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Sample records for microbiol mol biol

  1. Riddhi Siddhi Gluco Biols Ltd RSGBL | Open Energy Information

    Open Energy Info (EERE)

    Place: 591307, Karnataka, India Sector: Biomass Product: Karnataka-based starch and glucose manufacturer and biomass project developers. References: Riddhi Siddhi Gluco Biols...

  2. MOL.19980331.0174 PARTICULATE MATTEX AMBIENT A I R QUALITY

    National Nuclear Security Administration (NNSA)

    MOL.19980331.0174 PARTICULATE MATTEX AMBIENT A I R QUALITY DATA REPORT FOR 1989 AND 1990 WBS No. 1.2.5.4.2 Contract No. DE-AC08-87NVl0576 March 1992 Prepared by: Radiological/Environmental Field Programs Department Science Applications International Corporation Technical & Management Support Services Las Vegas, Nevada 1.0 MECUTIVE SUMMARY Routine particulate matter ambient air quality monitoring has been performed at two stations in the Yucca Mountain air monitoring network since the spring

  3. Phase transformation and wear studies of plasma sprayed yttria stabilized zirconia coatings containing various mol% of yttria

    SciTech Connect (OSTI)

    Aruna, S.T. Balaji, N.; Rajam, K.S.

    2011-07-15

    Plasma sprayable grade zirconia powders doped with various mol% of yttria (0, 2, 3, 4, 6, 8 and 12 mol%) were synthesized by a chemical co-precipitation route. The coprecipitation conditions were adjusted such that the powders possessed good flowability in the as calcined condition and thus avoiding the agglomeration step like spray drying. Identical plasma spray parameters were used for plasma spraying all the powders on stainless steel plates. The powders and plasma sprayed coatings were characterized by X-ray diffractometry, Scanning Electron Microscopy and Raman spectroscopy. Zirconia powders are susceptible to phase transformations when subjected to very high temperatures during plasma spraying and XRD is insensitive to the presence of some non crystalline phases and hence Raman spectroscopy was used as an important tool. The microstructure of the plasma sprayed coatings showed a bimodal distribution containing fully melted and unmelted zones. The microhardness and wear resistance of the plasma sprayed coatings were determined. Among the plasma sprayed coatings, 3 mol% yttria stabilized zirconia coating containing pure tetragonal zirconia showed the highest wear resistance. - Research Highlights: {yields} Preparation plasma sprayable YSZ powders without any agglomeration process and plasma spraying {yields} Phase transformation studies of plasma sprayed YSZ coatings by XRD and Raman spectroscopy {yields} Microstructure of the plasma sprayed coatings exhibited bimodal distribution {yields} Plasma sprayed 3 mol% YSZ coating exhibited the highest wear resistance {yields} Higher wear resistance is due to the higher fracture toughness of tetragonal 3 mol% YSZ phase.

  4. Structure and optical homogeneity of LiNbO{sub 3}:Zn (0.034.5 mol.%) crystals

    SciTech Connect (OSTI)

    Sidorov, Nikolay E-mail: tepl-na@chemy.kolasc.net.ru E-mail: Jovial1985@yandex.ru Tepljakova, Natalja E-mail: tepl-na@chemy.kolasc.net.ru E-mail: Jovial1985@yandex.ru Gabain, Aleksei E-mail: tepl-na@chemy.kolasc.net.ru E-mail: Jovial1985@yandex.ru Yanichev, Aleksander E-mail: tepl-na@chemy.kolasc.net.ru E-mail: Jovial1985@yandex.ru Palatnikov, Mikhail E-mail: tepl-na@chemy.kolasc.net.ru E-mail: Jovial1985@yandex.ru

    2014-11-14

    Structure and optical homogeneity of LiNbO{sub 3}:Zn (0.034.5 mol.%) crystals were searched by photoinduced light scattering and by Raman spectroscopy. The photorefractive effect depends on Zn{sup 2+} concentration nonmonotonically. Decrease of photorefractive effect is explained by decrease of structure defects with localized electrons. The Zn{sup 2+} cations replace structure defects Nb{sub Li} and Li{sub Nb}, trapping levels appear near the bottom of the conduction band and photo electrons recombine with emission under laser radiation. By the Raman spectra the area of the high structure order is found. In this area the own alternation, the alternation of impurity cations and the vacancies along the polar axis is almost perfect.

  5. mol2.3.dvi

    Office of Scientific and Technical Information (OSTI)

    ... Figure 3 shows the XANES data for cerocene and two reference standards: a Ce(III) standard, CeN(Si(CH 3 ) 3 ) 2 3 , and a Ce(IV) standard, Ce5,7,12,14-Me 4 -2,3:9,10-di- ...

  6. Improving olefin tolerance and production in E. coli using native...

    Office of Scientific and Technical Information (OSTI)

    ... Mol Microbiol 78(2):320-330. Jarboe LR, Zhang X, Wang X, Moore JC, Shanmugam KT, Ingram LO. 2010. Metabolic engineering for production of biorenewable fuels and chemicals: ...

  7. Microsoft Word - MolJACSrev28.doc

    Office of Scientific and Technical Information (OSTI)

    ... J. L.; Immer, C. D.; Fisk, Z.; Booth, C. H.; Figueroa, E.; Lawrence, J. M.; Modler, R.; Cornelius, A. L.; Hundley, M. F.; Kwei, G. H.; Thompson, J. D.; Bridges, F. Phys. Rev. ...

  8. Disruption of Wnt/[beta]-Catenin Signaling and Telomeric Shortening...

    Office of Scientific and Technical Information (OSTI)

    Disruption of Wntbeta-Catenin Signaling and Telomeric Shortening Are Inextricable ... Resource Type: Journal Article Resource Relation: Journal Name: Mol. Cell Biol.; Journal ...

  9. PowerPoint Presentation

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

    T. Anderson (Biology, PSU) Ying Gu (Biochem & Mol Biol, PSU) Seong Kim (Chem Eng, PSU) James Kubicki (Geosciences, PSU) Manish Kumar (Chem Eng, PSU) Janna Maranas (Chem Eng,...

  10. Broad Temperature Pinning Study of 15 mol.% Zr-Added (Gd, Y)-Ba-Cu-O MOCVD Coated Conductors

    SciTech Connect (OSTI)

    Xu, AX; Khatri, N; Liu, YH; Majkic, G; Galstyan, E; Selvamanickam, V; Chen, YM; Lei, CH; Abraimov, D; Hu, XB; Jaroszynski, J; Larbalestier, D

    2015-06-01

    BaZrO3 (BZO) nanocolumns have long been shown to be very effective for raising the pinning force F-p of REBa2Cu3Ox (REBCO, where RE = rare earth) films at high temperatures and recently at low temperatures too. We have successfully incorporated a high density of BZO nanorods into metal organic chemical vapor deposited (MOCVD) REBCO coated conductors via Zr addition. We found that, compared to the 7.5% Zr-added coated conductor, dense BZO nanorod arrays in the 15% Zr-added conductor are effective over the whole temperature range from 77 K down to 4.2 K. We attribute the substantially enhanced J(c) at 30 K to the weak uncorrelated pinning as well as the strong correlated pinning. Meanwhile, by tripling the REBCO layer thickness to similar to 2.8 mu m, the engineering critical current density J(e) at 30 K exceeds J(e) of optimized Nb-Ti wires at 4.2 K.

  11. Threshold Photoelectron Photoion Coincidence (TPEPICO) Studies: The Road to ? 0.1 kJ/mol Thermochemistry

    SciTech Connect (OSTI)

    Baer, Tomas

    2013-10-14

    The threshold photoelectron photoion coincidence (TPEPICO) technique is utilized to investigate the dissociation dynamics and thermochemistry of energy selected medium to large organic molecular ions. The reactions include parallel and consecutive steps that are modeled with the statistical theory in order to extract dissociation onsets for multiple dissociation paths. These studies are carried out with the aid of molecular orbital calculations of both ions and the transition states connecting the ion structure to their products. The results of these investigations yield accurate heats of formation of ions, free radicals, and stable molecules. In addition, they provide information about the potential energy surface that governs the dissociation process. Isomerization reactions prior to dissociation are readily inferred from the TPEPICO data.

  12. Microsoft Word - threading.2.21_jmb.doc

    Office of Scientific and Technical Information (OSTI)

    PEW 510/3 (was 422/2), accepted for publication in J Mol Biol 7/24/03 New local potential useful for genome annotation and 3D modeling. John-Marc Chandonia 1,2 and Fred E. Cohen 1 1 Department of Cellular and Molecular Pharmacology, University of California, San Francisco, CA 94143-2240, USA 2 current address: Berkeley Structural Genomics Center, Berkeley National Lab, Berkeley, CA 94720, USA Address for Correspondence: Fred Cohen Department of Cellular and Molecular Pharmacology Genentech Hall

  13. Microsoft Word - Document1

    Office of Scientific and Technical Information (OSTI)

    ... Microbiol. 3, 675 (2005). 7. R. Jain, M. C. Rivera, J. A. Lake, Proc. Natl. Acad. Sci. U. S. A. 96, 3801 (1999). 5 8. M. C. Rivera, R. Jain, J. E. Moore, J. A. Lake, Proc. Natl. ...

  14. Structures of GRP94-Nucleotide Complexes Reveal Mechanistic Difference...

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

    an Hsp90 chaperone. J Biol Chem 279, 46162-46171. Nicchitta, C.V. (1998). Biochemical, cell biological and immunological issues surrounding the endoplasmic reticulum chaperone...

  15. A Novel Mechanism for Binding of Galactose-terminated Glycans...

    Office of Scientific and Technical Information (OSTI)

    Resource Type: Journal Article Resource Relation: Journal Name: J. Biol. Chem.; Journal Volume: 290; Journal Issue: (27) ; 07, 2015 Research Org: Advanced Photon Source (APS), ...

  16. Memo Is Homologous to Nonheme Iron Dioxygenases and Binds an...

    Office of Scientific and Technical Information (OSTI)

    Resource Type: Journal Article Resource Relation: Journal Name: J. Biol. Chem.; Journal Volume: 283; Journal Issue: (5) ; 02, 2008 Research Org: Advanced Photon Source (APS), ...

  17. Human Cytochrome P450 21A2, the Major Steroid 21-Hydroxylase...

    Office of Scientific and Technical Information (OSTI)

    Resource Type: Journal Article Resource Relation: Journal Name: J. Biol. Chem.; Journal Volume: 290; Journal Issue: (21) ; 05, 2015 Research Org: Advanced Photon Source (APS), ...

  18. J.B. (comp.) 63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTANT...

    Office of Scientific and Technical Information (OSTI)

    AND OTHER ENVIRON. POLLUTANT EFFECTS ON LIVING ORGS. AND BIOL. MAT.; 62 RADIOLOGY AND NUCLEAR MEDICINE; 99 GENERAL AND MISCELLANEOUSMATHEMATICS, COMPUTING, AND INFORMATION...

  19. Helix Dipole Movement and Conformational Variability Contribute to Allosteric GDP Release in G[alpha] Subunits

    SciTech Connect (OSTI)

    Preininger, Anita M.; Funk, Michael A.; Oldham, William M.; Meier, Scott M.; Johnston, Christopher A.; Adhikary, Suraj; Kimple, Adam J.; Siderovski, David P.; Hamm, Heidi E.; Iverson, Tina M.

    2009-06-01

    Heterotrimeric G proteins (Galphabetagamma) transmit signals from activated G protein-coupled receptors (GPCRs) to downstream effectors through a guanine nucleotide signaling cycle. Numerous studies indicate that the carboxy-terminal alpha5 helix of Galpha subunits participates in Galpha-receptor binding, and previous EPR studies suggest this receptor-mediated interaction induces a rotation and translation of the alpha5 helix of the Galpha subunit [Oldham, W. M., et al. (2006) Nat. Struct. Mol. Biol. 13, 772-777]. On the basis of this result, an engineered disulfide bond was designed to constrain the alpha5 helix of Galpha(i1) into its EPR-measured receptor-associated conformation through the introduction of cysteines at position 56 in the alpha1 helix and position 333 in the alpha5 helix (I56C/Q333C Galpha(i1)). A functional mimetic of the EPR-measured alpha5 helix dipole movement upon receptor association was additionally created by introduction of a positive charge at the amino terminus of this helix, D328R Galpha(i1). Both proteins exhibit a dramatically elevated level of basal nucleotide exchange. The 2.9 A resolution crystal structure of I56C/Q333C Galpha(i1) in complex with GDP-AlF(4)(-) reveals the shift of the alpha5 helix toward the guanine nucleotide binding site that is anticipated by EPR measurements. The structure of the I56C/Q333C Galpha(i1) subunit further revealed altered positions for the switch regions and throughout the Galpha(i1) subunit, accompanied by significantly elevated crystallographic temperature factors. Combined with previous evidence in the literature, the structural analysis supports the critical role of electrostatics of the alpha5 helix dipole and overall conformational variability during nucleotide release.

  20. Iron(IV)hydroxide pKa and the Role of Thiolate Ligation in C...

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

    and M. Green, Science 330, 933 (2010) C. Krest, E. Onderko, T. Yosca, J. Calixto, R. Karp, J. Livada, J. Rittle, and M. Green, J. Biol. Chem. 88, 17074 (2013) Primary Citation:...

  1. Fragment Screen against HIV Protease: Discovery of Two Allosteric...

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

    Screen against HIV Protease. Chem. Biol. Drug Des. 75: 257-268. References Brenner, B., Routy, J-P., Quan, Y., Moisi, D., Oliveira, M., Turner, D., Wainberg, M. A. &...

  2. Low-melting point heat transfer fluid

    DOE Patents [OSTI]

    Cordaro, Joseph Gabriel (Oakland, CA); Bradshaw, Robert W. (Livermore, CA)

    2010-11-09

    A low-melting point, heat transfer fluid made of a mixture of five inorganic salts including about 29.1-33.5 mol % LiNO.sub.3, 0-3.9 mol % NaNO.sub.3, 2.4-8.2 mol % KNO.sub.3, 18.6-19.9 mol % NaNO.sub.2, and 40-45.6 mol % KNO.sub.2. These compositions can have liquidus temperatures below 80.degree. C. for some compositions.

  3. Analysis of Metabolic Pathways and Fluxes in a Newly Discovered...

    Office of Scientific and Technical Information (OSTI)

    a maximum ethanol yield of 0.38+-0.07 mol mol-1 more glucose. In silico flux balance modeling demonstrates that lactate and acetate production from G. thermoglucosidasius...

  4. Promoting uranium immobilization by the activities of microbial phophatases

    SciTech Connect (OSTI)

    Sobecky, Patricia A.

    2005-06-01

    The first objective of this project is to determine the relationship of phosphatase activity to metal resistance in subsurface strains and the role of lateral gene transfer (LGT) in dissemination of nonspecific acid phosphatase genes. Nonspecific acid phosphohydrolases are a broad group of secreted microbial phosphatases that function in acidic-to-neutral pH ranges and utilize a wide range of organophosphate substrates. We have previously shown that PO43- accumulation during growth on a model organophosphorus compound was attributable to the overproduction of alkaline phosphatase by genetically modified subsurface pseudomonads [Powers et al. (2002) FEMS Microbiol. Ecol. 41:115-123]. During this report period, we have extended these results to include indigenous metal resistant subsurface microorganisms cultivated from the Field Research Center (FRC), in Oak Ridge Tennessee.

  5. ORGANIC SPECIES IN GEOTHERMAL WATERS IN LIGHT OF FLUID INCLUSION...

    Open Energy Info (EERE)

    that indicate H2 concentrations > 0.001 mol % typically have ethane > ethylene, propane > propylene, and butane > butylene. There are three end member fluid compositions:...

  6. Fluid Inclusion Analysis At Coso Geothermal Area (2003) | Open...

    Open Energy Info (EERE)

    that indicate H2 concentrations > 0.001 mol % typically have ethane > ethylene, propane > propylene, and butane > butylene. There are three end member fluid compositions...

  7. Li corrosion resistant glasses for headers in ambient temperature Li batteries

    DOE Patents [OSTI]

    Hellstrom, E.E.; Watkins, R.D.

    1985-10-11

    Glass compositions containing 10 to 50 mol% CaO, 10 to 50 mol% Al/sub 2/O/sub 3/, 30 to 60 mol% B/sub 2/O/sub 3/, and 0 to 30 mol% MgO are provided. These compositions are capable of forming a stable glass-to-metal seal possessing electrical insulating properties for use in a lithium battery. Also provided are lithium cells containing a stainless steel body and molybdenum center pin electrically insulated by means of a seal produced according to the invention.

  8. Silicon nitride ceramic having high fatigue life and high toughness

    DOE Patents [OSTI]

    Yeckley, Russell L. (Oakham, MA)

    1996-01-01

    A sintered silicon nitride ceramic comprising between about 0.6 mol % and about 3.2 mol % rare earth as rare earth oxide, and between about 85 w/o and about 95 w/o beta silicon nitride grains, wherein at least about 20% of the beta silicon nitride grains have a thickness of greater than about 1 micron.

  9. Metal-air cell comprising an electrolyte with a room temperature ionic liquid and hygroscopic additive

    DOE Patents [OSTI]

    Friesen, Cody A.; Krishnan, Ramkumar; Tang, Toni; Wolfe, Derek

    2014-08-19

    An electrochemical cell comprising an electrolyte comprising water and a hydrophobic ionic liquid comprising positive ions and negative ions. The electrochemical cell also includes an air electrode configured to absorb and reduce oxygen. A hydrophilic or hygroscopic additive modulates the hydrophobicity of the ionic liquid to maintain a concentration of the water in the electrolyte is between 0.001 mol % and 25 mol %.

  10. Low-melting point heat transfer fluid

    DOE Patents [OSTI]

    Cordaro, Joseph G. (Oakland, CA); Bradshaw, Robert W. (Livermore, CA)

    2011-04-12

    A low-melting point, heat transfer fluid comprising a mixture of LiNO.sub.3, NaNO.sub.3, KNO.sub.3, NaNO.sub.2 and KNO.sub.2 salts where the Li, Na and K cations are present in amounts of about 20-33.5 mol % Li, about 18.6-40 mol % Na, and about 40-50.3 mol % K and where the nitrate and nitrite anions are present in amounts of about 36-50 mol % NO.sub.3, and about 50-62.5 mol % NO.sub.2. These compositions can have liquidus temperatures between 70.degree. C. and 80.degree. C. for some compositions.

  11. SREL Reprint #3225

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

    5 A new set of microsatellite loci for Laptonycteris yerbabuenae and cross species amplification with other glossophagines Jose Antonio Romero-Meza1, Stacey L. Lance2, and Jorge Ortega1 1Laboratorio de Ictiología y Limnología, Posgrado en Ciencias Quimicobiológicas, Departamento de Zoología, Escuela Nacional de Ciencias Biológicas, Instituto Politécnico Nacional, Prolongación de Carpio y Plan de Ayala s/n, Col. Sto. Tomas, 11340 Mexico, DF, Mexico 2Savannah River Ecology Laboratory,

  12. SREL Reprint #3272

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

    2 Development of microsatellite loci for the Honduran white-bat (Ectophylla alba) by using Illumina paired-end sequences Alberto Morales-Leyva1, Rodrigo A. Medellín2, Stacey L. Lance3, Bernal Rodríguez-Herrera4, Melina Del Real-Monroy1, and Jorge Ortega1 1Laboratorio de Bioconservación y Manejo, Posgrado en Ciencias Quimicobiológicas, Departamento de Zoología, Escuela Nacional de Ciencias Biológicas, Instituto Politécnico Nacional, Prolongación de Carpio y Plan de Ayala s/n, Col. Sto.

  13. 2009 Publications | Stanford Synchrotron Radiation Lightsource

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

    09 Publications Journal Papers J. Abendroth, A. C. Kreger and W. G. J. Hol, "The Dimer Formed by the Periplasmic Domain of EpsL from the Type 2 Secretion System of Vibrio parahaemolyticus", J. Struct. Biol. 168, 313 (2009) doi: 10.1016/j.jsb.2009.07.022 J. Abendroth, D. D. Mitchell, K. V. Korotkov, T. L. Johnson, A. Kreger, M. Sandkvist and W. G. J. Hol, "The Three-dimensional Structure of the Cytoplasmic Domains of EpsF from the Type 2 Secretion System of Vibrio cholerae",

  14. Center for Nanophase Materials Sciences (CNMS) - Publications

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

    8 PUBLICATIONS Links to individual papers are provided when available online. These links will take you to other web sites and will open in a new window. Subscription may be required to access online publications. Alexander, N. R., K. M. Branch, I. C. Iwueke, S. A. Guelcher, and A. M. Weaver, "Extracellular Matrix Rigidity Promotes Invadopodia Activity," Curr. Biol. 18(17), 1295-9 (2008). Ankner, J. F., X. Tao, C. E. Halbert, J. F. Browning, S. M. Kilbey III, O. A. Swader, M. D.

  15. Solubility Measurements of Crystalline NiO in Aqueous Solution as a Function of Temperature and pH

    SciTech Connect (OSTI)

    Palmer, Donald; Benezeth, Pascale; Xiao, Caibin {nmn}; Wesolowski, David J; Anovitz, Lawrence {Larry} M

    2011-01-01

    Abstract Results of solubility experiments involving crystalline nickel oxide (bunsenite) in aqueous solutions are reported as functions of temperature (0 to 350 C) and pH at pressures slightly exceeding (with one exception) saturation vapor pressure. These experiments were carried out in either flow-through reactors or a hydrogen-electrode concentration cell for mildly acidic to near neutral pH solutions. The results were treated successfully with a thermodynamic model incorporating only the unhydrolyzed aqueous nickel species (viz., Ni2+ ) and the neutrally charged hydrolyzed species (viz., Ni(OH)02 ). The thermodynamic quantities obtained at 25 C and infinite dilution are, with 2 uncertainties: log10Ko s0 = (12.40 0.29), rGo m = (70.8 1.7) kJ mol 1; rHo m = (105.6 1.3) kJ mol 1; rSo m = (116.6 3.2) J K 1 mol 1; rCo p,m = (0 13) J K 1 mol 1; and log10Ko s2 = (8.76 0.15); rGo m = (50.0 1.7) kJ mol 1; rHo m = (17.7 1.7) kJ mol 1; rSo m = (108 7) J K 1 mol 1; rCo p,m = (108 3) J K 1 mol 1. These results are internally consistent, but the latter set differs from those gleaned from previous studies recorded in the literature. The corresponding thermodynamic quantities for the formation of Ni2+ and Ni(OH)02 are also estimated. Moreover, the Ni(OH) 3 anion was never observed, even in relatively strong basic solutions (mOH = 0.1 mol kg 1), contrary to the conclusions drawn from all but one previous study.

  16. LPG--a direct source of C/sub 3/-C/sub 4/ olefins

    SciTech Connect (OSTI)

    Pujado, P.R.; Berg, R.C.; Vora, B.V.

    1983-03-28

    This article describes the selective production of olefins by the catalytic dehydrogenation of the corresponding paraffins by means of UOP's Oleflex process. In this process, propylene can be obtained at about 85 mol % selectivity by the catalytic dehydrogenation of propane. Isobutylene can be obtained at selectivities in excess of 90 mol % from isobutane, and n-butenes (1-butene plus 2-butene) at about 80 mol % from n-butane. The availability of this technology, coupled with an abundant supply of LPG (C/sub 3/ and C/sub 4/ paraffins), opens new avenues for the selective production of propylene and butylenes.

  17. Greengenes: 16S rRNA Database and Workbench Compatible with ARB

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

    DeSantis, T. Z.; Hugenholtz, P.; Larsen, N.; Rojas, M.; Brodie, E. L.; Keller, K.; Huber, T.; Dalevi, D. Hu, P. Andersen, G. L.

    Greengenes was developed, as the abstract of an AEM reprint states, to "addresse limitations of public repositories by providing chimera screening, standard alignment, and taxonomic classification using multiple published taxonomies. It was found that there is incongruent taxonomic nomenclature among curators even at the phylum level. Putative chimeras were identified in 3% of environmental sequences and in 0.2% of records derived from isolates. Environmental sequences were classified into 100 phylum-level lineages in the Archaea and Bacteria....Greengenes is also a functional workbench to assist in analysis of user-generated 16S rRNA gene sequences. Batches of sequencing reads can be uploaded for quality-based trimming and creation of multiple-sequence alignments (9). Three types of non-MSA similarity searches are also available, seed extension by BLAST (1), similarity based on shared 7-mers by a tool called Simrank, and a direct degenerative pattern match for probe/primer evaluation. Results are displayed using user-preferred taxonomic nomenclature and can be saved between sessions. [Taken from DeSantis, T. Z., P. Hugenholtz, N. Larsen, M. Rojas, E. L. Brodie, K. Keller, T. Huber, D. Dalevi, P. Hu, and G. L. Andersen. 2006. Greengenes, a Chimera-Checked 16S rRNA Gene Database and Workbench Compatible with ARB. Appl Environ Microbiol 72:5069-72, pages 1 and 3] (Specialized Interface)

  18. Microsoft Word - 0918rir.doc

    Office of Legacy Management (LM)

    ... The seven steps used to design the sampling and analysis programs are: 1) statement of the ... meter mlg milliliters per gram Mol Wt molecular weight DOE Areas Remedial Investigation ...

  19. The Crystal Structure of Human, Nicotine Metabolizing Cytochrome...

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

    using PyMOL (pymol.sourceforge.net). There are over 50 mammalian cytochrome P450 genes in at least 17 families. Microsomal cytochrome P450 enzymes catalyze specific steps in...

  20. Microsoft Word - benzyl-ms-Revisednoyellow.doc

    Office of Scientific and Technical Information (OSTI)

    ... The difference is clearly a solid state effect, where the ensemble prevents the ... -1 does not compensate fully the loss of entropy, which leads to an adduct 4.8 kcal mol -1 ...

  1. Fuel Cell Handbook (Seventh Edition)

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

    ... having equal number of mols of gas reactants and products, has a negligible change in entropy and thus a negligible heat effect if carried out reversibly at constant temperature. ...

  2. Information Request, "THE REPORT TO THE PRESIDENT AND THE CONGRESS...

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

    ... Memorandum from D.G. Huizenga (U.S. DOE Office of Environmental Management EM) to L.H. Barrett (OCRWM). July 11, 2001. ACC: MOL.20010821.0087. SCRWMS M&O, 1995, Generic ...

  3. RussiaSNL2-web.indd

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

    ... with angle 81,78680, Plane (111) and planar 7. a b c d Modifi ed for the Web Visualizers Futures MolDraw ACDStructure Drawing Applet MW3D Crystal Lab Crystal Studio ...

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

    Office of Scientific and Technical Information (OSTI)

    with an exchangeable proton is eventually formed We have determined the bond dissociation free energy and pKa of the new O H bond in to be kcal mol and respectively in CH CN...

  5. Final Technical Report

    Office of Scientific and Technical Information (OSTI)

    ... plex (F ig.lA ) is com posed o f three proteins encoded by qm oABC (Pires et al., 2003) ... from hydrogen in Desulfovibrio bacteria: a structural biology review. Prog. Biophys. Mol. ...

  6. Spectroscopic properties of erbium-doped yttria-stabilised zirconia crystals

    SciTech Connect (OSTI)

    Ryabochkina, P A; Sidorova, N V; Ushakov, S N; Lomonova, E E

    2014-02-28

    Yttria-stabilised zirconia crystals ZrO{sub 2} Y{sub 2}O{sub 3} (6 mol %) Er{sub 2}O{sub 3} (5.85 mol %) are grown by directional crystallisation in a cold container using direct RF melting. The spectral and luminescent properties of these crystals are studied in order to use them as active media of solid state lasers emitting in the wavelength range 1.5 1.7 ?m. (active media)

  7. An accurate and efficient computational protocol for obtaining the complete basis set limits of the binding energies of water clusters at the MP2 and CCSD(T) levels of theory: Application to (H?O)m, m=2-6, 8, 11, 16 and 17

    SciTech Connect (OSTI)

    Miliordos, Evangelos; Xantheas, Sotiris S.

    2015-06-21

    We report MP2 and CCSD(T) binding energies with basis sets up to pentuple zeta quality for the m = 2-6, 8 clusters. Or best CCSD(T)/CBS estimates are -4.99 kcal/mol (dimer), -15.77 kcal/mol (trimer), -27.39 kcal/mol (tetramer), -35.9 0.3 kcal/mol (pentamer), -46.2 0.3 kcal/mol (prism hexamer), -45.9 0.3 kcal/mol (cage hexamer), -45.4 0.3 kcal/mol (book hexamer), -44.3 0.3 kcal/mol (ring hexamer), -73.0 0.5 kcal/mol (D2d octamer) and -72.9 0.5 kcal/mol (S4 octamer). We have found that the percentage of both the uncorrected (dimer) and BSSE-corrected (dimerCPe) binding energies recovered with respect to the CBS limit falls into a narrow range for each basis set for all clusters and in addition this range was found to decrease upon increasing the basis set. Relatively accurate estimates (within < 0.5%) of the CBS limits can be obtained when using the 2/3, 1/3 (for the AVDZ set) or the , (for the AVTZ, AVQZ and AV5Z sets) mixing ratio between dimere and dimerCPe. Based on those findings we propose an accurate and efficient computational protocol that can be used to estimate accurate binding energies of clusters at the MP2 (for up to 100 molecules) and CCSD(T) (for up to 30 molecules) levels of theory. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multi program national laboratory operated for DOE by Battelle. This research also used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. AC02-05CH11231.

  8. Genomic Sequencing of Single Microbial Cells from Environmental Samples

    SciTech Connect (OSTI)

    Ishoey, Thomas; Woyke, Tanja; Stepanauskas, Ramunas; Novotny, Mark; Lasken, Roger S.

    2008-02-01

    Recently developed techniques allow genomic DNA sequencing from single microbial cells [Lasken RS: Single-cell genomic sequencing using multiple displacement amplification, Curr Opin Microbiol 2007, 10:510-516]. Here, we focus on research strategies for putting these methods into practice in the laboratory setting. An immediate consequence of single-cell sequencing is that it provides an alternative to culturing organisms as a prerequisite for genomic sequencing. The microgram amounts of DNA required as template are amplified from a single bacterium by a method called multiple displacement amplification (MDA) avoiding the need to grow cells. The ability to sequence DNA from individual cells will likely have an immense impact on microbiology considering the vast numbers of novel organisms, which have been inaccessible unless culture-independent methods could be used. However, special approaches have been necessary to work with amplified DNA. MDA may not recover the entire genome from the single copy present in most bacteria. Also, some sequence rearrangements can occur during the DNA amplification reaction. Over the past two years many research groups have begun to use MDA, and some practical approaches to single-cell sequencing have been developed. We review the consensus that is emerging on optimum methods, reliability of amplified template, and the proper interpretation of 'composite' genomes which result from the necessity of combining data from several single-cell MDA reactions in order to complete the assembly. Preferred laboratory methods are considered on the basis of experience at several large sequencing centers where >70% of genomes are now often recovered from single cells. Methods are reviewed for preparation of bacterial fractions from environmental samples, single-cell isolation, DNA amplification by MDA, and DNA sequencing.

  9. Assessment of G3(MP2)//B3 theory including a pseudopotential for molecules containing first-, second-, and third-row representative elements

    SciTech Connect (OSTI)

    Rocha, Carlos Murilo Romero; Morgon, Nelson Henrique; Custodio, Rogrio; Pereira, Douglas Henrique; Departamento de Cincias Exatas e Biotecnolgicas, Universidade Federal do Tocantins, Campus de Gurupi, 77410-530 Gurupi, Tocantins

    2013-11-14

    G3(MP2)//B3 theory was modified to incorporate compact effective potential (CEP) pseudopotentials, providing a theoretical alternative referred to as G3(MP2)//B3-CEP for calculations involving first-, second-, and third-row representative elements. The G3/05 test set was used as a standard to evaluate the accuracy of the calculated properties. G3(MP2)//B3-CEP theory was applied to the study of 247 standard enthalpies of formation, 104 ionization energies, 63 electron affinities, 10 proton affinities, and 22 atomization energies, comprising 446 experimental energies. The mean absolute deviations compared with the experimental data for all thermochemical results presented an accuracy of 1.4 kcal mol{sup ?1} for G3(MP2)//B3 and 1.6 kcal mol{sup ?1} for G3(MP2)//B3-CEP. Approximately 75% and 70% of the calculated properties are found with accuracy between 2 kcal mol{sup ?1} for G3(MP2)//B3 and G3(MP2)//B3-CEP, respectively. Considering a confidence interval of 95%, the results may oscillate between 4.2 kcal mol{sup ?1} and 4.6 kcal mol{sup ?1}, respectively. The overall statistical behavior indicates that the calculations using pseudopotential present similar behavior with the all-electron theory. Of equal importance to the accuracy is the CPU time, which was reduced by between 10% and 40%.

  10. Supercritical Fluid Extraction of Plutonium and Americium from Soil using Thenoyltrifluoroacetone and Tributylphosphate Complexation

    SciTech Connect (OSTI)

    Mincher, Bruce Jay; Fox, Robert Vincent; Holmes, R.; Robbins, R; Boardman, C.

    2001-10-01

    Samples of clean soil from the source used to backfill pits at the Idaho National Engineering and Environmental Laboratory's Radioactive Waste Management Complex were spiked with Pu-239 and Am-241 to evaluate ligand-assistedsupercritical fluid extraction as a decontamination method. The actual soil in the pits has been subject to approximately three decades of weatheringsince it was originally contaminated. No surrogate soil can perfectly simulate the real event, but actual contaminated soil was not available for research purposes. However, fractionation of Am and Pu in the surrogate soil was found to be similar to that previously measured in the real soil using asequential aqueous extraction procedure. This suggests that Pu and Am behavior are similar in the two soils. The surrogate was subjected to supercritical carbon dioxide extraction, in the presence of the fluorinated beta diketone thenoyltrifluoroacetone (TTA), and tributylphosphate (TBP). As much as 69% of the Pu and 88% of the Am were removed from the soil using 3.2mol% TTA and 2.7 mol % TBP, in a single 45 minute extraction. Extraction conditions employing a 5 mol % ethanol modifier with 0.33 mol % TTA and 0.27 mol %TBP resulted in 66% Pu and 68% Am extracted. To our knowledge, this is thefirst report of the use of supercritical fluid extraction (SFE) for the removal of actinides from soil.

  11. Hybrid Quantum Mechanics/Molecular Mechanics-Based Molecular Dynamics Simulation of Acid-Catalyzed Dehydration of Polyols in Liquid Water

    SciTech Connect (OSTI)

    Caratzoulas, Stavros; Courtney, Timothy; Vlachos, Dionisios G.

    2011-01-01

    We use the conversion of protonated glycerol to acrolein for a case study of the mechanism of acid-catalyzed dehydration of polyols in aqueous environments. We employ hybrid Quamtum Mechanics/Molecular Mechanics Molecular Dynamics (QM/MM MD) simulations with biased sampling and perform free energy calculations for the elementary steps of the reaction. We investigate the effects of solvent dynamics and in particular the role of quantum mechanical water in the dehydration mechanism. We present results supporting a mechanism that proceeds via water-mediated proton transfers and thus through an enol intermediate. We find that the first dehydration may take place by two, low-energy pathways requiring, respectively, 20.9 and 18.8 kcal/mol of activation free energy. The second dehydration requires 19.9 kcal/mol of activation free energy while for the overall reaction we compute a free energy change of -8 kcal/mol.

  12. Diffusion of CO{sub 2} on Rutile TiO{sub 2}(110) Surface

    SciTech Connect (OSTI)

    Lee, Junseok; Sorescu, Dan C.; Deng, Xingyi; Jordan, Kenneth D.

    2011-12-15

    The diffusion of CO{sub 2} molecules on a reduced rutile TiO{sub 2}(110)-(11) surface has been investigated using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The STM feature associated with a CO{sub 2} molecule at an oxygen vacancy (V{sub O}) becomes increasingly streaky with increasing temperature, indicating thermally activated CO{sub 2} diffusion from the V{sub O} site. From temperature-dependent tunneling current measurements, the barrier for diffusion of CO{sub 2} from the V{sub O} site is estimated to be 3.31 0.23 kcal/mol. The corresponding value from the DFT calculations is 3.80 kcal/mol. In addition, the DFT calculations give a barrier for diffusion of CO{sub 2} along Ti rows of only 1.33 kcal/mol.

  13. Influences of ureaglycerol mixtures as mixed mesopore-controlling agents on tailoring physicochemical properties and photocatalytic H{sub 2} production activity of solgel-derived mesoporous-assembled TiO{sub 2} nanocrystals

    SciTech Connect (OSTI)

    Sreethawong, Thammanoon; Ngamsinlapasathian, Supachai; Yoshikawa, Susumu

    2013-01-15

    Graphical abstract: Display Omitted Highlights: ? Mesoporous-assembled TiO{sub 2} nanocrystals were synthesized by modified solgel process. ? Ureaglycerol mixtures were applied as mixed mesopore-controlling agents. ? Urea and glycerol contents affected physicochemical properties of synthesized TiO{sub 2}. ? Photocatalytic H{sub 2} production activity also depended on urea and glycerol contents. ? 75 mol% urea and 25 mol% glycerol yielded the most photocatalytically active TiO{sub 2}. -- Abstract: In this work, the mesoporous-assembled TiO{sub 2} nanocrystal photocatalysts were successfully synthesized by a solgel process with the aid of ureaglycerol mixtures used as mixed mesopore-controlling agents. The photocatalytic activity of the synthesized mesoporous-assembled TiO{sub 2} nanocrystal photocatalysts was investigated for hydrogen production from the water splitting reaction using methanol as a hole scavenger under UV light irradiation. The synthesized TiO{sub 2} nanocrystal photocatalysts were systematically characterized by TGDTA, N{sub 2} adsorptiondesorption, SEM, high resolution TEM, and XRD analyses. The characterization results showed that the well-controlled contents of urea and glycerol in a ureaglycerol mixture at 75 mol% urea and 25 mol% glycerol resulted in not only the most highly porous network (i.e. the highest specific surface area and total pore volume, and the smallest mean mesopore diameter), but also the smallest crystallite size of the synthesized TiO{sub 2} nanocrystal photocatalyst. The photocatalytic reaction results, hence, revealed a much superior photocatalytic hydrogen production activity of the mesoporous-assembled TiO{sub 2} nanocrystal synthesized with 75 mol% urea and 25 mol% glycerol to the other synthesized TiO{sub 2} nanocrystals, also being much higher than those of the commercially available P-25 TiO{sub 2} and ST-01 TiO{sub 2} powders.

  14. Preconversion catalytic deoxygenation of phenolic functional groups. Quarterly technical progress report, January 1, 1992--March 31, 1992

    SciTech Connect (OSTI)

    Kubiak, C.P.

    1992-08-01

    The deoxygenation of phenols is a conceptually simple, but unusually difficult chemical transformation to achieve. The phenolic C-O bond energy of 103 kcal/mol is as strong as a benzene C-H bond and over a 10 kcal/mol stronger than the C-O bonds of methanol and ethanol. The consequence of this is that the hydrogenation/deoxygenation methods in current use require severe conditions and give low selectivities. The ongoing research described herein is based on the unprecedented, but thermodynamically promising, use of carbon monoxide as the oxygen atom acceptor for the catalytic deoxygenation of phenols.

  15. Terpolymerization of ethylene, sulfur dioxide and carbon monoxide

    DOE Patents [OSTI]

    Johnson, Richard (Shirley, NY); Steinberg, Meyer (Huntington Station, NY)

    1981-01-01

    This invention relates to a high molecular weight terpolymer of ethylene, sulfur dioxide and carbon monoxide stable to 280.degree. C. and containing as little as 36 mol % ethylene and about 41-51 mol % sulfur dioxide; and to the method of producing said terpolymer by irradiation of a liquid and gaseous mixture of ethylene, sulfur dioxide and carbon monoxide by means of Co-60 gamma rays or an electron beam, at a temperature of about 10.degree.-50.degree. C., and at a pressure of about 140 to 680 atmospheres, to initiate polymerization.

  16. Visible absorption spectra of crystal violet in supercritical ethane - methanol solution.

    SciTech Connect (OSTI)

    Dimitrijevic, N. M.; Takahashi, K.; Jonah, C. D.; Chemistry

    2002-11-01

    The effects of concentration and mole fraction of methanol in supercritical ethane on the absorption spectra of crystal violet (CV) were examined. Keeping the concentration of CV in the cell constant at 50 {mu}mol l{sup -1}, both the methanol concentration (from 0.4 to 1.2 mol l{sup -1}) and pressure of ethane (from 60 to 150 bar) were varied. The degree of solvation of CV depends both on the mole fraction and concentration of cosolvent. The dimerization of CV was found to decrease with pressure, and with the ratio between methanol and CV concentrations.

  17. Organic Rankine-Cycle Power Systems Working Fluids Study: Topical report No. 3, 2-methylpyridine/water

    SciTech Connect (OSTI)

    Cole, R.L.; Demirgian, J.C.; Allen, J.W.

    1987-09-01

    A mixture of 35 mole percent (mol %) 2-methylpyridine and 65 mol % water was tested at 575, 625, and 675/degree/F in a dynamic loop. Samples of the degraded fluid were chemically analyzed to determine the identities of major degradation products and the quantity of degradation. Computed degradation rates were found to be higher than those for Fluorinol 85 or toluene. For this reason (and other reasons, related to fluid handling), other fluids are recommended as the first choice for service in organic Rankine-cycle systems in preference to 2-methylpyridine/water. 7 refs., 39 figs., 39 tabs.

  18. Oxidation kinetics of calcium-doped palladium powders

    SciTech Connect (OSTI)

    Jain, S.; Kodas, T.T.; Hampden-Smith, M. [Univ. of New Mexico, Albuquerque, NM (United States)

    1997-04-01

    The oxidation kinetics of submicron Ca-containing Pd powders produced by spray pyrolysis were studied in the temperature range 600 to 675 C using thermogravimetric analysis. The oxidation of pure Pd powder had an activation energy of {approximately}230 kJ/mol in the region 27% < oxidation < 70% and 65 kJ/mol for oxidation > 70%. The activation energies for Pd particles containing 0.01 weight percent (w/o) and 0.4 w/o Ca in the region 27% < oxidation < 70% were {approximately}230 kJ/mol and {approximately}50 kJ/mol, respectively. Transmission electron microscopy suggested that the conversion of Pd to Pd{sup II}O (stoichiometric PdO) proceeds from the particle surface into the interior and not homogeneously throughout the particle. The predictions of a variety of models and rate laws (shrinking core, parabolic, cubic, logarithmic, and inverse logarithmic) were compared with the data. The comparison suggested a mechanism in which oxidation of pure Pd proceeds by chemisorption and diffusion of oxygen to form a substoichiometric oxide, followed by the conversion of substoichiometric PdO to Pd{sup II}O. Oxidation of pure Pd is then probably limited by the diffusion of oxygen through the substoichiometric PdO and/or Pd{sup II}O. The addition of Ca increased the oxidation resistance of Pd most likely by inhibiting oxygen diffusion through the metal oxide layers surrounding the Pd.

  19. A study of radiolytic stability of 25,27-bis(2-propyloxy) calix[4]-26,28-crown-6 (iPR-C[4]C-6)

    SciTech Connect (OSTI)

    Jianchen, Wang; Chongli, Song

    2008-07-01

    The radiolytic stability of 25,27-bis(2-propyloxy)calix[4] arene -26,28-crown-6 (iPr-C[4]C-6) was studied. {sup 60}co was used as a radiation source. Its dose rate was 437 Gy/min., and the total absorbed dose of the iPr-C[4]C-6 was from 10{sup 4} to 10{sup 6} Gy. The iPr-C[4]C-6 solid and 0.025 mol/L iPr-C[4]C-6/n-octanol which were pre-equilibrated with 0.01 mol/L and 3 mol/L nitric acid, respectively, were given different doses, and their extraction performance was researched. Their degradation mechanism was investigated by mass spectrometry (MS) and infrared spectroscopy (IR). The results show that radiolytic stability of the iPr-C[4]C-6 solid and 0.025 mol/L iPr-C[4]C-6/n-octanol are good when their absorbed dose is less than 10{sup 6} Gy. The extracting system of iPr-C[4]C-6/n-octanol is promising for separating cesium from high-level liquid waste(HLLW)

  20. Vibrationally resolved transitions in ion-molecule and atom-molecular ion slow collisions

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

    The data tables and interactive graphs made available here contain theoretical integral cross sections for vibrational excitation and vibrationally resolved charge transfer from vibrationally excited states of H2 and H2+ with protons and hydrogen atoms, respectively. [From http://www-cfadc.phy.ornl.gov/h2mol/home.html] (Specialized Interface)

  1. Annealing of paramagnetic centres in electron- and ion-irradiated yttria-stabilized zirconia: effect of yttria content

    SciTech Connect (OSTI)

    Costantini, Jean-Marc; Beuneu, Francois; Weber, William J

    2014-01-01

    We have studied the effect of the yttria content on the recovery of paramagnetic centres in electron-irradiated yttria-stabilized zirconia (ZrO2: Y3+). Single crystals with 9.5 mol% or 18 mol% Y2O3 were irradiated with electrons of 1.0, 1.5, 2.0 and 2.5 MeV. Paramagnetic centre thermal annealing was studied by X-band EPR spectroscopy. Hole-centres are found to be annealed more quickly, or at a lower temperature, for 18 mol% than for 9.5 mol% Y2O3. At long annealing times, a non-zero asymptotic behaviour is observed in the isothermal annealing curves of hole-centres and F+-type centres between 300 and 500 K. The normalized asymptotic concentration of both defects has a maximum value of about 0.5 for annealing temperatures near 375 K, below the onset of the (isochronal) recovery stage, regardless of the yttria content. Such an uncommon behaviour is analyzed on the basis of either kinetic rate equations of charge transfer or equilibria between point defects with different charge states.

  2. Non-Equilibrium Pathways during Electrochemical Phase Transformations...

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

    lithium-manganese spinel cathode material - Li1+xMn2-xO4 - is one of the state-of-the-art materials for Li-ion batteries. During the electrochemical reaction, up to 2 mol Li can...

  3. Heterogeneity and dynamics in villin headpiece crystal structures

    SciTech Connect (OSTI)

    Meng, Jianmin; McKnight, Christopher James, E-mail: cjmck@bu.edu [Boston University School of Medicine (United States)

    2009-05-01

    New crystal structures of the well studied protein-folding model system villin headpiece in a new space group provide insights into the conformations available in the folded state. The villin headpiece domain (HP67) is the C-terminal F-actin-binding motif that confers F-actin-bundling activity to villin, a component of the actin bundles that support the brush-border microvilli. It has been investigated extensively by both experimental and theoretical measurements. Our laboratory, for example, has determined both its NMR and its crystal structures. This study presents the structures of HP67 and its pH-stabilized mutant (H41Y) in a different crystal form and space group. For both constructs, two molecules are found in each asymmetric unit in the new space group P6{sub 1}. While one of the two structures (Mol A) is structurally similar to our previously determined structure (Mol X), the other (Mol B) has significant deviations, especially in the N-terminal subdomain, where lattice contacts do not appear to contribute to the difference. In addition, the structurally most different crystal structure, Mol B, is actually closer to the averaged NMR structure. Harmonic motions, as suggested by the B-factor profiles, differ between these crystal structures; crystal structures from the same space group share a similar pattern. Thus, heterogeneity and dynamics are observed in different crystal structures of the same protein even for a protein as small as villin headpiece.

  4. Analysis of emission spectra of Ho{sup 3+}:LFBCd glasses

    SciTech Connect (OSTI)

    Naresh, V. Buddhudu, S.

    2014-04-24

    In the present paper, we report on the absorption and emission properties of (0.1-1.5 mol %) Ho{sup 3+} doped LFBCd (Li{sub 2}O{sub ?}LiF{sub ?}B{sub 2}O{sub 3?}CdO) glasses prepared via melt quenching method. On exciting these glasses at (?{sub exci}) = 452 nm, two emissions at 556 nm ({sup 5}S{sub 2}?{sup 5}I{sub 8}; Green), 655 nm ({sup 5}F{sub 5}?{sup 5}I{sub 8}; Red) have been obtained. Upon exciting these glasses with a 980 nm diode laser, NIR emissions at 1195 nm ({sup 5}I{sub 6}?{sup 5}I{sub 8}), 1951 nm ({sup 5}I{sub 7}?{sup 5}I{sub 8}) have been measured for 1 mol % Ho{sup 3+}:LFBCd glass. For higher concentration beyond 1.0 mol %, emission quenching of Ho{sup 3+} glass has been noticed and which has successfully been explained in terms of an energy level diagram. From absorption cross-section data, stimulated emission cross-section has been evaluated by applying McCumber's theory and further cross-sectional gain has also been computed for the emissions at 1195 nm (?1.20 ?m) and 1951 nm (?2.0 ?m) of 1 mol % Ho{sup 3+}:LFBCd glass.

  5. Roaming radical pathways for the decomposition of alkanes.

    SciTech Connect (OSTI)

    Harding, L. B.; Klippenstein, S. J.

    2010-01-01

    CASPT2 calculations predict the existence of roaming radical pathways for the decomposition of propane, n-butane, isobutane and neopentane. The roaming radical paths lead to the formation of an alkane and an alkene instead of the expected radical products. The predicted barriers for the roaming radical paths lie {approx}1 kcal/mol below the corresponding radical asymptotes.

  6. Determination of rate constants for the reaction between 2-(2-amino-ethoxy) ethanol and carbonyl sulfide

    SciTech Connect (OSTI)

    Singh, M.; Bullin, J.A. (Texas A and M Univ., College Station, TX (US))

    1988-01-01

    The kinetics of the reaction between carbonyl sulfide (COS) and aqueous 2-(2-amino-ethoxy) ethanol (Diglycolamine or DGA) in aqueous solutions were investigated over a temperature range of 307 K to 322 K and pressure range of 345-414 kPa. The experimental data were correlated by assuming the reaction to be kinetically controlled. The observed reaction rates were significantly larger than those for the COS/H/sub 2/O system. Therefore, it was concluded that DGA had a catalytic effect on the COS hydrolysis reaction. The analysis indicated that the reaction followed a second order rate equation: first order in COS and first order in DGA. Justification for assuming kinetic control of the absorption was demonstrated by doubling and tripling the stirring speed which produced no significant change in the absorption rate (mol/s). Another series of tests were carried out which showed that the absorption rate (mol/s) was proportional to the reactor volume. In addition, the activation energy was out of the range of ordinary mass transfer control.

  7. Thermodynamic properties of a geothermal working fluid; 90% isobutane-10% isopentane: Final report

    SciTech Connect (OSTI)

    Gallagher, J.S.; Linsky, D.; Morrison, G.; Levelt Sengers, J.M.H.

    1987-04-01

    We present tables of thermodynamic properties, and dew and bubble properties, of a mixture of 90 mol % isobutane and 10 mol % isopentane, a working fluid in a binary geothermal power cycle. The tables are generated by a formulation of the Helmholtz free energy, in which the mixture properties are mapped onto the known properties of pure isobutane by means of the principle of generalized corresponding states. The data base for the Helmholtz free energy formulation is new. We report data obtained in three different apparatus: critical-line and isopentane vapor pressure data obtained in a visual cell; vapor-liquid equilibria data obtained in a mercury-operated variable-volume cell; and pressure-volume-temperature data for the 90 mol %-10 mol % mixture obtained in a semi-automated Burnett-isochoric apparatus. The principles of the methods, and estimates of the reliability, are discussed and all experimental data are compared with the surface. The results are tables of specific volume, enthalpy, entropy, specific heat and density and temperature derivatives of the pressure at 10 K temperature increments from 240 to 600 K along isobars from 0.01 to 20 MPa. Separate tables are prepared from the dew and bubble properties of the 90-10 mixture. Estimates of the effects of isomeric impurity of isobutane are given in graphical form.

  8. Appendix C Analytical Chemistry Data

    Office of Legacy Management (LM)

    Analytical Chemistry Data This page intentionally left blank Contents Section Analytical Data for Deleted Contaminants of Concern ............................................................. C1.O Mol~tezuma Creek Hardness Dat Surface Water Copper Data Summa ................ CI-9 Surface Water Radium-228 Dat Surface Water Radon-222 Data Summary ....................... ....................................... . . . . . . . . . . . C l - I 2 Alluvial Ground Water Aln~noniuu~ as Nitrogen Data

  9. Thermal decomposition of 1,3,3-trinitroazetidine (TNAZ): A density functional theory and ab initio study

    SciTech Connect (OSTI)

    Veals, Jeffrey D.; Thompson, Donald L.

    2014-04-21

    Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO{sub 2} or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO{sub 2} elimination by NN and CN bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO{sub 2} group elimination or by a concerted H-atom and nitroalkyl NO{sub 2} group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO{sub 2} elimination by NN bond fission, HONO elimination involving the nitramine NO{sub 2} group, HONO elimination involving a nitroalkyl NO{sub 2} group, and finally NO{sub 2} elimination by CN bond fission.

  10. Energy Landscape of Water and Ethanol on Silica Surfaces

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

    Wu, Di; Guo, Xiaofeng; Sun, Hui; Navrotsky, Alexandra

    2015-06-26

    Fundamental understanding of small molecule–silica surface interactions at their interfaces is essential for the scientific, technological, and medical communities. We report direct enthalpy of adsorption (Δhads) measurements for ethanol and water vapor on porous silica glass (CPG-10), in both hydroxylated and dehydroxylated (hydrophobic) forms. Results suggest a spectrum of energetics as a function of coverage, stepwise for ethanol but continuous for water. The zero-coverage enthalpy of adsorption for hydroxylated silica shows the most exothermic enthalpies for both water (-72.7 ± 3.1 kJ/mol water) and ethanol (-78.0 ± 1.9 kJ/mol ethanol). The water adsorption enthalpy becomes less exothermic gradually until reachingmore » its only plateau (-20.7 ± 2.2 kJ/mol water) reflecting water clustering on a largely hydrophobic surface, while the enthalpy of ethanol adsorption profile presents two well separated plateaus, corresponding to strong chemisorption of ethanol on adsorbate-free silica surface (-66.4 ± 4.8 kJ/mol ethanol), and weak physisorption of ethanol on ethanol covered silica (-4.0 ± 1.6 kJ/mol ethanol). On the other hand, dehydroxylation leads to missing water–silica interactions, whereas the number of ethanol binding sites is not impacted. The isotherms and partial molar properties of adsorption suggest that water may only bind strongly onto the silanols (which are a minor species on silica glass), whereas ethanol can interact strongly with both silanols and the hydrophobic areas of the silica surface.« less

  11. Carbonic anhydrase-facilitated CO2 absorption with polyacrylamide buffering bead capture

    SciTech Connect (OSTI)

    Dilmore, Robert; Griffith, Craid; Liu, Zhu; Soong, Yee; Hedges, Sheila W.; Koepsel, Richard; Ataai, M [Ataai, Mohammad

    2009-07-01

    A novel CO2 separation concept is described wherein the enzyme carbonic anhydrase (CA) is used to increase the overall rate Of CO2 absorption after which hydrated CO2 reacts with regenerable amine-bearing polyacrylamide buffering beads (PABB). Following saturation of the material's immobilized tertiary amines, CA-bearing carrier water is separated and recycled to the absorption stage while CO2-loaded material is thermally regenerated. Process application of this concept would involve operation of two or more columns in parallel with thermal regeneration with low-pressure steam taking place after the capacity of a column of amine-bearing polymeric material was exceeded. PABB CO2- bearing capacity was evaluated by thermogravimetric analysis (TGA) for beads of three acrylamido buffering monomer ingredient concentrations: 0 mol/kg bead, 0.857 mol/kg bead, and 2 mol/kg bead. TGA results demonstrate that CO2- bearing capacity increases with increasing PABB buffering concentration and that up to 78% of the theoretical CO2- bearing capacity was realized in prepared PABB samples (0.857 mol/kg recipe). The highest observed CO2-bearing capacity of PABB was 1.37 mol of CO2 per kg dry bead. TGA was also used to assess the regenerability Of CO2-loaded PABB. Preliminary results suggest that CO2 is partially driven from PABB samples at temperatures as low as 55 degrees C, with complete regeneration occurring at 100 degrees C. Other physical characteristics of PABB are discussed. In addition, the effectiveness of bovine carbonic anhydrase for the catalysis Of CO2 dissolution is evaluated. Potential benefits and drawbacks of the proposed process are discussed. Published by Elsevier Ltd.

  12. Energy Landscape of Water and Ethanol on Silica Surfaces

    SciTech Connect (OSTI)

    Wu, Di; Guo, Xiaofeng; Sun, Hui; Navrotsky, Alexandra

    2015-06-26

    Fundamental understanding of small moleculesilica surface interactions at their interfaces is essential for the scientific, technological, and medical communities. We report direct enthalpy of adsorption (?hads) measurements for ethanol and water vapor on porous silica glass (CPG-10), in both hydroxylated and dehydroxylated (hydrophobic) forms. Results suggest a spectrum of energetics as a function of coverage, stepwise for ethanol but continuous for water. The zero-coverage enthalpy of adsorption for hydroxylated silica shows the most exothermic enthalpies for both water (-72.7 3.1 kJ/mol water) and ethanol (-78.0 1.9 kJ/mol ethanol). The water adsorption enthalpy becomes less exothermic gradually until reaching its only plateau (-20.7 2.2 kJ/mol water) reflecting water clustering on a largely hydrophobic surface, while the enthalpy of ethanol adsorption profile presents two well separated plateaus, corresponding to strong chemisorption of ethanol on adsorbate-free silica surface (-66.4 4.8 kJ/mol ethanol), and weak physisorption of ethanol on ethanol covered silica (-4.0 1.6 kJ/mol ethanol). On the other hand, dehydroxylation leads to missing watersilica interactions, whereas the number of ethanol binding sites is not impacted. The isotherms and partial molar properties of adsorption suggest that water may only bind strongly onto the silanols (which are a minor species on silica glass), whereas ethanol can interact strongly with both silanols and the hydrophobic areas of the silica surface.

  13. Radiotherapy margin design with particular consideration of high curvature CTVs

    SciTech Connect (OSTI)

    Herschtal, Alan; Kron, Tomas; Fox, Chris [Peter MacCallum Cancer Centre, St. Andrews Place, E. Melbourne, Victoria 3002 (Australia)

    2009-03-15

    In applying 3D conformal radiation therapy to a tumor clinical target volume (CTV), a margin is added around the CTV to account for any sources of error in the application of treatment which may result in misalignment between the CTV and the dose distribution actually delivered. The volume enclosed within the CTV plus the margin is known as the PTV, or planning target volume. The larger the errors are anticipated to be, the wider the margin will need to be to accommodate those errors. Based on the approach of van Herk et al. [''The probability of correct target dosage: Dose-population histograms for deriving treatment margins in radiotherapy,'' Int. J. Radiat. Oncol. Biol., Phys. 47(4), 1121-1135 (2000)] this paper develops the mathematical theory behind the calculation of the margin width required to ensure that the entire CTV receives sufficiently high dose with sufficiently high probability. The margin recipe developed not only considers the magnitude of the errors but also includes a term to adjust for curved CTV surfaces. In doing so, the accuracy of the margin recipe is enhanced yet remains mathematically concise enough to be readily implemented in the clinical setting. The results are particularly relevant for clinical situations in which the uncertainties in treatment are large relative to the size of the CTV.

  14. Engineering Ascorbate Peroxidase Activity Into Cytochrome C Peroxidase

    SciTech Connect (OSTI)

    Meharenna, Y.T.; Oertel, P.; Bhaskar, B.; Poulos, T.L.

    2009-05-26

    Cytochrome c peroxidase (CCP) and ascorbate peroxidase (APX) have very similar structures, and yet neither CCP nor APX exhibits each others activities with respect to reducing substrates. APX has a unique substrate binding site near the heme propionates where ascorbate H-bonds with a surface Arg and one heme propionate (Sharp et al. (2003) Nat. Struct. Biol. 10, 303--307). The corresponding region in CCP has a much longer surface loop, and the critical Arg residue that is required for ascorbate binding in APX is Asn in CCP. In order to convert CCP into an APX, the ascorbate-binding loop and critical arginine were engineered into CCP to give the CCP2APX mutant. The mutant crystal structure shows that the engineered site is nearly identical to that found in APX. While wild-type CCP shows no APX activity, CCP2APX catalyzes the peroxidation of ascorbate at a rate of {approx}12 min{sup -1}, indicating that the engineered ascorbate-binding loop can bind ascorbate.

  15. 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.

  16. Ternary ceramic alloys of Zr-Ce-Hf oxides

    DOE Patents [OSTI]

    Becher, P.F.; Funkenbusch, E.F.

    1990-11-20

    A ternary ceramic alloy is described which produces toughening of zirconia and zirconia composites through the stress transformation from tetragonal phase to monoclinic phase. This alloy, having the general formula Ce[sub x]Hf[sub y]Zr[sub 1[minus]x[minus]y]O[sub 2], is produced through the addition of appropriate amounts of ceria and hafnia to the zirconia. Typically, improved toughness is achieved with about 5 to about 15 mol % ceria and up to about 40 mol % hafnia. The preparation of alloys of these compositions are given together with data as to the densities, tetragonal phase content, hardness and fracture toughness. The alloys are useful in preparing zirconia bodies as well as reinforcing ceramic composites. 1 fig.

  17. Kinetics of Methane Hydrate Decomposition Studied via in Situ Low Temperature X-ray Powder Diffraction

    SciTech Connect (OSTI)

    Everett, Susan M; Rawn, Claudia J; Keffer, David J.; Mull, Derek L; Payzant, E Andrew; Phelps, Tommy Joe

    2013-01-01

    Gas hydrates are known to have a slowed decomposition rate at ambient pressure and temperatures below the melting point of ice termed self-preservation or anomalous preservation. As hydrate exothermically decomposes, gas is released and water of the clathrate cages transforms into ice. Two regions of slowed decomposition for methane hydrate, 180 200 K and 230 260 K, were observed, and the kinetics were studied by in situ low temperature x-ray powder diffraction. The kinetic constants for ice formation from methane hydrate were determined by the Avrami model within each region and activation energies, Ea, were determined by the Arrhenius plot. Ea determined from the data for 180 200 K was 42 kJ/mol and for 230 260 K was 22 kJ/mol. The higher Ea in the colder temperature range was attributed to a difference in the microstructure of ice between the two regions.

  18. Effects of Ti-Based Additives on the Hydrogen Storage Properties of a L i B H 4 / C a H 2 Destabilized System

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

    Yang, Hongwei; Ibikunle, Adeola; Goudy, Andrew J.

    2010-01-01

    Tmore » he hydrogen storage properties of a destabilized LiBH 4 / CaH 2 system ball-milled with TiCl 3 , TiF 3 , and TiO 2 additives have been investigated. It is found that the system with TiCl 3 additive has a lower dehydrogenation temperature than the ones with other additives. Further study shows that a higher amount of TiCl 3 is more effective in reducing the desorption temperature of the LiBH 4 / CaH 2 system, since it leads to a lower activation energy of dehydrogenation. The activations energies for mixtures containing 4, 10, and 25 mol% of TiCl 3 are 141, 126, and 110 kJ/mol, respectively. However, the benefits of higher amounts of TiCl 3 are offset by a larger reduction in hydrogen capacity of the mixtures.« less

  19. Erbium hydride decomposition kinetics.

    SciTech Connect (OSTI)

    Ferrizz, Robert Matthew

    2006-11-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.

  20. Synthesis and stability of liquid molecular DT

    SciTech Connect (OSTI)

    Souers, P.C.; Fearon, E.M.; Garza, R.G.; Griffith, C.M.; Mayhugh, S.R.; Mapoles, E.R.; Tsurgawa, R.T.; Sater, J.D.; Collins, G.W.; Gaines, J.R.

    1988-01-01

    Regular equimolar deuterium-tritium is a mixture of 25 mol% T/sub 2/-50% DT-25% D/sub 2/. We have synthesized molecular DT of greater purity by the reaction LiT + CH/sub 3/OD ..-->.. DT + LiOCH/sub 3/, run at 243/degree/K. With both the alcohol and reactor-to-cryostat transfer lines at room temperature, we obtain 88 mol% DT purity. By cooling the alcohol and holding the transfer lines at 80/degree/K, the yield rose to 95% DT. The DT disproportionated to D/sub 2/ and T/sub 2/ with a le-time constant of about 100 hours in the liquid at 20.5/degree/K. Nuclear magnetic resonance data showed that the eventual T/sub 2/-DT-D/sub 2/ equilibrium is probably a /open quotes/hot-atom/close quotes/ one.

  1. Synthesis and stability of liquid molecular DT

    SciTech Connect (OSTI)

    Souers, P.C.; Fearon, E.M.; Garza, R.G.; Friffith, C.M.; Mayhugh, S.R.; Mapoles, E.R.; Tsugawa, R.T.; Sater, J.D.; Collins, G.W.; Gaines, J.R.

    1988-05-01

    Regular equimolar deuterium-tritium is a mixture of 25 mol% T/sub 2/-50% DT-25% D/sub 2/. We have synthesized molecular DT of greater purity by the reaction LiT + CH/sub 3/OD ..-->.. DT + LiOCH/sub 3/, run at 243/degree/K. With both the alcohol and reactor-to-cryostat transfer lines at room temperature, we obtain 88 mol% DT purity. By cooling the alcohol and holding the transfer lines at 80/degree/K, the yield rose to 95% DT. The DT disproportionated to D/sub 2/ and T/sub 2/ with a 1e time constant of about 100 h in the liquid at 20.5/degree/K. Nuclear magnetic resonance data showed that the eventual T/sub 2/-DT-D/sub 2/ equilibrium is probably a /open quotes/hot-atom/close quotes/ one. 15 refs., 4 figs., 1 tab.

  2. Synthesis and stability of liquid molecular DT

    SciTech Connect (OSTI)

    Pearon, E.M.; Garza, R.G.; Griffith, C.M.; Mayhugh, S.R.; Mapoles, E.R.; Sater, J.D.; Souers, P.C.; Tsugawa, R.T.; Gaines, J.R.; Collins, G.W.

    1988-09-01

    Regular equimolar deuterium-tritium is a mixture of 25 mol% T/sub 2/-50% DT-25% D/sub 2/. The authors have synthesized molecular DT of greater purity by the reaction LiT + CH/sub 3/OD /yields/ DT + LiOCH/sub 3/, run at 243 K. With both the alcohol and reactor-to-cryostat transfer lines at room temperature, they obtain the 88 mol% DT purity. By cooling the alcohol and holding the transfer lines at 80 K, the yield rose to 95% DT. The DT disproportionated to D/sub 2/ and T/sub 2/ with a 1/e time constant of about 100 hr in the liquid at 20.5 K. Nuclear magnetic resonance data showed that the eventual T/sub 2/-DT-D/sub 2/ equilibrium is probably a hot-atom one.

  3. Porous Vycor membranes modified by chemical vapor deposition of boron nitride for gas separation

    SciTech Connect (OSTI)

    Levy, R.A.; Ravindranath, C.; Krasnoperov, L.N.; Opyrchal, J.; Ramos, E.S.

    1997-01-01

    This study focuses on the characterization of porous Vycor membranes modified by chemical vapor deposition of boron nitride (B-N-C-H) for gas separation. The B-N-C-H films were deposited on mesoporous Vycor tubes using triethylamine borane complex and ammonia as precursors. The effects of deposition temperature and reactant flow geometry on permselectivity of membranes with respect to various permeant gases were investigated. High selectivities (up to 50,000) were achieved between small molecules (He, H{sub 2}) and large molecules (N{sub 2}, Ar, C{sub 6}H{sub 5}CH{sub 3}). The measured activation energies for the He and H{sub 2} permeability are 9.5 kcal/mol and 12 kcal/mol, respectively. The membranes synthesized at lower temperatures and lower ammonia flow rates showed good mechanical and chemical stability.

  4. Improved spectrophotometric analysis of barium styphnate

    SciTech Connect (OSTI)

    Brown, N E; Blasi, J A

    1983-01-01

    A spectrophotometric procedure to determine the purity of barium styphnate monohydrate based upon the absorbance of the styphnate ion at 326 and 413.3 nm has been developed. The purity is determined by comparing the absorbance of the styphnate ion in barium styphnate and in styphnic acid. Our investigation has shown that the molar absorptivity and lambda maxima of the styphnate ion are quite pH dependent; therefore, the pH is buffered to 6.8 to 7.0 with ammonium acetate. Under these conditions the molar absorptivity is 1.6 x 10/sup 4/ L/mol-cm. Analyses following the procedure in the Navy specification WS13444A using water were found to give low molar absorptivities (1.3 x 10/sup 4/ L/mol-cm) for the styphnic acid calibration resulting in erroneous values for barium styphnate purity.

  5. Ternary ceramic alloys of ZR-CE-HF oxides

    DOE Patents [OSTI]

    Becher, Paul F. (Oak Ridge, TN); Funkenbusch, Eric F. (White Bear Lake, MN)

    1990-01-01

    A ternary ceramic alloy which produces toughening of zirconia and zirconia composites through the stress transformation from tetragonal phase to monoclinic phase. This alloy, having the general formula Ce.sub.x Hf.sub.y Zn.sub.1-x-y O.sub.2, is produced through the addition of appropriate amounts of ceria and hafnia to the zirconia. Typically, improved toughness is achieved with about 5 to about 15 mol % ceria and up to about 40 mol % hafnia. The preparation of alloys of these compositions are given together with data as to the densities, tetragonal phase content, hardness and fracture toughness. The alloys are useful in preparing zirconia bodies as well as reinforcing ceramic composites.

  6. Effects of Ti-Based Additives on the Hydrogen Storage Properties of aLiBH4/CaH2Destabilized System

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

    Yang, Hongwei; Ibikunle, Adeola; Goudy, Andrew J.

    2010-01-01

    The hydrogen storage properties of a destabilizedLiBH4/CaH2system ball-milled withTiCl3,TiF3, andTiO2additives have been investigated. It is found that the system withTiCl3additive has a lower dehydrogenation temperature than the ones with other additives. Further study shows that a higher amount ofTiCl3is more effective in reducing the desorption temperature of theLiBH4/CaH2system, since it leads to a lower activation energy of dehydrogenation. The activations energies for mixtures containing 4, 10, and 25?mol% ofTiCl3are 141, 126, and 110?kJ/mol, respectively. However, the benefits of higher amounts ofTiCl3are offset by a larger reduction in hydrogen capacity of the mixtures.

  7. EVALUATION OF CARBON DIOXIDE CAPTURE FROM EXISTING COAL FIRED PLANTS BY HYBRID SORPTION USING SOLID SORBENTS

    SciTech Connect (OSTI)

    Benson, Steven; Palo, Daniel; Srinivasachar, Srivats; Laudal, Daniel

    2014-12-01

    Under contract DE-FE0007603, the University of North Dakota conducted the project Evaluation of Carbon Dioxide Capture from Existing Coal Fired Plants by Hybrid Sorption Using Solid Sorbents. As an important element of this effort, an Environmental Health and Safety (EH&S) Assessment was conducted by Barr Engineering Co. (Barr) in association with the University of North Dakota. The assessment addressed air and particulate emissions as well as solid and liquid waste streams. The magnitude of the emissions and waste streams was estimated for evaluation purposes. EH&S characteristics of materials used in the system are also described. This document contains data based on the mass balances from both the 40 kJ/mol CO2 and 80 kJ/mol CO2 desorption energy cases evaluated in the Final Technical and Economic Feasibility study also conducted by Barr Engineering.

  8. Activation energy and enthalpy of decomposition for the Fe{sub 17}Sm{sub 2} nitride

    SciTech Connect (OSTI)

    Cabral, F.A.; Gama, S.; Ribeiro, C.A.

    1997-04-01

    Decomposition studies of the Fe{sub 17}Sm{sub 2}N{sub 3} compound were done using a Calvet-type microcalorimeter and a simultaneous gravimetric and differential thermal analyzer (DTA). The results show that the decomposition has onset temperature of 570{degree}C and proceeds up to 900{degree}C, and presents only one well determined exothermic thermal event. The calorimetric measurement shows that the enthalpy associated with the decomposition is 69 kJ/mol. The activation energy of the process was also determined using the Kissinger method applied to the DTA signal. It was observed that there was only one activation energy for the decomposition process, with a value of 339 kJ/mol. {copyright} {ital 1997 American Institute of Physics.}

  9. THE ABUNDANCE OF MOLECULAR HYDROGEN AND ITS CORRELATION WITH MIDPLANE PRESSURE IN GALAXIES: NON-EQUILIBRIUM, TURBULENT, CHEMICAL MODELS

    SciTech Connect (OSTI)

    Mac Low, Mordecai-Mark; Glover, Simon C. O. E-mail: glover@uni-heidelberg.de

    2012-02-20

    Observations of spiral galaxies show a strong linear correlation between the ratio of molecular to atomic hydrogen surface density R{sub mol} and midplane pressure. To explain this, we simulate three-dimensional, magnetized turbulence, including simplified treatments of non-equilibrium chemistry and the propagation of dissociating radiation, to follow the formation of H{sub 2} from cold atomic gas. The formation timescale for H{sub 2} is sufficiently long that equilibrium is not reached within the 20-30 Myr lifetimes of molecular clouds. The equilibrium balance between radiative dissociation and H{sub 2} formation on dust grains fails to predict the time-dependent molecular fractions we find. A simple, time-dependent model of H{sub 2} formation can reproduce the gross behavior, although turbulent density perturbations increase molecular fractions by a factor of few above it. In contradiction to equilibrium models, radiative dissociation of molecules plays little role in our model for diffuse radiation fields with strengths less than 10 times that of the solar neighborhood, because of the effective self-shielding of H{sub 2}. The observed correlation of R{sub mol} with pressure corresponds to a correlation with local gas density if the effective temperature in the cold neutral medium of galactic disks is roughly constant. We indeed find such a correlation of R{sub mol} with density. If we examine the value of R{sub mol} in our local models after a free-fall time at their average density, as expected for models of molecular cloud formation by large-scale gravitational instability, our models reproduce the observed correlation over more than an order-of-magnitude range in density.

  10. Water and Carbon Dioxide Adsorption at Olivine Surfaces

    SciTech Connect (OSTI)

    Kerisit, Sebastien N.; Bylaska, Eric J.; Felmy, Andrew R.

    2013-11-14

    Plane-wave density functional theory (DFT) calculations were performed to simulate water and carbon dioxide adsorption at the (010) surface of five olivine minerals, namely, forsterite (Mg2SiO4), calcio-olivine (Ca2SiO4), tephroite (Mn2SiO4), fayalite (Fe2SiO4), and Co-olivine (Co2SiO4). Adsorption energies per water molecule obtained from energy minimizations varied from -78 kJ mol-1 for fayalite to -128 kJ mol-1 for calcio-olivine at sub-monolayer coverage and became less exothermic as coverage increased. In contrast, carbon dioxide adsorption energies at sub-monolayer coverage ranged from -20 kJ mol-1 for fayalite to -59 kJ mol-1 for calcio-olivine. Therefore, the DFT calculations show a strong driving force for carbon dioxide displacement by water at the surface of all olivine minerals in a competitive adsorption scenario. Additionally, adsorption energies for both water and carbon dioxide were found to be more exothermic for the alkaline-earth (AE) olivines than for the transition-metal (TM) olivines and to not correlate with the solvation enthalpies of the corresponding divalent cations. However, a correlation was obtained with the charge of the surface divalent cation indicating that the more ionic character of the AE cations in the olivine structure relative to the TM cations leads to greater interactions with adsorbed water and carbon dioxide molecules at the surface and thus more exothermic adsorption energies for the AE olivines. For calcio-olivine, which exhibits the highest divalent cation charge of the five olivines, ab initio molecular dynamics simulations showed that this effect leads both water and carbon dioxide to react with the surface and form hydroxyl groups and a carbonate-like species, respectively.

  11. ENERGY EFFICIENCY LIMITS FOR A RECUPERATIVE BAYONET SULFURIC ACID DECOMPOSITION REACTOR FOR SULFUR CYCLE THERMOCHEMICAL HYDROGEN PRODUCTION

    SciTech Connect (OSTI)

    Gorensek, M.; Edwards, T.

    2009-06-11

    A recuperative bayonet reactor design for the high-temperature sulfuric acid decomposition step in sulfur-based thermochemical hydrogen cycles was evaluated using pinch analysis in conjunction with statistical methods. The objective was to establish the minimum energy requirement. Taking hydrogen production via alkaline electrolysis with nuclear power as the benchmark, the acid decomposition step can consume no more than 450 kJ/mol SO{sub 2} for sulfur cycles to be competitive. The lowest value of the minimum heating target, 320.9 kJ/mol SO{sub 2}, was found at the highest pressure (90 bar) and peak process temperature (900 C) considered, and at a feed concentration of 42.5 mol% H{sub 2}SO{sub 4}. This should be low enough for a practical water-splitting process, even including the additional energy required to concentrate the acid feed. Lower temperatures consistently gave higher minimum heating targets. The lowest peak process temperature that could meet the 450-kJ/mol SO{sub 2} benchmark was 750 C. If the decomposition reactor were to be heated indirectly by an advanced gas-cooled reactor heat source (50 C temperature difference between primary and secondary coolants, 25 C minimum temperature difference between the secondary coolant and the process), then sulfur cycles using this concept could be competitive with alkaline electrolysis provided the primary heat source temperature is at least 825 C. The bayonet design will not be practical if the (primary heat source) reactor outlet temperature is below 825 C.

  12. Routine production of copper-64 using 11.7MeV protons

    SciTech Connect (OSTI)

    Jeffery, C. M.; Smith, S. V.; Asad, A. H.; Chan, S.; Price, R. I.

    2012-12-19

    Reliable production of copper-64 ({sup 64}Cu) was achieved by irradiating enriched nickel-64 ({sup 64}Ni, >94.8%) in an IBA 18/9 cyclotron. Nickel-64 (19.1 {+-} 3.0 mg) was electroplated onto an Au disc (125{mu}m Multiplication-Sign 15mm). Targets were irradiated with 11.7 MeV protons for 2 hours at 40{mu}A. Copper isotopes ({sup 60,61,62,64}Cu) were separated from target nickel and cobalt isotopes ({sup 55,57,61}Co) using a single ion exchange column, eluted with varying concentration of low HCl alcohol solutions. The {sup 64}Ni target material was recovered and reused. The {sup 64}Cu production rate was 1.46{+-}0.3MBq/{mu}A.hr/mg{sup 64}Ni(n = 10) (with a maximum of 2.6GBq of {sup 64}Cu isolated after 2hr irradiation at 40uA. Radionuclidic purity of the {sup 64}Cu was 98.7 {+-} 1.6 % at end of separation. Cu content was < 6mg/L (n = 21). The specific activity of {sup 64}Cu was determined by ICP-MS and by titration with Diamsar to be 28.9{+-}13.0GBq/{mu}mol[0.70{+-}0.35Ci/{mu}mol]/({mu}A.hr/mg{sup 64}Ni)(n = 10) and 13.1{+-}12.0GBq/{mu}mol[0.35{+-}0.32Ci/{mu}mol]/({mu}A.hr/mg{sup 64}Ni)(n 9), respectively; which are in agreement, however, further work is required.

  13. Low-temperature aqueous-phase reforming of ethanol on bimetallic PdZn catalysts

    SciTech Connect (OSTI)

    Xiong, Haifeng; DelaRiva, Andrew; Wang, Yong; Dayte, Abhaya

    2015-01-01

    Bimetallic PdZn catalysts supported on carbon black (CB) and carbon nanotubes (CNTs) were found to be selective for CO-free H-2 production from ethanol at low temperature (250 degrees C). On Pd, the H-2 yield was low (similar to 0.3 mol H-2/mol ethanol reacted) and the CH4/CO2 ratio was high (similar to 1.7). Addition of Zn to Pd formed the intermetallic PdZn beta phase (atomic ratio of Zn to Pd is 1) with increased H-2 yield (similar to 1.9 mol H-2/mol ethanol reacted) and CH4/CO2 ratio of <1. The higher H-2 yield and low CH4 formation was related to the improved dehydrogenation activity of the L1(0) PdZn beta phase. The TOF increased with particle size and the CNTs provided the most active and selective catalysts, which may be ascribed to pore-confinement effects. Furthermore, no significant changes in either the supports or the PdZn beta particles was found after aqueous-phase reforming (APR) indicating that the metal nanoparticles and the carbon support are hydrothermally stable in the aqueous phase at elevated temperatures and pressures (>200 degrees C, 65 bar). No CO was detected for all the catalysts performed in aqueous-phase reaction, indicating that both monometallic Pd and bimetallic PdZn catalysts have high water-gas shift activity during APR. However, the yield of H-2 is considerably lower than the theoretical value of 6 H-2 per mole ethanol which is due to the presence of oxygenated products and methane on the PdZn catalysts.

  14. Quantum effects and anharmonicity in the H{sub 2}-Li{sup +}-benzene complex: A model for hydrogen storage materials

    SciTech Connect (OSTI)

    Kolmann, Stephen J.; D'Arcy, Jordan H.; Jordan, Meredith J. T.

    2013-12-21

    Quantum and anharmonic effects are investigated in H{sub 2}-Li{sup +}-benzene, a model for hydrogen adsorption in metal-organic frameworks and carbon-based materials. Three- and 8-dimensional quantum diffusion Monte Carlo (QDMC) and rigid-body diffusion Monte Carlo (RBDMC) simulations are performed on potential energy surfaces interpolated from electronic structure calculations at the M05-2X/6-31+G(d,p) and M05-2X/6-311+G(2df,p) levels of theory using a three-dimensional spline or a modified Shepard interpolation. These calculations investigate the intermolecular interactions in this system, with three- and 8-dimensional 0 K H{sub 2} binding enthalpy estimates, ?H{sub bind} (0 K), being 16.5 kJmol{sup ?1} and 12.4 kJmol{sup ?1}, respectively: 0.1 and 0.6 kJmol{sup ?1} higher than harmonic values. Zero-point energy effects are 35%of the value of ?H{sub bind} (0 K) at M05-2X/6-311+G(2df,p) and cannot be neglected; uncorrected electronic binding energies overestimate ?H{sub bind} (0 K) by at least 6 kJmol{sup ?1}. Harmonic intermolecular binding enthalpies can be corrected by treating the H{sub 2} helicopter and ferris wheel rotations as free and hindered rotations, respectively. These simple corrections yield results within 2% of the 8-dimensional anharmonic calculations. Nuclear ground state probability density histograms obtained from the QDMC and RBDMC simulations indicate the H{sub 2} molecule is delocalized above the Li{sup +}-benzene system at 0 K.

  15. Evaluation of crystallinity and film stress in yttria-stabilized zirconia

    Office of Scientific and Technical Information (OSTI)

    thin films (Journal Article) | SciTech Connect Journal Article: Evaluation of crystallinity and film stress in yttria-stabilized zirconia thin films Citation Details In-Document Search Title: Evaluation of crystallinity and film stress in yttria-stabilized zirconia thin films Yttria (3 mol %)-stabilized zirconia (YSZ) thin films were deposited using radio frequency (rf) magnetron sputtering. The YSZ thin films were deposited over a range of temperatures (22-300 deg. C), pressures (5-25

  16. Structure and Activation Mechanism of the CHK2 DNA Damage Checkpoint Kinase

    Office of Scientific and Technical Information (OSTI)

    (Journal Article) | SciTech Connect Structure and Activation Mechanism of the CHK2 DNA Damage Checkpoint Kinase Citation Details In-Document Search Title: Structure and Activation Mechanism of the CHK2 DNA Damage Checkpoint Kinase Authors: Cai, Zhenjian ; Chehab, Nabil H. ; Pavletich, Nikola P. ; MSKCC) [1] + Show Author Affiliations ( Publication Date: 2010-01-28 OSTI Identifier: 1006023 Resource Type: Journal Article Resource Relation: Journal Name: Mol. Cell; Journal Volume: 35; Journal

  17. Engineering Database of Liquid Salt Thermophysical and Thermochemical Properties

    SciTech Connect (OSTI)

    Manohar S. Sohal; Matthias A. Ebner; Piyush Sabharwall; Phil Sharpe

    2010-03-01

    The purpose of this report is to provide a review of thermodynamic and thermophysical properties of candidate molten salt coolants, which may be used as a primary coolant within a nuclear reactor or heat transport medium from the Next Generation Nuclear Plant (NGNP) to a processing plant, for example, a hydrogen-production plant. Thermodynamic properties of four types of molten salts, including LiF-BeF2 (67 and 33 mol%, respectively; also known as FLiBe), LiF-NaF-KF (46.5, 11.5, and 52 mol%, also known as FLiNaK), and KCl-MgCl2 (67 and 33 mol%), and sodium nitrate-sodium nitrite-potassium nitrate (NaNO3NaNO2KNO3, (7-49-44 or 7-40-53 mol%) have been investigated. Limitations of existing correlations to predict density, viscosity, specific heat capacity, surface tension, and thermal conductivity, were identified. The impact of thermodynamic properties on the heat transfer, especially Nusselt number was also discussed. Stability of the molten salts with structural alloys and their compatibility with the structural alloys was studied. Nickel and alloys with dense Ni coatings are effectively inert to corrosion in fluorides but not so in chlorides. Of the chromium containing alloys, Hastelloy N appears to have the best corrosion resistance in fluorides, while Haynes 230 was most resistant in chloride. In general, alloys with increasing carbon and chromium content are increasingly subject to corrosion by the fluoride salts FLiBe and FLiNaK, due to attack and dissolution of the intergranular chromium carbide. Future research to obtain needed information was identified.

  18. Biographical sketch - Kevin Redding | Center for Bio-Inspired Solar Fuel

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

    Production Kevin Redding a. Professional Preparation Rice University Biochemistry B. S., 1987 Stanford University Biochemistry Ph. D., 1993 University of Geneva Mol. Biology Postdoctoral studies, 1994 - 1998 b. Area of Specialization: Structure/function analysis of biological electron transfer c. Appointments Arizona State University, Associate Professor of Chemistry (1/1/08 - present) Chercheur associé (CNRS), Institut de Biologie Physico-Chimique, Paris (8/15/07-7/20/08) and Fulbright

  19. Crack growth rates and metallographic examinations of Alloy 600 and Alloy 82/182 from field components and laboratory materials tested in PWR environments.

    SciTech Connect (OSTI)

    Alexandreanu, B.; Chopra, O. K.; Shack, W. J.

    2008-05-05

    In light water reactors, components made of nickel-base alloys are susceptible to environmentally assisted cracking. This report summarizes the crack growth rate results and related metallography for field and laboratory-procured Alloy 600 and its weld alloys tested in pressurized water reactor (PWR) environments. The report also presents crack growth rate (CGR) results for a shielded-metal-arc weld of Alloy 182 in a simulated PWR environment as a function of temperature between 290 C and 350 C. These data were used to determine the activation energy for crack growth in Alloy 182 welds. The tests were performed by measuring the changes in the stress corrosion CGR as the temperatures were varied during the test. The difference in electrochemical potential between the specimen and the Ni/NiO line was maintained constant at each temperature by adjusting the hydrogen overpressure on the water supply tank. The CGR data as a function of temperature yielded activation energies of 252 kJ/mol for a double-J weld and 189 kJ/mol for a deep-groove weld. These values are in good agreement with the data reported in the literature. The data reported here and those in the literature suggest that the average activation energy for Alloy 182 welds is on the order of 220-230 kJ/mol, higher than the 130 kJ/mol commonly used for Alloy 600. The consequences of using a larger value of activation energy for SCC CGR data analysis are discussed.

  20. Thermodynamic study of orthorhombic T{sup x} and tetragonal T? lanthanum cuprate, La{sub 2}CuO{sub 4}

    SciTech Connect (OSTI)

    Lilova, K.I.; Hord, R.; Alff, L.; Albert, B.; Navrotsky, A.

    2013-08-15

    The enthalpies of transition among the T{sup x}, T?, and TLa{sub 2}CuO{sub 4} phases are obtained from a combination of differential scanning calorimetry, high temperature oxide melt solution calorimetry, and transposed temperature drop calorimetry. The enthalpy of transformation of T{sup x} to T is 2.320.07 kJ/mol and the corresponding entropy of transition is 4.380.13 J/(mol K). The T? modification, with an average of 1.40 kJ/mol, is less stable in enthalpy than T{sup x} but at 0.96 kJ/mol, more stable in enthalpy than T. Although we cannot rule out a small stability field at temperatures near the T{sup x}T transition at 530 K, T? is most likely metastable at all temperatures. - Graphical abstract: Crystal structure of T{sup x} (orthorhombic), T? and T (tetragonal) modifications of La{sub 2}CuO{sub 4} (left to right). The space group for orthorhombic T{sup x} is Cmce and I4/mmm for both T? and T structures; copper cations are presented as small purple, lanthanum as large blue and oxygen as large green circles. Highlights: The enthalpies of transition among the T{sup x} , T?, and T-La{sub 2}CuO{sub 4} phases are obtained. The T{sup x} phase is the lowest in energy, the T? higher and the T highest. T? phase is metastable at all temperatures.

  1. Characterization and comparison of pore landscapes in crystalline porous

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

    materials | Center for Gas SeparationsRelevant to Clean Energy Technologies | Blandine Jerome Characterization and comparison of pore landscapes in crystalline porous materials Previous Next List Marielle Pinheiro, Richard L. Martin, Chris H. Rycroft, Andrew Jones, Enrique Iglesia, Maciej Haranczyk, J. Mol. Graphics Modell., 44, 208-219 (2013) DOI: 10.1016/j.jmgm.2013.05.007 Abstract: Crystalline porous materials have many applications, including catalysis and separations. Identifying

  2. Dielectric behavior of samarium-doped BaZr{sub 0.2}Ti{sub 0.8}O{sub 3} ceramics

    SciTech Connect (OSTI)

    Li, Yuanliang; Wang, Ranran; Ma, Xuegang; Li, Zhongqiu; Sang, Rongli; Qu, Yuanfang

    2014-01-01

    Graphical abstract: - Highlights: We investigate dielectric properties and phase transition of Sm{sup 3+}-doped BaZr{sub 0.2}Ti{sub 0.8}O{sub 3} ceramics. The additive amount of Sm{sub 2}O{sub 3} can greatly affect the dielectric properties. The materials undergo a diffuse type ferroelectric phase transition. There is an alternation of substitution preference of Sm{sup 3+} ion for the host cations in perovskite lattice. - Abstract: The dielectric properties and phase transition of Sm{sup 3+}-doped BaZr{sub 0.2}Ti{sub 0.8}O{sub 3} (BZT20) ceramics were investigated. Room temperature X-ray diffraction study suggested that the compositions had single-phase cubic symmetry. Microstructure studies showed that the grain size decreased and that the Sm{sub 2}O{sub 3} amount markedly affected the dielectric properties of BZT20. A dielectric constant of 5700 at 0.2 mol% Sm{sub 2}O{sub 3} and a dissipation factor of only 0.0011 at 2 mol% Sm{sub 2}O{sub 3} were observed, indicating that BZT20 had significant potential applications. Moreover, the dielectric constant, dissipation factor, phase-transition temperature, and maximum dielectric constant increased with increased Sm{sub 2}O{sub 3} amount at ?0.2 mol% Sm{sub 2}O{sub 3} but decreased with increased Sm{sub 2}O{sub 3} amount at >0.2 mol% Sm{sub 2}O{sub 3}.

  3. Blocking effect of crystalglass interface in lanthanum doped barium strontium titanate glassceramics

    SciTech Connect (OSTI)

    Wang, Xiangrong; Zhang, Yong; Baturin, Ivan; Liang, Tongxiang

    2013-10-15

    Graphical abstract: The blocking effect of the crystalglass interface on the carrier transport behavior in the lanthanum doped barium strontium titanate glassceramics: preparation and characterization. - Highlights: La{sub 2}O{sub 3} addition promotes the crystallization of the major crystalline phase. The Z? and M? peaks exist a significant mismatch for 0.5 mol% La{sub 2}O{sub 3} addition. The Z? and M? peaks separate obviously for 1.0 mol% La{sub 2}O{sub 3} addition. Crystallite impedance decreases while crystalglass interface impedance increases. La{sub 2}O{sub 3} addition increases blocking factor of the crystalglass interface. - Abstract: The microstructures and dielectric properties in La{sub 2}O{sub 3}-doped barium strontium titanate glassceramics have been investigated by scanning electron microscopy (SEM) and impedance spectroscopy. SEM analysis indicated that La{sub 2}O{sub 3} additive decreases the average crystallite size. Impedance spectroscopy revealed that the positions of Z? and M? peaks are close for undoped samples. When La{sub 2}O{sub 3} concentration is 0.5 mol%, the Z? and M? peaks show a significant mismatch. Furthermore, these peaks separate obviously for 1.0 mol% La{sub 2}O{sub 3} addition. With increasing La{sub 2}O{sub 3} concentration, the contribution of the crystallite impedance becomes smaller, while the contribution of the crystalglass interface impedance becomes larger. More interestingly, it was found that La{sub 2}O{sub 3} additive increases blocking factor of the crystalglass interface in the temperature range of 250450 C. This may be attributed to a decrease of activation energy of the crystallite and an increase of the crystalglass interface area.

  4. Reversible Electrocatalytic Production and Oxidation of Hydrogen at Low Overpotentials by a Functional Hydrogenase Mimic

    SciTech Connect (OSTI)

    Smith, Stuart E.; Yang, Jenny Y.; DuBois, Daniel L.; Bullock, Morris

    2012-03-26

    A new bis(diphosphine) nickel(II) complex, [Ni(PPh2NR2)2](BF4)2, 1, (R = CH2CH2OCH3) is described. A {Delta}G{sup o} of 0.84 kcal/mol{sup -1} for hydrogen addition for this complex was calculated from the experimentally determined equilibrium constant. This complex displays reversible electrocatalytic activity for hydrogen production and oxidation at low overpotentials, a characteristic most commonly associated with hydrogenase enzymes.

  5. Fundamental aspects of recoupled pair bonds. II. Recoupled pair bond dyads in carbon and sulfur difluoride

    SciTech Connect (OSTI)

    Dunning, Thom H. Takeshita, Tyler Y.; Xu, Lu T.

    2015-01-21

    Formation of a bond between a second ligand and a molecule with a recoupled pair bond results in a recoupled pair bond dyad. We examine the recoupled pair bond dyads in the a{sup 3}B{sub 1} states of CF{sub 2} and SF{sub 2}, which are formed by the addition of a fluorine atom to the a{sup 4}?{sup ?} states of CF and SF, both of which possess recoupled pair bonds. The two dyads are very different. In SF{sub 2}, the second FSF bond is very strong (D{sub e} = 106.3 kcal/mol), the bond length is much shorter than that in the SF(a{sup 4}?{sup ?}) state (1.666 versus 1.882 ), and the three atoms are nearly collinear (?{sub e} = 162.7) with only a small barrier to linearity (0.4 kcal/mol). In CF{sub 2}, the second FCF bond is also very strong (D{sub e} = 149.5 kcal/mol), but the bond is only slightly shorter than that in the CF(a{sup 4}?{sup ?}) state (1.314 versus 1.327 ), and the molecule is strongly bent (?{sub e} = 119.0) with an 80.5 kcal/mol barrier to linearity. The a{sup 3}B{sub 1} states of CF{sub 2} and SF{sub 2} illustrate the fundamental differences between recoupled pair bond dyads formed from 2s and 3p lone pairs.

  6. TRANSITION STATE FOR THE GAS-PHASE REACTION OF URANIUM HEXAFLUORIDE WITH WATER

    SciTech Connect (OSTI)

    Garrison, S; James Becnel, J

    2008-03-18

    Density Functional Theory and small-core, relativistic pseudopotentials were used to look for symmetric and asymmetric transitions states of the gas-phase hydrolysis reaction of uranium hexafluoride, UF{sub 6}, with water. At the B3LYP/6-31G(d,p)/SDD level, an asymmetric transition state leading to the formation of a uranium hydroxyl fluoride, U(OH)F{sub 5}, and hydrogen fluoride was found with an energy barrier of +77.3 kJ/mol and an enthalpy of reaction of +63.0 kJ/mol (both including zero-point energy corrections). Addition of diffuse functions to all atoms except uranium led to only minor changes in the structure and relative energies of the reacting complex and transition state. However, a significant change in the product complex structure was found, significantly reducing the enthalpy of reaction to +31.9 kJ/mol. Similar structures and values were found for PBE0 and MP2 calculations with this larger basis set, supporting the B3LYP results. No symmetric transition state leading to the direct formation of uranium oxide tetrafluoride, UOF{sub 4}, was found, indicating that the reaction under ambient conditions likely includes several more steps than the mechanisms commonly mentioned. The transition state presented here appears to be the first published transition state for the important gas-phase reaction of UF{sub 6} with water.

  7. The effect of Au and Ni doping on the heavy fermion state of the Kondo lattice antiferromagnet CePtZn

    SciTech Connect (OSTI)

    Dhar, S. K.; Aoki, Y.; Suemitsu, B.; Miyazaki, R.; Provino, A.; Manfrinetti, P.

    2014-05-07

    We have probed the effect of doping CePtZn with Au and Ni and also investigated in detail the magnetic behavior of the iso-structural CeAuZn. A magnetic ground state is observed in both CePt{sub 0.9}Au{sub 0.1}Zn and CePt{sub 0.9}Ni{sub 0.1}Zn with T{sub N}?=?2.1 and 1.1?K and the coefficient of the linear term of electronic heat capacity ??=?0.34 and 0.9?J/mol K{sup 2}, respectively. The corresponding values for CePtZn are 1.7?K and 0.6?J/mol K{sup 2}. The altered values of T{sub N} and ? show that the electronic correlations in CePtZn are affected by doping with Au and Ni. CeAuZn orders magnetically near 1.7?K and its electrical resistivity shows a normal metallic behavior. Together with a ? of 0.022?J/mol K{sup 2} the data indicate a weak 4f-conduction electron hybridization in CeAuZn characteristic of normal trivalent cerium based systems.

  8. Thermodynamic analysis of hydration in human serum heme-albumin

    SciTech Connect (OSTI)

    Baroni, Simona; Pariani, Giorgio; Fanali, Gabriella; Longo, Dario; Ascenzi, Paolo; Aime, Silvio; Fasano, Mauro

    2009-07-31

    Ferric human serum heme-albumin (heme-HSA) shows a peculiar nuclear magnetic relaxation dispersion (NMRD) behavior that allows to investigate structural and functional properties. Here, we report a thermodynamic analysis of NMRD profiles of heme-HSA between 20 and 60 {sup o}C to characterize its hydration. NMRD profiles, all showing two Lorentzian dispersions at 0.3 and 60 MHz, were analyzed in terms of modulation of the zero field splitting tensor for the S = {sup 5}/{sub 2} manifold. Values of correlation times for tensor fluctuation ({tau}{sub v}) and chemical exchange of water molecules ({tau}{sub M}) show the expected temperature dependence, with activation enthalpies of -1.94 and -2.46 {+-} 0.2 kJ mol{sup -1}, respectively. The cluster of water molecules located in the close proximity of the heme is progressively reduced in size by increasing the temperature, with {Delta}H = 68 {+-} 28 kJ mol{sup -1} and {Delta}S = 200 {+-} 80 J mol{sup -1} K{sup -1}. These results highlight the role of the water solvent in heme-HSA structure-function relationships.

  9. New sulfur adsorbents derived from layered double hydroxides: II. DRIFTS study of COS and H2S adsorption

    SciTech Connect (OSTI)

    Toops, Todd J [ORNL; Crocker, Mark [University of Kentucky

    2008-01-01

    H2S and COS adsorption were studied on two calcined layered double hydroxides (LDHs), Mg0.75Al0.25(OH)2(CO3)0.125 and Mg0.65Al0.35(OH)2(CO3)0.175, using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) and a chemisorption apparatus. Both demonstrated the ability to irreversibly adsorb H2S, corresponding to uptakes of 1.54 and 1.76 mol/m2 respectively, but Mg0.75Al0.25 had a significantly larger capacity for COS, 1.62 mol/m2 compared to 0.80 mol/m2 for Mg0.65Al0.35. Analysis of the DRIFT spectra suggests the adsorption of H2S proceeds via the substitution of lattice oxygen with sulfur, resulting in the formation of H2O on the surface. COS adsorption is more complicated, although it appears that a similar substitution of lattice oxygen with sulfur occurs. This results in the formation of CO2 and subsequently bicarbonates and carbonates. The formation of hydrogen thiocarbonate is also involved, although this form is generally only observed in the later stages of adsorption and appears to form at the expense of bicarbonate. The Mg0.75Al0.25 LDH retained its ability to adsorb COS in the presence of propene.

  10. A thiocyanate hydrolase of Thiobacillus thioparus. A novel enzyme catalyzing the formation of carbonyl sulfide from thiocyanate

    SciTech Connect (OSTI)

    Katayama, Y.; Narahara, Y.; Inoue, Y.; Amano, F.; Kanagawa, T.; Kuraishi, H. (Faculty of Agriculture, Tokyo University of Agriculture and Technology, (Japan))

    1992-05-05

    A thiocyanate hydrolase that catalyzes the first step in thiocyanate degradation was purified to homogeneity from Thiobacillus thioparus, an obligate chemolithotrophic eubacterium metabolizing thiocyanate to sulfate as an energy source. The thiocyanate hydrolase was purified 52-fold by steps involving ammonium sulfate precipitation, DEAE-Sephacel column chromatography, and hydroxylapatite column chromatography. The enzyme hydrolyzed 1 mol of thiocyanate to form 1 mol of carbonyl sulfide and 1 mol of ammonia as follows: SCN- + 2H2O----COS + NH3 + OH-. This is the first report describing the hydrolysis of thiocyanate to carbonyl sulfide by an enzyme. The enzyme had a molecular mass of 126 kDa and was composed of three different subunits: alpha (19 kDa), beta (23 kDa), and gamma (32 kDa). The enzyme exhibited optimal activities at pH 7.5-8.0 and at temperatures ranging from 30 to 40 degrees C. The Km value for thiocyanate was approximately 11 mM. Immunoblot analysis with polyclonal antibodies against the purified enzyme suggested that it was induced in T. thioparus cells when the cells were grown with thiocyanate.

  11. Development of high strength hydroxyapatite for bone tissue regeneration using nanobioactive glass composites

    SciTech Connect (OSTI)

    Shrivastava, Pragya; Dalai, Sridhar; Vijayalakshmi, S.; Sudera, Prerna; Sivam, Santosh Param; Sharma, Pratibha

    2013-02-05

    With an increasing demand of biocompatible bone substitutes for the treatment of bone diseases and bone tissue regeneration, bioactive glass composites are being tested to improvise the osteoconductive as well as osteoinductive properties. Nanobioactive glass (nBG) composites, having composition of SiO{sub 2} 70 mol%, CaO 26 mol % and P{sub 2}O{sub 5} 4 mol% were prepared by Freeze drying method using PEG-PPG-PEG co-polymer. Polymer addition improves the mechanical strength and porosity of the scaffold of nBG. Nano Bioactive glass composites upon implantation undergo specific reactions leading to the formation of crystalline hydroxyapatite (HA). This is tested in vitro using Simulated Body Fluid (SBF). This high strength hydroxyapatite (HA) layer acts as osteoconductive in cellular environment, by acting as mineral base of bones, onto which new bone cells proliferate leading to new bone formation. Strength of the nBG composites as well as HA is in the range of cortical and cancellous bone, thus proving significant for bone tissue regeneration substitutes.

  12. Nanoscale Strontium Titanate Photocatalysts for Overall Water Splitting

    SciTech Connect (OSTI)

    Townsend, Troy K.; Browning, Nigel D.; Osterloh, Frank

    2012-08-28

    SrTiO3 (STO) is a large band gap (3.2 eV) semiconductor that catalyzes the overall water splitting reaction under UV light irradiation in the presence of a NiO cocatalyst. As we show here, the reactivity persists in nanoscale particles of the material, although the process is less effective at the nanoscale. To reach these conclusions, Bulk STO, 30 5 nm STO, and 6.5 1 nm STO were synthesized by three different methods, their crystal structures verified with XRD and their morphology observed with HRTEM before and after NiO deposition. In connection with NiO, all samples split water into stoichiometric mixtures of H2 and O2, but the activity is decreasing from 28 ?mol H2 g1 h1 (bulk STO), to 19.4 ?mol H2 g1 h1 (30 nm STO), and 3.0 ?mol H2 g1 h1 (6.5 nm STO). The reasons for this decrease are an increase of the water oxidation overpotential for the smaller particles and reduced light absorption due to a quantum size effect. Overall, these findings establish the first nanoscale titanate photocatalyst for overall water splitting.

  13. TRIMOLECULAR REACTIONS OF URANIUM HEXAFLUORIDE WITH WATER

    SciTech Connect (OSTI)

    Westbrook, M.; Becnel, J.; Garrison, S.

    2010-02-25

    The hydrolysis reaction of uranium hexafluoride (UF{sub 6}) is a key step in the synthesis of uranium dioxide (UO{sub 2}) powder for nuclear fuels. Mechanisms for the hydrolysis reactions are studied here with density functional theory and the Stuttgart small-core scalar relativistic pseudopotential and associated basis set for uranium. The reaction of a single UF{sub 6} molecule with a water molecule in the gas phase has been previously predicted to proceed over a relatively sizeable barrier of 78.2 kJ {center_dot} mol{sup -1}, indicating this reaction is only feasible at elevated temperatures. Given the observed formation of a second morphology for the UO{sub 2} product coupled with the observations of rapid, spontaneous hydrolysis at ambient conditions, an alternate reaction pathway must exist. In the present work, two trimolecular hydrolysis mechanisms are studied with density functional theory: (1) the reaction between two UF{sub 6} molecules and one water molecule, and (2) the reaction of two water molecules with a single UF{sub 6} molecule. The predicted reaction of two UF{sub 6} molecules with one water molecule displays an interesting 'fluorine-shuttle' mechanism, a significant energy barrier of 69.0 kJ {center_dot} mol{sup -1} to the formation of UF{sub 5}OH, and an enthalpy of reaction ({Delta}H{sub 298}) of +17.9 kJ {center_dot} mol{sup -1}. The reaction of a single UF{sub 6} molecule with two water molecules displays a 'proton-shuttle' mechanism, and is more favorable, having a slightly lower computed energy barrier of 58.9 kJ {center_dot} mol{sup -1} and an exothermic enthalpy of reaction ({Delta}H{sub 298}) of -13.9 kJ {center_dot} mol{sup -1}. The exothermic nature of the overall UF{sub 6} + 2 {center_dot} H{sub 2}O trimolecular reaction and the lowering of the barrier height with respect to the bimolecular reaction are encouraging; however, the sizable energy barrier indicates further study of the UF{sub 6} hydrolysis reaction mechanism is warranted to resolve the remaining discrepancies between the predicted mechanisms and experimental observations.

  14. Effect of Antimicrobial Peptide on Dynamics of Phosphocholine Membrane. Role of Cholesterol and Physical State of Bilayer

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

    Sharma, Veerendra K; Mamontov, Eugene; Anunciado, Divina B; O'Neill, Hugh Michael; Urban, Volker S

    2015-06-24

    Antimicrobial peptides are universal in all forms of life and are well known for their strong interaction with the cell membrane. This makes them a popular target for investigation of peptide-lipid interactions. Here we report the effect of melittin, an important antimicrobial peptide, on the dynamics of membranes based on 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid in both the solid gel and fluid phases. To probe the phase transition, elastic neutron intensity temperature scans have been carried out on DMPC-based unilamellar vesicles (ULV) with and without melittin. We have found that addition of a small amount (0.2 mol%) melittin eliminates the steep fallmore » in the elastic intensity at 296 K associated with the solid gel to fluid phase transition, which is observed for pure DMPC vesicles. Quasielastic neutron scattering (QENS) experiments have been carried out on DMPC ULV in the solid gel and fluid phases with and without 0.2 mol % melittin. The data analysis invariably shows the presence of lateral and internal motions of the DMPC molecule. We found that melittin does have a profound effect on the dynamics of lipid molecules, especially on the lateral motion, and affects it in a different way, depending on the phase of the bilayers. In the solid gel phase, it acts as a plasticizer, enhancing the lateral motion of DMPC. However, in the fluid phase it acts as a stiffening agent, restricting the lateral motion of the lipid molecules. These observations are consistent with the mean squared displacements extracted from the elastic intensity temperature scans. Cholesterol is a vital component of eukaryotic membrane, which is a natural target for melittin. To investigate the effect of melittin on vesicles supplemented with cholesterol, QENS experiments have also been carried out on DMPC ULV with 20 mol% cholesterol in the presence and absence of 0.2 mol% melittin. Remarkably, the effects of melittin on the membrane dynamics disappear in the presence of 20 mol % cholesterol. Thus, our measurements indicate that the destabilizing effect of the peptide melittin on membranes can be mitigated by the presence of cholesterol.« less

  15. Effect of Antimicrobial Peptide on Dynamics of Phosphocholine Membrane: Role of Cholesterol and Physical State of Bilayer

    SciTech Connect (OSTI)

    Sharma, Veerendra K [ORNL; Mamontov, Eugene [ORNL; Anunciado, Divina B [ORNL; O'Neill, Hugh Michael [ORNL; Urban, Volker S [ORNL

    2015-01-01

    Antimicrobial peptides are universal in all forms of life and are well known for their strong interaction with the cell membrane. This makes them a popular target for investigation of peptide-lipid interactions. Here we report the effect of melittin, an important antimicrobial peptide, on the dynamics of membranes based on 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid in both the solid gel and fluid phases. To probe the phase transition, elastic neutron intensity temperature scans have been carried out on DMPC-based unilamellar vesicles (ULV) with and without melittin. We have found that addition of a small amount (0.2 mol%) melittin eliminates the steep fall in the elastic intensity at 296 K associated with the solid gel to fluid phase transition, which is observed for pure DMPC vesicles. Quasielastic neutron scattering (QENS) experiments have been carried out on DMPC ULV in the solid gel and fluid phases with and without 0.2 mol % melittin. The data analysis invariably shows the presence of lateral and internal motions of the DMPC molecule. We found that melittin does have a profound effect on the dynamics of lipid molecules, especially on the lateral motion, and affects it in a different way, depending on the phase of the bilayers. In the solid gel phase, it acts as a plasticizer, enhancing the lateral motion of DMPC. However, in the fluid phase it acts as a stiffening agent, restricting the lateral motion of the lipid molecules. These observations are consistent with the mean squared displacements extracted from the elastic intensity temperature scans. Cholesterol is a vital component of eukaryotic membrane, which is a natural target for melittin. To investigate the effect of melittin on vesicles supplemented with cholesterol, QENS experiments have also been carried out on DMPC ULV with 20 mol% cholesterol in the presence and absence of 0.2 mol% melittin. Remarkably, the effects of melittin on the membrane dynamics disappear in the presence of 20 mol % cholesterol. Thus, our measurements indicate that the destabilizing effect of the peptide melittin on membranes can be mitigated by the presence of cholesterol.

  16. Efficient photocatalytic hydrogen generation by silica supported and platinum promoted titanium dioxide

    SciTech Connect (OSTI)

    Joshi, Meenal M.; Labhsetwar, Nitin K.; Parwate, D.V.; Rayalu, Sadhana S.

    2013-09-01

    Graphical abstract: Titanium dioxide was supported on mesoporous silica and promoted with Pt and Ru. The supported photocatalysts show high surface area and better photocatalytic activity in visible light as compared to the benchmark Degussa P25. These photocatalysts were characterized using XRD, BET-SA, and UV-DRS techniques. The surface area of supported photocatalyst was 140.6 m{sup 2}/g which is higher than Degussa P-25. Supported photocatalyst was evaluated for hydrogen evolution via water splitting reaction using ethanol as a sacrificial donor. Hydrogen yield observed is 4791.43 ?mol/h/g of TiO{sub 2} and that for P-25 is 161 ?mol/h/g of TiO{sub 2} under visible light irradiation. The value is 30 times higher than benchmark material Degussa P-25. This photocatalyst is also found stable up to 24 h without replenishing with sacrificial donor ethanol. - Highlights: Semiconductor titanium dioxide has been supported on silica gel and promoted with Pt by simple wet impregnation route. This synthesized photocatalyst is showing high surface area of 140.6 m{sup 2}/g with crystallite size in the range of 15.44 ?. This photocatalyst is showing enhanced hydrogen yield of about 4791.43 ?mol/h/g of TiO{sub 2}. This photocatalyst is also found stable up to 24 h without replenishing with sacrificial donor ethanol. The effect of various operating parameters on supported photocatalyst also has been studied. - Abstract: Titanium dioxide was supported on mesoporous silica and promoted with Pt and Ru. The supported photocatalysts show high surface area and better photocatalytic activity in visible light as compared to the benchmark Degussa P25. These photocatalysts were characterized using XRD, BET-SA, and UV-DRS techniques. The surface area of supported photocatalyst was 140.6 m{sup 2}/g which is higher than Degussa P-25. Supported photocatalyst was evaluated for hydrogen evolution via water splitting reaction using ethanol as a sacrificial donor. Hydrogen yield observed is 4791.43 ?mol/h/g of TiO{sub 2} and that for P-25 is 161 ?mol/h/g of TiO{sub 2} under visible light irradiation. The value is 30 times higher than benchmark material Degussa P-25. This photocatalyst is also found stable up to 24 h without replenishing with sacrificial donor ethanol. However silica gel/TiO{sub 2}/Ru does not show any exciting result for hydrogen generation. The effect of various operating parameters like photocatalyst loading, Illumination time and intensity of light on supported photocatalyst also has been studied.

  17. Respiration-Correlated Image Guidance Is the Most Important Radiotherapy Motion Management Strategy for Most Lung Cancer Patients

    SciTech Connect (OSTI)

    Korreman, Stine, E-mail: korreman@ruc.dk [Department of Science, Systems and Models, Roskilde University, Roskilde (Denmark); Department of Radiation Oncology, The Finsen Centre, Rigshospitalet, Copenhagen (Denmark); Niels Bohr Institute, University of Copenhagen, Copenhagen (Denmark); Department of Human Oncology, University of Wisconsin School of Medicine and Public Health, Madison (United States); Persson, Gitte; Nygaard, Ditte [Department of Radiation Oncology, The Finsen Centre, Rigshospitalet, Copenhagen (Denmark); Brink, Carsten [Laboratory of Radiation Physics, Odense University Hospital, Odense (Denmark); Faculty of Health Sciences, University of Southern Denmark, Odense (Denmark); Juhler-Nottrup, Trine [Department of Oncology, Herlev Hospital, Copenhagen (Denmark)

    2012-07-15

    Purpose: The purpose of this study was to quantify the effects of four-dimensional computed tomography (4DCT), 4D image guidance (4D-IG), and beam gating on calculated treatment field margins in a lung cancer patient population. Materials and Methods: Images were acquired from 46 lung cancer patients participating in four separate protocols at three institutions in Europe and the United States. Seven patients were imaged using fluoroscopy, and 39 patients were imaged using 4DCT. The magnitude of respiratory tumor motion was measured. The required treatment field margins were calculated using a statistical recipe (van Herk M, et al. Int J Radiat Oncol Biol Phys 2000;474:1121-1135), with magnitudes of all uncertainties, except respiratory peak-to-peak displacement, the same for all patients, taken from literature. Required margins for respiratory motion management were calculated using the residual respiratory tumor motion for each patient for various motion management strategies. Margin reductions for respiration management were calculated using 4DCT, 4D-IG, and gated beam delivery. Results: The median tumor motion magnitude was 4.4 mm for the 46 patients (range 0-29.3 mm). This value corresponded to required treatment field margins of 13.7 to 36.3 mm (median 14.4 mm). The use of 4DCT, 4D-IG, and beam gating required margins that were reduced by 0 to 13.9 mm (median 0.5 mm), 3 to 5.2 mm (median 5.1 mm), and 0 to 7 mm (median 0.2 mm), respectively, to a total of 8.5 to 12.4 mm (median 8.6 mm). Conclusion: A respiratory management strategy for lung cancer radiotherapy including planning on 4DCT scans and daily image guidance provides a potential reduction of 37% to 47% in treatment field margins. The 4D image guidance strategy was the most effective strategy for >85% of the patients.

  18. Radioprotectors and Tumors: Molecular Studies in Mice

    SciTech Connect (OSTI)

    Gayle Woloschak, David Grdina

    2010-03-10

    This proposal investigated effects of radiation using a set of archival tissues. Main interests of this proposal were to investigate effects of irradiation alone or in the presence or radioprotectors; to investigate these effects on different tissues; and to use/develop molecular biology techniques that would be suitable for work with archived tissues. This work resulted in several manuscripts published or in preparation. Approach for evaluation of gene copy numbers by quantitative real time PCR has been developed and we are striving to establish methods to utilize Q-RT-PCR data to evaluate genomic instability caused by irradiation(s) and accompanying treatments. References: 1. Paunesku D, Paunesku T, Wahl A, Kataoka Y, Murley J, Grdina DJ, Woloschak GE. Incidence of tissue toxicities in gamma ray and fission neutron-exposed mice treated with Amifostine. Int J Radiat Biol. 2008, 84(8):623-34. PMID: 18661379, http://informahealthcare.com/doi/full/10.1080/09553000802241762?cookieSet=1 2. Wang Q, Paunesku T and Woloschak GE. Tissue and data archives from irradiation experiments conducted at Argonne National Laboratory over a period of four decades, in press in Radiation and Environmental Biophysics. 3. Alcantara M, Paunesku D, Rademaker A, Paunesku T and Woloschak GE. A RETROSPECTIVE ANALYSIS OF TISSUE TOXICITIES IN B6CF1 MICE IRRADIATED WITH FISSION NEUTRONS OR COBALT 60 GAMMA RAYS: Gender modulates accumulation of tissue toxicities caused by low dose rate fractionated irradiation; in preparation; this document has been uploaded as STI product 4. Wang Q, Paunesku T Wanzer B and Woloschak GE. Mitochondrial gene copy number differences in different tissues of irradiated and control mice with lymphoid cancers; in preparation 5. Wang Q, Raha, S, Paunesku T and Woloschak GE. Evaluation of gene copy number differences in different tissues of irradiated and control mice; in preparation

  19. Benchmark Theoretical Study of the ?? Binding Energy in the Benzene Dimer

    SciTech Connect (OSTI)

    Miliordos, Evangelos; Apra, Edoardo; Xantheas, Sotiris S.

    2014-09-04

    We establish a new estimate for the interaction energy between two benzene molecules in the parallel displaced (PD) conformation by systematically converging (i) the intra- and intermolecular geometry at the minimum geometry, (ii) the expansion of the orbital basis set and (iii) the level of electron correlation. The calculations were performed at the second order Mller - Plesset perturbation (MP2) and the Coupled Cluster including Singles, Doubles and a perturbative estimate of Triples replacements [CCSD(T)] levels of electronic structure theory. At both levels of theory, by including results corrected for Basis Set Superposition Error (BSSE), we have estimated the Complete Basis Set (CBS) limit by employing the family of Dunnings correlation consistent polarized valence basis sets. The largest MP2 calculation was performed with the cc-pV6Z basis set (2,772 basis functions), whereas the largest CCSD(T) calculation with the cc-pV5Z basis set (1,752 basis functions). The cluster geometries were optimized with basis sets up to quadruple-? quality, observing that both its intra- and inter-molecular parts have practically converged with the triple-? quality sets. The use of converged geometries was found to play an important role for obtaining accurate estimates for the CBS limits. Our results demonstrate that the binding energies with the families of the plain (cc-pVnZ) and augmented (aug-cc-pVnZ) sets converge [to within < 0.01 kcal/mol for MP2 and < 0.15 kcal/mol for CCSD(T)] to the same CBS limit. In addition, the average of the uncorrected and BSSEcorrected binding energies was found to converge to the same CBS limit must faster than either of the two constituents (uncorrected or BSSE-corrected binding energies). Due to the fact that the family of augmented basis sets (especially for the larger sets) causes serious linear dependency problems, the plain basis sets (for which no linear dependencies were found) are deemed as a more efficient and straightforward path for obtaining an accurate CBS limit. We considered extrapolations of the uncorrected (?𝐸) and BSSE-corrected (?𝐸!") binding energies, their average value (?𝐸!"#) as well as the average of the latter over the plain and augmented sets (?𝐸!"#) with the cardinal number of the basis set n. Our best estimate of the CCSD(T)/CBS limit for the ?-? interaction energy in the PD benzene dimer is De = 2.65 0.02 kcal/mol. The best CCSD(T)/cc-pV5Z calculated value is 2.62 kcal/mol, just 0.03 kcal/mol away from the CBS limit. For comparison, the MP2/CBS limit estimate is 5.00 0.01 kcal/mol, demonstrating a 90% overbinding with respect to CCSD(T). The Spin-Component-Scaled (SCS) MP2 variant was found to closely reproduce the CCSD(T) results for each basis set, while Scaled-Opposite-Spin (SOS) yielded results that are too low when compared to CCSD(T).

  20. Luminescent nanocrystals in the rare-earth niobatezirconia system formed via hydrothermal method

    SciTech Connect (OSTI)

    Hirano, Masanori Dozono, Hayato

    2013-08-15

    Luminescent nanocrystals based on the rare-earth niobates (Ln{sub 3}NbO{sub 7}, Ln=Y, Eu) and zirconia (ZrO{sub 2}) that were composed of 50 mol% Ln{sub 3}NbO{sub 7} and 50 mol% ZrO{sub 2}, were hydrothermally formed as cubic phase under weakly basic conditions at 240 C. The lattice parameter of the as-prepared nanoparticles corresponding to the composition of Y{sub 3?x}Eu{sub x}NbO{sub 7}4ZrO{sub 2} that was estimated as a single phase of cubic gradually increased as the content of europium x increased. The existence of small absorbance peaks at 395 and 466 nm corresponding to the Eu{sup 3+7}F{sub 0}?{sup 5}L{sub 6}, and {sup 7}F{sub 0}?{sup 5}D{sub 2} excitation transition, respectively, was clearly observed in the diffuse reflectance spectra of the as-prepared samples containing europium. The optical band gap of the as-prepared samples was in the range from 3.5 to 3.7 eV. The photoluminescence spectra of the as-prepared nanocrystals containing europium showed orange and red luminescences with main peaks at 590 and 610 nm, corresponding to {sup 5}D{sub 0}?{sup 7}F{sub 1} and {sup 5}D{sub 0}?{sup 7}F{sub 2} transitions of Eu{sup 3+}, respectively, under excitation at 395 nm Xe lamp. The emission intensity corresponding to {sup 5}D{sub 0}?{sup 7}F{sub 2} transition increased as heat-treatment temperature rose from 800 to 1200 C. - Graphical abstract: This graphical abstract shows the excitation and emission spectra and a transmission electron microscopy image of nanocrystals (with composition based on the rare-earth niobates (Ln{sub 3}NbO{sub 7}, Ln=Y, Eu) and zirconia (ZrO{sub 2}) that were composed of 50 mol% Ln{sub 3}NbO{sub 7} and 50 mol% ZrO{sub 2}) formed via hydrothermal route. Display Omitted - Highlights: Nanocrystals composed of 50 mol% Y{sub 3?x}Eu{sub x}NbO{sub 7} and 50 mol% ZrO{sub 2} was directly formed. The nanocrystals were hydrothermally formed under weakly basic conditions at 240 C. The Y{sub 3}NbO{sub 7} showed an UV-blue and broad-band emission under excitation at 240 nm. The emission is originated from the niobate octahedral group [NbO{sub 6}]{sup 7?}. The nanocrystals showed orange and red luminescences ({sup 5}D{sub 0}?{sup 7}F{sub 1} and {sup 5}D{sub 0}?{sup 7}F{sub 2} , Eu{sup 3+})

  1. Transjugular Insertion of Bare-Metal Biliary Stent for the Treatment of Distal Malignant Obstructive Jaundice Complicated by Coagulopathy

    SciTech Connect (OSTI)

    Tsauo Jiaywei Li Xiao Li Hongcui Wei Bo Luo Xuefeng Zhang Chunle Tang Chengwei; Wang Weiping

    2013-04-15

    This study was designed to investigate retrospectively the feasibility of transjugular insertion of biliary stent (TIBS) for the treatment of distal malignant obstructive jaundice complicated by coagulopathy. Between April 2005 and May 2010, six patients with distal malignant obstructive jaundice associated with coagulopathy that was unable to be corrected underwent TIBS at our institution for the palliation of jaundice. Patients' medical record and imaging results were reviewed to obtain information about demographics, procedure details, complications, and clinical outcomes. The intrahepatic biliary tract was successfully accessed in all six patients via transjugular approach. The procedure was technically successfully in five of six patients, with a bare-metal stent implanted after traversing the biliary strictures. One procedure failed, because the guidewire could not traverse the biliary occlusion. One week after TIBS, the mean serum bilirubin in the five successful cases had decreased from 313 {mu}mol/L (range 203.4-369.3) to 146.2 {mu}mol/L (range 95.8-223.3) and had further decreased to 103.6 {mu}mol/L (range 29.5-240.9) at 1 month after the procedure. No bleeding, sepsis, or other major complications were observed after the procedure. The mean survival of these five patients was 4.5 months (range 1.9-5.8). On imaging follow-up, there was no evidence of stent stenosis or migration, with 100 % primary patency. When the risks of hemorrhage from percutaneous transhepatic cholangiodrainage are high, TIBS may be an effective alternative for the treatment of distal malignant obstructive jaundice.

  2. Variation of the Side Chain Branch Position Leads to Vastly Improved Molecular Weight and OPV Performance in 4,8-dialkoxybenzo[1,2-b:4,5-b′]dithiophene/2,1,3-benzothiadiazole Copolymers

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

    Coffin, Robert C.; MacNeill, Christopher M.; Peterson, Eric D.; Ward, Jeremy W.; Owen, Jack W.; McLellan, Claire A.; Smith, Gregory M.; Noftle, Ronald E.; Jurchescu, Oana D.; Carroll, David L.

    2011-01-01

    Tmore » hrough manipulation of the solubilizing side chains, we were able to dramatically improve the molecular weight ( M w ) of 4,8-dialkoxybenzo[1,2- b :4,5- b ′ ]dithiophene (BDT)/2,1,3-benzothiadiazole (BT) copolymers. When dodecyl side chains ( P1 ) are employed at the 4- and 8-positions of the BDT unit, we obtain a chloroform-soluble copolymer fraction with M w of 6.3 kg/mol. Surprisingly, by moving to the commonly employed 2-ethylhexyl branch ( P2 ), M w decreases to 3.4 kg/mol. This is despite numerous reports that this side chain increases solubility and M w . By moving the ethyl branch in one position relative to the polymer backbone (1-ethylhexyl, P3 ), M w is dramatically increased to 68.8 kg/mol. As a result of this M w increase, the shape of the absorption profile is dramatically altered, with λ max = 637 nm compared with 598 nm for P1 and 579 nm for P2 . The hole mobility as determined by thin film transistor (TFT) measurements is improved from ~ 1 × 10 − 6  cm 2 /Vs for P1 and P2 to 7 × 10 − 4  cm 2 /Vs for P3 , while solar cell power conversion efficiency in increased to 2.91 % for P3 relative to 0.31 % and 0.19 % for P1 and P2 , respectively.« less

  3. Development of palladium composite membranes for hydrogen separation

    SciTech Connect (OSTI)

    Paglieri, S. N. (Stephen N.); Birdsell, S. A. (Stephen A.); Snow, R. C. (Ronny C.); Smith, F. M. (Frank M.); Tewell, C. R. (Craig R.)

    2004-01-01

    Two types of palladium composite membrane were investigated for hydrogen separation. A palladium alloy membrane was prepared by electroless plating a layer of palladium ({approx}20 {micro}m) and then copper onto a commercially available porous (nominal 0.2 {micro}m pores) {alpha}-alumina substrate. The resulting multilayer metal film was annealed at 355 C for several days to promote metallic interdiffusion and alloy formation. During the heat treatment, a maximum hydrogen flux of 0.15 mol (STP)/m{sup 2} {center_dot} s was observed at 355 C and a pressure drop ({Delta}P) across the membrane of 6.8 atm. The H{sub 2}/Ar ideal separation factor was 68 at these conditions, however, the separation factor decreased upon thermal cycling. The other type of membrane fabricated was a palladium coated vanadium-copper alloy foil where the main advantage is the reduction in palladium film coating thickness to 100 nm per side. New methods are being developed for welding the thin foil into modules for testing. The hydrogen flux through a pinhole-free, 75 {micro}m thick Pd/VCu{sub 1.1}/Pd (atomic %) composite membrane was 0.66 mol (STP)/m{sup 2} {center_dot} at 350 C and {Delta}P = 3.5 atm compared to 0.44 mol (STP)/m{sup 2} {center_dot} s for a 71 {micro}m thick Pd/VCu{sub 10}/Pd membrane. Vanadium alloy composition was checked using Auger electron spectroscopy (AES).

  4. Impact of solvent for individual steps of phenol hydrodeoxygenation with Pd/C and HZSM-5 as catalysts

    SciTech Connect (OSTI)

    He, Jiayue; Zhao, Chen; Lercher, Johannes A.

    2014-01-01

    Impacts of water, methanol, and hexadecane solvents on the individual steps of phenol hydrodeoxygenation are investigated over Pd/C and HZSM-5 catalyst components at 473 Kin presence of H-2. Hydrodeoxygenation of phenol to cyclohexane includes four individual steps of phenol hydrogenation to cyclohexanone on Pd/C, cyclohexanone hydrogenation to cyclohexanol on Pd/C, cyclohexanol dehydration to cyclohexene on HZSM-5, and cyclohexene hydrogenation to cyclohexane on Pd/C. Individual phenol and cyclohexanone hydrogenation rates are much lower in methanol and hexadecane than in water, while rates of cyclohexanol dehydration and cyclohexene hydrogenation are similar in three solvents. The slow rate in methanol is due to the strong solvation of reactants and the adsorption of methanol on Pd, as well as to the reaction between methanol and the cyclohexanone intermediate. The low solubility of phenol and strong interaction of hexadecane with Pd lead to the slow rate in hexadecane. The apparent activation energies for hydrogenation follow the order E-a phenol > E-a cyclonexanone > E-a cyclohexene, and the sequences of individual reaction rates are reverse in three solvents. The dehydration rates (1.1-1.8 x 10(3) mol mol(BAS)(-1) h(-1))and apparent activation energies (115-124 kJ mol(-1)) are comparable in three solvents. In situ liquid-phase IR spectroscopy shows the rates consistent with kinetics derived from chromatographic evidence in the aqueous phase and verifies that hydrogenation of phenol and cyclohexanone follows reaction orders of 1.0 and 0.55 over Pd/C, respectively. Conversion of cyclohexanol with HZSM-5 shows first-order dependence in approaching the dehydration-hydration equilibrium in the aqueous phase.

  5. Photocatalytic pure water splitting activities for ZnGa{sub 2}O{sub 4} synthesized by various methods

    SciTech Connect (OSTI)

    Zeng, Chunmei; Hu, Tao; Hou, Nianjun; Liu, Siyao; Gao, Wenliang; Cong, Rihong; Yang, Tao

    2015-01-15

    Highlights: High temperature solid state reaction, hydrothermal, sol-gel methods were applied. All ZnGa{sub 2}O{sub 4} samples show UV-light catalytic activities on pure water splitting. Bulk ZnGa{sub 2}O{sub 4} has a good photocatalytic activity per specific surface area. Sol-gel is a superior method to prepare nanosized ZnGa{sub 2}O{sub 4} with a high activity. The AQY for SG-ZnGa{sub 2}O{sub 4} is 2.6% for pure water splitting under 313 nm irradiation. - Abstract: We studied and compared the photocatalytic water splitting performances for ZnGa{sub 2}O{sub 4} prepared by high temperature solid state reaction (HTSSR), hydrothermal (HY) and sol-gel (SG) methods. HTSSR-ZnGa{sub 2}O{sub 4} has a relative large photocatalytic activity per surface area (1.6 ?mol/h/m{sup 2}) in pure water by UV irradiation due to its high crystallinity. The HY- and SG-samples both have small particle sizes (20?30 nm) and therefore high surface area (20 and 29 m{sup 2}/g, respectively), which leads to superior photocatalytic H{sub 2} evolution rates per unit mass (11.5 and 28.5 ?mol/h/g). The apparent quantum yield of SG-ZnGa{sub 2}O{sub 4} for pure water splitting under 313 nm irradiation is 2.6%. The existence of substantial surface defects is the major problem for HY- and SG-ZnGa{sub 2}O{sub 4}. Consequently, the usage of sacrificial agents could greatly enhance the activities and indeed the H{sub 2} evolution rates in 20 Vol. % methanol aqueous solution increase to 100 and 142 ?mol/h/g for HY- and SG-ZnGa{sub 2}O{sub 4}, respectively.

  6. Kinetic studies of the [NpO? (CO?)?]?? ion at alkaline conditions using C NMR

    SciTech Connect (OSTI)

    Panasci, Adele F.; Harley, Stephen J.; Zavarin, Mavrik; Casey, William H.

    2014-04-21

    Carbonate ligand-exchange rates on the [NpO? (CO?)?]?? ion were determined using a saturation-transfer C nuclear magnetic resonance (NMR) pulse sequence in the pH range of 8.1 ? pH ? 10.5. Over the pH range 9.3 ? pH ? 10.5, which compares most directly with previous work of Stout et al.,1 we find an average rate, activation energy, enthalpy, and entropy of k298ex = 40.6(4.3) s?, Ea =45.1(3.8) kJ mol?, ?H = 42.6(3.8) kJ mol?, and ?S = -72(13) J mol? K?, respectively. These activation parameters are similar to the Stout et al. results at pH 9.4. However, their room-temperature rate at pH 9.4, k298ex = 143(1.0) s?, is ~3 times faster than what we experimentally determined at pH 9.3: k298ex = 45.4(5.3) s?. Our rates for [NpO? (CO?)?]?? are also faster by a factor of ~3 relative to the isoelectronic [UO?(CO?)?]?? as reported by Brucher et al.2 of k298ex = 13(3) s?. Consistent with results for the [UO?(CO?)?]?? ion, we find evidence for a proton-enhanced pathway for carbonate exchange for the [NpO?(CO?)?]?? ion at pH < 9.0.

  7. Hydrolysis of COS and CS{sub 2} over alumina catalysts at lower temperature

    SciTech Connect (OSTI)

    Shangguan Ju; Li Chunhu; Guo Hanxian [Taiyuan Univ. of Technology, Shanxi (China). Research Inst. of Chemical Engineering for Coal

    1997-12-31

    Carbonyl sulfide (COS) and carbon disulfide (CS{sub 2}) widely exist in chemical processing gases from natural gas, coal, Claus tail gas, and petroleum. Those sulfur compound are a major factor of deactivation of synthesis catalysts. Since it is difficult to remove COS and CS{sub 2} completely by the conventional desulfurization, a hydrolysis process has been developed in recent years. The activity of COS and CS{sub 2} hydrolysis was measured in a fixed bed reactor and the surface basicity was studied by CO{sub 2}-TPD. The results showed that the apparent reaction activation energies of COS over three catalysts are 57.80, 52.50 and 44.71 kJ/mol at lower temperature, and those of CS{sub 2}, 55.53, 38.70 and 35.30 kJ/mol, respectively. The apparent activation energies of desorption for weak type basic center over three catalysts were 25.97, 27.92 and 29.77kJ/mol respectively. The surface basicity on catalysts played an important role in the hydrolysis of COS and CS{sub 2}.The weak basic center was the catalytic active center of COS hydrolysis, while the weak and the weaker basic centers took part in catalytic reaction of CS{sub 2} hydrolysis. The K{sub 2}O and Pt loaded on active {gamma}-Al{sub 2}O{sub 3} could greatly change the distribution of surface basicity over catalysts and increase organic sulfide catalytic hydrolysis.

  8. Thermodynamic studies of CaLaFe??O??(s)

    SciTech Connect (OSTI)

    Rakshit, S.K.; Parida, S.C.; Lilova, Kristina; Navrotsky, Alexandra

    2013-05-01

    Thermodynamic studies on CaLaFe??O??(s) were carried out using Knudsen effusion mass spectrometry and calorimetry, viz. differential scanning calorimetry and high temperature oxide melt solution calorimetry. Standard molar Gibbs free energy of formation (?{sub f}G?{sub m}), enthalpy of formation and heat capacity (C?{sub ?,m}) of the compound were calculated as a function of temperature for the first time. C?{sub ?,m}(CaLaFe??O??) was determined and used for second law analysis, from which enthalpy and entropy of formation of the compound were calculated and the respective values are: ?{sub f}H?{sub m}(298.15 K)/kJ mol?=-6057(8) and S?{sub m}(298.15 K)/J K? mol?=427(5). ?{sub f}H?{sub m}(298.15 K)/kJ mol?: -6055(6) was also calculated using oxide melt solution calorimetry, which is in close agreement with the second law value. A heat capacity anomaly was also observed at T=684 K. A table of thermodynamic data from 298.15 K to 1000 K for CaLaFe??O??(s) was also constructed to represent an optimized set of data. - graphical abstract: Variation of standard molar heat capacities of CaLaF??O??(s) and MFe??O??(s) (M=Sr, Ba and Pb) as a function of temperature. Highlights: Thermodynamic studies on CaLaFe??O??(s) were performed using KEQMS and solution calorimetry. It was synthesized using gel combustion route and characterized by XRD technique. The compound is magnetic in nature and shows a heat capacity anomaly at 684 K. Thermodynamic table was constructed from 298 K to 1000 K.

  9. Sub-5 nm Domains in Ordered Poly(cyclohexylethylene)-block-poly(methyl methacrylate) Block Polymers for Lithography.

    SciTech Connect (OSTI)

    Kennemur, Justin; Yao, Li; Bates, Frank Stephen; Hillmyer, Marc

    2014-01-01

    A series of poly(cyclohexylethylene)-block-poly- (methyl methacrylate) (PCHE PMMA) diblock copolymers with varying molar mass (4.9 kg/mol Mn 30.6 kg/mol) and narrow molar mass distribution were synthesized through a combination of anionic and atom transfer radical polymerization (ATRP) techniques. Heterogeneous catalytic hydrogenation of -(hydroxy)polystyrene (PS-OH) yielded -(hydroxy)poly(cyclohexylethylene) (PCHEOH) with little loss of hydroxyl functionality. PCHE-OH was reacted with -bromoisobutyryl bromide (BiBB) to produce an ATRP macroinitiator used for the polymerization of methyl methacrylate. PCHE PMMA is a glassy, thermally stable material with a large effective segment segment interaction parameter, eff = (144.4 6.2)/T (0.162 0.013), determined by meanfield analysis of order-to-disorder transition temperatures (TODT) measured by dynamic mechanical analysis and differential scanning calorimetry. Ordered lamellar domain pitches (9 D 33 nm) were identified by small-angle X-ray scattering from neat BCPs containing 43 52 vol % PCHE ( f PCHE). Atomic force microscopy was used to show 7.5 nm lamellar features (D = 14.8 nm) which are some of the smallest observed to date. The lowest molar mass sample (Mn = 4.9 kg/mol, f PCHE = 0.46) is characterized by TODT = 173 3 C and sub-5 nm nanodomains, which together with the sacrificial properties of PMMA and the high overall thermal stability place this material at the forefront of high- systems for advanced nanopatterning applications.

  10. Photo-oxidation of gaseous ethanol on photocatalyst prepared by acid leaching of titanium oxide/hydroxyapatite composite

    SciTech Connect (OSTI)

    Ono, Y.; Rachi, T.; Yokouchi, M.; Kamimoto, Y.; Nakajima, A.; Okada, K.

    2013-06-01

    Highlights: ? Photocatalyst powder was prepared by acid leaching of TiO{sub 2}/apatite composite. ? The photocatalytic activity was evaluated from in situ FT-IR study using ethanol. ? Apatite in the composite had positive effect for the photo-oxidation of ethanol. ? The enhanced oxidation rate was explained by the difference in deactivation rate. - Abstract: Highly active photocatalysts were synthesized by leaching of heat-treated titanium dioxide (TiO{sub 2})/hydroxyapatite (HAp) powder with hydrochloric acid at 0.25, 0.50, 0.75 mol/l, and their photocatalytic activities were evaluated from in situ Fourier transform infrared (FT-IR) study of photo-oxidation of gaseous ethanol. By changing the acid concentration, the TiO{sub 2}/HAp composite had different atomic ratios of Ca/Ti (0.02.8) and P/Ti (0.32.1). It was found that phosphate group remained on the surface of TiO{sub 2} particle even in the sample treated with concentrated acid (0.75 mol/l). These acid-treated samples showed higher rates for ethanol photo-oxidation than the commercial TiO{sub 2} powder, Degussa P25. The highest rate was obtained in the TiO{sub 2}/HAp composite treated with the dilute (0.25 mol/l) acid in spite of its low content of TiO{sub 2} photocatalyst. This enhanced photocatalytic activity was attributed to the result that the deactivation with repeated injections of ethanol gas was suppressed in the TiO{sub 2}/HAp composites compared with the TiO{sub 2} powders.

  11. Analysis of fixed bed data for the extraction of a rate mechanism for the reaction of hematite with methane

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

    Breault, Ronald W.; Monazam, Esmail R.

    2015-04-01

    In this study, chemical looping combustion is a promising technology for the capture of CO2 involving redox materials as oxygen carriers. The effects of reduction conditions, namely, temperature and fuel partial pressure on the conversion products are investigated. The experiments were conducted in a laboratory fixed-bed reactor that was operated cyclically with alternating reduction and oxidation periods. Reactions are assumed to occur in the shell surrounding the particle grains with diffusion of oxygen to the surface from the grain core. Activation energies for the shell and core reactions range from 9 to 209 kJ/mol depending on the reaction step.

  12. The reaction of cobaloximes with hydrogen: Products and thermodynamics

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

    Estes, Deven P.; Grills, David C.; Norton, Jack R.

    2014-11-26

    In this study, a cobalt hydride has been proposed as an intermediate in many reactions of the Co(dmgBF₂)₂L₂ system, but its observation has proven difficult. We have observed the UV–vis spectra of Co(dmgBF₂)₂L₂ (1) in CH₃CN under hydrogen pressures up to 70 atm. A Co(I) compound (6), with an exchangeable proton, is eventually formed. We have determined the bond dissociation free energy and pKa of the new O–H bond in 6 to be 50.5 kcal/mol and 13.4, respectively, in CH₃CN, matching previous reports.

  13. The reaction of cobaloximes with hydrogen: Products and thermodynamics

    SciTech Connect (OSTI)

    Estes, Deven P.; Grills, David C.; Norton, Jack R.

    2014-11-26

    In this study, a cobalt hydride has been proposed as an intermediate in many reactions of the Co(dmgBF?)?L? system, but its observation has proven difficult. We have observed the UVvis spectra of Co(dmgBF?)?L? (1) in CH?CN under hydrogen pressures up to 70 atm. A Co(I) compound (6), with an exchangeable proton, is eventually formed. We have determined the bond dissociation free energy and pKa of the new OH bond in 6 to be 50.5 kcal/mol and 13.4, respectively, in CH?CN, matching previous reports.

  14. High Capacity Hydrogen Storage Nanocomposite - Energy Innovation Portal

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

    Hydrogen and Fuel Cell Hydrogen and Fuel Cell Energy Storage Energy Storage Advanced Materials Advanced Materials Find More Like This Return to Search High Capacity Hydrogen Storage Nanocomposite Processes to add metal hydrideds to nanocarbon structures to yield high capacity hydrogen storage materials Savannah River National Laboratory Contact SRNL About This Technology Plot of Number of hydrogen atoms per lithium atom vs the Mol ratio of C<sub>60</sub>:Li.&nbsp; An ratio of 1:6

  15. Deducing the Energetic Cost of Protein Folding in Zinc Finger Proteins Using Designed Metallopeptides

    SciTech Connect (OSTI)

    Reddi,A.; Guzman, T.; Breece, r.; Tierney, D.; Gibney, B.

    2007-01-01

    Zinc finger transcription factors represent the largest single class of metalloproteins in the human genome. Binding of Zn(II) to their canonical Cys4, Cys3His1, or Cys2His2 sites results in metal-induced protein folding events required to achieve their proper structure for biological activity. The thermodynamic contribution of Zn(II) in each of these coordination spheres toward protein folding is poorly understood because of the coupled nature of the metal-ligand and protein-protein interactions. Using an unstructured peptide scaffold, GGG, we have employed fluorimetry, potentiometry, and calorimetry to determine the thermodynamics of Zn(II) binding to the Cys4, Cys3His1, and Cys2His2 ligand sets with minimal interference from protein folding effects. The data show that Zn(II) complexation is entropy driven and modulated by proton release. The formation constants for Zn(II)-GGG with a Cys4, Cys3His1, or Cys2His2 site are 5.6 x 1016, 1.5 x 1015, or 2.5 x 1013 M-1, respectively. Thus, the Zn(II)-Cys4, Zn(II)-Cys3His1, and Zn(II)-Cys2His2 interactions can provide up to 22.8, 20.7, and 18.3 kcal/mol, respectively, in driving force for protein stabilization, folding, and/or assembly at pH values above the ligand pKa values. While the contributions from the three coordination motifs differ by 4.5 kcal/mol in Zn(II) affinity at pH 9.0, they are equivalent at physiological pH, ?G = -16.8 kcal/mol or a Ka = 2.0 x 1012 M-1. Calorimetric data show that this is due to proton-based enthalpy-entropy compensation between the favorable entropic term from proton release and the unfavorable enthalpic term due to thiol deprotonation. Since protein folding effects have been minimized in the GGG scaffold, these peptides possess nearly the tightest Zn(II) affinities possible for their coordination motifs. The Zn(II) affinities in each coordination motif are compared between the GGG scaffold and natural zinc finger proteins to determine the free energy required to fold the latter. Several proteins have identical Zn(II) affinities to GGG. That is, little, if any, of their Zn(II) binding energy is required to fold the protein, whereas some have affinities weakened by up to 5.7 kcal/mol; i.e., the Zn(II) binding energy is being used to fold the protein.

  16. Hydrocracking with molten zinc chloride catalyst containing 2-12% ferrous chloride

    DOE Patents [OSTI]

    Zielke, Clyde W.; Bagshaw, Gary H.

    1981-01-01

    In a process for hydrocracking heavy aromatic polynuclear carbonaceous feedstocks to produce hydrocarbon fuels boiling below about 475.degree. C. by contacting the feedstocks with hydrogen in the presence of a molten zinc chloride catalyst and thereafter separating at least a major portion of the hydrocarbon fuels from the spent molten zinc chloride catalyst, an improvement comprising: adjusting the FeCl.sub.2 content of the molten zinc chloride to from about 2 to about 12 mol percent based on the mixture of ferrous chloride and molten zinc chloride.

  17. Browse by Discipline -- E-print Network Subject Pathways: Energy Storage,

    Office of Scientific and Technical Information (OSTI)

    Conversion and Utilization -- Energy, science, and technology for the research community -- hosted by the Office of Scientific and Technical Information, U.S. Department of Energy D E F G H I J K L M N O P Q R S T U V W X Y Z Cacciani, Patrice (Patrice Cacciani) - Laboratoire de Physique des Lasers Atomes et Molécules & Centre de Recherches Lasers et Applications, Cahill, Kevin (Kevin Cahill) - Department of Physics and Astronomy, University of New Mexico Caldarelli, Guido (Guido

  18. 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.

  19. Iron(IV)hydroxide pKa and the Role of Thiolate Ligation in C-H Bond

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

    Activation by Cytochrome P450 | Stanford Synchrotron Radiation Lightsource Iron(IV)hydroxide pKa and the Role of Thiolate Ligation in C-H Bond Activation by Cytochrome P450 Saturday, May 31, 2014 Cytochrome P450s (P450s) are a family of monooxygenase enzymes that are nearly ubiquitous in nature. P450s are often described as biological blowtorches due to their incredible oxidizing power:1 They can hydroxylate C-H bonds of about 98-100 kcal/mol. P450s are responsible for the phase I metabolism

  20. Thermal behavior of the amorphous precursors of the ZrO{sub 2}-SnO{sub 2} system

    SciTech Connect (OSTI)

    Stefanic, Goran Music, Svetozar; Ivanda, Mile

    2008-11-03

    Thermal behavior of the amorphous precursors of the ZrO{sub 2}-SnO{sub 2} system on the ZrO{sub 2}-rich side of the concentration range, prepared by co-precipitation from aqueous solutions of the corresponding salts, was monitored using differential thermal analysis, X-ray powder diffraction, Raman spectroscopy, field emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray spectrometry (EDS). The crystallization temperature of the amorphous precursors increased with an increase in the SnO{sub 2} content, from 405 deg. C (0 mol% SnO{sub 2}) to 500 deg. C (40 mol% SnO{sub 2}). Maximum solubility of Sn{sup 4+} ions in the ZrO{sub 2} lattice ({approx}25 mol%) occurred in the metastable products obtained upon crystallization of the amorphous precursors. A precise determination of unit-cell parameters, using both Rietveld and Le Bail refinements of the powder diffraction patterns, shows that the incorporation of Sn{sup 4+} ions causes an asymmetric distortion of the monoclinic ZrO{sub 2} lattice. The results of phase analysis indicate that the incorporation of Sn{sup 4+} ions has no influence on the stabilization of cubic ZrO{sub 2} and negligible influence on the stabilization of tetragonal ZrO{sub 2}. Partial stabilization of tetragonal ZrO{sub 2} in products having a tin content above its solid-solubility limit was attributed to the influence of ZrO{sub 2}-SnO{sub 2} surface interactions. In addition to phases closely structurally related to cassiterite, monoclinic ZrO{sub 2} and tetragonal ZrO{sub 2}, a small amount of metastable ZrSnO{sub 4} phase appeared in the crystallization products of samples with 40 and 50 mol% of SnO{sub 2} calcined at 1000 deg. C. Further temperature treatments caused a decrease in and disappearance of metastable phases. The results of the micro-structural analysis show that the sinterability of the crystallization products significantly decreases with an increase in the SnO{sub 2} content.

  1. In-core and ex-core calculations of the VENUS simulated PWR benchmark experiment

    SciTech Connect (OSTI)

    Williams, M.L.; Chowdhury, P.; Landesman, M.; Kam, F.B.K.

    1985-01-01

    The VENUS PWR engineering mockup experiment was established to simulate a beginning-of-life, generic PWR configuration at the zero-power VENUS critical facility located at CEN/SCK, Mol, Belgium. The experimental measurement program consists of (1) gamma scans to determine the core power distribution, (2) in-core and ex-core foil activations, (3) neutron spectrometer measurements, and (4) gamma heating measurements with TLD's. Analysis of the VENUS benchmark has been performed with two-dimensional discrete ordinates transport theory, using the DOT-IV code.

  2. Polarization reversal and domain kinetics in magnesium doped stoichiometric lithium tantalate

    SciTech Connect (OSTI)

    Shur, V. Ya., E-mail: vladimir.shur@urfu.ru; Akhmatkhanov, A. R.; Baturin, I. S. [Institute of Natural Sciences, Ural Federal University, 620000 Ekaterinburg (Russian Federation); Labfer Ltd., 620014 Ekaterinburg (Russian Federation); Chuvakova, M. A. [Institute of Natural Sciences, Ural Federal University, 620000 Ekaterinburg (Russian Federation)

    2014-10-13

    The polarization reversal process has been studied in 1?mol.?% MgO doped stoichiometric lithium tantalate (LT) single crystal. The revealed stages of domain structure evolution represent (1) continuous nucleation and growth of isolated hexagonal domains with walls oriented along Y directions and (2) continuous motion of the plane domain walls stimulated by merging with isolated domains. The activation field dependence of the switching time has been revealed. The coercive field for quasi-static switching is about 150?V/mm. The bulk screening process has been analyzed. The main parameters of the switching process have been compared with other representatives of LT family.

  3. PHOTOSYNTHESIS AND RESOURCE ALLOCATION OF THREE MOJAVE DESERT GRASSES IN RESPONSE TO ELEVATED ATMOSPHERIC CO2

    SciTech Connect (OSTI)

    L. A. DEFALCO; C. K. IVANS; P. VIVIN; J. R. SEEMANN; R. S. NOWAK

    2004-01-01

    Gas exchange, biomass and N allocation were compared among three Mojave Desert grasses representing different functional types to determine if photosynthetic responses and the associated allocation of resources within the plant changed after prolonged exposure to elevated CO{sub 2}. Leaf gas exchange characteristics were measured for Bromus madritensis ssp. rubens (C{sub 3} invasive annual), Achnatherum hymenoides (C{sub 3} native perennial) and Pleuraphis rigida (C{sub 4} native perennial) exposed to 360 {micro}mol mol{sup -1} (ambient) and 1000 {micro}mol mol{sup -1} (elevated) CO{sub 2} concentrations in a glasshouse experiment, and tissue biomass and total N pools were quantified from three harvests during development. The maximum rate of carboxylation by the N-rich enzyme Rubisco (Vc{sub max}), which was inferred from the relationship between net CO{sub 2} assimilation (A{sub net}) and intracellular CO{sub 2} concentration (c{sub i}), declined in the C{sub 3} species Bromus and Achnatherum across all sampling dates, but did not change at elevated CO{sub 2} for the C{sub 4} Pleuraphis. Whole plant N remained the same between CO{sub 2} treatments for all species, but patterns of allocation differed for the short- and long-lived C{sub 3} species. For Bromus, leaf N used for photosynthesis was reallocated to reproduction at elevated CO{sub 2} as inferred from the combination of lower Vc{sub max} and N per leaf area (NLA) at elevated CO{sub 2}, but similar specific leaf area (SLA, cm{sup 2} g{sup -1}), and of greater reproductive effort (RE) for the elevated CO{sub 2} treatment. Vc{sub max}, leaf N concentration and NLA declined for the perennial Achnatherum at elevated CO{sub 2} potentially due to accumulation of carbohydrates or changes in leaf morphology inferred from lower SLA and greater total biomass at elevated CO{sub 2}. In contrast, Vc{sub max} for the C{sub 4} perennial Pleuraphis did not change at elevated CO{sub 2}, and tissue biomass and total N were the same between CO{sub 2} treatments. Adjustments in photosynthetic capacity at elevated CO{sub 2} may optimize N allocation of C{sub 3} species in the Mojave Desert, which may influence plant performance and plant-plant interactions of these co-occurring species.

  4. In situ treatment of arsenic contaminated groundwater by aquifer iron coating: Experimental Study

    SciTech Connect (OSTI)

    Xie, Xianjun; Wang, Yanxin; Pi, Kunfu; Liu, Chongxuan; Li, Junxia; Liu, Yaqing; Wang, Zhiqiang; Duan, Mengyu

    2015-09-15

    In situ arsenic removal from groundwater by an iron coating method has great potential to be a cost effective and simple groundwater remediation technique, especially in rural and remote areas where groundwater is used as the main source of drinking water. The in situ arsenic removal technique was first optimized by simulating arsenic removal in various quartz sand columns under anoxic conditions., Its effectiveness was then evaluated in an actual high-arsenic groundwater environment. The mechanism of arsenic removal by the iron coating was investigated under different conditions using scanning electron microscopy (SEM)/X-ray absorption spectroscopy, an electron microprobe, and Fourier transformation infrared spectroscopy. A 4-step alternative cycle aquifer iron coating method was developed. A continuous injection of 5 mmol/L FeSO4 and 2.5 mmol/L NaClO for 96 hours can create a uniform coating of crystalline goethite on the surface of quartz sand in the columns without causing clogging. At a flow rate of 0.45 cm/min of the injection reagents (vi), the time for arsenic (as Na2HAsO4) to pass through the iron-coated quartz sand column was approximately 35 hours, which was much longer than that for tracer fluorescein sodium (approximately 2 hours). The retardation factor of arsenic was 23, and its adsorption capacity was 0.11 mol As per mol Fe, leading to an excellent arsenic removal. In situ arsenic removal from groundwater in an aquifer was achieved by simultaneous injections of As (V) and Fe (II) reagents. When the arsenic content in the groundwater was 233 ?g/L, the aqueous phase arsenic was completely removed with an arsenic adsorption of 0.05 mol As per mol Fe. Arsenic fixation resulted from a process of adsorption/co-precipitation, in which arsenic and iron likely formed the arsenic-bearing iron mineral phases with poor crystallinity by way of bidentate binuclear complexes. Thus, the high arsenic removal efficiency of the technique likely resulted from the expanded specific iron oxide/hydroxide surface area with poor crystallinity and from coprecipitation.

  5. J

    National Nuclear Security Administration (NNSA)

    J - MOL.19980416.0733 i W B S 1.2.8.4.2 QA: NA Civilian Radioactive Waste Management System Management and Operating Contractor Meteorological Monitoring Program Particulate Matter Ambient Air Quality Monitoring Report . January through December 1996 BA0000000-01717-570500001 REV 00 April 16,1997 Prepared for: U.S. Department of Energy Yucca Mountain Site Characterization Office P.O. Box 30307 North Las Vegas, Nevada 89036-0307 Prepared by: TRW Environmental Safety Systems, Inc. 11 80 Town

  6. PROTON-CONDUCTING DENSE CERAMIC MEMBRANES FOR HYDROGEN SEPARATION

    SciTech Connect (OSTI)

    Jerry Y. S. Lin; Scott Cheng; Vineet Gupta

    2003-12-01

    Dense perovskite-type structured ceramic membranes, SrCe{sub 0.95}Tm{sub 0.05}O{sub 3} (SCTm), of different thickness, were prepared by the dry-press method. Membrane thickness was varied from 3 mm to 150 {micro}m. The hydrogen permeation flux was found to be inversely proportional to the thickness of the dense films, indicating that the bulk diffusion rather than the surface reaction played a dominant role in the H{sub 2} transport through these dense membranes within the studied thickness range. Hydrogen permeation flux increases with increasing upstream hydrogen partial pressure and decreasing downstream hydrogen partial pressure. The activation energy for hydrogen permeation through the SCTm membrane is about 116 kJ/mol in 600-700 C and 16 kJ/mol in 750-950 C. This indicates a change in the electrical and protonic conduction mechanism at around 700 C. Pd-Cu thin films were synthesized with elemental palladium and copper targets by the sequential R.F. sputter deposition on porous substrates. Pd-Cu alloy films could be formed after proper annealing. The deposited Pd-Cu films were gas-tight. This result demonstrated the feasibility of obtaining an ultrathin SCTm film by the sequential sputter deposition of Sr, Ce and Tm metals followed by proper annealing and oxidation. Such ultrathin SCTm membranes will offer sufficiently high hydrogen permeance for practical applications.

  7. Kinetics of hydrogen isotope exchange in ?-phase Pd-H-D

    SciTech Connect (OSTI)

    Luo, Weifang; Cowgill, Donald F.

    2015-07-22

    Hydrogen isotope gas exchange within palladium powders is examined using a batch-type reactor coupled to a residual gas analyzer (RGA). Furthermore, the exchange rates in both directions (H2 + PdD and D2 + PdH) are measured in the temperature range 178323 K for the samples with different particle sizes. The results show this batch-type exchange is closely approximated as a first-order kinetic process with a rate directly proportional to the surface area of the powder particles. An exchange rate constant of 1.40 0.24 ?mol H2/atm cm2 s is found for H2 + PdD at 298 K, 1.4 times higher than that for D2 + PdH, with an activation energy of 25.0 3.2 kJ/mol H for both exchange directions. Finally, a comparison of exchange measurement techniques shows these coefficients, and the fundamental exchange probabilities are in good agreement with those obtained by NMR and flow techniques.

  8. Modifications under irradiation of a self-assembled monolayer grafted on a nano-porous silica glass: a solid-state NMR characterization

    SciTech Connect (OSTI)

    Le Caer, S.; Chatelain, C.; Renault, J.Ph.; Brunet, F.; Charpentier, T.; Durand, D.; Dauvois, V.

    2012-02-15

    Controlled pore glasses with a pore size of 8 nm are grafted with chlorodimethylsilane (ClSi(CH{sub 3}){sub 2}H). The surface of the glass is carefully characterized before and after irradiation with 10 MeV electrons by solid-state NMR measurements. {sup 1}H MAS NMR experiments in one and two dimensions (2D double quantum and 2D exchange) have been used to reveal the grafting of the chlorodimethylsilane at the silica surface and evidence the formation of a homogeneous layer on the surface. Irradiation leads to a high H{sub 2} yield (3.3 * 10{sup -7} mol/J) due to the efficient cleavage of the Si H bond. Methane is detected in smaller quantities (5.5 * 10{sup -8} mol/J), indicating that the Si-H bond is preferentially cleaved over the Si-C bond. The H{sub 2} production arising from OH groups on the surface is very minor in comparison to the S- H and Si-C radiolysis. (authors)

  9. Concentration effect of Er{sup 3+} ions on structural and spectroscopic properties of CdNb{sub 2}O{sub 6} phosphors

    SciTech Connect (OSTI)

    Ghafouri, Sanaz Aian; Erdem, Murat; Ekmeki, M. Kaan; Mergen, Ayhan; zen, Gnl

    2014-12-15

    Excitation and emission spectra of a visible room-temperature Er{sup 3+} ions luminescence from powders. - Highlights: This is the first report on spectroscopic properties of CdNb{sub 2}O{sub 6}:Er{sup 3+}. The crystalline sizes are affected as the concentration of Er{sup 3+} ions increased. Quenching of the luminescence was observed to be above 1.0 mol% Er{sup 3+}. - Abstract: This study is focused on the synthesis and characterization of CdNb{sub 2}O{sub 6} compounds doped with of Er{sup 3+} ions. Powders were synthesized by using the molten salt method and annealed at 900 C for 4 h. The synthesized particles were structurally characterized by using X-ray diffraction, scanning electron microscopy. A single phase of the CdNb{sub 2}O{sub 6} was determined and the size of the particles was found to be affected by the presence and the concentration of Er{sup 3+} ions. Luminescence properties of each sample were investigated by measuring accurately the emission and excitation spectra at room temperature in the wavelength range of 2001700 nm by exciting the Er{sup 3+} ions at 379 nm and 805 nm. Quenching of the luminescence in both visible and near infrared spectral regions was observed to be above 1.0 mol% Er{sup 3+} concentration.

  10. Kinetics of Hydrogen Isotope Exchange in ?-phase Pd-H-D

    SciTech Connect (OSTI)

    Luo, Weifang; Cowgill, Donald F.

    2015-07-22

    Hydrogen isotope gas exchange within palladium powders is examined using a batch-type reactor coupled to a residual gas analyzer (RGA). Furthermore, the exchange rates in both directions (H2 + PdD and D2 + PdH) are measured in the temperature range 178323 K for the samples with different particle sizes. The results show this batch-type exchange is closely approximated as a first-order kinetic process with a rate directly proportional to the surface area of the powder particles. An exchange rate constant of 1.40 0.24 ?mol H2/atm cm2 s is found for H2 + PdD at 298 K, 1.4 times higher than that for D2 + PdH, with an activation energy of 25.0 3.2 kJ/mol H for both exchange directions. Finally, a comparison of exchange measurement techniques shows these coefficients, and the fundamental exchange probabilities are in good agreement with those obtained by NMR and flow techniques.

  11. Computational Study of Bond Dissociation Enthalpies for Substituted $\\beta$-O-4 Lignin Model Compounds

    SciTech Connect (OSTI)

    Younker, Jarod M; Beste, Ariana; Buchanan III, A C

    2011-01-01

    The biopolymer lignin is a potential source of valuable chemicals. Phenethyl phenyl ether (PPE) is representative of the dominant $\\beta$-O-4 ether linkage. Density functional theory (DFT) is used to calculate the Boltzmann-weighted carbon-oxygen and carbon-carbon bond dissociation enthalpies (BDEs) of substituted PPE. These values are important in order to understand lignin decomposition. Exclusion of all conformers that have distributions of less than 5\\% at 298 K impacts the BDE by less than 1 kcal mol$^{-1}$. We find that aliphatic hydroxyl/methylhydroxyl substituents introduce only small changes to the BDEs (0-3 kcal mol$^{-1}$). Substitution on the phenyl ring at the $ortho$ position substantially lowers the C-O BDE, except in combination with the hydroxyl/methylhydroxyl substituents, where the effect of methoxy substitution is reduced by hydrogen bonding. Hydrogen bonding between the aliphatic substituents and the ether oxygen in the PPE derivatives has a significant influence on the BDE. CCSD(T)-calculated BDEs and hydrogen bond strengths of $ortho$-substituted anisoles when compared with M06-2X values confirm that the latter method is sufficient to describe the molecules studied and provide an important benchmark for lignin model compounds.

  12. Plasmon-enhanced reverse water gas shift reaction over oxide supported Au catalysts

    SciTech Connect (OSTI)

    Upadhye, AA; Ro, I; Zeng, X; Kim, HJ; Tejedor, I; Anderson, MA; Dumesic, JA; Huber, GW

    2015-01-01

    We show that localized surface plasmon resonance (LSPR) can enhance the catalytic activities of different oxide-supported Au catalysts for the reverse water gas shift (RWGS) reaction. Oxide-supported Au catalysts showed 30 to 1300% higher activity for RWGS under visible light compared to dark conditions. Au/TiO2 catalyst prepared by the deposition-precipitation (DP) method with 3.5 nm average Au particle size showed the highest activity for the RWGS reaction. Visible light is converted into chemical energy for this reaction with up to a 5% overall efficiency. A shift in the apparent activation energy (from 47 kJ mol(-1) in dark to 35 kJ mol(-1) in light) and apparent reaction order with respect to CO2 (from 0.5 in dark to 1.0 in light) occurs due to the LSPR. Our kinetic results indicate that the LSPR increases the rate of either the hydroxyl hydrogenation or carboxyl decomposition more than any other steps in the reaction network.

  13. Room-temperature ionic liquid-amine solutions: tunable solvents for efficient and reversible capture of CO{sub 2}

    SciTech Connect (OSTI)

    Dean Camper; Jason E. Bara; Douglas L. Gin; Richard D. Noble

    2008-11-05

    Solutions of room-temperature ionic liquids (RTILs) and commercially available amines were found to be effective for the capture of CO{sub 2} as carbamate salts. RTIL solutions containing 50 mol % (16% v/v) monoethanolamine (MEA) are capable of rapid and reversible capture of 1 mol of CO{sub 2} per 2 moles MEA to give an insoluble MEA-carbamate precipitate that helps to drive the capture reaction (as opposed to aqueous amine systems). Diethanolamine (DEA) can also be used in the same manner for CO{sub 2} capture in RTILs containing a pendant hydroxyl group. The captured CO{sub 2} in the resulting RTIL-carbamate salt mixtures can be readily released by either heating and/or subjecting them to reduced pressure. Using this unprecedented and industrially attractive mixing approach, the desirable properties of RTILs (i.e., nonvolatility, enhancedCO{sub 2} solubility, lower heat capacities) can be combined with the performance of amines for CO{sub 2} capture without the use of specially designed, functionalized 'task-specific' ionic liquids. By mixing RTILs with commercial amines, reactive solvents with a wide range of amine loading levels can be tailored to capture CO{sub 2} in a variety of conditions and processes. These RTIL-amine solutions behave similarly to their water-based counterparts but may offer many advantages, including increased energy efficiency, compared to current aqueous amine technologies.

  14. Optimizing white light luminescence in Dy{sup 3+}-doped Lu{sub 3}Ga{sub 5}O{sub 12} nano-garnets

    SciTech Connect (OSTI)

    Haritha, P.; Linganna, K.; Venkatramu, V.; Martn, I. R.; Monteseguro, V.; Rodrguez-Mendoza, U. R.; Babu, P.; Len-Luis, S. F.; Jayasankar, C. K.; Lavn, V.

    2014-11-07

    Trivalent dysprosium-doped Lu{sub 3}Ga{sub 5}O{sub 12} nano-garnets have been prepared by sol-gel method and characterized by X-ray powder diffraction, high-resolution transmission electron microscopy, dynamic light scattering, and laser excited spectroscopy. Under a cw 457?nm laser excitation, the white luminescence properties of Lu{sub 3}Ga{sub 5}O{sub 12} nano-garnets have been studied as a function of the optically active Dy{sup 3+} ion concentration and at low temperature. Decay curves for the {sup 4}F{sub 9/2} level of Dy{sup 3+} ion exhibit non-exponential nature for all the Dy{sup 3+} concentrations, which have been well-fitted to a generalized energy transfer model for a quadrupole-quadrupole interaction between Dy{sup 3+} ions without diffusion. From these data, a simple rate-equations model can be applied to predict that intense white luminescence could be obtained from 1.8?mol% Dy{sup 3+} ions-doped nano-garnets, which is in good agreement with experimental results. Chromaticity color coordinates and correlated color temperatures have been determined as a function of temperature and are found to be within the white light region for all Dy{sup 3+} concentrations. These results indicate that 2.0?mol% Dy{sup 3+} ions doped nano-garnet could be useful for white light emitting device applications.

  15. Do TFSA anions slither? Pressure exposes the role of TFSA conformational exchange in self-diffusion

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

    Suarez, Sophia N.; Wishart, James F.; Rua, Armando; Cuffari, David; Pilar, Kartik; Hatcher, Jasmine L.; Ramati, Sharon

    2015-10-28

    Multi-nuclear (1H, 2H, and 19F) magnetic resonance spectroscopy techniques as functions of temperature and pressure were applied to the study of selectively deuterated 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (EMIM TFSA) ionic liquid isotopologues and related ionic liquids. For EMIM TFSA, temperature-dependent 2H T1 data indicate stronger electric field gradients in the alkyl chain region compared to the imidazolium ring. Most significantly, the pressure dependences of the EMIM and TFSA self-diffusion coefficients revealed that the displacements of the cations and anions are independent, with diffusion of the TFSA anions being slowed much more by increasing pressure than for the EMIM cations, as shown bymore » their respective activation volumes (28.8 ± 2.5 cm³/mol for TFSA vs. 14.6 ± 1.3 cm³/mol for EMIM). Increasing pressure may lower the mobility of the TFSA anion by hindering its interconversion between trans and cis conformers, a process that is coupled to diffusion according to published molecular dynamics simulations. Measured activation volumes (ΔV‡) for ion self-diffusion in EMIM bis(fluoromethylsulfonyl)amide and EMIM tetrafluoroborate support this hypothesis.« less

  16. Assessment of reduction behavior of hematite iron ore pellets in coal fines for application in sponge ironmaking

    SciTech Connect (OSTI)

    Kumar, M.; Patel, S.K.

    2009-07-01

    Studies on isothermal reduction kinetics (with F grade coal) in fired pellets of hematite iron ores, procured from four different mines of Orissa, were carried out in the temperature range of 850-1000C to provide information for the Indian sponge iron plants. The rate of reduction in all the fired iron ore pellets increased markedly with a rise of temperature up to 950C, and thereafter it decreased at 1000C. The rate was more intense in the first 30 minutes. All iron ores exhibited almost complete reduction in their pellets at temperatures of 900 and 950C in 2 hours' heating time duration, and the final product morphologies consisted of prominent cracks. The kinetic model equation 1-(1-a){sup 1/3}=kt was found to fit best to the experimental data, and the values of apparent activation energy were evaluated. Reductions of D. R. Pattnaik and M. G. Mohanty iron ore pellets were characterized by higher activation energies (183 and 150 kJ mol{sup -1}), indicating carbon gasification reaction to be the rate-controlling step. The results established lower values of activation energy (83 and 84 kJ mol{sup -1}) for the reduction of G. M. OMC Ltd. and Sakaruddin iron ore pellets, proposing their overall rates to be controlled by indirect reduction reactions.

  17. Effects of Light and Temperature on Fatty Acid Production in Nannochloropsis Salina

    SciTech Connect (OSTI)

    Van Wagenen, Jonathan M.; Miller, Tyler W.; Hobbs, Samuel J.; Hook, Paul W.; Crowe, Braden J.; Huesemann, Michael H.

    2012-03-12

    Accurate prediction of algal biofuel yield will require empirical determination of physiological responses to the climate, particularly light and temperature. One strain of interest, Nannochloropsis salina, was subjected to ranges of light intensity (5-850 {mu}mol m{sup -2} s{sup -1}) and temperature (13-40 C); exponential growth rate, total fatty acids (TFA) and fatty acid composition were measured. The maximum acclimated growth rate was 1.3 day{sup -1} at 23 C and 250 {mu}mol m{sup -2} s{sup -1}. Fatty acids were detected by gas chromatography with flame ionization detection (GC-FID) after transesterification to corresponding fatty acid methyl esters (FAME). A sharp increase in TFA containing elevated palmitic acid (C16:0) and palmitoleic acid (C16:1) during exponential growth at high light was observed, indicating likely triacylglycerol accumulation due to photo-oxidative stress. Lower light resulted in increases in the relative abundance of unsaturated fatty acids; in thin cultures, increases were observed in palmitoleic and eicosapentaenoeic acids (C20:5{omega}3). As cultures aged and the effective light intensity per cell converged to very low levels, fatty acid profiles became more similar and there was a notable increase of oleic acid (C18:1{omega}9). The amount of unsaturated fatty acids was inversely proportional to temperature, demonstrating physiological adaptations to increase membrane fluidity. This data will improve prediction of fatty acid characteristics and yields relevant to biofuel production.

  18. Effects of Amines on the Surface Charge Poperties of Iron Oxides.

    SciTech Connect (OSTI)

    Benezeth, Pascale; Wesolowski, David J; Palmer, Donald; Machesky, Michael L.

    2009-07-01

    Specific studies detailing the effects of amines, used as pH control agents for corrosion inhibition in power plants, on the surface charge of iron oxides provide data to assess the mechanism of how these amines impact deposition rate. The current study was undertaken in order to determine accurately the dissociation constants of the relevant amines at Pressurized Water Reactor (PWR) operating conditions and to investigate the effect of sorption of two of these amines (morpholine and dimethylamine) by magnetite. The acid-dissociation equilibria of morpholine (MOR), dimethylamine (DMA) and ethanolamine (ETA) were measured potentiometrically with a hydrogen-electrode concentration cell (HECC) from 0 to 290 C in sodium trifluoromethanesulfonate (NaTr) solutions at ionic strengths up to 1 mol {center_dot} kg{sup -1}. Magnetite surface titrations were performed at an ionic strength of 0.03 mol {center_dot} kg{sup -1} (NaTr medium) in the presence or absence of morpholine and dimethylamine buffers over a wide range of pH and total amine concentrations at 150-250 C.

  19. The solubility of zinc oxide in 0.03 m NaTr as a function of temperature, with in situ pH measurement

    SciTech Connect (OSTI)

    Benezeth, P.; Palmer, D.A.; Wesolowski, D.J.

    1999-05-01

    The solubility of zincite (ZnO) has been measured in noncomplexing solutions over a wide range of pH{sub m} (4--11), and temperature (75--200 C) at 0.03 mol/kg ionic strength in NaTr media (sodium trifluoromethanesulfonate, a noncomplexing 1:1 electrolyte), in a hydrogen electrode concentration cell (HECC), which provided continuous in situ measurement of hydrogen ion molality. Total zinc content was analyzed by atomic absorption using graphite furnace, flame, and inductively coupled plasma (ICP) spectrometers. The direction of approach to the equilibrium saturation state was varied to demonstrate that the system was reversible thermodynamically. Separate experiments were performed in alkaline solutions (0.03 mol/kg NaOH) at 25 and 50 C in polypropylene syringes, and between 50 and 290 C in a Teflon-lined pressure vessel. The aim of these experiments was to reach higher pH{sub m} (>8 depending on the temperature) to determine the thermodynamic properties of the negatively charged species, Zn(OH){sub 3}{sup {minus}}. A least-squares regression of the results obtained at this ionic strength was used to determine the molal solubility products (Q{sub sn}) of zincite. The solubility products (Q{sub sn}) were extrapolated to infinite dilution (K{sub sn}), permitting calculation of the thermodynamic properties of aqueous species of zinc for comparison with previous work.

  20. The structural and magnetic properties of Pr{sub 1−x}Er{sub x}Al{sub 2}

    SciTech Connect (OSTI)

    Pathak, Arjun K.; Gschneidner, K. A.; Pecharsky, V. K.

    2015-05-07

    We report on the effect of Er addition to PrAl{sub 2} on the lattice parameters, magnetic behavior, heat capacity, and magnetocaloric effect by using x-ray diffraction, magnetization, and heat capacity measurements. Unlike Pr{sub 0.6}Er{sub 0.4}Al{sub 2}, other alloys we studied in the pseudobinary (Pr{sub 1−x}Er{sub x})Al{sub 2} system do not exhibit a sharp peak in heat capacity with the application of magnetic field. Both the cubic lattice parameter and the Curie temperature decrease with increasing Er concentration. The nuclear specific heat coefficient decreases from 660 mJ K mol{sup −1} for x = 0.05 to a nearly negligible value for x = 0.95. The magnetic entropy and adiabatic temperature change varies from 2 to 4 J mol{sup −1} K{sup −1} and 2.5 to 5 K at ΔH = 20 kOe for x = 0.05 to 0.95, respectively. These values of the magnetocaloric effect are comparable to those of the other rare-earth dialuminides systems.

  1. Thermodynamic characterization of new palladium alloy tritides

    SciTech Connect (OSTI)

    Hoelder, J.S.; Wermer, J.R.

    1994-08-09

    The decay of tritium in a metal tritide generates {sup 3}He in the lattice which tends to degrade the performance of the material over time. It is desired to develop a material which minimizes the tritium aging effects and may be tailored to a particular tritium processing application. Pd alloys with Ni and Co have been investigated, as Pd tritide is known to be resistant to tritium aging effects and alloying provides a means for adjusting the plateau pressure of the metal tritide. Sets of tritium desorption isotherms were acquired at temperatures between 273 and 338 K over the pressure range of 1 to 900 kPa. The thermodynamic parameters of {Delta}H and {Delta}S for the {beta}-{alpha} phase transition of the metal tritides were determined across the plateau regions of the P-C-T curves. The average values of {Delta}H (kJ/mol{center_dot}T) and {Delta}S (J/K/mol{center_dot}T) were found to be 15.8 and 50.1 for Pd(2.8 wt. %)Ni, 13.7 and 50.3 for Pd(5.2 wt. %)Ni, 15.9 and 51.3 for Pd(2.8 wt. %)Co, and 13.6 and 51.8 for Pd(5.2 wt. %)Co, respectively.

  2. Molecular basis of endosomal-membrane association for the dengue virus envelope protein

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

    Rogers, David M.; Kent, Michael S.; Rempe, Susan B.

    2015-01-02

    Dengue virus is coated by an icosahedral shell of 90 envelope protein dimers that convert to trimers at low pH and promote fusion of its membrane with the membrane of the host endosome. We provide the first estimates for the free energy barrier and minimum for two key steps in this process: host membrane bending and protein–membrane binding. Both are studied using complementary membrane elastic, continuum electrostatics and all-atom molecular dynamics simulations. The predicted host membrane bending required to form an initial fusion stalk presents a 22–30 kcal/mol free energy barrier according to a constrained membrane elastic model. Combined continuummore »and molecular dynamics results predict a 15 kcal/mol free energy decrease on binding of each trimer of dengue envelope protein to a membrane with 30% anionic phosphatidylglycerol lipid. The bending cost depends on the preferred curvature of the lipids composing the host membrane leaflets, while the free energy gained for protein binding depends on the surface charge density of the host membrane. The fusion loop of the envelope protein inserts exactly at the level of the interface between the membrane's hydrophobic and head-group regions. As a result, the methods used in this work provide a means for further characterization of the structures and free energies of protein-assisted membrane fusion.« less

  3. Magnetic order and heavy fermion behavior in CePd{sub 1+x}Al{sub 6-x}: Synthesis, structure, and physical properties

    SciTech Connect (OSTI)

    Tobash, Paul H., E-mail: ptobash@lanl.go [Materials Physics and Application Division, MPA-10, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716 (United States); Ronning, Filip; Thompson, J.D. [Materials Physics and Application Division, MPA-10, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Bobev, Svilen [Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716 (United States); Bauer, Eric D. [Materials Physics and Application Division, MPA-10, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

    2010-03-15

    The physical properties including magnetic susceptibility, specific heat, and electrical resistivity of single crystals are reported for the compound CePd{sub 1+x}Al{sub 6-x} (x=0.5) which crystallizes in the tetragonal SrAu{sub 2}Ga{sub 5}-type structure (space group P4/mmm). The compound was grown from an excess of molten Al flux from the respective elements and the crystal structure was established from single-crystal X-ray diffraction. Anomalies in the low temperature specific heat C{sub p}(T) and electrical resistivity rho(T) show that the compound undergoes ferromagnetic order at T{sub C}=2.8 K. In the ordered state, CePd{sub 1.5}Al{sub 5.5} displays heavy fermion behavior with a Sommerfeld coefficient of ca. 500 mJ/mol-K{sup 2}. - Graphical abstract: The compound CePd{sub 1+x}Al{sub 6-x} (x=0.5) has been synthesized and structurally characterized by single-crystal X-ray diffraction. The measured physical properties of temperature and field dependent magnetic susceptibility, specific heat, and electrical resistivity suggests that the compound undergoes ferromagnetic order at ca. 2.8 K and further exhibits relatively heavy fermion behavior with a Sommerfeld coefficient of 500 mJ/mol-K2.

  4. Lithium ion conducting electrolytes

    DOE Patents [OSTI]

    Angell, C.A.; Liu, C.

    1996-04-09

    A liquid, predominantly lithium-conducting, ionic electrolyte is described having exceptionally high conductivity at temperatures of 100 C or lower, including room temperature, and comprising the lithium salts selected from the group consisting of the thiocyanate, iodide, bromide, chloride, perchlorate, acetate, tetrafluoroborate, perfluoromethane sulfonate, perfluoromethane sulfonamide, tetrahaloaluminate, and heptahaloaluminate salts of lithium, with or without a magnesium-salt selected from the group consisting of the perchlorate and acetate salts of magnesium. Certain of the latter embodiments may also contain molecular additives from the group of acetonitrile (CH{sub 3}CN), succinnonitrile (CH{sub 2}CN){sub 2}, and tetraglyme (CH{sub 3}--O--CH{sub 2}--CH{sub 2}--O--){sub 2} (or like solvents) solvated to a Mg{sup +2} cation to lower the freezing point of the electrolyte below room temperature. Other particularly useful embodiments contain up to about 40, but preferably not more than about 25, mol percent of a long chain polyether polymer dissolved in the lithium salts to provide an elastic or rubbery solid electrolyte of high ambient temperature conductivity and exceptional 100 C conductivity. Another embodiment contains up to about but not more than 10 mol percent of a molecular solvent such as acetone. 2 figs.

  5. Lithium ion conducting electrolytes

    DOE Patents [OSTI]

    Angell, C. Austen (Tempe, AZ); Liu, Changle (Tempe, AZ)

    1996-01-01

    A liquid, predominantly lithium-conducting, ionic electrolyte having exceptionally high conductivity at temperatures of 100.degree. C. or lower, including room temperature, and comprising the lithium salts selected from the group consisting of the thiocyanate, iodide, bromide, chloride, perchlorate, acetate, tetrafluoroborate, perfluoromethane sulfonate, perfluoromethane sulfonamide, tetrahaloaluminate, and heptahaloaluminate salts of lithium, with or without a magnesium-salt selected from the group consisting of the perchlorate and acetate salts of magnesium. Certain of the latter embodiments may also contain molecular additives from the group of acetonitrile (CH.sub.3 CN) succinnonitrile (CH.sub.2 CN).sub.2, and tetraglyme (CH.sub.3 --O--CH.sub.2 --CH.sub.2 --O--).sub.2 (or like solvents) solvated to a Mg.sup.+2 cation to lower the freezing point of the electrolyte below room temperature. Other particularly useful embodiments contain up to about 40, but preferably not more than about 25, mol percent of a long chain polyether polymer dissolved in the lithium salts to provide an elastic or rubbery solid electrolyte of high ambient temperature conductivity and exceptional 100.degree. C. conductivity. Another embodiment contains up to about but not more than 10 mol percent of a molecular solvent such as acetone.

  6. State-to-state reaction dynamics of {sup 18}O+{sup 32}O{sub 2} studied by a time-dependent quantum wavepacket method

    SciTech Connect (OSTI)

    Xie, Wenbo; Liu, Lan; Sun, Zhigang; Guo, Hua; Dawes, Richard

    2015-02-14

    The title isotope exchange reaction was studied by converged time-dependent wave packet calculations, where an efficient 4th order split operator was applied to propagate the initial wave packet. State-to-state differential and integral cross sections up to the collision energy of 0.35 eV were obtained with {sup 32}O{sub 2} in the hypothetical j{sub 0} = 0 state. It is discovered that the differential cross sections are largely forward biased in the studied collision energy range, due to the fact that there is a considerable part of the reaction occurring with large impact parameter and short lifetime relative to the rotational period of the intermediate complex. The oscillations of the forward scattering amplitude as a function of collision energy, which result from coherent contribution of adjacent resonances, may be a sensitive probe for examining the quality of the underlying potential energy surface. A good agreement between the theoretical and recent experimental integral and differential cross sections at collision energy of 7.3 kcal/mol is obtained. However, the theoretical results predict slightly too much forward scattering and colder rotational distributions than the experimental observations at collision energy of 5.7 kcal/mol.

  7. Molecular metal-Oxo catalysts for generating hydrogen from water

    DOE Patents [OSTI]

    Long, Jeffrey R; Chang, Christopher J; Karunadasa, Hemamala I

    2015-02-24

    A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition having the general formula [(PY5W.sub.2)MO].sup.2+, wherein PY5W.sub.2 is (NC.sub.5XYZ)(NC.sub.5H.sub.4).sub.4C.sub.2W.sub.2, M is a transition metal, and W, X, Y, and Z can be H, R, a halide, CF.sub.3, or SiR.sub.3, where R can be an alkyl or aryl group. The two accompanying counter anions, in one embodiment, can be selected from the following Cl.sup.-, I.sup.-, PF.sub.6.sup.-, and CF.sub.3SO.sub.3.sup.-. In embodiments of the invention, water, such as tap water containing electrolyte or straight sea water can be subject to an electric potential of between 1.0 V and 1.4 V relative to the standard hydrogen electrode, which at pH 7 corresponds to an overpotential of 0.6 to 1.0 V, with the result being, among other things, the generation of hydrogen with an optimal turnover frequency of ca. 1.5 million mol H.sub.2/mol catalyst per h.

  8. Thermodynamics of formation of coffinite, USiO?

    SciTech Connect (OSTI)

    Guo, Xiaofeng; Szenknect, Stphanie; Mesbah, Adel; Labs, Sabrina; Clavier, Nicolas; Poinssot, Christophe; Curtius, Hildegard; Bosbach, Dirk; Ewing, Rodney C.; Burns, Peter C.; Dacheux, Nicolas; Navrotsky, Alexandra

    2015-05-26

    Coffinite, USiO?, is an important U(IV) mineral, but its thermodynamic properties are not well-constrained. In this work, two different coffinite samples were synthesized under hydrothermal conditions and purified from a mixture of products. The enthalpy of formation was obtained by high temperature oxide melt solution calorimetry. Coffinite is energetically metastable with respect to a mixture of UO? (uraninite) and SiO? (quartz) by 25.6 3.9 kJ/mol. Its standard enthalpy of formation from the elements at 25 C is -1,970.0 4.2 kJ/mol. Decomposition of the two samples was characterized by X-ray diffraction and by thermogravimetry and differential scanning calorimetry coupled with mass spectrometric analysis of evolved gases. Coffinite slowly decomposes to U?O? and SiO? starting around 450 C in air and thus has poor thermal stability in the ambient environment. The energetic metastability explains why coffinite cannot be synthesized directly from uraninite and quartz but can be made by low temperature precipitation in aqueous and hydrothermal environments. These thermochemical constraints are in accord with observations of the occurrence of coffinite in nature and are relevant to spent nuclear fuel corrosion.

  9. Theoretical Study of Trimethylacetic Acid Adsorption on CeO 2 (111) Surface

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

    Wang, Weina; Thevuthasan, S.; Wang, Wenliang; Yang, Ping

    2016-01-11

    We investigated trimethylacetic acid (TMAA) adsorption on stoichiometric and oxygen-deficient CeO2(111) surfaces using density functional theory that accounts for the on-site Coulomb interaction via a Hubbard term (DFT+U) and long-range dispersion correction. Both the molecular state and dissociative state (TMAA → TMA– + H+) were identified on stoichiometric and oxygen-deficient CeO2(111) surfaces. For the stoichiometric surface, two thermodynamically favorable configurations with adsorption energies of the order of -30 kcal/mol are identified; one is a molecule adsorption state, and the other one is a dissociative state. For the oxygen-deficient surface, dissociative states are more favorable than molecular states. Moreover, the mostmore » favorable configuration is the dissociative adsorption of TMAA with the adsorption energy of the order of -77 kcal/mol. The dissociated TMA moiety takes the position of oxygen vacancy, forming three Ce–O bonds. The signature vibrational frequencies for these thermodynamically stable structures are reported as well as their electronic structures. The effects of long-range dispersion interactions are found to be negligible for geometries but important for adsorption energies.« less

  10. Formation of the diphenyl molecule in the crossed beam reaction of phenyl radicals with benzene

    SciTech Connect (OSTI)

    Zhang Fangtong; Gu Xibin; Kaiser, Ralf I.

    2008-02-28

    The chemical dynamics to form the D5-diphenyl molecule, C{sub 6}H{sub 5}C{sub 6}D{sub 5}, via the neutral-neutral reaction of phenyl radicals (C{sub 6}H{sub 5}) with D6-benzene (C{sub 6}D{sub 6}), was investigated in a crossed molecular beams experiment at a collision energy of 185 kJ mol{sup -1}. The laboratory angular distribution and time-of-flight spectra of the C{sub 6}H{sub 5}C{sub 6}D{sub 5} product were recorded at mass to charge m/z of 159. Forward-convolution fitting of our data reveals that the reaction dynamics are governed by an initial addition of the phenyl radical to the {pi} electron density of the D6-benzene molecule yielding a short-lived C{sub 6}H{sub 5}C{sub 6}D{sub 6} collision complex. The latter undergoes atomic deuterium elimination via a tight exit transition state located about 30 kJ mol{sup -1} above the separated reactants; the overall reaction to form D5-diphenyl from phenyl and D6-benzene was found to be weakly exoergic. The explicit identification of the D5-biphenyl molecules suggests that in high temperature combustion flames, a diphenyl molecule can be formed via a single collision event between a phenyl radical and a benzene molecule.

  11. Efficient photoluminescence of Dy{sup 3+} at low concentrations in nanocrystalline ZrO{sub 2}

    SciTech Connect (OSTI)

    Diaz-Torres, L.A.; Rosa, E. de la Salas, P.; Romero, V.H.; Angeles-Chavez, C.

    2008-01-15

    Nanocrystalline ZrO{sub 2}:Dy{sup 3+} were prepared by sol-gel and the structural and photoluminescence properties characterized. The crystallite size ranges from 20 to 50 nm and the crystalline phase is a mixture of tetragonal and monoclinic structure controlled by dopant concentration. Strong white light produced by the host emission band centered at {approx}460 nm and two strong Dy{sup 3+} emission bands, blue (488 nm) and yellow (580 nm), under direct excitation at 350 nm were observed. The highest efficiency was obtained for 0.5 mol% of Dy{sup 3+}. Emission is explained in terms of high asymmetry of the host suggesting that Dy{sup 3+} are substituted mainly into Zr{sup 4+} lattice sites at the crystallite surface. Luminescence quenching is explained in terms of cross-relaxation of intermediate Dy{sup 3+} levels. - Graphical abstract: White light emission from {approx}70 nm ZrO{sub 2}:Dy{sup 3+} nanocrystals. The highest efficiency was obtained for 0.5 mol% of dopant and the dominant crystalline structure was monoclinic.

  12. Preparation, characterization of the Ta-doped ZnO nanoparticles and their photocatalytic activity under visible-light illumination

    SciTech Connect (OSTI)

    Kong Jizhou; Li Aidong; Zhai Haifa; Gong Youpin; Li Hui; Wu Di

    2009-08-15

    This paper describes a novel catalyst of the Ta-doped ZnO nanocrystals prepared by a modified polymerizable complex method using the water-soluble tantalum precursor as the sources of Ta. The catalysts were characterized by means of various analytical techniques as a function of Ta content (x=0-4 mol%) systematically. A remarkable advantage of the results was confirmed that dopant Ta enhanced the visible-light absorption of ZnO and the low-solubility tantalum doping could restrain the growth of crystal and minish the particle size. The relationship between the physicochemical property and the photocatalytic performance was discussed, and it was found that the photocatalytic activity in the photochemical degradation of methylene blue under visible-light irradiation (lambda>=420 nm) was dependent on the contents of the dopant, which could affect the particle size, concentration of surface hydroxyl groups and active hydrogen-related defect sites, and the visible-light absorption. The highest photocatalytic activity was obtained for the 1.0 mol% Ta-doped ZnO sample. - Graphical abstract: The addition of the tantalum into ZnO prepared by a modified polymerizable complex method not only restrains the growth of crystal, minish the particle size, but also changes the nanocrystal morphology.

  13. Synthesis of Aza-m-Xylylene diradicals with large singlet-triplet energy gap and statistical analyses of their EPR spectra

    SciTech Connect (OSTI)

    Olankitwanit, Arnon; Pink, Maren; Rajca, Suchada; Rajca, Andrzej

    2014-10-08

    We describe synthesis and characterization of a derivative of aza-m-xylylene, diradical 2, that is persistent in solution at room temperature with the half-life measured in minutes (~80250 s) and in which the triplet ground state is below the lowest singlet state by >10 kcal mol?. The triplet ground states and ?EST of 2 in glassy solvent matrix are determined by a new approach based on statistical analyses of their EPR spectra. Characterization and analysis of the analogous diradical 1 are carried out for comparison. Statistical analyses of their EPR spectra reliably provide improved lower bounds for ?EST (from >0.4 to >0.6 kcal mol?) and are compatible with a wide range of relative contents of diradical vs monoradical, including samples in which the diradical and monoradical are minor and major components, respectively. This demonstrates a new powerful method for the determination of the triplet ground states and ?EST applicable to moderately pure diradicals in matrices.

  14. Ultra-low-temperature reactions of C({sup 3}P{sub 0}) atoms with benzene molecules in helium droplets

    SciTech Connect (OSTI)

    Krasnokutski, Serge A. Huisken, Friedrich

    2014-12-07

    The reaction of carbon atoms with benzene has been investigated in liquid helium droplets at T = 0.37 K. We found an addition of the carbon atom to form an initial intermediate complex followed by a ring opening and the formation of a seven-membered ring. In contrast to a previous gas phase study, the reaction is frozen after these steps and the loss of hydrogen does not occur. A calorimetric technique was applied to monitor the energy balance of the reaction. It was found that more than 267 kJ mol{sup ?1} were released in this reaction. This estimation is in line with quantum chemical calculations of the formation energy of a seven-membered carbon ring. It is suggested that reactions of this kind could be responsible for the low abundance of small polycyclic aromatic hydrocarbon molecules in the interstellar medium. We also found the formation of weakly bonded water-carbon adducts, in which the carbon atom is linked to the oxygen atom of the water molecule with a binding energy of about 33.4 kJ mol{sup ?1}.

  15. The role of hydrogen bonds in protein folding and protein association

    SciTech Connect (OSTI)

    Ben-Naim, A. (National Inst. of Health, Bethesda, MD (USA))

    1991-02-07

    The contribution of a pair of functional groups that can form either intermolecular or intramolecular hydrogen bonds to the total standard free energy of the process of protein folding or protein association is examined. It is found that this contribution can be quite large, either positive or negative, depending on the particular process and on the solvent density. This is in contrast to the common belief that the hydrogen-bond energies tend to be compensated in these processes. For the binding process, in which the two functional groups are completely removed from the aqueous environment, the contribution of such a pair of functional groups to {Delta}G can be as high as +6.4 kcal/mol. This is the main reason why hydrophobic rather than hydrophilic surfaces tend to attach to each other. In contrast, when the two functional groups are only partially removed from the aqueous environment, as in the case of the formation of {alpha}-helix, their contribution to {Delta}G can be negative and of the order of about 1 kcal/mol.

  16. Mechanism and kinetics of peptide partitioning into membranes

    SciTech Connect (OSTI)

    Ulmschneider, Martin [University of Oxford; Killian, J Antoinette [University of Utrecht; Doux, Jacques P. F. [University of Utrecht; Smith, Jeremy C [ORNL; Ulmschneider, Jakob [University of Heidelberg

    2010-02-01

    Partitioning properties of transmembrane (TM) polypeptide segments directly determine membrane protein folding, stability, and function, and their understanding is vital for rational design of membrane active peptides. However, direct determination of water-to-bilayer transfer of TM peptides has proved difficult. Experimentally, sufficiently hydrophobic peptides tend to aggregate, while atomistic computer simulations at physiological temperatures cannot yet reach the long time scales required to capture partitioning. Elevating temperatures to accelerate the dynamics has been avoided, as this was thought to lead to rapid denaturing. However, we show here that model TM peptides (WALP) are exceptionally thermostable. Circular dichroism experiments reveal that the peptides remain inserted into the lipid bilayer and are fully helical, even at 90 C. At these temperatures, sampling is 50 500 times faster, sufficient to directly simulate spontaneous partitioning at atomic resolution. A folded insertion pathway is observed, consistent with three-stage partitioning theory. Elevated temperature simulation ensembles further allow the direct calculation of the insertion kinetics, which is found to be first-order for all systems. Insertion barriers are Hin = 15 kcal/mol for a general hydrophobic peptide and 23 kcal/mol for the tryptophan-flanked WALP peptides. The corresponding insertion times at room temperature range from 8.5 s to 163 ms. High-temperature simulations of experimentally validated thermostable systems suggest a new avenue for systematic exploration of peptide partitioning properties.

  17. Lasing characteristics of ZrO{sub 2}Y{sub 2}O{sub 3}Ho{sub 2}O{sub 3} crystal

    SciTech Connect (OSTI)

    Borik, M A; Lomonova, E E; Kulebyakin, A V; Ushakov, S N; Lyapin, A A; Ryabochkina, P A; Chabushkin, A N

    2013-09-30

    The spectral dependences of the gain cross section of the {sup 5}I{sub 8} ? {sup 5}I{sub 7}, {sup 5}I{sub 7} ? {sup 5}I{sub 8} transition of Ho{sup 3+} ions in the ZrO{sub 2} 13.6 mol % Y{sub 2}O{sub 3} 0.4 mol % Ho{sub 2}O{sub 3} crystal are calculated at different relative population inversions using the absorption and luminescence spectra of the {sup 5}I{sub 8} ? {sup 5}I{sub 7} and {sup 5}I{sub 7} ? {sup 5}I{sub 8} transitions of Ho{sup 3+} ions at T=''300'' K. Lasing of these crystals at the {sup 5}I{sub 7} ? {sup 5}I{sub 8} transition is obtained for the first time under pumping by a Tm : YLiF{sub 4} laser (?{sub p} = 1.905 ?m). The lasing wavelength is 2.17 ?m. (lasers)

  18. Thermodynamics of formation of coffinite, USiO₄

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

    Guo, Xiaofeng; Szenknect, Stéphanie; Mesbah, Adel; Labs, Sabrina; Clavier, Nicolas; Poinssot, Christophe; Ushakov, Sergey V.; Curtius, Hildegard; Bosbach, Dirk; Ewing, Rodney C.; et al

    2015-05-26

    Coffinite, USiO₄, is an important U(IV) mineral, but its thermodynamic properties are not well-constrained. In this work, two different coffinite samples were synthesized under hydrothermal conditions and purified from a mixture of products. The enthalpy of formation was obtained by high temperature oxide melt solution calorimetry. Coffinite is energetically metastable with respect to a mixture of UO₂ (uraninite) and SiO₂ (quartz) by 25.6 ± 3.9 kJ/mol. Its standard enthalpy of formation from the elements at 25 °C is -1,970.0 ± 4.2 kJ/mol. Decomposition of the two samples was characterized by X-ray diffraction and by thermogravimetry and differential scanning calorimetry coupledmore » with mass spectrometric analysis of evolved gases. Coffinite slowly decomposes to U₃O₈ and SiO₂ starting around 450 °C in air and thus has poor thermal stability in the ambient environment. The energetic metastability explains why coffinite cannot be synthesized directly from uraninite and quartz but can be made by low temperature precipitation in aqueous and hydrothermal environments. These thermochemical constraints are in accord with observations of the occurrence of coffinite in nature and are relevant to spent nuclear fuel corrosion.« less

  19. Activation of small alkanes in Ga-exchanged zeolites: A quantum chemical study of ethane dehydrogenation

    SciTech Connect (OSTI)

    Frash, M.V.; Santen, R.A. van

    2000-03-23

    Quantum chemical calculations on the mechanism of ethane dehydrogenation catalyzed by Ga-exchanged zeolites have been undertaken. Two forms of gallium, adsorbed dihydride gallium ion GaH{sub 2}+Z{sup {minus}} and adsorbed gallyl ion [Ga=O]{sup +}Z{sup {minus}}, were considered. It was found that GaH{sub 2}{sup +}Z{sup {minus}} is the likely active catalyst. On the contrary, [Ga=O]{sup +}Z{sup {minus}} cannot be a working catalyst in nonoxidative conditions, because regeneration of this form is very difficult. Activation of ethane by GaH{sub 2}{sup +}Z{sup {minus}} occurs via an alkyl mechanism and the gallium atom acts as an acceptor of the ethyl group. The carbenium activation of ethane, with gallium abstracting a hydride ion, is much (ca. 51 kcal/mol) more difficult. The catalytic cycle for the alkyl activation consists of three elementary steps: (1) rupture of the ethane C-H bond; (2) formation of dihydrogen from the Bronsted proton and hydrogen bound to Ga; and (3) formation of ethene from the ethyl group bound to Ga. The best estimates (MP2/6--311++G(2df,p)//B3LYP/6--31G*) for the activation energies of these three steps are 36.9, ca. 0, and 57.9 kcal/mol, respectively.

  20. A novel plug-flow digester for biogasification of conventional and hazardous organics

    SciTech Connect (OSTI)

    Ghosh, S.; Kato, Y.; Liu, T.; Fukushi, K.

    1996-12-31

    A novel plug-flow digestion system of simple construction was designed, fabricated and operated for several years with a synthetic mixture of solid and liquid wastes simulating conditions south of the US-Mexican border and other developing countries. Benzene, toluene, and o-xylene (BTX) were mixed with the synthetic feed in several phases of this research to simulate field conditions where these solvents are discharged to public sewers and mixed with non-hazardous pollutants. The mesophilic plug-flow digester exhibited a high gas yield of 0.46 SCM /kg VS added, a methane content of 77 mol%, and a VS reduction of 75% at an HRT of 13 days with a 96% biodegradation of the feed toluene. At a feed concentration of 50 mg/l, toluene did not inhibit anaerobic fermentation. Gas and methane yields, and VS and COD conversion efficiencies were about the same with or without toluene present in the feed. At a reduced HRT of 8 days, a high feed COD concentration of 50,000 mg/l, and a loading rate of 0.48 kg VS/m{sup 3}-day, the digester afforded a gas yield of 3.1 SCM /kg VS added, and a methane content of 67 mol%. Benzene, toluene, and o-xylene were biodegraded at efficiencies of 94%, 90%, and 88%, respectively. The degradation kinetics of the xenobiotic compound could be described by a model based on cometabolic degradation of these secondary substrates.

  1. Interaction of alkanes with unsaturated metal centers. 2. Complexes of alkanes and fluoroalkanes with W(CO) sub 5 in the gas phase

    SciTech Connect (OSTI)

    Brown, C.E.; Ishikawa, Yoichi; Hackett, P.A.; Rayner, D.M. )

    1990-03-28

    Time-resolved infrared spectroscopy has been used to study the interaction of a range of open-chain, cyclic, and fluorine-substituted alkanes with the 16-electron species W(CO){sub 5}. W(CO){sub 5} forms reversible complexes with all the unsubstituted alkanes studied except CH{sub 4}. The equilibrium constant K{sub p} = (W(CO){sub 5}L)/((W(CO){sub 5})p(L)), at 300 K, increases with carbon number from 610 {plus minus} 100 atm{sup {minus}1} in cyclohexane. binding energies have also been obtained through temperature studies. They are in the range 7-11 kcal mol{sup {minus}1}, again increasing with the size of the alkanes. In the case of CH{sub 4}, a binding energy K5 kcal mol{sup {minus}1} is implied by their inability to observe a complex. Correlation of the binding energies with C-H {sigma} MO stabilization energies is consistent with a simple molecular orbital picture involving formation of a 2-electron, 3-center C-H-M bond through {sigma} {yields} M electron donation.

  2. Determination of hydrogen diffusion coefficients in F82H by hydrogen depth profiling with a tritium imaging plate technique

    SciTech Connect (OSTI)

    Higaki, M.; Otsuka, T.; Hashizume, K.; Tokunaga, K.; Ezato, K.; Suzuki, S.; Enoeda, M.; Akiba, M.

    2015-03-15

    Hydrogen diffusion coefficients in a reduced activation ferritic/martensitic steel (F82H) and an oxide dispersion strengthened F82H (ODS-F82H) have been determined from depth profiles of plasma-loaded hydrogen with a tritium imaging plate technique (TIPT) in the temperature range from 298 K to 523 K. Data on hydrogen diffusion coefficients, D, in F82H, are summarized as D [m{sup 2}*s{sup -1}] =1.1*10{sup -7}exp(-16[kJ mol{sup -1}]/RT). The present data indicate almost no trapping effect on hydrogen diffusion due to an excess entry of energetic hydrogen by the plasma loading, which results in saturation of the trapping sites at the surface and even in the bulk. In the case of ODS-F82H, data of hydrogen diffusion coefficients are summarized as D [m{sup 2}*s{sup -1}] =2.2*10{sup -7}exp(-30[kJ mol{sup -1}]/RT) indicating a remarkable trapping effect on hydrogen diffusion caused by tiny oxide particles (Y{sub 2}O{sub 3}) in the bulk of F82H. Such oxide particles introduced in the bulk may play an effective role not only on enhancement of mechanical strength but also on suppression of hydrogen penetration by plasma loading.

  3. Characterization of tungsten films and their hydrogen permeability

    SciTech Connect (OSTI)

    Nemani?, Vincenc Kova?, Janez; Lungu, Cristian; Porosnicu, Corneliu; Zajec, Bojan

    2014-11-01

    Prediction of tritium migration and its retention within fusion reactors is uncertain due to a significant role of the structural disorder that is formed on the surface layer after plasma exposure. Tungsten films deposited by any of the suitable methods are always disordered and contain a high density of hydrogen traps. Experiments on such films with hydrogen isotopes present a suitable complementary method, which improves the picture of the hydrogen interaction with fusion relevant materials. The authors report on the morphology, composition, and structure of tungsten films deposited by the thermionic vacuum arc method on highly permeable Eurofer substrates. Subsequently, hydrogen permeation studies through these films were carried out in a wide pressure range from 20 to 1000 mbars at 400?C. The final value of the permeation coefficient for four samples after 24?h at 400?C was between P?=?3.2??10{sup ?14}?mol?H{sub 2}/(m?s?Pa{sup 0.5}) and P?=?1.1??10{sup ?15}?mol H{sub 2}/(m s Pa{sup 0.5}). From the time evolution of the permeation flux, it was shown that diffusivity was responsible for the difference in the steady fluxes, as solubility was roughly the same. This is confirmed by XRD data taken on these samples.

  4. Synthesis, characterization and optical properties of hybrid PVAZnO nanocomposite: A composition dependent study

    SciTech Connect (OSTI)

    Hemalatha, K.S. [Department of Physics, Bangalore University, Bangalore 560 056, Karnataka (India); Department of Physics, Maharani's Science College for Women, Palace Road, Bangalore 560 001, Karnataka (India); Rukmani, K., E-mail: rukmani9909@yahoo.co.in [Department of Physics, Bangalore University, Bangalore 560 056, Karnataka (India); Suriyamurthy, N. [Radiological Safety Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, Tamil Nadu (India); Nagabhushana, B.M. [Department of Chemistry, M.S. Ramaiah Institute of Technology, Bangalore 560 054, Karnataka (India)

    2014-03-01

    Graphical abstract: - Highlights: ZnO nanoparticles were prepared by solution combustion method. PVAZnO nanocomposites were synthesized by solution casting method. Doped and undoped films were characterized using different techniques. Red shift in optical band gap was observed in Nanocomposite films with respect to nano ZnO. Photoluminescence intensity was found to be optimum for PVA10 mol% ZnO nanocomposite film. - Abstract: Nanocomposites of poly vinyl alcohol (PVA) and ZnO have been synthesized using the solution casting technique for different concentrations of nano ZnO powder prepared by low temperature solution combustion method. The formation of polymer nanocomposite and changes in the structural and micro structural properties of the materials were investigated by X-ray diffraction, Energy dispersive X ray spectroscopy and optical microscopy techniques (FTIR and UVVisible). The surface morphology of PVAZnO nanocomposite films were elucidated using Scanning Electron Microscopy. The optical absorption spectrum of nano ZnO shows blue shift in the optical band gap energy with respect to characteristic bulk ZnO at room temperature, whereas PVAZnO hybrid films show red shift with respect to nano ZnO. The photoluminescence studies show that the intensity of the blue emission (470 nm) varies with change in concentration of ZnO with an optimum intensity observed at 10 mol% of ZnO.

  5. Glass-ceramic joint and method of joining

    DOE Patents [OSTI]

    Meinhardt, Kerry D [Richland, WA; Vienna, John D [West Richland, WA; Armstrong, Timothy R [Clinton, TN; Pederson, Larry R [Kennewick, WA

    2003-03-18

    The present invention is a glass-ceramic material and method of making useful for joining a solid ceramic component and at least one other solid component. The material is a blend of M1-M2-M3, wherein M1 is BaO, SrO, CaO, MgO, or combinations thereof, M2 is Al.sub.2 O.sub.3, present in the blend in an amount from 2 to 15 mol %, M3 is SiO.sub.2 with up to 50 mol % B.sub.2 O.sub.3 that substantially matches a coefficient of thermal expansion of the solid electrolyte. According to the present invention, a series of glass ceramics in the M1-Al.sub.2 O.sub.3 -M3 system can be used to join or seal both tubular and planar solid oxide fuel cells, oxygen electrolyzers, and membrane reactors for the production of syngas, commodity chemicals and other products.

  6. Catalytic Ionic Hydrogenation of Ketones by {[Cp*Ru(CO)2]2(-H)}+

    SciTech Connect (OSTI)

    Bullock, R.M.; Fagan, P.J.; Voges, M.H.

    2010-02-22

    {l_brace}[Cp*Ru(CO){sub 2}]{sub 2}({mu}-H){r_brace}{sup +}OTf{sup -} functions as a homogeneous catalyst precursor for hydrogenation of ketones to alcohols, with hydrogenations at 1 mol % catalyst loading at 90 C under H{sub 2} (820 psi) proceeding to completion and providing >90% yields. Hydrogenation of methyl levulinate generates {gamma}-valerolactone, presumably by ring-closing of the initially formed alcohol with the methyl ester. Experiments in neat Et{sub 2}C=O show that the catalyst loading can be <0.1 mol % and that at least 1200 turnovers of the catalyst can be obtained. These reactions are proposed to proceed by an ionic hydrogenation pathway, with the highly acidic dihydrogen complex [Cp*Ru(CO){sub 2}({eta}{sup 2}-H{sub 2})]{sup +}OTf{sup -} being formed under the reaction conditions from reaction of H2 with {l_brace}[Cp*Ru(CO){sub 2}]{sub 2}({mu}-H){r_brace}{sup +}OTf{sup -}.

  7. Kinetics of hydrogen isotope exchange in β-phase Pd-H-D

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

    Luo, Weifang; Cowgill, Donald F.

    2015-07-22

    Hydrogen isotope gas exchange within palladium powders is examined using a batch-type reactor coupled to a residual gas analyzer (RGA). Furthermore, the exchange rates in both directions (H2 + PdD and D2 + PdH) are measured in the temperature range 178–323 K for the samples with different particle sizes. The results show this batch-type exchange is closely approximated as a first-order kinetic process with a rate directly proportional to the surface area of the powder particles. An exchange rate constant of 1.40 ± 0.24 μmol H2/atm cm2 s is found for H2 + PdD at 298 K, 1.4 times highermore » than that for D2 + PdH, with an activation energy of 25.0 ± 3.2 kJ/mol H for both exchange directions. Finally, a comparison of exchange measurement techniques shows these coefficients, and the fundamental exchange probabilities are in good agreement with those obtained by NMR and flow techniques.« less

  8. Kinetic and Thermodynamic Investigation of Hydrogen Release from Ethane 1,2-di-amineborane

    SciTech Connect (OSTI)

    Neiner, Doinita; Karkamkar, Abhijeet J.; Bowden, Mark; Choi, Young Joon; Luedtke, Avery T.; Holladay, Jamelyn D.; Fisher, Allison M.; Szymczak, Nathaniel; Autrey, Thomas

    2011-07-18

    The thermodynamics and kinetics of hydrogen (H2) release from ethane 1,2-di-amineborane (EDAB, BH3NH2CH2CH2NH2BH3) were measured using Calvet and differential scanning calorimetry (DSC), pressure-composition isotherms, and volumetric gas-burette experiments. The results presented here indicate that EDAB releases ~ 9 wt.% H2 at temperatures ranging from 100 C to 200 C in two moderately exothermic steps, approximately -101 kJ/mol H2 and -3.81 kJ/mol H2. Isothermal kinetic analysis shows that EDAB is more stable than ammonia borane (AB) at temperatures lower than 100C; however, the rates of hydrogen release are faster for EDAB than for AB at temperatures higher than 120C. In addition, no volatile impurities in the H2 released by EDAB were detected by mass spectrometry upon heating with 1C/min to 200C in a calorimeter.

  9. Ethylenediamine salt of 5-nitrotetrazole and preparation

    DOE Patents [OSTI]

    Lee, Kien-yin (Los Alamos, NM); Coburn, Michael D. (Los Alamos, NM)

    1985-01-01

    Ethylenediamine salt of 5-nitrotetrazole and preparation. This salt has been found to be useful as an explosive alone and in eutectic mixtures with ammonium nitrate and/or other explosive compounds. Its eutectic with ammonium nitrate has been demonstrated to behave in a similar manner to a monomolecular explosive such as TNT, and is less sensitive than the pure salt. Moreover, this eutectic mixture, which contains 87.8 mol % of ammonium nitrate, is close to the CO.sub.2 -balanced composition of 90 mol %, and has a relatively low melting point of 110.5 C. making it readily castable. The ternary eutectic system containing the ethylenediamine salt of 5-nitrotetrazole, ammonium nitrate and ethylenediamine dinitrate has a eutectic temperature of 89.5 C. and gives a measured detonation pressure of 24.8 GPa, which is 97.6% of the calculated value. Both the pure ethylenediamine salt and its known eutectic compounds behave in substantially ideal manner. Methods for the preparation of the salt are described.

  10. Molecular dynamics simulations of the electrical double layer on smectite surfaces contacting concentrated mixed electrolyte (NaCl-CaCl?) solutions

    SciTech Connect (OSTI)

    Bourg, Ian C.; Sposito, Garrison

    2011-01-01

    We report new molecular dynamics results elucidating the structure of the electrical double layer (EDL) on smectite surfaces contacting mixed NaClCaCl2 electrolyte solutions in the range of concentrations relevant to pore waters in geologic repositories for CO2 or high-level radioactive waste (0.341.83 molc dm-3). Our results confirm the existence of three distinct ion adsorption planes (0-, ?-, and d-planes), often assumed in EDL models, but with two important qualifications: (1) the location of the ?- and d-planes are independent of ionic strength or ion type and (2) indifferent electrolyte ions can occupy all three planes. Charge inversion occurred in the diffuse ion swarm because of the affinity of the clay surface for CaCl+ ion pairs. Therefore, at concentrations {>=0.34 molc dm-3}, properties arising from long-range electrostatics at interfaces (electrophoresis, electro-osmosis, co-ion exclusion, colloidal aggregation) will not be correctly predicted by most EDL models. Co-ion exclusion, typically neglected by surface speciation models, balanced a large part of the clay mineral structural charge in the more concentrated solutions. Water molecules and ions diffused relatively rapidly even in the first statistical water monolayer, contradicting reports of rigid ice-like structures for water on clay mineral surfaces.

  11. Aluminum doped zirconia nanopowders: Wet-chemical synthesis and structural analysis by Rietveld refinement

    SciTech Connect (OSTI)

    Srdic, Vladimir V. Rakic, Srdan; Cvejic, Zeljka

    2008-10-02

    Alumina/zirconia nanopowders, with up to 20 mol% Al{sub 2}O{sub 3}, were prepared by wet-chemical synthesis technique, using controlled hydrolysis of alkoxides. The as-synthesized powders are amorphous, have very high specific surface area and the corresponding particle size smaller than 4 nm. Amorphous powders with 0, 10 and 20 mol% Al{sub 2}O{sub 3} crystallize at 460, 692 and 749 deg. C, respectively, as a single-phase tetragonal zirconia, without any traces of alumina phases. Rietvled refinement of X-ray diffraction data, used for the detailed structural analysis of annealed nanopowders, showed that the high-temperature zirconia phase is stabilized due to the formation of ZrO{sub 2}/Al{sub 2}O{sub 3} solid solutions. High solubility of alumina in the tetragonal zirconia (up to 28.6 at% Al{sup 3+}) and stabilization of tetragonal zirconia solid solution up to high temperature (as high as 1150 deg. C) were also confirmed.

  12. Effect of Yttria Content on the Zirconia Unit Cell Parameters

    SciTech Connect (OSTI)

    Krogstad, Jessica A.; Lepple, Maren; Gao, Yan; Lipkin, Don M.; Levi, Carlos G.

    2012-02-06

    The relationship between yttria concentration and the unit cell parameters in partially and fully stabilized zirconia has been reassessed, motivated by the need to improve the accuracy of phase analysis upon decomposition of t{prime}-based thermal barrier coatings. Compositions ranging from 6 to 18 mol% YO{sub 1.5} were synthesized and examined by means of high-resolution X-ray diffraction. Lattice parameters were determined using the Rietveld refinement method, a whole-pattern fitting procedure. The revised empirical relationships fall within the range of those published previously. However, efforts to achieve superior homogeneity of the materials, as well as accuracy of the composition and lattice parameters, provide increased confidence in the reliability of these correlations for use in future studies. Additional insight into the potential sources for scatter previously reported for the transition region ({approx}12-14 mol% YO{sub 1.5}), where tetragonal and cubic phases have been observed to coexist, is also provided. Implications on the current understanding of stabilization mechanisms in zirconia are discussed.

  13. Molecular basis of endosomal-membrane association for the dengue virus envelope protein

    SciTech Connect (OSTI)

    Rogers, David M.; Kent, Michael S.; Rempe, Susan B.

    2015-01-02

    Dengue virus is coated by an icosahedral shell of 90 envelope protein dimers that convert to trimers at low pH and promote fusion of its membrane with the membrane of the host endosome. We provide the first estimates for the free energy barrier and minimum for two key steps in this process: host membrane bending and protein–membrane binding. Both are studied using complementary membrane elastic, continuum electrostatics and all-atom molecular dynamics simulations. The predicted host membrane bending required to form an initial fusion stalk presents a 22–30 kcal/mol free energy barrier according to a constrained membrane elastic model. Combined continuum and molecular dynamics results predict a 15 kcal/mol free energy decrease on binding of each trimer of dengue envelope protein to a membrane with 30% anionic phosphatidylglycerol lipid. The bending cost depends on the preferred curvature of the lipids composing the host membrane leaflets, while the free energy gained for protein binding depends on the surface charge density of the host membrane. The fusion loop of the envelope protein inserts exactly at the level of the interface between the membrane's hydrophobic and head-group regions. As a result, the methods used in this work provide a means for further characterization of the structures and free energies of protein-assisted membrane fusion.

  14. Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water–acetonitrile mixture

    SciTech Connect (OSTI)

    Kasai, Yukako; Yoshida, Norio Nakano, Haruyuki

    2015-05-28

    The co-solvent effect on the proton transfer reaction of glycine in a water–acetonitrile mixture was examined using the reference interaction-site model self-consistent field theory. The free energy profiles of the proton transfer reaction of glycine between the carboxyl oxygen and amino nitrogen were computed in a water–acetonitrile mixture solvent at various molar fractions. Two types of reactions, the intramolecular proton transfer and water-mediated proton transfer, were considered. In both types of the reactions, a similar tendency was observed. In the pure water solvent, the zwitterionic form, where the carboxyl oxygen is deprotonated while the amino nitrogen is protonated, is more stable than the neutral form. The reaction free energy is −10.6 kcal mol{sup −1}. On the other hand, in the pure acetonitrile solvent, glycine takes only the neutral form. The reaction free energy from the neutral to zwitterionic form gradually increases with increasing acetonitrile concentration, and in an equally mixed solvent, the zwitterionic and neutral forms are almost isoenergetic, with a difference of only 0.3 kcal mol{sup −1}. The free energy component analysis based on the thermodynamic cycle of the reaction also revealed that the free energy change of the neutral form is insensitive to the change of solvent environment but the zwitterionic form shows drastic changes. In particular, the excess chemical potential, one of the components of the solvation free energy, is dominant and contributes to the stabilization of the zwitterionic form.

  15. Equations of state of ice VI and ice VII at high pressure and high temperature

    SciTech Connect (OSTI)

    Bezacier, Lucile; Hanfland, Michael; Journaux, Baptiste; Perrillat, Jean-Philippe; Cardon, Herv; Daniel, Isabelle

    2014-09-14

    High-pressure H{sub 2}O polymorphs among which ice VI and ice VII are abundant in the interiors of large icy satellites and exo-planets. Knowledge of the elastic properties of these pure H{sub 2}O ices at high-temperature and high-pressure is thus crucial to decipher the internal structure of icy bodies. In this study we assess for the first time the pressure-volume-temperature (PVT) relations of both polycrystalline pure ice VI and ice VII at high pressures and temperatures from 1 to 9 GPa and 300 to 450 K, respectively, by using in situ synchrotron X-ray diffraction. The PVT data are adjusted to a second-order Birch-Murnaghan equation of state and give V{sub 0} = 14.17(2) cm{sup 3}?mol{sup ?1}, K{sub 0} = 14.05(23) GPa, and ?{sub 0} = 14.6(14) 10{sup ?5} K{sup ?1} for ice VI and V{sub 0} = 12.49(1) cm{sup 3}?mol{sup ?1}, K{sub 0} = 20.15(16) GPa, and ?{sub 0} = 11.6(5) 10{sup ?5} K{sup ?1} for ice VII.

  16. The solubility of hydrogen in plutonium in the temperature range 475 to 825 degrees centigrade

    SciTech Connect (OSTI)

    Allen, T.H.

    1991-01-01

    The solubility of hydrogen (H) in plutonium metal (Pu) was measured in the temperature range of 475 to 825{degree}C for unalloyed Pu (UA) and in the temperature range of 475 to 625{degree}C for Pu containing two-weight-percent gallium (TWP). For TWP metal, in the temperature range 475 to 600{degree}C, the saturated solution has a maximum hydrogen to plutonium ration (H/Pu) of 0.00998 and the standard enthalpy of formation ({Delta}H{degree}{sub f(s)}) is (-0.128 {plus minus} 0.0123) kcal/mol. The phase boundary of the solid solution in equilibrium with plutonium dihydride (PuH{sub 2}) is temperature independent. In the temperature range 475 to 625{degree}C, UA metal has a maximum solubility at H/Pu = 0.011. The phase boundary between the solid solution region and the metal+PuH{sub 2} two-phase region is temperature dependent. The solubility of hydrogen in UA metal was also measured in the temperature range 650 to 825{degree}C with {Delta}H{degree}{sub f(s)} = (-0.104 {plus minus} 0.0143) kcal/mol and {Delta}S{degree}{sub f(s)} = 0. The phase boundary is temperature dependent and the maximum hydrogen solubility has H/Pu = 0.0674 at 825{degree}C. 52 refs., 28 figs., 9 tabs.

  17. Hydrogen isotope trapping in Al-Cu binary alloys

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

    Chao, Paul; Karnesky, Richard A.

    2016-02-03

    In this study, the trapping mechanisms for hydrogen isotopes in Al–X Cu (0.0 at. % < X < 3.5 at. %) alloys were investigated using thermal desorption spectroscopy (TDS), electrical conductivity, and differential scanning calorimetry. Constant heating rate TDS was used to determine microstructural trap energies and occupancies. In addition to the trapping states in pure Al reported in the literature (interstitial lattice sites, dislocations, and vacancies), a trap site due to Al–Cu intermetallic precipitates is observed. The binding energy of this precipitate trap is (18 ± 3) kJ•mol–1 (0.19 ± 0.03 eV). Typical occupancy of this trap is high;more » for Al–2.6 at. % Cu (a Cu composition comparable to that in AA2219) charged at 200 °C with 130 MPa D2 for 68 days, there is ca. there is 3.15×10–7 mol D bound to the precipitate trap per mol of Al, accounting for a third of the D in the charged sample.« less

  18. Multiphoton photoluminescence contrast in switched Mg:LiNbO{sub 3} and Mg:LiTaO{sub 3} single crystals

    SciTech Connect (OSTI)

    Reichenbach, P., E-mail: philipp.reichenbach@iapp.de; Kmpfe, T.; Thiessen, A.; Haumann, A.; Eng, L. M. [Institut fr Angewandte Photophysik, Technische Universitt Dresden, George-Bhr-Str. 1, 01069 Dresden (Germany); Woike, T. [Institut fr Strukturphysik, Technische Universitt Dresden, Zellescher Weg 16, 01069 Dresden (Germany)

    2014-09-22

    We observed a multiphoton luminescence contrast between virgin and single-switched domains in Mg-doped LiNbO{sub 3} (LNO) and LiTaO{sub 3} (LTO) single crystals with different doping levels of 07?mol. % and 08?mol. %, respectively. A luminescence contrast in the range of 3% was measured between as-grown and electrically inverted domain areas in Mg:LNO samples, while the contrast reaches values of up to 30% for the Mg:LTO case. Under annealing, an exponential decay of the domain contrast was observed. The activation energy of about 1?eV being determined for the decay allowed a comparison with reported activation energies of associated defects, clearly illustrating a strong connection between thermal contrast decay and the H{sup +} and Li{sup +}-ion mobility. Finally, performing similar experiments on oxidized samples undoubtedly demonstrated that the origin of the reported luminescence contrast is strongly connected with lithium ions.

  19. 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.

  20. Thermal analysis and temperature dependent dielectric responses of Co doped anatase TiO{sub 2} nanoparticles

    SciTech Connect (OSTI)

    Alamgir; Khan, Wasi; Ahammed, Nashiruddin; Naqvi, A. H.; Ahmad, Shabbir

    2015-05-15

    Nanoparticles (NPs) of pure and 5?mol % cobalt doped TiO{sub 2} synthesized through acid modified sol-gel method were characterized to understand their thermal, structural, morphological, and temperature dependent dielectric properties. Thermogravimetric analysis (TGA) has been used for thermal studies and indicates the weight loss in two steps due to the removal of residual organics. X-ray diffraction study was employed to confirm the formation of single anatase phase with tetragonal symmetry for both pure and 5?mol % Co doped TiO{sub 2} NPs. The average crystallite size of both samples was calculated from the Scherrers formula and was found in the range from 9-11?nm. TEM micrographs of these NPs reflect their shape and distribution. The dielectric constant (??), dielectric loss (tan?) and ac conductivity (?{sub ac}) were also studied as a function of temperature at different frequencies. Electrical responses of the synthesized NPs have been analyzed carefully in the framework of relevant models. It is also noticed that the dielectric constant (??) of the samples found to decrease with increasing frequency but increases with increasing temperature up to a particular value and then sharply decreases. Temperature variation of dielectric constant exhibits step like escalation and shows relaxation behavior. Study of dielectric properties shows dominant dependence on the grain size as well as Co ion incorporation in TiO{sub 2}.

  1. The hydrogenation of acetylene catalyzed by palladium: Hydrogen pressure dependence

    SciTech Connect (OSTI)

    Molero, H.; Bartlett, B.F.; Tysoe, W.T.

    1999-01-01

    The kinetics of acetylene hydrogenation catalyzed by a clean palladium foil at high pressures are measured and yield an activation energy of 9.6 {+-} 0.1 kcal/mol when using hydrogen. The rate exhibits a deuterium isotope effect such that the reaction activation energy is 9.0 {+-} 0.2 kcal/mol for reaction with deuterium. The hydrogen pressure reaction order is 1.04 {+-} 0.02 at 300 K with an acetylene pressure of 100 Torr and the acetylene order is {minus}0.66 at 300 K and with a hydrogen pressure of 100 Torr. These reaction kinetics closely mimic those of supported model catalysts. In addition, it is found that the rate of benzene formation is accelerated by the addition of hydrogen to the reaction mixture. This is rationalized by proposing that hydrogen enhances the coverage of acetylene under catalytic conditions. This notion can be used to successfully calculate the hydrogen pressure dependence for acetylene hydrogenation as a function of temperature, a value which varies between {approximately}1.05 and 1.3 as the temperature changes from 300 to 380 K. Possible origins for this effect are discussed.

  2. Ethylenediamine salt of 5-nitrotetrazole and preparation

    DOE Patents [OSTI]

    Lee, K.; Coburn, M.D.

    1984-05-17

    The ethylenediamine salt of 5-nitrotetrazole has been found to be useful as an explosive alone and in eutectic mixtures with ammonium nitrate and/or other explosive compounds. Its eutectic with ammonium nitrate has been demonstrated to behave in a similar manner to a monomolecular explosive such as TNT, and is less sensitive than the pure salt. Moreover, this eutectic mixture, which contains 87.8 mol% of ammonium nitrate, is close to the CO/sub 2/-balanced composition of 90 mol%, and has a relatively low melting point of 110.5 C making it readily castable. The ternary eutectic system containing the ethylenediamine salt of 5-nitrotetrazole, ammonium nitrate and ethylenediamine dinitrate has a eutectic temperature of 89.5 C and gives a measured detonation pressure of 24.8 GPa, which is 97.6% of the calculated value. Both the pure ethylenediamine salt and its known eutectic compounds behave in substantially ideal manner. Methods for the preparation of the salt are described.

  3. Do TFSA anions slither? Pressure exposes the role of TFSA conformational exchange in self-diffusion

    SciTech Connect (OSTI)

    Suarez, Sophia N.; Wishart, James F.; Rua, Armando; Cuffari, David; Pilar, Kartik; Hatcher, Jasmine L.; Ramati, Sharon

    2015-10-28

    Multi-nuclear (1H, 2H, and 19F) magnetic resonance spectroscopy techniques as functions of temperature and pressure were applied to the study of selectively deuterated 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (EMIM TFSA) ionic liquid isotopologues and related ionic liquids. For EMIM TFSA, temperature-dependent 2H T1 data indicate stronger electric field gradients in the alkyl chain region compared to the imidazolium ring. Most significantly, the pressure dependences of the EMIM and TFSA self-diffusion coefficients revealed that the displacements of the cations and anions are independent, with diffusion of the TFSA anions being slowed much more by increasing pressure than for the EMIM cations, as shown by their respective activation volumes (28.8 2.5 cm/mol for TFSA vs. 14.6 1.3 cm/mol for EMIM). Increasing pressure may lower the mobility of the TFSA anion by hindering its interconversion between trans and cis conformers, a process that is coupled to diffusion according to published molecular dynamics simulations. Measured activation volumes (?V) for ion self-diffusion in EMIM bis(fluoromethylsulfonyl)amide and EMIM tetrafluoroborate support this hypothesis.

  4. Development and field testing of a rapid and ultra-stable atmospheric carbon dioxide spectrometer

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

    Xiang, B.; Nelson, D. D.; McManus, J. B.; Zahniser, M. S.; Wehr, R. A.; Wofsy, S. C.

    2014-12-15

    We present field test results for a new spectroscopic instrument to measure atmospheric carbon dioxide (CO2) with high precision (0.02 μmol mol-1, or ppm at 1 Hz) and demonstrate high stability (within 0.1 ppm over more than 8 months), without the need for hourly, daily, or even monthly calibration against high-pressure gas cylinders. The technical novelty of this instrument (ABsolute Carbon dioxide, ABC) is the spectral null method using an internal quartz reference cell with known CO2 column density. Compared to a previously described prototype, the field instrument has better stability and benefits from more precise thermal control of themore » optics and more accurate pressure measurements in the sample cell (at the mTorr level). The instrument has been deployed at a long-term ecological research site (the Harvard Forest, USA), where it has measured for 8 months without on-site calibration and with minimal maintenance, showing drift bounds of less than 0.1 ppm. Field measurements agree well with those of a commercially available cavity ring-down CO2 instrument (Picarro G2301) run with a standard calibration protocol. This field test demonstrates that ABC is capable of performing high-accuracy, unattended, continuous field measurements with minimal use of reference gas cylinders.« less

  5. Fundamental studies in production of C{sub 2}-C{sub 4} hydrocarbons from coal. Final report, 1 September 1988--31 August 1992

    SciTech Connect (OSTI)

    Wiser, W.H.; Oblad, A.G.

    1993-03-01

    The following conclusions can be drawn from the result obtained in this kinetic study of single stage coal gasification to hydrocarbon (HC) gases high in C{sub 2}-C{sub 4} hydrocarbons. It was observed that the direct conversion of coal to HC gases involves two steps. The first step is thermal cleavage of the coal structure to produce liquids with small amounts of gases and coke. The second step is conversion of liquids to gases. Coal to liquids occurs very rapidly and was completed within 10 minutes. Liquids to gases is the rate-determining step of the overall process. The conversion of liquids to gases was observed to follow first order kinetics. The first order kinetics treatment of the data by isothermal approximation gave an apparent activation energy of approximately 23 kcal/mol. The first order kinetics treatment of the data by a more rigorous non-isothermal method gave an activation energy of 26 kcal/mol. The quantity of HC gases produced directly from coal reached a constant value of about l0% of the dmmf coal at a reaction time of 10 miutes. Most of the HC gases were produced from the liquids. The study of model compounds shows that conversion of liquids to HC gases.proceeds through a carbonium ion mechanism, and this accounts for the production of C{sub 2}-C{sub 4} gases. Liquid to gases occurs by a catalytic hydrocracking reaction.

  6. Fundamental studies in production of C[sub 2]-C[sub 4] hydrocarbons from coal

    SciTech Connect (OSTI)

    Wiser, W.H.; Oblad, A.G.

    1993-03-01

    The following conclusions can be drawn from the result obtained in this kinetic study of single stage coal gasification to hydrocarbon (HC) gases high in C[sub 2]-C[sub 4] hydrocarbons. It was observed that the direct conversion of coal to HC gases involves two steps. The first step is thermal cleavage of the coal structure to produce liquids with small amounts of gases and coke. The second step is conversion of liquids to gases. Coal to liquids occurs very rapidly and was completed within 10 minutes. Liquids to gases is the rate-determining step of the overall process. The conversion of liquids to gases was observed to follow first order kinetics. The first order kinetics treatment of the data by isothermal approximation gave an apparent activation energy of approximately 23 kcal/mol. The first order kinetics treatment of the data by a more rigorous non-isothermal method gave an activation energy of 26 kcal/mol. The quantity of HC gases produced directly from coal reached a constant value of about l0% of the dmmf coal at a reaction time of 10 miutes. Most of the HC gases were produced from the liquids. The study of model compounds shows that conversion of liquids to HC gases.proceeds through a carbonium ion mechanism, and this accounts for the production of C[sub 2]-C[sub 4] gases. Liquid to gases occurs by a catalytic hydrocracking reaction.

  7. On the competition between hydrogen abstraction versus C-O bond fission in initiating dimethyl ether combustion

    SciTech Connect (OSTI)

    Francisco, J.

    1999-07-01

    There has been a growing interest in the potential use of dimethyl ether (DME) as a diesel fuel in compression ignition engines. There are two initiation steps involved in the combustion of DME, one involving C-O bond fission and the other involving hydrogen abstraction by molecular oxygen. The kinetics and thermodynamics of C-O bond fission were explored computationally in a previous paper. The present paper addresses the competing process--hydrogen abstraction by molecular oxygen. Ab initio molecular orbital calculations are used to study the structures and energetics of the reactants, products, and the transition state for the CH{sub 3}OCH{sub 3} + O{sub 2} reaction. The calculations predict a barrier for hydrogen abstraction from CH{sub 3}OCH{sub 3} by O{sub 2} of 47.4 kcal/mol. This is lower than the barrier height for C-O bond fission previously calculated to be 81.1 kcal/mol. The results support values used in current models for the combustion of DME. Moreover, an examination of rates for C-O bond fission versus hydrogen abstraction by O{sub 2} suggests that the bimolecular process is the dominant pathway.

  8. Activation Energy of Tantalum-Tungsten Oxide Thermite Reaction

    SciTech Connect (OSTI)

    Cervantes, O; Kuntz, J; Gash, A; Munir, Z

    2010-02-25

    The activation energy of a high melting temperature sol-gel (SG) derived tantalum-tungsten oxide thermite composite was determined using the Kissinger isoconversion method. The SG derived powder was consolidated using the High Pressure Spark Plasma Sintering (HPSPS) technique to 300 and 400 C to produce pellets with dimensions of 5 mm diameter by 1.5 mm height. A custom built ignition setup was developed to measure ignition temperatures at high heating rates (500-2000 C {center_dot} min{sup -1}). Such heating rates were required in order to ignite the thermite composite. Unlike the 400 C samples, results show that the samples consolidated to 300 C undergo an abrupt change in temperature response prior to ignition. This change in temperature response has been attributed to the crystallization of the amorphous WO{sub 3} in the SG derived Ta-WO{sub 3} thermite composite and not to a pre-ignition reaction between the constituents. Ignition temperatures for the Ta-WO{sub 3} thermite ranged from approximately 465-670 C. The activation energy of the SG derived Ta-WO{sup 3} thermite composite consolidated to 300 and 400 C were determined to be 37.787 {+-} 1.58 kJ {center_dot} mol{sup -1} and 57.381 {+-} 2.26 kJ {center_dot} mol{sup -1}, respectively.

  9. Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules

    SciTech Connect (OSTI)

    DePalma, Joseph W.; Wang, Jian; Wexler, Anthony S.; Johnston, Murray V.

    2015-10-21

    Quantum chemical calculations were employed to model the interactions of the [(NH4+)4(HSO4-)4] ammonium bisulfate cluster with one or more molecular products of monoterpene oxidation. A strong interaction was found between the bisulfate ion of the cluster and a carboxylic acid, aldehyde or ketone functionality of the organic molecule. Free energies of adsorption for carboxylic acids were in the -70 to -73 kJ/mol range, while those for aldehydes and ketones were in the -46 to -50 kJ/mol range. These values suggest that a small ambient ammonium bisulfate cluster, such as the [(NH4+)4(SO4-)4] cluster, is able to adsorb an oxygenated organic molecule. Although adsorption of the first molecule is highly favorable, adsorption of subsequent molecules is not, suggesting that sustained uptake of organic molecules does not occur, and thus is not a pathway for continuing growth of the cluster. This result is consistent with ambient measurements showing that particles below ~1 nm grow slowly, while those above 1 nm grow at an increasing rate presumably due to a lower surface energy barrier enabling the uptake of organic molecules. This work provides insight into the molecular level interactions which affect sustained cluster growth by uptake of organic molecules.

  10. Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules

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

    DePalma, Joseph W.; Wang, Jian; Wexler, Anthony S.; Johnston, Murray V.

    2015-10-21

    Quantum chemical calculations were employed to model the interactions of the [(NH4+)4(HSO4-)4] ammonium bisulfate cluster with one or more molecular products of monoterpene oxidation. A strong interaction was found between the bisulfate ion of the cluster and a carboxylic acid, aldehyde or ketone functionality of the organic molecule. Free energies of adsorption for carboxylic acids were in the -70 to -73 kJ/mol range, while those for aldehydes and ketones were in the -46 to -50 kJ/mol range. These values suggest that a small ambient ammonium bisulfate cluster, such as the [(NH4+)4(SO4-)4] cluster, is able to adsorb an oxygenated organic molecule.more » Although adsorption of the first molecule is highly favorable, adsorption of subsequent molecules is not, suggesting that sustained uptake of organic molecules does not occur, and thus is not a pathway for continuing growth of the cluster. This result is consistent with ambient measurements showing that particles below ~1 nm grow slowly, while those above 1 nm grow at an increasing rate presumably due to a lower surface energy barrier enabling the uptake of organic molecules. This work provides insight into the molecular level interactions which affect sustained cluster growth by uptake of organic molecules.« less

  11. Effect of Gaseous Impurities on Long-Term Thermal Cycling and Aging Properties of Complex Hydrides for Hydrogen Storage

    SciTech Connect (OSTI)

    Chandra, Dhanesh; Lamb, Joshua; Chien, Wen-Ming; Talekar, Anjali; and Pal, Narendra.

    2011-03-28

    This program was dedicated to understanding the effect of impurities on Long-Term Thermal Cycling and aging properties of Complex Hydrides for Hydrogen Storage. At the start of the program we found reversibility between Li2NH+LiH  LiH+LiNH2 (yielding ~5.8 wt.%H capacity). Then we tested the effect of impurity in H2 gas by pressure cycling at 255oC; first with industrial gas containing ppm levels of O2 and H2O as major impurities. Both these impurities had a significant impact on the reversibility and decreased the capacity by 2.65 wt.%H. Further increase in number of cycles from 500 to 1100 showed only a 0.2 wt%H more weight loss, showing some capacity is still maintained after a significant number of cycles. The loss of capacity is attributed to the formation of ~55 wt% LiH and ~30% Li2O, as major contaminant phases, along with the hydride Li2NH phase; suggesting loss of nitrogen during cycling. The effect of 100 ppm H2O in H2 also showed a decrease of ~2.5 wt.%H (after 560 cycles), and 100ppm O2 in H2; a loss of ~4.1 wt.%. Methane impurity (100 ppm, 100cycles), showed a very small capacity loss of 0.9 wt.%H under similar conditions. However, when Li3N was pressure cycled with 100ppmN2-H2 there were beneficial effects were observed (255oC); the reversible capacity increased to 8.4wt.%H after 853 cycles. Furthermore, with 20 mol.%N2-H2 capacity increased to ~10 wt.%H after 516 cycles. We attribute this enhancement to the reaction of nitrogen with liquid lithium during cycling as the Gibbs free energy of formation of Li3N (Go = -98.7 kJ/mol) is more negative than that of LiH (Go = -50.3 kJ/mol). We propose that the mitigation of hydrogen capacity losses is due to the destabilization of the LiH phase that tends to accumulate during cycling. Also more Li2NH phase was found in the cycled product. Mixed Alanates (3LiNH2:Li3AlH6) showed that 7 wt% hydrogen desorbed under dynamic vacuum. Equilibrium experiments (maximum 12 bar H2) showed up to 4wt% hydrogen reversibly stored in the material after the first desorption. The activation energy was found to be 51 kJ/mol, as compared to 81 kJ/mol for pure lithium alanate. It is proposed that based on the data obtained and CALPHAD modeling that the improvement in cycling is due to the formation of pure lithium (liquid at 255oC), which is able to react with nitrogen specifically forming Li3N. The presence of nitrogen in the 80/20 molar mixtures in a hydride bed along with hydrogen causes Li to form Li3N rather than LiH, and subsequently regenerates the Li2NH phase and yields a ~10 wt.%H reversibly.

  12. Kinetic and Crystallgraphic Studies of a Redesigned Manganese-Binding Site in Cytochrome c Peroxidase

    SciTech Connect (OSTI)

    Pfister,T.; Mirarefi, A.; Gengenbach, A.; Zhao, X.; Danstrom , C.; Conatser, N.; Gao, Y.; Robinson, H.; Zukoski, C.; et al.

    2007-01-01

    Manganese peroxidase (MnP) from the white rot fungus Phanerochaete chrysosporium contains a manganese-binding site that plays a critical role in its function. Previously, a Mn{sup II}-binding site was designed into cytochrome c peroxidase (CcP) based on sequence homology (Yeung et al. in Chem. Biol. 4:215-222, 1997; Gengenbach et al. in Biochemistry 38:11425-11432, 1999). Here, we report a redesign of this site based on X-ray structural comparison of MnP and CcP. The variant, CcP(D37E, V45E, H181E), displays 2.5-fold higher catalytic efficiency (k{sub cat}/k{sub M}) than the variant in the original design, mostly due to a stronger k{sub M} of 1.9 mM (vs. 4.1 mM). High-resolution X-ray crystal structures of a metal-free form and a form with Co{sup II} at the designed Mn{sup II} site were also obtained. The metal ion in the engineered metal-binding site overlays well with Mn{sup II} bound in MnP, suggesting that this variant is the closest structural model of the Mn{sup II}-binding site in MnP for which a crystal structure exists. A major difference arises in the distances of the ligands to the metal; the metal-ligand interactions in the CcP variant are much weaker than the corresponding interactions in MnP, probably owing to partial occupancy of metal ion at the designed site, difference in the identity of metal ions (Co{sup II} rather than Mn{sup II}) and other interactions in the second coordination sphere. These results indicate that the metal ion, the ligands, and the environment around the metal-binding site play important roles in tuning the structure and function of metalloenzymes.

  13. Near optimal energy selective x-ray imaging system performance with simple detectors

    SciTech Connect (OSTI)

    Alvarez, Robert E.

    2010-02-15

    Purpose: This article describes a method to achieve near optimal performance with low energy resolution detectors. Tapiovaara and Wagner [Phys. Med. Biol. 30, 519-529 (1985)] showed that an energy selective x-ray system using a broad spectrum source can produce images with a larger signal to noise ratio (SNR) than conventional systems using energy integrating or photon counting detectors. They showed that there is an upper limit to the SNR and that it can be achieved by measuring full spectrum information and then using an optimal energy dependent weighting. Methods: A performance measure is derived by applying statistical detection theory to an abstract vector space of the line integrals of the basis set coefficients of the two function approximation to the x-ray attenuation coefficient. The approach produces optimal results that utilize all the available energy dependent data. The method can be used with any energy selective detector and is applied not only to detectors using pulse height analysis (PHA) but also to a detector that simultaneously measures the total photon number and integrated energy, as discussed by Roessl et al. [Med. Phys. 34, 959-966 (2007)]. A generalization of this detector that improves the performance is introduced. A method is described to compute images with the optimal SNR using projections in a ''whitened'' vector space transformed so the noise is uncorrelated and has unit variance in both coordinates. Material canceled images with optimal SNR can also be computed by projections in this space. Results: The performance measure is validated by showing that it provides the Tapiovaara-Wagner optimal results for a detector with full energy information and also a conventional detector. The performance with different types of detectors is compared to the ideal SNR as a function of x-ray tube voltage and subject thickness. A detector that combines two bin PHA with a simultaneous measurement of integrated photon energy provides near ideal performance across a wide range of operating conditions. Conclusions: Low energy resolution detectors can be used in energy selective x-ray imaging systems to produce images with near optimal performance.

  14. Final Report for Award DE-FG02-09ER64721

    SciTech Connect (OSTI)

    somerville, chris

    2014-04-26

    The original goal of this award was to develop a proteoglycan chip containing suitable oligosaccharides that could be used as substrates for glycosyltransferases involved in synthesis or proteoglycans in higher plant cell walls. We had previously developed a suite of cloned enzymes that could be used to cleave most of the relevant glycosidic linkages in plant cell walls. The next step, supported by the previous award and this award, was to produce a series of transgenic plants in which synthetic proteins were introduced that contained each of the known sequence motifs that induce prolyl hydroxylation, and subsequent glycosylation. This work was completed and published in Estevez et al (2006). We then engaged on a series of experiments to define the properties of the prolyl hydroxylases that convert certain prolyl resides to hydroxyproline for subsequent glycosylation. This proved to be a challenging goal that required recruitment of an international team of complementary skills and several additional years or research. However, the effort was successful and has been published in Science recenty (Velasquez et al., 2011). In the course of this project, the postdoc supported by the award (Jose Estevez) was asked to provide technical assistance to a colleague at Stanford because of his expertise in marine polysaccharides. This led to the important discovery that marine algae have compounds that could be classified as lignin (Martone et al., 2009). Publications supported by the award Estvez, J.M., Kieliszewski, M.J., Khitrov, N., Somerville, C. (2006) Characterization of synthetic hydroxyproline-rich proteoglycans with AGP- and extensin-motifs in Arabidopsis. Plant Physiol., 142,458-470 Martone, P.T., Estevez, J.M., Lu, F., Ruel, K., Ralph, J., Denny, M.W., Somerville, C.R. (2009) Discovery of lignin in seaweed reveals convergent evolution of cell-wall architecture. Curr. Biol., 19, 169-175 Velasquez, S.M., M. Ricardi, M.M., Dorosz, J.G., Fernandez, P.V., Nadra, A.D., Pol-Fachin, L., Egelund, J., Gille, S., Harholt, J., Ciancia, M., Verli, H., Pauly, M., Bacic, A., Olsen, C.E., r Ulvskov, P., Petersen, B.L., Somerville, C., Iusem, N.D. & Estevez, J.M. (2011) O-glycosylated cell wall proteins are essential in root hair growth. Science 332,1401-1403

  15. Structure and dynamics of complexes of the uranyl ion with nonamethylimidodiphosphoramide (NIPA). 2. NMR studies of complexes (UO/sub 2/(NIPA)/sub 2/X)(CIO/sub 4/)/sub 2/ with X = H/sub 2/O, MeOH, EtOH, or Me/sub 2/CO

    SciTech Connect (OSTI)

    Rodehueser, L.; Rubini, P.R.; Bokolo, K.; Delpuech, J.J.

    1982-03-01

    The /sup 31/P and /sup 1/H spectra at -90/sup 0/C of the title uranyl complex ions (prepared as solutions of the solid perchlorates in inert anhydrous organic solvents (CH/sub 3/NO/sub 2/, CH/sub 2/Cl/sub 2/)) reveal a pentacoordinated arrangement of two symmetrically doubly bonded NIPA molecules and one solvent molecule about the uranyl group. In the case of (UO/sub 2/(NIPA)/sub 2/(EtOH))(ClO/sub 4/)/sub 2/, an intermolecular exchange between bound and free ethanol molecules is observed above -75/sup 0/C upon addition of ethanol to a solution of the complex. The observed rate law, k/sub inter/ = kK(EtOH)/(1 + K(EtOH) is accounted for by the existence of an outer-sphere complex (UO/sub 2//sup 2 +/(NIPA)/sub 2/(EtOH))EtOH in fast equilibrium (K) with the initial complex and free ethanol. The rate-determining step (k) consists of an outer-sphere to inner-sphere interchange of ethanol molecules. The thermodynamic and kinetic parameters are K(25/sup 0/C) = 15.8 dm/sup 3/ mol/sup -1/, k(25/sup 0/C) = 1.0 x 10/sup 4/s/sup -1/, ..delta..H and ..delta..H/sub inter//sup + +/ = -4.8 and 7.6 kcal mol/sup -1/, and ..delta..S and ..delta..S/sub inter//sup + +/ = 10.7 and -14.7 eu. A second exchange takes place at higher temperatures (above -30/sup 0/C) yielding full dynamic equivalence of the phosphorus nuclei of the coordinated NIPA molecules. The observed rate law k/sub intra/ = k/sub ex/(1 + K(EtOH)) reveals that the internal rearrangement of NIPA molecules occurs on the complex ion (UO/sub 2/(NIPA)/sub 2/(EtOH))/sup 2 +/ but not on the outer-sphere complex: k/sub ex/(25/sup 0/C) = 0.91 x 10/sup 3/s/sup -1/, ..delta..H/sub intra//sup + +/ = 10.6 kcal mol/sup -1/ and ..delta..S/sub intra//sup + +/ = -9.4 eu. Possible mechanisms for this exchange are discussed. 5 figures, 2 tables.

  16. Effect of La{sub 2}O{sub 3}-treatment on textural and solid-solid interactions in ferric/cobaltic oxides system

    SciTech Connect (OSTI)

    Fagal, Gehan A.; Badawy, Abdelrahman A.; Hassan, Neven A.; El-Shobaky, Gamil A.

    2012-10-15

    Pure and La{sub 2}O{sub 3}-containing (0.75-3.0 mol%) Fe{sub 2}O{sub 3}/Co{sub 3}O{sub 4} solids were prepared by thermal treatment of their carbonates at 500-700 Degree-Sign C. The produced solids were characterized using XRD, HRTEM, EDX and nitrogen adsorption at -196 Degree-Sign C. The results revealed that pure solids calcined at 600 and 700 Degree-Sign C consisted of nanosized CoFe{sub 2}O{sub 4} phase, while pure mixed solids calcined at 500 Degree-Sign C consisted of trace amount of CoFe{sub 2}O{sub 4} and unreacted Fe{sub 2}O{sub 3}, Co{sub 3}O{sub 4} phases. The presence of 0.75 mol% La{sub 2}O{sub 3} enhanced solid-solid interaction between Fe{sub 2}O{sub 3} and Co{sub 3}O{sub 4} at 500 Degree-Sign C yielding CoFe{sub 2}O{sub 4}. The ferrite phase existed also in all mixed oxides upon treated with La{sub 2}O{sub 3} besides LaCoO{sub 3} phase. LaCoO{sub 3} existed as a major phase in all mixed oxides treated with 3 mol% La{sub 2}O{sub 3}. La{sub 2}O{sub 3}-treatment modified the crystallite size of all phases present to an extent dependent on calcination temperature and amount of La{sub 2}O{sub 3} content. This treatment decreased effectively the S{sub BET} of all mixed solids. - Graphical Abstract: TEM photographs of pure mixed oxides calcined at 500 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Cobalt ferrite exhibit chemical stability, low electric loss and high coercivity. Black-Right-Pointing-Pointer Cobalt ferrite is used in microwave devices, computer memories and magnetic storage. Black-Right-Pointing-Pointer Solid-solid interactions in ferric/cobaltic oxides system were investigated. Black-Right-Pointing-Pointer La{sub 2}O{sub 3}-treatment modified surface compositions of the system investigated. Black-Right-Pointing-Pointer All phases present in various solids existed as nanosized solids.

  17. Progress Report on FY15 Crystalline Experiments M4FT-15LL0807052

    SciTech Connect (OSTI)

    Zavarin, M.; Zhao, P.; Joseph, C.; Begg, J.; Dai, Z.; Kersting, A. B.

    2015-08-13

    Colloid-facilitated plutonium transport is expected to be the dominant mechanism in its migration through the environment. The forms of Pu colloids (intrinsic versus pseudo-colloid) and their stabilities control temporal and spatial scales of Pu transport in the environment. In the present study, we examine the stability of Pu intrinsic colloids freshly prepared in alkaline solution relative to Pu-montmorillonite pseudo-colloids using a dialysis device and modeling approaches. Intrinsic colloids prepared under alkaline conditions were found to be unstable over a timescale of months. The kinetics of multiple processes, including hydrolysis/precipitation of Pu(IV), dissolution of intrinsic colloids in the absence and presence of the clay colloids, transport of dissolved Pu species across the dialysis membrane, and formation of pseudo-colloids were examined. The dissolution of intrinsic colloids was the rate-limiting process in most cases. The apparent intrinsic colloid dissolution rate constants range from 6×10-7 to 1×10- 6 mol·m-2·day-1 and 4×10-6 to 8×10-6 mol·m-2·day-1 at 25 and 80°C, respectively, while the apparent diffusion rate constants for Pu ions crossing the dialysis membrane are >200 times higher. Elevated temperatures enhance dissolution of Pu colloids and the activation energy for the process is estimated to be 28 kJ mol-1. The sorption of Pu to montmorillonite appears to be endothermic as the affinity of Pu for the clay increases with increasing temperature. Our results provide an in-depth understanding of how intrinsic and pseudo-colloids interact with each other kinetically. Although the fact that intrinsic colloids tend to dissolve in the presence of montmorillonite and transform into pseudo-colloids may limit the migration of intrinsic colloids, the thermodynamically more stable pseudo-colloids may play an important role in Pu transport in the environment over significant temporal and spatial scales.

  18. Modeling Solute Thermokinetics in LiCI-KCI Molten Salt for Nuclear Waste Separation

    SciTech Connect (OSTI)

    Morgan, Dane; Eapen, Jacob

    2013-10-01

    Recovery of actinides is an integral part of a closed nuclear fuel cycle. Pyrometallurgical nuclear fuel recycling processes have been developed in the past for recovering actinides from spent metallic and nitride fuels. The process is essentially to dissolve the spent fuel in a molten salt and then extract just the actinides for reuse in a reactor. Extraction is typically done through electrorefining, which involves electrochemical reduction of the dissolved actinides and plating onto a cathode. Knowledge of a number of basic thermokinetic properties of salts and salt-fuel mixtures is necessary for optimizing present and developing new approaches for pyrometallurgical waste processing. The properties of salt-fuel mixtures are presently being studied, but there are so many solutes and varying concentrations that direct experimental investigation is prohibitively time consuming and expensive (particularly for radioactive elements like Pu). Therefore, there is a need to reduce the number of required experiments through modeling of salt and salt-fuel mixture properties. This project will develop first-principles-based molecular modeling and simulation approaches to predict fundamental thermokinetic properties of dissolved actinides and fission products in molten salts. The focus of the proposed work is on property changes with higher concentrations (up to 5 mol%) of dissolved fuel components, where there is still very limited experimental data. The properties predicted with the modeling will be density, which is used to assess the amount of dissolved material in the salt; diffusion coefficients, which can control rates of material transport during separation; and solute activity, which determines total solubility and reduction potentials used during electrorefining. The work will focus on La, Sr, and U, which are chosen to include the important distinct categories of lanthanides, alkali earths, and actinides, respectively. Studies will be performed using LiCl-KCl salt at the eutectic composition (58 mol% LiCl, 42 mol% KCl), which is used for treating spent EBR-II fuel. The same process being used for EBRII fuel is currently being studied for widespread international implementation. The methods will focus on first-principles and first- principles derived interatomic potential based simulations, primarily using molecular dynamics. Results will be validated against existing literature and parallel ongoing experimental efforts. The simulation results will be of value for interpreting experimental results, validating analytical models, and for optimizing waste separation by potentially developing new salt configurations and operating conditions.

  19. Theoretical study of the rhodium dimer interaction with the hydrogen molecule

    SciTech Connect (OSTI)

    Castillo, S.; Cruz, A.; Cuan, A.

    1995-12-31

    The C{sub 2v} potential energy surfaces for the end-on and side-on approaches of H{sub 2} to the rhodium dimer were studied through self-consistent-field (SCF) and multiconfigurational SCF calculations, followed by extensive variational plus second-order multireference Moller-Plesset perturbational configuration interaction (CIPSI) calculations. Relativistic effective core potentials were used to replace the core electrons of the rhodium atoms. Together with the Rh{sub 2}-H{sub 2} interaction, the spectroscopic constants for the {sup 5}{summation}{sub g}{sup +}, {sup 1}{summation}{sub g}{sup +}, {sup 3}II{sub {mu}}, and {sup 1}II{sub {mu}} states of Rh{sub 2} are reported. It was found that the potential energy curves of the parallel and the perpendicular Rh{sub 2}({sup 5}{summation}{sub g}) interaction with H{sub 2} show that the rhodium dimer has the ability to capture and break the H{sub 2} molecule. The parallel interaction presents a soft potential barrier of 7.8 kcal/mol, energy necessary to surmount before the capture and breaking of the H-H bond. In the perpendicular interaction, Rh{sub 2} captures and breaks spontaneously H{sub 2}. The potential energy curve of the parallel Rh{sub 2}({sup 1}{summation}{sub g}) + H{sub 2} interaction shows that Rh{sub 2} also captures and breaks spontaneously the H{sub 2}, with a very deep well of 92.7 kcal/mol, while in the perpendicular approach, Rh{sub 2} has to surmount again a soft barrier of 5.2 kcal/mol to capture and break the H{sub 2} molecule. Finally, the energy curves of the parallel Rh{sub 2}({sup 1,3}II{sub {mu}}) + H{sub 2} interactions present capture and breaking with very small barriers. The perpendicular interactions capture and scisse the hydrogen molecule spontaneously. 35 refs., 6 tabs.

  20. Ultraviolet photodissociation dynamics of the n-propyl and i-propyl radicals

    SciTech Connect (OSTI)

    Song, Yu; Zheng, Xianfeng; Zhou, Weidong; Lucas, Michael; Zhang, Jingsong

    2015-06-14

    Ultraviolet (UV) photodissociation dynamics of jet-cooled n-propyl (n-C{sub 3}H{sub 7}) radical via the 3s Rydberg state and i-propyl (i-C{sub 3}H{sub 7}) radical via the 3p Rydberg states are studied in the photolysis wavelength region of 230260 nm using high-n Rydberg atom time-of-flight and resonance enhanced multiphoton ionization techniques. The H-atom photofragment yield spectra of the n-propyl and i-propyl radicals are broad and in good agreement with the UV absorption spectra. The H + propene product translational energy distributions, P(E{sub T})s, of both n-propyl and i-propyl are bimodal, with a slow component peaking around 5-6 kcal/mol and a fast one peaking at ?50 kcal/mol (n-propyl) and ?45 kcal/mol (i-propyl). The fraction of the average translational energy in the total excess energy, ?f{sub T}?, is 0.3 for n-propyl and 0.2 for i-propyl, respectively. The H-atom product angular distributions of the slow components of n-propyl and i-propyl are isotropic, while that of the fast component of n-propyl is anisotropic (with an anisotropy parameter ?0.8) and that of i-propyl is nearly isotropic. Site-selective loss of the ? hydrogen atom is confirmed using the partially deuterated CH{sub 3}CH{sub 2}CD{sub 2} and CH{sub 3}CDCH{sub 3} radicals. The bimodal translational energy and angular distributions indicate two dissociation pathways to the H + propene products in the n-propyl and i-propyl radicals: (i) a unimolecular dissociation pathway from the hot ground-state propyl after internal conversion from the 3s and 3p Rydberg states and (ii) a direct, prompt dissociation pathway coupling the Rydberg excited states to a repulsive part of the ground-state surface, presumably via a conical intersection.

  1. Concept Feasibility Report for Electroplating Zirconium onto Uranium Foil - Year 2

    SciTech Connect (OSTI)

    Coffey, Greg W.; Meinhardt, Kerry D.; Joshi, Vineet V.; Pederson, Larry R.; Lavender, Curt A.; Burkes, Douglas

    2015-03-01

    The Fuel Fabrication Capability within the U.S. High Performance Research Reactor Conversion Program is funded through the National Nuclear Security Administration (NNSA) NA-26 (Office of Material Management and Minimization). An investigation was commissioned to determine the feasibility of using electroplating techniques to apply a coating of zirconium onto depleted uranium/molybdenum alloy (U-10Mo). Electroplating would provide an alternative method to the existing process of hot roll-bonding zirconium foil onto the U-10Mo fuel foil during the fabrication of fuel elements for high-performance research reactors. The objective of this research was to develop a reproducible and scalable plating process that will produce a uniform, 25 ?m thick zirconium metal coating on U-10Mo foil. In previous work, Pacific Northwest National Laboratory (PNNL) established a molten salt electroplating apparatus and protocol to plate zirconium metal onto molybdenum foil (Coffey 2015). During this second year of the research, PNNL furthered this work by moving to the U-10Mo alloy system (90 percent uranium:10 percent molybdenum). The original plating apparatus was disassembled and re-assembled in a laboratory capable of handling low-level radioactive materials. Initially, the work followed the previous years approach, and the salt bath composition was targeted at the eutectic composition (LiF:NaF:ZrF4 = 26:37:37 mol%). Early results indicated that the formation of uranium fluoride compounds would be problematic. Other salt bath compositions were investigated in order to eliminate the uranium fluoride production (LiF:NaF = 61:39 mol% and LiF:NaF:KF = 46.5:11.5:42 mol% ). Zirconium metal was used as the crucible for the molten salt. Three plating methods were usedisopotential, galvano static, and pulsed plating. The molten salt method for zirconium metal application provided high-quality plating on molybdenum in PNNLs previous work. A key advantage of this approach is that plating can be performed under conditions that would greatly reduce the quantity of intermetallics that form at the interface between the zirconium and U-10Mo; unlike roll bonding, the molten salt plating approach would allow for complete coverage of the U-10Mo foil with zirconium. When utilizing the experimental parameters developed for zirconium plating onto molybdenum, a uranium fluoride reaction product was formed at the Zr/U-10Mo interface. By controlling the initial plating potential, the uranium fluoride could be prevented; however, the targeted zirconium thickness (25 12.5 ?m) could not be achieved while maintaining 100% coverage.

  2. Molten Salt Fuel Version of Laser Inertial Fusion Fission Energy (LIFE)

    SciTech Connect (OSTI)

    Moir, R W; Shaw, H F; Caro, A; Kaufman, L; Latkowski, J F; Powers, J; Turchi, P A

    2008-10-24

    Molten salt with dissolved uranium is being considered for the Laser Inertial Confinement Fusion Fission Energy (LIFE) fission blanket as a backup in case a solid-fuel version cannot meet the performance objectives, for example because of radiation damage of the solid materials. Molten salt is not damaged by radiation and therefore could likely achieve the desired high burnup (>99%) of heavy atoms of {sup 238}U. A perceived disadvantage is the possibility that the circulating molten salt could lend itself to misuse (proliferation) by making separation of fissile material easier than for the solid-fuel case. The molten salt composition being considered is the eutectic mixture of 73 mol% LiF and 27 mol% UF{sub 4}, whose melting point is 490 C. The use of {sup 232}Th as a fuel is also being studied. ({sup 232}Th does not produce Pu under neutron irradiation.) The temperature of the molten salt would be {approx}550 C at the inlet (60 C above the solidus temperature) and {approx}650 C at the outlet. Mixtures of U and Th are being considered. To minimize corrosion of structural materials, the molten salt would also contain a small amount ({approx}1 mol%) of UF{sub 3}. The same beryllium neutron multiplier could be used as in the solid fuel case; alternatively, a liquid lithium or liquid lead multiplier could be used. Insuring that the solubility of Pu{sup 3+} in the melt is not exceeded is a design criterion. To mitigate corrosion of the steel, a refractory coating such as tungsten similar to the first wall facing the fusion source is suggested in the high-neutron-flux regions; and in low-neutron-flux regions, including the piping and heat exchangers, a nickel alloy, Hastelloy, would be used. These material choices parallel those made for the Molten Salt Reactor Experiment (MSRE) at ORNL. The nuclear performance is better than the solid fuel case. At the beginning of life, the tritium breeding ratio is unity and the plutonium plus {sup 233}U production rate is {approx}0.6 atoms per 14.1 MeV neutron.

  3. Preparation, photoluminescent properties and luminescent dynamics of BaAlF{sub 5}:Eu{sup 2+} nanophosphors

    SciTech Connect (OSTI)

    Zhang, Wei; Hua, Ruinian; Liu, Tianqing; Zhao, Jun; Na, Liyan; Chen, Baojiu

    2014-12-15

    Graphical abstract: Rice-shaped BaAlF{sub 5}:Eu{sup 2+} nanophosphors were synthesized via one-pot hydrothermal process. The as-prepared BaAlF{sub 5}:Eu{sup 2+} are composed of many particles with an average diameter of 40 nm. When excited at 260 nm, the sharp line emission located at 361 nm of Eu{sup 2+} was observed. The optimum doping concentration of Eu{sup 2+} was confirmed to be 5 mol%. The strong ultraviolet emission of Eu{sup 2+} ions in BaAlF{sub 5}:Eu{sup 2+} nanoparticles suggests that these nanoparticles may have potential applications for sensing, solid-state lasers and spectrometer calibration. - Highlights: • BaAlF{sub 5}:Eu{sup 2+} nanophosphors were synthesized via a mild hydrothermal process. • The Van and Huang models were used to research the mechanism of concentration quenching. • The optimum doping concentration of Eu2+ was confirmed to be 5 mol%. - Abstract: Eu{sup 2+}-doped BaAlF{sub 5} nanophosphors were synthesized via a facile one-pot hydrothermal method. The final products were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and photoluminescence (PL) spectroscopy. XRD results showed that the prepared samples are single-phase. The FE-SEM and TEM images indicated that the prepared BaAlF{sub 5}:Eu{sup 2+} nanophosphors are composed of many rice-shaped particles with an average diameter of 40 nm. When excited at 260 nm, BaAlF{sub 5}:Eu{sup 2+} nanophosphors exhibit the sharp line emissions of Eu{sup 2+} at room temperature. The optimum doping concentration of Eu{sup 2+} was confirmed to be 5 mol%. The Van and Huang models were used to study the mechanism of concentration quenching and the electric dipole–dipole interaction between Eu{sup 2+} can be deduced to be a dominant for quenching fluorescence in BaAlF{sub 5}:Eu{sup 2+} nanophosphors. The strong ultraviolet emission of Eu{sup 2+} in BaAlF{sub 5}:Eu{sup 2+} nanophosphors suggests that these nanoparticles may have potential applications for sensing, spectrometer calibration and solid-state lasers.

  4. Synthesis and peferentially loading of nickel nanoparticle on CdS surface and its photocatalytic performance for hydrogen evolution under visible light

    SciTech Connect (OSTI)

    Li, Xiying; Wang, Hui; Chu, Tingting; Li, Danzhen; Mao, Liqun

    2014-09-15

    Graphical abstract: Ni nanoparticles were prepared via chemical reduction of aqueous NiCl{sub 2} by borohydride reducing agent in the presence of polyvinlylpyrolidone as a modifier to prevent fast growth of Ni crystals and their aggregation, and then preferentially deposited on (1 0 0), (0 0 2), and (1 0 1) crystal planes of CdS by photo-induced electrons while water splitting reaction occurred simultaneously. Resultant nickel nanoparticles have a size of about 3 nm, and contributes to decreasing the photoluminescence peak intensity of CdS, which means that nickel functions as the trapper of photo-generated electrons thereby quenching the photoluminescence of CdS. Therefore, nano-Ni/CdS photocatalyst with a Ni loading of 2.5% possesses the best visible-light catalytic activity for water splitting-hydrogen evolution and provides a hydrogen production rate of up to 9050 ?mol h{sup ?1} g{sup ?1}, while it exhibits stabilized activity towards H{sub 2} evolution as well. - Highlights: Ni nanoparticles are prepared by chemical reduction and then loaded on CdS surface by photo-reduction. Non-noble metal Ni nanoparticles (size: about 3 nm) act as co-catalyst for photocatalytic H{sub 2} evolution. Nano-Ni/CdS exhibits high activity (9050 ?mol h{sup ?1} g{sup ?1}) and perfect stability. - Abstract: Ni nanoparticles were prepared via chemical reduction of NiCl{sub 2} by NaBH{sub 4} in the presence of polyvinlylpyrolidone (PVP), and loaded on the surface of CdS by photo-induced electrons while water splitting reaction occurred simultaneously. Resultant Ni/CdS was characterized by high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, ultravioletvisible light diffuse reflectance spectrometry, and photoluminescence spectrometry. It was found that as-prepared Ni nanoparticles are about 3 nm, and preferentially deposited on (1 0 0), (0 0 2), and (1 0 1) crystal planes of CdS. Meanwhile, loading nickel decreases the photoluminescence intensity of CdS, which means nickel functions as the trapper of photo-generated electrons. Therefore, nano-Ni/CdS photocatalyst with a Ni loading of 2.5% possesses the best visible-light catalytic activity for water splitting-hydrogen evolution and provides a hydrogen production rate of up to 9050 ?mol h{sup ?1} g{sup ?1}, while it exhibits stabilized activity towards H{sub 2} evolution as well.

  5. The oxidation-reduction kinetics of palladium powder

    SciTech Connect (OSTI)

    Munir, Z.A.; Coombs, P.G.

    1983-03-01

    The cyclic oxidation-reduction of submicrometer sized palladium powder was investigated over the temperature range 848 to 923 K. The total oxygen uptake decreased with increasing number of cycles as a consequence of sintering. Sintering was restricted to the reduction steps in these cycles. The relationships for the rate constants of the oxidation and reduction processes are, respectively, (1.04)10/sup 6/ exp(-(74.1)10/sup 3//RT), and (7.63)10/sup 12/ exp(-(207.9)10/sup 3//RT). The activation energies for the oxidation of palladium powder and the reduction of palladium oxide are 74.1 and 207.9 kJ mol/sup -1/, respectively.

  6. The adsorption and reaction of vinyl acetate on Au/Pd(100) alloy surfaces

    SciTech Connect (OSTI)

    Li, Zhenjun [Pacific Northwest National Laboratory (PNNL); Calaza, Florencia C [ORNL; Tysoe, Wilfred [University of Wisconsin, Milwaukee

    2012-01-01

    The surface chemistry of vinyl acetate monomer (VAM) is studied on Au/Pd(100) alloys as a function of alloy composition using temperature-programmed desorption and reflection adsorption infrared spectroscopy. VAM adsorbs weakly on isolated palladium sites on the alloy with a heat of adsorption of ~55 kJ/mol, with the plane of the VAM adsorbed close to parallel to the surface. The majority of the VAM adsorbed on isolated sites desorbs molecularly with only a small portion decomposing. At lower gold coverages (below ~0.5 ML of gold), where palladium palladium bridge sites are present, VAM binds to the surface in a distorted geometry via a rehybridized vinyl group. A larger proportion of this VAM decomposes and this reaction is initiated by C\\O bond scission in the VAM to form adsorbed acetate and vinyl species. The implication of this surface chemistry for VAM synthesis on Au/Pd(100) alloys is discussed.

  7. Infrared and Raman spectra, DFT-calculations and spectral assignments of germacyclohexane

    SciTech Connect (OSTI)

    Aleksa, V. Ozerenskis, D.; Pucetaite, M.; Sablinskas, V.; Cotter, C.; Guirgis, G. A.

    2015-03-30

    Raman spectra of germacyclohexane in liquid and solid states were recorded and depolarization data obtained. Infrared absorption spectra of the vapor and liquid have been studied. The wavenumbers of the vibrational modes were derived in the harmonic and anharmonic approximation in B3LYP/ccpVTZ calculations. According to the calculations, germacyclohexane exists in the stable chair conformation, whereas a possible twist form should have more than 15?kJmol{sup -1} higher enthalpy of formation what makes this conformer experimentally not observable. The 27 A' and 21 A'' fundamentals were assigned on the basis of the calculations and infrared and Raman band intensities, contours of gas phase infrared spectral bands and Raman depolarization measurements. An average discrepancy of ca. 0.77 % was found between the observed and the calculated anharmonic wavenumbers for the 48 modes. Substitution of carbon atom with Ge atom in the cyclohexane ring is reasoning flattening of the ring.

  8. Application of electron stimulated desorption techniques to measure the isotherm and the mean residence time of hydrogen physisorbed on a metal surface

    SciTech Connect (OSTI)

    Arakawa, Ichiro Shimizu, Hideyuki; Kawarabuki, Taku; Yamakawa, Koichiro; Miura, Takashi

    2015-03-15

    Electron stimulated desorption techniques were applied to probe the density of H{sub 2} physisorbed on a cold surface. The adsorption isotherm of H{sub 2} on a copper surface was measured in the equilibrium pressure range between 10{sup ?9} and 10{sup ?4} Pa at surface temperatures of 6.5 and 4.2?K. The mean residence times of H{sub 2} on copper were obtained from the observation of the time development of the surface density in a transitional state approaching equilibrium, and are 50500?s for the coverage between 1 and 0.18 at 4.2?K of the substrate temperature. The adsorption energies of 1.181.27?kJ/mol, and the condensation coefficient of 0.0740.018 were also deduced.

  9. Intermolecular triple proton and deuteron transfer in crystalline 3,5-dimethylpyrazole studied by NMR, NQR, and x-ray methods

    SciTech Connect (OSTI)

    Wehrle, B.; Aguilar-Parrilla, F.; Limbach, H.H. ); de la Concepcion Foces-Foces, M.; Cano, F.H. ); Elguero, J. ); Baldy, A.; Pierrot, M. ); Khurshid, M.M.T.; Larcombe-McDouall, J.B.; Smith, J.A.S. )

    1989-09-13

    A combination of {sup 13}C, {sup 15}N magnetic resonance, {sup 14}N quadrupole double resonance, and x-ray studies of solid 3,5-dimethylpyrazole between 270 and 350 K has shown that the NH...N hydrogen bond units present in the crystal are dynamically disordered, so that each nitrogen atom is on average attached to half a hydrogen atom. The molecules form discrete hydrogen-bonded cyclic trimers, in which the hydrogen atoms move in a double minimum potential energy surface which is symmetrical, to within experimental error. The experimental evidence in this temperature range is consistent with disorder by means of correlated triple hydrogen jumps with an activation energy of 45 kJ mol{sup {minus}1}. There is a large kinetic hydrogen (HHH)/deuterium (DDD) isotope effort of >20 at 299 K and equal to 8 at 347 K.

  10. Dynamics of CN+alkane reactions by crossed-beam dc slice imaging

    SciTech Connect (OSTI)

    Huang Cunshun; Li Wen; Estillore, Armando D.; Suits, Arthur G.

    2008-08-21

    The hydrogen atom abstraction reactions of CN (X {sup 2}{sigma}{sup +}) with alkanes have been studied using the crossed molecular beam technique with dc slice ion imaging at collision energies of 7.5 and 10.8 kcal/mol. The product alkyl radical images were obtained via single photon ionization at 157 nm for the reactions of CN (X {sup 2}{sigma}{sup +}) with n-butane, n-pentane, n-hexane, and cyclohexane. From analysis of the images, we obtained the center-of-mass frame product angular distributions and translational energy distributions directly. The results indicate that the products are largely backscattered and that most of the available energy ({approx}80%-85%) goes to the internal energy of the products. The reaction dynamics is discussed in light of recent kinetics data, theoretical calculations, and results for related halogen and oxygen atom reactions.

  11. In situ characterization of strontium surface segregation in epitaxial La{sub 0.7}Sr{sub 0.3}MnO{sub 3} thin films as a function of oxygen partial pressure

    SciTech Connect (OSTI)

    Fister, Tim T.; Fong, Dillon D.; Eastman, Jeffrey A.; Baldo, Peter M.; Highland, Matthew J.; Fuoss, Paul H.; Balasubramaniam, Kavaipatti R.; Meador, Joanna C.; Salvador, Paul A.

    2008-10-13

    Using in situ synchrotron measurements of total reflection x-ray fluorescence, we find evidence of strontium surface segregation in (001)-oriented La{sub 0.7}Sr{sub 0.3}MnO{sub 3} thin films over a wide range of temperatures (25-900 deg. C) and oxygen partial pressures (pO{sub 2}=0.15-150 Torr). The strontium surface concentration is observed to increase with decreasing pO{sub 2}, suggesting that the surface oxygen vacancy concentration plays a significant role in controlling the degree of segregation. Interestingly, the enthalpy of segregation becomes less exothermic with increasing pO{sub 2}, varying from -9.5 to -2.0 kJ/mol. In contrast, the La{sub 0.7}Sr{sub 0.3}MnO{sub 3} film thickness and epitaxial strain state have little impact on segregation behavior.

  12. Fluorohydrogenate Cluster Ions in the Gas Phase: Electrospray Ionization Mass Spectrometry of the [1-Ethyl-3-methylimidazolium+][F(HF)2.3] Ionic Liquid

    SciTech Connect (OSTI)

    Gary S. Groenewold; James E. Delmore; Michael T. Benson; Tetsuya Tsuda; Rika Hagiwara

    2013-12-01

    Electrospray ionization of the fluorohydrogenate ionic liquid [1-ethyl-3-methylimidazolium][F(HF)2.3] ionic liquid was conducted to understand the nature of the anionic species as they exist in the gas phase. Abundant fluorohydrogenate clusters were produced; however, the dominant anion in the clusters was [FHF-], and not the fluoride-bound HF dimers or trimers that are seen in solution. Density functional theory (DFT) calculations suggest that HF molecules are bound to the clusters by about 30 kcal/mol. The DFT-calculated structures of the [FHF-]-bearing clusters show that the favored interactions of the anions are with the methynic and acetylenic hydrogen atoms on the imidazolium cation, forming planar structures similar to those observed in the solid state. A second series of abundant negative ions was also formed that contained [SiF5-] together with the imidazolium cation and the fluorohydrogenate anions that originate from reaction of the spray solution with silicate surfaces.

  13. Impact of Biodiesel on the Oxidation Kinetics and Morphology of Diesel Particulate

    SciTech Connect (OSTI)

    Strzelec, Andrea; Toops, Todd J; Daw, C Stuart

    2011-01-01

    We compare the oxidation characteristics of four different diesel particulates generated with a modern light-duty engine. The four particulates represent engine fueling with conventional ultra-low sulfur diesel (ULSD), biodiesel, and two intermediate blends of these fuels. The comparisons discussed here are based on complementary measurements implemented in a laboratory micro-reactor, including temperature programmed desorption and oxidation, pulsed isothermal oxidation, and BET surface area. From these measurements we have derived models that are consistent with the observed oxidation reactivity differences. When accessible surface area effects are properly accounted for, the oxidation kinetics of the fixed carbon components were found to consistently exhibit an Arrhenius activation energy of 113 6 kJ/mol. Release of volatile carbon from the as-collected particulate appears to follow a temperaturedependent rate law.

  14. Radiation-Induced Decomposition of PETN and TATB under Extreme Conditions

    SciTech Connect (OSTI)

    Giefers, Hubertus; Pravica, Michael

    2008-11-03

    We conducted a series of experiments investigating decomposition of secondary explosives PETN and TATB at varying static pressures and temperatures using synchrotron radiation. As seen in our earlier work, the decomposition rate of TATB at ambient temperature slows systematically with increasing pressure up to at least 26 GPa but varies little with pressure in PETN at ambient temperature up to 15.7 GPa, yielding important information pertaining to the activation complex volume in both cases. We also investigated the radiation-induced decomposition rate as a function of temperature at ambient pressure and 26 GPa for TATB up to 403 K, observing that the decomposition rate increases with increasing temperature as expected. The activation energy for the TATB reaction at ambient temperature was experimentally determined to be 16 {+-} 3 kJ/mol.

  15. One-photon band gap engineering of borate glass doped with ZnO for photonics applications

    SciTech Connect (OSTI)

    Abdel-Baki, Manal; Abdel-Wahab, Fathy A.; El-Diasty, Fouad

    2012-04-01

    Lithium tungsten borate glass of the composition (0.56-x)B{sub 2}O{sub 3}-0.4Li{sub 2}O-xZnO-0.04WO{sub 3} (0 {<=}x{<=} 0.1 mol. %) is prepared for photonics applications. The glass is doped with ZnO to tune the glass absorption characteristics in a wide spectrum range (200-2500 nm). Chemical bond approach, including chemical structure, electronegativity, bond ionicity, nearest-neighbor coordination, and other chemical bonding aspect, is used to analyze and to explain the obtained glass properties such as: transmittance, absorption, electronic structure parameters (bandgap, Fermi level, and Urbach exciton-phonon coupling), Wannier free excitons excitation (applying Elliott's model), and two-photon absorption coefficient as a result of replacement of B{sub 2}O{sub 3} by ZnO.

  16. Size and charge effects of dopant M on the unit-cell parameters of monoclinic zirconia solid solutions Zr{sub 0.98}M{sub 0.02}O{sub 2{minus}{delta}} (M = Ce, La, Nd, Sm, Y, Er, Yb, Sc, Mg, Ca)

    SciTech Connect (OSTI)

    Yashima, Masatomo; Kakihana, Masato; Yoshimura, Masahiro; Hirose, Teruo; Suzuki, Yasuo

    1997-01-01

    The crystal structure of monoclinic phase [P2{sub 1}/c, Z = 4] has been refined by the Rietveld analysis of X-ray powder diffraction data to study the size and charge effects of dopant M{sup n+} on the unit-cell parameters of monoclinic ZrO{sub 2}-2 mol% MO{sub n/2} solid solutions (n = 4 for M = Ce; n = 3 for M = La, Nd, Sm, Y, Er, Yb, Sc; and n = 2 for M = Mg and Ca). For trivalent dopant (n = 3), the unit-cell parameters a{sub m}, b{sub m}, c{sub m} and unit-cell volume increase and {beta}{sub m} decreases with an increase of dopant size. Unit-cell volume increases with increasing of dopant charge n.

  17. Stabilization of lead lithium iron tungstate with adding barium titanate

    SciTech Connect (OSTI)

    Lu, C.; Fang, B.

    1997-01-01

    The kinetics of formation, phase stabilities, and dielectric constants of Pb(Li{sub 1/4}Fe{sub 1/4}W{sub 1/2})O{sub 3} and BaTiO{sub 3}-added Pb(Li{sub 1/4}Fe{sub 1/4}W{sub 1/2})O{sub 3} have been compared. The addition of 2 mol{percent} BaTiO{sub 3} in Pb(Li{sub 1/4}Fe{sub 1/4}W{sub 1/2})O{sub 3} was confirmed to promote the complete formation of the perovskite phase at 700{degree}C. Also the thermal stability of the perovskite phase was significantly enhanced, which results in an increase of the dielectric permittivity. {copyright} {ital 1997 Materials Research Society.}

  18. Modeling of NOx Destruction Options for INEEL Sodium-Bearing Waste Vitrification

    SciTech Connect (OSTI)

    Wood, Richard Arthur

    2001-09-01

    Off-gas NOx concentrations in the range of 1-5 mol% are expected as a result of the proposed vitrification of sodium-bearing waste at the Idaho National Engineering and Environmental Laboratory. An existing kinetic model for staged combustion (originally developed for NOx abatement from the calcination process) was updated for application to vitrification offgas. In addition, two new kinetic models were developed to assess the feasibility of using selective non-catalytic reduction (SNCR) or high-temperature alone for NOx abatement. Each of the models was developed using the Chemkin code. Results indicate that SNCR is a viable option, reducing NOx levels to below 1000 ppmv. In addition, SNCR may be capable of simultaneously reducing CO emissions to below 100 ppmv. Results for using high-temperature alone were not as promising, indicating that a minimum NOx concentration of 3950 ppmv is achievable at 3344F.

  19. Intermolecular interactions involving C-H bonds, 3, Structure and energetics of the interaction between CH{sub 4} and CN{sup {minus}}

    SciTech Connect (OSTI)

    Novoa, J.J.; Whangbo, Myung-Hwan; Williams, J.M.

    1991-12-31

    On the basis of SCF and single reference MP2 calculations, the full potential energy surface of the interaction between CH{sub 4} and CN{sup {minus}} was studied using extended basis sets of up to near Hartree-Fock limit quality. Colinear arrangements C-N{sup {minus}}{hor_ellipsis}H-CH{sub 3} and N-C{sup {minus}}{hor_ellipsis}H-CH{sub 3} are found to be the only two energy minima. The binding energies of these two structures are calculated to be 2.5 and 2.1 kcal/mol, respectively, at the MP2 level. The full vibrational analyses of two structures show a red shift of about 30 cm{sup {minus}1} for the v{sub s} C-H stretching.

  20. Communication: Towards the binding energy and vibrational red shift of the simplest organic hydrogen bond: Harmonic constraints for methanol dimer

    SciTech Connect (OSTI)

    Heger, Matthias; Suhm, Martin A.; Mata, Ricardo A.

    2014-09-14

    The discrepancy between experimental and harmonically predicted shifts of the OH stretching fundamental of methanol upon hydrogen bonding to a second methanol unit is too large to be blamed mostly on diagonal and off-diagonal anharmonicity corrections. It is shown that a decisive contribution comes from post-MP2 electron correlation effects, which appear not to be captured by any of the popular density functionals. We also identify that the major deficiency is in the description of the donor OH bond. Together with estimates for the electronic and harmonically zero-point corrected dimer binding energies, this work provides essential constraints for a quantitative description of this simple hydrogen bond. The spectroscopic dissociation energy is predicted to be larger than 18 kJ/mol and the harmonic OH-stretching fundamental shifts by about ?121 cm{sup ?1} upon dimerization, somewhat more than in the anharmonic experiment (?111 cm{sup ?1})

  1. Crossed-beam DC slice imaging of fluorine atom reactions with linear alkanes

    SciTech Connect (OSTI)

    Shi, Yuanyuan; Kamasah, Alexander; Joalland, Baptiste; Suits, Arthur G.

    2015-05-14

    We report the reaction dynamics of F atom with selected alkanes studied by crossed beam scattering with DC slice ion imaging. The target alkanes are propane, n-butane, and n-pentane. The product alkyl radicals are probed by 157 nm single photon ionization following reaction at a collision energy of ∼10 kcal mol{sup −1}. The analyzed data are compared with the corresponding theoretical studies. Reduced translational energy distributions for each system show similar trends with little of the reaction exoergicity appearing in translation. However, the pentane reaction shows a somewhat smaller fraction of available energy in translation than the other two, suggesting greater energy channeled into pentyl internal degrees of freedom. The center-of-mass angular distributions all show backscattering as well as sharp forward scattering that decreases in relative intensity with the size of the molecule. Possible reasons for these trends are discussed.

  2. Partial substitution of Mo{sup 6+} by S{sup 6+} in the fast oxide ion conductor La{sub 2}Mo{sub 2}O{sub 9}: Synthesis, structure and sulfur depletion

    SciTech Connect (OSTI)

    Mhadhbi, Noureddine; Corbel, Gwenaeel; Lacorre, Philippe; Bulou, Alain

    2012-06-15

    Powder-solid state reaction route using La{sub 2}(SO{sub 4}){sub 3} as sulfur source was used to prepare compositions of the solid solution La{sub 2}Mo{sub 2-y}S{sub y}O{sub 9}. Single phases were only obtained in the substitution range extending up to y=0.8 (40 mol% S) at the annealing temperature of 850 Degree-Sign C with regard to the limit of stability of the lanthanum sulphate reactant. Within the synthesis conditions, a stabilization of the high temperature {beta}-form is observed from and above y=0.1 (5 mol% S). Temperature-controlled X-ray diffraction and thermogravimetric analyses have shown that La{sub 2}Mo{sub 2-y}S{sub y}O{sub 9} raw powders undergo thermal decompositions in two steps. Heating above 900 Degree-Sign C, a sulfur depletion to the benefit of molybdenum in La{sub 2}Mo{sub 2-y}S{sub y}O{sub 9} raw powders leads to the formation of La{sub 2}SO{sub 6}. At higher temperature, the exsolved La{sub 2}SO{sub 6} phase then decomposes into La{sub 2}O{sub 3}, which in turn reacts with the sulfur-depleted La{sub 2}Mo{sub 2}O{sub 9} phase to form La{sub 2}MoO{sub 6}. The present study also reveals that depending on the substitution rate y, the sulfur depletion can be induced by ball-milling of raw powders. Along the La{sub 2}Mo{sub 2-y}S{sub y}O{sub 9} series, the isovalent substitution of molybdenum by sulfur tends to restrict in magnitude, or even to suppress above 400 Degree-Sign C, the distortive thermal expansion of the cubic {beta}-type structure, thus strongly decreasing the conductance at high temperature. - Graphical abstract: La{sub 2}O{sub 3}-MoO{sub 3}-'SO{sub 3}' ternary phase diagram showing the exsolution path at low temperature (white arrows) and the total decomposition path at high temperature (black arrows) of {beta}-La{sub 2}Mo{sub 2-y}S{sub y}O{sub 9} raw powders. Highlights: Black-Right-Pointing-Pointer Isovalent substitution of molybdenum by sulfur in La{sub 2}Mo{sub 2}O{sub 9} up to 40 mol%. Black-Right-Pointing-Pointer Stabilization of the {beta}-form for a sulfur content greater than or equal to 5 mol%. Black-Right-Pointing-Pointer Decomposition by sulfur exsolution induced by thermal treatment or ball-milling. Black-Right-Pointing-Pointer Reduction or even cancellation of the distortive thermal expansion above 400 Degree-Sign C. Black-Right-Pointing-Pointer Decrease of conductance at high T involved by the low thermal expansion above 400 Degree-Sign C.

  3. Broadband sensitization of downconversion phosphor YPO{sub 4} by optimizing TiO{sub 2} substitution in host lattice co-doped with Pr{sup 3+}-Yb{sup 3+} ion-couple

    SciTech Connect (OSTI)

    Li, Kai-Yu; Liu, Li-Ying; Wang, Ru-Zhi Yan, Hui; Xiao, Si-Guo; Zhou, Hua

    2014-03-28

    This study demonstrates a feasible and efficient route to alleviate the absorption problem of the terrestrial solar spectrum and enhance broadband luminescence from a promising down conversion powder phosphor YPO{sub 4} co-doped with Pr{sup 3+}-Yb{sup 3+} lanthanide ion-couple: incorporating a third sensitizing transition metal ion, e.g., Ti{sup 4+}. The x-ray powder diffraction results confirm the lattice substitution by the solid-state reaction doping rather than the formation of any secondary phase. The emission spectral results and the luminescence decay curve analysis show that the downconversion luminescence can be enhanced by 200%300% and the quantum efficiency enhanced by more than 20% at the wavelength of around 980?nm, the best response spectrum for Si-based solar cells, by optimizing TiO{sub 2} doping concentration at 7?mol. %.

  4. Thermodynamics of methane adsorption on copper HKUST-1 at low pressure

    SciTech Connect (OSTI)

    Wu, Di; Guo, Xiaofeng; Sun, Hui; Navrotsky, Alexandra

    2015-06-11

    Metalorganic frameworks (MOFs) can be engineered as natural gas storage materials by tuning the pore structures and surface properties. Here we report the direct measurement of CH? adsorption enthalpy on a paddlewheel MOF (Cu HKUST-1) using gas adsorption calorimetry at 25 C at low pressures (below 1 bar). In this pressure region, the CH?CH? intermolecular interactions are minimized and the energetics solely reflects the CH?MOF interactions. Our results suggest moderately exothermic physisorption with an enthalpy of -21.1 1.1 kJ/mol CH? independent of coverage. The calorimetric investigation complements previous computational and crystallographic studies by providing zero coverage enthalpies of CH? adsorption. The analysis of the new and literature data suggests that in initial stages of adsorption the CH?HKUST-1 interaction tends to be more sensitive to the pore dimension than to the guest polarizability, suggesting a less specific chemical binding role for the open Cu site.

  5. Extremely strong tubular stacking of aromatic oligoamide macrocycles

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

    Kline, Mark A.; Wei, Xiaoxi; Horner, Ian J.; Liu, Rui; Chen, Shuang; Chen, Si; Yung, Ka Yi; Yamato, Kazuhiro; Cai, Zhonghou; Bright, Frank V.; et al

    2015-01-01

    As the third-generation rigid macrocycles evolved from progenitor 1, cyclic aromatic oligoamides 3, with a backbone of reduced constraint, exhibit extremely strong stacking with an astoundingly high affinity (estimated lower limit of Kdimer > 1013 M-1 in CHCl3), which leads to dispersed tubular stacks that undergo further assembly in solution. Computational study reveals a very large binding energy (-49.77 kcal mol-1) and indicates highly cooperative local dipole interactions that account for the observed strength and directionality for the stacking of 3. In the solid-state, X-ray diffraction (XRD) confirms that the aggregation of 3 results in well-aligned tubular stacks. The persistentmore » tubular assemblies of 3, with their non-deformable sub-nm pore, are expected to possess many interesting functions. One such function, transmembrane ion transport, is observed for 3.« less

  6. Spectroscopic properties of (PVA+ZnO):Mn{sup 2+} polymer films

    SciTech Connect (OSTI)

    Rani, Ch.; Raju, D. Siva; Bindu, S. Hima; Krishna, J. Suresh; Raju, Ch. Linga

    2015-05-15

    Electron Paramagnetic Resonance (EPR), optical absorption and infrared spectral studies have been carried out on Mn{sup 2+} ions doped in poly(vinyl alcohol) complexed with zinc oxide polymer films prepared by solution cast technique. The EPR spectra of 1 mol% Mn{sup 2+} ions doped polymer complex (PVA+ZnO) at room temperature exhibit sextet hyperfine structure (hfs), centered at 2.01. The spin-Hamiltonian parameter values indicate that the ground state of Mn{sup 2+} ion in d{sup 5} and the site symmetry around Mn{sup 2+} ions in tetragonally distorted octa hedral site. The optical absorption spectra exhibits two bands centered at 275nm at 437nm. The FTIR spectrum exhibits bands characteristic of stretching and banding vibrations of O-H, C-H and C=C groups.

  7. Non-covalent interactions of nitrous oxide with aromatic compounds: Spectroscopic and computational evidence for the formation of 1:1 complexes

    SciTech Connect (OSTI)

    Cao, Qian; School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275 ; Gor, Gennady Y.; Krogh-Jespersen, Karsten; Khriachtchev, Leonid

    2014-04-14

    We present the first study of intermolecular interactions between nitrous oxide (N{sub 2}O) and three representative aromatic compounds (ACs): phenol, cresol, and toluene. The infrared spectroscopic experiments were performed in a Ne matrix and were supported by high-level quantum chemical calculations. Comparisons of the calculated and experimental vibrational spectra provide direct identification and characterization of the 1:1 N{sub 2}O-AC complexes. Our results show that N{sub 2}O is capable of forming non-covalently bonded complexes with ACs. Complex formation is dominated by dispersion forces, and the interaction energies are relatively low (about ?3 kcal mol{sup ?1}); however, the complexes are clearly detected by frequency shifts of the characteristic bands. These results suggest that N{sub 2}O can be bound to the amino-acid residues tyrosine or phenylalanine in the form of ? complexes.

  8. Evolution of structure in Na{sub 0.5}Bi{sub 0.5}TiO{sub 3} single crystals

    Office of Scientific and Technical Information (OSTI)

    with BaTiO{sub 3} (Journal Article) | SciTech Connect Evolution of structure in Na{sub 0.5}Bi{sub 0.5}TiO{sub 3} single crystals with BaTiO{sub 3} Citation Details In-Document Search Title: Evolution of structure in Na{sub 0.5}Bi{sub 0.5}TiO{sub 3} single crystals with BaTiO{sub 3} The structural, dielectric, and piezoelectric properties of Na{sub 0.5}Bi{sub 0.5}TiO{sub 3}-x mol. %BaTiO{sub 3} (NBT-x%BT) crystals have been investigated. The dielectric and piezoelectric properties of NBT-x%BT

  9. Viscosity correlations for binary supercritical fluids

    SciTech Connect (OSTI)

    Tilly, K.D.; Foster, N.R.; Macnaughton, S.J.; Tomasko, D.L. . School of Chemical Engineering and Industrial Chemistry)

    1994-03-01

    The viscosities and densities of supercritical mixtures of methanol, ethanol, n-propanol, isopropanol, n-pentane, n-hexane, n-heptane, and acetone in carbon dioxide, at concentrations between 1 and 5 mol %, were determined using a falling weight viscometer at pressures up to 240 bar and at temperatures between 313 and 328 K. The effects of pressure, temperature, cosolvent concentration, and the physical properties of the cosolvents on the mixture viscosity and density were examined. The viscosities and the densities of the mixtures were found to increase with the size, polarity, and concentration of the cosolvent molecule. The mixture viscosity was correlated with several empirical dense gas viscosity correlations. The best correlation was the Ely and Hanley technique modified with a density-dependent noncorrespondence factor. The Peng-Robinson equation of state was used to correlate the mixture densities.

  10. Near-ambient X-ray photoemission spectroscopy and kinetic approach to the mechanism of carbon monoxide oxidation over lanthanum substituted cobaltites

    SciTech Connect (OSTI)

    Hueso, J. L.; Martinez-Martinez, D.; Cabalerro, Alfonso; Gonzalez-Elipe, Agustin Rodriguez; Mun, Bongjin Simon; Salmeron, Miquel

    2009-07-31

    We have studied the oxidation of carbon monoxide over a lanthanum substituted perovskite (La0.5Sr0.5CoO3-d) catalyst prepared by spray pyrolysis. Under the assumption of a first-order kinetics mechanism for CO, it has been found that the activation energy barrier of the reaction changes from 80 to 40 kJ mol-1 at a threshold temperature of ca. 320 oC. In situ XPS near-ambient pressure ( 0.2 torr) shows that the gas phase oxygen concentration over the sample decreases sharply at ca. 300 oC. These two observations suggest that the oxidation of CO undergoes a change of mechanism at temperatures higher than 300 oC.

  11. 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.

  12. Hydrogenated 5-carbon compound and method of making

    DOE Patents [OSTI]

    Elliott, D.C.; Frye, J.G.

    1999-03-16

    The present invention is based upon the surprising discovery that a 5-carbon compound selected from the group of 4-oxopentanoic acid, at least one lactone of 4-oxopentanoic acid, and combinations thereof, may be hydrogenated with a bimetallic catalyst of a noble metal in combination with a second metal and preserve the pendant methyl group. It was further unexpectedly discovered that the same conditions of bimetallic catalyst in the presence of hydrogen are useful for catalyzing the different intermediate reactions, for example, angelicalactone to gamma-valerolactone and gamma-valerolactone to 1,4-pentanediol. Finally, it was surprising that levulinic acid could be converted to 2-methyltetrahydrofuran with heating in the presence of the bimetallic catalyst and hydrogen in a single process vessel. The method of the present invention unexpectedly produced a fuel or fuel component having 2-methyltetrahydrofuran either in a yield greater than 4.5 mol % or in combination with alcohols. 8 figs.

  13. The reaction of acetylene with hydroxyl radicals.

    SciTech Connect (OSTI)

    Klippenstein, Stephen J.; Senosiain, Juan P.; Miller, James A.

    2005-02-01

    The potential energy surface for the reaction between OH and acetylene has been calculated using the RQCISD(T) method and extrapolated to the complete basis-set limit. Rate coefficients were determined for a wide range of temperatures and pressures, based on this surface and the solution of the one-dimensional and two-dimensional master equations. With a small adjustment to the association energy barrier (1.1 kcal/mol), agreement with experiments is good, considering the discrepancies in such data. The rate coefficient for direct hydrogen abstraction is significantly smaller than that commonly used in combustion models. Also in contrast to previous models, ketene + H is found to be the main product at normal combustion conditions. At low temperatures and high pressures, stabilization of the C{sub 2}H{sub 2}OH adduct is the dominant process. Rate coefficient expressions for use in modeling are provided.

  14. Dynamic Mechanical Thermal Analysis of Virgin TR-55 Silicone Rubber

    SciTech Connect (OSTI)

    Small IV, W; Wilson, T S

    2009-10-09

    Dynamic mechanical thermal analysis (DMTA) of virgin TR-55 silicone rubber specimens was conducted. Dynamic frequency/temperature sweep tests were conducted over the ranges 0.1-100 rad/s and 30-100 C using a parallel plate test geometry. A strain of 0.2% was used, which was near the upper limit of the linear viscoelastic region of the material based on initial dynamic strain sweep tests. Master curves of G{prime} and G{double_prime} as a function of frequency were generated using time-temperature superposition (horizontal shift with initial vertical correction). The activation energy calculated from an Arrhenius fit to the horizontal shift factors was 178-355 kJ/mol. The calculated percent load retention at {approx}50 years was 61-68%.

  15. Purification of 1-aminocyclopropane-1-carboxylate synthase from apple fruits using s-adenosyl (3,4 sup 14 C)-methionine (SAM) as a probe

    SciTech Connect (OSTI)

    Yip, Wingkip; Dong, Jianguo,; Yang, Shang Fa )

    1989-04-01

    Tomato ACC synthase is inactivated by its substrate SAM, with the moiety of aminobutyrate being covalently linked to ACC synthase during the catalytic reactions. A partial purified ACC synthase (the catalytic activity 100 {mu}mol/h{center dot}mg protein) from pellets of apple extract was incubated with (3,4{sup 14}C) SAM. Only one radioactive peak was revealed in a C-4 reverse phase HPLC and one radioactive band on SDS-PAGE with an M.W. of 48 kDa. Apple ACC synthase in native form is resistant to V8, {alpha}-chromtrypsin and carboxylpeptidase A digestion, but effectively inactivated by trypsin and ficin, as demonstrated by both the activity assay and SAM labeling. The radioactive protein cut from the SDS-PAGE was injected to three mice, two of the mice showed responses to the protein in western blot analysis. The antibodies from mice is currently under characterization.

  16. Effect of CaF{sub 2} addition on optical properties of barium phosphate glasses

    SciTech Connect (OSTI)

    Kumar, N. Manoj Rao, G. Venkateswara Akhila, B. E. Shashikala, H. D.

    2014-04-24

    Ternary barium phosphate glasses, (50?X)BaO?XCaF{sub 2}?50P{sub 2}O{sub 5} have been prepared by adding 0-10 mol% of CaF{sub 2} to binary barium phosphate glasses. The amorphous nature of the prepared glasses was confirmed by X-ray diffraction technique. The UV-Visible absorption spectra have been recorded, optical band gap energy Eopt and Urbach energy Etail were determined. Shift in Eopt and Etail with increase in concentration of CaF{sub 2} is noted. FTIR analysis was carried out to investigate the short and intermediate-range orders in glasses. Shift of (P-O-P) band to higher wave number with the substitution of BaO with CaF{sub 2} shows the shortening of the phosphate chains. Hardness and density of glass samples were measured and correlated with the composition of glasses.

  17. Spectroscopic studies of silver boro tellurite glasses

    SciTech Connect (OSTI)

    Kumar, E. Ramesh Kumari, K. Rajani Rao, B. Appa Bhikshamaiah, G.

    2014-04-24

    The FTIR absorption and Raman scattering studies were used to obtain the structural information of AgI?Ag{sub 2}O?[(1?x)B{sub 2}O{sub 3}?xTeO{sub 2}] (x=0 to 1 mol% in steps of 0.2) glasses. The glassy nature of the compounds has been confirmed by X-ray diffraction. FTIR and Raman spectra were recorded for all samples at room temperature. FTIR spectra which provides the information about the change in bond structure of the glasses. Raman spectra provide the effect of TeO{sub 2} on SBT glass system is that as increasing the concentration of TeO{sub 2} the band intensity at 707 cm{sup ?1} increase.

  18. Catalytic Ionic Hydrogenation of Ketones by {[Cp*Ru(CO)2]2(? H)}+

    SciTech Connect (OSTI)

    Fagan, Paul J.; Voges, Mark H.; Bullock, R. Morris

    2010-02-22

    {[Cp*Ru(CO)2]2(? H)}+OTf functions as a homogeneous catalyst precursor for hydrogenation of ketones to alcohols, with hydrogenations at 1 mol % catalyst loading at 90 C under H2 (820 psi) proceeding to completion and providing >90% yields. Hydrogenation of methyl levulinate generates ?-valerolactone, presumably by ring-closing of the initially formed alcohol with the methyl ester. Experiments in neat Et2C=O show that the catalyst loading can be <0.1 mole %, and that at least 1200 turnovers of the catalyst can be obtained. These reactions are proposed to proceed by an ionic hydrogenation pathway, with the highly acidic dihydrogen complex [Cp*Ru(CO)2(?2-H2)]+OTf- being formed under the reaction conditions from reaction of H2 with {[Cp*Ru(CO)2]2(? H)}+OTf .

  19. Investigations of Near-Field Thermal-Hydrologic-Mechanical-Chemical Models for Radioactive Waste Disposal in Clay/Shale Rock

    SciTech Connect (OSTI)

    Liu, H.H.; Li, L.; Zheng, L.; Houseworth, J.E.; Rutqvist, J.

    2011-06-20

    Clay/shale has been considered as potential host rock for geological disposal of high-level radioactive waste throughout the world, because of its low permeability, low diffusion coefficient, high retention capacity for radionuclides, and capability to self-seal fractures. For example, Callovo-Oxfordian argillites at the Bure site, France (Fouche et al., 2004), Toarcian argillites at the Tournemire site, France (Patriarche et al., 2004), Opalinus Clay at the Mont Terri site, Switzerland (Meier et al., 2000), and Boom clay at the Mol site, Belgium (Barnichon and Volckaert, 2003) have all been under intensive scientific investigation (at both field and laboratory scales) for understanding a variety of rock properties and their relationships to flow and transport processes associated with geological disposal of radioactive waste. Figure 1-1 presents the distribution of clay/shale formations within the USA.

  20. Hydrogenated 5-carbon compound and method of making

    DOE Patents [OSTI]

    Elliott, Douglas C. (Richland, WA); Frye, John G. (Richland, WA)

    1999-01-01

    The present invention is based upon the surprising discovery that a 5-carbon compound selected from the group of 4-oxopentanoic acid, at least one lactone of 4-oxopentanoic acid, and combinations thereof, may be hydrogenated with a bimetallic catalyst of a noble metal in combination with a second metal and preserve the pendant methyl group. It was further unexpectedly discovered that the same conditions of bimetallic catalyst in the presence of hydrogen are useful for catalyzing the different intermediate reactions for example angelicalactone to gamma-valerolactone and gamma-valerolactone to 1,4-pentanediol. Finally, it was surprising that levulinic acid could be converted to 2-methyltetrahydrofuran with heating in the presence of the bimetallic catalyst and hydrogen in a single process vessel. The method of the present invention unexpectedly produced a fuel or fuel component having 2-methyltetrahydrofuran either in a yield greater than 4.5 mol % or in combination with alcohols.

  1. Effect of seawater temperature on uranium recovery from seawater using amidoxime adsorbents

    SciTech Connect (OSTI)

    Sekiguchi, Koji; Saito, Kyoichi; Konishi, Satoshi; Furusaki, Shintaro . Dept. of Chemical Engineering); Sugo, Takanobu . Takasaki Radiation Chemistry Research Establishment); Nobukawa, Hisashi . Dept. of Naval Architecture and Ocean Engineering)

    1994-03-01

    Porous amidoxime hollow fibers, which were prepared by radiation-induced graft polymerization of acrylonitrile onto porous polyethylene hollow fibers and subsequent amidoximation, were used as packing materials of the adsorption bed for uranium recovery from seawater. Seawater was forced to flow through the bed charged with the amidoxime hollow fibers either by pumping or by ocean current. Uranium concentration decay through the bed could be well correlated with residence time based on the adsorption rate expressed in terms of the overall mass-transfer coefficient. The resultant activation energy of 20 kcal/mol for uranium adsorption was indicative of the chelate formation of the amidoxime group with uranyl species as a rate-determining step.

  2. Poly(lactide)-block-poly([epsilon]-caprolactone-co-[epsilon]-decalactone)-block-poly(lactide) copolymer elastomers

    SciTech Connect (OSTI)

    Schneiderman, Deborah K.; Hill, Erin M.; Martello, Mark T.; Hillmyer, Marc A.

    2015-08-28

    Batch ring opening transesterification copolymerization of ?-caprolactone and ?-decalactone was used to generate statistical copolymers over a wide range of compositions and molar masses. Reactivity ratios determined for this monomer pair, rCL = 5.9 and rDL = 0.03, reveal ?-caprolactone is added preferentially regardless of the propagating chain end. Relative to poly(?-caprolactone) the crystallinity and melting point of these statistical copolymers were depressed by the addition of ?-decalactone; copolymers containing greater than 31 mol% (46 wt%) ?-decalactone were amorphous. Poly(lactide)-block-poly(?-caprolactone-co-?-decalactone)-block-poly(lactide) triblock polymers were also prepared and used to explore the influence of midblock composition on the temperature dependent Flory-Huggins interaction parameter (?). In addition, uniaxial extension tests were used to determine the effects of midblock composition, poly(lactide) content, and molar mass on the mechanical properties of these new elastomeric triblocks.

  3. Effect of filler metal composition on the strength of yttria stabilized zirconia joints brazed with Pd-Ag-CuOx

    SciTech Connect (OSTI)

    Darsell, Jens T.; Weil, K. Scott

    2008-09-08

    The Ag-CuOx system is of interest to be used to be used as an air braze filler metal for joining high temperature electrochemical devices. Previous work has shown that the melting temperatures can be increased by adding palladium to Ag-CuOx and it is expected that this may aid high temperature stability. This work compares the room temperature bend strength of joints made between yttria-stabilized zirconia (YSZ) air brazed using Ag-CuOx without palladium and with 5 and 15mol% palladium additions. It has been found that in general palladium decreases joint strength, especially in low copper oxide compositions filler metals. At high copper oxide contents, brittle fracture through both copper oxide rich phases and the YSZ limits joint strength.

  4. X-ray diffraction and electron microscope studies of yttria stabilized zirconia (YSZ) ceramic coatings exposed to vanadia. Master's thesis

    SciTech Connect (OSTI)

    Kondos, K.G.

    1992-09-01

    The U.S. Navy sometimes has the requirement to use low cost fuels containing significant amounts of vanadium and sulfur in gas turbine engines. Unfortunately the yttria stabilized zirconia (YSZ) witch is used as a thermal barrier coating on gas turbine blades can be severely attacked by vanadia. Powders of YSZ containing 8-mol% Y203 and pure zirconia containing various and mounts Of V205 were annealed at 900 deg. C. These were then examined by X-ray diffraction and electron microscopy, as well as single crystals of pure Zro2 and YSZ ( 20% Wt Y203 ) exposed to V205 Melts, to study how the vanadia degrades the YSZ by reacting with the stabilizer to form YVO4 and how the vanadium transforms the cubic and tetragonal YSZ crystal structures to monoclinic which degrades rapidly as a gas turbine blade coating.

  5. Transport properties of lithium- lead-vanadium-telluride glass and glass ceramics

    SciTech Connect (OSTI)

    Sathish, M.; Eraiah, B.

    2014-04-24

    Glasses with the chemical composition 35Li{sub 2}O-(45-x)V{sub 2}O{sub 5?}20PbO-xTeO{sub 2} (where x = 2.5, 5, 7.5, 10, 15 mol %) have prepared by conventional melt quenching method. The electrical conductivity of Li{sup +} ion conducting lead vanadium telluride glass samples has been carried out both as a function of temperature and frequency in the temperature range 503K-563K and over frequencies 40 Hz to 10 MHz. The electronic conduction has been observed in the present systems. When these samples annealed around 400C for 2hour become the glass ceramic, which also shows increase tendency of conductivity. SEM confines glass and glass ceramic nature of the prepared samples.

  6. The glass transition temperature of glassy polymers using dynamic mechanical analysis

    SciTech Connect (OSTI)

    Rodriguez, E.L.

    1994-09-01

    Dynamic Mechanical Analysis (DMA) is presented for four glassy polymers. Poly(vinyl acetate), poly(vinyl chloride), poly(styrene), and poly(carbonate) were studied as a function of the heating rate using ramp and step heating programs and a constant frequency of 1 Hz. The effect of frequency on the dynamic mechanical parameters was also examined from 0.01 Hz to 10 Hz. The dynamic elastic storage modulus (E{double_prime}), the dynamic elastic loss modulus (E{double_prime}) and the tan{delta} (E{double_prime}/E{prime}) were affected by both the heating rate and the frequency. Apparent activation energies for the glass transition were also determined for the four polymers which were in the range from 98 of 194 kcal/mol.

  7. Hydration of Kr(aq) in dilute and concentrated solutions

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

    Chaudhari, Mangesh I.; Sabo, Dubravko; Pratt, Lawrence R.; Rempe, Susan B.

    2014-10-13

    Molecular dynamics simulations of water with both multi-Kr and single Kr atomic solutes are carried out to implement quasi-chemical theory evaluation of the hydration free energy of Kr(aq). This approach obtains free energy differences reflecting Kr–Kr interactions at higher concentrations. Those differences are negative changes in hydration free energies with increasing concentrations at constant pressure. The changes are due to a slight reduction of packing contributions in the higher concentration case. The observed Kr–Kr distributions, analyzed with the extrapolation procedure of Krüger et al., yield a modestly attractive osmotic second virial coefficient, B2 ≈ -60 cm3/mol. Moreover, the thermodynamic analysismore » interconnecting these two approaches shows that they are closely consistent with each other, providing support for both approaches.« less

  8. Microsoft Word - CR.doc

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

    March 2004 Table 1. Estimated composition of REDOX HLW released from Tank 108 to the vadose zone in 1969 (from Jones et al., 2000). Temperature (° C) 100 H 2 O mole fraction 0.539 H 2 O weight fraction 0.304 Solution density (g/cm 3 ) 2.09 Ionic strength 18.02 Primary Chemical Species (mol/L) Al(OH) 4 - 3.36 K + 7.39 x 10 -2 Na + 19.6 OH - 5.25 NO 3 - 5.46 NO 2 - 4.42 Cl - 0.34 CO 3 2- 3.25 x 10 -2 SO 4 2- 2.77 x 10 -2 CrO 4 2- 4.13 x 10 -1 137 Cs + 6.51 x 10 -5 Table 1. Estimated composition

  9. Structural basis for thermostability revealed through the identification and characterization of a highly thermostable phosphotriesterase-like lactonase from Geobacillus stearothermophilus

    SciTech Connect (OSTI)

    Hawwa, Renda; Aikens, John; Turner, Robert J.; Santarsiero, Bernard D.; Mescar, Andrew D.

    2009-08-31

    A new enzyme homologous to phosphotriesterase was identified from the bacterium Geobacillus stearothermophilus (GsP). This enzyme belongs to the amidohydrolase family and possesses the ability to hydrolyze both lactone and organophosphate (OP) compounds, making it a phosphotriesterase-like lactonase (PLL). GsP possesses higher OP-degrading activity than recently characterized PLLs, and it is extremely thermostable. GsP is active up to 100 C with an energy of activation of 8.0 kcal/mol towards ethyl paraoxon, and it can withstand an incubation temperature of 60 C for two days. In an attempt to understand the thermostability of PLLs, the X-ray structure of GsP was determined and compared to those of existing PLLs. Based upon a comparative analysis, a new thermal advantage score and plot was developed and reveals that a number of different factors contribute to the thermostability of PLLs.

  10. Palladium-coated zirconium membranes for oxidative extraction of hydrogen

    SciTech Connect (OSTI)

    Hsu, C.; Buxbaum, R.E.

    1987-01-01

    Palladium-coated metal membranes are attractive choices for low pressure, high temperature hydrogen and hydrogen isotope extractions, e.g. from fusion blanket fluids. The authors present experimental data on hydrogen transport through palladium-coated zirconium membranes at 600 - 700/sup 0/K. The upstream hydrogen pressure range is 10/sup -4/ to 10/sup -6/ torr and an oxygen-containing gas flows over the downstream side of the membrane. Thus, the irreversible oxidation reaction drives the flux. Deuterium permeabilities in zirconium are 2.00x10/sup -6/exp(59/T)+-20% g-mol/m.s.Pa/sup 1/2/, similar to the values obtained from diffusivity and solubility measurements. Extrapolated deuterium absorptive sticking coefficients on palladium are about .05.

  11. Amorphization and crystallization processes of the ball-milled Al-Y-Fe-TM alloys (TM=Ni, Co, Cu, and Fe) (Prop. 2003-037)

    SciTech Connect (OSTI)

    Wilson, Timothy W.; Choo, Hahn; Porter, Wallace D; Speakman, Scott A; Fan, Chang; Liaw, Peter K

    2006-01-01

    High-energy ball milling was used to synthesize aluminum-based alloys containing amorphous and nanocrystalline phases to investigate the compositional effects of transition metals (TM) on the amorphization and crystallization processes of the ball-milled Al{sub 85}Y{sub 7}Fe{sub 5}TM{sub 3} alloys (TM = Ni, Co, Cu, and Fe) were investigated. The crystallization kinetics of the ball-milled Al-Y-Fe-TM nanocomposite powders were studied using differential scanning calorimetry (DSC). The DSC results of Al{sub 83}Y{sub 7}Fe{sub 5}Ni{sub 5} show that the crystallization temperature and the activation energy of crystallization are 668 K and 310 kJ/mol, respectively. In-situ high-temperature X-ray diffraction showed that the crystallization was a complex process involving growth of the nanocrystalline phase along with crystallization of the amorphous matrix phase.

  12. Organotin piezo- and pyroelectric polymer films. [Synthesis, glass transition, and piezo- and pyroelectric activity

    SciTech Connect (OSTI)

    Liepins, R.; Timmons, M.L.; Morosoff, N.; Surles, J.

    1983-01-01

    The synthesis of a new class of piezo- and pyroelectrically active materials of various co- and terpolymers of tributylin methacrylate (TBTM) and trimethyltin methacrylate (TMTM) is described. A description of sample preparation, poling techniques, and measurement system is given in some detail. Films of the various polymer compositions were evaluated for tin current, glass transition temperature (Tg), crystallinity or ordering of the amorphous phase and piezo- and pytoelectric activity. Experimental results on 25 to 30 mol% TBTM/methyl methacrylate copolymers, which possessed good piezoelectric activity, antifouling properties and paint-formulation characteristics, are discussed in detail. Solvent-induced orientation effects that lead to piezoelectric activity in amorphous, unpoled, polymers are also described.

  13. Extremely strong tubular stacking of aromatic oligoamide macrocycles

    SciTech Connect (OSTI)

    Kline, Mark A.; Wei, Xiaoxi; Horner, Ian J.; Liu, Rui; Chen, Shuang; Chen, Si; Yung, Ka Yi; Yamato, Kazuhiro; Cai, Zhonghou; Bright, Frank V.; Zeng, Xiao Cheng; Gong, Bing

    2015-01-01

    As the third-generation rigid macrocycles evolved from progenitor 1, cyclic aromatic oligoamides 3, with a backbone of reduced constraint, exhibit extremely strong stacking with an astoundingly high affinity (estimated lower limit of Kdimer > 1013 M-1 in CHCl3), which leads to dispersed tubular stacks that undergo further assembly in solution. Computational study reveals a very large binding energy (-49.77 kcal mol-1) and indicates highly cooperative local dipole interactions that account for the observed strength and directionality for the stacking of 3. In the solid-state, X-ray diffraction (XRD) confirms that the aggregation of 3 results in well-aligned tubular stacks. The persistent tubular assemblies of 3, with their non-deformable sub-nm pore, are expected to possess many interesting functions. One such function, transmembrane ion transport, is observed for 3.

  14. Quantification of Kinetic Rate Law Parameters of Uranium Release from Sodium Autunite as a Function of Aqueous Bicarbonate Concentrations

    SciTech Connect (OSTI)

    Gudavalli, Ravi; Katsenovich, Yelena; Wellman, Dawn M.; Lagos, Leonel; Tansel, Berrin

    2013-09-05

    ABSTRACT: Hydrogen carbonate is one of the most significant components within the uranium geochemical cycle. In aqueous solutions, hydrogen carbonate forms strong complexes with uranium. As such, aqueous bicarbonate may significantly increase the rate of uranium release from uranium minerals. Quantifying the relationship of aqueous hydrogen carbonate solutions to the rate of uranium release during dissolution is critical to understanding the long-term fate of uranium within the environment. Single-pass flow-through (SPTF) experiments were conducted to estimate the rate of uranium release from Na meta-autunite as a function of bicarbonate solutions (0.0005-0.003 M) under the pH range of 6-11 and temperatures of 5-60oC. Consistent with the results of previous investigation, the rate of uranium release from sodium autunite exhibited minimal dependency on temperature; but were strongly dependent on pH and increasing concentrations of bicarbonate solutions. Most notably at pH 7, the rate of uranium release exhibited 370 fold increases relative to the rate of uranium release in the absence of bicarbonate. However, the effect of increasing concentrations of bicarbonate solutions on the release of uranium was significantly less under higher pH conditions. It is postulated that at high pH values, surface sites are saturated with carbonate, thus the addition of more bicarbonate would have less effect on uranium release. Results indicate the activation energies were unaffected by temperature and bicarbonate concentration variations, but were strongly dependent on pH conditions. As pH increased from 6 to 11, activation energy values were observed to decrease from 29.94 kJ mol-1 to 13.07 kJ mol-1. The calculated activation energies suggest a surface controlled dissolution mechanism.

  15. Extracting Uranium from Seawater: Promising AF Series Adsorbents

    SciTech Connect (OSTI)

    Janke, Christopher James; Das, Sadananda; Mayes, Richard T; Kuo, Li-Jung; Gill, Gary; Wood, Jordana; Dai, Sheng

    2015-11-02

    A new family of high surface area polyethylene fiber adsorbents (AF series) was recently developed at the Oak Ridge National Laboratory (ORNL). The AF series of were synthesized by radiation-induced graft polymerization of acrylonitrile and itaconic acid (at different monomer/co-monomer mol ratios) onto high surface area polyethylene fibers. The degree of grafting (%DOG) of AF series adsorbents was found to be 154 354%. The grafted nitrile groups were converted to amidoxime groups by treating with hydroxylamine. The amidoximated adsorbents were then conditioned with 0.44M KOH at 80 C followed by screening at ORNL with simulated seawater spiked with 8 ppm uranium. Uranium adsorption capacity in simulated seawater screening ranged from 170-200 g-U/kg-ads irrespective of %DOG. A monomer/co-monomer mol ratio in the range of 7.57-10.14 seemed to be optimum for highest uranium loading capacity. Subsequently, the adsorbents were also tested with natural seawater at Pacific Northwest National Laboratory (PNNL) using flow-through exposure uptake experiments to determine uranium loading capacity with varying KOH conditioning time at 80 C. The highest adsorption capacity of AF1 measured after 56 days of marine testing was demonstrated as 3.9 g-U/kg-adsorbent and 3.2 g-U/kg-adsorbent for 1hr and 3hrs of KOH conditioning at 80 C, respectively. Based on capacity values of several AF1 samples, it was observed that changing KOH conditioning from 3hrs to 1hr at 80 C resulted in 22-27% increase in uranium loading capacity in seawater.

  16. Iron oxidation kinetics for H-2 and CO production via chemical looping

    SciTech Connect (OSTI)

    Stehle, RC; Bobek, MM; Hahn, DW

    2015-01-30

    Solar driven production of fuels by means of an intermediate reactive metal for species splitting has provided a practical and potentially efficient pathway for disassociating molecules at significantly lower thermal energies. The fuels of interest are of or derive from the separation of oxygen from H2O and CO2 to form hydrogen and carbon monoxide, respectively. The following study focuses on iron oxidation through water and CO2 splitting to explore the fundamental reaction kinetics and kinetic rates that are relevant to these processes. In order to properly characterize the reactive metal potential and to optimize a scaled-up solar reactor system, a monolith-based laboratory reactor was implemented to investigate reaction temperatures over a range from 990 to 1400 K. The presence of a single, solid monolith as a reacting surface allowed for a limitation in mass transport effects in order to monitor kinetically driven reaction steps. The formation of oxide layers on the iron monoliths followed Cabrera-Mott models for oxidation of metals with kinetic rates being measured using real-time mass spectrometry to calculate kinetic constants and estimate oxide layer thicknesses. Activation energies of 47.3 kJ/mol and 32.8 kJ/mol were found for water-splitting and CO2 splitting, respectively, and the conclusions of the independent oxidation reactions where applied to experimental results for syngas (H-2-CO) production to explore ideal process characteristics. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

  17. An efficient and practical synthesis of [2-11C]indole via superfast nucleophilic [11C]cyanation and RANEY® Nickel catalyzed reductive cyclization

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

    So Jeong Lee; Fowler, Joanna S.; Alexoff, David; Schueller, Michael; Kim, Dohyun; Nauth, Alexander; Weber, Carina; Kim, Sung Won; Hooker, Jacob M.; Ma, Ling; et al

    2015-09-21

    We developed a rapid method for the synthesis of carbon-11 radiolabeled indole using a sub-nanomolar quantity of no-carrier-added [11C]cyanide as radio-precursor. Based upon a reported synthesis of 2-(2-nitrophenyl)acetonitrile (2), a highly reactive substrate 2-nitrobenzyl bromide (1) was evaluated for nucleophilic [11C]cyanation. Additionally, related reaction conditions were explored with the goal of obtaining of highly reactive 2-(2-nitrophenyl)-[1-11C]acetonitrile ([11C]-2) while inhibiting its rapid conversion to 2,3-bis(2-nitrophenyl)-[1-11C]propanenitrile ([11C]-3). Next, a Raney Nickel catalyzed reductive cyclization method was utilized for synthesizing the desired [2-11C]indole with hydrazinium monoformate as the active reducing agent. Extensive and iterative screening of basicity, temperature and stoichiometry was required tomore » overcome the large stoichiometry bias that favored 2-nitrobenzylbromide (1) over [11C]cyanide, which both caused further alkylation of the desired nitrile and poisoned the Raney Nickel catalyst. The result is an efficient two-step, streamlined method to reliably synthesize [2-11C]indole with an entire radiochemical yield of 21 ± 2.2% (n = 5, ranging from 18 – 24%). The radiochemical purity of the final product was > 98% and specific activity was 176 ± 24.8 GBq/μmol (n = 5, ranging from 141 – 204 GBq/μmol). The total radiosynthesis time including product purification by semi-preparative HPLC was 50 – 55 min from end of cyclotron bombardment.« less

  18. {gamma}-Radiolysis of NaCl Brine in the Presence of UO{sub 2}(s): Effects of Hydrogen and Bromide

    SciTech Connect (OSTI)

    Metz, Volker; Bohnert, Elke; Kelm, Manfred; Schild, Dieter; Kienzler, Bernhard

    2007-07-01

    A concentrated NaCl solution was {gamma}-irradiated in autoclaves under a pressure of 25 MPa. A set of experiments were conducted in 6 mol (kg H{sub 2}O){sup -1} NaCl solution in the presence of UO{sub 2}(s) pellets; in a second set of experiments, {gamma}-radiolysis of the NaCl brine was studied without UO{sub 2}(s). Hydrogen, oxygen and chlorate were formed as long-lived radiolysis products. Due to the high external pressure, all radiolysis products remained dissolved. H{sub 2} and O{sub 2} reached steady state concentrations in the range of 5.10{sup -3} to 6.10{sup -2} mol (kg H{sub 2}O){sup -1} corresponding to a partial gas pressure of {approx}2 to {approx}20 MPa. Radiolytic formation of hydrogen and oxygen increased with the concentration of bromide added to solution. Both, in the presence of bromide, resulting in a relatively high radiolytic yield, and in the absence of bromide surfaces of the UO{sub 2}(s) samples were oxidized, and concentration of dissolved uranium reached the solubility limit of the schoepite / NaUO{sub 2}O(OH)(cr) transition. At the end of the experiments, the pellets were covered by a surface layer of a secondary solid phase having a composition close to Na{sub 2}U{sub 2}O{sub 7}. The experimental results demonstrate that bromide counteracts an H{sub 2} inhibition effect on radiolysis gas production, even at a concentration ratio of [H{sub 2}] / [Br{sup -}] > 100. The present observations are related to the competitive reactions of OH radicals with H{sub 2}, Br{sup -} and Cl{sup -}. A similar competition of hydrogen and bromide, controlling the yield of {gamma}-radiolysis products, is expected for solutions of lower Cl{sup -} concentration. (authors)

  19. Purification and Characterization of OleA from Xanthomonas campestris and Demonstration of a Non-decarboxylative Claisen Condensation Reaction

    SciTech Connect (OSTI)

    Frias, JA; Richman, JE; Erickson, JS; Wackett, LP

    2011-03-25

    OleA catalyzes the condensation of fatty acyl groups in the first step of bacterial long-chain olefin biosynthesis, but the mechanism of the condensation reaction is controversial. In this study, OleA from Xanthomonas campestris was expressed in Escherichia coli and purified to homogeneity. The purified protein was shown to be active with fatty acyl-CoA substrates that ranged from C(8) to C(16) in length. With limiting myristoyl-CoA (C(14)), 1 mol of the free coenzyme A was released/mol of myristoyl-CoA consumed. Using [(14)C] myristoyl-CoA, the other products were identified as myristic acid, 2-myristoylmyristic acid, and 14-heptacosanone. 2-Myristoylmyristic acid was indicated to be the physiologically relevant product of OleA in several ways. First, 2-myristoylmyristic acid was the major condensed product in short incubations, but over time, it decreased with the concomitant increase of 14-heptacosanone. Second, synthetic 2-myristoylmyristic acid showed similar decarboxylation kinetics in the absence of OleA. Third, 2-myristoylmyristic acid was shown to be reactive with purified OleC and OleD to generate the olefin 14-heptacosene, a product seen in previous in vivo studies. The decarboxylation product, 14-heptacosanone, did not react with OleC and OleD to produce any demonstrable product. Substantial hydrolysis of fatty acyl-CoA substrates to the corresponding fatty acids was observed, but it is currently unclear if this occurs in vivo. In total, these data are consistent with OleA catalyzing a non-decarboxylative Claisen condensation reaction in the first step of the olefin biosynthetic pathway previously found to be present in at least 70 different bacterial strains.

  20. Selectivity Principles in Anion Separation by Crystallization of Hydrogen-Bonding Capsules

    SciTech Connect (OSTI)

    Custelcean, Radu; Bock, Aurelien; Moyer, Bruce A

    2010-01-01

    The fundamental factors controlling anion selectivity in the crystallization of hydrogen-bonding capsules [Mg(H2O)6][X L2] (X = SO42-, 1a; SeO42-, 1b; SO32-, 1c; CO32-, 1d; L = tris[2-(3-pyridylurea)ethyl]-amine) from water have been investigated by solution and solid-state thermodynamic measurements, anion competition experiments, and X-ray structural analysis. The crystal structures of 1a-d are isomorphous, thereby simplifying the interpretation of the observed selectivities based on differences in anion coordination geometries. The solubilities of 1a-d in water follow the order: 1a < 1b < 1c < 1d, which is consistent with the selectivity for the tetrahedral sulfate and selenate anions observed in competitive crystallization experiments. Crystallization of the capsules is highly exothermic, with the most favorable {Delta}H{sub cryst}{sup o} of -99.1 and -108.5 kJ/mol corresponding to SO42- and SeO42-, respectively, in agreement with the X-ray structural data showing shape complementarity between these tetrahedral anions and the urea-lined cavities of the capsules. Sulfite, on the other hand, has a significantly less negative {Delta}H{sub cryst}{sup o} of -64.6 kJ/mol, which may be attributed to its poor fit inside the capsules, involving repulsive interactions. The more favorable entropy of crystallization for this anion, however, partly offsets the enthalpic disadvantage, resulting in a solubility product very similar to that of the selenate complex. Because of their very similar shape and size, SO42- and SeO42- have a propensity to form solid solutions, which limits the selectivity between these two anions in competitive crystallizations. In the end, a comprehensive picture of contributing factors to anion selectivity in crystalline hydrogen-bonding capsules emerges.

  1. Investigations of α-helix↔β-sheet transition pathways in a miniprotein using the finite-temperature string method

    SciTech Connect (OSTI)

    Ovchinnikov, Victor; Karplus, Martin; Laboratoire de Chimie Biophysique, ISIS, Université de Strasbourg, 67000 Strasbourg

    2014-05-07

    A parallel implementation of the finite-temperature string method is described, which takes into account the invariance of coordinates with respect to rigid-body motions. The method is applied to the complex α-helix↔β-sheet transition in a β-hairpin miniprotein in implicit solvent, which exhibits much of the complexity of conformational changes in proteins. Two transition paths are considered, one derived from a linear interpolant between the endpoint structures and the other derived from a targeted dynamics simulation. Two methods for computing the conformational free energy (FE) along the string are compared, a restrained method, and a tessellation method introduced by E. Vanden-Eijnden and M. Venturoli [J. Chem. Phys. 130, 194103 (2009)]. It is found that obtaining meaningful free energy profiles using the present atom-based coordinates requires restricting sampling to a vicinity of the converged path, where the hyperplanar approximation to the isocommittor surface is sufficiently accurate. This sampling restriction can be easily achieved using restraints or constraints. The endpoint FE differences computed from the FE profiles are validated by comparison with previous calculations using a path-independent confinement method. The FE profiles are decomposed into the enthalpic and entropic contributions, and it is shown that the entropy difference contribution can be as large as 10 kcal/mol for intermediate regions along the path, compared to 15–20 kcal/mol for the enthalpy contribution. This result demonstrates that enthalpic barriers for transitions are offset by entropic contributions arising from the existence of different paths across a barrier. The possibility of using systematically coarse-grained representations of amino acids, in the spirit of multiple interaction site residue models, is proposed as a means to avoid ad hoc sampling restrictions to narrow transition tubes.

  2. Effects of lithium salt concentration on graphited carbon microbead anodes in the piperidinium-based hybrid electrolytes

    SciTech Connect (OSTI)

    Gao, Kun; Li, Shu-Dan

    2015-01-15

    Graphical abstract: Lithium aggregates usually cause a significant decrease in Li{sup +} mobility and transfer efficiency. Therefore, as important as the problem of SEI, the content of lithium salt and the interaction between Li{sup +} and ILs anions should be taken into consideration in the optimization of ILs-based electrolytes for Li-ion batteries. - Highlights: Lithium aggregates in piperidinium-based electrolytes are evidenced by IR and NMR. High LiPF{sub 6} content could decrease Li{sup +} mobility due to ionic aggregates. Lithium salt concentration is an important factor affecting graphite performances. - Abstract: The variations in LiPF{sub 6} concentration lead to the very different electrochemical performances of carbon microbeads anodes in the piperidinium-based hybrid electrolytes. The two peaks behaviors of lithium plating observed in cyclic voltammetry tests, and some detailed changes in infrared spectra and nuclear magnetic resonance indicates that the formation of ionic aggregates related to lithium ions. Therefore, the excessive lithium salts in the piperidinium-based hybrid electrolytes, usually cause a significant decrease in Li{sup +} mobility and transfer efficiency. The main behaviors are that, when LiPF{sub 6} concentrations increased from 0.2 to 1.2 mol kg{sup ?1}, the apparent migration energies (E{sub a}) increase largely from 8.83 to 21.16 kJ mol{sup ?1}, while the lithium transference numbers (t{sub Li{sup +}}) drop markedly from 0.538 to 0.292.

  3. Leaching behavior of copper from waste printed circuit boards with Brnsted acidic ionic liquid

    SciTech Connect (OSTI)

    Huang, Jinxiu; Chen, Mengjun Chen, Haiyan; Chen, Shu; Sun, Quan

    2014-02-15

    Highlights: A Brnsted acidic ILs was used to leach Cu from WPCBs for the first time. The particle size of WPCBs has significant influence on Cu leaching rate. Cu leaching rate was higher than 99% under the optimum leaching conditions. The leaching process can be modeled with shrinking core model, and the E{sub a} was 25.36 kJ/mol. - Abstract: In this work, a Brnsted acidic ionic liquid, 1-butyl-3-methyl-imidazolium hydrogen sulfate ([bmim]HSO{sub 4}), was used to leach copper from waste printed circuit boards (WPCBs, mounted with electronic components) for the first time, and the leaching behavior of copper was discussed in detail. The results showed that after the pre-treatment, the metal distributions were different with the particle size: Cu, Zn and Al increased with the increasing particle size; while Ni, Sn and Pb were in the contrary. And the particle size has significant influence on copper leaching rate. Copper leaching rate was higher than 99%, almost 100%, when 1 g WPCBs powder was leached under the optimum conditions: particle size of 0.10.25 mm, 25 mL 80% (v/v) ionic liquid, 10 mL 30% hydrogen peroxide, solid/liquid ratio of 1/25, 70 C and 2 h. Copper leaching by [bmim]HSO{sub 4} can be modeled with the shrinking core model, controlled by diffusion through a solid product layer, and the kinetic apparent activation energy has been calculated to be 25.36 kJ/mol.

  4. Density functional theory based generalized effective fragment potential method

    SciTech Connect (OSTI)

    Nguyen, Kiet A. E-mail: ruth.pachter@wpafb.af.mil; Pachter, Ruth E-mail: ruth.pachter@wpafb.af.mil; Day, Paul N.

    2014-06-28

    We present a generalized Kohn-Sham (KS) density functional theory (DFT) based effective fragment potential (EFP2-DFT) method for the treatment of solvent effects. Similar to the original Hartree-Fock (HF) based potential with fitted parameters for water (EFP1) and the generalized HF based potential (EFP2-HF), EFP2-DFT includes electrostatic, exchange-repulsion, polarization, and dispersion potentials, which are generated for a chosen DFT functional for a given isolated molecule. The method does not have fitted parameters, except for implicit parameters within a chosen functional and the dispersion correction to the potential. The electrostatic potential is modeled with a multipolar expansion at each atomic center and bond midpoint using Stone's distributed multipolar analysis. The exchange-repulsion potential between two fragments is composed of the overlap and kinetic energy integrals and the nondiagonal KS matrices in the localized molecular orbital basis. The polarization potential is derived from the static molecular polarizability. The dispersion potential includes the intermolecular D3 dispersion correction of Grimme et al. [J. Chem. Phys. 132, 154104 (2010)]. The potential generated from the CAMB3LYP functional has mean unsigned errors (MUEs) with respect to results from coupled cluster singles, doubles, and perturbative triples with a complete basis set limit (CCSD(T)/CBS) extrapolation, of 1.7, 2.2, 2.0, and 0.5 kcal/mol, for the S22, water-benzene clusters, water clusters, and n-alkane dimers benchmark sets, respectively. The corresponding EFP2-HF errors for the respective benchmarks are 2.41, 3.1, 1.8, and 2.5 kcal/mol. Thus, the new EFP2-DFT-D3 method with the CAMB3LYP functional provides comparable or improved results at lower computational cost and, therefore, extends the range of applicability of EFP2 to larger system sizes.

  5. Advanced heat exchanger development for molten salts

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

    Sabharwall, Piyush; Clark, Denis; Glazoff, Michael; Zheng, Guiqiu; Sridharan, Kumar; Anderson, Mark

    2014-12-01

    This study addresses present work concerned with advanced heat exchanger development for molten salt in nuclear and non nuclear thermal systems. The molten salt systems discussed herein use alloys, such as Hastelloy N and 242, which show corrosion resistance to molten salt at nominal operating temperatures up to 700°C. These alloys were diffusion welded, and the corresponding information is presented. Test specimens were prepared for exposing diffusion welds to molten salt environments. Hastelloy N and 242 were found to be weldable by diffusion welding, with ultimate tensile strengths about 90% of base metal values. Both diffusion welds and sheet materialmore » in Hastelloy N were corrosion tested in?58 mol% KF and 42 mol% ZrF4 at 650, 700, and 850°C for 200, 500, and 1,000 hours. Corrosion rates found were similar between welded and nonwelded materials, typically <10 mils per year. For materials of construction, nickel and alloys with dense nickel coatings are effectively inert to corrosion in fluorides, but not so in chlorides. Hence, additional testing of selected alloys for resistance to intergranular corrosion is needed, as is a determination of corrosion rate as a function of contaminant type and alloy composition with respect to chromium and carbon to better define the optimal chromium and carbon composition, independent of galvanic or differential solubility effects. Also presented is the division of the nuclear reactor and high temperature components per ASME standards, along with design requirements for a subcritical Rankine power cycle heat exchanger that has to overcome pressure difference of about 17 MPa.« less

  6. Advanced heat exchanger development for molten salts

    SciTech Connect (OSTI)

    Sabharwall, Piyush; Clark, Denis; Glazoff, Michael; Zheng, Guiqiu; Sridharan, Kumar; Anderson, Mark

    2014-12-01

    This study addresses present work concerned with advanced heat exchanger development for molten salt in nuclear and non nuclear thermal systems. The molten salt systems discussed herein use alloys, such as Hastelloy N and 242, which show corrosion resistance to molten salt at nominal operating temperatures up to 700°C. These alloys were diffusion welded, and the corresponding information is presented. Test specimens were prepared for exposing diffusion welds to molten salt environments. Hastelloy N and 242 were found to be weldable by diffusion welding, with ultimate tensile strengths about 90% of base metal values. Both diffusion welds and sheet material in Hastelloy N were corrosion tested in?58 mol% KF and 42 mol% ZrF4 at 650, 700, and 850°C for 200, 500, and 1,000 hours. Corrosion rates found were similar between welded and nonwelded materials, typically <10 mils per year. For materials of construction, nickel and alloys with dense nickel coatings are effectively inert to corrosion in fluorides, but not so in chlorides. Hence, additional testing of selected alloys for resistance to intergranular corrosion is needed, as is a determination of corrosion rate as a function of contaminant type and alloy composition with respect to chromium and carbon to better define the optimal chromium and carbon composition, independent of galvanic or differential solubility effects. Also presented is the division of the nuclear reactor and high temperature components per ASME standards, along with design requirements for a subcritical Rankine power cycle heat exchanger that has to overcome pressure difference of about 17 MPa.

  7. MAIN-BELT COMET P/2012 T1 (PANSTARRS)

    SciTech Connect (OSTI)

    Hsieh, Henry H.; Kaluna, Heather M.; Yang Bin; Haghighipour, Nader; Micheli, Marco; Denneau, Larry; Jedicke, Robert; Kleyna, Jan; Veres, Peter; Wainscoat, Richard J.; Ansdell, Megan; Elliott, Garrett T.; Keane, Jacqueline V.; Meech, Karen J.; Riesen, Timm E.; Sonnett, Sarah; Novakovic, Bojan; Fitzsimmons, Alan; Moskovitz, Nicholas A.; Sheppard, Scott S.; and others

    2013-07-01

    We present initial results from observations and numerical analyses aimed at characterizing the main-belt comet P/2012 T1 (PANSTARRS). Optical monitoring observations were made between 2012 October and 2013 February using the University of Hawaii 2.2 m telescope, the Keck I telescope, the Baade and Clay Magellan telescopes, Faulkes Telescope South, the Perkins Telescope at Lowell Observatory, and the Southern Astrophysical Research Telescope. The object's intrinsic brightness approximately doubles from the time of its discovery in early October until mid-November and then decreases by {approx}60% between late December and early February, similar to photometric behavior exhibited by several other main-belt comets and unlike that exhibited by disrupted asteroid (596) Scheila. We also used Keck to conduct spectroscopic searches for CN emission as well as absorption at 0.7 {mu}m that could indicate the presence of hydrated minerals, finding an upper limit CN production rate of Q{sub CN} < 1.5 Multiplication-Sign 10{sup 23} mol s{sup -1}, from which we infer a water production rate of Q{sub H{sub 2O}}<5 Multiplication-Sign 10{sup 25} mol s{sup -1}, and no evidence of the presence of hydrated minerals. Numerical simulations indicate that P/2012 T1 is largely dynamically stable for >100 Myr and is unlikely to be a recently implanted interloper from the outer solar system, while a search for potential asteroid family associations reveals that it is dynamically linked to the {approx}155 Myr old Lixiaohua asteroid family.

  8. On the thermal stability of physical vapor deposited oxide-hardened nanocrystalline gold thin films

    SciTech Connect (OSTI)

    Argibay, Nicolas; Mogonye, J. E.; Michael, Joseph R.; Goeke, Ronald S.; Kotula, Paul G.; Scharf, T. W.; Dugger, Michael Thomas; Prasad, Somuri V.

    2015-04-08

    We describe a correlation between electrical resistivity and grain size for PVD synthesized polycrystalline oxide-hardened metal-matrix thin films in oxide-dilute (<5 vol. % oxide phase) compositions. The correlation is based on the Mayadas-Shatzkes (M-S) electron scattering model, predictive of grain size evolution as a function of composition in the oxide-dilute regime for 2 ?m thick Au-ZnO films. We describe a technique to investigate grain boundary (GB) mobility and the thermal stability of GBs based on in situelectrical resistivity measurements during annealing experiments, interpreted using a combination of the M-S model and the Michels et al. model describing solute drag stabilized grain growth kinetics. Using this technique, activation energy and pre-exponential Arrhenius parameter values of Ea = 21.6 kJ/mol and Ao = 2.3 1017 m2/s for Au-1 vol. % ZnO and Ea =12.7 kJ/mol and Ao = 3.1 1018 m2/s for Au-2 vol.% ZnO were determined. In the oxide-dilute regime, the grain size reduction of the Au matrix yielded a maximum hardness of 2.6 GPa for 5 vol. % ZnO. A combined model including percolation behavior and grain refinement is presented that accurately describes the composition dependent change in electrical resistivity throughout the entire composition range for Au-ZnO thin films. As a result, the proposed correlations are supported by microstructural characterization using transmission electron microscopy and electron diffraction mapping for grain size determination.

  9. Structural, thermal, optical properties and simulation of white light of titanium-tungstate-tellurite glasses doped with dysprosium

    SciTech Connect (OSTI)

    Jyothi, L. [School of Physics, University of Hyderabad, Hyderabad 500046 (India); Upender, G. [Glass Science and Technology Section, Glass Division, CSIR-CGCRI, Kolkata 700032 (India); Kuladeep, R. [School of Physics, University of Hyderabad, Hyderabad 500046 (India); Rao, D. Narayana, E-mail: dnrsp@uohyd.ernet.in [School of Physics, University of Hyderabad, Hyderabad 500046 (India)

    2014-02-01

    Graphical abstract: CIE coordinate diagram of different concentrations of the Dy{sup 3+}-doped TTWD glasses with coordinates in the white light region. - Highlights: Radiative lifetime of {sup 4}F{sub 9/2} level of Dy{sup 3+} ions is longer in the tellurite glass. Quantum efficiency is found to be high. These glasses are suitable materials for generating white light. - Abstract: Structural, thermal, optical properties and simulation of white light of Dy{sup 3+}-doped tellurite glasses of composition TTWD: (75 ? x)TeO{sub 2} ? 10TiO{sub 2} ? 15WO{sub 3} ? xDy{sub 2}O{sub 3} (x = 0, 0.1, 0.5, 1.0 and 2.0 mol%) were investigated. Raman spectra revealed that the glass contains TeO{sub 4}, TeO{sub 3}, WO{sub 4} and WO{sub 6} units. Differential scanning calorimetry (DSC) measurements were carried out to measure the glass transition temperature of all the glasses. From the optical absorption spectra, luminescence spectra and using the JuddOfelt (JO) analysis, we estimated the radiative transition probabilities, emission cross-sections, branching ratios and radiative lifetimes. The decay curves at lower concentrations are exponential while they show a non-exponential behavior at higher concentrations (?0.5 mol%) due to energy transfer processes. The effective lifetime for the {sup 4}F{sub 9/2} level decreases with increase in Dy{sub 2}O{sub 3} concentration for the glasses under investigation. The non-exponential decay curves could fit well to the InokutiHirayama (IH) model with S = 6, indicating that the nature of interaction responsible for energy transfer is of dipoledipole type. Simulation of white light is examined with varying concentration and the results indicate that these glasses are suitable for white light emitting diode applications.

  10. Probing charge transfer in a novel class of luminescent perovskite-based heterostructures composed of quantum dots bound to RE-activated CaTiO3 phosphors

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

    Crystal S. Lewis; Wong, Stanislaus S.; Liu, Haiqing; Han, Jinkyu; Wang, Lei; Yue, Shiyu; Brennan, Nicholas A.

    2016-01-04

    We report on the synthesis and structural characterization of novel semiconducting heterostructures composed of cadmium selenide (CdSe) quantum dots (QDs) attached onto the surfaces of novel high-surface area, porous rare-earth-ion doped alkaline earth titanate micron-scale spherical motifs, i.e. both Eu-doped and Pr-doped CaTiO3, composed of constituent, component nanoparticles. These unique metal oxide perovskite building blocks were created by a multi-pronged synthetic strategy involving molten salt and hydrothermal protocols. Subsequently, optical characterization of these heterostructures indicated a clear behavioral dependence of charge transfer in these systems upon a number of parameters such as the nature of the dopant, the reaction temperature,more » and particle size. Specifically, 2.7 nm diameter ligand-functionalized CdSe QDs were anchored onto sub-micron sized CaTiO3-based spherical assemblies, prepared by molten salt protocols. We found that both the Pr- and Eu-doped CaTiO3 displayed pronounced PL emissions, with maximum intensities observed using optimized lanthanide concentrations of 0.2 mol% and 6 mol%, respectively. Analogous experiments were performed on Eu-doped BaTiO3 and SrTiO3 motifs, but CaTiO3 still performed as the most effective host material amongst the three perovskite systems tested. Furthermore, the ligand-capped CdSe QD-doped CaTiO3 heterostructures exhibited effective charge transfer between the two individual constituent nanoscale components, an assertion corroborated by the corresponding quenching of their measured PL signals.« less

  11. Dynamics of the reaction of C{sub 2} with C{sub 6}H{sub 2}: An implication for the formation of interstellar C{sub 8}H

    SciTech Connect (OSTI)

    Sun, Yi-Lun; Huang, Wen-Jian; Chin, Chih-Hao; Lee, Shih-Huang

    2014-11-21

    The reaction C{sub 2} + C{sub 6}H{sub 2} → C{sub 8}H + H was investigated for the first time. Reactant C{sub 2} (C{sub 6}H{sub 2}) was synthesized from 1% C{sub 3}F{sub 6}/He (5% C{sub 2}H{sub 2}/He) by pulsed high-voltage discharge. We measured the translational-energy distribution, the angular distribution, and the photoionization spectrum of product C{sub 8}H in a crossed molecular-beam apparatus using synchrotron vacuum-ultraviolet ionization. This reaction released average translational energy of 8.5 kcal mol{sup −1} corresponding to a fraction of 0.37 in translation. C{sub 8}H was identified as octatetranyl based on the maximal translational-energy release 23 ± 2 kcal mol{sup −1} and the ionization threshold 8.9 ± 0.2 eV. Kinematic constraints can qualitatively account for the nearly isotropic angular distribution. The quantum-chemical calculations indicate that the exothermic reactions C{sub 2} (X {sup 1}Σ{sub g}{sup +}/a {sup 3}Π{sub u}) + HC{sub 6}H → C{sub 8}H + H can proceed without entrance and exit barriers, implying the importance in the cold interstellar medium. This work verifies that interstellar C{sub 8}H can be formed through the C{sub 2} + C{sub 6}H{sub 2} reaction.

  12. Distinguishing tautomerism in the crystal structure of (Z)-N-(5-ethyl-2,3-di-hydro-1,3,4-thiadiazol-2-ylidene) -4-methylbenzenesulfonamide using DFT-D calculations and {sup 13}C solid-state NMR

    SciTech Connect (OSTI)

    Li, Xiaozhou; Bond, Andrew D.; Johansson, Kristoffer E.; Van de Streek, Jacco

    2014-08-01

    The crystal structure of (Z)-N-(5-ethyl-2,3-di-hydro-1,3,4-thiadiazol-2-ylidene) -4-methylbenzenesulfonamide contains an imine tautomer, rather than the previously reported amine tautomer. The tautomers can be distinguished using dispersion-corrected density functional theory calculations and by comparison of calculated and measured {sup 13}C solid-state NMR spectra. The crystal structure of the title compound, C{sub 11}H{sub 13}N{sub 3}O{sub 2}S{sub 2}, has been determined previously on the basis of refinement against laboratory powder X-ray diffraction (PXRD) data, supported by comparison of measured and calculated {sup 13}C solid-state NMR spectra [Hangan et al. (2010 ▶). Acta Cryst. B66, 615–621]. The mol@@ecule is tautomeric, and was reported as an amine tautomer [systematic name: N-(5-ethyl-1,3,4-thia@@diazol-2-yl)-p-toluene@@sulfonamide], rather than the correct imine tautomer. The protonation site on the mol@@ecule’s 1,3,4-thia@@diazole ring is indicated by the inter@@molecular contacts in the crystal structure: N—H⋯O hydrogen bonds are established at the correct site, while the alternative protonation site does not establish any notable inter molecular inter@@actions. The two tautomers provide essentially identical Rietveld fits to laboratory PXRD data, and therefore they cannot be directly distinguished in this way. However, the correct tautomer can be distinguished from the incorrect one by previously reported qu@@anti@@tative criteria based on the extent of structural distortion on optimization of the crystal structure using dispersion-corrected density functional theory (DFT-D) calculations. Calculation of the {sup 13}C SS-NMR spectrum based on the correct imine tautomer also provides considerably better agreement with the measured {sup 13}C SS-NMR spectrum.

  13. Extracting uranium from seawater: Promising AF series adsorbents

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

    Das, Sadananda; Oyola, Y.; Mayes, Richard T.; Janke, Christopher James; Kuo, Li-Jung; Gill, Gary; Wood, Jordana; Dai, Sheng

    2015-11-02

    Here, a new family of high surface area polyethylene fiber adsorbents (AF series) was recently developed at the Oak Ridge National Laboratory (ORNL). The AF series of were synthesized by radiation-induced graft polymerization of acrylonitrile and itaconic acid (at different monomer/co-monomer mol ratios) onto high surface area polyethylene fibers. The degree of grafting (%DOG) of AF series adsorbents was found to be 154 354%. The grafted nitrile groups were converted to amidoxime groups by treating with hydroxylamine. The amidoximated adsorbents were then conditioned with 0.44M KOH at 80 C followed by screening at ORNL with simulated seawater spiked with 8more » ppm uranium. Uranium adsorption capacity in simulated seawater screening ranged from 170-200 g-U/kg-ads irrespective of %DOG. A monomer/co-monomer mol ratio in the range of 7.57-10.14 seemed to be optimum for highest uranium loading capacity. Subsequently, the adsorbents were also tested with natural seawater at Pacific Northwest National Laboratory (PNNL) using flow-through exposure uptake experiments to determine uranium loading capacity with varying KOH conditioning time at 80 C. The highest adsorption capacity of AF1 measured after 56 days of marine testing was demonstrated as 3.9 g-U/kg-adsorbent and 3.2 g-U/kg-adsorbent for 1hr and 3hrs of KOH conditioning at 80 C, respectively. Based on capacity values of several AF1 samples, it was observed that changing KOH conditioning from 3hrs to 1hr at 80 C resulted in 22-27% increase in uranium loading capacity in seawater.« less

  14. Global scale environmental control of plant photosynthetic capacity

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

    Ali, Ashehad; Xu, Chonggang; Rogers, Alistair; McDowell, Nathan G.; Medlyn, Belinda E.; Fisher, Rosie A.; Wullschleger, Stan D.; Reich, Peter B.; Bauerle, William L.; Wilson, Cathy J.; et al

    2015-12-01

    Photosynthetic capacity, determined by light harvesting and carboxylation reactions, is a key plant trait that determines the rate of photosynthesis; however, in Earth System Models (ESMs) at a reference temperature, it is either a fixed value for a given plant functional type or derived from a linear function of leaf nitrogen content. In this study, we conducted a comprehensive analysis that considered correlations of environmental factors with photosynthetic capacity as determined by maximum carboxylation (Vc,m) rate scaled to 25°C (i.e., Vc,25; μmol CO2·m–2·s–1) and maximum electron transport rate (Jmax) scaled to 25°C (i.e., J25; μmol electron·m–2·s–1) at the global scale.more » Our results showed that the percentage of variation in observed Vc,25 and J25 explained jointly by the environmental factors (i.e., day length, radiation, temperature, and humidity) were 2–2.5 times and 6–9 times of that explained by area-based leaf nitrogen content, respectively. Environmental factors influenced photosynthetic capacity mainly through photosynthetic nitrogen use efficiency, rather than through leaf nitrogen content. The combination of leaf nitrogen content and environmental factors was able to explain ~56% and ~66% of the variation in Vc,25 and J25 at the global scale, respectively. As a result, our analyses suggest that model projections of plant photosynthetic capacity and hence land–atmosphere exchange under changing climatic conditions could be substantially improved if environmental factors are incorporated into algorithms used to parameterize photosynthetic capacity in ESMs.« less

  15. Interactions of aqueous amino acids and proteins with the (110) surface of ZnS in molecular dynamics simulations

    SciTech Connect (OSTI)

    Nawrocki, Grzegorz; Cieplak, Marek

    2014-03-07

    The growing usage of nanoparticles of zinc sulfide as quantum dots and biosensors calls for a theoretical assessment of interactions of ZnS with biomolecules. We employ the molecular-dynamics-based umbrella sampling method to determine potentials of mean force for 20 single amino acids near the ZnS (110) surface in aqueous solutions. We find that five amino acids do not bind at all and the binding energy of the remaining amino acids does not exceed 4.3 kJ/mol. Such energies are comparable to those found for ZnO (and to hydrogen bonds in proteins) but the nature of the specificity is different. Cysteine can bind with ZnS in a covalent way, e.g., by forming the disulfide bond with S in the solid. If this effect is included within a model incorporating the Morse potential, then the potential well becomes much deeperthe binding energy is close to 98 kJ/mol. We then consider tryptophan cage, a protein of 20 residues, and characterize its events of adsorption to ZnS. We demonstrate the relevance of interactions between the amino acids in the selection of optimal adsorbed conformations and recognize the key role of cysteine in generation of lasting adsorption. We show that ZnS is more hydrophobic than ZnO and that the density profile of water is quite different than that forming near ZnOit has only a minor articulation into layers. Furthermore, the first layer of water is disordered and mobile.

  16. Advanced heat exchanger development for molten salts

    SciTech Connect (OSTI)

    Sabharwall, Piyush; Clark, Denis; Glazoff, Michael; Zheng, Guiqiu; Sridharan, Kumar; Anderson, Mark

    2014-12-01

    This study addresses present work concerned with advanced heat exchanger development for molten salt in nuclear and non nuclear thermal systems. The molten salt systems discussed herein use alloys, such as Hastelloy N and 242, which show corrosion resistance to molten salt at nominal operating temperatures up to 700C. These alloys were diffusion welded, and the corresponding information is presented. Test specimens were prepared for exposing diffusion welds to molten salt environments. Hastelloy N and 242 were found to be weldable by diffusion welding, with ultimate tensile strengths about 90% of base metal values. Both diffusion welds and sheet material in Hastelloy N were corrosion tested in?58 mol% KF and 42 mol% ZrF4 at 650, 700, and 850C for 200, 500, and 1,000 hours. Corrosion rates found were similar between welded and nonwelded materials, typically <10 mils per year. For materials of construction, nickel and alloys with dense nickel coatings are effectively inert to corrosion in fluorides, but not so in chlorides. Hence, additional testing of selected alloys for resistance to intergranular corrosion is needed, as is a determination of corrosion rate as a function of contaminant type and alloy composition with respect to chromium and carbon to better define the optimal chromium and carbon composition, independent of galvanic or differential solubility effects. Also presented is the division of the nuclear reactor and high temperature components per ASME standards, along with design requirements for a subcritical Rankine power cycle heat exchanger that has to overcome pressure difference of about 17 MPa.

  17. The addition of hydrogen atoms to diacetylene and the heats of formation of i-C4H3 and n-C4H3.

    SciTech Connect (OSTI)

    Klippenstein, Stephen J.; Miller, James A.

    2005-01-01

    In this article, we discuss in detail the addition of hydrogen atoms to diacetylene and the reverse dissociation reactions, H + C{sub 4}H{sub 2} {leftrightarrow} i-C{sub 4}H{sub 3} (R1) and H + C{sub 4}H{sub 2} n-C{sub 4}H{sub 3} (R2). The theory utilizes high-level electronic structure methodology to characterize the potential energy surface, Rice-Ramsperger-Kassel-Marcus (RRKM) theory to calculate microcanonical/J-resolved rate coefficients, and a two-dimensional master-equation approach to extract phenomenological (thermal) rate coefficients. Comparison is made with experimental results where they are available. The rate coefficients k{sub 1}(T, p) and k{sub 2}(T, p) are cast in forms that can be used in chemical kinetic modeling. In addition, we predict values of the heats of formation of i-C{sub 4}H{sub 3} and n-C{sub 4}H{sub 3} and discuss their importance in flame chemistry. Our basis-set extrapolated, quadratic-configuration-interaction with single and double excitations (and triple excitations added perturbatively), QCISD(T), predictions of these heats of formation at 298 K are 130.8 kcal/mol for n-C{sub 4}H{sub 3} and 119.3 kcal/mol for the i-isomer; multireference CI calculations with a nine-electron, nine-orbital, complete-active-space (CAS) reference wavefunction give just slightly larger values for these parameters. Our results are in good agreement with the recent focal-point analysis of Wheeler et al. (J. Chem. Phys. 2004, 121, 8800-8813), but they differ substantially for {Delta} H{sub f 298}{sup 0}(n-C{sub 4}H{sub 3}) with the earlier diffusion Monte Carlo predictions of Krokidis et al.

  18. Characteristics of a new creep regime in polycrystalline NiAl

    SciTech Connect (OSTI)

    Raj, S.V.; Farmer, S.C. )

    1995-02-01

    Constant-load creep tests were conducted on fine-grained ([approximately]23 [mu]m) Ni-50.6 (at. pct) Al in the temperature range of 1,000 to 1,400 K. Power-law creep with a stress exponent, n [approx] 6.5, and an activation energy, Q[sub c] [approx] 290 kJ mol[sup [minus]1], was observed above 25 MPa, while a new mechanism with n [approx] 2 and Q[sub c] [approx] 100 kJ mol[sup [minus]1] dominates when [sigma] < 25 MPa, where [sigma] is the applied stress. A comparison of the creep behavior of fine- and course-grained NiAl established that the mechanism in the n [approx] 2 region was dependent on grain size, and the magnitude of the grain-size exponent was estimated to be about 2. Transmission electron microscopy (TEM) observations of the deformed specimens revealed a mixture of dislocation tangles, dipoles, loops, and subboundary networks in the power-law creep regime. The deformation microstructures were inhomogeneous in the n [approx] 2 creep regime, and many grains did not reveal any dislocation activity. However, bands of dislocation loops were observed in a few grains, where these loops appeared to have been emitted from the grain boundaries. The observed creep characteristics of the low-stress region suggest the dominance of an accommodated grain-boundary sliding (GBS) mechanism, although the experimental creep rates were lower than those predicted by theoretical models by over seven orders of magnitude. The low value of Q[sub c] in this region, which is approximately one-third that for lattice self-diffusion, is attributed to the possible existence of interconnected vacancy flow channels, or nanotubes'', at the grain boundaries.

  19. One Year Clinical Outcomes of Renal Artery Stenting: The Results of ODORI Registry

    SciTech Connect (OSTI)

    Sapoval, M.; Tamari, I.; Goffette, P.; Downes, M.; Senechal, Q.; Fanelli, F.; Reimer, P.; Negaiwi, Z.; Cassin, P. De; Heye, S.; Korobov, V.; Tsetis, D.; Abada, H.

    2010-06-15

    The safety, efficacy and long term clinical benefits of renal artery revascularization by stenting are still a matter of debate. The aim of our study was to define the safety and efficacy of renal artery stenting with the Tsunami peripheral stent (Terumo Corporation, Tokyo, Japan). The ODORI was a prospective, multicentre registry which enrolled 251 consecutive patients, (276 renal arteries) in 36 centres across Europe. The primary endpoint was acute procedural success defined as <30% residual stenosis after stent placement. Secondary endpoints included major adverse events, blood pressure control, serum creatinine level, and target lesion revascularization (TLR) at 6 and 12 months. Patients were 70 {+-} 10 years old, 59% were male, 33% had diabetes, and 96% hypertension. The main indications for renal stent implantation were hypertension in 83% and renal salvage in 39%. Direct stent implantation was performed in 76% of the cases. Acute success rate was 100% with residual stenosis of 2.5 {+-} 5.4%. Systolic/diastolic blood pressure decreased from a mean of 171/89 at baseline to 142/78 mmHg at 6 months (p < 0.0001 vs. baseline), and 141/80 mmHg at 12 months (p < 0.0001 vs. baseline). Mean serum creatinine concentration did not change significantly in the total population. However, there was significant improvement in the highest tercile (from 283 {mu}mol/l at baseline to 205 and 209 {mu}mol/l at 6 and 12 months respectively). At 12-months, rates of restenosis and TLR were 6.6 and 0.8% respectively. The 12 month cumulative rate of all major clinical adverse events was 6.4% while the rate of device or procedure related events was 2.4%. In hypertensive patients with atherosclerotic renal artery stenosis Tsunami peripheral balloon-expandable stent provides a safe revascularization strategy, with a potential beneficial impact on hypertension control and renal function in the highest risk patients.

  20. Carbon Dioxide, Hydrographic, and Chemical Data Obtained During the Nine R/V Korr Cruises Comprising the Indian Ocean CO2Survey (WOCE Sections I8SI9S, I9N, I8NI5E, I3, I5WI4, I7N, I1, I10, and I2; December 1, 1994-January 19, 1996)

    SciTech Connect (OSTI)

    Kozyr, A.V.

    2003-09-15

    This document describes the procedures and methods used to measure total carbon dioxide (TCO{sub 2}) and total alkalinity (TALK) at hydrographic stations taken during the R/V Knorr Indian Ocean cruises (Sections I8SI9S, I9N, I8NI5E, I3, I5WI4, I7N, I1, I10, and I2) in 1994-1996. The measurements were conducted as part of the World Ocean Circulation Experiment (WOCE). The expedition began in Fremantle, Australia, on December 1, 1994, and ended in Mombasa, Kenya, on January 22, 1996. During the nine cruises, 12 WOCE sections were occupied. Total carbon dioxide was extracted from water samples and measured using single-operator multiparameter metabolic analyzers (SOMMAs) coupled to coulometers. The overall precision and accuracy of the analyses was {+-} 1.20 {micro}mol/kg. The second carbonate system parameter, TALK, was determined by potentiometric titration. The precision of the measurements determined from 962 analyses of certified reference material was {+-} 4.2 {micro}mol/kg (REFERENCE). This work was supported by grants from the National Science Foundation, the U. S. Department of Energy, and the National Oceanographic and Atmospheric Administration. The R/V Knorr Indian Ocean data set is available as a numeric data package (NDP) from the Carbon Dioxide Information Analysis Center (CDIAC). The NDP consists of 18 oceanographic data files, two FORTRAN 77 data retrieval routine files, a readme file, and this printed documentation, which describes the contents and format of all files as well as the procedures and methods used to obtain the data. Instructions for accessing the data are provided.

  1. Decomposition and vibrational relaxation in CH{sub 3}I and self-reaction of CH{sub 3} radicals.

    SciTech Connect (OSTI)

    Yang, X.; Goldsmith, C. F.; Tranter, R. S.

    2009-07-01

    Vibrational relaxation and dissociation of CH{sub 3}I, 2-20% in krypton, have been investigated behind incident shock waves in a diaphragmless shock tube at 20, 66, 148, and 280 Torr and 630-2200 K by laser schlieren densitometry. The effective collision energy obtained from the vibrational relaxation experiments has a small, positive temperature dependence, {Delta}E{sub down} = 63 x (T/298){sup 0.56} cm{sup -1}. First-order rate coefficients for dissociation of CH{sub 3}I show a strong pressure dependence and are close to the low-pressure limit. Restricted-rotor Gorin model RRKM calculations fit the experimental results very well with {Delta}E{sub down} = 378 x (T/298){sup 0.457} cm{sup -1}. The secondary chemistry of this reaction system is dominated by reactions of methyl radicals and the reaction of the H atom with CH{sub 3}I. The results of the decomposition experiments are very well simulated with a model that incorporates methyl recombination and reactions of methylene. Second-order rate coefficients for ethane dissociation to two methyl radicals were derived from the experiments and yield k = (4.50 {+-} 0.50) x 10{sup 17} exp(-32709/T) cm{sup 3} mol{sup -1} s{sup -1}, in good agreement with previous measurements. Rate coefficients for H + CH{sub 3}I were also obtained and give k = (7.50 {+-} 1.0) x 10{sup 13} exp(-601/T) cm{sup 3} mol{sup -1} s{sup -1}, in reasonable agreement with a previous experimental value.

  2. Activation of ethane in the presence of solid acids: Sulfated zirconia, iron- and manganese-promoted sulfated zirconia, and zeolites

    SciTech Connect (OSTI)

    Cheung, Tsz-Keung; Gates, B.

    1997-06-01

    Ethane was activated in the presence of solid acids [sulfated zirconia (SZ), iron- and manganese-promoted sulfated zirconia (FMSZ), HZSM-5, and USY zeolite] at 1 atm, 200-450{degrees}C, and ethane partial pressures in the range 0.014.2 atm. The data were measured with a flow reactor at low conversions (<0.005) such that reaction of ethane took place in the near absence of alkenes. Catalysis was demonstrated for ethane conversion in the presence of FMSZ at 450{degrees}C and 0.2 atm ethane partial pressure, but the reactions were not shown to be catalytic for the other solid acids and other conditions. FMSZ was active for converting ethane into methane, ethene, and butane at an ethane partial pressure of 0.2 atm and at temperatures of 200-300{degrees}C; the other solid acids had no detectable activities under these conditions. At higher temperatures, each of the solid acids was active for conversion of ethane into ethene; butane and methane were also formed in the presence of FMSZ, HZSM-5, and USY zeolite, whereas methane was the only other hydrocarbon observed in the presence of SZ. The initial (5 min on stream) selectivities to ethene at approximately 0.1 % conversion, ethane partial pressure of 0.2 atm, and 450{degrees}C were approximately 98, 94, 97, and 99%, for SZ, FMSZ, HZSM-5, and USY zeolite, respectively. Under the same reaction conditions, the initial rates of ethane conversion were 0. 1 5 x 10{sup -8}, 3.5 x 10{sup -8} 3.9 x 10{sup -8}, and 0.56 x 10{sup -8} mol/(s {circ} g) for SZ, FMSZ, HZSM-5, and USY zeolite, respectively. The reactivities are consistent with chemistry analogous to that occurring in superacidic solutions and with the suggestion that FMSZ is a stronger acid than the others investigated here. 25 refs., 13 figs., 1 tab.

  3. Carbon Dioxide, Hydrographic, and Chemical Data Obtained During the R/V Meteor Cruise 22/5 in the South Atlantic Ocean (WOCE Section A10, December 1992-January 1993)

    SciTech Connect (OSTI)

    Kozyr, A.

    1998-12-01

    This data documentation discusses the procedures and methods used to measure total carbon dioxide (TCO{sub 2}) and total alkalinity (TALK) at hydrographic stations, as well as the underway partial pressure of CO{sub 2} (pCO{sub 2}) during the R/V Meteor Cruise 22/5 in the South Atlantic Ocean (Section A10). Conducted as part of the World Ocean Circulation Experiment (WOCE), the cruise began in Rio de Janeiro on December 27, 1992, and ended after 36 days at sea in Capetown, South Africa, on January 31, 1993. Measurements made along WOCE Section A10 included pressure, temperature, and salinity [measured by conductivity, temperature, and depth (CTD) sensor], bottle salinity, bottle oxygen, phosphate, nitrate, nitrite, silicate, chlorofluorocarbons (CFC-1 1 , CFC-12), TCO{sub 2}, TALK, and underway pCO{sub 2}. The TCO{sub 2} was measured by using two Single-Operator Multiparameter Metabolic Analyzers (SOMMAs) for extracting CO{sub 2} from seawater samples that were coupled to a coulometer for detection of the extracted CO{sub 2}. The overall precision and accuracy of the analyses was {+-} 1.9 {micro}mol/kg. Samples collected for TALK were measured by potentiometric titration; precision was {+-}2.0 {micro}mol/kg. Underway pCO{sub 2} was measured by infrared photometry with a precision of {+-} 2.0 {micro}atm. The work aboard the R/V Meteor was supported by the U.S. Department of Energy under contract DE-AC02-76CHOO016, and the Bundesministerium fir Forschung und Technologies through grants 03F0545A and MPG 099/1.

  4. Effect of hydroxamate siderophores on Fe release and Pb(II) adsorption by goethite

    SciTech Connect (OSTI)

    Kraemer, Stephan M.; Cheah, Sing-Foong; Zapf, Rita; Xu, Jide; Raymond, Kenneth N.; Sposito, Garrison

    1998-08-01

    Hydroxamate siderophores are biologically-synthesized, Fe(III)-specific ligands which are common in soil environments. In this paper, we report an investigation of their adsorption by the iron oxyhydroxide, goethite; their influence on goethite dissolution kinetics; and their ability to affect Pb(II) adsorption by the goethite surface. The siderophores used were desferrioxamine B (DFO-B), a fungal siderophore, and desferrioxamine D1, an acetyl derivative of DFO-B (DFO-D1). Siderophore adsorption isotherms yielded maximum surface concentrations of 1.5 (DFO-B) or 3.5 (DFO-D1) mu-mol/g at pH 6.6, whereas adsorption envelopes showed either cation-like (DFO-B) or ligand-like (DFO-D1) behavior. Above pH 8, the adsorbed concentrations of both siderophores were similar. The dissolution rate of goethite in the presence of 240 mu M DFO-B or DFO-D1 was 0.02 or 0.17 mu-mol/g hr, respectively. Comparison of these results with related literature data on the reactions between goethite and acetohydroxamic acid, a monohydroxamate ligand, suggested that the three hydroxamate groups in DFO-D1 coordinate to Fe(III) surface sites relatively independently. The results also demonstrated a significant depleting effect of 240 mu-M DFO-B or DFO-D1 on Pb(II) adsorption by goethite at pH > 6.5, but there was no effect of adsorbed Pb(II) on the goethite dissolution rate.

  5. Paramagnetic Defects in Electron-Irradiated Yttria-Stabilized Zirconia: Effect of Yttria Content

    SciTech Connect (OSTI)

    Costantini, Jean-Marc; Beuneu, Francois; Morrison-Smith, Sarah; Devanathan, Ram; Weber, William J

    2011-01-01

    We have studied the effect of the yttria content on the paramagnetic centres in electron-irradiated yttria-stabilized zirconia (ZrO2: Y3+) or YSZ. Single crystals with 9.5 mol% or 18 mol% Y2O3 were irradiated with electrons of 1.0, 1.5, 2.0 and 2.5 MeV. The paramagnetic centre production was studied by X-band EPR spectroscopy. The same paramagnetic centres were identified for both chemical compositions, namely two electron centres, i.e. i) F+-type centres (involving singly ionized oxygen vacancies), and ii) so-called T centres (Zr3+ in a trigonal symmetry site), and hole-centres. A strong effect is observed on the production of hole-centres which are strongly enhanced when doubling the yttria content. However, no striking effect is found on the electron centres (except the enhancement of an extra line associated to the F+-type centres). It is concluded that hole-centres are produced by inelastic interactions, whereas F+-type centres are produced by elastic collisions with no effect of the yttria content on the defect production rate. In the latter case, the threshold displacement energy (Ed) of oxygen is estimated from the electron-energy dependence of the F+-type centre production rate, with no significant effect of the yttria content on Ed. An Ed value larger than 120 eV is found. Accordingly, classical molecular dynamics (MD) simulations with a Buckingham-type potential show that Ed values for Y and O are likely to be in excess of 200 eV. Due to the difficulty in displacing O or Y atoms, the radiation-induced defects may alternatively be a result of Zr atom displacements for Ed = 80 1 eV with subsequent defect re-arrangement.

  6. Paramagnetic defects in electron-irradiated yttria-stabilized zirconia: Effect of yttria content

    SciTech Connect (OSTI)

    Costantini, Jean-Marc; Beuneu, Francois; Morrison-Smith, Sarah E.; Devanathan, Ramaswami; Weber, William J.

    2011-12-20

    We have studied the effect of the yttria content on the paramagnetic centres in electron-irradiated yttria-stabilized zirconia (ZrO2: Y3+) or YSZ. Single crystals with 9.5 mol% or 18 mol% Y2O3 were irradiated with electrons of 1.0, 1.5, 2.0 and 2.5 MeV. The paramagnetic centre production was studied by X-band EPR spectroscopy. The same paramagnetic centres were identified for both chemical compositions, namely two electron centres, i.e. i) F+-type centres (involving singly ionized oxygen vacancies), and ii) so-called T centres (Zr3+ in a trigonal symmetry site), and hole-centres. A strong effect is observed on the production of hole-centres which are strongly enhanced when doubling the yttria content. However, no striking effect is found on the electron centres (except the enhancement of an extra line associated to the F+-type centres). It is concluded that hole-centres are produced by inelastic interactions, whereas F+-type centres are produced by elastic collisions with no effect of the yttria content on the defect production rate. In the latter case, the threshold displacement energy (Ed) of oxygen is estimated from the electron-energy dependence of the F+-type centre production rate, with no significant effect of the yttria content on Ed. An Ed value larger than 120 eV is found. Accordingly, classical molecular dynamics (MD) simulations with a Buckingham-type potential show that Ed values for Y and O are likely to be in excess of 200 eV. It is concluded that F+-type centres might be actually oxygen divacancies (F2+-type centres). Due to the difficulty in displacing O or Y atoms, the radiation-induced defects may alternatively be a result of Zr atom displacements for Ed = 80 1 eV with subsequent defect re-arrangement.

  7. A density functional theory study of the oxidation of methanol to formaldehyde over vanadia supported on silica, titania, and zirconia

    SciTech Connect (OSTI)

    Khaliullin, Rustam Z.; Bell, Alexis T.

    2002-09-05

    Density functional theory was used to investigate the mechanism and kinetics of methanol oxidation to formaldehyde over vanadia supported on silica, titania, and zirconia. The catalytically active site was modeled as an isolated VO{sub 4} unit attached to the support. The calculated geometry and vibrational frequencies of the active site are in good agreement with experimental measurements both for model compounds and oxide-supported vanadia. Methanol adsorption is found to occur preferentially with the rupture of a V-O-M bond (M = Si, Ti, Zr) and with preferential attachment of a methoxy group to V. The vibrational frequencies of the methoxy group are in good agreement with those observed experimentally as are the calculated isobars. The formation of formaldehyde is assumed to occur via the transfer of an H atom of a methoxy group to the O atom of the V=O group. The activation energy for this process is found to be in the range of 199-214 kJ/mol and apparent activation energies for the overall oxidation of methanol to formaldehyde are predicted to lie in the range of 112-123 kJ/mol, which is significantly higher than that found experimentally. Moreover, the predicted turnover frequency (TOF) for methanol oxidation is found to be essentially independent of support composition, whereas experiments show that the TOF is 10{sup 3} greater for titania- and zirconia-supported vanadia than for silica-supported vanadia. Based on these findings, it is proposed that the formation of formaldehyde from methoxy groups may require pairs of adjacent VO{sub 4} groups or V{sub 2}O{sub 7} dimer structures.

  8. On the thermal stability of physical vapor deposited oxide-hardened nanocrystalline gold thin films

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

    Argibay, Nicolas; Mogonye, J. E.; Michael, Joseph R.; Goeke, Ronald S.; Kotula, Paul G.; Scharf, T. W.; Dugger, Michael Thomas; Prasad, Somuri V.

    2015-04-08

    We describe a correlation between electrical resistivity and grain size for PVD synthesized polycrystalline oxide-hardened metal-matrix thin films in oxide-dilute (<5 vol. % oxide phase) compositions. The correlation is based on the Mayadas-Shatzkes (M-S) electron scattering model, predictive of grain size evolution as a function of composition in the oxide-dilute regime for 2 μm thick Au-ZnO films. We describe a technique to investigate grain boundary (GB) mobility and the thermal stability of GBs based on in situelectrical resistivity measurements during annealing experiments, interpreted using a combination of the M-S model and the Michels et al. model describing solute drag stabilizedmore » grain growth kinetics. Using this technique, activation energy and pre-exponential Arrhenius parameter values of Ea = 21.6 kJ/mol and Ao = 2.3 × 10-17 m2/s for Au-1 vol. % ZnO and Ea =12.7 kJ/mol and Ao = 3.1 × 10-18 m2/s for Au-2 vol.% ZnO were determined. In the oxide-dilute regime, the grain size reduction of the Au matrix yielded a maximum hardness of 2.6 GPa for 5 vol. % ZnO. A combined model including percolation behavior and grain refinement is presented that accurately describes the composition dependent change in electrical resistivity throughout the entire composition range for Au-ZnO thin films. As a result, the proposed correlations are supported by microstructural characterization using transmission electron microscopy and electron diffraction mapping for grain size determination.« less

  9. Homoepitaxy of ZnO and MgZnO Films at 90 C

    SciTech Connect (OSTI)

    Ehrentraut, Dirk; Goh, Gregory K.L.; Fujii, Katsushi; Ooi, Chin Chun; Quang, Le Hong; Fukuda, Tsuguo; Kano, Masataka; Zhang, Yuantao; Matsuoka, Takashi

    2014-06-01

    The aqueous synthesis of uniform single crystalline homoepitaxial zinc oxide, ZnO, and magnesium zinc oxide, Mg{sub x}Zn{sub 1?x}O, films under very low temperature conditions at T=90 C and ambient pressure has been explored. A maximum Mg content of 1 mol% was recorded by energy dispersive spectroscopy. The growth on the polar (0 0 0 1) and (0 0 0 1) faces resulted in films that are strongly different in their structural and optical quality as evidenced by high-resolution X-ray diffraction, secondary electron microscopy, and photoluminescence. This is a result of the chemistry and temperature of the solution dictating the stability range of growth-governing metastable species. The use of trisodium citrate, Na{sub 3}C{sub 6}H{sub 5}O{sub 7}, yielded coalesced, mirror-like homoepitaxial films whereas adding magnesium nitrate hexahydrate, Mg(NO{sub 3}){sub 2}6H{sub 2}O, favors the growth of films with pronounced faceting. - Graphical abstract: Homoepitaxial ZnO films grown from aqueous solution below boiling point of water on a ZnO substrate with off-orientation reveal parallel grooves that are characterized by (1 0 1{sup } 1) facets. Adding trisodium citrate yields closed, single-crystalline ZnO films, which can further be functionalized. Alloying with MgO yields MgZnO films with low Mg content only. - Highlights: A simple method to synthesize uniform single crystalline homoepitaxial ZnO and MgZnO films. ZnO growth on (0 0 0 1) and (0 0 0 1{sup }) face resulted in films that are strongly different in their structural and optical quality. Single crystalline MgZnO film was fabricated under mild conditions (90 C and ambient pressure). Mg incorporation of nearly 1 mol% was obtained while maintaining single phase wurtzite structure.

  10. Study of metallic powder behavior in very low pressure plasma spraying (VLPPS) Application to the manufacturing of titaniumaluminum coatings

    SciTech Connect (OSTI)

    Vautherin, B.; Planche, M.-P.; Montavon, G.; Lapostolle, F.; Quet, A.; Bianchi, L.

    2015-08-28

    In this study, metallic materials made of aluminum and titanium were manufactured implementing very low pressure plasma spraying (VLPPS). Aluminum was selected at first as a demonstrative material due to its rather low vaporization enthalpy (i.e., 381.9 kJmol?). Developments were then carried out with titanium which exhibits a higher vaporization enthalpy (i.e., 563.6 kJmol?). Optical emission spectroscopy (OES) was implemented to analyze the behavior of each solid precursor (metallic powders) when it is injected into the plasma jet under very low pressure (i.e., in the 150 Pa range). Besides, aluminum, titanium and titaniumaluminum coatings were deposited in the same conditions implementing a stick-cathode plasma torch operated at 50 kW, maximum power. Coating phase compositions were identified by X-Ray Diffraction (XRD). Coating elementary compositions were quantified by Glow Discharge Optical Emission Spectroscopy (GDOES) and Energy Dispersive Spectroscopy (EDS) analyses. The coating structures were observed by Scanning Electron Microscopy (SEM). The coating void content was determined by Ultra-Small Angle X-ray Scattering (USAXS). The coatings exhibit a two-scale structure corresponding to condensed vapors (smaller scale) and solidified areas (larger scale). Titaniumaluminum sprayed coatings, with various Ti/Al atomic ratios, are constituted of three phases: metastable ?-Ti, Al and metastable ??-Ti?Al. This latter is formed at elevated temperature in the plasma flow, before being condensed. Its rather small fraction, impeded by the rather small amount of vaporized Ti, does not allow modifying however the coating hardness.

  11. The Negative Ion Photoelectron Spectrum of Cyclopropane-1,2,3-Trione Radical Anion (CO)(3)- - A Joint Experimental and Computational Study

    SciTech Connect (OSTI)

    Chen, Bo; Hrovat, David; West, Robert C.; Deng, Shihu; Wang, Xue B.; Borden, Weston

    2014-09-03

    Negative Ion Photoelectron (NIPE) spectra of the radical anion of cyclopropane-1,2,3-trione, (CO)3?, have been obtained at 20 K, using both 355 and 266 nm lasers for electron photodetachment. The spectra show broadened bands, due to the short lifetimes of both the singlet and triplet states of (CO)3. The smaller intensity of the band with the lower electron binding energy suggests that the singlet is the ground state of (CO)3. From the NIPE spectra, the electron affinity (EA) and the singlet-triplet energy gap of (CO)3 are estimated to be, respectively, EA = 3.1 0.1 eV and ?EST = ?14 3 kcal/mol. High-level, (U)CCSD(T)/aug-cc-pVQZ//(U)CCSD(T)/aug-cc-pVTZ, calcu-lations give EA = 3.04 eV for the 1A1 ground state of (CO)3 and ?EST = ?13.8 kcal/mol for the energy gap between the 1A1 and 3A2 states, in excellent agreement with values from the NIPE spectra. In addition, simulations of the vibrational structures for formation of these states of (CO)3 from the 2A2? state of (CO)3? provide a good fit to the shapes of broad bands in the 266 nm NIPE spectrum. The NIPE spectrum of (CO)3? and the analysis of the spectrum by high-quality electronic structure calculations demonstrate that NIPES can not only access and provide information about transition structures, but NIPES can also access and provide information about hilltops on potential energy surfaces.

  12. Dose calculation for permanent prostate implants incorporating spatially anisotropic linearly time-resolving edema

    SciTech Connect (OSTI)

    Monajemi, T. T.; Clements, Charles M.; Sloboda, Ron S.

    2011-04-15

    Purpose: The objectives of this study were (i) to develop a dose calculation method for permanent prostate implants that incorporates a clinically motivated model for edema and (ii) to illustrate the use of the method by calculating the preimplant dosimetry error for a reference configuration of {sup 125}I, {sup 103}Pd, and {sup 137}Cs seeds subject to edema-induced motions corresponding to a variety of model parameters. Methods: A model for spatially anisotropic edema that resolves linearly with time was developed based on serial magnetic resonance imaging measurements made previously at our center to characterize the edema for a group of n=40 prostate implant patients [R. S. Sloboda et al., ''Time course of prostatic edema post permanent seed implant determined by magnetic resonance imaging,'' Brachytherapy 9, 354-361 (2010)]. Model parameters consisted of edema magnitude, {Delta}, and period, T. The TG-43 dose calculation formalism for a point source was extended to incorporate the edema model, thus enabling calculation via numerical integration of the cumulative dose around an individual seed in the presence of edema. Using an even power piecewise-continuous polynomial representation for the radial dose function, the cumulative dose was also expressed in closed analytical form. Application of the method was illustrated by calculating the preimplant dosimetry error, RE{sub preplan}, in a 5x5x5 cm{sup 3} volume for {sup 125}I (Oncura 6711), {sup 103}Pd (Theragenics 200), and {sup 131}Cs (IsoRay CS-1) seeds arranged in the Radiological Physics Center test case 2 configuration for a range of edema relative magnitudes ({Delta}=[0.1,0.2,0.4,0.6,1.0]) and periods (T=[28,56,84] d). Results were compared to preimplant dosimetry errors calculated using a variation of the isotropic edema model developed by Chen et al. [''Dosimetric effects of edema in permanent prostate seed implants: A rigorous solution,'' Int. J. Radiat. Oncol., Biol., Phys. 47, 1405-1419 (2000)]. Results: As expected, RE{sub preplan} for our edema model indicated underdosage in the calculation volume with a clear dependence on seed and calculation point positions, and increased with increasing values of {Delta} and T. Values of RE{sub preplan} were generally larger near the ends of the virtual prostate in the RPC phantom compared with more central locations. For edema characteristics similar to the population average values previously measured at our center, i.e., {Delta}=0.2 and T=28 d, mean values of RE{sub preplan} in an axial plane located 1.5 cm from the center of the seed distribution were 8.3% for {sup 131}Cs seeds, 7.5% for {sup 103}Pd seeds, and 2.2% for {sup 125}I seeds. Maximum values of RE{sub preplan} in the same plane were about 1.5 times greater. Note that detailed results strictly apply only for loose seed implants where the seeds are fixed in tissue and move in synchrony with that tissue. Conclusions: A dose calculation method for permanent prostate implants incorporating spatially anisotropic linearly time-resolving edema was developed for which cumulative dose can be written in closed form. The method yields values for RE{sub preplan} that differ from those for spatially isotropic edema. The method is suitable for calculating pre- and postimplant dosimetry correction factors for clinical seed configurations when edema characteristics can be measured or estimated.

  13. New Pathways and Metrics for Enhanced, Reversible Hydrogen Storage in Boron-Doped Carbon Nanospaces

    SciTech Connect (OSTI)

    Pfeifer, Peter; Wexler, Carlos; Hawthorne, M. Frederick; Lee, Mark W.; Jalistegi, Satish S.

    2014-08-14

    This project, since its start in 2007entitled Networks of boron-doped carbon nanopores for low-pressure reversible hydrogen storage (2007-10) and New pathways and metrics for enhanced, reversible hydrogen storage in boron-doped carbon nanospaces (2010-13)is in support of the DOE's National Hydrogen Storage Project, as part of the DOE Hydrogen and Fuel Cells Programs comprehensive efforts to enable the widespread commercialization of hydrogen and fuel cell technologies in diverse sectors of the economy. Hydrogen storage is widely recognized as a critical enabling technology for the successful commercialization and market acceptance of hydrogen powered vehicles. Storing sufficient hydrogen on board a wide range of vehicle platforms, at energy densities comparable to gasoline, without compromising passenger or cargo space, remains an outstanding technical challenge. Of the main three thrust areas in 2007metal hydrides, chemical hydrogen storage, and sorption-based hydrogen storagesorption-based storage, i.e., storage of molecular hydrogen by adsorption on high-surface-area materials (carbons, metal-organic frameworks, and other porous organic networks), has emerged as the most promising path toward achieving the 2017 DOE storage targets of 0.055 kg H2/kg system (5.5 wt%) and 0.040 kg H2/liter system. The objective of the project is to develop high-surface-area carbon materials that are boron-doped by incorporation of boron into the carbon lattice at the outset, i.e., during the synthesis of the material. The rationale for boron-doping is the prediction that boron atoms in carbon will raise the binding energy of hydro- gen from 4-5 kJ/mol on the undoped surface to 10-14 kJ/mol on a doped surface, and accordingly the hydro- gen storage capacity of the material. The mechanism for the increase in binding energy is electron donation from H2 to electron-deficient B atoms, in the form of sp2 boron-carbon bonds. Our team is proud to have demonstrated the predicted increase in binding energy experimentally, currently at ~10 kJ/mol. The synthetic route for incorporation of boron at the outset is to create appropriately designed copoly- mers, with a boron-free and a boron-carrying monomer, followed by pyrolysis of the polymer, yielding a bo- ron-substituted carbon scaffold in which boron atoms are bonded to carbon atoms by synthesis. This is in contrast to a second route (funded by DE-FG36-08GO18142) in which first high-surface area carbon is cre- ated and doped by surface vapor deposition of boron, with incorporation of the boron into the lattice the final step of the fabrication. The challenge in the first route is to create high surface areas without compromising sp2 boron-carbon bonds. The challenge in the second route is to create sp2 boron-carbon bonds without com- promising high surface areas.

  14. Molybdenum Hydride and Dihydride Complexes Bearing Diphosphine Ligands with a Pendant Amine: Formation of Complexes With Bound Amines

    SciTech Connect (OSTI)

    Zhang, Shaoguang; Bullock, R. Morris

    2015-07-06

    CpMo(CO)(PNP)H complexes (PNP = (R2PCH2)2NMe, R = Et or Ph) were synthesized by displacement of two CO ligands of CpMo(CO)3H by the PNP ligand; these complexes were characterized by IR and variable temperature 1H and 31P NMR spectroscopy. CpMo(CO)(PNP)H complexes are formed as mixture of cis and trans-isomers. Both cis-CpMo(CO)(PEtNMePEt)H and trans-CpMo(CO)(PPhNMePPh)H were analyzed by single crystal X-ray diffraction. Electrochemical oxidation of CpMo(CO)(PEtNMePEt)H and CpMo(CO)(PPhNMePPh)H in CH3CN are both irreversible at slow scan rates and quasi-reversible at higher scan rates, with E1/2 = -0.36 V (vs. Cp2Fe+/0) for CpMo(CO)(PEtNMePEt)H and E1/2 = -0.18 V for CpMo(CO)(PPhNMePPh)H. Hydride abstraction from CpMo(CO)(PNP)H with [Ph3C]+[A]- (A = B(C6F5)4 or BArF4; [ArF = 3,5-bis(trifluoromethyl)phenyl]) afforded “tuck-in” [CpMo(CO)(κ3-PNP)]+ complexes that feature the amine bound to the metal. Displacement of the κ3 Mo-N bond by CD3CN gives [CpMo(CO)(PNP)(CD3CN)]+. The kinetics of this reaction were studied by NMR spectroscopy, providing the activation parameters ΔH‡ = 22.1 kcal/mol, ΔS‡ = 1.89 cal/(mol·K), Ea = 22.7 kcal/mol. Protonation of CpMo(CO)(PEtNMePEt)H affords [CpMo(CO)(κ2-PEtNMePEt)(H)2]+ as a Mo dihydride complex, which loses H2 to generate [CpMo(CO)(κ3-PEtNMePEt)]+ at room temperature. CpMo(CO)(dppp)H (dppp = 1,2-bis(diphenylphosphino)propane) was studied as a Mo diphosphine analogue without a pendant amine, and the product of protonation of this complex gives [CpMo(CO)(dppp)(H)2]+. Our results show that the pendant amine has a strong driving force to form stable “tuck-in” [CpMo(CO)(κ3-PNP)]+ complexes, and also promotes hydrogen elimination from [CpMo(CO)(PNP)(H)2]+ complexes by formation of Mo-N dative bond. We thank the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences for support. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy. We thank Monte Helm, Elliott Hulley and Deanna Miller for help on the crystallography, and Ming Fang for assistance on the electrochemical experiments.

  15. Thermodynamics of the Hydrolysis Reactions of 1,4-beta-D-xylobiose, 1,4-beta-D-xylotriose, D-cellobiose, and D-Maltose

    SciTech Connect (OSTI)

    Tewari, Y. B.; Lang, B. E.; Decker, S. R.; Goldberg, R. N.

    2008-10-01

    Microcalorimetry and high-performance liquid chromatography have been used to conduct a thermodynamic investigation of the following reactions: (1) 1,4-{beta}-Dxylobiose(aq)+H{sub 2}O(I)=2D-xylose(aq); (2) 1,4-{beta}-D-xylotriose+2H{sub 2}O(I)=3D-xylose(aq); (3) D-maltose(aq)+H{sub 2}O(I)=2{alpha}-D-glucose(aq); and (4) D-cellobiose(aq)+H{sub 2}O(I)=2{alpha}-D-glucose(aq). The results of the equilibrium measurements were K = (1.46 {+-} 0.15) {center_dot} 10{sup 3} for reaction (1) and K = (551 {+-} 34) for reaction (3). Although it was not possible to measure directly a value for the equilibrium constant for reaction (4), it was possible to obtain the value K = 657 for this reaction via a thermochemical pathway calculation. The results of the calorimetric measurements were standard enthalpies of reaction {Delta}{sub r}H{sup o} = (0.12 {+-} 0.26) kJ {center_dot} mol{sup -1} for reaction (1) and {Delta}{sub r}H{sup o} = -(0.06 {+-} 0.18) kJ {center_dot} mol{sup -1} for reaction (2). It is noted that values of {Delta}{sub r}H{sup o} for reactions (1) and (2) are equal to each other within their respective experimental errors. This fact is consistent with earlier observations that, for reactions involving the making/breaking of N saccharide linkages, the assignment of characteristic values of {Delta}{sub r}H{sup o}/N or {Delta}{sub r}G{sup o}/N or {Delta}{sub r}S{sup o}/N for a specified linkage, is accurate in predicting the values of {Delta}{sub r}H{sup o}, {Delta}{sub r}G{sup o}, and {Delta}{sub r}S{sup o} for reactions involving saccharides that contain multiples or combinations of such linkages. Also, the values of the standard entropy changes {Delta}{sub r}S{sup o} for the hydrolysis reactions (3) and (4) fall into the range of values {l_brace}(32 to 48) J {center_dot} K{sup -1} {center_dot} mol{sup -1}{r_brace} previously noted for the hydrolysis of six-carbon disaccharides. In order to tie the results of this study into the thermochemical literature, a reaction catalog of related property values was created. Selected property values from this reaction catalog were then used to calculate 'best' values of the standard Gibbs free energy of formation {Delta}{sub r}G{sup o}, the standard enthalpy of formation {Delta}{sub r}H{sup o}, the standard molar entropy S{sub m}{sup o}, and the standard molar heat capacity C{sub p,m}{sup o}, for the substances of interest to this investigation.

  16. Physicochemical and catalytic properties of palladium supported on poly(o-methoxyaniline)

    SciTech Connect (OSTI)

    Drelinkiewicz, A. . E-mail: drelinki@chemia.uj.edu.pl; Hasik, M.; Sobczak, J.W.; Sobczak, E.; Bernasik, A.; Bielanska, E.

    2005-05-18

    Palladium was introduced into a conjugated polymer poly(o-methoxyaniline) (POM) by reacting the powdered polymer with aqueous solution of PdCl{sub 2} of low acidity (PdCl{sub 2}: 2.3 x 10{sup -3} mol/dm{sup 3}, HCl: 0.66 x 10{sup -3} mol/dm{sup 3}). Various Pd{sup 2+} complexes with Cl{sup -}, H{sub 2}O, OH{sup -} ligands coexisted in this solution but predominated [PdCl{sub 2}(H{sub 2}O){sub 2}] ones. Several techniques like X-ray powder diffraction, scanning electron microscopy, X-ray photoelectron and Raman spectroscopy, extended X-ray absorption fine structure have been used to characterize the poly(o-methoxyaniline)-Pd systems. In particular, the state of Pd species in the Pd/POM of various content of palladium (2-8 wt.% Pd) and chemical changes in the polymer matrix induced by insertion of palladium were studied. The protonation and redox reactions involved on palladium incorporation resulted in palladium ions and Pd metal in the final samples. Metallic Pd produced due to spontaneous reduction of palladium ions by the polymer formed large crystalline particles 200-1000 nm in size. The Pd{sup 2+} species in the form of anionic complexes like [PdCl{sub 4}]{sup 2-} acted as the counterions at low content of palladium (2-4 wt.% Pd). At high palladium content (8 wt.% Pd), several atoms like Cl, N and/or O were identified by extended X-ray absorption fine structure (EXAFS) technique in the nearest environment of Pd atoms. The structural groups of POM (like N groups and/or OCH{sub 3}) as well as H{sub 2}O, OH{sup -} molecules are, therefore, considered as probable species in the coordination sphere of palladium. The catalytic properties were studied for the as-prepared Pd/POM and the samples additionally reduced with aqueous solution of NaH{sub 2}PO{sub 2}. They were used in the hydrogenation of C=C bonds in maleic acid (MAC) and C=O groups in 2-ethylanthraquinone (eAQ) at 60 deg. C and atmospheric pressure of hydrogen using xylene-octanol-2 or water medium. The correlation between Pd/POM activities and the content of Pd metal was found. Activation of the as-prepared Pd/POM with NaH{sub 2}PO{sub 2} improved their catalytic properties. Much higher and much stable activities were then obtained in both MAC and eAQ hydrogenation reactions.

  17. A Screening Model to Predict Microalgae Biomass Growth in Photobioreactors and Raceway Ponds

    SciTech Connect (OSTI)

    Huesemann, Michael H.; Van Wagenen, Jonathan M.; Miller, Tyler W.; Chavis, Aaron R.; Hobbs, Watts B.; Crowe, Braden J.

    2013-06-01

    A microalgae biomass growth model was developed for screening novel strains for their potential to exhibit high biomass productivities under nutrient-replete conditions in photobioreactors or outdoor ponds. Growth is modeled by first estimating the light attenuation by biomass according to Beer-Lamberts law, and then calculating the specific growth rate in discretized culture volume slices that receive declining light intensities due to attenuation. The model requires only two physical and two species-specific biological input parameters, all of which are relatively easy to determine: incident light intensity, culture depth, as well as the biomass light absorption coefficient and the specific growth rate as a function of light intensity. Roux bottle culture experiments were performed with Nannochloropsis salina at constant temperature (23 C) at six different incident light intensities (5, 10, 25, 50, 100, 250, and 850 ?mol/m2? sec) to determine both the specific growth rate under non-shading conditions and the biomass light absorption coefficient as a function of light intensity. The model was successful in predicting the biomass growth rate in these Roux bottle cultures during the light-limited linear phase at different incident light intensities. Model predictions were moderately sensitive to minor variations in the values of input parameters. The model was also successful in predicting the growth performance of Chlorella sp. cultured in LED-lighted 800 L raceway ponds operated at constant temperature (30 C) and constant light intensity (1650 ?mol/m2? sec). Measurements of oxygen concentrations as a function of time demonstrated that following exposure to darkness, it takes at least 5 seconds for cells to initiate dark respiration. As a result, biomass loss due to dark respiration in the aphotic zone of a culture is unlikely to occur in highly mixed small-scale photobioreactors where cells move rapidly in and out of the light. By contrast, as supported also by the growth model, biomass loss due to dark respiration occurs in the dark zones of the relatively less well mixed pond cultures. In addition to screening novel microalgae strains for high biomass productivities, the model can also be used for optimizing the pond design and operation. Additional research is needed to validate the biomass growth model for other microalgae species and for the more realistic case of fluctuating temperatures and light intensities observed in outdoor pond cultures.

  18. Efficient electrochemical CO2 conversion powered by renewable energy

    SciTech Connect (OSTI)

    Kauffman, Douglas R.; Thakkar, Jay; Siva, Rajan; Matranga, Christopher; Ohodnicki, Paul R.; Zeng, Chenjie; Jin, Rongchao

    2015-06-29

    The catalytic conversion of CO2 into industrially relevant chemicals is one strategy for mitigating greenhouse gas emissions. Along these lines, electrochemical CO2 conversion technologies are attractive because they can operate with high reaction rates at ambient conditions. However, electrochemical systems require electricity, and CO2 conversion processes must integrate with carbon-free, renewable-energy sources to be viable on larger scales. We utilize Au25 nanoclusters as renewably powered CO2 conversion electrocatalysts with CO2 → CO reaction rates between 400 and 800 L of CO2 per gram of catalytic metal per hour and product selectivities between 80 and 95%. These performance metrics correspond to conversion rates approaching 0.8–1.6 kg of CO2 per gram of catalytic metal per hour. We also present data showing CO2 conversion rates and product selectivity strongly depend on catalyst loading. Optimized systems demonstrate stable operation and reaction turnover numbers (TONs) approaching 6 × 106 mol CO2 molcatalyst–1 during a multiday (36 hours total hours) CO2electrolysis experiment containing multiple start/stop cycles. TONs between 1 × 106 and 4 × 106 molCO2 molcatalyst–1 were obtained when our system was powered by consumer-grade renewable-energy sources. Daytime photovoltaic-powered CO2 conversion was demonstrated for 12 h and we mimicked low-light or nighttime operation for 24 h with a solar-rechargeable battery. This proof-of-principle study provides some of the initial performance data necessary for assessing the scalability and technical viability of electrochemical CO2 conversion technologies. Specifically, we show the following: (1) all electrochemical CO2 conversion systems will produce a net increase in CO2 emissions if they do not integrate with renewable-energy sources, (2) catalyst loading vs activity trends can be used to tune process rates and product distributions, and (3) state-of-the-art renewable-energy technologies are sufficient to power larger-scale, tonne per day CO2 conversion systems.

  19. Synthesis and luminescent properties of spindle-like CaWO{sub 4}:Sm{sup 3+} phosphors

    SciTech Connect (OSTI)

    Tian, Yue [College of Life Science, Dalian Nationalities University, Dalian, Liaoning 116600 (China) [College of Life Science, Dalian Nationalities University, Dalian, Liaoning 116600 (China); Department of Physics, Dalian Maritime University, Dalian, Liaoning 116026 (China); Liu, Yu [Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology, Dalian, Liaoning 116024 (China)] [Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology, Dalian, Liaoning 116024 (China); Hua, Ruinian, E-mail: rnhua@dlnu.edu.cn [College of Life Science, Dalian Nationalities University, Dalian, Liaoning 116600 (China)] [College of Life Science, Dalian Nationalities University, Dalian, Liaoning 116600 (China); Na, Liyan [College of Life Science, Dalian Nationalities University, Dalian, Liaoning 116600 (China)] [College of Life Science, Dalian Nationalities University, Dalian, Liaoning 116600 (China); Chen, Baojiu, E-mail: chenmbj@sohu.com [Department of Physics, Dalian Maritime University, Dalian, Liaoning 116026 (China)] [Department of Physics, Dalian Maritime University, Dalian, Liaoning 116026 (China)

    2012-01-15

    Graphical abstract: In this paper, spindle-like CaWO{sub 4}:Sm{sup 3+} phosphors were prepared via a polyvinylpyrrolidone (PVP)-assisted sonochemical process. Dependence of emission intensity on Sm{sup 3+} ions concentration in the CaWO{sub 4}:Sm{sup 3+} phosphor were also calculated via a nonlinear fitting by using the formula y = ax/(1 + bx{sup c}). Highlights: Black-Right-Pointing-Pointer The samples were prepared via a PVP assisted sonochemical process. Black-Right-Pointing-Pointer The color coordinates for 1 mol% Sm{sup 3+} doped CaWO{sub 4} phosphor were calculated. Black-Right-Pointing-Pointer The D-D interaction is responsible for concentration quenching between Sm{sup 3+} ions. Black-Right-Pointing-Pointer The critical energy transfer distances (R{sub c}) were obtained. -- Abstract: Spindle-like CaWO{sub 4}:Sm{sup 3+} phosphors were prepared via a Polyvinylpyrrolidone (PVP)-assisted sonochemical process, and characterized by using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and photoluminescence spectroscopy (PL). The XRD results suggested that the prepared samples are single-phase. The FE-SEM images indicated that the prepared CaWO{sub 4}:Sm{sup 3+} phosphors are composed of many spindles with maximum average diameter of 150 nm and maximum average length of 500 nm. Under 404 nm excitation, the characteristic emissions corresponding to {sup 4}G{sub 5/2} {yields} {sup 6}H{sub J} (J = 5/2, 7/2, 9/2 and 11/2) transitions of Sm{sup 3+} in CaWO{sub 4} phosphors were observed. The color coordinates for 1 mol% Sm{sup 3+} doped CaWO{sub 4} phosphor were calculated to be (0.595, 0.404). The fluorescent concentration quenching of Sm{sup 3+} doped spindle-like phosphors was studied based on the Van Uitert's model, and it was found that the electric dipole-dipole (D-D) interaction is the dominant energy transfer mechanism between Sm{sup 3+} ions in the CaWO{sub 4}:Sm{sup 3+} phosphors. The critical energy transfer distance was estimated.

  20. Carbon dioxide, hydrographic, and chemical data obtained in the Central South Pacific Ocean (WOCE sections P17S and P16S) during the tunes-2-expedition of the R/V Thomas Washington, July--August 1991

    SciTech Connect (OSTI)

    1991-12-31

    This data documentation discusses the procedures and methods used to measure total carbon dioxide (TCO{sub 2}), discrete partial pressure of TCO{sub 2} (pCO{sub 2}), and total alkalinity (TALK), during the Research Vessel (R/V) Thomas Washington TUNES Leg 2 Expedition in the central South Pacific Ocean. Conducted as part of the World Ocean Circulation Experiment (WOCE), the cruise began in Papeete, Tahiti, French Polynesia, on July 16, 1991, and returned to Papeete on August 25, 1991. WOCE Meridional Sections P17S along 135{degrees} W and P16S along 150{degrees} W were completed during the 40-day expedition. A total of 97 hydrographic stations were occupied. Hydrographic and chemical measurements made along WOCE Sections P17S and P16S included pressure, temperature, salinity, and oxygen measured by conductivity, temperature and depth sensor; bottle salinity; oxygen; phosphate; nitrate; nitrite; silicate; CFC-12; CFC- 11; TCO{sub 2}; TALK; and pCO{sub 2} measured at 20{degrees}C. The TCO{sub 2} concentration in 1000 seawater samples was determined with a coulometric analysis system, the pCO{sub 2} in 940 water samples was determined with an equilibrator/gas chromatograph system, while the TALK concentration in 139 samples was determined on shore at the laboratory of C. Goyet of Woods Hole Oceanographic Institution with an alkalinity titration system. In addition, 156 coulometric measurements for the Certified Reference Material (Batch {number_sign}6) were made and yielded a mean value of 2303.2 {plus_minus} 1.5 {mu}mol/kg. This mean value agrees within a standard deviation of the 2304.6 {plus_minus} 1.6 {mu}mol/kg (N=9) value determined with the manometer of C. D. Keeling at Scripps Institution of Oceanography (SIO). Replicate samples from 11 Niskin bottles at 4 stations were also collected for later shore-based reference analyses of TCO{sub 2} and TALK by vacuum extraction and manometry in the laboratory of C. D. Keeling of SIO.

  1. Reaction dynamics and photochemistry of divalent systems

    SciTech Connect (OSTI)

    Davis, H.F.

    1992-05-01

    Results are presented of molecular beam studies of bimolecular and unimolecular reactions of Ba. Chapter 1 discusses the reaction Ba + NO{sub 2}. Formation of the dominant BaO({sup 1}{Sigma}) + NO products resulted primarily from decay of long-lived Ba{sup +}NO{sub 2}{sup {minus}} collision complexes. Secondary mechanisms led to formation of forward scattered, internally excited BaO, and BaNO + O. D{sub o}(Ba-NO) = 65{plus_minus}20 kcal/mol. Reactions of ground state and electronically excited Ba with water and alcohols are examined in Chapter 2. Reaction of Ba({sup 1}S) + H{sup 2}O led to BaO + H{sub 2}, whereas excited state Ba({sup 1}D) + H{sub 2}O reacted to form BaOH + H. Collisions between Ba and CH{sub 3}OH led to BaOCH{sub 3} + H. Radical channels involve H-atom migration and are promoted by excitation of the incident Ba atom. In Chapter 3, reactions of Ba({sup 1}S) with ClO{sub 2}2 and O{sub 3} are discussed. Again, direct and complex mechanisms were observed. Formation of BaCl + O{sub 2} from decomposition of Ba{sup +}ClO{sub 2}{sup {minus}} accounted for 10% of total reaction crass section. Although Ba + O{sub 3} {yields} BaO + 0{sub 2} occurs primarily by direct reaction mechanisms, the secondary channel Ba + 0{sub 3} {yields} BaO{sub 2} + 0 involved decay of long lived Ba{sup +}O{sub 3}{sup {minus}} intermediates. D{sub o}(Ba{minus}O{sub 2}) = 120 {plus_minus}20 kcal/mol. Photodissociation dynamics of NO{sub 3} is explored in chapter 4. Visible excitation leads to formation of NO + 0{sub 2} and NO{sub 2} + O. Wavelength dependence of branching ratios is investigated. D{sub o}(O-NO{sub 2}) = 48.55 kcal/mole ;and calculate {Delta}H{sub f}(NO{sub 3}) = 17.75 kcal/mole (298K). Chapter 5 discusses the photodissociation of OClO in a molecular beam. Although ClO({sup 2}II) + O({sup 3}P) is dominant, Cl({sup 2}P) + O{sub 2} also forms, with a max yield of 3.9{plus_minus}0.8% near 404nm.

  2. Reaction dynamics and photochemistry of divalent systems. [Reaction of Ba with NO sub 2 , H sub 2 O, methanol, ClO sub 2 , O sub 3; photodissociation of NO sub 3 radical and OClO

    SciTech Connect (OSTI)

    Davis, H.F.

    1992-05-01

    Results are presented of molecular beam studies of bimolecular and unimolecular reactions of Ba. Chapter 1 discusses the reaction Ba + NO{sub 2}. Formation of the dominant BaO({sup 1}{Sigma}) + NO products resulted primarily from decay of long-lived Ba{sup +}NO{sub 2}{sup {minus}} collision complexes. Secondary mechanisms led to formation of forward scattered, internally excited BaO, and BaNO + O. D{sub o}(Ba-NO) = 65{plus minus}20 kcal/mol. Reactions of ground state and electronically excited Ba with water and alcohols are examined in Chapter 2. Reaction of Ba({sup 1}S) + H{sup 2}O led to BaO + H{sub 2}, whereas excited state Ba({sup 1}D) + H{sub 2}O reacted to form BaOH + H. Collisions between Ba and CH{sub 3}OH led to BaOCH{sub 3} + H. Radical channels involve H-atom migration and are promoted by excitation of the incident Ba atom. In Chapter 3, reactions of Ba({sup 1}S) with ClO{sub 2}2 and O{sub 3} are discussed. Again, direct and complex mechanisms were observed. Formation of BaCl + O{sub 2} from decomposition of Ba{sup +}ClO{sub 2}{sup {minus}} accounted for 10% of total reaction crass section. Although Ba + O{sub 3} {yields} BaO + 0{sub 2} occurs primarily by direct reaction mechanisms, the secondary channel Ba + 0{sub 3} {yields} BaO{sub 2} + 0 involved decay of long lived Ba{sup +}O{sub 3}{sup {minus}} intermediates. D{sub o}(Ba{minus}O{sub 2}) = 120 {plus minus}20 kcal/mol. Photodissociation dynamics of NO{sub 3} is explored in chapter 4. Visible excitation leads to formation of NO + 0{sub 2} and NO{sub 2} + O. Wavelength dependence of branching ratios is investigated. D{sub o}(O-NO{sub 2}) = 48.55 kcal/mole ;and calculate {Delta}H{sub f}(NO{sub 3}) = 17.75 kcal/mole (298K). Chapter 5 discusses the photodissociation of OClO in a molecular beam. Although ClO({sup 2}II) + O({sup 3}P) is dominant, Cl({sup 2}P) + O{sub 2} also forms, with a max yield of 3.9{plus minus}0.8% near 404nm.

  3. Running Title: C and N Allocation in Pine

    SciTech Connect (OSTI)

    Ball, J. Timothy

    1996-12-01

    A long standing challenge has been understanding how plants and ecosystems respond to shifts in the balance of resource availabilities. The continuing rise in atmospheric CO{sub 2} will induce changes in the availability and use of several terrestrial ecosystem resources. We report on the acquisition and allocation of carbon and nitrogen in Pinus ponderosa Laws. seedlings grown at three levels of atmospheric carbon dioxide (370, 525, and 700 {micro}mol mol{sup -1}) and three levels of soil nitrogen supply in a controlled environment experiment. Nitrogen was applied (0, 100, and 200 {micro}g N g soil{sup -1}) at planting and again at week 26 of a 58-week, 4-harvest experiment. At the final harvest, plants grown with variety low available soil nitrogen showed no significant response to atmospheric CO{sub 2}. Plants at higher N levels responded positively to CO{sub 2} with the highest biomass at the middle CO{sub 2} level. Plants growing at the lowest N levels immediately allocated a relatively large portion of their nitrogen and biomass to roots. Plants growing at near present ambient CO{sub 2} levels allocated relatively little material to roots when N was abundant but moved both carbon and nitrogen below-ground when N was withheld. Plants growing at higher CO{sub 2} levels, allocated more C and N to roots even when N was abundant, and made only small shifts in allocation patterns when N was no longer supplied. In general, allocation of C and N to roots tended to increase when N supply was restricted and also with increasing atmospheric CO{sub 2} level. These allocation responses were consistent with patterns suggesting a functional balance in the acquisition of above-ground versus below-ground resources. In particular, variation in whole tree average nitrogen concentration can explain 68% of the variation ratio of root biomass to shoot biomass across the harvests. The capability to respond to temporal variation in nutrient conditions, the dynamics of nutrient uptake, and the dynamics of nutrient use were all seen to be influenced by the interplay between previous N supply, previous C supply, and the concentration of CO{sub 2} in the atmosphere. The data suggest that in an elevated CO{sub 2} atmosphere ponderosa pine seedlings will have higher root biomass and be likely to capture more N compared to seedlings today. Further, the combined growth and allocation responses of Ponderosa pine at elevated CO{sub 2} resulted in higher growth per unit N (nitrogen productivity) and lower N per gram of tissue (all tissues not just leaves) when nitrogen was not in abundant supply.

  4. Incorporating a completely renormalized coupled cluster approach into a composite method for thermodynamic properties and reaction paths

    SciTech Connect (OSTI)

    Nedd, Sean; DeYonker, Nathan; Wilson, Angela; Piecuch, Piotr; Gordon, Mark

    2012-04-12

    The correlation consistent composite approach (ccCA), using the S4 complete basis set two-point extrapolation scheme (ccCA-S4), has been modified to incorporate the left-eigenstate completely renormalized coupled cluster method, including singles, doubles, and non-iterative triples (CR-CC(2,3)) as the highest level component. The new ccCA-CC(2,3) method predicts thermodynamic properties with an accuracy that is similar to that of the original ccCA-S4 method. At the same time, the inclusion of the single-reference CR-CC(2,3) approach provides a ccCA scheme that can correctly treat reaction pathways that contain certain classes of multi-reference species such as diradicals, which would normally need to be treated by more computationally demanding multi-reference methods. The new ccCA-CC(2,3) method produces a mean absolute deviation of 1.7 kcal/mol for predicted heats of formation at 298 K, based on calibration with the G2/97 set of 148 molecules, which is comparable to that of 1.0 kcal/mol obtained using the ccCA-S4 method, while significantly improving the performance of the ccCA-S4 approach in calculations involving more demanding radical and diradical species. Both the ccCA-CC(2,3) and ccCA-S4 composite methods are used to characterize the conrotatory and disrotatory isomerization pathways of bicyclo[1.1.0]butane to trans-1,3-butadiene, for which conventional coupled cluster methods, such as the CCSD(T) approach used in the ccCA-S4 model and, in consequence, the ccCA-S4 method itself might fail by incorrectly placing the disrotatory pathway below the conrotatory one. The ccCA-CC(2,3) scheme provides correct pathway ordering while providing an accurate description of the activation and reaction energies characterizing the lowest-energy conrotatory pathway. The ccCA-CC(2,3) method is thus a viable method for the analyses of reaction mechanisms that have significant multi-reference character, and presents a generally less computationally intensive alternative to true multi-reference methods, with computer costs and ease of use that are similar to those that characterize the more established, CCSD(T)-based, ccCA-S4 methodology.

  5. A comparative study of SrO and BaO doping to CeO{sub 2}-ZrO{sub 2}: Characteristic and its catalytic performance for three-way catalysts

    SciTech Connect (OSTI)

    Guo, Jiaxiu; National Engineering Research Center for Flue Gas Desulfurization, Chengdu 610065 ; Shi, Zhonghua; Wu, Dongdong; Yin, Huaqiang; National Engineering Research Center for Flue Gas Desulfurization, Chengdu 610065 ; Gong, Maochu; Chen, Yaoqiang; National Engineering Research Center for Flue Gas Desulfurization, Chengdu 610065

    2013-02-15

    Graphical abstract: Display Omitted Highlights: ? The prepared materials have a face-centered cubic structure and nanosize particles. ?Comparing to CZB, aged CZS has 494 ?mol/g of OSC and 30 m{sup 2}/g of surface area. ? CZS and CZB have similar NO sorption and reductive properties and different H{sub 2} uptake. ? T{sub 50} of Pt-Rh/CZS/LA is as low as 199 C for CO, 228 C for NO, and 252 C for C{sub 3}H{sub 8}. ? Pt-Rh/CZS/LA has wider working-window at 320 C under different ? value. -- Abstract: Ceria-zirconia-strontia (Ce{sub 0.35}Zr{sub 0.55}Sr{sub 0.10}O{sub 1.9}) and ceria-zirconia-baria (Ce{sub 0.35}Zr{sub 0.55}Ba{sub 0.10}O{sub 1.9}) were synthesized using an oxidation-co-precipitation method with hydrogen peroxide (H{sub 2}O{sub 2}) as oxidant. The physical and chemical properties of the prepared materials were investigated using BrunauerEmmettTeller surface area characterization, transmission electron microscopy, X-ray diffraction, Raman spectra, X-ray photoelectron spectroscopy, and oxygen pulse reaction. The prepared materials were used in preparing three-way catalysts with low Pt and Rh content. Moreover, catalytic activities were evaluated at a fixed bed under a simulated gaseous mixture. The results are as follows: (1) the prepared materials have a face-centered cubic structure and are nano-sized; (2) aged Ce{sub 0.35}Zr{sub 0.55}Sr{sub 0.10}O{sub 1.9} has higher oxygen storage capacity (494 ?mol/g), better thermal stability (30 m{sup 2}/g), good low-temperature reducibility, and high hydrogen uptake after TPR-redox cycles; (3) the light-off temperature (T{sub 50}) of Pt-Rh/CZS/LA can be as low as 199 C for CO, 228 C for NO, and 252 C for C{sub 3}H{sub 8}; and (4) Pt-Rh/CZS/LA has a fairly wide working-window.

  6. Copper(II) imidazolate frameworks as highly efficient photocatalysts for reduction of CO{sub 2} into methanol under visible light irradiation

    SciTech Connect (OSTI)

    Li, Jingtian; Luo, Deliang; Yang, Chengju; He, Shiman; Chen, Shangchao; Lin, Jiawei; Zhu, Li; Li, Xin

    2013-07-15

    Three copper(II) imidazolate frameworks were synthesized by a hydrothermal (or precipitation) reaction. The catalysts were characterized by X-ray diffraction (XRD), nitrogen adsorption, transmission electron microscopy (TEM), ultravioletvisible spectroscopy (UVvis), Fourier transform infrared spectra (FTIR), thermogravimetry (TG). Meanwhile, the photocatalytic activities of the samples for reduction of CO{sub 2} into methanol and degradation of methylene blue (MB) under visible light irradiation were also investigated. The results show that the as-prepared samples exhibit better photocatalytic activities for the reduction of carbon dioxide into methanol with water and degradation of MB under visible light irradiation. The orthorhombic copper(II) imidazolate frameworks with a band gap of 2.49 eV and green (G) color has the best photocatalytic activity for reduction of CO{sub 2} into methanol, 1712.7 ?mol/g over 5 h, which is about three times as large as that of monoclinic copper(II) imidazolate frameworks with a band gap 2.70 eV and blue (J) color. The degradation kinetics of MB over three photocatalysts fitted well to the apparent first-order rate equation and the apparent rate constants for the degradation of MB over G, J and P (with pink color) are 0.0038, 0.0013 and 0.0016 min{sup ?1}, respectively. The synergistic effects of smallest band gap and orthorhombic crystal phase structure are the critical factors for the better photocatalytic activities of G. Moreover, three frameworks can also be stable up to 250 C. The investigation of Cu-based zeolitic imidazolate frameworks maybe provide a design strategy for a new class of photocatalysts applied in degradation of contaminations, reduction of CO{sub 2}, and even water splitting into hydrogen and oxygen under visible light. - Graphical abstract: Carbon dioxide was reduced into methanol with water over copper(II) imidazolate frameworks under visible light irradiation. - Highlights: Three copper(II) imidazolate frameworks were first applied in the photo-reduction of CO{sub 2}. The photocatalytic activities of the frameworks depend on their band gap and phase structures. The photocatalytic activity of orthorhombic frameworks is 3 times that of monoclinic frameworks. The degradation kinetics of MB over three photocatalysts followed the first-order rate equation. The largest yield for reduction of CO{sub 2} into methanol on green framworks was 1712.7 ?mol/g over 5 h.

  7. Efficient electrochemical CO2 conversion powered by renewable energy

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

    Kauffman, Douglas R.; Thakkar, Jay; Siva, Rajan; Matranga, Christopher; Ohodnicki, Paul R.; Zeng, Chenjie; Jin, Rongchao

    2015-06-29

    The catalytic conversion of CO2 into industrially relevant chemicals is one strategy for mitigating greenhouse gas emissions. Along these lines, electrochemical CO2 conversion technologies are attractive because they can operate with high reaction rates at ambient conditions. However, electrochemical systems require electricity, and CO2 conversion processes must integrate with carbon-free, renewable-energy sources to be viable on larger scales. We utilize Au25 nanoclusters as renewably powered CO2 conversion electrocatalysts with CO2 → CO reaction rates between 400 and 800 L of CO2 per gram of catalytic metal per hour and product selectivities between 80 and 95%. These performance metrics correspond tomore » conversion rates approaching 0.8–1.6 kg of CO2 per gram of catalytic metal per hour. We also present data showing CO2 conversion rates and product selectivity strongly depend on catalyst loading. Optimized systems demonstrate stable operation and reaction turnover numbers (TONs) approaching 6 × 106 mol CO2 molcatalyst–1 during a multiday (36 hours total hours) CO2electrolysis experiment containing multiple start/stop cycles. TONs between 1 × 106 and 4 × 106 molCO2 molcatalyst–1 were obtained when our system was powered by consumer-grade renewable-energy sources. Daytime photovoltaic-powered CO2 conversion was demonstrated for 12 h and we mimicked low-light or nighttime operation for 24 h with a solar-rechargeable battery. This proof-of-principle study provides some of the initial performance data necessary for assessing the scalability and technical viability of electrochemical CO2 conversion technologies. Specifically, we show the following: (1) all electrochemical CO2 conversion systems will produce a net increase in CO2 emissions if they do not integrate with renewable-energy sources, (2) catalyst loading vs activity trends can be used to tune process rates and product distributions, and (3) state-of-the-art renewable-energy technologies are sufficient to power larger-scale, tonne per day CO2 conversion systems.« less

  8. Dynamics of the reaction of C{sub 3}(a{sup 3}Π{sub u}) radicals with C{sub 2}H{sub 2}: A new source for the formation of C{sub 5}H

    SciTech Connect (OSTI)

    Huang, Wen-Jian; Sun, Yi-Lun; Chin, Chih-Hao; Lee, Shih-Huang

    2014-09-28

    The reaction C{sub 3}(a{sup 3}Π{sub u}) + C{sub 2}H{sub 2} → C{sub 5}H + H was investigated at collision energy 10.9 kcal mol{sup −1} that is less than the enthalpy of ground-state reaction C{sub 3}(X{sup 1}Σ{sub g}{sup +}) + C{sub 2}H{sub 2} → C{sub 5}H + H. C{sub 3}(a{sup 3}Π{sub u}) radicals were synthesized from 1% C{sub 4}F{sub 6}/He by pulsed high-voltage discharge. The title reaction was conducted in a crossed molecular-beam apparatus equipped with a quadrupole-mass filter. Product C{sub 5}H was interrogated with time-of-flight spectroscopy and synchrotron vacuum-ultraviolet ionization. Reactant C{sub 3}(a{sup 3}Π{sub u}) and product C{sub 5}H were identified using photoionization spectroscopy. The ionization thresholds of C{sub 3}(X{sup 1}Σ{sub g}{sup +}) and C{sub 3}(a{sup 3}Π{sub u}) are determined as 11.6 ± 0.2 eV and 10.0 ± 0.2 eV, respectively. The C{sub 5}H product is identified as linear pentynylidyne that has an ionization energy 8.4 ± 0.2 eV. The title reaction releases translational energy 10.6 kcal mol{sup −1} in average and has an isotropic product angular distribution. The quantum-chemical calculation indicates that the C{sub 3}(a{sup 3}Π{sub u}) radical attacks one of the carbon atoms of C{sub 2}H{sub 2} and subsequently a hydrogen atom is ejected to form C{sub 5}H + H, in good agreement with the experimental observation. As far as we are aware, the C{sub 3}(a{sup 3}Π{sub u}) + C{sub 2}H{sub 2} reaction is investigated for the first time. This work gives an implication for the formation of C{sub 5}H from the C{sub 3}(a{sup 3}Π{sub u}) + C{sub 2}H{sub 2} reaction occurring in a combustion or discharge process of C{sub 2}H{sub 2}.

  9. CO2 stimulation of photosynthesis is not sustained during long-term (12 years) FACE treatments in Liquidambar styraciflua

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

    Warren, Jeffrey; Jensen, Anna M; Medlyn, Belinda; Norby, Richard J; Tissue, David Thomas

    2015-01-01

    Elevated atmospheric CO2 (eCO2) often increases photosynthetic CO2 assimilation (A) in field studies of temperate tree species, although there is evidence that the increases may decline through time due to biochemical and morphological acclimation, and environmental constraints. Indeed, at the free air CO2 enrichment (FACE) study in Oak Ridge, Tennessee, A was increased in 12-year-old sweetgum trees following two years of ~40% enhancement of CO2. A was re-assessed a decade later to determine if initial enhancement of CO2 was sustained through time. Measurements were conducted at prevailing CO2 and temperature on detached, re-hydrated branches using a portable gas exchange system.more » Photosynthetic CO2 response curves (A-Ci curves) were contrasted with earlier measurements using consistent leaf photosynthesis model equations. Relationships between maximum electron transport rate (Jmax), maximum Rubisco activity (Vcmax) and foliar nitrogen (N) and chlorophyll content were assessed. In 1999, light-saturated photosynthesis (Asat) for eCO2 treatments was 15.4 0.8 mol m-2 s-1, 22% higher than aCO2 treatments (P<0.01). By 2009, Asat declined to <50% of 1999 values, and there was no longer a significant effect of eCO2 (Asat = 6.9 or 5.7 0.7 mol m-2 s-1 for eCO2 or aCO2, respectively). In 1999, there was no treatment effect on area-based foliar N; however, by 2008, N content in eCO2 foliage was 17% less than in aCO2 foliage. Photosynthetic N use efficiency (Asat:N) was greater in eCO2 in 1999 resulting in greater Asat despite similar N content, but the enhanced efficiency in eCO2 trees was lost as foliar N declined to sub-optimal levels. There was no treatment difference in the declining linear relationships between Jmax or Vcmax with declining N, or in the ratio of Jmax:Vcmax through time. Results suggest that initial enhancement of photosynthesis to elevated CO2 will not be sustained through time if nitrogen becomes limited.« less

  10. The effect of warm-season precipitation on the diel cycle of the surface energy balance and carbon dioxide at a Colorado subalpine forest site

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

    Burns, S. P.; Blanken, P. D.; Turnipseed, A. A.; Monson, R. K.

    2015-06-16

    Precipitation changes the physical and biological characteristics of an ecosystem. Using a precipitation-based conditional sampling technique and a 14 year dataset from a 25 m micrometeorological tower in a high-elevation subalpine forest, we examined how warm-season precipitation affected the above-canopy diel cycle of wind and turbulence, net radiation Rnet, ecosystem eddy covariance fluxes (sensible heat H, latent heat LE, and CO2 net ecosystem exchange NEE) and vertical profiles of scalars (air temperature Ta, specific humidity q, and CO2 dry mole fraction ?c). This analysis allowed us to examine how precipitation modified these variables from hourly (i.e., the diel cycle) tomoremulti-day time-scales (i.e., typical of a weather-system frontal passage). During mid-day we found: (i) even though precipitation caused mean changes on the order of 5070% to Rnet, H, and LE, the surface energy balance (SEB) was relatively insensitive to precipitation with mid-day closure values ranging between 7080%, and (ii) compared to a typical dry day, a day following a rainy day was characterized by increased ecosystem uptake of CO2 (NEE increased by ≈ 10%), enhanced evaporative cooling (mid-day LE increased by ≈ 30 W m-2), and a smaller amount of sensible heat transfer (mid-day H decreased by ≈ 70 W m-2). Based on the mean diel cycle, the evaporative contribution to total evapotranspiration was, on average, around 6% in dry conditions and 20% in wet conditions. Furthermore, increased LE lasted at least 18 h following a rain event. At night, precipitation (and accompanying clouds) reduced Rnet and increased LE. Any effect of precipitation on the nocturnal SEB closure and NEE was overshadowed by atmospheric phenomena such as horizontal advection and decoupling that create measurement difficulties. Above-canopy mean ?c during wet conditions was found to be about 23 ?mol mol-1 larger than ?c on dry days. This difference was fairly constant over the full diel cycle suggesting that it was due to synoptic weather patterns (different air masses and/or effects of barometric pressure). In the evening hours during wet conditions, weakly stable conditions resulted in smaller vertical ?c differences compared to those in dry conditions. Finally, the effect of clouds on the timing and magnitude of daytime ecosystem fluxes is described.less

  11. Structural, thermal, magnetic, and electronic transport properties of the LaNi₂(Ge1-xPx)₂ system

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

    Goetsch, R. J.; Anand, V. K.; Pandey, Abhishek; Johnston, D. C.

    2012-02-29

    Polycrystalline samples of LaNi₂(Ge1-xPx)₂ (x=0,0.25,0.50,0.75,1) were synthesized and their properties investigated by x-ray diffraction (XRD) measurements at room temperature and by heat capacity Cp, magnetic susceptibility χ, and electrical resistivity ρ measurements versus temperature T from 1.8 to 350 K. Rietveld refinements of powder XRD patterns confirm that these compounds crystallize in the body-centered-tetragonal ThCr₂Si₂-type structure (space group I4/mmm) with composition-dependent lattice parameters that slightly deviate from Vegard's law. The ρ(T) measurements showed a positive temperature coefficient for all samples from 1.8 to 300 K, indicating that all compositions in this system are metallic. The low-T Cp measurements yield amore » rather large Sommerfeld electronic specific heat coefficient γ=12.4(2) mJ/mol K² for x=0, reflecting a large density of states at the Fermi energy that is comparable with the largest values found for the AFe₂As₂ class of materials with the same crystal structure. The γ decreases approximately linearly with x to 7.4(1) mJ/mol K² for x=1. The χ measurements show nearly temperature-independent paramagnetic behavior across the entire range of compositions except for LaNi₂Ge₂, where a broad peak is observed at ≈300 K from χ(T) measurements up to 1000 K that may arise from short-range antiferromagnetic correlations in a quasi-two-dimensional magnetic system. High-accuracy Padé approximants representing the Debye lattice heat capacity and Bloch-Grüneisen electron-phonon resistivity functions versus T are presented and are used to analyze our experimental Cp(T) and ρ(T) data, respectively, for 1.8K≤T≤300 K. The T dependences of ρ for all samples are well-described over this T range by the Bloch-Grüneisen model, although the observed ρ(300 K) values are larger than calculated from this model. A significant T dependence of the Debye temperature determined from the Cp(T) data was observed for each composition. No clear evidence for bulk superconductivity or any other long-range phase transition was found for any of the LaNi₂(Ge1-xPx)₂ compositions studied.« less

  12. Ab Initio Kinetics and Thermal Decomposition Mechanism of Mononitrobiuret and 1,5- Dinitrobiuret

    SciTech Connect (OSTI)

    Sun, Hongyan; Vaghjiani, Ghanshyam G.

    2015-05-26

    Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 , due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV? Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via RiceRamspergerKasselMarcus/multi-well master equation simulations, the results of which reveal the formation of (NO2 + H2O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klaptke et al. [Combust. Flame 139, 358366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.

  13. Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

    SciTech Connect (OSTI)

    Sun, Hongyan E-mail: ghanshyam.vaghjiani@us.af.mil; Vaghjiani, Ghanshyam L. E-mail: ghanshyam.vaghjiani@us.af.mil

    2015-05-28

    Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 , due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV? Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH{sub 2} group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C{sub 2v} symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via RiceRamspergerKasselMarcus/multi-well master equation simulations, the results of which reveal the formation of (NO{sub 2} + H{sub 2}O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klaptke et al. [Combust. Flame 139, 358366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.

  14. Photocatalytic CO{sub 2} reduction by CH{sub 4} over montmorillonite modified TiO{sub 2} nanocomposites in a continuous monolith photoreactor

    SciTech Connect (OSTI)

    Tahir, Muhammad; Tahir, Beenish

    2015-03-15

    Highlights: TiO{sub 2}/MMT supported monolith photo-reactor was tested for CO{sub 2} reduction with CH{sub 4}. MMT inhibited crystal growth and enhanced TiO{sub 2} photo-activity in monolith reactor. CO{sub 2} was reduced by CH{sub 4} to CO, CH{sub 3}OH, C{sub 2}H{sub 6}, C{sub 3}H{sub 6} and C{sub 3}H{sub 8} in a monolith reactor. CO yield over TiO{sub 2}/MMT was 237.5 ?mol g-catal.{sup ?1} h{sup ?1}, a 2.52 fold than TiO{sub 2}. Stability test revealed TiO{sub 2}/MMT partially lost photo-activity in reused cyclic runs. - Abstract: In this study, the performance of montmorillonite (MMT) modified TiO{sub 2} nanocomposites for photocatalytic CO{sub 2} reduction with CH{sub 4} in a continuous monolith photoreactor has been investigated. The MMT modified TiO{sub 2} nanocomposites were dip-coated over monolith channels and were characterized by XRD, SEM, TEM, XPS, N{sub 2}-adsorptiondesorption and UVvis spectroscopy. The MMT produced anatase phase of TiO{sub 2} and reduced TiO{sub 2} crystallite size from 19 nm to 13 nm. CO was the major reduction product with a yield rate of 237.5 ?mol g-catal.{sup ?1} h{sup ?1} over 10 wt.% MMT-loaded TiO{sub 2} at 100 C, and CO{sub 2}/CH{sub 4} feed ratio 1.0. The photoactivity of MMT-loaded TiO{sub 2} monolithic catalyst was 2.52 times higher than bare TiO{sub 2}. Likewise, low concentrations of C{sub 2}H{sub 6}, CH{sub 3}OH, C{sub 3}H{sub 6} and C{sub 3}H{sub 8} were detected in the products mixture. These results inferred MMT modified TiO{sub 2} and monolith photoreactor were beneficial for enhancing photocatalysis process with appreciable productivity. The stability test revealed photoactivity of MMT-loaded TiO{sub 2} nanocomposites partially diminished in recycle runs.

  15. Photoluminescence of titanium-doped zinc spinel blue-emitting nanophosphors

    SciTech Connect (OSTI)

    Tsai, Mu-Tsun; Chang, Yee-Shin; Chou, You-Hsin; Tsai, Kai-Min

    2014-06-01

    A blue-emitting phosphor of titanium-doped zinc spinel (ZnAl{sub 2}O{sub 4}:Ti; Ti=06.0 mol% in relation to Al) nanopowders was prepared by a simple solgel method. On annealing at 1000 C, single-phase ZnAl{sub 2}O{sub 4}:Ti powders had primary particles of 2530 nm in size and most Ti ions in the form of Ti{sup 4+}. Under UV excitation at 280 nm, a strong and broad blue emission centered at 435 nm was observed. The sources of the excitation and emission were assigned to the charge-transfer excitation and recombination between O{sup 2}Ti{sup 4+} and Ti{sup 3+}O{sup } ion pairs. Optimum brightness occurred at a doping of 2.0 mol% Ti. The decay lifetime of ZnAl{sub 2}O{sub 4}:2%Ti was calculated to be 3.0 ms for the blue emission with CIE coordinates of x=0.168 and y=0.153. The results suggest that ZnAl{sub 2}O{sub 4}:Ti is a promising candidate for application as a blue component phosphor for UV-converting white light-emitting diodes. - Graphical abstract: The absorption band around 270 nm is associated with the charge-transfer processes between octahedral Ti{sup 4+} and O{sup 2?} ions. The excitation band around 280 nm corresponds to the charge-transfer excitations from O{sup 2}(2p){sup 6} electrons to Ti{sup 4+} (3d{sup 0}). Under 280 nm excitation, the PL spectrum shows a strong blue emission with a peak at around 435 nm. - Highlights: Single-phase ZnAl{sub 2}O{sub 4}:Ti nanocrystals have been synthesized by a solgel process. Under UV excitation at 280 nm, the blue emission centered at 435 nm is observed. Blue emission is attributed to a charge-transfer transition involving the Ti{sup 4+} ions.

  16. SISGR-Fundamental Experimental and Theoretical Studies on a Novel Family of Oxide Catalyst Supports for Water Electrolysis

    SciTech Connect (OSTI)

    Kumta, Prashant

    2014-10-03

    Identification and development of non-noble metal based electro-catalysts or electro-catalysts with significant reduction of expensive noble metal contents (E.g. IrO2, Pt) with comparable electrochemical performance as the standard noble metal/metal oxide for proton exchange membrane (PEM) based water electrolysis would constitute a major breakthrough in the generation of hydrogen by water electrolysis. Accomplishing such a system would not only result reduction of the overall capital costs of PEM based water electrolyzers, but also help attain the targeted hydrogen production cost [< $ 3.0 / gallon gasoline equivalent (gge)] comparable to conventional liquid fuels. In line with these goals, it was demonstrated that fluorine doped IrO2 thin films and nanostructured high surface area powders display remarkably higher electrochemical activity, and comparable durability as pure IrO2 electro-catalyst for the oxygen evolution reaction (OER) in PEM based water electrolysis. Furthermore, corrosion resistant SnO2 and NbO2 support has been doped with F and coupled with IrO2 or RuO2 for use as an OER electro-catalyst. A solid solution of SnO2:F or NbO2:F with only 20 - 30 mol.% IrO2 or RuO2 yielding a rutile structure in the form of thin films and bulk nanoparticles displays similar electrochemical activity and stability as pure IrO2/RuO2. This would lead to more than 70 mol.% reduction in the noble metal oxide content. Novel nanostructured ternary (Ir,Sn,Nb)O2 thin films of different compositions FUNDAMENTAL STUDY OF NANOSTRUCTURED ELECTRO-CATALYSTS WITH REDUCED NOBLE METAL CONTENT FOR PEM BASED WATER ELECTROLYSIS 4 have also been studied. It has been shown that (Ir0.40Sn0.30Nb0.30)O2 shows similar electrochemical activity and enhanced chemical robustness as compared to pure IrO2. F doping of the ternary (Ir,Sn,Nb)O2 catalyst helps in further decreasing the noble metal oxide content of the catalyst. As a result, these reduced noble metal oxide catalyst systems would potentially be preferred as OER electro-catalysts for PEM electrolysis. The excellent performance of the catalysts coupled with its robustness would make them great candidates for contributing to significant reduction in the overall capital costs of PEM based water electrolyzers. This s.thesis provides a detailed fundamental study of the synthesis, materials, characterization, theoretical studies and detailed electrochemical response and potential mechanisms of these novel electro-catalysts for OER processes.

  17. An experimental test plan for the characterization of molten salt thermochemical properties in heat transport systems

    SciTech Connect (OSTI)

    Pattrick Calderoni

    2010-09-01

    Molten salts are considered within the Very High Temperature Reactor program as heat transfer media because of their intrinsically favorable thermo-physical properties at temperatures starting from 300 C and extending up to 1200 C. In this context two main applications of molten salt are considered, both involving fluoride-based materials: as primary coolants for a heterogeneous fuel reactor core and as secondary heat transport medium to a helium power cycle for electricity generation or other processing plants, such as hydrogen production. The reference design concept here considered is the Advanced High Temperature Reactor (AHTR), which is a large passively safe reactor that uses solid graphite-matrix coated-particle fuel (similar to that used in gas-cooled reactors) and a molten salt primary and secondary coolant with peak temperatures between 700 and 1000 C, depending upon the application. However, the considerations included in this report apply to any high temperature system employing fluoride salts as heat transfer fluid, including intermediate heat exchangers for gas-cooled reactor concepts and homogenous molten salt concepts, and extending also to fast reactors, accelerator-driven systems and fusion energy systems. The purpose of this report is to identify the technical issues related to the thermo-physical and thermo-chemical properties of the molten salts that would require experimental characterization in order to proceed with a credible design of heat transfer systems and their subsequent safety evaluation and licensing. In particular, the report outlines an experimental R&D test plan that would have to be incorporated as part of the design and operation of an engineering scaled facility aimed at validating molten salt heat transfer components, such as Intermediate Heat Exchangers. This report builds on a previous review of thermo-physical properties and thermo-chemical characteristics of candidate molten salt coolants that was generated as part of the same project [1]. However, this work focuses on two materials: the LiF-BeF2 eutectic (67 and 33 mol%, respectively, also known as flibe) as primary coolant and the LiF-NaF-KF eutectic (46.5, 11.5, and 52 mol%, respectively, also known as flinak) as secondary heat transport fluid. At first common issues are identified, involving the preparation and purification of the materials as well as the development of suitable diagnostics. Than issues specific to each material and its application are considered, with focus on the compatibility with structural materials and the extension of the existing properties database.

  18. Seasonal trend of photosynthetic parameters and stomatal conductance of blue oak (Quercus douglasii) under prolonged summer drought and high temperature

    SciTech Connect (OSTI)

    Xu, L; Baldocchi, DD

    2003-09-01

    OAK-B135 Understanding seasonal changes in photosynthetic parameters and stomatal conductance is crucial for modeling long-term carbon uptake and energy fluxes of ecosystems. Gas exchange measurements of CO{sub 2} and light response curves on blue oak leaves (Quercus douglasii H. & A.) were conducted weekly throughout the growing season to study the seasonality of photosynthetic capacity (V{sub cmax}) and Ball-Berry slope (m) under prolonged summer drought and high temperature. A leaf photosynthetic model was used to determine V{sub cmax}. There was a pronounced seasonal pattern in V{sub cmax}. The maximum value of V{sub cmax}, 127 {micro}molm{sup -2} s{sup -1},was reached shortly after leaf expansion in early summer, when air temperature was moderate and soil water availability was high. Thereafter, V{sub cmax} declined as the soil water profile became depleted and the trees experienced extreme air temperatures, exceeding 40 C. The decline in V{sub cmax} was gradual in midsummer, however, despite extremely low predawn leaf water potentials ({Psi}{sub pd}, {approx} -4.0 MPa). Overall, temporal changes in V{sub cmax} were well correlated with changes in leaf nitrogen content. During spring leaf development, high rates of leaf dark respiration (R{sub d}, 5-6 {micro}mol m{sup -2} s{sup -1}) were observed. Once a leaf reached maturity, R{sub d} remained low, around 0.5 {micro}mol m{sup -2} s{sup -1}. In contrast to the strong seasonality of V{sub cmax}, m and marginal water cost per unit carbon gain ({partial_derivative}E/{partial_derivative}A) were relatively constant over the season, even when leaf {Psi}{sub pd} dropped to -6.8 MPa. The constancy of {partial_derivative}E/{partial_derivative}A suggests that stomata behaved optimally under severe water-stress conditions. We discuss the implications of our findings in the context of modeling carbon and water vapor exchange between ecosystems and the atmosphere.

  19. Effects of Cell Phone Radiofrequency Signal Exposure on Brain Glucos Metabolism

    SciTech Connect (OSTI)

    Volkow, N.D.; Wang, G.; Volkow, N.D.; Tomasi, D.; Wang, G.-J.; Vaska, P.; Fowler, J.S.; Telang, F.; Alexoff, D.; Logan, J.; Wong, C.

    2011-03-01

    The dramatic increase in use of cellular telephones has generated concern about possible negative effects of radiofrequency signals delivered to the brain. However, whether acute cell phone exposure affects the human brain is unclear. To evaluate if acute cell phone exposure affects brain glucose metabolism, a marker of brain activity. Randomized crossover study conducted between January 1 and December 31, 2009, at a single US laboratory among 47 healthy participants recruited from the community. Cell phones were placed on the left and right ears and positron emission tomography with ({sup 18}F)fluorodeoxyglucose injection was used to measure brain glucose metabolism twice, once with the right cell phone activated (sound muted) for 50 minutes ('on' condition) and once with both cell phones deactivated ('off' condition). Statistical parametric mapping was used to compare metabolism between on and off conditions using paired t tests, and Pearson linear correlations were used to verify the association of metabolism and estimated amplitude of radiofrequency-modulated electromagnetic waves emitted by the cell phone. Clusters with at least 1000 voxels (volume >8 cm{sup 3}) and P < .05 (corrected for multiple comparisons) were considered significant. Brain glucose metabolism computed as absolute metabolism ({micro}mol/100 g per minute) and as normalized metabolism (region/whole brain). Whole-brain metabolism did not differ between on and off conditions. In contrast, metabolism in the region closest to the antenna (orbitofrontal cortex and temporal pole) was significantly higher for on than off conditions (35.7 vs 33.3 {micro}mol/100 g per minute; mean difference, 2.4 [95% confidence interval, 0.67-4.2]; P = .004). The increases were significantly correlated with the estimated electromagnetic field amplitudes both for absolute metabolism (R = 0.95, P < .001) and normalized metabolism (R = 0.89; P < .001). In healthy participants and compared with no exposure, 50-minute cell phone exposure was associated with increased brain glucose metabolism in the region closest to the antenna. This finding is of unknown clinical significance.

  20. The energetics of lanthanum tantalate materials

    SciTech Connect (OSTI)

    Forbes, Tori Z.; Nyman, May; Rodriguez, Mark A.; Navrotsky, Alexandra

    2010-11-15

    Lanthanum tantalates are important refractory materials with application in photocatalysis, solid oxide fuel cells, and phosphors. Soft-chemical synthesis utilizing the Lindqvist ion, [Ta{sub 6}O{sub 19}]{sup 8-}, has yielded a new phase, La{sub 2}Ta{sub 2}O{sub 7}(OH){sub 2}. Using the hydrated phase as a starting material, a new lanthanum orthotantalate polymorph was formed by heating to 850 {sup o}C, which converts to a previously reported LaTaO{sub 4} polymorph at 1200 {sup o}C. The stabilities of La{sub 2}Ta{sub 2}O{sub 7}(OH){sub 2} (LaTa-OH), the intermediate LaTaO{sub 4} polymorph (LaTa-850), and the high temperature phase (LaTa-1200) were investigated using high-temperature oxide melt solution calorimetry. The enthalpy of formation from the oxides were calculated from the enthalpies of drop solution to be -87.1{+-}9.6, -94.9{+-}8.8, and -93.1{+-}8.7 kJ/mol for LaTa-OH, LaTa-850, and LaTa-1200, respectively. These results indicate that the intermediate phase, LaTa-850, is the most stable. This pattern of energetics may be related to cation-cation repulsion of the tantalate cations. We also investigated possible LnTaO{sub 4} and Ln{sub 2}Ta{sub 2}O{sub 7}(OH){sub 2} analogues of Ln=Pr, Nd to examine the relationship between cation size and the resulting phases. - Graphical abstract: The energetics of three lanthanum tantalates were investigated by the high-temperature oxide melt solution calorimetry. The enthalpies of formation from the oxides were calculated from the enthalpies of drop solution to be -87.1{+-}9.6, -94.9{+-}8.8, and -93.1{+-}8.7 kJ/mol for La{sub 2}Ta{sub 2}O{sub 7}(OH){sub 2}, LaTaO{sub 4} (850 {sup o}C), and LaTaO{sub 4} (1200 {sup o}C), respectively. These results indicate that the intermediate phase, LaTaO{sub 4} (850 {sup o}C), is the most stable in energy. Display Omitted

  1. CO2 stimulation of photosynthesis is not sustained during long-term (12 years) FACE treatments in Liquidambar styraciflua

    SciTech Connect (OSTI)

    Warren, Jeffrey; Jensen, Anna M; Medlyn, Belinda; Norby, Richard J; Tissue, David Thomas

    2015-01-01

    Elevated atmospheric CO2 (eCO2) often increases photosynthetic CO2 assimilation (A) in field studies of temperate tree species, although there is evidence that the increases may decline through time due to biochemical and morphological acclimation, and environmental constraints. Indeed, at the free air CO2 enrichment (FACE) study in Oak Ridge, Tennessee, A was increased in 12-year-old sweetgum trees following two years of ~40% enhancement of CO2. A was re-assessed a decade later to determine if initial enhancement of CO2 was sustained through time. Measurements were conducted at prevailing CO2 and temperature on detached, re-hydrated branches using a portable gas exchange system. Photosynthetic CO2 response curves (A-Ci curves) were contrasted with earlier measurements using consistent leaf photosynthesis model equations. Relationships between maximum electron transport rate (Jmax), maximum Rubisco activity (Vcmax) and foliar nitrogen (N) and chlorophyll content were assessed. In 1999, light-saturated photosynthesis (Asat) for eCO2 treatments was 15.4 0.8 mol m-2 s-1, 22% higher than aCO2 treatments (P<0.01). By 2009, Asat declined to <50% of 1999 values, and there was no longer a significant effect of eCO2 (Asat = 6.9 or 5.7 0.7 mol m-2 s-1 for eCO2 or aCO2, respectively). In 1999, there was no treatment effect on area-based foliar N; however, by 2008, N content in eCO2 foliage was 17% less than in aCO2 foliage. Photosynthetic N use efficiency (Asat:N) was greater in eCO2 in 1999 resulting in greater Asat despite similar N content, but the enhanced efficiency in eCO2 trees was lost as foliar N declined to sub-optimal levels. There was no treatment difference in the declining linear relationships between Jmax or Vcmax with declining N, or in the ratio of Jmax:Vcmax through time. Results suggest that initial enhancement of photosynthesis to elevated CO2 will not be sustained through time if nitrogen becomes limited.

  2. Ground-state proton-transfer tautomer of the salicylate anion

    SciTech Connect (OSTI)

    Friedrich, D.M.; Wang, Z.; Joly, A.G.; Peterson, K.A.; Callis, P.R.

    1999-12-02

    Solutions of sodium salicylate in anhydrous polar solvents exhibit a weak, temperature-dependent absorption band ({lambda}{sub max} {approx} 325 nm) lying in the Stokes gap between the main absorption (296 nm) and the fluorescence band (396 nm, acetonitrile). This weak, longer wavelength absorption band is hardly observable in aqueous solution, but its intensity increases with temperature and increases with polarity in anhydrous organic solvents in the order of ethanol < acetonitrile < dimethyl sulfoxide at room temperature. After correction for solvent thermal contraction, the temperature-dependent absorption spectrum of salicylate in acetonitrile solutions reveals a clear isosbestic point ({epsilon}{sub 310}= 2,000 M{sup {minus}1} cm{sup {minus}1}) characteristic of an equilibrium between two salicylate species with band-maximum extinction coefficients of {epsilon}{sub 325} = 3,400 M{sup {minus}1} cm{sup {minus}1} and {epsilon}{sub 296} = 3,586 M{sup {minus}1} cm{sup {minus}1}. In acetonitrile at room temperature (298 K) the concentration equilibrium constant (minor/major) for the interconversion reaction between the two species is K{sub 298} = 0.11, with {Delta}H = 1.6 kcal mol{sup {minus}1} and {Delta}S = 0.97 cal{center{underscore}dot}mol{sup {minus}1} K{sup {minus}1}. The fluorescence lifetime (4.8 ns in acetonitrile) and the shape of the fluorescence spectrum are independent of excitation wavelength. The fluorescence quantum yield for excitation in the long-wavelength shoulder (340 nm) is approximately 60% larger than the yield for excitation in the main band at 296 nm ({phi}{sub 340} = 0.29, {phi}{sub 296} = 0.18) in acetonitrile at room temperature. These results are consistent with assignment of the shoulder band to the proton-transfer tautomer of the salicylate anion. Electronic structure calculations support assignment of the 325 nm absorption band to the ground-state tautomer (phenoxide anion form) of the salicylate anion. Absorption transition moments for both the normal and tautomer forms are parallel to the emission transition moment, are electronically allowed, and are consistent with {sup 1}L{sub b} assignment for both absorbing and emitting transitions. The static dipole moments are in the order of {mu}(N*) {ge} {mu}(N) > {mu}(T*) > {mu}(T) for the normal (N) and tautomer (T) ground and electronic excited states.

  3. Recovery of lithium and cobalt from waste lithium ion batteries of mobile phone

    SciTech Connect (OSTI)

    Jha, Manis Kumar, E-mail: mkjha@nmlindia.org; Kumari, Anjan; Jha, Amrita Kumari; Kumar, Vinay; Hait, Jhumki; Pandey, Banshi Dhar

    2013-09-15

    Graphical abstract: Recovery of valuable metals from scrap batteries of mobile phone. - Highlights: Recovery of Co and Li from spent LIBs was performed by hydrometallurgical route. Under the optimum condition, 99.1% of lithium and 70.0% of cobalt were leached. The mechanism of the dissolution of lithium and cobalt was studied. Activation energy for lithium and cobalt were found to be 32.4 kJ/mol and 59.81 kJ/mol, respectively. After metal recovery, residue was washed before disposal to the environment. - Abstract: In view of the stringent environmental regulations, availability of limited natural resources and ever increasing need of alternative energy critical elements, an environmental eco-friendly leaching process is reported for the recovery of lithium and cobalt from the cathode active materials of spent lithium-ion batteries of mobile phones. The experiments were carried out to optimize the process parameters for the recovery of lithium and cobalt by varying the concentration of leachant, pulp density, reductant volume and temperature. Leaching with 2 M sulfuric acid with the addition of 5% H{sub 2}O{sub 2} (v/v) at a pulp density of 100 g/L and 75 C resulted in the recovery of 99.1% lithium and 70.0% cobalt in 60 min. H{sub 2}O{sub 2} in sulfuric acid solution acts as an effective reducing agent, which enhance the percentage leaching of metals. Leaching kinetics of lithium in sulfuric acid fitted well to the chemical controlled reaction model i.e. 1 ? (1 ? X){sup 1/3} = k{sub c}t. Leaching kinetics of cobalt fitted well to the model ash diffusion control dense constant sizes spherical particles i.e. 1 ? 3(1 ? X){sup 2/3} + 2(1 ? X) = k{sub c}t. Metals could subsequently be separated selectively from the leach liquor by solvent extraction process to produce their salts by crystallization process from the purified solution.

  4. Synthesis and characterization of the LDH hydrotalcite-pyroaurite solid-solution series

    SciTech Connect (OSTI)

    Rozov, K.; Berner, U.; Taviot-Gueho, C.; Leroux, F.; Renaudin, G.; Kulik, D.; Diamond, L.W.

    2010-08-15

    A layered double hydroxide (LDH) hydrotalcite-pyroaurite solid-solution series Mg{sub 3}(Al{sub x}Fe{sub 1-x})(CO{sub 3}){sub 0.5}(OH){sub 8} with 1 - x = 0.0, 0.1...1.0 was prepared by co-precipitation at 23 {+-} 2 {sup o}C and pH = 11.40 {+-} 0.03. The compositions of the solids and the reaction solutions were determined using ICP-OES (Mg, Al, Fe, and Na) and TGA techniques (CO{sub 3}{sup 2-}, OH{sup -}, and H{sub 2}O). Powder X-ray diffraction was employed for phase identification and determination of the unit cell parameters a{sub o} and c{sub o} from peak profile analysis. The parameter a{sub o} = b{sub o} was found to be a linear function of the composition. This dependency confirms Vegard's law and indicates the presence of a continuous solid-solution series in the hydrotalcite-pyroaurite system. TGA data show that the temperatures at which interlayer H{sub 2}O molecules and CO{sub 3}{sup 2-} anions are lost, and at which dehydroxylation of the layers occurs, all decrease with increasing mole fraction of iron within the hydroxide layers. Features of the Raman spectra also depend on the iron content. The absence of Raman bands for Fe-rich members (x{sub Fe} > 0.5) is attributed to possible fluorescence phenomena. Based on chemical analysis of both the solids and the reaction solutions after synthesis, preliminary Gibbs free energies of formation have been estimated. Values of {Delta}G{sup o}{sub f}(hydrotalcite) = - 3773.3 {+-} 51.4 kJ/mol and {Delta}G{sup o}{sub f}(pyroaurite) = - 3294.5 {+-} 95.8 kJ/mol were found at 296.15 K. The formal uncertainties of these formations constants are very high. Derivation of more precise values would require carefully designed solubility experiments and improved analytical techniques.

  5. CO2 EFFECTS ON MOJAVE DESERT PLANT INTERACTIONS

    SciTech Connect (OSTI)

    L. A. DEFALCO; G. C. FERNANDEZ; S. D. SMITH; R. S. NOWAK

    2004-01-01

    Seasonal and interannual droughts characteristic of deserts have the potential to modify plant interactions as atmospheric CO{sub 2} concentrations continue to rise. At the Nevada Desert FACE (free-air CO{sub 2} enrichment) facility in the northern Mojave Desert, the effects of elevated atmospheric C02 (550 vs. ambient {approx}360 {micro}mol mol{sup -1}) on plant interactions were examined during two years of high and low rainfall. Results suggest that CO{sub 2} effects on the interaction between native species and their understory herbs are dependent on the strength of competition when rainfall is plentiful, but are unimportant during annual drought. Seasonal rainfall for 1999 was 23% the long-term average for the area, and neither elevated CO{sub 2} nor the low production of herbaceous neighbors had an effect on relative growth rate (RGR, d{sup -1}) and reproductive effort (RE, number of flowers g{sup -1}) for Achnatherum hymenoides (early season perennial C{sub 3} grass), Pleuraphis rigida (late season perennial C{sub 4} grass), and Larrea tridentata (evergreen C{sub 3} shrub). In contrast, 1998 received 213% the average rainfall. Consequently, the decrease in RGR and increase in RE for Achnatherum, whose period of growth overlaps directly with that of its neighbors, was exaggerated at elevated CO{sub 2}. However, competitive effects of neighbors on Eriogonum trichopes (a winter annual growing in shrub interspaces), Pleuraphis and Larrea were not affected by elevated CO{sub 2}, and possible explanations are discussed. Contrary to expectations, the invasive annual neighbor Bromus madritensis ssp. rubens had little influence on target plant responses because densities in 1998 and 1999 at this site were well below those found in other studies where it has negatively affected perennial plant growth. The extent that elevated CO{sub 2} reduces the performance of Achnatherum in successive years to cause its loss from the plant community depends more on future pressure from herbaceous neighbors and less on the extent that CO{sub 2} enhances Achnatherum growth during periods of severe drought.

  6. Towards a specific reaction parameter density functional for reactive scattering of H{sub 2} from Pd(111)

    SciTech Connect (OSTI)

    Boereboom, J. M.; Wijzenbroek, M.; Somers, M. F.; Kroes, G. J.

    2013-12-28

    Recently, an implementation of the specific reaction parameter (SRP) approach to density functional theory (DFT) was used to study several reactive scattering experiments of H{sub 2} on Cu(111). It was possible to obtain chemical accuracy (1 kcal/mol ? 4.2 kJ/mol), and therefore, accurately model this paradigmatic example of activated H{sub 2} dissociation on a metal surface. In this work, the SRP-DFT methodology is applied to the dissociation of hydrogen on a Pd(111) surface, in order to test whether the SRP-DFT approach is also applicable to non-activated H{sub 2}-metal systems. In the calculations, the BornOppenheimer static surface approximations are used. A comparison to molecular beam sticking experiments, performed at incidence energies ?125 meV, on H{sub 2} + Pd(111) suggested the PBE-vdW [where the Perdew, Burke, and Ernzerhof (PBE) correlation is replaced by van der Waals correlation] functional as a candidate SRP density functional describing the reactive scattering of H{sub 2} on Pd(111). Unfortunately, quantum dynamics calculations are not able to reproduce the molecular beam sticking results for incidence energies <125 meV. From a comparison to initial state-resolved (degeneracy averaged) sticking probabilities it seems clear that for H{sub 2} + Pd(111) dynamic trapping and steering effects are important, and that these effects are not yet well modeled with the potential energy surfaces considered here. Applying the SRP-DFT method to systems where H{sub 2} dissociation is non-activated remains difficult. It is suggested that a density functional that yields a broader barrier distribution and has more non-activated pathways than PBE-vdW (i.e., non-activated dissociation at some sites but similarly high barriers at the high energy end of the spectrum) should allow a more accurate description of the available experiments. Finally, it is suggested that new and better characterized molecular beam sticking experiments be done on H{sub 2} + Pd(111), to facilitate the development of a more accurate theoretical description of this system.

  7. Bright reddish-orange emission and good piezoelectric properties of Sm{sub 2}O{sub 3}-modified (K{sub 0.5}Na{sub 0.5})NbO{sub 3}-based lead-free piezoelectric ceramics

    SciTech Connect (OSTI)

    Hao, Jigong; Xu, Zhijun Chu, Ruiqing; Li, Wei; Du, Juan

    2015-05-21

    Reddish orange-emitting 0.948(K{sub 0.5}Na{sub 0.5})NbO{sub 3}-0.052LiSbO{sub 3}-xmol%Sm{sub 2}O{sub 3} (KNN-5.2LS-xSm{sub 2}O{sub 3}) lead-free piezoelectric ceramics with good piezoelectric properties were fabricated in this study, and the photoluminescence and electrical properties of the ceramics were systematically studied. Results showed that Sm{sub 2}O{sub 3} substitution into KNN-5.2LS induces a phase transition from the coexistence of orthorhombic and tetragonal phases to a pseudocubic phase and shifts the polymorphic phase transition (PPT) to below room temperature. The temperature stability and fatigue resistance of the modified ceramics were significantly improved by Sm{sub 2}O{sub 3} substitution. The KNN-5.2LS ceramic with 0.4?mol. % Sm{sub 2}O{sub 3} exhibited temperature-independent properties (25150?C), fatigue-free behavior (up to 10{sup 6} cycles), and good piezoelectric properties (d{sub 33}{sup *?}=?230?pm/V, d{sub 33}?=?176 pC/N, k{sub p}?=?35%). Studies on the photoluminescence properties of the samples showed strong reddish-orange emission upon blue light excitation; these emission intensities were strongly dependent on the doping concentration and sintering temperature. The 0.4?mol. % Sm{sub 2}O{sub 3}-modified sample exhibited temperature responses over a wide temperature range of 10443?K. The maximum sensing sensitivity of the sample was 7.5??10{sup ?4} K at 293?K, at which point PPT occurred. A relatively long decay lifetime ? of 1.271.40?ms and a large quantum yield ? of 0.170.19 were obtained from the Sm-modified samples. These results suggest that the KNN-5.2LS-xSm{sub 2}O{sub 3} system presents multifunctional properties and significant technological potential in novel multifunctional devices.

  8. Development of membranes for hydrogen separation: Pd-coated V-10Pd

    SciTech Connect (OSTI)

    Paglieri, Stephen N; Wermer, Joseph R; Buxbaum, Robert E; Ciocco, Michael V; Howard, Bret H; Morreale, Bryan D

    2009-01-01

    Numerous Group IVB and VB alloys were prepared and tested as potential membrane materials but most of these materials were brittle or exhibited cracking during hydrogen exposure. One of the more ductile alloys, V-10Pd (at. %), was fabricated into a thin (107-{micro}m thick) composite membrane coated with 100 nm of Pd on each side. The material was tested for hydrogen permeability, resistance to hydrogen embrittlement, and long term hydrogen flux stability. The hydrogen permeability, {phi}, of the V-10Pd membrane was 3.86 x 10{sup -8} mol H{sub 2} m{sup -1} s{sup -1} Pa{sup -0.5} (avg. of three different samples) at 400 C, which is slightly higher than the permeability of Pd-23Ag at that temperature. A 1400 h hydrogen flux test at 400 C demonstrated that the rate of metallic interdiffusion was slow between the V-10Pd foil and the 100-nm-thick Pd coating on the surface. However, at the end of testing the membrane cracked at 118 C because of hydrogen embrittlement.

  9. Palladium was supported on superparamagnetic nanoparticles: A magnetically recoverable catalyst for Heck reaction

    SciTech Connect (OSTI)

    Zhang, Fengwei; Niu, Jianrui; Wang, Haibo; Yang, Honglei; Jin, Jun; Liu, Na; Zhang, Yubin; Li, Rong; Ma, Jiantai

    2012-02-15

    Highlights: Black-Right-Pointing-Pointer Palladium-based heterogeneous catalyst was prepared facilely via the co-precipitation method. Black-Right-Pointing-Pointer The particles are nearly spherical in shape with an average size of 20 {+-} 1.0 nm. Black-Right-Pointing-Pointer The developed magnetic catalyst showed high activity for Heck reaction. Black-Right-Pointing-Pointer The catalyst was easily recovered from the reaction mixture with external magnetic field. Black-Right-Pointing-Pointer The catalytic efficiency for Heck reaction remains unaltered even after 6 repeated cycles. -- Abstract: A novel and high-performance palladium-based catalyst for Heck reaction was prepared easily by the co-precipitation method. The catalyst was characterized by transmission electron microscopy (TEM), X-ray powder diffraction (XRD), vibrating sample magnetometry (VSM), X-ray photoelectron spectroscopy (XPS) and atomic absorption spectrophotometry (AAS). The catalyst afforded a fast conversion of the 4-bromonitrobenzene to 4-nitrostilbene at a catalyst loading of 5 mol%, and the efficiency of the catalyst remains unaltered even after 6 repeated cycles. The excellent catalytic performance of the Pd/Fe{sub 3}O{sub 4} catalyst might be attributed to the enhanced synergistic effect between Pd nanoparticles and magnetite.

  10. Performance and results of the LBNE 35 ton membrane cryostat prototype

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

    Montanari, David; Adamowski, Mark; Hahn, Alan; Norris, Barry; Reichenbacher, Juergen; Rucinski, Russell; Stewart, Jim; Tope, Terry

    2015-07-15

    We report on the performance and commissioning of the first membrane cryostat to be used for scientific application. The Long Baseline Neutrino Experiment (LBNE) has designed and fabricated a membrane cryostat prototype in collaboration with Ishikawajima-Harima Heavy Industries Co., Ltd. (IHI). LBNE has designed and fabricated the supporting cryogenic system infrastructure and successfully commissioned and operated the first membrane cryostat. Original goals of the prototype are: to demonstrate the membrane cryostat technology in terms of thermal performance, feasibility for liquid argon and leak tightness; to demonstrate that we can remove all the impurities from the vessel and achieve the puritymore » requirements in a membrane cryostat without evacuation; to demonstrate that we can achieve and maintain the purity requirements of the liquid argon using mol sieve and copper filters. The purity requirements of a large liquid argon detector such as LBNE are contaminants below 200 parts per trillion (ppt) oxygen equivalent. LBNE is planning the design and construction of a large liquid argon detector. This presentation will present requirements, design and construction of the LBNE 35 ton membrane cryostat prototype, and detail the commissioning and performance. The experience and results of this prototype are extremely important for the development of the LBNE detector.« less

  11. Machine learning predictions of molecular properties: Accurate many-body potentials and nonlocality in chemical space

    SciTech Connect (OSTI)

    Hansen, Katja; Biegler, Franziska; Ramakrishnan, Raghunathan; Pronobis, Wiktor; von Lilienfeld, O. Anatole; Müller, Klaus -Robert; Tkatchenko, Alexandre

    2015-06-04

    Simultaneously accurate and efficient prediction of molecular properties throughout chemical compound space is a critical ingredient toward rational compound design in chemical and pharmaceutical industries. Aiming toward this goal, we develop and apply a systematic hierarchy of efficient empirical methods to estimate atomization and total energies of molecules. These methods range from a simple sum over atoms, to addition of bond energies, to pairwise interatomic force fields, reaching to the more sophisticated machine learning approaches that are capable of describing collective interactions between many atoms or bonds. In the case of equilibrium molecular geometries, even simple pairwise force fields demonstrate prediction accuracy comparable to benchmark energies calculated using density functional theory with hybrid exchange-correlation functionals; however, accounting for the collective many-body interactions proves to be essential for approaching the “holy grail” of chemical accuracy of 1 kcal/mol for both equilibrium and out-of-equilibrium geometries. This remarkable accuracy is achieved by a vectorized representation of molecules (so-called Bag of Bonds model) that exhibits strong nonlocality in chemical space. The same representation allows us to predict accurate electronic properties of molecules, such as their polarizability and molecular frontier orbital energies.

  12. Performance and results of the LBNE 35 ton membrane cryostat prototype

    SciTech Connect (OSTI)

    Montanari, David; Adamowski, Mark; Hahn, Alan; Norris, Barry; Reichenbacher, Juergen; Rucinski, Russell; Stewart, Jim; Tope, Terry

    2015-07-15

    We report on the performance and commissioning of the first membrane cryostat to be used for scientific application. The Long Baseline Neutrino Experiment (LBNE) has designed and fabricated a membrane cryostat prototype in collaboration with Ishikawajima-Harima Heavy Industries Co., Ltd. (IHI). LBNE has designed and fabricated the supporting cryogenic system infrastructure and successfully commissioned and operated the first membrane cryostat. Original goals of the prototype are: to demonstrate the membrane cryostat technology in terms of thermal performance, feasibility for liquid argon and leak tightness; to demonstrate that we can remove all the impurities from the vessel and achieve the purity requirements in a membrane cryostat without evacuation; to demonstrate that we can achieve and maintain the purity requirements of the liquid argon using mol sieve and copper filters. The purity requirements of a large liquid argon detector such as LBNE are contaminants below 200 parts per trillion (ppt) oxygen equivalent. LBNE is planning the design and construction of a large liquid argon detector. This presentation will present requirements, design and construction of the LBNE 35 ton membrane cryostat prototype, and detail the commissioning and performance. The experience and results of this prototype are extremely important for the development of the LBNE detector.

  13. Multireference configuration interaction calculations of the first six ionization potentials of the uranium atom

    SciTech Connect (OSTI)

    Bross, David H.; Parmar, Payal; Peterson, Kirk A.

    2015-11-12

    The first 6 ionization potentials (IPs) of the uranium atom have been calculated using multireference configuration interaction (MRCI+Q) with extrapolations to the complete basis set (CBS) limit using new all-electron correlation consistent basis sets. The latter were carried out with the third-order Douglas-Kroll-Hess Hamiltonian. Correlation down through the 5s5p5d electrons have been taken into account, as well as contributions to the IPs due to the Lamb shift. Spin-orbit coupling contributions calculated at the 4-component Kramers restricted configuration interaction level, as well as the Gaunt term computed at the Dirac-Hartree-Fock level, were added to the best scalar relativistic results. As a result, the final ionization potentials are expected to be accurate to at least 5 kcal/mol (0.2 eV), and thus more reliable than the current experimental values of IP3 through IP6.

  14. Gas Phase Uranyl Activation: Formation of a Uranium Nitrosyl Complex from Uranyl Azide

    SciTech Connect (OSTI)

    Gong, Yu; De Jong, Wibe A.; Gibson, John K.

    2015-05-13

    Activation of the oxo bond of uranyl, UO22+, was achieved by collision induced dissociation (CID) of UO2(N3)Cl2 in a quadrupole ion trap mass spectrometer. The gas phase complex UO2(N3)Cl2 was produced by electrospray ionization of solutions of UO2Cl2 and NaN3. CID of UO2(N3)Cl2 resulted in the loss of N2 to form UO(NO)Cl2, in which the inert uranyl oxo bond has been activated. Formation of UO2Cl2 via N3 loss was also observed. Density functional theory computations predict that the UO(NO)Cl2 complex has nonplanar Cs symmetry and a singlet ground state. Analysis of the bonding of the UO(NO)Cl2 complex shows that the side-on bonded NO moiety can be considered as NO3, suggesting a formal oxidation state of U(VI). Activation of the uranyl oxo bond in UO2(N3)Cl2 to form UO(NO)Cl2 and N2 was computed to be endothermic by 169 kJ/mol, which is energetically more favorable than formation of NUOCl2 and UO2Cl2. The observation of UO2Cl2 during CID is most likely due to the absence of an energy barrier for neutral ligand loss.

  15. Machine learning of parameters for accurate semiempirical quantum chemical calculations

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

    Dral, Pavlo O.; von Lilienfeld, O. Anatole; Thiel, Walter

    2015-04-14

    We investigate possible improvements in the accuracy of semiempirical quantum chemistry (SQC) methods through the use of machine learning (ML) models for the parameters. For a given class of compounds, ML techniques require sufficiently large training sets to develop ML models that can be used for adapting SQC parameters to reflect changes in molecular composition and geometry. The ML-SQC approach allows the automatic tuning of SQC parameters for individual molecules, thereby improving the accuracy without deteriorating transferability to molecules with molecular descriptors very different from those in the training set. The performance of this approach is demonstrated for the semiempiricalmore »OM2 method using a set of 6095 constitutional isomers C7H10O2, for which accurate ab initio atomization enthalpies are available. The ML-OM2 results show improved average accuracy and a much reduced error range compared with those of standard OM2 results, with mean absolute errors in atomization enthalpies dropping from 6.3 to 1.7 kcal/mol. They are also found to be superior to the results from specific OM2 reparameterizations (rOM2) for the same set of isomers. The ML-SQC approach thus holds promise for fast and reasonably accurate high-throughput screening of materials and molecules.« less

  16. GAS ANALYSES FROM HEADSPACE OF PLUTONIUM-BEARING MATERIALS CONTAINERS

    SciTech Connect (OSTI)

    Almond, P.; Livingston, R.; Traver, L.; Arnold, M.; Bridges, N.; Kessinger, G.; Duffey, J.

    2010-02-01

    The Savannah River National Laboratory (SRNL) 3013 destructive examination program performs surveillances on 3013 containers originating from multiple sites across the DOE complex. The bases for the packaging, storage, and surveillance activities are derived from the Department of Energy's 3013 Standard (DOE-STD-3013-2004). During destructive examination, headspace gas samples are obtained from the 3013 inner container and the annulus between the outer and inner containers. To characterize gas species, the samples are analyzed by gas chromatography (GC), direct-inlet mass spectrometry (DIMS), and Fourier-transform infrared spectroscopy (FTIR). The GC results, as well as other parameters, are utilized as input into the gas evaluation software tool (GEST) program for computation of pre-puncture gas compositions and pressures. Over 30 containers from the Hanford Site and the Rocky Flats Environmental Technology Site (RFETS) have been examined in the first three years of the surveillance program. Several containers were shown to have appreciable hydrogen content (some greater than 30 mol %), yet little or no oxygen was detected in any of the containers, including those exhibiting high hydrogen concentrations. Characteristics including moisture content, surface area, and material composition, along with the headspace gas composition, are utilized in an attempt to explain the chemical behavior of the packaged materials.

  17. Aqueous Co-precipitation of Pd-doped Cerium Oxide Nanoparticles: Chemistry Structure and Particle Growth

    SciTech Connect (OSTI)

    Liang H.; Zhang L.; Raitano J.M.; He G.; Akey A.J.; Herman I.P.; Chan S.-W.

    2012-01-01

    Nanoparticles of palladium-doped cerium oxide (Pd-CeO{sub 2}) have been prepared by aqueous co-precipitation resulting in a single phase cubic structure after calcination according to X-ray diffraction (XRD). Inhomogeneous strain, calculated using the Williamson-Hall method, was found to increase with palladium content, and the lattice contracts slightly, relative to nano-cerium oxide, as palladium content is increased. Moreover, high resolution transmission electron microscopy reveals some instances of defective microstructure. These factors combined imply that palladium is in solid solution with CeO{sub 2} in these nanoparticles, but palladium (II) oxide (PdO) peaks in the Raman spectra indicate that solid solution formation is partial and that highly dispersed PdO is present as well as the solid solution. Nevertheless, the addition of palladium to the CeO{sub 2} lattice inhibits the growth of the 6% Pd-CeO{sub 2} particles compared to pure CeO{sub 2} between 600 and 850 C. Activation energies for grain growth of 54 {+-} 7 and 79 {+-} 8 kJ/mol were determined for 6% Pd-CeO{sub 2} and pure CeO{sub 2}, respectively, along with pre-exponential Arrhenius factors of 10 for the doped sample and 600 for pure cerium oxide.

  18. Radiolytic Degradation in Lanthanide/Actinide Separation LigandsNOPOPO: Radical Kinetics and Efficiencies Determinations

    SciTech Connect (OSTI)

    Katy L. Swancutt; Stephen P. Mezyk; Richard D. Tillotson; Sylvie Pailloux; Manab Chakravarty; Robert T. Paine; Leigh R. Martin

    2011-07-01

    Trivalent lanthanide/actinide separations from used nuclear fuel occurs in the presence radiation fields that degrades the extraction ligands and solvents. Here we have investigated the stability of a new ligand for lanthanide/actinide separation; 2,6-bis[(di(2-ethylhexyl)phosphino)methyl] pyridine N,P,P-trioxide, TEH(NOPOPO). The impact of {gamma}-radiolysis on the distribution ratios for actinide (Am) and Lanthanide (Eu) extraction both in the presence and absence of an acidic aqueous phase by TEH(NOPOPO) was determined. Corresponding reaction rate constants for the two major radicals, hydroxyl and nitrate, were determined for TEH(NOPOPO) in the aqueous phase, with room temperature values of (3.49 {+-} 0.10) x 10{sup 9} and (1.95 {+-} 0.15) x 10{sup 8} M{sup -1} s{sup -1}, respectively. The activation energy for this reaction was found to be 30.2 {+-} 4.1 kJ mol{sup -1}. Rate constants for two analogues (2-methylphosphonic acid pyridine N,P-dioxide and 2,6-bis(methylphosphonic acid) pyridine N,P,P-trioxide) were also determined to assist in determining the major reaction pathways.

  19. A comparison of the alpha and gamma radiolysis of CMPO

    SciTech Connect (OSTI)

    Bruce J. Mincher; Stephen P. Mezyk; Gary Groenewold; Gracy Elias

    2011-06-01

    The radiation chemistry of CMPO has been investigated using a combination of irradiation and analytical techniques. The {alpha}-, and {gamma}-irradiation of CMPO resulted in identical degradation rates (G-value, in {mu}mol Gy{sup -1}) for both radiation types, despite the difference in their linear energy transfer (LET). Similarly, variations in {gamma}-ray dose rates did not affect the degradation rate of CMPO. The solvent extraction behavior was different for the two radiation types, however. Gamma-irradiation resulted in steadily increasing distribution ratios for both forward and stripping extractions, with respect to increasing absorbed radiation dose. This was true for samples irradiated as a neat organic solution, or irradiated in contact with the acidic aqueous phase. In contrast, {alpha}-irradiated samples showed a rapid drop in distribution ratios for forward and stripping extractions, followed by essentially constant distribution ratios at higher absorbed doses. These differences in extraction behavior are reconciled by mass spectrometric examination of CMPO decomposition products under the different irradiation sources. Irradiation by {gamma}-rays resulted in the rupture of phosphoryl-methylene bonds with the production of phosphinic acid products. These species are expected to be complexing agents for americium that would result in higher distribution ratios. Irradiation by {alpha}-sources appeared to favor rupture of carbamoyl-methylene bonds with the production of less deleterious acetamide products.

  20. Oligomeric Dithienopyrrole-Thienopyrroledione (DTP-TPD) Donor-Acceptor Copolymer for Organic Photovoltaics

    SciTech Connect (OSTI)

    Hammond, S. R.; Braunecker, W.; Garcia, A.; Larsen, R.; Owczarczyk, Z.; Olson, D.; Ginley, D.

    2011-01-01

    A new donor-acceptor copolymer system based upon a dithienopyrrole (DTP) donor moiety and a thienopyrrolodione (TPD) accepting moiety has been designed and synthesized for organic photovoltaic (OPV) applications. The TPD accepting moiety has recently gained significant attention in the OPV community and is being incorporated into a number of different polymer systems. In contrast, the DTP donor moiety has received only limited attention, likely due in part to synthetic difficulties relating to the monomer. In our hands, the bis(trimethyltin)-DTP monomer was indelibly contaminated with {approx}5% of the mono-destannylated DTP, which limited the Stille polymerization with the dibromo-TPD monomer (>;99% pure) to produce material with M{sub n} {approx} 4130 g/mol (PDI = 1.10), corresponding to around eight repeat units. Despite this limitation, UV-visible absorption spectroscopy demonstrates strong absorption for this material with a band gap of {approx}1.6 eV. Cyclic voltammetry indicates a highest occupied molecular orbital (HOMO) energy level of -5.3 eV, which is much lower than calculations predicted. Initial bulk heterojunction OPV devices fabricated with the fullerene acceptor phenyl C61 butyric acid methyl ester (PCBM) exhibit V{sub oc} {approx} 700 mV, which supports the deep HOMO value obtained from CV. These results suggest the promise of this copolymer system.

  1. Quantum oscillations in the heavy-fermion compound YbPtBi

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

    Mun, E.; Bud'ko, S. L.; Lee, Y.; Martin, C.; Tanatar, M. A.; Prozorov, R.; Canfield, P. C.

    2015-08-01

    We present quantum oscillations observed in the heavy-fermion compound YbPtBi in magnetic fields far beyond its field-tuned, quantum critical point. Quantum oscillations are observed in magnetic fields as low as 60 kOe at 60 mK and up to temperatures as high as 3 K, which confirms the very high quality of the samples as well as the small effective mass of the conduction carriers far from the quantum critical point. Although the electronic specific heat coefficient of YbPtBi reaches ~7.4 J/molK2 in zero field, which is one of the highest effective mass values among heavy-fermion systems, we suppress it quicklymore » by an applied magnetic field. The quantum oscillations were used to extract the quasiparticle effective masses of the order of the bare electron mass, which is consistent with the behavior observed in specific heat measurements. Furthermore, such small effective masses at high fields can be understood by considering the suppression of Kondo screening.« less

  2. Quantum oscillations in the heavy-fermion compound YbPtBi

    SciTech Connect (OSTI)

    Mun, E.; Bud'ko, S. L.; Lee, Y.; Martin, C.; Tanatar, M. A.; Prozorov, R.; Canfield, P. C.

    2015-08-01

    We present quantum oscillations observed in the heavy-fermion compound YbPtBi in magnetic fields far beyond its field-tuned, quantum critical point. Quantum oscillations are observed in magnetic fields as low as 60 kOe at 60 mK and up to temperatures as high as 3 K, which confirms the very high quality of the samples as well as the small effective mass of the conduction carriers far from the quantum critical point. Although the electronic specific heat coefficient of YbPtBi reaches ~7.4 J/molK2 in zero field, which is one of the highest effective mass values among heavy-fermion systems, we suppress it quickly by an applied magnetic field. The quantum oscillations were used to extract the quasiparticle effective masses of the order of the bare electron mass, which is consistent with the behavior observed in specific heat measurements. Furthermore, such small effective masses at high fields can be understood by considering the suppression of Kondo screening.

  3. Antiferromagnetic Kondo lattice in the layered compound CePd1xBi? and comparison to the superconductor LaPd1xBi?

    SciTech Connect (OSTI)

    Han, Fei; Wan, Xiangang; Phelan, Daniel; Stoumpos, Constantinos C.; Sturza, Mihai; Malliakas, Christos D.; Li, Qing'an; Han, Tian-Heng; Zhao, Qingbiao; Chung, Duck Young; Kanatzidis, Mercouri G.

    2015-07-13

    The layered compound CePd1xBi? with the tetragonal ZrCuSi?-type structure was obtained from excess Bi flux. Magnetic susceptibility data of CePd1xBi? show an antiferromagnetic ordering below 6 K and are anisotropic along the c axis and the ab plane. The anisotropy is attributed to crystal-electric-field (CEF) effects and a CEF model which is able to describe the susceptibility data is given. An enhanced Sommerfeld coefficient ? of 0.191 J mol Ce? K? obtained from specific-heat measurement suggests a moderate Kondo effect in CePd1xBi?. Other than the antiferromagnetic peak at 6 K, the resistivity curve shows a shoulderlike behavior around 75 K which could be attributed to the interplay between Kondo and CEF effects. Magnetoresistance and Hall-effect measurements suggest that the interplay reconstructs the Fermi-surface topology of CePd1xBi? around 75 K. Electronic structure calculations reveal that the Pd vacancies are important to the magnetic structure and enhance the CEF effects which quench the orbital moment of Ce at low temperatures.

  4. Magnetic properties of nanocrystalline KNbO{sub 3}

    SciTech Connect (OSTI)

    Golovina, I. S. Shanina, B. D.; Kolesnik, S. P.; Geifman, I. N.; Andriiko, A. A.

    2013-11-07

    Newly synthesized undoped and iron-doped nanoscale powders of KNbO{sub 3} are investigated using magnetic resonance and static magnetization methods in order to determine how the crystal size and doping affect the structure of magnetic defects and material properties. Although the bulk crystals of KNbO{sub 3} are nonmagnetic, the undoped KNbO{sub 3} powder with average particle size of 80?nm exhibits magnetic properties. The ferromagnetic resonance signal and the magnetization curve registered on the powder are thoroughly analyzed. It is concluded that the appearance of the defect driven ferromagnetism in the undoped powder is due to the nano-size of the particles. This effect disappears in the iron-doped KNbO{sub 3} powder with particle sizes above 300?nm. In case of low doping (<1?mol. % Fe), a new electron paramagnetic resonance signal with g{sub eff}?=?4.21 is found out in the KNbO{sub 3}:Fe powder. Such a signal has not been observed in the bulk crystals of KNbO{sub 3}:Fe. We suppose that this signal corresponds to individual paramagnetic Fe{sup 3+} ions having rhombic symmetry.

  5. n-Alkanes on MgO(100). I: Coverage-Dependent Desorption Kinetics of n-Butane

    SciTech Connect (OSTI)

    Tait, Steven L.; Dohnalek, Zdenek; Campbell, C T.; Kay, Bruce D.

    2005-04-22

    High quality temperature programmed desorption (TPD) measurements of n-butane from MgO(100) have been made for a large number of initial butane coverages (0-3.70 ML) and a wide range of heating ramp rates (0.3-10 K/s). We present a TPD analysis technique which allows the coverage-dependent desorption energy to be accurately determined by mathematical inversion of a TPD spectrum, assuming only that the prefactor is coverage-independent. A variational method is used to determine the prefactor that minimizes the difference between a set of simulated TPD spectra and corresponding experimental data. The best fit for butane desorption from MgO is obtained with a prefactor of 1015.7?1.6 s-1. The desorption energy is 34.9?3.4 kJ/mol at 0.5 ML coverage, and varies with coverage. Simulations based on these results can accurately reproduce TPD experiments for submonolayer initial coverages over a wide range of heating ramp rates (0.3-10 K/s). Advantages and limitations of this method are discussed.

  6. Separation of vapour and gas mixtures using a thin zeolite MFI membrane

    SciTech Connect (OSTI)

    Vroon, Z.A.E.P.; Gilde, M.J.; Kiezer, K.

    1994-12-31

    Zeolite MFI composite membranes were prepared by in situ crystallisation. A very thin (L < 5 {mu}m) polycrystalline MFI layer was grown on a flat {alpha}-Al{sub 2}O{sub 3} support (pore radii 80 nm). XRD and SEM showed that the layer was built of small MFI particles ({+-}200 nm). The single gas flux of methane, n-butane and iso-butane are respectively 9.7, 2.7 and 0.032 10{sup -3} mol.m{sup -2}.s{sup -1} at 25{degrees}C and 100 kPa. The separation of n-butane/methane is reversible. At 25{degrees}C it is possible to separate n-butane from methane. At 200{degrees}C it is possible to separate methane from n-butane. The separation factor for 50 n-butane/50 iso-butane is 26 at 50{degrees}C. Experiments with large molecules showed that the zeolite MFI membrane contains no pores larger than inherent to the zeolite.

  7. Machine learning predictions of molecular properties: Accurate many-body potentials and nonlocality in chemical space

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

    Hansen, Katja; Biegler, Franziska; Ramakrishnan, Raghunathan; Pronobis, Wiktor; von Lilienfeld, O. Anatole; Müller, Klaus -Robert; Tkatchenko, Alexandre

    2015-06-04

    Simultaneously accurate and efficient prediction of molecular properties throughout chemical compound space is a critical ingredient toward rational compound design in chemical and pharmaceutical industries. Aiming toward this goal, we develop and apply a systematic hierarchy of efficient empirical methods to estimate atomization and total energies of molecules. These methods range from a simple sum over atoms, to addition of bond energies, to pairwise interatomic force fields, reaching to the more sophisticated machine learning approaches that are capable of describing collective interactions between many atoms or bonds. In the case of equilibrium molecular geometries, even simple pairwise force fields demonstratemore » prediction accuracy comparable to benchmark energies calculated using density functional theory with hybrid exchange-correlation functionals; however, accounting for the collective many-body interactions proves to be essential for approaching the “holy grail” of chemical accuracy of 1 kcal/mol for both equilibrium and out-of-equilibrium geometries. This remarkable accuracy is achieved by a vectorized representation of molecules (so-called Bag of Bonds model) that exhibits strong nonlocality in chemical space. The same representation allows us to predict accurate electronic properties of molecules, such as their polarizability and molecular frontier orbital energies.« less

  8. Thermodynamics of methane adsorption on copper HKUST-1 at low pressure

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

    Wu, Di; Guo, Xiaofeng; Sun, Hui; Navrotsky, Alexandra

    2015-06-11

    Metal–organic frameworks (MOFs) can be engineered as natural gas storage materials by tuning the pore structures and surface properties. Here we report the direct measurement of CH₄ adsorption enthalpy on a paddlewheel MOF (Cu HKUST-1) using gas adsorption calorimetry at 25 °C at low pressures (below 1 bar). In this pressure region, the CH₄–CH₄ intermolecular interactions are minimized and the energetics solely reflects the CH₄–MOF interactions. Our results suggest moderately exothermic physisorption with an enthalpy of -21.1 ± 1.1 kJ/mol CH₄ independent of coverage. The calorimetric investigation complements previous computational and crystallographic studies by providing zero coverage enthalpies of CH₄more » adsorption. The analysis of the new and literature data suggests that in initial stages of adsorption the CH₄–HKUST-1 interaction tends to be more sensitive to the pore dimension than to the guest polarizability, suggesting a less specific chemical binding role for the open Cu site.« less

  9. Direct production of nanostructured copper-nickel (Cu-Ni) alloy particles

    SciTech Connect (OSTI)

    Apaydin, Ramazan Oguzhan; Ebin, Burcak; Gurmen, Sebahattin

    2013-12-16

    Copper-Nickel (CuNi) nanostructured alloy particles were produced by Ultrasonic Spray Pyrolysis and Hydrogen Reduction Method (USP-HR) from high purity copper and nickel nitrate aqueous solutions. The effect of the precursor solution in the range of 0.1 and 0.5 mol/L on the morphology and crystallite size of CuNi nanoparticles were investigated under 2 h running time, 700 C operating temperature and 0.5 L/min H{sub 2} flow rate. Particle size, morphology, composition and crystallite structure were characterized by Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS) and X-Ray Diffraction (XRD). Particle characterization studies show that nanostructured alloy particles have cubic crystal structure and they are in submicron size range with spherical morphology. The crystallite sizes of the particles calculated with Scherrer formula are 40 and 34 nm and average particles sizes observed from the SEM images are 300 and 510 nm for each experiment respectively.

  10. Studies on the reduction kinetics of hematite iron ore pellets with noncoking coals for sponge iron plants

    SciTech Connect (OSTI)

    Kumar, M.; Mohapatra, P.; Patel, S.K.

    2009-07-01

    In the present investigation, fired pellets were made by mixing hematite iron ore fines of -100, -16+18, and -8+10 mesh size in different ratios and studies on their reduction kinetics in Lakhanpur, Orient OC-2 and Belpahar coals were carried out at temperatures ranging from 850{sup o}C to 1000{sup o}C with a view toward promoting the massive utilization of fines in ironmaking. The rate of reduction in all the fired iron ore pellets increased markedly with an increase in temperature up to 1000{sup o}C, and it was more intense in the first 30min. The values of activation energy, calculated from integral and differential approaches, for the reduction of fired pellets (prepared from iron ore fines of -100 mesh size) in coals were found to be in the range 131-148 and 130-181 kJ mol{sup -1} (for =0.2 to 0.8), indicating the process is controlled by a carbon gasification reaction. The addition of selected larger size particles in the matrix of -100 mesh size fines up to the extent studied decreased the activation energy and slightly increased the reduction rates of resultant fired pellets. In comparison to coal, the reduction of fired pellets in char was characterized by significantly lower reduction rates and higher activation energy.

  11. Dynamic in-situ X-ray Diffraction of Catalyzed Alanates

    SciTech Connect (OSTI)

    Gross, K.J.; Sandrock, G.; Thomas, G.J.

    2000-11-01

    The discovery that hydrogen can be reversible absorbed and desorbed from NaAlH{sub 4} by the addition of catalysts has created an entirely new prospect for lightweight hydrogen storage. NaAlH{sub 4} releases hydrogen through the following set of decomposition reactions: NaAlH{sub 4} {r_arrow} 1/3({alpha}-Na{sub 3}AlH{sub 6}) + 2/3Al + H{sub 2} {r_arrow} NaH + Al + 3/2H{sub 2}. These decomposition reactions as well as the reverse recombination reactions were directly observed using time-resolved in-situ x-ray powder diffraction. These measurements were performed under conditions similar to those found in PEM fuel cell operations (hydrogen absorption: 50--70 C, 10--15 bar Hz, hydrogen resorption: 80--110 C, 5--100 mbar H{sub 2}). Catalyst doping was found to dramatically improve kinetics under these conditions. In this study, the alanate was doped with a catalyst by dry ball-milling NaAlH{sub 4} with 2 mol.% solid TiCl{sub 3}. X-ray diffraction clearly showed that TiCl{sub 3} reacts with NaAlH{sub 4} to form NaCl during the doping process. Partial desorption of NaAlH{sub 4} was even observed to occur during the catalyst doping process.

  12. The role of the Ganges-Brahmaputra mixing zone in supplying barium and [sup 226]Ra to the Bay of Bengal

    SciTech Connect (OSTI)

    Carroll, J. Univ. of Alaska, Fairbanks ); Falkner, K.K. CNES, Toulouse ); Brown, E.T. ); Moore, W.S. )

    1993-07-01

    The Ganges-Brahmaputra river system is ranked fourth among world rivers as a source of freshwater to the oceans and is believed to supply more sediment to the ocean than any other; 1.5 [times] 10[sup 12] kg/yr (Milliman and Meade, 1983). Barium and [sup 226]Ra are typically enriched in waters where sediment-laden rivers enter the ocean. As such, the Ganges-Brahmaputra is likely to produce globally significant barium and [sup 226]Ra fluxes to the ocean. Water samples for barium and [sup 226]Ra were collected within four major channels of the Ganges-Brahmaputra mixing zone during a period of low sediment and freshwater discharge. The data suggest that in addition to suspended sediments supplied directly from rivers, river sediments deposited during high discharge in mangroves and on islands are desorbing barium and [sup 226]Ra to seawater. The release of barium and [sup 226]Ra from these sediment deposits is out-of-phase with the direct supply of sediments from the rivers. Estimates of the annual fluxes of barium and [sup 226]Ra from the Ganges-Brahmaputra mixing zone were also derived. The fluxes of barium and [sup 226]Ra are 5.3 [times] 10[sup 8] mol barium/yr and 9.5 [times] 10[sub 14] dpm radium/yr. The first silicate and phosphate mixing profiles for this system are reported. 29 refs., 6 figs., 3 tabs.

  13. Glucose sensing molecules having selected fluorescent properties

    DOE Patents [OSTI]

    Satcher, Jr., Joe H.; Lane, Stephen M.; Darrow, Christopher B.; Cary, Douglas R.; Tran, Joe Anh

    2004-01-27

    An analyte sensing fluorescent molecule that employs intramolecular electron transfer is designed to exhibit selected fluorescent properties in the presence of analytes such as saccharides. The selected fluorescent properties include excitation wavelength, emission wavelength, fluorescence lifetime, quantum yield, photostability, solubility, and temperature or pH sensitivity. The compound comprises an aryl or a substituted phenyl boronic acid that acts as a substrate recognition component, a fluorescence switch component, and a fluorophore. The fluorophore and switch component are selected such that the value of the free energy for electron transfer is less than about 3.0 kcal mol.sup.-1. Fluorescent compounds are described that are excited at wavelengths greater than 400 nm and emit at wavelengths greater than 450 nm, which is advantageous for optical transmission through skin. The fluorophore is typically selected from transition metal-ligand complexes and thiazine, oxazine, oxazone, or oxazine-one as well as anthracene compounds. The fluorescent compound can be immobilized in a glucose permeable biocompatible polymer matrix that is implantable below the skin.

  14. Development and Validation of a Slurry Model for Chemical Hydrogen Storage in Fuel Cell Applications

    SciTech Connect (OSTI)

    Brooks, Kriston P.; Pires, Richard P.; Simmons, Kevin L.

    2014-07-25

    The US Department of Energy's (DOE) Hydrogen Storage Engineering Center of Excellence (HSECoE) is developing models for hydrogen storage systems for fuel cell-based light duty vehicle applications for a variety of promising materials. These transient models simulate the performance of the storage system for comparison to the DOEs Technical Targets and a set of four drive cycles. The purpose of this research is to describe the models developed for slurry-based chemical hydrogen storage materials. The storage systems of both a representative exothermic system based on ammonia borane and endothermic system based on alane were developed and modeled in Simulink. Once complete the reactor and radiator components of the model were validated with experimental data. The model was then run using a highway cycle, an aggressive cycle, cold-start cycle and hot drive cycle. The system design was adjusted to meet these drive cycles. A sensitivity analysis was then performed to identify the range of material properties where these DOE targets and drive cycles could be met. Materials with a heat of reaction greater than 11 kJ/mol H2 generated and a slurry hydrogen capacity of greater than 11.4% will meet the on-board efficiency and gravimetric capacity targets, respectively.

  15. Calix[4]pyrrole: A New Ion-Pair Receptor As Demonstrated by Liquid-Liquid Extraction

    SciTech Connect (OSTI)

    Wintergerst, Mr. Matthieu; Levitskaia, Tatiana G.; Moyer, Bruce A; Sessler, Jonathan L.; Delmau, Laetitia Helene

    2008-01-01

    Solvent extraction studies provide confirming evidence that meso-octamethylcalix[4]pyrrole acts as an ion-pair receptor for cesium chloride and cesium bromide in nitrobenzene solution. The stoichiometry of the interaction under extraction conditions from water to nitrobenzene was determined from plots of the cesium distribution ratios vs. cesium salt and receptor concentration, indicating the formation of an ion-paired 1:1:1 cesium:calix[4]pyrrole:halide complex. The extraction results were modeled to evaluate the equilibria inherent to the solvent extraction system, either with chloride or bromide. The binding energy between the halide anion and the calix[4]pyrrole was found to be about 7 kJ/mol larger for cesium chloride than for the cesium bromide. The ion-pairing free energies between the calix[4]pyrrole-halide complex and the cesium cation are nearly the same within experimental uncertainty for either halide, consistent with a structural model in which the Cs+ cation resides in the calix bowl. These results are unexpected since nitrobenzene is a very polar solvent that generally leads to dissociated complexes in the organic phase when used as a diluent in extraction studies of univalent ions. Control studies involving nitrate revealed no evidence of ion-pairing for CsNO3 under conditions identical to those where it is observed for CsCl and CsBr.

  16. Calix[4]pyrrole: A New Ion-Pair Receptor As Demonstrated by Liquid-Liquid Extraction

    SciTech Connect (OSTI)

    Wintergerst, Mr. Matthieu; Levitskaia, Tatiana G.; Moyer, Bruce A; Sessler, Jonathan L.; Delmau, Laetitia Helene

    2008-01-01

    Solvent-extraction studies provide confirming evidence that meso-octamethylcalix[4]pyrrole acts as an ion-pair receptor for cesium chloride and cesium bromide in nitrobenzene solution. The stoichiometry of the interaction under extraction conditions from water to nitrobenzene was determined from plots of the cesium distribution ratios vs cesium salt and receptor concentration, indicating the formation of an ionpaired 1:1:1 cesium:calix[4]pyrrole:halide complex. The extraction results were modeled to evaluate the equilibria inherent to the solvent-extraction system, with either chloride or bromide. The binding energy between the halide anion and the calix[4]pyrrole was found to be about 7 kJ/mol larger for cesium chloride than for the cesium bromide. The ion-pairing free energies between the calix[4]pyrrole-halide complex and the cesium cation are nearly the same within experimental uncertainty for either halide, consistent with a structural model in which the Cs+ cation resides in the calix bowl. These results are unexpected since nitrobenzene is a polar solvent that generally leads to dissociated complexes in the organic phase when used as a diluent in extraction studies of univalent ions. Control studies involving nitrate revealed no evidence of ion pairing for CsNO3 under conditions identical to those where it is observed for CsCl and CsBr.

  17. Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization

    SciTech Connect (OSTI)

    Custelcean, Radu; Sloop Jr, Frederick {Fred} V; Rajbanshi, Arbin; Wan, Shun; Moyer, Bruce A

    2015-01-01

    ABSTRACT: The thermodynamics and kinetics of crystallization of sodium sulfate with a tripodal tris-urea receptor (L1) from aqueous alkaline solutions have been measured in the 15 55 C temperature range, with the goal of identifying the optimal conditions for efficient and quick sulfate removal from nuclear wastes. The use of radiolabeled Na235SO4 provided a practical way to monitor the sulfate concentration in solution by liquid scintillation counting. Our results are consistent with a two-step crystallization mechanism, involving relatively quick dissolution of crystalline L1 followed by the rate-limiting crystallization of the Na2SO4(L1)2(H2O)4 capsules. We found that temperature exerted relatively little influence over the equilibrium sulfate concentration, which ranged between 0.004 and 0.011 M. This corresponds to 77 91% removal of sulfate from a solution containing 0.0475 M initial sulfate concentration, as found in a typical Hanford waste tank. The apparent pseudo-first-order rate constant for sulfate removal increased 20-fold from 15 to 55 C, corresponding to an activation energy of 14.1 kcal/mol. At the highest measured temperature of 55 C, 63% and 75% of sulfate was removed from solution within 8 h and 24 h, respectively.

  18. Mode I Fracture Toughness Prediction for Multiwalled-Carbon-Nanotube Reinforced Ceramics

    SciTech Connect (OSTI)

    Nguyen, Ba Nghiep; Henager, Charles H.

    2015-08-27

    This article develops a multiscale model to predict fracture toughness of multiwalled-carbon-nanotube (MWCNT) reinforced ceramics. The model bridges different scales from the scale of a MWCNT to that of a composite domain containing a macroscopic crack. From the nano, micro to meso scales, Eshelby-Mori-Tanaka models combined with a continuum damage mechanics approach are explored to predict the elastic damage behavior of the composite as a function of MWCNT volume fraction. MWCNTs are assumed to be randomly dispersed in a ceramic matrix subject to cracking under loading. A damage variable is used to describe matrix cracking that causes reduction of the elastic modulus of the matrix. This damage model is introduced in a modified boundary layer modeling approach to capture damage initiation and development at a tip of a pre-existing crack. Damage and fracture are captured only in a process window containing the crack tip under plane strain Mode I loading. The model is validated against the published experimental fracture toughness data for a MWCNT 3 mol% yttria stabilized zirconia composite system. In addition, crack resistance curves as a function of MWCNT content are predicted and fitted by a power law as observed in the experiments on zirconia.

  19. Degradation chemistry of PETN and its homologues

    SciTech Connect (OSTI)

    Shepodd, T.; Behrens, R.; Anex, D.; Miller, D.; Anderson, K.

    1997-11-01

    Pentaerythritol tetranitrate (PETN) is used throughout the stockpile as an energetic material. The formulation of PETN into XTX8003 (80% PETN, 20% Sylgard 182) creates an extrudable energetic composite. PETN and XTX8003 are used in the firesets for the retired W68 (MC2370) and the W76 (MC3028). When faced with potential lifetime extensions, energetic materials are naturally suspect regarding their output after prolonged aging. The authors have studied PETN and XTX8003 by looking at 25-year-old samples from retired MC2370s and newer materials. Both the old and new materials have also been placed in various accelerated aging protocols to investigate any decomposition that might occur over time. PETN is known to decompose autocatalytically even in the early stages of decomposition, but the process is poorly understood. Published values for the activation energy of decomposition vary by >40 kcal/mol. The 12 million year half life predicted for room temperature PETN would be dramatically shortened by chemical influences that lead to lower energy decomposition pathways. Degree of confinement, purity, and crystal size all influence degradation rates. In this paper, the authors observe the effects of chemical and thermal aging on PETN. They anticipate changes in mechanism at higher temperature aging, and before trying to extrapolate to lower temperatures, they want to make sure that they understand the different chemical processed involved.

  20. Antiferromagnetic Kondo lattice in the layered compound CePd1–xBi₂ and comparison to the superconductor LaPd1–xBi₂

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

    Han, Fei; Wan, Xiangang; Phelan, Daniel; Stoumpos, Constantinos C.; Sturza, Mihai; Malliakas, Christos D.; Li, Qing'an; Han, Tian-Heng; Zhao, Qingbiao; Chung, Duck Young; et al

    2015-07-13

    The layered compound CePd1–xBi₂ with the tetragonal ZrCuSi₂-type structure was obtained from excess Bi flux. Magnetic susceptibility data of CePd1–xBi₂ show an antiferromagnetic ordering below 6 K and are anisotropic along the c axis and the ab plane. The anisotropy is attributed to crystal-electric-field (CEF) effects and a CEF model which is able to describe the susceptibility data is given. An enhanced Sommerfeld coefficient γ of 0.191 J mol Ce⁻¹ K⁻² obtained from specific-heat measurement suggests a moderate Kondo effect in CePd1–xBi₂. Other than the antiferromagnetic peak at 6 K, the resistivity curve shows a shoulderlike behavior around 75 Kmore » which could be attributed to the interplay between Kondo and CEF effects. Magnetoresistance and Hall-effect measurements suggest that the interplay reconstructs the Fermi-surface topology of CePd1–xBi₂ around 75 K. Electronic structure calculations reveal that the Pd vacancies are important to the magnetic structure and enhance the CEF effects which quench the orbital moment of Ce at low temperatures.« less

  1. Impact of corrosion test container material in molten fluorides

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

    Olson, Luke C.; Fuentes, Roderick E.; Martinez-Rodriguez, Michael J.; Ambrosek, James W.; Sridharan, Kumar; Anderson, Mark H.; Garcia-Diaz, Brenda L.; Gray, Joshua; Allen, Todd R.

    2015-10-15

    The effects of crucible material choice on alloy corrosion rates in immersion tests in molten LiF–NaF–KF (46.5–11.5-42 mol. %) salt held at 850 °C for 500 hrs are described. Four crucible materials were studied. Molten salt exposures of Incoloy-800H in graphite, Ni, Incoloy-800H, and pyrolytic boron nitride (PyBN) crucibles all led to weight-loss in the Incoloy-800H coupons. Alloy weight loss was ~30 times higher in the graphite and Ni crucibles in comparison to the Incoloy-800H and PyBN crucibles. It is hypothesized galvanic coupling between the alloy coupons and crucible materials contributed to the higher corrosion rates. Alloy salt immersion inmore » graphite and Ni crucibles had similar weight-loss hypothesized to occur due to the rate limiting out diffusion of Cr in the alloys to the surface where it reacts with and dissolves into the molten salt, followed by the reduction of Cr from solution at the molten salt and graphite/Ni interfaces. As a result, both the graphite and the Ni crucibles provided sinks for the Cr, in the formation of a Ni–Cr alloy in the case of the Ni crucible, and Cr carbide in the case of the graphite crucible.« less

  2. Catalyzed CO.sub.2-transport membrane on high surface area inorganic support

    DOE Patents [OSTI]

    Liu, Wei

    2014-05-06

    Disclosed are membranes and methods for making the same, which membranes provide improved permeability, stability, and cost-effective manufacturability, for separating CO.sub.2 from gas streams such as flue gas streams. High CO.sub.2 permeation flux is achieved by immobilizing an ultra-thin, optionally catalyzed fluid layer onto a meso-porous modification layer on a thin, porous inorganic substrate such as a porous metallic substrate. The CO.sub.2-selective liquid fluid blocks non-selective pores, and allows for selective absorption of CO.sub.2 from gas mixtures such as flue gas mixtures and subsequent transport to the permeation side of the membrane. Carbon dioxide permeance levels are in the order of 1.0.times.10.sup.-6 mol/(m.sup.2sPa) or better. Methods for making such membranes allow commercial scale membrane manufacturing at highly cost-effective rates when compared to conventional commercial-scale CO.sub.2 separation processes and equipment for the same and such membranes are operable on an industrial use scale.

  3. Water transport and clustering behavior in homopolymer and graft copolymer polylactide

    SciTech Connect (OSTI)

    Du, An; Koo, Donghun; Theryo, Grayce; Hillmyer, Marc A.; Cairncross, Richard A.

    2015-02-19

    Polylactide is a bio-based and biodegradable polymer well-known for its renewable origins. Water sorption and clustering behavior in both a homopolymer polylactide and a graft copolymer of polylactide was studied using the quartz crystal microbalance/heat conduction calorimetry (QCM/HCC) technique. The graft copolymer, poly(1,5-cyclooctadiene-co-5-norbornene-2-methanol-graft-D,L-lactide), contained polylactide chains (95 wt.%) grafted onto a hydrophobic rubbery backbone (5 wt.%). Clustering is an important phenomenon in the study of water transport properties in polymers since the presence of water clusters can affect the water diffusivity. The HCC method using the thermal power signals and Van't Hoff's law were both employed to estimate the water sorption enthalpy. Sorption enthalpy of water in both polymers was determined to be approximately -40 kJ/mol for all water activity levels. Zimm-Lundberg analysis showed that water clusters start to form at a water activity of 0.4. The engaged species induced clustering (ENSIC) model was used to curve fit sorption isotherms and showed that the affinity among water molecules is higher than that between water molecules and polymer chains. All the methods used indicate that clustering of water molecules exists in both polymers.

  4. Theoretical hot methane line lists up to T = 2000 K for astrophysical applications

    SciTech Connect (OSTI)

    Rey, M.; Tyuterev, Vl. G.; Nikitin, A. V.

    2014-07-01

    The paper describes the construction of complete sets of hot methane lines based on accurate ab initio potential and dipole moment surfaces and extensive first-principle calculations. Four line lists spanning the [0-5000] cm{sup 1} infrared region were built at T = 500, 1000, 1500, and 2000 K. For each of these four temperatures, we have constructed two versions of line lists: a version for high-resolution applications containing strong and medium lines and a full version appropriate for low-resolution opacity calculations. A comparison with available empirical databases is discussed in detail for both cold and hot bands giving a very good agreement for line positions, typically <0.1-0.5 cm{sup 1} and ?5% for intensities of strong lines. Together with numerical tests using various basis sets, this confirms the computational convergence of our results for the most important lines, which is the major issue for theoretical spectra predictions. We showed that transitions with lower state energies up to 14,000 cm{sup 1} could give significant contributions to the methane opacity and have to be systematically taken into account. Our list at 2000 K calculated up to J = 50 contains 11.5 billion transitions for I > 10{sup 29} cm mol{sup 1}. These new lists are expected to be quantitatively accurate with respect to the precision of available and currently planned observations of astrophysical objects with improved spectral resolution.

  5. Accurate quantum dynamics calculations of vibrational spectrum of dideuteromethane CH{sub 2}D{sub 2}

    SciTech Connect (OSTI)

    Yu, Hua-Gen

    2015-05-21

    We report a rigorous variational study of the infrared (IR) vibrational spectra of both CH{sub 2}D{sub 2} and {sup 13}CH{sub 2}D{sub 2} isotopomers using an exact molecular Hamiltonian. Calculations are carried out using a recently developed multi-layer Lanczos algorithm based on the accurate refined Wang and Carrington potential energy surface of methane and the low-order truncated ab initio dipole moment surface of Yurchenko et al. [J. Mol. Spectrosc. 291, 69 (2013)]. All well converged 357 vibrational energy levels up to 6100 cm{sup ?1} of CH{sub 2}D{sub 2} are obtained, together with a comparison to previous calculations and 91 experimental bands available. The calculated frequencies are in excellent agreement with the experimental results and give a root-mean-square error of 0.67?cm{sup ?1}. In particular, we also compute the transition intensities from the vibrational ground state for both isotopomers. Based on the theoretical results, 20 experimental bands are suggested to be re-assigned. Surprisingly, an anomalous C isotopic effect is discovered in the n?{sub 5} modes of CH{sub 2}D{sub 2}. The predicted IR spectra provide useful information for understanding those unknown bands.

  6. DNA-Based Optomechanical Molecular Motor

    SciTech Connect (OSTI)

    McCullagh, Martin; Franco, Ignacio; Ratner, Mark A.; Schatz, George C.

    2011-03-16

    An azobenzene-capped DNA hairpin coupled to an AFM is presented as an optically triggered single-molecule motor. The photoinduced trans to cis isomerization of azobenzene affects both the overall length of the molecule and the ability of the DNA bases to hybridize. Using a combination of molecular dynamics simulations and free energy calculations the unfolding of both isomers along the O5'-O3' extension coordinate is monitored. The potentials of mean force (PMFs) along this coordinate indicate that there are two major differences induced by photoisomerization. The first is that the interbase hydrogen bond and stacking interactions are stable for a greater range of extensions in the trans system than in the cis system. The second difference is due to a decreased chain length of the cis isomer with respect to the trans isomer. These differences are exploited to extract work in optomechanical cycles. The disruption of the hairpin structure gives a maximum of 3.4 kcal mol-1 of extractable work per cycle with an estimated maximum efficiency of 2.4%. Structure-function insights into the operation of this motor are provided, and the effect of the cantilever stiffness on the extractable work is characterized.

  7. 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.

  8. N-(N-[2-(3,5-Difluorophenyl)acetyl]-(S)-alanyl)-(S)-phenylglycine tert-butyl ester (DAPT): an inhibitor of ?-secretase, revealing fine electronic and hydrogen-bonding features

    SciTech Connect (OSTI)

    Czerwinski, Andrzej; Valenzuela, Francisco; Afonine, Pavel; Dauter, Miroslawa; Dauter, Zbigniew

    2010-12-01

    The title compound, C{sub 23}H{sub 26}F{sub 2}N{sub 2}O{sub 4}, is a dipeptidic inhibitor of ?-secretase, one of the enzymes involved in Alzheimers dis@@ease. The mol@@ecule adopts a compact conformation, without intra@@molecular hydrogen bonds. In the crystal structure, one of the amide N atoms forms the only inter@@molecular NH?O hydrogen bond; the second amide N atom does not form hydrogen bonds. High-resolution synchrotron diffraction data permitted the unequivocal location and refinement without restraints of all H atoms, and the identification of the characteristic shift of the amide H atom engaged in the hydrogen bond from its ideal position, resulting in a more linear hydrogen bond. Significant residual densities for bonding electrons were revealed after the usual SHELXL refinement, and modeling of these features as additional inter@@atomic scatterers (IAS) using the program PHENIX led to a significant decrease in the R factor from 0.0411 to 0.0325 and diminished the r.m.s. deviation level of noise in the final difference Fourier map from 0.063 to 0.037 e {sup ?3}.

  9. Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization

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

    Custelcean, Radu; Sloop Jr, Frederick; Rajbanshi, Arbin; Wan, Shun; Moyer, Bruce A

    2015-01-01

    ABSTRACT: The thermodynamics and kinetics of crystallization of sodium sulfate with a tripodal tris-urea receptor (L1) from aqueous alkaline solutions have been measured in the 15 55 C temperature range, with the goal of identifying the optimal conditions for efficient and quick sulfate removal from nuclear wastes. The use of radiolabeled Na235SO4 provided a practical way to monitor the sulfate concentration in solution by liquid scintillation counting. Our results are consistent with a two-step crystallization mechanism, involving relatively quick dissolution of crystalline L1 followed by the rate-limiting crystallization of the Na2SO4(L1)2(H2O)4 capsules. We found that temperature exerted relatively little influencemore » over the equilibrium sulfate concentration, which ranged between 0.004 and 0.011 M. This corresponds to 77 91% removal of sulfate from a solution containing 0.0475 M initial sulfate concentration, as found in a typical Hanford waste tank. The apparent pseudo-first-order rate constant for sulfate removal increased 20-fold from 15 to 55 C, corresponding to an activation energy of 14.1 kcal/mol. At the highest measured temperature of 55 C, 63% and 75% of sulfate was removed from solution within 8 h and 24 h, respectively.« less

  10. Assessing electronic structure approaches for gas-ligand interactions in metal-organic frameworks: The CO{sub 2}-benzene complex

    SciTech Connect (OSTI)

    Witte, Jonathon; Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 ; Neaton, Jeffrey B.; Head-Gordon, Martin; Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720

    2014-03-14

    Adsorption of gas molecules in metal-organic frameworks is governed by many factors, the most dominant of which are the interaction of the gas with open metal sites, and the interaction of the gas with the ligands. Herein, we examine the latter class of interaction in the context of CO{sub 2} binding to benzene. We begin by clarifying the geometry of the CO{sub 2}benzene complex. We then generate a benchmark binding curve using a coupled-cluster approach with single, double, and perturbative triple excitations [CCSD(T)] at the complete basis set (CBS) limit. Against this ?CCSD(T)/CBS standard, we evaluate a plethora of electronic structure approximations: Hartree-Fock, second-order Mller-Plesset perturbation theory (MP2) with the resolution-of-the-identity approximation, attenuated MP2, and a number of density functionals with and without different empirical and nonempirical van der Waals corrections. We find that finite-basis MP2 significantly overbinds the complex. On the other hand, even the simplest empirical correction to standard density functionals is sufficient to bring the binding energies to well within 1 kJ/mol of the benchmark, corresponding to an error of less than 10%; PBE-D in particular performs well. Methods that explicitly include nonlocal correlation kernels, such as VV10, vdW-DF2, and ?B97X-V, perform with similar accuracy for this system, as do ?B97X and M06-L.

  11. An Assessment of Density Functional Methods for Potential Energy Curves of Nonbonded Interactions: The XYG3 and B97-D Approximations

    SciTech Connect (OSTI)

    Vazquez-Mayagoitia, Alvaro; Sherrill, David; Apra, Edoardo; Sumpter, Bobby G

    2010-01-01

    A recently proposed double-hybrid functional called XYG3 and a semilocal GGA functional (B97-D) with a semiempirical correction for van der Waals interactions have been applied to study the potential energy curves along the dissociation coordinates of weakly bound pairs of molecules governed by London dispersion and induced dipole forces. Molecules treated in this work were the parallel sandwich, T-shaped, and parallel-displaced benzene dimer, (C6H6)2; hydrogen sulfide and benzene, H2S C6H6; methane and benzene, CH4 C6H6; the methane dimer, (CH4)2; and the pyridine dimer, (C5H5N)2. We compared the potential energy curves of these functionals with previously published benchmarks at the coupled cluster singles, doubles, and perturbative triplets [CCSD(T)] complete-basis-set limit. Both functionals, XYG3 and B97-D, exhibited very good performance, reproducing accurate energies for equilibrium distances and a smooth behavior along the dissociation coordinate. Overall, we found an agreement within a few tenths of one kcal mol-1 with the CCSD(T) results across the potential energy curves.

  12. Diffusion of benzene confined in the oriented nanochannels of chrysotile asbestos fibers

    SciTech Connect (OSTI)

    Mamontov, E.; Kumzerov, Yu.A.; Vakhrushev, S.B.

    2005-11-01

    We used quasielastic neutron scattering to study the dynamics of benzene that completely fills the nanochannels of chrysotile asbestos fibers with a characteristic diameter of about 5 nm. The macroscopical alignment of the nanochannels in fibers provided an interesting opportunity to study anisotropy of the dynamics of confined benzene by means of collecting the data with the scattering vector either parallel or perpendicular to the fibers axes. The translational diffusive motion of benzene molecules was found to be isotropic. While bulk benzene freezes at 278.5 K, we observed the translational dynamics of the supercooled confined benzene on the time scale of hundreds of picoseconds even below 200 K, until at about 160 K its dynamics becomes too slow for the {mu}eV resolution of the neutron backscattering spectrometer. The residence time between jumps for the benzene molecules measured in the temperature range of 260 K to 320 K demonstrated low activation energy of 2.8 kJ/mol.

  13. Will water act as a photocatalyst for cluster phase chemical reactions? Vibrational overtone-induced dehydration reaction of methanediol

    SciTech Connect (OSTI)

    Kramer, Zeb C.; Takahashi, Kaito; Skodje, Rex T.; Vaida, Veronica

    2012-04-28

    The possibility of water catalysis in the vibrational overtone-induced dehydration reaction of methanediol is investigated using ab initio dynamical simulations of small methanediol-water clusters. Quantum chemistry calculations employing clusters with one or two water molecules reveal that the barrier to dehydration is lowered by over 20 kcal/mol because of hydrogen-bonding at the transition state. Nevertheless, the simulations of the reaction dynamics following OH-stretch excitation show little catalytic effect of water and, in some cases, even show an anticatalytic effect. The quantum yield for the dehydration reaction exhibits a delayed threshold effect where reaction does not occur until the photon energy is far above the barrier energy. Unlike thermally induced reactions, it is argued that competition between reaction and the irreversible dissipation of photon energy may be expected to raise the dynamical threshold for the reaction above the transition state energy. It is concluded that quantum chemistry calculations showing barrier lowering are not sufficient to infer water catalysis in photochemical reactions, which instead require dynamical modeling.

  14. Communication: Ultraviolet photodissociation dynamics of the simplest Criegee intermediate CH{sub 2}OO

    SciTech Connect (OSTI)

    Lehman, Julia H.; Li, Hongwei; Beames, Joseph M.; Lester, Marsha I.

    2013-10-14

    The velocity and angular distributions of O {sup 1}D photofragments arising from UV excitation of the CH{sub 2}OO intermediate on the B {sup 1}A??X {sup 1}A? transition are characterized using velocity map ion imaging. The anisotropic angular distribution yields the orientation of the transition dipole moment, which reflects the ?*?? character of the electronic transition associated with the COO group. The total kinetic energy release distributions obtained at several photolysis wavelengths provide detail on the internal energy distribution of the formaldehyde cofragments and the dissociation energy of CH{sub 2}OO X {sup 1}A? to O {sup 1}D + H{sub 2}CO X {sup 1}A{sub 1}. A common termination of the total kinetic energy distributions, after accounting for the different excitation energies, gives an upper limit for the CH{sub 2}OO X {sup 1}A? dissociation energy of D{sub 0}? 54 kcal mol{sup ?1}, which is compared with theoretical predictions including high level multi-reference ab initio calculations.

  15. Distributions of methyl group rotational barriers in polycrystalline organic solids

    SciTech Connect (OSTI)

    Beckmann, Peter A. E-mail: wangxianlong@uestc.edu.cn; Conn, Kathleen G.; Division of Education and Human Services, Neumann University, One Neumann Drive, Aston, Pennsylvania 19014-1298 ; Mallory, Clelia W.; Department of Chemistry, Bryn Mawr College, 101 North Merion Ave., Bryn Mawr, Pennsylvania 19010-2899 ; Mallory, Frank B.; Rheingold, Arnold L.; Rotkina, Lolita; Wang, Xianlong E-mail: wangxianlong@uestc.edu.cn

    2013-11-28

    We bring together solid state {sup 1}H spin-lattice relaxation rate measurements, scanning electron microscopy, single crystal X-ray diffraction, and electronic structure calculations for two methyl substituted organic compounds to investigate methyl group (CH{sub 3}) rotational dynamics in the solid state. Methyl group rotational barrier heights are computed using electronic structure calculations, both in isolated molecules and in molecular clusters mimicking a perfect single crystal environment. The calculations are performed on suitable clusters built from the X-ray diffraction studies. These calculations allow for an estimate of the intramolecular and the intermolecular contributions to the barrier heights. The {sup 1}H relaxation measurements, on the other hand, are performed with polycrystalline samples which have been investigated with scanning electron microscopy. The {sup 1}H relaxation measurements are best fitted with a distribution of activation energies for methyl group rotation and we propose, based on the scanning electron microscopy images, that this distribution arises from molecules near crystallite surfaces or near other crystal imperfections (vacancies, dislocations, etc.). An activation energy characterizing this distribution is compared with a barrier height determined from the electronic structure calculations and a consistent model for methyl group rotation is developed. The compounds are 1,6-dimethylphenanthrene and 1,8-dimethylphenanthrene and the methyl group barriers being discussed and compared are in the 212 kJ?mol{sup ?1} range.

  16. Advanced materials for solid oxide fuel cells: Hafnium-Praseodymium-Indium Oxide System

    SciTech Connect (OSTI)

    Bates, J.L.; Griffin, C.W.; Weber, W.J.

    1988-06-01

    The HfO/sub 2/-PrO/sub 1.83/-In/sub 2/O/sub 3/ system has been studied at the Pacific Northwest Laboratory to develop alternative, highly electrically conducting oxides as electrode and interconnection materials for solid oxide fuel cells. A coprecipitation process was developed for synthesizing single-phase, mixed oxide powders necessary to fabricate powders and dense oxides. A ternary phase diagram was developed, and the phases and structures were related to electrical transport properties. Two new phases, an orthorhombic PrInO/sub 3/ and a rhombohedral Hf/sub 2/In/sub 2/O/sub 7/ phase, were identified. The highest electronic conductivity is related to the presence of a bcc, In/sub 2/O/sub 3/ solid solution (ss) containing HfO/sub 2/ and PrO/sub 1.83/. Compositions containing more than 35 mol % of the In/sub 2/O/sub 3/ ss have electrical conductivities greater than 10/sup /minus/1/ (ohm-cm)/sup /minus/1/, and the two or three phase structures that contain this phase appear to exhibit mixed electronic-ionic conduction. The high electrical conductivities and structures similar to the Y/sub 2/O/sub 3/-stabilized ZrO/sub 2/(HfO/sub 2/) electrolyte give these oxides potential for use as cathodes in solid oxide fuel cells. 21 refs.

  17. Templated assembly of photoswitches significantly increases the energy-storage capacity of solar thermal fuels

    SciTech Connect (OSTI)

    Kucharski, TJ; Ferralis, N; Kolpak, AM; Zheng, JO; Nocera, DG; Grossman, JC

    2014-04-13

    Large-scale utilization of solar-energy resources will require considerable advances in energy-storage technologies to meet ever-increasing global energy demands. Other than liquid fuels, existing energy-storage materials do not provide the requisite combination of high energy density, high stability, easy handling, transportability and low cost. New hybrid solar thermal fuels, composed of photoswitchable molecules on rigid, low-mass nanostructures, transcend the physical limitations of molecular solar thermal fuels by introducing local sterically constrained environments in which interactions between chromophores can be tuned. We demonstrate this principle of a hybrid solar thermal fuel using azobenzene-functionalized carbon nanotubes. We show that, on composite bundling, the amount of energy stored per azobenzene more than doubles from 58 to 120 kJ mol(-1), and the material also maintains robust cyclability and stability. Our results demonstrate that solar thermal fuels composed of molecule-nanostructure hybrids can exhibit significantly enhanced energy-storage capabilities through the generation of template-enforced steric strain.

  18. A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states

    SciTech Connect (OSTI)

    Nguyen, Trong-Nghia; Putikam, Raghunath; Lin, M. C.

    2015-03-28

    We have discovered a new and highly competitive product channel in the unimolecular decay process for small Criegee intermediates, CH{sub 2}OO and anti/syn-CH{sub 3}C(H)OO, occurring by intramolecular insertion reactions via a roaming-like transition state (TS) based on quantum-chemical calculations. Our results show that in the decomposition of CH{sub 2}OO and anti-CH{sub 3}C(H)OO, the predominant paths directly produce cis-HC(O)OH and syn-CH{sub 3}C(O)OH acids with >110 kcal/mol exothermicities via loose roaming-like insertion TSs involving the terminal O atom and the neighboring CH bonds. For syn-CH{sub 3}C(H)OO, the major decomposition channel occurs by abstraction of a H atom from the CH{sub 3} group by the terminal O atom producing CH{sub 2}C(H)OOH. At 298 K, the intramolecular insertion process in CH{sub 2}OO was found to be 600 times faster than the commonly assumed ring-closing reaction.

  19. Pizza.py Toolkit

    Energy Science and Technology Software Center (OSTI)

    2006-01-01

    Pizza.py is a loosely integrated collection of tools, many of which provide support for the LAMMPS molecular dynamics and ChemCell cell modeling packages. There are tools to create input files. convert between file formats, process log and dump files, create plots, and visualize and animate simulation snapshots. Software packages that are wrapped by Pizza.py. so they can invoked from within Python, include GnuPlot, MatLab, Raster3d. and RasMol. Pizza.py is written in Python and runs onmore » any platform that supports Python. Pizza.py enhances the standard Python interpreter in a few simple ways. Its tools are Python modules which can be invoked interactively, from scripts, or from GUIs when appropriate. Some of the tools require additional Python packages to be installed as part of the users Python. Others are wrappers on software packages (as listed above) which must be available on the users system. It is easy to modify or extend Pizza.py with new functionality or new tools, which need not have anything to do with LAMMPS or ChemCell.« less

  20. Pyroprocess for processing spent nuclear fuel

    DOE Patents [OSTI]

    Miller, William E.; Tomczuk, Zygmunt

    2002-01-01

    This is a pyroprocess for processing spent nuclear fuel. The spent nuclear fuel is chopped into pieces and placed in a basket which is lowered in to a liquid salt solution. The salt is rich in ZrF.sub.4 and containing alkali or alkaline earth fluorides, and in particular, the salt chosen was LiF-50 mol % ZrF.sub.4 with a eutectic melting point of 500.degree. C. Prior to lowering the basket, the salt is heated to a temperature of between 550.degree. C. and 700.degree. C. in order to obtain a molten solution. After dissolution the oxides of U, Th, rare earth and other like oxides, the salt bath solution is subject to hydro-fluorination to remove the oxygen and then to a fluorination step to remove U as gaseous UF.sub.6. In addition, after dissolution, the basket contains PuO.sub.2 and undissolved parts of the fuel rods, and the basket and its contents are processed to remove the Pu.

  1. Adsorption of carbonyl sulfide on nickel and tungsten films

    SciTech Connect (OSTI)

    Saleh, J.M.; Nasser, F.A.K.

    1985-07-18

    The interaction of carbonyl sulfide with evaporated nickel and tungsten films has been investigated in the temperature range 195-450 K using gas pressures ranging from 1 to 13 N m/sup -2/. Rapid but mainly associative chemisorption of COS occurred on both metals at 195 K. Further adsorption of COS on W at temperatures 293-450 K was extremely slow and accompanied by more CO desorption than COS adsorbed. Sulfidation of Ni film by COS occurred at temperatures greater than or equal to 293 K with the liberation of carbon monoxide. The rate of adsorption increased with temperature but was independent of COS pressure. The activation energy (E/sub x/) increased with extent (X) of sulfidation to a limiting value of 97 kJ mol/sup -1/. A linear relationship was obtained from the plot of E/sub x/ against 1/X, suggesting the applicability of Cabrera-Mott theory to the sulfidation of Ni film by COS. 20 references, 2 figures, 1 table.

  2. Can Vanadium Be Substituted into LiFePO[subscript 4]?

    SciTech Connect (OSTI)

    Omenya, Fredrick; Chernova, Natasha A.; Upreti, Shailesh; Zavalij, Peter Y.; Nam, Kyung-Wan; Yang, Xiao-Qing; Whittingham, M. Stanley

    2015-10-15

    Vanadium is shown to substitute for iron in the olivine LiFePO{sub 4} up to at least 10 mol %, when the synthesis is carried out at 550 C. In the solid solution LiFe{sub 1-3y/2}V{sub y}PO{sub 4}, the a and b lattice parameters and cell volume decrease with increasing vanadium content, while the c lattice parameter increases slightly. However, when the synthesis is performed at 650 C, a NASICON phase, Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}, is also formed, showing that solid solution is a function of the synthesis temperature. X-ray absorption near-edge structure indicates vanadium is in the 3+ oxidation state and in an octahedral environment. Magnetic studies reveal a shift of the antiferromagnetic ordering transition toward lower temperatures with increasing vanadium substitution, confirming solid solution formation. The addition of vanadium enhances the electrochemical performance of the materials especially at high current densities.

  3. Photophysics of size-selected InP nanocrystals: Exciton recombination kinetics

    SciTech Connect (OSTI)

    Kim, S.; Wolters, R.H.; Heath, J.R.

    1996-11-01

    We report here on the size-dependent kinetics of exciton recombination in a III{endash}V quantum dot system, InP. The measurements reported include various frequency dependent quantum yields as a function of temperature, frequency dependent luminescence decay curves, and time-gated emission spectra. This data is fit to a three-state quantum model which has been previously utilized to explain photophysical phenomena in II{endash}VI quantum dots. The initial photoexcitation is assumed to place an electron in a (delocalized) bulk conduction band state. Activation barriers for trapping and detrapping of the electron to surface states, as well as activation barriers for surface-state radiationless relaxation processes are measured as a function of particle size. The energy barrier to detrapping is found to be the major factor limiting room temperature band-edge luminescence. This barrier increases with decreasing particle size. For 30 A particles, this barrier is found to be greater than 6 kJ/mol{emdash}a barrier which is more than an order of magnitude larger than that previously found for 32 A CdS nanocrystals. {copyright} {ital 1996 American Institute of Physics.}

  4. A medium-energy photoemission and ab-initio investigation of cubic yttria-stabilised zirconia

    SciTech Connect (OSTI)

    Cousland, G. P.; Cui, X. Y.; Smith, A. E.; Stampfl, C. M.; Wong, L.; Tayebjee, M.; Yu, D.; Triani, G.; Evans, P. J.; Ruppender, H.-J.; Jang, L.-Y.; Stampfl, A. P. J.

    2014-04-14

    Experimental and theoretical investigations into the electronic properties and structure of cubic yttria-stabilized zirconia are presented. Medium-energy x-ray photoemission spectroscopy measurements have been carried out for material with a concentration of 8-9?mol.?% yttria. Resonant photoemission spectra are obtained for a range of photon energies that traverse the L2 absorption edge for both zirconium and yttrium. Through correlation with results from density-functional theory (DFT) calculations, based on structural models proposed in the literature, we assign photoemission peaks appearing in the spectra to core lines and Auger transitions. An analysis of the core level features enables the identification of shifts in the core level energies due to different local chemical environments of the constituent atoms. In general, each core line feature can be decomposed into three contributions, with associated energy shifts. Their identification with results of DFT calculations carried out for proposed atomic structures, lends support to these structural models. The experimental results indicate a multi-atom resonant photoemission effect between nearest-neighbour oxygen and yttrium atoms. Near-edge x-ray absorption fine structure spectra for zirconium and yttrium are also presented, which correlate well with calculated Zr- and Y-4d electron partial density-of-states and with Auger electron peak area versus photon energy curve.

  5. Anisotropic Hc2 , thermodynamic and transport measurements, and pressure dependence of Tc in K2Cr3As3 single crystals

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

    Kong, Tai; Bud'ko, Sergey L.; Canfield, Paul C.

    2015-01-30

    We present a detailed study of single crystalline K2Cr3As3 and analyze its thermodynamic and transport properties, anisotropic Hc2(T), and initial pressure dependence of Tc. In zero field, the temperature-dependent resistivity is metallic. Deviation from a linear temperature dependence is evident below 100 K and a T3 dependence is roughly followed from just above Tc (~10K) to ~40K. Anisotropic Hc2(T) data were measured up to 140 kOe with field applied along and perpendicular to the rodlike crystals. For the applied field perpendicular to the rod, Hc2(T) is linear with a slope ~–70 kOe/K. For field applied along the rod, the slopemore » is about –120 kOe/K below 70 kOe. Above 70 kOe, the magnitude of the slope decreases to ~–70 kOe/K. The electronic specific heat coefficient γ, just above Tc, is 73 mJ/mol K2; the Debye temperature ΘD is 220 K. As a result, the specific heat jump at the superconducting transition ΔC~2.2γTc. Finally, for hydrostatic pressures up to ~7 kbar, Tc decreases under pressure linearly at a rate of –0.034K/kbar.« less

  6. Application of /sup 13/C, /sup 2/H, /sup 1/H NMR and GPC to the study of structural evolution of subbituminous coal in tetralin at 427/sup 0/C

    SciTech Connect (OSTI)

    Franz, J.A.; Camaioni, D.M.; Skiens, W.E.

    1981-01-01

    The products from the treatment of subbituminous coal at 427/sup 0/C in tetralin or 1,1-d/sub 2/-tetralin for times varying from 2.5 to 120 min were examined by /sup 13/C, /sup 2/H, and /sup 1/H Fourier transform nuclear magnetic resonance (FTNMR), gel permeation chromatography (GPC), and elemental and hydroxyl group analysis. NMR and elemental analysis revealed that the flash hydroliquefaction products contained about 10% of aromatic ether carbon and phenolic carbon in roughly equal amounts, but no aliphatic ether, carboxyl, or quinine carbon. The combined asphaltenes and preasphaltenes from a 10-min reaction exhibited 68% carbon, 30% hydrogen, and 30% deuterium aromaticity, with aromaticity slowly increasing at longer reaction times. GPC analysis revealed that approximately 10% of the products were greater than 1500 mol wt, with number-average molecular weights reduced from 840 to 500 over a 2-hr reaction. Deuterium NMR revealed that the majority of deuterium transferred to coal appeared at benzylic carbons.

  7. The effect of Ce{sup 4+} incorporation on structural, morphological and photocatalytic characters of ZnO nanoparticles

    SciTech Connect (OSTI)

    Kannadasan, N.; Shanmugam, N. Cholan, S.; Sathishkumar, K.; Viruthagiri, G.; Poonguzhali, R.

    2014-11-15

    We report a simple chemical precipitation method for the preparation of undoped and cerium doped ZnO nanocrystals. The concentration of cerium in the products can be controlled in the range of 0.0250.125 mol. The structure and chemical compositions of the products were characterized by X-ray diffraction, X-ray photoelectron spectroscopy; energy dispersive spectrum and Fourier transform infrared spectroscopy. The results demonstrate that Ce{sup 4+} ions were successfully incorporated into the lattice position of Zn{sup 2+} ions in ZnO. The morphology of the products was analyzed by field emission scanning electron microscopy and confirmed by high resolution transmission electron microscope analysis. The optical properties of the products were studied by ultravioletvisible and room temperature photoluminescence measurements. The photoluminescence emission spectra of Ce-doped ZnO showed enhanced visible emissions as a result of 5d ? 4f transition of cerium. In particular, a novel photocatalytic activity of the products was assessed using methylene blue. The obtained result reveals that Ce-doped products show higher reduction efficiency for methylene blue than the undoped ZnO. - Highlights: Nanocrystals of ZnO and ZnO:Ce{sup 4+} were grown. XPS results confirmed the incorporated cerium in tetravalence. PL emission exhibited 5d ? 4f transition on cerium doping. Doped ZnO decolorizes MB faster than undoped ZnO.

  8. Glucose oxidase-graphene-chitosan modified electrode for direct electrochemistry and glucose sensing

    SciTech Connect (OSTI)

    Kang, Xinhuang; Wang, Jun; Wu, Hong; Aksay, Ilhan A.; Liu, Jun; Lin, Yuehe

    2009-11-01

    Direct electrochemistry of a glucose oxidase (GOD)/graphene/chitosan nanocomposite was studied. The immobilized enzyme retains its bioactivity, exhibits a surface confined, reversible two-proton and two-electron transfer reaction, and has good stability, activity and a fast heterogeneous electron transfer rate with the rate constant (ks) of 2.83 s-1. A much higher enzyme loading (1.12 10-9 mol/cm2) is obtained as compared to the bare glass carbon surface. This GOD/graphene/chitosan nanocomposite film can be used for sensitive detection of glucose. The biosensor exhibits a wider linearity range from 0.08 mM to 12 mM glucose with a detection limit of 0.02 mM and much higher sensitivity (37.93 ?A mM-1 cm-2) as compared with other nanostructured supports. The excellent performance of the biosensor is attributed to large surface-to-volume ratio and high conductivity of graphene, and good biocompatibility of chitosan, which enhances the enzyme absorption and promotes direct electron transfer between redox enzymes and the surface of electrodes.

  9. High temperature two component explosive

    DOE Patents [OSTI]

    Mars, James E. (Vashon, WA); Poole, Donald R. (Woodinville, WA); Schmidt, Eckart W. (Bellevue, WA); Wang, Charles (Lafayette, IN)

    1981-01-01

    A two component, high temperature, thermally stable explosive composition comprises a liquid or low melting oxidizer and a liquid or low melting organic fuel. The oxidizer and fuel in admixture are incapable of substantial spontaneous exothermic reaction at temperatures on the order of 475.degree. K. At temperatures on the order of 475.degree. K., the oxidizer and fuel in admixture have an activation energy of at least about 40 kcal/mol. As a result of the high activation energy, the preferred explosive compositions are nondetonable as solids at ambient temperature, and become detonable only when heated beyond the melting point. Preferable oxidizers are selected from alkali or alkaline earth metal nitrates, nitrites, perchlorates, and/or mixtures thereof. Preferred fuels are organic compounds having polar hydrophilic groups. The most preferred fuels are guanidinium nitrate, acetamide and mixtures of the two. Most preferred oxidizers are eutectic mixtures of lithium nitrate, potassium nitrate and sodium nitrate, of sodium nitrite, sodium nitrate and potassium nitrate, and of potassium nitrate, calcium nitrate and sodium nitrate.

  10. Highly robust hydrogen generation by bio-inspired Ir complexes for dehydrogenation of formic acid in water: Experimental and theoretical mechanistic investigations at different pH

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

    Wang, Wan -Hui; Fujita, Etsuko; Ertem, Mehmed Z.; Xu, Shaoan; Onishi, Naoya; Manaka, Yuichi; Suna, Yuki; Kambayashi, Hide; Muckerman, James T.; Himeda, Yuichiro

    2015-07-30

    Hydrogen generation from formic acid (FA), one of the most promising hydrogen storage materials, has attracted much attention due to the demand for the development of renewable energy carriers. Catalytic dehydrogenation of FA in an efficient and green manner remains challenging. Here, we report a series of bio-inspired Ir complexes for highly robust and selective hydrogen production from FA in aqueous solutions without organic solvents or additives. One of these complexes bearing an imidazoline moiety (complex 6) achieved a turnover frequency (TOF) of 322,000 h⁻¹ at 100 °C, which is higher than ever reported. The novel catalysts are very stablemore » and applicable in highly concentrated FA. For instance, complex 3 (1 μmol) affords an unprecedented turnover number (TON) of 2,050,000 at 60 °C. Deuterium kinetic isotope effect experiments and density functional theory (DFT) calculations employing a “speciation” approach demonstrated a change in the rate-determining step with increasing solution pH. This study provides not only more insight into the mechanism of dehydrogenation of FA but also offers a new principle for the design of effective homogeneous organometallic catalysts for H₂ generation from FA.« less

  11. The vibrational spectrum of FeO{sub 2}{sup +} isomersTheoretical benchmark and experiment

    SciTech Connect (OSTI)

    Maier, Toni M.; Boese, A. Daniel; Sauer, Joachim; Wende, Torsten; Fagiani, Matias; Asmis, Knut R.

    2014-05-28

    Infrared photodissociation is used to record the vibrational spectrum of FeO{sub 2}{sup +}(He){sub 24} which shows three bands at 1035, 980, and 506 cm{sup ?1}. Quantum chemical multi-reference configuration interaction calculations (MRCISD) of structures and harmonic frequencies show that these bands are due to two different isomers, an inserted dioxo complex with Fe in the +V oxidation state and a side-on superoxo complex with Fe in the +II oxidation state. These two are separated by a substantial barrier, 53 kJ/mol, whereas the third isomer, an end-on complex between Fe{sup +} and an O{sub 2} molecule, is easily converted into the side-on complex. For all three isomers, states of different spin multiplicity have been considered. Our best energies are computed at the MRCISD+Q level, including corrections for complete active space and basis set extension, core-valence correlation, relativistic effects, and zero-point vibrational energy. The average coupled pair functional (ACPF) yields very similar energies. Density functional theory (DFT) differs significantly from our best estimates for this system, with the TPSS functional yielding the best results. The other functionals tested are BP86, PBE, B3LYP, TPSSh, and B2PLYP. Complete active space second order perturbation theory (CASPT2) performs better than DFT, but less good than ACPF.

  12. Materials corrosion in molten LiF-NaF-KF eutectic salt under different reduction-oxidation conditions

    SciTech Connect (OSTI)

    Sellers, R. S.; Cheng, W. J.; Anderson, M. H.; Sridharan, K.; Wang, C. J.; Allen, T. R.

    2012-07-01

    Molten fluoride salts such as FLiNaK (LiF-NaF-KF: 46.5-11.5-42 mol %) have been proposed for use as secondary reactor coolants, media for transfer of high temperature process heat from nuclear reactors to chemical plants, and for concentrated solar power thermal energy storage. In molten fluoride salts, passive oxide films are chemically unstable, and corrosion is driven largely by the thermodynamically driven dissolution of alloying elements into the molten salt environment. Two alloys, Hastelloy{sup R} N and 316L stainless steel were exposed to molten FLiNaK salt in a 316L stainless steel crucible under argon cover gas for 1000 hours at 850 deg. C. Graphite was present in some of the crucibles with the goal of studying corrosion behavior of relevant reactor material combinations. In addition, a technique to reduce alloy corrosion through modification of the reduction-oxidation state was tested by the inclusion of zirconium to the system. Corrosion of 316L stainless steel was noted to occur primarily through surface depletion of chromium, an effect that was enhanced by the presence of graphite. Hastelloy{sup R} N experienced weight gain through electrochemical plating of corrosion products derived from the 316L stainless steel crucible. In the presence of zirconium, both alloys gained weight through plating of zirconium and as a result formed intermetallic layers. (authors)

  13. 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

  14. The dissociation of diacetyl : a shock-tube and theoretical study.

    SciTech Connect (OSTI)

    Yang, X.; Jasper, A. W.; Kiefer, J. H.; Tranter, R. S.

    2009-07-01

    The dissociation of diacetyl dilute in krypton has been studied in a shock tube using laser schlieren densitometry at 1200-1800 K and reaction pressures of 55 {+-} 2, 120 {+-} 3, and 225 {+-} 5 Torr. The experimentally determined rate coefficients show falloff and an ab initio/Master Equation/VRC-TST analysis was used to determine pressure-dependent rate coefficient expressions that are in good agreement with the experimental data. From the theoretical calculations k{sub {infinity}} (T) = 5.029 x 10{sup 19} (T/298 K){sup -3.40} exp(-37665/T) s{sup -1} for 300 < T < 2000 K. The laser schlieren profiles were simulated using a model for methyl recombination with appropriate additions for diacetyl. From the simulations rate coefficients were determined for CH{sub 3} + CH{sub 3} = C{sub 2}H{sub 6} and CH{sub 3} + C{sub 4}H{sub 6}O{sub 2} = CH{sub 3}CO + CH{sub 2}CO + CH{sub 4} (k(T) = 2.818T{sup 4.00} exp(-5737/T) cm{sup 3} mol{sup -1} s{sup -1}). Excellent agreement is found between the simulations and experimental profiles, and Troe type parameters have been calculated for the dissociation of diacetyl and the recombination of methyl radicals.

  15. An experimental and theoretical high temperature kinetic study of the thermal unimolecular dissociation of fluoroethane.

    SciTech Connect (OSTI)

    Giri, B. R.; Kiefer, J. H.; Xu, H.; Klippenstein, S. J.; Tranter, R. S.; Chemical Sciences and Engineering Division; Univ. of Illinois

    2008-01-01

    The thermal dissociation of fluoroethane has been studied using shock tube (ST)/time-of-flight mass spectrometry (TOF-MS) at 500 and 1200 Torr over the temperature range 1200-1550 K. The ST/TOF-MS experiments confirm that elimination of HF is the only reaction channel and rate coefficients for this reaction were extracted from concentration/time profiles derived from the mass spectra. Results from a novel diaphragmless shock tube coupled to the TOF-MS are also presented and demonstrate the unique ability of this apparatus to generate sufficiently reproducible shock waves that signal averaging can be performed over multiple experiments; something that is not possible with a conventional shock tube. The dissociation is also studied with ab initio transition state theory based master equation simulations. A modest increase in the calculated barrier height i.e., by 1 kcal mol{sup -1} yields predicted high pressure rate coefficients that are in good agreement with the existing literature data. The present pressure dependent observations are accurately reproduced for a downwards energy transfer for neon at 1200 to 1500 K of {approx} 270 cm{sup -1}, which is somewhat smaller than that found in previous studies on fluorinated ethanes with the same bath gases.

  16. TiO2 Nanotubes/MWCNTs Nanocomposite Photocatalysts: Synthesis, Characterization and Photocatalytic Hydrogen Evolution Under UV-Vis Light Illumination

    SciTech Connect (OSTI)

    Li, Hao-Peng; Zhang, Xiao-Yan; Cui, Xiao-Li; Lin, Yuehe

    2012-03-01

    Nanocomposite of TiO2 nanotubes (TiO2NTs) and multiwalled carbon nanotubes (MWCNTs) has been synthesized by a hydrothermal method and firstly used in photocatalytic hydrogen production. The obtained TiO2 NTs/MWCNTs composites were characterized by X-ray diffraction, transmission electron microscopy, Raman spectrum and ultraviolet-visible diffuse reflectance spectroscopy. The experimental results revealed that the MWCNTs were decorated with well dispersed anatase TiO2 nanotubes with a diameter of 8-15 nm. A slight blue shift and weak symmetry was observed for the strongest Raman peak which resulted from strain gradients originating from interface integration between TiO2 nanotubes and MWCNTs. The photocatalytic activity of the as-prepared samples was evaluated by hydrogen evolution from water splitting using Na2S and Na2SO3 as sacrificial reagents under UV-vis light irradiation. Enhanced photocatalytic activity compared with P25 has been observed for the resulted samples. The nanocomposite with optimized MWCNTs content of 1% displayed a hydrogen production rate of 161 u mol/h/g. Good photocatalytic stability of the as-synthesized samples was observed as well.

  17. Synthesis and characterization of furazan energetics ADAAF and DOATF

    SciTech Connect (OSTI)

    Veauthier, Jaqueline M; Chavez, David E; Tappan, Bryce C; Parrish, Damon

    2009-01-01

    The synthesis and structural characterization of bis[4-aminofurazanyl-3-azoxy]azofurazan (ADAAF) and 3,4:7,8:11,12:15,16-tetrafurazano-1,2,5,6,9,10,13,14-octaazacyclohexadeca-1,3,5,7,9,11,13,15-octaene-1,10-dioxide (DOATF) are described. Explosive sensitivity properties of both materials were determined. The heat of formation of ADAAF was measured to be 300 kcal/mol while the detonation velocity and pressure of ADAAF were measured to be 7.88 km/s and 299 kbar, respectively at 94% theoretical maximum density. We also investigated the burning rate characteristics of ADAAF. We have reported two new synthetic procedures and the first X-ray crystal structures for the azoxyfurazan compounds ADAAF (4) and DOATF (5). These new energetic materials were found to be significantly more sensitive to mechanical initiation than DAAF (3) and the heat of formation of 4 was found to be nearly three times that of 3. The detonation velocity and pressure for 4 are comparable to 2 while its burning rate characteristics are similar to HMX. Further studies to elucidate sensitivity behavior are ongoing.

  18. Suspension chemistry and electrophoretic deposition of zirconia electrolyte on conducting and non-conducting substrates

    SciTech Connect (OSTI)

    Das, Debasish; Basu, Rajendra N.

    2013-09-01

    Graphical abstract: - Highlights: Stable suspension of yttria stabilized zirconia (YSZ) obtained in isopropanol medium. Suspension chemistry and process parameters for electrophoretic deposition optimized. Deposited film quality changed with iodine and water (dispersants) concentration. Dense YSZ film (?5 ?m) fabricated onto non-conducting porous NiO-YSZ anode substrate. - Abstract: Suspensions of 8 mol% yttria stabilized zirconia (YSZ) particulates in isopropanol medium are prepared using acetylacetone, iodine and water as dispersants. The effect of dispersants concentration on suspension stability, particle size distribution, electrical conductivity and pH of the suspensions are studied in detail to optimize the suspension chemistry. Electrophoretic deposition (EPD) has been conducted to produce thin and dense YSZ electrolyte films. Deposition kinetics have been studied in depth and good quality films on conducting substrate are obtained at an applied voltage of 15 V for 3 min. YSZ films are also fabricated on non-conducting NiO-YSZ anode substrate using a steel plate on the reverse side of the substrate. Upon co-firing at 1400 C for 6 h a dense YSZ film of thickness ?5 ?m is obtained. Such a half cell (anode + electrolyte) can be used to fabricate a solid oxide fuel cell on applying a suitable cathode layer.

  19. Impact of corrosion test container material in molten fluorides

    SciTech Connect (OSTI)

    Olson, Luke C.; Fuentes, Roderick E.; Martinez-Rodriguez, Michael J.; Ambrosek, James W.; Sridharan, Kumar; Anderson, Mark H.; Garcia-Diaz, Brenda L.; Gray, Joshua; Allen, Todd R.

    2015-10-15

    The effects of crucible material choice on alloy corrosion rates in immersion tests in molten LiFNaFKF (46.511.5-42 mol. %) salt held at 850 C for 500 hrs are described. Four crucible materials were studied. Molten salt exposures of Incoloy-800H in graphite, Ni, Incoloy-800H, and pyrolytic boron nitride (PyBN) crucibles all led to weight-loss in the Incoloy-800H coupons. Alloy weight loss was ~30 times higher in the graphite and Ni crucibles in comparison to the Incoloy-800H and PyBN crucibles. It is hypothesized galvanic coupling between the alloy coupons and crucible materials contributed to the higher corrosion rates. Alloy salt immersion in graphite and Ni crucibles had similar weight-loss hypothesized to occur due to the rate limiting out diffusion of Cr in the alloys to the surface where it reacts with and dissolves into the molten salt, followed by the reduction of Cr from solution at the molten salt and graphite/Ni interfaces. As a result, both the graphite and the Ni crucibles provided sinks for the Cr, in the formation of a NiCr alloy in the case of the Ni crucible, and Cr carbide in the case of the graphite crucible.

  20. Optimization of esterification of oleic acid and trimethylolpropane (TMP) and pentaerythritol (PE)

    SciTech Connect (OSTI)

    Mahmud, Hamizah Ammarah; Salimon, Jumat

    2014-09-03

    Vegetable oil (VO) is the most potential alternative to replace mineral oil for lubricant due to better lubricating properties and great physicochemical properties. Chemical modification has to be done to overcome low temperature performance and low oxidation instability due to the presence of ?-hydrogen atoms of glycerol molecule. The optimization of esterification of oleic acid and polyhydric alcohol with sulfuric acid catalyst was carried out to find the optimum conditions with the highest yield. Reeaction variables such as; molar ratio, temperature, duration and catalyst concentration. Two types of polyhydric alcohol have been used; TMP and PE. The optimum results showed oleic acid successfully converted 91.2% ester TMP and 92.7% ester PE at duration: 5 hours (Ester TMP), 6 hours (Ester PE); temperature: 150C (ester TMP), 180C (Ester PE); catalyst concentration: 1.5% (w/w); and mol ratio: 3.9:1 (ester TMP), 4.9:1 (ester PE). From the data obtained, mole ratio showed most influenced factors to the increasing yields of ester conversions.. The TMP/PE ester was confirmed using gas chromatography (GC-FID), Fourier Transform Infrared Spectroscopy (FTIR) and Nuclear Magnetic Resonance (NMR)

  1. High critical currents in heavily doped (Gd,Y)Ba2Cu3Ox superconductor tapes

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

    Selvamanickam, V.; Gharahcheshmeh, M. Heydari; Xu, A.; Galstyan, E.; Delgado, L.; Cantoni, C.

    2015-01-20

    REBa2Cu3Ox superconductor tapes with moderate levels of dopants have been optimized for high critical current density in low magnetic fields at 77 K, but they do not exhibit exemplary performance in conditions of interest for practical applications, i.e., temperatures less than 50 K and fields of 2–30 T. Heavy doping of REBCO tapes has been avoided by researchers thus far due to deterioration in properties. Here, we report achievement of critical current densities (Jc) above 20 MA/cm2 at 30 K, 3 T in heavily doped (25 mol. % Zr-added) (Gd,Y)Ba2Cu3Ox superconductor tapes, which is more than three times higher thanmore » the Jc typically obtained in moderately doped tapes. Pinning force levels above 1000 GN/m3 have also been attained at 20 K. A composition map of lift factor in Jc (ratio of Jc at 30 K, 3 T to the Jc at 77 K, 0 T) has been developed which reveals the optimum film composition to obtain lift factors above six, which is thrice the typical value. A highly c-axis aligned BaZrO3 (BZO) nanocolumn defect density of nearly 7 × 1011 cm–2 as well as 2–3nm sized particles rich in Cu and Zr have been found in the high Jc films.« less

  2. Electrophoretic Study of the SnO2/Aqueous Solution Interface up to 260 degrees C.

    SciTech Connect (OSTI)

    Rodriguez-Santiago, V; Fedkin, Mark V.; Wesolowski, David J

    2009-07-01

    An electrophoresis cell developed in our laboratory was utilized to determine the zeta potential at the SnO{sub 2} (cassiterite)/aqueous solution (10{sup -3} mol kg{sup -1} NaCl) interface over the temperature range from 25 to 260 C. Experimental techniques and methods for the calculation of zeta potential at elevated temperature are described. From the obtained zeta potential data as a function of pH, the isoelectric points (IEPs) of SnO{sub 2} were obtained for the first time. From these IEP values, the standard thermodynamic functions were calculated for the protonation-deprotonation equilibrium at the SnO{sub 2} surface, using the 1-pK surface complexation model. It was found that the IEP values for SnO{sub 2} decrease with increasing temperature, and this behavior is compared to the predicted values by the multisite complexation (MUSIC) model and other semitheoretical treatments, and were found to be in excellent agreement.

  3. Pulse radiolysis studies of the reaction of nitrogen dioxide with the vitamin B?? complexes Cob(II)alamin and nitrocobalamin

    SciTech Connect (OSTI)

    Brasch, Nicola E.; Cabelli, Diane E.; Dassanayake, Rohan S.

    2014-10-06

    Although now recognized to be an important reactive nitrogen species in biological systems that modifies the structures of proteins, DNA and lipids, there few studies on the reactivity of ?NO2, including the reactions between ?NO2 and transition metal complexes. We report kinetic studies on the reaction of ?NO2 with two forms of vitamin B12 cob(II)alamin and nitrocobalamin. UV-vis spectroscopy and HPLC analysis of the product solution show that ?NO2 cleanly oxidizes the metal center of cob(II)alamin to form nitrocobalamin, with a second-order rate constant of (3.5 0.3) 10? M? s ? (pH 7.0 and 9.0, RT, I = 0.20 M). The stoichiometry of the reaction is 1:1. No reaction is detected by UV-vis spectroscopy and by HPLC analysis of the product solution when nitrocobalamin is exposed to up to 2.0 mol equiv.?NO2.

  4. Solar-thermal Water Splitting Using the Sodium Manganese Oxide Process & Preliminary H2A Analysis

    SciTech Connect (OSTI)

    Francis, Todd M; Lichty, Paul R; Perkins, Christopher; Tucker, Melinda; Kreider, Peter B; Funke, Hans H; Lewandowski, A; Weimer, Alan W

    2012-10-24

    There are three primary reactions in the sodium manganese oxide high temperature water splitting cycle. In the first reaction, Mn2O3 is decomposed to MnO at 1,500C and 50 psig. This reaction occurs in a high temperature solar reactor and has a heat of reaction of 173,212 J/mol. Hydrogen is produced in the next step of this cycle. This step occurs at 700C and 1 atm in the presence of sodium hydroxide. Finally, water is added in the hydrolysis step, which removes NaOH and regenerates the original reactant, Mn2O3. The high temperature solar-driven step for decomposing Mn2O3 to MnO can be carried out to high conversion without major complication in an inert environment. The second step to produce H2 in the presence of sodium hydroxide is also straightforward and can be completed. The third step, the low temperature step to recover the sodium hydroxide is the most difficult. The amount of energy required to essentially distill water to recover sodium hydroxide is prohibitive and too costly. Methods must be found for lower cost recovery. This report provides information on the use of ZnO as an additive to improve the recovery of sodium hydroxide.

  5. Ionic liquids for rechargeable lithium batteries

    SciTech Connect (OSTI)

    Salminen, Justin; Papaiconomou, Nicolas; Kerr, John; Prausnitz,John; Newman, John

    2005-09-29

    We have investigated possible anticipated advantages of ionic-liquid electrolytes for use in lithium-ion batteries. Thermal stabilities and phase behavior were studied by thermal gravimetric analysis and differential scanning calorimetry. The ionic liquids studied include various imidazoliumTFSI systems, pyrrolidiniumTFSI, BMIMPF{sub 6}, BMIMBF{sub 4}, and BMIMTf. Thermal stabilities were measured for neat ionic liquids and for BMIMBF{sub 4}-LiBF{sub 4}, BMIMTf-LiTf, BMIMTFSI-LiTFSI mixtures. Conductivities have been measured for various ionic-liquid lithium-salt systems. We show the development of interfacial impedance in a Li|BMIMBF{sub 4} + LiBF{sub 4}|Li cell and we report results from cycling experiments for a Li|BMIMBF{sub 4} + 1 mol/kg LIBF{sub 4}|C cell. The interfacial resistance increases with time and the ionic liquid reacts with the lithium electrode. As expected, imidazolium-based ionic liquids react with lithium electrodes. We seek new ionic liquids that have better chemical stabilities.

  6. Photoluminescence properties of Ho{sup 3+} ion in lithium-fluoroborate glass containing different modifier oxides

    SciTech Connect (OSTI)

    Balakrishna, A. Rajesh, D. Ratnakaram, Y. C.

    2014-04-24

    Trivalent holmium (0.5 mol%) doped lithium fluoro-borate glasses with the chemical compositions 49.5Li{sub 2}B{sub 4}O{sub 7?}20BaF{sub 2?}10NaF?20MO (where M=Mg, Ca, Cd and Pb), 49.5Li{sub 2}B{sub 4}O{sub 7?}20BaF{sub 2?}10NaF?10MgO?10CaO and 49.5Li{sub 2}B{sub 4}O{sub 7?}20BaF{sub 2?}10NaF?10CdO?10PbO were synthesized and investigated their photoluminescence properties. The variation in chemical composition by varying modifier oxides causes changes in the structural spectroscopic behavior of Ho{sup 3+} ions. These changes are examined by UV-VIS- NIR and luminescence spectroscopic techniques. The visible luminescence spectra were obtained by exciting samples at 409 nm radiation.

  7. Synthesis and studies on microhardness of alkali zinc borate glasses

    SciTech Connect (OSTI)

    Subhashini, Bhattacharya, Soumalya Shashikala, H. D. Udayashankar, N. K.

    2014-04-24

    The mixed alkali effect on zinc borate glasses have been reported. The glass systems of nominal composition 10Zn+xLi{sub 2}O+yNa{sub 2}O+80B{sub 2}O{sub 3} (x = y = 0, 5, 10, 15 mol%) were prepared using standard melt quenching method. The structural, physical and mechanical properties of the samples have been studied using X-ray diffraction(XRD), density measurement and Vickers hardness measurement, respectively. A consistent increase in the density was observed, which explains the role of the modifiers (Li{sub 2}O and Na{sub 2}O) in the network modification of borate structure. The molar volume is decreasing linearly with the alkali concentration, which is attributed to the conversion of tetrahedral boron (BO{sub 4/2}){sup ?} into (BO{sub 3/2}){sup ?}. The microhardness studies reveals the anisotropy nature of the material. It further confirms that the samples belong to hard glass category.

  8. Synthesis and CO{sub 2} adsorption study of modified MOF-5 with multi-wall carbon nanotubes and expandable graphite

    SciTech Connect (OSTI)

    Ullah, Sami E-mail: azmibustam@petronas.com.my E-mail: lkhlfh@gmail.com E-mail: nadiariazz@gmail.com; Bustam, M. A. E-mail: azmibustam@petronas.com.my E-mail: lkhlfh@gmail.com E-mail: nadiariazz@gmail.com; Shariff, A. M. E-mail: azmibustam@petronas.com.my E-mail: lkhlfh@gmail.com E-mail: nadiariazz@gmail.com; Elkhalifah, Ali E. I. E-mail: azmibustam@petronas.com.my E-mail: lkhlfh@gmail.com E-mail: nadiariazz@gmail.com; Murshid, G. E-mail: azmibustam@petronas.com.my E-mail: lkhlfh@gmail.com E-mail: nadiariazz@gmail.com; Riaz, Nadia E-mail: azmibustam@petronas.com.my E-mail: lkhlfh@gmail.com E-mail: nadiariazz@gmail.com

    2014-10-24

    MOF-5 was synthesized by solvothermal method and its reactivation under anhydrous conditions. This research is conducted to investigate the effect of MOF-5 and MOF-5 modified with multi-wall carbon nanotubes (MWCNTs) and expandable graphite (EG) on the performance of CO{sub 2} adsorption. The synthesized MOFs were characterized using Field emission scanning electron microscopy (FESEM) for surface morphology, Thermogravimetric analysis (TGA) for thermal stability, X-ray diffraction (XRD) for crystals plane, Brunauer-Emmet-Teller (BET) for surface area and CO{sub 2} adsorption. The result had showed that the modified MOF-5 enhanced the CO{sub 2} adsorption compared to the pure MOF-5. The increment in the CO{sub 2} uptake capacities of MOF materials was attributed to the decrease in the pore size and enhancement of micropore volume of MOF-5 by multi-walled carbon nanotube and EG incorporation. The BET surface area of the synthesized MOF-5@MWCNTs is more than MOF-5. The CO{sub 2} sorption capacities of MOF-5 and MOF-5@MWCNTs were observed to increase from 0.00008 to 0.00048 mol g-1 at 298 K and 1 bar. The modified MOF-5@MWCNTs resulted in the highest CO{sub 2} adsorption followed by the modified MOF-5@ EG and lastly, MOF-5.

  9. Electrical studies on silver based fast ion conducting glassy materials

    SciTech Connect (OSTI)

    Rao, B. Appa Kumar, E. Ramesh Kumari, K. Rajani Bhikshamaiah, G.

    2014-04-24

    Among all the available fast ion conductors, silver based glasses exhibit high conductivity. Further, glasses containing silver iodide enhances fast ion conducting behavior at room temperature. Glasses of various compositions of silver based fast ion conductors in the AgI?Ag{sub 2}O?[(1?x)B{sub 2}O{sub 3}?xTeO{sub 2}] (x=0 to1 mol% in steps of 0.2) glassy system have been prepared by melt quenching method. The glassy nature of the compounds has been confirmed by X-ray diffraction. The electrical conductivity (AC) measurements have been carried out in the frequency range of 1 KHz3MHz by Impedance Analyzer in the temperature range 303423K. The DC conductivity measurements were also carried out in the temperature range 300523K. From both AC and DC conductivity studies, it is found that the conductivity increases and activation energy decreases with increasing the concentration of TeO{sub 2} as well as with temperature. The conductivity of the present glass system is found to be of the order of 10{sup ?2} S/cm at room temperature. The ionic transport number of these glasses is found to be 0.999 indicating that these glasses can be used as electrolyte in batteries.

  10. Acid Strength and Bifunctional Catalytic Behavior of Alloys Comprised of Noble Metals and Oxophilic Metal Promoters

    SciTech Connect (OSTI)

    Hibbitts, David D.; Tan, Qiaohua; Neurock, Matthew

    2014-06-01

    The promotion of metal catalysts with partially oxidized oxophilic MOx species, such as ReOx-promoted Rh, has been demonstrated to produce Brnsted acid sites that can promote hydrogenolysis of oxygenate intermediates such as those found in biomass-derived species. A wide variety of alloy compositions and structures are examined in this work to investigate strongly acidic promoters by using DFT-calculated deprotonation energies (DPE) as a measure of acid strength. Sites with the highest acid strength had DPE less than 1100 kJ mol-1, similar to DPE values of heteropolyacids or acid-containing zeolites, and were found on alloys composed of an oxophilic metal (such as Re or W) with a noble metal (such as Rh or Pt). NH3 adsorbs more strongly to sites with increasing acid strength and the activation barriers for acid-catalyzed ring opening of a furan ring decrease with increasing acid strength, which was also shown to be stronger for OH acid sites bound to multiple oxophilic metal atoms in a three-fold configuration rather than OH sites adsorbed in an atop configuration on one oxophilic metal, indicating that small MOx clusters may yield sites with the highest acid strength.

  11. Ag(I) Ion Functionalized Porous Organic Polymers As a New Platform for Highly Selective Adsorption of Ethylene over Ethane

    SciTech Connect (OSTI)

    LI, Baiyan; Zhang, Yiming; Ma, Dingxuan; Wu, Zili; Ma, Shengqian

    2014-01-01

    We report herein a strategy of incorporating air stable Ag(I) ions into water stable, high surface area porous organic polymer (POP) affording significant increase in ethylene uptake capacity and extremely high Qst for ethylene (over 100 kJ/mol at low ethylene load-ing) as illustrated in the context of Ag(I) ion functionalized PAF-1, PAF-1-SO3Ag. IAST calculations using single-component-isotherm data and equimolar ethylene/ethane ratio at 296 K reveal PAF-1-SO3Ag shows exceptionally high ethylene/ethane adsorption selectivi-ty (Sads: 27 to 125), far surpassing benchmark zeolite and any other MOF reported in literature. This alongside excellent water/air stability, high ethylene uptake capacity, and mild regeneration requirements make PAF-1-SO3Ag hold promise for adsorption-based eth-ylene/ethane separations, paving a way to develop Ag(I) ion function-alized POPs as a new platform for highly selective adsorption of eth-ylene over ethane.

  12. Introduction of ?-Complexation into Porous Aromatic Framework for Highly Selective Adsorption of Ethylene over Ethane

    SciTech Connect (OSTI)

    Li, Baiyan; Zhang, Yiming; Krishna, Rajamani; Yao, Kexin; Han, Yu; Wu, Zili; Ma, Dingxuan; Shi, Zhan; Pham, Tony; Space, Brian; Liu, Jian; Thallapally, Praveen K.; Liu, Jun; Matthew, Chrzanowski; Ma, Shengqian

    2014-06-05

    We report herein a strategy of incorporating air stable Ag(I) ions into water stable, high surface area porous organic polymer (POP) affording significant increase in ethylene uptake capacity and extremely high Qst for ethylene (over 100 kJ/mol at low ethylene load-ing) as illustrated in the context of Ag(I) ion functionalized PAF-1, PAF-1-SO3Ag. IAST calculations using single-component-isotherm data and equimolar ethylene/ethane ratio at 296 K reveal PAF-1-SO3Ag shows exceptionally high ethylene/ethane adsorption selectivi-ty (Sads: 27 to 125), far surpassing benchmark zeolite and any other MOF reported in literature. This alongside excellent water/air stability, high ethylene uptake capacity, and mild regeneration requirements make PAF-1-SO3Ag hold promise for adsorption-based eth-ylene/ethane separations, paving a way to develop Ag(I) ion function-alized POPs as a new platform for highly selective adsorption of eth-ylene over ethane.

  13. Interaction of planar and nonplanar organic contaminants with coal fly ash: Effects of polar and nonpolar solvent solutions

    SciTech Connect (OSTI)

    Burgess, R.M.; Ryba, S.A.; Cantwell, M.G.; Gundersen, J.L.; Tien, R.; Perron, M.M.

    2006-08-15

    Coal fly ash has a very high sorption capacity for a variety of anthropogenic contaminants and has been used to cleanse wastewater of pollutants for approximately 40 years. Like other black carbons, the planar structure of the residual carbon in fly ash results in elevated affinities for planar organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs) and some polychlorinated biphenyls (PCBs). The present study was performed to understand better the mechanisms affecting the strong interaction between planar contaminants and coal fly ash. The removal of 10 PCBs and 10 PAHs by several fly ashes and other sorbents was evaluated under different experimental conditions to highlight the intermolecular forces influencing adsorption. Varying fly ash concentration and solvent system composition indicated that dispersive interactions were most prevalent. For the PCBs, empirical results also were compared to molecular modeling estimates of the energy necessary for the PCB molecule to assume a planar conformation (PCe). The PCe levels ranged from 8 to 25 kcal/mol, depending on the degree of ortho-substituted chlorination of the PCB. A significant correlation between PCe and PCB removal from solution was observed for the fly ashes and activated carbon, whereas the nonplanar sorbent octadecyl (C{sub 18}) indicated no relationship. These findings demonstrate the strong interaction between black carbon fly ash and planar organic contaminants. Furthermore, as exemplified by the PCBs, these results show how this interaction is a function of a contaminant's ability to assume a planar conformation.

  14. Post-treatment of fly ash by ozone in a fixed bed reactor

    SciTech Connect (OSTI)

    Kim Hougaard Pedersen; Merc Casanovas Meli; Anker Degn Jensen; Kim Dam-Johansen

    2009-01-15

    The residual carbon in fly ash produced from pulverized coal combustion can adsorb the air-entraining admixtures (AEAs) added to enhance air entrainment in concrete. This behavior of the ash can be suppressed by exposing the fly ash to oxidizing species, which oxidizes the carbon surface and thus prevents the AEA to be adsorbed. In the present work, two fly ashes have been ozonated in a fixed bed reactor and the results showed that ozonation is a potential post-treatment method that can lower the AEA requirements of a fly ash up to 6 times. The kinetics of the carbon oxidation by ozone was found to be fast. A kinetic model has been formulated, describing the passivation of carbon, and it includes the stoichiometry of the ozone consumption (0.8 mol of O{sub 3}/kg of C) and an ineffective ozone loss caused by catalytic decomposition. The simulated results correlated well with the experimental data. 28 refs., 7 figs., 3 tabs.

  15. Chloride, bromide and iodide scintillators with europium doping

    DOE Patents [OSTI]

    Zhuravleva, Mariya; Yang, Kan

    2014-08-26

    A halide scintillator material is disclosed where the halide may comprise chloride, bromide or iodide. The material is single-crystalline and has a composition of the general formula ABX.sub.3 where A is an alkali, B is an alkali earth and X is a halide which general composition was investigated. In particular, crystals of the formula ACa.sub.1-yEu.sub.yI.sub.3 where A=K, Rb and Cs were formed as well as crystals of the formula CsA.sub.1-yEu.sub.yX.sub.3 (where A=Ca, Sr, Ba, or a combination thereof and X=Cl, Br or I or a combination thereof) with divalent Europium doping where 0.ltoreq.y.ltoreq.1, and more particularly Eu doping has been studied at one to ten mol %. The disclosed scintillator materials are suitable for making scintillation detectors used in applications such as medical imaging and homeland security.

  16. Synthesis of novel MoS{sub 2}/g-C{sub 3}N{sub 4} heterojunction photocatalysts with enhanced hydrogen evolution activity

    SciTech Connect (OSTI)

    Tian, Yuming; Ge, Lei; Wang, Kaiyue; Chai, Yuesheng

    2014-01-15

    Novel MoS{sub 2}/g-C{sub 3}N{sub 4} heterojunction photocatalysts were synthesized via a simple impregnation and heating methods. The products were characterized by X-ray diffraction, transmission electron microscopy and UVvis diffuse reflectance spectra. The photocatalytic activities of MoS{sub 2}/g-C{sub 3}N{sub 4} samples were evaluated based on the hydrogen evolution experiments under visible light irradiation (? > 400 nm). The UVvis diffuse reflectance spectra revealed that the MoS{sub 2}/g-C{sub 3}N{sub 4} photocatalysts had strong absorption in the visible light region. The photocatalytic results indicated that the highest H{sub 2} evolution rate of 23.10 ?molh{sup ?1} was achieved on the 0.5 wt.% MoS{sub 2}g-C{sub 3}N{sub 4} sample, which was enhanced by 11.3 times compared to pure g-C{sub 3}N{sub 4}. This study may provide an approach to the development of novel heterojunction photocatalysts for hydrogen production under visible light irradiation. - Highlights: MoS{sub 2}/g-C{sub 3}N{sub 4} photocatalyst is obtained by simple impregnation and heating methods. and determined by XRD, TEM, UV-vis diffuse reflectance spectra. the photocatalysts had strong absorption in the visible light region. the highest H2 evolution rate was achieved on the 0.5wt% samples.

  17. Effect of landfill leachate organic acids on trace metal adsorption by kaolinite

    SciTech Connect (OSTI)

    Schroth, B.; Garrison, Sposito

    1997-02-01

    Hexanoic (hex) and fulvic acid (FA), representing early and later stages of landfill leachate evolution, were examined for influence on trace metal adsorption by a poorly crystallized kaolinite (KGa-2). Our experiments represented a model approach to examine possible reaction mechanisms in an environmentally important ternary metal-ligand-mineral surface system. Batch experiments were conducted in 0.01 mol kg(-1) NaClO4 at pH 3-8. Concentrations of metals (Cu, Cd, and Pb) and ligands were representative of those found typically in groundwater immediately downgradient of a landfill. The presence of FA resulted in enhancement of metal adsorption below pH 5, whereas the presence of hex produced no significant net change in metal uptake. Measured surface charge properties of KGa-2 were combined with binary and ternary system data in constructing a quantitative model of the system. The simple combination of binary system results was not effective in predicting the observed ternary system behavior. In both ternary systems, the addition of ternary surface complexes (TSCs) to the models resulted in a satisfactory fit to the data. Our work suggests the strong possibility that TSC involvement in surface reactions of natural adsorbents may be a useful concept.

  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. Experiences in seeking stabilizers for zirconia having hot corrosion-resistance and high temperature tetragonal (t`) stability. Interim report

    SciTech Connect (OSTI)

    Jones, R.L.

    1996-04-16

    This report summarizes the results of a research effort aimed at identifying hot corrosion-resistant stabilizers for zirconia (ZrO2) which could be used in zirconia-based thermal barrier coatings (TBCs) for engines operating on marine fuel under sea-going conditions. Among the oxides investigated were TiO2, CeO2, Y2O3, MgO, Sc2O3, In2O3, and SnO2. A brief overview of the hot corrosion of zirconia TBCs is given to illustrate the rationale used in evaluating the hot corrosion performance of the candidate oxides. The most promising stabilizer found for hot corrosion resistance was Sc2O3, or perhaps mixtures of Sc2O3 and small amounts of Y2O3. It was also discovered that Sc2Os, Y2O3- stabilized ZrO2 (SYSZ), of approx. 7 mol% of total stabilizer of which 5-20% is Y2O3, shows improved 1400 deg C stability of the tetragonal (t`) phase as compared to present-day Y2O3-stabilized ZrO2 TBC compositions. This new material may have potential for TBC use in future high temperature, high efficiency gas turbine engines.

  20. EPR and magnetic susceptibility investigation of iron-zinc-phosphate glass ceramics

    SciTech Connect (OSTI)

    Popa, A.; Stefan, R.; Bosca, M.; Dan, V.; Pop, V.; Pascuta, P.

    2013-11-13

    (Fe{sub 2}O{sub 3}){sub x}?(P{sub 2}O{sub 5}){sub 40}?(ZnO){sub 60?x} glass ceramics containing different concentrations of Fe{sub 2}O{sub 3} ranging from 1 to 20 mol% were obtained by heat treatment of glass samples at 650 C for 2 h. The structural and magnetic properties of these glass ceramics were investigated by means of electron paramagnetic resonance (EPR) and magnetic susceptibility measurements. The EPR spectra of the studied samples revealed absorptions centered at g ? 2.0 and 4.3. The compositional variations of the intensity and line width of these absorption lines was interpreted in terms of the variation in Fe{sup 3+} and Fe{sup 2+} ions concentration in the glass ceramics as well as the interaction between the iron ions. The magnetic susceptibility data evidenced the presence of both Fe{sup 3+} and Fe{sup 2+} ions, with their relative content depending on the Fe{sub 2}O{sub 3} concentration. Dipolar and superexchange interactions involving iron ions were revealed depending on the iron content of the sample.

  1. Effect of composition on electrical properties of lead-free Bi{sub 0.5}(Na{sub 0.80}K{sub 0.20}){sub 0.5}TiO{sub 3}-(Ba{sub 0.98}Nd{sub 0.02})TiO{sub 3} piezoelectric ceramics

    SciTech Connect (OSTI)

    Jaita, Pharatree; Watcharapasorn, Anucha; Jiansirisomboon, Sukanda

    2013-07-14

    Lead-free piezoelectric ceramics with the composition of (1-x)Bi{sub 0.5}(Na{sub 0.80}K{sub 0.20}){sub 0.5}TiO{sub 3}-x(Ba{sub 0.98}Nd{sub 0.02})TiO{sub 3} or (1-x) BNKT-xBNdT (with x = 0-0.20 mol fraction) have been synthesized by a conventional mixed-oxide method. The compositional dependence of phase structure and electrical properties of the ceramics were systemically studied. The optimum sintering temperature of all BNKT-BNdT ceramics was found to be 1125 Degree-Sign C. X-ray diffraction pattern suggested that BNdT effectively diffused into BNKT lattice during sintering to form a solid solution with a perovskite structure. Scanning electron micrographs showed a slight reduction of grain size when BNdT was added. It was found that BNKT-0.10BNdT ceramic exhibited optimum electrical properties ({epsilon}{sub r} = 1716, tan{delta} = 0.0701, T{sub c} = 327 Degree-Sign C, and d{sub 33} = 211 pC/N), suggesting that this composition has a potential to be one of a promising lead-free piezoelectric candidate for dielectric and piezoelectric applications.

  2. Multireference configuration interaction calculations of the first six ionization potentials of the uranium atom

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

    Bross, David H.; Parmar, Payal; Peterson, Kirk A.

    2015-11-12

    The first 6 ionization potentials (IPs) of the uranium atom have been calculated using multireference configuration interaction (MRCI+Q) with extrapolations to the complete basis set (CBS) limit using new all-electron correlation consistent basis sets. The latter were carried out with the third-order Douglas-Kroll-Hess Hamiltonian. Correlation down through the 5s5p5d electrons have been taken into account, as well as contributions to the IPs due to the Lamb shift. Spin-orbit coupling contributions calculated at the 4-component Kramers restricted configuration interaction level, as well as the Gaunt term computed at the Dirac-Hartree-Fock level, were added to the best scalar relativistic results. As amore » result, the final ionization potentials are expected to be accurate to at least 5 kcal/mol (0.2 eV), and thus more reliable than the current experimental values of IP3 through IP6.« less

  3. The Morphology of Emulsion Polymerized Latex Particles

    DOE R&D Accomplishments [OSTI]

    Wignall, G. D.; Ramakrishnan, V. R.; Linne, M. A.; Klein, A.; Sperling, L. H.; Wai, M. P.; Gelman, R. A.; Fatica, M. G.; Hoerl, R. H.; Fisher, L. W.

    1987-11-01

    Under monomer starved feed conditions, emulsion polymerization of perdeuterated methyl methacrylate and styrene in the presence of preformed polymethylmethacrylate latexes resulted in particles with a core-shell morphology, as determined by small-angle neutron scattering (SANS) analysis for a hollow sphere. The locus of polymerization of the added deuterated monomer is therefore at the particle surface. In similar measurements a statistical copolymer of styrene and methyl methacrylate was used as seed particles for further polymerization of trideuteromethyl methacrylate. The resulting polymer latex was again shown to have a core-shell morphological structure as determined by SANS. SANS experiments were also undertaken on polystyrene latexes polymerized by equilibrium swelling methods, with deuterated polymer forming the first or second step. The experiments covered a molecular weight range of 6 x 10{sup 4} 10{sup 6} the molecular weights are consistent with the experimental errors, indicating that the deuterium labeled molecules are randomly distributed in the latex. These results led to the finding that the polymer chains were constrained in the latex particles by factors of 2 to 4 from the relaxed coil dimensions. For M < 10{sup 6} g/mol SANS gave zero angle scattering intensities much higher than expected on the basis of a random distribution of labeled molecules. Several models were examined, including the possible development of core-shell structures at lower molecular weights.

  4. Characterization of self-propagating formation reactions in Ni/Zr multilayered foils using reaction heats, velocities, and temperature-time profiles

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

    Barron, S. C.; Knepper, R.; Walker, N.; Weihs, T. P.

    2011-01-11

    We report on intermetallic formation reactions in vapor-deposited multilayered foils of Ni/Zr with 70 nm bilayers and overall atomic ratios of Ni:Zr, 2 Ni:Zr, and 7 Ni:2 Zr. The sequence of alloy phase formation and the stored energy is evaluated at slow heating rates (~1 K/s) using differential scanning calorimetry (DSC) traces to 725ºC. All three chemistries initially form a Ni-Zr amorphous phase which crystallizes first to the intermetallic NiZr. The heat of reaction to the final phase is 34-36 kJ/mol atom for all chemistries. Intermetallic formation reactions are also studied at rapid heating rates (greater than 105 K/s) inmore » high temperature, self-propagating reactions which can be ignited in these foils by an electric spark. We find that reaction velocities and maximum reaction temperatures (Tmax) are largely independent of foil chemistry at 0.6 ± 0.1 m/s and 1220 ± 50 K, respectively, and that the measured Tmax is more than 200 K lower than predicted adiabatic temperatures (Tad). The difference between Tmax and Tad is explained by the prediction that transformation to the final intermetallic phases occurs after Tmax and results in the release of 20-30 % of the total heat of reaction and a delay in rapid cooling.« less

  5. Selective CO2 Capture from Flue Gas Using Metal-Organic Frameworks?A Fixed Bed Study

    SciTech Connect (OSTI)

    Liu, Jian; Tian, Jian; Thallapally, Praveen K.; McGrail, B. Peter

    2012-05-03

    It is important to capture carbon dioxide from flue gas which is considered to be the main reason to cause global warming. CO2/N2 separation by novel adsorbents is a promising method to reduce CO2 emission but effect of water and CO2/N2 selectivity is critical to apply the adsorbents into practical applications. A very well known, Metal Organic Framework, NiDOBDC (Ni-MOF-74 or CPO-27-Ni) was synthesized through a solvothermal reaction and the sample (500 to 800 microns) was used in a fixed bed CO2/N2 breakthrough study with and without H2O. The Ni/DOBDC pellet has a high CO2 capacity of 3.74 mol/kg at 0.15 bar and a high CO2/N2 selectivity of 38, which is much higher than those of reported MOFs and zeolites under dry condition. Trace amount of water can impact CO2 adsorption capacity as well as CO2/N2 selectivity for the Ni/DOBDC. However, Ni/DOBDC can retain a significant CO2 capacity and CO2/N2 selectivity at 0.15 bar CO2 with 3% RH water. These results indicate a promising future to use the Ni/DOBDC in CO2 capture from flue gas.

  6. The Role of Organic Capping Layers of Platinum Nanoparticles in Catalytic Activity of CO Oxidation

    SciTech Connect (OSTI)

    Park, Jeong Y.; Aliaga, Cesar; Renzas, J. Russell; Lee, Hyunjoo; Somorjai, Gabor A.

    2008-12-17

    We report the catalytic activity of colloid platinum nanoparticles synthesized with different organic capping layers. On the molecular scale, the porous organic layers have open spaces that permit the reactant and product molecules to reach the metal surface. We carried out CO oxidation on several platinum nanoparticle systems capped with various organic molecules to investigate the role of the capping agent on catalytic activity. Platinum colloid nanoparticles with four types of capping layer have been used: TTAB (Tetradecyltrimethylammonium Bromide), HDA (hexadecylamine), HDT (hexadecylthiol), and PVP (poly(vinylpyrrolidone)). The reactivity of the Pt nanoparticles varied by 30%, with higher activity on TTAB coated nanoparticles and lower activity on HDT, while the activation energy remained between 27-28 kcal/mol. In separate experiments, the organic capping layers were partially removed using ultraviolet light-ozone generation techniques, which resulted in increased catalytic activity due to the removal of some of the organic layers. These results indicate that the nature of chemical bonding between organic capping layers and nanoparticle surfaces plays a role in determining the catalytic activity of platinum colloid nanoparticles for carbon monoxide oxidation.

  7. Isothermal Solid-State Transformation Kinetics Applied to Pd/Cu Alloy Membrane Fabrication

    SciTech Connect (OSTI)

    Pomerantz, Natalie L; Payzant, E Andrew; Ma, Yi Hua

    2010-01-01

    In this work, time-resolved, in situ high-temperature X-ray diffraction (HT-XRD) was used to study the solid-state transformation kinetics of the formation of the fcc Pd/Cu alloy from Pd/Cu bi-layers for the purpose of fabricating sulfur tolerant Pd/Cu membranes for H2 separation. Thin layers of Pd and Cu (total ~15 wt% Cu) were deposited on porous stainless steel (PSS) with the electroless deposition method and annealed in H2 at 500, 550 and 600 C. The kinetics of the annealing process were successfully described by the Avrami nucleation and growth model showing that the annealing process was diffusion controlled and one dimensional. The activation energy for the solid-state transformation was 175 kJ/mol, which was similar to the activation energy of Pd-Cu bulk interdiffusion. Furthermore, the Avrami model was able to successfully describe the changes in permeance and activation energy observed in Pd/Cu alloy membranes during characterization as they were annealed at high temperatures.

  8. Catalysts for the selective oxidation of hydrogen sulfide to sulfur

    DOE Patents [OSTI]

    Srinivas, Girish; Bai, Chuansheng

    2000-08-08

    This invention provides catalysts for the oxidation of hydrogen sulfide. In particular, the invention provides catalysts for the partial oxidation of hydrogen sulfide to elemental sulfur and water. The catalytically active component of the catalyst comprises a mixture of metal oxides containing titanium oxide and one or more metal oxides which can be selected from the group of metal oxides or mixtures of metal oxides of transition metals or lanthanide metals. Preferred metal oxides for combination with TiO.sub.2 in the catalysts of this invention include oxides of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Hf, Ta, W, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Catalysts which comprise a homogeneous mixture of titanium oxide and niobium (Nb) oxide are also provided. A preferred method for preparing the precursor homogenous mixture of metal hydroxides is by coprecipitation of titanium hydroxide with one or more other selected metal hydroxides. Catalysts of this invention have improved activity and/or selectivity for elemental sulfur production. Further improvements of activity and/or selectivity can be obtained by introducing relatively low amounts (up to about 5 mol %)of a promoter metal oxide (preferably of metals other than titanium and that of the selected second metal oxide) into the homogeneous metal/titanium oxide catalysts of this invention.

  9. Ultrathin Palladium Membranes Prepared by a Novel Electric Field Assisted Activation

    SciTech Connect (OSTI)

    Yun, Samhun; Ko, Joon Ho; Oyama, S. Ted

    2011-03-01

    Ultra-thin Pd composite membranes with a thickness of 1 ?m were prepared by a novel electric-field assisted activation technique followed by electroless deposition of Pd on a hollow-fiber ?-alumina support. The novel activation method places Pd precursors and a reducing agent on opposite sides of a porous substrate and uses an electric field to cause migration of Pd ions to the outer surface where they are reduced to form seeds in high density in a narrow spatial region. The resulting membranes showed a high hydrogen permeance in the range of 4.05.0 10{sup ?6} mol m{sup ?2} s{sup ?1} Pa{sup ?1} and stable H{sub 2}/N{sub 2} selectivity of 30009000 during stability tests for 150 h at 733 K with H{sub 2} flow. The formation of the thin, defect-less and robust Pd layer can be ascribed to the evenly distributed Pd seeds on the support layer and the enhanced bonding between the Pd layer and the support layer resulting from the strong anchoring of the Pd seeds onto the support in the new activation step.

  10. The Vapor Pressure of 1-(2,2,3,3-Tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-prop anol

    SciTech Connect (OSTI)

    Steele, W.V.

    2002-01-29

    The vapor pressure of the compound 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol was measured over the temperature range 62 to 92 C using a Knudsen effusion technique. This compound, known as Cs-7SB, is the modifier component in the caustic-side solvent extraction process solvent. The vapor pressure is related to temperature by the equation ln(p/Pa) = (32.202 {+-} 0.265) - (12154 {+-} 93)/T, where p is the pressure, expressed in pascals; Pa is the reference pressure of 1 pascal; and T is the temperature, expressed in degrees kelvin. The derived heat of vaporization is 101.1 {+-} 0.8{sup kJ{center_dot}mol{sup 1} at 351 K. Because the vapor pressures over the temperature range of 15 to 50 C were lower than the design capabilities of the Knudsen effusion apparatus, the vapor pressures at these temperature limits were obtained by extrapolation. The estimated values are 4.6 {+-} 0.3E-05 (3.5 {+-} 0.2E-07 mm Hg) and 4.5 {+-} 0.1E-03 Pa (3.4 {+-} 0.1E-05 mm Hg) for 15 C and 50 C, respectively.

  11. Zero-point energy, tunneling, and vibrational adiabaticity in the Mu + H2 reaction

    SciTech Connect (OSTI)

    Mielke, Steven L.; Garrett, Bruce C.; Fleming, Donald G.; Truhlar, Donald G.

    2015-01-09

    Abstract: Isotopic substitution of muonium for hydrogen provides an unparalleled opportunity to deepen our understanding of quantum mass effects on chemical reactions. A recent topical review [Aldegunde et al., Mol. Phys. 111, 3169 (2013)] of the thermal and vibrationally-stateselected reaction of Mu with H2 raises a number of issues that are addressed here. We show that some earlier quantum mechanical calculations of the Mu + H2 reaction, which are highlighted in this review and which have been used to benchmark approximate methods, are in error by as much as 19% in the low-temperature limit. We demonstrate that an approximate treatment of the BornOppenheimer diagonal correction that was used in some recent studies is not valid for treating the vibrationally-state-selected reaction. We also discuss why vibrationally adiabatic potentials that neglect bend zero-point energy are not a useful analytical tool for understanding reaction rates and why vibrationally nonadiabatic transitions cannot be understood by considering tunneling through vibrationally adiabatic potentials. Finally, we present calculations on a hierarchical family of potential energy surfaces to assess the sensitivity of rate constants to the quality of the potential surface.

  12. Method for making a uranium chloride salt product

    DOE Patents [OSTI]

    Miller, William E. (Naperville, IL); Tomczuk, Zygmunt (Lockport, IL)

    2004-10-05

    The subject apparatus provides a means to produce UCl.sub.3 in large quantities without incurring corrosion of the containment vessel or associated apparatus. Gaseous Cl is injected into a lower layer of Cd where CdCl.sub.2 is formed. Due to is lower density, the CdCl.sub.2 rises through the Cd layer into a layer of molten LiCl--KCL salt where a rotatable basket containing uranium ingots is suspended. The CdCl.sub.2 reacts with the uranium to form UCl.sub.3 and Cd. Due to density differences, the Cd sinks down to the liquid Cd layer and is reused. The UCl.sub.3 combines with the molten salt. During production the temperature is maintained at about 600.degree. C. while after the uranium has been depleted the salt temperature is lowered, the molten salt is pressure siphoned from the vessel, and the salt product LiCl--KCl-30 mol % UCl.sub.3 is solidified.

  13. Synthesis and structure of K{sub 10}Tl{sub 7}: The first binary trielide containing naked pentagonal bipyramidal Tl{sub 7} clusters

    SciTech Connect (OSTI)

    Kaskel, S.; Corbett, J.D.

    2000-02-21

    The title compound is synthesized by direct fusion of the elements at 400 C followed by annealing at 330 C, quenching to room temperature, and subsequent annealing at 120 and 100 C for days to weeks. The compound crystallizes in the monoclinic space group P2{sub 1}/c (No. 14), with Z = 4, a = 10.132(1){angstrom}, b = 22.323(2){angstrom}, c = 13.376(1){angstrom}, and {beta} = 93.14(1){degree}, and consists of Tl{sub 7}{sup 7{minus}} clusters embedded in a matrix of potassium ions. The cluster is an axially compressed pentagonal bipyramid close to D{sub 5h} symmetry. The apex-apex bond distance (3.462(1){angstrom}) is little longer than the bonds in the pentagonal waist (3.183(1)--3.247(1){angstrom}). Structurally the compound is not electron-precise: K{sub 10}Tl{sub 7} has three extra electrons per Tl{sub 7} cluster and is Pauli paramagnetic ({chi}{sub 300} = 2.25 x 10{sup {minus}4} emu/mol).

  14. Highly robust hydrogen generation by bio-inspired Ir complexes for dehydrogenation of formic acid in water: Experimental and theoretical mechanistic investigations at different pH

    SciTech Connect (OSTI)

    Wang, Wan -Hui; Fujita, Etsuko; Ertem, Mehmed Z.; Xu, Shaoan; Onishi, Naoya; Manaka, Yuichi; Suna, Yuki; Kambayashi, Hide; Muckerman, James T.; Himeda, Yuichiro

    2015-07-30

    Hydrogen generation from formic acid (FA), one of the most promising hydrogen storage materials, has attracted much attention due to the demand for the development of renewable energy carriers. Catalytic dehydrogenation of FA in an efficient and green manner remains challenging. Here, we report a series of bio-inspired Ir complexes for highly robust and selective hydrogen production from FA in aqueous solutions without organic solvents or additives. One of these complexes bearing an imidazoline moiety (complex 6) achieved a turnover frequency (TOF) of 322,000 h? at 100 C, which is higher than ever reported. The novel catalysts are very stable and applicable in highly concentrated FA. For instance, complex 3 (1 ?mol) affords an unprecedented turnover number (TON) of 2,050,000 at 60 C. Deuterium kinetic isotope effect experiments and density functional theory (DFT) calculations employing a speciation approach demonstrated a change in the rate-determining step with increasing solution pH. This study provides not only more insight into the mechanism of dehydrogenation of FA but also offers a new principle for the design of effective homogeneous organometallic catalysts for H? generation from FA.

  15. Model Investigation of Temperature and Concentration Dependent Luminescence of Erbium-doped Tellurite Glasses

    SciTech Connect (OSTI)

    Ghoshal, S. K.; Sahar, M. R.; Rohani, M. S.; Tewari, H. S.

    2011-11-22

    Improving the up-conversion efficiency is the key issue in tellurite glasses. The quantum efficiency, radiative transition rate and lifetimes of excited states are greatly influenced by the optical properties of the host material, ligand field, multiphonon relaxation processes, impurities, temperature and concentration of erbium ions. We develop a comprehensive 4-level model to examine the radiative and nonradiative (NR) decay processes for the green ({sup 4}S{sub 3/2}{yields}{sup 4}I{sub 15/2}) and red ({sup 4}F{sub 9/2}{yields}{sup 4}I{sub 15/2}) emission over a temperature range of (10-340 K) and concentration range of (0.1-4.5 mol.%). Concentration dependent enhancement and thermal quenching of efficiency for up-conversion is investigated using the derived rate equations. These features are attributed to the NR energy transfer processes, trapped impurity effects, and thermal assisted hopping. The unusual nature of temperature and concentration dependent quenching effects for green and red emission is queries for further investigations. It is further suggested that to achieve higher infrared to visible up-converted efficiency in tellurite glasses the NR channels for energy and charge transfer by phonon and impurity mediated process has to be minimized. Our results on pump power dependent emission intensity, quantum efficiency, luminescence intensity, radiative lifetimes, and transition probabilities are in conformity with other experimental findings.

  16. Atomistic Insight on the Charging Energetics in Sub-nanometer Pore Supercacitors

    SciTech Connect (OSTI)

    Qiao, Rui; Huang, Jingsong; Sumpter, Bobby G; Meunier, Vincent; Feng, Guang

    2010-01-01

    Electrodes featuring sub-nanometer pores can significantly enhance the capacitance and energy density of supercapacitors. However, ions must pay an energy penalty to enter sub-nanometer pores as they have to shed part of their solvation shell. The magnitude of such energy penalty plays a key role in determining the accessibility and charging/discharging of these sub-nanometer pores. Here we report on the atomistic simulation of Na+ and Cl ions entering a polarizable slit pore with a width of 0.82 nm. We show that the free energy penalty for these ions to enter the pore is less than 14 kJ/mol for both Na+ and Cl ions. The surprisingly small energy penalty is caused by the van der Waals attractions between ion and pore walls, the image charge effects, the moderate (19-26%) de-hydration of the ions inside the pore, and the strengthened interactions between ions and their hydration water molecules in the sub-nanometer pore. The results provide strong impetus for further developing nanoporous electrodes featuring sub- nanometer pores.

  17. A novel activated carbon for supercapacitors

    SciTech Connect (OSTI)

    Shen, Haijie; Liu, Enhui; Xiang, Xiaoxia; Huang, Zhengzheng; Tian, Yingying; Wu, Yuhu; Wu, Zhilian; Xie, Hui

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer A novel activated carbon was prepared from phenol-melamine-formaldehyde resin. Black-Right-Pointing-Pointer The carbon has large surface area with microporous, and high heteroatom content. Black-Right-Pointing-Pointer Heteroatom-containing functional groups can improve the pseudo-capacitance. Black-Right-Pointing-Pointer Physical and chemical properties lead to the good electrochemical properties. -- Abstract: A novel activated carbon has been prepared by simple carbonization and activation of phenol-melamine-formaldehyde resin which is synthesized by the condensation polymerization method. The morphology, thermal stability, surface area, elemental composition and surface chemical composition of samples have been investigated by scanning electron microscope, thermogravimetry and differential thermal analysis, Brunauer-Emmett-Teller measurement, elemental analysis and X-ray photoelectron spectroscopy, respectively. Electrochemical properties have been studied by cyclic voltammograms, galvanostatic charge/discharge, and electrochemical impedance spectroscopy measurements in 6 mol L{sup -1} potassium hydroxide. The activated carbon shows good capacitive behavior and the specific capacitance is up to 210 F g{sup -1}, which indicates that it may be a promising candidate for supercapacitors.

  18. Preparation and characterization of nanostructured NiO/MnO{sub 2} composite electrode for electrochemical supercapacitors

    SciTech Connect (OSTI)

    Liu Enhui Li Wen; Li Jian; Meng Xiangyun; Ding Rui; Tan Songting

    2009-05-06

    Nanostructured nickel-manganese oxides composite was prepared by the sol-gel and the chemistry deposition combination new route. The surface morphology and structure of the composite were characterized by scanning electron microscope and X-ray diffraction. The as-synthesized NiO/MnO{sub 2} samples exhibit higher surface area of 130-190 m{sup 2} g{sup -1}. Cyclic voltammetry and galvanostatic charge/discharge measurements were applied to investigate the electrochemical performance of the composite electrodes with different ratios of NiO/MnO{sub 2}. When the mass ratio of MnO{sub 2} and NiO in composite material is 80:20, the specific capacitance value of NiO/MnO{sub 2} calculated from the cyclic voltammetry curves is 453 F g{sup -1}, for pure NiO and MnO{sub 2} are 209, 330 F g{sup -1} in 6 mol L{sup -1} KOH electrolyte and at scan rate of 10 mV s{sup -1}, respectively. The specific capacitance of NiO/MnO{sub 2} electrode is much larger than that of each pristine component. Moreover, the composite electrodes showed high power density and stable electrochemical properties.

  19. Preparation and electrochemical properties of lamellar MnO{sub 2} for supercapacitors

    SciTech Connect (OSTI)

    Yan, Jun; Wei, Tong; Cheng, Jie; Fan, Zhuangjun; Zhang, Milin

    2010-02-15

    Lamellar birnessite-type MnO{sub 2} materials were prepared by changing the pH of the initial reaction system via hydrothermal synthesis. The interlayer spacing of MnO{sub 2} with a layered structure increased gradually when the initial pH value varied from 12.43 to 2.81, while the MnO{sub 2}, composed of {alpha}-MnO{sub 2} and {gamma}-MnO{sub 2}, had a rod-like structure at pH 0.63. Electrochemical studies indicated that the specific capacitance of birnessite-type MnO{sub 2} was much higher than that of rod-like MnO{sub 2} at high discharge current densities due to the lamellar structure with fast intercalation/deintercalation of protons and high utilization of MnO{sub 2}. The initial specific capacitance of MnO{sub 2} prepared at pH 2.81 was 242.1 F g{sup -1} at 2 mA cm{sup -2} in 2 mol L{sup -1} (NH{sub 4}){sub 2}SO{sub 4} aqueous electrolyte. The capacitance increased by about 8.1% of initial capacitance after 200 cycles at a current density of 100 mA cm{sup -2}.

  20. Dimethyl ether synthesis from syngas in slurry phase

    SciTech Connect (OSTI)

    Han, Y.Z.; Fujimoto, K.; Shikata, T.

    1997-12-31

    Dimethyl ether (DME) is one of the important chemicals derived from synthesis gas. It can be widely used in syngas conversion, production of olefins, or MTG gasoline. Recently, is has been noticed as a substitute of LPG used as home fuel. In the present study, dimethyl ether was effectively synthesized from CO rich syngas (H{sub 2}/CO=1/1) over hybrid catalyst containing a Cu-Zn-Al(O) based methanol synthesis catalyst and {gamma}-alumina in an agitated slurry reactor under relatively mild reaction conditions: temperature 230--300 C, pressure 2.0--5.0 MPa, contact time 2.0--10 gram-cat.-h/mol. The catalysts used as the methanol active components were commercially available Cu-Zn-Al(O) based catalysts, BASF S385 and ICI 51-2. Two kinds of {gamma}-alumina ALO4 (standard catalyst of the Catalysis Society of Japan) and N612N (NIKKI Co., Japan) were used as the methanol dehydration components. The slurry was prepared by mixing the fine powder (<100 mesh) of catalyst components with purified n-hexadecane. The catalysts were reduced by a mixing gas containing 20% syngas and 80% nitrogen with a three-hour programmed temperature raising from room temperature to the final temperature. All products were analyzed by gas chromatographs. Results are given and discussed.

  1. New clean fuel from coal -- Direct dimethyl ether synthesis from hydrogen and carbon monoxide

    SciTech Connect (OSTI)

    Ogawa, T.; Ono, M.; Mizuguchi, M.; Tomura, K.; Shikada, T.; Ohono, Y.; Fujimoto, K.

    1997-12-31

    Dimethyl ether (DME), which has similar physical properties to propane and is easily liquefied at low pressure, has a significant possibility as a clean and non-toxic fuel from coal or coal bed methane. Equilibrium calculation also shows a big advantage of high carbon monoxide conversion of DME synthesis compared to methanol synthesis. By using a 50 kg/day DME bench scale test plant, direct synthesis of DME from hydrogen and carbon monoxide has been studied with newly developed catalysts which are very fine particles. This test plant features a high pressure three-phase slurry reactor and low temperature DME separator. DME is synthesized at temperatures around 533--553 K and at pressures around 3--5 MPa. According to the reaction stoichiometry, the same amount of hydrogen and carbon monoxide react to DME and carbon dioxide. Carbon conversion to DME is one third and the rest of carbon is converted to carbon dioxide. As a result of the experiments, make-up CO conversion is 35--50% on an once-through basis, which is extremely high compared to that of methanol synthesis from hydrogen and carbon monoxide. DME selectivity is around 60 c-mol %. Most of the by-product is CO{sub 2} with a small amount of methanol and water. No heavy by-products have been recognized. Effluent from the reactor is finally cooled to 233--253 K in a DME separator and liquid DME is recovered as a product.

  2. Polyacrylamide medium for the electrophoretic separation of biomolecules

    DOE Patents [OSTI]

    Madabhushi, Ramakrishna S.; Gammon, Stuart A.

    2003-11-11

    A polyacryalmide medium for the electrophoretic separation of biomolecules. The polyacryalmide medium comprises high molecular weight polyacrylamides (PAAm) having a viscosity average molecular weight (M.sub.v) of about 675-725 kDa were synthesized by conventional red-ox polymerization technique. Using this separation medium, capillary electrophoresis of BigDye DNA sequencing standard was performed. A single base resolution of .about.725 bases was achieved in .about.60 minute in a non-covalently coated capillary of 50 .mu.m i.d., 40 cm effective length, and a filed of 160 V/cm at 40.degree. C. The resolution achieved with this formulation to separate DNA under identical conditions is much superior (725 bases vs. 625 bases) and faster (60 min. vs. 75 min.) to the commercially available PAAm, such as supplied by Amersham. The formulation method employed here to synthesize PAAm is straight-forward, simple and does not require cumbersome methods such as emulsion polymerizaiton in order to achieve very high molecular weights. Also, the formulation here does not require separation of PAAm from the reaction mixture prior to reconstituting the polymer to a final concentration. Furthermore, the formulation here is prepared from a single average mol. wt. PAAm as opposed to the mixture of two different average mo. wt. PAAm previously required to achieve high resolution.

  3. Pulse radiolysis studies of the reaction of nitrogen dioxide with the vitamin B₁₂ complexes Cob(II)alamin and nitrocobalamin

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

    Brasch, Nicola E.; Cabelli, Diane E.; Dassanayake, Rohan S.

    2014-10-06

    Although now recognized to be an important reactive nitrogen species in biological systems that modifies the structures of proteins, DNA and lipids, there few studies on the reactivity of ˙NO2, including the reactions between ˙NO2 and transition metal complexes. We report kinetic studies on the reaction of ˙NO2 with two forms of vitamin B12 – cob(II)alamin and nitrocobalamin. UV-vis spectroscopy and HPLC analysis of the product solution show that ˙NO2 cleanly oxidizes the metal center of cob(II)alamin to form nitrocobalamin, with a second-order rate constant of (3.5 ± 0.3) × 10⁸ M⁻¹ s ⁻¹ (pH 7.0 and 9.0, RT, Imore » = 0.20 M). The stoichiometry of the reaction is 1:1. No reaction is detected by UV-vis spectroscopy and by HPLC analysis of the product solution when nitrocobalamin is exposed to up to 2.0 mol equiv.˙NO2.« less

  4. Capture and isotopic exchange method for water and hydrogen isotopes on zeolite catalysts up to technical scale for pre-study of processing highly tritiated water

    SciTech Connect (OSTI)

    Michling, R.; Braun, A.; Cristescu, I.; Dittrich, H.; Gramlich, N.; Lohr, N.; Glugla, M.; Shu, W.; Willms, S.

    2015-03-15

    Highly tritiated water (HTW) may be generated at ITER by various processes and, due to the excessive radio toxicity, the self-radiolysis and the exceedingly corrosive property of HTW, a potential hazard is associated with its storage and process. Therefore, the capture and exchange method for HTW utilizing Molecular Sieve Beds (MSB) was investigated in view of adsorption capacity, isotopic exchange performance and process parameters. For the MSB, different types of zeolite were selected. All zeolite materials were additionally coated with platinum. The following work comprised the selection of the most efficient zeolite candidate based on detailed parametric studies during the H{sub 2}/D{sub 2}O laboratory scale exchange experiments (about 25 g zeolite per bed) at the Tritium Laboratory Karlsruhe (TLK). For the zeolite, characterization analytical techniques such as Infrared Spectroscopy, Thermogravimetry and online mass spectrometry were implemented. Followed by further investigation of the selected zeolite catalyst under full technical operation, a MSB (about 22 kg zeolite) was processed with hydrogen flow rates up to 60 mol*h{sup -1} and deuterated water loads up to 1.6 kg in view of later ITER processing of arising HTW. (authors)

  5. Experimental Observation of Nuclear Reactions in Palladium and Uranium

    SciTech Connect (OSTI)

    J. Dufour; D. Murat; X. Dufour; J. Foos

    2001-11-12

    By submitting various metals (Pd, U) containing hydrogen (from 2000 to 700 000 atoms of hydrogen for 1 000 000 atoms of the host metal) to the combined action of electrical currents and magnetic fields, we have observed a sizeable exothermal effect (from 0.1 to 8 W for 500 mg of metal used). This effect is beyond experimental errors, the energy output being typically 130 to 250{percent} of the energy input and not of chemical origin (exothermal effect in the range of 7000 MJ/mol of metal in the case of palladium and of 60 MJ/mol in the case of uranium). New chemical species also appear in the processes metals. It has been shown by a QED calculation that resonances of long lifetime (s), nuclear dimensions (fm), and low energy of formation (eV) could exist. This concept seems to look like the 'shrunken hydrogen atoms' proposed by various authors. It is indeed very different in two ways (a) being a metastable state, it needs energy to be formed (a few eV) and reverts to normal hydrogen after a few seconds, liberating back its energy of formation (it is thus not the source of the energy observed); (b) its formation can be described as the electron spin/proton nuclear spin interaction becoming first order in the lattice environment (whereas it is third order in a normal hydrogen atom). Moreover, we consider that the hydrex cannot yield a neutron because this reaction is strongly endothermic. To explain our results, we put forward the following working hypothesis: In a metal lattice and under proper conditions, the formation of such resonances (metastable state) could be favored. We propose to call them HYDREX, and we assume that they are actually formed in cold fusion (CF) and low-energy nuclear reaction (LENR) experiments. Once formed, a number of HYDREX could gather around a nucleus of the lattice to form a cluster of nuclear size and of very long life time compared to nuclear time (10{sup -22} s). In this cluster, nuclear rearrangements could take place, yielding mainly {sup 4}He, nuclei of atomic masses smaller than that of the host metal and small amounts of {sup 3}He and tritium. Because this nuclear rearrangement is a many-body reaction, the products formed should be stable products in their ground states, most of the reaction energy being carried away as kinetic energy by the alpha particles formed. The HYDREX hypothesis describes CF and LENR as fundamentally the same phenomenon, which we propose to call NUCLEAR CATALYSIS. Depending on the conditions of a CF or LENR experiment, the products formed may look very different, but the initial step is always the synthesis of HYDREX. When this synthesis is mastered, CF and LENR experiments should become fully reproducible.

  6. O and H diffusion in uraninite: Implications for fluid-uraninite interactions, nuclear waste disposal, and nuclear forensics

    SciTech Connect (OSTI)

    Fayek, Mostafa [University of Manitoba, Canada; Anovitz, Lawrence {Larry} M [ORNL; Cole, David [Ohio State University; Bostick, Debra A [ORNL

    2011-01-01

    Diffusion coefficients for oxygen and hydrogen were determined from a series of natural uraninite H2O experiments between 50 and 700 C. Under hydrous conditions there are two diffusion mechanisms: (1) an initial extremely fast-path diffusion mechanism that overprinted the oxygen isotopic composition of the entire crystals regardless of temperature and (2) a slower volume-diffusive mechanism dominated by defect clusters that displace or eject nearest neighbor oxygen atoms to form two interstitial sites and two partial vacancies, and by vacancy migration. Using the volume diffusion coefficients in the temperature range of 400 600 C, diffusion coefficients for oxygen can be represented by D = 1.90e5 exp (123,382 J/RT) cm2/s and for temperatures between 100 and 300 C the diffusion coefficients can be represented by D = 1.95e10 exp (62484 J/ RT) cm2/s, where the activation energies for uraninite are 123.4 and 62.5 kJ/mol, respectively. Hydrogen diffusion in uraninite appears to be controlled by similar mechanisms as oxygen. Using the volume diffusion coefficients for temperatures between 50 and 700 C, diffusion coefficients for hydrogen can be represented by D = 9.28e6 exp (156,528 J/RT) cm2/s for temperatures between 450 and 700 C and D = 1.39e14 exp (34518 J/RT) cm2/s for temperatures between 50 and 400 C, where the activation energies for uraninite are 156.5 and 34.5 kJ/mol, respectively. Results from these new experiments have implications for isotopic exchange during natural UO2 water interactions. The exceptionally low d18O values of natural uraninites (i.e. 32& to 19.5&) from unconformity-type uranium deposits in Saskatchewan, in conjunction with theoretical and experimental uraninite water and UO3 water fractionation factors, suggest that primary uranium mineralization is not in oxygen isotopic equilibrium with coeval clay and silicate minerals. The low d18O values have been interpreted as resulting from the low temperature overprinting of primary uranium mineralization in the presence of relatively modern meteoric fluids having d18O values of ca. 18&, despite petrographic and U Pb isotope data that indicate limited alteration. Our data show that the anomalously low oxygen isotopic composition of the uraninite from the Athabasca Basin can be due to meteoric water overprinting under reducing conditions, and meteoric water or groundwater can significantly affect the oxygen isotopic composition of spent nuclear fuel in a geologic repository, with minimal change to the chemical composition or texture. Moreover, the rather fast oxygen and hydrogen diffusion coefficients for uraninite, especially at low temperatures, suggest that oxygen and hydrogen diffusion may impart characteristic isotopic signals that can be used to track the route of fissile material.

  7. Rotationally resolved spectroscopy of a librational fundamental band of hydrogen fluoride tetramer

    SciTech Connect (OSTI)

    Blake, Thomas A.; Sharpe, Steven W.; Xantheas, Sotiris S.

    2000-07-08

    The rotationally resolved spectrum of a fundamental band of hydrogen fluoride tetramer has been recorded using a pulsed slit-jet, diode laser spectrometer. The band has a parallel rotational structure and is assigned as the H-F out-of-plane libration fundamental with A{sub u} symmetry. Ninety-five ground state combination differences were fit to a symmetric top Hamiltonian to give the following ground state rotational constants: B{sup ''}=0.132 081(7) cm{sup -1}, D{sub J}{sup ''}=7.1(7)x10{sup -7} cm{sup -1}, D{sub JK}{sup ''}=-9(2)x10{sup -7} cm{sup -1}, H{sub JJJ}{sup ''}=6(2)x10{sup -10} cm{sup -1}, H{sub JJK}{sup ''}=9(7)x10{sup -10} cm{sup -1}, H{sub JKK}{sup ''}=-1.3(8)x10{sup -10} cm{sup -1}. A total of 190 transitions were fit to determine the upper state spectroscopic constants: v{sub 4}=714.7849(1) cm{sup -1}, B{sup '}=0.129 634(5) cm{sup -1}, {delta}(C-B)=0.001 344 cm{sup -1}, D{sub J}{sup '}=6.4(5)x10{sup -7} cm{sup -1}, D{sub JK}{sup '}=-4.5(6)x10{sup -7} cm{sup -1}, {delta}D{sub K}=2.92(8)x10{sup -6} cm{sup -1}, H{sub JJJ}{sup '}=3(1)x10{sup -10} cm{sup -1}, H{sub JKK}{sup '}=-1.55(6)x10{sup -8} cm{sup -1}; {delta}H{sub KKK}=-4.65(6)x10{sup -8} cm{sup -1}. Furthermore, a perpendicular band centered at 752.7 cm{sup -1} was observed. The band has a rotational line spacing that gives an approximate B{sup ''} value of 0.132 cm{sup -1}; it has been assigned as the E{sub u} symmetry, H-F in-plane libration fundamental of the HF tetramer. Finally, a parallel band was observed at 741.0 cm{sup -1} with B{sup ''}=0.076 cm{sup -1} and has been assigned as the A{sup ''} symmetry, H-F out-of-plane libration fundamental of the HF pentamer. Structural parameters and harmonic vibrational frequencies are estimated from first-principles, correlated MP2 and CCSD(T) calculations. These are the largest calculations performed to date for this system with respect to both orbital basis set and level of electron correlation. The CCSD(T) harmonic frequencies are, in particular, the first reported for the tetramer at this level of theory. Based on our results, we suggest ''best estimates'' of R{sub FF}=2.51 Aa, r{sub HF}=0.947 Aa, and {theta}{sub HFF}=9.7 degree sign for the structural parameters and a range for D{sub e} of 27.4 to 28.1 kcal/mol (D{sub 0}=19.7 to 20.4 kcal/mol) for the parameters and for the energy of the tetramer dissociating into four monomers. (c) 2000 American Institute of Physics.

  8. Remote Sensing and Sea-Truth Measurements of Methane Flux to the Atmosphere (HYFLUX project)

    SciTech Connect (OSTI)

    Ian MacDonald

    2011-05-31

    A multi-disciplinary investigation of distribution and magnitude of methane fluxes from seafloor gas hydrate deposits in the Gulf of Mexico was conducted based on results obtained from satellite synthetic aperture radar (SAR) remote sensing and from sampling conducted during a research expedition to three sites where gas hydrate occurs (MC118, GC600, and GC185). Samples of sediments, water, and air were collected from the ship and from an ROV submersible using sediments cores, niskin bottles attached to the ROV and to a rosette, and an automated sea-air interface collector. The SAR images were used to quantify the magnitude and distribution of natural oil and gas seeps that produced perennial oil slicks on the ocean surface. A total of 176 SAR images were processed using a texture classifying neural network algorithm, which segmented the ocean surface into oil-free and oil-covered water. Geostatistical analysis indicates that there are a total of 1081 seep formations distributed over the entire Gulf of Mexico basin. Oil-covered water comprised an average of 780.0 sq. km (sd 86.03) distributed with an area of 147,370 sq. km. Persistent oil and gas seeps were also detected with SAR sampling on other ocean margins located in the Black Sea, western coast of Africa, and offshore Pakistan. Analysis of sediment cores from all three sites show profiles of sulfate, sulfide, calcium and alkalinity that indicated anaerobic oxidation of methane with precipitation of authigenic carbonates. Difference among the three sampling sites may reflect the relative magnitude of methane flux. Methane concentrations in water column samples collected by ROV and rosette deployments from MC118 ranged from {approx}33,000 nM at the seafloor to {approx}12 nM in the mixed layer with isolated peaks up to {approx}13,670 nM coincident with the top of the gas hydrate stability field. Average plume methane, ethane, and propane concentrations in the mixed layer are 7, 630, and 9,540 times saturation, respectively. Based on the contemporaneous wind speeds at this site, contemporary estimates of the diffusive fluxes from the mixed layer to the atmosphere for methane, ethane, and propane are 26.5, 2.10, and 2.78 {micro}mol/m{sup 2}d, respectively. Continuous measurements of air and sea surface concentrations of methane were made to obtain high spatial and temporal resolution of the diffusive net sea-to-air fluxes. The atmospheric methane fluctuated between 1.70 ppm and 2.40 ppm during the entire cruise except for high concentrations (up to 4.01 ppm) sampled during the end of the occupation of GC600 and the transit between GC600 and GC185. Results from interpolations within the survey areas show the daily methane fluxes to the atmosphere at the three sites range from 0.744 to 300 mol d-1. Considering that the majority of seeps in the GOM are deep (>500 m), elevated CH{sub 4} concentrations in near-surface waters resulting from bubble-mediated CH4 transport in the water column are expected to be widespread in the Gulf of Mexico.

  9. Hydrogenation of Acetylene-Ethylene Mixtures over Pd and Pd-Ag Alloys: First-Principles Based Kinetic Monte Carlo Simulations

    SciTech Connect (OSTI)

    Mei, Donghai; Neurock, Matthew; Smith, C Michael

    2009-10-22

    The kinetics for the selective hydrogenation of acetylene-ethylene mixtures over model Pd(111) and bimetallic Pd-Ag alloy surfaces were examined using first principles based kinetic Monte Carlo (KMC) simulations to elucidate the effects of alloying as well as process conditions (temperature and hydrogen partial pressure). The mechanisms that control the selective and unselective routes which included hydrogenation, dehydrogenation and C-?C bond breaking pathways were analyzed using first-principle density functional theory (DFT) calculations. The results were used to construct an intrinsic kinetic database that was used in a variable time step kinetic Monte Carlo simulation to follow the kinetics and the molecular transformations in the selective hydrogenation of acetylene-ethylene feeds over Pd and Pd-Ag surfaces. The lateral interactions between coadsorbates that occur through-surface and through-space were estimated using DFT-parameterized bond order conservation and van der Waal interaction models respectively. The simulation results show that the rate of acetylene hydrogenation as well as the ethylene selectivity increase with temperature over both the Pd(111) and the Pd-Ag/Pd(111) alloy surfaces. The selective hydrogenation of acetylene to ethylene proceeds via the formation of a vinyl intermediate. The unselective formation of ethane is the result of the over-hydrogenation of ethylene as well as over-hydrogenation of vinyl to form ethylidene. Ethylidene further hydrogenates to form ethane and dehydrogenates to form ethylidyne. While ethylidyne is not reactive, it can block adsorption sites which limit the availability of hydrogen on the surface and thus act to enhance the selectivity. Alloying Ag into the Pd surface decreases the overall rated but increases the ethylene selectivity significantly by promoting the selective hydrogenation of vinyl to ethylene and concomitantly suppressing the unselective path involving the hydrogenation of vinyl to ethylidene and the dehydrogenation ethylidene to ethylidyne. This is consistent with experimental results which suggest only the predominant hydrogenation path involving the sequential addition of hydrogen to form vinyl and ethylene exists over the Pd-Ag alloys. Ag enhances the desorption of ethylene and hydrogen from the surface thus limiting their ability to undergo subsequent reactions. The simulated apparent activation barriers were calculated to be 32-44 kJ/mol on Pd(111) and 26-31 kJ/mol on Pd-Ag/Pd(111) respectively. The reaction was found to be essentially first order in hydrogen over Pd(111) and Pd-Ag/Pd(111) surfaces. The results reveal that increases in the hydrogen partial pressure increase the activity but decrease ethylene selectivity over both Pd and Pd-Ag/Pd(111) surfaces. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  10. Toward Molecular Catalysts by Computer

    SciTech Connect (OSTI)

    Raugei, Simone; DuBois, Daniel L.; Rousseau, Roger J.; Chen, Shentan; Ho, Ming-Hsun; Bullock, R. Morris; Dupuis, Michel

    2015-02-17

    Rational design of molecular catalysts requires a systematic approach to designing ligands with specific functionality and precisely tailored electronic and steric properties. It then becomes possible to devise computer protocols to predict accurately the required properties and ultimately to design catalysts by computer. In this account we first review how thermodynamic properties such as oxidation-reduction potentials (E0), acidities (pKa), and hydride donor abilities (ΔGH-) form the basis for a systematic design of molecular catalysts for reactions that are critical for a secure energy future (hydrogen evolution and oxidation, oxygen and nitrogen reduction, and carbon dioxide reduction). We highlight how density functional theory allows us to determine and predict these properties within “chemical” accuracy (~ 0.06 eV for redox potentials, ~ 1 pKa unit for pKa values, and ~ 1.5 kcal/mol for hydricities). These quantities determine free energy maps and profiles associated with catalytic cycles, i.e. the relative energies of intermediates, and help us distinguish between desirable and high-energy pathways and mechanisms. Good catalysts have flat profiles that avoid high activation barriers due to low and high energy intermediates. We illustrate how the criterion of a flat energy profile lends itself to the prediction of design points by computer for optimum catalysts. This research was carried out in the Center for Molecular Electro-catalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory (PNNL) is operated for the DOE by Battelle.

  11. Effect of antisymmetric CH stretching excitation on the dynamics of O({sup 1}D) + CH{sub 4} ? OH + CH{sub 3}

    SciTech Connect (OSTI)

    Pan, Huilin; Yang, Jiayue; Zhang, Dong; Shuai, Quan; Jiang, Bo [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China)] [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China); Dai, Dongxu; Wu, Guorong, E-mail: wugr@dicp.ac.cn, E-mail: xmyang@dicp.ac.cn; Yang, Xueming, E-mail: wugr@dicp.ac.cn, E-mail: xmyang@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China) [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China)

    2014-04-21

    The effect of antisymmetric CH stretching excitation of CH{sub 4} on the dynamics and reactivity of the O({sup 1}D) + CH{sub 4} ? OH + CD{sub 3} reaction at the collision energy of 6.10 kcal/mol has been investigated using the crossed-beam and time-sliced velocity map imaging techniques. The antisymmetric CH stretching mode excited CH{sub 4} molecule was prepared by direct infrared excitation. From the measured images of the CH{sub 3} products with the infrared laser on and off, the product translational energy and angular distributions were derived for both the ground and vibrationally excited reactions. Experimental results show that the vibrational energy of the antisymmetric stretching excited CH{sub 4} reagent is channeled exclusively into the vibrational energy of the OH co-products and, hence, the OH products from the excited-state reaction are about one vibrational quantum hotter than those from the ground-state reaction, and the product angular distributions are barely affected by the vibrational excitation of the CH{sub 4} reagent. The reactivity was found to be suppressed by the antisymmetric stretching excitation of CH{sub 4} for all observed CH{sub 3} vibrational states. The degree of suppression is different for different CH{sub 3} vibrational states: the suppression is about 40%60% for the ground state and the umbrella mode excited CH{sub 3} products, while for the CH{sub 3} products with one quantum symmetric stretching mode excitation, the suppression is much less pronounced. In consequence, the vibrational state distribution of the CH{sub 3} product from the excited-state reaction is considerably different from that of the ground-state reaction.

  12. STUDIES OF THE SPONTANEOUS COMBUSTION OF LOW RANK COALS AND LIGNITES

    SciTech Connect (OSTI)

    Joseph M. Okoh; Joseph N.D. Dodoo

    2005-07-26

    Spontaneous combustion has always been a problem in coal utilization especially in the storage and transportation of coal. In the United States, approximately 11% of underground coal mine fires are attributed to spontaneous coal combustion. The incidence of such fires is expected to increase with increased consumption of lower rank coals. The cause is usually suspected to be the reabsorption of moisture and oxidation. To understand the mechanisms of spontaneous combustion this study was conducted to (1) define the initial and final products during the low temperature (10 to 60 C) oxidation of coal at different partial pressures of O{sub 2}, (2) determine the rate of oxidation, and (3) measure the reaction enthalpy. The reaction rate (R) and propensity towards spontaneous combustion were evaluated in terms of the initial rate method for the mass gained due to adsorbed O{sub 2}. Equipment that was used consisted of a FT-IR (Fourier Transform-Infrared Spectrometer, Perkin Elmer), an accelerated surface area porosimeter (ASAP, Micromeritics model 2010), thermogravimetric analyzer (TGA, Cahn Microbalance TG 121) and a differential scanning calorimeter (DSC, Q1000, thermal analysis instruments). Their combination yielded data that established a relation between adsorption of oxygen and reaction enthalpy. The head space/ gas chromatograph/ mass spectrometer system (HS/GC/MS) was used to identify volatiles evolved during oxidation. The coal samples used were Beulah lignite and Wyodak (sub-bituminous). Oxygen (O{sub 2}) absorption rates ranged from 0.202 mg O{sub 2}/mg coal hr for coal sample No.20 (Beulah pyrolyzed at 300 C) to 6.05 mg O{sub 2}/mg coal hr for coal sample No.8 (wyodak aged and pyrolyzed at 300 C). Aging of coal followed by pyrolysis was observed to contribute to higher reaction rates. Reaction enthalpies ranged from 0.42 to 1580 kcal/gm/mol O{sub 2}.

  13. Silica and boron-containing ultraphosphate laser glass with low concentration quenching and improved thermal shock resistance

    DOE Patents [OSTI]

    Cook, Lee M.; Stokowski, Stanley E.

    1987-04-28

    Neodymium-doped phosphate glasses having a refractive index, nd>1.520; an Abbe number, Vd, <60; a density <3.0 g/cm.sup.3, a thermal expansion coefficient, .alpha., .ltoreq.110.times.10.sup.-7 .degree.C..sup.-1 ; a Young's Modulus, E, <70.times.10.sup.3 N/mm.sup.2 ; a Poisson's Ratio, .nu., <0.28; a thermal conductivity, K, >0.5 W/m.multidot.K, a thermal FOM=(1-.nu.).multidot.K/.alpha.E>0.7, consisting essentially of, in mol. %: P.sub.2 O.sub.5 : 40-70% SiO.sub.2 : 0-20% B.sub.2 O.sub.3 : 5-20% Sum SiO.sub.2 +B.sub.2 O.sub.3 : 5-35% Sum Li.sub.2 O+Na.sub.2 O+K.sub.2 O: 5-20% Sum La.sub.2 O.sub.3 +Nd.sub.2 O.sub.3 : 3-10% Sum MgO+CaO+SrO+BaO+ZnO: 0-10% and preferably containing an amount of Nd.sub.2 O.sub.3 effective for laser activity having an emission cross-section, .sigma., >3.5.times.10.sup.-20 cm.sup.2 ; a fluorescence linewidth (.DELTA..lambda..sub.f1)<23.5 nm; a first e-folding time of the Nd.sup.3+ fluorescence at 0.5 wt. % Nd.sub.2 O.sub.3 >375 .mu.sec, and a first e-folding time of the Nd.sup.3+ fluorescence at 10 wt. % >175 .mu.sec at 10 wt. %, have very low self-concentration quenching rates.

  14. A Joint Theory and Experimental Project in the Synthesis and Testing of Porous COFs for On-Board Vehicular Hydrogen Storage

    SciTech Connect (OSTI)

    Yaghi, Omar M.; Goddard, William A.

    2013-06-29

    Conventional storage of large amounts of hydrogen in its molecular form is difficult and expensive because it requires employing either extremely high pressure gas or very low temperature liquid. Because of the importance of hydrogen as a fuel, the DOE has set system targets for hydrogen storage of gravimetric (5.5 wt%) and volumetric (40 g/L) densities to be achieved by 2015. From our continuous efforts on hydrogen storage, it is believed that metalation of highly porous solids with high-valence metals is promising and provides a rational direction to realize high volumetric hydrogen density near room temperature. This grant was focused on the study of high surface area covalent organic frameworks (COFs) with these specific objectives (1) to introduce potential metal binding sites through the COF synthesis and (2) to implement metalation experiments and evaluate their respective hydrogen adsorption properties. To maximize our efforts, simulation calculations were also performed (prior to experiments) for the prediction of binding enthalpy of hydrogen for molecular building units containing transition metals and promising COF structures to increase volumetric hydrogen uptake at room temperature. In this effort, first molecular building units with optimal binding energy for hydrogen storage (20 kJ/mol) were designed by quantum mechanical (QM) methods. Employing these results, it was revealed that one of metalated COFs takes up 60 g/L (total) of H2 at 100 bar and 298 K. To realize proposed COF structures, chemistry of COF synthesis has been developed; for instance, new air stable COFs were synthesized via hydrazone (COF-41 to 43) and imine condensation (COF-301, 320, 340, and 366) and some of them were tested the effect on metalation. Finally, a new triazine COF with high volumetric hydrogen uptake capacity was presented as a proposed future direction.

  15. Hydrogen storage in sodium aluminum hydride.

    SciTech Connect (OSTI)

    Ozolins, Vidvuds; Herberg, J.L.; McCarty, Kevin F.; Maxwell, Robert S.; Stumpf, Roland Rudolph; Majzoub, Eric H.

    2005-11-01

    Sodium aluminum hydride, NaAlH{sub 4}, has been studied for use as a hydrogen storage material. The effect of Ti, as a few mol. % dopant in the system to increase kinetics of hydrogen sorption, is studied with respect to changes in lattice structure of the crystal. No Ti substitution is found in the crystal lattice. Electronic structure calculations indicate that the NaAlH{sub 4} and Na{sub 3}AlH{sub 6} structures are complex-ionic hydrides with Na{sup +} cations and AlH{sub 4}{sup -} and AlH{sub 6}{sup 3-} anions, respectively. Compound formation studies indicate the primary Ti-compound formed when doping the material at 33 at. % is TiAl{sub 3} , and likely Ti-Al compounds at lower doping rates. A general study of sorption kinetics of NaAlH{sub 4}, when doped with a variety of Ti-halide compounds, indicates a uniform response with the kinetics similar for all dopants. NMR multiple quantum studies of solution-doped samples indicate solvent interaction with the doped alanate. Raman spectroscopy was used to study the lattice dynamics of NaAlH{sub 4}, and illustrated the molecular ionic nature of the lattice as a separation of vibrational modes between the AlH{sub 4}{sup -} anion-modes and lattice-modes. In-situ Raman measurements indicate a stable AlH{sub 4}{sup -} anion that is stable at the melting temperature of NaAlH{sub 4}, indicating that Ti-dopants must affect the Al-H bond strength.

  16. Synthesis and structural studies of multi-component strontium zinc silicate glass-ceramics

    SciTech Connect (OSTI)

    Tiwari, Babita; Pandey, M.; Kothiyal, G. P.; Gadkari, S. C.

    2013-02-05

    Glass having composition 40SrO-10ZnO-40SiO{sub 2}-2B{sub 2}O{sub 3}-2Al{sub 2}O{sub 3}-2TiO{sub 2}-2Cr{sub 2}O{sub 3}-2Y{sub 2}O{sub 3}, (mol %) was prepared by melt-quench technique and converted into glass-ceramics by subjecting it to varying heat treatments. Thermal properties were measured by thermo-mechanical analyzer and differential thermal analyzer. The XRD revealed that initially Sr{sub 2}ZnSi{sub 2}O{sub 7} phase at lower temperature and later SrSiO{sub 3}/Sr{sub 3}Si{sub 3}O{sub 9} phase crystallized. The structural elucidation by Raman spectroscopy shows the presence of mainly Q{sup 1} structural units along with Q{sup 2} and Q{sup 0} units in the base glass. Raman spectra revealed that during crystallization initially crystalline phase having Q{sup 1} structural units (corresponding to Sr{sub 2}ZnSi{sub 2}O{sub 7} phase) are formed and later crystalline phase having Q{sup 2} structural units with 3 member ring type structure crystallizes. Thus, Raman spectroscopy and XRD together confirm that in early stage of crystallization, Sr{sub 2}ZnSi{sub 2}O{sub 7} phase and later Sr{sub 3}Si{sub 3}O{sub 9} phase formed in the glass-ceramics.

  17. Low-temperature superacid catalysis: Reactions of n - butane and propane catalyzed by iron- and manganese-promoted sulfated zirconia

    SciTech Connect (OSTI)

    Tsz-Keung, Cheung; d`Itri, J.L.; Lange, F.C.; Gates, B.C.

    1995-12-31

    The primary goal of this project is to evaluate the potential value of solid superacid catalysts of the sulfated zirconia type for light hydrocarbon conversion. The key experiments catalytic testing of the performance of such catalysts in a flow reactor fed with streams containing, for example, n-butane or propane. Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion of n-butane at atmospheric pressure, 225-450{degrees}C, and n-butane partial pressures in the range of 0.0025-0.01 atm. At temperatures <225{degrees}C, these reactions were accompanied by cracking; at temperatures >350{degrees}C, cracking and isomerization occurred. Catalyst deactivation, resulting at least in part from coke formation, was rapid. The primary cracking products were methane, ethane, ethylene, and propylene. The observation of these products along with an ethane/ethylene molar ratio of nearly 1 at 450{degrees}C is consistent with cracking occurring, at least in part, by the Haag-Dessau mechanism, whereby the strongly acidic catalyst protonates n-butane to give carbonium ions. The rate of methane formation from n-butane cracking catalyzed by Fe- and Mn-promoted sulfated zirconia at 450{degrees}C was about 3 x 10{sup -8} mol/(g of catalyst {center_dot}s). The observation of butanes, pentanes, and methane as products is consistent with Olah superacid chemistry, whereby propane is first protonated by a very strong acid to form a carbonium ion. The carbonium ion then decomposes into methane and an ethyl cation which undergoes oligocondensation reactions with propane to form higher molecular weight alkanes. The results are consistent with the identification of iron- and manganese-promoted sulfated zirconia as a superacid.

  18. Cracking of n-butane catalyzed by iron- and maganese-promoted sulfated zirconia

    SciTech Connect (OSTI)

    Cheung, T.K.; d`Itri, J.L.; Gates, B.C.

    1995-05-01

    Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion of n-butane at atmospheric pressure and n-butane partial pressures in the range of 0.0025-0.01 atm. At temperatures <225{degrees}C, the significant reactions were isomerization and disproportionation; in the range of 225-300{degrees}C, these reactions were accompanied by cracking, and at temperatures >350{degrees}C, cracking and isomerization occurred. Catalyst deactivation, resulting at least in part from coke formation, was rapid. The primary cracking products were methane, ethane, ethylene, and propylene. The observation of these products along with an ethane/ethylene molar ratio of nearly 1 at 450{degrees}C is consistent with cracking occurring, at least in part, by the Haag-Dessau mechanism, whereby the strongly acidic catalyst protonates n-butane to give carbonium ions. The rate of methane formation from n-butane cracking catalyzed by Fe- and Mn-promoted sulfated zirconia at 450{degrees}C was about 3 x 10{sup {minus}9}mol/(g of catalyst {center_dot}s). This comparison suggests that the catalytic activity of the promoted sulfated zirconia at 450{degrees}C is about the same as that of the zeolite, although its activity for n-butane isomerization and disproportionation at temperatures <100{degrees}C is orders of magnitude greater than those of zeolites. Thus the indication of superacidity of the promoted sulfated zirconia does not extend to high temperatures. The results raise questions about the nature of the presumed superacidity: perhaps the low-temperature reactions may involve catalyst functions other than the acidic function responsible for high-temperature cracking reactions or perhaps superacidic sites may be very rapidly poisoned at cracking temperatures. 14 refs., 8 figs., 3 tabs.

  19. Differential Effects Of Octanoate And Heptanoate On Myocardial Metabolism During Extracorporeal Membrane Oxygenation In An Infant Swine Model

    SciTech Connect (OSTI)

    Kajimoto, Masaki; Ledee, Dolena R.; Isern, Nancy G.; Olson, Aaron; Des Rosiers, Christine; Portman, Michael A.

    2015-10-01

    Background: Nutritional energy support during extracorporeal membrane oxygenation (ECMO) should promote successful myocardial adaptation and eventual weaning from the ECMO circuit. Fatty acids (FAs) are a major myocardial energy source, and medium-chain FAs (MCFAs) are easily taken up by cell and mitochondria without membrane transporters. Oddnumbered MCFAs supply carbons to the citric acid cycle (CAC) via anaplerotic propionyl-CoA as well as acetyl-CoA, the predominant betaoxidation product for even-numbered MCFA. Theoretically, this anaplerotic pathway enhances carbon entry into the CAC, and provides superior energy state and preservation of protein synthesis. We tested this hypothesis in an immature swine model undergoing ECMO. Methods: Fifteen male Yorkshire pigs (26-45 days old) with 8-hour ECMO were received either normal saline, heptanoate (odd-numbered MCFA) or octanoate (even-numbered MCFA) at 2.3 ?mol/kg body wt/min as MCFAs systemically during ECMO (n = 5 per group). The 13-Carbon (13C)-labeled substrates ([2-13C]lactate, [5,6,7-13C3]heptanoate and [U-13C6]leucine) were systemically infused as metabolic markers for the final 60 minutes before left ventricular tissue extraction. Extracted tissues were analyzed for the 13C-labeled and absolute concentrations of metabolites by nuclear magnetic resonance and gas chromatography-mass spectrometry. Results: Octanoate produced markedly higher myocardial citrate concentration, and led to a higher [ATP]/[ADP] ratio compared with other http://mc.manuscriptcentral.com/jpen Journal of Parenteral and Enteral Nutrition For Peer Review groups. Unexpectedly, octanoate increased the flux of propionyl-CoA relative to acetyl-CoA into the CAC as well as heptanoate. MCFAs promoted increases in leucine oxidation, but were not associated with a difference in fractional protein synthesis rate. Conclusion: Octanoate provides energetic advantages to the heart over heptanoate, while preserving protein synthesis.

  20. Wireless Transmission of Monitoring Data out of an Underground Repository: Results of Field Demonstrations Performed at the HADES Underground Laboratory - 13589

    SciTech Connect (OSTI)

    Schroeder, T.J.; Rosca-Bocancea, E.; Hart, J.

    2013-07-01

    As part of the European 7. framework project MoDeRn, Nuclear Research and Consultancy Group (NRG) performed experiments in order to demonstrate the feasibility of wireless data transmission through the subsurface over large distances by low frequency magnetic fields in the framework of the geological disposal of radioactive waste. The main objective of NRG's contribution is to characterize and optimize the energy use of this technique within the specific context of post-closure monitoring of a repository. For that, measurements have been performed in the HADES Underground Research Laboratory (URL) located at Mol, Belgium, at 225 m depth. The experimental set-up utilizes a loop antenna for the transmitter that has been matched to the existing infrastructure of the HADES. Between 2010 and 2012 NRG carried out several experiments at the HADES URL in order to test the technical set-up and to characterize the propagation behavior of the geological medium and the local background noise pattern. Transmission channels have been identified and data transmission has been demonstrated at several frequencies, with data rates up to 10 bit/s and bit error rates <1%. A mathematical model description that includes the most relevant characteristics of the transmitter, transmission path, and receiver has been developed and applied to analyze possible options to optimize the set-up. With respect to the energy-efficiency, results so far have shown that data transmission over larger distances through the subsurface is a feasible option. To support the conclusions on the energy need per bit of transmitted data, additional experiments are foreseen. (authors)

  1. Progress towards a PETN Lifetime Prediction Model

    SciTech Connect (OSTI)

    Burnham, A K; Overturf III, G E; Gee, R; Lewis, P; Qiu, R; Phillips, D; Weeks, B; Pitchimani, R; Maiti, A; Zepeda-Ruiz, L; Hrousis, C

    2006-09-11

    Dinegar (1) showed that decreases in PETN surface area causes EBW detonator function times to increase. Thermal aging causes PETN to agglomerate, shrink, and densify indicating a ''sintering'' process. It has long been a concern that the formation of a gap between the PETN and the bridgewire may lead to EBW detonator failure. These concerns have led us to develop a model to predict the rate of coarsening that occurs with age for thermally driven PETN powder (50% TMD). To understand PETN contributions to detonator aging we need three things: (1) Curves describing function time dependence on specific surface area, density, and gap. (2) A measurement of the critical gap distance for no fire as a function of density and surface area for various wire configurations. (3) A model describing how specific surface area, density and gap change with time and temperature. We've had good success modeling high temperature surface area reduction and function time increase using a phenomenological deceleratory kinetic model based on a distribution of parallel nth-order reactions having evenly spaced activation energies where weighing factors of the reactions follows a Gaussian distribution about the reaction with the mean activation energy (Figure 1). Unfortunately, the mean activation energy derived from this approach is high (typically {approx}75 kcal/mol) so that negligible sintering is predicted for temperatures below 40 C. To make more reliable predictions, we've established a three-part effort to understand PETN mobility. First, we've measured the rates of step movement and pit nucleation as a function of temperature from 30 to 50 C for single crystals. Second, we've measured the evaporation rate from single crystals and powders from 105 to 135 C to obtain an activation energy for evaporation. Third, we've pursued mechanistic kinetic modeling of surface mobility, evaporation, and ripening.

  2. Near-infrared spectroscopy of CH{sub 2} by frequency modulated diode laser absorption

    SciTech Connect (OSTI)

    Marr, A.J.; Sears, T.J.; Chang, B.

    1998-09-01

    A diode laser spectrometer incorporating a multi-pass Herriott type cell and frequency modulation detection was used to record a previously unaccessed region of the near-infrared singlet{l_arrow}singlet absorption spectrum of methylene between 10thinsp000 cm{sup {minus}1} and 10thinsp600 cm{sup {minus}1}. With this spectrometer, signal-to-noise ratios close to the quantum noise limit have been attained. Identification of rovibronic transitions to five previously unobserved levels, K=1 {tilde a}(0,9,0), K=2thinsp{tilde b}(0,1,0), K=2thinsp{tilde a}(1,6,0), K=3thinsp{tilde b}(0,1,0) and K=3thinsp{tilde a}(0,10,0), was made. Despite the fact that the present spectra access levels within approximately 1300 cm{sup {minus}1} of the barrier to linearity, the spectrum is dense and perturbed, characteristics in common with spectra recorded in many previous studies at shorter wavelengths. Recent spectroscopic observations of halomethylenes [J. Mol. Spectrosc. {bold 188}, 68 (1998)] had suggested that the CH{sub 2} spectrum might become simpler at longer wavelengths, but this was not evident in the observed spectra. The mixed nature of the singlet states is evidenced by the assignment of rovibronic transitions to levels containing primarily {tilde a}thinsp{sup 1}A{sub 1} state character. The new measurements provide a stringent test for modern theoretical models for CH{sub 2} and will enable refinement of the electronic potential surfaces. {copyright} {ital 1998 American Institute of Physics.}

  3. Metal tritides helium emission

    SciTech Connect (OSTI)

    Beavis, L.C.

    1980-02-01

    Over the past several years, we have been measuring the release of helium from metal tritides (primarily erbium tritide). We find that qualitatively all tritides of interest to us behave the same. When they are first formed, the helium is released at a low rate that appears to be related to the amount of surface area which has access to the outside of the material (either film or bulk). For example, erbium tritide films initially release about 0.3% of the helium generated. Most tritide films emit helium at about this rate initially. At some later time, which depends upon the amount of helium generated, the parent occluding element and the degree of tritium saturation of the dihydride phase the helium emission changes to a new mode in which it is released at approximately the rate at which it is generated (for example, we measure this value to be approx. = .31 He/Er for ErT/sub 1/./sub 9/ films). If erbium ditritide is saturated beyond 1.9 T/Er, the critical helium/metal ratio decreases. For example, in bulk powders ErT/sub 2/./sub 15/ reaches critical release concentration at approx. = 0.03. Moderate elevation of temperature above room temperature has little impact on the helium release rate. It appears that the process may have approx. = 2 kcal/mol activation energy. The first helium formed is well bound. As the tritide ages, the helium is found in higher energy sites. Similar but less extensive measurements on scandium, titanium, and zirconium tritides are also described. Finally, the thermal desorption of erbium tritides of various ages from 50 days to 3154 days is discussed. Significant helium is desorbed along with the tritium in all but the youngest samples during thermodesorption.

  4. Decomposition of amino diazeniumdiolates (NONOates): Molecular mechanisms

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

    Shaikh, Nizamuddin; Valiev, Marat; Lymar, Sergei V.

    2014-08-23

    Although diazeniumdiolates (X[N(O)NO]-) are extensively used in biochemical, physiological, and pharmacological studies due to their ability to release NO and/or its congeneric nitroxyl, the mechanisms of these processes remain obscure. In this work, we used a combination of spectroscopic, kinetic, and computational techniques to arrive at a quantitatively consistent molecular mechanism for decomposition of amino diazeniumdiolates (amino NONOates: R2N[N(O)NO]-, where R = —N(C2H5)2(1), —N(C3H4NH2)2(2), or —N(C2H4NH2)2(3)). Decomposition of these NONOates is triggered by protonation of their [NN(O)NO]- group with the apparent pKa and decomposition rate constants of 4.6 and 1 s-1 for 1; 3.5 and 0.083 s-1 for 2; andmore » 3.8 and 0.0033 s-1 for 3. Although protonation occurs mainly on the O atoms of the functional group, only the minor R2N(H)N(O)NO tautomer (population ~ 10-7, for 1) undergoes the N—N heterolytic bond cleavage (kd ~ 107 s-1 for 1) leading to amine and NO. Decompositions of protonated amino NONOates are strongly temperature-dependent; activation enthalpies are 20.4 and 19.4 kcal/mol for 1 and 2, respectively, which includes contributions from both the tautomerization and bond cleavage. Thus, the bond cleavage rates exhibit exceptional sensitivity to the nature of R substituents which strongly modulate activation entropy. At pH < 2, decompositions of all three NONOates that have been investigated are subject to additional acid catalysis that occurs through di-protonation of the [NN(O)NO]- group.« less

  5. Visualiser of two-micron laser radiation based on Ho:CaF{sub 2} crystals

    SciTech Connect (OSTI)

    Lyapin, A A; Ryabochkina, P A; Ushakov, S N; Fedorov, P P

    2014-06-30

    The anti-Stokes luminescence spectra of Ho:CaF{sub 2} crystals corresponding to the {sup 5}G{sub 4} ? {sup 5}I{sub 8}, {sup 5}G{sub 5} ? {sup 5}I{sub 8}, {sup 5}F{sub 3} ? {sup 5}I{sub 8}, {sup 5}F{sub 4}({sup 5}S{sub 2}) ? {sup 5}I{sub 8}, {sup 5}F{sub 5} ? {sup 5}I{sub 8}, {sup 5}S{sub 2} ? {sup 5}I{sub 7}, {sup 5}I{sub 4} ? {sup 5}I{sub 8}, {sup 5}I{sub 5} ? {sup 5}I{sub 8}, {sup 5}F{sub 5} ? {sup 5}I{sub 7}, {sup 5}F{sub 3} ? {sup 5}I{sub 6}, {sup 5}I{sub 6} ? {sup 5}I{sub 8}, {sup 5}F{sub 5} ? {sup 5}I{sub 6}, and {sup 5}I{sub 5} ? {sup 5}I{sub 7} transitions upon excitation of the {sup 5}I{sub 7} level of Ho{sup 3+} ions are studied. A method for visualisation of IR radiation in the two-micron range using Ho:CaF{sub 2} crystals is proposed. The energy efficiency of conversion of two-micron laser radiation to radiation in the red spectral range 620 690 nm by a 1 mol % HoF{sub 3}:CaF{sub 2} crystal is estimated to be no higher than 0.02%. (nonlinear optical phenomena)

  6. Carbon monoxide alleviates ethanol-induced oxidative damage and inflammatory stress through activating p38 MAPK pathway

    SciTech Connect (OSTI)

    Li, Yanyan; Gao, Chao; Shi, Yanru; Tang, Yuhan; Liu, Liang; Xiong, Ting; Du, Min; Xing, Mingyou; Liu, Liegang; Yao, Ping

    2013-11-15

    Stress-inducible protein heme oxygenase-1(HO-1) is well-appreciative to counteract oxidative damage and inflammatory stress involving the pathogenesis of alcoholic liver diseases (ALD). The potential role and signaling pathways of HO-1 metabolite carbon monoxide (CO), however, still remained unclear. To explore the precise mechanisms, ethanol-dosed adult male Balb/c mice (5.0 g/kg.bw.) or ethanol-incubated primary rat hepatocytes (100 mmol/L) were pretreated by tricarbonyldichlororuthenium (II) dimmer (CORM-2, 8 mg/kg for mice or 20 ?mol/L for hepatocytes), as well as other pharmacological reagents. Our data showed that CO released from HO-1 induction by quercetin prevented ethanol-derived oxidative injury, which was abolished by CO scavenger hemoglobin. The protection was mimicked by CORM-2 with the attenuation of GSH depletion, SOD inactivation, MDA overproduction, and the leakage of AST, ALT or LDH in serum and culture medium induced by ethanol. Moreover, CORM-2 injection or incubation stimulated p38 phosphorylation and suppressed abnormal Tnfa and IL-6, accompanying the alleviation of redox imbalance induced by ethanol and aggravated by inflammatory factors. The protective role of CORM-2 was abolished by SB203580 (p38 inhibitor) but not by PD98059 (ERK inhibitor) or SP600125 (JNK inhibitor). Thus, HO-1 released CO prevented ethanol-elicited hepatic oxidative damage and inflammatory stress through activating p38 MAPK pathway, suggesting a potential therapeutic role of gaseous signal molecule on ALD induced by naturally occurring phytochemicals. - Highlights: CO alleviated ethanol-derived liver oxidative and inflammatory stress in mice. CO eased ethanol and inflammatory factor-induced oxidative damage in hepatocytes. The p38 MAPK is a key signaling mechanism for the protective function of CO in ALD.

  7. Methane dissociative chemisorption and detailed balance on Pt(111): Dynamical constraints and the modest influence of tunneling

    SciTech Connect (OSTI)

    Donald, S. B.; Navin, J. K.; Harrison, I.

    2013-12-07

    A dynamically biased (d-) precursor mediated microcanonical trapping (PMMT) model of the activated dissociative chemisorption of methane on Pt(111) is applied to a wide range of dissociative sticking experiments, and, by detailed balance, to the methane product state distributions from the thermal associative desorption of adsorbed hydrogen with coadsorbed methyl radicals. Tunneling pathways were incorporated into the d-PMMT model to better replicate the translational energy distribution of the desorbing methane product from the laser induced thermal reaction of coadsorbed hydrogen and methyl radicals occurring near T{sub s} = 395 K. Although tunneling is predicted to be inconsequential to the thermal dissociative chemisorption of CH{sub 4} on Pt(111) at the high temperatures of catalytic interest, once the temperature drops to 395 K the tunneling fraction of the reactive thermal flux reaches 15%, and as temperatures drop below 275 K the tunneling fraction exceeds 50%. The d-PMMT model parameters of (E{sub 0} = 58.9?kJ/mol,?s = 2,??{sub v} = 0.40) describe the apparent threshold energy for CH{sub 4}/Pt(111) dissociative chemisorption, the number of surface oscillators involved in the precursor complex, and the efficacy of molecular vibrational energy to promote reaction, relative to translational energy directed along the surface normal. Molecular translations parallel to the surface and rotations are treated as spectator degrees of freedom. Transition state vibrational frequencies are derived from generalized gradient approximation-density functional theory electronic structure calculations. The d-PMMT model replicates the diverse range of experimental data available with good fidelity, including some new effusive molecular beam and ambient gas dissociative sticking measurements. Nevertheless, there are some indications that closer agreement between theory and experiments could be achieved if a surface efficacy less than one was introduced into the modeling as an additional dynamical constraint.

  8. Solid polymer electrolyte from phosphorylated chitosan

    SciTech Connect (OSTI)

    Fauzi, Iqbal Arcana, I Made

    2014-03-24

    Recently, the need of secondary battery application continues to increase. The secondary battery which using a liquid electrolyte was indicated had some weakness. A solid polymer electrolyte is an alternative electrolytes membrane which developed in order to replace the liquid electrolyte type. In the present study, the effect of phosphorylation on to polymer electrolyte membrane which synthesized from chitosan and lithium perchlorate salts was investigated. The effect of the components composition respectively on the properties of polymer electrolyte, was carried out by analyzed of its characterization such as functional groups, ion conductivity, and thermal properties. The mechanical properties i.e tensile resistance and the morphology structure of membrane surface were determined. The phosphorylation processing of polymer electrolyte membrane of chitosan and lithium perchlorate was conducted by immersing with phosphoric acid for 2 hours, and then irradiated on a microwave for 60 seconds. The degree of deacetylation of chitosan derived from shrimp shells was obtained around 75.4%. Relative molecular mass of chitosan was obtained by viscometry method is 796,792 g/mol. The ionic conductivity of chitosan membrane was increase from 6.33 10{sup ?6} S/cm up to 6.01 10{sup ?4} S/cm after adding by 15 % solution of lithium perchlorate. After phosphorylation, the ionic conductivity of phosphorylated lithium chitosan membrane was observed 1.37 10{sup ?3} S/cm, while the tensile resistance of 40.2 MPa with a better thermal resistance. On the strength of electrolyte membrane properties, this polymer electrolyte membrane was suggested had one potential used for polymer electrolyte in field of lithium battery applications.

  9. Staged Transcatheter Treatment of Portal Hypoplasia and Congenital Portosystemic Shunts in Children

    SciTech Connect (OSTI)

    Bruckheimer, Elchanan Dagan, Tamir; Atar, Eli; Schwartz, Michael; Kachko, Ludmila; Superina, Riccardo; Amir, Gabriel; Shapiro, Rivka; Birk, Einat

    2013-12-15

    Purpose: Congenital portosystemic shunts (CPSS) with portal venous hypoplasia cause hyperammonemia. Acute shunt closure results in portal hypertension. A transcatheter method of staged shunt reduction to afford growth of portal vessels followed by shunt closure is reported. Methods: Pressure measurements and angiography in the CPSS or superior mesenteric artery (SMA) during temporary occlusion of the shunt were performed. If vessels were diminutive and the pressure was above 18 mmHg, a staged approach was performed, which included implantation of a tailored reducing stent to reduce shunt diameter by {approx}50 %. Recatheterization was performed approximately 3 months later. If the portal pressure was below 18 mmHg and vessels had developed, the shunt was closed with a device. Results: Six patients (5 boys, 1 girl) with a median age of 3.3 (range 0.5-13) years had CPSS portal venous hypoplasia and hyperammonemia. Five patients underwent staged closure. One patient tolerated acute closure. One patient required surgical shunt banding because a reducing stent could not be positioned. At median follow-up of 3.8 (range 2.2-8.4) years, a total of 21 procedures (20 transcatheter, 1 surgical) were performed. In all patients, the shunt was closed with a significant reduction in portal pressure (27.7 {+-} 11.3 to 10.8 {+-} 1.8 mmHg; p = 0.016), significant growth of the portal vessels (0.8 {+-} 0.5 to 4.0 {+-} 2.4 mm; p = 0.037), and normalization of ammonia levels (202.1 {+-} 53.6 to 65.7 {+-} 9.6 {mu}mol/L; p = 0.002) with no complications. Conclusion: Staged CPSS closure is effective in causing portal vessel growth and treating hyperammonemia.

  10. Nucleation of nanocrystalline diamond by fragmentation of fullerene precursors.

    SciTech Connect (OSTI)

    Gruen, D. M.

    1998-05-04

    Growth of diamond films from C{sub 60}/Ar microwave discharges results in a nanocrystalline microstructure with crystallite sizes in the range 3-10 nm. Heterogeneous nucleation rates of 10{sup 10} cm{sup {minus}2} sec are required to account for the results. The nucleation mechanism presented here fulfills this requirement and is based on the insertion of carbon dimer, C{sub 2}, molecules, produced by fragmentation of C{sub 60}, into the n-bonded dimer rows of the reconstructed (100) surface of diamond. Density functional theory is used to calculate the energetic of C{sub 2} insertion into carbon clusters that model the (100) surface. The reaction of singlet C{sub 2} with the double bond of the C{sub 9}H{sub 12} cluster leads to either carbene structures or a cyclobutynelike structure. At the HF/6-31G* level, the carbene product has a C{sub 2v} structure, while at the B3LYP/6-31G* levels of theory, it has a C{sub s} structure with the inserted C{sub 2} tilted. No barrier for insertion into the C=C double bond of the C{sub 9}H{sub 12} cluster was found at the HF/6-31G* and B3LYP/6-31G* levels of theory. Thus, calculations including correlation energy and geometry optimization indicate that insertion of C{sub 2} into a C=C double bond leads to a large energy lowering, {approximately}120 kcal/mol for a C{sub 9}H{sub 12} cluster, and there is no barrier for insertion.

  11. Development of metal-coated ceramic anodes for molten carbonate fuel cells. Final report

    SciTech Connect (OSTI)

    Khandkar, A.C.; Elangovan, S.; Marianowski, L.G.

    1990-03-01

    This report documents the developmental efforts on metal coating of various ceramic substrates (LiAlO{sub 2}, SrTiO{sub 3}, and LiFeO{sub 2}) and the critical issues associated with fabricating anodes using metal-coated LiAlO{sub 2} substrates. Electroless Ni and Cu coating technology was developed to achieve complete metal coverage on LiAlO{sub 2} powder substrates. Metal coated SrTiO{sub 3} powders were fabricated into anodes by a process identical to that reported in the GE literature. Microstructural examination revealed that the grains of the ceramic had fused together, with the metal having dewetted from the surface of the ceramic. Alternate substrates that might allow for better wetting of the metal on the ceramic such as LiFeO{sub 2} and Li{sub 2}MnO{sub 3} were identified. Cu/Ni-coated (50:50 mol ratio, 50 w/o metal loading) LiFeO{sub 2} anodes were optimized to meet the MCFC anode specifications. Metal-coated gamma-LiAlO{sub 2} substrates were also developed. By using suitable chemical surface modification methods, the gamma-UAlO{sub 2} substrate surface may be modified to allow a stable metal coated anode to be fabricated. Creep testing of the metal coated ceramic anodes were conducted at IGT. It was determined that the predominant creep mechanism is due to particle rearrangement. The anode porosity, and mean pore size had significant effect on the creep of the anode. Lower porosity and pore size consistent with performance criteria are desired to reduce creep. Lower metal loading with uniformity of coverage will result in lower creep behavior of the anode. Of the two substrates evaluated, LiFeO{sub 2} in general exhibited lower creep which was attributed to superior metal adhesion.

  12. Development of metal-coated ceramic anodes for molten carbonate fuel cells

    SciTech Connect (OSTI)

    Khandkar, A.C.; Elangovan, S.; Marianowski, L.G.

    1990-03-01

    This report documents the developmental efforts on metal coating of various ceramic substrates (LiAlO{sub 2}, SrTiO{sub 3}, and LiFeO{sub 2}) and the critical issues associated with fabricating anodes using metal-coated LiAlO{sub 2} substrates. Electroless Ni and Cu coating technology was developed to achieve complete metal coverage on LiAlO{sub 2} powder substrates. Metal coated SrTiO{sub 3} powders were fabricated into anodes by a process identical to that reported in the GE literature. Microstructural examination revealed that the grains of the ceramic had fused together, with the metal having dewetted from the surface of the ceramic. Alternate substrates that might allow for better wetting of the metal on the ceramic such as LiFeO{sub 2} and Li{sub 2}MnO{sub 3} were identified. Cu/Ni-coated (50:50 mol ratio, 50 w/o metal loading) LiFeO{sub 2} anodes were optimized to meet the MCFC anode specifications. Metal-coated gamma-LiAlO{sub 2} substrates were also developed. By using suitable chemical surface modification methods, the gamma-UAlO{sub 2} substrate surface may be modified to allow a stable metal coated anode to be fabricated. Creep testing of the metal coated ceramic anodes were conducted at IGT. It was determined that the predominant creep mechanism is due to particle rearrangement. The anode porosity, and mean pore size had significant effect on the creep of the anode. Lower porosity and pore size consistent with performance criteria are desired to reduce creep. Lower metal loading with uniformity of coverage will result in lower creep behavior of the anode. Of the two substrates evaluated, LiFeO{sub 2} in general exhibited lower creep which was attributed to superior metal adhesion.

  13. Growth of polyphenyls via ion-molecule reactions: An experimental and theoretical mechanistic study

    SciTech Connect (OSTI)

    Aysina, Julia; Tosi, Paolo; Ascenzi, Daniela; Maranzana, Andrea; Tonachini, Glauco

    2013-05-28

    The reactivity of biphenylium cations C{sub 12}H{sub 9}{sup +} with benzene C{sub 6}H{sub 6} is investigated in a joint experimental and theoretical approach. Experiments are performed by using a triple quadruple mass spectrometer equipped with an atmospheric pressure chemical ion source to generate C{sub 12}H{sub 9}{sup +} via dissociative ionization of various isomers of the neutral precursor hydroxybiphenyl (C{sub 12}H{sub 10}O). C-C coupling reactions leading to hydrocarbon growth are observed. The most abundant ionic products are C{sub 18}H{sub 15}{sup +}, C{sub 18}H{sub 13}{sup +}, C{sub 17}H{sub 12}{sup +}, and C{sub 8}H{sub 7}{sup +}. The dependence of product ion yields on the kinetic energy of reagent ions, as well as further experiments performed using partial isotopic labelling of reagents, support the idea that the reaction proceeds via a long lived association product, presumably the covalently bound protonated terphenyl C{sub 18}H{sub 15}{sup +}. Its formation is found to be exothermic and barrierless and, therefore, might occur under the low pressure and temperature conditions typical of planetary atmospheres and the interstellar medium. Theoretical calculations have focussed on the channel leading to C{sub 8}H{sub 7}{sup +} plus C{sub 10}H{sub 8}, identifying, as the most probable fragments, the phenylethen-1-ylium cation and naphthalene, thus suggesting that the pathway leading to them might be of particular interest for the synthesis of polycyclic aromatic hydrocarbons. Both experiments and theory agree in finding this channel exoergic but hampered by small barriers of 2.7 and 3.7 kcal mol{sup -1} on the singlet potential energy surface.

  14. Thermodynamic Features of Benzene-1,2-Diphosphonic Acid Complexes with Several Metal Ions

    SciTech Connect (OSTI)

    Syouhei Nishihama; Ryan P. Witty; Leigh R Martin; Kenneth L. Nash

    2013-08-01

    Among his many contributions to the advancement of f-element chemistry and separation science, Professor Gregory R. Choppins research group completed numerous investigations featuring the application of distribution techniques to the determination of metal complexation equilibrium quotients. Most of these studies focused on the chemistry of lanthanide and actinide complexes. In keeping with that tradition, this report discusses the complex formation equilibrium constants for complexes of trivalent europium (Eu3+) with benzene-1,2-diphosphonic acid (H4BzDP) determined using solvent extraction distribution experiments in 0.2 M (Na,H)ClO4 media in the temperature range of 5 45 degrees C. Protonation constants for HnBzDP4-n and stoichiometry and stability of BzDP4- complexes with Zn2+, Ni2+, and Cu2+ have also been determined using potentiometric titration (at I = 0.1 M) and 31P NMR spectroscopy. Heats of protonation of HnBzDPn-4 species have been determined by titration calorimetry. From the temperature dependence of the complex Eu3+-HnBzDPn-4 equilibrium constant, a composite enthalpy (?H = -15.1 (+/-1.0) kJ mol-1) of complexation has been computed. Comparing these thermodynamic parameters with literature reports on other diphosphonic acids and structurally similar carboxylic acids indicates that exothermic heats of complexation are unique to the Eu-BzDP system. Comparisons with thermodynamic data from the literature indicate that the fixed geometry imposed by the benzene ring enhances complex stability.

  15. Complexes of HNO? and NO? with NO? and N?O?, and their potential role in atmospheric HONO formation

    SciTech Connect (OSTI)

    Kamboures, Michael A.; Raff, Jonathan D.; Miller, Y.; Phillips, Leon F.; Finlayson-Pitts, Barbara J.; Gerber, Robert B.

    2008-08-11

    Calculations were performed to determine the structures, energetics, and spectroscopy of the atmospherically relevant complexes (HNO?)(NO?), (HNO?)(N?O?), (NO?)(NO?), and (NO?)(N?O?). The binding energies indicate that three of the four complexes are quite stable, with the most stable (NO?)(N?O?) possessing binding energy of almost -14 kcal mol. Vibrational frequencies were calculated for use in detecting the complexes by infrared and Raman spectroscopy. An ATR-FTIR experiment showed features at 1632 and 1602 cm that are attributed to NO? complexed to NO? and HNO?, respectively. The electronic states of (HNO?)(N?O?) and (NO?)( N?O?) were investigated using an excited state method and it was determined that both complexes possess one low-lying excited state that is accessible through absorption of visible radiation. Evidence for the existence of (NO?)( N?O?) was obtained from UV/vis absorption spectra of N?O? in concentrated HNO?, which show a band at 320 nm that is blue shifted by 20 nm relative to what is observed for N?O? dissolved in organic solvents. Finally, hydrogen transfer reactions within the (HNO?)(NO?) and (HNO?)( N?O?) complexes leading to the formation of HONO, were investigated. In both systems the calculated potential profiles rule out a thermal mechanism, but indicate the reaction could take place following the absorption of visible radiation. We propose that these complexes are potentially important in the thermal and photochemical production of HONO observed in previous laboratory and field studies.

  16. On the amorphization behavior and hydrogenation performance of high-energy ball-milled Mg{sub 2}Ni alloys

    SciTech Connect (OSTI)

    Kou, Hongchao; Hou, Xiaojiang; Zhang, Tiebang, E-mail: tiebangzhang@nwpu.edu.cn; Hu, Rui; Li, Jinshan; Xue, Xiangyi

    2013-06-15

    Amorphous Mg{sub 2}Ni alloy was prepared by high energy ball-milling starting with polycrystalline Mg{sub 2}Ni which was prepared with the help of a metallurgy method by using a SPEX 8000D mill. The microstructural and phase structure characterization of the prepared materials was performed via scanning electron microscopy, transition electron microscope and X-ray diffraction. The thermal stabilities were investigated by differential scanning calorimetry. The apparent activation energies were determined by means of the Kissinger method. The first and second crystallization reactions take place at ? 255 C and ? 410 C, and the corresponding activation energy of crystallization is E{sub a1} = 276.9 and E{sub a2} = 382.4 kJ/mol, respectively. At 3 MPa hydrogen pressure and 250 C, the hydrogen absorption capacities of crystalline, partially and fully amorphous Mg{sub 2}Ni alloy are 2.0 wt.%, 3.2 wt.% and 3.5 wt.% within 30 min, respectively. - Graphical Abstract: We mainly focus on the amorphization behavior of crystalline Mg{sub 2}Ni alloy in the high energy ball-milling process and the crystallization behavior of the amorphous Mg{sub 2}Ni alloy in a follow-up heating process. The relationship of milling, microstructure and hydrogenation properties is established and explained by models. - Highlights: Amorphous Mg{sub 2}Ni has been obtained by high energy ball milling the as-cast alloy. The amorphization behavior of polycrystalline Mg{sub 2}Ni is presented. The crystallization behavior of the amorphous Mg{sub 2}Ni alloy is illustrated. Establish the relationship of milling, microstructure and hydrogenation properties.

  17. Physicochemical controls on absorbed water film thickness in unsaturated geological media

    SciTech Connect (OSTI)

    Tokunaga, T.

    2011-06-14

    Adsorbed water films commonly coat mineral surfaces in unsaturated soils and rocks, reducing flow and transport rates. Therefore, it is important to understand how adsorbed film thickness depends on matric potential, surface chemistry, and solution chemistry. Here, the problem of adsorbed water film thickness is examined through combining capillary scaling with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Novel aspects of this analysis include determining capillary influences on film thicknesses, and incorporating solution chemistry-dependent electrostatic potential at air-water interfaces. Capillary analysis of monodisperse packings of spherical grains provided estimated ranges of matric potentials where adsorbed films are stable, and showed that pendular rings within drained porous media retain most of the 'residual' water except under very low matric potentials. Within drained pores, capillary contributions to thinning of adsorbed films on spherical grains are shown to be small, such that DLVO calculations for flat surfaces are suitable approximations. Hamaker constants of common soil minerals were obtained to determine ranges of the dispersion component to matric potential-dependent film thickness. The pressure component associated with electrical double layer forces was estimated using the compression and linear superposition approximations. The pH-dependent electrical double layer pressure component is the dominant contribution to film thicknesses at intermediate values of matric potential, especially in lower ionic strength solutions (< 10 mol m{sup -3}) on surfaces with higher magnitude electrostatic potentials (more negative than - 50 mV). Adsorbed water films are predicted to usually range in thickness from 1 to 20 nm in drained pores and fractures of unsaturated environments.

  18. FY-2010 Process Monitoring Technology Final Report

    SciTech Connect (OSTI)

    Orton, Christopher R.; Bryan, Samuel A.; Casella, Amanda J.; Hines, Wes; Levitskaia, Tatiana G.; henkell, J.; Schwantes, Jon M.; Jordan, Elizabeth A.; Lines, Amanda M.; Fraga, Carlos G.; Peterson, James M.; Verdugo, Dawn E.; Christensen, Ronald N.; Peper, Shane M.

    2011-01-01

    During FY 2010, work under the Spectroscopy-Based Process Monitoring task included ordering and receiving four fluid flow meters and four flow visible-near infrared spectrometer cells to be instrumented within the centrifugal contactor system at Pacific Northwest National Laboratory (PNNL). Initial demonstrations of real-time spectroscopic measurements on cold-stream simulants were conducted using plutonium (Pu)/uranium (U) (PUREX) solvent extraction process conditions. The specific test case examined the extraction of neodymium nitrate (Nd(NO3)3) from an aqueous nitric acid (HNO3) feed into a tri-n-butyl phosphate (TBP)/ n-dodecane solvent. Demonstration testing of this system included diverting a sample from the aqueous feed meanwhile monitoring the process in every phase using the on-line spectroscopic process monitoring system. The purpose of this demonstration was to test whether spectroscopic monitoring is capable of determining the mass balance of metal nitrate species involved in a cross-current solvent extraction scheme while also diverting a sample from the system. The diversion scenario involved diverting a portion of the feed from a counter-current extraction system while a continuous extraction experiment was underway. A successful test would demonstrate the ability of the process monitoring system to detect and quantify the diversion of material from the system during a real-time continuous solvent extraction experiment. The system was designed to mimic a PUREX-type extraction process with a bank of four centrifugal contactors. The aqueous feed contained Nd(NO3)3 in HNO3, and the organic phase was composed of TBP/n-dodecane. The amount of sample observed to be diverted by on-line spectroscopic process monitoring was measured to be 3 mmol (3 x 10-3 mol) Nd3+. This value was in excellent agreement with the 2.9 mmol Nd3+ value based on the known mass of sample taken (i.e., diverted) directly from the system feed solution.

  19. Trajectory surface hopping study of the O({sup 3}P) + C{sub 2}H{sub 2} reaction dynamics: Effect of collision energy on the extent of intersystem crossing

    SciTech Connect (OSTI)

    Rajak, Karunamoy; Maiti, Biswajit

    2014-01-28

    Intersystem crossing (ISC) dynamics plays an important role in determining the product branching in the O({sup 3}P) + C{sub 2}H{sub 2} reaction despite the necessarily small spin-orbit coupling constant values. In this study we investigate the effect of collision energy on the extent of the contribution of a spin non-conserving route through ISC dynamics to the product distributions at the initial collision energies 8.2, 9.5, and 13.1 kcal/mol. A direct dynamics trajectory surface hopping method is employed with potential energy surfaces generated at the unrestricted B3LYP/6-31G(d,p) level of theory to perform nonadiabatic dynamics. To make our calculation simpler, nonadibatic transitions were only considered at the triplet-singlet intersections. At the crossing points, Landau-Zener transition probabilities were calculated using spin-orbit coupling constant values computed at the same geometry. The Landau-Zener model for the title reaction is validated against a more rigorous Tully's fewest switches method and found to be working reasonably well as expected because of weak spin-orbit coupling. We have compared our results with the recent crossed molecular beam experiments and observed a very good agreement with respect to the primary product branching ratios. Our calculation revealed that there is no noticeable effect of the initial collision energy on the overall product distributions that corroborates the recent experimental findings. Our calculation indicates, however, that the extent of intersystem crossing contributions varies significantly with collision energy, needed to be verified, experimentally.

  20. Interdiffusion and Reaction between Zr and Al Alloys from 425 degrees to 625 degrees C

    SciTech Connect (OSTI)

    J. Dickson; L. Zhou; A. Ewh; M. Fu; D. D. Keiser, Jr.; Y. H. Sohn; A. Paz y Puente

    2014-06-01

    Zirconium has recently garnered attention for use as a diffusion barrier between UMo nuclear fuels and Al cladding alloys. Interdiffusion and reactions between Zr and Al, Al-2 wt.% Si, Al-5 wt.% Si or AA6061 were investigated using solid-to-solid diffusion couples annealed in the temperature range of 425 degrees to 625 degrees C. In the binary Al and Zr system, the Al3Zr and Al2Zr phases were identified, and the activation energy for the growth of the Al3Zr phase was determined to be 347 kJ/mol. Negligible diffusional interactions were observed for diffusion couples between Zr vs. Al-2 wt.% Si, Al-5 wt.% Si and AA6061 annealed at or below 475 degrees C. In diffusion couples with the binary AlSi alloys at 560 degrees C, a significant variation in the development of the phase constituents was observed including the thick t1 (Al5SiZr2) with Si content up to 12 at.%, and thin layers of (Si,Al)2Zr, (Al,Si)3Zr, Al3SiZr2 and Al2Zr phases. The use of AA6061 as a terminal alloy resulted in the development of both T1 (Al5SiZr2) and (Al,Si)3Zr phases with a very thin layer of (Al,Si)2Zr. At 560 degrees C, with increasing Si content in the AlSi alloy, an increase in the overall rate of diffusional interaction was observed; however, the diffusional interaction of Zr in contact with multicomponent AA6061 with 0.40.8 wt.% Si was most rapid.