed optical characterizations of Rh-coated mirrors as well as results of erosion tests performed both under laboratory conditions and in the TEXTOR tokamak are presented in this paper.

  17. Scoring System Utilization Through Business Jesus Omana Iglesias, James Thorburn, Trevor Parsons, John Murphy and Patrick O'Sullivan

    E-Print Network [OSTI]

    Murphy, John

    Scoring System Utilization Through Business Profiles Jesus Omana Iglesias, James Thorburn, Trevor:patosullivan@ie.ibm.com Abstract--Understanding system utilization is currently a diffi- cult challenge for industry. Current utilized is essential for understanding business cost, workload migrations and future investment require

  18. Low Infrastructure Hydro-Electric Power Generation Team Trevor Doney, Tyler Hogenson, Ginny Llewellyn, Dean Simmonds, Aaron Wernerehl

    E-Print Network [OSTI]

    van den Berg, Jur

    PowerPail Low Infrastructure Hydro-Electric Power Generation Team Trevor Doney, Tyler Hogenson near potential hydro-electric power generation sources. There are several disadvantages to hydro Pipe PowerPail http://mrenergy.co.in/run-of-river-hydro.html #12;

  19. 1,2-Migration in Rhodium(II) Carbene Transfer Reaction: Remarkable Steric Effect on

    E-Print Network [OSTI]

    Wang, Jianbo

    1,2-Migration in Rhodium(II) Carbene Transfer Reaction: Remarkable Steric Effect on Migratory the steric effect in 1,2-migration reaction of rhodium(II) carbene. Through the investigation on the diazo effect of the substituent. 1,2-Migration represents a fundamental reaction pathway for both free carbenes

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

    E-Print Network [OSTI]

    Armbrust, Kurt W. (Kurt Willes)

    2014-01-01

    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 ...

  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 mediated bond activation: from synthesis to catalysis

    SciTech Connect (OSTI)

    Ho, Hung-An

    2012-03-06

    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 Brønsted 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.

  3. Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

    SciTech Connect (OSTI)

    Coble, Inger M

    2008-08-15

    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.

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

    E-Print Network [OSTI]

    Bao, Xinhe

    are not commercialized yet. Current industrial technologies for the production of chemicals from methane are mainly basedAcetic Acid from the Carbonylation of Chloride Methane Over Rhodium Based Catalysts Yafang Fan Æ attracted much attention as a potential route to obtain chemicals. Methane, the main component of natural

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

    E-Print Network [OSTI]

    Abdou, Hanan E.

    Evaluation of Polymer-Supported Rhodium Catalysts in 1-Octene Hydroformylation in Supercritical Carbon Dioxide Zulema K. Lopez-Castillo, Roberto Flores, Ibrahim Kani,,§ John P. Fackler Jr., and Aydin using a Rh-based catalyst. The catalyst is attached to a polymer backbone that has fluoroacrylate

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

    E-Print Network [OSTI]

    Dempsey, Jillian Lee

    2005-01-01

    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. 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

    2004-09-30

    investigated the triisopropylbenzoato complexes of some metals which are known for their ability to form a vast array of tetracarboxylato complexes, namely chromium, copper, molybdenum, and rhodium, and have found that these novel compounds display some...

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

    DOE Patents [OSTI]

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

    2011-07-12

    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. Time-Resolved Structural Characterization of Formation and Break-up of Rhodium Clusters Supported in Highly Dealuminated Y Zeolite

    SciTech Connect (OSTI)

    Liang, Ann J.; Gates, Bruce C.

    2009-06-12

    Mononuclear rhodium complexes incorporating two ethylene ligands and anchored to dealuminated zeolite Y by two Rh-O bonds were characterized by transient extended X-ray absorption fine structure (EXAFS) spectroscopy and infrared (IR) spectroscopy as they were converted in the presence of H{sub 2}. EXAFS spectra indicate reduction of the rhodium in the complex at 298 K to form rhodium clusters less than 3 {angstrom} in average diameter. Contacting of the resultant clusters with C{sub 2}H{sub 4} led to their oxidative fragmentation, and the process was reversible. When the H{sub 2} treatment was carried out at a higher temperature (373 K), larger clusters formed. The reduction and oxidation of the rhodium were confirmed by X-ray absorption near edge spectra. During the ethylene treatments, ethyl groups formed on the rhodium, as indicated by IR spectra; treatment in H{sub 2} led to hydrogenation of these groups to form ethane, and the ethyl groups are inferred to be intermediates in the catalytic hydrogenation of ethylene. Ethylene in the gas phase helps to stabilize rhodium in the form of mononuclear complexes on the zeolite during catalysis, hindering the cluster formation.

  10. Agnes Houser | Y-12 National Security Complex

    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: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantity ofkandz-cm11 OutreachProductswsicloudwsiclouddenDVA N C E D B L O O D S TA I N P A T T E R N A NABPA's ProposedInformation

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

    E-Print Network [OSTI]

    Long, Brandon

    2009-01-01

    Rhodium complexes within the pores of zeolite ZSM-5 with varying Si/Al ratios (Si/Al 23, Si/Al 50, and Si/Al 280) were prepared from Rh1+(CO)2(C5H7O2), Rh22+(CO2CH3)4, and Rh3+(C5H7O2)3 followed by thermal treatment in He. IR results indicate...

  12. Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene

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

    Xu, Songchen; Boschen, Jeffery S.; Biswas, Abhranil; Kobayashi, Takeshi; Pruski, Marek; Windus, Theresa L.; Sadow, Aaron D.

    2015-08-17

    An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{?³-N,Si,C-PhB(OxMe²)(OxMe²SiHPh)ImMes}Rh(H)CO][HB(C?F?)?] (2, OxMe² = 4,4-dimethyl-2-oxazoline; ImMes = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(OxMe²)?ImMes}RhH(SiH2Ph)CO (1) and B(C6F5)3. The unusual oxazoline-coordinated silylene structure in 2 is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(OxMe²)?ImMes}RhH(SiHPh)CO][HB(C?F?)?] generated by H abstraction. Complex 2 catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenationmore »of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C?F?)? catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH? as the reducing agent.« less

  13. 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

    2009-04-28

    Researchers at the Center for Environmentally Beneficial Catalysis (CEBC) had previously reported a novel rhodium-based hydroformylation process concept based on the use of CO2-expanded liquids (CXLs) to intensify rates ...

  14. MERCURY-NITRITE-RHODIUM-RUTHENIUM INTERACTIONS IN NOBLE METAL CATALYZED HYDROGEN GENERATION FROM FORMIC ACID DURING NUCLEAR WASTE PROCESSING AT THE SAVANNAH RIVER SITE - 136C

    SciTech Connect (OSTI)

    Koopman, D.; Pickenheim, B.; Lambert, D.; Newell, J; Stone, M.

    2009-09-02

    Chemical pre-treatment of radioactive waste at the Savannah River Site is performed to prepare the waste for vitrification into a stable waste glass form. During pre-treatment, compounds in the waste become catalytically active. Mercury, rhodium, and palladium become active for nitrite destruction by formic acid, while rhodium and ruthenium become active for catalytic conversion of formic acid into hydrogen and carbon dioxide. Nitrite ion is present during the maximum activity of rhodium, but is consumed prior to the activation of ruthenium. Catalytic hydrogen generation during pre-treatment can exceed radiolytic hydrogen generation by several orders of magnitude. Palladium and mercury impact the maximum catalytic hydrogen generation rates of rhodium and ruthenium by altering the kinetics of nitrite ion decomposition. New data are presented that illustrate the interactions of these various species.

  15. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis -- 2011 Progress Report

    SciTech Connect (OSTI)

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

    2011-10-01

    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. Research during FY 2011 continued to examine the performance of RhMn catalysts on alternative supports including selected zeolite, silica, and carbon supports. Catalyst optimization continued using both the Davisil 645 and Merck Grade 7734 silica supports. Research also was initiated in FY 2011, using the both Davisil 645 silica and Hyperion CS-02C-063 carbon supports, to evaluate the potential for further improving catalyst performance, through the addition of one or two additional metals as promoters to the catalysts containing Rh, Mn, and Ir.

  16. 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.

    2012-11-01

    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.

  17. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis -- 2010 Progress Report

    SciTech Connect (OSTI)

    Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O.; White, J. F.; Rummel, Becky L.; Stevens, Don J.

    2010-10-01

    Pacific Northwest National Laboratory has been conducting research for the U.S. Department of Energy, Energy Efficiency Renewable Energy, Biomass Program to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas. In recent years this research has primarily involved the further development of a silica-supported catalyst containing rhodium and manganese that was selected from earlier catalyst screening tests. A major effort during 2010 was to examine alternative catalyst supports to determine whether other supports, besides the Davisil 645 silica, would improve performance. Optimization of the Davisil 645 silica-supported catalyst also was continued with respect to candidate promoters iridium, platinum, and gallium, and examination of selected catalyst preparation and activation alternatives for the baseline RhMn/SiO2 catalyst.

  18. Synthesis, NMR spectra, and structure of rhodium hydride complexes with Rh-Sn bonds

    SciTech Connect (OSTI)

    Krut'ko, B.P.; Permin, A.B.; Petrosyan, V.S.; Reutov, O.A.

    1985-06-20

    The authors study the hydride complexes using Sn 119 and H 1 NMR spectroscopy. The spectra were taken in a pulse mode on a Varian FT-80A spectrometer equipped with a wideband system at 29.66 and 79.54 MHz. The Sn 119 and H 1 NMR spectral parameters for a solution of the complex (Bu/sub 4/N)/sub 3/ (HRh(SnCl/sub 3/)/sub 5/) in CD/sub 3/CN are shown, the spectra show that the (HRh(SnCl/sub 3/)/sub 5/)/sup 3 -/ anion has octahedral structure with four equatorial and one axial Rh-Sn bonds. New rhodium hydride complexes with general formula (R/sub 4/N)/sub 3/(HRh(SnCl/sub 3/)/sub 5/) were synthesized.

  19. CO-and NO-Induced Disintegration and Redispersion of Three-Way Catalysts Rhodium, Palladium, and Platinum: An ab Initio

    E-Print Network [OSTI]

    Li, Weixue

    CO- and NO-Induced Disintegration and Redispersion of Three-Way Catalysts Rhodium, Palladium increase of Pt adatom self-diffusion in the presence of hydrogen due to the formation of mobile Pt- hydrogen complexes33 and CO-induced Smoluchowski ripen- ing of Pt clusters on graphe

  20. Synthesis and reactions of Cp-linked phosphine complexes of rhodium

    SciTech Connect (OSTI)

    Lefort, L.; Crane, T.W.; Farwell, M.D.; Baruch, D.M.; Kaeuper, J.A.; Lachicotte, R.J.; Jones, W.D.

    1998-08-31

    The linked Cp ligand [C{sub 5}H{sub 4}SiMe{sub 2}CH{sub 2}PPh{sub 2}]{sup {minus}} has been used to synthesize several rhodium derivatives. Reaction with [RhClL{sub 2}]{sub 2} where L = C{sub 2}H{sub 4}, C{sub 8}H{sub 14}, or CO, gives ({eta}{sup 5}:{eta}{sup 1}-C{sub 5}H{sub 4}SiMe{sub 2}-CH{sub 2}PPh{sub 2})Rh(L) complexes, which have been characterized by single-crystal X-ray diffraction. Reaction of the ethylene complex with CO or PMe{sub 3} gives the carbonyl- and phosphine-substituted derivatives, respectively. Irradiation of the ethylene complex in the presence of hydrogen gives a new binuclear polyhydride, also structurally characterized, in which the chelating ligand spans the two metal centers. Reaction of the ethylene complex with iodine leads to the formation of the diiodide ({eta}{sup 5}:{eta}{sup 1}-C{sub 5}H{sub 4}SiMe{sub 2}CH{sub 2}PPh{sub 2})RhI{sub 2}, which in turn can be converted to the dihydride ({eta}{sup 5}:{eta}{sup 1}-C{sub 5}H{sub 4}SiMe{sub 2}CH{sub 2}PPh{sub 2})RhH{sub 2} by reaction with NaAl(OCH{sub 2}CH{sub 2}OCH{sub 3}){sub 2}H{sub 2}. The reactivity of the dihydride toward C-H bond activation has been investigated. While benzene does not give a stable oxidative addition adduct, pentafluorobenzene yields ({eta}{sup 5}:{eta}{sup 1}-C{sub 5}H{sub 4}SiMe{sub 2}CH{sub 2}PPh{sub 2})Rh(C{sub 6}F{sub 5})H, which was structurally characterized as its chloro derivative. Reaction of the dihydride with C{sub 6}F{sub 6} gives the {eta}{sup 2} complex ({eta}{sup 5}:{eta}{sup 1}-C{sub 5}H{sub 4}SiMe{sub 2}CH{sub 2}PPh{sub 2})Rh({eta}{sup 2}-C{sub 6}F{sub 6}), also structurally characterized.

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

    SciTech Connect (OSTI)

    Xu, Songchen; Manna, Kuntal; Ellern, Arkady; Sadow, Aaron D

    2014-12-08

    In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbene–bis(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 C–H 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.

  2. 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.

    or benzene leads to thermal rearrangement to the C-C activation product, (C5Me5)Rh(PMe3)(CH3)(CN) (4C-H vs C-C Bond Activation of Acetonitrile and Benzonitrile via Oxidative Addition: Rhodium vs of the C-H activation product, (C5Me5)Rh(PMe3)(CH2CN)H (2). Thermolysis of this product in acetonitrile

  3. 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)

    2013-07-01

    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)

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

    SciTech Connect (OSTI)

    Colby, Denise; Bergman, Robert; Ellman, Jonathan

    2010-05-13

    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.

  5. Toward Libraries for Real-time Java Trevor Harmon

    E-Print Network [OSTI]

    Schoeberl, Martin

    University of Technology, Austria mschoebe@mail.tuwien.ac.at Raimund Kirner Institute of Computer Engineering Vienna University of Technology, Austria raimund@vmars.tuwien.ac.at Raymond Klefstad Electrical. Efforts such as the Javolution [2] library mitigate these problems, but its reliance on exception han

  6. Neutron Deficient Isotopes of Rhodium and Palladium

    E-Print Network [OSTI]

    Perlman, I.

    2010-01-01

    S OF RHODI U! \\~ AFD PALLADIUM by Manfred Lindner and I.Isotopes of B." odinm. and Palladium Hanfred Lindner and 1.i.a ABSTRACT A palladium activit;)r assigned to mass

  7. Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

    E-Print Network [OSTI]

    Coble, Inger M

    2008-01-01

    respectively. 7.2.2 CO Oxidation Catalytic reactions weresurface for CO oxidation under catalytic conditions for1 . 8.2.3 CO Oxidation Measurements Catalytic measurements

  8. 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 for organic chemists to develop highly enantiose- lective reactions for the preparation of enantiomerically pure compounds in a cost-effective manner. Lactams are a versatile motif in organic chemistry and when

  9. 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

  10. & CH Activation Rhodium Bis(quinolinyl)benzene Complexes for Methane

    E-Print Network [OSTI]

    Goddard III, William A.

    on using the steam-methane reformation process to convert it to syngas (a CO and H2 mixture catalytic process, many ligand frameworks have been explored for the Pt system,[6] and efforts have been

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

    SciTech Connect (OSTI)

    Lavernia, Enrique J.; Yang, Nancy Y. C.; Ong, Markus D.

    2011-08-01

    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. Exploring Oxidation of Half-Sandwich Rhodium Complexes: Oxygen Atom Insertion into the Rhodium-Carbon Bond of 2

    E-Print Network [OSTI]

    Jones, William D.

    -(2-pyridyl)phenol formed. Deactivation of the organometallic species, probably due to oxidative degradation

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

    E-Print Network [OSTI]

    Darrell, Trevor

    Daylight Wavelength (nm.)Wavelength (nm.) C. Tungsten Lightbulb Photons Photons #P 400 500 600 700 #P 400

  14. 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

  15. Abstract Dialectical Frameworks for Legal Latifa AL-ABDULKARIM, Katie ATKINSON, Trevor BENCH-CAPON

    E-Print Network [OSTI]

    Atkinson, Katie

    local to each par- ticular node. Such local acceptance conditions allow structured argu- mentation attackers be defeated) with acceptance conditions local to each particular node: for example some nodes could be acceptable if at least one attacker were defeated. Such local acceptance conditions allow

  16. The U.S. Army Research Laboratory (ARL) has a significant program involving the development of UGS

    E-Print Network [OSTI]

    Zhu, Zhigang

    , and thermal using an accelerometer, microphone, and passive infrared (PIR) transducers respectively signature collection, algorithm validation, and emplacement studies Jeff Houser U.S. Army Research

  17. INTERNATIONAL OPPORTUNITIES FAIR 2014 Florence, Italy

    E-Print Network [OSTI]

    Lennard, William N.

    Ugwuegbula India #12;Barbados Tiffany Laporte #12;Barbados Tiffany Laporte #12;Hong Kong Trevor Weiss #12

  18. Recording the Nation: Folk Music and the Government in Roosevelt’s New Deal, 1936–1941

    E-Print Network [OSTI]

    Davidson, Mark A.

    2015-01-01

    Technologies, Memory, and Cultural Practices. Amsterdam: Amsterdam University Press, Bijsterveld, Karin and Trevor Pinch,

  19. Pose Estimation using 3D View-Based Eigenspaces Louis-Philippe Morency Patrik Sundberg Trevor Darrell

    E-Print Network [OSTI]

    Darrell, Trevor

    is a classic problem in computer vision and has many useful applications. We are particu- larly interested an iterative view registration algorithm [13]. This computation uses intensity information as well as depth (if of the subject's head, and could be provided with 2D or stereo images as input, depending on the view

  20. 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

  1. UBC Social Ecological Economic Development Studies (SEEDS) Student Report Hao Chun Liao, Jui Feng Chung, Trevor Yu, Yilun Song

    E-Print Network [OSTI]

    of primary and secondary sources. The primary sources came in the form of a departmental survey). The secondary sources came through online databases such as Google Scholar and the UBC library databases in this report to determine the recommended cartridge. In addition to the sources, there were several constraints

  2. Play Type Recognition in Real-World Football Video Sheng Chen, Zhongyuan Feng, Qingkai Lu, Behrooz Mahasseni, Trevor Fiez

    E-Print Network [OSTI]

    Play Type Recognition in Real-World Football Video Sheng Chen, Zhongyuan Feng, Qingkai Lu, Behrooz a vision system for recognizing the sequence of plays in amateur videos of American football games (e, and professional football teams. Recognizing football plays is particularly challeng- ing in the context

  3. Assimilation of Remotely Sensed Snow Observations into the NSIPP Land Surface Model

    E-Print Network [OSTI]

    Walker, Jeff

    Walker, UMBC-GEST/Hydrological Sciences Branch, cejpw@land.gsfc.nasa.gov Paul Houser and James Foster, Laboratory for Hydrospheric Processes NASA/GSFC, Paul.Houser@gsfc.nasa.gov, jfoster with observations. 2. Snow observation data Dr Foster has commenced work on the processing of SMMR and SSM/I passive

  4. Scanning multichannel microwave radiometer snow water equivalent assimilation

    E-Print Network [OSTI]

    Walker, Jeff

    ,2 Jeffrey P. Walker,3 Paul R. Houser,4 and Chaojiao Sun2,5 Received 16 February 2006; revised 7 December. Citation: Dong, J., J. P. Walker, P. R. Houser, and C. Sun (2007), Scanning multichannel microwave; Rodell et al., 2004]. [3] Space-borne passive microwave sensors provide an alternate capability

  5. Submitted to: M. E. Maiden, H. K. Ramapriyan, and J. K. Entin (Program Managers/Program Scientists)

    E-Print Network [OSTI]

    Pan, Ming

    Investigator:E. F. Wood (Princeton University) Co-Investigators: P. R. Houser (George Mason University), D. P. Lettenmaier2 Alok K. Sahoo3 , Gabriëlle J. M. De Lannoy3 , Paul R. Houser3 Rachel T. Pinker4 , Yingtao Ma4 ............................................................................................................ 3 2 Soil Moisture from Passive Microwave Remote Sensing ...................................... 1 2

  6. 73A.N. Popper and A. Hawkins (eds.), The Effects of Noise on Aquatic Life, Advances in Experimental Medicine and Biology 730, DOI 10.1007/978-1-4419-7311-5_16,

    E-Print Network [OSTI]

    Reichmuth, Colleen

    95060, USA e-mail: coll@ucsc.edu D. Houser National Marine Mammal Foundation, San Diego, CA 92106, USA e-mail: dorian.houser@nmmfoundation.org 1 Background The majority of research on marine mammal hearing and neural adaptations that support sensitive passive hearing and a refined echolocation system. Fewer

  7. Effect of support on catalytic behavior of dispersed rhodium for hydrocarbon hydrogenolyses 

    E-Print Network [OSTI]

    Khalifa, Amina Ahmed

    1986-01-01

    . Pyrex sample station G. Inlet septum Z. Thermal equilibrium tube J. Oxygen scavenger column K. Adsorbate gas flow control valve L. Adsorbate gas toggle valve M. Adsorbate gas a. Sample outgassing station b. Calibration gas flow meter c. Thermal.../4 in. O. D. pyrex tubing sample cell and outgassing station that connect to the copper tubing by quick-connect fittings. The commercially obtained system was modified to facilitate chemisorption measurements as well as physical adsorption...

  8. Potassium niobate nanoscrolls incorporating rhodium hydroxide nanoparticles for photocatalytic hydrogen evolution

    E-Print Network [OSTI]

    catalysts for UV light- driven hydrogen evolution from aqueous methanol solutions, and their activity can hydrogen evolution Renzhi Ma,ab Yoji Kobayashi,b W. Justin Youngbloodb and Thomas E. Mallouk*b Received 14th July 2008, Accepted 18th September 2008 First published as an Advance Article on the web 5th

  9. Hydroformylation of Mixed Octenes Using RhodiumBulky Phosphonite Complexes with Excellent Catalytic Activity and Stability

    E-Print Network [OSTI]

    Kim, Ji Man

    , and 20.7 wt % of normal octenes. Rh2(CH3CO2)4 was added to a SUS-316 autoclave reactor (300 m via butene dimerization. A C4 fraction obtained by removing butadiene and isobutene from a naphtha,11 After reac- tion, the product containing C4-, C8-, and C12 fraction was dis- tilled to separate a C8

  10. Diastereoselective Intermolecular Rhodium-Catalyzed [4 + 2 + 2] Carbocyclization Reactions: Computational and Experimental Evidence for

    E-Print Network [OSTI]

    Baik, Mu-Hyun

    ,6- enynes and various -components (carbon monoxide, alkynes, 1,3- butadienes, etc.) provide an expeditious] carbocyclization reaction of the substituted 1,6-enyne 1 (R1/R2 ) Me, R3 ) H) with 1,3-butadiene to afford(III)-d6 metallacyclo- pentene iii. Binding of 1,3-butadiene gives intermediate iv, which presumably

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

    E-Print Network [OSTI]

    Xie, Zhuanzhuan

    2013-05-31

    Hydroformylation for producing industrial chemical intermediates such as aldehydes and alcohols from olefinic substrates is a 15 billion lb/year industry and a potential route for increasing the carbon chain of light olefins ...

  12. A detailed surface reaction model for syngas production from butane over Rhodium catalyst

    E-Print Network [OSTI]

    Daraio, Chiara

    online 30 July 2011 Keywords: Butane reforming Surface reaction mechanism Micro solid oxide fuel cell a b solid oxide fuel cells (micro SOFCs) have promising potential to provide an alternative al. [16] reported the optimization of a detailed reaction mechanism for methane combustion

  13. Evaluation of Promoters for Rhodium-Based Catalysts for Mixed Alcohol Synthesis

    SciTech Connect (OSTI)

    Gerber, Mark A.; White, James F.; Gray, Michel J.; Stevens, Don J.

    2008-12-08

    Pacific Northwest National Laboratory (PNNL) and National Renewable Energy Laboratory (NREL) are conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). PNNL is tasked with obtaining commercially-available catalysts or preparing promising mixed-alcohol catalysts and screening them in a laboratory-scale reactor system. Commercially-available catalysts and the most promising experimental catalysts are provided to NREL for testing using a slipstream from a pilot-scale biomass gasifier. A total of 28 tests were conducted to evaluate 22 different promoters as well as an unpromoted catalyst. The following general trends were observed for the test results: • The highest carbon selectivity to C2+ oxygenates occurred at the lowest reaction temperatures and accompanying lowest space time yields (STYs). • The lowest carbon selectivity to C2+ oxygenates occurred at the highest reaction temperatures because of high carbon conversion to hydrocarbons. • The highest C2+-oxygenate STYs occurred between 300°C and 325°C, with the gas hourly space velocity (GHSV) adjusted when necessary to maintain carbon conversion ranges between ~ 30 and 40 percent. Higher carbon selectivity to hydrocarbons at higher temperatures resulted in lower C2+-oxygenate STYs. • When catalysts were heated to between 300°C and 325°C the catalysts showed evidence of some deactivation with respect to C2+ oxygenate productivity, accompanied by reduced chain growth for the hydrocarbon products. The degree of deactivation and the temperature at which it occurred varied between the different catalysts tested. Of all of the catalysts evaluated, the Li-promoted catalysts had the highest carbon selectivity to C2+ oxygenates (47 percent) under the conditions at which the maximum C2+-oxygenate STYs were obtained.

  14. The New Face of Rhodium Alloys: Revealing Ordered Structures from First Principles

    E-Print Network [OSTI]

    Hart, Gus

    ; 1999. (3) The rare earths lanthanum and lutetium are sometimes also refered to as transition metals

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

    E-Print Network [OSTI]

    Lundwall, Matthew James

    2012-02-14

    by dispersing nanoparticles leading to inhibition of catalytic pathways. Moreover, the relationships between high index single crystals, oxide supported nanoparticles, and high surface area technical catalysts are established. Overall, the results demonstrate...

  16. Catalytic Arene H/D Exchange with Novel Rhodium and Iridium Complexes

    E-Print Network [OSTI]

    Jones, William D.

    . Branched alkyl substituents in alkyl aromatics showed an affinity toward deuterium exchange in the -alkyl. Fagnou has shown the mechanism of palladium acetate direct arylation, through theoretical calculations

  17. 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: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantityBonneville Power Administration wouldMass map shinesSolarNew scholarship supports returningNewStaff Research Physicists atNM,New

  18. 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: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantity ofkandz-cm11 Outreach Home RoomPreservation of Fe(II) by Carbon-RichProton DeliveryRadioactiveRare Iron Oxide inSolar

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

    E-Print Network [OSTI]

    Petrick, Elizabeth

    2012-01-01

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

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

    E-Print Network [OSTI]

    Perkel, Daniel

    2011-01-01

    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.

  1. For Immediate Release --Wednesday, April 9, 2014 Advisory

    E-Print Network [OSTI]

    Morris, Joy

    of Management 403-329-2019 403-329-2163 (cell) zyna.taylor@uleth.ca Trevor Kenney, News & Information Manager 403-329-2710 #12;403-360-7639 (cell) trevor.kenney@uleth.ca #12;

  2. 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.

    2010-01-01

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

  3. Land Surface Model Data Assimilation for Atmospheric Prediction

    E-Print Network [OSTI]

    Walker, Jeff

    predictions from different models even when using the same parameters, inputs, and initial conditions (Houser remote sensing studies, using visible, thermal infrared (surface temperature) and microwave (passive and active) electromagnetic radiation. Of these, passive microwave soil moisture measurement has been

  4. A review of "The Journal of William Dowsing: Iconoclasm in East Anglia During the English Civil War." by Trevor Cooper, ed. 

    E-Print Network [OSTI]

    Charles W. A. Prior

    2002-01-01

    as three copies of Foxe?s Actes and Monuments. All of these he annotated in a manner common for the period: underlining, quarrelling and, most significantly, correcting mis-rendered passages of scripture. Both Morrill?s essay and this edition as...

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

    E-Print Network [OSTI]

    Dwyer, D.

    2011-01-01

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

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

    E-Print Network [OSTI]

    Renzas, James R.

    2010-01-01

    Foundry ..Laboratory’s Molecular Foundry Figure 3.8 Common XRD Setup,Laboratory’s Molecular Foundry Once the electron reaches the

  7. DFT Virtual Screening Identifies Rhodium-Amidinate Complexes As Potential Homogeneous Catalysts for Methane-to-Methanol

    E-Print Network [OSTI]

    Goddard III, William A.

    for Methane-to-Methanol Oxidation Ross Fu, Robert J. Nielsen,* and William A. Goddard, III* Materials methane using trifluoroacetic acid (TFAH) or water as a solvent. In particular, we designed the (NNF transition state barrier (G = 27.6 kcal/mol) for methane activation in TFAH from a pool of four different

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

    SciTech Connect (OSTI)

    Renzas, James R.

    2010-03-08

    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.

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

    E-Print Network [OSTI]

    Renzas, James R.

    2010-01-01

    K. ; Goodman, D. W. , Catalytic oxidation of CO by platinumand studied in the catalytic oxidation of CO by NO. Simplediodes during catalytic CO oxidation. Nano Lett. 2008, 8 (

  10. Synthesis and Characterization of (Tris(3,5-dimethylpyrazolyl)borato)rhodium Alkyl and Vinyl Chloride Complexes

    E-Print Network [OSTI]

    Jones, William D.

    -reducing side reactions. Additionally, secondary derivatives of normal alkanes cannot be prepared by this method, it is not economical due to the sacrifice of 1 equiv of neopentyl isocyanide. Chambron and co-workers have reported. Powell and co-workers have reported a method for synthesizing a wide range of air-stable Rh

  11. Steric and Electronic Effects on the Insertion of a Rhodium Phosphine Complex into the C-S Bond of

    E-Print Network [OSTI]

    Jones, William D.

    toward understanding the des- ulfurization of coal and petroleum feedstocks.1 As it becomes necessary to employ heavier, more contami- nated petroleum fractions and to remove a higher fraction of sulfur compounds (deep desulfurization), these studies offer the opportunity to discover more efficient

  12. 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

  13. 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 Irène

    2010-01-01

    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

  14. Reabsorption of Soft X-Ray Emission at High X-Ray Free-Electron...

    Office of Scientific and Technical Information (OSTI)

    McQueen, Trevor ; Laksmono, Hartawan ; Kennedy, Brian ; Eckert, Sebastian ; Schlesinger, Daniel ; Nordlund, Dennis ; Ogasawara, Hirohito ; Sierra, Raymond G. ; Segtnan, Vegard H....

  15. LOCAL ARRANGEMENTS FOR WASTE DISPOSAL (BEGBROKE SITE) Landfill (England & Wales) Regulations 2002

    E-Print Network [OSTI]

    Paxton, Anthony T.

    labelled or is inadequately packaged will NOT be accepted. WASTE OIL To dispose of waste oil, please contact Trevor Knibbs (83711) who will arrange for you to bring your oil to the waste oil store. Trevor1 LOCAL ARRANGEMENTS FOR WASTE DISPOSAL (BEGBROKE SITE) Landfill (England & Wales) Regulations 2002

  16. 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

  17. Amrys O. Williams History of Technology

    E-Print Network [OSTI]

    Wisconsin at Madison, University of

    , Thomas P. Hughes, and Trevor Pinch (eds.), The Social Construction of Technological Systems: NewAmrys O. Williams History of Technology Preliminary Exam Reading List, 2008 Supervised by Eric Schatzberg Overviews and Syntheses (18) General (8) Harry Collins and Trevor Pinch, The Golem at Large: What

  18. For Immediate Release --Wednesday, November 20, 2013 Advisory

    E-Print Network [OSTI]

    Morris, Joy

    -- Contact: Trevor Kenney, News & Information Manager 403-329-2710 403-360-7639 (cell) trevor.kenney@uleth.ca Richard Westlund, Director of Public Affairs 403-332-5251 403-393-2216 (cell) richard.westlund@uleth.ca #12;

  19. Frequency domain surface nuclear magnetic resonance forward modeling on an adaptive octree mesh Trevor Irons*, Colorado School of Mines, United States Geological Survey; Yaoguo Li, Center for Gravity, Electrical,

    E-Print Network [OSTI]

    to directly detect hydrogen in liquids. In near surface applications wire loops may be deployed on the surface be monitored inductively on the earth's surface using wire loops that measure the changing emf due

  20. 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

    as additives to gasoline, diesel, and aviation fuel [2,3]. For these reasons, the production of butanol,5]. Alternatively, alcohols could be produced by hydrogenation of aldehydes derived from the hydroformylation an attractive extension of existing technology to the production of transporta- tion fuel. The challenge

  1. NMR studies of chiral P,S-chelate platinum, rhodium, and iridium complexes and the X-ray structure of a palladium(II) allyl derivative

    SciTech Connect (OSTI)

    Albinati, A. [Univ. of Milan (Italy)] [Univ. of Milan (Italy); Eckert, J. [Los Alamos National Lab., NM (United States)] [Los Alamos National Lab., NM (United States); Pregosin, P.; Ruegger, H.; Salzmann, R.; Stoessel, C. [ETH-Zentrum, Zuerich (Switzerland)] [ETH-Zentrum, Zuerich (Switzerland)

    1997-02-18

    Several Rh(I), Ir(III), and Pt(II) complexes of the chiral P,S-bidentate ligand 2 have been prepared and characterized. Detailed two-dimensional NMR studies show that (i) the boat-type chelate ring and the stereogenic sulfur center can invert rapidly at ambient temperature and (ii) the sulfur donor may dissociate, essentially destroying the chiral pocket. The solid-state structure of [Pt({eta}{sup 3}-C{sub 3}H{sub 5})(2)]PF{sub 6} (3) has been determined and the sulfur substituent shown to have an axial orientation. The six-membered chelate ring takes up a boat-like conformation. As shown by an X-ray diffraction study for 3, and via incoherent inelastic neutron scattering (IINS) measurements for the Pd analog, 4, the OH group is remote from the metal atom. 42 refs., 11 figs., 6 tabs.

  2. 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-

    2012-08-16

    ) and 45 (bottom, 4.5 kHz spinning speed). ............................................................................ 141 4.5 29Si CP/MAS spectra of 44 (top, 0 kHz spinning speed; middle: 1.5 kHz spinning speed; bottom, 10 kHz spinning speed...). ...................................... 142 4.6 29Si CP/MAS spectra of 44 (top, 1.5 kHz spinning speed) and 45 (bottom, 5 kHz spinning speed). ................................................................ 143 4.7 31P NMR spectrum of 47 in CDCl3...

  3. 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

    2014-07-02

    The discovery of the antitumor properties of cisplatin revolutionized the field of medicinal inorganic chemistry and fostered the development of metal-based anticancer drugs, a topic that continues to play a prominent role ...

  4. Australian Root Zone Soil Moisture: Assimilation of Remote Sensing Observations

    E-Print Network [OSTI]

    Walker, Jeff

    parameters and atmospheric forcing (Houser et al., 2002). Advances in passive microwave remote sensing have. Ursinob , R.B. Graysona and P.R. Houserc a Department of Civil and Environmental Engineering, University. The C-band passive microwave remote sensing data from the Scanning Multi-frequency Microwave Radiometer

  5. MoistureMap: A soil moisture monitoring, prediction and reporting system for sustainable land and water management

    E-Print Network [OSTI]

    Walker, Jeff

    algorithms or rainfall forecasts provide. It is widely recognised that passive microwave is the most promising remote sensing method for soil moisture measurement [Njoku et al., 2002]. While passive microwave must be combined by data assimilation [Walker and Houser, 2005], with point measurements used

  6. UNCORRECTEDPROOF 2 Requirements of a global near-surface soil moisture satellite

    E-Print Network [OSTI]

    Walker, Jeff

    : accuracy, repeat time, and spatial resolution 4 Jeffrey P. Walker a,b,*, Paul R. Houser a 5 a Hydrological) remote sensing studies, using 53both thermal infrared and microwave (passive and ac- 54tive) electromagnetic radiation. Of these, passive 55microwave soil moisture measurement has been the 56most promising

  7. UNIVERSITY OF WASHINGTON FACULTY COUNCIL ON FACULTY AFFAIRS

    E-Print Network [OSTI]

    Van Volkenburgh, Elizabeth

    to discuss the Medicare Billing investigation/Winn/Houser settlements and related effects on the Medical clinical, 1 science/clinical) and operates in a team environment with the University of Washington Medical investigation that began at the end of 1999. Early in this investigation, the Dean's Office realized

  8. Walking the Tightrope: Workplace Bullying and the Human Resource Professional 

    E-Print Network [OSTI]

    Cowan, Renee L.

    2010-07-14

    and shaped my life in the most unexpected and wonderful ways: Dr. Marian Houser, Dr. Mary Hoffman, and Dr. Timothy Mottet. Thank you for all of your guidance and support with this project and throughout my academic pursuits. I reserve special thanks...

  9. Kate Brodie & Nick Spore ERDC-CHL-COAB

    E-Print Network [OSTI]

    US Army Corps of Engineers

    Kate Brodie & Nick Spore ERDC-CHL-COAB Coastal Sediments 2015 ­ San Diego, CA "Understanding-impact prediction models (e.g. Sallenger 2000, Stockdon et al. 2007) characterize dunes by: ­ Dune Toe ­ Dune Crest variations in morphology (Houser 2013) ­ Vegetation coverage, pore space and infiltration rate (Palmsten

  10. Comprehensive Scenarios of Millennial Timescale Carbon Cycle and Climate

    E-Print Network [OSTI]

    Williamson, Mark

    Cyr-1 (high) Land C sink = 1.1 GtCyr-1 (low) Idealised long-term fossil fuel emissions scenarios: ~1-Science: Trevor Cooper-Chadwick, Simon Cox, John Darlington, Murtaza Gulamali, Steven Newhouse, Andrew Price, Gang

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

    ScienceCinema (OSTI)

    Riedemann, Trevor

    2013-03-01

    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.

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

    ScienceCinema (OSTI)

    Riedemann, Trevor

    2013-03-01

    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.

  13. 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

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

    ScienceCinema (OSTI)

    Riedemann, Trevor

    2013-03-01

    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.

  15. Introducing Performance Engineering by means of Tools and Practical Exercises

    E-Print Network [OSTI]

    Murphy, John

    , Trevor Parsons, Lucian M. Patcas, John Murphy and Liam Murphy Performance Engineering Laboratory, School Performance Engineering Lab, School of Computer Science and Informatics, University College Dublin. PermissionIntroducing Performance Engineering by means of Tools and Practical Exercises Alexander Ufimtsev

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

    SciTech Connect (OSTI)

    Riedemann, Trevor

    2011-01-01

    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.

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

    SciTech Connect (OSTI)

    Riedemann, Trevor

    2011-01-01

    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.

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

    SciTech Connect (OSTI)

    Riedemann, Trevor

    2011-01-01

    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.

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

    SciTech Connect (OSTI)

    Riedemann, Trevor

    2011-01-01

    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.

  20. 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

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

    ScienceCinema (OSTI)

    Riedemann, Trevor

    2013-03-01

    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.

  2. The Legacy of Oil Spills

    E-Print Network [OSTI]

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

    2010-01-01

    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

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

    SciTech Connect (OSTI)

    Wagner, Trevor [OpGen, Inc

    2010-06-03

    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

  4. Books Received Books listed below that are marked with a

    E-Print Network [OSTI]

    : The MIT Press (Inside Technology Series, edited by Wiebe E. Bijker, W. Bernard Carlson, and Trevor Pinch Boi Faltings and Peter Struss, editors (Swiss Federal Institute of Technology and Siemens Corporate

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

    E-Print Network [OSTI]

    Waidzunas, Thomas John

    2010-01-01

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

  6. Universal informatics : building cyberinfrastructure, interoperating the geosciences

    E-Print Network [OSTI]

    Ribes, David

    2006-01-01

    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.

  7. For Immediate Release --Friday, October 3, 2014 Community invited to University of Lethbridge Open

    E-Print Network [OSTI]

    Morris, Joy

    -- Contact: #12; Trevor Kenney, News & Information Manager 403-329-2710 403 403-329-2762 natasha.buisdeering@uleth.ca Carma Leishman, National Recruitment Manager 403-329-2762 carma.leishman@uleth.ca #12;

  8. For Immediate Release --Monday, November 18, 2013 Advisory

    E-Print Network [OSTI]

    Morris, Joy

    & Information Manager 403-329-2710 403-360-7639 (cell) trevor.kenney@uleth.ca Richard Westlund, Director of Public Affairs 403-332-5251 403-393-2216 (cell) richard

  9. A review of "Mohawk Saint: Catherine Tekakwitha and the Jesuits." by Allan Greer 

    E-Print Network [OSTI]

    Br. Benet Exton, O.S.B.

    2005-01-01

    of black bile without dismissing the existence of black bile itself ? (192). Douglas Trevor?s The Poetics of Melancholy is a theoretically informed, his- torically grounded, and critically nuanced account of the influence of schol- arly melancholy... in those days. He shows how difficult it was for the first Jesuit missionaries, especially the North American Martyrs. The Indians were brutal with their captives, usually torturing them to death. He reflects that it would have been better to be killed...

  10. Estimation of aboveground biomass and inorganic nutrient content of a 25-year-old loblolly pine (Pinus taeda L.) plantation 

    E-Print Network [OSTI]

    Houser, James Nelson

    1980-01-01

    ESTIMATION OF ABOVEGROUND BIOMASS AND INORGANIC NUTRIENT CONTENT OF A 25-YEAR-OLD LOBLOLLY PINE (PINUS TAEDA L. ) PLANTATION A Thesis by JAMES NELSON MOUSER Submitted to the Graduate College of Texas ARM University in partial fulfillment... of the requirement for the degree of MASTER OF SCIENCE August lqBO Major Si bject: Forestry ESTIMATION OF ABOVEGROUND BIOMASS AND INORGANIC NUTRIENT CONTENT OF A 25-YEAR-OLD LOBLOLLY PINE (PINUS TAEDA L. ) PLANTATION A Thesis by JAMES NELSON HOUSER Approved...

  11. Platinum Nanoclusters Out-Perform Single Crystals

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

    in platinum. Exploring metals that catalyze other important reactions-such as palladium, silver, copper, rhodium, iron, and cobalt-might also help researchers determine...

  12. Nanocatalysts at Work | The Ames Laboratory

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

    chemical environment. Scientists showcased the power of their method using a 50:50 palladium-rhodium catalyst in an oxygen environment. Without any oxygen, a palladium shell...

  13. Search for: All records | DOE PAGES

    Office of Scientific and Technical Information (OSTI)

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

  14. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    (1) organometallic compounds (1) reaction intermediates (1) rhodium compounds (1) solar energy (1) solar energy solar energy conversion, physical chemistry (1) spectroscopy...

  15. New enantioselective metal-catalysed conjugate addition-initiated reactions of alkenyl(aza)arenes 

    E-Print Network [OSTI]

    Saxena, Aakarsh

    2013-06-29

    I. Enantioselective Rhodium-Catalysed Arylation of Electron-Deficient Alkenylarenes ?-substituted alkenyl-para-nitroarenes, an unexplored substrate class for catalytic asymmetric addition reactions, undergo highly ...

  16. TITLE AUTHORS SUBJECT SUBJECT RELATED DESCRIPTION PUBLISHER AVAILABILI...

    Office of Scientific and Technical Information (OSTI)

    Real time sub math display inline mi mi math ngstrom imaging of reversible and irreversible conformations in rhodium catalysts and graphene Kisielowski Christian Wang Lin Wang...

  17. Real-time sub-Ångstrom...

    Office of Scientific and Technical Information (OSTI)

    Real-time sub-ngstrom imaging of reversible and irreversible conformations in rhodium catalysts and graphene Kisielowski, Christian; Wang,...

  18. "Title","Creator/Author","Publication Date","OSTI Identifier...

    Office of Scientific and Technical Information (OSTI)

    Real-time sub-ngstrom imaging of reversible and irreversible conformations in rhodium catalysts and graphene","Kisielowski, Christian;...

  19. 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. ;...

  20. Real-time sub- Å 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 Title: Real-time sub- ngstrom imaging of reversible and irreversible conformations...

    1. 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.

      1986-01-01

      CI(CO)(PHs)z by Hz addition yields two isomeric products. The possible pathways of approach for the Hz upon the Rh complex were studied and analyzed. The results of the study showed that the controlling factor governing the most feasible approach... for the activation of hydrogen by RhC1(PHs)s. " The purpose of his study was not to discuss the path of reaction, but to sort out the factors accounting for its feasibility. He felt the activation of the hydrogen could be due to two influences: (1) the transfer...

    2. DEAN'S LIST HONORABLE MENTION Fall Semester 2010

      E-Print Network [OSTI]

      Wong, Pak Kin

      Kathleen Powell, James W. Psyk, Katherine Joan Pucelik, Amber L. Purdy, Stephen C. Rainey, Joseph D. Rapp, Jeffrey T. Clutter, Anthony T. Coffin, James G. Conatser, Stephen G. Cook, Sarah Ann Cordon, Michael J. Cox, Jonathan A. Craig, Danielle R. Cuthbertson, Trevor J. Davis, Johnathon M. Davis, Trent Wilford

    3. Congratulations to these students for earning a 3.5 -4.0 grade point average on 12 -14 units in spring 2012 DEAN'S LIST HONORABLE MENTION

      E-Print Network [OSTI]

      Wong, Pak Kin

      Berry, Matthew James Blomberg, Cheryl Ann Brent, Joshua I. Bruening, Garrick W. Bui, Julie Cahill, Erin. Chong, Kyle James Colbert, Anthony Earl Coleman, Andrew J. Conatser, Stephen G. Cook, Sarah Ann Cordova, Dana Lee Corrales, Saul Patino Cota, Lucio Ismael Cox, Jonathan A. Cuthbertson, Trevor J. Davis

    4. Development and Testing of a Prototype Pilot Expansion Valve for Vapor Compression Systems 

      E-Print Network [OSTI]

      Youmsi Pete, Edwin Larry

      2015-02-16

      , Chris Price, Rawand Jalal, Priyam Parikh, Franco Morelli, Trevor Terrill and Shuangshuang Liang for their help and advice. I would also like to thank all my professors and teachers at Texas A&M University, Sacred Heart College, Mankon and PNEU Douala...

    5. IBM Systems Journal Q3 2002 Comparing Autonomic & Proactive Computing

      E-Print Network [OSTI]

      Somayaji, Anil

      IBM Systems Journal Q3 2002 Comparing Autonomic & Proactive Computing Roy Want , Trevor Pering between proactive computing and autonomic computing, considering the design of systems that are beyond principles we call proactive computing, enabling the transition from today's interactive systems to proactive

    6. Correction To the Formula For the Total Frequency Integral of the Ion Velocity Spectrum

      E-Print Network [OSTI]

      Killian, Thomas C.

      Correction To the Formula For the Total Frequency Integral of the Ion Velocity Spectrum Trevor integral of the ion velocity spectrum is incorrect, while the equation for the spectrum itself is correct, there are slightly different forms of this equation running around in which camera corrections and spatial integrals

    7. Modeling Power Consumption of NAND Flash Memories using FlashPower

      E-Print Network [OSTI]

      Gurumurthi, Sudhanva

      1 Modeling Power Consumption of NAND Flash Memories using FlashPower Vidyabhushan Mohan, Trevor of consumer electronics products, such as cell-phones and music players, use flash memory for storage space requires detailed insights into the power characteristics of flash memory. In this paper, we

    8. Reviewers for Volume 39 This journal has a knowledgeable and hard-working editorial board, listed on the jour-

      E-Print Network [OSTI]

      ¨ubler Christopher Potts Trevor Cohn Tom Kwiatkowski Richard J. D. Power Ann Copestake Guy Lapalme Sameer Pradhan Brian E. Roark Michael Strube Andreas Vlachos Mike Rosner Lin Sun Michael White Paolo Rosso Weiwei Sun Shuly Wintner Dan Roth Xu Sun Richard Wojcik Guillermo Ruiz Eric Tellez Nianwen Xue David Schlangen

    9. Big Data Analytics in Financial Statement

      E-Print Network [OSTI]

      ;Demographic and Weather Big Data · OfficeMax personalizes online landing pages based on customerBig Data Analytics in Financial Statement Audits Min Cao Roman Chychyla Trevor Stewart February 26th, 2015 #12;Big Data Analytics · Big Data analytics is the process of inspecting, cleaning

    10. ANR @ MSUANR @ MSU AgBioResearchAgBioResearch Expert Search

      E-Print Network [OSTI]

      .2 GDD50 2261 2355 1680 1959 2124 2009.4 WEATHER No precipitation occurred this past week. However, we collecting down at the base of the trees. A reminder to growers that TSSM turn an orange color in the fall PROJECTS Search #12;2006 Trevor Nichols Research Complex Trapline Data Compound Trade Name Life

    11. Approved Module Information for SE4031, 2014/5 Module Title/Name: Extended Integrative Option Module Code: SE4031

      E-Print Network [OSTI]

      Neirotti, Juan Pablo

      Approved Module Information for SE4031, 2014/5 Module Title/Name: Extended Integrative Option Module Code: SE4031 School: Engineering and Applied Science Module Type: Standard Module New Module? No Module Credits: 30 Module Management Information Module Leader Name Trevor Oliver Email Address t

    12. Arabidopsis LTPG Is a Glycosylphosphatidylinositol-Anchored Lipid Transfer Protein Required for Export of Lipids to the

      E-Print Network [OSTI]

      Kunst, Ljerka

      for Export of Lipids to the Plant Surface W OA Allan DeBono,a Trevor H. Yeats,b Jocelyn K.C. Rose,b David such hydrophobic compounds are exported to the cuticle, especially through the hydrophilic plant cell wall. These data suggest that LTPG may function as a component of the cuticular lipid export machinery

    13. CodeTopics: Which Topic am I Coding Now? Malcom Gethers

      E-Print Network [OSTI]

      Poshyvanyk, Denys

      information might be too coarse- grained: a source code artifact the developer is coding may by related and Mary Williamsburg, VA, USA mgethers@cs.wm.edu Trevor Savage HCI Institute Carnegie Mellon University@unisa.it ABSTRACT Recent studies indicated that showing the similarity between the source code being developed

    14. Data Mining to Characterize Signatures of Impending System Events

      E-Print Network [OSTI]

      Data Mining to Characterize Signatures of Impending System Events or Performance from PMU or Performance from PMU Measurements Final Project Report Project Team Vijay Vittal, Project Leader Trevor Werho Mining to Characterize Signatures of Impending System Events or Performance from PMU Measurements

    15. X-ray and EUV Observations of GOES C8 Solar Flare

      E-Print Network [OSTI]

      Wolfe, Patrick J.

      X-ray and EUV Observations of GOES C8 Solar Flare Events Kathy Reeves1, Trevor Bowen1,2, Paola;Solar Flares Tuesday, February 19, 2013 #12;Solar Flares Tuesday, February 19, 2013 #12;Solar Dynamics Veronig et al, A&A, 2002 Tuesday, February 19, 2013 #12;Flare Timing GOESflux(Wm-2) Rise Decay Tuesday

    16. Flexible Statistical Models for Growth Fragments: a Study of Bone Mineral Acquisition

      E-Print Network [OSTI]

      Hastie, Trevor

      Flexible Statistical Models for Growth Fragments: a Study of Bone Mineral Acquisition Trevor J describe some statistical modeling of longitudinal data from a pediatric study of bone mineral acquisition- surements of bone mineral density are available for each subject, taken roughly one year apart, and between

    17. Ames Lab 101: Lanthanum Decanting

      ScienceCinema (OSTI)

      Riedemann, Trevor

      2012-08-29

      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.

    18. Palouse Subbasin Management Plan 3. Management Plan

      E-Print Network [OSTI]

      Palouse Subbasin Management Plan 3. Management Plan FINAL DRAFT ~ May 2004 Project Lead: Palouse-Rock Lake Conservation District Trevor Cook, Project Manager PO Box 438 St. John WA 99171 (509) 648;Palouse Subbasin Plan: MANAGEMENT PLAN Management Plan: Page 3 - 1 3. Management Plan 3.1 Background

    19. 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 Perception¨lthoff HH (2011) Talk to the Virtual Hands: Self-Animated Avatars Improve Communication in Head

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

      E-Print Network [OSTI]

      Mamo, Andrew Benedict

      2011-01-01

      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 (

    1. Face-responsive interfaces: from direct manipulation to perceptive presence

      E-Print Network [OSTI]

      Tollmar, Konrad

      Face-responsive interfaces: from direct manipulation to perceptive presence Trevor Darrell, Konrad for human-computer interface applications. We are developing prototype systems for face-responsive interaction, ex- ploring three different interface paradigms: direct manipulation, gaze- mediated agent dialog

    2. For Immediate Release --Wednesday, November 27, 2013 Study examines sexual rights and barriers people with

      E-Print Network [OSTI]

      Morris, Joy

      and in confidentiality. Interested people should contact research assistant Gillian Ayers (403 -- Contact: Trevor Kenney, News & Information Manager 403-329-2710 403 of Sociology 403-329-2738 claudia.malacrida@uleth.ca Gillian Ayers 403-332-4591 gillian

    3. Phase selectively soluble polymer supports to facilitate homogeneous catalysis 

      E-Print Network [OSTI]

      Ortiz-Acosta, Denisse

      2009-05-15

      and selectivity, and they often allow the use of mild reaction conditions. However, the metals used in the catalytic reactions most popular in organic synthesis like palladium, rhodium, and platinum are generally very expensive. The organic ligands...

    4. Cross-linking proteins with bimetallic tetracarboxylate compounds of transition metals

      DOE Patents [OSTI]

      Kostic, N.M.; Chen, J.

      1991-03-05

      Stable cross-linked complexes of transition-metal tetracarboxylates and proteins are formed. The preferred transition-metal is rhodium. The protein may be collagen or an enzyme such as a proteolytic enzyme. No Drawings

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

      E-Print Network [OSTI]

      Smith, Donna Lee

      2013-11-28

      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 ...

    6. 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)

      1992-01-01

      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.

    7. Production of hydrogen from alcohols

      DOE Patents [OSTI]

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

      2007-08-14

      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.

    8. Delivered by Ingenta to: IP : 90.148.96.123

      E-Print Network [OSTI]

      Azad, Abdul-Majeed

      hydrogen (for PEMFCs) or hydrogen-rich reformate (for SOFCs) for extended periods, and deliver hydrogen Ceramic Powders, Ceria, Precious Metals, Ruthenium, Palladium, Rhodium, Sulfur-Tolerant Catalysts, Fuel Reforming, Hydrogen. CONTENTS 1. Introduction

    9. Novel Nanoscale Catalysts and Desulfurizers for Aviation Fuels Martin Duran* and Abdul-Majeed Azad

      E-Print Network [OSTI]

      Azad, Abdul-Majeed

      in terms of hydrogen yield and sulfur-tolerance; catalysts containing small levels of palladium and rhodium) to hydrogen through steam reforming poses a challenge since these fuels contain sulfur up to about 1000 ppm

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

      E-Print Network [OSTI]

      Iglesia, Enrique

      2004-01-01

      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

    11. Synthesis and crystal structure of two new cerium rhodium oxides: Ce{sub 2/3-x}Rh{sup 3+}{sub 2}O{sub 4} (x{approx}0.12) with Ce mixed valency and Ce{sup 4+}Rh{sup 3+}{sub 2}O{sub 5}

      SciTech Connect (OSTI)

      Mizoguchi, Hiroshi; Zakharov, L.N.; Bhuvanesh, N.S.P.; Sleight, A.W.; Subramanian, M.A.

      2011-06-15

      The new compounds Ce{sub 2/3-x}Rh{sub 2}O{sub 4} (x{approx}0.11-0.14) and CeRh{sub 2}O{sub 5} have been prepared. Their structures were determined from single crystal X-ray diffraction data. Electrical and magnetic properties were also evaluated. Based on the structural analysis and physical properties, oxidation states for CeRh{sub 2}O{sub 5} can be assigned as Ce{sup 4+}Rh{sup 3+}{sub 2}O{sub 5}. A small variation in x was detected for Ce{sub 2/3-x}Rh{sub 2}O{sub 4} indicating a formula ranging from Ce{sup 3.64+}{sub 0.55}Rh{sup 3+}{sub 2}O{sub 4} to Ce{sup 3.81+}{sub 0.525}Rh{sup 3+}{sub 2}O{sub 4}. - Graphical abstract: The new compounds Ce{sub 2/3-x}Rh{sub 2}O{sub 4} (x{approx}0.11-0.14) and CeRh{sub 2}O{sub 5} have been prepared and their structures were determined from single crystal X-ray diffraction data. Electrical and magnetic properties were also evaluated. Highlights: > The new compounds CeRh{sub 2}O{sub 5} and Ce{sub 2/3-x}Rh{sub 2}O{sub 4} (x{approx}0.11-0.14) have been prepared. > Their structures were determined from single crystal X-ray diffraction data. > Valence picture is Ce{sup 4+}Rh{sup 3+}{sub 2}O{sub 5} and Ce{sup 3.64+}{sub 0.55}Rh{sup 3+}{sub 2}O{sub 4} to Ce{sup 3.81+}{sub 0.525}Rh{sup 3+}{sub 2}O{sub 4}.

    12. News you can use Disease management

      E-Print Network [OSTI]

      Isaacs, Rufus

      moth model. TNRC Pheromone Trapline Data For growers who use the trapline data from the Trevor Nichols&WINENEWSLETTER M I C H I G A N M a y 2 1 , 2 0 1 0 V O L 1 , I S S U E 3 Base 50 from April 1Base 50 from April 1 but overall vines look good considering the extreme weather conditions this spring. Most growers report

    13. Impulsivity in disorders of food and drug misuse

      E-Print Network [OSTI]

      Mole, T. B.; Irvine, M. A.; Worbe, Y.; Collins, P.; Mitchell, S. P.; Bolton, S.; Harrison, N. A.; Robbins, T. W.; Voon, V.

      2014-08-14

      , Simon P. Mitchell1,3, Sorcha Bolton1, Neil A. Harrison4, Trevor W. Robbins2, Valerie Voon1,2,3 1Department of Psychiatry, University of Cambridge, Cambridge, UK 2Behavioural and Clinical Neuroscience Institute, University of Cambridge, Cambridge, UK... BB, Djamshidian, A, O'Sullivan, SS, Housden, CR, Roiser, JP & Lees, AJ (2013). Uncertainty about mapping future actions into rewards may underlie performance on multiple measures of impulsivity in behavioral addiction: Evidence from Parkinson...

    14. 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)

      1992-01-01

      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.

    15. Vapor deposition of thin films

      SciTech Connect (OSTI)

      Smith, D.C.; Pattillo, S.G.; Laia, J.R. Jr.; Sattelberger, A.P.

      1990-10-05

      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.

    16. S-H bond activation in H{sub 2}S and thiols by [RhMn(CO){sub 4}(Ph{sub 2}PCH{sub 2}PPh{sub 2}){sub 2}]. Compounds containing terminal or bridging sulfhydryl and thiolato groups

      SciTech Connect (OSTI)

      Li-Sheng Wang; McDonald, R.; Cowie, M. [Univ. of Alberta, Edmonton (Canada)

      1994-08-17

      A rhodium-magnesium carbonyl-phosphines reacted with thiols to yield the products of S-H addition. Further reactions result in bridging sulfide can be alkylated or protonated at the sulfur. The compound, [RhMn(CO){sub 4}({mu}-S)(dppm){sub 2}], was structurally characterized by X-ray crystallography.

    17. This article was published in an Elsevier journal. The attached copy is furnished to the author for non-commercial research and

      E-Print Network [OSTI]

      Daraio, Chiara

      converts it into syngas (H2 and CO), which is used by the fuel cell to produce electric energy of Thermodynamics in Emerging Technologies, Institute of Energy Technology, ETH Zurich, 8092 Zurich, Switzerland is important, because it can have economic effects due to saving of the precious catalyst rhodium. 2007

    18. On-Line Estimation of Inlet and Outlet Composition in Catalytic Partial Ali Al-Matouq , Tyrone Vincent

      E-Print Network [OSTI]

      Vincent, Tyrone

      On-Line Estimation of Inlet and Outlet Composition in Catalytic Partial Oxidation Ali Al and outlet composition of catalytic partial oxidation (CPOX) of methane over rhodium catalyst using simple experiments are conducted to verify the accuracy of the estimator. Keywords: Catalytic Partial Oxidation

    19. Homologation process making higher alcohols

      DOE Patents [OSTI]

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

      1990-01-01

      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.

    20. Kinetics of the Homogeneous Catalytic Hydrogenation of Olefins in Supercritical Carbon Dioxide Using a Fluoroacrylate Copolymer

      E-Print Network [OSTI]

      Abdou, Hanan E.

      Kinetics of the Homogeneous Catalytic Hydrogenation of Olefins in Supercritical Carbon Dioxide a fluoroacrylate copolymer grafted rhodium catalyst in supercritical carbon dioxide (scCO2) are reported field of chemical reaction engineering.3-8 Specifically, supercritical carbon dioxide (scCO2

    1. Received 9 May 2015 | Accepted 9 Sep 2015 | Published 9 Oct 2015 High-intensity power-resolved radiation

      E-Print Network [OSTI]

      MacDonald, Mark

      to image high-intensity fast-neutron and gamma-ray fields simultaneously. This system has been deployed. Monitoring systems, such as fission chambers and rhodium detector systems are expensive and have limited high temperatures, corrosion, extreme radiation levels and miniaturization. In-core monitoring systems

    2. Cobalt discovery replaces precious metals as industrial catalyst

      E-Print Network [OSTI]

      chemistry #12;- 2 - LOS ALAMOS, N.M., November 26, 2012--Cobalt, a common metal, holds promise. 26 in the international edition of the chemistry journal Angewandte Chemie, Los Alamos National. They are the noble metal elements such as platinum, palladium, rhodium, and ruthenium, which are a prohibitively

    3. Reactivity studies of antitumor active dirhodium compounds with DNA oligonucleotides 

      E-Print Network [OSTI]

      Kang, Mijeong

      2007-04-25

      are clearly less stable. Reaction of cis-[Rh2(DAP)(O2CCH3)3(CH3OH)](O2CCH3) (DAP = 1,12- diazaperylene) with 5'-CTCTCAACTTCC produced a major adduct in which DAP group intercalates between 6A and 7A in the double stranded adduct with the rhodium atom...

    4. USGS Mineral Resources Program Platinum-Group Elements--So Many Excellent Properties

      E-Print Network [OSTI]

      as jewelry and as an investment commodity, the major applications of PGE are industrial. Their leading use industry, platinum-supported catalysts are needed to refine crude oil and to produce high-octane gasoline alloys an ideal choice for jewelry. Platinum, palladium, and rhodium are used for investment in the form

    5. Catalytic oxidative dehydrogenation process

      DOE Patents [OSTI]

      Schmidt, Lanny D. (Minneapolis, MN); Huff, Marylin (St. Paul, MN)

      2002-01-01

      A process for the production of a mono-olefin from a gaseous paraffinic hydrocarbon having at least two carbon atoms or mixtures thereof comprising reacting said hydrocarbons and molecular oxygen in the presence of a platinum catalyst. The catalyst consist essentially of platinum supported on alumina or zirconia monolith, preferably zirconia and more preferably in the absence of palladium, rhodium and gold.

    6. Two-electron mixed-valence complexes small molecule activation and photocatalytic hydrogen production

      E-Print Network [OSTI]

      Heyduk, Alan F. (Alan Frank), 1974-

      2001-01-01

      Two-electron mixed-valence complexes of rhodium may be supported by diphosphazane ligands (RN(PY2)2). Whereas diphosphazane ligands with strongly [pi]-acidic phosphine groups (Y = F, OCH2CF3) react with RhI starting materials ...

    7. Journal of Power Sources 182 (2008) 558564 Contents lists available at ScienceDirect

      E-Print Network [OSTI]

      Daraio, Chiara

      2008-01-01

      Keywords: Start-up Heat source Micro-SOFC Rhodium Reformer Post-combustor a b s t r a c t The start that especially micro-solid oxide fuel cells ( SOFC) show a high potential due to the high power density capability in cartridges. Hotz et al. [11] optimized a whole SOFC system from the exergetic point of view

    8. CCFE-R(15)26-supplement February 2015

      E-Print Network [OSTI]

      ;CONTENTS CCFE-R(15)26-supplement PKA distributions Contents Hydrogen 6 Helium 8 Lithium 9 Beryllium 14 Zirconium 257 Niobium 264 Molybdenum 270 Ruthenium 277 Rhodium 284 Palladium 289 Silver 295 Cadmium 301;Hydrogen CCFE-R(15)26-supplement PKA distributions Hydrogen CCFE Page 7 of 520 106 108 1010 10 0 10 2 10 4

    9. Hindawi Publishing Corporation Advances in Materials Science and Engineering

      E-Print Network [OSTI]

      Azad, Abdul-Majeed

      to convert sulfur-laden logistic fuels into hydrogen-rich reformate and deliver to the fuel cell stack in their performance. Presence of ruthenium and/or rhodium in formulations containing palladium showed improved sulfur for higher hydrogen yields in the logistic fuel reformate. Duration of steady hydrogen production was higher

    10. Association between MAPT haplotype and memory function in patients with Parkinson’s disease and healthy aging individuals

      E-Print Network [OSTI]

      Winder-Rhodes, Sophie E.; Hampshire, Adam; Rowe, James B.; Peelle, Jonathan E.; Robbins, Trevor W.; Owen, Adrian M.; Barker, Roger A.

      2014-12-11

      , University of Cambridge, Cambridge, UK b y, InstituAssociation between MAPT haplotype an patients with Parkinson’s disease and h Sophie E. Winder-Rhodes a,b,*, Adam Hampshire c,d Jonathan E. Peelle f, Trevor W. Robbins e, Adrian M.Inc. This is an open access... subcomponents of memory encoding, focusing our analysis on medial temporal lobe regions, particularly the hippocampus, which are known to be crucial for the registration of new information (Fernández et al., 1998; Milner et al., 1998). Our aims were to Table 1...

    11. Oxford Postgraduate: Year One (1963-4)

      E-Print Network [OSTI]

      Macfarlane, Alan

      2015-06-16

      -6, the DPhil years were in laying the foundations of what I did over the following 45 years. Among these were: a. Teaching and supervising undergraduates - at Hertford b. Lecturing - the WEA classes c. Examining - the entrance exams at Worcester with HGP d... . High Tale (don's) life - with HGP and Keith Thomas e. Life histories - conversations, especially with Lady Clay, but also Hugh Trevor- Roper, E-P and others - leading later into the interviews. f. The breaking up of information - one fact, one card...

    12. Horizontal Well Placement Optimization in Gas Reservoirs Using Genetic Algorithms 

      E-Print Network [OSTI]

      Gibbs, Trevor Howard

      2011-08-08

      saturation and believed to be a volumetric reservoir with no water drive. The reservoir temperature is at 275 deg F. The gas gravity, relative density to air, is 0.68, and the permeability of the gas reservoir is 0.1 md. Case-specific differences... PLACEMENT OPTIMIZATION IN GAS RESERVOIRS USING GENETIC ALGORITHMS A Thesis by TREVOR HOWARD GIBBS Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment of the requirements for the degree of MASTER...

    13. Photochemical reaction dynamics

      SciTech Connect (OSTI)

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

      1993-12-01

      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.

    14. Studies of Immobilized Homogeneous Metal Catalysts on Silica Supports

      SciTech Connect (OSTI)

      Keith James Stanger

      2003-05-31

      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.

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

      SciTech Connect (OSTI)

      Bertch, Timothy C,

      2014-03-31

      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.

    16. Base-Mediated Cascade Rearrangements of Aryl-Substituted Diallyl Ethers

      E-Print Network [OSTI]

      Reid, Jolene P.; McAdam, Catherine A.; Johnston, Adam J. S.; Grayson, Matthew N.; Goodman, Jonathan M.; Cook, Matthew J.

      2014-12-16

      temperatures using ruthenium, rhodium, palladium and iridium catalysts which allow for a concomitant Claisen rearrangement.21 These approaches generally lead to epimerization of the ?-stereogenic center in the presence of the Lewis acidic metal catalysts... 60 14 To further strengthen our mechanistic understanding of these reactions a series of deuterium labeling experiments were conducted. Firstly, the vinyl silane was investigated and deuterated analog 23 was prepared and subjected to the reaction...

    17. 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

      2010-05-15

      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.

    18. Model for the Prediction of the Hydriding Thermodynamics of Pd-Rh-Co Ternary Alloys

      SciTech Connect (OSTI)

      Teter, D.F.; Thoma, D.J.

      1999-03-01

      A dilute solution model (with respect to the substitutional alloying elements) has been developed, which accurately predicts the hydride formation and decomposition thermodynamics and the storage capacities of dilute ternary Pd-Rh-Co alloys. The effect of varying the rhodium and cobalt compositions on the thermodynamics of hydride formation and decomposition and hydrogen capacity of several palladium-rhodium-cobalt ternary alloys has been investigated using pressure-composition (PC) isotherms. Alloying in the dilute regime (<10 at.%) causes the enthalpy for hydride formation to linearly decrease with increasing alloying content. Cobalt has a stronger effect on the reduction in enthalpy than rhodium for equivalent alloying amounts. Also, cobalt reduces the hydrogen storage capacity with increasing alloying content. The plateau thermodynamics are strongly linked to the lattice parameters of the alloys. A near-linear dependence of the enthalpy of hydride formation on the lattice parameter was observed for both the binary Pd-Rh and Pd-Co alloys, as well as for the ternary Pd-Rh-Co alloys. The Pd-5Rh-3Co (at. %) alloy was found to have similar plateau thermodynamics as a Pd-10Rh alloy, however, this ternary alloy had a diminished hydrogen storage capacity relative to Pd-10Rh.

    19. Mechanistic aspects of [Rh(nbd)CI][sub 2]initiated oligomerization of new acetylenic monomers

      SciTech Connect (OSTI)

      Densmore, C.G. (Crystal G); Rasmussen, P.G. (Paul G.)

      2004-01-01

      Although a number of papers report the use of rhodium-based initiators, very little has been said about the mechanism of acetylene polymerizations. Kishimoto and coworkers recently proposed an insertion mechanism for the rhodium-initiated polymerization of phenylacetylenes. The initiator consisted of the tetracoordinate rhodium complex, Rh(C{triple_bond}CC{sub 6}H{sub 5})(nbd)(PPh{sub 3}) with 4-(dimethylamino)-pyidine. The product was found to be stereoregular poly(phenylacety1ene) with a cis-transoidal backbone microstructure. Gorman and coworkers found palladium and nickel-based catalysts to be successful in the polymerization of cyanoacetylene. Zhan and Yang addressed the polymerization mechanism of acetylenes using palladium and nickel acetylide catalysts. They propose that the initial activation step, and also the rate-determining step, involve coordination of a nickel or palladium acetylide catalyst with an acetylene. Based on NMR and elemental analysis, we propose a more complete mechanistic picture of acetylene polymerizations, especially those with electron-withdrawing substituents.

    20. DNDO Report

      SciTech Connect (OSTI)

      Liegey, Lauren Rene; Wilcox, Trevor; Mckinney, Gregg Walter

      2015-08-07

      My internship program was the Domestic Nuclear Detection Office Summer Internship Program. I worked at Los Alamos National Laboratory with Trevor A. Wilcox and Gregg W. McKinney in the NEN-5 group. My project title was “MCNP Physical Model Interoperability & Validation”. The goal of my project was to write a program to predict the solar modulation parameter for dates in the future and then implement it into MCNP6. This update to MCNP6 can be used to calculate the background more precisely, which is an important factor in being able to detect Special Nuclear Material. We will share our work in a published American Nuclear Society (ANS) paper, an ANS presentation, and a LANL student poster session. Through this project, I gained skills in programming, computing, and using MCNP. I also gained experience that will help me decide on a career or perhaps obtain employment in the future.

    1. Catalytic partial oxidation of hydrocarbons

      DOE Patents [OSTI]

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

      2007-08-28

      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.

    2. Catalytic partial oxidation of hydrocarbons

      DOE Patents [OSTI]

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

      2009-05-19

      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.

    3. A study of the reaction between metal ions and thiomalic acid 

      E-Print Network [OSTI]

      Michel, Clyde Ernest

      1963-01-01

      stated that copper(II) was reduced to copper(I) by thiomalic ac1d. Wagner and Yoee reported spectrophoto- metric methods of analysis for palladium and rhodium. The precipitation of zirconium using thiomalic acid was reported by Sant and Sant...~. Thiomalic acid precipitated zirconium from a boiling solution contain1ng a zirconyl salt when the total acidity of the solution was 0. 1 to 0. 2N. It was the purpose of this research to expand the knowledge concerning the reaction of metal 1ons with thio...

    4. Regional Production Economics for Ethylene and Propylene Derivatives 

      E-Print Network [OSTI]

      McCormack, G.; Pavone, T.

      1990-01-01

      copolymer (PP-BC) * Acrylonit~ile (ACN) * P~opylene glycol (PG) * Cumene (CUM) * 2-Ethylhexanol (2EH) * Isop~opyl alcohol (IPA) 59 TECHNOLOGY ALTERNATIVES Most of the olefin derivatives c~r be made using a variety of processes and sla~ting materlals... * PG- Dow chlo~ohydrin * CUM- benzene alkylation * 2-EH- Union Carbide rhodium * IPA- Deutsche Texaco direct hydration REPRESENTATIVE CAPACITY One requirement fo~ establishing ESL-IE-90-06-10 Proceedings from the 12th National Industrial Energy...

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

      SciTech Connect (OSTI)

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

      2014-07-22

      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.

    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)

      1997-01-01

      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.

      1997-02-11

      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. Method and system for ethanol production

      DOE Patents [OSTI]

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

      1983-01-01

      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.

    9. Method and system for ethanol production

      DOE Patents [OSTI]

      Feder, H.M.; Chen, M.J.

      1981-09-24

      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.

    10. Thermally tolerant multilayer metal membrane

      DOE Patents [OSTI]

      Dye, Robert C. (Los Alamos, NM); Snow, Ronny C. (Los Alamos, NM)

      2001-01-01

      A composite metal membrane including a first metal layer of a Group IVB or Group VB metal sandwiched between two layers of a Group VIIIB metal selected from the group consisting of palladium, platinum, nickel, rhodium, iridium, cobalt, and alloys thereof, and a non-continuous layer of a metal chalcogenide upon one layer of the Group VIIIB metal is disclosed together with a process for the recovery of hydrogen from a gaseous mixture using such a composite membrane and a process for forming such a composite metal membrane.

    11. 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.

      2014-07-29

      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.

    12. 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)

      2015-01-01

      Rhodium sulfide (Rh2S3) on carbon support was synthesized by refluxing rhodium chloride with ammonium thiosulfate. Thermal treatment of Rh2S3 at high temperatures (600°C to 850°C) 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.

    13. Mixed Alcohol Synthesis Catalyst Screening

      SciTech Connect (OSTI)

      Gerber, Mark A.; White, James F.; Stevens, Don J.

      2007-09-03

      National Renewable Energy Laboratory (NREL) and Pacific Northwest National Laboratory (PNNL) are conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). PNNL is tasked with obtaining commercially available or preparing promising mixed-alcohol catalysts and screening them in a laboratory-scale reactor system. Commercially available catalysts and the most promising experimental catalysts are provided to NREL for testing using a slipstream from a pilot-scale biomass gasifier. From the standpoint of producing C2+ alcohols as the major product, it appears that the rhodium catalyst is the best choice in terms of both selectivity and space-time yield (STY). However, unless the rhodium catalyst can be improved to provide minimally acceptable STYs for commercial operation, mixed alcohol synthesis will involve significant production of other liquid coproducts. The modified Fischer-Tropsch catalyst shows the most promise for providing both an acceptable selectivity to C2+ alcohols and total liquid STY. However, further optimization of the Fischer-Tropsch catalysts to improve selectivity to higher alcohols is highly desired. Selection of a preferred catalyst will likely entail a decision on the preferred coproduct slate. No other catalysts tested appear amenable to the significant improvements needed for acceptable STYs.

    14. 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

      2010-10-01

      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 DOE’s 2010 and 2015 targets for system wt%.

    15. Development of an advanced, continuous mild gasification process for the production of co-products. Quarterly technical progress report, October--December 1991

      SciTech Connect (OSTI)

      Runge, B.D.; Ness, R.O. Jr.

      1992-01-01

      On November 6, 1991, a meeting was held at the AMAX Research and Development Center in Golden, Colorado. Those in attendance at the meeting included Brian Runge and Robert Ness of the EERC, Scott McFeely of Xoi, Frank Hogsett and Mahesh Jha of AMAX, and Jerry Sinor and Trevor Ellis of J.E- Sinor Consultants. Items on the agenda included framing the scope of work to be conducted by Sinor on the market assessment for mild gasification products. An attempt was made to draft an integrated time line for the completion of all subcontracts issued under the project. The commercial process flowsheet under development by XBi was presented for review. The goals to be achieved by the technical and economic assessment to be performed by XBi were outlined. Frank Hogsett reported on the progress of the coal cleaning being conducted by AMAX. As soon as sufficient coal has been cleaned, the mild gasification reactors at the EERC will be run to generate sufficient quantities of products to allow testing of product upgrading and utilization methods. The next project review meeting was held on December 12, 1991, in the Houston, Texas, offices of XBi. The major work conducted during this meeting focused on review of the preliminary process flow diagrams (PFOS) prepared by XBi. Several modifications were discussed and will be reflected in the updated PFDs.

    16. SPONTANEOUS CATALYTIC WET AIR OXIDATION DURING PRE-TREATMENT OF HIGH-LEVEL RADIOACTIVE WASTE SLUDGE

      SciTech Connect (OSTI)

      Koopman, D.; Herman, C.; Pareizs, J.; Bannochie, C.; Best, D.; Bibler, N.; Fellinger, T.

      2009-10-01

      Savannah River Remediation, LLC (SRR) operates the Defense Waste Processing Facility for the U.S. Department of Energy at the Savannah River Site. This facility immobilizes high-level radioactive waste through vitrification following chemical pretreatment. Catalytic destruction of formate and oxalate ions to carbon dioxide has been observed during qualification testing of non-radioactive analog systems. Carbon dioxide production greatly exceeded hydrogen production, indicating the occurrence of a process other than the catalytic decomposition of formic acid. Statistical modeling was used to relate the new reaction chemistry to partial catalytic wet air oxidation of both formate and oxalate ions driven by the low concentrations of palladium, rhodium, and/or ruthenium in the waste. Variations in process conditions led to increases or decreases in the total oxidative destruction, as well as partially shifting the preferred species undergoing destruction from oxalate ion to formate ion.

    17. 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.

      1991-01-01

      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.

    18. 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)

      2003-02-18

      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).

    19. 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)

      1997-01-01

      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.

    20. 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.

      1997-04-01

      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.

    1. 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; Sanchez del Rio, M.; Hoorani, H.

      2009-09-15

      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).

    2. High temperature coatings for gas turbines

      DOE Patents [OSTI]

      Zheng, Xiaoci Maggie

      2003-10-21

      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.

    3. Reactivity of Metal Ions Bound to Water-Soluble Polymers

      SciTech Connect (OSTI)

      Sauer, N.N.; Watkins, J.G.; Lin, M.; Birnbaum, E.R.; Robison, T.W.; Smith, B.F.; Gohdes, J.W.; McDonald, J.G.

      1999-06-29

      The intent of this work is to determine the effectiveness of catalysts covalently bound to polymers and to understand the consequences of supporting the catalysts on catalyst efficiency and selectivity. Rhodium phosphine complexes with functional groups for coupling to polymers were prepared. These catalyst precursors were characterized using standard techniques including IR, NMR, and elemental analysis. Studies on the modified catalysts showed that they were still active hydrogenation catalysts. However, tethering of the catalysts to polyamines gave systems with low hydrogenation activity. Analogous biphasic systems were also explored. Phosphine ligands with a surfactant-like structure have been synthesized and used to prepare catalytically active complexes of palladium. The palladium complexes were utilized in Heck-type coupling reactions (e.g. coupling of iodobenzene and ethyl acrylate to produce ethyl cinnamate) under vigorously stirred biphasic reaction conditions, and were found to offer superior performance over a standard water-soluble palladium catalyst under analogous conditions.

    4. Evaluation of a Novel Temperature Sensing Probe for Monitoring and Controlling Glass Temperature in a Joule-Heated Glass Melter

      SciTech Connect (OSTI)

      A. D. Watkins; C. A. Musick; C. Cannon (AccuTru Int'l Corp); N. M. Carlson; P. D. Mullenix (INEEL); R. D. Tillotson

      1999-04-29

      A self-verifying temperature sensor that employs advanced contact thermocouple probe technology was tested in a laboratory-scale, joule-heated, refractory-lined glass melter used for radioactive waste vitrification. The novel temperature probe monitors melt temperature at any given level of the melt chamber. The data acquisition system provides the real-time temperature for molten glass. Test results indicate that the self-verifying sensor is more accurate and reliable than classic platinum/rhodium thermocouple and sheath assemblies. The results of this test are reported as well as enhancements being made to the temperature probe. To obtain more reliable temperature measurements of the molten glass for improving production efficiency and ensuring consistent glass properties, optical sensing was reviewed for application in a high temperature environment.

    5. Interplay of light transmission and catalytic exchange current in photoelectrochemical systems

      SciTech Connect (OSTI)

      Fountaine, Katherine T.; Lewerenz, Hans J.; Atwater, Harry A.

      2014-10-27

      We develop an analytic current-voltage expression for a variable junction photoelectrochemical (PEC) cell and use it to investigate and illustrate the influence of the optical and electrical properties of catalysts on the optoelectronic performance of PEC devices. Specifically, the model enables a simple, yet accurate accounting of nanostructured catalyst optical and electrical properties through incorporation of an optical transmission factor and active catalytic area factor. We demonstrate the utility of this model via the output power characteristics of an exemplary dual tandem solar cell with indium gallium phosphide and indium gallium arsenide absorbers with varying rhodium catalyst nanoparticle loading. The approach highlights the importance of considering interactions between independently optimized components for optimal PEC device design.

    6. X-ray source for mammography

      DOE Patents [OSTI]

      Logan, Clinton M. (Pleasanton, CA)

      1994-01-01

      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.

    7. X-ray source for mammography

      DOE Patents [OSTI]

      Logan, C.M.

      1994-12-20

      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.

    8. 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]

      Karpuškien?, R; Kisielius, R

      2015-01-01

      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...

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

      DOE Patents [OSTI]

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

      1998-01-01

      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.

    10. Lightweight, durable lead-acid batteries

      DOE Patents [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)

      2011-09-13

      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).

    11. Lightweight, durable lead-acid batteries

      DOE Patents [OSTI]

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

      2013-05-21

      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).

    12. 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.

      2014-02-10

      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-µm 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-µm in length.

    13. 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

      2015-02-01

      Rhodium sulfide (Rh2S3) on carbon support was synthesized by refluxing rhodium chloride with ammonium thiosulfate. Thermal treatment of Rh2S3 at high temperatures (600°C to 850°C) 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 exchangemore »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.« less

    14. Applicability of Density Functional Theory in Reproducing Accurate Vibrational Spectra of Surface Bound Species

      SciTech Connect (OSTI)

      Matanovic, Ivana; Atanassov, Plamen; Kiefer, Boris; Garzon, Fernando; Henson, Neil J.

      2014-10-05

      The structural equilibrium parameters, the adsorption energies, and the vibrational frequencies of the nitrogen molecule and the hydrogen atom adsorbed on the (111) surface of rhodium have been investigated using different generalized-gradient approximation (GGA), nonlocal correlation, meta-GGA, and hybrid functionals, namely, Perdew, Burke, and Ernzerhof (PBE), Revised-RPBE, vdW-DF, Tao, Perdew, Staroverov, and Scuseria functional (TPSS), and Heyd, Scuseria, and Ernzerhof (HSE06) functional in the plane wave formalism. Among the five tested functionals, nonlocal vdW-DF and meta-GGA TPSS functionals are most successful in describing energetics of dinitrogen physisorption to the Rh(111) surface, while the PBE functional provides the correct chemisorption energy for the hydrogen atom. It was also found that TPSS functional produces the best vibrational spectra of the nitrogen molecule and the hydrogen atom on rhodium within the harmonic formalism with the error of 22.62 and 21.1% for the NAN stretching and RhAH stretching frequency. Thus, TPSS functional was proposed as a method of choice for obtaining vibrational spectra of low weight adsorbates on metallic surfaces within the harmonic approximation. At the anharmonic level, by decoupling the RhAH and NAN stretching modes from the bulk phonons and by solving one- and two-dimensional Schr€odinger equation associated with the RhAH, RhAN, and NAN potential energy we calculated the anharmonic correction for NAN and RhAH stretching modes as 231 cm21 and 277 cm21 at PBE level. Anharmonic vibrational frequencies calculated with the use of the hybrid HSE06 function are in best agreement with available experiments.

    15. Intrinsic Uncertainties in Modeling Complex Systems.

      SciTech Connect (OSTI)

      Cooper, Curtis S; Bramson, Aaron L.; Ames, Arlo L.

      2014-09-01

      Models are built to understand and predict the behaviors of both natural and artificial systems. Because it is always necessary to abstract away aspects of any non-trivial system being modeled, we know models can potentially leave out important, even critical elements. This reality of the modeling enterprise forces us to consider the prospective impacts of those effects completely left out of a model - either intentionally or unconsidered. Insensitivity to new structure is an indication of diminishing returns. In this work, we represent a hypothetical unknown effect on a validated model as a finite perturba- tion whose amplitude is constrained within a control region. We find robustly that without further constraints, no meaningful bounds can be placed on the amplitude of a perturbation outside of the control region. Thus, forecasting into unsampled regions is a very risky proposition. We also present inherent difficulties with proper time discretization of models and representing in- herently discrete quantities. We point out potentially worrisome uncertainties, arising from math- ematical formulation alone, which modelers can inadvertently introduce into models of complex systems. Acknowledgements This work has been funded under early-career LDRD project %23170979, entitled %22Quantify- ing Confidence in Complex Systems Models Having Structural Uncertainties%22, which ran from 04/2013 to 09/2014. We wish to express our gratitude to the many researchers at Sandia who con- tributed ideas to this work, as well as feedback on the manuscript. In particular, we would like to mention George Barr, Alexander Outkin, Walt Beyeler, Eric Vugrin, and Laura Swiler for provid- ing invaluable advice and guidance through the course of the project. We would also like to thank Steven Kleban, Amanda Gonzales, Trevor Manzanares, and Sarah Burwell for their assistance in managing project tasks and resources.

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

      SciTech Connect (OSTI)

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

      2015-01-01

      Rhodium sulfide (Rh2S3) on carbon support was synthesized by refluxing rhodium chloride with ammonium thiosulfate. Thermal treatment of Rh2S3 at high temperatures (600°C to 850°C) 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.

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

      SciTech Connect (OSTI)

      Wayland, B.B.

      2009-08-31

      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.

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

      DOE Patents [OSTI]

      McDowell, William J. (Knoxville, TN)

      1980-01-01

      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.

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

      DOE Patents [OSTI]

      Wilcoxon, Jess P. (Albuquerque, NM)

      1992-01-01

      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.

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

      SciTech Connect (OSTI)

      Oji, L

      2005-06-01

      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.

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

      SciTech Connect (OSTI)

      Oji, L

      2005-05-05

      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.

    2. US Department of Energy radioisotope customers with summary of radioisotope shipments, FY 1988

      SciTech Connect (OSTI)

      Van Houten, N.C.

      1989-06-01

      Pacific Northwest Laboratory (PNL) prepared this edition of the radioisotope customer list at the request of the Office of Health and Environmental Research (ER-73), Office of Energy Research, US Department of Energy (DOE). This is the 25th report in a series dating from 1964. This report covers DOE radioisotope sales and distribution activities by its facilities to domestic, foreign and other DOE facilities for FY 1988. The report is divided into five sections: radioisotope suppliers, facility contacts, and radioisotopes or services supplied; a list of customers, suppliers, and radioisotopes purchased; a list of radioisotopes purchased cross-referenced to customer numbers; geographic locations of radioisotope customers; and radioisotope sales and transfers -- FY 1988. Radioisotopes not previously reported in this series of reports were argon-37, arsenic-72, arsenic-73, bismuth-207, gadolinium-151, rhenium-188, rhodium-101, selenium-72, xenon-123 and zirconium-88. The total value of DOE radioisotope sales for FY 1988 was $11.1 million, an increase of 3% from FY 1987.

    3. 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.

      2013-08-07

      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.

    4. Adjustments to the ICVGT scale of INRIM

      SciTech Connect (OSTI)

      Steur, P. P. M.; Giraudi, D. [Istituto Nazionale di Ricerca Metrologica (INRIM), Torino (Italy)] [Istituto Nazionale di Ricerca Metrologica (INRIM), Torino (Italy)

      2013-09-11

      At the 8{sup th} Temperature Symposium the results have been presented for the Interpolating Constant Volume Gas thermometer at INRIM (then IMGC), featuring a cryogenic pressure transducer, with an expanded uncertainty of less then 1.5 mK. However, for its fixed points this scale still relied on a NPL calibration as carried by rhodium-iron thermometer 232324. After the clarification, in 2005, by the Consultative Committee on Thermometry (CCT) of the definition of the equilibrium hydrogen (e-H2) triple point this scale was due to be adjusted for the isotopic content in the e-H2 fixed point cell. Only when this thermometer was re-calibrated in 2010 at INRIM at the three fixed points of the ICVGT was this adjustment performed, being the isotopic composition of the hydrogen cell known. With the start of the Neon Project in 2005, it became clear that a second adjustment would soon be needed, once the CCT will have decided on the way to deal with the isotopic composition of neon. The paper presents the experimental data of 2010, discusses the stability of the thermometer, and the size of the correction at the hydrogen point and of the likely correction (and its uncertainty) to be applied to the neon point, the isotopic composition of this cell being known as well.

    5. Dendrimer Templated Synthesis of One Nanometer Rh and Pt Particles Supported on Mesoporous Silica: Catalytic Activity for Ethylene and Pyrrole Hydrogenation.

      SciTech Connect (OSTI)

      Huang, Wenyu; Kuhn, John N.; Tsung, Chia-Kuang; Zhang, Yawen; Habas, Susan E.; Yang, Peidong; Somorjai, Gabor A.

      2008-05-09

      Monodisperse rhodium (Rh) and platinum (Pt) nanoparticles as small as {approx}1 nm were synthesized within a fourth generation polyaminoamide (PAMAM) dendrimer, a hyperbranched polymer, in aqueous solution and immobilized by depositing onto a high-surface-area SBA-15 mesoporous support. X-ray photoelectron spectroscopy indicated that the as-synthesized Rh and Pt nanoparticles were mostly oxidized. Catalytic activity of the SBA-15 supported Rh and Pt nanoparticles was studied with ethylene hydrogenation at 273 and 293 K in 10 torr of ethylene and 100 torr of H{sub 2} after reduction (76 torr of H{sub 2} mixed with 690 torr of He) at different temperatures. Catalysts were active without removing the dendrimer capping but reached their highest activity after hydrogen reduction at a moderate temperature (423 K). When treated at a higher temperature (473, 573, and 673 K) in hydrogen, catalytic activity decreased. By using the same treatment that led to maximum ethylene hydrogenation activity, catalytic activity was also evaluated for pyrrole hydrogenation.

    6. Hydrogen sorption characteristics of nanostructured Pd–10Rh processed by cryomilling

      SciTech Connect (OSTI)

      Yang, Nancy; Yee, Joshua K.; Zhang, Zhihui; Kurmanaeva, Lilia; Cappillino, Patrick; Stavila, Vitalie; Lavernia, Enrique J.; San Marchi, Chris

      2014-10-03

      Palladium and its alloys are model systems for studying solid-state storage of hydrogen. Mechanical milling is commonly used to process complex powder systems for solid-state hydrogen storage; however, milling can also be used to evolve nanostructured powder to modify hydrogen sorption characteristics. In the present study, cryomilling (mechanical attrition milling in a cryogenic liquid) is used to produce nanostructured palladium-rhodium alloy powder. Characterization of the cryomilled Pd-10Rh using electron microscopy, X-ray diffraction, and surface area analysis reveals that (i) particle morphology evolves from spherical to flattened disk-like particles; while the (ii) crystallite size decreases from several microns to less than 100 nm and (iii) dislocation density increases with increased cryomilling time. Hydrogen absorption and desorption isotherms as well as the time scales for absorption were measured for cryomilled Pd-10Rh, and correlated with observed microstructural changes induced by the cryomilling process. In short, as the microstructure of the Pd-10Rh alloy is refined by cryomilling: (i) the maximum hydrogen concentration in the ?-phase increases, (ii) the pressure plateau becomes flatter, and (iii) the equilibrium hydrogen capacity at 760 Torr increases. In addition, the rate of hydrogen absorption was reduced by an order of magnitude compared to non-cryomilled (atomized) powder.

    7. 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.

      1987-12-29

      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.

    8. Hydrogen sorption characteristics of nanostructured Pd–10Rh processed by cryomilling

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

      Yang, Nancy; Yee, Joshua K.; Zhang, Zhihui; Kurmanaeva, Lilia; Cappillino, Patrick; Stavila, Vitalie; Lavernia, Enrique J.; San Marchi, Chris

      2014-10-03

      Palladium and its alloys are model systems for studying solid-state storage of hydrogen. Mechanical milling is commonly used to process complex powder systems for solid-state hydrogen storage; however, milling can also be used to evolve nanostructured powder to modify hydrogen sorption characteristics. In the present study, cryomilling (mechanical attrition milling in a cryogenic liquid) is used to produce nanostructured palladium-rhodium alloy powder. Characterization of the cryomilled Pd-10Rh using electron microscopy, X-ray diffraction, and surface area analysis reveals that (i) particle morphology evolves from spherical to flattened disk-like particles; while the (ii) crystallite size decreases from several microns to less thanmore »100 nm and (iii) dislocation density increases with increased cryomilling time. Hydrogen absorption and desorption isotherms as well as the time scales for absorption were measured for cryomilled Pd-10Rh, and correlated with observed microstructural changes induced by the cryomilling process. In short, as the microstructure of the Pd-10Rh alloy is refined by cryomilling: (i) the maximum hydrogen concentration in the ?-phase increases, (ii) the pressure plateau becomes flatter, and (iii) the equilibrium hydrogen capacity at 760 Torr increases. In addition, the rate of hydrogen absorption was reduced by an order of magnitude compared to non-cryomilled (atomized) powder.« less

    9. Method for bonding thin film thermocouples to ceramics

      DOE Patents [OSTI]

      Kreider, Kenneth G. (Potomac, MD)

      1993-01-01

      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. Process for functionalizing alkanes

      DOE Patents [OSTI]

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

      1988-01-01

      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.

    11. Process for functionalizing alkanes

      DOE Patents [OSTI]

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

      1985-01-01

      Process for functionalizing saturated hydrocarbons selectively in the terminal position comprising: (a) reacting said saturated hydrocarbons of the formula: RH where: H represents a hydrogen atom, and R represents a saturated hydrocarbon radical, with a metal complex of the formula: CpRhPMe.sub.3 H.sub.2 where: Cp represents a pentamethylated cyclopentadienyl radical, Rh represents a rhodium atom, P represents a phosphorous atom, Me represents a methyl group, H represents a hydrogen atom, in the presence of ultraviolet radiation at a temperature maintained at about -60.degree. to -17.degree. C. to form a hydridoalkyl complex of the formula: CpRhPMe.sub.3 RH (b) reacting said hydridoalkyl complex with a haloform of the formula: CHX.sub.3 where: X represents a 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.

    12. 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)

      2002-01-01

      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.

    13. Ternary Pt/Rh/SnO2 Electrocatalysts for Oxidizing Ethanol to CO2

      SciTech Connect (OSTI)

      Kowal, A.; Li, M; Shao, M; Sasaki, K; Vukmirovic, M; Zhang, J; Marinkovic, N; Liu, P; Frenkel, A; Adzic, R

      2009-01-01

      Ethanol, with its high energy density, likely production from renewable sources and ease of storage and transportation, is almost the ideal combustible for fuel cells wherein its chemical energy can be converted directly into electrical energy. However, commercialization of direct ethanol fuel cells has been impeded by ethanol's slow, inefficient oxidation even at the best electrocatalysts1, 2. We synthesized a ternary PtRhSnO2/C electrocatalyst by depositing platinum and rhodium atoms on carbon-supported tin dioxide nanoparticles that is capable of oxidizing ethanol with high efficiency and holds great promise for resolving the impediments to developing practical direct ethanol fuel cells. This electrocatalyst effectively splits the C-C bond in ethanol at room temperature in acid solutions, facilitating its oxidation at low potentials to CO2, which has not been achieved with existing catalysts. Our experiments and density functional theory calculations indicate that the electrocatalyst's activity is due to the specific property of each of its constituents, induced by their interactions. These findings help explain the high activity of Pt-Ru for methanol oxidation and the lack of it for ethanol oxidation, and point to the way to accomplishing the C-C bond splitting in other catalytic processes.

    14. Ternary Pt/Rh/SnO2 Electrocatalysts for Oxidizing Ethanol to CO2

      SciTech Connect (OSTI)

      Adzic, R.R.; Kowal, A.; Li, M.; Shao, M.; Sasaki, K.; Vukmirovic, M.B.; Zhang, J.; Marinkovic, N.S. Liu, P.; Frenkel, A.I.

      2009-04-01

      Ethanol, with its high energy density, likely production from renewable sources and ease of storage and transportation, is almost the ideal combustible for fuel cells wherein its chemical energy can be converted directly into electrical energy. However, commercialization of direct ethanol fuel cells has been impeded by ethanol's slow, inefficient oxidation even at the best electrocatalysts. We synthesized a ternary PtRhSnO{sub 2}/C electrocatalyst by depositing platinum and rhodium atoms on carbon-supported tin dioxide nanoparticles that is capable of oxidizing ethanol with high efficiency and holds great promise for resolving the impediments to developing practical direct ethanol fuel cells. This electrocatalyst effectively splits the C-C bond in ethanol at room temperature in acid solutions, facilitating its oxidation at low potentials to CO{sub 2}, which has not been achieved with existing catalysts. Our experiments and density functional theory calculations indicate that the electrocatalyst's activity is due to the specific property of each of its constituents, induced by their interactions. These findings help explain the high activity of Pt-Ru for methanol oxidation and the lack of it for ethanol oxidation, and point to the way to accomplishing the C-C bond splitting in other catalytic processes.

    15. 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.

      1985-01-01

      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.

    16. 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

      2009-09-01

      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.

    17. Synthesis of few-walled carbon nanotube-Rh nanoparticles by arc discharge: Effect of selective oxidation

      SciTech Connect (OSTI)

      Zhang Yanfeng

      2012-06-15

      Highly crystalline rhodium (Rh) nanoparticles supported on carbon nanotubes were prepared by selective oxidation method. Carbon nanotubes and FeRh nanoparticles were simultaneously generated in hydrogen arc plasma. The as-grown nanomaterials can be purified by heat treatment in open air and by soaking in HCl. X-ray diffraction and selected area electron diffraction results reveal that as-grown FeRh nanoparticles have a typical chemical CsCl-type structure which can be transformed into a face-centered cubic structure by thermal annealing in the purification process. The purification process is selective toward the removal of the amorphous carbon coating the nanoparticles, and transforms Fe to Fe{sub 2}O{sub 3}. Fe{sub 2}O{sub 3} can be easily dissolved in hydrochloric acid, leaving carbon nanotubes-Rh nanoparticles. Rh nanoparticles with diameters of 2-60 nm are deposited uniformly on the surface of the carbon nanotube bundles. This simple and selective chemistry offers a new process for synthesizing and controlling Fe content in carbon nanotube-FeRh nanoparticles. Highlights: Black-Right-Pointing-Pointer High-crystallinity CNTs and FeRh nanoparticles were simultaneously generated in arc plasma. Black-Right-Pointing-Pointer The diameter distribution of CNTs depends on different gases. Black-Right-Pointing-Pointer Heat treatment in open air and soaking in HCl can convert CNTs-FeRh to CNTs-Rh. Black-Right-Pointing-Pointer The selective oxidation mechanisms of metal nanoparticles and carbon materials differ.

    18. Monochromatic wavelength dispersive x-ray fluorescence providing sensitive and selective detection of uranium

      SciTech Connect (OSTI)

      Havrilla, George J [Los Alamos National Laboratory; Collins, Michael L [Los Alamos National Laboratory; Montoya, Velma M [Los Alamos National Laboratory; Chen, Zewu [XOS; Wei, Fuzhong [XOS

      2010-01-01

      Monochromatic wavelength dispersive X-ray fluorescence (MWDXRF) is a sensitive and selective method for elemental compositional analyses. The basis for this instrumental advance is the doubly curved crystal (DCC) optic. Previous work has demonstrated the feasibility of sensitive trace element detection for yttrium as a surrogate for curium in aqueous solutions. Additional measurements have demonstrated similar sensitivity in several different matrix environments which attests to the selectivity of the DCC optic as well as the capabilities of the MWDXRF concept. The objective of this effort is to develop an improved Pu characterization method for nuclear fuel reprocessing plants. The MWDXRF prototype instrument is the second step in a multi-year effort to achieve an improved Pu assay. This work will describe a prototype MWDXRF instrument designed for uranium detection and characterization. The prototype consists of an X-ray tube with a rhodium anode and a DCC excitation optic incorporated into the source. The DCC optic passes the RhK{alpha} line at 20.214 keV for monochromatic excitation of the sample. The source is capable of 50 W power at 50 kV and 1.0 mA operation. The x-ray emission from the sample is collected by a DCC optic set at the UL{alpha} line of 13.613 keV. The collection optic transmits the UL{alpha} x-rays to the silicon drift detector. The x-ray source, sample, collection optic and detector are all mounted on motion controlled stages for the critical alignment of these components. The sensitivity and selectivity of the instrument is obtained through the monochromatic excitation and the monochromatic detection. The prototype instrument performance has a demonstrated for sensitivity for uranium detection of around 2 ppm at the current state of development. Further improvement in sensitivity is expected with more detailed alignment.

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

      SciTech Connect (OSTI)

      Seymour, R.G.

      1995-06-07

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

      SciTech Connect (OSTI)

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

      2010-12-01

      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.

    1. An Assessment of the Current Day Impact of Various Materials Associated with the U.S. Nuclear Test Program in the Marshall Island

      SciTech Connect (OSTI)

      Robison, W L; Noshkin, V E; Hamilton, T F; Conrado, C L; Bogen, K T

      2001-05-01

      Different stable elements, and some natural and man-made radionuclides, were used as tracers or associated in other ways with nuclear devices that were detonated at Bikini and Enewetak Atolls as part of the U.S. nuclear testing program from 1946 through 1958. The question has been raised whether any of these materials dispersed by the explosions could be of sufficient concentration in either the marine environment or on the coral islands to be of a health concern to people living, or planning to live, on the atolls. This report addresses that concern. An inventory of the materials involved during the test period was prepared and provided to us by the Office of Defense Programs (DP) of the United States Department of Energy (DOE). The materials that the DOE and the Republic of the Marshall Islands (RMI) ask to be evaluated are--sulfur, arsenic, yttrium, tantalum, gold, rhodium, indium, tungsten, thallium, thorium-230,232 ({sup 230,232}Th), uranium-233,238 ({sup 233,238}U), polonium-210 ({sup 210}Po), curium-232 ({sup 232}Cu), and americium-241 ({sup 241}Am). The stable elements were used primarily as tracers for determining neutron energy and flux, and for other diagnostic purposes in the larger yield, multistage devices. It is reasonable to assume that these materials would be distributed in a similar manner as the fission products subsequent to detonation. A large inventory of fission product and uranium data was available for assessment. Detailed calculations show only a very small fraction of the fission products produced during the entire test series remain at the test site atolls. Consequently, based on the information provided, we conclude that the concentration of these materials in the atoll environment pose no adverse health effects to humans.

    2. Detection limits for actinides in a monochromatic, wavelength-dispersive x-ray fluorescence instrument

      SciTech Connect (OSTI)

      Collins, Michael L [Los Alamos National Laboratory; Havrilla, George J [Los Alamos National Laboratory

      2009-01-01

      Recent developments in x-ray optics have made it possible to examine the L x-rays of actinides using doubly-curved crystals in a bench-top device. A doubly-curved crystal (DCC) acts as a focusing monochromatic filter for polychromatic x-rays. A Monochromatic, Wavelength-Dispersive X-Ray Fluorescence (MWDXRF) instrument that uses DCCs to measure Cm and Pu in reprocessing plant liquors was proposed in 2007 by the authors at Los Alamos National Laboratory. A prototype design of this MWDXRF instrument was developed in collaboration with X-ray Optical Systems Inc. (XOS), of East Greenbush, New York. In the MWDXRF instrument, x-rays from a Rhodium-anode x-ray tube are passed through a primary DCC to produce a monochromatic beam of 20.2-keV photons. This beam is focused on a specimen that may contain actinides. The 20.2-keV interrogating beam is just above the L3 edge of Californium; each actinide (with Z = 90 to 98) present in the specimen emits characteristic L x-rays as the result of L3-shell vacancies. In the LANL-XOS prototype MWDXRf, these x-rays enter a secondary DCC optic that preferentially passes 14.961-keV photons, corresponding to the L-alpha-1 x-ray peak of Curium. In the present stage of experimentation, Curium-bearing specimens have not been analyzed with the prototype MWDXRF instrument. Surrogate materials for Curium include Rubidium, which has a K-beta-l x-ray at 14.961 keV, and Yttrium, which has a K-alpha-1 x-ray at 14.958 keV. In this paper, the lower limit of detection for Curium in the LANL-XOS prototype MWDXRF instrument is estimated. The basis for this estimate is described, including a description of computational models and benchmarking techniques used. Detection limits for other actinides are considered, as well as future safeguards applications for MWDXRF instrumentation.

    3. Process for alkane group dehydrogenation with organometallic catalyst

      DOE Patents [OSTI]

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

      1998-07-14

      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.

    4. Process for alkane group dehydrogenation with organometallic catalyst

      DOE Patents [OSTI]

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

      1998-01-01

      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.

    5. 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

      2006-09-01

      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 Wisconsin’s 1.7MV Tandem Accelerator Facility. This facility is now capable of irradiating of materials to high dose while controlling sample temperature up to 800ºC.

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

      SciTech Connect (OSTI)

      Johnson, F.

      2012-05-01

      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.

    7. 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.

      2013-11-18

      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.

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

      SciTech Connect (OSTI)

      Koopman, D. C.

      2013-01-22

      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.

    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

      2012-03-01

      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 INL’s 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 INL’s 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, UT’s 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. IMPACT OF NOBLE METALS AND MERCURY ON HYDROGEN GENERATION DURING HIGH LEVEL WASTE PRETREATMENT AT THE SAVANNAH RIVER SITE

      SciTech Connect (OSTI)

      Stone, M; Tommy Edwards, T; David Koopman, D

      2009-03-03

      The Defense Waste Processing Facility (DWPF) at the Savannah River Site vitrifies radioactive High Level Waste (HLW) for repository internment. The process consists of three major steps: waste pretreatment, vitrification, and canister decontamination/sealing. HLW consists of insoluble metal hydroxides (primarily iron, aluminum, calcium, magnesium, manganese, and uranium) and soluble sodium salts (carbonate, hydroxide, nitrite, nitrate, and sulfate). The pretreatment process in the Chemical Processing Cell (CPC) consists of two process tanks, the Sludge Receipt and Adjustment Tank (SRAT) and the Slurry Mix Evaporator (SME) as well as a melter feed tank. During SRAT processing, nitric and formic acids are added to the sludge to lower pH, destroy nitrite and carbonate ions, and reduce mercury and manganese. During the SME cycle, glass formers are added, and the batch is concentrated to the final solids target prior to vitrification. During these processes, hydrogen can be produced by catalytic decomposition of excess formic acid. The waste contains silver, palladium, rhodium, ruthenium, and mercury, but silver and palladium have been shown to be insignificant factors in catalytic hydrogen generation during the DWPF process. A full factorial experimental design was developed to ensure that the existence of statistically significant two-way interactions could be determined without confounding of the main effects with the two-way interaction effects. Rh ranged from 0.0026-0.013% and Ru ranged from 0.010-0.050% in the dried sludge solids, while initial Hg ranged from 0.5-2.5 wt%, as shown in Table 1. The nominal matrix design consisted of twelve SRAT cycles. Testing included: a three factor (Rh, Ru, and Hg) study at two levels per factor (eight runs), three duplicate midpoint runs, and one additional replicate run to assess reproducibility away from the midpoint. Midpoint testing was used to identify potential quadratic effects from the three factors. A single sludge simulant was used for all tests and was spiked with the required amount of noble metals immediately prior to performing the test. Acid addition was kept effectively constant except to compensate for variations in the starting mercury concentration. SME cycles were also performed during six of the tests.

    11. Sediment studies at Bikini Atoll part 3. Inventories of some long-lived gamma-emitting radionuclides associated with lagoon surface sediments

      SciTech Connect (OSTI)

      Noshkin, V.E.

      1997-12-01

      Surface sediment samples were collected during 1979 from 87 locations in the lagoon at Bikini Atoll. The collections were made to better define the concentrations and distribution of long-lived radionuclides associated with the bottom material and to show what modifications occurred to the composition of the surface sediment from the nuclear testing program conducted by the United States at the Atoll between 1946 and 1958. This is the last of three reports on Bikini sediment studies. In this report, we discuss the concentrations and inventories of the residual long-lived gamma-emitting radionuclides in sediments from the lagoon. The gamma-emitting radionuclides detected most frequently in sediments collected in 1979, in addition to Americium-241 ({sup 241}Am) (discussed in the second report of this series), included Cesium-137 ({sup 137}Cs), Bismuth-207 ({sup 207}Bi), Europium-155 ({sup 155}Eu), and Cobalt-60 ({sup 60}Co). Other man-made, gamma-emitting radionuclides such as Europium-152,154 ({sup 152,154}Eu), Antimony-125 ({sup 125}Sb), and Rhodium-101,102m ({sup 101,102m}Rh) were occasionally measured above detection limits in sediments near test site locations. The mean inventories for {sup 137}Cs, {sup 207}Ei, {sup 155}Eu, and {sup 60}Co in the surface 4 cm of the lagoon sediment to be 1.7, 0.56, 7.76, and 0.74 TBq, respectively. By June 1997, radioactive decay would reduce these values to 1.1, 0.38, 0.62, and 0.07 TBq, respectively. Some additional loss results from a combination of different processes that continuously mobilize and return some amount of the radionuclides to the water column. The water and dissolved constituents are removed from the lagoon through channels and exchange with the surface waters of the north equatorial Pacific Ocean. Highest levels of these radionuclides are found in surface deposits lagoonward of the Bravo Crater. Lowest concentrations and inventories are associated with sediment lagoonward of the eastern reef. The quantities in the 0-4 cm surface layer are estimated to be less than 35% of the total inventory to depth in the sediment column.

    12. 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

      2010-11-01

      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.

    13. Small, Inexpensive Combined NOx Sensor and O2 Sensor

      SciTech Connect (OSTI)

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

      2008-09-08

      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.

    14. Small, Inexpensive Combined NOx and O2 Sensor

      SciTech Connect (OSTI)

      W. Lawless; C. Clark

      2008-09-01

      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.

    15. 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

      2012-12-17

      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

    16. DWPF Hydrogen Generation Study-Form of Noble Metal SRAT Testing

      SciTech Connect (OSTI)

      Bannochie, C

      2005-09-01

      The Defense Waste Processing Facility, DWPF, has requested that the Savannah River National Laboratory, SRNL, investigate the factors that contribute to hydrogen generation to determine if current conservatism in setting the DWPF processing window can be reduced. A phased program has been undertaken to increase understanding of the factors that influence hydrogen generation in the DWPF Chemical Process Cell, CPC. The hydrogen generation in the CPC is primarily due to noble metal catalyzed decomposition of formic acid with a minor contribution from radiolytic processes. Noble metals have historically been added as trim chemicals to process simulations. The present study investigated the potential conservatism that might be present from adding the catalytic species as trim chemicals to the final sludge simulant versus co-precipitating the noble metals into the insoluble sludge solids matrix. Two sludge simulants were obtained, one with co-precipitated noble metals and one without noble metals. Co-precipitated noble metals were expected to better match real waste behavior than using trimmed noble metals during CPC simulations. Portions of both sludge simulants were held at 97 C for about eight hours to qualitatively simulate the effects of long term storage on particle morphology and speciation. The two original and two heat-treated sludge simulants were then used as feeds to Sludge Receipt and Adjustment Tank, SRAT, process simulations. Testing was done at relatively high acid stoichiometries, {approx}175%, and without mercury in order to ensure significant hydrogen generation. Hydrogen generation rates were monitored during processing to assess the impact of the form of noble metals. The following observations were made on the data: (1) Co-precipitated noble metal simulant processed similarly to trimmed noble metal simulant in most respects, such as nitrite to nitrate conversion, formate destruction, and pH, but differently with respect to hydrogen generation: (A) The peak hydrogen generation rate occurred three to five hours later for the regular and heat-treated co-precipitated noble metal slurries than for the slurries with trimmed noble metals. (B) The peak hydrogen generation rate was lower during processing of the co-precipitated noble metal simulant relative to the trimmed noble metal simulant data. (C) Trimmed noble metals appeared to be conservative relative to co-precipitated noble metals under the conditions of these tests as long as the peak hydrogen generation rate occurred early in the SRAT boiling period. (2) If the peak hydrogen generation rate with trimmed noble metals is near or above the DWPF limit, and if the peak occurs late in the SRAT cycle, then a potential SME cycle hydrogen generation rate issue could be anticipated when using co-precipitated noble metals, since the peak is expected to be delayed relative to trimmed noble metals. (3) The peak hydrogen generation rate increased from about 1.3 to about 3.7 lbs H{sub 2}/hr on the range of 170-190% stoichiometry, or about 0.1 lbs. H{sub 2}/hr per % change in the stoichiometric factor at DWPF scale. (4) The peak generation rate was slightly higher during processing of the heat-treated coprecipitated noble metal simulant relative to the trimmed noble metal heat-treated simulant, but this probably due to somewhat more excess acid being added to the co-precipitated noble metal test than intended. (5) The variations in the peak hydrogen generation rate appeared to track the quantity of dissolved rhodium in the SRAT product. (6) A noble metal apparently activated and then de-activated during the final hour of formic acid addition. The associated peak generation rate was <3% of the maximum rate seen in each test. Palladium may have been responsible based on literature data. (7) Planned comparisons between heat-treated and un-heat-treated simulants were complicated by the significantly altered base equivalents following heat-treatment. This necessitated making small adjustments to the stoichiometric acid factor to attempt to match the excess acid contents