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Sample records for geothermometry cation geothermometers

  1. Cation Geothermometers | Open Energy Information

    Open Energy Info (EERE)

    prospect the fastest is obtaining attractive chemical confirmation (geothermometry, gas analyses) that a thermal resource exists in that location. As with all geothermal...

  2. Improvements in geothermometry. Final technical report

    SciTech Connect (OSTI)

    Potter, J.; Dibble, W.; Parks, G.; Nur, A.

    1982-07-01

    The following are covered: the basis of the Na-K-Ca geothermometer, geothermometry via model calculations, non ideality and complexing, and experimental calibration.

  3. Geothermometry At Yellowstone Region (Fournier, 1979) | Open...

    Open Energy Info (EERE)

    Geothermal Region Exploration Technique Geothermometry Activity Date Usefulness useful DOE-funding Unknown Notes Enthalpy-Chloride digram. Not exactly cation geothermometry...

  4. Multicomponent Equilibrium Models for Testing Geothermometry Approaches

    SciTech Connect (OSTI)

    Cooper, D. Craig; Palmer, Carl D.; Smith, Robert W.; McLing, Travis L.

    2013-02-01

    Geothermometry is an important tool for estimating deep reservoir temperature from the geochemical composition of shallower and cooler waters. The underlying assumption of geothermometry is that the waters collected from shallow wells and seeps maintain a chemical signature that reflects equilibrium in the deeper reservoir. Many of the geothermometers used in practice are based on correlation between water temperatures and composition or using thermodynamic calculations based a subset (typically silica, cations or cation ratios) of the dissolved constituents. An alternative approach is to use complete water compositions and equilibrium geochemical modeling to calculate the degree of disequilibrium (saturation index) for large number of potential reservoir minerals as a function of temperature. We have constructed several “forward” geochemical models using The Geochemist’s Workbench to simulate the change in chemical composition of reservoir fluids as they migrate toward the surface. These models explicitly account for the formation (mass and composition) of a steam phase and equilibrium partitioning of volatile components (e.g., CO2, H2S, and H2) into the steam as a result of pressure decreases associated with upward fluid migration from depth. We use the synthetic data generated from these simulations to determine the advantages and limitations of various geothermometry and optimization approaches for estimating the likely conditions (e.g., temperature, pCO2) to which the water was exposed in the deep subsurface. We demonstrate the magnitude of errors that can result from boiling, loss of volatiles, and analytical error from sampling and instrumental analysis. The estimated reservoir temperatures for these scenarios are also compared to conventional geothermometers. These results can help improve estimation of geothermal resource temperature during exploration and early development.

  5. Geothermometry At Coso Geothermal Area (1980) | Open Energy Informatio...

    Open Energy Info (EERE)

    DOE-funding Unknown Exploration Basis Fluid temperature of feed water Notes Cation and sulfate isotope geothermometers indicate that the reservoir feeding water to the Coso Hot...

  6. Geothermometry | Open Energy Information

    Open Energy Info (EERE)

    In The Past 20 Years- Geochemistry In Geothermal Exploration Resource Evaluation And Reservoir Management Geothermometry (Powell and Cumming, 2010) Any Spreadsheets for...

  7. Liquid Geothermometry | Open Energy Information

    Open Energy Info (EERE)

    Exploration Group: Geochemical Techniques Exploration Sub Group: Geochemical Data Analysis Parent Exploration Technique: Geothermometry Information Provided by Technique...

  8. Gas Geothermometry | Open Energy Information

    Open Energy Info (EERE)

    Exploration Group: Geochemical Techniques Exploration Sub Group: Geochemical Data Analysis Parent Exploration Technique: Geothermometry Information Provided by Technique...

  9. Isotope Geothermometry | Open Energy Information

    Open Energy Info (EERE)

    Exploration Group: Geochemical Techniques Exploration Sub Group: Geochemical Data Analysis Parent Exploration Technique: Geothermometry Information Provided by Technique...

  10. Category:Gas Geothermometry | Open Energy Information

    Open Energy Info (EERE)

    Gas Geothermometry Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Geothermalpower.jpg Looking for the Gas Geothermometry page? For detailed information on Gas...

  11. Category:Geothermometry | Open Energy Information

    Open Energy Info (EERE)

    Technique Subcategories This category has the following 2 subcategories, out of 2 total. G Gas Geothermometry 1 pages I Isotope Geothermometry 1 pages Pages in...

  12. Evaluation Of Chemical Geothermometers For Calculating Reservoir...

    Open Energy Info (EERE)

    Geothermometers For Calculating Reservoir Temperatures At Nevada Geothermal Power Plants Jump to: navigation, search OpenEI Reference LibraryAdd to library Conference Paper:...

  13. Improvements in geothermometry. Final technical report. Rev

    SciTech Connect (OSTI)

    Potter, J.; Dibble, W.; Parks, G.; Nur, A.

    1982-08-01

    Alkali and alkaline earth geothermometers are useful for estimating geothermal reservoir temperatures, though a general theoretical basis has yet to be established and experimental calibration needs improvement. Equilibrium cation exchange between feldspars provided the original basis for the Na-K and Na-K-Ca geothermometers (Fournier and Truesdell, 1973), but theoretical, field and experimental evidence prove that neither equilibrium nor feldspars are necessary. Here, evidence is summarized in support of these observations, concluding that these geothermometers can be expected to have a surprisingly wide range of applicability, but that the reasons behind such broad applicability are not yet understood. Early experimental work proved that water-rock interactions are slow at low temperatures, so experimental calibration at temperatures below 150/sup 0/ is impractical. Theoretical methods and field data were used instead for all work at low temperatures. Experimental methods were emphasized for temperatures above 150/sup 0/C, and the simplest possible solid and solution compositions were used to permit investigation of one process or question at a time. Unexpected results in experimental work prevented complete integration of the various portions of the investigation.

  14. Geothermometry At Lassen Volcanic National Park Area (Janik ...

    Open Energy Info (EERE)

    sample taken had a pH of 8.35 and contained 2100 ppm Cl and 0.55 ppm NH3. Ratios of Na+K+ and Na+Cl remained nearly constant throughout the flow test. Cation geothermometers...

  15. Integrated Chemical Geothermometry System for Geothermal Exploration |

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Department of Energy Chemical Geothermometry System for Geothermal Exploration Integrated Chemical Geothermometry System for Geothermal Exploration DOE Geothermal Peer Review 2010 - Presentation. Develop practical and reliable system to predict geothermal reservoir temperatures from integrated chemical analyses of spring and well fluids. tracers_spycher_integrated_chemical.pdf (272.32 KB) More Documents & Publications Integrated Chemical Geothermometry System for Geothermal Exploration

  16. Derivation and calibration of semi-empirical gas geothermometers for Mahanagdong Geothermal Project, Philippines

    SciTech Connect (OSTI)

    Sanchez, D.R.

    1996-12-31

    The dissolved CO{sub 2}, H{sub 2}S, and H{sub 2} gases in Mahanagdong aquifer fluids are controlled by specific gas-mineral equilibria. At temperature range of 250 to 310 {degrees}C, CO{sub 2} is buffered by clinozoisite + K-feldspar + calcite + muscovite (illite) + quartz mineral assemblage. For H{sub 2}S and H{sub 2} dissolved gases, they are more likely buffered by pyrrhotite + pyrite + magnetite mineral assemblage at similar temperature range. Calibration of five Mahanagdong (MG) gas geothermometers is presented, three of which used CO{sub 2}, H{sub 2}S, and H{sub 2} concentration in steam. The remaining two use CO{sub 2}/H{sub 2} and H{sub 2}S/H{sub 2} ratios. The calibration is based on the relation between gas content of drillhole discharges and measured aquifer temperatures. After establishing the gas content in the aquifer, gas concentrations were computed in steam after adiabatic boiling to atmospheric condition (100 {degrees}C), to obtain gas geothermometry functions. These functions could also be used in evaluating fraction of steam condensation and temperature of phase separation. A demonstration given the Mahanagdong fumarole data, indicates that there is generally a fair relation between computed temperatures using Mahanagdong gas geothermometers and the actual field trend`s temperatures.

  17. Geothermometry At Central Nevada Seismic Zone Region (Shevenell...

    Open Energy Info (EERE)

    Geothermometry At Central Nevada Seismic Zone Region (Shevenell & De Rocher, 2005) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry...

  18. Geothermometry At Nw Basin & Range Region (Shevenell & De Rocher...

    Open Energy Info (EERE)

    Geothermometry At Nw Basin & Range Region (Shevenell & De Rocher, 2005) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Nw...

  19. Geothermometry At Blackfoot Reservoir Area (Hutsinpiller & Parry...

    Open Energy Info (EERE)

    Activity Details Location Blackfoot Reservoir Area Exploration Technique Geothermometry Activity Date Usefulness useful DOE-funding Unknown References Amy Hutsinpiller, W. T....

  20. Cation Geothermometers At Lightning Dock Geothermal Area (Witcher...

    Open Energy Info (EERE)

    Usefulness useful DOE-funding Unknown Exploration Basis Part of the Geothermal Resource Evaluation and Definition (GRED) Program administered by DOE-AAO under Cooperative...

  1. Colorado thermal spring water geothermometry (public dataset...

    Open Energy Info (EERE)

    chemical geothermometers for Colorado thermal springs. Data citations include Barrett, J. K. and Pearl, R. H. (1976), George, R. D., Curtis, H. A., Lester, O. C., Crook, J. K.,...

  2. Improved Geothermometry Through Multivariate Reaction-path Modeling and Evaluation of Geomicrobiological Influences on Geochemical Temperature Indicators: Final Report

    SciTech Connect (OSTI)

    Mattson, Earl; Smith, Robert; Fujita, Yoshiko; McLing, Travis; Neupane, Ghanashyam; Palmer, Carl; Reed, David; Thompson, Vicki

    2015-03-01

    The project was aimed at demonstrating that the geothermometric predictions can be improved through the application of multi-element reaction path modeling that accounts for lithologic and tectonic settings, while also accounting for biological influences on geochemical temperature indicators. The limited utilization of chemical signatures by individual traditional geothermometer in the development of reservoir temperature estimates may have been constraining their reliability for evaluation of potential geothermal resources. This project, however, was intended to build a geothermometry tool which can integrate multi-component reaction path modeling with process-optimization capability that can be applied to dilute, low-temperature water samples to consistently predict reservoir temperature within ±30 °C. The project was also intended to evaluate the extent to which microbiological processes can modulate the geochemical signals in some thermal waters and influence the geothermometric predictions.

  3. Geothermometry At Lassen Volcanic National Park Area (Thompson...

    Open Energy Info (EERE)

    Thompson, 1985) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Lassen Volcanic National Park Area (Thompson, 1985) Exploration...

  4. Geothermometry At Chena Geothermal Area (Kolker, 2008) | Open...

    Open Energy Info (EERE)

    1973 - 1974 Usefulness not indicated DOE-funding Unknown Exploration Basis Masters thesis Norma Biggar, Geophysical Institute University of Alaska Notes Geothermometry...

  5. Geothermometry At Fish Lake Valley Area (DOE GTP) | Open Energy...

    Open Energy Info (EERE)

    Fish Lake Valley Area (DOE GTP) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Fish Lake Valley Area (DOE GTP) Exploration...

  6. Geothermometry At Akutan Fumaroles Area (Kolker, Et Al., 2010...

    Open Energy Info (EERE)

    Geothermometry Activity Date Usefulness useful DOE-funding Unknown Notes The chemistry of the hot springs strongly suggests the existence of a neutral chloride reservoir...

  7. Geothermometry At Desert Queen Area (Garchar & Arehart, 2008...

    Open Energy Info (EERE)

    Desert Queen Area (Garchar & Arehart, 2008) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Desert Queen Area (Garchar &...

  8. Geothermometry At Walker-Lane Transitional Zone Region (Shevenell...

    Open Energy Info (EERE)

    (Shevenell & De Rocher, 2005) Exploration Activity Details Location Walker-Lane Transition Zone Geothermal Region Exploration Technique Geothermometry Activity Date Usefulness...

  9. Geothermometry At Walker-Lane Transitional Zone Region (Laney...

    Open Energy Info (EERE)

    Zone Region (Laney, 2005) Exploration Activity Details Location Walker-Lane Transition Zone Geothermal Region Exploration Technique Geothermometry Activity Date Usefulness...

  10. Geothermometry At Blue Mountain Geothermal Area (Casteel, Et...

    Open Energy Info (EERE)

    Details Location Blue Mountain Geothermal Area Exploration Technique Geothermometry Activity Date 2010 - 2010 Usefulness useful DOE-funding Unknown Exploration Basis A water...

  11. Geothermometry At Upper Hot Creek Ranch Area (Benoit & Blackwell...

    Open Energy Info (EERE)

    Activity Details Location Upper Hot Creek Ranch Area Exploration Technique Geothermometry Activity Date Usefulness useful DOE-funding Unknown Notes Ten water samples were collected...

  12. Geothermometry At Clear Lake Area (Thompson, Et Al., 1992) |...

    Open Energy Info (EERE)

    Activity Details Location Clear Lake Area Exploration Technique Geothermometry Activity Date Usefulness useful DOE-funding Unknown Notes Based on the above discussion,...

  13. Geothermometry At Silver Peak Area (DOE GTP) | Open Energy Information

    Open Energy Info (EERE)

    Silver Peak Area (DOE GTP) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Silver Peak Area (DOE GTP) Exploration Activity...

  14. Geothermometry At Alum Area (DOE GTP) | Open Energy Information

    Open Energy Info (EERE)

    Alum Area (DOE GTP) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Alum Area (DOE GTP) Exploration Activity Details Location...

  15. Geothermometry At The Needles Area (DOE GTP) | Open Energy Information

    Open Energy Info (EERE)

    The Needles Area (DOE GTP) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At The Needles Area (DOE GTP) Exploration Activity...

  16. Geothermometry At New River Area (DOE GTP) | Open Energy Information

    Open Energy Info (EERE)

    New River Area (DOE GTP) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At New River Area (DOE GTP) Exploration Activity Details...

  17. Geothermometry At Fort Bliss Area (DOE GTP) | Open Energy Information

    Open Energy Info (EERE)

    Fort Bliss Area (DOE GTP) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Fort Bliss Area (DOE GTP) Exploration Activity...

  18. Geothermometry At Nevada Test And Training Range Area (Sabin...

    Open Energy Info (EERE)

    Nevada Test And Training Range Area (Sabin, Et Al., 2004) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Nevada Test And...

  19. Geothermometry At Mt St Helens Area (Shevenell & Goff, 1995)...

    Open Energy Info (EERE)

    St Helens Area (Shevenell & Goff, 1995) Jump to: navigation, search GEOTHERMAL ENERGYGeothermal Home Exploration Activity: Geothermometry At Mt St Helens Area (Shevenell & Goff,...

  20. Geothermometry At Teels Marsh Area (Coolbaugh, Et Al., 2006)...

    Open Energy Info (EERE)

    useful DOE-funding Unknown Notes Follow up (to ASTER satellite imaging) analysis of spring and well waters yielded geothermometer reservoir estimates up to 192C References...

  1. Geothermometry At Rhodes Marsh Area (Coolbaugh, Et Al., 2006...

    Open Energy Info (EERE)

    useful DOE-funding Unknown Notes Follow up (to ASTER satellite imaging) analysis of spring and well waters yielded geothermometer reservoir estimates up to 162C References...

  2. New Mexico conservative ion water chemistry data and chalcedony geothermometry

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Shari Kelley

    2015-10-21

    Compilation of boron, lithium, bromine, and silica data from wells and springs throughout New Mexico from a wide variety of sources. The chalcedony geothermometry calculation is included in this file.

  3. Microbial impacts on geothermometry temperature predictions

    SciTech Connect (OSTI)

    Yoshiko Fujita; David W. Reed; Kaitlyn R. Nowak; Vicki S. Thompson; Travis L. McLing; Robert W. Smith

    2013-02-01

    Conventional geothermometry approaches assume that the composition of a collected water sample originating in a deep geothermal reservoir still reflects chemical equilibration of the water with the deep reservoir rocks. However, for geothermal prospecting samples whose temperatures have dropped to <120°C, temperature predictions may be skewed by the activity of microorganisms; microbial metabolism can drastically and rapidly change the water’s chemistry. We hypothesize that knowledge of microbial impacts on exploration sample geochemistry can be used to constrain input into geothermometry models and thereby improve the reliability of reservoir temperature predictions. To evaluate this hypothesis we have chosen to focus on sulfur cycling, because of the significant changes in redox state and pH associated with sulfur chemistry. Redox and pH are critical factors in defining the mineral-fluid equilibria that form the basis of solute geothermometry approaches. Initially we are developing assays to detect the process of sulfate reduction, using knowledge of genes specific to sulfate reducing microorganisms. The assays rely on a common molecular biological technique known as quantitative polymerase chain reaction (qPCR), which allows estimation of the number of target organisms in a particular sample by enumerating genes specific to the organisms rather than actually retrieving and characterizing the organisms themselves. For quantitation of sulfate reducing genes using qPCR, we constructed a plasmid (a piece of DNA) containing portions of two genes (known as dsrA and dsrB) that are directly involved with sulfate reduction and unique to sulfate reducing microorganisms. Using the plasmid as well as DNA from other microorganisms known to be sulfate reducers or non-sulfate reducers, we developed qPCR protocols and showed the assay’s specificity to sulfate reducers and that a qPCR standard curve using the plasmid was linear over >5 orders of magnitude. As a first test

  4. Mineral Selection for Multicomponent Equilibrium Geothermometry

    SciTech Connect (OSTI)

    Plamer, C. D.; Ohly, S. R.; Smith, R. W.; Neupane, G.; McLing, T.; Mattson, E.

    2015-04-01

    Multicomponent geothermometry requires knowledge of the mineral phases in the reservoir with which the geothermal fluids may be equilibrated. These minerals phases are most often alteration products rather than primary minerals. We have reviewed the literature on geothermal systems representing most major geologic environments typically associated with geothermal activity and identified potential alteration products in various environments. We have included this information in RTEst, a code we have developed to estimate reservoir conditions (temperature, CO2 fugacity) from the geochemistry of near-surface geothermal waters. The information has been included in RTEst through the addition of filters that decrease the potential number of minerals from all possibilities based on the basis species to those that are more relevant to the particular conditions in which the user is interested. The three groups of filters include host rock type (tholeiitic, calc-alkaline, silicic, siliciclastic, carbonate), water type (acidic, neutral), and the temperature range over which the alteration minerals were formed (low, medium, high). The user-chosen mineral assemblage is checked to make sure that it does not violate the Gibbs phase rule. The user can select one of three mineral saturation weighting schemes that decrease the chance the optimization from being skewed by reaction stoichiometry or analytical uncertainty.

  5. Mineral Selection for Multicomponent Equilibrium Geothermometry

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

    Plamer, C. D.; Ohly, S. R.; Smith, R. W.; Neupane, G.; McLing, T.; Mattson, E.

    2015-04-01

    Multicomponent geothermometry requires knowledge of the mineral phases in the reservoir with which the geothermal fluids may be equilibrated. These minerals phases are most often alteration products rather than primary minerals. We have reviewed the literature on geothermal systems representing most major geologic environments typically associated with geothermal activity and identified potential alteration products in various environments. We have included this information in RTEst, a code we have developed to estimate reservoir conditions (temperature, CO2 fugacity) from the geochemistry of near-surface geothermal waters. The information has been included in RTEst through the addition of filters that decrease the potential numbermore » of minerals from all possibilities based on the basis species to those that are more relevant to the particular conditions in which the user is interested. The three groups of filters include host rock type (tholeiitic, calc-alkaline, silicic, siliciclastic, carbonate), water type (acidic, neutral), and the temperature range over which the alteration minerals were formed (low, medium, high). The user-chosen mineral assemblage is checked to make sure that it does not violate the Gibbs phase rule. The user can select one of three mineral saturation weighting schemes that decrease the chance the optimization from being skewed by reaction stoichiometry or analytical uncertainty.« less

  6. New Improved Equations For Na-K, Na-Li And Sio2 Geothermometers...

    Open Energy Info (EERE)

    Improved Equations For Na-K, Na-Li And Sio2 Geothermometers By Outlier Detection And Rejection Jump to: navigation, search OpenEI Reference LibraryAdd to library Journal Article:...

  7. Improved Geothermometry Through Multivariate Reaction Path Modeling and Evaluation of Geomicrobiological Influences on Geochemical Temperature Indicators

    Broader source: Energy.gov [DOE]

    Improved Geothermometry Through Multivariate Reaction Path Modeling and Evaluation of Geomicrobiological Influences on Geochemical Temperature Indicators presentation at the April 2013 peer review meeting held in Denver, Colorado.

  8. Improved Geothermometry Through Multivariate Reaction Path Modeling and Evaluation of Geomicrobiological Influences on Geochemical Temperature Indicators

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Improved Geothermometry Through Multivariate Reaction Path Modeling and Evaluation of Geomicrobiological Influences on Geochemical Temperature Indicators Project Officer: Eric Hass Total Project Funding: $999,000 April 24, 2013 Craig Cooper Larry Hull Idaho National Laboratory This presentation does not contain any proprietary confidential, or otherwise restricted information. 2 | US DOE Geothermal Program eere.energy.gov Relevance/Impact of Research Geothermometry enables estimation of

  9. Geochemistry Sampling for Traditional and Multicomponent Equilibrium Geothermometry in Southeast Idaho

    SciTech Connect (OSTI)

    Cannon, Cody; Wood, Thomas; Neupane, Ghanashyam; McLing, Travis; Mattson, Earl; Dobson, Patrick; Conrad, Mark

    2014-10-01

    The Eastern Snake River Plain (ESRP) is an area of high regional heat flux due the movement of the North American Plate over the Yellowstone Hotspot beginning ca.16 Ma. Temperature gradients between 45-60 °C/km (up to double the global average) have been calculated from deep wells that penetrate the upper aquifer system (Blackwell 1989). Despite the high geothermal potential, thermal signatures from hot springs and wells are effectively masked by the rapid flow of cold groundwater through the highly permeable basalts of the Eastern Snake River Plain aquifer (ESRPA) (up to 500+ m thick). This preliminary study is part of an effort to more accurately predict temperatures of the ESRP deep thermal reservoir while accounting for the effects of the prolific cold water aquifer system above. This study combines the use of traditional geothermometry, mixing models, and a multicomponent equilibrium geothermometry (MEG) tool to investigate the geothermal potential of the ESRP. In March, 2014, a collaborative team including members of the University of Idaho, the Idaho National Laboratory, and the Lawrence Berkeley National Laboratory collected 14 thermal water samples from and adjacent to the Eastern Snake River Plain. The preliminary results of chemical analyses and geothermometry applied to these samples are presented herein.

  10. Multicomponent Geothermometers | Open Energy Information

    Open Energy Info (EERE)

    of using full chemical analyses of water samples to compute the saturation indices (log(QK)) of reservoir minerals over a range of temperatures. The saturation indices are graphed...

  11. Silica Geothermometers | Open Energy Information

    Open Energy Info (EERE)

    in the Past 20 Years: Geochemistry in Geothermal Exploration, Resource Evaluation and Reservoir Management 2.0 2.1 Lectures on Geochemical Interpretation of Hydrothermal...

  12. The Role of Cation-Water Disorder during Cation Exchange in Small...

    Office of Scientific and Technical Information (OSTI)

    The Role of Cation-Water Disorder during Cation Exchange in Small-Pore Zeolite Sodium Natrolite Citation Details In-Document Search Title: The Role of Cation-Water Disorder during ...

  13. Cationic electrodepositable coating composition comprising lignin

    DOE Patents [OSTI]

    Fenn, David; Bowman, Mark P; Zawacky, Steven R; Van Buskirk, Ellor J; Kamarchik, Peter

    2013-07-30

    A cationic electrodepositable coating composition is disclosed. The present invention in directed to a cationic electrodepositable coating composition comprising a lignin-containing cationic salt resin, that comprises (A) the reaction product of: lignin, an amine, and a carbonyl compound; (B) the reaction product of lignin, epichlorohydrin, and an amine; or (C) combinations thereof.

  14. Geology, hydrothermal petrology, stable isotope geochemistry, and fluid inclusion geothermometry of LASL geothermal test well C/T-1 (Mesa 31-1), East Mesa, Imperial Valley, California, USA

    SciTech Connect (OSTI)

    Miller, K.R.; Elders, W.A.

    1980-08-01

    Borehole Mesa 31-1 (LASL C/T-1) is an 1899-m (6231-ft) deep well located in the northwestern part of the East Mesa Geothermal Field. Mesa 31-1 is the first Calibration/Test Well (C/T-1) in the Los Alamos Scientific Laboratory (LASL), Geothermal Log Interpretation Program. The purpose of this study is to provide a compilation of drillhole data, drill cuttings, well lithology, and formation petrology that will serve to support the use of well LASL C/T-1 as a calibration/test well for geothermal logging. In addition, reviews of fluid chemistry, stable isotope studies, isotopic and fluid inclusion geothermometry, and the temperature log data are presented. This study provides the basic data on the geology and hydrothermal alteration of the rocks in LASL C/T-1 as background for the interpretation of wireline logs.

  15. ADSORPTION METHOD FOR SEPARATING METAL CATIONS

    DOE Patents [OSTI]

    Khym, J.X.

    1959-03-10

    The chromatographic separation of fission product cations is discussed. By use of this method a mixture of metal cations containing Zr, Cb, Ce, Y, Ba, and Sr may be separated from one another. Mentioned as preferred exchange adsorbents are resins containing free sulfonic acid groups. Various eluants, such as tartaric acid, HCl, and citric acid, used at various acidities, are employed to effect the selective elution and separation of the various fission product cations.

  16. Role of Cation-Water Disorder during Cation Exchange in Small-Pore Zeolite

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

    Sodium Natrolite | Stanford Synchrotron Radiation Lightsource Role of Cation-Water Disorder during Cation Exchange in Small-Pore Zeolite Sodium Natrolite Thursday, October 31, 2013 Structural changes leading to disordering of the cation-water arrangement within the pores of zeolite natrolite while exchanging sodium (Na+) with potassium (K+) have been investigated using x-ray diffraction (XRD) and oxygen K-edge x-ray absorption spectroscopy (XAS). cation in zeolite sodium natrolite fig1

  17. Method for encapsulating and isolating hazardous cations, medium for encapsulating and isolating hazardous cations

    DOE Patents [OSTI]

    Wasserman, Stephen R.; Anderson, Kenneth B.; Song, Kang; Yuchs, Steven E.; Marshall, Christopher L.

    1998-01-01

    A method for encapsulating hazardous cations is provided comprising supplying a pretreated substrate containing the cations; contacting the substrate with an organo-silane compound to form a coating on the substrate; and allowing the coating to cure. A medium for containing hazardous cations is also provided, comprising a substrate having ion-exchange capacity and a silane-containing coating on the substrate.

  18. Advancements in Anion Exchange Membrane Cations

    SciTech Connect (OSTI)

    Sturgeon, Matthew R.; Long, Hai; Park, Andrew M.; Pivovar, Bryan S.

    2015-10-15

    Anion-exchange membrane fuel cells (AME-FCs) are of increasingly popular interest as they enable the use of non-Pt fuel cell catalysts, the primary cost limitation of proton exchange membrane fuel cells. Benzyltrimethyl ammonium (BTMA) is the standard cation that has historically been utilized as the hydroxide conductor in AEMs. Herein we approach AEMs from two directions. First and foremost we study the stability of several different cations in a hydroxide solution at elevated temperatures. We specifically targeted BTMA and methoxy and nitro substituted BTMA. We've also studied the effects of adding an akyl spacer units between the ammonium cation and the phenyl group. In the second approach we use computational studies to predict stable ammonium cations, which are then synthesized and tested for stability. Our unique method to study cation stability in caustic conditions at elevated temperatures utilizes Teflon Parr reactors suitable for use under various temperatures and cation concentrations. NMR analysis was used to determine remaining cation concentrations at specific time points with GCMS analysis verifying product distribution. We then compare the experimental results with calculated modeling stabilities. Our studies show that the electron donating methoxy groups slightly increase stability (compared to that of BTMA), while the electron withdrawing nitro groups greatly decrease stability in base. These results give insight into possible linking strategies to be employed when tethering a BTMA like ammonium cation to a polymeric backbone; thus synthesizing an anion exchange membrane.

  19. Method for encapsulating and isolating hazardous cations, medium for encapsulating and isolating hazardous cations

    DOE Patents [OSTI]

    Wasserman, S.R.; Anderson, K.B.; Song, K.; Yuchs, S.E.; Marshall, C.L.

    1998-04-28

    A method for encapsulating hazardous cations is provided comprising supplying a pretreated substrate containing the cations; contacting the substrate with an organo-silane compound to form a coating on the substrate; and allowing the coating to cure. A medium for containing hazardous cations is also provided, comprising a substrate having ion-exchange capacity and a silane-containing coating on the substrate. 3 figs.

  20. ABSORPTION METHOD FOR SEPARATING METAL CATIONS

    DOE Patents [OSTI]

    Tompkins, E.R.; Parker, G.W.

    1959-03-10

    An improved method is presented for the chromatographic separation of fission products wherein a substantial reduction in liquid volume is obtained. The process consists in contacting a solution containing fission products with a body of ion-exchange adsorbent to effect adsorption of fission product cations. The loaded exchange resin is then contacted with a small volume of a carboxylic acid eluant, thereby recovering the fission products. The fission product carrying eluate is acidified without increasing its volume to the volume of the original solution, and the acidified eluate is then used as a feed solution for a smaller body of ion-exchange resin effecting readsorption of the fission product cations.

  1. Process and apparatus for the production of BI-213 cations

    DOE Patents [OSTI]

    Horwitz, E. Philip; Hines, John J.; Chiarizia, Renato; Dietz, Mark

    1998-01-01

    A process for producing substantially impurity-free Bi-213 cations is disclosed. An aqueous acid feed solution containing Ac-225 cations is contacted with an ion exchange medium to bind the Ac-225 cations and form an Ac-225-laden ion exchange medium. The bound Ac-225 incubates on the ion exchange medium to form Bi-213 cations by radioactive decay. The Bi-213 cations are then recovered from the Ac-225-laden ion exchange medium to form a substantially impurity-free aqueous Bi-213 cation acid solution. An apparatus for carrying out this process is also disclosed.

  2. Process and apparatus for the production of Bi-213 cations

    DOE Patents [OSTI]

    Horwitz, E.P.; Hines, J.J.; Chiarizia, R.; Dietz, M.

    1998-12-29

    A process for producing substantially impurity-free Bi-213 cations is disclosed. An aqueous acid feed solution containing Ac-225 cations is contacted with an ion exchange medium to bind the Ac-225 cations and form an Ac-225-laden ion exchange medium. The bound Ac-225 incubates on the ion exchange medium to form Bi-213 cations by radioactive decay. The Bi-213 cations are then recovered from the Ac-225-laden ion exchange medium to form a substantially impurity-free aqueous Bi-213 cation acid solution. An apparatus for carrying out this process is also disclosed. 7 figs.

  3. Role of Cation-Water Disorder during Cation Exchange in Small...

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

    while exchanging sodium (Na+) with potassium (K+) have been investigated using x-ray diffraction (XRD) and oxygen K-edge x-ray absorption spectroscopy (XAS). cation in zeolite...

  4. Alkaline earth cation extraction from acid solution

    DOE Patents [OSTI]

    Dietz, Mark; Horwitz, E. Philip

    2003-01-01

    An extractant medium for extracting alkaline earth cations from an aqueous acidic sample solution is described as are a method and apparatus for using the same. The separation medium is free of diluent, free-flowing and particulate, and comprises a Crown ether that is a 4,4'(5')[C.sub.4 -C.sub.8 -alkylcyclohexano]18-Crown-6 dispersed on an inert substrate material.

  5. Nanoheterostructure Cation Exchange: Anionic Framework Conservation

    SciTech Connect (OSTI)

    Jain, Prashant K.; Amirav, Lilac; Aloni, Shaul; Alivisatos, A. Paul

    2010-05-11

    In ionic nanocrystals the cationic sub-lattice can be replaced with a different metal ion via a fast, simple, and reversible place-exchange, allowing post-synthetic modification of the composition of the nanocrystal, while preserving its size and shape. Here, we demonstrate for the first time that during such an exchange, the anionic framework of the crystal is preserved. When applied to nanoheterostructures, this phenomenon ensures that compositional interfaces within the heterostructure are conserved throughout the transformation. For instance, a morphology composed of a CdSe nanocrystal embedded in a CdS rod (CdSe/CdS) was exchanged to a PbSe/PbS nanorod via a Cu2Se/Cu2S structure. During every exchange cycle, the seed size and position within the nanorod were preserved, as evident by excitonic features, Z-contrast imaging, and elemental line-scans. Anionic framework conservation extends the domain of cation exchange to the design of more complex and unique nanostructures.

  6. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOE Patents [OSTI]

    O`Neill, M.A.; Pellerin, P.J.M.; Warrenfeltz, D.; Vidal, S.; Darvill, A.G.; Albersheim, P.

    1999-03-02

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations. 15 figs.

  7. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOE Patents [OSTI]

    O'Neill, Malcolm A.; Pellerin, Patrice J. M.; Warrenfeltz, Dennis; Vidal, Stephane; Darvill, Alan G.; Albersheim, Peter

    1999-01-01

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations.

  8. Colloid-Facilitated Transport of Cations in an Unsaturated Fractured...

    Office of Scientific and Technical Information (OSTI)

    Fractured Soil Under Transient Conditions Citation Details In-Document Search Title: Colloid-Facilitated Transport of Cations in an Unsaturated Fractured Soil Under Transient ...

  9. CATION EXCHANGE METHOD FOR THE RECOVERY OF PROTACTINIUM

    DOE Patents [OSTI]

    Studier, M.H.; Sullivan, J.C.

    1959-07-14

    A cation exchange prccess is described for separating protactinium values from thorium values whereby they are initially adsorbed together from an aqueous 0.1 to 2 N hydrochloric acid on a cation exchange resin in a column. Then selectively eluting the thorium by an ammonium sulfate solution and subsequently eluting the protactinium by an oxalate solution.

  10. High capacity nickel battery material doped with alkali metal cations

    DOE Patents [OSTI]

    Jackovitz, John F.; Pantier, Earl A.

    1982-05-18

    A high capacity battery material is made, consisting essentially of hydrated Ni(II) hydroxide, and about 5 wt. % to about 40 wt. % of Ni(IV) hydrated oxide interlayer doped with alkali metal cations selected from potassium, sodium and lithium cations.

  11. Improved Geothermometry Through Multivariate Reaction Path Modeling...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    at the April 2013 peer review meeting held in Denver, Colorado. geothermometrycooperpeer2013.pdf (922.86 KB) More Documents & Publications track 4: enhanced geothermal ...

  12. Geothermometry (Klein, 2007) | Open Energy Information

    Open Energy Info (EERE)

    In The Past 20 Years- Geochemistry In Geothermal Exploration Resource Evaluation And Reservoir Management Additional References Retrieved from "http:en.openei.orgw...

  13. Integrated Chemical Geothermometry System for Geothermal Exploration

    Broader source: Energy.gov [DOE]

    DOE Geothermal Peer Review 2010 - Presentation. Develop practical and reliable system to predict geothermal reservoir temperatures from integrated chemical analyses of spring and well fluids.

  14. Method for the chromatographic separation of cations from aqueous samples

    DOE Patents [OSTI]

    Horwitz, E. Philip (Naperville, IL); Chiarizia, Renato (Elmhurst, IL); Dietz, Mark L. (Evanston, IL)

    1998-12-22

    An extraction chromatographic material for extracting metal cations from a liquid stream. The extraction chromatographic material is prepared by adsorbing a diesterified methanediphosphonic acid on an inert particulate support.

  15. Method for the chromatographic separation of cations from aqueous samples

    DOE Patents [OSTI]

    Horwitz, E. Philip (Naperville, IL); Chiarizia, Renato (Elmhurst, IL); Dietz, Mark L. (Evanston, IL)

    1997-01-01

    An extraction chromatographic material for extracting metal cations from a iquid stream. The extraction chromatographic material is prepared by adsorbing a diesterified methanediphosphonic acid on an inert particulate support.

  16. Method for the chromatographic separation of cations from aqueous samples

    DOE Patents [OSTI]

    Horwitz, E.P.; Chiarizia, R.; Dietz, M.L.

    1997-07-29

    An extraction chromatographic material is described for extracting metal cations from a liquid stream. The extraction chromatographic material is prepared by adsorbing a diesterified methanediphosphonic acid on an inert particulate support. 7 figs.

  17. Method for the chromatographic separation of cations from aqueous samples

    DOE Patents [OSTI]

    Horwitz, E.P.; Chiarizia, R.; Dietz, M.L.

    1998-12-22

    An extraction chromatographic material is described for extracting metal cations from a liquid stream. The extraction chromatographic material is prepared by adsorbing a diesterified methane-diphosphonic acid on an inert particulate support. 7 figs.

  18. Mechanistic Insight into the Formation of Cationic Naked Nanocrystals

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

    Generated Under Equilibrium Control - Joint Center for Energy Storage Research October 24, 2014, Research Highlights Mechanistic Insight into the Formation of Cationic Naked Nanocrystals Generated Under Equilibrium Control Pre-JCESR stripping chemistries (for cationic NC): NOBF4 (strong oxidant, not suitable for many compositions, ~$600/mol) Et3OBF4 (mild, but still causes adatom desorption for some sensitive compositions, ~$800/mol) New ligand-stripping chemistry developed within JCESR:

  19. Characterization of Selective Binding of Alkali Cations with Carboxylate

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

    Characterization of Selective Binding of Alkali Cations with Carboxylate Characterization of Selective Binding of Alkali Cations with Carboxylate Print Wednesday, 24 September 2008 00:00 During its lifetime, a cell spends a considerable fraction of its energy pumping sodium and calcium out and potassium in. This balancing process is similar to that found in the coils of the DNA double helix, where specific ions nestle and help stabilize this macromolecule. These are only two examples of

  20. Cation Uptake and Allocation by Red Pine Seedlings under Cation-Nutrient Stress in a Column Growth Experiment

    SciTech Connect (OSTI)

    Shi, Zhenqing; Balogh-Brunstad, Zsuzsanna; Grant, Michael R.; Harsh, James B.; Gill, Richard; Thomashow, Linda; Dohnalkova, Alice; Stacks, Daryl; Letourneau, Melissa; Keller, Chester K.

    2014-01-10

    Background and Aims Plant nutrient uptake is affected by environmental stress, but how plants respond to cation-nutrient stress is poorly understood. We assessed the impact of varying degrees of cation-nutrient limitation on cation uptake in an experimental plant-mineral system. Methods Column experiments, with red pine (Pinus resinosa Ait.) seedlings growing in sand/mineral mixtures, were conducted for up to nine months under a range of Ca- and K-limited conditions. The Ca and K were supplied from both minerals and nutrient solutions with varying Ca and K concentrations. Results Cation nutrient stress had little impact on carbon allocation after nine months of plant growth and K was the limiting nutrient for biomass production. The Ca/Sr and K/Rb ratio results allowed independent estimation of dissolution incongruency and discrimination against Sr and Rb during cation uptake processes. The fraction of K in biomass from biotite increased with decreasing K supply from nutrient solutions. The mineral anorthite was consistently the major source of Ca, regardless of nutrient treatment. Conclusions Red pine seedlings exploited more mineral K in response to more severe K deficiency. This did not occur for Ca. Plant discrimination factors must be carefully considered to accurately identify nutrient sources using cation tracers.

  1. Chemical Geothermometers And Mixing Models For Geothermal Systems...

    Open Energy Info (EERE)

    to outline favorable places to explore for geothermal energy. Some of the qualitative methods, such as the delineation of mercury and helium anomalies in soil gases, do not...

  2. Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations

    DOE Patents [OSTI]

    Marks, Tobin J.; Chen, You-Xian

    1999-01-01

    A cationic metallocene complex with trisperfluorobiphenyl borate for use as a polymerization catalyst.

  3. In situ remediation process using divalent metal cations

    DOE Patents [OSTI]

    Brady, Patrick V.; Khandaker, Nadim R.; Krumhansl, James L.; Teter, David M.

    2004-12-14

    An in situ process for treating ambient solid materials (e.g., soils, aquifer solids, sludges) by adding one or more divalent metal cations to the ambient solid material. The added divalent metal cations, such as Cu.sup.2+ or Zn.sup.2+, combine with metal oxide/hydroxides (e.g., ferric oxide/hydroxide or aluminum oxide/hydroxide) already present in the ambient solid material to form an effective sorbent material having a large number of positively-charged surface complexes that binds and immobilizes anionic contaminant species (e.g., arsenic or chromate). Divalent metal cations can be added, for example, by injecting an aqueous solution of CuSO.sub.4 into an aquifer contaminated with arsenic or chromate. Also, sludges can be stabilized against leaching of anionic contaminants through the addition of divalent metal cations. Also, an inexpensive sorbent material can be easily formed by mixing divalent metal cations with soil that has been removed from the ground.

  4. All-inorganic Germanium nanocrystal films by cationic ligand exchange

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

    Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; Anderson, Nicholas C.; Beard, Matthew C.; Neale, Nathan R.

    2016-01-21

    In this study, we introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport inmore » germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.« less

  5. Bistability of Cation Interstitials in II-VI Semiconductors

    SciTech Connect (OSTI)

    Wei, S. H.; Dalpian, G. M.

    2005-11-01

    The stability of cation interstitials in II-VI semiconductors is studied using ab initio methods. We find that interstitials in the neutral charge state are more stable in the tetrahedral interstitial site near the cation, whereas in the (2+) charge state, they are more stable near the anion. The diffusion energy barrier changes when the defect charge state changes. Therefore, if electrons/holes are taken from the defect level by light, changing its charge state, the interstitial atom will be able to diffuse almost spontaneously due to a reduced diffusion barrier.

  6. Geochemical Techniques | Open Energy Information

    Open Energy Info (EERE)

    Geothermometers Multicomponent Geothermometers Silica Geothermometers Thermal Ion Dispersion Thermochronometry References General References Technical References No exploration...

  7. Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations

    DOE Patents [OSTI]

    Marks, T.J.; Chen, Y.X.

    1999-01-05

    A cationic metallocene complex with trisperfluorobiphenyl borate is described for use as a polymerization catalyst. 7 figs.

  8. Characterization of Selective Binding of Alkali Cations with Carboxylate

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

    Characterization of Selective Binding of Alkali Cations with Carboxylate Print During its lifetime, a cell spends a considerable fraction of its energy pumping sodium and calcium out and potassium in. This balancing process is similar to that found in the coils of the DNA double helix, where specific ions nestle and help stabilize this macromolecule. These are only two examples of selective ion interactions in biology; there are many others also vital to life. The existence of these interactions

  9. Characterization of Selective Binding of Alkali Cations with Carboxylate

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

    Characterization of Selective Binding of Alkali Cations with Carboxylate Print During its lifetime, a cell spends a considerable fraction of its energy pumping sodium and calcium out and potassium in. This balancing process is similar to that found in the coils of the DNA double helix, where specific ions nestle and help stabilize this macromolecule. These are only two examples of selective ion interactions in biology; there are many others also vital to life. The existence of these interactions

  10. Characterization of Selective Binding of Alkali Cations with Carboxylate

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

    Characterization of Selective Binding of Alkali Cations with Carboxylate Print During its lifetime, a cell spends a considerable fraction of its energy pumping sodium and calcium out and potassium in. This balancing process is similar to that found in the coils of the DNA double helix, where specific ions nestle and help stabilize this macromolecule. These are only two examples of selective ion interactions in biology; there are many others also vital to life. The existence of these interactions

  11. Characterization of Selective Binding of Alkali Cations with Carboxylate

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

    Characterization of Selective Binding of Alkali Cations with Carboxylate Print During its lifetime, a cell spends a considerable fraction of its energy pumping sodium and calcium out and potassium in. This balancing process is similar to that found in the coils of the DNA double helix, where specific ions nestle and help stabilize this macromolecule. These are only two examples of selective ion interactions in biology; there are many others also vital to life. The existence of these interactions

  12. Characterization of Selective Binding of Alkali Cations with Carboxylate

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

    Characterization of Selective Binding of Alkali Cations with Carboxylate Print During its lifetime, a cell spends a considerable fraction of its energy pumping sodium and calcium out and potassium in. This balancing process is similar to that found in the coils of the DNA double helix, where specific ions nestle and help stabilize this macromolecule. These are only two examples of selective ion interactions in biology; there are many others also vital to life. The existence of these interactions

  13. Solvation Structure and Transport Properties of Alkali Cations in Dimethyl

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

    Sulfoxide Under Exogenous Static Electric Fields - Joint Center for Energy Storage Research June 14, 2015, Research Highlights Solvation Structure and Transport Properties of Alkali Cations in Dimethyl Sulfoxide Under Exogenous Static Electric Fields Top: Snapshots of molecular dynamics simulations of alkali ions in DMSO at 298 K and zero-applied electric field: (left) Li+ and (right) Cs+. Sulfur atoms are shown in yellow, oxygen atoms in red, and methyl groups in gray. Graph: Average

  14. Selective Facet Reactivity During Cation Exchange in Cadmium Sulfide Nanorods

    SciTech Connect (OSTI)

    Sadtler, Bryce; Demchenko, Denis; Zheng, Haimei; Hughes, Steven; Merkle, Maxwell; Dahmen, Ulrich; Wang, Lin-Wang; Alivisatos, A. Paul

    2008-12-18

    The partial transformation of ionic nanocrystals through cation exchange has been used to synthesize nanocrystal heterostructures. We demonstrate that the selectivity for cation exchange to take place at different facets of the nanocrystal plays an important role in determining the resulting morphology of the binary heterostructure. In the case of copper I (Cu+) cation exchange in cadmium sulfide (CdS) nanorods, the reaction starts preferentially at the ends of the nanorods such that copper sulfide (Cu2S) grows inwards from either end. The resulting morphology is very different from the striped pattern obtained in our previous studies of silver I (Ag+) exchange in CdS nanorods where non-selective nucleation of silver sulfide (Ag2S) occurs. From interface formation energies calculated for several models of epitaxialconnections between CdS and Cu2S or Ag2S, we infer the relative stability of each interface during the nucleation and growth of Cu2S or Ag2S within the CdS nanorods. The epitaxial connections of Cu2S to the end facets of CdS nanorods minimize the formation energy, making these interfaces stable throughout the exchange reaction. However, as the two end facets of wurtzite CdS nanorods are crystallographically nonequivalent, asymmetric heterostructures can be produced.

  15. Advective (heat sweep) geothermal systems | Open Energy Information

    Open Energy Info (EERE)

    temperatures can be predicted from the unchecked application of cation-based Na-K-Ca geo-thermometers. This study shows that in half of the prospects fully equilibrated...

  16. Spontaneous Superlattice Formation in Nanorods through PartialCation Exchange

    SciTech Connect (OSTI)

    Robinson, Richard D.; Sadtler, Bryce; Demchenko, Denis O.; Erdonmez, Can K.; Wang, Lin-Wang; Alivisatos, A. Paul

    2007-03-14

    Lattice mismatch strains are widely known to controlnanoscale pattern formation in heteroepitaxy, but such effects have notbeen exploited in colloidal nanocrystal growth. We demonstrate acolloidal route to synthesizing CdS-Ag2S nanorod superlattices throughpartial cation exchange. Strain induces the spontaneous formation ofperiodic structures. Ab initio calculations of the interfacial energy andmodeling of strain energies show that these forces drive theself-organization. The nanorod superlattices exhibit high stabilityagainst ripening and phase mixing. These materials are tunablenear-infrared emitters with potential applications as nanometer-scaleoptoelectronic devices.

  17. CATIONIC EXCHANGE PROCESS FOR THE SEPARATION OF RARE EARTHS

    DOE Patents [OSTI]

    Choppin, G.R.; Thompson, S.G.; Harvey, B.G.

    1960-02-16

    A process for separating mixtures of elements in the lanthanum and actinium series of the periodic table is described. The mixture of elements is dissolved in 0.05 M HCI, wherein the elements exist as tripositive ions. The resulting solution is then transferred to a column of cationic exchange resin and the column eluted with 0.1 to 0.6 M aqueous ammonium alpha hydroxy isobutyrate solution of pH 3.8 to 5.0. The use of ammonium alpha hydroxy isobutyrate as an eluting agent results in sharper and more rapid separations than previously obtainable with eluants such as citric, tartaric, glycolic, and lactic acids.

  18. Nitrogen-doped zirconia: A comparison with cation stabilized zirconia

    SciTech Connect (OSTI)

    Lee, Jong-Sook . E-mail: jong-sook.lee@fkf.mpg.de; Lerch, Martin; Maier, Joachim

    2006-01-15

    The conductivity behavior of nitrogen-doped zirconia is compared with that of zirconia doped with lower-valent cations and discussed in the framework of defect-defect interactions. While nominally introducing the same number of vacancies as yttrium, nitrogen dopants introduced in the anion sublattice of zirconia lead to substantially different defect kinetics and energetics. Compared to the equivalent yttrium doping nitrogen doping in the Y-Zr-O-N system substantially increases the activation energy and correspondingly decreases the conductivity at temperatures below 500{sup -}bar C in the vacancy range below 4mol%. The comparison of N-doped zirconia and zirconia systems doped with size-matched cation stabilizers, such as Sc, Yb and Y, shows that elastically driven vacancy-vacancy ordering interactions can phenomenologically account for the temperature- and composition-dependence. It is striking that materials with superior high-temperature conductivities due to weak dopant-vacancy interactions undergo severe deterioration at low temperature due to the strong vacancy-ordering. The analysis also explains qualitatively similar effects of Y co-doping in Yb-, Sc-, and N-doped zirconia. Small amount of Y in N-doped zirconia as well as in Sc-doped zirconia appears to hinder the formation of the long-range ordered phase and thus enhance the conductivity substantially.

  19. Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical

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

    Peter R. Craig; Miller, John R.; Havlas, Zdenek; Trujillo, Marianela; Rempala, Pawel; Kirby, James P.; Noll, Bruce C.; Michl, Josef

    2016-05-02

    In this study, properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative 1a have been measured and calculated. The B3LYP/TZP optimized geometry of the free cation 1 agrees with a single-crystal X-ray diffraction structure except that in the crystal one of the phenyl substituents is strongly twisted to permit a close-packing interaction of two of its hydrogens with a nearby BF–4 anion. The low-energy parts of the solution electronic absorption and magnetic circular dichroism (MCD) spectra of 1 and 1a have been interpreted by comparison with TD-DFT (B3LYP/TZP) results. Reduction or pulse radiolysis lead to a neutral 19-electron radical,more » whose visible absorption and MCD spectra have been recorded and interpreted as well. The reduction is facilitated by ~0.1 V upon going from 1 to 1a« less

  20. Insights into dynamic processes of cations in pyrochlores and other complex oxides

    SciTech Connect (OSTI)

    Uberuaga, Blas Pedro; Perriot, Romain

    2015-08-26

    Complex oxides are critical components of many key technologies, from solid oxide fuel cells and superionics to inert matrix fuels and nuclear waste forms. In many cases, understanding mass transport is important for predicting performance and, thus, extensive effort has been devoted to understanding mass transport in these materials. However, most work has focused on the behavior of oxygen while cation transport has received relatively little attention, even though cation diffusion is responsible for many phenomena, including sintering, radiation damage evolution, and deformation processes. Here, we use accelerated molecular dynamics simulations to examine the kinetics of cation defects in one class of complex oxides, A₂B₂O₇ pyrochlore. In some pyrochlore chemistries, B cation defects are kinetically unstable, transforming to A cation defects and antisites at rates faster than they can diffuse. When this occurs, transport of B cations occurs through defect processes on the A sublattice. Further, these A cation defects, either interstitials or vacancies, can interact with antisite disorder, reordering the material locally, though this process is much more efficient for interstitials than vacancies. Whether this behavior occurs in a given pyrochlore depends on the A and B chemistry. Pyrochlores with a smaller ratio of cation radii exhibit this complex behavior, while those with larger ratios exhibit direct migration of B interstitials. Similar behavior has been reported in other complex oxides such as spinels and perovskites, suggesting that this coupling of transport between the A and B cation sublattices, while not universal, occurs in many complex oxide.

  1. Cation-exchange fiber reduces iron oxide leakage

    SciTech Connect (OSTI)

    MacClure, S.L.

    1993-10-01

    This article describes how addition of new fiber in powdered-resin precoat improves demineralizer crud-retention capability and reduces disposal cost for radioactive spent resin. Various attempts have been made to reduce the concentrations of iron oxide at the outlet of filter/demineralizer (FTD) vessels. Each vessel is fitted with an array of tubular septa that are precoated with powdered ion-exchange resin. The coatings perform filtering and ion-exchange actions on incoming feedwater, removing both suspended and dissolved solids. Experience at Duane Arnold Energy Center (CAED) indicates that use of a powdered-resin precoat containing cation-exchange fibers rather than cellulose fibers can reduce iron oxide levels in FTD effluent significantly.

  2. Separation of certain carboxylic acids utilizing cation exchange membranes

    DOE Patents [OSTI]

    Chum, Helena L. (Arvada, CO); Sopher, David W. (Maarssenbroek, NL)

    1984-01-01

    A method of substantially separating monofunctional lower carboxylic acids from a liquid mixture containing the acids wherein the pH of the mixture is adjusted to a value in the range of from about 1 to about 5 to form protonated acids. The mixture is heated to an elevated temperature not greater than about 100.degree. C. and brought in contact with one side of a perfluorinated cation exchange membrane having sulfonate or carboxylate groups or mixtures thereof with the mixture containing the protonated acids. A pressure gradient can be established across the membrane with the mixture being under higher pressure, so that protonated monofunctional lower carboxylic acids pass through the membrane at a substantially faster rate than the remainder of the mixture thereby substantially separating the acids from the mixture.

  3. Kinetics for Tautomerizations and Dissociations of Triglycine Radical Cations

    SciTech Connect (OSTI)

    Siu, Chi-Kit; Zhao, Junfang; Laskin, Julia; Chu, Ivan K.; Hopkinson, Alan C.; Siu , K W Michael

    2009-06-01

    Fragmentations of tautomers of the α-centered radical triglycine radical cation, [GGG*]+, [GG*G]+, and [G*GG]+, are charge-driven, giving b-type ions; these are processes that are facilitated by a mobile proton, as in the fragmentation of protonated triglycine (Rodriquez, C.F. et al. J. Am. Chem. Soc. 2001, 123, 3006 - 3012). By contrast, radical centers are less mobile. Two mechanisms have been examined theoretically utilizing density functional theory and Rice-Ramsperger-Kassel-Marcus modeling: (1) a direct hydrogen-atom migration between two α-carbons, and (2) a two-step proton migration involving a canonical [GGG]*+ as an intermediate. Predictions employing the latter mechanism are in good agreement with results of recent CID experiments (Chu, I.K. et al. J. Am. Chem. Soc. 2008, 130, 7862 - 7872).

  4. Influence of rubidium cations on hydrogen and deuterium electrosorption in palladium

    SciTech Connect (OSTI)

    Czerwinski, A.; Frydrych, J.; Kiersztyn, I.

    1996-11-01

    A comparative cyclic voltammetric study of the hydrogen and deuterium sorptions into a thin layer palladium electrode has been performed in acidic and basic solutions containing rubidium cations. As in the case of other alkali cations, rubidium appears to clearly influence the {alpha}- to {beta}- phase transition only in basic solution.

  5. Method of separating and recovering uranium and related cations from spent Purex-type systems

    DOE Patents [OSTI]

    Mailen, J.C.; Tallent, O.K.

    1987-02-25

    A process for separating uranium and related cations from a spent Purex-type solvent extraction system which contains degradation complexes of tributylphosphate wherein the system is subjected to an ion-exchange process prior to a sodium carbonate scrubbing step. A further embodiment comprises recovery of the separated uranium and related cations. 5 figs.

  6. Novel alkyd-type coating resins produced using cationic polymerization

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

    Chisholm, Bret J.; Kalita, Harjyoti; Alam, Samim; Jayasooriyamu, Anurad; Fernando, Shashi; Samanata, Satyabrata; Bahr, James; Selvakumar, Sermadurai; Sibi, Mukund; Vold, Jessica; et al

    2015-05-06

    Novel, partially bio-based poly(vinyl ether) copolymers derived from soybean oil and cyclohexyl vinyl ether (CHVE) were produced by cationic polymerization and investigated for application as alkyd-type surface coatings. Compared to conventional alkyd resins, which are produced by high temperature melt condensation polymerization, the poly(v9nyl ether)s provide several advantages. These advantages include milder, more energy efficient polymer synthesis, elimination of issues associated with gelation during polymer synthesis, production of polymers with well-defined composition and relatively narrow molecular weight distribution, and elimination of film formation and physical property issues associated with entrained monomers, dimers, trimers, etc. The results of the studied showedmore » that the thermal, mechanical, and physical properties of the coatings produced from these novel polymers varied considerably as a function of polymer composition and cure temperature. Overall, the results suggest a good potential for these novel copolymers to be used for coatings cured by autoxidation.« less

  7. Ionic Liquids with Ammonium Cations as Lubricants or Additives

    SciTech Connect (OSTI)

    Qu, Jun; Blau, Peter Julian; Dai, Sheng; Luo, Huimin; Truhan, Jr., John J

    2006-01-01

    Friction and wear are estimated to cost 6% of the US gross national product, or around $700 billion annually. A new class of more effective lubricants could lead to huge energy savings. Limited recent literature has suggested potential for using room-temperature ionic liquids as lubricants, however only a few out of millions (or more) of species have been evaluated. Recent ORNL work discovered a new category of ionic liquids with ammonium cations that have demonstrated promising lubricating properties as net lubricants or lubricant additives, particularly in lubricating difficult-to-lubricate metals like aluminum. More than 30% friction reduction has been observed on ammonium-based ionic liquids compared to conventional hydrocarbon oils. The inherent polarity of ionic liquids is believed to provide strong adhesion to contact surfaces and form a boundary lubricating film leading to friction and wear reductions. Other advantages of ionic liquids include (1) negligible volatility, (2) high thermal stability, (3) non-flammability, and (4) better intrinsic properties that eliminate the necessity of many expensive lubricant additives. With very flexible molecular structures, this new class of lubricants, particularly ammonium-based ionic liquids, can be tailored to fit a big variety of applications including but not limited to bearings, combustion engines, MEMS, and metal forming.

  8. Cation exchange pretreatment studies for high recovery - Yuma desalting plant

    SciTech Connect (OSTI)

    Kaakinen, J.W.; Laverty, P.E.

    1983-10-01

    The main purpose of the High Recovery Test Program was to obtain feasibility design data for cation exchange softening to allow a greater fractional recovery of desalted product water at the YDP(Yuma Desalting Plant). Compared to the original YDP design with 70-percent desalting recovery, additional removal of calcium in the desalting feed would allow recoveries over 90 percent. Pilot plant equipment to test this process was operated at the YDTF(Yuma Desalting Test Facility) and consisted of an IX unit and an electrodialyzer to supply reject-brine regenerant for the IX experiments. Gypsum scale buildup in the resin bed could be avoided by regeneration with a high upward flow rate causing a fluidized bed. Reuse of regenerant was also beneficial. Results show that the ion exchange high recovery pretreatment process is highly feasible, and that it is technically possible to achieve high recovery in the YDP. Numerous recommendations for a plant design are given and future studies are noted.

  9. Organic cation secretion by Cancer borealis urinary bladder

    SciTech Connect (OSTI)

    Miller, D.S.; Holliday, C.W.

    1987-01-01

    In the crab, Cancer borealis, initial clearance studies showed a potent renal excretory system for the model organic cation, tetraethylammonium (TEA). (/sup 14/C)-TEA clearance averaged 145 +/- 32 ml/day, which was 18 times the paired polyethylene glycol clearance. TEA uptake by slices of urinary bladder was concentrative, saturable, inhibitable by N/sup 1/-methylnicotinamide chloride, and dependent on glycolytic, but not oxidative, metabolism. When mounted in flux chambers, bladders exhibited a large net secretory flux. For 0.1 mM TEA, the ratio of secretory to reabsorptive fluxes was 65. Urinary bladders from another crab, Cancer irroratus, and a lobster, Homarus americanus, also exhibited net TEA secretion. In C. borealis bladder, secretory transport was concentrative, saturable, and nearly abolished by addition of 1 mM quinine to the serosol bath. Reabsorptive transport was not concentrative and was not reduced by luminal quinine. The data are consistent with a secretory pathway that is transcellular and mediated by carriers at both the serosal and luminal membranes.

  10. Insights into dynamic processes of cations in pyrochlores and other complex oxides

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

    Uberuaga, Blas Pedro; Perriot, Romain

    2015-08-26

    Complex oxides are critical components of many key technologies, from solid oxide fuel cells and superionics to inert matrix fuels and nuclear waste forms. In many cases, understanding mass transport is important for predicting performance and, thus, extensive effort has been devoted to understanding mass transport in these materials. However, most work has focused on the behavior of oxygen while cation transport has received relatively little attention, even though cation diffusion is responsible for many phenomena, including sintering, radiation damage evolution, and deformation processes. Here, we use accelerated molecular dynamics simulations to examine the kinetics of cation defects in onemore » class of complex oxides, A₂B₂O₇ pyrochlore. In some pyrochlore chemistries, B cation defects are kinetically unstable, transforming to A cation defects and antisites at rates faster than they can diffuse. When this occurs, transport of B cations occurs through defect processes on the A sublattice. Further, these A cation defects, either interstitials or vacancies, can interact with antisite disorder, reordering the material locally, though this process is much more efficient for interstitials than vacancies. Whether this behavior occurs in a given pyrochlore depends on the A and B chemistry. Pyrochlores with a smaller ratio of cation radii exhibit this complex behavior, while those with larger ratios exhibit direct migration of B interstitials. Similar behavior has been reported in other complex oxides such as spinels and perovskites, suggesting that this coupling of transport between the A and B cation sublattices, while not universal, occurs in many complex oxide.« less

  11. Geochemistry And Geothermometry Of Spring Water From The Blackfoot...

    Open Energy Info (EERE)

    for eight springs along the Corral Creek drainage. The springs along Corral Creek have Na-K-Ca temperatures that average 354C, a direct result of high potassium concentrations in...

  12. Geothermometry At Lualualei Valley Area (Thomas, 1986) | Open...

    Open Energy Info (EERE)

    have been commonly used in Hawaii for identifying geothermal potential (i.e. silica concentration and chloride to magnesium ion ratios) were anomalous in the groundwater of this...

  13. Geothermometry At Long Valley Caldera Geothermal Area (McKenzie...

    Open Energy Info (EERE)

    published in 1976 (Mariner and Willey, 1976). Details of sampling practices and field treatment are detailed in the text. Water samples were passed through a 0.7x4 cm column...

  14. Geothermometry At Socorro Mountain Area (Owens, Et Al., 2005...

    Open Energy Info (EERE)

    thermal waters with a minimum of 82oC at depth References Lara Owens, Richard Baars, David Norman, Harold Tobin (2005) New Methods In Exploration At The Socorro Peak Kgra- A...

  15. Geothermometry At Lahaina-Kaanapali Area (Thomas, 1986) | Open...

    Open Energy Info (EERE)

    Date Usefulness not indicated DOE-funding Unknown Notes Groundwater temperature and chemistry surveys were similarly unable to identify any detectable thermal influence on...

  16. Geothermometry At Long Valley Caldera Geothermal Area (Mariner...

    Open Energy Info (EERE)

    California R.O. Fournier, Michael L. Sorey, Robert H. Mariner, Alfred H. Truesdell (1979) Chemical and Isotopic Prediction of Aquifer Temperatures in the Geothermal System at Long...

  17. Geothermometry At Coso Geothermal Area (1978) | Open Energy Informatio...

    Open Energy Info (EERE)

    analysis to determine fluid origin. The surface expression of fumarole and acid sulfate pools and shallow steam wells gives a false indication of an extensive vapor...

  18. Geothermometry At Kawaihae Area (Thomas, 1986) | Open Energy...

    Open Energy Info (EERE)

    however, the data that are available strongly substantiate the presence of a thermal resource. A measured water temperature of 31 degrees C in one well is clearly above normal...

  19. Geothermometry At U.S. Midwest Region (Vugrinovich, 1987) | Open...

    Open Energy Info (EERE)

    Activity Date Usefulness useful DOE-funding Unknown Notes Michigan "The silica heat flow estimator does provide estimates of surface heat flow which appear to be in good...

  20. Geothermal Reservoir Temperatures in Southeastern Idaho using Multicomponent Geothermometry

    SciTech Connect (OSTI)

    Neupane, Ghanashyam; Mattson, Earl D.; McLing, Travis L.; Palmer, Carl D.; Smith, Robert W.; Wood, Thomas R.; Podgorney, Robert K.

    2015-03-01

    Southeastern Idaho exhibits numerous warm springs, warm water from shallow wells, and hot water within oil and gas test wells that indicate a potential for geothermal development in the area. Although the area exhibits several thermal expressions, the measured geothermal gradients vary substantially (19 – 61 ºC/km) within this area, potentially suggesting a redistribution of heat in the overlying ground water from deeper geothermal reservoirs. We have estimated reservoir temperatures from measured water compositions using an inverse modeling technique (Reservoir Temperature Estimator, RTEst) that calculates the temperature at which multiple minerals are simultaneously at equilibrium while explicitly accounting for the possible loss of volatile constituents (e.g., CO2), boiling and/or water mixing. Compositions of a selected group of thermal waters representing southeastern Idaho hot/warm springs and wells were used for the development of temperature estimates. The temperature estimates in the the region varied from moderately warm (59 ºC) to over 175 ºC. Specifically, hot springs near Preston, Idaho resulted in the highest temperature estimates in the region.

  1. Geothermometry At Northern Basin & Range Region (Cole, 1983)...

    Open Energy Info (EERE)

    Fish (Wilson), Twin Peak, Cudahy, Laverkin, Grantsville, Crystal Prison, Arrowhead, Red Hill, Monroe, Joseph, Castilla, Saratoga, Thermo, Crater, Wasatch, Beck, Deseret, Big...

  2. Geothermometry At Reese River Area (Henkle & Ronne, 2008) | Open...

    Open Energy Info (EERE)

    DOE-funding Unknown Notes Four formation water samples were collected from well 56-4, during an airlift test which took place between November 11 and November 14, 2007....

  3. Geothermometry At Roosevelt Hot Springs Geothermal Area (Ward...

    Open Energy Info (EERE)

    Area. References S. H. Ward, W. T. Parry, W. P. Nash, W. R. Sill, K. L. Cook, R. B. Smith, D. S. Chapman, F. H. Brown, J. A. Whelan, J. R. Bowman (1978) A Summary of the...

  4. Geothermometry At Raft River Geothermal Area (1980) | Open Energy...

    Open Energy Info (EERE)

    River geothermal system, Cassia County, Idaho Urban, T.C.; Diment, W.H.; Nathenson, M.; Smith, E.P.; Ziagos, J.P.; Shaeffer, M.H. (1 January 1986) Temperature,...

  5. Geothermometry At Long Valley Caldera Geothermal Area (Sorey...

    Open Energy Info (EERE)

    studies, and seem to prove useful in most cases (Flexser, 1991; Goff et al., 1991; Smith and Suemnicht, 1991). Results from these studies are also summarized in Sorey et al....

  6. Geothermometry At Salt Wells Area (Edmiston & Benoit, 1984) ...

    Open Energy Info (EERE)

    and drilled during the early 1980's that had not been documented previously in the literature, (2) summarize and compare chemical and temperature data from known moderate- to...

  7. Isotope Geothermometry At Lightning Dock Geothermal Area (Witcher...

    Open Energy Info (EERE)

    Usefulness useful DOE-funding Unknown Exploration Basis Part of the Geothermal Resource Evaluation and Definition (GRED) Program administered by DOE-AAO under Cooperative...

  8. Geothermometry At Gabbs Alkali Flat Area (Kratt, Et Al., 2008...

    Open Energy Info (EERE)

    Mark Coolbaugh, Chris Sladek, Rick Zehner, Robin Penfield, Ben Delwiche (2008) A New Gold Pan For The West- Discovering Blind Geothermal Systems With Shallow Temperature Surveys...

  9. Geothermometry At Columbus Salt Marsh Area (Shevenell, Et Al...

    Open Energy Info (EERE)

    References Lisa Shevenell, Mark Coolbaugh, Chris Sladek, Rick Zehner, Chris Kratt, James Faulds, Robin Penfield (2008) Our Evolving Knowledge Of Nevada'S Geothermal Resource...

  10. Geothermometry At Teels Marsh Area (Shevenell, Et Al., 2008)...

    Open Energy Info (EERE)

    References Lisa Shevenell, Mark Coolbaugh, Chris Sladek, Rick Zehner, Chris Kratt, James Faulds, Robin Penfield (2008) Our Evolving Knowledge Of Nevada'S Geothermal Resource...

  11. Geothermometry At Rhodes Marsh Area (Shevenell, Et Al., 2008...

    Open Energy Info (EERE)

    References Lisa Shevenell, Mark Coolbaugh, Chris Sladek, Rick Zehner, Chris Kratt, James Faulds, Robin Penfield (2008) Our Evolving Knowledge Of Nevada'S Geothermal Resource...

  12. Geothermometry At Long Valley Caldera Geothermal Area (Farrar...

    Open Energy Info (EERE)

    stages of hydrothermal activity, flow, and recharge in the Long Valley caldera groundwater system. Fluids were sampled from LVEW during flow testing in May 2000, July 2000,...

  13. Geothermometry At Salt Wells Area (Coolbaugh, Et Al., 2006) ...

    Open Energy Info (EERE)

    and ICP emission for anions. The hottest sampled spring appears to match the location and temperature of the Borax Spring, first described in 1885, but reportedly inactive in 1981...

  14. Geothermometry At Salt Wells Area (Henkle, Et Al., 2005) | Open...

    Open Energy Info (EERE)

    were carried out in conjunction with geologic mapping to test the application of these ground-based techniques to geothermal exploration at three prospects in Nevada by Henkle...

  15. Geothermometry At Hot Springs Ranch Area (Szybinski, 2006) |...

    Open Energy Info (EERE)

    of two distinct waters in this group of samples (Tom Powell of Thermochem Inc., personal communication, 2005). Powell found that MDH, TRS-1 and TRS-6 are the most prospective...

  16. Geothermometry At Mt Princeton Hot Springs Geothermal Area (Pearl...

    Open Energy Info (EERE)

    Celcius References R.H. Pearl, J.K. Barrett (1976) Geothermal resources of the Upper San Luis and Arkansas valleys, Colorado Additional References Retrieved from "http:...

  17. Geothermometry At Northern Basin & Range Region (Laney, 2005...

    Open Energy Info (EERE)

    Nevada, Shevenell and Garside. The objective of this project is to obtain geochemical data from springs (and some wells) for which data are not publicly available, or for which...

  18. Geothermometry At Buffalo Valley Hot Springs Area (Laney, 2005...

    Open Energy Info (EERE)

    Nevada, Shevenell and Garside. The objective of this project is to obtain geochemical data from springs (and some wells) for which data are not publicly available, or for which...

  19. Geothermometry At Nw Basin & Range Region (Laney, 2005) | Open...

    Open Energy Info (EERE)

    Nevada, Shevenell and Garside. The objective of this project is to obtain geochemical data from springs (and some wells) for which data are not publicly available, or for which...

  20. Geothermometry At Central Nevada Seismic Zone Region (Laney,...

    Open Energy Info (EERE)

    Nevada, Shevenell and Garside. The objective of this project is to obtain geochemical data from springs (and some wells) for which data are not publicly available, or for which...

  1. Cationic Liposome-Microtuble Complexes: Lipid-Protein Bio-Nanotubles with

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

    Open or Closed Ends Cationic Liposome-Microtubule Complexes: Lipid-Protein Bio-Nanotubes with Open or Closed Ends Uri Raviv,*,+ Daniel J. Needleman,*,+ Youli Li,*,+ Herbert P. Miller,+ Leslie Wilson,+ and Cyrus R. Safinya *,+ *Materials Department, Physics Department +Molecular, Cellular, and Developmental Biology Department, Biomolecular Science and Engineering Program, University of California, Santa Barbara, CA 93106 In this work we explored the structured that form when cationic

  2. Infrared spectroscopy of the methanol cation and its methylene-oxonium isomer

    SciTech Connect (OSTI)

    Mosley, J. D.; Young, J. W.; Duncan, M. A. E-mail: maduncan@uga.edu; Huang, M.; McCoy, A. B. E-mail: maduncan@uga.edu

    2015-03-21

    The carbenium ion with nominal formula [C,H{sub 4},O]{sup +} is produced from methanol or ethylene glycol in a pulsed-discharge supersonic expansion source. The ion is mass selected, and its infrared spectrum is measured from 2000 to 4000 cm{sup ?1} using laser photodissociation spectroscopy and the method of rare gas atom tagging. Computational chemistry predicts two isomers, the methanol and methylene-oxonium cations. Predicted vibrational spectra based on scaled harmonic and reduced dimensional treatments are compared to the experimental spectra. The methanol cation is the only isomer produced when methanol is used as a precursor. When ethylene glycol is used as the precursor, methylene-oxonium is produced in addition to the methanol cation. Theoretical results at the CCSD(T)/cc-pVTZ level show that methylene-oxonium is lower in energy than methanol cation by 6.4 kcal/mol, and is in fact the global minimum isomer on the [C,H{sub 4},O]{sup +} potential surface. Methanol cation is trapped behind an isomerization barrier in our source, providing a convenient method to produce and characterize this transient species. Analysis of the spectrum of the methanol cation provides evidence for strong CH stretch vibration/torsion coupling in this molecular ion.

  3. Enhanced Mixed Electronic-Ionic Conductors through Cation Ordering

    SciTech Connect (OSTI)

    Jacobson, Allan J.; Morgan, Dane; Grey, Clare

    2014-08-31

    The performance of many energy conversion and storage devices depend on the properties of mixed ionic-electronic conducting (miec) materials. Mixed or ambipolar conductors simultaneously transport ions and electrons and provide the critical interface between chemical and electrical energy in devices such as fuel cells, ion transport membranes, and batteries. Enhancements in storage capacity, reversibility, power density and device lifetime all require new materials and a better understanding of the fundamentals of ambipolar conductivity and surface reactivity.The high temperature properties of the ordered perovksites AA’B2O5+x, where A = rare earth ion, Y and B = Ba, Sr were studied. The work was motivated by the high oxygen transport and surface exchange rates observed for members of this class of mixed ionic and electronic conductors. A combined experimental and computational approach, including structural, electrochemical, and transport characterization and modeling was used. The approach attacks the problem simultaneously at global (e.g., neutron diffraction and impedance spectroscopy), local (e.g., pair distribution function, nuclear magnetic resonance) and molecular (ab initio thermokinetic modeling) length scales. The objectives of the work were to understand how the cation and associated anion order lead to exceptional ionic and electronic transport properties and surface reactivity in AA’B2O5+x perovskites. A variety of compounds were studied by X-ray and neutron diffraction, measurements of thermodynamics and transport and theoretically. These included PrBaCo2O5+x and NdBaCo2O5+x, PrBaCo2-xFexO6- δ (x = 0, 0.5, 1.0, 1.5 and 2) and LnBaCoFeO6- δ (Ln = La, Pr, Nd, Sm, Eu and Gd), Sr3YCo4O10.5, YBaMn2O5+x. A0.5A’0.5BO3 (where A=Y, Sc, La, Ce, Pr, Nd, Pm, Sm; A’= Sr

  4. Effect of cation ordering on oxygen vacancy diffusion pathways in double perovskites

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

    Uberuaga, Blas Pedro; Pilania, Ghanshyam

    2015-07-08

    Perovskite structured oxides (ABO3) are attractive for a number of technological applications, including as superionics because of the high oxygen conductivities they exhibit. Double perovskites (AA’BB’O6) provide even more flexibility for tailoring properties. Using accelerated molecular dynamics, we examine the role of cation ordering on oxygen vacancy mobility in one model double perovskite SrLaTiAlO6. We find that the mobility of the vacancy is very sensitive to the cation ordering, with a migration energy that varies from 0.6 to 2.7 eV. In the extreme cases, the mobility is both higher and lower than either of the two end member single perovskites.more » Further, the nature of oxygen vacancy diffusion, whether one-dimensional, two-dimensional, or three-dimensional, also varies with cation ordering. We correlate the dependence of oxygen mobility on cation structure to the distribution of Ti4+ cations, which provide unfavorable environments for the positively charged oxygen vacancy. The results demonstrate the potential of using tailored double perovskite structures to precisely control the behavior of oxygen vacancies in these materials.« less

  5. Colloid Facilitated Transport of Radioactive Cations in the Vadose Zone: Field Experiments Oak Ridge

    SciTech Connect (OSTI)

    James E. Saiers

    2012-09-20

    The overarching goal of this study was to improve understanding of colloid-facilitated transport of radioactive cations through unsaturated soils and sediments. We conducted a suite of laboratory experiments and field experiments on the vadose-zone transport of colloids, organic matter, and associated contaminants of interest to the U.S. Department of Energy (DOE). The laboratory and field experiments, together with transport modeling, were designed to accomplish the following detailed objectives: 1. Evaluation of the relative importance of inorganic colloids and organic matter to the facilitation of radioactive cation transport in the vadose zone; 2. Assessment of the role of adsorption and desorption kinetics in the facilitated transport of radioactive cations in the vadose zone; 3. Examination of the effects of rainfall and infiltration dynamics and in the facilitated transport of radioactive cations through the vadose zone; 4. Exploration of the role of soil heterogeneity and preferential flow paths (e.g., macropores) on the facilitated transport of radioactive cations in the vadose zone; 5. Development of a mathematical model of facilitated transport of contaminants in the vadose zone that accurately incorporates pore-scale and column-scale processes with the practicality of predicting transport with readily available parameters.

  6. Mesophase stabilization in ionic liquid crystals through pairing equally shaped mesogenic cations and anions

    SciTech Connect (OSTI)

    Stappert, Kathrin; Lipinski, Gregor; Kopiec, Gabriel; Spielberg, Eike T.; Mudring, Anja -Verena

    2015-07-23

    The synthesis and properties of a set of novel ionic liquid crystals with congruently shaped cations and anions are reported to check whether pairing mesogenic cations with mesogenic anions leads to a stabilization of a liquid crystalline phase. To that avail 1-alkyl-3-methyl-triazolium cations with an alkyl chain length of 10, 12, and 14 carbon atoms have been combined with p-alkyloxy-benzenesulfonate anions with different alkyl chain lengths (n = 10, 12, and 14). The corresponding triazolium iodides have been synthesized as reference compounds where the cation and anion have strong size and shape mismatch. The mesomorphic behavior of all compounds is studied by differential scanning calorimetry and polarizing optical microscopy. All compounds except 1-methyl-3-decyltriazolium iodide, which qualifies as an ionic liquid, are thermotropic ionic liquid crystals. All other compounds adopt smectic A phases. As a result, a comparison of the thermal phase behavior of the 1-methyl-3-decyltriazolium bromides to the corresponding p-alkoxy-benzensulfonates reveals that definitely the mesophase is stabilized by pairing the rod-shaped 1-alkyl-3-methyltriazolium cation with a rod-like anion of similar size.

  7. Mesophase stabilization in ionic liquid crystals through pairing equally shaped mesogenic cations and anions

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

    Stappert, Kathrin; Lipinski, Gregor; Kopiec, Gabriel; Spielberg, Eike T.; Mudring, Anja -Verena

    2015-07-23

    The synthesis and properties of a set of novel ionic liquid crystals with congruently shaped cations and anions are reported to check whether pairing mesogenic cations with mesogenic anions leads to a stabilization of a liquid crystalline phase. To that avail 1-alkyl-3-methyl-triazolium cations with an alkyl chain length of 10, 12, and 14 carbon atoms have been combined with p-alkyloxy-benzenesulfonate anions with different alkyl chain lengths (n = 10, 12, and 14). The corresponding triazolium iodides have been synthesized as reference compounds where the cation and anion have strong size and shape mismatch. The mesomorphic behavior of all compounds ismore » studied by differential scanning calorimetry and polarizing optical microscopy. All compounds except 1-methyl-3-decyltriazolium iodide, which qualifies as an ionic liquid, are thermotropic ionic liquid crystals. All other compounds adopt smectic A phases. As a result, a comparison of the thermal phase behavior of the 1-methyl-3-decyltriazolium bromides to the corresponding p-alkoxy-benzensulfonates reveals that definitely the mesophase is stabilized by pairing the rod-shaped 1-alkyl-3-methyltriazolium cation with a rod-like anion of similar size.« less

  8. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

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

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-04-05

    Here, benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt−1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through a combinationmore » of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

  9. Properties of some ionic liquids based on1-methyl-3-octylimidazolium and 4-methyl-N-butylpyridinium cations.

    SciTech Connect (OSTI)

    Papaiconomou, Nicolas; Yakelis, Neal; Salminen, Justin; Bergman,Robert; Prausnitz, John M.

    2005-09-29

    Syntheses are reported for ionic liquids containing 1-methyl-3octylimidazolium and 4-methyl-N-butylpyridinium cations, and trifluoromethansulfonate, dicyanamide, bis(trifluoromethylsulfonyl)imide, and nonafluorobutanesulfonate anions. Densities, melting points and glass transition points, solubility in water as well as polarities have been measured. Ionic liquids based on pyridinium cations exhibit higher melting points, lower solubility in water, and higher polarity than those based on imidazolium cations.

  10. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

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

    Kim, M. J.; Zoerb, M. C.; Campbell, N. R.; Zimmermann, K. J.; Blomquist, B. W.; Huebert, B. J.; Bertram, T. H.

    2015-10-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e. DMS, ?-caryophyllene) as well as previously studied VOCs (i.e., isoprene, ?-pinene). Using a field deployable chemical ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt?1) to DMS, isoprene, and ?-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a weaker electric field, demonstrated that ion-molecule reactions likely proceed through amorecombination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (R2=0.80) over a wide range of sampling conditions.less

  11. Differential inhibition of organic cations by the renal tubule of the chicken: relationship to Tm

    SciTech Connect (OSTI)

    Springate, J.; Hasan, M.; Rennick, B.; Acara, M.

    1986-03-01

    The ability of organic cations to differentially inhibit the renal excretion of two prototypical organic cations, tetraethylammonium (TEA) and N/sup 1/-methylnicotinamide (NMN), was investigated using the Sperber technique in chickens. /sup 3/H-TEA and /sup 14/C-NMN were infused simultaneously into the renal portal circulation and their transport efficiencies (TE) determined to be 106 +/- 11% and 81 +/- 13% respectively. Quinine, unlabelled NMN or TEA, added in increasing amounts, produced differential inhibition of TEA, NMN, or cimetidine (infused in separate experiments). Data using other competing organic cations (guinidine, ranitidine, triethylcholine) indicated that TEA was never more susceptible to inhibition than NMN. These results suggest that the magnitude of T/sub m/ is directly related to susceptibility to inhibition and indirectly to inhibitory potency.

  12. Non-immunogenic, hydrophilic/cationic block copolymers and uses thereof

    DOE Patents [OSTI]

    Scales, Charles W.; Huang, Faqing; McCormick, Charles L.

    2010-05-18

    The present invention provides novel non-immunogenic, hydrophilic/cationic block copolymers comprising a neutral-hydrophilic polymer and a cationic polymer, wherein both polymers have well-defined chain-end functionality. A representative example of such a block copolymer comprises poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA) and poly(N-[3-(dimethylamino)propyl]methacrylamide) (PDMAPMA). Also provided is a synthesis method thereof in aqueous media via reversible addition fragmentation chain transfer (RAFT) polymerization. Further provided are uses of these block copolymers as drug delivery vehicles and protection agents.

  13. DFT studies of all fluorothiophenes and their cations as candidate monomers for conductive polymers

    SciTech Connect (OSTI)

    Shirani, Hossein; Jameh-Bozorghi, Saeed; Yousefi, Ali

    2015-01-22

    In this paper, electronic, structural, and properties of mono-, di-, tri-, and tetrafluorothiophenes and their radical cations are studied using the density functional theory and B3LYP method with 6-311++G** basis set. Also, the effects of the number and position of the substituent of fluorine atoms on the properties of the thiophene ring have been studied using optimized structures obtained for these molecules and their radical cations; vibrational frequencies, spin-density distribution, size and direction of the dipole moment vector, ionization potential, electric Polarizabilities, HOMO–LUMO gaps and NICS values of these compounds have been calculated and analyzed.

  14. High energy electron beam curing of epoxy resin systems incorporating cationic photoinitiators

    DOE Patents [OSTI]

    Janke, C.J.; Lopata, V.J.; Havens, S.J.; Dorsey, G.F.; Moulton, R.J.

    1999-03-02

    A mixture of epoxy resins such as a semi-solid triglycidyl ether of tris (hydroxyphenyl) methane and a low viscosity bisphenol A glycidyl ether and a cationic photoinitiator such as a diaryliodonium salt is cured by irradiating with a dosage of electron beams from about 50 to about 150 kGy, forming a cross-linked epoxy resin polymer.

  15. Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations

    DOE Patents [OSTI]

    Marks, Tobin J.; Chen, You-Xian

    2002-01-01

    Organo-Lewis acids of the formula BR'R".sub.2 wherein B is boron, R' is fluorinated biphenyl, and R" is a fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic fused ring group, and cationic metallocene complexes formed therewith. Such complexes are useful as polymerization catalysts.

  16. Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations

    DOE Patents [OSTI]

    Marks, Tobin J.; Chen, You-Xian

    2001-01-01

    Organo-Lewis acids of the formula BR'R".sub.2 wherein B is boron, R' is fluorinated biphenyl, and R" is a fluorinated phenyl, fluorinated biphenyl, or fluorinated polycyclic fused ring group, and cationic metallocene complexes formed therewith. Such complexes are useful as polymerization catalysts.

  17. Spectroscopic signatures of proton transfer dynamics in the water dimer cation

    SciTech Connect (OSTI)

    Kamarchik, Eugene; Kostko, Oleg; Bowman, Joel M.; Ahmed, Musahid; Krylov, Anna I.

    2009-12-21

    Using full dimensional EOM-IP-CCSD/aug-cc-pVTZ potential energy surfaces, the photoelectron spectrum, vibrational structure, and ionization dynamics of the water dimer radical cation, (H2O)+2, were computed. We also report an experimental photoelectron spectrum which is derived from photoionization efficiency measurements and compares favorably with the theoretical spectrum. The vibrational structure is also compared with the recent experimental work of Gardenier et al. [J. Phys. Chem. A 113, 4772 (2009)] and the recent theoretical calculations by Cheng et al. [J. Phys. Chem. A 113 13779 (2009)]. A reduced dimensionality nuclear Hamiltonian was used to compute the ionization dynamics for both the ground state and first excited state of the cation. The dynamics show markedly different behavior and spectroscopic signatures depending on which state of the cation is accessed by the ionization. Ionization to the ground-state cation surface induces a hydrogen transfer which is complete within 50 femtoseconds, whereas ionization to the first excited state results in a much slower process.

  18. High energy electron beam curing of epoxy resin systems incorporating cationic photoinitiators

    DOE Patents [OSTI]

    Janke, Christopher J.; Lopata, Vincent J.; Havens, Stephen J.; Dorsey, George F.; Moulton, Richard J.

    1999-01-01

    A mixture of epoxy resins such as a semi-solid triglycidyl ether of tris (hydroxyphenyl) methane and a low viscosity bisphenol A glycidyl ether and a cationic photoinitiator such as a diaryliodonium salt is cured by irradiating with a dosage of electron beams from about 50 to about 150 kGy, forming a cross-linked epoxy resin polymer.

  19. Misfit strain driven cation inter-diffusion across an epitaxial multiferroic thin film interface

    SciTech Connect (OSTI)

    Sankara Rama Krishnan, P. S.; Munroe, Paul; Nagarajan, V.; Morozovska, Anna N.; Eliseev, Eugene A.; Ramasse, Quentin M.; Kepaptsoglou, Demie; Liang, Wen-I.; Chu, Ying-Hao

    2014-02-07

    Cation intermixing at functional oxide interfaces remains a highly controversial area directly relevant to interface-driven nanoelectronic device properties. Here, we systematically explore the cation intermixing in epitaxial (001) oriented multiferroic bismuth ferrite (BFO) grown on a (001) lanthanum aluminate (LAO) substrate. Aberration corrected dedicated scanning transmission electron microscopy and electron energy loss spectroscopy reveal that the interface is not chemically sharp, but with an intermixing of ?2?nm. The driving force for this process is identified as misfit-driven elastic strain. Landau-Ginzburg-Devonshire-based phenomenological theory was combined with the Sheldon and Shenoy formula in order to understand the influence of boundary conditions and depolarizing fields arising from misfit strain between the LAO substrate and BFO film. The theory predicts the presence of a strong potential gradient at the interface, which decays on moving into the bulk of the film. This potential gradient is significant enough to drive the cation migration across the interface, thereby mitigating the misfit strain. Our results offer new insights on how chemical roughening at oxide interfaces can be effective in stabilizing the structural integrity of the interface without the need for misfit dislocations. These findings offer a general formalism for understanding cation intermixing at highly strained oxide interfaces that are used in nanoelectronic devices.

  20. Phosphonium-Organophosphate Ionic Liquids as Lubricant Additives: Effects of Cation Structure on Physicochemical and Tribological Characteristics

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

    Barnhill, William C.; Qu, Jun; Luo, Huimin; Meyer III, Harry M.; Ma, Cheng; Chi, Miaofang; Papke, Brian L.

    2014-11-17

    In our previous work we suggest great potential for a phosphonium-organophosphate ionic liquid (IL) as an antiwear lubricant additive. In this study, a set of five ILs were carefully designed and synthesized, with identical organophosphate anions but dissimilar phosphonium cations, to allow systematic investigation of the effects of cation alkyl chain length and symmetry on physicochemical and tribological properties. Symmetric cations with shorter alkyl chains seem to increase the density and thermal stability due to closer packing. On the other hand, either higher cation symmetry or longer alkyl moieties induce a higher viscosity, though the viscosity index is dependent moremore » on molecular mass than on symmetry. While a larger cation size generally increases an IL’s solubility in nonpolar hydrocarbon oils, six-carbon seems to be the critical minimum alkyl chain length for high oil miscibility. Both the two ILs, that are mutually oil miscible, have demonstrated promising lubricating performance at 1.04% treat rate, though the symmetric-cation IL moderately outperformed the asymmetric-cation IL. Moreover, characterizations on the tribofilm formed by the best-performing symmetric-cation IL revealed the film thickness, nanostructure, and chemical composition. Our results provide fundamental insights for future molecular design in developing oil-soluble ILs as lubricant additives.« less

  1. Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

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

    Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; Zimmermann, Kathryn J.; Blomquist, Byron W.; Huebert, Barry J.; Bertram, Timothy H.

    2016-01-01

    Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt−1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through a combination of ligand-switching and directmore » charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

  2. Effect of Divalent Cation Removal on the Structure of Gram-Negative Bacterial Outer Membrane Models

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

    Clifton, Luke A.; Skoda, Maximilian W. A.; Le Brun, Anton P.; Ciesielski, Filip; Kuzmenko, Ivan; Holt, Stephen A.; Lakey, Jeremy H.

    2014-12-09

    The Gram-negative bacterial outer membrane (GNB-OM) is asymmetric in its lipid composition with a phospholipid-rich inner leaflet and an outer leaflet predominantly composed of lipopolysaccharides (LPS). LPS are polyanionic molecules, with numerous phosphate groups present in the lipid A and core oligosaccharide regions. The repulsive forces due to accumulation of the negative charges are screened and bridged by the divalent cations (Mg2+ and Ca2+) that are known to be crucial for the integrity of the bacterial OM. Indeed, chelation of divalent cations is a well-established method to permeabilize Gram-negative bacteria such as Escherichia coli. Here, we use X-ray and neutronmore » reflectivity (XRR and NR, respectively) techniques to examine the role of calcium ions in the stability of a model GNB-OM. Using XRR we show that Ca2+ binds to the core region of the rough mutant LPS (RaLPS) films, producing more ordered structures in comparison to divalent cation free monolayers. Using recently developed solid-supported models of the GNB-OM, we study the effect of calcium removal on the asymmetry of DPPC:RaLPS bilayers. We show that without the charge screening effect of divalent cations, the LPS is forced to overcome the thermodynamically unfavorable energy barrier and flip across the hydrophobic bilayer to minimize the repulsive electrostatic forces, resulting in about 20% mixing of LPS and DPPC between the inner and outer bilayer leaflets. These results reveal for the first time the molecular details behind the well-known mechanism of outer membrane stabilization by divalent cations. This confirms the relevance of the asymmetric models for future studies of outer membrane stability and antibiotic penetration.« less

  3. Effect of Divalent Cation Removal on the Structure of Gram-Negative Bacterial Outer Membrane Models

    SciTech Connect (OSTI)

    Clifton, Luke A.; Skoda, Maximilian W. A.; Le Brun, Anton P.; Ciesielski, Filip; Kuzmenko, Ivan; Holt, Stephen A.; Lakey, Jeremy H.

    2014-12-09

    The Gram-negative bacterial outer membrane (GNB-OM) is asymmetric in its lipid composition with a phospholipid-rich inner leaflet and an outer leaflet predominantly composed of lipopolysaccharides (LPS). LPS are polyanionic molecules, with numerous phosphate groups present in the lipid A and core oligosaccharide regions. The repulsive forces due to accumulation of the negative charges are screened and bridged by the divalent cations (Mg2+ and Ca2+) that are known to be crucial for the integrity of the bacterial OM. Indeed, chelation of divalent cations is a well-established method to permeabilize Gram-negative bacteria such as Escherichia coli. Here, we use X-ray and neutron reflectivity (XRR and NR, respectively) techniques to examine the role of calcium ions in the stability of a model GNB-OM. Using XRR we show that Ca2+ binds to the core region of the rough mutant LPS (RaLPS) films, producing more ordered structures in comparison to divalent cation free monolayers. Using recently developed solid-supported models of the GNB-OM, we study the effect of calcium removal on the asymmetry of DPPC:RaLPS bilayers. We show that without the charge screening effect of divalent cations, the LPS is forced to overcome the thermodynamically unfavorable energy barrier and flip across the hydrophobic bilayer to minimize the repulsive electrostatic forces, resulting in about 20% mixing of LPS and DPPC between the inner and outer bilayer leaflets. These results reveal for the first time the molecular details behind the well-known mechanism of outer membrane stabilization by divalent cations. This confirms the relevance of the asymmetric models for future studies of outer membrane stability and antibiotic penetration.

  4. A New Improved Na-K Geothermometer By Artificial Neural Networks...

    Open Energy Info (EERE)

    567-577), Truesdell (1975; Proc. 2nd UN Symposium), Tonani (1980; Proc. Adv. Eur. Geoth. Research, 2nd Symposium), Fournier (1979a; J. Volcanol. Geotherm. Res. 5, 1-16), Nieva and...

  5. An Empirical Na-K-Ca Geothermometer For Natural Waters | Open...

    Open Energy Info (EERE)

    temperature environments ranging from 4 to 340C. The data for most geothermal waters cluster near a straight line when plotted as the function vs reciprocal of absolute...

  6. Are the Radical Centers in Peptide Radical Cations Mobile? The Generation, Tautomerism, and Dissociation of Isomeric α-Carbon-Centered Triglycine Radical Cations in the Gas Phase

    SciTech Connect (OSTI)

    Chu, Ivan K.; Zhao, Junfang; Xu, Minjie; Siu, Shiu On; Hopkinson, Alan C.; Siu , K W Michael

    2008-05-31

    The mobility of the radical center in three isomeric triglycine radical cationss[G•GG]+, [GG•G]+, and [GGG•]+shas been investigated theoretically via density functional theory (DFT) and experimentally via tandem mass spectrometry. These radical cations were generated by collision-induced dissociations (CIDs) of Cu(II)-containing ternary complexes that contain the tripeptides YGG, GYG, and GGY, respectively (G and Y are the glycine and tyrosine residues, respectively). Dissociative electron transfer within the complexes led to observation of [Y•GG]+, [GY•G]+, and [GGY•]+; CID resulted in cleavage of the tyrosine side chain as p-quinomethide, yielding [G•GG]+, [GG•G]+, and [GGG•]+, respectively. Interconversions between these isomeric triglycine radical cations have relatively high barriers (g44.7 kcal/mol), in support of the thesis that isomerically pure [G•GG]+, [GG•G]+, and [GGG•]+ can be experimentally produced. This is to be contrasted with barriers < 17 kcal/mol that were encountered in the tautomerism of protonated triglycine [Rodriquez C. F. et al. J. Am. Chem. Soc. 2001, 123, 3006-3012]. The CID spectra of [G•GG]+, [GG•G]+, and [GGG•]+ were substantially different, providing experimental proof that initially these ions have distinct structures. DFT calculations showed that direct dissociations are competitive with interconversions followed by dissociation.

  7. Controlling the actuation properties of MXene paper electrodes upon cation intercalation

    SciTech Connect (OSTI)

    Come, Jeremy E.; Black, Jennifer M.; Naguib, Michael; Lukatskaya, Maria R.; Beidaghi, Majid; Wesolowski, David J.; Gogotsi, Yury; Rondinone, Adam J.; Balke, Nina; Kalinin, Sergei V.

    2015-08-05

    Atomic force microscopy was used to monitor the macroscopic deformation in a delaminated Ti₃C₂ paper electrode in-situ, during charge/discharge in a variety of aqueous electrolytes to examine the effect of the cation intercalation on the electrochemical behavior and mechanical response. The results show a strong dependence of the electrode deformation on cation size and charge. The electrode undergoes a large contraction during Li⁺, Na⁺ or Mg²⁺ intercalation, differentiating the Ti₃C₂ paper from conventional electrodes where redox intercalation of ions (e.g. Li⁺) into the bulk phase (e.g. graphite, silicon) results in volumetric expansion. This feature may explain the excellent rate performance and cyclability reported for MXenes. We also demonstrated that the variation of the electromechanical contraction can be easily adjusted by electrolyte exchange, and shows interesting characteristics for the design of actuators based on 2D metal carbides.

  8. Preferential solvation of lithium cations and impacts on oxygen reduction in lithium–air batteries

    SciTech Connect (OSTI)

    Zheng, Dong; Qu, Deyu; Yang, Xiao -Qing; Lee, Hung -Sui; Qu, Deyang

    2015-09-16

    The solvation of Li⁺ with eleven non-aqueous solvents commonly used as the electrolytes for Li batteries were studied. The solvation preferences of different solvents were compared by means of electrospray mass spectrometry and collision-induced dissociation. The relative strength of the solvent for the solvation of Li⁺ was determined. The Lewis acidity of the solvated Li⁺ cations was determined by the preferential solvation of the solvent in the solvation shell. The kinetics of the catalytic disproportionation of the O₂⁻ depends on the relative Lewis acidity of the solvated Li⁺ ion. The impact of the solvated Li⁺ cation on the O₂ redox reaction was also investigated.

  9. Controlling the actuation properties of MXene paper electrodes upon cation intercalation

    SciTech Connect (OSTI)

    Come, Jeremy E.; Black, Jennifer M.; Naguib, Michael; Lukatskaya, Maria R.; Beidaghi, Majid; Wesolowski, David J.; Gogotsi, Yury; Rondinone, Adam J.; Balke, Nina; Kalinin, Sergei V.

    2015-08-05

    Atomic force microscopy was used to monitor the macroscopic deformation in a delaminated Ti?C? paper electrode in-situ, during charge/discharge in a variety of aqueous electrolytes to examine the effect of the cation intercalation on the electrochemical behavior and mechanical response. The results show a strong dependence of the electrode deformation on cation size and charge. The electrode undergoes a large contraction during Li?, Na? or Mg? intercalation, differentiating the Ti?C? paper from conventional electrodes where redox intercalation of ions (e.g. Li?) into the bulk phase (e.g. graphite, silicon) results in volumetric expansion. This feature may explain the excellent rate performance and cyclability reported for MXenes. We also demonstrated that the variation of the electromechanical contraction can be easily adjusted by electrolyte exchange, and shows interesting characteristics for the design of actuators based on 2D metal carbides.

  10. Aza Cope Rearrangement of Propargyl Enammonium Cations Catalyzed By a Self-Assembled `Nanozyme

    SciTech Connect (OSTI)

    Hastings, Courntey J.; Fiedler, Dorothea; Bergman, Robert G.; Raymond, Kenneth N.

    2008-02-27

    The tetrahedral [Ga{sub 4}L{sub 6}]{sup 12-} assembly (L = N,N-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene) encapsulates a variety of cations, including propargyl enammonium cations capable of undergoing the aza Cope rearrangement. For propargyl enammonium substrates that are encapsulated in the [Ga{sub 4}L{sub 6}]{sup 12-} assembly, rate accelerations of up to 184 are observed when compared to the background reaction. After rearrangement, the product iminium ion is released into solution and hydrolyzed allowing for catalytic turnover. The activation parameters for the catalyzed and uncatalyzed reaction were determined, revealing that a lowered entropy of activation is responsible for the observed rate enhancements. The catalyzed reaction exhibits saturation kinetics; the rate data obey the Michaelis-Menten model of enzyme kinetics, and competitive inhibition using a non-reactive guest has been demonstrated.

  11. Preferential solvation of lithium cations and impacts on oxygen reduction in lithium–air batteries

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

    Zheng, Dong; Qu, Deyu; Yang, Xiao -Qing; Lee, Hung -Sui; Qu, Deyang

    2015-09-16

    The solvation of Li⁺ with eleven non-aqueous solvents commonly used as the electrolytes for Li batteries were studied. The solvation preferences of different solvents were compared by means of electrospray mass spectrometry and collision-induced dissociation. The relative strength of the solvent for the solvation of Li⁺ was determined. The Lewis acidity of the solvated Li⁺ cations was determined by the preferential solvation of the solvent in the solvation shell. The kinetics of the catalytic disproportionation of the O₂⁻ depends on the relative Lewis acidity of the solvated Li⁺ ion. The impact of the solvated Li⁺ cation on the O₂ redoxmore » reaction was also investigated.« less

  12. Water soluble/dispersible and easy removable cationic adhesives and coating for paper recycling

    DOE Patents [OSTI]

    Deng, Yulin; Yan, Zegui

    2005-11-29

    The present invention is an adhesive or coating composition that is dispersible or dissolvable in water, making it useful in as a coating or adhesive in paper intended for recycling. The composition of the present invention is cationically charged thereby binding with the fibers of the paper slurry and thus, resulting in reduced deposition of adhesives on equipment during the recycling process. The presence of the composition of the present invention results in stronger interfiber bonding in products produced from the recycled fibers.

  13. Cloning and first functional characterization of a plant cyclic nucleotide-gated cation channel

    SciTech Connect (OSTI)

    Leng, Q.; Mercier, R.W.; Yao, W.; Berkowitz, G.A.

    1999-11-01

    Cyclic nucleotide-gated (cng) non-selective cation channels have been cloned from a number of animal systems. These channels are characterized by direct gating upon cAMO or cGMO binding to the intracellular portion of the channel protein, which leads to an increase in channel conductance. Animal cng channels are involved in signal transduction systems; they translate stimulus-induced changes in cytosolic cyclic nucleotide into altered cell membrane potential and/or cation flux as part of a signal cascade pathway. Putative plant homologs of animal cng channels have been identified. However, functional characterization (i.e., demonstration of cyclic-nucleotide-dependent ion currents) of a plant cng channel has not yet been accomplished. The authors report the cloning and first functional characterization of a plant member of this family of ion channels. The Arabidopsis cDNA AtCNGC2 encodes a polypeptide with deduced homology to the {alpha}-subunit of animal channels, and facilitates cyclic nucleotide-dependent cation currents upon expression in a number of heterologous systems. AtCNGC2 expression in a yeast mutant lacking a low-affinity K{sup +} uptake system complements growth inhibition only when lipophilic nucleotides are present in the culture medium. Voltage clamp analysis indicates that Xenopus lawvis oocytes injected with AtCNGC2 cRNA demonstrate cyclic-nucleotide-dependent, inward-rectifying K{sup +} currents. Human embryonic kidney cells (HEK293) transfected with AtCNGC2 cDNA demonstrate increased permeability to Ca{sup 2+} only in the presence of lipophilic cyclic nucleotides. The evidence presented here supports the functional classification of AtCNGC2 as a cyclic-nucleotide-gated cation channel, and presents the first direct evidence identifying a plant member of this ion channel family.

  14. Enhancing Cation-Exchange Capacity of Biochar for Soil Amendment and Global

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

    Carbon Sequestration - Energy Innovation Portal Biomass and Biofuels Biomass and Biofuels Find More Like This Return to Search Enhancing Cation-Exchange Capacity of Biochar for Soil Amendment and Global Carbon Sequestration Oak Ridge National Laboratory Contact ORNL About This Technology Technology Marketing SummaryPhotosynthesis captures more carbon dioxide from the atmosphere than any other process on Earth. However, because biomass is not stable and is always decomposing, it is of limited

  15. The Lightest Organic Radical Cation for Charge Storage in Redox Flow

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

    Batteries - Joint Center for Energy Storage Research August 25, 2016, Research Highlights The Lightest Organic Radical Cation for Charge Storage in Redox Flow Batteries A family of dimethoxybenzene derivatives have been designed and screened using a systematic pruning approach and a stepwise work flow. Compound 6 and 7 not only show promising results in the screening work flow, including cyclic voltammetry, bulk electrolysis cell tests, flow cell tests and EPR kinetic test, but also offer

  16. Strategies to Suppress Cation Vacancies in Metal Oxide Alloys: Consequences for Solar Energy Conversion

    SciTech Connect (OSTI)

    Toroker, Maytal; Carter, Emily A.

    2015-09-01

    First-row transition metal oxides (TMOs) are promising alternative materials for inexpensive and efficient solar energy conversion. However, their conversion efficiency can be deleteriously affected by material imperfections, such as atomic vacancies. In this work, we provide examples showing that in some iron-containing TMOs, iron cation vacancy formation can be suppressed via alloying. We calculate within density functional theory+U theory the iron vacancy formation energy in binary rock-salt oxide alloys that contain iron, manganese, nickel, zinc, and/or magnesium. We demonstrate that formation of iron vacancies is less favorable if we choose to alloy iron(II) oxide with metals that cannot readily accept vacancy-generated holes, e.g., magnesium, manganese, nickel, or zinc. Since there are less available sites for holes and the holes are forced to reside on iron cations, the driving force for iron vacancy formation decreases. These results are consistent with an experiment observing a sharp drop in cation vacancy concentration upon alloying iron(II) oxide with manganese.

  17. HYDROGENATION OF PAH CATIONS: A FIRST STEP TOWARD H{sub 2} FORMATION

    SciTech Connect (OSTI)

    Boschman, L.; Cazaux, S.; Spaans, M.; Reitsma, G.; Schlathoelter, T.; Hoekstra, R.; Gonzalez-Magana, O.

    2012-12-20

    Molecular hydrogen is the most abundant molecule in the universe. A large fraction of H{sub 2} forms by association of hydrogen atoms adsorbed on polycyclic aromatic hydrocarbons (PAHs), where formation rates depend crucially on the H sticking probability. We have experimentally studied PAH hydrogenation by exposing coronene cations, confined in a radio-frequency ion trap, to gas phase atomic hydrogen. A systematic increase of the number of H atoms adsorbed on the coronene with the time of exposure is observed. Odd coronene hydrogenation states dominate the mass spectrum up to 11 H atoms attached. This indicates the presence of a barrier preventing H attachment to these molecular systems. For the second and fourth hydrogenations, barrier heights of 72 {+-} 6 meV and 40 {+-} 10 meV, respectively, are found, which are in good agreement with theoretical predictions for the hydrogenation of neutral PAHs. Our experiments, however, prove that the barrier does not vanish for higher hydrogenation states. These results imply that PAH cations, as their neutral counterparts, exist in highly hydrogenated forms in the interstellar medium. Due to this catalytic activity, PAH cations and neutrals seem to contribute similarly to the formation of H{sub 2}.

  18. Use of MgO doped with a divalent or trivalent metal cation for removing arsenic from water

    DOE Patents [OSTI]

    Moore, Robert C; Holt-Larese, Kathleen C; Bontchev, Ranko

    2013-08-13

    Systems and methods for use of magnesium hydroxide, either directly or through one or more precursors, doped with a divalent or trivalent metal cation, for removing arsenic from drinking water, including water distribution systems. In one embodiment, magnesium hydroxide, Mg(OH).sub.2 (a strong adsorbent for arsenic) doped with a divalent or trivalent metal cation is used to adsorb arsenic. The complex consisting of arsenic adsorbed on Mg(OH).sub.2 doped with a divalent or trivalent metal cation is subsequently removed from the water by conventional means, including filtration, settling, skimming, vortexing, centrifugation, magnetic separation, or other well-known separation systems. In another embodiment, magnesium oxide, MgO, is employed, which reacts with water to form Mg(OH).sub.2. The resulting Mg(OH).sub.2 doped with a divalent or trivalent metal cation, then adsorbs arsenic, as set forth above. The method can also be used to treat human or animal poisoning with arsenic.

  19. Effect of a-site cation deficiency and YSZ additions on sintering and properties of doped lanthanum manganite

    SciTech Connect (OSTI)

    Stevenson, J.W.; Armstrong, T.R.; Weber, W.J.

    1995-06-01

    The sintering behavior of Ca- and Sr-doped lanthanum manganite (the preferred SOFC cathode material) is highly dependent on the relative proportion of A and B site cations in the material. In general, A-site cation deficiency increases sintered density. The effect of additions of YSZ to lanthanum manganite (to expand the reactive region at the cathode/electrolyte interface and improve thermal expansion and sintering shrinkage matches) on sintering and other properties will also be reported.

  20. Gas-phase energies of actinide oxides -- an assessment of neutral and cationic monoxides and dioxides from thorium to curium

    SciTech Connect (OSTI)

    Marcalo, Joaquim; Gibson, John K.

    2009-08-10

    An assessment of the gas-phase energetics of neutral and singly and doubly charged cationic actinide monoxides and dioxides of thorium, protactinium, uranium, neptunium, plutonium, americium, and curium is presented. A consistent set of metal-oxygen bond dissociation enthalpies, ionization energies, and enthalpies of formation, including new or revised values, is proposed, mainly based on recent experimental data and on correlations with the electronic energetics of the atoms or cations and with condensed-phase thermochemistry.

  1. Functional Mn–Mg{sub k} cation complexes in GaN featured by Raman spectroscopy

    SciTech Connect (OSTI)

    Devillers, T. Bonanni, A.; Leite, D. M. G.; Dias da Silva, J. H.

    2013-11-18

    The evolution of the optical branch in the Raman spectra of (Ga,Mn)N:Mg epitaxial layers as a function of the Mn and Mg concentrations, reveals the interplay between the two dopants. We demonstrate that the various Mn-Mg-induced vibrational modes can be understood in the picture of functional Mn–Mg{sub k} complexes formed when substitutional Mn cations are bound to k substitutional Mg through nitrogen atoms, the number of ligands k being driven by the ratio between the Mg and the Mn concentrations.

  2. Ionic charge transport between blockages: Sodium cation conduction in freshly excised bulk brain tissue

    SciTech Connect (OSTI)

    Emin, David; Akhtari, Massoud; Ellingson, B. M.; Mathern, G. W.

    2015-08-15

    We analyze the transient-dc and frequency-dependent electrical conductivities between blocking electrodes. We extend this analysis to measurements of ions’ transport in freshly excised bulk samples of human brain tissue whose complex cellular structure produces blockages. The associated ionic charge-carrier density and diffusivity are consistent with local values for sodium cations determined non-invasively in brain tissue by MRI (NMR) and diffusion-MRI (spin-echo NMR). The characteristic separation between blockages, about 450 microns, is very much shorter than that found for sodium-doped gel proxies for brain tissue, >1 cm.

  3. Synergistic extraction of some univalent cations into nitrobenzene by using cesium dicarbollylcobaltate and calix[4]arene-...

    SciTech Connect (OSTI)

    Makrlik, Emanuel; Selucky, P.; Vanura, Petr; Moyer, Bruce A

    2013-01-01

    From extraction experiments and c-activity measurements, the exchange extraction constants corresponding to the general equilibrium M+ (aq) + CsL+ (nb) , ML+ (nb) + Cs+ (aq) taking place in the two-phase water nitrobenzene system (M+ = K+, Rb+, NH+4,Ag+, Tl+; L = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Furthermore, the stability constants of the ML+ complexes in nitrobenzene saturated with water were calculated; they were found to increase in the following cation order: NH+4 < K+ < Ag+ < Rb+ < Tl+.

  4. Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries

    DOE Patents [OSTI]

    Manthiram, Arumugam; Choi, Wongchang

    2014-05-13

    The present invention includes compositions and methods of making cation-substituted and fluorine-substituted spinel cathode compositions by firing a LiMn.sub.2-y-zLi.sub.yM.sub.zO.sub.4 oxide with NH.sub.4HF.sub.2 at low temperatures of between about 300 and 700.degree. C. for 2 to 8 hours and a .eta. of more than 0 and less than about 0.50, mixed two-phase compositions consisting of a spinel cathode and a layered oxide cathode, and coupling them with unmodified or surface modified graphite anodes in lithium ion cells.

  5. In-Situ TEM and DFT Study of Large Cation Transport and Failure Mechanism

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

    In Single SnO2 Nanowire - Joint Center for Energy Storage Research July 18, 2013, Research Highlights In-Situ TEM and DFT Study of Large Cation Transport and Failure Mechanism In Single SnO2 Nanowire (Top)Captured in-situ TEM movie frame showing the pristine SnO2 nanowire, displacement reaction upon Na insertion leads to two phases materials and the corresponding electron diffraction pattern. Upon desodiation, pore forms, leading to high impedence of the electrode. (Bottom) High resolution

  6. Elucidating the Higher Stability of Vanadium (V) Cations in Mixed Acid Based Redox Flow Battery Electrolytes

    SciTech Connect (OSTI)

    Vijayakumar, M.; Wang, Wei; Nie, Zimin; Sprenkle, Vincent L.; Hu, Jian Z.

    2013-11-01

    The Vanadium (V) cation structures in mixed acid based electrolyte solution were analysed by density functional theory (DFT) based computational modelling and 51V and 35Cl Nuclear Magnetic Resonance (NMR) spectroscopy. The Vanadium (V) cation exists as di-nuclear [V2O3Cl2.6H2O]2+ compound at higher vanadium concentrations (≥1.75M). In particular, at high temperatures (>295K) this di-nuclear compound undergoes ligand exchange process with nearby solvent chlorine molecule and forms chlorine bonded [V2O3Cl2.6H2O]2+ compound. This chlorine bonded [V2O3Cl2.6H2O]2+ compound might be resistant to the de-protonation reaction which is the initial step in the precipitation reaction in Vanadium based electrolyte solutions. The combined theoretical and experimental approach reveals that formation of chlorine bonded [V2O3Cl2.6H2O]2+ compound might be central to the observed higher thermal stability of mixed acid based Vanadium (V) electrolyte solutions.

  7. Modeling cation diffusion in compacted water-saturatedNa-bentonite at low ionic strength

    SciTech Connect (OSTI)

    Bourg, Ian C.; Sposito, Garrison; Bourg, Alain C.M.

    2007-08-28

    Sodium bentonites are used as barrier materials for the isolation of landfills and are under consideration for a similar use in the subsurface storage of high-level radioactive waste. The performance of these barriers is determined in large part by molecular diffusion in the bentonite pore space. We tested two current models of cation diffusion in bentonite against experimental data on the relative apparent diffusion coefficients of two representative cations, sodium and strontium. On the 'macropore/nanopore' model, solute molecules are divided into two categories, with unequal pore-scale diffusion coefficients, based on location: in macropores or in interlayer nanopores. On the 'surface diffusion' model, solute molecules are divided into categories based on chemical speciation: dissolved or adsorbed. The macropore/nanopore model agrees with all experimental data at partial montmorillonite dry densities ranging from 0.2 (a dilute bentonite gel) to 1.7 kg dm{sup -3} (a highly compacted bentonite with most of its pore space located in interlayer nanopores), whereas the surface diffusion model fails at partial montmorillonite dry densities greater than about 1.2 kg dm{sup -3}.

  8. Electron channeling X-ray microanalysis for cation configuration in irradiate magnesium aluminate spinel

    SciTech Connect (OSTI)

    Matsumura, S.; Soeda, T.; Zaluzec, N. J.; Kinoshita, C.

    1999-12-22

    High angular resolution electron channeling X-ray spectroscopy (HARECXS) was examined as a practical tool to locate lattice-ions in spinel crystals. The orientation dependent intensity distribution of emitted X-rays obtained by HARECXS is so sensitive to lattice-ion configuration in the illuminated areas that the occupation probabilities on specific positions in the crystal lattice can be determined accurately through comparison with the theoretical rocking curves. HARECXS measurements have revealed partially disordered cation arrangement in MgO{center_dot}nAl{sub 2}O{sub 3} with n = 1.0 and 2.4. Most Al{sup 3+} lattice-ions occupy the octahedral (VIII) sites, while Mg{sup 2} lattice-ions reside on both the tetrahedral (IV) and the octahedral (VIII) sites. The structural vacancies are enriched in the IV-sites. Further evacuation of cations from the IV-sites to the VIII-sites is recognized in a disordering process induced by irradiation with 1 MeV Ne{sup +} ions up to 8.9 dpa at 870 K.

  9. Solvation structure and transport properties of alkali cations in dimethyl sulfoxide under exogenous static electric fields

    SciTech Connect (OSTI)

    Kerisit, Sebastien; Vijayakumar, M. E-mail: karl.mueller@pnnl.gov; Han, Kee Sung; Mueller, Karl T. E-mail: karl.mueller@pnnl.gov

    2015-06-14

    A combination of molecular dynamics simulations and pulsed field gradient nuclear magnetic resonance spectroscopy is used to investigate the role of exogenous electric fields on the solvation structure and dynamics of alkali ions in dimethyl sulfoxide (DMSO) and as a function of temperature. Good agreement was obtained, for select alkali ions in the absence of an electric field, between calculated and experimentally determined diffusion coefficients normalized to that of pure DMSO. Our results indicate that temperatures of up to 400 K and external electric fields of up to 1 V nm{sup −1} have minimal effects on the solvation structure of the smaller alkali cations (Li{sup +} and Na{sup +}) due to their relatively strong ion-solvent interactions, whereas the solvation structures of the larger alkali cations (K{sup +}, Rb{sup +}, and Cs{sup +}) are significantly affected. In addition, although the DMSO exchange dynamics in the first solvation shell differ markedly for the two groups, the drift velocities and mobilities are not significantly affected by the nature of the alkali ion. Overall, although exogenous electric fields induce a drift displacement, their presence does not significantly affect the random diffusive displacement of the alkali ions in DMSO. System temperature is found to have generally a stronger influence on dynamical properties, such as the DMSO exchange dynamics and the ion mobilities, than the presence of electric fields.

  10. Controlling the actuation properties of MXene paper electrodes upon cation intercalation

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

    Come, Jeremy E.; Black, Jennifer M.; Naguib, Michael; Lukatskaya, Maria R.; Beidaghi, Majid; Wesolowski, David J.; Gogotsi, Yury; Rondinone, Adam J.; Balke, Nina; Kalinin, Sergei V.

    2015-08-05

    Atomic force microscopy was used to monitor the macroscopic deformation in a delaminated Ti₃C₂ paper electrode in-situ, during charge/discharge in a variety of aqueous electrolytes to examine the effect of the cation intercalation on the electrochemical behavior and mechanical response. The results show a strong dependence of the electrode deformation on cation size and charge. The electrode undergoes a large contraction during Li⁺, Na⁺ or Mg²⁺ intercalation, differentiating the Ti₃C₂ paper from conventional electrodes where redox intercalation of ions (e.g. Li⁺) into the bulk phase (e.g. graphite, silicon) results in volumetric expansion. This feature may explain the excellent rate performancemore » and cyclability reported for MXenes. We also demonstrated that the variation of the electromechanical contraction can be easily adjusted by electrolyte exchange, and shows interesting characteristics for the design of actuators based on 2D metal carbides.« less

  11. Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes

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

    Berg, John M.; Gaunt, Andrew J.; May, Iain; Pugmire, Alison L.; Reilly, Sean D.; Scott, Brian L.; Wilkerson, Marianne P.

    2015-04-22

    A-type tri-lacunary heteropolyoxotungstate anions (e.g., [PW9O34]9-, [AsW9O34]9-, [SiW9O34]10- and [GeW9O34]10-) are multi-dentate oxygen donor ligands that readily form sandwich complexes with actinyl cations ({UO2}2+, {NpO2}+, {NpO2}2+ & {PuO2}2+) in near neutral/slightly alkaline aqueous solutions. Two or three actinyl cations are sandwiched between two trilacunary anions, with additional cations (Na+, K+ or NH4 +) also often held within the cluster. Studies thus far have indicated that it is these additional +I cations, rather than the specific actinyl cation, that direct the structural variation in the complexes formed. We now report the structural characterization of the neptunyl (VI) cluster complex (NH4)13 [Na(NpO2)2(A-α-more » PW9O34)2]·12H2O. The anion in this complex, [Na(NpO2)2(PW9O34)2]13-, contains one Na+ cation and two {NpO2}2+ cations held between two [PW9O34]9- anions – with an additional partial occupancy NH4 + or {NpO2}2+ cation also present. In the analogous uranium (VI) system, under similar reaction conditions that includes an excess of NH4Cl in the parent solution, it was previously shown that [(NH4)2(UVIO2)2(A-PW9O34)2]12- is the dominant species in both solution and the crystallized salt. Spectroscopic studies provide further proof of differences in the observed chemistry for the {NpO2}2+/[PW9O34]9- and {UO2}2+/[PW9O34]9- systems, both in solution and in solid state complexes crystallized from comparable salt solutions. The work revealed that varying the actinide element (Np vs. U) can indeed measurably impact structure and complex stability in the cluster chemistry of actinyl (VI) cations with A-type tri-lacunary heteropolyoxotungstate anions.« less

  12. Gas-phase reactions of polycyclic aromatic hydrocarbon cations and their nitrogen-containing analogs with H atoms

    SciTech Connect (OSTI)

    Demarais, Nicholas J.; Yang, Zhibo; Bierbaum, Veronica M. [Department of Chemistry and Biochemistry, 215 UCB, University of Colorado, Boulder, CO 80309-0215 (United States); Snow, Theodore P., E-mail: Nicholas.Demarais@Colorado.edu, E-mail: Zhibo.Yang@ou.edu, E-mail: Veronica.Bierbaum@Colorado.edu, E-mail: Theodore.Snow@Colorado.edu [Center for Astrophysics and Space Astronomy, 389 UCB, University of Colorado, Boulder, CO 80309-0389 (United States)

    2014-03-20

    We have studied the reactions of polycyclic aromatic hydrocarbon cations and their nitrogen-containing analogs with H atoms. Reaction rate constants are measured at 300 K using a flowing afterglow-selected ion flow tube. We have implemented the laser induced acoustic desorption technique to allow the study of large, non-volatile species in the gas phase. The extension of this work from previous studies shows that the reactivity of polycyclic aromatic hydrocarbon cations with H atoms reaches a constant value for large cations. There is a small difference in reactivity when comparing molecules of different size and geometry; however, no difference in reactivity was found when nitrogen was incorporated into the ring.

  13. Aqueous precipitation: Population balance modeling and control in multi-cation systems

    SciTech Connect (OSTI)

    Voigt, J.A.

    1996-03-01

    Efficient separation of metal species from aqueous streams by precipitation techniques requires a fundamental understanding of the processes that occur during precipitation. These processes include particle nucleation, particle growth by solute deposition, agglomerate formation, and agglomerate breakup. Population balance method has been used to develop a kinetic model that accounts for these competing kinetic processes. The usefulness of the model is illustrated through its application to precipitation of yttrium hydroxynitrate, YHN. Kinetic parameters calculated from the model equations and system-specific solution chemistry are used to describe several aspects of the effect of pH on YHN precipitation. Implications for simultaneous precipitation of more than one cation type are discussed with examples. Effects of solution chemistry, precipitator design, and solvent choice are considered.

  14. Single-stage separation and esterification of cation salt carboxylates using electrodeionization

    DOE Patents [OSTI]

    Lin, YuPo J.; Henry, Michael; Hestekin, Jamie; Snyder, Seth W.; St. Martin, Edward J.

    2006-11-28

    A method of and apparatus for continuously making an organic ester from a lower alcohol and an organic acid is disclosed. An organic acid or salt is introduced or produced in an electrode ionization (EDI) stack with a plurality of reaction chambers each formed from a porous solid ion exchange resin wafer interleaved between anion exchange membranes or an anion exchange membrane and a cation exchange membrane or an anion exchange membrane and a bipolar exchange membranes. At least some reaction chambers are esterification chambers and/or bioreactor chambers and/or chambers containing an organic acid or salt. A lower alcohol in the esterification chamber reacts with an anion to form an organic ester and water with at least some of the water splitting with the ions leaving the chamber to drive the reaction.

  15. Phenolic cation-exchange resin material for recovery of cesium and strontium. [Patent application

    DOE Patents [OSTI]

    Ebra, M.A.; Wallace, R.M.

    1982-05-05

    A phenolic cation exchange resin with a chelating group has been prepared by reacting resorcinol with iminodiacetic acid in the presence of formaldehyde at a molar ratio of about 1:1:6. The material is highly selective for the simultaneous recovery of both cesium and strontium from aqueous alkaline solutions, such as, aqueous alkaline nuclear wate solutions. The organic resins are condensation polymers of resorcinol and formaldehyde with attached chelating groups. The column performance of the resins compares favorably with that of commercially available resins for either cesium or strontium removal. By combining Cs/sup +/ and Sr/sup 2 +/ removal in the same bed, the resins allow significant reduction of the size and complexity of facilities for processing nuclear waste.

  16. Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries

    DOE Patents [OSTI]

    Manthiram, Arumugam; Choi, Wonchang

    2010-05-18

    The present invention includes compositions and methods of making cation-substituted and fluorine-substituted spinel cathode compositions by firing a LiMn2-y-zLiyMzO4 oxide with NH4HF2 at low temperatures of between about 300 and 700.degree. C. for 2 to 8 hours and a .eta. of more than 0 and less than about 0.50, mixed two-phase compositions consisting of a spinel cathode and a layered oxide cathode, and coupling them with unmodified or surface modified graphite anodes in lithium ion cells.

  17. Opposite correlations between cation disordering and amorphization resistance in spinels versus pyrochlores

    SciTech Connect (OSTI)

    Uberuaga, Blas Pedro; Tang, Ming; Jiang, Chao; Valdez, James A.; Smith, Roger; Wang, Yongqiang; Sickafus, Kurt E.

    2015-10-29

    Understanding and predicting radiation damage evolution in complex materials is crucial for developing next-generation nuclear energy sources. Here, using a combination of ion beam irradiation, transmission electron microscopy and X-ray diffraction, we show that, contrary to the behaviour observed in pyrochlores, the amorphization resistance of spinel compounds correlates directly with the energy to disorder the structure. Using a combination of atomistic simulation techniques, we ascribe this behaviour to structural defects on the cation sublattice that are present in spinel but not in pyrochlore. Specifically, because of these structural defects, there are kinetic pathways for the relaxation of disorder in spinel that are absent in pyrochlore. This leads to a direct correlation between amorphization resistance and disordering energetics in spinel, the opposite of that observed in pyrochlores. Furthermore, these results provide new insight into the origins of amorphization resistance in complex oxides beyond fluorite derivatives.

  18. Opposite correlations between cation disordering and amorphization resistance in spinels versus pyrochlores

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

    Uberuaga, Blas Pedro; Tang, Ming; Jiang, Chao; Valdez, James A.; Smith, Roger; Wang, Yongqiang; Sickafus, Kurt E.

    2015-10-29

    Understanding and predicting radiation damage evolution in complex materials is crucial for developing next-generation nuclear energy sources. Here, using a combination of ion beam irradiation, transmission electron microscopy and X-ray diffraction, we show that, contrary to the behaviour observed in pyrochlores, the amorphization resistance of spinel compounds correlates directly with the energy to disorder the structure. Using a combination of atomistic simulation techniques, we ascribe this behaviour to structural defects on the cation sublattice that are present in spinel but not in pyrochlore. Specifically, because of these structural defects, there are kinetic pathways for the relaxation of disorder in spinelmore » that are absent in pyrochlore. This leads to a direct correlation between amorphization resistance and disordering energetics in spinel, the opposite of that observed in pyrochlores. Furthermore, these results provide new insight into the origins of amorphization resistance in complex oxides beyond fluorite derivatives.« less

  19. Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

    DOE Patents [OSTI]

    Skotheim, Terje A.; Okamoto, Yoshiyuki; Lee, Hung S.

    1989-01-01

    The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10.sup.-4 to 10.sup.-7 S cm.sup.-1 at room temperature.

  20. Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

    DOE Patents [OSTI]

    Skotheim, T.A.; Okamoto, Yoshiyuki; Lee, H.S.

    1989-11-21

    The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10[sup [minus]4] to 10[sup [minus]7] S cm[sup [minus]1] at room temperature.

  1. A theoretical study of the reaction paths for cobalt cation + propane

    SciTech Connect (OSTI)

    Fedorov, D.G.; Gordon, M.S.

    2000-03-23

    The triplet potential energy surface for the reaction of cobalt cation with propane has been studied along the two main reaction pathways leading to the formation of (1) hydrogen and propene and (2) methane and ethene. Effective core potentials for all elements have been used for all calculations. The geometries have been optimized at the complete active space self-consistent field (CASSCF) level of theory, and the final energetics have been refined at the multireference second-order perturbation theory (MRMP2) level with polarization function augmented basis sets. Reasonable agreement with the experimental energetics has been obtained, and the predicted mechanism is consistent with the experimentally determined mechanism of Haynes, Fisher, and Armentrout (J.Phys.Chem. 1996, 100, 18300).

  2. A Hybrid Redox-Supercapacitor System with Anionic Catholyte and Cationic Anolyte

    SciTech Connect (OSTI)

    Wang, B; Macia-Agullo, JA; Prendiville, DG; Zheng, X; Liu, D; Zhang, Y; Boettcher, SW; Ji, X; Stucky, GD

    2014-04-11

    A significant challenge for energy storage technologies is to realize battery-level energy density and capacitor-level durability and power density in one device. By introducing an electrolyte composed of an anionic catholyte and a cationic anolyte into a symmetric carbon-based supercapacitor configuration, a hybrid electrochemical battery-supercapacitor system using soluble redox species delivers significantly improved energy density from 20 to 42 W.h/kg (based on the electrode mass) and stable capacities for > 10(4) cycles. The ionic species formed in the electrolyte are studied by UV-Vis, Raman and mass spectroscopy to probe the energy storage mechanism. The strategy is general and may provide a route to critically-needed fast-charging devices with both high energy density and power. (C) 2014 The Electrochemical Society. All rights reserved.

  3. Cationic quaternization of cellulose with methacryloyloxy ethyl trimethyl ammonium chloride via ATRP method

    SciTech Connect (OSTI)

    Supeno; Daik, Rusli; El-Sheikh, Said M.

    2014-09-03

    The synthesis of a cationic cellulose copolymer from cellulose macro-initiator (MCC-BiB) and quaternary compound monomer (METMA) via atom transfer radical polymerization (ATRP) was studied. By using dimethylformamide (DMF), the optimum condition for successful synthesis was at the mole ratio of MCC-BIB:Catalyst:METMA = 1:1:26. The highest copolymer recovery was 93.2 % for 6 h and at 40°C. The copolymer was insoluble in weak polar solvents such as THF and DMF but soluble in methanol and water. The chemistry of cellulose copolymer was confirmed by the FTIR and TGA in which the METMA monomer was used as a reference. The absence of CC bond in the CiB-g-METMA spectrum indicated that graft copolymerization occurred.

  4. Room-temperature ferroelectricity of SrTiO{sub 3} films modulated by cation concentration

    SciTech Connect (OSTI)

    Yang, Fang; Zhang, Qinghua; Yang, Zhenzhong; Gu, Junxing; Liang, Yan; Li, Wentao; Wang, Weihua; Jin, Kuijuan; Gu, Lin; Guo, Jiandong

    2015-08-24

    The room-temperature ferroelectricity of SrTiO{sub 3} is promising for oxide electronic devices controlled by multiple fields. An effective way to control the ferroelectricity is highly demanded. Here, we show that the off-centered antisite-like defects in SrTiO{sub 3} films epitaxially grown on Si (001) play the determinative role in the emergence of room-temperature ferroelectricity. The density of these defects changes with the film cation concentration sensitively, resulting in a varied coercive field of the ferroelectric behavior. Consequently, the room-temperature ferroelectricity of SrTiO{sub 3} films can be effectively modulated by tuning the temperature of metal sources during the molecular beam epitaxy growth. Such an easy and reliable modulation of the ferroelectricity enables the flexible engineering of multifunctional oxide electronic devices.

  5. Phenolic cation exchange resin material for recovery of cesium and strontium

    DOE Patents [OSTI]

    Ebra, Martha A.; Wallace, Richard M.

    1983-01-01

    A phenolic cation exchange resin with a chelating group has been prepared by reacting resorcinol with iminodiacetic acid in the presence of formaldehyde at a molar ratio of about 1:1:6. The material is highly selective for the simultaneous recovery of both cesium and strontium from aqueous alkaline solutions, such as, aqueous alkaline nuclear waste solutions. The organic resins are condensation polymers of resorcinol and formaldehyde with attached chelating groups. The column performance of the resins compares favorably with that of commercially available resins for either cesium or strontium removal. By combining Cs.sup.+ and Sr.sup.2+ removal in the same bed, the resins allow significant reduction of the size and complexity of facilities for processing nuclear waste.

  6. Self-Assembly of Hexanuclear Clusters of 4f and 5f Elements with Cation Specificity

    SciTech Connect (OSTI)

    Diwu, J.; Good, Justin J.; DiStefano, Victoria H.; Albrecht-Schmitt, Thomas E.

    2011-02-10

    Six hexanuclear clusters of 4f and 5f elements were synthesized by room-temperature slow concentration experiments. Cerium(IV), thorium(IV), and plutonium(IV) each form two different hexanuclear clusters, among which the cerium and plutonium clusters are isotypic, whereas the thorium clusters show more diversity. The change in ionic radii of approximately 0.08 Å between these different metal ions tunes the cavity size so that NH{sub 4}{sup +} (1.48 Å) has the right dimensions to assemble the cerium and plutonium clusters, whereas Cs{sup +} (1.69 Å) is necessary to assemble the thorium clusters. If these cations are not used in the reactions, only amorphous material is obtained.

  7. Computational study of the energetics of charge and cation mixing in U1-xCexO₂

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

    Hanken, B. E.; Stanek, C. R.; Grønbech-Jensen, N.; Asta, M.

    2011-08-26

    The formalism of electronic density-functional theory (DFT), with Hubbard-U corrections (DFT+U), is employed in a computational study of the energetics of fluorite-structured U1-xCexO₂ mixtures. The computational approach makes use of a procedure which facilitates convergence of the calculations to multiple self-consistent DFT+U solutions for a given cation arrangement, corresponding to different charge states for the U and Ce ions in several prototypical cation arrangements. Results indicate a significant dependence of the structural and energetic properties on the nature of both charge and cation ordering. With the effective Hubbard-U parameters that reproduce well the measured oxidation-reduction energies for urania and ceria,more » we find that charge transfer between U⁴⁺ and Ce⁴⁺ ions, leading to the formation of U⁵⁺ and Ce³⁺, gives rise to an increase in the mixing energy in the range of 4–14 kJ/mol of the formula unit, depending on the nature of the cation ordering. The results suggest that although charge transfer between uranium and cerium ions is disfavored energetically, it is likely to be entropically stabilized at the high temperatures relevant to the processing and service of urania-based solid solutions.« less

  8. Cation ordering and effect of biaxial strain in double perovskite CsRbCaZnCl6

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

    Pilania, G.; Uberuaga, B. P.

    2015-03-19

    Here, we investigate the electronic structure, energetics of cation ordering, and effect of biaxial strain on double perovskite CsRbCaZnCl6 using first-principles calculations based on density functional theory. The two constituents (i.e., CsCaCl3 and RbZnCl3) forming the double perovskite exhibit a stark contrast. While CsCaCl3 is known to exist in a cubic perovskite structure and does not show any epitaxial strain induced phase transitions within an experimentally accessible range of compressive strains, RbZnCl3 is thermodynamically unstable in the perovskite phase and exhibits ultra-sensitive response at small epitaxial strains if constrained in the perovskite phase. We show that combining the two compositionsmore » in a double perovskite structure not only improves overall stability but also the strain-polarization coupling of the material. Our calculations predict a ground state with P4/nmm space group for the double perovskite, where A-site cations (i.e., Cs and Rb) are layer-ordered and B-site cations (i.e., Ca and Zn) prefer a rocksalt type ordering. The electronic structure and bandgap in this system are shown to be quite sensitive to the B-site cation ordering and is minimally affected by the ordering of A-site cations. We find that at experimentally accessible compressive strains CsRbCaZnCl6 can be phase transformed from its paraelectric ground state to an antiferroelectric state, where Zn atoms contribute predominantly to the polarization. Furthermore, both energy difference and activation barrier for a transformation between this antiferroelectric state and the corresponding ferroelectric configuration are predicted to be small. As a result, the computational approach presented here opens a new pathway towards a rational design of novel double perovskites with improved strain response and functionalities.« less

  9. Colloid-Facilitated Transport of Cations in an Unsaturated Fractured Soil Under Transient Conditions

    SciTech Connect (OSTI)

    Ryan, Joseph

    2015-01-31

    Rainfall experiments were conducted using intact soil cores and an instrumented soil pedon to examine the effect of physical heterogeneity and rainfall characteristics on the mobilization of colloids, organic matter, cesium, and strontium in a fractured soil. To measure the spatial variability of infiltration of colloids and contaminants, samples were collected through a 19-port grid placed below the soil core in laboratory study and in 27 samplers at multiple depths in the soil pedon in the field study. Cesium and strontium were applied to the soil cores and the soil pedon prior to mobilization experiments. Rainwater solutions of multiple ionic strengths and organic matter concentrations were applied to the soil cores and soil pedon to mobilize in situ colloids, cesium, and strontium. The mobilization of colloids and metal cations occurred through preferential flow paths in the soil cores. Compared to steady rainfall, greater amounts of colloids were mobilized during rainfall interrupted by pauses, which indicates that the supply of colloids to be mobilized was replenished during the pauses. A maximum in the amount of mobilized colloids were mobilized during a rainfall following a pause of 2.5 d. Pauses of shorter or longer duration resulted in less colloid mobilization. Freeze-thaw cycles, a transient condition in winter, enhanced colloid mobilization and colloid-facilitated transport of cesium and strontium in the soil cores. The exchange of solutes between the soil matrix and macropores caused a hysteretic mobilization of colloids, cesium, and strontium during changes in ionic strength. Colloid-facilitated mobilization of cesium and strontium was important at low ionic strength in fractures where slow flow allowed greater exchange of flow between the fractures and the surrounding matrix. The release of cesium and strontium by cation exchange occurred at high ionic strength in fractures where there is a little exchange of pore water with the surrounding matrix

  10. Millisecond Kinetics of Nanocrystal Cation Exchange UsingMicrofluidic X-ray Absorption Spectroscopy

    SciTech Connect (OSTI)

    Chan, Emory M.; Marcus, Matthew A.; Fakra, Sirine; Elnaggar,Mariam S.; Mathies, Richard A.; Alivisatos, A. Paul

    2007-05-07

    We describe the use of a flow-focusing microfluidic reactorto measure the kinetics of theCdSe-to-Ag2Se nanocrystal cation exchangereaction using micro-X-ray absorption spectroscopy (mu XAS). The smallmicroreactor dimensions facilitate the millisecond mixing of CdSenanocrystal and Ag+ reactant solutions, and the transposition of thereaction time onto spatial coordinates enables the in situ observation ofthe millisecond reaction with mu XAS. XAS spectra show the progression ofCdSe nanocrystals to Ag2Se over the course of 100 ms without the presenceof long-lived intermediates. These results, along with supporting stoppedflow absorption experiments, suggest that this nanocrystal cationexchange reaction is highly efficient and provide insight into how thereaction progresses in individual particles. This experiment illustratesthe value and potential of in situ microfluidic X-ray synchrotrontechniques for detailed studies of the millisecond structuraltransformations of nanoparticles and other solution-phase reactions inwhich diffusive mixing initiates changes in local bond structures oroxidation states.

  11. Ionic liquids composed of phosphonium cations and organophosphate, carboxylate, and sulfonate as lubricant antiwear additives

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

    Zhou, Yan; Dyck, Jeffrey; Graham, Todd; Luo, Huimin; Leonard, Donovan N.; Qu, Jun

    2014-10-20

    Oil-soluble phosphonium-based ionic liquids (ILs) have recently been reported as potential ashless lubricant additives. This study is to expand the IL chemistry envelope and to achieve fundamental correlations between the ion structures and ILs’ physiochemical and tribological properties. Here we present eight ILs containing two different phosphonium cations and seven different anions from three groups: organophosphate, carboxylate, and sulfonate. The oil solubility of ILs seems largely governed by the IL molecule size and structure complexity. When used as oil additives, the ranking of effectiveness in wear protection for the anions are: organophosphate > carboxylate > sulfonate. All selected ILs outperformedmore » a commercial ashless anti-wear additive. Surface characterization from the top and the cross-section revealed the nanostructures and compositions of the tribo-films formed by the ILs. Some fundamental insights were achieved: branched and long alkyls improve the IL’s oil solubility, anions of a phosphonium-phosphate IL contribute most phosphorus in the tribofilm, and carboxylate anions, though free of P, S, N, or halogen, can promote the formation of an anti-wear tribofilm.« less

  12. Atomistic Studies of Cation Transport in Tetragonal ZrO2 During Zirconium Corrosion

    SciTech Connect (OSTI)

    Xian-Ming Bai; Yongfeng Zhang; Michael R. Tonks

    2013-10-01

    Zirconium alloys are the major fuel cladding materials in current reactors. The water-side corrosion is one of the major degradation mechanisms of these alloys. During corrosion the transport of oxidizing species in zirconium dioxide (ZrO2) determines the corrosion kinetics. Previously it has been argued that the outward diffusion of cation ions is important for forming protective oxides. In this work, the migration of Zr defects in tetragonal ZrO2 is studied with temperature accelerated dynamics and molecular dynamics simulations. The results show that Zr interstitials have anisotropic diffusion and migrate preferentially along the [001] or c direction in tetragonal ZrO2. The compressive stresses can increase the Zr interstitial migration barrier significantly. The migration barriers of some defect clusters can be much lower than those of point defects. The migration of Zr interstitials at some special grain boundaries is much slower than in a bulk oxide. The implications of these atomistic simulation results in the Zr corrosion are discussed.

  13. Independent control of the shape and composition of ionic nanocrystals through sequential cation exchange reactions

    SciTech Connect (OSTI)

    Luther, Joseph Matthew; Zheng, Haimei; Sadtler, Bryce; Alivisatos, A. Paul

    2009-07-06

    Size- and shape-controlled nanocrystal growth is intensely researched for applications including electro-optic, catalytic, and medical devices. Chemical transformations such as cation exchange overcome the limitation of traditional colloidal synthesis, where the nanocrystal shape often reflects the inherent symmetry of the underlying lattice. Here we show that nanocrystals, with established synthetic protocols for high monodispersity, can be templates for independent composition control. Specifically, controlled interconversion between wurtzite CdS, chalcocite Cu2S, and rock salt PbS occurs while preserving the anisotropic dimensions unique to the as-synthesized materials. Sequential exchange reactions between the three sulfide compositions are driven by the disparate solubilites of the metal ion exchange pair in specific coordinating molecules. Starting with CdS, highly anisotropic PbS nanorods are created, which serve as an important material for studying strong 2-dimensional quantum confinement, as well as for optoelectronic applications. Furthermore, interesting nanoheterostructures of CdS|PbS are obtained by precise control over ion insertion and removal.

  14. A search for the sulphur hexafluoride cation with intense, few cycle laser pulses

    SciTech Connect (OSTI)

    Dota, Krithika; Mathur, Deepak; Centre for Atomic and Molecular Physics, Manipal University, Manipal 576 104 ; Dharmadhikari, Aditya K.; Dharmadhikari, Jayashree A.; Patra, Kaustuv; Tiwari, Ashwani K.

    2013-11-21

    It is well established that upon ionization of sulphur hexafluoride, the SF{sub 6}{sup +} ion is never observed in mass spectra. Recent work with ultrashort intense laser pulses has offered indications that when strong optical field are used, the resulting bond hardening can induce changes in the potential energy surfaces of molecular cations such that molecular ions that are normally unstable may, indeed, become metastable enough to enable their detection by mass spectrometry. Do intense, ultrashort laser pulses permit formation of SF{sub 6}{sup +}? We have utilized intense pulses of 5 fs, 11 fs, and 22 fs to explore this possibility. Our results are negative: no evidence is discovered for SF{sub 6}{sup +}. However, multiply charged sulphur and fluorine ions from highly charged SF{sub 6}{sup q+} ions are observed that enable us to resolve the controversy regarding the kinetic energy release accompanying formation of F{sup +} fragment ions. Quantum chemical computations of field-distorted potential energy curves of SF{sub 6} and its molecular ion enable us to rationalize our non-observation of SF{sub 6}{sup +}. Our findings have implications for high harmonic generation from SF{sub 6} in the few-cycle regime.

  15. Ionic liquids composed of phosphonium cations and organophosphate, carboxylate, and sulfonate as lubricant antiwear additives

    SciTech Connect (OSTI)

    Zhou, Yan; Dyck, Jeffrey; Graham, Todd; Luo, Huimin; Leonard, Donovan N.; Qu, Jun

    2014-10-20

    Oil-soluble phosphonium-based ionic liquids (ILs) have recently been reported as potential ashless lubricant additives. This study is to expand the IL chemistry envelope and to achieve fundamental correlations between the ion structures and ILs’ physiochemical and tribological properties. Here we present eight ILs containing two different phosphonium cations and seven different anions from three groups: organophosphate, carboxylate, and sulfonate. The oil solubility of ILs seems largely governed by the IL molecule size and structure complexity. When used as oil additives, the ranking of effectiveness in wear protection for the anions are: organophosphate > carboxylate > sulfonate. All selected ILs outperformed a commercial ashless anti-wear additive. Surface characterization from the top and the cross-section revealed the nanostructures and compositions of the tribo-films formed by the ILs. Some fundamental insights were achieved: branched and long alkyls improve the IL’s oil solubility, anions of a phosphonium-phosphate IL contribute most phosphorus in the tribofilm, and carboxylate anions, though free of P, S, N, or halogen, can promote the formation of an anti-wear tribofilm.

  16. Interaction of the cesium cation with calix[4]arene-bis(t-octylbenzo-18-crown-6): Extraction and DFT study

    SciTech Connect (OSTI)

    Makrlik, Emanuel; Toman, Petr; Vanura, Petr; Moyer, Bruce A

    2013-01-01

    From extraction experiments and c-activity measurements, the extraction constant corresponding to the equilibrium Cs+ (aq) + I (aq) + 1 (org),1Cs+ (org) + I (org) taking place in the two-phase water-phenyltrifluoromethyl sulfone (abbrev. FS 13) system (1 = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, org = FS 13 phase) was evaluated as logKex (1Cs+, I) = 2.1 0.1. Further, the stability constant of the 1Cs+ complex in FS 13 saturated with water was calculated for a temperature of 25 C: log borg (1Cs+) = 9.9 0.1. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complex species 1Cs+ was derived. In the resulting 1Cs+ complex, the central cation Cs+ is bound by eight bond interactions to six oxygen atoms of the respective 18-crown-6 moiety and to two carbons of the corresponding two benzene rings of the parent ligand 1 via cation p interaction.

  17. Gas-Phase Reactions of Doubly Charged Lanthanide Cations with Alkanes and Alkenes. Trends in Metal(2+) Reactivity

    SciTech Connect (OSTI)

    Gibson, John K.; Marcalo, Joaquim; Santos, Marta; Pires de Matos, Antonio; Haire, Richard G.

    2008-12-08

    The gas-phase reactivity of doubly-charged lanthanide cations, Ln2+ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), with alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) was studied by Fourier transform ion cyclotron resonance mass spectrometry. The reaction products consisted of different combinations of doubly-charged organometallic ions?adducts or species formed via metal-ion-induced hydrogen, dihydrogen, alkyl, or alkane eliminations from the hydrocarbons?and singly-charged ions that resulted from electron, hydride, or methide transfers from the hydrocarbons to the metal ions. The only lanthanide cations capable of activating the hydrocarbons to form doubly-charged organometallic ions were La2+, Ce2+, Gd2+, and Tb2+, which have ground-state or low-lying d1 electronic configurations. Lu2+, with an accessible d1 electronic configuration but a rather high electron affinity, reacted only through transfer channels. The remaining Ln2+ reacted via transfer channels or adduct formation. The different accessibilities of d1 electronic configurations and the range of electron affinities of the Ln2+ cations allowed for a detailed analysis of the trends for metal(2+) reactivity and the conditions for occurrence of bond activation, adduct formation, and electron, hydride, and methide transfers.

  18. A theoretical study on the interstellar synthesis of H{sub 2}NCS{sup +} and HNCSH{sup +} cations

    SciTech Connect (OSTI)

    Gronowski, Marcin; Kołos, Robert E-mail: rkolos@ichf.edu.pl

    2014-09-10

    HNCS and NCSH molecules, recently discovered in the interstellar medium, are likely formed via the dissociative recombination of H{sub 2}NCS{sup +} or HNCSH{sup +} isomeric ions. Interstellar synthesis of the latter is discussed on theoretical grounds. The analysis of relevant potential energy surfaces suggests a key role for chemical processes in which CSH{sup +} or HCS{sup +} cations (most likely formed in CS+H{sub 3}{sup +} collisions) react with NH{sub 2} or NH{sub 3}. The astrochemical kinetic database (kida.uva.2011), appended with 7 sulfur-bearing molecules and 48 corresponding reactions, has been applied to model the evolution of HNCS, NCSH, and their cationic precursors in a quiescent molecular cloud. Based on the model and on spectroscopic predictions, for an object like TMC-1, we expect the total intensity of H{sub 2}NCS{sup +} microwave lines to be comparable to that observed for HSCN. Theoretically derived molecular parameters, of interest for radio spectroscopy, are given for the most stable cations sharing the H{sub 2}NCS{sup +} stoichiometry.

  19. Cation substitution in β-tricalcium phosphate investigated using multi-nuclear, solid-state NMR

    SciTech Connect (OSTI)

    Grigg, Andrew T.; Mee, Martin; Mallinson, Phillip M.; Fong, Shirley K.; Gan, Zhehong; Dupree, Ray; Holland, Diane

    2014-04-01

    The substitution of aluminium, gallium and sodium cations into β-tricalcium phosphate (β-TCP; Ca{sub 3}(PO{sub 4}){sub 2}) has been investigated, and the Ca sites involved successfully determined, using a combination of 1D {sup 31}P, {sup 27}Al, {sup 71}Ga, {sup 23}Na and {sup 43}Ca (natural abundance) NMR and 2D {sup 27}Al({sup 31}P), {sup 71}Ga({sup 31}P) and {sup 23}Na({sup 31}P) rotary-resonance-recoupled heteronuclear multiple-quantum correlation (R{sup 3}-HMQC) NMR. Over the compositional range studied, substitution of Ca{sup 2+} by Al{sup 3+} or Ga{sup 3+} was observed only on the Ca(5) site, whilst substitution by Na{sup +} was confined to the Ca(4) site. Some AlPO{sub 4} or GaPO{sub 4} second phase was observed at the highest doping levels in the Al{sup 3+} and Ga{sup 3+} substituted samples. - Graphical abstract: 2D contour plots with skyline projections showing recoupling of {sup 27}Al, {sup 71}Ga and {sup 23}Na to different {sup 31}P sites. - Highlights: • β-Ca{sub 3}(PO{sub 4}){sub 2} has been prepared pure and also with Al{sup 3+}, Ga{sup 3+} and Na{sup +} substituents. • Multi-nuclear 1D NMR and heteronuclear X({sup 31}P) recoupling have been used. • Models for substitution correctly predict site preference and occupancy. • Progressive changes in {sup 31}P spectra have been explained. • Al{sup 3+} and Ga{sup 3+} substitute onto the Ca(5) site, and Na{sup +} onto the Ca(4) site.

  20. Doping against the native propensity of MoS₂: Degenerate hole doping by cation substitution

    SciTech Connect (OSTI)

    Suh, Joonki; Park, Tae-Eon; Lin, Der-Yuh; Fu, Deyi; Park, Joonsuk; Jung, Hee Joon; Chen, Yabin; Ko, Changhyun; Jang, Chaun; Sun, Yinghui; Sinclair, Robert; Chang, Joonyeon; Tongay, Sefaattin; Wu, Junqiao

    2014-12-10

    Layered transition metal dichalcogenides (TMDs) draw much attention as the key semiconducting material for two-dimensional electrical, optoelectronic, and spintronic devices. For most of these applications, both n- and p-type materials are needed to form junctions and support bipolar carrier conduction. However, typically only one type of doping is stable for a particular TMD. For example, molybdenum disulfide (MoS₂) is natively an n-type presumably due to omnipresent electron-donating sulfur vacancies, and stable/controllable p-type doping has not been achieved. The lack of p-type doping hampers the development of charge-splitting p–n junctions of MoS₂, as well as limits carrier conduction to spin-degenerate conduction bands instead of the more interesting, spin-polarized valence bands. Traditionally, extrinsic p-type doping in TMDs has been approached with surface adsorption or intercalation of electron-accepting molecules. However, practically stable doping requires substitution of host atoms with dopants where the doping is secured by covalent bonding. In this work, we demonstrate stable p-type conduction in MoS₂ by substitutional niobium (Nb) doping, leading to a degenerate hole density of ~3 × 10¹⁹ cm⁻³. Structural and X-ray techniques reveal that the Nb atoms are indeed substitutionally incorporated into MoS₂ by replacing the Mo cations in the host lattice. van der Waals p–n homojunctions based on vertically stacked MoS₂ layers are fabricated, which enable gate-tunable current rectification. A wide range of microelectronic, optoelectronic, and spintronic devices can be envisioned from the demonstrated substitutional bipolar doping of MoS₂. From the miscibility of dopants with the host, it is also expected that the synthesis technique demonstrated here can be generally extended to other TMDs for doping against their native unipolar propensity.

  1. Kinetics of ion-ion mutual neutralization: Halide anions with polyatomic cations

    SciTech Connect (OSTI)

    Shuman, Nicholas S.; Wiens, Justin P.; Miller, Thomas M.; Viggiano, Albert A.

    2014-06-14

    The binary mutual neutralization (MN) of a series of 17 cations (O{sub 2}{sup +}, NO{sup +}, NO{sub 2}{sup +}, CO{sup +}, CO{sub 2}{sup +}, Cl{sup +}, Cl{sub 2}{sup +}, SO{sub 2}{sup +}, CF{sub 3}{sup +}, C{sub 2}F{sub 5}{sup +}, NH{sub 3}{sup +}, H{sub 3}{sup +}, D{sub 3}{sup +}, H{sub 2}O{sup +}, H{sub 3}O{sup +}, ArH{sup +}, ArD{sup +}) with 3 halide anions (Cl{sup −}, Br{sup −}, I{sup −}) has been investigated in a flowing afterglow-Langmuir probe apparatus using the variable electron and neutral density attachment mass spectrometry technique. The MN rate constants of atom-atom reactions are dominated by the chemical nature of the system (i.e., the specific locations of curve crossings). As the number of atoms in the system increases, the MN rate constants become dominated instead by the physical nature of the system (e.g., the relative velocity of the reactants). For systems involving 4 or more atoms, the 300 K MN rate constants are well described by 2.7 × 10{sup −7} μ{sup −0.5}, where the reduced mass is in Da and the resulting rate constants in cm{sup 3} s{sup −1}. An upper limit to the MN rate constants appears well described by the complex potential model described by Hickman assuming a cross-section to neutralization of 11 000 Å{sup 2} at 300 K, equivalent to 3.5 × 10{sup −7} μ{sup −0.5}.

  2. Glass-water interactions: Effect of high-valence cations on glass structure and chemical durability

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

    Pierce, Eric M.; Kerisit, Sebastien N.; Charpentier, Thibault; Angeli, Frederic; Icenhower, J. P.; McGrail, B. Pete; Charles F. Windisch; Burton, Sarah D.; Hopf, Juliane

    2016-02-27

    Spectroscopic measurements, dissolution experiments, and Monte Carlo simulations were performed to investigate the effect of high valence cations (HVC) on the mechanisms of glass dissolution under dilute and near-saturated conditions. Raman and NMR spectroscopy were used to determine the structural changes that occur in glass, specifically network formers (e.g., Al, Si, and B), with the addition of the HVC element hafnium in the Na2O Al2O3 B2O3 HfO2 SiO2 system (e.g., Na/(Al+B) = 1.0 and HfO2/SiO2 from 0.0 to 0.42). Spectroscopic measurements revealed that increasing hafnium content decreases N4 and increases the amount of Si–O–Hf moieties in the glass. Results frommore » flow through experiments conducted under dilute and near saturated conditions show a decrease of approximately 100 or more in the dissolution rate over the series from 0 to 20 mol% HfO2. Comparing the average steady-state rates obtained under dilute conditions to the rates obtained for near-saturated conditions reveal a divergence in the magnitude between the average steady state rates measured in these different conditions. The reason for this divergence was investigated more thoroughly using Monte Carlo simulations. Simulations indicate that the divergence in glass dissolution behavior under dilute and near-saturated conditions result from the formation of a low coordination Si sites when Si from the saturated solution adsorbs to Hf on the glass surface. The residence time of the newly formed low coordination Si sites is longer at the glass surface and increases the density of anchor sites from which altered layers with higher Si densities can form than in the absence of Hf. These results illustrate the importance of understanding solid water/solid-fluid interactions by linking macroscopic reaction kinetics to nanometer scale interfacial processes.« less

  3. Carbon-carbon bond formation in cationic aryl-olefin-platinum (II) complexes

    SciTech Connect (OSTI)

    De Felice, V.; Renzi, A.D.; Tesauro, D.; Vitagliano, A.

    1992-11-01

    Cationic five-coordinate [Pt(3-R{sup 1}-4-R{sup 2}-C{sub 6}H{sub 3})(MeCN) (6-Me-py-2-CH=NPh)(C{sub 2}H{sub 4})]{sup +} complexes (R{sup 1}, R{sup 2} = H, Me, OMe) undergo an unexpected rearrangement at 0{degrees}C in chloroform solution, affording, after treatment with aqueous LiCl, the neutral four-coordinate species [Pt(2-Et-4-R{sup 1}-5-R{sup 2}-C{sub 6}H{sub 2})Cl(6-Me-py-1-CH=NPh)]. Pt-C{sub aryl} bond breaking and making is involved in the whole process, resulting in a 1,2-shift of the platinum atom to an adjacent position of the benzene ring. The same compound is obtained, together with products deriving from a typical insertion, when an equimolar amount of ethylene is added to a chloroform solution of [Pt(3-R{sub 1}-4-R{sup 2}-C{sub 6}H{sub 3})(MeCN)(6-Me-py-2-CH=NPh)]{sup +} at 0{degrees}C. When higher ethylene/Pt ratios are used, only five-coordinate [Pt(3-R{sup 1}-4-R{sup 2}-C{sub 6}H{sub 3}CH{sub 2}CH{sub 2})Cl(6-Me-py-2-CH{double_bond}NPh)(C{sub 2}H{sub 4})] complex is isolated. As the experimental data rule out the possibility of a (2-arylethyl)platinum to (2-ethylaryl)platinum rearrangement, different reaction paths are suggested for the two processes. When the two reactions are combined in a {open_quotes}one-pot{close_quotes} sequence, a regiocontrolled double alkylation of the aryl system can be obtained. The behavior substrates containing bidenate nitrogen ligands having different five-coordination stabilizing effects is examined, and data concerning the reactions of propene and styrene are reported. 13 refs., 3 tabs.

  4. Cationic Gold Clusters Ligated with Differently Substituted Phosphines: Effect of Substitution on Ligand Reactivity and Binding

    SciTech Connect (OSTI)

    Johnson, Grant E.; Olivares, Astrid M.; Hill, David E.; Laskin, Julia

    2015-01-01

    We present a systematic study of the effect of the number of methyl (Me) and cyclohexyl (Cy) functional groups in monodentate phosphine ligands on the solution-phase synthesis of ligated sub-nanometer gold clusters and their gas-phase fragmentation pathways. Small mixed ligand cationic gold clusters were synthesized using ligand exchange reactions between pre-formed triphenylphosphine ligated (PPh3) gold clusters and monodentate Me- and Cy-substituted ligands in solution and characterized using electrospray ionization mass spectrometry (ESI-MS) and collision-induced dissociation (CID) experiments. Under the same experimental conditions, larger gold-PPh3 clusters undergo efficient exchange of unsubstituted PPh3 ligands for singly Me- and Cy-substituted PPh2Me and PPh2Cy ligands. The efficiency of ligand exchange decreases with an increasing number of Me or Cy groups in the substituted phosphine ligands. CID experiments performed for a series of ligand-exchanged gold clusters indicate that loss of a neutral Me-substituted ligand is preferred over loss of a neutral PPh¬3 ligand while the opposite trend is observed for Cy-substituted ligands. The branching ratio of the competing ligand loss channels is strongly correlated with the electron donating ability of the phosphorous lone pair as determined by the relative proton affinity of the ligand. The results indicate that the relative ligand binding energies increase in the order PMe3 < PPhMe2 < PPh2Me < PPh3< PPh2Cy < PPhCy2< PCy3. Furthermore, the difference in relative ligand binding energies increases with the number of substituted PPh3-mMem or PPh3-mCym ligands (L) exchanged onto each cluster. This study provides the first experimental determination of the relative binding energies of ligated gold clusters containing differently substituted monophosphine ligands, which are important to controlling their synthesis and reactivity in solution. The results also indicate that ligand substitution is an important

  5. New iodocuprates(I) with N-heterocyclic molecules as the cations

    SciTech Connect (OSTI)

    Zhao, Jin-Jing; Zhang, Xiao; Wang, Yan-Ning; Jia, Hong-Li; Yu, Jie-Hui; Xu, Ji-Qing

    2013-11-15

    Under the hydrothermal conditions, the reactions between CuI, KI and bp/bpp (bp=4,4′-bipiperidine, bpp=1,3-bis(4-piperidyl)propane) in an acidic alcohol solution produced three new organically templated iodocuprates(I) as [H{sub 2}bp]{sub 2}[Cu{sub 2}I{sub 6}] 1, [tmbp][Cu{sub 2}I{sub 4}] 2 and [tmbpp] 2 [Cu{sub 4}I{sub 8}]·2H{sub 2}O 3 (tmbp{sup 2+}=N,N,N′,N′-tetramethyl-4,4′-bipiperidinium; tmbpp{sup 2+}=N,N,N′,N′-tetramethyl-1,3-bis(4-piperidyl)propane dication). X-ray analysis revealed that (i) tmbp{sup 2+} and tmbpp{sup 2+} in compounds 2 and 3 originated from the complete N-alklation of bp/bpp with CH{sub 3}OH; (ii) templated by H{sub 2}bp{sup 2+}, the inorganic anion [Cu{sub 2}I{sub 6}]{sup 2−} of 1 possesses a dinuclear structure, whereas templated by tmbp{sup 2+}, the inorganic anion [Cu{sub 2}I{sub 4}]{sup 2−} of 2 exhibits a one-dimensional (1D) chain structure; (iii) templated by tmbpp{sup 2+}, the inorganic anion [Cu{sub 4}I{sub 8}]{sup 4−} of 3 shows a cubane-like structure modified by four terminal I{sup −} ions. The photoluminescence analysis indicates that compounds 1 and 2 emit blue light, while compound 3 emits green light. - Graphical abstract: By employing hydrothermal in situ N-alkylation of bp/bpp with CH{sub 3}OH, three new organically templated iodocuprates(I) were obtained. Display Omitted - Highlights: • Three new organically templated iodocuprates(I) were reported. • Cations tmbp{sup 2+} and tmbpp{sup 2+} originated from in situ alkylation of bp/bpp with CH{sub 3}OH. • H{sup +} and I{sup −} play a key role in alkylation of bp/bpp with CH{sub 3}OH. • Photoluminescence emission for iodocuprates(I) is related to Cu···Cu interaction.

  6. Dating thermal events at Cerro Prieto using fission-track annealing

    SciTech Connect (OSTI)

    Sanford, S.J.; Elders, W.A.

    1981-01-01

    The duration of heating in the Cerro Prieto reservoir was estimated by relating the fading of spontaneous fission tracks in detrital apatite to observed temperatures. The rate of fading is a function of both time and temperature. The apparent fission track age of the detrital apatites then, is a function of both their source age and their time-temperature history. Data from laboratory experiments and geologic fading studies were compiled from published sources to produce lines of iso-annealing for apatite in time-temperature space. Fission track ages were calculated for samples from two wells at Cerro Prieto, one with an apparently simple and one with an apparently complex thermal history. Temperatures were estimated by empirical vitrinite reflectance geothermometry, fluid inclusion homogenization and oxygen isotope equilibrium. These estimates were compared with logs of measured borehole temperatures. The temperature in well T-366, where complete annealing first occurs, was estimated to be between 160 and 180{sup 0}C. Complete annealing at these temperatures requires 10{sup 4} and 10{sup 3} years, respectively. Well M-94 has an apparently complex thermal history. Geothermometers in this well indicate temperatures some 50 to 100{sup 0}C higher than those measured directly in the borehole. Fission tracks are partially preserved in M-94 where paleotemperatures were as high as 200{sup 0}C and are erased where geothermometers indicate temperatures of 250{sup 0}C. This implies a thermal event less than 10{sup 1} years and greater than 10{sup 0} years in duration.

  7. Chemistry Data for Geothermometry Mapping of Deep Hydrothermal Reservoirs in Southeastern Idaho

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Earl Mattson

    2016-01-18

    This dataset includes chemistry of geothermal water samples of the Eastern Snake River Plain and surrounding area. The samples included in this dataset were collected during the springs and summers of 2014 and 2015. All chemical analysis of the samples were conducted in the Analytical Laboratory at the Center of Advanced Energy Studies in Idaho Falls, Idaho. This data set supersedes #425 submission and is the final submission for AOP 3.1.2.1 for INL. Isotopic data collected by Mark Conrad will be submitted in a separate file.

  8. One-photon mass-analyzed threshold ionization (MATI) spectroscopy of pyridine: Determination of accurate ionization energy and cationic structure

    SciTech Connect (OSTI)

    Lee, Yu Ran; Kang, Do Won; Kim, Hong Lae E-mail: hlkim@kangwon.ac.kr; Kwon, Chan Ho E-mail: hlkim@kangwon.ac.kr

    2014-11-07

    Ionization energies and cationic structures of pyridine were intensively investigated utilizing one-photon mass-analyzed threshold ionization (MATI) spectroscopy with vacuum ultraviolet radiation generated by four-wave difference frequency mixing in Kr. The present one-photon high-resolution MATI spectrum of pyridine demonstrated a much finer and richer vibrational structure than that of the previously reported two-photon MATI spectrum. From the MATI spectrum and photoionization efficiency curve, the accurate ionization energy of the ionic ground state of pyridine was confidently determined to be 73 570 ± 6 cm{sup −1} (9.1215 ± 0.0007 eV). The observed spectrum was almost completely assigned by utilizing Franck-Condon factors and vibrational frequencies calculated through adjustments of the geometrical parameters of cationic pyridine at the B3LYP/cc-pVTZ level. A unique feature unveiled through rigorous analysis was the prominent progression of the 10 vibrational mode, which corresponds to in-plane ring bending, and the combination of other totally symmetric fundamentals with the ring bending overtones, which contribute to the geometrical change upon ionization. Notably, the remaining peaks originate from the upper electronic state ({sup 2}A{sub 2}), as predicted by high-resolution photoelectron spectroscopy studies and symmetry-adapted cluster configuration interaction calculations. Based on the quantitatively good agreement between the experimental and calculated results, it was concluded that upon ionization the pyridine cation in the ground electronic state should have a planar structure of C{sub 2v} symmetry through the C-N axis.

  9. AMENDMENT OF SOLlClTATlONlMODlFlCATION OF CONTRACT 1 I . CONTR"CT ID CODE

    National Nuclear Security Administration (NNSA)

    SOLlClTATlONlMODlFlCATION OF CONTRACT 1 I . CONTR"CT ID CODE BWXT Pantex, LLC Route 726, Mt. Athos Road Lynchburg, VA 24506 PAGE 1 OF 2 PAGES Albuquerque, NM 8718Ii4400 I Amarillo, TX 79120 9B. DATED (SEE m M 11) 10A. MODIFICATION OF CONTRACTIORDER NO. 8. NAME AND ADDRESS OF CONTRACTOR (No., street, county, &ate, ZIP Code) I ( DE-ACOCOOAL66620 10B. DATED (SEE / E M 13) 2. AMENDMENT/MODIFICATION NO. M097 9A. AMENDMENT OF SOLICITATION NO. Offera must a d t n d e d p rsceipt of this m e n

  10. Combined Quantum Chemical/Raman Spectroscopic Analyses of Li+ Cation Solvation: Cyclic Carbonate Solvents - Ethylene Carbonate and Propylene Earbonate

    SciTech Connect (OSTI)

    Allen, Joshua L.; Borodin, Oleg; Seo, D. M.; Henderson, Wesley A.

    2014-12-01

    Combined computational/Raman spectroscopic analyses of ethylene carbonate (EC) and propylene carbonate (PC) solvation interactions with lithium salts are reported. It is proposed that previously reported Raman analyses of (EC)n-LiX mixtures have utilized faulty assumptions. In the present studies, density functional theory (DFT) calculations have provided corrections in terms of both the scaling factors for the solvent's Raman band intensity variations and information about band overlap. By accounting for these factors, the solvation numbers obtained from two different EC solvent bands are in excellent agreement with one another. The same analysis for PC, however, was found to be quite challenging. Commercially available PC is a racemic mixture of (S)- and (R)-PC isomers. Based upon the quantum chemistry calculations, each of these solvent isomers may exist as multiple conformers due to a low energy barrier for ring inversion, making deconvolution of the Raman bands daunting and inherently prone to significant error. Thus, Raman spectroscopy is able to accurately determine the extent of the EC...Li+ cation solvation interactions using the provided methodology, but a similar analysis of PC...Li+ cation solvation results in a significant underestimation of the actual solvation numbers.

  11. Alkali metal cation complexation by 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds

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

    Surowiec, Malgorzata A.; Custelcean, Radu; Surowiec, Kazimierz; Bartsch, Richard A.

    2014-04-23

    Alkali metal cation extraction behavior for two series of 1,3-alternate, mono-ionizable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionizable group is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the proton-ionizable group is attached to one para position in the calixarene framework, thus positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs+ efficiency and selectivity. Single-species extraction pH profiles of Cs+ for Series 1 and 2 ligands with the same proton-ionizable groupmore » are very similar. Thus, association of Cs+ with the calixcrown ring is more important than the the proton-ionizable group’s position in relation to the crown ether cavity. Solid-state structures are presented for two unionized ligands from Series 2, as is a crystal containing two different ionized ligand–Cs+ complexes.« less

  12. Highly Active Electrolytes for Rechargeable Mg Batteries Based on [Mg2(?-Cl)2]2+ Cation Complex in Dimethoxyethane

    SciTech Connect (OSTI)

    Cheng, Yingwen; Stolley, Ryan M.; Han, Kee Sung; Shao, Yuyan; Arey, Bruce W.; Washton, Nancy M.; Mueller, Karl T.; Helm, Monte L.; Sprenkle, Vincent L.; Liu, Jun; Li, Guosheng

    2015-01-01

    Highly active electrolytes based on a novel [Mg2(?-Cl)2]2+ cation complex for reversible Mg deposition were developed and analyzed in this work. These electrolytes were formulated in dimethoxyethane through dehalodimerization of non-nucleophilic MgCl2 by reacting with either Mg salts (such as Mg(TFSI)2, TFSI= bis(trifluoromethane)sulfonylimide) or Lewis acid salts (such as AlEtCl2 or AlCl3). The cation complex was identified for the first time as [Mg2(?-Cl)2(DME)4]2+ (DME=dimethoxyethane) and its molecular structure was characterized by single crystal X-ray diffraction, Raman spectroscopy and NMR. The electrolyte synthesis process was studied and rational approaches for formulating highly active electrolytes were proposed. Through control of the anions, electrolytes with efficiency close to 100%, wide electrochemical window (up to 3.5V) and high ionic conductivity (> 6 mS/cm) were obtained. The electrolyte synthesis and understandings developed in this work could bring significant opportunities for rational formulation of electrolytes with the general formula [Mg2(?-Cl)2(DME)4][anion]x for practical Mg batteries.

  13. Alkali metal cation complexation by 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds

    SciTech Connect (OSTI)

    Surowiec, Malgorzata A.; Custelcean, Radu; Surowiec, Kazimierz; Bartsch, Richard A.

    2014-04-23

    Alkali metal cation extraction behavior for two series of 1,3-alternate, mono-ionizable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionizable group is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the proton-ionizable group is attached to one para position in the calixarene framework, thus positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs+ efficiency and selectivity. Single-species extraction pH profiles of Cs+ for Series 1 and 2 ligands with the same proton-ionizable group are very similar. Thus, association of Cs+ with the calixcrown ring is more important than the the proton-ionizable group’s position in relation to the crown ether cavity. Solid-state structures are presented for two unionized ligands from Series 2, as is a crystal containing two different ionized ligand–Cs+ complexes.

  14. Unravelling the low thermal expansion coefficient of cation-substituted YBaCo4O7+δ

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

    Manthiram, Arumugam; Huq, Ashfia; Kan, Wang Hay; Lai, Ke -Yu

    2016-01-12

    With an aim to understand the origin of the low thermal expansion coefficients (TECs), cation substituted YBaCo4O7-type oxides have been investigated by in-situ neutron diffraction, bond valence sum (BVS), thermogravimetric analysis, and dilatometry. The compositions YBaCo4O7+δ, Y0.9ln0.1BaCo3ZnO7+δ, and Y0.9ln0.1BaCo3Zn0.6Fe0.4O7+δ) were synthesized by solid-state reaction at 1200 °C. Here, Rietveld refinement of the joint synchrotron X-ray and neutron diffraction data shows that the Zn and Fe dopants have different preferences to substitute the Co ions in the 6c and 2a sites.

  15. Full cell study of Diels Alder poly(phenylene) anion and cation exchange membranes in vanadium redox flow batteries

    SciTech Connect (OSTI)

    Pezeshki, Alan M.; Fujimoto, Cy; Sun, Che -Nan; Mench, Matthew M.; Zawodzinski, Thomas A.; Tang, Z. J.

    2015-11-14

    In this paper, we report on the performance of Diels Alder poly(phenylene) membranes in vanadium redox flow batteries. The membranes were functionalized with quaternary ammonium groups to form an anion exchange membrane (QDAPP) and with sulfonic acid groups to form a cation exchange membrane (SDAPP). Both membrane classes showed similar conductivities in the battery environment, suggesting that the ion conduction mechanism in the material is not strongly affected by the moieties along the polymer backbone. The resistance to vanadium permeation in QDAPP was not improved relative to SDAPP, further suggesting that the polarity of the functional groups do not play a significant role in the membrane materials tested. Both QDAPP and SDAPP outperformed Nafion membranes in cycling tests, with both achieving voltage efficiencies above 85% while maintaining 95% coulombic efficiency while at a current density of 200 mA/cm2.

  16. Full cell study of Diels Alder poly(phenylene) anion and cation exchange membranes in vanadium redox flow batteries

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

    Pezeshki, Alan M.; Fujimoto, Cy; Sun, Che -Nan; Mench, Matthew M.; Zawodzinski, Thomas A.; Tang, Z. J.

    2015-11-14

    In this paper, we report on the performance of Diels Alder poly(phenylene) membranes in vanadium redox flow batteries. The membranes were functionalized with quaternary ammonium groups to form an anion exchange membrane (QDAPP) and with sulfonic acid groups to form a cation exchange membrane (SDAPP). Both membrane classes showed similar conductivities in the battery environment, suggesting that the ion conduction mechanism in the material is not strongly affected by the moieties along the polymer backbone. The resistance to vanadium permeation in QDAPP was not improved relative to SDAPP, further suggesting that the polarity of the functional groups do not playmore » a significant role in the membrane materials tested. Both QDAPP and SDAPP outperformed Nafion membranes in cycling tests, with both achieving voltage efficiencies above 85% while maintaining 95% coulombic efficiency while at a current density of 200 mA/cm2.« less

  17. AMENDMENT OF SOLIr ATI ON/MODIFI CATION OF CONTRACT 1. CONTRACT ID CODE PAGE OF PAGES

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

    SOLIr ATI ON/MODIFI CATION OF CONTRACT 1. CONTRACT ID CODE PAGE OF PAGES 2 AMENDMENT/lIVDDIFICATiON NC 3. EFFECTIVE DATE [4 REDUISITION/PURCHASE REC NO IE PR3JECT NC (if applicable) 09 ISoe Bloo , 16- - ISee Soheoule S ISSUED D> CODE 7 ~ ADMINISTERED BY (if otnertrian ItemS CO DE Of fice of Ri-.er PoDLecOLODn office of Riv'er P-oCQ-ec-.iQ .S. Cet:F O<men of E-nerov,, I.S. Deparo:merio c-' Enrgv P.O. Box 4'5C 0 ... Box 45C .io ao 1 31 W YS: (-876 B. NAME AND ADDRESS CF CONTRACTOR (No seve

  18. Crystal Structure of an Integron Gene Cassette-Associated Protein from Vibrio cholerae Identifies a Cationic Drug-Binding Module

    SciTech Connect (OSTI)

    Deshpande, Chandrika N.; Harrop, Stephen J.; Boucher, Yan; Hassan, Karl A.; Di Leo, Rosa; Xu, Xiaohui; Cui, Hong; Savchenko, Alexei; Chang, Changsoo; Labbate, Maurizio; Paulsen, Ian T.; Stokes, H.W.; Curmi, Paul M.G.; Mabbutt, Bridget C.

    2012-02-15

    The direct isolation of integron gene cassettes from cultivated and environmental microbial sources allows an assessment of the impact of the integron/gene cassette system on the emergence of new phenotypes, such as drug resistance or virulence. A structural approach is being exploited to investigate the modularity and function of novel integron gene cassettes. We report the 1.8 {angstrom} crystal structure of Cass2, an integron-associated protein derived from an environmental V. cholerae. The structure defines a monomeric beta-barrel protein with a fold related to the effector-binding portion of AraC/XylS transcription activators. The closest homologs of Cass2 are multi-drug binding proteins, such as BmrR. Consistent with this, a binding pocket made up of hydrophobic residues and a single glutamate side chain is evident in Cass2, occupied in the crystal form by polyethylene glycol. Fluorescence assays demonstrate that Cass2 is capable of binding cationic drug compounds with submicromolar affinity. The Cass2 module possesses a protein interaction surface proximal to its drug-binding cavity with features homologous to those seen in multi-domain transcriptional regulators. Genetic analysis identifies Cass2 to be representative of a larger family of independent effector-binding proteins associated with lateral gene transfer within Vibrio and closely-related species. We propose that the Cass2 family not only has capacity to form functional transcription regulator complexes, but represents possible evolutionary precursors to multi-domain regulators associated with cationic drug compounds.

  19. Cation Intermixing And Electronic Deviations At The Insulating LaCrO3/SrTiO3(001) Interface

    SciTech Connect (OSTI)

    Colby, Robert J.; Qiao, Liang; Zhang, Hongliang; Shutthanandan, V.; Ciston, Jim; Kabius, Bernd C.; Chambers, Scott A.

    2013-10-29

    The interface between polar perovskite LaCrO3 (LCO) and non-polar SrTiO3(001) (STO), grown by molecular beam epitaxy, is examined using a combination of electron microscopy, spectroscopy, and Rutherford backscattering spectrometry. The LCO/STO(001) interface is insulating, a potential counter example for the claim that polar/nonpolar perovskite interfaces should be conductive by virtue of an electronic reconstruction to alleviate the polar discontinuity. The A-site cations of these ABO3 perovskites are found to diffuse across the interface to a greater extent than the B-site cations, based on high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), energy dispersive x-ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS). The B-site cation valences are shown to be partially reduced near the interface by analysis of EELS near-edge structures. The location and direction of these electronic modifications do not intuitively compensate the charge imbalance imposed by uneven cation inter-diffusion, and yet both the film and interface are insulating. These results highlight the importance of both the physical and electronic structure of such complex interfaces in determining their characteristics. Furthermore, the extent of inter-diffusion is shown to increase with increasing LCO film thickness, suggesting a potential mechanism behind the critical thickness for interfacial conductivity in other polar/non-polar oxide systems, and a fundamental limitation on the formation of abrupt interfaces in LCO/STO(001).

  20. Coverage Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-selected Ions

    SciTech Connect (OSTI)

    Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

    2012-11-29

    The ionic charge state of monodisperse cationic gold clusters on surfaces may be controlled by selecting the coverage of mass-selected ions soft landed onto a substrate. Polydisperse diphosphine-capped gold clusters were synthesized in solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine in the presence of 1,3-bis(diphenylphosphino)propane. The polydisperse gold clusters were introduced into the gas phase by electrospray ionization and mass selection was employed to select a multiply charged cationic cluster species (Au11L53+, m/z = 1409, L = 1,3-bis(diphenylphosphino)propane) which was delivered to the surfaces of four different self-assembled monolayers on gold (SAMs) at coverages of 1011 and 1012 clusters/mm2. Employing the spatial profiling capabilities of in-situ time-of-flight secondary ion mass spectrometry (TOF-SIMS) it is shown that, in addition to the chemical functionality of the monolayer (as demonstrated previously: ACS Nano, 2012, 6, 573) the coverage of cationic gold clusters on the surface may be used to control the distribution of ionic charge states of the soft-landed multiply charged clusters. In the case of a 1H,1H,2H,2H-perfluorodecanethiol SAM (FSAM) almost complete retention of charge by the deposited Au11L53+ clusters was observed at a lower coverage of 1011 clusters/mm2. In contrast, at a higher coverage of 1012 clusters/mm2, pronounced reduction of charge to Au11L52+ and Au11L5+ was observed on the FSAM. When soft landed onto 16- and 11-mercaptohexadecanoic acid surfaces on gold (16,11-COOH-SAMs), the mass-selected Au11L53+ clusters exhibited partial reduction of charge to Au11L52+ at lower coverage and additional reduction of charge to both Au11L52+ and Au11L5+ at higher coverage. The reduction of charge was found to be more pronounced on the surface of the shorter (thinner) C11 than the longer (thicker) C16-COOH-SAM. On the surface of the 1-dodecanethiol (HSAM) monolayer, the most abundant charge state

  1. Location and valence state of strontium cations on the framework of a carbon dioxide selective porous silicoaluminophosphate

    SciTech Connect (OSTI)

    Zhang, Li; Rivera-Ramos, Milton E.; Hernández-Maldonado, Arturo J.

    2014-05-28

    A Sr{sup 2+}-SAPO-34 material that displays superior CO2 adsorption selectivity and capacity was characterized via XPS and UV-vis spectroscopy to elucidate the valence state of strontium cations and framework silicon environment. Most importantly, the location of the strontium has been estimated from a Rietveld refinement analysis of synchrotron diffraction data. The XPS analysis indicated that the apparent valence state of the strontium is less than 2, an indication of its interaction with the large anionic framework. Furthermore, UV-vis tests pointed to changes in the silicon environment, plausibly related to this valence state or framework faulting. For the refinement, the analysis found that strontium occupied two unique sites: a site Sr1 slightly displaced from six-membered rings and a site Sr2 positioned at the top or bottom of the eight-membered rings. The latter position favors the interaction of the alkaline earth metal with CO{sub 2}, probably resulting in an enhanced electric field-quadrupole moment interaction.

  2. Combined Utilization of Cation Exchanger and Neutral Receptor to Volume Reduction of Alkaline Tank Waste by Separation of Sodium Salts

    SciTech Connect (OSTI)

    Levitskaia, Tatiana G.; Lumetta, Gregg J.; Moyer, Bruce A.

    2004-03-29

    In this report, novel approaches to the selective liquid-liquid extraction separation of sodium hydroxide and sodium nitrate from high-level alkaline tank waste will be discussed. Sodium hydroxide can be successfully separated from alkaline tank-waste supernatants by weakly acidic lipophilic hydroxy compounds via a cation-exchange mechanism referred to as pseudo hydroxide extraction. In a multi-cycle process, as sodium hydroxide in the aqueous phase becomes depleted, it is helpful to have a neutral sodium receptor in the extraction system to exploit the high nitrate concentration in the waste solution to promote sodium removal by an ion-pair extraction process. Simultaneous utilization of an ionizable organic hydroxy compound and a neutral extractant (crown ether) in an organic phase results in the synergistic enhancement of ion exchange and improved separation selectivity due to the receptor's strong and selective sodium binding. Moreover, combination of the hydroxy compound and the crown ether provides for mutually increased solubility, even in a non-polar organic solvent. Accordingly, application of Isopar{reg_sign} L, a kerosene-like alkane solvent, becomes feasible. This investigation involves examination of such dual-mechanism extraction phases for sodium extraction from simulated and actual salt cake waste solutions. Sodium salts can be regenerated upon the contact of the loaded extraction phases with water. Finally, conditions of potential extraction/strip cycling will be discussed.

  3. Swelling properties of montmorillonite and beidellite clay minerals from molecular simulation: Comparison of temperature interlayer cation, and charge location effects

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

    Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Jove-Colon, Carlos F.; Cygan, Randall Timothy

    2015-08-27

    In this study, the swelling properties of smectite clay minerals are relevant to many engineering applications including environmental remediation, repository design for nuclear waste disposal, borehole stability in drilling operations, and additives for numerous industrial processes and commercial products. We used molecular dynamics and grand canonical Monte Carlo simulations to study the effects of layer charge location, interlayer cation, and temperature on intracrystalline swelling of montmorillonite and beidellite clay minerals. For a beidellite model with layer charge exclusively in the tetrahedral sheet, strong ion–surface interactions shift the onset of the two-layer hydrate to higher water contents. In contrast, for amore » montmorillonite model with layer charge exclusively in the octahedral sheet, weaker ion–surface interactions result in the formation of fully hydrated ions (two-layer hydrate) at much lower water contents. Clay hydration enthalpies and interlayer atomic density profiles are consistent with the swelling results. Water adsorption isotherms from grand canonical Monte Carlo simulations are used to relate interlayer hydration states to relative humidity, in good agreement with experimental findings.« less

  4. The use Na, Li, K cations for modification of ZSM-5 zewolite to control hydrocarbon cold-start emission

    SciTech Connect (OSTI)

    Golubeva V.; Rohatgi U.; Korableva, A.; Anischenko, O.; Kustov, L.; Nissenbaum, V; Viola, M.B.

    2012-08-29

    This paper addresses the problem of controlling hydrocarbon emissions from cold-start of engines by investigating the adsorbents which could adsorb the hydrocarbons at cold temperatures and hold them to 250-300 ?. The materials, that has been studied, are based on the modification of ZSM-5 (SiO{sub 2}/Al{sub 2}O{sub 3} = 35) zeolite with Li, K, Na cations. It has been shown that the introduction of Li, Na and K in an amount that is equivalent to the content of Al in zeolite results in occurrence of toluene temperature desorption peaks at high-temperatures. The toluene temperature desorption curves for 5%Li-ZSM-5 and 2.3%Na-ZSM-5 zeolites are identical and have peak toluene desorption rate between 200 to 400 ?. Upon analysis of toluene adsorption isotherms for 2.3%Na-ZSM-5 and 5%Li-ZSM-5, it was concluded that the toluene diffusion inside of the modified zeolites channels is extremely slow and the sorption capacity of 2.3%Na-ZSM-5 is higher than with 5%Li-ZSM-5. The 2.3%Na-ZSM-5 didn't change toluene temperature programmed desorption (TPD) rate of curve after the treatment in environment with 10% ?{sub 2}? at 750-800 ? for about 28 h. The 2.3%Na-ZSM-5 zeolite is very promising as adsorbent to control the cold-start hydrocarbon emissions.

  5. Swelling properties of montmorillonite and beidellite clay minerals from molecular simulation: Comparison of temperature interlayer cation, and charge location effects

    SciTech Connect (OSTI)

    Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Jove-Colon, Carlos F.; Cygan, Randall Timothy

    2015-08-27

    In this study, the swelling properties of smectite clay minerals are relevant to many engineering applications including environmental remediation, repository design for nuclear waste disposal, borehole stability in drilling operations, and additives for numerous industrial processes and commercial products. We used molecular dynamics and grand canonical Monte Carlo simulations to study the effects of layer charge location, interlayer cation, and temperature on intracrystalline swelling of montmorillonite and beidellite clay minerals. For a beidellite model with layer charge exclusively in the tetrahedral sheet, strong ion–surface interactions shift the onset of the two-layer hydrate to higher water contents. In contrast, for a montmorillonite model with layer charge exclusively in the octahedral sheet, weaker ion–surface interactions result in the formation of fully hydrated ions (two-layer hydrate) at much lower water contents. Clay hydration enthalpies and interlayer atomic density profiles are consistent with the swelling results. Water adsorption isotherms from grand canonical Monte Carlo simulations are used to relate interlayer hydration states to relative humidity, in good agreement with experimental findings.

  6. An ab initio study of the electronic structure of the boron oxide neutral (BO), cationic (BO{sup +}), and anionic (BO{sup ?}) species

    SciTech Connect (OSTI)

    Magoulas, Ilias; Kalemos, Apostolos

    2014-09-28

    The BO neutral, cationic, and anionic molecular species have been painstakingly studied through multireference configuration interaction and single reference coupled cluster methods employing basis sets of quintuple cardinality. Potential energy curves have been constructed for 38 (BO), 37 (BO{sup +}), and 12 (BO{sup ?}) states and the usual molecular parameters have been extracted most of which are in very good agreement with the scarce experimental data. Numerous avoided crossings appear on more or less all of the studied states of the neutral and cationic species challenging the validity of the Born Oppenheimer approximation. Finally, all excited states of the anionic system lie above the ground state of the neutral BO system and are therefore resonances.

  7. A comparative study of optical absorption and photocatalytic properties of nanocrystalline single-phase anatase and rutile TiO{sub 2} doped with transition metal cations

    SciTech Connect (OSTI)

    Kernazhitsky, L.; Shymanovska, V.; Gavrilko, T.; Naumov, V.; Kshnyakin, V.; Khalyavka, T.

    2013-02-15

    The effect of nanocrystalline TiO{sub 2} doping with transition metal cations (Cu{sup 2+}, Fe{sup 3+}, Co{sup 2+}, Cr{sup 3+}) on their optical absorption and photocatalytic properties was investigated. The obtained metal-doped TiO{sub 2} samples were characterized by X-ray diffraction, scanning electron microscopy, and UV-vis absorption spectroscopy. It is shown that doping effect on anatase (A) and rutile (R) properties is quite different, being much stronger and complicated on A than on R. Contrary to doped R, doped A revealed a significant red shift of the absorption edge along with the band gap narrowing. Photocatalytic activity of anatase increases upon doping in the order: AR/Co>R/Cu>R/Fe>R/Cr, indicating the inhibitory effect of impurity cations. This fact correlates with the decrease in the UV absorption of the doped rutile in the region of the Hg-lamp irradiation at 4.88 eV. - Graphical abstract: A red shift of the absorption edge of nanocrystalline single-phase anatase after doping with transition metal cations. Highlights: Black-Right-Pointing-Pointer Single-phase anatase and rutile powders surface-doped with transition metal cations. Black-Right-Pointing-Pointer Absorption edge and band gap of rutile do not change with surface doping. Black-Right-Pointing-Pointer Band gap of surface-doped anatase reduces being the lowest for A/Fe. Black-Right-Pointing-Pointer The surface-doping improves photocatalytic activity of anatase. Black-Right-Pointing-Pointer The surface-doping inhibits photocatalytic activity of rutile.

  8. Calix[4]arene-bis(t-octylbenzo-18-crown-6) as an extraordinarily effective macrocyclic receptor for the univalent thallium cation

    SciTech Connect (OSTI)

    Makrlik, Emanuel; Toman, Petr; Vanura, Petr; Moyer, Bruce A

    2013-01-01

    From extraction experiments and -activity measurements, the exchange extraction constant corresponding to the equilibrium Tl+ (aq) + 1 Cs+ (org) 1 Tl+ (org) + Cs+ (aq) taking place in the two-phase water phenyltrifluoromethyl sulfone (abbrev. FS 13) system (1 = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, org = FS 13 phase) was evaluated as log Kex (Tl+, 1 Cs+) = 1.7 0.1. Further, the extraordinarily high stability constant of the 1 Tl+ complex in FS 13 saturated with water was calculated for a temperature of 25 C: log org(1 Tl+) = 13.1 0.2. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complex species 1 Tl+ was derived. In the resulting 1 Tl+ complex, the central cation Tl+ is bound by eight bond interactions to six oxygen atoms from the respective 18-crown-6 moiety and to two carbons of the corresponding two benzene rings of the parent receptor 1 via cation interaction.

  9. Influence of cationic substitutions on the first charge and reversible capacities of lithium-rich layered oxide cathodes

    SciTech Connect (OSTI)

    Wang, Chih-Chieh; Manthiram, Arumugam

    2013-06-24

    The reversible capacity values of lithium-rich layered oxide cathodes depend on the length (capacity) of the plateau region during the first charge. With an aim to understand the factors that control the length of the plateau region and thereby enhance the reversible capacity, the effects of various cationic substitutions in Li1.2Mn0.6Ni0.2O2 have been investigated systematically. Specifically, substitutions of (i) M3+ = Al3+, Cr3+, Fe3+, Co3+, and Ga3+ for equal amounts of Mn4+and Ni2+ in Li1.2Mn0.6-0.5xNi0.2-0.5xMxO2 with x = 0.06, 0.13, and 0.2, (ii) Ti4+ for Mn4+ in Li1.2Mn0.6-xTixNi0.2O2 with x = 0.025, 0.05, and 0.1, and (iii) Mg2+ for Ni2+ in Li1.2Mn0.6Ni0.2-xMgxO2 with x = 0.025, 0.05, and 0.1 have been investigated. The cationic substitutions affect the first charge capacity values both in the sloping region corresponding to the oxidation of the transition-metal ions to the 4+ state and in the plateau region corresponding to the oxidation of O2- ions to O2 and/or transition-metal ions beyond 4+, which control the reversible capacity values in subsequent cycles. While the changes in the sloping-region capacity could be readily understood by considering the redox activities of the transition-metal ions, the plateau-region capacity is found to depend sensitively on the metaloxygen covalence, which is dictated by the relative positions of the metal:3d band with respect to the top of the O2-:2p band, and electron delocalization. For instance, an overlap of the Co3+/4+:t2g band with the top of the O2-:2p band along with a partially filled t 2g band

  10. Unraveling the voltage fade mechanism in layer Li-Mn-rich electrode: formation of the tetrahedral cations for spinel conversion

    SciTech Connect (OSTI)

    Mohanty, Debasish; Li, Jianlin; Abraham, Daniel P; Huq, Ashfia; Payzant, E Andrew; Wood III, David L; Daniel, Claus

    2014-01-01

    Discovery of high-voltage layered lithium-and manganese-rich (LMR) composite oxide electrode has dramatically enhanced the energy density of current Li-ion energy storage systems. However, practical usage of these materials is currently not viable because of their inability to maintain a consistent voltage profile (voltage fading) during subsequent charge-discharge cycles. This report rationalizes the cause of this voltage fade by providing the evidence of layer to spinel-like (LSL) structural evolution pathways in the host Li1.2Mn0.55Ni0.15Co0.1O2 LMR composite oxide. By employing neutron powder diffraction, and temperature dependent magnetic susceptibility, we show that LSL structural rearrangement in LMR oxide occurs through a tetrahedral cation intermediate via: i) diffusion of lithium atoms from octahedral to tetrahedral sites of the lithium layer [(LiLioct LiLitet] which is followed by the dispersal of the lithium ions from the adjacent octahedral site of the metal layer to the tetrahedral sites of lithium layer [LiTM oct LiLitet]; and ii) migration of Mn from the octahedral sites of the transition metal layer to the permanent octahedral site of lithium layer via tetrahedral site of lithium layer [MnTMoct MnLitet MnLioct)]. The findings opens the door to the potential routes to mitigate this atomic restructuring in the high-voltage LMR composite oxide cathodes by manipulating the composition/structure for practical use in high-energy-density lithium-ion batteries.

  11. Selectivity Control in Synergistic Liquid-Liquid Anion Exchange of Univalent Anions via Structure-Specific Cooperativity between Quaternary Ammonium Cations and Anion Receptors

    SciTech Connect (OSTI)

    Borman, Christopher J; Bonnesen, Peter V; Moyer, Bruce A

    2012-01-01

    Two anion receptors enhance liquid-liquid anion exchange when added to quaternary alkylammonium chloride anion exchangers, but with a striking dependence upon the structure of the alkylammonium cation. Two anion receptors were investigated, meso-octamethylcalix[4]pyrrole (C4P) and the bisthiourea tweezer 1,1'-(propane-1,3-diyl)bis(3-(4-sec-butylphenyl)thiourea (BTU). C4P has the unique ability in its cone anion-binding conformation to accept an appropriately sized electropositive species in the resulting cup formed by its four electron-rich pyrrole groups, while BTU is not expected to be predisposed for a specific host-guest interaction with the quaternary ammonium cations. It was therefore hypothesized that synergism between C4P and methyltri(C8,10)alkylammonium chloride (Aliquat 336) would be uniquely pronounced owing to insertion of the methyl group of the Aliquat cation into the C4P cup, and we present herein data supporting this expectation. While synergism is comparatively weak for both exchangers with the BTU receptor, synergism between C4P and Aliquat 336 is indeed so strong that anion exchange prefers chloride over more extractable nitrate and trifluoroacetate, effectively overcoming the ubiquitous Hofmeister bias. A thermochemical analysis of synergistic anion exchange has been provided for the first time, unraveling the observed selectivity behavior and resulting in the estimation of binding constants for C4P with the ion pairs of A336+ with Cl , Br , OAcF3 , NO3 , and I . The uniquely strong positive cooperativity between A336 and C4P underscores the advantage of a supramolecular approach in the design of synergistic anion exchange systems.

  12. Communication: Transfer ionization in a thermal reaction of a cation and anion: Ar{sup +} with Br{sup −} and I{sup −}

    SciTech Connect (OSTI)

    Shuman, Nicholas S.; Miller, Thomas M.; Viggiano, Albert A.; Johnsen, Rainer

    2013-11-07

    We present experimental evidence that reactions of argon cations Ar{sup +} with the halogen anions Br{sup −} and I{sup −} do not occur exclusively by mutual neutralization, but also produce the cations Br{sup +} or I{sup +} ions by transfer ionization (TI). The experiments were carried out in flowing-afterglow plasmas at gas temperatures between and 300 and 500 K, and employed a variant of the Variable Electron and Neutral Density Attachment Mass Spectrometry method. The measured TI rate coefficients are 1.9 ± 0.6 × 10{sup −9} cm{sup 3} s{sup −1} and 1.1 ± {sub 0.3}{sup 0.8}× 10{sup −9} cm{sup 3} s{sup −1} for the Br{sup −} and I{sup −} reactions, respectively. We find that the TI rate coefficients decline with temperature as T{sup −0.5} to T{sup −1}. No indication of TI was found in the reaction with Cl{sup −}, where it is endoergic.

  13. Photoionization of cold gas phase coronene and its clusters: Autoionization resonances in monomer, dimer, and trimer and electronic structure of monomer cation

    SciTech Connect (OSTI)

    Bréchignac, Philippe Falvo, Cyril; Parneix, Pascal; Pino, Thomas; Pirali, Olivier; Garcia, Gustavo A.; Nahon, Laurent; Joblin, Christine; Kokkin, Damian; Bonnamy, Anthony; Mulas, Giacomo

    2014-10-28

    Polycyclic aromatic hydrocarbons (PAHs) are key species encountered in a large variety of environments such as the Interstellar Medium (ISM) and in combustion media. Their UV spectroscopy and photodynamics in neutral and cationic forms are important to investigate in order to learn about their structure, formation mechanisms, and reactivity. Here, we report an experimental photoelectron-photoion coincidence study of a prototypical PAH molecule, coronene, and its small clusters, in a molecular beam using the vacuum ultraviolet (VUV) photons provided by the SOLEIL synchrotron facility. Mass-selected high resolution threshold photoelectron (TPES) and total ion yield spectra were obtained and analyzed in detail. Intense series of autoionizing resonances have been characterized as originating from the monomer, dimer, and trimer neutral species, which may be used as spectral fingerprints for their detection in the ISM by VUV absorption spectroscopy. Finally, a full description of the electronic structure of the monomer cation was made and discussed in detail in relation to previous spectroscopic optical absorption data. Tentative vibrational assignments in the near-threshold TPES spectrum of the monomer have been made with the support of a theoretical approach based on density functional theory.

  14. Fabrication, characterization and photocatalytic properties of Ag/AgI/BiOI heteronanostructures supported on rectorite via a cation-exchange method

    SciTech Connect (OSTI)

    Chen, Yunfang; Fang, Jianzhang; Lu, Shaoyou; Wu, Yan; Chen, Dazhi; Huang, Liyan; Xu, Weicheng; Zhu, Ximiao; Fang, Zhanqiang

    2015-04-15

    Highlights: • Ag/AgI/BiOI-rectorite was prepared by twice cation-exchange process. • Ag/AgI/BiOI-rectorite photocatalyst possessed SPR and adsorption capacity. • Ag/AgI/BiOI-rectorite exhibited highly photocatalytic activity. • Trapped holes and ·O{sub 2}{sup −} were formed active species in the photocatalytic system. - Abstract: In this work, a new plasmonic photocatalyst Ag/AgI/BiOI-rectorite was prepared via a cation exchange process. The photocatalyst had been characterized by X-ray powder diffraction (XRD), Raman spectra, nitrogen sorption (BET), field-emission scanning electron microscope (FE-SEM), X-ray photoelectron spectroscopy (XPS) and UV–vis diffuse reflectance spectroscopy (DRS). The photocatalytic activity, which was evaluated by degradation of rhodamine B (RhB) and bisphenol A (BPA) under visible light irradiation, was enhanced significantly by loading Ag/AgI/BiOI nanoparticles onto rectorite. The photogenerated holes and superoxide radical (·O{sub 2}{sup −}) were both formed as active species for the photocatalytic reactions under visible light irradiation. The existence of metallic Ag particles, which possess the surface plasmon resonance effect, acted as an indispensable role in the photocatalytic reaction.

  15. Warm white light emitting ThO{sub 2}:Sm{sup 3+} nanorods: Cationic surfactant assisted reverse micellar synthesis and Photoluminescence properties

    SciTech Connect (OSTI)

    Gupta, Santosh K.; Gupta, Ruma; Natarajan, V.; Godbole, S.V.

    2014-01-01

    Graphical abstract: - Highlights: • ThO{sub 2}:Sm{sup 3+} nanoparticles have been synthesized using cationic surfactant assisted reverse micellar route. • HRTEM shows the formation of thoria nanorods. • Photoluminescence investigation shows host as well as samarium ion emission. • Time resolved fluorescence spectroscopy shows the presence of two types of samarium ion in thoria host. - Abstract: Sm{sup 3+} activated thorium oxide nanorods were synthesized by cationic surfactant assisted reverse micellar route. Phase purity, morphological and luminescent properties were investigated by X-ray diffraction, high resolution transmission electron microscopy and photoluminescence spectroscopy. Upon UV light excitation (245 nm), ThO{sub 2}:Sm{sup 3+} exhibited host emission at 447 nm, along with characteristic emission lines of Sm{sup 3+} at 569, 609, 662 and 716 nm. Lifetime spectroscopy shows the presence of two types of Sm{sup 3+} (τ = 1.1 ms and 4.9 ms) with different asymmetric ratios.

  16. Electronic structure of cation-codoped TiO{sub 2} for visible-light photocatalyst applications from hybrid density functional theory calculations

    SciTech Connect (OSTI)

    Long, Run; English, Niall J.

    2011-04-04

    The electronic structures of Mg/Ca- and/or Mo/W- (mono- and co-) doped anatase TiO{sub 2} have been investigated via generalized Kohn-Sham theory with the Heyd-Scuseria-Ernzerhof hybrid functional for exchange-correlation (J. Heyd et al., [J. Chem. Phys. 118, 8207 (2003)], J. Heyd et al., [J. Chem. Phys. 124, 219906 (2006)], and J. Paier et al., [J. Chem. Phys. 125, 249901 (2006)]), in the context of density functional theory. Gap narrowing is small for monodoping, which also creates impuritiy bands in the ''forbidden gap,'' either as acceptor or donor states, limiting possible utility as visible-light photocatalysts. However, codoping of Mg/Ca and Mo/W not only induces appreciable gap narrowing, but also serves to passivate the impurity bands, which can harvest visible-light to a greater extent. Considering ionic radii, Mg and Mo should constitute the best cation-pair.

  17. Effect of Siloxane Ring Strain and Cation Charge Density on the Formation of Coordinately Unsaturated Metal Sites on Silica: Insights from DFT Studies

    SciTech Connect (OSTI)

    Das, Ujjal; Zhang, Guanghui; Hu, Bo; Hock, Adam S.; Redfern, Paul C.; Miller, Jeffrey T.; Curtiss, Larry A.

    2015-12-01

    Amorphous silica (SiO2) is commonly used as a support in heterogeneous catalysis. However, due to the structural disorder and temperature induced change of surface morphology, the structures of silica supported metal catalysts are difficult to determine. Most studies are primarily focused on understanding the interactions of different types of surface hydroxyl groups with metal ions. In comparison, the effect of siloxane ring size on the structure of silica supported metal catalysts and how it affects catalytic activity is poorly understood. Here, we have used density functional theory calculations to understand the effect of siloxane ring strain on structure and activity of different monomeric Lewis acid metal sites on silica. In particular, we have found that large siloxane rings favor strong dative bonding interaction between metal ion and surface hydroxyls, leading to the formation of high-coordinate metal sites. In comparison, metal-silanol interaction is weak in small siloxane rings, resulting in low-coordinate metal sites. The physical origin of this size dependence is associated with siloxane ring strain, and, a correlation between metal-silanol interaction energy and ring strain energy has been observed. In addition to ring strain, the strength of the metal-silanol interaction also depends on the positive charge density of the cations. In fact, a correlation also exists between metal-silanol interaction energy and charge density of several first-row transition and post-transition metals. The theoretical results are compared with the EXAFS data of monomeric Zn(II) and Ga(III) ions grafted on silica. The molecular level insights of how metal ion coordination on silica depends on siloxane ring strain and cation charge density will be useful in the synthesis of new catalysts.

  18. Novel chemically stable Ba3Ca1.18Nb1.82-xYxO9- proton conductor: improved proton conductivity through tailored cation ordering

    SciTech Connect (OSTI)

    Wang, Siwei; Chen, Yan; Fang, Shumin; Zhang, Lingling; Tang, Ming; An, Ke; Brinkman, Dr. Kyle S.; Chen, Fanglin

    2014-01-01

    Simple perovskite-structured proton conductors encounter significant challenges to simultaneously achieving excellent chemical stability and proton conductivity that are desirable for many important applications in energy conversion and storage. This work demonstrates that Y-doped complex-perovskite-structured Ba3Ca1.18Nb1.82 xYxO9 materials possess both improved proton conductivity and exceptional chemical stability. Neutron powder diffraction refinement revealed a Fm3 m perovskite-structure and increased oxygen vacancy concentration due to the Y doping. High-resolution TEM analysis confirmed the perturbation of the B site cation ordering in the structure for the Ba3Ca1.18Nb1.82 xYxO9 materials. Such combined effects led to improved proton conductivity with a value of 5.3 10 3 S cm 1 at 600 C for Ba3Ca1.18Nb1.52Y0.3O9 (BCNY0.3), a value 2.4 times higher compared with that of the undoped Ba3Ca1.18Nb1.82O9 . The Ba3Ca1.18Nb1.82 xYxO9 materials showed remarkable chemical stability toward water and demonstrated no observable reactions to CO2 exposure. Ionic transport number studies showed that BCNY0.3 had predominantly proton conduction below 600 C. Solid oxide fuel cells using BCNY0.3 as an electrolyte demonstrated cell power output of 103 mW cm 2 at 750 C. These results suggest that a doping strategy that tailors the cation ordering in complex perovskites provides a new direction in the search for novel proton conducting ceramics.

  19. Scandium induced structural transformation and B?:B? cationic ordering in Pb(Fe{sub 0.5}Nb{sub 0.5})O{sub 3} multiferroic ceramics

    SciTech Connect (OSTI)

    Mallesham, B.; Ranjith, R.; Manivelraja, M.

    2014-07-21

    The current study explores non-magnetic Sc{sup 3+} induced structural transformation, evolution of local B-site cation ordering and associated effect on ferroelectric phase transition temperature T{sub max} (temperature corresponding to dielectric maxima) on increasing the atom percent of Sc substitution in [Pb(Fe{sub 0.5}Nb{sub 0.5})O{sub 3} (PFN)] ceramics. In this regard, the phase pure Pb[(Fe{sub 0.5?x}Sc{sub x})Nb{sub 0.5}]O{sub 3} ceramics with x varying from 0 to 0.5 were synthesized through solid state reaction route. The detailed structural analysis through Rietveld refinement confirms the room temperature transformation from a monoclinic Cm to rhombohedral R3m structure at x?=?0.3?mol.?% of Sc. Absorption spectra studies show that there is a considerable increment in the bandgap at higher scandium content. Most interestingly, the T{sub max} exhibited an increment for lower scandium contents (x?=?0.1 to 0.25) followed by a drop in T{sub max} (x?=?0.3 to 0.5). Such anomalous behavior in T{sub max} is expected to arise due to the onset of B?, B? local cation ordering beyond Sc content x?=?0.25. The B-site cation ordering at and beyond x?=?0.3 was also confirmed by the evolution of cation order induced Pb-O coupled vibrational mode in Raman scattering studies. In addition, the Mssbauer spectra of PFN (x?=?0) and Pb(Fe{sub 0.4}Sc{sub 0.1}Nb{sub 0.5})O{sub 3} (x?=?0.1) are reported to verify the spin state and oxidation state of iron. The lattice distortion due to the radius ratio difference between a Sc{sup 3+} cation and Fe{sup 3+} cation in low spin state is responsible for the structural transformation, which in turn facilitates a B?:B? cation ordering.

  20. Propane ammoxidation over the Mo-V-Te-Nb-O M1 phase: Reactivity of surface cations in hydrogen abstraction steps

    SciTech Connect (OSTI)

    Muthukumar, Kaliappan; Yu, Junjun; Xu, Ye; Guliants, Vadim V.

    2011-01-01

    Density functional theory calculations (GGA-PBE) have been performed to investigate the adsorption of C3 (propane, isopropyl, propene, and allyl) and H species on the proposed active center present in the surface ab planes of the bulk Mo-V-Te-Nb-O M1 phase in order to better understand the roles of the different surface cations in propane ammoxidation. Modified cluster models were employed to isolate the closely spaced V=O and Te=O from each other and to vary the oxidation state of the V cation. While propane and propene adsorb with nearly zero adsorption energy, the isopropyl and allyl radicals bind strongly to V=O and Te=O with adsorption energies, {Delta}E, being {le} -1.75 eV, but appreciably more weakly on other sites, such as Mo=O, bridging oxygen (Mo-O-V and Mo-O-Mo), and empty metal apical sites ({Delta}E > -1 eV). Atomic H binds more strongly to Te = O ({Delta}E {le} -3 eV) than to all the other sites, including V = O ({Delta}E = -2.59 eV). The reduction of surface oxo groups by dissociated H and their removal as water are thermodynamically favorable except when both H atoms are bonded to the same Te=O. Consistent with the strong binding of H, Te=O is markedly more active at abstracting the methylene H from propane (E{sub a} {le} 1.01 eV) than V = O (E{sub a} = 1.70 eV on V{sup 5+} = O and 2.13 eV on V{sup 4+} = O). The higher-than-observed activity and the loose binding of Te = O moieties to the mixed metal oxide lattice of M1 raise the question of whether active Te = O groups are in fact present in the surface ab planes of the M1 phase under propane ammoxidation conditions.

  1. Cation mixing, band offsets and electric fields at LaAlO3/SrTiO3(001) heterojunctions with variable La:Al atom ratio

    SciTech Connect (OSTI)

    Qiao, Liang; Droubay, Timothy C.; Kaspar, Tiffany C.; Sushko, P. V.; Chambers, Scott A.

    2011-08-01

    Interfacial intermixing and electronic structure were investigated at thin (35 unit cells.), epitaxial La1 ? xAl1 + xO3/SrTiO3(001) heterojunctions for x = 0 and 0.05. Angle-resolved X-ray photoelectron spectroscopy reveals rather extensive cation intermixing for all films, independent of composition. The valence band offset for the nominally stoichiometric (x = 0) film is 0.16 0.10 eV, with the valence band maximum of SrTiO3 being deeper in binding energy than that of LaAlO3. Similar values are obtained for x = 0.05. There is no measurable band bending in either the LaAlO3 or the SrTiO3 near the interface. These results are at odds with first principles theoretical predictions based on perfect stoichiometry and an abrupt interface model. However, inclusion of intermixing in the compositional description of the interface results in successful prediction of the valence band offset and absence of band bending.

  2. The impacts of cation stoichiometry and substrate surface quality on nucleation, structure, defect formation, and intermixing in complex oxide heteroepitaxy LaCrO3 on SrTiO3(001)

    SciTech Connect (OSTI)

    Qiao, Liang; Zhang, K. H. L; Bowden, Mark E; Varga, Tamas; Shutthanandan, Vaithiyalingam; Colby, Robert; Du, Yingge; Kabius, Bernd; Sushko, Peter V; Biegalski, Michael D; Chambers, S. A.

    2013-01-01

    Our ability to design and fabricate electronic devices with reproducible properties using complex oxides is critically dependent on our ability to controllably synthesize these materials in thin-film form. Structure-property relationships are intimately tied to film and interface composition Here we report on the effect of cation stoichiometry on structural quality and defect formation in LaCrO3 heteroepitaxial films prepared using molecular beam epitaxy. We calculate from first principles the regions of stability of various candidate defects as a function of Cr and O chemical potential, along with the predicted effects of these defects on structural parameters. We show that epitaxial LaCrO3 films readily nucleate and remain coherently strained on SrTiO3(001) over a wide range of La-to-Cr atom ratios, but that La-rich films are of considerably lower structural quality than stoichiometric and Cr-rich films. Cation imbalances are accompanied by anti-site defect formation, as deduced by comparing experimental trends in the c lattice parameter with those from first-principles calculations. Cation mixing occurs at the interface for all La-to-Cr ratios investigated, and is not quenched by deposition on SrTiO3(001) at ambient temperature. Indiffused La atoms occupy Sr sites, most likely facilitated by Sr vacancy formation in STO resulting from high-temperature oxygen annealing required to prepare the substrate. Intermixing is effectively quenched by using molecular beam epitaxy to deposit LaCrO3 at ambient temperature on defect free Si(001). However, analogous pulsed laser deposition on Si is accompanied by cation mixing.

  3. Nanoscale Phase Separation, Cation Ordering, and Surface Oxygen Chemistry in Pristine Li1.2Ni0.2Mn0.6O2 for Li-Ion Batteries

    SciTech Connect (OSTI)

    Gu, Meng; Genc, Arda; Belharouak, Ilias; Wang, Dapeng; Amine, Khalil; Thevuthasan, Suntharampillai; Baer, Donald R.; Zhang, Jiguang; Browning, Nigel D.; Liu, Jun; Wang, Chong M.

    2013-05-14

    Li-rich layered material Li1.2Ni0.2Mn0.6O2 possesses high voltage and high specific capacity, which makes it an attractive candidate for the transportation industry and sustainable energy storage systems. The rechargeable capacity of the Li-ion battery is linked largely to the structural stability of the cathode materials during the charge-discharge cycles. However, the structure and cation distribution in pristine (un-cycled) Li1.2Ni0.2Mn0.6O2 have not yet been fully characterized. Using a combination of aberration-corrected scanning/transmission electron microscopy, X-ray dispersive energy spectroscopy (XEDS), electron energy loss spectroscopy (EELS), and complementary multislice image simulation, we have probed the crystal structure, cation/anion distribution, and electronic structure of Li1.2Ni0.2Mn0.6O2 nanoparticle. We discovered that the electronic structure and valence state of transition metal ions show significant variations, which have been identified to be attributed to the oxygen deficiency near the particle surfaces. Characterization of the nanoscale phase separation and cation ordering in the pristine material are critical for understanding the capacity and voltage fading of this material for battery application.

  4. Magnetic moment directions and distributions of cations in Cr (Co) substituted spinel ferrites Ni{sub 0.7}Fe{sub 2.3}O{sub 4}

    SciTech Connect (OSTI)

    Xue, L. C.; Lang, L. L.; Li, Z. Z.; Qi, W. H.; Tang, G. D. Wu, L. Q.; Xu, J.

    2015-09-15

    Powder samples of the spinel ferrites M{sub x}Ni{sub 0.7−x}Fe{sub 2.3}O{sub 4} (M = Cr, Co and 0.0 ≤ x ≤ 0.3) and Cr{sub x}Ni{sub 0.7}Fe{sub 2.3−x}O{sub 4} (0.0 ≤ x ≤ 0.3) were synthesized using the chemical co-precipitation method. The XRD spectra confirmed that the samples had a single-phase cubic spinel structure. Magnetic measurements showed that the magnetic moments (μ{sub exp}) per formula both at 10 K and 300 K increased with Co substitution, while the values of μ{sub exp} decreased with Cr substitution. Applying the assumption that the magnetic moments of Cr{sup 2+} and Cr{sup 3+} lie antiparallel to those of the divalent and trivalent Fe, Co, and Ni cations in the same sublattice of spinel ferrites, these interesting behaviors could be easily interpreted. The cation distributions of the three series of samples were estimated successfully by fitting the dependences of μ{sub exp}, measured at 10 K, on the doping level x, using a quantum-mechanical potential barrier model earlier proposed by our group. The results obtained for the Cr cation distributions at the (A) and [B] sites are very close to those obtained elsewhere using neutron diffraction.

  5. inner-sphere complexation of cations at the rutile-water interface: A concise surface structural interpretation with the CD and MUSIC model

    SciTech Connect (OSTI)

    Ridley, Mora K.; Hiemstra, T; Van Riemsdijk, Willem H.; Machesky, Michael L.

    2009-01-01

    Acid base reactivity and ion-interaction between mineral surfaces and aqueous solutions is most frequently investigated at the macroscopic scale as a function of pH. Experimental data are then rationalized by a variety of surface complexation models. These models are thermodynamically based which in principle does not require a molecular picture. The models are typically calibrated to relatively simple solid-electrolyte solution pairs and may provide poor descriptions of complex multicomponent mineral aqueous solutions, including those found in natural environments. Surface complexation models may be improved by incorporating molecular-scale surface structural information to constrain the modeling efforts. Here, we apply a concise, molecularly-constrained surface complexation model to a diverse suite of surface titration data for rutile and thereby begin to address the complexity of multi-component systems. Primary surface charging curves in NaCl, KCl, and RbCl electrolyte media were fit simultaneously using a charge distribution (CD) and multisite complexation (MUSIC) model [Hiemstra T. and Van Riemsdijk W. H. (1996) A surface structural approach to ion adsorption: the charge distribution (CD) model. J. Colloid Interf. Sci. 179, 488 508], coupled with a Basic Stern layer description of the electric double layer. In addition, data for the specific interaction of Ca2+ and Sr2+ with rutile, in NaCl and RbCl media, were modeled. In recent developments, spectroscopy, quantum calculations, and molecular simulations have shown that electrolyte and divalent cations are principally adsorbed in various inner-sphere configurations on the rutile 110 surface [Zhang Z., Fenter P., Cheng L., Sturchio N. C., Bedzyk M. J., Pr edota M., Bandura A., Kubicki J., Lvov S. N., Cummings P. T., Chialvo A. A., Ridley M. K., Be ne zeth P., Anovitz L., Palmer D. A., Machesky M. L. and Wesolowski D. J. (2004) Ion adsorption at the rutile water interface: linking molecular and macroscopic

  6. Does fluoride disrupt hydrogen bond network in cationic lipid bilayer? Time-dependent fluorescence shift of Laurdan and molecular dynamics simulations

    SciTech Connect (OSTI)

    Pokorna, Sarka; Jurkiewicz, Piotr; Hof, Martin; Vazdar, Mario; Cwiklik, Lukasz; Jungwirth, Pavel

    2014-12-14

    Time-dependent fluorescence shift (TDFS) of Laurdan embedded in phospholipid bilayers reports on hydration and mobility of the phospholipid acylgroups. Exchange of H{sub 2}O with D{sub 2}O prolongs the lifetime of lipid-water and lipid-water-lipid interactions, which is reflected in a significantly slower TDFS kinetics. Combining TDFS measurements in H{sub 2}O and D{sub 2}O hydrated bilayers with atomistic molecular dynamics (MD) simulations provides a unique tool for characterization of the hydrogen bonding at the acylgroup level of lipid bilayers. In this work, we use this approach to study the influence of fluoride anions on the properties of cationic bilayers composed of trimethylammonium-propane (DOTAP). The results obtained for DOTAP are confronted with those for neutral phosphatidylcholine (DOPC) bilayers. Both in DOTAP and DOPC H{sub 2}O/D{sub 2}O exchange prolongs hydrogen-bonding lifetime and does not disturb bilayer structure. These results are confirmed by MD simulations. TDFS experiments show, however, that for DOTAP this effect is cancelled in the presence of fluoride ions. We interpret these results as evidence that strongly hydrated fluoride is able to steal water molecules that bridge lipid carbonyls. Consequently, when attracted to DOTAP bilayer, fluoride disrupts the local hydrogen-bonding network, and the differences in TDFS kinetics between H{sub 2}O and D{sub 2}O hydrated bilayers are no longer observed. A distinct behavior of fluoride is also evidenced by MD simulations, which show different lipid-ion binding for Cl{sup −} and F{sup −}.

  7. Unraveling the Voltage-Fade Mechanism in High-Energy-Density Lithium-Ion Batteries: Origin of the Tetrahedral Cations for Spinel Conversion

    SciTech Connect (OSTI)

    Mohanty, Debasish; Li, Jianlin; Abraham, Daniel P.; Huq, Ashfia; Payzant, E. Andrew; Wood, David L.; Daniel, Claus

    2014-09-30

    Discovery of high-voltage layered lithium-and manganese-rich (LMR) composite oxide electrode has dramatically enhanced the energy density of current Li-ion energy storage systems. However, practical usage of these materials is currently not viable because of their inability to maintain a consistent voltage profile (voltage fading) during subsequent charge-discharge cycles. This report rationalizes the cause of this voltage fade by providing the evidence of layer to spinel-like (LSL) structural evolution pathways in the host Li1.2Mn0.55Ni0.15Co0.1O2 LMR composite oxide. By employing neutron powder diffraction, and temperature dependent magnetic susceptibility, we show that LSL structural rearrangement in LMR oxide occurs through a tetrahedral cation intermediate via: i) diffusion of lithium atoms from octahedral to tetrahedral sites of the lithium layer [(LiLioct →LiLitet] which is followed by the dispersal of the lithium ions from the adjacent octahedral site of the metal layer to the tetrahedral sites of lithium layer [LiTM oct → LiLitet]; and ii) migration of Mn from the octahedral sites of the transition metal layer to the permanent octahedral site of lithium layer via tetrahedral site of lithium layer [MnTMoct MnLitet MnLioct)]. The findings opens the door to the potential routes to mitigate this atomic restructuring in the high-voltage LMR composite oxide cathodes by manipulating the composition/structure for practical use in high-energy-density lithium-ion batteries.

  8. High cation transport polymer electrolyte

    DOE Patents [OSTI]

    Gerald, II, Rex E.; Rathke, Jerome W.; Klingler, Robert J.

    2007-06-05

    A solid state ion conducting electrolyte and a battery incorporating same. The electrolyte includes a polymer matrix with an alkali metal salt dissolved therein, the salt having an anion with a long or branched chain having not less than 5 carbon or silicon atoms therein. The polymer is preferably a polyether and the salt anion is preferably an alkyl or silyl moiety of from 5 to about 150 carbon/silicon atoms.

  9. Four homochiral coordination polymers contain N-acetyl-L-tyrosine and different N-donor ligand: Influence of metal cations, ancillary ligands and coordination modes

    SciTech Connect (OSTI)

    Li, Meng-Li; Song, Hui-Hua

    2013-10-15

    Using the chiral ligand N-acetyl-L-tyrosine (Hacty) and maintaining identical reaction conditions, Zn(II), Co(II), and Cd(II) salts provided four novel homochiral coordination polymers ([Zn(acty)(bipy){sub 2}(H{sub 2}O){sub 2}]NO{sub 3}2H{sub 2}O){sub n}1, ([Co(acty)(bipy){sub 2}(H{sub 2}O){sub 2}]NO{sub 3}2H{sub 2}O){sub n}2, ([Cd(acty){sub 2}(bipy)H{sub 2}O]H{sub 2}O){sub n}3, and ([Cd(acty)(bpe){sub 2}(Ac)]6H{sub 2}O){sub n}4 (bipy=4,4?-bipyridine; bpe=1,2-di(4-pyridyl)ethane) in the presence of ancillary ligands. Compounds 1 and 2 are isostructural 1D chain structures. The neighboring chains are further linked into a 3D supramolecular structure via ??? stacking and hydrogen bond interactions. Compound 3 shows a 2D network and 4 generates 1D infinite chains along the c-axis. Compounds 3 and 4 are further connected into 3D supramolecular network by hydrogen bond interactions. More importantly, coordination in acyl oxygen atoms and ancillary ligands (bpe) as monodentate decorating ligands in 4 are rarely reported. Ancillary ligands and metal cations significantly influence the structure of the complexes. The photoluminescence properties of 1, 3, and 4 were studied at room temperature. Circular dichroism (CD) of the complexes have been investigated. - Graphical abstract: Four new homochiral coordination polymers were prepared and structurally characterized, which investigate the influence of the ancillary ligands and metal ions on the design and synthesis of coordination polymers. Display Omitted - Highlights: It is rarely reported that the chiral coordination polymers prepared with N-acetyl-L-tyrosine ligands. The alkalescent acetyl oxygen atom is difficult to participate in coordination but it is happened in the N-acetyl-L-tyrosine ligands. The ancillary ligands (4,4?-bipy and bpe) are present in an unusual coordination modes, monodentate decorating ligands in 1, 2 and 4. Structure comparative analyses results indicate that the secondary ligands and

  10. Electronic and Electrochemical Properties of Li 1–x Mn 1.5 Ni 0.5 O 4 Spinel Cathodes As a Function of Lithium Content and Cation Ordering

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

    Moorhead-Rosenberg, Zach; Huq, Ashfia; Goodenough, John B.; Manthiram, Arumugam

    2015-10-05

    The electronic and electrochemical properties of the high-voltage spinel LiMn1.5Ni0.5O4 as a function of cation ordering and lithium content have been investigated. Conductivity and activation energy measurements confirm that charge transfer occurs by small polaron hopping and the charge carrier conduction is easier in the Ni:3d band than in the in Mn:3d band. Seebeck coefficient data reveal that the Ni2+/3+. and Ni3+/4+ redox couples are combined in a single,3d band, and that maximum charge carrier concentration occurs where the average Ni oxidation state is close to 3+, corresponding to x = 0.5 in Li Li1-xMn1.5Ni0.5O4. Furthermore, maximum electronic conductivity ismore » found at x = 0.5, regardless of cation ordering. The thermodynamically stable phases formed during cycling were investigated by recording the X-ray diffraction (XRD) of chemically delithiated powders. The more ordered spinels maintained two separate two-phase regions upon lithium extraction, while the more disordered samples exhibited a solid-solubility region from LiMn1.5Ni0.5O4 to Li0.5Mn1.5Ni0.5O4. The conductivity and phase-transformation data of four samples with varying degrees of cation ordering were compared to the electrochemical data collected with lithium cells. Only the most ordered spinel showed inferior rate performance, while the sample annealed for a shorter time performed comparable to the unannealed or disordered samples. Our results challenge the most common beliefs about high-voltage spinel: (i) low Mn3+ content is responsible for poor rate performance and (ii) thermodynamically stable solid-solubility is critical for fast kinetics.« less

  11. Cation disorder and phase transitions in the four-layer ferroelectric Aurivillius phases ABi{sub 4}Ti{sub 4}O{sub 15} (A=Ca, Sr, Ba, Pb)

    SciTech Connect (OSTI)

    Kennedy, Brendan J. Zhou Qingdi; Ismunandar; Kubota, Yoshika; Kato, Kenichi

    2008-06-15

    Crystal structures of a series of bi-layered compounds ABi{sub 4}Ti{sub 4}O{sub 15} (A=Ca, Sr, Ba, Pb) have been investigated using a combination of synchrotron X-ray and neutron powder diffraction data. All four oxides adopt an orthorhombic structure at room temperature and the structures have been refined in space group A2{sub 1}am. This orthorhombic structure is a consequence of a combination of rotation of the TiO{sub 6}, resulting from the less than optimal size of the A-type cation, and displacement of the Ti atoms towards the Bi{sub 2}O{sub 2} layers. There is partial disorder of the Bi and A-type cations over two of the three available sites, which increases in the order Ca

  12. Systematic approach for simultaneously correcting the band-gap andp-dseparation errors of common cation III-V or II-VI binaries in density functional theory calculations within a local density approximation

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

    Wang, Jianwei; Zhang, Yong; Wang, Lin-Wang

    2015-07-31

    We propose a systematic approach that can empirically correct three major errors typically found in a density functional theory (DFT) calculation within the local density approximation (LDA) simultaneously for a set of common cation binary semiconductors, such as III-V compounds, (Ga or In)X with X = N,P,As,Sb, and II-VI compounds, (Zn or Cd)X, with X = O,S,Se,Te. By correcting (1) the binary band gaps at high-symmetry points , L, X, (2) the separation of p-and d-orbital-derived valence bands, and (3) conduction band effective masses to experimental values and doing so simultaneously for common cation binaries, the resulting DFT-LDA-based quasi-first-principles methodmore » can be used to predict the electronic structure of complex materials involving multiple binaries with comparable accuracy but much less computational cost than a GW level theory. This approach provides an efficient way to evaluate the electronic structures and other material properties of complex systems, much needed for material discovery and design.« less

  13. The Impacts of Cation Stoichiometry and Substrate Surface Quality on Nucleation, Structure, Defect Formation, and Intermixing in Complex Oxide HeteroepitaxyLaCrO3 on SrTiO3(001)

    SciTech Connect (OSTI)

    Qiao, Liang; Zhang, Hongliang; Bowden, Mark E.; Varga, Tamas; Shutthanandan, V.; Colby, Robert J.; Du, Yingge; Kabius, Bernd C.; Sushko, P. V.; Biegalski, Michael D.; Chambers, Scott A.

    2013-06-20

    Our ability to design and fabricate electronic devices with reproducible properties using complex oxides is critically dependent on our ability to controllably synthesize these materials in thin-film form. Structure-property relationships are intimately tied to film and interface composition. Here we report on the effects of cation stoichiometry in LaCrO3 heteroepitaxial films prepared using molecular beam epitaxy. We show that LaCrO3 films grow pseudomorphically on SrTiO3(001) over an wide range of La-to-Cr atom ratios. However, the growth mode and structural quality are sensitive to the La-to-Cr ratio, with La-rich films being of considerably lower structural quality than Cr-rich films. Cation mixing occurs at the interface for all La-to-Cr ratios investigated, and is not quenched by deposition at ambient temperature. Indiffused La atoms occupy Sr sites in the substrate. The presence of defects in the SrTiO3 substrate is implicated in promoting La indiffusion by comparing the properties of LaCrO3/SrTiO3 with those of LaCrO3/Si, both prepared at ambient temperature. Additionally, pulsed laser deposition is shown to result in more extensive interfacial mixing than molecular beam epitaxy for deposition at ambient temperature on Si.

  14. Hot Pot Geothermal Area | Open Energy Information

    Open Energy Info (EERE)

    of Replacement Wells: Average Temperature of Geofluid: Sanyal Classification (Wellhead): Reservoir Temp (Geothermometry): Reservoir Temp (Measured): Sanyal Classification...

  15. Tungsten Mountain Geothermal Area | Open Energy Information

    Open Energy Info (EERE)

    of Replacement Wells: Average Temperature of Geofluid: Sanyal Classification (Wellhead): Reservoir Temp (Geothermometry): Reservoir Temp (Measured): Sanyal Classification...

  16. McGuinness Hills Geothermal Area | Open Energy Information

    Open Energy Info (EERE)

    of Replacement Wells: Average Temperature of Geofluid: Sanyal Classification (Wellhead): Reservoir Temp (Geothermometry): Reservoir Temp (Measured): Sanyal Classification...

  17. Dixie Meadows Geothermal Area | Open Energy Information

    Open Energy Info (EERE)

    of Geofluid: Sanyal Classification (Wellhead): Reservoir Temp (Geothermometry): Reservoir Temp (Measured): Sanyal Classification (Reservoir): Depth to Top of Reservoir:...

  18. Jersey Valley Geothermal Area | Open Energy Information

    Open Energy Info (EERE)

    of Replacement Wells: Average Temperature of Geofluid: Sanyal Classification (Wellhead): Reservoir Temp (Geothermometry): Reservoir Temp (Measured): Sanyal Classification...

  19. Drum Mountain Geothermal Area | Open Energy Information

    Open Energy Info (EERE)

    of Geofluid: Sanyal Classification (Wellhead): Reservoir Temp (Geothermometry): Reservoir Temp (Measured): Sanyal Classification (Reservoir): Depth to Top of Reservoir:...

  20. EERE PowerPoint 97-2004 Template: Green Version

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    thermal expressions, analyze samples for chemical concentrations, use INL's geothermometry ... Results and Progress * Historical chemical analyses are generally valid to ...

  1. Hydroprobe | Open Energy Information

    Open Energy Info (EERE)

    Provided by Technique Lithology: StratigraphicStructural: Hydrological: Collection of ground water samples for geochemistry and geothermometry Thermal: Temperature measurements...

  2. Understanding chemical reactions of CO{sub 2} and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS{sub 2} in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

    SciTech Connect (OSTI)

    Cabao, M. Isabel, E-mail: isabelcabaco@ist.utl.pt [Departamento de Fsica, Instituto Superior Tcnico, UTL, Av. Rovisco Pais 1049-001 Lisboa (Portugal); Centro de Fsica Atmica da UL, Av. Prof. Gama Pinto 2, 1649-003 Lisboa (Portugal); Besnard, Marcel; Danten, Yann [GSM Institut des Sciences Molculaires, CNRS (UMR 5255), Universit de Bordeaux, 351, Cours de la Libration 33405 Talence Cedex (France); Chvez, Fabin Vaca [Centro de Fsica da Matria Condensada da UL, Av. Prof. Gama Pinto 2, 1694-003 Lisboa (Portugal); Pinaud, Nol [CESAMO Institut des Sciences Molculaires, CNRS (UMR 5255), Universit de Bordeaux, 351, Cours de la Libration 33405 Talence Cedex (France); Sebastio, Pedro J. [Departamento de Fsica, Instituto Superior Tcnico, UTL, Av. Rovisco Pais 1049-001 Lisboa (Portugal); Centro de Fsica da Matria Condensada da UL, Av. Prof. Gama Pinto 2, 1694-003 Lisboa (Portugal); Coutinho, Joo A. P. [CICECO, Departamento de Qumica, Universidade de Aveiro 3810-193 Aveiro (Portugal)

    2014-06-28

    NMR spectroscopy ({sup 1}H, {sup 13}C, {sup 15}N) shows that carbon disulfide reacts spontaneously with 1-butyl-1-methylpyrrolidinium acetate ([BmPyrro][Ac]) in the liquid phase. It is found that the acetate anions play an important role in conditioning chemical reactions with CS{sub 2} leading, via coupled complex reactions, to the degradation of this molecule to form thioacetate anion (CH{sub 3}COS{sup ?}), CO{sub 2}, OCS, and trithiocarbonate (CS{sub 3}{sup 2?}). In marked contrast, the cation does not lead to the formation of any adducts allowing to conclude that, at most, its role consists in assisting indirectly these reactions. The choice of the [BmPyrro]{sup +} cation in the present study allows disentangling the role of the anion and the cation in the reactions. As a consequence, the ensemble of results already reported on CS{sub 2}-[Bmim][Ac] (1), OCS-[Bmim][Ac] (2), and CO{sub 2}-[Bmim][Ac] (3) systems can be consistently rationalized. It is argued that in system (1) both anion and cation play a role. The CS{sub 2} reacts with the acetate anion leading to the formation of CH{sub 3}COS{sup ?}, CO{sub 2}, and OCS. After these reactions have proceeded the nascent CO{sub 2} and OCS interact with the cation to form imidazolium-carboxylate ([Bmim] CO{sub 2}) and imidazolium-thiocarboxylate ([Bmim] COS). The same scenario also applies to system (2). In contrast, in the CO{sub 2}-[Bmim] [Ac] system a concerted cooperative process between the cation, the anion, and the CO{sub 2} molecule takes place. A carbene issued from the cation reacts to form the [Bmim] CO{sub 2}, whereas the proton released by the ring interacts with the anion to produce acetic acid. In all these systems, the formation of adduct resulting from the reaction between the solute molecule and the carbene species originating from the cation is expected. However, this species was only observed in systems (2) and (3). The absence of such an adduct in system (1) has been theoretically investigated

  3. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    (2) electrons (2) elements (2) geothermal energy (2) geothermometers (2) ... are useful for estimating geothermal reservoir temperatures, though a ...

  4. Property:HydroInfo | Open Energy Information

    Open Energy Info (EERE)

    Multicomponent Geothermometers N Near Infrared Surveys O Oblique Aerial & Ground Visible Band & Thermographic Imaging Over Core Stress P Paleomagnetic Measurements...

  5. Electrochemical characterization of B-site cation-excess Pr2Ni0.75Cu0.25Ga0.05O4+δ cathode for IT-SOFCs

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

    Meng, Xiangwei; Lü, Shiquan; Liu, Shouxiu; Liu, Xiaoyan; Sui, Yingrui; Li, Xiuyan; Pang, Mingjun; Wang, Biao; Ji, Yuan; Hu, Michael Z.

    2015-06-15

    In this paper, the B-site cation-excess K2NiF4-type structure oxide, Pr2Ni0.75Cu0.25Ga0.05O4+δ (PNCG) is investigated as a cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). XRD result shows that PNCG cathode is chemically compatible with the electrolyte Gd0.1Ce0.9O2-δ (GDC) at 900 °C for 5 h. The PNCG material exhibits a semiconductor to metal transition around 425 °C. The thermal expansion coefficient (TEC) of the PNCG sample is 12.72×10-6 K-1 between 30 and 850 °C in air. The polarization resistance (Rp) of PNCG cathode on GDC electrolyte is 0.105, 0.197 and 0.300 Ω cm2 at 800, 750, 700 °C, respectively. A maximum powermore » density of 371 mW cm-2 is obtained at 800 °C for single-cell with 300 μm thick GDC electrolyte and PNCG cathode. Finally, the results of this study demonstrate that PNCG can be a promising cathode material for IT-SOFCs.« less

  6. Electrochemically influenced cation inter-diffusion and Co3O4 formation on La0.6Sr0.4CoO3 infiltrated into SOFC cathodes

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

    Song, Xueyan; Lee, Shiwoo; Chen, Yun; Gerdes, Kirk

    2015-06-18

    Nanosized LSC electrocatalyst was infiltrated into a porous scaffold cathode composed of Sm2O3-doped CeO2 (SDC) and La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) in a commercial button solid oxide fuel cell (SOFC). To understand the stability of cathodes infiltrated with LSC, the infiltrated composite cells were subjected to both electrochemical operating and thermal aging states at 750 °C for 1500 h. Nanostructure and local chemistry evolution of La0.6Sr0.4CoO3 (LSC) infiltrated cathodes upon operation and aging were investigated by transmission electron microscopy. After operation, the LSC remained a cubic perovskite, and the crystal grains exhibit comparable size to as-infiltrated LSC grains. Inter-diffusion of Fe from themore » LSCF to a Fe-incorporated LSC layer developed on the LSCF backbone. However, only sharp interfaces were observed between LSC and SDC backbone in the as-infiltrated cathode and such interfaces remain after operation. The infiltrated LSC on the SDC backbone also retains granular particle morphology. Furthermore, newly grown Co3O4 nanocrystals were found in the operated cathode. After thermal aging, on the other hand, cation inter-diffusion across the interfaces of the infiltrate particles and the cathode backbones is less than that from the operated cells. Lastly, the following hypothesis is proposed: Co3O4 forms on LSC arising from local charge balancing between cobalt and oxygen vacancies.« less

  7. Mutual neutralization of atomic rare-gas cations (Ne{sup +}, Ar{sup +}, Kr{sup +}, Xe{sup +}) with atomic halide anions (Cl{sup −}, Br{sup −}, I{sup −})

    SciTech Connect (OSTI)

    Shuman, Nicholas S.; Miller, Thomas M.; Viggiano, Albert A.; Johnsen, Rainer

    2014-01-28

    We report thermal rate coefficients for 12 reactions of rare gas cations (Ne{sup +}, Ar{sup +}, Kr{sup +}, Xe{sup +}) with halide anions (Cl{sup −}, Br{sup −}, I{sup −}), comprising both mutual neutralization (MN) and transfer ionization. No rate coefficients have been previously reported for these reactions; however, the development of the Variable Electron and Neutral Density Attachment Mass Spectrometry technique makes it possible to measure the difference of the rate coefficients for pairs of parallel reactions in a Flowing Afterglow-Langmuir Probe apparatus. Measurements of 18 such combinations of competing reaction pairs yield an over-determined data set from which a consistent set of rate coefficients of the 12 MN reactions can be deduced. Unlike rate coefficients of MN reactions involving at least one polyatomic ion, which vary by at most a factor of ∼3, those of the atom-atom reactions vary by at least a factor 60 depending on the species. It is found that the rate coefficients involving light rare-gas ions are larger than those for the heavier rare-gas ions, but the opposite trend is observed in the progression from Cl{sup −} to I{sup −}. The largest rate coefficient is 6.5 × 10{sup −8} cm{sup 3} s{sup −1} for Ne{sup +} with I{sup −}. Rate coefficients for Ar{sup +}, Kr{sup +}, and Xe{sup +} reacting with Br{sub 2}{sup −} are also reported.

  8. Cationic phospholipids: structure transfection activity relationships...

    Office of Scientific and Technical Information (OSTI)

    lipids, they form stable complexes (lipoplexes) with the polyanionic nucleic acids. ... MIXTURES; MOLECULAR STRUCTURE; NUCLEIC ACIDS; PHOSPHATES; PHOSPHOLIPIDS Word ...

  9. Cationic Phospholipids Forming Cubic Phases: Lipoplex Structure...

    Office of Scientific and Technical Information (OSTI)

    phase state is a factor that does not seem to correlate with transfection activity. ... our previous studies is that the critical factor in lipid-mediated transfection is the ...

  10. Opposite correlations between cation disordering and amorphization...

    Office of Scientific and Technical Information (OSTI)

    Authors: Uberuaga, Blas Pedro 1 ; Tang, Ming 1 ; Jiang, Chao 2 ; Valdez, James A. 1 ; Smith, Roger 3 ; Wang, Yongqiang 1 ; Sickafus, Kurt E. 4 + Show Author ...

  11. Cationic phospholipids: structure transfection activity relationships...

    Office of Scientific and Technical Information (OSTI)

    Sponsoring Org: USDOE Country of Publication: United States Language: ENGLISH Subject: 59 ... LIPIDS; MEMBRANES; MIXTURES; MOLECULAR STRUCTURE; NUCLEIC ACIDS; PHOSPHATES; ...

  12. RECOVERY OF TETRAVALENT CATIONS FROM AQUEOUS SOLUTIONS

    DOE Patents [OSTI]

    Moore, R.L.

    1958-05-01

    The recovery of plutonium, zirconium, and tetravalent cerium values from aqueous solutions is described. It consists of adding an alkyl phosphate to a nnineral acid aqueous solution containing the metal to be recovered, whereby a precipitate forms with the tetravalent values, and separating the precipitate from the solution. All alkyl phosphates, if water-soluble, are suitable for the process; however, monobutyl phosphate has been found best.

  13. Systematic approach for simultaneously correcting the band-gap andp-dseparation errors of common cation III-V or II-VI binaries in density functional theory calculations within a local density approximation

    SciTech Connect (OSTI)

    Wang, Jianwei; Zhang, Yong; Wang, Lin-Wang

    2015-07-31

    We propose a systematic approach that can empirically correct three major errors typically found in a density functional theory (DFT) calculation within the local density approximation (LDA) simultaneously for a set of common cation binary semiconductors, such as III-V compounds, (Ga or In)X with X = N,P,As,Sb, and II-VI compounds, (Zn or Cd)X, with X = O,S,Se,Te. By correcting (1) the binary band gaps at high-symmetry points , L, X, (2) the separation of p-and d-orbital-derived valence bands, and (3) conduction band effective masses to experimental values and doing so simultaneously for common cation binaries, the resulting DFT-LDA-based quasi-first-principles method can be used to predict the electronic structure of complex materials involving multiple binaries with comparable accuracy but much less computational cost than a GW level theory. This approach provides an efficient way to evaluate the electronic structures and other material properties of complex systems, much needed for material discovery and design.

  14. Reese River Geothermal Area | Open Energy Information

    Open Energy Info (EERE)

    Reservoir Temp (Geothermometry): Reservoir Temp (Measured): Sanyal Classification (Reservoir): Depth to Top of Reservoir: Depth to Bottom of Reservoir: Average Depth to...

  15. Isotopic Analysis- Fluid At Fenton Hill HDR Geothermal Area ...

    Open Energy Info (EERE)

    Interactions in the Fenton Hill, New Mexico, Hot Dry Rock Geothermal Systems I. Fluid Mixing and Chemical Geothermometry Additional References Retrieved from "http:...

  16. Compound and Elemental Analysis At Fenton Hill HDR Geothermal...

    Open Energy Info (EERE)

    Interactions in the Fenton Hill, New Mexico, Hot Dry Rock Geothermal Systems I. Fluid Mixing and Chemical Geothermometry Additional References Retrieved from "http:...

  17. Category:Geochemical Data Analysis | Open Energy Information

    Open Energy Info (EERE)

    category, out of 4 total. G Geochemical Data Analysis Geothermometry T Thermal Ion Dispersion Thermochronometry Retrieved from "http:en.openei.orgwindex.php?titleCategory:Ge...

  18. Deep Geothermal Reservoir Temperatures in the Eastern Snake River...

    Office of Scientific and Technical Information (OSTI)

    Geothermal Reservoir Temperatures in the Eastern Snake River Plain, Idaho using Multicomponent Geothermometry Citation Details In-Document Search Title: Deep Geothermal Reservoir ...

  19. Compound and Elemental Analysis At Blackfoot Reservoir Area ...

    Open Energy Info (EERE)

    References Amy Hutsinpiller, W. T. Parry (1985) Geochemistry And Geothermometry Of Spring Water From The Blackfoot Reservoir Region, Southeastern Idaho Additional References...

  20. Geology and Geothermal Potential of the Roosevelt Hot Springs...

    Open Energy Info (EERE)

    Field Mapping At Roosevelt Hot Springs Geothermal Area (Petersen, 1975) Geothermal Literature Review At Roosevelt Hot Springs Geothermal Area (Petersen, 1975) Geothermometry At...

  1. Property:ExplorationTimePerMetric | Open Energy Information

    Open Energy Info (EERE)

    Techniques Geothermal Literature Review Geothermometry Gravity Methods Gravity Techniques Ground Electromagnetic Techniques Groundwater Sampling H Hand-held X-Ray Fluorescence...

  2. Conceptual Geologic Model and Native State Model of the Roosevelt...

    Open Energy Info (EERE)

    (Faulder, 1991) Geothermometry At Roosevelt Hot Springs Geothermal Area (Faulder, 1991) Ground Gravity Survey At Roosevelt Hot Springs Geothermal Area (Faulder, 1991) Isotopic...

  3. David A. Wark | Inventors | GE Global Research

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

    By David Wark Alloys for Bond Coatings and Articles Incorporating the Same TitaniQ: A Titanium-in-Quartz Geothermometer Grain-Scale Permeabilities of Texturally Equilibrated, ...

  4. Geochemistry of the Wendel-Amedee Geothermal System-California...

    Open Energy Info (EERE)

    have been identified based on the concentrations of the conservative elements C1 and B, fluid enthalpies, and the application of chemical geothermometers. One is characterized by...

  5. Property:StratInfo | Open Energy Information

    Open Energy Info (EERE)

    Microhole Array Multicomponent Geothermometers N Near Infrared Surveys O Oblique Aerial & Ground Visible Band & Thermographic Imaging Observation Wells Over Core Stress P...

  6. Property:LithologyInfo | Open Energy Information

    Open Energy Info (EERE)

    Geothermometers N Near Infrared Surveys Numerical Modeling O Oblique Aerial & Ground Visible Band & Thermographic Imaging Observation Wells Over Core Stress P PSInSAR...

  7. Electrochemical characterization of B-site cation-excess Pr2Ni0.75Cu0.25Ga0.05O4+δ cathode for IT-SOFCs

    SciTech Connect (OSTI)

    Meng, Xiangwei; Lü, Shiquan; Liu, Shouxiu; Liu, Xiaoyan; Sui, Yingrui; Li, Xiuyan; Pang, Mingjun; Wang, Biao; Ji, Yuan; Hu, Michael Z.

    2015-06-15

    In this paper, the B-site cation-excess K2NiF4-type structure oxide, Pr2Ni0.75Cu0.25Ga0.05O4+δ (PNCG) is investigated as a cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). XRD result shows that PNCG cathode is chemically compatible with the electrolyte Gd0.1Ce0.9O2-δ (GDC) at 900 °C for 5 h. The PNCG material exhibits a semiconductor to metal transition around 425 °C. The thermal expansion coefficient (TEC) of the PNCG sample is 12.72×10-6 K-1 between 30 and 850 °C in air. The polarization resistance (Rp) of PNCG cathode on GDC electrolyte is 0.105, 0.197 and 0.300 Ω cm2 at 800, 750, 700 °C, respectively. A maximum power density of 371 mW cm-2 is obtained at 800 °C for single-cell with 300 μm thick GDC electrolyte and PNCG cathode. Finally, the results of this study demonstrate that PNCG can be a promising cathode material for IT-SOFCs.

  8. Hydrophobic Moiety of Cationic Lipids Strongly Modulates Their...

    Office of Scientific and Technical Information (OSTI)

    In view of the important role that electrostatic interactions with the polyanionic nucleic ... LECITHINS; LIPIDS; MEMBRANES; NUCLEIC ACIDS; STRUCTURE-ACTIVITY RELATIONSHIPS; ...

  9. Novel Fluorescent Cationic Phospholipid, O-4-Napthylimido-1-Butyl...

    Office of Scientific and Technical Information (OSTI)

    Language: ENGLISH Subject: 59 BASIC BIOLOGICAL SCIENCES; 60 APPLIED LIFE SCIENCES; ANHYDRIDES; CARDIOLIPIN; DNA; ENCAPSULATION; HYDRATION; LECITHINS; LIPIDS; MIXTURES; MORPHOLOGY...

  10. ENERGY COMMISSION APPL.lCATION FOR SOURCE MATERIAL LICENSE

    Office of Legacy Management (LM)

    ... MATERIAL LICENSE . Pursuant to the Atomic Energy Act of 1954, and Title 10, Code of ... specified in Section 183 of the Atotic Energy Act of 1954 and is subject to all ...

  11. Pore-size-distribution of cationic polyacrylamide hydrogels. Progress report

    SciTech Connect (OSTI)

    Kremer, M.; Prausnitz, J.M.

    1992-06-01

    The pore size distribution of a AAm/MAPTAC (acrylamide copolymerized with (3-methacrylamidopropyl)trimethylammonium chloride) hydrogel was investigated using Kuga`s mixed-solute-exclusion method, taking into account the wall effect. A Brownian-motion model is also used. Results show the feasibility of determining pore-size distribution of porous materials using the mixed-solute-exclusion method in conjunction with solution of the Fredholm equation; good agreement was obtained with experiment, even for bimodal pore structures. However, different pore size distributions were calculated for the two different probe-solutes (Dextran and poly(ethylene glycol/oxide)). Future work is outlined. 32 figs, 25 refs.

  12. Pore-size-distribution of cationic polyacrylamide hydrogels

    SciTech Connect (OSTI)

    Kremer, M.; Prausnitz, J.M.

    1992-06-01

    The pore size distribution of a AAm/MAPTAC (acrylamide copolymerized with (3-methacrylamidopropyl)trimethylammonium chloride) hydrogel was investigated using Kuga's mixed-solute-exclusion method, taking into account the wall effect. A Brownian-motion model is also used. Results show the feasibility of determining pore-size distribution of porous materials using the mixed-solute-exclusion method in conjunction with solution of the Fredholm equation; good agreement was obtained with experiment, even for bimodal pore structures. However, different pore size distributions were calculated for the two different probe-solutes (Dextran and poly(ethylene glycol/oxide)). Future work is outlined. 32 figs, 25 refs.

  13. PHOTODISSOCIATION DYNAMICS OF METHYLAMINE CATION AND ITS RELEVANCE...

    Office of Scientific and Technical Information (OSTI)

    in Titan's ionosphere. Our experimental and theoretical observations show that hydrogen loss from CHsub 3NHsub 2 sup + has two channels: one giving rise to the triplet...

  14. Uncovering the roles of oxygen vacancies in cation migration...

    Office of Scientific and Technical Information (OSTI)

    Journal Name: Physical Chemistry Chemical Physics; Journal Volume: 16; Journal Issue: 16 Research Org: Oak Ridge National Laboratory (ORNL); Center for Nanophase Materials ...

  15. Characterization of Selective Binding of Alkali Cations with...

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

    x-rays, such as provided by the ALS. The team's measurements indicated carboxylate groups characteristic of proteins preferred sodium over potassium ions. These results lend...

  16. Predicting proton titration in cationic micelle and bilayer environments

    SciTech Connect (OSTI)

    Morrow, Brian H.; Shen, Jana K.; Eike, David M.; Murch, Bruce P.; Koenig, Peter H.

    2014-08-28

    Knowledge of the protonation behavior of pH-sensitive molecules in micelles and bilayers has significant implications in consumer product development and biomedical applications. However, the calculation of pK{sub a}s in such environments proves challenging using traditional structure-based calculations. Here we apply all-atom constant pH molecular dynamics with explicit ions and titratable water to calculate the pK{sub a} of a fatty acid molecule in a micelle of dodecyl trimethylammonium chloride and liquid as well as gel-phase bilayers of diethyl ester dimethylammonium chloride. Interestingly, the pK{sub a} of the fatty acid in the gel bilayer is 5.4, 0.4 units lower than that in the analogous liquid bilayer or micelle, despite the fact that the protonated carboxylic group is significantly more desolvated in the gel bilayer. This work illustrates the capability of all-atom constant pH molecular dynamics in capturing the delicate balance in the free energies of desolvation and Coulombic interactions. It also shows the importance of the explicit treatment of ions in sampling the protonation states. The ability to model dynamics of pH-responsive substrates in a bilayer environment is useful for improving fabric care products as well as our understanding of the side effects of anti-inflammatory drugs.

  17. Nitrogen-doped zirconia: A comparison with cation stabilized...

    Office of Scientific and Technical Information (OSTI)

    DOI: 10.1016j.jssc.2005.10.012; PII: S0022-4596(05)00462-7; Copyright (c) 2005 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: ...

  18. A proposal for positive cooperativity in anion-cation binding in yttrium and lutetium complexes based on o-amino-substituted phenolate ligands. On the way to coordination polymers by self-assembly. Molecular structures of [ClLu(OAr){sub 3}Na] (X-ray) and [ClY(OAr{prime}){sub 3}Y(OAr{prime}){sub 3}Na] (X-ray and {sup 89}Y-NMR)

    SciTech Connect (OSTI)

    Hogerheide, M.P.; Ringelberg, S.N.; Grove, D.M.

    1996-02-28

    The authors prepared the hetero(poly)metallic complexes [ClM(OAr){sub 3}Na] (M = Lu (3a), Y (3b)) and [ClY(OAr`){sub 3}Y(OAR`){sub 3}Na] (4) (OAr = OC{sub 6}H{sub 2}(CH{sub 2}NMe{sub 2}){sub 2}-2,6,Me-4; OAr` = OC{sub 6}H{sub 4}(CH{sub 2}NMe{sub 2})-2). Structural analysis was afforded by NMR spectroscopy and X-ray diffraction. The structures show evidence for anion-cation cooperativity in bonding and are discussed in detail for the compounds in both the solid state and in solution.

  19. Cationic disorder and Mn{sup 3+}/Mn{sup 4+} charge ordering in the B? and B? sites of Ca{sub 3}Mn{sub 2}NbO{sub 9} perovskite: a comparison with Ca{sub 3}Mn{sub 2}WO{sub 9}

    SciTech Connect (OSTI)

    Lpez, C.A.; Saleta, M.E.; Pedregosa, J.C.; Snchez, R.D.; Alonso, J.A.; and others

    2014-02-15

    We describe the preparation, crystal structure determination, magnetic and transport properties of two novel Mn-containing perovskites, with a different electronic configuration for Mn atoms located in B site. Ca{sub 3}Mn{sup 3+}{sub 2}WO{sub 9} and Ca{sub 3}Mn{sup 3+/4+}{sub 2}NbO{sub 9} were synthesized by standard ceramic procedures; the crystallographic structure was studied from X-ray powder diffraction (XRPD) and neutron powder diffraction (NPD). Both phases exhibit a monoclinic symmetry (S.G.: P2{sub 1}/n); Ca{sub 3}Mn{sub 2}WO{sub 9} presents a long-range ordering over the B sites, whereas Ca{sub 3}Mn{sub 2}NbO{sub 9} is strongly disordered. By in-situ NPD, the temperature evolution of the structure study presents an interesting evolution in the octahedral size (?MnO?) for Ca{sub 3}Mn{sub 2}NbO{sub 9}, driven by a charge ordering effect between Mn{sup 3+} and Mn{sup 4+} atoms, related to the anomaly observed in the transport measurements at T?160 K. Both materials present a magnetic order below T{sub C}=30 K and 40 K for W and Nb materials, respectively. The magneto-transport measurements display non-negligible magnetoresistance properties in the paramagnetic regime. - Graphical abstract: Comparison between the octahedron size and the magnetic behaviour for Ca{sub 3}Mn{sub 2}NbO{sub 9} in the temperature region where the charge and magnetic order occur. Display Omitted - Highlights: Two novel Mn-containing double perovskites were obtained by solid-state reactions. Both double perovskites are monoclinic (P2{sub 1}/n) determined by XRPD and NPD. Ca{sub 3}Mn{sub 2}WO{sub 9} contains Mn{sup 3+} while Ca{sub 3}Mn{sub 2}NbO{sub 9} includes mixed-valence cations Mn{sup 3+}/Mn{sup 4+}. Ca{sub 3}Mn{sub 2}NbO{sub 9} presents a charge-ordering effect between Mn{sup 3+} and Mn{sup 4+} evidenced by NPD. The magnetic and transport studies evidenced the charge ordering in Ca{sub 3}Mn{sub 2}NbO{sub 9}.

  20. Geochemistry and Isotopes of Fluids from Sulphur Springs, Valles...

    Open Energy Info (EERE)

    >Non-condensible gases consist of roughly 99% CO2 with minor amounts of H2S, H2, and CH4. Empirical gas geothermometry suggests a deep reservoir temperature of 215 to 280C....

  1. Trace Element Geochemical Zoning in the Roosevelt Hot Springs...

    Open Energy Info (EERE)

    this distribution may be a useful solid geothermometer. Authors O.D. Christensen, J.N. Moore and R.M. Capuano Conference GRC Annual Meeting; Salt Lake City, UT; 09091980...

  2. Chemistry Of Thermal And Nonthermal Springs In The Vicinity Of...

    Open Energy Info (EERE)

    depths. Thermal waters at Drakesbad and in Little Hot Springs Valley have neutral-pH, low-Cl concentrations and have estimated Na-K-Ca and Na-Li geothermometer temperatures...

  3. Charge trapping by anionic quinones electrostatically bound to a highly charged cationic quinone-viologen polymer or a cationic poly(3-viologen-thiophene)

    SciTech Connect (OSTI)

    Hable, C.T.; Crooks, R.M.; Valentine, J.R.; Giasson, R.; Wrighton, M.S. )

    1993-06-03

    Charge associated with quinone reduction is trapped at low pH in systems composed of sulfonated anthraquinones electrostatically bound to a polymer derived from a monomer consisting of a quinone unit flanked by two viologen units. Each monomer repeat unit carries 6 equiv of positive charge which can be charge compensated by monosulfonated anthraquinone to yield a quinone-viologen ratio of nearly 7:2. At low pH, electrostatic binding is persistent, and the amount of trapped charge is 90% of the theoretical maximum. Some of the electrostatically bound quinine can be replaced with Fe(CN)[sub 6][sup 3[minus

  4. Favorable Geochemistry from Springs and Wells in COlorado

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Zehner, Richard E.

    2012-02-01

    Citation Information: Originator: Geothermal Development Associates, Reno Nevada Originator: United States Geological Survey (USGS) Originator: Colorado Geological Survey Publication Date: 2012 Title: Favorable Geochemistry Edition: First Publication Information: Publication Place: Reno Nevada Publisher: Geothermal Development Associates, Reno, Nevada Description: This layer contains favorable geochemistry for high-temperature geothermal systems, as interpreted by Richard "Rick" Zehner. The data is compiled from the data obtained from the USGS. The original data set combines 15,622 samples collected in the State of Colorado from several sources including 1) the original Geotherm geochemical database, 2) USGS NWIS (National Water Information System), 3) Colorado Geological Survey geothermal sample data, and 4) original samples collected by R. Zehner at various sites during the 2011 field season. These samples are also available in a separate shapefile FlintWaterSamples.shp. Data from all samples were reportedly collected using standard water sampling protocols (filtering through 0.45 micron filter, etc.) Sample information was standardized to ppm (micrograms/liter) in spreadsheet columns. Commonly-used cation and silica geothermometer temperature estimates are included. Spatial Domain: Extent: Top: 4515595.841032 m Left: 149699.513964 m Right: 757959.309388 m Bottom: 4104156.435530 m Contact Information: Contact Organization: Geothermal Development Associates, Reno, Nevada Contact Person: Richard “Rick” Zehner Address: 3740 Barron Way City: Reno State: NV Postal Code: 89511 Country: USA Contact Telephone: 775-737-7806 Spatial Reference Information: Coordinate System: Universal Transverse Mercator (UTM) WGS’1984 Zone 13N False Easting: 500000.00000000 False Northing: 0.00000000 Central Meridian: -105.00000000 Scale Factor: 0.99960000 Latitude of Origin: 0.00000000 Linear Unit: Meter Datum: World Geodetic System 1984 (WGS ’1984) Prime Meridian: Greenwich

  5. Evaluation of cation-exchanged zeolite adsorbents for post-combustion carbon dioxide capture

    SciTech Connect (OSTI)

    Bae, TH; Hudson, MR; Mason, JA; Queen, WL; Dutton, JJ; Sumida, K; Micklash, KJ; Kaye, SS; Brown, CM; Long, JR

    2013-01-01

    A series of zeolite adsorbents has been evaluated for potential application in post-combustion CO2 capture using a new high-throughput gas adsorption instrument capable of measuring 28 samples in parallel. Among the zeolites tested, Ca-A exhibits the highest CO2 uptake (3.72 mmol g(-1) and 5.63 mmol cm(-3)) together with an excellent CO2 selectivity over N-2 under conditions relevant to capture from the dry flue gas stream of a coal-fired power plant. The large initial isosteric heat of adsorption of -58 kJ mol(-1) indicates the presence of strong interactions between CO2 and the Ca-A framework. Neutron and X-ray powder diffraction studies reveal the precise location of the adsorption sites for CO2 in Ca-A and Mg-A. A detailed study of CO2 adsorption kinetics further shows that the performance of Ca-A is not limited by slow CO2 diffusion within the pores. Significantly, Ca-A exhibited a higher volumetric CO2 uptake and CO2/N-2 selectivity than Mg-2(dobdc) (dobdc(4-) = 1,4-dioxido-2,5-benzenedicarboxylate; Mg-MOF-74, CPO-27-Mg), one of the best performing adsorbents. The exceptional performance of Ca-A was maintained in CO2 breakthrough simulations.

  6. Methods of producing sulfate salts of cations from heteroatomic compounds and dialkyl sulfates and uses thereof

    DOE Patents [OSTI]

    Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

    2015-09-29

    Methods of preparing sulfate salts of heteroatomic compounds using dialkyl sulfates as a primary reactant are disclosed. Also disclosed are methods of making ionic liquids from the sulfate salts of the heteroatomic compound, and electrochemical cells comprising the ionic liquids.

  7. How to stabilize highly active Cu+ cations in a mixed-oxide catalyst

    SciTech Connect (OSTI)

    Mudiyanselage, Kumudu; Luo, Si; Kim, Hyun You; Yang, Xiaofang; Baber, Ashleigh E.; Hoffmann, Friedrich M.; Senanayake, Sananayake; Rodriguez, Jose A.; Chen, Jingguang G.; Liu, Ping; Stacchiola, Dario J.

    2015-09-12

    Mixed-metal oxides exhibit novel properties that are not present in their isolated constituent metal oxides and play a significant role in heterogeneous catalysis. In this study, a titanium-copper mixed-oxide (TiCuOx) film has been synthesized on Cu(111) and characterized by complementary experimental and theoretical methods. At sub-monolayer coverages of titanium, a Cu2O-like phase coexists with TiCuOx and TiOx domains. When the mixed-oxide surface is exposed at elevated temperatures (600–650 K) to oxygen, the formation of a well-ordered TiCuOx film occurs. Stepwise oxidation of TiCuOx shows that the formation of the mixed-oxide is faster than that of pure Cu2O. As the Ti coverage increases, Ti-rich islands (TiOx) form. The adsorption of CO has been used to probe the exposed surface sites on the TiOx–CuOx system, indicating the existence of a new Cu+ adsorption site that is not present on Cu2O/Cu(111). Adsorption of CO on Cu+ sites of TiCuOx is thermally more stable than on Cu(111), Cu2O/Cu(111) or TiO2(110). The Cu+ sites in TiCuOx domains are stable under both reducing and oxidizing conditions whereas the Cu2O domains present on sub-monolayer loads of Ti can be reduced or oxidized under mild conditions. Furthermore, the results presented here demonstrate novel properties of TiCuOx films, which are not present on Cu(111), Cu2O/Cu(111), or TiO2(110), and highlight the importance of the preparation and characterization of well-defined mixed-metal oxides in order to understand fundamental processes that could guide the design of new materials.

  8. Microdomain Formation, Oxidation, and Cation Ordering in LaCa2Fe3O8+y

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

    Price, Patrick M.; Browning, Nigel D.; Butt, Darryl P.

    2015-03-23

    The compound LaCa2Fe3O8+y, also known as the Grenier phase, is known to undergo an order-disorder transformation (ODT) at high temperatures. Oxidation has been observed when the compound is cooled in air after the ODT. In this study, we have synthesized the Grenier compound in air using traditional solid state reactions and investigated the structure and composition before and after the ODT. Thermal analysis showed that the material undergoes an order-disorder transformation in both oxygen and argon atmospheres with dynamic, temperature dependent, oxidation upon cooling. Results from scanning transmission electron microscopy (STEM) suggest that the Grenier phase has preferential segregation ofmore »Ca and La on the two crystallographic A-sites before the ODT, but a random distribution above the ODT temperature. Furthermore, STEM images suggest the possibility that oxygen excess may exist in La-rich regions within microdomains rather than at microdomain boundaries.« less

  9. Electrochemical study of uranium cations in LiCl-KCl melt using a rotating disk electrode

    SciTech Connect (OSTI)

    Bae, Sang-Eun; Kim, Dae-Hyun; Kim, Jong-Yoon; Park, Tae-Hong; Cho, Young Hwan; Yeon, Jei-Won; Song, Kyuseok

    2013-07-01

    A rotating disk electrode (RDE) measurement technique was employed to investigate the electrochemical REDOX reactions of actinide (An) and lanthanide (Ln) ions in LiCl-KCl molten salt. By using RDE, it is possible to access more exact values of the diffusion coefficient, Tafel slope, and exchange current density. In this work, we constructed RDE setup and electrodes for RDE measurements in high temperature molten salt and measured the electrochemical parameters of the An and Ln ions. The RDE setup is composed of a Pine model MSRX rotator equipped with a rod type of W electrode. The active electrode area was confined to the planar part of the W rod by making meniscus at the LiCl-KCl melt surface.

  10. Observation of Radiolytic Field Alteration of the Uranyl Cation in Bicarbonate Solution

    SciTech Connect (OSTI)

    Snow, Lanee A.; McNamara, Bruce K.; Sinkov, Sergey I.; Cho, Herman M.; Friese, Judah I.

    2006-12-01

    In previous work we demonstrated that radiolysis of uranyl tris carbonate in near neutral pH to alkaline carbonate solutions, could be followed by 13C NMR. Radiolysis of the complex produced novel uranyl peroxo carbonate solution state species, whose structures depended on the pH and radiolytic dose rate. In this work, we investigate speciation of the uranyl carbonate trimer which is predominant in bicarbonate solution near pH 5.9. We observe radiolytically derived speciation to different mixed peroxy carbonate species than seen in the higher pH solutions. Auto radiolysis of uranium (VI) carbonate solutions between pH 5.9 and 7.2 is shown to alter the uranium speciation over relatively short periods of time and was followed by 13C NMR and visible spectrophotometry, using dissolved 233(UO2)3(CO3)6 6- both as the radiolysis source (D= 14.9 Gy/hr) and as a trap for the newly formed hydrogen peroxide. Direct addition of hydrogen peroxide to solutions of the uranyl-carbonate trimer is shown to reproduce the 13 C NMR signatures of the complexe(s) formed by radiolysis, but additionally a variety of new complexes are revealed. Ratios of H2O2/trimer < 1.5 produced a uranyl peroxo carbonate adduct, that is shown to be common to the radiolytically produced species. Ratios of H2O2/ trimer >1 resulted in formation of stable higher order peroxo carbonate complexes. The 13C NMR signatures and visible spectra of these complexes are described here. Rigorous characterization of the species is an ongoing effort.

  11. Lubricants or lubricant additives composed of ionic liquids containing ammonium cations

    DOE Patents [OSTI]

    Qu, Jun (Knoxville, TN) [Knoxville, TN; Truhan, Jr.,; John J. (Cookeville, TN) [Cookeville, TN; Dai, Sheng (Knoxville, TN) [Knoxville, TN; Luo, Huimin (Knoxville, TN) [Knoxville, TN; Blau, Peter J. (Knoxville, TN) [Knoxville, TN

    2010-07-13

    A lubricant or lubricant additive is an ionic liquid alkylammonium salt. The alkylammonium salt has the structure R.sub.xNH.sub.(4-x).sup.+,[F.sub.3C(CF.sub.2).sub.yS(O).sub.2].sub.2N.sup- .- where x is 1 to 3, R is independently C.sub.1 to C.sub.12 straight chain alkyl, branched chain alkyl, cycloalkyl, alkyl substituted cycloalkyl, cycloalkyl substituted alkyl, or, optionally, when x is greater than 1, two R groups comprise a cyclic structure including the nitrogen atom and 4 to 12 carbon atoms, and y is independently 0 to 11. The lubricant is effective for the lubrication of many surfaces including aluminum and ceramics surfaces.

  12. Electrochemical study of uranium cations in LiCl-KCl melt using...

    Office of Scientific and Technical Information (OSTI)

    Resource Relation: Conference: GLOBAL 2013: International Nuclear Fuel Cycle Conference - Nuclear Energy at a Crossroads, Salt Lake City, UT (United States), 29 Sep - 3 Oct 2013; ...

  13. How to stabilize highly active Cu+ cations in a mixed-oxide catalyst

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

    Mudiyanselage, Kumudu; Luo, Si; Kim, Hyun You; Yang, Xiaofang; Baber, Ashleigh E.; Hoffmann, Friedrich M.; Senanayake, Sananayake; Rodriguez, Jose A.; Chen, Jingguang G.; Liu, Ping; et al

    2015-09-12

    Mixed-metal oxides exhibit novel properties that are not present in their isolated constituent metal oxides and play a significant role in heterogeneous catalysis. In this study, a titanium-copper mixed-oxide (TiCuOx) film has been synthesized on Cu(111) and characterized by complementary experimental and theoretical methods. At sub-monolayer coverages of titanium, a Cu2O-like phase coexists with TiCuOx and TiOx domains. When the mixed-oxide surface is exposed at elevated temperatures (600–650 K) to oxygen, the formation of a well-ordered TiCuOx film occurs. Stepwise oxidation of TiCuOx shows that the formation of the mixed-oxide is faster than that of pure Cu2O. As the Timore » coverage increases, Ti-rich islands (TiOx) form. The adsorption of CO has been used to probe the exposed surface sites on the TiOx–CuOx system, indicating the existence of a new Cu+ adsorption site that is not present on Cu2O/Cu(111). Adsorption of CO on Cu+ sites of TiCuOx is thermally more stable than on Cu(111), Cu2O/Cu(111) or TiO2(110). The Cu+ sites in TiCuOx domains are stable under both reducing and oxidizing conditions whereas the Cu2O domains present on sub-monolayer loads of Ti can be reduced or oxidized under mild conditions. Furthermore, the results presented here demonstrate novel properties of TiCuOx films, which are not present on Cu(111), Cu2O/Cu(111), or TiO2(110), and highlight the importance of the preparation and characterization of well-defined mixed-metal oxides in order to understand fundamental processes that could guide the design of new materials.« less

  14. Protein binding studies of technetium-99m-labeled phosphine and isocyanide cationic complexes

    SciTech Connect (OSTI)

    Zanelli, G.D.; Cook, N.; Lahiri, A.; Ellison, D.; Webbon, P.; Woolley, G.

    1988-01-01

    Most /sup 99m/Tc/phosphine/isocyanide complexes synthesized to date show preferential uptake by the myocardium of many animal species but not in man. A new complex has been synthesized, (/sup 99m/Tc(DEPE)2(CNR)2), +(DEPIC), where R = t - butyl isocyanide, which in three animal species images the myocardium very well, but in humans it remains primarily in the blood pool. One reason for the difference in the behavior of these complexes in different species could be the characteristics of their binding to plasma proteins. The protein binding characteristics of DEPIC and two other well-known complexes have therefore been studied. Whereas the other complexes bind nonspecifically to many proteins both in animal and human plasma, DEPIC binds almost exclusively to prealbumin in humans but nonspecifically to other proteins in the rabbit. The binding sites in human plasma appear to be those normally occupied by thyroxine on the prealbumin tetramer and these can be blocked by sodium salicylate.

  15. PHOTODISSOCIATION DYNAMICS OF METHYLAMINE CATION AND ITS RELEVANCE TO TITAN'S IONOSPHERE

    SciTech Connect (OSTI)

    Singh, Prashant Chandra; Shen Lei; Zhou Jia; Schlegel, H. Bernhard; Suits, Arthur G.

    2010-02-10

    Photodissociation of CH{sub 3}NH{sub 2} {sup +} has been studied using the DC sliced ion imaging technique and ab initio calculations in order to understand the formation of HCNH{sup +}, an important molecule in Titan's ionosphere. Our experimental and theoretical observations show that hydrogen loss from CH{sub 3}NH{sub 2} {sup +} has two channels: one giving rise to the triplet species CH{sub 3}NH{sup +}, while the other product is CH{sub 2}NH{sub 2} {sup +}. The latter then decomposes further to form HCNH{sup +}. H{sub 2} loss from CH{sub 3}NH{sub 2} {sup +} has only one channel, yielding CH{sub 2}NH{sup +}. This species further loses H to form HCNH{sup +}. The branching ratio of the H, H{sub 2}, and H+H{sub 2} loss channels is found to be 4.2:1:2.5. This is ascribed to the fact that, at these energies, the H loss has one stable triplet product channel, while most of the H{sub 2} loss product further decomposes to HCNH{sup +}.

  16. Effect of A-site cation size mismatch on charge ordering behavior...

    Office of Scientific and Technical Information (OSTI)

    arrangements of Mnsup 3+ and Mnsup 4+ ions. copyright 2001 American Institute of Physics. ... OSTI Identifier: 40204399 Resource Type: Journal Article Resource Relation: ...

  17. Microdomain Formation, Oxidation, and Cation Ordering in LaCa2Fe3O8+y

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

    Price, Patrick M.; Browning, Nigel D.; Butt, Darryl P.

    2015-03-23

    The compound LaCa2Fe3O8+y, also known as the Grenier phase, is known to undergo an order-disorder transformation (ODT) at high temperatures. Oxidation has been observed when the compound is cooled in air after the ODT. In this study, we have synthesized the Grenier compound in air using traditional solid state reactions and investigated the structure and composition before and after the ODT. Thermal analysis showed that the material undergoes an order-disorder transformation in both oxygen and argon atmospheres with dynamic, temperature dependent, oxidation upon cooling. Results from scanning transmission electron microscopy (STEM) suggest that the Grenier phase has preferential segregation ofmore » Ca and La on the two crystallographic A-sites before the ODT, but a random distribution above the ODT temperature. Furthermore, STEM images suggest the possibility that oxygen excess may exist in La-rich regions within microdomains rather than at microdomain boundaries.« less

  18. Isotherms for Water Adsorption on Molecular Sieve 3A: Influence of Cation Composition

    SciTech Connect (OSTI)

    Lin, Ronghong; Ladshaw, Austin; Nan, Yue; Liu, Jiuxu; Yiacoumi, Sotira; Tsouris, Costas; DePaoli, David W.; Tavlarides, Lawrence L.

    2015-06-16

    This study is part of our continuing efforts to address engineering issues related to the removal of tritiated water from off-gases produced in used nuclear fuel reprocessing facilities. In the current study, adsorption equilibrium of water on molecular sieve 3A beads was investigated. Adsorption isotherms for water on the UOP molecular sieve 3A were measured by a continuous-flow adsorption system at 298, 313, 333, and 353 K. Experimental data collected were analyzed by the Generalized Statistical Thermodynamic Adsorption (GSTA) isotherm model. The K+/Na+ molar ratio of this particular type of molecular sieve 3A was ~4:6. Our results showed that the GSTA isotherm model worked very well to describe the equilibrium behavior of water adsorption on molecular sieve 3A. The optimum number of parameters for the current experimental data was determined to be a set of four equilibrium parameters. This result suggests that the adsorbent crystals contain four energetically distinct adsorption sites. In addition, it was found that water adsorption on molecular sieve 3A follows a three-stage adsorption process. This three-stage adsorption process confirmed different water adsorption sites in molecular sieve crystals. In addition, the second adsorption stage is significantly affected by the K+/Na+ molar ratio. In this stage, the equilibrium adsorption capacity at a given water vapor pressure increases as the K+/Na+ molar ratio increases.

  19. Isotherms for Water Adsorption on Molecular Sieve 3A: Influence of Cation Composition

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

    Lin, Ronghong; Ladshaw, Austin; Nan, Yue; Liu, Jiuxu; Yiacoumi, Sotira; Tsouris, Costas; DePaoli, David W.; Tavlarides, Lawrence L.

    2015-06-16

    This study is part of our continuing efforts to address engineering issues related to the removal of tritiated water from off-gases produced in used nuclear fuel reprocessing facilities. In the current study, adsorption equilibrium of water on molecular sieve 3A beads was investigated. Adsorption isotherms for water on the UOP molecular sieve 3A were measured by a continuous-flow adsorption system at 298, 313, 333, and 353 K. Experimental data collected were analyzed by the Generalized Statistical Thermodynamic Adsorption (GSTA) isotherm model. The K+/Na+ molar ratio of this particular type of molecular sieve 3A was ~4:6. Our results showed that themore » GSTA isotherm model worked very well to describe the equilibrium behavior of water adsorption on molecular sieve 3A. The optimum number of parameters for the current experimental data was determined to be a set of four equilibrium parameters. This result suggests that the adsorbent crystals contain four energetically distinct adsorption sites. In addition, it was found that water adsorption on molecular sieve 3A follows a three-stage adsorption process. This three-stage adsorption process confirmed different water adsorption sites in molecular sieve crystals. In addition, the second adsorption stage is significantly affected by the K+/Na+ molar ratio. In this stage, the equilibrium adsorption capacity at a given water vapor pressure increases as the K+/Na+ molar ratio increases.« less

  20. Cation and Vacancy Disorder in U1-yNdyO2.00-X Alloys

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

    Barabash, Rozaliya I.; Voit, Stewart L.; Aidhy, Dilpuneet S.; Lee, Seung Min; Knight, Travis W.; Sprouster, David J.; Ecker, Lynne E.

    2015-09-14

    In this study, the intermixing and clustering of U/Nd, O, and vacancies were studied by both laboratory and synchrotron-based x-ray diffraction in U1-yNdyO2-X alloys. It was found that an increased holding time at the high experimental temperature during initial alloy preparation results in a lower disorder of the Nd distribution in the alloys. Adjustment of the oxygen concentration in the U1-yNdyO2-X alloys with different Nd concentrations was accompanied by the formation of vacancies on the oxygen sublattice and a nanocrystalline component. The lattice parameters in the U1-yNdyO2-X alloys were also found to deviate significantly from Vegard's law when the Ndmore » concentration was high (53%) and decreased with increasing oxygen concentration. Such changes indicate the formation of large vacancy concentrations during oxygen adjustment at these high temperatures. Finally, the change in the vacancy concentration after the oxygen adjustment was estimated relative to Nd concentration and oxygen stoichiometry.« less

  1. Organo-Lewis acid as cocatalyst for cationic homogenous metallocene Ziegler-Natta olefin polymerizations

    DOE Patents [OSTI]

    Marks, Tobin J.; Chen, You-Xian

    2000-01-01

    The synthesis of the organo-Lewis acid perfluorobiphenylborane (PBB) and the activation of metallocenes for the formation of a variety of highly active homogeneous Ziegler-Natta metallocene olefin polymerization, copolymerization and ring-opening polymerization catalysts is described.

  2. New electrolyte systems for capillary zone electrophoresis of metal cations and non-ionic organic compounds

    SciTech Connect (OSTI)

    Shi, Y.

    1995-06-19

    Excellent separations of metal ions can be obtained very quickly by capillary electrophoresis provided a weak complexing reagent is incorporated into the electrolyte to alter the effective mobilities of the sample ions. Indirect photometric detection is possible by also adding a UV-sensitive ion to the electrolyte. Separations are described using phthalate, tartrate, lactate or hydroxyisobutyrate as the complexing reagent. A separation of twenty-seven metal ions was achieved in only 6 min using a lactate system. A mechanism for the separation of lanthanides is proposed for the hydroxyisobutyrate system.

  3. Mobility of singly-charged lanthanide cations in rare gases: Theoretical assessment of the state specificity

    SciTech Connect (OSTI)

    Buchachenko, Alexei A.; Viehland, Larry A.

    2014-03-21

    High quality, ab initio calculations are reported for the potential energy curves governing the interactions of four singly-charged lanthanide ions (Yb{sup +}, Eu{sup +}, Lu{sup +}, and Gd{sup +}) with the rare gases (RG = HeXe). Scalar-relativistic coupled cluster calculations are used for the first three S-state ions, but for Gd{sup +}({sup 10}D) it is necessary to take the interaction anisotropy into account with the help of the multi-reference technique. The potential energy curves are used to determine the ion mobility and other transport properties describing the motion of the ions through the dilute RG, both as functions of the temperature, T, in the low-field limit, and at fixed T as functions of the ratio of the electrostatic field strength to the gas number density, E/N. The calculated mobilities are in good agreement with the very limited experimental data that have become available recently. The calculations show a pronounced dependence of the transport properties on the electronic configuration of the ion, as well as a significant effect of the spin-orbit coupling on the transport properties of the Gd{sup +} ion, and predict that state-specific mobilities could be detectable in Gd{sup +}RG experiments.

  4. Tularosa Basin Play Fairway Analysis: Partial Basin and Range Heat and Zones of Critical Stress Maps

    SciTech Connect (OSTI)

    Adam Brandt

    2015-11-15

    Interpolated maps of heat flow, temperature gradient, and quartz geothermometers are included as TIF files. Zones of critical stress map is also included as a TIF file. The zones are given a 5km diameter buffer. The study area is only a part of the Basin and Range, but it does includes the Tularosa Basin.

  5. Tularosa Basin Play Fairway Analysis: Water Chemistry

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Adam Brandt

    2015-12-15

    This shapefile contains 409 well data points on Tularosa Basin Water Chemistry, each of which have a location (UTM), temperature, quartz and Potassium/Magnesium geothermometer; as well as concentrations of chemicals like Mn, Fe, Ba, Sr, Cs, Rb, As, NH4, HCO3, SO4, F, Cl, B, SiO2, Mg, Ca, K, Na, and Li.

  6. The radiation induced chemistry of uranyl cation in aqueous carbonate bicarbonate solutions as followed by NMR spectroscopy

    SciTech Connect (OSTI)

    McNamara, Bruce K.; Snow, Lanee A.; Soderquist, Chuck Z.; Sinkov, Sergei I.; Cho, Herman M.; Friese, Judah I.

    2006-05-01

    Alpha radiation induced formation of hydrogen peroxide in carbonate ?bicarbonate media was followed by 13C NMR using dissolved [233UO2(13CO3)3]4- as the alpha source (Dalpha= 12.1 Gy/hr). Between the pH region between 5.9 and 11.6 hydrogen peroxide causes a varied speciation of the uranyl carbonates that is a function of the uranium, carbonate and the hydrogen peroxide concentrations. It is shown that the speciation of the peroxy carbonates (or other species) formed in solution by titration with hydrogen peroxide are common to those formed by hydrogen peroxide generated by radiolysis. The radiolysis experiment was carried out above pH = 9.96 to minimize the loss of 13CO2 over a 2800 hr period. Radiolytic generation of hydrogen peroxide was followed by formation of a uranyl peroxy carbonate complex and complex formation accelerated for about 1200 hours. Complex formation was observed to terminate at a concentration between 1x10-4 and 5x10-4 M. It is assumed that either a steady state H2O2 production rate was established in solution or that some limiting feature of the experiment was responsible for slowing the yield of product.

  7. Molecular dynamics simulations and thermochemistry of reactive ion etching of silicon by chlorine, chlorine dimer, bromine, and bromine dimer cations

    SciTech Connect (OSTI)

    Valone, S.M.; Hanson, D.E.; Kress, J.D.

    1998-05-08

    Simulations of Cl plasma etch of Si surfaces with MD techniques agree reasonably well with the available experimental information on yields and surface morphologies. This information has been supplied to a Monte Carlo etch profile resulting in substantial agreement with comparable inputs provided through controlled experiments. To the extent that more recent measurements of etch rates are more reliable than older ones, preliminary MD simulations using bond-order corrections to the atomic interactions between neighboring Si atoms on the surface improves agreement with experiment through an increase in etch rate and improved agreement with XPS measurements of surface stoichiometry. Thermochemical and geometric analysis of small Si-Br molecules is consistent with the current notions of the effects of including brominated species in etchant gases.

  8. Water-Chemistry Evolution and Modeling of Radionuclide Sorption and Cation Exchange during Inundation of Frenchman Flat Playa

    SciTech Connect (OSTI)

    Hershey, Ronald; Cablk, Mary; LeFebre, Karen; Fenstermaker, Lynn; Decker, David

    2013-08-01

    Atmospheric tests and other experiments with nuclear materials were conducted on the Frenchman Flat playa at the Nevada National Security Site, Nye County, Nevada; residual radionuclides are known to exist in Frenchman Flat playa soils. Although the playa is typically dry, extended periods of winter precipitation or large single-event rainstorms can inundate the playa. When Frenchman Flat playa is inundated, residual radionuclides on the typically dry playa surface may become submerged, allowing water-soil interactions that could provide a mechanism for transport of radionuclides away from known areas of contamination. The potential for radionuclide transport by occasional inundation of the Frenchman Flat playa was examined using geographic information systems and satellite imagery to delineate the timing and areal extent of inundation; collecting water samples during inundation and analyzing them for chemical and isotopic content; characterizing suspended/precipitated materials and archived soil samples; modeling water-soil geochemical reactions; and modeling the mobility of select radionuclides under aqueous conditions. The physical transport of radionuclides by water was not evaluated in this study. Frenchman Flat playa was inundated with precipitation during two consecutive winters in 2009-2010 and 2010-2011. Inundation allowed for collection of multiple water samples through time as the areal extent of inundation changed and ultimately receded. During these two winters, precipitation records from a weather station in Frenchman Flat (Well 5b) provided information that was used in combination with geographic information systems, Landsat imagery, and image processing techniques to identify and quantify the areal extent of inundation. After inundation, water on the playa disappeared quickly, for example, between January 25, 2011 and February 10, 2011, a period of 16 days, 92 percent of the areal extent of inundation receded (2,062,800 m2). Water sampling provided valuable information about chemical processes occurring during inundation as the water disappeared. Important observations from water-chemistry analyses included: 1) total dissolved solids (TDS) and chloride ion (Cl-) concentrations were very low (TDS: < 200 mg/L and Cl-: < 3.0 mg/L, respectively) for all water samples regardless of time or areal extent; 2) all dissolved constituents were at concentrations well below what might be expected for evaporating shallow surface waters on a playa, even when 98 to 99 percent of the water had disappeared; 3) the amount of evaporation for the last water samples collected at the end of inundation, estimated with the stable isotopic ratios δ2H or δ18O, was approximately 60 percent; and 4) water samples analyzed by gamma spectroscopy did not show any man-made radioactivity; however, the short scanning time (24 hours) and relative chemical diluteness of the water samples (TDS ranged between 39 and 190 mg/L) may have contributed to none being detected. Additionally, any low-energy beta emitting radionuclides would not have been detected by gamma spectroscopy. From these observations, it was apparent that a significant portion of water on the playa did not evaporate, but rather infiltrated into the subsurface (approximately 40 percent). Consistent with this water chemistry-based conclusion is particle-size analysis of two archived Frenchman Flat playa soils samples, which showed low clay content in the near surface soil that also suggested infiltration. Infiltration of water from the playa during inundation into the subsurface does not necessarily imply that groundwater recharge is occurring, but it does provide a mechanism for moving residual radionuclides downward into the subsurface of Frenchman Flat playa. Water-mineral geochemical reactions were modeled so that changes in the water chemistry could be identified and the extent of reactions quantified. Geochemical modeling showed that evaporation; equilibrium with atmospheric carbon dioxide and calcite; dissolution of sodium chloride, gypsum, and composite volcanic glass; and precipitation of composite clay and quartz represented changes in water as it disappeared from the playa. This modeling provided an understanding of the water-soil geochemical environment, which was then used to evaluate the potential mobility of residual radionuclides into the playa soils by water. Because there is no information on the chemical forms of anthropogenic radionuclides in Frenchman Flat playa soil, it was assumed that soil radionuclides go into solution when the playa is inundated. In mobility modeling, a select group of radionuclides were allowed to sorb onto, or exchange with, playa soil minerals to evaluate the likelihood that the radionuclides would be removed from water during playa inundation. Radionuclide mobility modeling suggested that there would be minimal sorption or exchange of several important radionuclides (uranium, cesium, and technetium) with playa minerals such that they may be mobile in water when the playa is inundated and could infiltrate into the subsurface. Mobility modeling also showed that plutonium may be much less mobile because of sorption onto calcite, but the amount of reactive surface area of playa soil calcite is highly uncertain. Plutonium is also known to sorb onto colloidal particles suspended in water, suspended colloidal particles will move with the water, providing a mechanism to redistribute plutonium when Frenchman Flat playa is inundated. Water chemistry, stable isotopes, and geochemical modeling showed that residual radionuclides in Frenchman Flat playa soils could be mobilized in water when the playa is inundated with precipitation. Also, there is potential for these radionuclides to infiltrate into the subsurface with water. As a result of the information obtained both during this study and the conclusions drawn from it, additional data collection, investigation, and modeling are recommended. Specifically: sampling the playa soil to search for evidence of surface-water infiltration and the presence of radionuclides; developing a preliminary unsaturated flow and transport model to guide soil sampling; characterizing the chemical forms of radionuclides on the playa surface and any radionuclides that might have migrated into the subsurface; and, refining the unsaturated flow and transport model with data obtained from sampling and analysis of soil samples to guide any future sampling, development of remediation strategies, and defining risk-based boundaries for Frenchman Flat playa.

  9. The Preston Geothermal Resources; Renewed Interest in a Known Geothermal Resource Area

    SciTech Connect (OSTI)

    Wood, Thomas R.; Worthing, Wade; Cannon, Cody; Palmer, Carl; Neupane, Ghanashyam; McLing, Travis L; Mattson, Earl; Dobson, Patric; Conrad, Mark

    2015-01-01

    The Preston Geothermal prospect is located in northern Cache Valley approximately 8 kilometers north of the city of Preston, in southeast Idaho. The Cache Valley is a structural graben of the northern portion of the Basin and Range Province, just south of the border with the Eastern Snake River Plain (ESRP). This is a known geothermal resource area (KGRA) that was evaluated in the 1970's by the State of Idaho Department of Water Resources (IDWR) and by exploratory wells drilled by Sunedco Energy Development. The resource is poorly defined but current interpretations suggest that it is associated with the Cache Valley structural graben. Thermal waters moving upward along steeply dipping northwest trending basin and range faults emanate in numerous hot springs in the area. Springs reach temperatures as hot as 84 C. Traditional geothermometry models estimated reservoir temperatures of approximately 125 C in the 1970s study. In January of 2014, interest was renewed in the areas when a water well drilled to 79 m (260 ft) yielded a bottom hole temperature of 104 C (217 F). The well was sampled in June of 2014 to investigate the chemical composition of the water for modeling geothermometry reservoir temperature. Traditional magnesium corrected Na-K-Ca geothermometry estimates this new well to be tapping water from a thermal reservoir of 227 C (440 F). Even without the application of improved predictive methods, the results indicate much higher temperatures present at much shallower depths than previously thought. This new data provides strong support for further investigation and sampling of wells and springs in the Northern Cache Valley, proposed for the summer of 2015. The results of the water will be analyzed utilizing a new multicomponent equilibrium geothermometry (MEG) tool called Reservoir Temperature Estimate (RTEst) to obtain an improved estimate of the reservoir temperature. The new data suggest that other KGRAs and overlooked areas may need to be

  10. PowerPoint Presentation

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Improved Geothermometry through Multivariate Reaction-path Modeling and Evaluation of Geomicrobiological Influences on Geochemical Temperature Indicators Earl D. Mattson 1 , Robert W. Smith 2 , Ghanashayam Neupane 1 , Carl D. Palmer 2 , Yoshiko Fujita 1 , Travis L. McLing 1 , David W. Reed 1 , and Vicki S. Thompson 1 1 Idaho National Laboratory, Idaho Falls, ID 83415; 2 University of Idaho, Moscow, ID 83844, Center for Advanced Energy Studies, Idaho Falls, ID 83401 INTRODUCTION A major barrier

  11. SE Great Basin Play Fairway Analysis

    SciTech Connect (OSTI)

    Adam Brandt

    2015-11-15

    This submission includes a Na/K geothermometer probability greater than 200 deg C map, as well as two play fairway analysis (PFA) models. The probability map acts as a composite risk segment for the PFA models. The PFA models differ in their application of magnetotelluric conductors as composite risk segments. These PFA models map out the geothermal potential in the region of SE Great Basin, Utah.

  12. CX-007389: Categorical Exclusion Determination | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    89: Categorical Exclusion Determination CX-007389: Categorical Exclusion Determination Advances in Hydrogeochemical Indicators for the Discovery of New Geothermal Resources in the Great Basin CX(s) Applied: A9, B3.6 Date: 12/21/2011 Location(s): Colorado Offices(s): Golden Field Office The Colorado School of Mines (CSM) would utilize DOE and cost share funds to develop and calibrate new hydrogeochemical indicators and geothermometers for cost effective discovery and management of geothermal

  13. Low-temperature geothermal assessment of the Santa Clara and Virgin River Valleys, Washington County, Utah

    SciTech Connect (OSTI)

    Budding, K.E.; Sommer, S.N.

    1986-01-01

    Exploration techniques included the following: (1) a temperature survey of springs, (2) chemical analyses and calculated geothermometer temperatures of water samples collected from selected springs and wells, (3) chemical analyses and calculated geothermometer temperatures of spring and well water samples in the literature, (4) thermal gradients measured in accessible wells, and (5) geology. The highest water temperature recorded in the St. George basin is 42/sup 0/C at Pah Tempe Hot Springs. Additional spring temperatures higher than 20/sup 0/C are at Veyo Hot Spring, Washington hot pot, and Green Spring. The warmest well water in the study area is 40/sup 0/C in Middleton Wash. Additional warm well water (higher than 24.5/sup 0/C) is present north of St. George, north of Washington, southeast of St. George, and in Dameron Valley. The majority of the Na-K-Ca calculated reservoir temperatures range between 30/sup 0/ and 50/sup 0/C. Anomalous geothermometer temperatures were calculated for water from Pah Tempe and a number of locations in St. George and vicinity. In addition to the known thermal areas of Pah Tempe and Veyo Hot Spring, an area north of Washington and St. George is delineated in this study to have possible low-temperature geothermal potential.

  14. Distribution of cations in wurtzitic InxGa1-xN and InxAl1-xN alloys: Consequences for energetics and quasiparticle electronic structures

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

    de Carvalho, Luiz Cláudio; Schleife, André; Furthmüller, Jürgen; Bechstedt, Friedhelm

    2012-03-27

    The ternary, isostructural, wurtzite-derived group-III mononitride alloys InxGa1-xN andInxAl1-xN are reexamined within a cluster expansion approach. Using density functional theory together with the AM05 exchange-correlation functional, the total energies and the optimized atomic geometries of all 22 clusters classes of the cluster expansion for each material system are calculated. The computationally demanding calculation of the corresponding quasiparticle electronic structures is achieved for all cluster classes by means of a recently developed scheme to approximately solve the quasiparticle equation based on the HSE06 hybrid functional and the G₀W₀ approach. Using two different alloy statistics, the configurational averages for the lattice parameters,more » the mixing enthalpies, and the bulk moduli are calculated. The composition-dependent electronic structures of the alloys are discussed based on configurationally averaged electronic states, band gaps, and densities of states. Ordered cluster arrangements are found to be energetically rather unfavorable, however, they possess the smallest energy gaps and, hence, contribute to light emission. The influence of the alloy statistics on the composition dependencies and the corresponding bowing parameters of the band gaps is found to be significant and should, hence, lead to different signatures in the optical-absorption or -emission spectra.« less

  15. Study of reactive collisions between electrons and molecular cations using multichannel quantum defect theory: Application to HD{sup +} and BeH{sup +}

    SciTech Connect (OSTI)

    Pop, N. Ilie, S.; Motapon, O.; Epée, M. D. Epée; Niyonzima, S.; Mezei, J. Zs.; Chakrabarti, K.; Schneider, I. F.

    2014-11-24

    The present work is aimed at performing the computation of cross sections and Maxwell rate coefficients in the framework of the stepwise version of the Multichannel Quantum Defect Theory (MQDT). Cross sections and rate coefficients suitable for the modelling of the kinetics of HD{sup +} and BeH{sup +} in fusion plasmas and in the stellar atmospheres are presented and discussed. A very good agreement is found between our results for rotational transitions for HD{sup +} and other computations, as well as with experiment.

  16. Structure of a CutA1 divalent-cation tolerance protein from Cryptosporidium parvum, the protozoal parasite responsible for cryptosporidiosis

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

    Buchko, Garry W.; Robinson, Howard; Abendroth, Jan; Clitfon, Mathew C.; Zhang, Yanfeng; Hewitt, Stephen N.; Staker, Bart L.; Van Voorhis, Wesley C.; Mylera, Peter J.

    2015-05-01

    Cryptosporidiosis is an infectious disease caused by protozoan parasites from the Cryptosporidium species. Infection is associated with mild to severe diarrhea that usually resolves spontaneously in healthy human adults, but may lead to severe complications in young children and in immunocompromised patients. The genome of Cryptosporidium parvum contains a gene, CUTA_CRYPI, that may play a role in regulating the intracellular concentration of copper, a toxic element if left unchecked. Here we report the crystal structure for this CutA1 protein, Cp-CutA1, is reported at 2.0 Å resolution (4E98). As observed for other CutA1 structures, the 117-residue protein is a trimer withmore » a core ferrodoxin-like fold. Circular dichroism spectroscopy shows little unfolding of Cp-CutA1 up to 353 K. This robustness is corroborated by ¹H-¹⁵N HSQC spectra at 333 K that is characteristic of a folded protein, suggesting NMR spectroscopy may be a useful tool to further probe the function of the CutA1 proteins. While robust, Cp-CutA1 is not as stable as the homologous protein from a hyperthermophile, perhaps due to a wide β-bulgein β2 that protrudes P48 and S49 outside the β-sheet.« less

  17. Synthesis of metal-metal oxide catalysts and electrocatalysts using a metal cation adsorption/reduction and adatom replacement by more noble ones

    DOE Patents [OSTI]

    Adzic, Radoslav; Vukmirovic, Miomir; Sasaki, Kotaro

    2010-04-27

    The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen. The invention also relates to methods of making the metal-metal oxide composites.

  18. Redox-active on-surface polymerization of single-site divalent cations from pure metals by a ketone-functionalized phenanthroline

    SciTech Connect (OSTI)

    Skomski, Daniel; Tempas, Christopher D.; Bukowski, Gregory S.; Smith, Kevin A.; Tait, Steven L.

    2015-03-14

    Metallic iron, chromium, or platinum mixing with a ketone-functionalized phenanthroline ligand on a single crystal gold surface demonstrates redox activity to a well-defined oxidation state and assembly into thermally stable, one dimensional, polymeric chains. The diverging ligand geometry incorporates redox-active sub-units and bi-dentate binding sites. The gold surface provides a stable adsorption environment and directs growth of the polymeric chains, but is inert with regard to the redox chemistry. These systems are characterized by scanning tunnelling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy under ultra-high vacuum conditions. The relative propensity of the metals to interact with the ketone group is examined, and it is found that Fe and Cr more readily complex the ligand than Pt. The formation and stabilization of well-defined transition metal single-sites at surfaces may open new routes to achieve higher selectivity in heterogeneous catalysts.

  19. Microdomain Formation, Oxidation, and Cation Ordering in LaCa2Fe3O8+y

    SciTech Connect (OSTI)

    Price, Patrick M.; Browning, Nigel D.; Butt, Darryl P.

    2015-03-23

    The compound LaCa2Fe3O8+y, also known as the Grenier phase, is known to undergo an order-disorder transformation (ODT) at high temperatures. Oxidation has been observed when the compound is cooled in air after the ODT. In this study, we have synthesized the Grenier compound in air using traditional solid state reactions and investigated the structure and composition before and after the ODT. Thermal analysis showed that the material undergoes an order-disorder transformation in both oxygen and argon atmospheres with dynamic, temperature dependent, oxidation upon cooling. Results from scanning transmission electron microscopy (STEM) suggest that the Grenier phase has preferential segregation of Ca and La on the two crystallographic A-sites before the ODT, but a random distribution above the ODT temperature. Furthermore, STEM images suggest the possibility that oxygen excess may exist in La-rich regions within microdomains rather than at microdomain boundaries.

  20. Structure of a CutA1 divalent-cation tolerance protein from Cryptosporidium parvum, the protozoal parasite responsible for cryptosporidiosis

    SciTech Connect (OSTI)

    Buchko, Garry W.; Robinson, Howard; Abendroth, Jan; Clitfon, Mathew C.; Zhang, Yanfeng; Hewitt, Stephen N.; Staker, Bart L.; Van Voorhis, Wesley C.; Mylera, Peter J.

    2015-05-01

    Cryptosporidiosis is an infectious disease caused by protozoan parasites from the Cryptosporidium species. Infection is associated with mild to severe diarrhea that usually resolves spontaneously in healthy human adults, but may lead to severe complications in young children and in immunocompromised patients. The genome of Cryptosporidium parvum contains a gene, CUTA_CRYPI, that may play a role in regulating the intracellular concentration of copper, a toxic element if left unchecked. Here we report the crystal structure for this CutA1 protein, Cp-CutA1, is reported at 2.0 resolution (4E98). As observed for other CutA1 structures, the 117-residue protein is a trimer with a core ferrodoxin-like fold. Circular dichroism spectroscopy shows little unfolding of Cp-CutA1 up to 353 K. This robustness is corroborated by H-?N HSQC spectra at 333 K that is characteristic of a folded protein, suggesting NMR spectroscopy may be a useful tool to further probe the function of the CutA1 proteins. While robust, Cp-CutA1 is not as stable as the homologous protein from a hyperthermophile, perhaps due to a wide ?-bulgein ?2 that protrudes P48 and S49 outside the ?-sheet.

  1. Syntheses and characterization of energetic compounds constructed from alkaline earth metal cations (Sr and Ba) and 1,2-bis(tetrazol-5-yl)ethane

    SciTech Connect (OSTI)

    Xia Zhengqiang; Chen Sanping; Wei Qing; Qiao Chengfang

    2011-07-15

    Two new energetic compounds, [M(BTE)(H{sub 2}O){sub 5}]{sub n} (M=Sr(1), Ba(2)) [H{sub 2}BTE=1,2-bis(tetrazol-5-yl)ethane], have been hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction analyses reveal that they are isomorphous and exhibit 2D (4,4) net framework, generated by 4-connected Sr{sub 2}(H{sub 2}O){sub 10}/Ba{sub 2}(H{sub 2}O){sub 10} SBUs linked up by two independent binding modes of H{sub 2}BTE, and the resulting 2D structure is interconnected by hydrogen-bond and strong face to face {pi}-{pi} stacking interactions between two tetrazole rings to lead to a 3D supramolecular architecture. DSC measurements show that they have significant catalytic effects on thermal decomposition of ammonium perchlorate. Moreover, the photoluminescence properties, thermogravimetric analyses, and flame colors of the as-prepared compounds are also investigated in this paper. - Graphical abstract: Two novel 2D isomorphous alkaline earth metal complexes were assembled by 4-connected Sr{sub 2}(H{sub 2}O){sub 10}/Ba{sub 2}(H{sub 2}O){sub 10} SBUs and two independent binding modes of H{sub 2}BTE ligands, and the catalytic performances toward thermal decomposition of ammonium perchlorate and photoluminescent properties of them were investigated. Highlights: > Two novel alkaline earth energetic coordination polymers have been prepared.{yields} Both structures are layered based on 4-connected Sr{sub 2}(H{sub 2}O){sub 10}/Ba{sub 2}(H{sub 2}O){sub 10} SBUs and two distinct H{sub 2}BTE coordination modes.{yields} The dehydrated products of the compounds possess good thermostability and significant catalytic effects on thermal decomposition of AP.

  2. Cationic (V, Y)-codoped TiO{sub 2} with enhanced visible light induced photocatalytic activity: A combined experimental and theoretical study

    SciTech Connect (OSTI)

    Khan, Matiullah E-mail: wbcao@ustb.edu.cn; Cao, Wenbin E-mail: wbcao@ustb.edu.cn

    2013-11-14

    To employ TiO{sub 2} as an efficient photocatalyst, high reactivity under visible light and improved separation of photoexcited carriers are required. An effective co-doping approach is applied to modify the photocatalytic properties of TiO{sub 2} by doping vanadium (transition metal) and yttrium (rare earth element). V and/or Y codoped TiO{sub 2} was prepared using hydrothermal method without any post calcination for crystallization. Based on density functional theory, compensated and noncompensated V, Y codoped TiO{sub 2} models were constructed and their structural, electronic, and optical properties were calculated. Through combined experimental characterization and theoretical modeling, V, Y codoped TiO{sub 2} exhibited high absorption coefficient with enhanced visible light absorption. All the prepared samples showed pure anatase phase and spherical morphology with uniform particle distribution. Electronic band structure demonstrates that V, Y codoping drastically reduced the band gap of TiO{sub 2}. It is found that both the doped V and Y exist in the form of substitutional point defects replacing Ti atom in the lattice. The photocatalytic activity, evaluated by the degradation of methyl orange, displays that the codoped TiO{sub 2} sample exhibits enhanced visible light photocatalytic activity. The synergistic effects of V and Y drastically improved the Brunauer-Emmett-Teller specific surface area, visible light absorption, and electron-hole pair's separation leading to the enhanced visible light catalytic activity.

  3. MxMn8O16 (M = Ag or K) as promising cathode materials for secondary Mg based batteries: The role of the cation M

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

    Huang, Jianping; Takeuchi, Esther S.; Altug S. Poyraz; Takeuchi, Kenneth J.; Marschilok, Amy C.

    2016-02-15

    Here, AgxMn8O16 (Ag-OMS-2) and KxMn8O16 (K-OMS-2) were investigated as high voltage cathode materials for Mg based batteries. Both MxMn8O16 materials delivered high initial capacities (>180 mA h g–1), and KxMn8O16 showed high cycle stability with a reversible capacity of >170 mA h g–1 after 20 cycles.

  4. Cyclization of N-alkyl azinium cations with bifunctional nucleophiles. 21. Regioisomeric 1,3,4-thiadiazino(5,6-b)quinoxalines

    SciTech Connect (OSTI)

    Baklykov, V.G.; Charushin, V.N.; Chupakhin, O.N.; Drozd, V.N.

    1987-10-01

    Thiobenzyhydrazides undergo cyclization with N-alkyl-quinoxalinium salts to give 5-alkyl-substituted 1,4,4a,5,10,10a-hexahydro-1,3,4-thiadiazino(5,6-b)quinoxalines, which undergo isomerization to 10-alkyl-substituted thiadiazinoquinoxalines when they are heated in ethanol or in the presence of acids. The IR spectra of suspensions of the compounds in mineral oil were recorded with a UR-20 spectrometer. The PMR spectra of solutions in d/sub 6/-DMSO were recorded with Perkin-Elmer R-12B (60 MHz) and Brucker WP-80 (80 MHz) spectrometers with tetramethylsilane (TMS) and hexamethyldisiloxane (HMDS) as the internal standards. The /sup 13/C NMR spectra of solutions in d/sub 6/-DMSO were recorded with Brucker WH-90 (22.62 MHz) and Varian FT-80A (20.13 MHz) spectrometers. The chemical shifts were measured with respect to the signal of the solvent (d/sub 6/-DMSO, 39.6 ppm).

  5. The structural diversity of ABS{sub 3} compounds with d{sup 0} electronic configuration for the B-cation

    SciTech Connect (OSTI)

    Brehm, John A. Bennett, Joseph W.; Schoenberg, Michael Rutenberg; Grinberg, Ilya; Rappe, Andrew M.

    2014-06-14

    We use first-principles density functional theory within the local density approximation to ascertain the ground state structure of real and theoretical compounds with the formula ABS{sub 3} (A = K, Rb, Cs, Ca, Sr, Ba, Tl, Sn, Pb, and Bi; and B = Sc, Y, Ti, Zr, V, and Nb) under the constraint that B must have a d{sup 0} electronic configuration. Our findings indicate that none of these AB combinations prefer a perovskite ground state with corner-sharing BS{sub 6} octahedra, but that they prefer phases with either edge- or face-sharing motifs. Further, a simple two-dimensional structure field map created from A and B ionic radii provides a neat demarcation between combinations preferring face-sharing versus edge-sharing phases for most of these combinations. We then show that by modifying the common Goldschmidt tolerance factor with a multiplicative term based on the electronegativity difference between A and S, the demarcation between predicted edge-sharing and face-sharing ground state phases is enhanced. We also demonstrate that, by calculating the free energy contribution of phonons, some of these compounds may assume multiple phases as synthesis temperatures are altered, or as ambient temperatures rise or fall.

  6. Unraveling the Voltage-Fade Mechanism in High-Energy-Density Lithium-Ion Batteries: Origin of the Tetrahedral Cations for Spinel Conversion

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

    Mohanty, Debasish; Li, Jianlin; Abraham, Daniel P.; Huq, Ashfia; Payzant, E. Andrew; Wood, David L.; Daniel, Claus

    2014-09-30

    Discovery of high-voltage layered lithium-and manganese-rich (LMR) composite oxide electrode has dramatically enhanced the energy density of current Li-ion energy storage systems. However, practical usage of these materials is currently not viable because of their inability to maintain a consistent voltage profile (voltage fading) during subsequent charge-discharge cycles. This report rationalizes the cause of this voltage fade by providing the evidence of layer to spinel-like (LSL) structural evolution pathways in the host Li1.2Mn0.55Ni0.15Co0.1O2 LMR composite oxide. By employing neutron powder diffraction, and temperature dependent magnetic susceptibility, we show that LSL structural rearrangement in LMR oxide occurs through a tetrahedral cationmore » intermediate via: i) diffusion of lithium atoms from octahedral to tetrahedral sites of the lithium layer [(LiLioct →LiLitet] which is followed by the dispersal of the lithium ions from the adjacent octahedral site of the metal layer to the tetrahedral sites of lithium layer [LiTM oct → LiLitet]; and ii) migration of Mn from the octahedral sites of the transition metal layer to the permanent octahedral site of lithium layer via tetrahedral site of lithium layer [MnTMoct MnLitet MnLioct)]. The findings opens the door to the potential routes to mitigate this atomic restructuring in the high-voltage LMR composite oxide cathodes by manipulating the composition/structure for practical use in high-energy-density lithium-ion batteries.« less

  7. Cation and Vacancy Disorder in U1-yNdyO2.00-X Alloys

    SciTech Connect (OSTI)

    Barabash, Rozaliya I.; Voit, Stewart L.; Aidhy, Dilpuneet S.; Lee, Seung Min; Knight, Travis W.; Sprouster, David J.; Ecker, Lynne E.

    2015-09-14

    In this study, the intermixing and clustering of U/Nd, O, and vacancies were studied by both laboratory and synchrotron-based x-ray diffraction in U1-yNdyO2-X alloys. It was found that an increased holding time at the high experimental temperature during initial alloy preparation results in a lower disorder of the Nd distribution in the alloys. Adjustment of the oxygen concentration in the U1-yNdyO2-X alloys with different Nd concentrations was accompanied by the formation of vacancies on the oxygen sublattice and a nanocrystalline component. The lattice parameters in the U1-yNdyO2-X alloys were also found to deviate significantly from Vegard's law when the Nd concentration was high (53%) and decreased with increasing oxygen concentration. Such changes indicate the formation of large vacancy concentrations during oxygen adjustment at these high temperatures. Finally, the change in the vacancy concentration after the oxygen adjustment was estimated relative to Nd concentration and oxygen stoichiometry.

  8. The interaction between cations and anionic groups inducing SHG enhancement in a series of apatite-like crystals: A first-principles study

    SciTech Connect (OSTI)

    Jing, Qun; Dong, Xiaoyu; Yang, Zhihua; Pan, Shilie; Zhang, Bingbing; Huang, Xuchu; Chen, Mingwei

    2014-11-15

    It is an interesting topic to reveal the origin of the SHG intensity enhancement after substitution from alkali and alkali-earth metal atoms to cadmium in a series of apatite-like borates KSr{sub 4}(BO{sub 3}){sub 3}, Ca{sub 5}(BO{sub 3}){sub 3}F, Cd{sub 5}(BO{sub 3}){sub 3}F. Combined with the first-principles method, SHG-density method and real-space atom-cutting method, the electronic structure, the optical properties and the contribution of respective ion and ion groups have been investigated. Second harmonic generation (SHG) responses are mainly attributed to BO{sub 3} groups with π conjugated configuration and their alignment framework. The contributions of A site are more important in CaBOF and CdBOF compounds than in KSrBO. It is also demonstrated that the strong covalent interactions between the boron–oxygen groups and the cadmium atoms contribute the enhancement of SHG responses after substitution from alkali and alkali-earth metal atoms. - graphical abstract: Combined with the first-principles method, SHG-density method and real-space atom-cutting method, the enhancement of SHG response are attributed to the interaction between cadmium and BO{sub 3} groups. - Highlights: • SHG response on a series of apatite-like borates was studied by a SHG-density method. • SHG responses are mainly attributed to BO{sub 3} groups and their alignment framework. • The contributions of A site are more important in CaBOF and CdBOF than in KSrBO. • Covalent interaction between BO and Cd is responsible for SHG of CdBOF.

  9. Cationic coordination compound Cs{sub 2}Hg{sub 3}I{sub 8} for IR NLO material: Synthesis, crystal growth and characterizations

    SciTech Connect (OSTI)

    Sathiskumar, S.; Kathiravan, P.; Balakrishnan, T.

    2015-06-24

    Single crystals Cs{sub 2}Hg{sub 3}I{sub 8} of dimensions 5 × 3 × 4   mm{sup 3} were grown by solution growth method at room temperature and structurally characterized by single crystal X – ray diffraction. Cs{sub 2}Hg{sub 3}I{sub 8} compound crystallizes in a noncentrosymmetric space group Cm with the crystal data of a = 7.4415 Å, b = 21.6629 Å, c = 7.6726 Å, α, β = 90°, γ = 108.05° and Z = 2. The grown crystals were characterized by powder X – ray diffraction analysis and the various diffraction planes are indexed. The presence of functional groups was identified qualitatively by Fourier transform infrared and FT – Raman spectral analyses. Ultraviolet – visible spectral analyses shows that the crystal has low UV cut off at 388 nm combined with very good transparency of 98 % in a wide range. The optical band gap was estimated to be 3 eV. Mechanical hardness of the grown crystal Cs{sub 2}Hg{sub 3}I{sub 8} was determined. The dielectric response of the crystal with varying frequencies was studied. Differential scanning calorimetry (DSC) analysis shows that the grown crystal has very good thermal stability up to 97.5°C.

  10. Alaska Open-file Report 144 Assessment of Thermal Springs Sites Aleutian Arc, Atka Island to Becherof Lake -- Preliminary Results and Evaluation

    SciTech Connect (OSTI)

    Motyka, R.J.; Moorman, M.A.; Liss, S.A.

    1981-12-01

    Twenty of more than 30 thermal spring areas reported to exist in the Aleutian arc extending from Atka Island to Becherof Lake were investigated during July and August, 1980. Thermal activity of three of these sites had diminished substantially or no longer existed. At least seven more sites where thermal-spring activity is probable or certain were not visited because of their remoteness or because of time constraints. The existence of several other reported thermal spring sites could not be verified; these sites are considered questionable. On the basis of geothermometry, subsurface reservoir temperatures in excess of 150 C are estimated for 10 of the thermal spring sites investigated. These sites all occur in or near regions of Recent volcanism. Five of the sites are characterized by fumaroles and steaming ground, indicating the presence of at least a shallow vapor-dominated zone. Two, the Makushin Valley and Glacier Valley thermal areas, occur on the flanks of active Mukushin Volcano located on Unalaska Island, and may be connected to a common source of heat. Gas geothermometry suggests that the reservoir feeding the Kliuchef thermal field, located on the flanks of Kliuchef volcano of northeast Atka Island, may be as high as 239 C.

  11. Interface Induced Carbonate Mineralization: A Fundamental Geochemical...

    Office of Scientific and Technical Information (OSTI)

    fundamental barrier, other than cation hydration, exists that prevents Mgsup 2+ and ... of water give us a first direct proof to support and quantify the cation hydration effect. ...

  12. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... Office of Nonproliferation and National Security (NN) (United States) USDOE Office of ... The Role of Cation-Water Disorder during Cation Exchange in Small-Pore Zeolite Sodium ...

  13. Optical amplification in disordered electrooptic Tm{sup 3+} and Ho{sup 3+} codoped lanthanum-modified lead zirconate titanate ceramics and study of spectroscopy and communication between cations

    SciTech Connect (OSTI)

    Zhao, Hua; Zhang, Kun; Xu, Long; Sun, Fankui; Zhang, Jingwen; Chen, Xuesheng; Li, Kewen K.

    2014-02-21

    Rare earth doped electro-optic (EO) ceramics of lanthanum-modified lead zirconate titanate (PLZT) are promising in building multifunctional optical devices, by taking advantage of both EO effect and optical activity. In this work, the combination of the measured spectra of absorption and photoluminescence, the fluorescent decay, the calculated Judd-Ofelt parameters, and measured single pass gain in Tm{sup 3+}, Ho{sup 3+} codoped PLZT ceramics have marked them out as promising gain media in building electrically controllable lasers/optical amplifiers and other multifunctional devices. Optical energy storage was also observed in the optical amplification dynamics.

  14. Infrared spectroscopy of Sc{sup +}(H{sub 2}O) and Sc{sup 2+}(H{sub 2}O) via argon complex predissociation: The charge dependence of cation hydration

    SciTech Connect (OSTI)

    Carnegie, P. D.; Bandyopadhyay, B.; Duncan, M. A.

    2011-01-07

    Singly and doubly charged scandium-water ion-molecule complexes are produced in a supersonic molecular beam by laser vaporization. These ions are mass analyzed and size selected in a specially designed reflectron time-of-flight spectrometer. To probe their structure, vibrational spectroscopy is measured for these complexes in the O-H stretching region using infrared laser photodissociation and the method of rare gas atom predissociation, also known as ''tagging.'' The O-H stretches in these systems are shifted to lower frequency than those for the free water molecule, and the intensity of the symmetric stretch band is strongly enhanced relative to the asymmetric stretch. These effects are more prominent for the doubly charged ions. Partially resolved rotational structure for the Sc{sup +}(H{sub 2}O)Ar complex shows that the H-O-H bond angle is larger than it is in the free water molecule. Fragmentation and spectral patterns indicate that the coordination of the Sc{sup 2+} ion is filled with six ligands (one water and five argons).

  15. Cation-poor complex metallic alloys in Ba(Eu)–Au–Al(Ga) systems: Identifying the keys that control structural arrangements and atom distributions at the atomic level

    SciTech Connect (OSTI)

    Smetana, Volodymyr; Steinberg, Simon; Mudryk, Yaroslav; Pecharsky, Vitalij; Miller, Gordon J.; Mudring, Anja -Verena

    2015-10-19

    Four complex intermetallic compounds BaAu6±xGa6±y (x = 1, y = 0.9) (I), BaAu6±xAl6±y (x = 0.9, y = 0.6) (II), EuAu6.2Ga5.8 (III), and EuAu6.1Al5.9 (IV) have been synthesized, and their structures and homogeneity ranges have been determined by single crystal and powder X-ray diffraction. Whereas I and II originate from the NaZn13-type structure (cF104–112, Fm3C), III (tP52, P4/nbm) is derived from the tetragonal Ce2Ni17Si9-type, and IV (oP104, Pbcm) crystallizes in a new orthorhombic structure type. Both I and II feature formally anionic networks with completely mixed site occupation by Au and triel (Tr = Al, Ga) atoms, while a successive decrease of local symmetry from the parental structures of I and II to III and, ultimately, to IV correlates with increasing separation of Au and Tr on individual crystallographic sites. Density functional theory-based calculations were employed to determine the crystallographic site preferences of Au and the respective triel element to elucidate reasons for the atom distribution (“coloring scheme”). Chemical bonding analyses for two different “EuAu6Tr6” models reveal maximization of the number of heteroatomic Au–Tr bonds as the driving force for atom organization. The Fermi levels fall in broad pseudogaps for both models allowing some electronic flexibility. Spin-polarized band structure calculations on the “EuAu6Tr6” models hint to singlet ground states for europium and long-range magnetic coupling for both EuAu6.2Ga5.8 (III) and EuAu6.1Al5.9 (IV). This is substantiated by experimental evidence because both compounds show nearly identical magnetic behavior with ferromagnetic transitions at TC = 6 K and net magnetic moments of 7.35 μB/f.u. at 2 K. As a result, the effective moments of 8.3 μB/f.u., determined from Curie–Weiss fits, point to divalent oxidation states for europium in both III and IV.

  16. Cation-poor complex metallic alloys in Ba(Eu)–Au–Al(Ga) systems: Identifying the keys that control structural arrangements and atom distributions at the atomic level

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

    Smetana, Volodymyr; Steinberg, Simon; Mudryk, Yaroslav; Pecharsky, Vitalij; Miller, Gordon J.; Mudring, Anja -Verena

    2015-10-19

    Four complex intermetallic compounds BaAu6±xGa6±y (x = 1, y = 0.9) (I), BaAu6±xAl6±y (x = 0.9, y = 0.6) (II), EuAu6.2Ga5.8 (III), and EuAu6.1Al5.9 (IV) have been synthesized, and their structures and homogeneity ranges have been determined by single crystal and powder X-ray diffraction. Whereas I and II originate from the NaZn13-type structure (cF104–112, Fm3C), III (tP52, P4/nbm) is derived from the tetragonal Ce2Ni17Si9-type, and IV (oP104, Pbcm) crystallizes in a new orthorhombic structure type. Both I and II feature formally anionic networks with completely mixed site occupation by Au and triel (Tr = Al, Ga) atoms, while a successivemore » decrease of local symmetry from the parental structures of I and II to III and, ultimately, to IV correlates with increasing separation of Au and Tr on individual crystallographic sites. Density functional theory-based calculations were employed to determine the crystallographic site preferences of Au and the respective triel element to elucidate reasons for the atom distribution (“coloring scheme”). Chemical bonding analyses for two different “EuAu6Tr6” models reveal maximization of the number of heteroatomic Au–Tr bonds as the driving force for atom organization. The Fermi levels fall in broad pseudogaps for both models allowing some electronic flexibility. Spin-polarized band structure calculations on the “EuAu6Tr6” models hint to singlet ground states for europium and long-range magnetic coupling for both EuAu6.2Ga5.8 (III) and EuAu6.1Al5.9 (IV). This is substantiated by experimental evidence because both compounds show nearly identical magnetic behavior with ferromagnetic transitions at TC = 6 K and net magnetic moments of 7.35 μB/f.u. at 2 K. As a result, the effective moments of 8.3 μB/f.u., determined from Curie–Weiss fits, point to divalent oxidation states for europium in both III and IV.« less

  17. K{sub 2}NaOsO{sub 5.5} and K{sub 3}NaOs{sub 2}O{sub 9}: The first osmium perovskites containing alkali cations at the 'A' site

    SciTech Connect (OSTI)

    Mogare, Kailash M.; Klein, Wilhelm; Jansen, Martin

    2012-07-15

    K{sub 2}NaOsO{sub 5.5} and K{sub 3}NaOs{sub 2}O{sub 9} were obtained from solid-state reactions of potassium superoxide, sodium peroxide and osmium metal at elevated oxygen pressures. K{sub 2}NaOsO{sub 5.5} crystallizes as an oxygen-deficient cubic double perovskite in space group Fm3{sup Macron }m with a=8.4184(5) A and contains isolated OsO{sub 6} octahedra. K{sub 3}NaOs{sub 2}O{sub 9} crystallizes hexagonally in P6{sub 3}/mmc with a=5.9998(4) A and c=14.3053(14) A. K{sub 3}NaOs{sub 2}O{sub 9} consists of face sharing Os{sub 2}O{sub 9} pairs of octahedra. According to magnetic measurements K{sub 2}NaOsO{sub 5.5} is diamagnetic, whereas K{sub 3}NaOs{sub 2}O{sub 9} displays strong antiferromagnetic coupling (T{sub N}=140 K), indicating enhanced magnetic interactions within the octahedral pair. - Graphical abstract: High oxidation states of Os, obtained by high oxygen pressure synthesis, are accommodated in double and triple perovskite matrices. K{sub 3}NaOs{sub 2}O{sub 9} displays enhanced magnetic interactions. Highlights: Black-Right-Pointing-Pointer New osmates containing highly oxidized Os were obtained by high O{sub 2} pressure synthesis. Black-Right-Pointing-Pointer High oxidation states of Os are accommodated in double and triple perovskite matrices. Black-Right-Pointing-Pointer Both compounds represent the first Os perovskites with an alkali metal at the A site. Black-Right-Pointing-Pointer K{sub 3}NaOs{sub 2}O{sub 9} displays enhanced magnetic interactions within the octahedral pair.

  18. Investigations of low-temperature geothermal potential in New York State

    SciTech Connect (OSTI)

    Hodge, D.S.; De Rito, R.; Hifiker, K.; Morgan, P.; Swanberg, C.A.

    1981-09-01

    Temperature gradient map and published heat flow data indicate a possible potential for a geothermal resource in western and central New York State. A new analysis of bottom-hole temperature data for New York State confirms the existence of three positive gradient anomalies: the East Aurora, Cayuga, and Elmira anomalies, with gradients as high as 32/sup 0/C/km, 36/sup 0/C/km, and 36/sup 0/C/km, respectively. Ground waters from two of these anomalies are enriched in silica relative to surrounding areas. Heat flows based on silica geothermometry are 50 to 70 mWm/sup -2/ for the anomalies and 41.4 mWm/sup -2/ for bordering regional flux. A correlation between Bouguer gravity anomalies and the temperature gradient map suggests that the geothermal anomalies may occur above radioactive granites in the basement.

  19. Cores from the Salton Sea scientific drilling program: Metamorphic reaction progress as a function of chemical and thermal environment: Final report

    SciTech Connect (OSTI)

    Papike, J.J.; Shearer, C.K.

    1987-05-13

    The study investigated the downhole progressive metamorphism at the Salton Sea site by monitoring and evaluating discontinuous and continuous metamorphic reactions. The main emphasis was placed on: (1) the addition of petrographic, geochemical, and mineralogical data to the Salton Sea data base; (2) determination of downhole reactions; (3) evaluation of the progress of individual continuous reaction (epsilon) and the overall reaction progress (epsilon/sub T/) during the transition from one metamorphic zone to the next; and (4) evaluation and correlation of mineral reactions and reaction progress with mineral phase and organic material geothermometry. To these ends, thirty-three samples from the Salton Sea core were analyzed for: (1) quantitative modal mineralogy using the x-ray diffraction reference intensity method (RIM), (2) 30 major and trace elements in the whole rock and (3) mineral chemistry and structural state. In addition, a subset of these samples were used for temperature determinations using vitrinite reflectivity.

  20. Colorado's hydrothermal resource base: an assessment

    SciTech Connect (OSTI)

    Pearl, R.H.

    1981-01-01

    As part of its effort to more accurately describe the nations geothrmal resource potential, the US Department of Energy/Division of Geothermal Energy contracted with the Colorado Geological survey to appraise the hydrothermal (hot water) geothermal resources of Colorado. Part of this effort required that the amount of energy that could possibly be contained in the various hydrothermal systems in Colorado be estimated. The findings of that assessment are presented. To make these estimates the geothermometer reservoir temperatures estimated by Barrett and Pearl (1978) were used. In addition, the possible reservoir size and extent were estimated and used. This assessment shows that the total energy content of the thermal systems in Colorado could range from 4.872 x 10{sup 15} BTU's to 13.2386 x 10{sup 15} BTU's.

  1. Carbonyl sulphide (COS) in geothermal fluids; An example from the Larderello field (Italy)

    SciTech Connect (OSTI)

    Chiodini, G. ); Cioni, R.; Raco, B. ); Scandiffio, G. )

    1991-01-01

    This paper reports that the carbonyl sulphide (COS) content in the fluids of 12 wells in the Larderello geothermal field ranges from 0.005 to 0.1 {mu}m mol/mol. Measured data are comparable with the theoretical concentrations, considering a homogeneous gas phase at the temperature and pressure conditions of the reservoir. However, the low temperature dependence of equilibrium constants of reactions involving COS prevents us from using them as geothermometers. On the contrary, P{sub CO{sub 2}} estimates in the gas equilibration zone can be inferred from the H{sub 2}S/COS ratio. The calculated CO{sub 2} partial pressures are comparable with those estimated by means of the H{sub 2}/CO ratio.

  2. Rare-earth elements in hot brines (165 to 190 degree C) from the Salton Sea geothermal field

    SciTech Connect (OSTI)

    Lepel, E.A.; Laul, J.C.; Smith, M.R.

    1988-01-01

    Rare-earth element (REE) concentrations are important indicators for revealing various chemical fractionation processes (water/rock interactions) and source region geochemistry. Since the REE patterns are characteristic of geologic materials (basalt, granite, shale, sediments, etc.) and minerals (K-feldspar, calcite, illite, epidote, etc.), their study in geothermal fluids may serve as a geothermometer. The REE study may also enable us to address the issue of groundwater mixing. In addition, the behavior of the REE can serve as analogs of the actinides in radioactive waste (e.g., neodymium is an analog of americium and curium). In this paper, the authors port the REE data for a Salton Sea Geothermal Field (SSGF) brine (two aliquots: port 4 at 165{degree}C and port 5 at 190{degree}C) and six associated core samples.

  3. Geothermal prospecting by geochemical methods on natural gas and water discharges in the Vulsini Mts Volcanic District (Central Italy)

    SciTech Connect (OSTI)

    Duchi, V.; Minissale, A.A.; Ortino, S.; Romani, L.

    1987-01-01

    The Latera and Torre Alfina geothermal fields were discovered in the Vulsini Mts district (central Italy) in the 70s. The fluid produced by the two geothermal systems is a high rhoCO/sub 2/(around 7 MPa) sodium chloride solution (T.D.S. is 9200 ppm at Latera and 7800 at Torre Alfina), with high SiO/sub 2/ and H/sub 3/BO/sub 3/ contents. The fluid temperature taken at well bottom is about 155/sup 0/C at Torre Alfina, whereas at Latera it ranges from 200 to over 350/sup 0/C. In spite of these temperatures, recorded in producing wells, previous geochemical prospectings using geothermometers in natural thermal manifestations had predicted temperatures no higher than 140/sup 0/C in all the Vulsini district. This contrasting feature between real temperatures and those evaluated during prospecting is caused by the fast circulation of large amounts of meteoric waters in the aquifer located in the shallow parts of the carbonate reservoir formations, and by the short interaction between the latter and the deep geothermal fluids. In the present study a new geochemical survey on thermal and cold springs, stream samples, as well as natural gas emissions has been carried out. A critical review of the main geothermometers, some considerations about the hydraulic behavior of the reservoir formations, and the cross comparison between NH/sub 4//sup +//B ratio, rhoCO/sub 2/ and SiO/sub 2/ content in both cold and thermal waters, have led to the conclusion that in the Vulsini Mts there are no shallow anomalous areas apart from those already discovered at Latera and Torre Alfina. The present method could be successfully applied in other geothermal systems, where the potential reservoir is represented by carbonate formations.

  4. ALS Capabilities Reveal How Like Can Attract Like

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

    R.C. Cohen, D. Prendergast, and R.J. Saykally, "Cation-cation contact pairing in water: Guanidinium," Journal of Chemical Physics 139, 035104 (2013). ALS Science Highlight 286...

  5. Cutting tools and wear resistant articles and material for same

    DOE Patents [OSTI]

    Tien, Tseng-Ying; Huang, Zhen-Kun

    2000-01-01

    A ceramic having a relatively high proportion of an alpha prime SiAlON phase and exhibiting high hardness and toughness. In a particularly preferred embodiment, a cation of Gd is used as a modifying cation.

  6. Metal-phosphate binders

    DOE Patents [OSTI]

    Howe, Beth Ann [Lewistown, IL; Chaps-Cabrera, Jesus Guadalupe [Coahuila, MX

    2009-05-12

    A metal-phosphate binder is provided. The binder may include an aqueous phosphoric acid solution, a metal-cation donor including a metal other than aluminum, an aluminum-cation donor, and a non-carbohydrate electron donor.

  7. Prediction of heat capacities of solid inorganic salts from group...

    Office of Scientific and Technical Information (OSTI)

    Subject: 36 MATERIALS SCIENCE; 99 MATHEMATICS, COMPUTERS, INFORMATION SCIENCE, MANAGEMENT, LAW, MISCELLANEOUS; SALTS; SPECIFIC HEAT; OXIDES; FLUORIDES; CHLORIDES; ANIONS; CATIONS; ...

  8. Anion exchange polymer electrolytes

    DOE Patents [OSTI]

    Kim, Yu Seung; Kim, Dae Sik

    2013-09-10

    Solid anion exchange polymer electrolytes include chemical compounds comprising a polymer backbone with side chains that include guanidinium cations.

  9. Polymide gas separation membranes

    DOE Patents [OSTI]

    Ding, Yong; Bikson, Benjamin; Nelson, Joyce Katz

    2004-09-14

    Soluble polyamic acid salt (PAAS) precursors comprised of tertiary and quaternary amines, ammonium cations, sulfonium cations, or phosphonium cations, are prepared and fabricated into membranes that are subsequently imidized and converted into rigid-rod polyimide articles, such as membranes with desirable gas separation properties. A method of enhancing solubility of PAAS polymers in alcohols is also disclosed.

  10. Bacterio-electric leaching of metals

    DOE Patents [OSTI]

    Lazaroff, Norman; Dugan, Patrick R.

    1992-07-07

    The separation of cationic materials from an ore body is assisted by the application of an electric potential, and resulting current, to the ore body, in association with iron or sulphur oxidizing bacteria. The combined process induces migration of cationic metals to a cathode suspended within the ore body so that the cationic metal can be preferentially separated from the ore body.

  11. Bacterio-electric leaching of metals

    DOE Patents [OSTI]

    Lazaroff, Norman; Dugan, Patrick R.

    1992-01-01

    The separation of cationic materials from an ore body is assisted by the application of an electric potential, and resulting current, to the ore body, in association with iron or sulphur oxidizing bacteria. The combined process induces migration of cationic metals to a cathode suspended within the ore body so that the cationic metal can be preferentially separated from the ore body.

  12. {open_quotes}Nb{sub 2-x}P{sub 3-y}O{sub 12},{close_quotes} a novel Nb{sup v} oxophosphate with disordered cation vacancies in a Sc{sub 2}(WO{sub 4}){sub 3}-type structure

    SciTech Connect (OSTI)

    Zah-Letho, J.J.; Verbaere, A.; Jouanneaux, A.

    1995-05-01

    The title compound was prepared at 360{degrees}C, starting from Nb{sub 2}O{sub 5} and NH{sub 4}H{sub 2}PO{sub 4}. The orthorhombic unit-cell parameters were determined by electron and X-ray diffractions: a = 12.0819 (2) {angstrom}, b = 8.6848 (1) {angstrom}, c = 8.7452 (1) {angstrom}, space group Pbcn. Reitveld refinements from X-ray powder diffraction data, chemical analyses, and the measured density show that the basic structure consists of a three-dimensional framework of the Sc{sub 2}(WO{sub 4}){sub 3} structure type, with NbO{sub 6} octahedra and PO{sub 4} tetrahedra sharing corners, and that both Nb and P vacancies occur. The actual formula is close to Nb{sub 2-x}P{sub 3-y}O{sub 12}. Comparative spectroscopic studies of the title compound and of Nb{sub 3}(NbO){sub 2}(PO{sub 4}){sub 7} confirm the occurrence of the vacancies, and thus an important local variation of the bond lengths near the defect sites. The presence of small amounts of H and N in the structure is discussed. Upon heating in air, the structure is preserved up to 900{degrees}C. The so-called {epsilon}-NbOPO{sub 4} has the same basic structure, and its existence seems questionable.

  13. Alum Innovative Exploration Project (Ram Power Inc.)

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Miller, Clay

    Data generated from the Alum Innovative Exploration Project, one of several promising geothermal properties located in the middle to upper Miocene (~11-5 Ma, or million years BP) Silver Peak-Lone Mountain metamorphic core complex (SPCC) of the Walker Lane structural belt in Esmeralda County, west-central Nevada. The geothermal system at Alum is wholly concealed; its upper reaches discovered in the late 1970s during a regional thermal-gradient drilling campaign. The prospect boasts several shallow thermal-gradient (TG) boreholes with TG >75oC/km (and as high as 440oC/km) over 200-m intervals in the depth range 0-600 m. Possibly boiling water encountered at 239 m depth in one of these boreholes returned chemical- geothermometry values in the range 150-230oC. GeothermEx (2008) has estimated the electrical- generation capacity of the current Alum leasehold at 33 megawatts for 20 years; and the corresponding value for the broader thermal anomaly extending beyond the property at 73 megawatts for the same duration.

  14. Alum Innovative Exploration Project (Ram Power Inc.)

    SciTech Connect (OSTI)

    Miller, Clay

    2010-01-01

    Data generated from the Alum Innovative Exploration Project, one of several promising geothermal properties located in the middle to upper Miocene (~11-5 Ma, or million years BP) Silver Peak-Lone Mountain metamorphic core complex (SPCC) of the Walker Lane structural belt in Esmeralda County, west-central Nevada. The geothermal system at Alum is wholly concealed; its upper reaches discovered in the late 1970s during a regional thermal-gradient drilling campaign. The prospect boasts several shallow thermal-gradient (TG) boreholes with TG >75oC/km (and as high as 440oC/km) over 200-m intervals in the depth range 0-600 m. Possibly boiling water encountered at 239 m depth in one of these boreholes returned chemical- geothermometry values in the range 150-230oC. GeothermEx (2008) has estimated the electrical- generation capacity of the current Alum leasehold at 33 megawatts for 20 years; and the corresponding value for the broader thermal anomaly extending beyond the property at 73 megawatts for the same duration.

  15. Geothermal Geodatabase for Wagon Wheel Hot Springs, Mineral County, Colorado

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Zehner, Richard

    2012-11-01

    Geothermal Geodatabase for Wagon Wheel Hot Springs, Mineral County, Colorado By Richard “Rick” Zehner Geothermal Development Associates Reno Nevada USA 775.737.7806 rzehner@gdareno.com For Flint Geothermal LLC, Denver Colorado Part of DOE Grant EE0002828 2013 This is an ESRI geodatabase version 10, together with an ESRI MXD file version 10.2 Data is in UTM Zone 13 NAD27 projection North boundary: approximately 4,189,000 South boundary: approximately 4,170,000 West boundary: approximately 330,000 East boundary: approximately 351,000 This geodatabase was built to cover several geothermal targets developed by Flint Geothermal in 2012 during a search for high-temperature systems that could be exploited for electric power development. Several of the thermal springs at Wagon Wheel Gap have geochemistry and geothermometry values indicative of high-temperature systems. The datasets in the geodatabase are a mixture of public domain data as well as data collected by Flint Geothermal, now being made public. It is assumed that the user has internet access, for the mxd file accesses ESRI’s GIS servers. Datasets include: 1. Results of reconnaissance shallow (2 meter) temperature surveys 2. Air photo lineaments 3. Groundwater geochemistry 4. Power lines 5. Georeferenced geologic map of Routt County 6. Various 1:24,000 scale topographic maps

  16. Geothermal Geodatabase for Routt Hot Springs, Routt County, Colorado

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Zehner, Richard

    2012-11-01

    Geothermal Geodatabase for Routt Hot Springs, Routt County, Colorado By Richard “Rick” Zehner Geothermal Development Associates Reno Nevada USA 775.737.7806 rzehner@gdareno.com For Flint Geothermal LLC, Denver Colorado Part of DOE Grant EE0002828 2013 This is an ESRI geodatabase version 10, together with an ESRI MXD file version 10.2 Data is in UTM Zone 13 NAD27 projection North boundary: approximately 4,500,000 South boundary: approximately 4,480,000 West boundary: approximately 330,000 East boundary: approximately 358,000 This geodatabase was built to cover several geothermal targets developed by Flint Geothermal in 2012 during a search for high-temperature systems that could be exploited for electric power development. Several of the thermal springs and wells in the Routt Hot Spring and Steamboat Springs areahave geochemistry and geothermometry values indicative of high-temperature systems. The datasets in the geodatabase are a mixture of public domain data as well as data collected by Flint Geothermal, now being made public. It is assumed that the user has internet access, for the mxd file accesses ESRI’s GIS servers. Datasets include: 1. Results of reconnaissance shallow (2 meter) temperature surveys 2. Air photo lineaments 3. Groundwater geochemistry 5. Georeferenced geologic map of Routt County 6. Various 1:24,000 scale topographic maps

  17. Washington Play Fairway Analysis Geothermal GIS Data

    SciTech Connect (OSTI)

    Corina Forson

    2015-12-15

    This file contains file geodatabases of the Mount St. Helens seismic zone (MSHSZ), Wind River valley (WRV) and Mount Baker (MB) geothermal play-fairway sites in the Washington Cascades. The geodatabases include input data (feature classes) and output rasters (generated from modeling and interpolation) from the geothermal play-fairway in Washington State, USA. These data were gathered and modeled to provide an estimate of the heat and permeability potential within the play-fairways based on: mapped volcanic vents, hot springs and fumaroles, geothermometry, intrusive rocks, temperature-gradient wells, slip tendency, dilation tendency, displacement, displacement gradient, max coulomb shear stress, sigma 3, maximum shear strain rate, and dilational strain rate at 200m and 3 km depth. In addition this file contains layer files for each of the output rasters. For details on the areas of interest please see the 'WA_State_Play_Fairway_Phase_1_Technical_Report' in the download package. This submission also includes a file with the geothermal favorability of the Washington Cascade Range based off of an earlier statewide assessment. Additionally, within this file there are the maximum shear and dilational strain rate rasters for all of Washington State.

  18. The low temperature hydrothermal system of Campiglia, Tuscany (Italy); A geochemical approach

    SciTech Connect (OSTI)

    Celati, R.; Grassi, S.; D'Amore, F.; Marcolini, L. )

    1991-01-01

    This paper reports on the Campiglia hydrothermal system which is a low temperature hydrothermal system located in southwestern Tuscany, a region of Italy characterized by intense geothermal activity and by the presence of high temperature exploited geothermal reservoirs. Six water-points, with temperatures ranging between 20 and 47{degrees} C and different chemical and isotopic compositions, are found close to the margins of outcrops of the main regional aquifer formation. Systematic hydrogeological, geochemical and isotopic observations and temperature measurements were carried out on the different springs and wells for a period of three years (1984-1986). Constant water characteristics with time were observed in four water-points; two wells had variable trends depending on mixing processes. A groundwater circulation model characterized by flowpaths of different length and depth is suggested by the variety of chemical and isotopic characteristics and is consistent with geothermometry, which indicates temperatures up to 25{degrees} C higher than those measured at the spring emergencies. An important water supply to the system comes from local recharge, although regional circulation may also be present, particularly in the eastern part of the investigated area.

  19. McGee Mountain Geoprobe Survey, Humboldt County, Nevada

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Richard Zehner

    2010-01-01

    This shapefile contains location and attribute data for a Geoprobe temperature survey conducted by Geothermal Technical Partners, Inc. during 2010. The purpose of direct push technology (“DPT”) probe activity at the McGee Mtn. Project, Nevada was to 1) determine bottom hole temperatures using nominal 1.5 inch probe tooling to place resistance temperature detectors (“RTD”) and 2) take water samples, if possible, to characterize the geothermometry of the system. A total of 23 holes were probed in five days for a cumulative total of 857.5 ft. at 21 sites at McGee Mountain. The probed holes ranged in depth from a maximum of 75 ft to a minimum of 10 ft and averaged 37.3ft. The average temperature of the 23 holes was 18.9⁰C, with a range of 12.0⁰C at site MMTG#1b to 42.0⁰C at site MMTG#19. . No water was encountered in any of the probed holes, with the exception of MMTG#10, and no water was collected for sampling. Zip file containing Arcview shapefile in UTM11 NAD83 projection. 5kb file size.

  20. Geology of the Pavana geothermal area, Departamento de Choluteca, Honduras, Central America: Field report

    SciTech Connect (OSTI)

    Eppler, D.B.; Heiken, G.; Wohletz, K.; Flores, W.; Paredes, J.R.; Duffield, W.A.

    1987-09-01

    The Pavana geothermal area is located in southern Honduras near the Gulf of Fonseca. This region is underlain by late Tertiary volcanic rocks. Within ranges near the geothermal manifestations, the rock sequences is characterized by intermediate to mafic laharic breccias and lavas overlain by silicic tuffs and lavas, which are in turn overlain by intermediate to mafic breccias, lavas, and tuffs. The nearest Quaternary volcanoes are about 40 km to the southwest, where the chain of active Central American volcanoes crosses the mouth of the Gulf of Fonseca. Structure of the Pavana area is dominated by generally northwest-trending, southwest-dipping normal faults. This structure is topographically expressed as northwest-trending escarpments that bound blocks of bedrock separated by asymmetric valleys that contain thin alluvial deposits. Thermal waters apparently issue from normal faults and are interpreted as having been heated during deep circulation along fault zones within a regional environment of elevated heat flow. Natural outflow from the main thermal area is about 3000 l/min of 60/sup 0/C water. Geothermometry of the thermal waters suggests a reservoir base temperature of about 150/sup 0/C.

  1. Resource investigation of low- and moderate-temperature geothermal areas in Paso Robles, California

    SciTech Connect (OSTI)

    Campion, L.F.; Chapman, R.H.; Chase, G.W.; Youngs, L.G.

    1983-01-01

    Ninety-eight geothermal wells and springs were identified and plotted, and a geologic map and cross sections were compiled. Detailed geophysical, geochemical, and geological surveys were conducted. The geological and geophysical work delineated the basement highs and trough-like depressions that can exercise control on the occurrence of the thermal waters. The Rinconada fault was also evident. Cross sections drawn from oil well logs show the sediments conforming against these basement highs and filling the depressions. It is along the locations where the sediments meet the basement highs that three natural warm springs in the area occur. Deep circulation of meteoric waters along faults seems to be a reasonable source for the warm water. The Santa Margarita, Pancho Rico, and Paso Robles Formations would be the first permeable zones that abut the faults through which water would enter. Temperatures and interpretation of well logs indicate the warmest aquifer at the base of the Paso Robles Formation. Warm water may be entering higher up in the section, but mixing with water from cooler zones seems to be evident. Geothermometry indicates reservoir temperatures could be as high as 91/sup 0/C (196/sup 0/F).

  2. Origin and diagenesis of clay minerals in relation to sandstone paragenesis: An example in eolian dune reservoirs and associated rocks, Permian upper part of the Minnelusa Formation, Powder River basin, Wyoming

    SciTech Connect (OSTI)

    Pollastro, R.M.; Schenk, C.J. )

    1991-06-01

    Eolian dune sandstones are the principal reservoir rocks in the Permian upper part of the Minnelusa Formation, Powder River basin, Wyoming. These sandstones formed as shorelines retreated and dunes migrated across siliciclastic sabkhas. Sandstones are mainly quartzarenites; on average, clay minerals constitute about 5 wt.% the whole rock. Although present in minor amounts, clay minerals play an important role in the diagenetic evolution of these sandstones. Allogenic clay minerals are present in shaly rock fragments and laminae. Early infiltration of clays into porous sabkha sands commonly form characteristic menisei or bridges between framework grains or, when more extensive, form coatings or rims on grain surfaces. Authigenic clays include nearly pure smectite, mixed-layer illite/smectite (I/S), and late diagenetic illite and corrensite; these clay minerals are present as pore-lining cements. In addition to the deposition and neoformation of clay minerals throughout sandstone paragenesis, the conversion of smectite to illite occurred as temperatures increased with progressive burial. A temperature of 103C is calculated at a present depth of 3,200 m using a geothermal gradient of 30C/km and a mean annual surface temperature of 7C. After correction for uplift and erosion (250 m), the maximum calculated temperature for the conversion of all random I/S to ordered I/S is 100C. This calculated temperature is in excellent agreement with temperatures of 100-110C implied from I/S geothermometry.

  3. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy

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

    Khatun, Sufia; Castner, Edward W.

    2014-11-26

    Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulkmore » IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.« less

  4. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy

    SciTech Connect (OSTI)

    Khatun, Sufia; Castner, Edward W.

    2014-11-26

    Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulk IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.

  5. Computational Modeling of Degradation of Substituted Benzyltrimethyl Ammonium: Preprint

    SciTech Connect (OSTI)

    Long, H.; Pivovar, B. S.

    2014-09-01

    The degradation of cations on the alkaline exchange membranes is the major challenge for alkaline membrane fuel cells. In this paper, we investigated the degradation barriers by density functional theory for substituted benzyltrimethyl ammonium (BTMA+) cations, which is one of the most commonly used cations for alkaline exchange membranes. We found that substituted cations with electron-releasing substituent groups at meta-position of the benzyl ring could result in improved degradation barriers. However, after investigating more than thirty substituted BTMA+ cations with ten different substituent groups, the largest improvement of degradation barriers is only 1.6 kcal/mol. This implies that the lifetime of alkaline membrane fuel cells could increase from a few months to a few years by using substituted BTMA+ cations, an encouraging but still limited improvement for real-world applications.

  6. Process and apparatus for recovery of fissionable materials from spent reactor fuel by anodic dissolution

    DOE Patents [OSTI]

    Tomczuk, Zygmunt; Miller, William E.; Wolson, Raymond D.; Gay, Eddie C.

    1991-01-01

    An electrochemical process and apparatus for the recovery of uranium and plutonium from spent metal clad fuel pins is disclosed. The process uses secondary reactions between U.sup.+4 cations and elemental uranium at the anode to increase reaction rates and improve anodic efficiency compared to prior art processes. In another embodiment of the process, secondary reactions between Cd.sup.+2 cations and elemental uranium to form uranium cations and elemental cadmium also assists in oxidizing the uranium at the anode.

  7. Fluorination utilizing thermodynamically unstable fluorides and fluoride salts thereof

    DOE Patents [OSTI]

    Bartlett, Neil; Whalen, J. Marc; Chacon, Lisa

    2000-12-12

    A method for fluorinating a carbon compound or cationic carbon compound utilizes a fluorination agent selected from thermodynamically unstable nickel fluorides and salts thereof in liquid anhydrous hydrogen fluoride. The desired carbon compound or cationic organic compound to undergo fluorination is selected and reacted with the fluorination agent by contacting the selected organic or cationic organic compound and the chosen fluorination agent in a reaction vessel for a desired reaction time period at room temperature or less.

  8. SEPARATION PROCESS USING COMPLEXING AND ADSORPTION

    DOE Patents [OSTI]

    Spedding, J.H.; Ayers, J.A.

    1958-06-01

    An adsorption process is described for separating plutonium from a solution of neutron-irradiated uranium containing ions of a compound of plutonium and other cations. The method consists of forming a chelate complex compound with plutoniunn ions in the solution by adding a derivative of 8- hydroxyquinoline, which derivative contains a sulfonic acid group, and adsorbing the remaining cations from the solution on a cation exchange resin, while the complexed plutonium remains in the solution.

  9. The use of Ahuachapan fluid chemistry to indicate natural state conditions and reservoir processes during exploitation

    SciTech Connect (OSTI)

    Treusdell, A.H. ); Aunzo, Z.; Bodvarsson, G. ); Alonso, J.; Campos, A. )

    1989-01-01

    Chemical analyses of production fluids from Ahuachapan, El Salvador, have been used to indicate natural state reservoir fluid temperatures and chloride concentrations and reservoir processes resulting from exploitation. Geothermometer temperatures (Na--K--Ca and SiO{sub 2}) and calculated aquifer Cl for early flows show a gradient from about 265{degree}C and 9000 ppM Cl in the western part of the well field to 235{degree}C and 6000 ppM Cl in the eastern part. The geochemical temperatures are 10--20{degree}C higher than early downhole measurements. Since exploitation started, pressures have declined over most of the drilled area with boiling and excess-enthalpy discharges in the eastern and western parts. In the center of the field, a number of wells show mixing with cooler, less-saline water. These wells are nearly coincident with a major NE-SW oriented fault that may be the conduit for downward recharge of cooler fluids from an overlying aquifer. 12 refs., 9 figs., 1 tab.

  10. Apacheta, a new geothermal prospect in Northern Chile

    SciTech Connect (OSTI)

    Urzua, Luis; Powell, Tom; Cumming, William B.; Dobson, Patrick

    2002-05-24

    The discovery of two high-temperature fumaroles, with gas geochemistry compatible with an economic geothermal system, established Apacheta as one of the most attractive geothermal exploration prospects in northern Chile. These remote fumaroles at 5,150 m elevation were first sampled in 1999 by ENAP and its partners, following up on the reports of a CODELCO water exploration well that flowed small amounts of dry steam at 4,540 m elevation in the valley 4.5 km east of the fumaroles. The prospect is associated with a Plio-Pleistocene volcanic complex located within a NW-trending graben along the axis of the high Andes. The regional water table is 4,200 masl. There are no hot springs, just the 88 degrees C steam well and the 109 degrees and 118 degrees C fumaroles with gas compositions that indicate reservoir temperatures of greater than or equal to 250 degrees C, using a variety of gas geothermometers. An MT-TDEM survey was completed in 2001-2002 by Geotermica del Norte (SDN), an ENAP-C ODELCO partnership, to explore the Apacheta geothermal concession. The survey results indicated that base of the low resistivity clay cap has a structural apex just west of the fumaroles, a pattern typically associated with shallow permeability within a high temperature geothermal resource. SGN plans to drill at least one exploration well in 2002-03 to characterize a possible economic resource at Apacheta.

  11. Three-Dimensional Geologic Characterization of Geothermal Systems: Astor Pass, Nevada, USA

    SciTech Connect (OSTI)

    Siler, Drew L; Mayhew, Brett; Faulds, James E

    2012-09-30

    Geothermal systems in the Great Basin, USA, are controlled by a variety of fault intersection and fault interaction areas. Understanding the specific geometry of the structures most conducive to geothermal circulation is crucial in order to both mitigate the costs of geothermal exploration (especially drilling) and to identify blind geothermal systems (no surface expression). Astor Pass, Nevada, one such blind geothermal system, lies near the boundary between two distinct structural domains, the Walker Lane and the Basin and Range, and exhibits characteristics of each setting. Both northwest-striking, left-stepping dextral faults of the Walker Lane and kinematically linked northerly striking normal faults associated with the Basin and Range are present at Astor Pass. Previous studies identified a blind geothermal system controlled by the intersection of northwest-striking dextral and north-northwest-striking normal faults. Wells drilled into the southwestern quadrant of the fault intersection yielded 94˚C fluids, with geothermometers suggesting significantly higher maximum temperatures. Additional data, including reprocessed 2D seismic data and petrologic analysis of well cuttings, were integrated with existing and reinterpreted geologic maps and cross-sections to aid construction of a 3D geologic model. This comprehensive 3D integration of multiple data sets allows characterization of the structural setting of the Astor Pass blind geothermal system at a level of detail beyond what independent data interpretation can provide. Our analysis indicates that the blind geothermal system is controlled by two north- to northwest-plunging fault intersections.

  12. I/S and C/S mixed layers, some indicators of recent physical-chemical changes in active geothermal systems: The case study of Chipilapa (El Salvador)

    SciTech Connect (OSTI)

    Beaufort, D.; Papapanagiotou, P.; patrier, P.; Fouillac, A.M.; Traineau, H.

    1996-01-24

    I/S and C/S mixed layers from the geothermal field of Chipilapa (El Salvador) have been studied in details in order to reevaluate their potential use as indicator of the thermodynamic conditions in which they were formed. It is funded that overprinting of clay bearing alteration stages is common. For a given alteration stage, the spatial variation of I/S and C/S mixed layer ininerals is controlled by kinetics of mixed layer transformation and not only by temperature. Clay geo-thermometers cannot give reliable results because the present crystal-chemical states of the I/S and C/S mixed layers is not their initial state, it was aquired during the overall hydrothermal history which post dated the nucleation of smectitic clay material at high temperature. Occurrences of smectites or smectite-rich mixed layers at high temperature in reservoirs is a promising guide for reconstruct the zones in which boiling or mixing of non isotherinal fluids occurred very recently or still presently.

  13. BACA Project: geothermal demonstration power plant. Final report

    SciTech Connect (OSTI)

    Not Available

    1982-12-01

    The various activities that have been conducted by Union in the Redondo Creek area while attempting to develop the resource for a 50 MW power plant are described. The results of the geologic work, drilling activities and reservoir studies are summarized. In addition, sections discussing the historical costs for Union's involvement with the project, production engineering (for anticipated surface equipment), and environmental work are included. Nineteen geothermal wells have been drilled in the Redondo Creek area of the Valles Caldera: a prominent geologic feature of the Jemez mountains consisting of Pliocene and Pleistocene age volcanics. The Redondo Creek area is within a complex longitudinal graben on the northwest flank of the resurgent structural dome of Redondo Peak and Redondo Border. The major graben faults, with associated fracturing, are geologically plausible candidates for permeable and productive zones in the reservoir. The distribution of such permeable zones is too erratic and the locations too imprecisely known to offer an attractive drilling target. Log analysis indicates there is a preferred mean fracture strike of N31W in the upper portion of Redondo Creek wells. This is approximately perpendicular to the major structure in the area, the northeast-striking Redondo Creek graben. The geothermal fluid found in the Redondo Creek reservoir is relatively benign with low brine concentrations and moderate H/sub 2/S concentrations. Geothermometer calculations indicate that the reservoir temperature generally lies between 500/sup 0/F and 600/sup 0/F, with near wellbore flashing occurring during the majority of the wells' production.

  14. Salt effects on isotope partitioning and their geochemical implications: An overview

    SciTech Connect (OSTI)

    Horita, J.; Cole, D.R.; Fortier, S.M.

    1996-01-01

    Essential to the use of stable isotopes as natural tracers and geothermometers is the knowledge of equilibrium isotope partitioning between different phases and species, which is usually a function of temperature only. The one exception known to date is oxygen and hydrogen isotope fractionation between liquid water and other phases (steam, gases, minerals), which changes upon the addition of salts to water, i.e., the isotope salt salt effect. Our knowledge of this effect, the difference between activity and composition (a-X) of isotopic water molecules in salt solutions, is very limited and controversial, especially at elevated temperatures. For the last several years, we have been conducting a detailed, systematic experimental study at Oak Ridge National Laboratory to determine the isotope salt effects from room temperature to elevated temperatures (currently to 500{degree}C). From this effort, a simple, coherent picture of the isotope salt effect is emerging, that differs markedly from the complex results reported in the literature. In this communication, we present an overview on the isotope salt effect, obtained chiefly from our study. Observed isotope salt effects in salt solutions are significant even at elevated temperatures. The importance and implications of the isotope salt effect for isotopic studies of brine-dominated systems are also discussed in general terms.

  15. Water information bulletin No. 30 geothermal investigations in Idaho

    SciTech Connect (OSTI)

    Mitchell, J.C.; Johnson, L.L.; Anderson, J.E.; Spencer, S.G.; Sullivan, J.F.

    1980-06-01

    There are 899 thermal water occurrences known in Idaho, including 258 springs and 641 wells having temperatures ranging from 20 to 93/sup 0/C. Fifty-one cities or towns in Idaho containing 30% of the state's population are within 5 km of known geothermal springs or wells. These include several of Idaho's major cities such as Lewiston, Caldwell, Nampa, Boise, Twin Falls, Pocatello, and Idaho Falls. Fourteen sites appear to have subsurface temperatures of 140/sup 0/C or higher according to the several chemical geothermometers applied to thermal water discharges. These include Weiser, Big Creek, White Licks, Vulcan, Roystone, Bonneville, Crane Creek, Cove Creek, Indian Creek, and Deer Creek hot springs, and Raft River, Preston, and Magic Reservoir areas. These sites could be industrial sites, but several are in remote areas away from major transportation and, therefore, would probably be best utilized for electrical power generation using the binary cycle or Magma Max process. Present uses range from space heating to power generation. Six areas are known where commercial greenhouse operations are conducted for growing cut and potted flowers and vegetables. Space heating is substantial in only two places (Boise and Ketchum) although numerous individuals scattered throughout the state make use of thermal water for space heating and private swimming facilities. There are 22 operating resorts using thermal water and two commercial warm-water fish-rearing operations.

  16. Hydrology and geochemistry of thermal ground water in southwestern Idaho and north-central Nevada

    SciTech Connect (OSTI)

    Young, H.W.; Lewis, R.E.

    1982-01-01

    Chemical analyses of water from 12 wells and 9 springs indicate that nonthermal waters are a calcium bicarbonate type; thermal waters are a sodium carbonate or bicarbonate type. Chemical geothermometers indicate probable maximum reservoir temperatures are near 100/sup 0/ Celsius. Concentration of tritium in the thermal water is near zero. Depletion of stable isotopes in the hot waters relative to present-day meteoric waters indicates recharge to the system probably occurred when the climate averaged 3/sup 0/ to 5/sup 0/ Celsius colder than at present. Temperatures about 3.5/sup 0/ Celsius colder than at present occurred during periods of recorded Holocene glacial advances and indicate a residence time of water in the system of at least several thousand years. Residence time calculated on the basis of reservoir volume and thermal-water discharge is 3400 to 6800 years for an effective reservoir porosity of 0.05 and 0.10, respectively. Preliminary analyses of carbon-14 determinations indicate an age of the hot waters of about 18,000 to 25,000 years. The proposed conceptual model for the area is one of an old system, where water has circulated for thousands, even tens of thousands, of years. Within constraints imposed by the model described, reservoir thermal energy for the geothermal system in southwestern Idaho and north-central Nevada is about 130 x 10/sup 18/ calories.

  17. Hydrogeochemistry and preliminary reservoir model of the Platanares Geothermal System, Honduras, Central America

    SciTech Connect (OSTI)

    Goff, F.; Shevenell, L.; Janik, C.J.; Truesdell, A.H.; Grigsby, C.O.; Paredes, R.

    1986-01-01

    A detailed hydrogeochemical investigation has been performed at Platanares, Honduras in preparation for shallow geothermal exploration drilling. Platanares is not associated with any Quaternary volcanism but lies in a tectonic zone of late Tertiary to Quaternary extension. Thermal fluids are characterized by pH between 7 and 10, Cl < 40 mg/l, HCO/sub 3/ > SO/sub 4/ > Cl, B less than or equal to 17 mg/l, Li less than or equal to 4 mg/l and As less than or equal to 1.25 mg/l. Various geochemical indicators show that mixing of hot and cold end-member fluids is an important hydrologic process at this site. Geothermometers indicate the geothermal system equilibrated at roughly 225/sup 0/C while trace element chemistry indicates the reservoir resides in Cretaceous red beds of the Valle de Angeles Group. Based on the discharge rates of thermal features, the minimum power output of the Platanares geothermal site is about 45 MW (thermal).

  18. Cask weeping mitigation

    DOE Patents [OSTI]

    Krumhansl, James L. (Albuquerque, NM); Brady, Patrick V. (Albuquerque, NM); Teter, David M. (Edgewood, NM); McConnell, Paul (Albuquerque, NM)

    2007-09-18

    A method (and concomitant kit) for treating a surface to reduce subsequent .sup.137Cs nuclide desorption comprising contacting the surface with a first cation-containing solution, the cation being one or more of Cs.sup.+, Rb.sup.+, Ag.sup.+, Tl.sup.+, K.sup.+, and NH.sub.4.sup.+, and contacting the surface with a second cation-containing solution, the cation being one or more of Cs.sup.+, Rb.sup.+, Ag.sup.+, Tl.sup.+, K.sup.+, and NH.sub.4.sup.+, thereby reducing amounts of radioactive cesium embedded in clays found on the surface.

  19. Superconducting materials and method of making same

    DOE Patents [OSTI]

    Bunker, B.C.; Lamppa, D.L.; Voigt, J.A.

    1988-02-25

    A new chemical method and apparatus for preparing precursor powders for metal oxide superconductor ceramics are described. Superconductors, free of contaminating cations, are thus obtained. 10 figs.

  20. Commercial Buildings Energy Consumption and Expenditures 1992

    U.S. Energy Information Administration (EIA) Indexed Site

    Appendix I Related EIA Publications on Energy Consumption For information about how to obtain these publi- cations, see the inside cover of this report. Please note that the...

  1. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    strengths and organic matter concentrations were ... The mobilization of colloids and metal cations occurred ... A mathematical framework for analysis of water tracers: Part ...

  2. High-Throughput and Combinatorial Screening of Hydrogen Storage...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    ternary system and find the cation matrix that stabilizes a certain anionic complex Theory guidance: Monte Carlo (MC) technique provides minimum energy structures for subsequent ...

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    ... ; Center for Quantum Science and Engineering, National Taiwan University, Taipei, ... February 2016 Cation stoichiometry optimization of SrTiOsub 3 (110) thin films with ...

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    Office of Scientific and Technical Information (OSTI)

    Debusschere, Bert J. ; Sargsyan, Khachik ; Safta, Cosmin The UQ Toolkit (UQTk) is a collection of libraries and tools for the quanti cation of uncer- tainty in numerical model ...

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    Office of Scientific and Technical Information (OSTI)

    ... This slow motion is attributed to properties of the cation structure. less ... Radial distribution functions (RDF) were computed and structure 14 functions were generated to compare ...

  6. Methods and energy storage devices utilizing electrolytes having surface-smoothing additives

    SciTech Connect (OSTI)

    Xu, Wu; Zhang, Jiguang; Graff, Gordon L; Chen, Xilin; Ding, Fei

    2015-11-12

    Electrodeposition and energy storage devices utilizing an electrolyte having a surface-smoothing additive can result in self-healing, instead of self-amplification, of initial protuberant tips that give rise to roughness and/or dendrite formation on the substrate and anode surface. For electrodeposition of a first metal (M1) on a substrate or anode from one or more cations of M1 in an electrolyte solution, the electrolyte solution is characterized by a surface-smoothing additive containing cations of a second metal (M2), wherein cations of M2 have an effective electrochemical reduction potential in the solution lower than that of the cations of M1.

  7. RussiaSNL2-web.indd

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

    ... Modifi ed for the Web Environ- ment Com- muni- cation Note A 1 A A S A T A 1 Collaboration between Sandia National Laboratories (SNL), ...

  8. DISCLAIMER

    Office of Legacy Management (LM)

    ... results for this sampling event under requisition number 18800. METALS I MAJOR CATIONS ANALYSIS Uranium was analyzed by inductively coupled plasma-mass spectrometry (ICP-MS). ...

  9. MONUMENT VALLEY

    Office of Legacy Management (LM)

    ... METALSIMAJOR CATIONS ANALYSIS The determination uranium was analyzed by inductively coupled plasma-mass spectrometry (ICP- MS. AU quality control requirements were met during the ...

  10. MONUMENT VALLEY

    Office of Legacy Management (LM)

    ... METALSMA JOR CATIONS ANALYSIS Uranium was analyzed by inductively coupled plasma-mass spectrometry (ICP-MS). No data validation flags were required. INORGANIC ANALYSIS Chloride, ...

  11. MONUMENT VALLEY

    Office of Legacy Management (LM)

    ... METALSIMAJOR CATIONS ANALYSES The determination of uranium was done using inductively coupled plasma-mass spectrometry (ICP-MS). All quality control requirements were met during ...

  12. Membrane Protein Crystallization in Lipidic Mesophases. Hosting...

    Office of Scientific and Technical Information (OSTI)

    Unexpectedly, all lipids produced high-quality, structure-grade crystals with gramicidin ... Subject: 59 BASIC BIOLOGICAL SCIENCES; 60 APPLIED LIFE SCIENCES; ANTIBIOTICS; CATIONS; ...

  13. Electrochemical Methods of Upgrading Pyrolysis Oils Presentation...

    Broader source: Energy.gov (indexed) [DOE]

    ... 2 - Approach (Technical) Organic Acid Separations Dual Membrane Cell (Cation and Anion Exchange) Anion Exchange Membrane Development Theoretical Prediction and Experimental ...

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    Office of Scientific and Technical Information (OSTI)

    ... and strontium from alkaline nitrate media simulating alkaline high level wastes ... Since a cation-exchange mechanism is operating in these systems, the influence of the IL ...

  15. Stoichiometry-driven metal-to-insulator transition in NdTiO{sub...

    Office of Scientific and Technical Information (OSTI)

    A direct correlation between cation stoichiometry, transport behavior, and the temperature ... Department of Chemical Engineering and Materials Science, University of Minnesota, ...

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    (1) biosynthesis (1) bisabolane (1) cations (1) cluster compounds (1) drugs (1) ethanol (1) ethanol fuels (1) food (1) fungal genomics (1) fungi (1) inorganic, organic, physical, ...

  17. Interlaced crystals having a perfect Bravais lattice and complex...

    Office of Scientific and Technical Information (OSTI)

    Here we report the synthesis and characterization of ternary nanoparticles (two cations and one anion) that exhibit a new form of crystal-line order: an uninterrupted, perfect, ...

  18. Search for: All records | DOE PAGES

    Office of Scientific and Technical Information (OSTI)

    ... Here we report the synthesis and characterization of ternary nanoparticles (two cations and one anion) that exhibit a new form of crystal-line order: an uninterrupted, perfect, ...

  19. Reversible Sigma C-C Bond Formation

    Office of Scientific and Technical Information (OSTI)

    ... This article shows that single electron transfer (SET) to a -symmetry LUMO of a ... shape that differ mainly by a scaling factor for the neutral and cationic adducts, ...

  20. Microsoft Word - Loan Guarantee Solicitation _final_ 8-14-06...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    ...CATIONS...... 3 C. PAYMENT TO DOE OF THE LOAN GUARANTEE SUBSIDY ... C. PAYMENT TO DOE OF THE LOAN GUARANTEE SUBSIDY COSTS Section 1702(b) of EPAct 2005 ...

  1. ~SPR~PUCED AT TM NATIONAL ARCHIVES

    Office of Legacy Management (LM)

    t - Division of Production IV - *&When senar&from encsz,urzs, handle this. documel Division of Military A .ppli- cation Division of Engineerir: Division of Research Secretariat

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    electrodes - solar, charge transport, materials and chemistry by design, optics, synthesis (novel materials) (2) atomic force microscopy (1) cation intercalation (1) ...

  3. Structural Interactions within Lithium Salt Solvates: Cyclic...

    Office of Scientific and Technical Information (OSTI)

    and ester solvents coordinate Li+ cations in electrolyte solutions for lithium batteries. One approach to gleaning significant insight into these interactions is to examine...

  4. Synthesis of electroactive ionic liquids for flow battery applications

    SciTech Connect (OSTI)

    Anderson, Travis Mark; Ingersoll, David; Staiger, Chad; Pratt, Harry

    2015-09-01

    The present disclosure is directed to synthesizing metal ionic liquids with transition metal coordination cations, where such metal ionic liquids can be used in a flow battery. A cation of a metal ionic liquid includes a transition metal and a ligand coordinated to the transition metal.

  5. Alkali slurry ozonation to produce a high capacity nickel battery material

    DOE Patents [OSTI]

    Jackovitz, John F.; Pantier, Earl A.

    1984-11-06

    A high capacity battery material is made, consisting essentially of hydrated Ni(II) hydroxide, and about 5 wt. % to about 40 wt. % of Ni(IV) hydrated oxide interlayer doped with alkali metal cations selected from potassium, sodium and lithium cations.

  6. ERYTHROPOIETIC FACTOR PURIFICATION

    DOE Patents [OSTI]

    White, W.F.; Schlueter, R.J.

    1962-05-01

    A method is given for purifying and concentrating the blood plasma erythropoietic factor. Anemic sheep plasma is contacted three times successively with ion exchange resins: an anion exchange resin, a cation exchange resin at a pH of about 5, and a cation exchange resin at a pH of about 6. (AEC)

  7. Crystalline bipyridinium radical complexes and uses thereof

    DOE Patents [OSTI]

    Fahrenbach, Albert C.; Barnes, Jonathan C.; Li, Hao; Stoddart, J. Fraser; Basuray, Ashish Neil; Sampath, Srinivasan

    2015-09-01

    Described herein are methods of generating 4,4'-bipyridinium radical cations (BIPY.sup..cndot.+), and methods for utilizing the radical-radical interactions between two or more BIPY.sup..cndot.+ radical cations that ensue for the creation of novel materials for applications in nanotechnology. Synthetic methodologies, crystallographic engineering techniques, methods of physical characterization, and end uses are described.

  8. Production of sodium-22 from proton irradiated aluminum

    DOE Patents [OSTI]

    Taylor, Wayne A.; Heaton, Richard C.; Jamriska, David J.

    1996-01-01

    A process for selective separation of sodium-22 from a proton irradiated minum target including dissolving a proton irradiated aluminum target in hydrochloric acid to form a first solution including aluminum ions and sodium ions, separating a portion of the aluminum ions from the first solution by crystallization of an aluminum salt, contacting the remaining first solution with an anion exchange resin whereby ions selected from the group consisting of iron and copper are selectively absorbed by the anion exchange resin while aluminum ions and sodium ions remain in solution, contacting the solution with an cation exchange resin whereby aluminum ions and sodium ions are adsorbed by the cation exchange resin, and, contacting the cation exchange resin with an acid solution capable of selectively separating the adsorbed sodium ions from the cation exchange resin while aluminum ions remain adsorbed on the cation exchange resin is disclosed.

  9. Self-regenerating column chromatography

    DOE Patents [OSTI]

    Park, Woo K.

    1995-05-30

    The present invention provides a process for treating both cations and anions by using a self-regenerating, multi-ionic exchange resin column system which requires no separate regeneration steps. The process involves alternating ion-exchange chromatography for cations and anions in a multi-ionic exchange column packed with a mixture of cation and anion exchange resins. The multi-ionic mixed-charge resin column works as a multi-function column, capable of independently processing either cationic or anionic exchange, or simultaneously processing both cationic and anionic exchanges. The major advantage offered by the alternating multi-function ion exchange process is the self-regeneration of the resins.

  10. Long-range magnetic ordering in Ba{sub 2}CoS{sub 3}: A neutron diffraction study

    SciTech Connect (OSTI)

    Headspith, D.A. [Department of Chemistry, University of Hull, Cottingham Road, Hull HU6 7RX (United Kingdom); Battle, P.D. [Inorganic Chemistry Laboratory, Oxford University, South Parks Road, Oxford OX1 3QR (United Kingdom); Francesconi, M.G. [Department of Chemistry, University of Hull, Cottingham Road, Hull HU6 7RX (United Kingdom)], E-mail: m.g.francesconi@hull.ac.uk

    2007-10-15

    Neutron powder diffraction has been used to determine the magnetic structure of the quasi-one-dimensional compound Ba{sub 2}CoS{sub 3}, which contains linear [001] chains of vertex-sharing CoS{sub 4} tetrahedra, spaced apart by Ba{sup 2+} cations. At 1.5 K the Co{sup 2+} cations in the chains are antiferromagnetically ordered with an ordered magnetic moment of 1.97(4) {mu}{sub B} per cation aligned along [100]. Each Co{sup 2+} cation is ferromagnetically aligned with four cation in neighbouring chains and antiferromagnetically aligned with two others. - Graphical abstract: Neutron powder diffraction has been used to prove that Ba{sub 2}CoS{sub 3} shows long-range antiferromagnetic order at low temperatures, despite the quasi-one-dimensional arrangement of the CoS{sub 4} tetrahedra in the crystal structure.

  11. Origins of secondary silica within Yucca Mountain, Nye County, southwestern Nevada

    SciTech Connect (OSTI)

    Moscati, R.J.; Whelan, J.F.

    1996-09-01

    The accuracy of predictions of the hydrologic response of Yucca Mountain to future climate depends largely on how well relations between past climate and hydrology can be resolved. To advance this reconstruction, secondary minerals in and near Yucca Mountain, deposited by ground waters that originated both as surficial recharge at Yucca Mountain and from regional aquifers, are being studied to determine past ground-water sources and chemistries. Preliminary data on stable oxygen isotopes indicate that, although silica (opal, quartz, and chalcedony) and calcite and have formed in similar settings and from somewhat similar fluids, the authors have found no compelling evidence of coprecipitation or formation from identical fluids. If verified by further analyses, this precludes the use of silica-calcite mineral pairs for precise geothermometry. The preliminary data also indicate that opal and calcite occurrences in pedogenic and unsaturated-zone settings are invariably compatible with formation under modern ambient surface or subsurface temperatures. Silica and calcite stable-isotope studies are being integrated with soil geochemical modeling. This modeling will define the soil geochemical condition (climate) leading to opal or calcite deposition and to the transfer functions that may apply at the meteorologic soil unsaturated-zone interfaces. Additional study of pedogenic and unsaturated-zone silica is needed to support these models. The hypothesis that the transformation of vapor-phase tridymite to quartz requires saturated conditions is being tested through stable oxygen-isotope studies of lithophysal tridymite/quartz mixtures. Should this hypothesis be verified, mineralogic analysis by X-ray diffraction theoretically would permit reconstruction of past maximum water-table elevations.

  12. Silver Peak Innovative Exploration Project (Ram Power Inc.)

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Miller, Clay

    2010-01-01

    Data generated from the Silver Peak Innovative Exploration Project, in Esmeralda County, Nevada, encompasses a deep-circulation (amagmatic) meteoric-geothermal system circulating beneath basin-fill sediments locally blanketed with travertine in western Clayton Valley (lithium-rich brines from which have been mined for several decades). Spring- and shallow-borehole thermal-water geochemistry and geothermometry suggest that a Silver Peak geothermal reservoir is very likely to attain the temperature range 260- 300oF (~125-150oC), and may reach 300-340oF (~150-170oC) or higher (GeothermEx, Inc., 2006). Results of detailed geologic mapping, structural analysis, and conceptual modeling of the prospect (1) support the GeothermEx (op. cit.) assertion that the Silver Peak prospect has good potential for geothermal-power production; and (2) provide a theoretical geologic framework for further exploration and development of the resource. The Silver Peak prospect is situated in the transtensional (regional shearing coupled with extension) Walker Lane structural belt, and squarely within the late Miocene to Pliocene (11 Ma to ~5 Ma) Silver Peak-Lone Mountain metamorphic core complex (SPCC), a feature that accommodated initial displacement transfer between major right-lateral strike- slip fault zones on opposite sides of the Walker Lane. The SPCC consists essentially of a ductiley-deformed lower plate, or core, of Proterozoic metamorphic tectonites and tectonized Mesozoic granitoids separated by a regionally extensive, low-angle detachment fault from an upper plate of severely stretched and fractured structural slices of brittle, Proterozoic to Miocene-age lithologies. From a geothermal perspective, the detachment fault itself and some of the upper-plate structural sheets could function as important, if secondary, subhorizontal thermal-fluid aquifers in a Silver Peak hydrothermal system.

  13. Silver Peak Innovative Exploration Project (Ram Power Inc.)

    SciTech Connect (OSTI)

    Miller, Clay

    2010-01-01

    Data generated from the Silver Peak Innovative Exploration Project, in Esmeralda County, Nevada, encompasses a “deep-circulation (amagmatic)” meteoric-geothermal system circulating beneath basin-fill sediments locally blanketed with travertine in western Clayton Valley (lithium-rich brines from which have been mined for several decades). Spring- and shallow-borehole thermal-water geochemistry and geothermometry suggest that a Silver Peak geothermal reservoir is very likely to attain the temperature range 260- 300oF (~125-150oC), and may reach 300-340oF (~150-170oC) or higher (GeothermEx, Inc., 2006). Results of detailed geologic mapping, structural analysis, and conceptual modeling of the prospect (1) support the GeothermEx (op. cit.) assertion that the Silver Peak prospect has good potential for geothermal-power production; and (2) provide a theoretical geologic framework for further exploration and development of the resource. The Silver Peak prospect is situated in the transtensional (regional shearing coupled with extension) Walker Lane structural belt, and squarely within the late Miocene to Pliocene (11 Ma to ~5 Ma) Silver Peak-Lone Mountain metamorphic core complex (SPCC), a feature that accommodated initial displacement transfer between major right-lateral strike- slip fault zones on opposite sides of the Walker Lane. The SPCC consists essentially of a ductiley-deformed lower plate, or “core,” of Proterozoic metamorphic tectonites and tectonized Mesozoic granitoids separated by a regionally extensive, low-angle detachment fault from an upper plate of severely stretched and fractured structural slices of brittle, Proterozoic to Miocene-age lithologies. From a geothermal perspective, the detachment fault itself and some of the upper-plate structural sheets could function as important, if secondary, subhorizontal thermal-fluid aquifers in a Silver Peak hydrothermal system.

  14. Final Scientific/Technical Report – DE-EE0002960 Recovery Act. Detachment faulting and Geothermal Resources - An Innovative Integrated Geological and Geophysical Investigation of Pearl Hot Spring, Nevada

    SciTech Connect (OSTI)

    Stockli, Daniel F.

    2015-11-30

    The Pearl Host Spring Geothermal Project funded by the DoE Geothermal Program was a joint academic (KU/UT & OU) and industry collaboration (Sierra and Ram Power) to investigate structural controls and the importance of low-angle normal faults on geothermal fluid flow through a multifaceted geological, geophysical, and geochemical investigation in west-central Nevada. The study clearly showed that the geothermal resources in Clayton Valley are controlled by the interplay between low-angle normal faults and active deformation related to the Walker Lane. The study not only identified potentially feasible blind geothermal resource plays in eastern Clayton Valley, but also provide a transportable template for exploration in the area of west-central Nevada and other regional and actively-deforming releasing fault bends. The study showed that deep-seated low-angle normal faults likely act as crustal scale permeability boundaries and could play an important role in geothermal circulation and funneling geothermal fluid into active fault zones. Not unique to this study, active deformation is viewed as an important gradient to rejuvenated fracture permeability aiding the long-term viability of blind geothermal resources. The technical approach for Phase I included the following components, (1) Structural and geological analysis of Pearl Hot Spring Resource, (2) (U-Th)/He thermochronometry and geothermometry, (3) detailed gravity data and modeling (plus some magnetic and resistivity), (4) Reflection and Refraction Seismic (Active Source), (5) Integration with existing and new geological/geophysical data, and (6) 3-D Earth Model, combining all data in an innovative approach combining classic work with new geochemical and geophysical methodology to detect blind geothermal resources in a cost-effective fashion.

  15. Geothermal Geodatabase for Rico Hot Springs Area and Lemon Hot Springs, Dolores and San Miguel Counties, Colorado

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Zehner, Richard

    2012-11-01

    Geothermal Geodatabase for Rico Hot Springs Area and Lemon Hot Springs, Dolores and San Miguel Counties, Colorado By Richard “Rick” Zehner Geothermal Development Associates Reno Nevada USA For Flint Geothermal LLC, Denver Colorado Part of DOE Grant EE0002828 2013 This is an ESRI geodatabase version 10, together with an ESRI MXD file version 10.2 Data is in UTM Zone 13 NAD27 projection North boundary: approximately 4,215,000 South boundary: approximately 4,160,000 West boundary: approximately 216,000 East boundary: approximately 245,000 This geodatabase was built to cover several geothermal targets developed by Flint Geothermal in 2012 during a search for high-temperature systems that could be exploited for electric power development. Several of the thermal springs have geochemistry and geothermometry values indicative of high-temperature systems. In addition, the explorationists discovered a very young Climax-style molybdenum porphyry system northeast of Rico, and drilling intersected thermal waters at depth. The datasets in the geodatabase are a mixture of public domain data as well as data collected by Flint Geothermal, now being made public. It is assumed that the user has internet access, for the mxd file accesses ESRI’s GIS servers. Datasets include: 1. Structural data collected by Flint Geothermal 2. Point information 3. Mines and prospects from the USGS MRDS dataset 4. Results of reconnaissance shallow (2 meter) temperature surveys 5. Air photo lineaments 6. Areas covered by travertine 7. Groundwater geochemistry 8. Land ownership in the Rico area 9. Georeferenced geologic map of the Rico Quadrangle, by Pratt et al. 10. Various 1:24,000 scale topographic maps

  16. Silver Peak Innovative Exploration Project (Ram Power Inc.)

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Miller, Clay

    Data generated from the Silver Peak Innovative Exploration Project, in Esmeralda County, Nevada, encompasses a deep-circulation (amagmatic) meteoric-geothermal system circulating beneath basin-fill sediments locally blanketed with travertine in western Clayton Valley (lithium-rich brines from which have been mined for several decades). Spring- and shallow-borehole thermal-water geochemistry and geothermometry suggest that a Silver Peak geothermal reservoir is very likely to attain the temperature range 260- 300oF (~125-150oC), and may reach 300-340oF (~150-170oC) or higher (GeothermEx, Inc., 2006). Results of detailed geologic mapping, structural analysis, and conceptual modeling of the prospect (1) support the GeothermEx (op. cit.) assertion that the Silver Peak prospect has good potential for geothermal-power production; and (2) provide a theoretical geologic framework for further exploration and development of the resource. The Silver Peak prospect is situated in the transtensional (regional shearing coupled with extension) Walker Lane structural belt, and squarely within the late Miocene to Pliocene (11 Ma to ~5 Ma) Silver Peak-Lone Mountain metamorphic core complex (SPCC), a feature that accommodated initial displacement transfer between major right-lateral strike- slip fault zones on opposite sides of the Walker Lane. The SPCC consists essentially of a ductiley-deformed lower plate, or core, of Proterozoic metamorphic tectonites and tectonized Mesozoic granitoids separated by a regionally extensive, low-angle detachment fault from an upper plate of severely stretched and fractured structural slices of brittle, Proterozoic to Miocene-age lithologies. From a geothermal perspective, the detachment fault itself and some of the upper-plate structural sheets could function as important, if secondary, subhorizontal thermal-fluid aquifers in a Silver Peak hydrothermal system.

  17. A striking effect of ionic-liquid anions in the extraction of Sr2+ and Cs+ by dicyclohexano-18-crown-6

    SciTech Connect (OSTI)

    Luo, Huimin; Dai, Sheng; Bonnesen, Peter V; Haverlock, Tamara; Moyer, Bruce A; Buchanan III, A C

    2006-01-01

    The nature of the ionic-liquid (IL) anion has been found to have a remarkable effect on the solvent extraction of Sr2+ and Cs+ by dicyclohexano-18-crown-6 dissolved in ionic liquids. In particular, the extraction efficiency increases with the hydrophobicity of the IL anion as reflected by the solubility in water of ILs having a common cation. Since a cation-exchange mechanism is operating in these systems, the influence of the IL anion is in large part attributable to an expected Le Chatelier effect in which a greater aqueous concentration of IL cation, obtained when using an IL anion of lower hydrophobicity, opposes cation exchange. This dependence is opposite to that found for IL cations, indicating a significant advantage of using ILs with hydrophobic anions for cation extraction. Furthermore, the extraction selectivity for Sr2+ over Na+, K+, and Cs+ can be significantly improved through the use of hydrophobic anions for the ILs containing 1-ethyl-3-methylimidazolium or 1-butyl-3-methylimidazolium cations.

  18. Evaluation of low-temperature geothermal potential in Cache Valley, Utah. Report of investigation No. 174

    SciTech Connect (OSTI)

    de Vries, J.L.

    1982-11-01

    Field work consisted of locating 90 wells and springs throughout the study area, collecting water samples for later laboratory analyses, and field measurement of pH, temperature, bicarbonate alkalinity, and electrical conductivity. Na/sup +/, K/sup +/, Ca/sup +2/, Mg/sup +2/, SiO/sub 2/, Fe, SO/sub 4//sup -2/, Cl/sup -/, F/sup -/, and total dissolved solids were determined in the laboratory. Temperature profiles were measured in 12 additional, unused walls. Thermal gradients calculated from the profiles were approximately the same as the average for the Basin and Range province, about 35/sup 0/C/km. One well produced a gradient of 297/sup 0/C/km, most probably as a result of a near-surface occurrence of warm water. Possible warm water reservoir temperatures were calculated using both the silica and the Na-K-Ca geothermometers, with the results averaging about 50 to 100/sup 0/C. If mixing calculations were applied, taking into account the temperatures and silica contents of both warm springs or wells and the cold groundwater, reservoir temperatures up to about 200/sup 0/C were indicated. Considering measured surface water temperatures, calculated reservoir temperatures, thermal gradients, and the local geology, most of the Cache Valley, Utah area is unsuited for geothermal development. However, the areas of North Logan, Benson, and Trenton were found to have anomalously warm groundwater in comparison to the background temperature of 13.0/sup 0/C for the study area. The warm water has potential for isolated energy development but is not warm enough for major commercial development.

  19. Conodonts of Bakken Formation (Devonian and Mississippian), Williston basin, North Dakota

    SciTech Connect (OSTI)

    Hayes, M.D.; Holland, F.D. Jr.

    1983-08-01

    The Bakken Formation is a thin (maximum 145 ft, 45 m), clastic unit in the subsurface of Williston basin in the United States and Canada. The Bakken is similar in lithologic character and stratigraphic position to other black shale units deposited on the North American craton during the Late Devonian and Early Mississippian. The Bakken was initially considered entirely Mississippian in age. Paleontologic study of regional physical equivalents and analysis of the macrofauna in Saskatchewan has suggested that the Bakken is actually both Devonian and Mississippian. Conodonts were obtained from cores of the Bakken in an effort to determine the age of the formation in North Dakota and to assess the oil generation potential. Nearly 700 conodonts have been recovered, but are unevenly distributed within the Bakken Formation. A majority was obtained from thin (approximately 0.5 cm), fossil-rich beds within the upper shale. Conodonts from the top of the upper shale reveal a Mississippian (Kinderhookian) age and are here assigned to the Lower Siphonodella crenulata Zone. Only rare, fragmentary conodonts have been found in the middle member. Conodont evidence from the middle of the lower shale suggests a late Devonian (Famennian) age (Upper Polygnathus styriacus Zone) for this member. Conodont color has been established as a geothermometer in carbonate rocks. Color alteration indices of conodonts from the Bakken range from 1.5 to approximately 2.5 and indicate a pattern of increasing temperature with depth. These results suggest possible hydrocarbon generation from shallower depths than has been reported previously for the Bakken. The lack of agreement in interpreted hydrocarbon generation depths may be due to, among other things, the clastic nature of the Bakken Formation.

  20. Monitoring of temperature-compensated conductivity in fossil power plants

    SciTech Connect (OSTI)

    Bursik, A.

    1995-01-01

    Specific conductivity is an inexpensive, reliable, on-line method for monitoring the overall level of contaminants and its trends in fossil plant cycles. The most important applications are the monitoring in makeup water and at the economizer inlet. In the makeup, the specific conductivity is related to the content of makeup ionic impurities and carbon dioxide. Specific conductivity at the economizer inlet is an indication of the ammonia level during normal operation, since other ionic impurity levels are relatively very low in relation to the ammonia content. Cation conductivity serves as an excellent diagnostic tool. The advantage of using strong-acid cation exchanger for the alkalizing agents elimination and for the great sensitivity improvement has already been recognized in the 1950`s. The cation conductivity is currently one of the most important {open_quotes}core parameters{close_quotes} in the Cycle Chemistry Improvement Project. In this project, the most important plant cycle locations where cation conductivity on-line monitoring is strongly advised are: condensate pump discharge; polisher outlet or economizer inlet; and hot reheat steam or main steam. An additional monitoring location is the blowdown or the downcomer of drum boilers. The cation conductivity monitoring at this location is becoming vital with the introduction of oxygenated chemistry and OH (sodium hydroxide) treatment in cycles with drum boilers. Degassed cation conductivity has been addressed. Applying this method, the effect of carbon dioxide on cation conductivity is eliminated by boiling off gaseous carbon dioxide before the actual cation conductivity monitoring. Therefore, the degassed cation conductivity reflects only the total non-volatile anionic impurity level.

  1. Photodissociation spectroscopy of the carbonyl sulfide ion with momentum analysis of the sulfur product ion

    SciTech Connect (OSTI)

    Snow, K.B.

    1993-01-01

    A Nuclide 12-90-G mass spectrometer was modified for use as a photofragment momentum spectrometer. The resultant apparatus was capable of obtaining both absolute cross sections for photodissociation with respect to wavelength and relative cross sections for photodissociation with respect to kinetic energy release. The kinetic energy release for the photodissociation reaction of the nitrous oxide cation (leading to the production of the nitric oxide cation and the nitrogen atom), was studied at 3080.4 [angstrom], 3371.3 [angstrom], and 3381.4 [angstrom]. When a nitrogen atom was produced in the [sup 4]S state, the nitric oxide cation was found to be formed predominantly with 5 to 7 quanta of vibrational energy. Nitrogen atoms were formed preferentially in the [sup 2]D state when it was energetically feasible at 3371.3 [angstrom] and 3080.4 [angstrom]. The kinetic energy release for the photodissociation reaction of the carbonyl sulfide cation (leading to the production of carbon monoxide and a sulfur cation), was studied at 2822.2 [angstrom], 2921.8 [angstrom], 2991.0 [angstrom], 2991.9 [angstrom], 3080.4 [angstrom], 3104.3 [angstrom], 3127.9 [angstrom], 3184.9 [angstrom], 3351.8 [angstrom], 3371.3 [angstrom], and 3393.0 [angstrom]. When sulfur cations were produced in the [sup 4]S state, the carbon monoxide products were formed predominantly with 5 to 7 quanta of vibrational energy. Sulfur cations were formed preferentially in the [sup 2]D state from hot bands at 3351.8 [angstrom], 3080.4 [angstrom], and 2991.9 [angstrom]. Sulfur cations were also produced in the [sup 2]D state at 2921.8 [angstrom] and 2822.2 [angstrom], where it was energetically feasible from the ground state of carbonyl sulfide cations.

  2. Electrocurtain coating process for coating solar mirrors

    DOE Patents [OSTI]

    Kabagambe, Benjamin; Boyd, Donald W.; Buchanan, Michael J.; Kelly, Patrick; Kutilek, Luke A.; McCamy, James W.; McPheron, Douglas A.; Orosz, Gary R.; Limbacher, Raymond D.

    2013-10-15

    An electrically conductive protective coating or film is provided over the surface of a reflective coating of a solar mirror by flowing or directing a cation containing liquid and an anion containing liquid onto the conductive surface. The cation and the anion containing liquids are spaced from, and preferably out of contact with one another on the surface of the reflective coating as an electric current is moved through the anion containing liquid, the conductive surface between the liquids and the cation containing liquid to coat the conductive surface with the electrically conductive coating.

  3. Hydroxide Degradation Pathways for Substituted Benzyltrimethyl Ammonium: A DFT Study

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

    Long, Hai; Pivovar, Bryan S.

    2014-11-01

    The stability of cations used in the alkaline exchange membranes has been a major challenge. In this paper, degradation energy barriers were investigated by density functional theory for substituted benzyltrimethyl ammonium (BTMA+) cations. Findings show that electron-donating substituent groups at meta-position(s) of the benzyl ring could result in increased degradation barriers. However, after investigating more than thirty substituted BTMA+ cations, the largest improvement in degradation barrier found was only 6.7 kJ/mol. This suggests a modest (8×) improvement in stability for this type of approach may be possible, but for anything greater other approaches will need to be pursued.

  4. Mixed oxide solid solutions

    DOE Patents [OSTI]

    Magno, Scott; Wang, Ruiping; Derouane, Eric

    2003-01-01

    The present invention is a mixed oxide solid solution containing a tetravalent and a pentavalent cation that can be used as a support for a metal combustion catalyst. The invention is furthermore a combustion catalyst containing the mixed oxide solid solution and a method of making the mixed oxide solid solution. The tetravalent cation is zirconium(+4), hafnium(+4) or thorium(+4). In one embodiment, the pentavalent cation is tantalum(+5), niobium(+5) or bismuth(+5). Mixed oxide solid solutions of the present invention exhibit enhanced thermal stability, maintaining relatively high surface areas at high temperatures in the presence of water vapor.

  5. Anion exchange membrane

    SciTech Connect (OSTI)

    Verkade, John G; Wadhwa, Kuldeep; Kong, Xueqian; Schmidt-Rohr, Klaus

    2013-05-07

    An anion exchange membrane and fuel cell incorporating the anion exchange membrane are detailed in which proazaphosphatrane and azaphosphatrane cations are covalently bonded to a sulfonated fluoropolymer support along with anionic counterions. A positive charge is dispersed in the aforementioned cations which are buried in the support to reduce the cation-anion interactions and increase the mobility of hydroxide ions, for example, across the membrane. The anion exchange membrane has the ability to operate at high temperatures and in highly alkaline environments with high conductivity and low resistance.

  6. Energy storage devices having anodes containing Mg and electrolytes utilized therein

    DOE Patents [OSTI]

    Shao, Yuyan; Liu, Jun

    2015-08-18

    For a metal anode in a battery, the capacity fade is a significant consideration. In energy storage devices having an anode that includes Mg, the cycling stability can be improved by an electrolyte having a first salt, a second salt, and an organic solvent. Examples of the organic solvent include diglyme, triglyme, tetraglyme, or a combination thereof. The first salt can have a magnesium cation and be substantially soluble in the organic solvent. The second salt can enhance the solubility of the first salt and can have a magnesium cation or a lithium cation. The first salt, the second salt, or both have a BH.sub.4 anion.

  7. Fe-V redox flow batteries

    DOE Patents [OSTI]

    Li, Liyu; Kim, Soowhan; Yang, Zhenguo; Wang, Wei; Zhang, Jianlu; Chen, Baowei; Nie, Zimin; Xia, Guanguang

    2014-07-08

    A redox flow battery having a supporting solution that includes Cl.sup.- anions is characterized by an anolyte having V.sup.2+ and V.sup.3+ in the supporting solution, a catholyte having Fe.sup.2+ and Fe.sup.3+ in the supporting solution, and a membrane separating the anolyte and the catholyte. The anolyte and catholyte can have V cations and Fe cations, respectively, or the anolyte and catholyte can each contain both V and Fe cations in a mixture. Furthermore, the supporting solution can contain a mixture of SO.sub.4.sup.2- and Cl.sup.- anions.

  8. Niobate-based octahedral molecular sieves

    DOE Patents [OSTI]

    Nenoff, Tina M.; Nyman, May D.

    2003-07-22

    Niobate-based octahedral molecular sieves having significant activity for multivalent cations and a method for synthesizing such sieves are disclosed. The sieves have a net negatively charged octahedral framework, comprising niobium, oxygen, and octahedrally coordinated lower valence transition metals. The framework can be charge balanced by the occluded alkali cation from the synthesis method. The alkali cation can be exchanged for other contaminant metal ions. The ion-exchanged niobate-based octahedral molecular sieve can be backexchanged in acidic solutions to yield a solution concentrated in the contaminant metal. Alternatively, the ion-exchanged niobate-based octahedral molecular sieve can be thermally converted to a durable perovskite phase waste form.

  9. Niobate-based octahedral molecular sieves

    DOE Patents [OSTI]

    Nenoff, Tina M.; Nyman, May D.

    2006-10-17

    Niobate-based octahedral molecular sieves having significant activity for multivalent cations and a method for synthesizing such sieves are disclosed. The sieves have a net negatively charged octahedral framework, comprising niobium, oxygen, and octahedrally coordinated lower valence transition metals. The framework can be charge balanced by the occluded alkali cation from the synthesis method. The alkali cation can be exchanged for other contaminant metal ions. The ion-exchanged niobate-based octahedral molecular sieve can be backexchanged in acidic solutions to yield a solution concentrated in the contaminant metal. Alternatively, the ion-exchanged niobate-based octahedral molecular sieve can be thermally converted to a durable perovskite phase waste form.

  10. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... thin films with three metal oxide thin layers is discussed. ... of Mn4+, Co3+ and Ni2+ cations inside an O2- framework. ... with small amounts of organic species with C-O and O-CO ...

  11. Isotopic generator for bismuth-212 and lead-212 from radium

    DOE Patents [OSTI]

    Atcher, Robert W.; Friedman, Arnold M.; Hines, John

    1987-01-01

    A method and apparatus for providing radionuclides of bismuth-212 and lead-212. Thorium-228 and carrier solution starting material is input to a radiologically contained portion of an isotopic generator system, and radium-224 is separated from thorium-228 which is retained by a strongly basic anion exchange column. The separated radium-224 is transferred to an accessible, strongly acidic cationic exchange column. The cationic column retains the radium-224, and natural radioactive decay generates bismuth-212 and lead-212. The cationic exchange column can also be separated from the contained portion of the system and utilized without the extraordinary safety measures necessary in the contained portion. Furthermore, the cationic exchange column provides over a relatively long time period the short lived lead-212 and bismuth-212 radionuclides which are useful for a variety of medical therapies.

  12. Isotopic generator for bismuth-212 and lead-212 based on radium

    DOE Patents [OSTI]

    Hines, J.J.; Atcher, R.W.; Friedman, A.M.

    1985-01-30

    Disclosed are method and apparatus for providing radionuclides of bismuth-212 and lead-212. Thorium-228 and carrier solution starting material is input to a radiologically contained portion of an isotopic generator system, and radium-224 is separated from thorium-228 which is retained by a strongly basic anion exchange column. The separated radium-224 is transferred to an accessible, strongly acidic cationic exchange column. The cationic column retains the radium-224, and natural radioactive decay generates bismuth-212 and lead-212. The cationic exchange column can also be separated from the contained portion of the system and utilized without the extraordinary safety measures necessary in the contained portion. Furthermore, the cationic exchange column provides over a relatively long time period the short lived lead-212 and bismuth-212 radionuclides which are useful for a variety of medical therapies.

  13. Interface-Induced Polarization in SrTiO3-LaCrO3 Superlattices...

    Office of Scientific and Technical Information (OSTI)

    Through x-ray absorption near edge spectroscopy and aberration-corrected scanning transmission electron microscopy we show that the Ti cations are displaced off-center in the TiO6 ...

  14. Reinventing cell penetrating peptides using glycosylated methionine sulfonium ion sequences

    SciTech Connect (OSTI)

    Kramer, Jessica R.; Schmidt, Nathan W.; Mayle, Kristine M.; Kamei, Daniel T.; Wong, Gerard C.L.; Deming, Timothy J.

    2015-04-15

    Cell penetrating peptides (CPPs) are intriguing molecules that have received much attention, both in terms of mechanistic analysis and as transporters for intracellular therapeutic delivery. Most CPPs contain an abundance of cationic charged residues, typically arginine, where the amino acid compositions, rather than specific sequences, tend to determine their ability to enter cells. Hydrophobic residues are often added to cationic sequences to create efficient CPPs, but typically at the penalty of increased cytotoxicity. Here, we examined polypeptides containing glycosylated, cationic derivatives of methionine, where we found these hydrophilic polypeptides to be surprisingly effective as CPPs and to also possess low cytotoxicity. X-ray analysis of how these new polypeptides interact with lipid membranes revealed that the incorporation of sterically demanding hydrophilic cationic groups in polypeptides is an unprecedented new concept for design of potent CPPs.

  15. Method for inhibiting silica precipitation and scaling in geothermal flow systems

    DOE Patents [OSTI]

    Harrar, J.E.; Lorensen, L.E.; Locke, F.E.

    1980-06-13

    A method for inhibiting silica scaling and precipitation in geothermal flow systems by on-line injection of low concentrations of cationic nitrogen-containing compounds, particularly polymeric imines, polymeric amines, and quaternary ammonium compounds is described.

  16. Reinventing cell penetrating peptides using glycosylated methionine sulfonium ion sequences

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

    Kramer, Jessica R.; Schmidt, Nathan W.; Mayle, Kristine M.; Kamei, Daniel T.; Wong, Gerard C.L.; Deming, Timothy J.

    2015-04-15

    Cell penetrating peptides (CPPs) are intriguing molecules that have received much attention, both in terms of mechanistic analysis and as transporters for intracellular therapeutic delivery. Most CPPs contain an abundance of cationic charged residues, typically arginine, where the amino acid compositions, rather than specific sequences, tend to determine their ability to enter cells. Hydrophobic residues are often added to cationic sequences to create efficient CPPs, but typically at the penalty of increased cytotoxicity. Here, we examined polypeptides containing glycosylated, cationic derivatives of methionine, where we found these hydrophilic polypeptides to be surprisingly effective as CPPs and to also possess lowmore » cytotoxicity. X-ray analysis of how these new polypeptides interact with lipid membranes revealed that the incorporation of sterically demanding hydrophilic cationic groups in polypeptides is an unprecedented new concept for design of potent CPPs.« less

  17. November 28, 2012 | Center for Gas SeparationsRelevant to Clean...

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

    November 28, 2012 Previous Next List Tae-Hyun Bae (Department of Chemistry, UC Berkeley) High-Throughput Evaluation of Cation-Exchanged Zeolites for Post-Combustion CO2 Capture...

  18. Roderick MacKinnon - Patents

    Office of Scientific and Technical Information (OSTI)

    Patents - Roderick MacKinnon (2003-2011) MacKinnon Page * Resources with Additional Information US 6,641,997 ASSAYS FOR SCREENING COMPOUNDS WHICH INTERACT WITH CATION CHANNEL ...

  19. Solvate Structures and Computational/Spectroscopic Characterization...

    Office of Scientific and Technical Information (OSTI)

    The present study characterizes the PF6- anion P-F Raman symmetric stretching vibrational band for evaluating the PF6-...Li+ cation interactions within LiPF6 crystalline solvates ...

  20. Process for loading weak-acid ion exchange resin with uranium

    DOE Patents [OSTI]

    Notz, Karl J.

    1976-01-01

    A method for loading ion exchange resins is described. The process comprises contacting a weak acid cation exchange resin in the ammonium form with a uranyl fluoride salt solution.

  1. Electrodialysis-ion exchange for the separation of dissolved salts. Final report

    SciTech Connect (OSTI)

    Harrison, J.L.; Baroch, C.J.; Litz, J.

    1996-07-19

    The program described in this report studies the suitability of electrodialysis-ion exchange (EDIX) to treat aqueous streams containing heavy metals and radioactive cations in a solution containing sodium and nitrates. The goal of the program was to produce a cation stream containing sodium, heavy metals, and radioactive cations; an anion stream of nitric acid free of heavy metals and radioactive cations; and a product stream that meets discharge criteria. The experimental results, described in detail, indicated that EDIX was not a suitable process for treating wastes containing metals that formed insoluble hydroxides in a basic solution; the metals precipitate in the catholyte and feed compartments, and in the cathode membrane. The test program was therefore terminated prior to completion of all planned activities. 2 refs., 22 figs., 8 tabs.

  2. Comment on 'A planar refractive x-ray lens made of nanocrystalline diamond'[J. Appl. Phys. 108, 123107 (2010)

    SciTech Connect (OSTI)

    Kroon, R. E.

    2013-05-28

    The material LuAG (lutetium aluminium garnet) has been confused with LAG (lanthanum aluminium garnet). In general, aluminium garnet phases only occur for the smaller trivalent metal cations and LAG is not known to have been synthesized.

  3. News Item

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

    switch composition from CdSe to PbSe, Cu2Se, and Ag2Se through cation exchange: The architecture of these porous films remained intact and the chemical transformations were...

  4. Microsoft Word - RIN 09072474_DVP.doc

    Office of Legacy Management (LM)

    ... Potassium J Major cation less than 5 times blank 0908109-45 0266 Iron J Negative calibration blank 0908109-45 0266 Manganese J Negative calibration blank 0908109-46 0267 Iron J ...

  5. Expanding the Repertoire of Chalcogenide Nanocrystal Networks...

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

    Yao, I. U. Arachchige, S. L. Brock Year: 2009 Abstract: Cation exchange is shown to be a simple and efficient method to prepare nanostructured Ag2Se gels and aerogels from CdSe...

  6. Contiguous Platinum Monolayer Oxygen Reduction Electrocatalysts...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    APPROACH 1. Prior work Pt monolayers on metal or alloy nanoparticles (NPs) are verified as ... atoms without changing the size of nanoparticles used as support for Pt. iii) cation ...

  7. Directed assembly of three-dimensional structures with micron-scale features

    DOE Patents [OSTI]

    Gratson, Gregory; Lewis, Jennifer A.

    2006-11-28

    The invention provides polyelectrolyte inks comprising a solvent, a cationic polyelectrolyte, dissolved in the solvent, and an anionic polyelectrolyte, dissolved in the solvent. The concentration of at least one of the polyelectrolytes in the solvent is in a semidilute regime.

  8. Method for inhibiting silica precipitation and scaling in geothermal flow systems

    DOE Patents [OSTI]

    Harrar, Jackson E.; Lorensen, Lyman E.; Locke, Frank E.

    1982-01-01

    A method for inhibiting silica scaling and precipitation in geothermal flow systems by on-line injection of low concentrations of cationic nitrogen-containing compounds, particularly polymeric imines, polymeric amines, and quaternary ammonium compounds.

  9. Local structure underlying anomalous tetragonal distortions in BiFeO{sub 3}-PbTiO{sub 3} ferroelectrics

    SciTech Connect (OSTI)

    Levin, I.; Krayzman, V.; Woicik, J. C.; Tucker, M. G.

    2014-06-16

    The local structure of tetragonal BiFeO{sub 3}-PbTiO{sub 3} solid solutions featuring anomalous lattice distortions has been determined using simultaneous fitting of neutron total scattering and extended X-ray absorption fine structure data. On the local scale, the large tetragonal distortion, promoted by the displacements of the A-cations (Bi and Pb), is accommodated primarily by the [FeO{sub 6}] octahedra, even though both Fe and Ti acquire (5+1)-fold coordination. Bi cations exhibit considerably larger displacements than Pb. The combination of the A-cation displacements and the ability of M-cations to adopt 5-fold coordination is suggested as key for stabilizing the large tetragonality in BiMO{sub 3}-PbTiO{sub 3} systems.

  10. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... (2) aluminates (1) amorphous state (1) atomic displacements (1) bifeo3 (1) bimno3 (1) ... Scanning TEM and x-ray energy dispersive spectroscopy indicate no significant heavy cation ...

  11. Center for Nanophase Materials Sciences (CNMS) - CNMS User Research

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

    Achievement: The material of choice for spintronics device today is FeMgOFe tunnel ... by modi?cation of the interface is an important topic in spintronics research. ...

  12. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    be of great interest in Li ion battery chemistry. The structure also exhibits cation disorder with 13.5% Co residing at the lithium (Li1)more site. Co seems to have an average...

  13. Complex oxides: Intricate disorder

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

    Uberuaga, Blas Pedro

    2016-02-29

    In this study, complex oxides such as pyrochlores have a myriad of potential technological applications, including as fast ion conductors and radiation-tolerant nuclear waste forms. They are also of interest for their catalytic and spin ice properties. Many of these functional properties are enabled by the atomic structure of the cation sublattices. Pyrochlores (A2B2O7) contain two different cations (A and B), typically a 3+ rare earth and a 4+ transition metal such as Hf, Zr, or Ti. The large variety of chemistries that can form pyrochlores leads to a rich space in which to search for exotic new materials. Furthermore,more » how cations order or disorder on their respective sublattices for a given chemical composition influences the functional properties of the oxide. For example, oxygen ionic conductivity is directly correlated with the level of cation disorder — the swapping of A and B cations1. Further, the resistance of these materials against amorphization has also been connected with the ability of the cations to disorder2, 3. These correlations between cation structure and functionality have spurred great interest in the structure of the cation sublattice under irradiation, with significant focus on the disordering mechanisms and disordered structure. Previous studies have found that, upon irradiation, pyrochlores often undergo an order-to-disorder transformation, in which the resulting structure is, from a diffraction point of view, indistinguishable from fluorite (AO2) (ref. 3). Shamblin et al. now reveal that the structure of disordered pyrochlore is more complicated than previously thought4.« less

  14. Manganese oxide nanowires, films, and membranes and methods of making

    DOE Patents [OSTI]

    Suib, Steven Lawrence (Storrs, CT); Yuan, Jikang (Storrs, CT)

    2011-02-15

    Nanowires, films, and membranes comprising ordered porous manganese oxide-based octahedral molecular sieves and methods of making the same are disclosed. A method for forming nanowires includes hydrothermally treating a chemical precursor composition in a hydrothermal treating solvent to form the nanowires, wherein the chemical precursor composition comprises a source of manganese cations and a source of counter cations, and wherein the nanowires comprise ordered porous manganese oxide-based octahedral molecular sieves.

  15. Research Highlights - Joint Center for Energy Storage Research

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

    Research Highlights August 25, 2016, Research Highlights The Lightest Organic Radical Cation for Charge Storage in Redox Flow Batteries By systematically shedding molecular fragments of 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene that are considered important for radical cation steric stabilization, we discovered a minimalistic structure that retains long-term stability in its oxidized form and exhibits the intrinsic capacity of 161 mAh/g. Read More August 20, 2016, Research Highlights

  16. Biochar production method and composition therefrom

    DOE Patents [OSTI]

    Lee, James W; Buchanan, III, Archibald C; Evans, Barbara R; Kidder, Michelle K

    2014-04-29

    The invention is directed to a method for producing an oxygenated biochar material possessing a cation-exchanging property, wherein a biochar source is reacted with one or more oxygenating compounds in such a manner that the biochar source homogeneously acquires oxygen-containing cation-exchanging groups in an incomplete combustion process. The invention is also directed to oxygenated biochar compositions and soil formulations containing the oxygenated biochar material.

  17. Biochar production method and composition therefrom

    SciTech Connect (OSTI)

    Lee, James W.; Buchanan, III, Archibald C.; Evans, Barbara R.; Kidder, Michelle K.

    2013-03-19

    The invention is directed to a method for producing an oxygenated biochar material possessing a cation-exchanging property, wherein a biochar source is reacted with one or more oxygenating compounds in such a manner that the biochar source homogeneously acquires oxygen-containing cation-exchanging groups in an incomplete combustion process. The invention is also directed to oxygenated biochar compositions and soil formulations containing the oxygenated biochar material.

  18. Catalysis using hydrous metal oxide ion exchanges

    DOE Patents [OSTI]

    Dosch, Robert G.; Stephens, Howard P.; Stohl, Frances V.

    1985-01-01

    In a process which is catalyzed by a catalyst comprising an active metal on a carrier, said metal being active as a catalyst for the process, an improvement is provided wherein the catalyst is a hydrous, alkali metal or alkaline earth metal titanate, zirconate, niobate or tantalate wherein alkali or alkaline earth metal cations have been exchanged with a catalytically effective amount of cations of said metal.

  19. Catalysis using hydrous metal oxide ion exchangers

    DOE Patents [OSTI]

    Dosch, R.G.; Stephens, H.P.; Stohl, F.V.

    1983-07-21

    In a process which is catalyzed by a catalyst comprising an active metal on a carrier, said metal being active as a catalyst for the process, an improvement is provided wherein the catalyst is a hydrous, alkali metal or alkaline earth metal titanate, zirconate, niobate or tantalate wherein alkali or alkaline earth metal cations have been exchanged with a catalytically effective amount of cations of said metal.

  20. Radiopharmaceuticals for imaging the heart

    DOE Patents [OSTI]

    Green, M.A.; Tsang, B.W.

    1994-06-28

    Radiopharmaceuticals for imaging myocardial tissues are prepared by forming lipophilic, cationic complexes of radioactive metal ions with metal chelating ligands comprising the Schiff base adducts of triamines and tetraamines with optionally substituted salicylaldehydes. The lipophilic, cationic, radioactive complexes of the invention exhibit high uptake and retention in myocardial tissues. Preferred gallium-68(III) complexes in accordance with this invention can be used to image the heart using positron emission tomography. 6 figures.