WorldWideScience

Sample records for oxidation state studies

  1. Study of uranium oxidation states in geological material.

    Science.gov (United States)

    Pidchenko, I; Salminen-Paatero, S; Rothe, J; Suksi, J

    2013-10-01

    A wet chemical method to determine uranium (U) oxidation states in geological material has been developed and tested. The problem faced in oxidation state determinations with wet chemical methods is that U redox state may change when extracted from the sample material, thereby leading to erroneous results. In order to quantify and monitor U redox behavior during the acidic extraction in the procedure, an analysis of added isotopic redox tracers, (236)U(VI) and (232)U(IV), and of variations in natural uranium isotope ratio ((234)U/(238)U) of indigenous U(IV) and U(VI) fractions was performed. Two sample materials with varying redox activity, U bearing rock and U-rich clayey lignite sediment, were used for the tests. The Fe(II)/Fe(III) redox-pair of the mineral phases was postulated as a potentially disturbing redox agent. The impact of Fe(III) on U was studied by reducing Fe(III) with ascorbic acid, which was added to the extraction solution. We observed that ascorbic acid protected most of the U from oxidation. The measured (234)U/(238)U ratio in U(IV) and U(VI) fractions in the sediment samples provided a unique tool to quantify U oxidation caused by Fe(III). Annealing (sample heating) to temperatures above 500 °C was supposed to heal ionizing radiation induced defects in the material that can disturb U redox state during extraction. Good agreement between two independent methods was obtained for DL-1a material: an average 38% of U(IV) determined by redox tracer corrected wet chemistry and 45% for XANES. Copyright © 2013 Elsevier Ltd. All rights reserved.

  2. Study on the solid state chemistry of ternary uranium oxides

    International Nuclear Information System (INIS)

    Yamashita, Toshiyuki

    1988-03-01

    With the increase of burnup of uranium oxide fuels, various kinds of fission products are formed, and the oxygen atoms combined with the consumed heavy atoms are freed. The solid state chemical and/or thermodynamic properties of these elements at high temperatures are complex, and have not been well clarified. In the present report, an approach was taken that the chemical interactions between UO 2 and these fission products can be regarded as causing overlapped effects of composing ternary uranium oxides, and formation reactions and phase behavior were studied for several ternary uranium oxides with typical fission product elements such as alkaline earth metals and rare earth elements. Precise determination methods for the composition of ternary uranium oxides were developed. The estimated accuracies for x and y values in M y U 1-y O 2+x were ± 0.006 and ± 0.004, respectively. The thermodynamic properties and the lattice parameters of the phases in the Ca-U-O and Pr-U-O systems were discussed in relation to the composition determined by the methods. Crystal structure analyses of cadmium monouranates were made with X-ray diffraction method. (author) 197 refs

  3. Studies of the Tc oxidation states in humic acid solutions

    International Nuclear Information System (INIS)

    Wang Bo; Liu Dejun; Yao Jun

    2010-01-01

    The oxidation state is an important aspect of the speciation of Tc in groundwater that contained organic substances due to it control the precipitation, complexation, sorption and colloid formation behavior of the Tc under HWL geological disposal conditions. In present work, the oxidation states of Tc were investigated using the LaCl 3 coagulation method and solution extraction method in aqueous solutions in which the humic acid concentration range is from 0 to 20 mg L -1 and the Tc (Ⅶ) concentration range is about 10 -8 mol l -1 . The radiocounting of 99 Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99 Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl 3 coagulation methods were carried out for the investigation of Tc oxidation states in humic acid aqueous systems at about pH 8. The tetraphenylarsonium chloride (IPA)-chloroform extraction method was used also simultaneously to investigation the concentrations of Tc (Ⅳ) and Tc (Ⅶ) for the availability of the LaCl 3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentrations are well agreement with the LaCl 3 precipitation method. These two experimental results demonstrated that Tc (Ⅶ) is very stable in the Tc (Ⅶ)-humic acid system during a 350 days experimental period, and the Tc (Ⅳ) concentrations are very lower, that is indicate that there didn't oxidizing reactions between the Fluka humic acid and Tc (Ⅶ) in aqueous solutions under anaerobic conditions. That is means the presence of humic acids even in anaerobic groundwater is disadvantage for the retardance of radionuclides. (authors)

  4. Studies of Tc oxidation states in humic acid solutions

    International Nuclear Information System (INIS)

    Wang Bo; Liu Dejun; Yao Jun

    2011-01-01

    The oxidation state of Tc is an important aspect of the speciation in groundwater which contained organic substances due to it control the precipitation, complexation, sorption and colloid formation behavior of the Tc under HWL geological disposal conditions. In present work, the oxidation states of Tc were investigated using the LaCl 3 coagulation method and solution extraction method in aqueous solutions in which the humic acid concentration range is from 0 to 20 mg/L and the Tc (VII) concentration is about 10 -8 mol/L. The radiocounting of 99 Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99 Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl 3 coagulation method was carried out for the investigation of Tc oxidation states in humic acid aqueous systems at about pH 8. The tetraphenylarsonium chloride (TPA)-chloroform extraction method was used also simultaneously to investigation the concentrations of Tc (IV) and Tc (VII) for the availability of the LaCl 3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentration are well agreement with the LaCl 3 precipitation method. These two experimental results demonstrated that Tc (VII) is very stable in the Tc (VII)-humic acid system during a 350 days experimental period, and the Tc (IV) concentrations are very lower, that is indicate that there didn't oxidizing reactions between the Fluka humic acid and Tc (VII) in aqueous solutions under anaerobic conditions. That means the presence of humic acids even in anaerobic groundwater is disadvantage for the retardance of radionuclides. (authors)

  5. Oxidation under electron bombardment. A tool for studying the initial states of silicon oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Carriere, B.; Deville, J.P.; El Maachi, A.

    1987-06-01

    The exciting beam of an Auger electron spectrometer has been used to monitor the oxidation of silicon single crystals at room temperature and very low pressures of oxygen (approx. 10/sup -7/ Torr). This process allows us to build ultra-thin layers of silica on silicon (down to 30 A) but it is mostly used to investigate the mechanisms of the initial stages of oxidation. Auger spectra recorded continuously during the oxidation process provide information on (1) the nature of the silicon-oxygen chemical bonds which are interpreted through fine structure in the Auger peak, and (2) the kinetics of oxide formation which are deduced from curves of Auger signal versus time. An account is given of the contribution of these Auger studies to the description of the intermediate oxide layer during the reaction between silicon and oxygen and the influence of surface structural disorder, induced mainly by argon-ion bombardment, is discussed in terms of reactivity and oxide coverage.

  6. Studies of surface states in zinc oxide nanopowders

    Science.gov (United States)

    Peters, Raul Mugabe

    The surface of ZnO semiconductor nanosystems is a key performance-defining factor in numerous applications. In this work we present experimental results for the surface defect-related properties of ZnO nanoscale systems. Surface photovoltage spectroscopy was used to determine the defect level energies within the band gap, the conduction vs. valence band nature of the defect-related transitions, and to probe key dynamic parameters of the surface on a number of commercially available ZnO nanopowders. In our experimental setup, surface photovoltage characterization is conducted in high vacuum in tandem with in situ oxygen remote plasma treatments. Surface photovoltage investigations of the as-received and plasma-processed samples revealed a number of common spectral features related to surface states. Furthermore, we observed significant plasma-induced changes in the surface defect properties. Ex situ positron annihilation and photoluminescence measurements were performed on the studied samples and correlated with surface photovoltage results. The average positron lifetimes were found to be substantially longer than in a bulk single crystalline sample, which is consistent with the model of grains with defect-rich surface and subsurface layers. Compression of the powders into pellets yielded reduction of the average positron lifetimes. Surface photovoltage, positron annihilation, and photoluminescence spectra consistently showed sample-to-sample differences due to the variation in the overall quality of the nanopowders, which partially obscures observation of the scaling effects. However, the results demonstrated that our approach is efficient in detecting specific surface states in nanoscale ZnO specimens and in elucidating their nature.

  7. Teaching the Properties of Chromium's Oxidation States with a Case Study Method

    Science.gov (United States)

    Ozdilek, Zehra

    2015-01-01

    The purpose of this study was to investigate how a mixed-method case study affects pre-service science teachers' awareness of hexavalent chromium pollution and content knowledge about the properties of chromium's different oxidation states. The study was conducted in Turkey with 55 sophomores during the fall semester of 2013-2014. The students…

  8. Raman spectroscopic study of the oxidation state of Eu in molten LiCl-KCl

    Energy Technology Data Exchange (ETDEWEB)

    Park, Seung; Yun, Jong-Il [KAIST, Daejeon(Korea, Republic of)

    2016-10-15

    Spectroscopy can provide high reliability for the quantitative analysis of such system. The molar absorptivity of Eu(II) at 325 nm is reported as about 1645 M{sup -1}cm{sup -1}, which is too high to apply to higher concentration. A high-temperature Raman spectroscopy has been set and employed for analyzing the molecular structure and coordination complex and investigating the oxidation state of europium in molten LiCl-KCl. Europium can be present in divalent state while many other lanthanides exist in trivalent state. The thermodynamic properties of europium ions have been studied using electrochemical methods, spectroscopic methods, and EPR technique. Although there has been discrepancy of the reduced amount of europium in previous works, the majority of Eu(III) is thought to be reduced to Eu(II) in molten LiCl-KCl spontaneously at relatively low concentration (< 7.5 × 10{sup -4} M). Raman spectroscopy was employed to investigate the oxidation state of EuClx in LiCl-KCl at 500 .deg. C. The Raman scattering results suggest the majority of trivalent europium is reduced to divalent state with the composition change by vaporization. The Raman bands show highly asymmetric structure, quite different from regular octahedral structure.

  9. Theoretical studies of positron states and annihilation characteristics at the oxidized Cu(100) surface

    Energy Technology Data Exchange (ETDEWEB)

    Fazleev, N. G. [Department of Physics, Box 19059, University of Texas at Arlington, Arlington Texas 76019 (United States) and Institute of Physics, Kazan Federal University, Kremlevskaya18, Kazan 420008 (Russian Federation); Weiss, A. H. [Department of Physics, Box 19059, University of Texas at Arlington, Arlington Texas 76019 (United States)

    2013-04-19

    In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. An ab-initio study of the electronic properties of the Cu(100) missing row reconstructed surface at various on surface and sub-surface oxygen coverages has been performed on the basis of the density functional theory (DFT) using the Dmol3 code and the generalized gradient approximation (GGA). Surface structures in calculations have been constructed by adding oxygen atoms to various surface hollow and sub-surface octahedral sites of the 0.5 monolayer (ML) missing row reconstructed phase of the Cu(100) surface with oxygen coverages ranging from 0.5 to 1.5 ML. The charge redistribution at the surface and variations in atomic structure and chemical composition of the topmost layers associated with oxidation and surface reconstruction have been found to affect the spatial extent and localization of the positron surface state wave function and annihilation probabilities of surface trapped positrons with relevant core electrons. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES). It has been shown that positron annihilation probabilities with Cu 3s and 3p core electrons decrease when total (on-surface and sub-surface) oxygen coverage of the Cu(100) surface increases up to 1 ML. The calculations show that for high oxygen coverage when total oxygen coverage is 1. 5 ML the positron is not bound to the surface.

  10. Moessbauer effect study of oxidation and coordination states of iron in some sodium borate glasse:;

    International Nuclear Information System (INIS)

    Eissa, N.A.; Sanad, A.M.; Youssef, S.M.; El-Henawii, S.A.; Gomaa, S.Sh.; Mostafa, A.G.

    1980-01-01

    A structural study of some sodium borate glasses containing iron was carried out applying ME spectroscopy. Both oxidation and coordination states of iron were investigated under the effect of gradual replacing of sodium carbonate by sodium nitrate in the glass batches. The glasses were melted in porcelain crucibles using an electrically heated furnace at 1000+-10 deg C, then were quenched on a steel plate at room temperature (R.T.). The ME source was 20 mCi radioactive Co-57 in chromium. The obtained ME spectra indicated that at lower sodium nitrate content both Fe 2+ and Fe 3+ are present in these glasses. At moderate concentrations some Fe 3+ ions were separated in a crystalline phase and the rest of the iron ions appeared as ferric ions in glassy state. At high sodium nitrate content only Fe 3+ ions in glassy state were detected. The values of the ME parameters for all iron ions indicated that all of them are in the octahedral coordination state. The density measurements confirm the separation of a crystalline phase at moderate sodium nitrate content. (author)

  11. Solid-state ionics: Studies of lithium-conducting sulfide glasses and a superconducting oxide compound

    International Nuclear Information System (INIS)

    Ahn, Byung Tae.

    1989-01-01

    The first part of this work studies lithium-conducting sulfide glasses for battery applications, while the second part studies the thermodynamic properties of a superconducting oxide compound by using an oxide electrolyte. Lithium conducting glasses based on the SiS 2 -Li 2 S system are possible solid electrolytes for high-energy-density lithium batteries. The foremost requirement for solid electrolytes is that they should have high ionic conductivities. Unfortunately, most crystalline lithium conductors have low ionic conductivities at room temperature. However, glass ionic conductors show higher ionic conductivities than do crystalline forms of the same material. In addition to higher ionic conductivities, glasses appear to have several advantages over crystalline materials. These advantages include isotropic conductivity, absence of grain boundary effects, ease of glass forming, and the potential for a wide range of stability to oxidizing and reducing conditions. Using pyrolitic graphite-coated quartz ampoules, new ternary compounds and glasses in the SiS 2 -Li 2 S system were prepared. Several techniques were used to characterize the materials: powder x-ray diffraction, differential thermal analysis, differential scanning calorimetry, and AC impedance spectroscopy. The measured lithium conductivity of the sulfide glasses was one of the highest among the known solid lithium conductors. Measuring the equilibrium open circuit voltages assisted in determining the electrochemical stabilities of the ternary compounds and glasses with respect to pure Li. A solid-state ionic technique called oxygen coulometric titration was used to measure the thermodynamic stability, the oxygen stoichiometry, and the effects of the oxygen stoichiometry, and the effects of the oxygen stoichiometry and the cooling rate on superconductivity of the YBa 2 Cu 3 O 7-x compound were investigated

  12. Electrochemical and spectroscopic studies of some less stable oxidation states of selected lanthanide and actinide elements

    International Nuclear Information System (INIS)

    Hobart, D.E.

    1981-06-01

    Simultaneous observation of electrochemical and spectroscopic properties (spectroelectrochemistry) at optically transparent electrodes (OTE's) was used to study some less stable oxidation states of selected lanthanide and actinide elements. Cyclic voltammetry at microelectrodes was used in conjunction with spectroelectrochemistry for the study of redox couples. Additional analytical techniques were used. The formal reduction potential (E 0 ') values of the M(III)/M(II) redox couples in 1 M KCl at pH 6 were -0.34 +- 0.01 V for Eu, -1.18 +- 0.01 V for Yb, and -1.50 +- 0.01 V for Sm. Spectropotentiostatic determination of E 0 ' for the Eu(III)/Eu(II) redox couple yielded a value of -0.391 +- 0.005 V. Spectropotentiostatic measurement of the Ce(IV)/Ce(III) redox couple in concentrated carbonate solution gave E 0 ' equal to 0.051 +- 0.005 V, which is about 1.7 V less positive than the E 0 ' value in noncomplexing solution. This same difference in potential was observed for the E 0 ' values of the Pr(IV)/Pr(III) and Tb(IV)/Tb(III) redox couples in carbonate solution, and thus Pr(IV) and Tb(IV) were stabilized in this medium. The U(VI)/U(V)/U(IV) and U(IV)/U(III) redox couples were studied in 1 M KCl at OTE's. Spectropotentiostatic measurement of the Np(VI)/Np(V) redox couple in 1 M HClO 4 gave an E 0 ' value of 1.140 +- 0.005 V. An E 0 ' value of 0.46 +- 0.01 V for the Np(VII)/Np(VI) couple was found by voltammetry. Oxidation of Am(III) was studied in concentrated carbonate solution, and a reversible cyclic voltammogram for the Am(IV)/Am(III) couple yielded E 0 ' = 0.92 +- 0.01 V in this medium; this value was used to estimate the standard reduction potential (E 0 ) of the couple as 2.62 +- 0.01 V. Attempts to oxidize Cm(III) in concentrated carbonate solution were not successful which suggests that the predicted E 0 value for the Cm(IV)/Cm(III) redox couple may be in error

  13. Structural oxidation state studies of the manganese cluster in the oxygen evolving complex of photosystem II

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Wenchuan [Univ. of California, Berkeley, CA (United States)

    1994-11-01

    X-ray absorption spectroscopy (XAS) was performed on Photosystem II (PSII)-enriched membranes prepared from spinach to explore: (1) the correlation between structure and magnetic spin state of the Mn cluster in the oxygen evolving complex (OEC) in the S2 state; and (2) the oxidation state changes of the Mn cluster in the flash-induced S-states. The structure of the Mn cluster in the S2 state with the g~4 electron paramagnetic resonance (EPR) signal (S2-g4 state) was compared with that in the S2 state with multiline signal (S2-MLS state) and the S1 state. The S2-g4 state has a higher XAS inflection point energy than that of the S1 state, indicating the oxidation of Mn in the advance from the S1 to the S2-g4 state. Differences in the edge shape and in the extended X-ray absorption fine structure (EXAFS) show that the structure of the Mn cluster in the S2-g4 state is different from that in the S2-MLS or the S1 state. In the S2-g4 state, the second shell of backscatterers from the Mn absorber contains two Mn-Mn distances of 2.73 Å and 2.85 Å. Very little distance disorder exists in the second shell of the S1 or S2-MLS states. The third shell of the S2-g4 state at about 3.3 Å also contains increased heterogeneity relative to that of the S2-MLS or the S1 state. Various S-states were prepared at room-temperature by saturating, single-turnover flashes. The flash-dependent oscillation in the amplitude of the MLS was used to characterize the S-state composition and to construct "pure" S-state Mn K-edge spectra. The edge position shifts to higher energy by 1.8 eV upon the S1 → S2 transition.

  14. Radiation oxidation of polypropylene: A solid-state 13C NMR study using selective isotopic labeling

    International Nuclear Information System (INIS)

    Mowery, Daniel M.; Assink, Roger A.; Derzon, Dora K.; Klamo, Sara B.; Bernstein, Robert; Clough, Roger L.

    2007-01-01

    Polypropylene samples, in which the three different carbon atoms along the chain were selectively labeled with carbon-13, were subjected to radiation under inert and air atmospheres, and to post-irradiation exposure in air at various temperatures. By using solid-state 13 C NMR measurements at room temperature, we have been able to identify and quantify the oxidation products. The isotopic labeling provides insight into chemical reaction mechanisms, since oxidation products can be traced back to their positions of origin on the macromolecule. The major products include peroxides and alcohols, both formed at tertiary carbon sites along the chain. Other products include methyl ketones, acids, esters, peresters, and hemiketals formed from reaction at the tertiary carbon, together with in-chain ketones and esters from reaction at the secondary chain carbon. No evidence is found of products arising from reactions at the methyl side chain. Significant temperature-dependent differences are apparent; for example much higher yields of chain-end methyl ketones, which are the indicator product of chain scission, are generated for both elevated temperature irradiation and for post-irradiation treatment at elevated temperatures. Time-dependent plots of yields of the various oxidation products have been obtained under a wide range of conditions, including the post-irradiation oxidation of a sample at room temperature in air that has been monitored for 2 years. Radiation-oxidation products of polypropylene are contrasted to products measured for 13 C-labeled polyethylene in an earlier investigation: the peroxides formed in irradiated polypropylene are remarkably longer lived, the non-peroxidic products are significantly different, and the overall ratios of oxidation products in polypropylene change relatively little as a function of the extent of oxidation

  15. Studi On Oxidation State Of U In Ba2NdUO6

    International Nuclear Information System (INIS)

    Firman Windarto, Hendri

    1996-01-01

    Ba 2 NdUO 6 is not of the important compounds that is formed from a solidification process for high level liquid waste using super high temperature method Ba 2 NdUO 6 has ordered perovskite structure. The objective of this study is to investigate oxidation state of U in Ba 2 NdUO 6 . The properties of Ba 2 NdUO 6 were observed by using Faraday-type torsion magnetometer and X-ray Photoelectron Spectrometer (XPS). The magnetic susceptibility measured in the temperature range of 4K to room temperature showed that the Ba 2 NdUO 6 is paramagnetism that obeys the Curie-Weiss law. The effective moment of Ba 2 NdUO 6 is 3.04 μB. The results of xPs spectrum showed that the peaks of U4f for Ba 2 NdUO 6 appeared exactly between binding energy of UO 2 and UO 3 . It can be concluded that Ba 2 NdUO 6 has binding energy peaks corresponding to pentavalent uranium

  16. Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, K.D.; Sposito, G.

    2010-02-01

    Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

  17. Electronic state of ruthenium deposited onto oxide supports: An XPS study taking into account the final state effects

    International Nuclear Information System (INIS)

    Larichev, Yurii V.; Moroz, Boris L.; Bukhtiyarov, Valerii I.

    2011-01-01

    The electronic state of ruthenium in the supported Ru/EO x (EO x = MgO, Al 2 O 3 or SiO 2 ) catalysts prepared by with the use of Ru(OH)Cl 3 or Ru(acac) 3 (acac = acetylacetonate) and reduced with H 2 at 723 K is characterized by X-ray photoelectron spectroscopy (XPS) in the Ru 3d, Cl 2p and O 1s regions. The influence of the final state effects (the differential charging and variation of the relaxation energy) on the binding energy (BE) of Ru 3d 5/2 core level measured for supported Ru nanoparticles is estimated by comparison of the Fermi levels and the modified Auger parameters determined for the Ru/EO x samples with the corresponding characteristics of the bulk Ru metal. It is found that the negative shift of the Ru 3d 5/2 peak which is observed in the spectrum of ruthenium deposited onto MgO (BE = 279.5-279.7 eV) with respect to that of Ru black (BE = 280.2 eV) or ruthenium supported on γ-Al 2 O 3 and SiO 2 (BE = 280.4 eV) is caused not by the transfer of electron density from basic sites of MgO, as considered earlier, but by the differential charging of the supported Ru particles compared with the support surface. Correction for the differential charging value reveals that the initial state energies of ruthenium in the Ru/EO x systems are almost identical (BE = 280.5 ± 0.1 eV) irrespectively of acid-base properties of the support, the mean size of supported Ru crystallites (within the range of 2-10 nm) and the surface Cl content. The results obtained suggest that the difference in ammonia synthesis activity between the Ru catalysts supported on MgO and on the acidic supports is accounted for by not different electronic state of ruthenium on the surface of these oxides but by some other reasons.

  18. A detailed study on the transition from the blocked to the superparamagnetic state of reduction-precipitated iron oxide nanoparticles

    International Nuclear Information System (INIS)

    Witte, K.; Bodnar, W.; Mix, T.; Schell, N.; Fulda, G.; Woodcock, T.G.; Burkel, E.

    2016-01-01

    Magnetic iron oxide nanoparticles were prepared by salt-assisted solid-state chemical precipitation method with alternating fractions of the ferric iron content. The physical properties of the precipitated nanoparticles mainly consisting of magnetite were investigated by means of transmission electron microscopy, high energy X-ray diffraction, vibrating sample magnetometry and Mössbauer spectroscopy. With particle sizes ranging from 16.3 nm to 2.1 nm, a gradual transition from the blocked state to the superparamagnetic state was observed. The transition was described as a dependence of the ferric iron content used during the precipitation. Composition, mean particle size, coercivity, saturation polarisation, as well as hyperfine interaction parameters and their evolution were studied systematically over the whole series of iron oxide nanoparticles. - Highlights: • Study of superparamagnetic transition of magnetite varying ferric iron content. • Coercivity is mainly influenced by the particle size. • Saturation polarisation influenced by the goethite content and the particle size. • Number of vacancies tend to increase with increasing ferric iron content. • Fe 3 O 4 B-sites are stronger effected by the reduction of particle size than A-sites.

  19. Electrochemistry and time dependent DFT study of a (vinylenedithio)-TTF derivative in different oxidation states

    NARCIS (Netherlands)

    Halpin, Yvonne; Schulz, Martin; Brooks, Andrew C.; Browne, Wesley R.; Wallis, John D.; Gonzalez, Leticia; Day, Peter; Vos, Johannes G.

    2013-01-01

    The electrochemical and spectroelectrochemical properties of a bis-pyrid-4-yl functionalised vinylenedithio-TFF derivative, 1, in solution are reported. The compound was immobilised on a Pt electrode and the resulting layers formed were investigated using electrochemical techniques. Two oxidation

  20. Study of the oxidation state of arsenic and uranium in individual particles from uranium mine tailings, Hungary

    International Nuclear Information System (INIS)

    Alsecz, A.; Osan, J.; Palfalvi, J.; Torok, Sz.; Sajo, I.; Mathe, Z.; Simon, R.; Falkenberg, G.

    2007-01-01

    Uranium ore mining and milling have been terminated in the Mecsek Mountains (southwest Hungary) in 1997. Mine tailings ponds are located between two important water bases, which are resources of the drinking water of the city of Pecs and the neighbouring villages. The average U concentration of the tailings material is 71.73 μg/g, but it is inhomogeneous. Some microscopic particles contain orders of magnitude more U than the rest of the tailings material. Other potentially toxic elements are As and Pb of which chemical state is important to estimate mobility, because in mobile form they can risk the water basis and the public health. Individual U-rich particles were selected with solid state nuclear track detector (SSNTD) and after localisation the particles were investigated by synchrotron radiation based microanalytical techniques. The distribution of elements over the particles was studied by micro beam X-ray fluorescence (μ-XRF) and the oxidation state of uranium and arsenic was determined by micro X-ray absorption near edge structure (μ-XANES) spectroscopy. Some of the measured U-rich particles were chosen for studying the heterogeneity with μ-XRF tomography. Arsenic was present mainly in As(V) and uranium in U(VI) form in the original uranium ore particles, but in the mine tailings samples uranium was present mainly in the less mobile U(IV) form. Correlation was found between the oxidation state of As and U in the same analyzed particles. These results suggest that dissolution of uranium is not expected in short term period. (authors)

  1. Experimental study of the oxide film structural phase state in the E635 and E110 alloys

    International Nuclear Information System (INIS)

    Shevyakov, A. Yu.; Shishov, V. N.; Novikov, V. V.

    2013-01-01

    The microstructure, phase and element compositions of oxide films of E110 (Zr-1%Nb) and E635 (Zr-1%Nb-0,35%Fe-1,2%Sn) alloys after autoclave tests in pure water had been studied by the method of transmission electron microscopy (TEM) with energy dispersive X-ray spectroscopy (EDS). TEM investigations of oxide film structure were carried on different oxide layers according to their thickness (near interface of “metal-oxide”, in central part of the oxide film and near outer surface) and in cross-section. The results of the tests show that oxide films of the alloys have different microstructure (grain size, fraction of tetragonal phase, content of defects, etc) and the phase compositions. The crystal structure of oxide films is mainly monoclinic, however, at the “metal-oxide” interface there are a significant fraction of the tetragonal phase. Researching of oxides on different stages of oxidation allow us to determine the kinetics of the second phase precipitate structure change: a) in E635 alloy at early oxidation stages of the amorphization process of the Laves phase precipitates begins with decreasing the content of iron and niobium; b) in E110 alloy the amorphization process of β-Nb precipitates begins at a later stage of oxidation. The influence of changes of the crystal structure and the chemical composition of the second phase precipitates on protective properties of the oxides had been determined. Researching of alloying element redistribution in E635 alloy oxide film shows that iron and niobium are concentrated in pores. Increased porosity of the E635 alloy oxide films at a later oxidation stage, in comparison with the E110 alloy, shows the influence of change composition and subsequent dissolution of the Laves phase particles on the pore formation in the oxide. (authors)

  2. Oxidizer Scoping Studies

    Energy Technology Data Exchange (ETDEWEB)

    Chancellor, Christopher John [Los Alamos National Laboratory

    2016-11-07

    The purpose of this report is to present the results of the acceptable knowledge (AK) review of oxidizers present in active waste streams, provide a technical analysis of the oxidizers, and report the results of the scoping study testing. This report will determine the fastest burning oxidizer to be used in the development of a Test Plan for Preparation and Testing of Sorbents Mixed with Oxidizer found in Transuranic Waste (DWT-TP-001). The companion report, DWT-RPT-002, Sorbent Scoping Studies, contains similar information for sorbents identified during the AK review of TRU waste streams. The results of the oxidizer and sorbent scoping studies will be used to inform the QL1 test plan. The QL1 test results will support the development of a basis of knowledge document that will evaluate oxidizing chemicals and sorbents in TRU waste and provide guidance for treatment.

  3. Correlation of the oxidation state of cerium in sol-gel glasses as a function of thermal treatment via optical spectroscopy and XANES studies.

    Science.gov (United States)

    Assefa, Zerihun; Haire, R G; Caulder, D L; Shuh, D K

    2004-07-01

    Sol-gel glass matrices containing lanthanides have numerous technological applications and their formation involves several chemical facets. In the case of cerium, its ability to exist in two different oxidation states or in mixed valence state provides additional complexities for the sol-gel process. The oxidation state of cerium present during different facets of preparation of sol-gel glasses, and also as a function of the starting oxidation state of cerium added, were studied both by optical spectroscopy and X-ray absorption near-edge structures (XANES). The findings acquired by each approach were compared. The primary focus was on the redox chemistries associated with sample preparation, gelation, and thermal treatment. When Ce3+ is introduced into the starting sols, the trivalent state normally prevails in the wet and room temperature-dried gels. Heating in air at >100 degrees C can generate a light yellow coloration with partial oxidation to the tetravalent state. Above 200 degrees C and up to approximately 1000 degrees C, cerium is oxidized to its tetravalent state. In contrast, when tetravalent cerium is introduced into the sol, both the wet and room temperature-dried gels lose the yellow-brown color of the initial ceric ammonium nitrate solution. When the sol-gel is heated to 110 degrees C it turns yellowish as the cerium tends to be re-oxidized. The yellow color is believed to represent the effect of oxidation and oligomerization of the cerium-silanol units in the matrix. The luminescence properties are also affected by these changes, the details of which are reported herein.

  4. Air oxidation of Zr65Cu17.5Ni10Al7.5 in its amorphous and supercooled liquid states, studied by thermogravimetric analysis

    International Nuclear Information System (INIS)

    Dhawan, A.; Sharma, S.K.; Raetzke, K.; Faupel, F.

    2003-01-01

    The oxidation behaviour of the bulk amorphous alloy Zr 65 Cu 17.5 Ni 10 Al 7.5 was studied in air at various temperatures in the temperature range 591-732 K using a thermogravimetric analyser (TGA). The oxidation kinetics of the alloy obeys the parabolic rate law showing two different linear regions (in the plots of mass gain versus square root of oxidation time) which are attributed to the amorphous and the supercooled liquid states of the alloy. The value of the activation energy Q for the amorphous state as calculated from the temperature dependence of the rate constants is found to be 1.80±0.1 eV and the corresponding value obtained for the supercooled liquid state is 1.20±0.1 eV. It is suggested that the rate controlling process during oxidation of the amorphous state is the back-diffusion of Ni, and possibly Cu also, while the oxidation in the supercooled liquid state is dominated by the inward diffusion of oxygen. (copyright 2003 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  5. Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Jernigan, Glenn Geoffrey [California Univ., Berkeley, CA (United States). Dept. of Chemistry

    1994-10-01

    Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu2O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu2O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu2O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N2 and CO2. At the end of each reaction, the catalyst was found to be Cu2O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

  6. Study concerning the compatibility of the mixture of nylon-6 and poly(propylene oxide) through solid state NMR

    International Nuclear Information System (INIS)

    Tavares, Maria I.B.; Costa, D.A.; Menezes, Sonia M.C.

    1993-01-01

    NMR has been frequently used for the determination of polymers compatibility. The utilization of the simple pulse technique together with the contact time variation technique has been enabling the evaluation of the compatibility of polymeric systems. This work presents the study of the behaviour of the mixture composed by nylon-6 with poly(propylene oxide) using these techniques. Results are presented

  7. Oxidation-state maxima in plutonium chemistry

    International Nuclear Information System (INIS)

    Silver, G.L.

    2013-01-01

    Maxima in the fractions of the trivalent and hexavalent oxidation states of plutonium are inherent in the algebra of its disproportionation reactions. The maxima do not support overall disproportionation equations as satisfactory representations of aqueous plutonium. (author)

  8. Multiscale Transient and Steady-State Study of the Influence of Microstructure Degradation and Chromium Oxide Poisoning on Solid Oxide Fuel Cell Cathode Performance

    Science.gov (United States)

    Li, Guanchen; von Spakovsky, Michael R.; Shen, Fengyu; Lu, Kathy

    2018-01-01

    Oxygen reduction in a solid oxide fuel cell cathode involves a nonequilibrium process of coupled mass and heat diffusion and electrochemical and chemical reactions. These phenomena occur at multiple temporal and spatial scales, making the modeling, especially in the transient regime, very difficult. Nonetheless, multiscale models are needed to improve the understanding of oxygen reduction and guide cathode design. Of particular importance for long-term operation are microstructure degradation and chromium oxide poisoning both of which degrade cathode performance. Existing methods are phenomenological or empirical in nature and their application limited to the continuum realm with quantum effects not captured. In contrast, steepest-entropy-ascent quantum thermodynamics can be used to model nonequilibrium processes (even those far-from equilibrium) at all scales. The nonequilibrium relaxation is characterized by entropy generation, which can unify coupled phenomena into one framework to model transient and steady behavior. The results reveal the effects on performance of the different timescales of the varied phenomena involved and their coupling. Results are included here for the effects of chromium oxide concentrations on cathode output as is a parametric study of the effects of interconnect-three-phase-boundary length, oxygen mean free path, and adsorption site effectiveness. A qualitative comparison with experimental results is made.

  9. Study of crystalline morphology and phase structure in poly(styrene-b-ethylene oxide-b-styrene) triblock copolymers bu solid state RMN spin diffusion

    International Nuclear Information System (INIS)

    Mantovani, Gerson L.; Phan, Trang; Bertin, Denis; Azevedo, Eduardo R. de; Bonagamba, Tito J.

    2009-01-01

    The phase structure and crystalline morphology of a series of polystyrene-b-polyethylene oxide-b-polystyrene (PS-b- PEO-b-PS) triblock copolymers, with different compositions and molecular weights, has been studied by solid-state NMR. WAXS and DSC measurements were used to detect the presence of crystalline domains of polyethylene oxide (PEO) blocks at room temperature as a function of the copolymer composition. 1 H NMR spin diffusion analyses provided an estimation of the size of the dispersed phases of the nano structured copolymers. (author)

  10. Photochemical oxidants: state of the science.

    Science.gov (United States)

    Kley, D; Kleinmann, M; Sanderman, H; Krupa, S

    1999-01-01

    Atmospheric photochemical processes resulting in the production of tropospheric ozone (O(3)) and other oxidants are described. The spatial and temporal variabilities in the occurrence of surface level oxidants and their relationships to air pollution meteorology are discussed. Models of photooxidant formation are reviewed in the context of control strategies and comparisons are provided of the air concentrations of O(3) at select geographic locations around the world. This overall oxidant (O(3)) climatology is coupled to human health and ecological effects. The discussion of the effects includes both acute and chronic responses, mechanisms of action, human epidemiological and plant population studies and briefly, efforts to establish cause-effect relationships through numerical modeling. A short synopsis is provided of the interactive effects of O(3) with other abiotic and biotic factors. The overall emphasis of the paper is on identifying the current uncertainties and gaps in our understanding of the state of the science and some suggestions as to how they may be addressed.

  11. Zircaloy oxidation studies

    International Nuclear Information System (INIS)

    Prater, J.T.; Beauchamp, R.H.; Saenz, N.T.

    1985-06-01

    The oxidation kinetics of Zircaloy-4 in steam have been determined at 1300-2400 0 C. Growth of the ZrO 2 and α-Zr layers display parabolic behavior over the entire temperature range studied. A discontinuity in the oxidation kinetics at 1510 0 C causes rates to increase above those previously established by the Baker-Just relationship. This increase coincides with the tetragonal-to-cubic phase transformation in ZrO/sub 2-x/. No discontinuity in the oxide growth rate is observed upon melting of Zr(0). The effects of temperature gradients have been taken into account and corrected values representative of near-isothermal conditions have been computed

  12. Using air quality modeling to study source-receptor relationships between nitrogen oxides emissions and ozone exposures over the United States.

    Science.gov (United States)

    Tong, Daniel Q; Muller, Nicholas Z; Kan, Haidong; Mendelsohn, Robert O

    2009-11-01

    Human exposure to ambient ozone (O(3)) has been linked to a variety of adverse health effects. The ozone level at a location is contributed by local production, regional transport, and background ozone. This study combines detailed emission inventory, air quality modeling, and census data to investigate the source-receptor relationships between nitrogen oxides (NO(x)) emissions and population exposure to ambient O(3) in 48 states over the continental United States. By removing NO(x) emissions from each state one at a time, we calculate the change in O(3) exposures by examining the difference between the base and the sensitivity simulations. Based on the 49 simulations, we construct state-level and census region-level source-receptor matrices describing the relationships among these states/regions. We find that, for 43 receptor states, cumulative NO(x) emissions from upwind states contribute more to O(3) exposures than the state's own emissions. In-state emissions are responsible for less than 15% of O(3) exposures in 90% of U.S. states. A state's NO(x) emissions can influence 2 to 40 downwind states by at least a 0.1 ppbv change in population-averaged O(3) exposure. The results suggest that the U.S. generally needs a regional strategy to effectively reduce O(3) exposures. But the current regional emission control program in the U.S. is a cap-and-trade program that assumes the marginal damage of every ton of NO(x) is equal. In this study, the average O(3) exposures caused by one ton of NO(x) emissions ranges from -2.0 to 2.3 ppm-people-hours depending on the state. The actual damage caused by one ton of NO(x) emissions varies considerably over space.

  13. Thermodynamic Ground States of Complex Oxide Heterointerfaces

    DEFF Research Database (Denmark)

    Gunkel, F.; Hoffmann-Eifert, S.; Heinen, R. A.

    2017-01-01

    The formation mechanism of 2-dimensional electron gases (2DEGs) at heterointerfaces between nominally insulating oxides is addressed with a thermodynamical approach. We provide a comprehensive analysis of the thermodynamic ground states of various 2DEG systems directly probed in high temperature...

  14. Higher Americium Oxidation State Research Roadmap

    Energy Technology Data Exchange (ETDEWEB)

    Mincher, Bruce J. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Law, Jack D. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Goff, George S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Moyer, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Burns, Jon D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lumetta, Gregg J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Sinkov, Sergey I. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Shehee, Thomas C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hobbs, David T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2015-12-18

    The partitioning of hexavalent Am from dissolved nuclear fuel requires the ability to efficiently oxidize Am(III) to Am(VI) and to maintain that oxidation state for a length of time sufficient to perform the separation. Several oxidants have been, or are being developed. Chemical oxidants include Ag-catalyzed ozone, Ag-catalyzed peroxydisulfate, Cu(III) periodate, and sodium bismuthate. Hexavalent americium has also now successfully been prepared by electrolysis, using functionalized electrodes. So-called auto-reduction rates of Am(VI) are sufficiently slow to allow for separations. However, for separations based on solvent extraction or ion exchange using organic resins, the high valence state must be maintained under the reducing conditions of the organic phase contact, and a holding oxidant is probably necessary. Until now, only Cu(III) periodate and sodium bismuthate oxidation have been successfully combined with solvent extraction separations. Bismuthate oxidation provided the higher DAm, since it acts as its own holding oxidant, and a successful hot test using centrifugal contactors was performed. For the other oxidants, Ag-catalyzed peroxydisulfate will not oxidize americium in nitric acid concentrations above 0.3 M, and it is not being further investigated. Peroxydisulfate in the absence of Ag catalysis is being used to prepare Am(V) in ion exchange work, discussed below. Preliminary work with Ag-catalyzed ozone has been unsuccessful for extractions of Am(VI) from 6.5 M HNO3, and only one attempt at extraction, also from 6.5 M HNO3, using the electrolytic oxidation has been attempted. However, this high acid concentration was based on the highest Am extraction efficiency using the bismuthate oxidant; which is only sparingly soluble, and thus the oxidation yield is based on bismuthate solubility. Lower acid concentrations may be sufficient with alternative oxidants and work with Ag-ozone, Cu(III) and electrolysis is on-going. Two non

  15. Operando XAS Study of the Surface Oxidation State on a Monolayer IrOx on RuOx and Ru Oxide Based Nanoparticles for Oxygen Evolution in Acidic Media

    DEFF Research Database (Denmark)

    Pedersen, Anders Filsøe; Escribano, Maria Escudero; Sebok, Bela

    2018-01-01

    that the average Ir oxidation state change is strongly affected by the coverage of atomic O. The observed shifts in oxidation state suggest that the surface has a high coverage of O at potentials just below the potential where oxygen evolution is exergonic in free energy. This observation is consistent...

  16. Charge state of oxide layer of SIMOX-structures

    CERN Document Server

    Askinazi, A Y; Dmitriev, V A; Miloglyadova, L V

    2001-01-01

    The charge state of the oxide layer of the SIMOX-structures, obtained in the course of forming the oxide layers, bricked up in the silicon volume, through the oxygen ions implantation into the Si, is studied. The charge state of the given structures is studied through the method of the layer-by-layer profiling, which makes it possible to obtain the dependence of the plane zones potential on the oxide layer thickness. It is established, that during the process of the SIMOX-structures formation in the oxide layer near the boundary with the Si there appear defects, responsible for the charge. The radiation from the near-the-ultraviolet (NUV) area without the applied electric field neutralizes the given charge. The simultaneous impact of the NUV-radiation and electric field leads to the formation of significantly positive charge

  17. A study of relaxation mechanisms in the A{sup 2}{Sigma}{sup +} state of nitric oxide by time resolved double resonant polarization spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Stampanoni-Panariello, A; Bombach, R; Hemmerling, B; Hubschmid, W [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    Double resonant polarization labeling spectroscopy is applied to detect nitric oxide in flames and to characterize rotational energy transfer and orientation changing collisions in its first excited electronic state. (author) 4 figs., 3 refs.

  18. Oxidation Resistant Graphite Studies

    Energy Technology Data Exchange (ETDEWEB)

    W. Windes; R. Smith

    2014-07-01

    The Very High Temperature Reactor (VHTR) Graphite Research and Development Program is investigating doped nuclear graphite grades exhibiting oxidation resistance. During a oxygen ingress accident the oxidation rates of the high temperature graphite core region would be extremely high resulting in significant structural damage to the core. Reducing the oxidation rate of the graphite core material would reduce the structural effects and keep the core integrity intact during any air-ingress accident. Oxidation testing of graphite doped with oxidation resistant material is being conducted to determine the extent of oxidation rate reduction. Nuclear grade graphite doped with varying levels of Boron-Carbide (B4C) was oxidized in air at nominal 740°C at 10/90% (air/He) and 100% air. The oxidation rates of the boronated and unboronated graphite grade were compared. With increasing boron-carbide content (up to 6 vol%) the oxidation rate was observed to have a 20 fold reduction from unboronated graphite. Visual inspection and uniformity of oxidation across the surface of the specimens were conducted. Future work to determine the remaining mechanical strength as well as graphite grades with SiC doped material are discussed.

  19. Oxidatively generated DNA/RNA damage in psychological stress states

    DEFF Research Database (Denmark)

    Jørgensen, Anders

    2013-01-01

    age-related somatic disorders. The overall aim of the PhD project was to investigate the relation between psychopathology, psychological stress, stress hormone secretion and oxidatively generated DNA and RNA damage, as measured by the urinary excretion of markers of whole-body DNA/RNA oxidation (8...... between the 24 h urinary cortisol excretion and the excretion of 8-oxodG/8-oxoGuo, determined in the same samples. Collectively, the studies could not confirm an association between psychological stress and oxidative stress on nucleic acids. Systemic oxidatively generated DNA/RNA damage was increased......Both non-pathological psychological stress states and mental disorders are associated with molecular, cellular and epidemiological signs of accelerated aging. Oxidative stress on nucleic acids is a critical component of cellular and organismal aging, and a suggested pathogenic mechanism in several...

  20. Kinetic Studies on State of the Art Solid Oxide Cells – A Comparison between Hydrogen/Steam and Reformate Fuels

    DEFF Research Database (Denmark)

    Njodzefon, Jean-Claude; Graves, Christopher R.; Mogensen, Mogens Bjerg

    2015-01-01

    Electrochemical reaction kinetics at the electrodes of Solid Oxide Cells (SOCs) were investigated at 700 °C for two cells with different fuel electrode microstructures as well as on a third cell with a reduced active electrode area. Three fuel mixtures were investigated – hydrogen/steam and refor......Electrochemical reaction kinetics at the electrodes of Solid Oxide Cells (SOCs) were investigated at 700 °C for two cells with different fuel electrode microstructures as well as on a third cell with a reduced active electrode area. Three fuel mixtures were investigated – hydrogen....../steam fuel split into two processes with opposing temperature behavior in the reformate fuels. An 87.5% reduction in active electrode area diminishes the gas conversion impedance in the hydrogen/steam fuel at high fuel flow rates. In both reformates, the second and third lowest frequency processes merged...

  1. Plutonium disproportionation. Hydrolysis and local oxidation-state maxima

    International Nuclear Information System (INIS)

    Silver, G.L.

    2014-01-01

    Local maxima in the fractions of the trivalent and hexavalent oxidation states are inherent in the algebra of Pu disproportionation reactions. A new method predicts the pH and the oxidation-state fractions at maximum. Tabulated results illustrate the effects of the Pu oxidation number and Pu(IV) hydrolysis on the maxima. This method suggests a new laboratory approach for discovering Pu oxidation-state maxima. (author)

  2. One-electron oxidation of the hydroquinonic form of vitamin K by OH· and N3· free radicals. A steady-state gamma radiolysis study

    International Nuclear Information System (INIS)

    Nguyen Van Binh, E.; Gardes-Albert, M.; Ferradini, C.; Acher, F.; Azerad, R.

    1991-01-01

    The oxidation of a water-soluble model of vitamin K hydroquinone, symbolised by KH 2 p, has been studied by γ radiolysis using OH· or N 3 · free radicals as oxidants. Irradiation doses were up to 300 Gy. The analysis of final products by spectrophotometric absorption and HPLC allowed to characterize the formation of the quinone K and to estimate the initial yield of KH 2 p-disappearance and K-formation. N 3 · radicals led selectively to the formation of the quinone K with a G-value of (3.0 ± 0.3) x 10 -7 mol/J, thus involving a simple one-electron oxidation mechanism. On the contrary, when OH· radicals oxidized KH 2 p, in addition to the quinone, other non identified species were simultaneously produced during the radiolysis, thus requiring a more complex oxidation mechanism [fr

  3. Study of niobium oxidation by photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Durand, C.

    1985-01-01

    The chemical composition of thin oxide layers, grown on clean niobium, in low oxygen pressure, was studied by a surface analysis method: X-ray Photoelectron Spectroscopy. The purpose of this study was to find the best conditions for the building of Nb/Nb oxide/Pb Josephson junctions, and particularly to minimise the interface thickness during the formation of the insulator film (Nb 2 O 5 ) on the metal (Nb). This interface is essentially formed by the monoxide (NbO) and dioxide (NbO 2 ). Nb 3d XPS core level peak positions and area ratios (obtained by the signal decomposition) of the components of the total peak, were used to determine the presence of the different oxidation states II, IV and V, their relative abundance, oxide thicknesses and their depth distribution. All this information was extracted by a special numerical procedure [fr

  4. A 121Sb Moessbauer Study of the Chemical State of Antimony in V-Sb-O Mixed-Oxide Catalysts for the Ammoxidation of Propane

    International Nuclear Information System (INIS)

    Stievano, L.; Wagner, F. E.; Zanthoff, H. W.; Calogero, S.

    2002-01-01

    The structural changes of two representative samples of a group of V-Sb-oxide catalysts, a vanadium-rich and an antimony-rich specimen, are investigated by 121 Sb Moessbauer spectroscopy after treatment under propene or hydrogen at 673 K. The as-prepared catalysts contain both Sb(V) and Sb(III) as crystalline and microcrystalline α-Sb 2 O 4 and VSbO 4 , as well as an additional amorphous V 5+ oxide phase. The oxidation state of antimony does not change upon exposure to propene, whereas a partial reduction can be obtained by a more intense reduction under hydrogen. The Moessbauer results indicate that the antimony in VSbO 4 can be reduced more easily than that in α-Sb 2 O 4 , which appears to be more stable. These results are discussed in view of the observed depletion of vanadium at the surface of the catalyst particles under reaction conditions.

  5. Oxidative Stress and Heart Failure in Altered Thyroid States

    Directory of Open Access Journals (Sweden)

    Pallavi Mishra

    2012-01-01

    Full Text Available Increased or reduced action of thyroid hormone on certain molecular pathways in the heart and vasculature causes relevant cardiovascular derangements. It is well established that hyperthyroidism induces a hyperdynamic cardiovascular state, which is associated with a faster heart rate, enhanced left ventricular systolic and diastolic function whereas hypothyroidism is characterized by the opposite changes. Hyperthyroidism and hypothyroidism represent opposite clinical conditions, albeit not mirror images. Recent experimental and clinical studies have suggested the involvement of ROS tissue damage under altered thyroid status. Altered-thyroid state-linked changes in heart modify their susceptibility to oxidants and the extent of the oxidative damage they suffer following oxidative challenge. Chronic increase in the cellular levels of ROS can lead to a catastrophic cycle of DNA damage, mitochondrial dysfunction, further ROS generation and cellular injury. Thus, these cellular events might play an important role in the development and progression of myocardial remodeling and heart failure in altered thyroid states (hypo- and hyper-thyroidism. The present review aims at elucidating the various signaling pathways mediated via ROS and their modulation under altered thyroid state and the possibility of antioxidant therapy.

  6. X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites.

    Science.gov (United States)

    Gandhiraman, Ram P; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E; Chen, Bin; Meyyappan, M

    2014-08-14

    The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties as the graphene oxide transformation to reduced-graphene oxide is a key step in the synthesis of the electrode materials. Polarized behavior of the synchrotron X-rays and the angular dependency of the near-edge X-ray absorption fine structures (NEXAFS) have been utilized to study the orientation of the σ and π bonds of the graphene oxide and graphene oxide-metal oxide nanocomposites. The core-level transitions of individual metal oxides and that of the graphene oxide nanocomposite showed that the interaction of graphene oxide with the metal oxide nanostructures has not altered the electronic structure of either of them. As the restoration of the π network is important for good electrical conductivity, the C K edge NEXAFS spectra of reduced graphene oxide nanocomposites confirms the same through increased intensity of the sp 2 -derived unoccupied states π* band. A pronounced angular dependency of the reduced sample and the formation of excitonic peaks confirmed the formation of extended conjugated network.

  7. Study of transition metal oxides by photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Rao, C.N.R.; Sarma, D.D.; Vasudevan, S.; Hegde, M.S.

    1979-01-01

    Systematics in the X-ray photoelectron spectra (X.p.e.s.) of Ti, V, Cr, Mn and Nb oxides with the metal ion in different oxidation states as well as of related series of mono-, sesqui- and di-oxides of the first row of transition metals have been investigated in detail. Core level binding energies, spin-orbit splittings and exchange splittings are found to exhibit interesting variations with the oxidation state of the metal or the nuclear charge. The 3d binding energies of the monoxides show a proportionality to Goodenough's (R - RC). Other aspects of interest in the study are the satellite structure and final state effects in the X.p.e.s. of the oxides, and identification of different valence states in oxides of the general formulae Mn02n-1 and M304. The nature of changes in the 3d bands of oxides undergoing metal-insulator transitions is also indicated. (author)

  8. Study of oxidation states of the transition metals in a series of Prussian blue analogs using x-ray absorption near edge structure (XANES) spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Adak, S. [Department of Physics, New Mexico State University, Las Cruces, NM, 88003 (United States); Hartl, M., E-mail: monika.hartl@esss.se [European Spallation Source ESS AB, 22100, Lund (Sweden); Manuel Lujan Jr. Neutron Scattering Center (LANSCE-LC), Los Alamos National Laboratory, Los Alamos, NM, 87545 (United States); Daemen, L. [Spallation Neutron Source, Oak Ridge National Laboratory, Oak Ridge, TN, 37830 (United States); Manuel Lujan Jr. Neutron Scattering Center (LANSCE-LC), Los Alamos National Laboratory, Los Alamos, NM, 87545 (United States); Fohtung, E.; Nakotte, H. [Department of Physics, New Mexico State University, Las Cruces, NM, 88003 (United States)

    2017-01-15

    Highlights: • Systematic XANES measurements on Prussian blue analogs shows oxidation state of transition metals. • Cobal-iron bimetallic hexacyanometallates show unexpected oxidation states. • Iron(II) ions in hexacyanometallates(III) show varying spin state depending on their bond to the “N” end or “C” end of the cyanide ligand. • Thermal expansion coefficients have been linked to the XANES results. - Abstract: There have been renewed interests in metal-organic framework classes of materials such as Prussian blue analogues (PBAs) due to their potential usage in energy storage applications. In particular, due to their high surface areas, controllable structures and excellent electrochemical properties, PBAs such as hexacyanometalates M{sup II}{sub 3}[A{sup III}(CN){sub 6}]{sub 2*}nH{sub 2}O (M = Mn, Fe, Co, Ni, Cu, Zn; A = Co, Fe, Cr; n = no. of water molecules present), M{sup II}{sub 2}[Fe{sup II}(CN){sub 6}]{sub 2*}nH{sub 2}O (M = Mn, Co, Ni, Cu, Zn) and mixed hexacyanometalates(III) (Fe{sub 1-x}Co{sub x}){sub 3}[B{sup III}(CN){sub 6}]{sub 2}·nH{sub 2}O (x = 0.25, 0.5, 0.75; B = Co, Fe) could have possible usage as a new class of cathode and even anode materials for rechargeable batteries. Detailed knowledge of the oxidation states of the transition metals in PBAs is required to improve efficiency and durability of such devices. Furthermore, a link between the thermal expansion observed in these materials and the oxidation state of the transition metal is of interest to synthesize materials with a desired thermal expansion behavior, Here we demonstrate the use of Synchrotron based X-ray absorption near-edge structure (XANES) spectra to identify transition metal oxidation states. Our analysis reveals the presence of divalent, trivalent and/or mixed valence transition metals in the materials as well as high-spin and low-spin complexes.

  9. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    International Nuclear Information System (INIS)

    Schacht, L.; Navarrete, J.; Schacht, P.; Ramirez, M. A.

    2010-01-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

  10. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Schacht, L. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Ciencia de Materiales, Av. IPN s/n, Edificio 9, Col. Lindavista, 07738 Mexico D. F. (Mexico); Navarrete, J.; Schacht, P.; Ramirez, M. A., E-mail: pschacha@imp.m [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D. F. (Mexico)

    2010-07-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

  11. A feasibility study on oxidation state of arsenic in cut tobacco, mainstream cigarette smoke and cigarette ash by X-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Liu, C.; Hu, J.; McAdam, K.G.

    2009-01-01

    This work describes the application of synchrotron-based X-ray Absorption Near-Edge Structure spectroscopy to study the oxidation state of arsenic in cigarette mainstream smoke, cut tobacco and cigarette ash. The level of arsenic in the total particulate matter of the smoke is approximately 1 ppm for the standard research reference cigarette 2R4F and its replacement 3R4F. Smoke particulate samples collected by a conventional glass-fiber membrane (commercially known as Cambridge filter pad) and a jet-impaction method were analyzed and compared. In addition smoke particulate samples were aged either at ambient temperature or at 195 K. X-ray Absorption Near-Edge Structure spectroscopy results revealed that the cut tobacco powder and cigarette ash contained almost exclusively As V . The smoke particulate samples however contained a mixture of As III and As V . The As V in the smoke particulate was reduced to As III upon aging. Stabilizing the smoke particulate matter at 195 K by solid CO 2 slowed down this aging reaction and revealed a higher percentage of As V . This behavior is consistent with the redox properties of the arsenic species and the smoke particulate matrix.

  12. Predicting spent fuel oxidation states in a tuff repository

    International Nuclear Information System (INIS)

    Einziger, R.E.; Woodley, R.E.

    1987-01-01

    Nevada Nuclear Waste Storage Investigations Project (NNWSI) is studying the suitability of the tuffaceous rocks at Yucca Mountain as a waste repository for spent fuel disposal. The oxidation state of the LWR spent fuel in the moist air environment of a tuff repository could be a significant factor in determining its leaching and dissolution characteristics. Predictions as to which oxidation states would be present are important in analyzing such a repository and thus the present study was undertaken. A set of TGA (thermogravimetric analysis) tests were conducted on well-controlled samples of irradiated PWR fuel with time and temperature as the only variables. The tests were conducted between 140 and 225 0 C for a duration up to 2200 hours. The weight gain curves were analyzed in terms of diffusion through a layer of U 3 O 7 , diffusion into the grains to form a solid solution, a simplified empirical representation of a combination of grain boundary diffusion and bulk grain oxidation. Reaction rate constants were determined in each case, but analysis of these data could not establish a definitive mechanism. 21 refs., 10 figs., 3 tabs

  13. Solid State Studies Section

    Energy Technology Data Exchange (ETDEWEB)

    None

    1974-12-31

    Research is summarized on fuel, fertile, and cladding materials. Results of studies in the field of solid state sciences are also reported. It was found during the studies on the thermal diffusion release of /sup 133/Xe from irradiated thoria--urania powders that during prolonged annealing at high temperatures, there were several sudden burst releases of /sup 133/Xe as a function of time. These sudden bursts appear to be related to the particle size of the powders. Studies on the phase composition of U/sub 3/O/sub 8//su established that the phase obtained at room temperature after heating at 850 deg K is always oxygen deficient. Results of studies on the different modifications of U/sub 3/O/sub 8/ indicated that the so-called delta-phase has a crystal structure almost identical with the beta-phase, yet there were differences in the heats of transition of each of these phases to the alpha-U/sub 3/O/sub 8/ phase at 130 deg C. Studies on fast neutron damage in stainless steel were initiated and results related to damage by void formation were obtained even when the fluencies were only moderately high. Studies on the phase transformations in solids brought out the unusual phase transition behavior of KNO/sub 3/. It was established that the phase transformation attributed to the orthorhombic (II) to the trigonal (I) transition at 129 deg C is essentially a 2-step transition. Results of differential scanning colorimeter (DSC) studies also revealed a peculiar feature which is as yet not understood, namely that on cooling, differential thermal analysis (DTA) showed a III to II phase transition; this is not seen in the DSC. The capabilities of the DSC technique to delineate temperatures of magnetic transitions were demonstrated by studying the transitions in a number of standard substances (metals, alloys, and compounds). In studies on KMnF/sub 3/, it was further demonstrated that the DSC technique is superior in measuring and detecting the heats of crystallographic and

  14. The oxidation state of sulfur in apatite: A new oxybarometer?

    Science.gov (United States)

    Fiege, A.; Konecke, B.; Kim, Y.; Simon, A. C.; Becker, U.; Parat, F.

    2016-12-01

    Oxygen fugacity (fO2) of magmatic and hydrothermal systems influences, for instance, crystallization and degassing processes as well as metal solubilities in melts and fluids. Apatite is a ubiquitous mineral in magmatic and hydrothermal environments that can record and preserve volatile zonation. It can contain several thousand μg/g of the redox sensitive element sulfur (S), making S-in-apatite a potential fO2 sensor. Despite the polyvalent properties of S (e.g., S2-, S4+, S6+), the oxidation state and incorporation mechanisms of S in the apatite structure are poorly understood. In this study, the oxidation state of S-in-apatite as a function of fO2 is investigated using X-ray absorption near-edge structures (XANES) spectroscopy at the S K-edge. Apatites crystallized from lamproitic melts at 1000°C, 300 MPa and over a broad range of fO2 and sulfur fugacities (fS2) were measured. Peaks corresponding to S6+ ( 2482 eV), S4+ ( 2478 eV) and S2- ( 2470 eV) were identified in apatite. The integrated S6+/STotal (STotal = S6+ + S4+ + S2-) peak area ratios show a distinct positive correlation with fO2, increasing from 0.17 at FMQ+0 to 0.96 at FMQ+3. Ab-initio calculations were performed to further understand the energetics and geometry of incorporation of S6+, S4+ and S2- into the apatite (F-, Cl-, OH-) end-members. The results confirm that apatite can contain three different oxidations states of S (S6+, S4+, S2-) as a function of fO2. This makes apatite probably the first geologically relevant mineral to incorporate reduced (S2-), intermediate (S4+), and oxidized (S6+) S in variable proportions. We emphasize that the strong dependence of the S oxidation state in apatite as a function of fO2 is also coupled with changing S content of apatite and co-existing melt (i.e., with changing fS2), resulting in a complex correlation between [1] apatite-melt (or fluid) partitioning, [2] redox conditions and [3] the melt and/or fluid composition, making the application of previously

  15. Experimentally Studied Thermal Piston-head State of the Internal-Combustion Engine with a Thermal Layer Formed by Micro-Arc Oxidation Method

    Directory of Open Access Journals (Sweden)

    N. Yu. Dudareva

    2015-01-01

    Full Text Available The paper presents results of experimental study to show the efficiency of reducing thermal tension of internal combustion engine (ICE pistons through forming a thermal barrier coating on the piston-head. During the engine operation the piston is under the most thermal stress. High temperatures in the combustion chamber may lead to the piston-head burnout and destruction and engine failure.Micro-arc oxidation (MAO method was selected as the technology to create a thermal barrier coating. MAO technology allows us to form the ceramic coating with a thickness of 400μm on the surface of aluminum alloy, which have high heat resistance, and have good adhesion to the substrate even under thermal cycling stresses.Deliverables of MAO method used to protect pistons described in the scientific literature are insufficient, as they are either calculated or experimentally obtained at the special plants (units, which do not reproduce piston operation in a real engine. This work aims to fill this gap. The aim of the work is an experimental study of the thermal protective ability of MAO-layer formed on the piston-head with simulation of thermal processes of the real engine.The tests were performed on a specially designed and manufactured stand free of motor, which reproduces operation conditions maximum close to those of the real engine. The piston is heated by a fire source - gas burner with isobutene balloon, cooling is carried out by the water circulation system through the water-cooling jacket.Tests have been conducted to compare the thermal state of the regular engine piston without thermal protection and the piston with a heat layer formed on the piston-head by MAO method. The study findings show that the thermal protective MAO-layer with thickness of 100μm allows us to reduce thermal tension of piston on average by 8,5 %. Thus at high temperatures there is the most pronounced effect that is important for the uprated engines.The obtained findings can

  16. Resonance Raman study on photoreduction of cytochrome c oxidase: distinction of cytochromes a and a3 in the intermediate oxidation states.

    Science.gov (United States)

    Ogura, T; Yoshikawa, S; Kitagawa, T

    1985-12-17

    Occurrence of photoreduction of bovine cytochrome c oxidase was confirmed with the difference absorption spectra and oxygen consumption measurements for the enzyme irradiated with laser light at 406.7, 441.6, and 590 nm. The resonance Raman spectra were obtained under the same experimental conditions as those adopted for the measurements of oxygen consumption and difference absorption spectra. The photoreduction was more effective upon irradiation at shorter wavelengths and was irreversible under anaerobic conditions. However, upon aeration into the cell, the original oxidized form was restored. It was found that aerobic laser irradiation produces a photo steady state of the catalytic dioxygen reduction and that the Raman scattering from this photo steady state probes cytochrome a2+ and cytochrome a3(3)+ separately upon excitations at 441.6 and 406.7 nm, respectively. The enzyme was apparently protected from the photoreduction in the spinning cell with the spinning speed between 1 and 1500 rpm. These results were explained satisfactorily with the reported rate constant for the electron transfer from cytochrome a to cytochrome a3 (0.58 s-1) and a comparable photoreduction rate of cytochrome a. The anaerobic photoreduction did give Raman lines at 1666 and 214 cm-1, which are characteristic of the ferrous high-spin cytochrome a3(2)+, but they were absent under aerobic photoreduction. The formyl CH = O stretching mode of the a3 heme was observed at 1671 cm-1 for a2+a3(2)+CO but at 1664 cm-1 for a2+a3(2)+CN-, indicating that the CH = O stretching frequency reflects the pi back-donation to the axial ligand similar to the oxidation state marker line (v4).

  17. Persistence of oxidation state III of gold in thione coordination

    Science.gov (United States)

    Jääskeläinen, Sirpa; Koskinen, Laura; Kultamaa, Matti; Haukka, Matti; Hirva, Pipsa

    2017-05-01

    Ligands N,N'-tetramethylthiourea and 2-mercapto-1-methyl-imidazole form stable Au(III) complexes [AuCl3(N,N'-tetramethylthiourea)] (1) and [AuCl3(2-mercapto-1-methyl-imidazole)] (2) instead of reducing the Au(III) metal center into Au(I), which would be typical for the attachment of sulfur donors. Compounds 1 and 2 were characterized by spectroscopic methods and by X-ray crystallography. The spectroscopic details were explained by simulation of the UV-Vis spectra via the TD-DFT method. Additionally, computational DFT studies were performed in order to find the reason for the unusual oxidation state in the crystalline materials. The preference for Au(III) can be explained via various weak intra- and intermolecular interactions present in the solid state structures. The nature of the interactions was further investigated by topological charge density analysis via the QTAIM method.

  18. Non-equilibrium oxidation states of zirconium during early stages of metal oxidation

    International Nuclear Information System (INIS)

    Ma, Wen; Yildiz, Bilge; Herbert, F. William; Senanayake, Sanjaya D.

    2015-01-01

    The chemical state of Zr during the initial, self-limiting stage of oxidation on single crystal zirconium (0001), with oxide thickness on the order of 1 nm, was probed by synchrotron x-ray photoelectron spectroscopy. Quantitative analysis of the Zr 3d spectrum by the spectrum reconstruction method demonstrated the formation of Zr 1+ , Zr 2+ , and Zr 3+ as non-equilibrium oxidation states, in addition to Zr 4+ in the stoichiometric ZrO 2 . This finding resolves the long-debated question of whether it is possible to form any valence states between Zr 0 and Zr 4+ at the metal-oxide interface. The presence of local strong electric fields and the minimization of interfacial energy are assessed and demonstrated as mechanisms that can drive the formation of these non-equilibrium valence states of Zr

  19. Proteomic indicators of oxidation and hydration state in colorectal cancer

    Directory of Open Access Journals (Sweden)

    Jeffrey M. Dick

    2016-07-01

    Full Text Available New integrative approaches are needed to harness the potential of rapidly growing datasets of protein expression and microbial community composition in colorectal cancer. Chemical and thermodynamic models offer theoretical tools to describe populations of biomacromolecules and their relative potential for formation in different microenvironmental conditions. The average oxidation state of carbon (ZC can be calculated as an elemental ratio from the chemical formulas of proteins, and water demand per residue ( ${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$ n ¯ H 2 O is computed by writing the overall formation reactions of proteins from basis species. Using results reported in proteomic studies of clinical samples, many datasets exhibit higher mean ZC or ${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$ n ¯ H 2 O of proteins in carcinoma or adenoma compared to normal tissue. In contrast, average protein compositions in bacterial genomes often have lower ZC for bacteria enriched in fecal samples from cancer patients compared to healthy donors. In thermodynamic calculations, the potential for formation of the cancer-related proteins is energetically favored by changes in the chemical activity of H2O and fugacity of O2 that reflect the compositional differences. The compositional analysis suggests that a systematic change in chemical composition is an essential feature of cancer proteomes, and the thermodynamic descriptions show that the observed proteomic transformations in host tissue could be promoted by relatively high microenvironmental oxidation and hydration states.

  20. Oxidation states of Fe and Ti in blue sapphire

    International Nuclear Information System (INIS)

    Wongrawang, P; Wongkokua, W; Monarumit, N; Thammajak, N; Wathanakul, P

    2016-01-01

    X-ray absorption near-edge spectroscopy (XANES) can be used to study the oxidation state of a dilute system such as transition metal defects in solid-state samples. In blue sapphire, Fe and Ti are defects that cause the blue color. Inter-valence charge transfer (IVCT) between Fe 2+ and Ti 4+ has been proposed to describe the optical color’s origin. However, the existence of divalent iron cations has not been thoroughly investigated. Fluorescent XANES is therefore employed to study K-edge absorptions of Fe and Ti cations in various blue sapphire samples including natural, synthetic, diffused and heat-treated sapphires. All the samples showed an Fe absorption edge at 7124 eV, corresponding to the Fe 3+ state; and Ti at 4984 eV, corresponding to Ti 4+ . From these results, we propose Fe 3+ -Ti 4+ mixed acceptor states located at 1.75 eV and 2.14 eV above the valence band of corundum, that correspond to 710 nm and 580 nm bands of UV–vis absorption spectra, to describe the cause of the color of blue sapphire. (paper)

  1. Oxidation study of Ta–Zr coatings

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yung-I, E-mail: yichen@mail.ntou.edu.tw; Chen, Sin-Min

    2013-02-01

    Refractory metal alloy coatings, such as Mo–Ru and Ta–Ru coatings, have been developed to protect glass molding dies. Forming intermetallic compounds in the coatings inhibits grain growth in high temperature environments when mass producing optical components. After annealing in oxygen containing atmospheres, a surface roughening of the Mo–Ru coatings and a soft oxide layer on the Ta–Ru coatings have been observed in our previous works. Oxidation resistance becomes critical in high-temperature applications. In this study, Ta–Zr coatings were deposited with a Ti interlayer on silicon wafers using direct current magnetron sputtering at 400 °C. The as-deposited Ta–Zr coatings possessed nanocrystallite or amorphous states, depending on the chemical compositions. The annealing treatments were conducted at 600 °C under atmospheres of 50 ppm O{sub 2}–N{sub 2} or 1% O{sub 2}–Ar, respectively. After the annealing treatment, this study investigated variations in crystalline structure, hardness, surface roughness, and chemical composition profiles. Preferential oxidation of Zr in the Ta–Zr coatings was verified using X-ray photoelectron spectroscopy, and the microstructure was observed using transmission electron microscopy. - Highlights: ►The as-deposited Ta-rich Ta–Zr coatings revealed an amorphous structure. ►The Zr-rich coatings presented a crystalline β-Zr phase and an amorphous matrix. ►Zr oxidized preferentially as Ta–Zr coatings annealed at 600 °C. ►The hardness of coatings revealed a parabolic relationship with the oxygen content. ►A protective oxide scale formed on the surface of the crystallized Zr-rich coatings.

  2. A microbial-mineralization-inspired approach for synthesis of manganese oxide nanostructures with controlled oxidation states and morphologies

    Energy Technology Data Exchange (ETDEWEB)

    Oba, Manabu; Oaki, Yuya; Imai, Hiroaki [Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan)

    2010-12-21

    Manganese oxide nanostructures are synthesized by a route inspired by microbial mineralization in nature. The combination of organic molecules, which include antioxidizing and chelating agents, facilitates the parallel control of oxidation states and morphologies in an aqueous solution at room temperature. Divalent manganese hydroxide (Mn(OH){sub 2}) is selectively obtained as a stable dried powder by using a combination of ascorbic acid as an antioxidizing agent and other organic molecules with the ability to chelate to manganese ions. The topotactic oxidation of the resultant Mn(OH){sub 2} leads to the selective formation of trivalent manganese oxyhydroxide ({beta}-MnOOH) and trivalent/tetravalent sodium manganese oxide (birnessite, Na{sub 0.55}Mn{sub 2}O{sub 4}.1.5H{sub 2}O). For microbial mineralization in nature, similar synthetic routes via intermediates have been proposed in earlier works. Therefore, these synthetic routes, which include in the present study the parallel control over oxidation states and morphologies of manganese oxides, can be regarded as new biomimetic routes for synthesis of transition metal oxide nanostructures. As a potential application, it is demonstrated that the resultant {beta}-MnOOH nanostructures perform as a cathode material for lithium ion batteries. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  3. Plutonium uptake by Scenedesmus obliquus as a function of isotope and oxidation state

    International Nuclear Information System (INIS)

    Tkacik, M.F.; Giesy, J.P.; Wilhite, E.L.; Corey, J.C.

    1979-01-01

    Uptake of 238 Pu 4+ , 238 Pu 6+ , 239 Pu 4+ and 239 Pu 6+ by the green alga Scenedesmus obliquus (Turp) Kutz was studied to determine whether isotope or oxidation state differences affect Pu uptake from aqueous medium by algal cells. At equivalent 238 Pu and 239 PU concentrations, even when initial oxidation states differed, accumulations of these isotopes by S.obliquus were not significantly (p>0.05) different. Plutonium accumulation by S.obliquus was log-linear. (author)

  4. Effect of microorganisms on the plutonium oxidation states

    International Nuclear Information System (INIS)

    Lukšienė, Benedikta; Druteikienė, Rūta; Pečiulytė, Dalia; Baltrūnas, Dalis; Remeikis, Vidmantas; Paškevičius, Algimantas

    2012-01-01

    Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to 239 Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state. - Highlights: ► Particular microbes from low-level radioactive waste repository were exposed to Pu (IV). ► Some tested bacteria induced slight Pu (IV) reduction at low pH under aerobic conditions. ► Tested fungi did not show peculiarities to alter Pu oxidation state. ► The modified radiochemical method was applied to differentiate Pu oxidation states.

  5. Effect of microorganisms on the plutonium oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Luksiene, Benedikta, E-mail: bena@ar.fi.lt [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Druteikiene, Ruta [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Peciulyte, Dalia [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania); Baltrunas, Dalis; Remeikis, Vidmantas [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Paskevicius, Algimantas [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania)

    2012-03-15

    Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to {sup 239}Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state. - Highlights: Black-Right-Pointing-Pointer Particular microbes from low-level radioactive waste repository were exposed to Pu (IV). Black-Right-Pointing-Pointer Some tested bacteria induced slight Pu (IV) reduction at low pH under aerobic conditions. Black-Right-Pointing-Pointer Tested fungi did not show peculiarities to alter Pu oxidation state. Black-Right-Pointing-Pointer The modified radiochemical method was applied to differentiate Pu oxidation states.

  6. Comparative Studies on Thermal, Mechanical, and Flame Retardant Properties of PBT Nanocomposites via Different Oxidation State Phosphorus-Containing Agents Modified Amino-CNTs.

    Science.gov (United States)

    Zhu, San-E; Wang, Li-Li; Chen, Hao; Yang, Wei; Yuen, Anthony Chun-Yin; Chen, Timothy Bo-Yuan; Luo, Cheng; Bi, Wen-Mei; Hu, En-Zhu; Zhang, Jian; Si, Jing-Yu; Lu, Hong-Dian; Hu, Kun-Hong; Chan, Qing Nian; Yeoh, Guan Heng

    2018-01-26

    High-performance poly(1,4-butylene terephthalate) (PBT) nanocomposites have been developed via the consideration of phosphorus-containing agents and amino-carbon nanotube (A-CNT). One-pot functionalization method has been adopted to prepare functionalized CNTs via the reaction between A-CNT and different oxidation state phosphorus-containing agents, including chlorodiphenylphosphine (DPP-Cl), diphenylphosphinic chloride (DPP(O)-Cl), and diphenyl phosphoryl chloride (DPP(O₃)-Cl). These functionalized CNTs, DPP(O x )-A-CNTs ( x = 0, 1, 3), were, respectively, mixed with PBT to obtain the CNT-based polymer nanocomposites through a melt blending method. Scanning electron microscope observations demonstrated that DPP(O x )-A-CNT nanoadditives were homogeneously distributed within PBT matrix compared to A-CNT. The incorporation of DPP(O x )-A-CNT improved the thermal stability of PBT. Moreover, PBT/DPP(O₃)-A-CNT showed the highest crystallization temperature and tensile strength, due to the superior dispersion and interfacial interactions between DPP(O₃)-A-CNT and PBT. PBT/DPP(O)-A-CNT exhibited the best flame retardancy resulting from the excellent carbonization effect. The radicals generated from decomposed polymer were effectively trapped by DPP(O)-A-CNT, leading to the reduction of heat release rate, smoke production rate, carbon dioxide and carbon monoxide release during cone calorimeter tests.

  7. Studies on O/M ratio determination in uranium oxide, plutonium oxide and uranium-plutonium mixed oxide

    International Nuclear Information System (INIS)

    Sampath, S.; Chawla, K.L.

    1975-01-01

    Thermogravimetric studies were carried out in unsintered and sintered samples of uranium oxide, plutonium oxide and uranium-plutonium mixed oxide under different atmospheric conditions (air, argon and moist argon/hydrogen). Moisture loss was found to occur below 200 0 C for uranium dioxide samples, upto 700 0 C for sintered plutonium dioxide and negligible for sintered samples. The O/M ratios for non-stoichiometric uranium dioxide (sintered and unsintered), plutonium dioxide and mixed uranium and plutonium oxides (sintered) could be obtained with a precision of +- 0.002. Two reference states UOsub(2.000) and UOsub(2.656) were obtained for uranium dioxide and the reference state MOsub(2.000) was used for other cases. For unsintered plutonium dioxide samples, accurate O/M ratios could not be obtained of overlap of moisture loss with oxygen loss/gain. (author)

  8. Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

    Energy Technology Data Exchange (ETDEWEB)

    Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Marry K.; Tyliszczak, T.; Thevuthasan, Suntharampillai; Baer, Donald R.; Orr, Galya

    2015-09-01

    Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells.

  9. Relationships among oxidation-reduction and acid-base properties of the actinides in high oxidation states

    International Nuclear Information System (INIS)

    Morss, L.R.

    1992-01-01

    The first chemical identification of plutonium, its subsequent isolation on the macroscopic scale, and more recent chemical separation schemes were achieved by taking advantage of the differences among the oxidation states of uranium, neptunium, and plutonium. Many acid-base properties modify the relative stabilities of oxidation states of the actinides. In the solid state, strongly basic compounds such as Cs 2 O yield complex oxides with oxidation states of Np(VII), Pu(VI), and Am(VI) whereas more acidic compounds such as CsF yield complex fluorides with lower oxidation states. In aqueous solution, high basicity and strongly covalent complexes favor high oxidation states. In nonaqueous solvent systems, high acidity generally favors low oxidation states. This paper elucidates and attempts to interpret the effects of these acid-base properties in a systematic fashion

  10. 15N and 31P solid-state NMR study of transmembrane domain alignment of M2 protein of influenza A virus in hydrated cylindrical lipid bilayers confined to anodic aluminum oxide nanopores.

    Science.gov (United States)

    Chekmenev, Eduard Y; Hu, Jun; Gor'kov, Peter L; Brey, William W; Cross, Timothy A; Ruuge, Andres; Smirnov, Alex I

    2005-04-01

    This communication reports the first example of a high resolution solid-state 15N 2D PISEMA NMR spectrum of a transmembrane peptide aligned using hydrated cylindrical lipid bilayers formed inside nanoporous anodic aluminum oxide (AAO) substrates. The transmembrane domain SSDPLVVA(A-15N)SIIGILHLILWILDRL of M2 protein from influenza A virus was reconstituted in hydrated 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine bilayers that were macroscopically aligned by a conventional micro slide glass support or by the AAO nanoporous substrate. 15N and 31P NMR spectra demonstrate that both the phospholipids and the protein transmembrane domain are uniformly aligned in the nanopores. Importantly, nanoporous AAO substrates may offer several advantages for membrane protein alignment in solid-state NMR studies compared to conventional methods. Specifically, higher thermal conductivity of aluminum oxide is expected to suppress thermal gradients associated with inhomogeneous radio frequency heating. Another important advantage of the nanoporous AAO substrate is its excellent accessibility to the bilayer surface for exposure to solute molecules. Such high accessibility achieved through the substrate nanochannel network could facilitate a wide range of structure-function studies of membrane proteins by solid-state NMR.

  11. Effect of particle size on iron nanoparticle oxidation state

    International Nuclear Information System (INIS)

    Lombardo, Jeffrey J.; Lysaght, Andrew C.; Goberman, Daniel G.; Chiu, Wilson K.S.

    2012-01-01

    Selecting catalyst particles is a very important part of carbon nanotube growth, although the properties of these nanoscale particles are unclear. In this article iron nanoparticles are analyzed through the use of atomic force microscopy and x-ray photoelectron spectroscopy in order to understand how the size affects the chemical composition of nanoparticles and thus their physical structure. Initially, atomic force microscopy was used to confirm the presence of iron particles, and to determine the average size of the particles. Next an analytical model was developed to estimate particle size as a function of deposition time using inputs from atomic force microscopy measurement. X-ray photoelectron spectroscopy analysis was then performed with a focus on the spectra relating to the 2p Fe electrons to study the chemical state of the particles as a function of time. It was shown that as the size of nanoparticles decreased, the oxidation state of the particles changed due to a high proportion of atoms on the surface.

  12. Nanoroses of nickel oxides: Synthesis, electron tomography study, and application in CO oxidation and energy storage

    KAUST Repository

    Fihri, Aziz; Sougrat, Rachid; Baby, Rakhi Raghavan; Rahal, Raed; Cha, Dong Kyu; Hedhili, Mohamed N.; Bouhrara, Mohamed; Alshareef, Husam N.; Polshettiwar, Vivek

    2012-01-01

    Nickel oxide and mixed-metal oxide structures were fabricated by using microwave irradiation in pure water. The nickel oxide self-assembled into unique rose-shaped nanostructures. These nickel oxide roses were studied by performing electron

  13. Pulse radiolytic study of the oxidation reaction of uric acid in presence of bovine serum albumin: evidence of possible complex formation in the transient state

    International Nuclear Information System (INIS)

    Adhikari, S.; Gopinathan, C.

    1996-01-01

    The pulse radiolytic and spectrophotometric study of uric acid in presence of bovine serum albumin (BSA) has been carried out. In the spectrophotometric study there is no evidence for ground state interaction between BSA and uric acid. The reaction of CCl 3 OO . radical with uric acid produces a transient having absorption maximum at 330 nm and that with BSA produces transient having absorption maximum at 410 nm. In a composition of equal concentration of uric acid and BSA the CCl 3 OO . radical produces a transient absorption spectrum which shows two peaks at 330 nm and 350 nm and a shoulder at 410 nm. The peak at 350 nm is ascribed due to weak complex formation between BSA and uric acid radicals. The rate constant of CCl 3 OO . radical with uric acid increases with the increase in BSA concentration which is explained as protection of BSA by uric acid from radical attack. (author). 4 refs., 2 figs., 1 tab

  14. Evolution of the Oxidation State of the Earth's Mantle

    Science.gov (United States)

    Danielson, L. R.; Righter, K.; Keller, L.; Christoffersen, E.; Rahman, Z.

    2015-01-01

    The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3(+) at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. In our previous experiments on shergottite compositions, variable fO2, T, and P less than 4 GPa, Fe3(+)/sigma Fe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3(+)/sigma Fe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3(+). Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Preliminary multi-anvil experiments with Knippa basalt as the starting composition were conducted at 5-7 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal to Fe3(+)/2(+). Experiments are underway to produce glassy samples that can be measured by EELS and XANES, and are conducted at higher pressures.

  15. Adsorption properties versus oxidation states of rutile TiO2(110)

    DEFF Research Database (Denmark)

    Martinez, Umberto; Hammer, Bjørk

    2011-01-01

    Using density functional theory we have studied the adsorption properties of different atoms and molecules deposited on a stoichiometric, reduced, and oxidized rutile TiO2(110) surface. Depending on the oxidation state of the surface, electrons can flow from or to the substrate and, therefore...... of the charge flow depends on the oxidation state of the rutile surface and on the adsorption site. Generally, the charging effect leads to more stable complexes. However, the increase in the binding energy of the adsorbates is highly dependent on the electronic states of the surface prior to the adsorption...... event. In this work we have analyzed in details these mechanisms and we have also established a direct correlation between the enhanced binding energy of the adsorbates and the induced gap states...

  16. Corrosion-product transport, oxidation state and remedial measures

    International Nuclear Information System (INIS)

    Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

    1998-10-01

    The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. Efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness and as a monitor of system corrosion effects. The discussion is based mostly on the results of observations from Ontario Hydro plants, and their comparisons with pressurized-water reactors. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of layup and various startup conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on CPT on the primary side of SGs are also discussed. (author)

  17. Corrosion-product transport, oxidation state and remedial measures

    International Nuclear Information System (INIS)

    Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

    1998-01-01

    The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. The efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness, and as a monitor of system corrosion effects. The discussion is based mostly on the results and observations from Ontario Hydro plants, and their comparisons with PWRs. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of lay-up and various start-up conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on corrosion-product transport on the primary side of steam generators are also discussed. (author)

  18. Influence of oxidation state on the pH dependence of hydrous iridium oxide films

    International Nuclear Information System (INIS)

    Steegstra, Patrick; Ahlberg, Elisabet

    2012-01-01

    Many electrochemical reactions taking place in aqueous solution consume or produce protons. The pH in the diffusion layer can therefore be significantly altered during the reaction and there is a need for in situ pH measurements tracing this near surface pH. In the present paper the rotating ring disc technique was used to measure near surface pH changes during oxygen reduction, utilising hydrous iridium oxide as the pH sensing probe. Before such experiments a good understanding of the pH sensing properties of these films is required and the impact of the oxidation state of the film on the pH sensing properties was investigated as well as the influence of solution redox species. The pH sensitivity (depicted by dE/dpH) was found to depend on the average oxidation state of the film in a manner resembling the cyclic voltammetry response. In all cases the pH response is “supernernstian” with more than one proton per electron. The origin of this behaviour is discussed in the context of acid-base properties of the film and the existence of both hydrous and anhydrous oxide phases. The pH response depends also on the redox properties of the solution but can be optimised for various purposes by conditioning the film at different potentials. This was clearly illustrated by adding hydrogen peroxide, an intermediate in the oxygen reduction reaction, to the solution. It was shown that hydrous iridium oxide can be used as a reliable in situ pH sensor provided that care is taken to optimise the oxidation state of the film.

  19. Pentavalent Uranium Chemistry - Synthetic Pursuit Of A Rare Oxidation State

    Energy Technology Data Exchange (ETDEWEB)

    Graves, Christopher R [Los Alamos National Laboratory; Kiplinger, Jaqueline L [Los Alamos National Laboratory

    2009-01-01

    This feature article presents a comprehensive overview of pentavalent uranium systems in non-aqueous solution with a focus on the various synthetic avenues employed to access this unusual and very important oxidation state. Selected characterization data and theoretical aspects are also included. The purpose is to provide a perspective on this rapidly evolving field and identify new possibilities for future developments in pentavalent uranium chemistry.

  20. Heterogeneous Oxidation of Atmospheric Organic Aerosol: Kinetics of Changes to the Amount and Oxidation State of Particle-Phase Organic Carbon.

    Science.gov (United States)

    Kroll, Jesse H; Lim, Christopher Y; Kessler, Sean H; Wilson, Kevin R

    2015-11-05

    Atmospheric oxidation reactions are known to affect the chemical composition of organic aerosol (OA) particles over timescales of several days, but the details of such oxidative aging reactions are poorly understood. In this study we examine the rates and products of a key class of aging reaction, the heterogeneous oxidation of particle-phase organic species by the gas-phase hydroxyl radical (OH). We compile and reanalyze a number of previous studies from our laboratories involving the oxidation of single-component organic particles. All kinetic and product data are described on a common basis, enabling a straightforward comparison among different chemical systems and experimental conditions. Oxidation chemistry is described in terms of changes to key ensemble properties of the OA, rather than to its detailed molecular composition, focusing on two quantities in particular, the amount and the oxidation state of the particle-phase carbon. Heterogeneous oxidation increases the oxidation state of particulate carbon, with the rate of increase determined by the detailed chemical mechanism. At the same time, the amount of particle-phase carbon decreases with oxidation, due to fragmentation (C-C scission) reactions that form small, volatile products that escape to the gas phase. In contrast to the oxidation state increase, the rate of carbon loss is nearly uniform among most systems studied. Extrapolation of these results to atmospheric conditions indicates that heterogeneous oxidation can have a substantial effect on the amount and composition of atmospheric OA over timescales of several days, a prediction that is broadly in line with available measurements of OA evolution over such long timescales. In particular, 3-13% of particle-phase carbon is lost to the gas phase after one week of heterogeneous oxidation. Our results indicate that oxidative aging represents an important sink for particulate organic carbon, and more generally that fragmentation reactions play a major

  1. Oxidation state analyses of uranium with emphasis on chemical speciation in geological media

    International Nuclear Information System (INIS)

    Ervanne, H.

    2004-01-01

    This thesis focuses on chemical methods suitable for the determination of uranium redox species in geological materials. Nd-coprecipitation method was studied for the determination of uranium oxidation states in ground waters. This method is ideally suited for the separation of uranium oxidation states in the field, which means that problems associated with the instability of U(IV) during transport are avoided. An alternative method, such as ion exchange, is recommended for the analysis of high saline and calcium- and iron-rich ground waters. U(IV)/Utot was 2.8-7.2% in ground waters in oxidizing conditions and 60-93% in anoxic conditions. From thermodynamic model calculations applied to results from anoxic ground waters it was concluded that uranium can act as redox buffer in granitic ground waters. An ion exchange method was developed for the analysis of uranium oxidation states in different solid materials of geological origin. These included uranium minerals, uraniumbearing minerals, fracture coatings and bulk rock. U(IV)/Utot was 50-70% in uraninites, 5.8-8.7% in secondary uranium minerals, 15-49% in different fracture coatings and 64- 77% in samples from deep bedrock. In the uranium-bearing minerals, U(IV)/Utot was 33-43% (allanites), 5.9% (fergusonite) and 93% (monazite). Although the ion exchange method gave reliable results, there is a risk for the conversion of uranium oxidation states during analysis of heterogeneous samples due to the redox reactions that take place in the presence of some iron compounds. This risk was investigated in a study of several common iron-bearing minerals. The risk for conversion of uranium oxidation states can be screened by sample selection and minimized with use of a redox buffer compound such as polyacrylic acid (PAA). In studies of several carboxylic acids, PAA was found to be the most suitable for extending the application of the method. The stability of uranium oxidation states during analysis and the selectivity

  2. Optoelectronic properties of valence-state-controlled amorphous niobium oxide

    Science.gov (United States)

    Onozato, Takaki; Katase, Takayoshi; Yamamoto, Akira; Katayama, Shota; Matsushima, Koichi; Itagaki, Naho; Yoshida, Hisao; Ohta, Hiromichi

    2016-06-01

    In order to understand the optoelectronic properties of amorphous niobium oxide (a-NbO x ), we have investigated the valence states, local structures, electrical resistivity, and optical absorption of a-NbO x thin films with various oxygen contents. It was found that the valence states of Nb ion in a-NbO x films can be controlled from 5+  to 4+  by reducing oxygen pressure during film deposition at room temperature, together with changing the oxide-ion arrangement around Nb ion from Nb2O5-like to NbO2-like local structure. As a result, a four orders of magnitude reduction in the electrical resistivity of a-NbO x films was observed with decreasing oxygen content, due to the carrier generation caused by the appearance and increase of an oxygen-vacancy-related subgap state working as an electron donor. The tunable optoelectronic properties of a-NbO x films by valence-state-control with oxygen-vacancy formation will be useful for potential flexible optoelectronic device applications.

  3. Chelation and stabilization of berkelium in oxidation state +IV

    Science.gov (United States)

    Deblonde, Gauthier J.-P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B.; An, Dahlia D.; Illy, Marie-Claire; Ralston, Corie Y.; Brabec, Jiri; de Jong, Wibe A.; Strong, Roland K.; Abergel, Rebecca J.

    2017-09-01

    Berkelium (Bk) has been predicted to be the only transplutonium element able to exhibit both +III and +IV oxidation states in solution, but evidence of a stable oxidized Bk chelate has so far remained elusive. Here we describe the stabilization of the heaviest 4+ ion of the periodic table, under mild aqueous conditions, using a siderophore derivative. The resulting Bk(IV) complex exhibits luminescence via sensitization through an intramolecular antenna effect. This neutral Bk(IV) coordination compound is not sequestered by the protein siderocalin—a mammalian metal transporter—in contrast to the negatively charged species obtained with neighbouring trivalent actinides americium, curium and californium (Cf). The corresponding Cf(III)-ligand-protein ternary adduct was characterized by X-ray diffraction analysis. Combined with theoretical predictions, these data add significant insight to the field of transplutonium chemistry, and may lead to innovative Bk separation and purification processes.

  4. The Behavior of the Ru-bda Water Oxidation Catalysts at Low Oxidation States.

    Science.gov (United States)

    Matheu, Roc; Ghaderian, Abolfazl; Francas, Laia; Chernev, Petko; Ertem, Mehmed; Benet-Buchholz, Jordi; Batista, Victor; Haumann, Michael; Gimbert-Suriñach, Carolina; Sala, Xavier; Llobet, Antoni

    2018-06-13

    The Ru complex [RuII(bda-κ-N2O2)(N-NH2)2], 1, (bda2- = (2,2'-bipyridine)-6,6'-dicarboxylate; N-NH2 = 4-(pyridin-4-yl)aniline) is used as a synthetic intermediate to prepare Ru-bda complexes that contain the NO+, acetonitrile (MeCN) or H2O ligands at oxidation states II and III. Complex 1 reacts with excess NO+ to form a Ru complex where the aryl amine ligands N-NH2 in 1 are transformed into diazonium salts (N-N2+ = 4-(pyridin-4-yl)benzenediazonium)) together with the formation of a new Ru-NO group at the equatorial zone, to generate [RuII(bda-κ-N2O)(NO)(N-N2)2]3+, 23+. Similarly, complex 1 can also react with a coordinating solvent, such as MeCN, at room temperature leading to complex [RuII(bda-κ-N2O)(MeCN)(N-NH2)2], 3. Finally in acidic aqueous solutions solvent water coordinates the Ru center forming {[RuII(bda-κ-(NO)3)(H2O)(N-NH3)2](H2O)n}2+, 42+, that is strongly hydrogen bonded with additional water molecules at the second coordination sphere. We have additionally characterized the one electron oxidized complex {[RuIII(bda-κ-(NO)3.5)(H2O)(N-NH3)2](H2O)n}3+, 53+. The coordination mode of the complexes has been studied both in the solid state and in solution through single-crystal XRD, X-ray absorption spectroscopy, variable-temperature NMR and DFT calculations. While the κ-N2O is the main coordination mode for 23+ and 3, an equilibrium that involves isomers with κ-N2O and κ-NO2 coordination modes and neighboring hydrogen bonded water molecules is observed for 42+ and 53+. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Status of Chronic Oxidation Studies of Graphite

    Energy Technology Data Exchange (ETDEWEB)

    Contescu, Cristian I. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Mee, Robert W. [Univ. of Tennessee, Knoxville, TN (United States)

    2016-05-01

    Graphite will undergo extremely slow, but continuous oxidation by traces of moisture that will be present, albeit at very low levels, in the helium coolant of HTGR. This chronic oxidation may cause degradation of mechanical strength and thermal properties of graphite components if a porous oxidation layer penetrates deep enough in the bulk of graphite components during the lifetime of the reactor. The current research on graphite chronic oxidation is motivated by the acute need to understand the behavior of each graphite grade during prolonged exposure to high temperature chemical attack by moisture. The goal is to provide the elements needed to develop predictive models for long-time oxidation behavior of graphite components in the cooling helium of HTGR. The tasks derived from this goal are: (1) Oxidation rate measurements in order to determine and validate a comprehensive kinetic model suitable for prediction of intrinsic oxidation rates as a function of temperature and oxidant gas composition; (2) Characterization of effective diffusivity of water vapor in the graphite pore system in order to account for the in-pore transport of moisture; and (3) Development and validation of a predictive model for the penetration depth of the oxidized layer, in order to assess the risk of oxidation caused damage of particular graphite grades after prolonged exposure to the environment of helium coolant in HTGR. The most important and most time consuming of these tasks is the measurement of oxidation rates in accelerated oxidation tests (but still under kinetic control) and the development of a reliable kinetic model. This report summarizes the status of chronic oxidation studies on graphite, and then focuses on model development activities, progress of kinetic measurements, validation of results, and improvement of the kinetic models. Analysis of current and past results obtained with three grades of showed that the classical Langmuir-Hinshelwood model cannot reproduce all

  6. The Effect of Precursor Ligands and Oxidation State in the Synthesis of Bimetallic Nano-Alloys

    KAUST Repository

    LaGrow, Alec P.; Knudsen, Kristian; AlYami, Noktan; Anjum, Dalaver H.; Bakr, Osman

    2015-01-01

    of variables on the characteristics of bimetallic nanomaterials are not completely understood. In this study, we used a continuous-flow synthetic strategy to explore the effects of the ligands and the oxidation state of a metal precursor in a shape

  7. Oxidation of extracellular cysteine/cystine redox state in bleomycin-induced lung fibrosis.

    Science.gov (United States)

    Iyer, Smita S; Ramirez, Allan M; Ritzenthaler, Jeffrey D; Torres-Gonzalez, Edilson; Roser-Page, Susanne; Mora, Ana L; Brigham, Kenneth L; Jones, Dean P; Roman, Jesse; Rojas, Mauricio

    2009-01-01

    Several lines of evidence indicate that depletion of glutathione (GSH), a critical thiol antioxidant, is associated with the pathogenesis of idiopathic pulmonary fibrosis (IPF). However, GSH synthesis depends on the amino acid cysteine (Cys), and relatively little is known about the regulation of Cys in fibrosis. Cys and its disulfide, cystine (CySS), constitute the most abundant low-molecular weight thiol/disulfide redox couple in the plasma, and the Cys/CySS redox state (E(h) Cys/CySS) is oxidized in association with age and smoking, known risk factors for IPF. Furthermore, oxidized E(h) Cys/CySS in the culture media of lung fibroblasts stimulates proliferation and expression of transitional matrix components. The present study was undertaken to determine whether bleomycin-induced lung fibrosis is associated with a decrease in Cys and/or an oxidation of the Cys/CySS redox state and to determine whether these changes were associated with changes in E(h) GSH/glutathione disulfide (GSSG). We observed distinct effects on plasma GSH and Cys redox systems during the progression of bleomycin-induced lung injury. Plasma E(h) GSH/GSSG was selectively oxidized during the proinflammatory phase, whereas oxidation of E(h) Cys/CySS occurred at the fibrotic phase. In the epithelial lining fluid, oxidation of E(h) Cys/CySS was due to decreased food intake. Thus the data show that decreased precursor availability and enhanced oxidation of Cys each contribute to the oxidation of extracellular Cys/CySS redox state in bleomycin-induced lung fibrosis.

  8. Study of radiosensitivity and antioxidant-oxidant state in workers exposed to ionizing radiation in the hospital environment; Estudio de la radiosensibilidad y estado antioxidante-oxidante en trabajadores expuestos a radiaciones ionizantes en el ámbito hospitalario

    Energy Technology Data Exchange (ETDEWEB)

    Sebastià, N.; Rodrigo, R.; Hervás, D.; Olivares-González, L; Óscar Alonso, O.; Marti, L.; Jambrina, E.; Sarrias, A.; Pérez-Calatayud, J.; García, T.; Gras, P.; Villaescusa, J.I.; Soriano, J.M.; León, Z.; Montoro, A.

    2014-07-01

    Prevention and protection of workers exposed to ionizing radiation is an objective of particular importance from the occupational health and safety point of view. This study establishes a technique for the evaluation of the individual radiosensibility of workers exposed to ionizing radiation in the Hospital environment using the cytogenetic biomarker known as the G2 –Test. In addition, using various oxidative stress biomarkers and antioxidant capacity, we evaluate the antioxidant-oxidant state of these workers. Both biomarkers could be established as additional tools in the medical control of workers exposed to ionizing radiation. [Spanish] La prevención y protección de los trabajadores expuestos a radiaciones ionizantes es un objetivo de gran relevancia desde el punto de vista de seguridad ocupacional y salud. Este estudio consiste en la puesta a punto de una técnica de evaluación de la radiosensibilidad individual de los trabajadores expuestos a radiaciones ionizantes en el ámbito hospitalario mediante el biomarcador citogenético conocido como Test G2. Además, utilizando diversos biomarcadores de estrés oxidativo y capacidad anti- oxidante, evaluamos el estado antioxidante-oxidante en estos trabajadores. Ambos biomarcadores podrían establecerse como una herramienta más dentro de la vigilancia médica de los trabajadores expuestos a radiación ionizante.

  9. Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

    International Nuclear Information System (INIS)

    Meublat, L.

    1989-10-01

    The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), CIO 2 + RuF 6 - , a new compound well identified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

  10. Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

    International Nuclear Information System (INIS)

    Meublat, L.

    1989-01-01

    The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), ClO 2 + RuF 6 - , a new compound well idendified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

  11. CO oxidation on gold nanoparticles: Theoretical studies

    DEFF Research Database (Denmark)

    Remediakis, Ioannis; Lopez, Nuria; Nørskov, Jens Kehlet

    2005-01-01

    We present a summary of our theoretical results regarding CO oxidation on both oxide-supported and isolated gold nanoparticles. Using Density Functional Theory we have studied the adsorption of molecules and the oxidation reaction of CO on gold clusters. Low-coordinated sites on the gold...... nanoparticles can adsorb small inorganic molecules such as O2 and CO, and the presence of these sites is the key factor for the catalytic properties of supported gold nanoclusters. Other contributions, induced by the presence of the support, can provide parallel channels for the reaction and modulate the final...

  12. The role of oxidation states in F A1 Tl n+ (n = 1, 3) lasers and CO interactions at the (1 0 0) surface of NaCl: An ab initio study

    International Nuclear Information System (INIS)

    Shalabi, A.S.; Abdel Aal, S.; Kamel, M.A.; Taha, H.O.; Ammar, H.Y.; Abdel Halim, W.S.

    2006-01-01

    The oxidation states of Thallium in F A1 Tl +n (n = 1, 3) color centers at the (1 0 0) surface of NaCl play important role in laser light generation and adsorbate-substrate interactions. Double-well potentials at these surfaces are investigated by using quantum mechanical ab initio methods. Quantum clusters of variable sizes were embedded in the simulated Coulomb fields that closely approximate the Madelung fields of the host surfaces, and ions that were the nearest neighbors to the F A1 Tl +n (n 1, 3) defect site were allowed to relax to equilibrium.The calculated Stokes shifts suggest that laser light generation is sensitive to the oxidation states of Thallium. The relaxed excited states of the defect-containing surface were deep below the lower edge of the conduction bands of the ground state defect-free surface, suggesting that the F A1 Tl +n (n = 1, 3) centers are suitable laser defects. The dependence of the orientational destruction and recording sensitivity on the oxidation state of Thallium is clarified. The Glasner-Tompkins empirical rule is generalized to include the oxidation state of the impurity cation. The adsorption energies of CO and OC over NaCl(1 0 0) was found to be sensitive to the oxidation state of the impurity cation. F A1 Tl +n (n = 1, 3) centers changed the physical adsorption of CO to chemical adsorption. While the artificial flow of charge was significant in the case of Tl +1 impurity, it was negligible in the case of Tl +3 impurity, and the results were explained in terms of the electrostatic potential curves

  13. Study of nitric oxide catalytic oxidation on manganese oxides-loaded activated carbon at low temperature

    Energy Technology Data Exchange (ETDEWEB)

    You, Fu-Tian [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China); Yu, Guang-Wei, E-mail: gwyu@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Wang, Yin, E-mail: yinwang@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Xing, Zhen-Jiao [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Liu, Xue-Jiao; Li, Jie [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China)

    2017-08-15

    Highlights: • Loading manganese oxides on activated carbon effectively promotes NO oxidation. • NO adsorption-desorption on activated carbon is fundamental to NO oxidation. • A high Mn{sup 4+}/Mn{sup 3+} ratio contributes to NO oxidation by promoting lattice O transfer. - Abstract: Nitric oxide (NO) is an air pollutant that is difficult to remove at low concentration and low temperature. Manganese oxides (MnO{sub x})-loaded activated carbon (MLAC) was prepared by a co-precipitation method and studied as a new catalyst for NO oxidation at low temperature. Characterization of MLAC included X-ray diffraction (XRD), scanning electron microscopy (SEM), N{sub 2} adsorption/desorption and X-ray photoelectron spectroscopy (XPS). Activity tests demonstrated the influence of the amount of MnO{sub x} and the test conditions on the reaction. MLAC with 7.5 wt.% MnO{sub x} (MLAC003) exhibits the highest NO conversion (38.7%) at 1000 ppm NO, 20 vol.% O{sub 2}, room temperature and GHSV ca. 16000 h{sup −1}. The NO conversion of MLAC003 was elevated by 26% compared with that of activated carbon. The results of the MLAC003 activity test under different test conditions demonstrated that NO conversion is also influenced by inlet NO concentration, inlet O{sub 2} concentration, reaction temperature and GHSV. The NO adsorption-desorption process in micropores of activated carbon is fundamental to NO oxidation, which can be controlled by pore structure and reaction temperature. The activity elevation caused by MnO{sub x} loading is assumed to be related to Mn{sup 4+}/Mn{sup 3+} ratio. Finally, a mechanism of NO catalytic oxidation on MLAC based on NO adsorption-desorption and MnO{sub x} lattice O transfer is proposed.

  14. Intestinal Oxidative State Can Alter Nutrient and Drug Bioavailability

    Directory of Open Access Journals (Sweden)

    Faria Ana

    2009-01-01

    Full Text Available Organic cations (OCs are substances of endogenous (e.g., dopamine, choline or exogenous (e.g., drugs like cimetidine origin that are positively charged at physiological ph. since many of these compounds can not pass the cell membrane freely, their transport in or out of cells must be mediated by specific transport systems. Transport by organic cation transporters (OCTs can be regulated rapidly by altering their trafficking and/or affinities in response to stimuli. However, for example, a specific disease could lead to modifications in the expression of OCTs. Chronic exposure to oxidative stress has been suggested to alter regulation and functional activity of proteins through several pathways. According to results from a previous work, oxidation-reduction pathways were thought to be involved in intestinal organic cation uptake modulation. The present work was performed in order to evaluate the influence of oxidative stressors, especially glutathione, on the intestinal organic cation absorption. For this purpose, the effect of compounds with different redox potential (glutathione, an endogenous antioxidant, and procyanidins, diet antioxidants was assessed on MPP+ (1-methyl-4-phenylpyridinium iodide uptake in an enterocyte cell line (Caco-2. Caco-2 cells were subcultured with two different media conditions (physiological: 5 mM glucose, referred as control cells; and high-glucose: 25 mM glucose, referred as HG cells. In HG cells, the uptake was significantly lower than in control cells. Redox changing interventions affected Mpp+ uptake, both in control and in high-glucose Caco-2 cells. Cellular glutathione levels could have an important impact on membrane transporter activity. The results indicate that modifications in the cellular oxidative state modulate MPP+ uptake by Caco-2 cells. Such modifications may reflect in changes of nutrient and drug bioavailability.

  15. How different oxidation states of crystalline myoglobin are influenced by X-rays.

    Science.gov (United States)

    Hersleth, Hans-Petter; Andersson, K Kristoffer

    2011-06-01

    X-ray induced radiation damage of protein crystals is well known to occur even at cryogenic temperatures. Redox active sites like metal sites seem especially vulnerable for these radiation-induced reductions. It is essential to know correctly the oxidation state of metal sites in protein crystal structures to be able to interpret the structure-function relation. Through previous structural studies, we have tried to characterise and understand the reactions between myoglobin and peroxides. These reaction intermediates are relevant because myoglobin is proposed to take part as scavenger of reactive oxygen species during oxidative stress, and because these intermediates are similar among the haem peroxidases and oxygenases. We have in our previous studies shown that these different myoglobin states are influenced by the X-rays used. In this study, we have in detail investigated the impact that X-rays have on these different oxidation states of myoglobin. An underlying goal has been to find a way to be able to determine mostly unreduced states. We have by using single-crystal light absorption spectroscopy found that the different oxidation states of myoglobin are to a different extent influenced by the X-rays (e.g. ferric Fe(III) myoglobin is faster reduced than ferryl Fe(IV)═O myoglobin). We observe that the higher oxidation states are not reduced to normal ferrous Fe(II) or ferric Fe(III) states, but end up in some intermediate and possibly artificial states. For ferric myoglobin, it seems that annealing of the radiation-induced/reduced state can reversibly more or less give the starting point (ferric myoglobin). Both scavengers and different dose-rates might influence to which extent the different states are affected by the X-rays. Our study shows that it is essential to do a time/dose monitoring of the influence X-rays have on each specific redox-state with spectroscopic techniques like single-crystal light absorption spectroscopy. This will determine to which

  16. Composition and oxidation state of sulfur in atmospheric particulate matter

    Directory of Open Access Journals (Sweden)

    A. F. Longo

    2016-10-01

    Full Text Available The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS and X-ray fluorescence (XRF microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

  17. Study of oxide layers in creep of Ti alloy

    International Nuclear Information System (INIS)

    Reis, D.A.P.; Moura Neto, C.; Machado, J.P.B.; Martins, G.V.; Barboza, M.J.R.

    2009-01-01

    The present study is about the effect of oxide layers in creep of Ti-6Al-4V alloy, in different atmospheres (air, nitrogen and argon). Ti-6Al-4V alloy was treated during 24 hours in a thermal treatment furnace at 600°C in different atmospheres (argon, nitrogen and air). The samples were analyzed by High Resolution X-Ray Diffraction, Scanning Electronic Microscopy (SEM), Atomic Force Microscopy (AFM) and microhardness test. The polished samples of Ti-6Al-4V alloy were treated during 24 hours at 600°C and the oxidation behavior in each case using argon, nitrogen and air atmospheres was observed. The oxidation was more aggressive in air atmosphere, forming TiO 2 film in the surface. The oxidation produced a weight gain through the oxide layer growth and hardening by oxygen dissolution. Ti-6Al-4V alloy specimens also were produced in order to test them in creep, at 250 MPa and 600 deg C, with argon, nitrogen and air atmospheres. When the Ti-6Al-4V alloy was tested under argon and nitrogen atmospheres oxidation effects are smaller and the behavior of the creep curves shows that the creep life time was better in atmospheres not so oxidant. It is observed a decreasing of steady state creep in function of the oxidation process reduction. It is shown that, for the Ti-6Al-4V alloy, their useful life is strongly affected by the atmosphere that is submitted, on account of the oxidation suffered by the material. (author)

  18. Determination of the oxidation states of metals and metalloids: An analytical review

    Science.gov (United States)

    Vodyanitskii, Yu. N.

    2013-12-01

    The hazard of many heavy metals/metalloids in the soil depends on their oxidation state. The problem of determining the oxidation state has been solved due to the use of synchrotron radiation methods with the analysis of the X-ray absorption near-edge structure (XANES). The determination of the oxidation state is of special importance for some hazardous heavy elements (arsenic, antimony, selenium, chromium, uranium, and vanadium). The mobility and hazard of each of these elements depend on its oxidation state. The mobilities are higher at lower oxidation states of As, Cr, V, and Se and at higher oxidation states of Sb and U. The determination of the oxidation state of arsenic has allowed revealing its fixation features in the rhizosphere of hydrophytes. The known oxidation states of chromium and uranium are used for the retention of these elements on geochemical barriers. Different oxidation states have been established for vanadium displacing iron in goethite. The determination of the oxidation state of manganese in the rhizosphere and the photosynthetic apparatus of plants is of special importance for agricultural chemists.

  19. 99Tc and Re incorporated into metal oxide polyoxometalates: oxidation state stability elucidated by electrochemistry and theory.

    Science.gov (United States)

    McGregor, Donna; Burton-Pye, Benjamin P; Mbomekalle, Israel M; Aparicio, Pablo A; Romo, Susanna; López, Xavier; Poblet, Josep M; Francesconi, Lynn C

    2012-08-20

    The radioactive element technetium-99 ((99)Tc, half-life = 2.1 × 10(5) years, β(-) of 253 keV), is a major byproduct of (235)U fission in the nuclear fuel cycle. (99)Tc is also found in radioactive waste tanks and in the environment at National Lab sites and fuel reprocessing centers. Separation and storage of the long-lived (99)Tc in an appropriate and stable waste-form is an important issue that needs to be addressed. Considering metal oxide solid-state materials as potential storage matrixes for Tc, we are examining the redox speciation of Tc on the molecular level using polyoxometalates (POMs) as models. In this study we investigate the electrochemistry of Tc complexes of the monovacant Wells-Dawson isomers, α(1)-P(2)W(17)O(61)(10-) (α1) and α(2)-P(2)W(17)O(61)(10-) (α2) to identify features of metal oxide materials that can stabilize the immobile Tc(IV) oxidation state accessed from the synthesized Tc(V)O species and to interrogate other possible oxidation states available to Tc within these materials. The experimental results are consistent with density functional theory (DFT) calculations. Electrochemistry of K(7-n)H(n)[Tc(V)O(α(1)-P(2)W(17)O(61))] (Tc(V)O-α1), K(7-n)H(n)[Tc(V)O(α(2)-P(2)W(17)O(61))] (Tc(V)O-α2) and their rhenium analogues as a function of pH show that the Tc-containing derivatives are always more readily reduced than their Re analogues. Both Tc and Re are reduced more readily in the lacunary α1 site as compared to the α2 site. The DFT calculations elucidate that the highest oxidation state attainable for Re is VII while, under the same electrochemistry conditions, the highest oxidation state for Tc is VI. The M(V)→ M(IV) reduction processes for Tc(V)O-α1 are not pH dependent or only slightly pH dependent suggesting that protonation does not accompany reduction of this species unlike the M(V)O-α2 (M = (99)Tc, Re) and Re(V)O-α1 where M(V/IV) reduction process must occur hand in hand with protonation of the terminal M═O to

  20. Experimental study of oxidative DNA damage

    DEFF Research Database (Denmark)

    Loft, Steffen; Deng, Xin-Sheng; Tuo, Jingsheng

    1998-01-01

    Animal experiments allow the study of oxidative DNA damage in target organs and the elucidation of dose-response relationships of carcinogenic and other harmful chemicals and conditions as well as the study of interactions of several factors. So far the effects of more than 50 different chemical ...

  1. Towards a Predictive Thermodynamic Model of Oxidation States of Uranium Incorporated in Fe (hydr) oxides

    Energy Technology Data Exchange (ETDEWEB)

    Bagus, Paul S. [Univ. of North Texas, Denton, TX (United States)

    2013-01-01

    -Level Excited States: Consequences For X-Ray Absorption Spectroscopy”, J. Elec. Spectros. and Related Phenom., 200, 174 (2015) describes our first application of these methods. As well as applications to problems and materials of direct interest for our PNNL colleagues, we have pursued applications of fundamental theoretical significance for the analysis and interpretation of XPS and XAS spectra. These studies are important for the development of the fields of core-level spectroscopies as well as to advance our capabilities for applications of interest to our PNNL colleagues. An excellent example is our study of the surface core-level shifts, SCLS, for the surface and bulk atoms of an oxide that provides a new approach to understanding how the surface electronic of oxides differs from that in the bulk of the material. This work has the potential to lead to a new key to understanding the reactivity of oxide surfaces. Our theoretical studies use cluster models with finite numbers of atoms to describe the properties of condensed phases and crystals. This approach has allowed us to focus on the local atomistic, chemical interactions. For these clusters, we obtain orbitals and spinors through the solution of the Hartree-Fock, HF, and the fully relativistic Dirac HF equations. These orbitals are used to form configuration mixing wavefunctions which treat the many-body effects responsible for the open shell angular momentum coupling and for the satellites of the core-level spectra. Our efforts have been in two complementary directions. As well as the applications described above, we have placed major emphasis on the enhancement and extension of our theoretical and computational capabilities so that we can treat complex systems with a greater range of many-body effects. Noteworthy accomplishments in terms of method development and enhancement have included: (1) An improvement in our treatment of the large matrices that must be handled when many-body effects are treated. (2

  2. Manganese oxidation state mediates toxicity in PC12 cells

    International Nuclear Information System (INIS)

    Reaney, S.H.; Smith, D.R.

    2005-01-01

    The role of the manganese (Mn) oxidation state on cellular Mn uptake and toxicity is not well understood. Therefore, undifferentiated PC12 cells were exposed to 0-200 μM Mn(II)-chloride or Mn(III)-pyrophosphate for 24 h, after which cellular manganese levels were measured along with measures of cell viability, function, and cytotoxicity (trypan blue exclusion, medium lactate dehydrogenase (LDH), 8-isoprostanes, cellular ATP, dopamine, serotonin, H-ferritin, transferrin receptor (TfR), Mn-superoxide dismutase (MnSOD), and copper-zinc superoxide dismutase (CuZnSOD) protein levels). Exposures to Mn(III) >10 μM produced 2- to 5-fold higher cellular manganese levels than equimolar exposures to Mn(II). Cell viability and ATP levels both decreased at the highest Mn(II) and Mn(III) exposures (150-200 μM), while Mn(III) exposures produced increases in LDH activity at lower exposures (≥50 μM) than did Mn(II) (200 μM only). Mn(II) reduced cellular dopamine levels more than Mn(III), especially at the highest exposures (50% reduced at 200 μM Mn(II)). In contrast, Mn(III) produced a >70% reduction in cellular serotonin at all exposures compared to Mn(II). Different cellular responses to Mn(II) exposures compared to Mn(III) were also observed for H-ferritin, TfR, and MnSOD protein levels. Notably, these differential effects of Mn(II) versus Mn(III) exposures on cellular toxicity could not simply be accounted for by the different cellular levels of manganese. These results suggest that the oxidation state of manganese exposures plays an important role in mediating manganese cytotoxicity

  3. Solid-state pH ultramicrosensor based on a tungstic oxide film fabricated on a tungsten nanoelectrode and its application to the study of endothelial cells

    International Nuclear Information System (INIS)

    Yamamoto, Katsunobu; Shi Guoyue; Zhou Tianshu; Xu Fan; Zhu Min; Liu Min; Kato, Takeshi; Jin Jiye; Jin Litong

    2003-01-01

    In this paper, preparation of a novel pH ultramicrosensor and its physiological application has been discussed. A tungsten nanoelectrode was produced by an etching method in 0.1 mol/l NaOH solution at the potential of +0.4 V (versus Ag/AgCl reference electrode) for about 100 s and the diameters ranged from 500 to 800 nm. The pH ultramicrosensor was fabricated by producing WO 3 at W nanoelectrode surface by electrooxidation in 2.0 mol/l H 2 SO 4 solution between 1.0 and 2.0 V. At last, Nafion was coated on the surface of WO 3 to protect the pH ultramicrosensor. The W/WO 3 pH ultramicrosensor exhibited a good pH linear region from 2.0 to 12.0 with a super-Nernstian slope of -53.5 ± 0.5 mV/pH unit. Response times ranged from 3 s at about pH 6.0-7.0 up to 15 s at high pH. An interference of various ions to the pH measurement was also studied in this paper. We also studied the lifetime, stability and reproducibility of the W/WO 3 pH ultramicrosensor. In order to testing the performance of W/WO 3 ultramicrosensor, we applied it to measure the extracellular pH values and a pH variation was also given about the normal, damaged and recovery endothelial cells

  4. Influence of microorganisms on the oxidation state distribution of multivalent actinides under anoxic conditions

    International Nuclear Information System (INIS)

    Reed, Donald Timothy; Borkowski, Marian; Lucchini, Jean-Francois; Ams, David; Richmann, M.K.; Khaing, H.; Swanson, J.S.

    2010-01-01

    The fate and potential mobility of multivalent actinides in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium, uranium and neptunium are the near-surface multivalent contaminants of concern and are also key contaminants for the deep geologic disposal of nuclear waste. Their mobility is highly dependent on their redox distribution at their contamination source as well as along their potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. Under anoxic conditions, indirect and direct bioreduction mechanisms exist that promote the prevalence of lower-valent species for multivalent actinides. Oxidation-state-specific biosorption is also an important consideration for long-term migration and can influence oxidation state distribution. Results of ongoing studies to explore and establish the oxidation-state specific interactions of soil bacteria (metal reducers and sulfate reducers) as well as halo-tolerant bacteria and Archaea for uranium, neptunium and plutonium will be presented. Enzymatic reduction is a key process in the bioreduction of plutonium and uranium, but co-enzymatic processes predominate in neptunium systems. Strong sorptive interactions can occur for most actinide oxidation states but are likely a factor in the stabilization of lower-valent species when more than one oxidation state can persist under anaerobic microbiologically-active conditions. These results for microbiologically active systems are interpreted in the context of their overall importance in defining the potential migration of multivalent actinides in the subsurface.

  5. Kinetic Studies of Catalytic Oxidation of Cyclohexene Using ...

    African Journals Online (AJOL)

    acer

    Kinetic Studies of Catalytic Oxidation of Cyclohexene Using Chromium VI Oxide in. Acetic Acid ... respect to the oxidant using pseudo-order approximation method. .... making the concentration of the cyclohexene in ..... on Titanium Silicate.

  6. X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites

    OpenAIRE

    Gandhiraman, Ram P.; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E.; Chen, Bin; Meyyappan, M.

    2014-01-01

    The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties...

  7. Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance

    Science.gov (United States)

    Hockaday, W.C.; Masiello, C.A.; Randerson, J.T.; Smernik, R.J.; Baldock, J.A.; Chadwick, O.A.; Harden, J.W.

    2009-01-01

    The oxidative ratio (OR) of the net ecosystem carbon balance is the ratio of net O2 and CO2 fluxes resulting from photosynthesis, respiration, decomposition, and other lateral and vertical carbon flows. The OR of the terrestrial biosphere must be well characterized to accurately estimate the terrestrial CO2 sink using atmospheric measurements of changing O2 and CO2 levels. To estimate the OR of the terrestrial biosphere, measurements are needed of changes in the OR of aboveground and belowground carbon pools associated with decadal timescale disturbances (e.g., land use change and fire). The OR of aboveground pools can be measured using conventional approaches including elemental analysis. However, measuring the OR of soil carbon pools is technically challenging, and few soil OR data are available. In this paper we test three solid-state nuclear magnetic resonance (NMR) techniques for measuring soil OR, all based on measurements of the closely related parameter, organic carbon oxidation state (Cox). Two of the three techniques make use of a molecular mixing model which converts NMR spectra into concentrations of a standard suite of biological molecules of known C ox. The third technique assigns Cox values to each peak in the NMR spectrum. We assess error associated with each technique using pure chemical compounds and plant biomass standards whose Cox and OR values can be directly measured by elemental analyses. The most accurate technique, direct polarization solid-state 13C NMR with the molecular mixing model, agrees with elemental analyses to ??0.036 Cox units (??0.009 OR units). Using this technique, we show a large natural variability in soil Cox and OR values. Soil Cox values have a mean of -0.26 and a range from -0.45 to 0.30, corresponding to OR values of 1.08 ?? 0.06 and a range from 0.96 to 1.22. We also estimate the OR of the carbon flux from a boreal forest fire. Analysis of soils from nearby intact soil profiles imply that soil carbon losses associated

  8. The problem of oxidation state stabilisation and some regularities of a Periodic system of the elements

    International Nuclear Information System (INIS)

    Kiselev, Yurii M; Tretyakov, Yuri D

    1999-01-01

    The general principles of the concept of oxidation state stabilisation are formulated. Problems associated with the preparation and provision of the highest valent forms of transition elements are considered. The empirical data concerning the synthesis of new compounds of rare-earth elements and d elements in unusually high oxidation states are analysed. The possibility of occurrence of the oxidation states + 9 and + 10 for some elements (for example, for iridium and platinum in tetraoxo ions) are discussed. Approaches to the realisation of these states are outlined and it is demonstrated that solid phases or matrices containing alkali metal cations are the most promising systems for the stabilisation of these high oxidation states. Selected thermodynamic features typical of metal halides and oxides and the regularities of the changes in the extreme oxidation states of d elements are considered. The bibliography includes 266 references.

  9. Extracellular redox state: refining the definition of oxidative stress in aging.

    Science.gov (United States)

    Jones, Dean P

    2006-01-01

    Oxidative stress in aging can result from an imbalance of prooxidants and antioxidants with excessive, destructive free radical chemistry. Thiol systems are important in the control of these processes, both by protecting against damage and serving in redox signaling mechanisms to sense danger and repair the damage. Studies by a number of research groups in collaboration with the Emory Clinical Biomarkers Laboratory show that the redox state of the central tissue antioxidant, glutathione (GSH), can be measured in human plasma and provides a quantitative systemic indicator of oxidative stress. Plasma GSH/GSSG redox in humans becomes oxidized with age, in response to chemotherapy, as a consequence of cigarette smoking, and in association with common age-related diseases (e.g., type 2 diabetes, cardiovascular disease). However, the GSH/GSSG redox is not equilibrated with the larger plasma cysteine/cystine (Cys/CySS) pool, and the Cys/CySS redox varies with age in a pattern that is distinct from that of GSH/GSSG redox. Furthermore, in vitro studies show that variation in Cys/CySS redox over the range found in vivo affects signaling pathways, which control cell proliferation and oxidant-induced apoptosis. The results point to the conclusion that free radical scavenging antioxidants are of increased importance when thiol/disulfide redox states are oxidized. Because thiol/disulfide redox states, per se, function in redox signaling and control as well as antioxidant protection, GSH/GSSG and Cys/CySS redox states may provide central parameters to link environmental influences and progression of changes associated with aging.

  10. Studies in solid state ionics

    International Nuclear Information System (INIS)

    Jakes, D.; Rosenkranz, J.

    1987-01-01

    Studies performed over 10 years by the high temperature chemistry group are reviewed. Attention was paid to different aspects of ionic solids from the point of view of practical as well as theoretical needs of nuclear technology. Thus ceramic fuel compound like uranates, urania-thoria system, solid electrolytes based on oxides and ionics transformations were studied under reactor irradiation. (author) 13 figs., 3 tabs., 46 refs

  11. Solubility study of Tc(IV) oxides

    International Nuclear Information System (INIS)

    Liu, D.J.; Fan, X.H.

    2005-01-01

    The deep geological disposal of the high level radioactive wastes is expected to be a safer disposal method in most countries. The long-lived fission product 99 Tc is present in large quantities in nuclear wastes and its chemical behavior in aqueous solution is of considerable interest. Under oxidizing conditions technetium exists as the anionic species TcO 4 - whereas under the reducing conditions, expected to exist in a deep geological repository, it is generally predicted that technetium will be present as TcO 2 ·nH 2 O. Hence, the mobility of Tc(IV) in reducing groundwater may be limited by the solubility of TcO 2 ·nH 2 O under these conditions. Due to this fact it is important to investigate the solubility of TcO 2 ·nH 2 O. The solubility determines the release of radionuclides from waste form and is used as a source term in radionuclide migration analysis in performance assessment of radioactive waste repository. Technetium oxide was prepared by reduction of a technetate solution with Sn 2 + . The solubility of Tc(IV) oxide has been determined in simulated groundwater and redistilled water under aerobic and anaerobic conditions. The effects of pH and CO 3 2- concentration of solution on solubility of Tc(IV) oxide were studied. The concentration of total technetium and Tc(IV) species in the solutions were periodically determined by separating the oxidized and reduced technetium species using a solvent extraction procedure and counting the beta activity of the 99 Tc with a liquid scintillation counter. The experimental results show that the rate of oxidation of Tc(IV) in simulated groundwater and redistilled water is about (1.49-1.86) x 10 -9 mol/(L·d) under aerobic conditions, but Tc(IV) in simulated groundwater and redistilled water is not oxidized under anaerobic conditions. Under aerobic or anaerobic conditions the solubility of Tc(IV) oxide in simulated groundwater and redistilled water is equal on the whole after centrifugation or ultrafiltration. The

  12. Defluoridation by Bacteriogenic Iron Oxides: Sorption Studies

    Science.gov (United States)

    Evans, K.; Ferris, F.

    2009-05-01

    At concentrations above 1 mg/L, fluoride in drinking water can lead to dental and skeletal fluorosis, a disease that causes mottling of the teeth, calcification of ligaments, crippling bone deformities and many other physiological disorders that can, ultimately, lead to death. Conservative estimates are that fluorosis afflicts tens of millions of people worldwide. As there is no treatment for fluorosis, prevention is the only means of controlling the disease. While numerous defluoridation techniques have been explored, no single method has been found to be both effective and inexpensive enough to implement widely. Our research began in India, with a large-scale geochemical study of the groundwater in a fluoride-contaminated region of Orissa. Having developed a better understanding of the geochemical relationships that exist between fluoride and other parameters present in an affected area, as well as the complex relationships that arise among those parameters that can impact the presence of fluoride, we began investigating certain remediation scenarios involving iron oxides. A common approach to remediation involves the partitioning of fluoride from groundwater by sorption onto a variety of materials, one of the most effective of which is iron oxide whose surface area acts as a scavenger for fluoride. In the presence of iron oxidizing bacteria, the oxidation rate of iron has been shown to be ˜6 times greater than in their absence; fluoride should, therefore, be removed from an aqueous environment by bacteriogenic iron oxides (BIOS) much more quickly than by abiotic iron oxides. Most recently, sorption studies have been conducted using both BIOS and synthetic hydrous ferric oxides in order to compare the behavior between biotic and abiotic sorbents. These studies have provided sorption isotherms that allow comparison of fluoride removed by sorption to BIOS versus synthetic iron oxides. Sorption affinity constants have also been determined, which allow for the

  13. Laboratory Studies of Hydrocarbon Oxidation Mechanisms

    Science.gov (United States)

    Orlando, J. J.; Tyndall, G. S.; Wallington, T. J.; Burkholder, J. B.; Bertman, S. B.; Chen, W.

    2001-12-01

    The oxidation of hydrocarbon species (alkanes, alkenes, halogenated species, and oxygenates of both natural and anthropogenic origin) in the troposphere leads to the generation of numerous potentially harmful secondary pollutants, such as ozone, organic nitrates and acids, and aerosols. These oxidations proceed via the formation of alkoxy radicals, whose complex chemistry controls the ultimate product distributions obtained. Studies of hydrocarbon oxidation mechanisms are ongoing at NCAR and Ford, using environmental chamber / FTIR absorption systems. The focus of these studies is often on the product distributions obtained at low temperature; these studies not only provide data of direct relevance to the free/upper troposphere, but also allow for a more fundamental understanding of the alkoxy radical chemistry (eg., from the determination of the Arrhenius parameters for unimolecular processes, and the quantification of the extent of the involvement of chemical activation in the alkoxy radical chemistry). In this paper, data will be presented on some or all of the following topics: kinetics/mechanisms for the reactions of OH with the unsaturated species MPAN, acrolein, and crotonaldehyde; the mechanism for the oxidation of ethyl chloride and ethyl bromide; and the mechanism for the reaction of OH with acetone and acetaldehyde at low temperature. The relevance of the data to various aspects of tropospheric chemistry will be discussed.

  14. Influence of steam generator surface state on corrosion and oxide formation

    International Nuclear Information System (INIS)

    Mazenc, Arnaud; Leclercq, Stephanie; Seyeux, Antoine; Galtayries, Anouk; Marcus, Philippe

    2012-09-01

    The corrosion and release of nickel-based alloy Steam Generator tubes are partly due to their surface state. Among the most important parameters influencing the corrosion, the effect of grain size and the effect of grain crystallographic orientation have been chosen to be studied. The aim of this study is to determine how these parameters have an impact on the corrosion of Steam Generator tubes. Thermal treatments (700 deg. C and 1050 deg. C) have been performed on several samples in Alloy 690 to obtain homogeneous grain sizes, varying from 25 μm to 110 μm. Two samples have been oxidised for four days in a recirculating autoclave, reproducing primary conditions. The changes of oxide composition and thickness were examined by ToF-SIMS on samples exposed to primary water conditions. The intensity profiles versus thicknesses of characteristic oxide anions, such as CrO - , NiO - or FeO - enable us to evaluate the effect of grain size and crystallographic orientation on the formation of an enriched inner chromium layer. As regards to the grain size, there was no effect on the growth, but smaller grains led to a chromium-rich oxide layer. The effect of crystallographic orientation was observed on the oxidation kinetics and the composition of oxide scales. (authors)

  15. Reduction Rates for Higher Americium Oxidation States in Nitric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Grimes, Travis Shane [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mincher, Bruce Jay [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schmitt, Nicholas C [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-09-30

    The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

  16. Glancing angle x-ray studies of oxide films

    International Nuclear Information System (INIS)

    Davenport, A.J.; Isaacs, H.S.

    1989-01-01

    High brightness synchrotron radiation incident at glancing angles has been used to study inhibiting species present in low concentrations in oxide films on aluminum. Glancing incident angle fluorescence measurements give surface-sensitive information on the valence state of elements from the shape of the x-ray absorption edge. Angle-resolved measurements show the depth distribution of the species present. 15 refs., 4 figs

  17. Quantum confinement-induced tunable exciton states in graphene oxide.

    Science.gov (United States)

    Lee, Dongwook; Seo, Jiwon; Zhu, Xi; Lee, Jiyoul; Shin, Hyeon-Jin; Cole, Jacqueline M; Shin, Taeho; Lee, Jaichan; Lee, Hangil; Su, Haibin

    2013-01-01

    Graphene oxide has recently been considered to be a potential replacement for cadmium-based quantum dots due to its expected high fluorescence. Although previously reported, the origin of the luminescence in graphene oxide is still controversial. Here, we report the presence of core/valence excitons in graphene-based materials, a basic ingredient for optical devices, induced by quantum confinement. Electron confinement in the unreacted graphitic regions of graphene oxide was probed by high resolution X-ray absorption near edge structure spectroscopy and first-principles calculations. Using experiments and simulations, we were able to tune the core/valence exciton energy by manipulating the size of graphitic regions through the degree of oxidation. The binding energy of an exciton in highly oxidized graphene oxide is similar to that in organic electroluminescent materials. These results open the possibility of graphene oxide-based optoelectronic device technology.

  18. In-Situ Optical Studies of Oxidation/Reduction Kinetics on SOFC Cermet Anodes

    Science.gov (United States)

    2010-12-28

    DATES COVERED (From - To) 1/29/10-9/30/10 4. TITLE AND SUBTITLE In situ optical studies of oxidation/reduction kinetics on SOFC cermet anodes 5a...0572 In-situ Optical Studies of Oxidation/Reduction Kinetics on SOFC Cermet Anodes Department of Chemistry and Biochemistry Montana State University...of Research In-situ Optical Studies of Oxidation/Reduction Kinetics on SOFC Cermet Anodes Principal Investigator Robert Walker Organization

  19. Study on single step solid state synthesis of WC@C nanocomposite and electrochemical stability of synthesized WC@C & Pt/WC@C for alcohol oxidation (methanol/ethanol)

    Energy Technology Data Exchange (ETDEWEB)

    Singla, Gourav, E-mail: gsinghla@gmail.com; Singh, K., E-mail: kusingh@thapar.edu; Pandey, O.P., E-mail: oppandey@thapar.edu

    2016-04-25

    WC@C nano composite was prepared by a single step solid–state reaction through in situ reduction and carburization of WO{sub 3} in the presence of Mg and activated charcoal. The XRD results and thermodynamics analysis showed that the optimization of reaction temperature facilitates the reduction as well as carburization of tungsten oxide(s) at different reaction temperature. Thermogravimetric analysis of the product was done to assess the thermal stability in air. The Raman spectroscopy was used to find out the nature (amorphous/graphitic) of carbon in the obtained phase. The N{sub 2} adsorption–desorption measurement showed a narrow pore size distribution from 3 to 4 nm with BET surface area of up to 522.5 m{sup 2}/g. TEM/HRTEM images confirmed formation of the WC nano particles with spherical morphology. Electrochemical stability of pure and platinized carbide sample (Pt/WC) has been investigated using cyclic voltammetry in acidic media for alcohol (methanol and ethanol) oxidation. - Highlights: • Tungsten carbide nano powder was synthesized using charcoal as carbon source. • Formation of WC occurs through the formation of lower tungsten oxide. • CO{sub 2}/CO ratio effect the formation of WC. • Mesoporous tungsten carbide with surface areas 522.5 m{sup 2}/g obtained by using charcoal. • Pt modified WC powder showed higher electrochemical stability.

  20. Coupled interactions between volatile activity and Fe oxidation state during arc crustal processes

    Science.gov (United States)

    Humphreys, Madeleine C.S.; Brooker, R; Fraser, D.C.; Burgisser, A; Mangan, Margaret T.; McCammon, C

    2015-01-01

    Arc magmas erupted at the Earth’s surface are commonly more oxidized than those produced at mid-ocean ridges. Possible explanations for this high oxidation state are that the transfer of fluids during the subduction process results in direct oxidation of the sub-arc mantle wedge, or that oxidation is caused by the effect of later crustal processes, including protracted fractionation and degassing of volatile-rich magmas. This study sets out to investigate the effect of disequilibrium crustal processes that may involve coupled changes in H2O content and Fe oxidation state, by examining the degassing and hydration of sulphur-free rhyolites. We show that experimentally hydrated melts record strong increases in Fe3+/∑Fe with increasing H2O concentration as a result of changes in water activity. This is relevant for the passage of H2O-undersaturated melts from the deep crust towards shallow crustal storage regions, and raises the possibility that vertical variations in fO2 might develop within arc crust. Conversely, degassing experiments produce an increase in Fe3+/∑Fe with decreasing H2O concentration. In this case the oxidation is explained by loss of H2 as well as H2O into bubbles during decompression, consistent with thermodynamic modelling, and is relevant for magmas undergoing shallow degassing en route to the surface. We discuss these results in the context of the possible controls on fO2 during the generation, storage and ascent of magmas in arc settings, in particular considering the timescales of equilibration relative to observation as this affects the quality of the petrological record of magmatic fO2.

  1. Solid state solubility of copper oxides in hydroxyapatite

    Science.gov (United States)

    Zykin, Mikhail A.; Vasiliev, Alexander V.; Trusov, Lev A.; Dinnebier, Robert E.; Jansen, Martin; Kazin, Pavel E.

    2018-06-01

    Samples containing copper oxide doped hydroxyapatite with the composition Ca10(PO4)6(CuxOH1-x-δ)2, x = 0.054 - 0.582, in the mixture with CuO/Cu2O were prepared by a solid-state high-temperature treatment at varying annealing temperatures and at different partial water vapor and oxygen pressures. The crystal structures of the apatite compounds were refined using powder X-ray diffraction patterns and the content of copper ions x in the apatite was determined. Copper ions enter exclusively into the apatite trigonal channels formally substituting protons of OH-groups and the hexagonal cell parameters grow approximately linearly with x, the channel volume mostly expanding while the remaining volume of the crystal lattice changing only slightly. The equilibrium copper content in the apatite increases drastically, by almost a factor of 10 with the annealing temperature rising from 800° to 1200°C. The reduction of the water partial pressure leads to a further increase of x, while the dependence of x on the oxygen partial pressure exhibits a maximum. The observed relations are consistent with the proposed chemical reactions implying the copper introduction is followed by the release of a considerable quantity of gaseous products - water and oxygen. The analysis of interatomic distances suggests that the maximum content of copper ions in the channel cannot exceed 2/3.

  2. Stabilization of actinides and lanthanides in unusually high oxidation states

    International Nuclear Information System (INIS)

    Eller, P.G.; Penneman, R.A.

    1986-01-01

    Chemical environments can be chosen which stabilize actinides and lanthanides in unusually high or low oxidation states and in unusual coordination. In many cases, one can rationalize the observed species as resulting from strong charge/size influences provided by specific sites in host lattices (e.g., Tb(IV) in BaTbO 3 or Am(IV) in polytungstate anions). In other cases, the unusual species can be considered from an acid-base viewpoint (e.g., U(III) in AsF 5 /HF solution or Pu(VII) in Li 5 PuO 6 ). In still other cases, an interplay of steric and redox effects can lead to interesting comparisons (e.g., instability of double fluoride salts of Pu(V) and Pu(VI) relative to U, Np, and Am analogues). Generalized ways to rationalize compounds containing actinides and lanthanides in unusual valences (particularly high valences), including the above and numerous other examples, will form the focus of this paper. Recently developed methods for synthesizing high valent f-element fluorides using superoxidizers and superacids at low temperatures will also be described. 65 refs., 8 figs., 9 tabs

  3. Positron Studies of Oxide-Semiconductor Structures

    OpenAIRE

    Uedono , A.; Wei , L.; Kawano , T.; Tanigawa , S.; Suzuki , R.; Ohgaki , H.; Mikado , T.

    1995-01-01

    The annihilation characteristics of positrons in SiO2 films grown on Si substrates were studied by using monoenergetic positron beams. Doppler broadening profiles of the annihilation radiation and lifetime spectra of positrons were measured as a function of incident positron energy for SiO2/Si structures fabricated by various oxidation techniques. From the measurements, it was found that the formation probability of positronium (Ps) atoms in SiO2 films strongly depends on the growth condition...

  4. a case study ondo state

    African Journals Online (AJOL)

    user

    the design of a Government Cloud (G-Cloud) network for Ondo State Government which will ... network for a developing economy; a case study of ... France is one of those countries that favour .... Arequipa city. .... Where region 0 = Akure, 1 =.

  5. The effect on phase separation of the oxidation state of molybdenum in a Na2O-B2O3-SiO2 glass

    International Nuclear Information System (INIS)

    Kawamoto, Y.; Clemens, K.; Tomozawa, M.; Warden, J.T.

    1981-01-01

    The effect of oxidation state on phase separation was studied for 13Na 2 O, 49B 2 O 3 , 38SiO 2 (mol%) glasses containing 1 mol% Mo oxide. The glasses were melted under various conditions to vary the oxidation states of Mo ions. The oxidation states of Mo ions were determined by chemical analysis and ESR. The crystallisation tendency, the immiscibility temperature, and the phase separation morphology of the glasses were examined by DTA, x-ray diffraction, opalescence method, and replica electron microscopy. Glasses containing Mo 4+ ions have a great tendency to precipitate MoO 2 crystals. The immiscibility temperature of glass goes through a minimum when the oxidation states of Mo ions are changed. It was suggested that there is an optimum oxidation state to prevent crystallisation and to suppress the phase separation tendency of this system. (author)

  6. Microbial utilization of low molecular weight organic substrates in soil depends on their carbon oxidation state

    Science.gov (United States)

    Gunina, Anna; Smith, Andrew; Jones, Davey; Kuzyakov, Yakov

    2017-04-01

    Removal of low molecular weight organic substances (LMWOS), originating from plants and microorganisms, from soil solution is regulated by microbial uptake. In addition to the concentration of LMWOS in soil solution, the chemical properties of each substance (e.g. C oxidation state, number of C atoms, number of -COOH groups) can affect their uptake and subsequent partitioning of C within the soil microbial community. The aim of this study was to trace the initial fate of three dominant classes of LMWOS in soil (sugars, carboxylic and amino acids), including their removal from solution and utilization by microorganisms, and to reveal the effect of substance chemical properties on these processes. Soil solution, spiked at natural abundance levels with 14C-labelled glucose, fructose, malate, succinate, formate, alanine or glycine, was added to the soil and 14C was traced in the dissolved organic carbon (DOC), CO2, cytosol and soil organic carbon (SOC) over 24 hours. The half-life time of all LMWOS in the DOC (T1 /2-solution) varied between 0.6-5.0 min showing extremely fast initial uptake of LMWOS. The T1 /2-solution of substances was dependent on C oxidation state, indicating that less oxidized organic substances (with C oxidation state "0") were retained longer in soil solution than oxidized substances. The LMWOS-C T1 /2-fast, characterizing the half-life time of 14C in the fast mineralization pool, ranged between 30 and 80 min, with the T1 /2-fast of carboxylic acids (malic acid) being the fastest and the T1 /2-fast of amino acids (glycine) being the slowest. An absence of correlation between T1 /2-fast and either C oxidation state, number of C atoms, or number of -COOH groups suggests that intercellular metabolic pathways are more important for LMWOS transformation in soil than their basic chemical properties. The CO2 release during LMWOS mineralization accounted for 20-90% of 14C applied. Mineralization of LMWOS was the least for sugars and the greatest for

  7. Study for the chlorination of zirconium oxide

    International Nuclear Information System (INIS)

    Seo, E.S.M.; Takiishi, H.; Paschoal, J.O.A.; Andreoli, M.

    1990-12-01

    In the development of new ceramic and metallic materials the chlorination process constitutes step in the formation of several intermediate compounds, such as metallic chlorides, used for the production of high, purity raw materials. Chlorination studies with the aim of fabrication special zirconium-base alloys have been carried out at IPEN. Within this program the chlorination technique has been used for zirconium tetrachloride production from zirconium oxide. In this paper some relevant parameters such as: time and temperature of reaction, flow rate of chloride gas and percentage of the reducing agent which influence the efficiency of chlorination of zirconium oxide are evaluated. Thermodynamical aspects about the reactions involved in the process are also presented. (author)

  8. Oxidized Nitrogen Balance over 15 Months at Rural and Urban New York State Locations

    Science.gov (United States)

    Schwab, J. J.; Ninneman, M.; Marto, J.; Edgerton, E. S.; Blanchard, C. L.; Shaw, S. L.

    2017-12-01

    Continuous measurements of oxidized nitrogen species (NO, NO2, and HNO3), families of species (NOy, alkyl nitrates [or ANs], and peroxyacetyl nitrates [or PANs]), and particle nitrate (pNO3) were carried out for a fifteen-month period from August 2016 through October 2017 at two locations in New York State. The two sites were a rural research station at Pinnacle State Park in Addison, NY and an urban research station at Queens College in New York City. Four different chemiluminescence analyzers with various converters and denuders were employed to make these measurements. Instrumentation used for the study will be described, as well as some of the challenges created by combining data from these independent analyzers to address the oxidized nitrogen budget at the two sites. The Pinnacle State Park site often experiences quite clean air with low ppb levels of total NOy and a greater fraction of oxidized nitrogen products (NOz species). This contrasts with the urban Queens College location, which experiences stronger NOx sources. Seasonal differences in the NOx/NOy and NOz/NOy ratios, and the makeup of the NOz species, are also significant and will be explored in the presentation.

  9. Molecular water oxidation mechanisms followed by transition metals: state of the art.

    Science.gov (United States)

    Sala, Xavier; Maji, Somnath; Bofill, Roger; García-Antón, Jordi; Escriche, Lluís; Llobet, Antoni

    2014-02-18

    One clean alternative to fossil fuels would be to split water using sunlight. However, to achieve this goal, researchers still need to fully understand and control several key chemical reactions. One of them is the catalytic oxidation of water to molecular oxygen, which also occurs at the oxygen evolving center of photosystem II in green plants and algae. Despite its importance for biology and renewable energy, the mechanism of this reaction is not fully understood. Transition metal water oxidation catalysts in homogeneous media offer a superb platform for researchers to investigate and extract the crucial information to describe the different steps involved in this complex reaction accurately. The mechanistic information extracted at a molecular level allows researchers to understand both the factors that govern this reaction and the ones that derail the system to cause decomposition. As a result, rugged and efficient water oxidation catalysts with potential technological applications can be developed. In this Account, we discuss the current mechanistic understanding of the water oxidation reaction catalyzed by transition metals in the homogeneous phase, based on work developed in our laboratories and complemented by research from other groups. Rather than reviewing all of the catalysts described to date, we focus systematically on the several key elements and their rationale from molecules studied in homogeneous media. We organize these catalysts based on how the crucial oxygen-oxygen bond step takes place, whether via a water nucleophilic attack or via the interaction of two M-O units, rather than based on the nuclearity of the water oxidation catalysts. Furthermore we have used DFT methodology to characterize key intermediates and transition states. The combination of both theory and experiments has allowed us to get a complete view of the water oxidation cycle for the different catalysts studied. Finally, we also describe the various deactivation pathways for

  10. Quantitative evaluation of the effect of H2O degassing on the oxidation state of magmas

    Science.gov (United States)

    Lange, R. A.; Waters, L.

    2014-12-01

    The extent to which degassing of the H2O component affects the oxidation state of hydrous magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of various magmas, whereas our focus is on the H2O component. There are two ways that degassing of H2O by itself may cause oxidation: (1) the reaction: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt), and/or (2) if dissolved water preferentially enhances the activity of ferrous vs. ferric iron in magmatic liquids. In this study, a comparison is made between the pre-eruptive oxidation states of 14 crystal-poor, jet-black obsidian samples (obtained from two Fe-Ti oxides) and their post-eruptive values (analyzed with the Wilson 1960 titration method tested against USGS standards). The obsidians are from Medicine Lake (CA), Long Valley (CA), and the western Mexican arc; all have low FeOT (1.1-2.1 wt%), rendering their Fe2+/Fe3+ ratios highly sensitive to the possible effects of substantial H2O degassing. The Fe-Ti oxide thermometer/oxybarometer of Ghiorso and Evans, (2008) gave temperatures for the 14 samples that range for 720 to 940°C and ΔNNO values of -0.9 to +1.4. With temperature known, the plagioclase-liquid hygrometer was applied and show that ≤ 6.5 wt% H2O was dissolved in the melts prior to eruption. In addition, pre-eruptive Cl and S concentrations were constrained on the basis of apatite analyses (Webster et al., 2009) and sulfur concentrations needed for saturation with pyrrhotite (Clemente et al., 2004), respectively. Maximum pre-eruptive chlorine and sulfur contents are 6000 and 200 ppm, respectively. After eruption, the rhyolites lost nearly all of their volatiles. Our results indicate no detectable change between pre- and post-eruptive Fe2+ concentrations, with an average deviation of ± 0.1 wt % FeO. Although degassing of large concentrations of S and/or Cl may affect the oxidation state of magmas, at the pre-eruptive levels

  11. Towards the improvement of the oxidation resistance of Nb-silicides in situ composites: A solid state diffusion approach

    International Nuclear Information System (INIS)

    Mathieu, S.; Knittel, S.; François, M.; Portebois, L.; Mathieu, S.; Vilasi, M.

    2014-01-01

    Highlights: •Local equilibrium is attained during oxidation at phase boundaries (steady state conditions). •A solid state diffusion model explains the oxidation mechanism of Nb-silicides composites. •The Nb ss fraction is not the only parameters governing the oxidation rate of Nb-silicides. •Aluminium increases the thermodynamic activity of Si in the Nb-silicides composites. •The results indicate the need to develop a Nb–Ti–Hf–Al–Cr–Si thermodynamic database. -- Abstract: The present study focuses on the oxidation mechanism of Nb-silicide composites and on the effect of the composition on the oxidation rate at 1100 °C. A theoretical approach is proposed based on experimental results and used to optimise the oxidation resistance. The growth model based on multiphase diffusion was experimentally tested and confirmed by manufacturing seven composites with different compositions. It was also found that the effect of the composition has to be evaluated at 1100 °C within a short time duration (50 h), where the oxide scale and the internal oxidation zone both grow according to parabolic kinetics

  12. Kinetic study of the alkaline metals oxidation by dry oxygen

    International Nuclear Information System (INIS)

    Touzain, Ph.

    1967-06-01

    The oxidation of lithium, sodium, potassium, rubidium, cesium and sodium-potassium alloys by dry oxygen is studied at several temperatures and in the oxygen pressure range 40 to 400 mmHg. One distinguishes three different oxidation behaviours (inflammation, ignition and slow combustion) whose zones are precised in function of the temperature. The slow oxidation kinetic laws, the composition of oxides and the motive of oxides colorations are determined. At least, the experimental data are construed theoretically. (author) [fr

  13. Effect of surface state on the oxidation behavior of welded 308L in simulated nominal primary water of PWR

    Science.gov (United States)

    Ming, Hongliang; Zhang, Zhiming; Wang, Jiazhen; Zhu, Ruolin; Ding, Jie; Wang, Jianqiu; Han, En-Hou; Ke, Wei

    2015-05-01

    The oxidation behavior of 308L weld metal (WM) with different surface state in the simulated nominal primary water of pressurized water reactor (PWR) was studied by scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) analyzer and X-ray photoelectron spectroscopy (XPS). After 480 h immersion, a duplex oxide film composed of a Fe-rich outer layer (Fe3O4, Fe2O3 and a small amount of NiFe2O4, Ni(OH)2, Cr(OH)3 and (Ni, Fe)Cr2O4) and a Cr-rich inner layer (FeCr2O4 and NiCr2O4) can be formed on the 308L WM samples with different surface state. The surface state has no influence on the phase composition of the oxide films but obviously affects the thickness of the oxide films and the morphology of the oxides (number & size). With increasing the density of dislocations and subgrain boundaries in the cold-worked superficial layer, the thickness of the oxide film, the number and size of the oxides decrease.

  14. Catalytic activity trends of CO oxidation – A DFT study

    DEFF Research Database (Denmark)

    Jiang, Tao

    theoretical study of CO oxidation with experimental studies. The latter shows promoted catalytic activity when gold particle size decreases to 5 nm. Oxidizing CO by N2O was found to involve a CO␣O transition state, with atomic O adsorbed on the gold B5 sites and CO on the corners. On the other hand, CO...... and experiment were found to be the same. The experiment findings are in good agreement with our theoretical calculations. The second part of the thesis focuses on improving the convergence property of Quasi-Newton algorithm. The eigenvalues of the Hessian matrix of 54 atoms bulk Cu model are calculated......, and the sizes of eigenvalues follow power-law distribution. It is found that the anharmonicity of the weak modes lead to poor Newton step and poor Hessian update in BFGS type Quasi-Newton algorithm, which slow down the geometry optimization. Line search that fulfills Wolff conditions is then applied to improve...

  15. Room air versus carbon dioxide pneumoperitoneum: effects on oxidative state, apoptosis and histology of splanchnic organs.

    Science.gov (United States)

    Ypsilantis, Petros; Lambropoulou, Maria; Tentes, Ioannis; Chryssidou, Maria; Georgantas, Themistoklis; Simopoulos, Constantinos

    2016-04-01

    Although CO2 is the insufflation gas of choice in laparoscopic procedures, room air is usually used in natural orifice transluminal endoscopic surgery. The aim of the present study was to compare the safety of room air versus CO2 pneumoperitoneum in terms of their effect on the oxidative state, apoptosis and tissue injury of splanchnic organs. Eighteen Wistar rats were assigned to three groups (n = 6 per group) and were subjected to 8 mm Hg room air (group Pne-Air) or CO2 pneumoperitoneum (group Pne-CO2) or sham operation for 60 min. Forty-five minutes postdeflation, tissue samples were excised from the liver, stomach, ileum and kidneys for reduced glutathione-to-glutathione disulfide (GSH/GSSG) ratio, caspase-8 and caspase-3 and hypoxia-inducible factor-1α (HIF-1α) immunohistochemical assessment and histopathologic examination. GSH/GSSG ratio substantially declined in both pneumoperitoneum groups. No change was noted in HIF-1α expression. Mild upregulation of caspase-8 and caspase-3 was noted in both pneumoperitoneum groups being less pronounced in group Pne-Air. Histopathologic score was increased in all organs studied, but the stomach, in both pneumoperitoneum groups. Pneumoperitoneum established by either room air or CO2 induced substantial oxidative stress, mild apoptosis and mild tissue injury in splanchnic organs. While air pneumoperitoneum conferred a less pronounced apoptotic effect, the oxidative state and histopathologic profile of splanchnic organs did not differ between insufflation gases.

  16. Laboratory studies of refractory metal oxide smokes

    International Nuclear Information System (INIS)

    Nuth, J.A.; Nelson, R.N.; Donn, B.

    1989-01-01

    Studies of the properties of refractory metal oxide smokes condensed from a gas containing various combinations of SiH4, Fe(CO)5, Al(CH3)3, TiCl4, O2 and N2O in a hydrogen carrier stream at 500 K greater than T greater than 1500 K were performed. Ultraviolet, visible and infrared spectra of pure, amorphous SiO(x), FeO(x), AlO(x) and TiO(x) smokes are discussed, as well as the spectra of various co-condensed amorphous oxides, such as FE(x)SiO(y) or Fe(x)AlO(y). Preliminary studies of the changes induced in the infrared spectra of iron-containing oxide smokes by vacuum thermal annealing suggest that such materials become increasingly opaque in the near infrared with increased processing: hydration may have the opposite effect. More work on the processing of these materials is required to confirm such a trend: this work is currently in progress. Preliminary studies of the ultraviolet spectra of amorphous Si2O3 and MgSiO(x) smokes revealed no interesting features in the region from 200 to 300 nm. Studies of the ultraviolet spectra of both amorphous, hydrated and annealed SiO(x), TiO(x), AlO(x) and FeO(x) smokes are currently in progress. Finally, data on the oxygen isotopic composition of the smokes produced in the experiments are presented, which indicate that the oxygen becomes isotopically fractionated during grain condensation. Oxygen in the grains is as much as 3 percent per amu lighter than the oxygen in the original gas stream. The authors are currently conducting experiments to understand the mechanism by which fractionation occurs

  17. Photoluminescence study in diaminobenzene functionalized graphene oxide

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Abhisek, E-mail: guptaabhisek017@gmail.com, E-mail: cnssks@iacs.res.in; Saha, Shyamal K., E-mail: guptaabhisek017@gmail.com, E-mail: cnssks@iacs.res.in [Department of Materials Science, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032 (India)

    2014-10-15

    Being an excellent electronic material graphene is a very poor candidate for optoelectronic applications. One of the major strategies to develop the optical property in GO is the functionalization of graphene oxide (GO). In the present work GO sheets are functionalized by o-phenylenediamine to achieve diaminobenzene functionalized GO composite (DAB-GO). Formation of DAB-GO composite is further characterized by FTIR, UV, Raman studies. Excellent photoluminescence is observed in DAB-GO composite via passivation of the surface reactive sites by ring-opening amination of epoxides of GO.

  18. Arsenic K-edge X-ray absorption near-edge spectroscopy to determine oxidation states of arsenic of a coastal aquifer–aquitard system

    International Nuclear Information System (INIS)

    Wang, Ya; Jiao, Jiu Jimmy; Zhu, Sanyuan; Li, Yiliang

    2013-01-01

    Determination of oxidation states of solid-phase arsenic in bulk sediments is a valuable step in the evaluation of its bioavailability and environmental fate in deposits, but is difficult when the sediments have low arsenic contents and heterogeneous distribution of arsenic species. As K-edge X-ray absorption near-edge spectroscopy (XANES) was used to determine quantitatively the oxidation states of arsenic in sediments collected from different depths of boreholes in the Pearl River Delta, China, where the highest aquatic arsenic concentration is 161.4 μg/L, but the highest solid arsenic content only 39.6 mg/kg. The results demonstrated that XANES is efficient in determining arsenic oxidation states of the sediments with low arsenic contents and multiple arsenic species. The study on the high-resolution vertical variations of arsenic oxidation states also indicated that these states are influenced strongly by groundwater activities. With the help of geochemical data, solid arsenic speciation, toxicity and availability were further discussed. -- Highlights: •XANES is efficient in determining arsenic oxidation states of the bulk sediments. •Distribution of arsenic oxidation states is consistent with geochemical conditions. •Arsenic oxidation states are influenced strongly by groundwater activities. -- As K-edge X-ray absorption near-edge spectroscopy is efficient in determining arsenic oxidation states of the bulk sediments with low arsenic contents and heterogeneous distribution of arsenic species

  19. Isotopic studies on oxidative methane coupling over samarium oxide

    International Nuclear Information System (INIS)

    Otsuka, Kiyoshi; Inaida, Masakatsu; Wada, Yuji; Komatsu, Takayuki; Morikawa, Akira

    1989-01-01

    The evident kinetic isotope effect was observed for the formations of ethylene and ethane through the oxidative coupling of methane on Sm 2 O 3 , when CH 4 and CD 4 were used as the reactants. Ethanes formed in the reaction of a mixture of CH 4 , CD 4 , and O 2 were C 2 H 6 , C 2 H 3 D 3 , and C 2 D 6 as major products. These results indicate that the rate-determining step of the reaction is abstraction of hydrogen from methane and that ethane is formed through the coupling of methyl intermediate. (author)

  20. Interface Controlled Oxidation States in Layered Cobalt Oxide Nanoislands on Gold

    DEFF Research Database (Denmark)

    Walton, Alexander; Fester, Jakob; Bajdich, Michal

    2015-01-01

    Layered cobalt oxides have been shown to be highly active catalysts for the oxygen evolution reaction (OER; half of the catalytic “water splitting” reaction), particularly when promoted with gold. However, the surface chemistry of cobalt oxides and in particular the nature of the synergistic effect...

  1. Origin of interface states and oxide charges generated by ionizing radiation

    International Nuclear Information System (INIS)

    Sah, C.T.

    1976-01-01

    The randomly located trivalent silicon atoms are shown to account for the thermally generated interface states at the SiO 2 -Si interface. The interface state density is greatly reduced in water containing ambients at low temperatures (450 0 C) by forming trivalent silicon hydroxide bonds. Interface states are regenerated when the /triple bond/Si-OH bonds are broken by ionizing radiation and the OH ions are drifted away. In the bulk of the oxide film, the trivalent silicon and the interstitial oxygen donor centers are shown to be responsible for the heat and radiation generated positive space charge build-up (oxide charge) in thermally grown silicon oxide

  2. Homogeneity of Continuum Model of an Unsteady State Fixed Bed Reactor for Lean CH4 Oxidation

    Directory of Open Access Journals (Sweden)

    Subagjo

    2014-07-01

    Full Text Available In this study, the homogeneity of the continuum model of a fixed bed reactor operated in steady state and unsteady state systems for lean CH4 oxidation is investigated. The steady-state fixed bed reactor system was operated under once-through direction, while the unsteady-state fixed bed reactor system was operated under flow reversal. The governing equations consisting of mass and energy balances were solved using the FlexPDE software package, version 6. The model selection is indispensable for an effective calculation since the simulation of a reverse flow reactor is time-consuming. The homogeneous and heterogeneous models for steady state operation gave similar conversions and temperature profiles, with a deviation of 0.12 to 0.14%. For reverse flow operation, the deviations of the continuum models of thepseudo-homogeneous and heterogeneous models were in the range of 25-65%. It is suggested that pseudo-homogeneous models can be applied to steady state systems, whereas heterogeneous models have to be applied to unsteady state systems.

  3. Diversity of Chemical Bonding and Oxidation States in MS4 Molecules of Group 8 Elements.

    Science.gov (United States)

    Huang, Wei; Jiang, Ning; Schwarz, W H Eugen; Yang, Ping; Li, Jun

    2017-08-04

    The geometric and electronic ground-state structures of 30 isomers of six MS 4 molecules (M=Group 8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density functional theory and correlated wavefunction approaches. The MS 4 species were compared to analogous MO 4 species recently investigated (W. Huang, W.-H. Xu, W. H. E. Schwarz, J. Li, Inorg. Chem. 2016, 55, 4616). A metal oxidation state (MOS) with a high value of eight appeared in the low-spin singlet T d geometric species (Os,Hs)S 4 and (Ru,Os,Hs)O 4 , whereas a low MOS of two appeared in the high-spin septet D 2d species Fe(S 2 ) 2 and (slightly excited) metastable Fe(O 2 ) 2 . The ground states of all other molecules had intermediate MOS values, with S 2- , S 2 2- , S 2 1- (and O 2- , O 1- , O 2 2- , O 2 1- ) ligands bonded by ionic, covalent, and correlative contributions. The known tendencies toward lower MOS on going from oxides to sulfides, from Hs to Os to Ru, and from Pu to Sm, and the specific behavior of Fe, were found to arise from the different atomic orbital energies and radii of the (n-1)p core and (n-1)d and (n-2)f valence shells of the metal atoms in row n of the periodic table. The comparative results of the electronic and geometric structures of the MO 4 and MS 4 species provides insight into the periodicity of oxidation states and bonding. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. The effect of interfaces on solid-state reactions between oxides

    International Nuclear Information System (INIS)

    Johnson, M.T.; Carter, C.B.

    1998-01-01

    A thin-film geometry has been used to study fundamental solid-state reaction processes occurring at interfaces in two spinel-forming oxide systems. In the first system, NiO/Al 2 O 3 , epitactic NiO films were deposited on various orientations of single-crystal α-Al 2 O 3 . In this case, the reaction kinetics were studied and correlated with the interfacial structure (or substrate orientation). In the second, In 2 O 3 /MgO, solid-state reactions were studied under the influence of an electric field. The electric field provides a driving force for mass transport that affects both the reaction process and the morphological stability of an interface

  5. Electron microscope study of irradiated beryllium oxide

    International Nuclear Information System (INIS)

    Bisson, A.A.

    1965-06-01

    The beryllium oxide is studied first by fractography, before and after irradiation, using sintered samples. The fractures are examined under different aspects. The higher density sintered samples, with transgranular fractures are the most interesting for a microscopic study. It is possible to mark the difference between the 'pores' left by the sintering process and the 'bubbles' of gases that can be produced by former thermal treatments. After irradiation, the grain boundaries are very much weakened. By annealing, it is possible to observe the evolution of the gases produced by the reaction (n, 2n) and (n. α) and gathered on the grain boundaries. The irradiated beryllium oxide is afterwards studied by transmission. For that, a simple method has been used: little chips of the crushed material are examined. Clusters of point defects produced by neutrons are thus detected in crystals irradiated at the three following doses: 6 x 10 19 , 9 x 10 19 and 2 x 10 20 n f cm -2 at a temperature below 100 deg. C. For the irradiation at 6 x 10 19 n f cm -2 , the defects are merely visible, but at 2 x l0 20 n f cm -2 the crystals an crowded with clusters and the Kikuchi lines have disappeared from the micro-diffraction diagrams. The evolution of the clusters into dislocation loops is studied by a series of annealings. The activation energy (0,37 eV) calculated from the annealing curves suggests that it must be interstitials that condense into dislocation loops. Samples irradiated at high temperatures (650, 900 and 1100 deg. C) are also studied. In those specimens the size of the loops is not the same as the equilibrium size obtained after out of pile annealing at the same temperature. Those former loops are more specifically studied and their Burgers vector is determined by micro-diffraction. (author) [fr

  6. Nanoroses of nickel oxides: Synthesis, electron tomography study, and application in CO oxidation and energy storage

    KAUST Repository

    Fihri, Aziz

    2012-04-11

    Nickel oxide and mixed-metal oxide structures were fabricated by using microwave irradiation in pure water. The nickel oxide self-assembled into unique rose-shaped nanostructures. These nickel oxide roses were studied by performing electron tomography with virtual cross-sections through the particles to understand their morphology from their interior to their surface. These materials exhibited promising performance as nanocatalysts for CO oxidation and in energy storage devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Effect of charge state and stoichiometry on the structure and reactivity of nickel oxide clusters with CO

    Science.gov (United States)

    Johnson, Grant E.; Reilly, Nelly M.; Castleman, A. W., Jr.

    2009-02-01

    The collision induced fragmentation and reactivity of cationic and anionic nickel oxide clusters with carbon monoxide were studied experimentally using guided-ion-beam mass spectrometry. Anionic clusters with a stoichiometry containing one more oxygen atom than nickel atom (NiO2-, Ni2O3-, Ni3O4- and Ni4O5-) were found to exhibit dominant products resulting from the transfer of a single oxygen atom to CO, suggesting the formation of CO2. Of these four species, Ni2O3- and Ni4O5- were observed to be the most reactive having oxygen transfer products accounting for approximately 5% and 10% of the total ion intensity at a maximum pressure of 15 mTorr of CO. Our findings, therefore, indicate that anionic nickel oxide clusters containing an even number of nickel atoms and an odd number of oxygen atoms are more reactive than those with an odd number of nickel atoms and an even number of oxygen atoms. The majority of cationic nickel oxides, in contrast to anionic species, reacted preferentially through the adsorption of CO onto the cluster accompanied by the loss of either molecular O2 or nickel oxide units. The adsorption of CO onto positively charged nickel oxides, therefore, is exothermic enough to break apart the gas-phase clusters. Collision induced dissociation experiments, employing inert xenon gas, were also conducted to gain insight into the structural properties of nickel oxide clusters. The fragmentation products were found to vary considerably with size and stoichiometry as well as ionic charge state. In general, cationic clusters favored the collisional loss of molecular O2 while anionic clusters fragmented through the loss of both atomic oxygen and nickel oxide units. Our results provide insight into the effect of ionic charge state on the structure of nickel oxide clusters. Furthermore, we establish how the size and stoichiometry of nickel oxide clusters influences their ability to oxidize CO, an important reaction for environmental pollution abatement.

  8. Ion bombardment effects on surface states in selected oxide systems: rutile and alkaline earth titanates

    International Nuclear Information System (INIS)

    Gruen, D.M.

    1978-01-01

    In this paper, the nature of the surface states of n-type TiO 2 and SrTiO 3 is discussed and the role of ion bombardment in modifying the properties of these states is elucidated. Insofar as possible, the interrelationships between oxide nonstoichiometry, surface states, ion bombardment effects and photoelectrolysis are explored

  9. Oxidation Kinetics of Copper: An Experiment in Solid State Chemistry.

    Science.gov (United States)

    Ebisuzaki, Y.; Sanborn, W. B.

    1985-01-01

    Oxidation kinetics in metals and the role defects play in diffusion-controlled reactions are discussed as background for a junior/senior-level experiment in the physical or inorganic chemistry laboratory. Procedures used and typical data obtained are provided for the experiment. (JN)

  10. Kinetic Studies of Catalytic Oxidation of Cyclohexene Using ...

    African Journals Online (AJOL)

    Cyclohexene was oxidized using chromium (VI) oxide (CrO3) in pure acetic acid medium. The products of oxidation were analysed using simple qualitative analysis, IR spectroscopy and Gas chromatography-Mass spectrometry (GC/MS). Kinetics studies were carried out to determine the order of reaction, rate constant and ...

  11. Study of inhibition on lipid oxidation of irradiated pork

    International Nuclear Information System (INIS)

    Ha Yiming

    2006-03-01

    It was studied that the effect factors of irradiation dose, preservation temperature, oxygen content and antioxidant on lipid oxidation of irradiated pork. A mechanism was explained on lipid oxidation of irradiated pork. The results showed that irradiation might aggravate lipid oxidation of pork and that decreased preservation temperature and oxygen content of the packaging, added antioxidant also could effectively inhibit lipid oxidation of irradiated pork. (authors)

  12. Magneto-optic studies of magnetic oxides

    Energy Technology Data Exchange (ETDEWEB)

    Gehring, Gillian A., E-mail: g.gehring@shef.ac.uk [Department of Physics and Astronomy, University of Sheffield, Sheffield S3 7RH (United Kingdom); Alshammari, Marzook S.; Score, David S.; Neal, James R.; Mokhtari, Abbas; Fox, A. Mark [Department of Physics and Astronomy, University of Sheffield, Sheffield S3 7RH (United Kingdom)

    2012-10-15

    A brief review of the use of magneto-optic methods to study magnetic oxides is given. A simple method to obtain the magnetic circular dichroism (MCD) of a thin film on a transparent substrate is described. The method takes full account of multiple reflections in the film and substrate. Examples of the magneto-optic spectra of Co-doped ZnO, Fe{sub 3}O{sub 4}, and GdMnO{sub 3} are given. The Maxwell-Garnett method is used to describe the effects of metallic cobalt inclusions in Co:ZnO samples, and the change of the MCD spectra of Fe{sub 3}O{sub 4} at the Verwey temperature is discussed. Data showing different MCD signals at different energies is presented for GdMnO{sub 3}.

  13. Magneto-optic studies of magnetic oxides

    International Nuclear Information System (INIS)

    Gehring, Gillian A.; Alshammari, Marzook S.; Score, David S.; Neal, James R.; Mokhtari, Abbas; Fox, A. Mark

    2012-01-01

    A brief review of the use of magneto-optic methods to study magnetic oxides is given. A simple method to obtain the magnetic circular dichroism (MCD) of a thin film on a transparent substrate is described. The method takes full account of multiple reflections in the film and substrate. Examples of the magneto-optic spectra of Co-doped ZnO, Fe 3 O 4 , and GdMnO 3 are given. The Maxwell–Garnett method is used to describe the effects of metallic cobalt inclusions in Co:ZnO samples, and the change of the MCD spectra of Fe 3 O 4 at the Verwey temperature is discussed. Data showing different MCD signals at different energies is presented for GdMnO 3 .

  14. Generalized molybdenum oxide surface chemical state XPS determination via informed amorphous sample model

    Energy Technology Data Exchange (ETDEWEB)

    Baltrusaitis, Jonas, E-mail: job314@lehigh.edu [Department of Chemical Engineering, Lehigh University, B336 Iacocca Hall, 111 Research Drive, Bethlehem, PA 18015 (United States); PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Mendoza-Sanchez, Beatriz [CRANN, Chemistry School, Trinity College Dublin, Dublin (Ireland); Fernandez, Vincent [Institut des Matériaux Jean Rouxel, 2 rue de la Houssinière, BP 32229, F-44322 Nantes Cedex 3 (France); Veenstra, Rick [PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Dukstiene, Nijole [Department of Physical and Inorganic Chemistry, Kaunas University of Technology, Radvilenu pl. 19, LT-50254 Kaunas (Lithuania); Roberts, Adam [Kratos Analytical Ltd, Trafford Wharf Road, Wharfside, Manchester, M17 1GP (United Kingdom); Fairley, Neal [Casa Software Ltd, Bay House, 5 Grosvenor Terrace, Teignmouth, Devon TQ14 8NE (United Kingdom)

    2015-01-30

    Highlights: • We analyzed and modeled spectral envelopes of complex molybdenum oxides. • Molybdenum oxide films of varying valence and crystallinity were synthesized. • MoO{sub 3} and MoO{sub 2} line shapes from experimental data were created. • Informed amorphous sample model (IASM) developed. • Amorphous molybdenum oxide XPS envelopes were interpreted. - Abstract: Accurate elemental oxidation state determination for the outer surface of a complex material is of crucial importance in many science and engineering disciplines, including chemistry, fundamental and applied surface science, catalysis, semiconductors and many others. X-ray photoelectron spectroscopy (XPS) is the primary tool used for this purpose. The spectral data obtained, however, is often very complex and can be subject to incorrect interpretation. Unlike traditional XPS spectra fitting procedures using purely synthetic spectral components, here we develop and present an XPS data processing method based on vector analysis that allows creating XPS spectral components by incorporating key information, obtained experimentally. XPS spectral data, obtained from series of molybdenum oxide samples with varying oxidation states and degree of crystallinity, were processed using this method and the corresponding oxidation states present, as well as their relative distribution was elucidated. It was shown that monitoring the evolution of the chemistry and crystal structure of a molybdenum oxide sample due to an invasive X-ray probe could be used to infer solutions to complex spectral envelopes.

  15. SOLID STATE ENERGY CONVERSION ALLIANCE DELPHI SOLID OXIDE FUEL CELL

    Energy Technology Data Exchange (ETDEWEB)

    Steven Shaffer; Sean Kelly; Subhasish Mukerjee; David Schumann; Gail Geiger; Kevin Keegan; John Noetzel; Larry Chick

    2003-12-08

    The objective of Phase I under this project is to develop a 5 kW Solid Oxide Fuel Cell power system for a range of fuels and applications. During Phase I, the following will be accomplished: Develop and demonstrate technology transfer efforts on a 5 kW stationary distributed power generation system that incorporates steam reforming of natural gas with the option of piped-in water (Demonstration System A). Initiate development of a 5 kW system for later mass-market automotive auxiliary power unit application, which will incorporate Catalytic Partial Oxidation (CPO) reforming of gasoline, with anode exhaust gas injected into an ultra-lean burn internal combustion engine. This technical progress report covers work performed by Delphi from January 1, 2003 to June 30, 2003, under Department of Energy Cooperative Agreement DE-FC-02NT41246. This report highlights technical results of the work performed under the following tasks: Task 1 System Design and Integration; Task 2 Solid Oxide Fuel Cell Stack Developments; Task 3 Reformer Developments; Task 4 Development of Balance of Plant (BOP) Components; Task 5 Manufacturing Development (Privately Funded); Task 6 System Fabrication; Task 7 System Testing; Task 8 Program Management; and Task 9 Stack Testing with Coal-Based Reformate.

  16. Oxidation of an aluminium-magnesium alloy in liquid state. Methodology of determination of mechanisms from not necessarily repeatable experiments

    International Nuclear Information System (INIS)

    Surla, Karine

    1998-01-01

    This research thesis reports the study of the oxidation of an aluminium-5 pc magnesium alloy in its liquid state in an oxygen environment, using thermogravimetric analysis and that of magnesium in its solid state. In a first part, the author reports a thermodynamic and bibliographical study on magnesium transformation in its solid state (Mg/O 2 and Mg/H 2 O systems, transformation with dry and humid synthetic air, oxidation inhibitors) and on Al-Mg alloy transformation in presence of oxygen (thermodynamic properties of aluminium-rich Al-Mg alloys, Al-Mg/O 2 /N 2 and Al-Mg/O 2 /N 2 /H 2 O systems). The next parts address the selection of reaction systems for the different cases (oxidation of solid magnesium in oxygen, oxidation of the Al-Mg alloy in oxygen), the modelling of the formation of magnesia from solid magnesium and from the Al-Mg alloy, and the modelling of the liquid Al-Mg A5182 alloy oxidation in oxygen [fr

  17. A STUDY OF OXIDATIVE STRESS IN DIABETES

    Directory of Open Access Journals (Sweden)

    Babu Rao

    2015-06-01

    Full Text Available Non - enzymatic free radical mediated oxidation of biological molecules, membranes and tissues is associated with a variety of pathological events such as cancer, aging and diabetes mellitus . [1] Increased oxidative stress is seen in both types of diabetes me llitus namely type 1 and type 2, irrespective of duration, complications and treatment. In diabetes mellitus, oxidative stress seems primarily due to both an increased plasma free radical concentration and a sharp decline in antioxidant defences . [1] Among the causes of enhanced free radical production, hyperglycemia and hyper insulinemia seem to play a major role , [2,3] Hyperglycemia is the more easily modifiable factor among the two and good glycemic control can reduce the oxidative stress. Controversy pers ists regarding the other possible mechanisms of increased oxidative stress in diabetes and whether oxidative stress normalizes with adequate metabolic control alone. The role of oxidative stress and diabetic complications has been extensively investigated. Oxidative stress has been suggested to be involved in the genesis of both macro and micro angiopathy [4,5] Prospective trials are now underway addressing the controversial issues of possible role of pharmacological antioxidants in preventing or at least de laying the onset of diabetic complications.

  18. Study on antimony oxide self-assembled inside HZSM-5

    International Nuclear Information System (INIS)

    Li Bin; Li Shijie; Wang Yingxia; Li Neng; Liu Xiyao; Lin Bingxiong

    2005-01-01

    Sb/ZSM-5 was obtained by solid-state reaction with the mixture of Sb 2 O 3 and zeolite HZSM-5 under a dry nitrogen flow at 773K. Characterization of the treated zeolite was undertaken with XRD, 27 Al MAS NMR, BET, TGA and FT-IR. The results revealed that part of the antimony oxides migrated into the channels of zeolite, and decreased the Bronsted acid sites in Sb/ZSM-5 remarkably. The other part of antimony oxides together with the amorphous alumino-silicate in the products distributed on the external surface of zeolite ZSM-5 and modified it, while the framework of ZSM-5 in crystal phase was retained. The structure of occluded antimony oxide inside the channels of ZSM-5 was studied by XRD Rietveld method. The result showed that their structure can be described as a chain of non-perfect [Sb 5 O 5 (H 2 O) 2 ] n 5n+ , which is parallel to the straight channel of ZSM-5. There is about 0.6 [Sb 5 O 5 (H 2 O) 2 ] 5+ unit in every cell of the ZSM-5 on an average

  19. The state of itinerant charge carriers and thermoelectric effects in correlated oxide metals

    International Nuclear Information System (INIS)

    Kuzemsky, A.L.; Abdus Salam International Centre for Theoretical Physics, Trieste

    2000-10-01

    We analyzed the physics of transport processes and, in particular, the thermoelectric power in the mercurocuprates and other cuprates to get a better insight into the state of the carriers in these compounds. The actual problems related to the complicated mechanisms of carriers scattering above Tc are discussed. The experimental studies of thermoelectric power showed that the state of carriers in cuprates can be influenced by many complicated scattering processes, however the underlying mechanism for the linear decreasing of the TEP with increasing the temperature for most hole-doped HTSC cuprates is still not yet known. The actual problems related to the complicated mechanisms of carriers scattering above Tc are discussed for a few models of charge transport. A comparison between the analytical and experimental results is also made. It is concluded that the crucial factor for the understanding of the transport properties of correlated oxide metals is the nature of itinerant charge carriers, i.e. renormalized quasiparticles. (author)

  20. A Reactive Oxide Overlayer on Rh Nanoparticles during CO Oxidation and Its Size Dependence Studied by in Situ Ambient Pressure XPS

    International Nuclear Information System (INIS)

    Grass, Michael E.; Zhang, Yawen; Butcher, Derek R.; Park, Jeong Y.; Li, Yimin; Bluhm, Hendrik; Bratlie, Kaitlin M.; Zhang, Tianfu; Somorjai, Gabor A.

    2008-01-01

    CO oxidation is one of the most studied heterogeneous reactions, being scientifically and industrially important, particularly for removal of CO from exhaust streams and preferential oxidation for hydrogen purification in fuel cell applications. The precious metals Ru, Rh, Pd, Pt, and Au are most commonly used for this reaction because of their high activity and stability. Despite the wealth of experimental and theoretical data, it remains unclear what is the active surface for CO oxidation under catalytic conditions for these metals. In this communication, we utilize in situ synchrotron ambient pressure X-ray photoelectron spectroscopy (APXPS) to monitor the oxidation state at the surface of Rh nanoparticles during CO oxidation and demonstrate that the active catalyst is a surface oxide, the formation of which is dependent on particle size. The amount of oxide formed and the reaction rate both increase with decreasing particle size.

  1. Coordination modes of tyrosinate-ligated catalase-type heme enzymes: magnetic circular dichroism studies of Plexaura homomalla allene oxide synthase, Mycobacterium avium ssp. paratuberculosis protein-2744c, and bovine liver catalase in their ferric and ferrous states.

    Science.gov (United States)

    Bandara, D M Indika; Sono, Masanori; Bruce, Grant S; Brash, Alan R; Dawson, John H

    2011-12-01

    Bovine liver catalase (BLC), catalase-related allene oxide synthase (cAOS) from Plexaura homomalla, and a recently isolated protein from the cattle pathogen Mycobacterium avium ssp. paratuberculosis (MAP-2744c (MAP)) are all tyrosinate-ligated heme enzymes whose crystal structures have been reported. cAOS and MAP have low (enzymes in their ferric and ferrous states using magnetic circular dichroism and UV-visible absorption spectroscopy. The MAP protein shows remarkable spectral similarities to cAOS and BLC in its native Fe(III) state, but clear differences from ferric proximal heme ligand His93Tyr Mb (myoglobin) mutant, which may be attributed to the presence of an Arg(+)-N(ω)-H···¯O-Tyr (proximal heme axial ligand) hydrogen bond in the first three heme proteins. Furthermore, the spectra of Fe(III)-CN¯, Fe(III)-NO, Fe(II)-NO (except for five-coordinate MAP), Fe(II)-CO, and Fe(II)-O(2) states of cAOS and MAP, but not H93Y Mb, are also similar to the corresponding six-coordinate complexes of BLC, suggesting that a tyrosinate (Tyr-O¯) is the heme axial ligand trans to the bound ligands in these complexes. The Arg(+)-N(ω)-H to ¯O-Tyr hydrogen bond would be expected to modulate the donor properties of the proximal tyrosinate oxyanion and, combined with the subtle differences in the catalytic site structures, affect the activities of cAOS, MAP and BLC. Copyright © 2011 Elsevier Inc. All rights reserved.

  2. Application of powerful oxidizers in the synthesis of new high-oxidation state actinide and related species

    International Nuclear Information System (INIS)

    Yeh, S.M.

    1984-11-01

    The fluorinating and oxide scavenging ability of XeF 6 have been studied by bringing XeF 6 into interaction with oxide-fluoride compounds of the third-transition-series elements (W, Re and Os) and uranium, in their highest oxidation states. A + MOF 5 - and A + M 2 O 2 F 9 - (A = K or Cs, M = W or U) were converted to A + MF 7 - by XeF 6 , but the rhenium and osmium compounds, K + ReO 2 F 4 - and XeF 5 + OsO 3 F 3 - , resisted interaction with XeF 6 . Strong interactions between XeF 2 or KrF 2 and the solvent have been observed for their solutions in anhydrous HF. Both XeF 2 and KrF 2 are seen to be effective in breaking up the polymeric (HF)/sub n/ chains. Only weak interactions occur between cations and anions of KrF + AuF 6 - and Kr 2 F 3 + AuF 6 - in HF. The AuF 6 - anions are slightly distorted from O/sub h/ symmetry. Kr 2 F 3 + cations in HF have the same dissymmetric V-shape which occurs in crystalline salts. A low-temperature orthorhombic form, β-ReF 6 + SbF 6 - , a high-temperature rhombohedral form, α-ReF 6 + SbF 6 - , and a ReF 6 + AuF 6 - have been prepared. These compounds possess only kinetic stability at ambient temperature and at approx. 20 0 C are best represented as ReF 6 + ReF 7 MF 6 - MF 5 . Thermochemical energy evaluations indicate that the ionization potential of ReF 6 is 261 kcal mole -1 and that the fluoride-ion affinity of ReF 6 + is -214 kcal mole -1 . This is more exothermal than the corresponding process for IF 6 + (-208 kcal mole -1 ). In contrast, ReOF 5 is shown to be a better fluoro-base than IOF 5 and also is a better base than ReF 7 . ReOF 4 + MF 6 - (M = Sb, Au and As) salts are of higher thermal stability than their ReF 6 + MF 6 - analogues

  3. SOLID STATE ENERGY CONVERSION ALLIANCE DELPHI SOLID OXIDE FUEL CELL

    Energy Technology Data Exchange (ETDEWEB)

    Steven Shaffer; Sean Kelly; Subhasish Mukerjee; David Schumann; Gail Geiger; Kevin Keegan; Larry Chick

    2004-05-07

    The objective of this project is to develop a 5 kW Solid Oxide Fuel Cell power system for a range of fuels and applications. During Phase I, the following will be accomplished: Develop and demonstrate technology transfer efforts on a 5 kW stationary distributed power generation system that incorporates steam reforming of natural gas with the option of piped-in water (Demonstration System A). Initiate development of a 5 kW system for later mass-market automotive auxiliary power unit application, which will incorporate Catalytic Partial Oxidation (CPO) reforming of gasoline, with anode exhaust gas injected into an ultra-lean burn internal combustion engine. This technical progress report covers work performed by Delphi from July 1, 2003 to December 31, 2003, under Department of Energy Cooperative Agreement DE-FC-02NT41246. This report highlights technical results of the work performed under the following tasks: Task 1 System Design and Integration; Task 2 Solid Oxide Fuel Cell Stack Developments; Task 3 Reformer Developments; Task 4 Development of Balance of Plant (BOP) Components; Task 5 Manufacturing Development (Privately Funded); Task 6 System Fabrication; Task 7 System Testing; Task 8 Program Management; Task 9 Stack Testing with Coal-Based Reformate; and Task 10 Technology Transfer from SECA CORE Technology Program. In this reporting period, unless otherwise noted Task 6--System Fabrication and Task 7--System Testing will be reported within Task 1 System Design and Integration. Task 8--Program Management, Task 9--Stack Testing with Coal Based Reformate, and Task 10--Technology Transfer from SECA CORE Technology Program will be reported on in the Executive Summary section of this report.

  4. An ab initio study of plutonium oxides surfaces

    International Nuclear Information System (INIS)

    Jomard, G.; Bottin, F.; Amadon, B.

    2007-01-01

    By means of first-principles calculations, we have studied the atomic structure as well as the thermodynamic stability of various plutonium dioxide surfaces in function of their environment (in terms of oxygen partial pressure and temperature). All these simulations have been performed with the ABINIT code. It is well known that DFT fails to describe correctly plutonium-based materials since 5f electrons in such systems are strongly correlated. In order to go beyond DFT, we have treated PuO 2 and β-Pu 2 O 3 in a DFT+U framework. We show that the couple of parameters (U,J) that works well for pure Pu is also well designed for describing ground state (GS) properties of these two oxides. The major improvement with respect with DFT is that we are able to predict an insulating GS in agreement with experiments. The presence of a gap in the DOS (Density of States) of plutonium oxides should play a significant role in the predicted surface reactivity. However, performing DFT+U calculations on surfaces of plutonium oxide from scratch was too ambitious. That is why we decided, as a first step, to study the stability of the (100), (110) and (111) surfaces of PuO 2 in a DFT-GGA framework. For each of these orientations, we considered various terminations. These ab initio results have been introduced in a thermodynamic model which allows us to predict the relative stability of the different terminations as a function of temperature and oxygen partial pressure (p O 2 ). We conclude that at room temperature and for p O 2 ∼10 atm., the polar O 2 -(100) termination is favoured. The stabilization of such a polar stoichiometric surface is surprising and should be confirmed by DFT+U calculations before any final conclusion. (authors)

  5. Effect of high doses of L-ascorbic acid on the antioxidative/oxidative state in the rats

    DEFF Research Database (Denmark)

    Niemiec, T.; Sawosz, E.; Chwalibog, André

    2005-01-01

    The objective of this study was to determine the effects of mega-doses of vitamin C (0.3, 0.6 and 0.9% of diet) as a dietary supplement for rats on selected indices of the antioxidative/oxidative state in 40 growing Wistar rats (4x10). It was found that L-ascorbic acid and Total Antioxidative State...... (TAS) in plasma did not increase with increasing vitamin C supply. The results indicate that high doses of L-ascorbic acid (0.3 and 0.9 but not 0.6%) increased the concentration of this antioxidant in plasma. Supplementation of vitamin C above 0.3% to the diets had pro-oxidative effects on lipid...... structures, while application of 0.9% promoted oxidative degradation of rat livers....

  6. Oxidation state of sulfur, iron and tin at the surface of float glasses

    International Nuclear Information System (INIS)

    Lagarde, P; Flank, A-M; Jupille, J; Montigaud, H

    2009-01-01

    Sulfur is an important element of glasses, not because of its amount, always very low (less than 0.4 % in weight of SO 3 ), but because of its role since it actively participates to the refinement process and, combined to other elements, it can be responsible for the coloration of the glass. Iron is also of a major importance in most of the glasses. In the case of the float glass, the two faces, because of the fabrication process, are different in terms of composition (presence of Sn for one face) and also in terms of oxidation state of these minority elements (Fe, Sn, S). There should be a subtle interplay between the concentrations and the oxidation states of these different minority elements, and anyway these variations occur over a thickness of the order of few micrometers below the surface. Using the high intensity and the focusing properties (3 x 3 μm 2 ) of the x-ray beam from the Lucia beamline, we have therefore studied the speciation of iron and sulfur near the face of a float glass in relation with the behavior of tin. This has been obtained by combining elemental x-ray fluorescence cartography and x-ray micro-absorption at the different K-edges.

  7. Oxidation state of sulfur, iron and tin at the surface of float glasses

    Energy Technology Data Exchange (ETDEWEB)

    Lagarde, P; Flank, A-M [Synchrotron SOLEIL, l' Orme des Merisiers, BP 48 91192 Gif/Yvette cedex (France); Jupille, J [IMPMC, Universite P. and M. Curie, Campus de Boucicaut, 140 rue de Lourmel 75015 Paris (France); Montigaud, H [Saint-Gobain Recherche 39, quai Lucien Lefranc, BP 135 93303 Aubervilliers Cedex (France)

    2009-11-15

    Sulfur is an important element of glasses, not because of its amount, always very low (less than 0.4 % in weight of SO{sub 3}), but because of its role since it actively participates to the refinement process and, combined to other elements, it can be responsible for the coloration of the glass. Iron is also of a major importance in most of the glasses. In the case of the float glass, the two faces, because of the fabrication process, are different in terms of composition (presence of Sn for one face) and also in terms of oxidation state of these minority elements (Fe, Sn, S). There should be a subtle interplay between the concentrations and the oxidation states of these different minority elements, and anyway these variations occur over a thickness of the order of few micrometers below the surface. Using the high intensity and the focusing properties (3 x 3 {mu}m{sup 2}) of the x-ray beam from the Lucia beamline, we have therefore studied the speciation of iron and sulfur near the face of a float glass in relation with the behavior of tin. This has been obtained by combining elemental x-ray fluorescence cartography and x-ray micro-absorption at the different K-edges.

  8. Photoluminescence study on amino functionalized dysprosium oxide-zinc oxide composite bifunctional nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Joseph, Aswathy; Praveen, G.L; Abha, K.; Lekha, G.M [Department of Chemistry, University of Kerala, Kariavattom, Kerala 695581 (India); George, Sony, E-mail: emailtosony@gmail.com [Department of Chemistry, University of Kerala, Kariavattom, Kerala 695581 (India)

    2012-08-15

    An organic dispersion of 9-15 nm size stable dysprosium oxide incorporated zinc oxide nanocomposites exhibiting luminescence in the visible region has been synthesised by a wet chemical precipitation technique at room temperature. Tetraethoxysilane TEOS [(C{sub 2}H{sub 5}O){sub 4}Si], (3-aminopropyl) trimethoxysilane (APTS) and a 1:1 mixture of TEOS-APTS have been used as capping agents to control the particle size as well as to achieve uniform dispersion of composite nanoparticles in methanol medium. X-ray diffractometer (XRD) analysis reveals the formation phase of amino-functionalised colloidal dysprosium oxide incorporated ZnO composite nanoparticles to be of zincite structure. The Transmission Electron Microscopy (TEM) images show that the particles are spheroids in shape, having average crystalline sizes ranging from 9 to 15 nm. The photoluminescence (PL) observed in these composites has been attributed to the presence of near band edge excitonic emission and existence of defect centres. The time correlated single photon counting studies of the composite nanoparticles exhibited three decay pathways. The enhanced PL emission intensity of solid state fluorescence spectra of samples is attributed to the absence of vibrational relaxation process. - Highlights: Black-Right-Pointing-Pointer Nano-composites are synthesised using a one step wet chemical precipitation method. Black-Right-Pointing-Pointer A significant fluorescence life time of 8.25 ns is obtained for the nano-composite. Black-Right-Pointing-Pointer Nano-composite particles exhibited pale yellow fluorescence rather than blue. Black-Right-Pointing-Pointer Vibrational cascade free enhanced fluorescence is obtained for the dry sample.

  9. Approaches to Determining the Oxidation State of Nitrogen and Carbon Atoms in Organic Compounds for High School Students

    Science.gov (United States)

    Jurowski, Kamil; Krzeczkowska, Malgorzata Krystyna; Jurowska, Anna

    2015-01-01

    The concept of oxidation state (or oxidation number) and related issues have always been difficult for students. In addition, there are misunderstandings and obscurities, which can cause improper balancing of the chemical equations (mostly in organic reactions). In particular, these problems are related to determination of the oxidation state of…

  10. Electrical impedance studies of uranium oxide

    International Nuclear Information System (INIS)

    Hampton, R.N.

    1986-11-01

    The thesis presents data on the electrical properties of uranium oxide at temperatures from 1700K to 4.2K, and pressures between 25 K bar and 70 K bar. The impedance data were analysed using the technique of complex plane representation to establish the conductivity and dielectric constant of uranium dioxide. The thermophysical data were compared with previously reported experimental and theoretical work on uranium dioxide and other fluorite structured oxides. (U.K.)

  11. Phase Behavior and Equations of State of the Actinide Oxides

    Science.gov (United States)

    Chidester, B.; Pardo, O. S.; Panero, W. R.; Fischer, R. A.; Thompson, E. C.; Heinz, D. L.; Prescher, C.; Prakapenka, V. B.; Campbell, A.

    2017-12-01

    The distribution of the long-lived heat-producing actinide elements U and Th in the deep Earth has important implications for the dynamics of the mantle and possibly the energy budget of Earth's core. The low shear velocities of the Large Low-Shear Velocity Provinces (LLSVPs) on the core-mantle boundary suggests that these regions are at least partially molten and may contain concentrated amounts of the radioactive elements, as well as other large cations such as the rare Earth elements. As such, by exploring the phase behavior of actinide-bearing minerals at extreme conditions, some insight into the mineralogy, formation, and geochemical and geodynamical effects of these regions can be gained. We have performed in situ high-pressure, high-temperature synchrotron X-ray diffraction experiments and calculations on two actinide oxide materials, UO2 and ThO2, to determine their phase behavior at the extreme conditions of the lower mantle. Experiments on ThO2 reached 60 GPa and 2500 K, and experiments on UO2 reached 95 GPa and 2500 K. We find that ThO2 exists in the fluorite-type structure to 20 GPa at high temperatures, at which point it transforms to the high-pressure cotunnite-type structure and remains thus up to 60 GPa. At room temperature, an anomalous expansion of the fluorite structure is observed prior to the transition, and may signal anion sub-lattice disorder. Similarly, UO2 exists in the fluorite-type structure at ambient conditions and up to 28 GPa at high temperatures. Above these pressures, we have observed a previously unidentified phase of UO2 with a tetragonal structure as the lower-temperature phase and the cotunnite-type phase at higher temperatures. Above 78 GPa, UO2 undergoes another transition or possible dissociation into two separate oxide phases. These phase diagrams suggest that the actinides could exist as oxides in solid solution with other analogous phases (e.g. ZrO2) in the cotunnite-type structure throughout much of Earth's lower mantle.

  12. On matrix stabilisation of d- and f-transition metal ions in unstable oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Kiselev, Yurii M [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation)

    2009-01-31

    The state-of-the-art in matrix stabilisation of d- and f-transition metal ions in unstable oxidation states is analysed. Main aspects of this problem concerning the genealogy of appropriate matrix systems are classified. Relevant examples are given and the data that contradict the scheme proposed are discussed. The thermodynamics of the matrix stabilisation effect is considered using the concept of isomorphic miscibility. The influence of defects and non-equilibrium on the matrix stabilisation effect is discussed. The problem of identification of the oxidation states in matrix systems is examined and various types of matrix systems are considered.

  13. On matrix stabilisation of d- and f-transition metal ions in unstable oxidation states

    International Nuclear Information System (INIS)

    Kiselev, Yurii M

    2009-01-01

    The state-of-the-art in matrix stabilisation of d- and f-transition metal ions in unstable oxidation states is analysed. Main aspects of this problem concerning the genealogy of appropriate matrix systems are classified. Relevant examples are given and the data that contradict the scheme proposed are discussed. The thermodynamics of the matrix stabilisation effect is considered using the concept of isomorphic miscibility. The influence of defects and non-equilibrium on the matrix stabilisation effect is discussed. The problem of identification of the oxidation states in matrix systems is examined and various types of matrix systems are considered.

  14. A mechanistic study on the oxidative coupling of methane over lithium doped magnesium oxide catalysts

    NARCIS (Netherlands)

    Geerts, J.W.M.H.; Kasteren, van J.M.N.; Wiele, van der K.; Imarisio, G.; Frias, M.; Berntgen, J.M.

    1988-01-01

    To elucidate the importance of various reaction steps in the oxidative convers ion of methane, experiments were carried out with three reaction products: ethane, ethylene and carbon monoxide. These products were studied seperately, in oxidation experiments with and without a catalyst. Moreover , the

  15. Tritium oxidation and exchange: preliminary studies

    International Nuclear Information System (INIS)

    Phillips, J.E.; Easterly, C.E.

    1978-05-01

    The radiological hazard resulting from an exposure to either tritium oxide or tritium gas is discussed and the factors contributing to the hazard are presented. From the discussion it appears that an exposure to tritium oxide vapor is 10 4 to 10 5 times more hazardous than exposure to tritium gas. Present and future sources of tritium are briefly considered and indicate that most of the tritium has been and is being released as tritium oxide. The likelihood of gaseous releases, however, is expected to increase in the future, calling to task the present general release assumption that 100% of all tritium released is as oxide. Accurate evaluation of the hazards from a gaseous release will require a knowledge of the conversion rate of tritium gas to tritium oxide. An experiment for determining the conversion rate of tritium gas to tritium oxide is presented along with some preliminary data. The conversion rates obtained for low initial concentrations (10 -4 to 10 -1 mCi/ml) indicate the conversion may proceed more rapidly than would be expected from an extrapolation of previous data taken at higher concentrations

  16. Extraction separation studies of uranium(VI) by amine oxides

    International Nuclear Information System (INIS)

    Ejaz, M.

    1975-01-01

    The extraction of uranium(VI) by two amine oxides, 4-(5-nonyl)pyridine oxide and trioctylamine oxide has been studied. The extraction behavior of these two N-oxides is compared. The dependence of extraction on the type of amine oxide and acid, nature of organic diluent, and amine oxide concentration has been investigated. The influence of the concentration of the metal and salting-out agents is described. The possible mechanism of extraction is discussed in the light of the results of extraction isotherms, loading radiodata, and log-log plots of amine oxide concentration vs distribution ratio. The separation factors for a number of metal ions are reported, and the separation of uranium from some fission elements has also been achieved

  17. Microanalysis of iron oxidation state in iron oxides using X Ray Absorption Near Edge Structure (XANES)

    Science.gov (United States)

    Sutton, S. R.; Delaney, J.; Bajt, S.; Rivers, M. L.; Smith, J. V.

    1993-01-01

    An exploratory application of x ray absorption near edge structure (XANES) analysis using the synchrotron x ray microprobe was undertaken to obtain Fe XANES spectra on individual sub-millimeter grains in conventional polished sections. The experiments concentrated on determinations of Fe valence in a suite of iron oxide minerals for which independent estimates of the iron speciation could be made by electron microprobe analysis and x ray diffraction.

  18. ESR study into mechanism of heterogeneous-catalytic oxidation on oxides

    Energy Technology Data Exchange (ETDEWEB)

    Topchieva, K V; Loginov, A Yu; Kostikov, S V [Moskovskij Gosudarstvennyj Univ. (USSR)

    1977-12-11

    The role of radical particles in heterogeneous-catalytic oxidation of H/sub 2/; CO; SO/sub 2/; NH/sub 3/; C/sub 3/H/sub 6/ on the rare earth oxides (yttrium, lanthanum, magnesium and scandium oxides) and alkaline earth metal oxides was studied by the ESR method. The conclusion was made about the great reactivity of the peroxide structures O/sub 2//sup -/ in the oxidation catalysis in comparison to other formulas of chemisorption oxigen on oxides. The kinetic investigations are chemisorption oxigen on oxides. The kinetic investigations are carried out on the change of the concentration of paramagnetic particles O/sub 2/ during the catalysis. On the basis of the received data the conclusion is made about the reaction process of catalytic oxidation on rare and alkaline-earth oxides according to radical-chain mechanism with the formation of radical particles O/sub 2//sup -/, CO/sub 3//sup -/, SO/sub 4//sup -/, CO/sub 2//sup -/ as interediate products.

  19. Study on cobalt oxide; Sanka kobaruto ni kansuru kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-11-28

    This is No.91 report of National Institute for Research in Inorganic Materials, concerning cobalt oxide. For the growth of single crystal by the Czochralski method, shape of interface and contamination of impurities are affected by the convection of molten liquid in the atmosphere. Various oxides besides CoO were investigated. Solid solutions of Cr2O3 and Al2O3 into CoO were also studied. Non-linear optic and dielectric properties of single crystals, such as Ba2NaNb5O15 and LiNbO3, were examined. It was considered that the positive electron having positive electric charge can be used for the study on the negative electric charge defect in materials. However, the positive electron itself is rare, which results in the too low efficiency of measurement. Efficiency improvement of 50 times was achieved by introducing a high performance 2D position detector, which was still low efficiency of one-hundredth compared with photoelectron spectroscopy. It was found that the aggregation structure of positive ion defects in CoO is a misunderstanding of phenomenon caused by the electronic state in bulk crystals. As a result of the study on the optical properties of f-electron transition metals, transparent ceramics with addition of various rare earth ions were described. 162 refs., 106 figs., 14 tabs.

  20. Oxide surfaces and metal/oxide interfaces studied by grazing incidence X-ray scattering

    Science.gov (United States)

    Renaud, Gilles

    important physical properties such as superconductivity or magnetism is also briefly reviewed. The strengths and limitations of the technique, such as the need for single crystals and surfaces of high crystalline quality are discussed. Finally, an outlook of future prospects in the field is given, such as the study of more complex oxide surfaces, vicinal surfaces, reactive metal/oxide interfaces, metal oxidation processes, the use of surfactants to promote wetting of a metal deposited on an oxide surface or the study of oxide/liquid interfaces in a non-UHV environment.

  1. Study of the oxidation behavior of zirconoium and its alloys

    International Nuclear Information System (INIS)

    Costa, I.

    1985-01-01

    The oxidation behavior of zirconium, zircaloy-4 and Zr-2,5% Nb alloy, as well as the influence of temperature, oxidising atmosphere, metal composition, heat treatment, surface treatment and specimen size on the oxidation of these materials in the temperature range 350 - 900 0 C and at atmospheric pressure have been studied with the aid of thermogravimetry. The results indicate that oxidation rate increases with temperature and the rate of oxidation of the zirconium alloys was appreciable beyond 600 0 C. At temperature higher than 500 0 C, the oxidation curves of the zirconium alloys revealed a rate transition, the kinetics after transition being either mixed parabolic and linear or linear. The transition produced an alteration in oxide characteristics, from being dark and adherent and protective, to white or grey and revealing at times cracks and scaling. The oxidation atmospheres were oxygen and air, and the results showed that the extent of oxidation in air was higher than that in oxygen. Among the metals, zirconium showed a low degree of oxidation, and the alloy Zr-2,5% Nb the lowest resistance to oxidation. Specimens heat treated in the α-phase showed the highest resistance to oxidation, and those heat treated in the β-phase the lowest. Surface treatments in aqueous solutions containing a high concentration of the fluoride ion, left behind fluorates on the surface and increased the oxidation rates of zirconium and zircaloy-4. Specimens with a high proportion of corners in relation to the total area, showed a high extent of oxidation giving rise to cracks in the oxide at the corners. (Author) [pt

  2. Visible light photoreactivity from hybridization states between carbon nitride bandgap states and valence states in Nb and Ti oxides

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Hosik, E-mail: hosiklee@gmail.com [School of Mechanical and Advanced Materials Engineering, Ulsan National Institute of Science and Technology (UNIST), Unist-gil 100 Eonyang-eup, Ulsan 689-798 (Korea, Republic of); Ohno, Takahisa, E-mail: OHNO.Takahisa@nims.go.jp [Global Research Center for Environment and Energy based on Nanomaterials Science (GREEN), National Institute for Material Science, 1-2-1 Sengen, Tsukuba (Japan); Computational Materials Science Unit (CMSU), National Institute for Materials Science (NIMS), Tsukuba, Ibaraki 305-0047 (Japan)

    2013-03-29

    Highlights: ► Origin of bandgap reduction for visible photoreactivity is suggested. ► Carbon nitride adsorption in interlayer space can induce the bandgap reduction. ► The electronic structures are studied by density functional theory calculations. - Abstract: For better efficiency as photocatalysts, N-doping for visible light reactivity has been intensively studied in Lamellar niobic and titanic solid acids (HNb{sub 3}O{sub 8}, H{sub 2}Ti{sub 4}O{sub 9}), and its microscopic structures have been debated in this decade. We calculate the layered solid acids’ structures and bandgaps. Bandgap reduction by carbon nitride adsorption in interlayer space is observed computationally. It originates from localized nitrogen states which form delocalized top-valence states by hybridizing with the host oxygen states and can contribute to photo-current.

  3. The oxidation states of elements in pure and Ca-doped BiCuSeO thermoelectric oxides

    International Nuclear Information System (INIS)

    Hsiao, Chun-Lung; Qi, Xiaoding

    2016-01-01

    Bi 1−x Ca x CuSeO (x = 0–0.3) was synthesized at 650 °C in an air-tight system flowing with pure argon. The Ca doping resulted in an increase in the thermoelectric figure of merit (ZT) as the consequence of increased carrier concentration. X-ray photoelectron spectroscopy (XPS) was carried out to check the oxidation states in Bi 1−x Ca x CuSeO. The results indicated that in addition to the expected Bi 3+ and Cu 1+ , there existed Bi 2+ and Cu 2+ in the undoped BiCuSeO, whereas in the Ca-doped BiCuSeO, Bi 4+ , Cu 3+ and Cu 2+ were observed. The Ca dopant was confirmed to be in the 2+ oxidation state. Two broad peaks centered at 54.22 and 58.59 eV were recorded in the vicinity around the binding energy of Se 3d. The former is often observed in the Se-containing intermetallics while the latter is often found in the Se-containing oxides, indicating that along with the expected Se–Cu bonding, a bonding between Se and O may also exist. Based on the XPS results, the charge compensation mechanisms were proposed for Bi 1−x Ca x CuSeO, which may shed some light on the origins of charge carriers. BiCuSeO based oxides have recently be discovered to have a large ZT comparable to the best alloys currently in use, because of the large Seebeck coefficient and small thermal conductivity. However, their electrical conductivity is lower compared to the best thermoelectrics. This work may provide some hints for the further improvement of ZT in BiCuSeO based oxides. - Graphical abstract: The oxidation states, charge compensation mechanisms, and origins of charge carriers in Bi 1−x Ca x CuSeO thermoelectrics. Display Omitted

  4. Ab initio molecular dynamics simulation of aqueous solution of nitric oxide in different formal oxidation states

    Science.gov (United States)

    Venâncio, Mateus F.; Rocha, Willian R.

    2015-10-01

    Ab initio molecular dynamics simulations were used to investigate the early chemical events involved in the dynamics of nitric oxide (NOrad), nitrosonium cation (NO+) and nitroxide anion (NO-) in aqueous solution. The NO+ ion is very reactive in aqueous solution having a lifetime of ∼4 × 10-13 s, which is shorter than the value of 3 × 10-10 s predicted experimentally. The NO+ reacts generating the nitrous acid as an intermediate and the NO2- ion as the final product. The dynamics of NOrad revealed the reversibly formation of a transient anion radical species HONOrad -.

  5. Study of internal oxidation kinetics of molybdenum base alloys

    International Nuclear Information System (INIS)

    Krushinskij, Yu.Yu.; Belyakov, B.G.; Belomyttsev, M.Yu.

    1989-01-01

    Metallographic and microdurometric method as well as new technique were used to study kinetics of internal oxidation (IO). It is shown that study of IO kinetics on the base of metallographic measurements of layers depth is not correct because it is related with insufficient sensitivity of the method. IO kinetics under conditions of formation of molybdenum oxide layer on saturated material surface as well as IO of alloy with high carbon content were investigated. Oxide film formation does not affect the IO kinetics; decarburization observed along with oxidation increases the apparent activation energy and K exponent on time dependence of diffusion layer depth

  6. Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States

    Directory of Open Access Journals (Sweden)

    Elixabet Díaz-de-Cerio

    2016-05-01

    Full Text Available Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high. The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production.

  7. Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States.

    Science.gov (United States)

    Díaz-de-Cerio, Elixabet; Verardo, Vito; Gómez-Caravaca, Ana María; Fernández-Gutiérrez, Alberto; Segura-Carretero, Antonio

    2016-05-11

    Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high). The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production.

  8. Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States

    Science.gov (United States)

    Díaz-de-Cerio, Elixabet; Verardo, Vito; Gómez-Caravaca, Ana María; Fernández-Gutiérrez, Alberto; Segura-Carretero, Antonio

    2016-01-01

    Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high). The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production. PMID:27187352

  9. Study of film graphene/graphene oxide obtained by partial reduction chemical of oxide graphite

    International Nuclear Information System (INIS)

    Gascho, J.L.S.; Costa, S.F.; Hoepfner, J.C.; Pezzin, S.H.

    2014-01-01

    This study investigated the morphology of graphene/graphene oxide film obtained by partial chemical reduction of graphite oxide (OG) as well as its resistance to solvents. Films of graphene/graphene oxide are great candidates for replacement of indium oxide doped with tin (ITO) in photoelectric devices. The OG was obtained from natural graphite, by Hummer's method modified, and its reduction is made by using sodium borohydride. Infrared spectroscopy analysis of Fourier transform (FTIR), Xray diffraction (XRD) and scanning electron microscopy, high-resolution (SEM/FEG) for the characterization of graphene/graphene oxide film obtained were performed. This film proved to be resilient, not dispersing in any of the various tested solvents (such as ethanol, acetone and THF), even under tip sonication, this resistance being an important property for the applications. Furthermore, the film had a morphology similar to that obtained by other preparation methods.(author)

  10. Oxidative Stress State Is Associated with Left Ventricular Mechanics Changes, Measured by Speckle Tracking in Essential Hypertensive Patients

    Directory of Open Access Journals (Sweden)

    Luis Antonio Moreno-Ruíz

    2015-01-01

    Full Text Available The oxidative stress state is characterized by an increase in oxygen reactive species that overwhelms the antioxidant defense; we do not know if these pathological changes are correlated with alterations in left ventricular mechanics. The aim was correlating the oxidative stress state with the left ventricular global longitudinal strain (GLS and the left ventricular end diastolic pressure (LVEDP. Twenty-five patients with essential hypertension and 25 controls paired by age and gender were studied. All of the participants were subjected to echocardiography and biochemical determination of oxidative stress markers. The hypertensive patients, compared with control subjects, had significantly (p<0.05 higher levels of oxidized proteins (5.03±1.05 versus 4.06±0.63 nmol/mg, lower levels of extracellular superoxide dismutase (EC-SOD activity (0.045±0.02 versus 0.082±0.02 U/mg, higher LVEDP (16.2±4.5 versus 11.3±1.6 mm Hg, and lower GLS (−12% versus −16%. Both groups had preserved ejection fraction and the results showed a positive correlation of oxidized proteins with GLS (r=0.386, p=0.006 and LVEDP (r=0.389, p=0.005; we also found a negative correlation of EC-SOD activity with GLS (r=-0.404, p=0.004 and LVEDP (r=-0.347, p=0.014.

  11. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Massachusetts Institute of Technology; Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.; Kessler, Sean H.; Canagaratna, Manjula R.; Wilson, Kevin R.; Altieri, Katye E.; Mazzoleni, Lynn R.; Wozniak, Andrew S.; Bluhm, Hendrik; Mysak, Erin R.; Smith, Jared D.; Kolb, Charles E.; Worsnop, Douglas R.

    2010-11-05

    A detailed understanding of the sources, transformations, and fates of organic species in the environment is crucial because of the central roles that organics play in human health, biogeochemical cycles, and Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of OSC , using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number (nC).

  12. The study of the oxidation of the natural flavonol fisetin confirmed quercetin oxidation mechanism

    International Nuclear Information System (INIS)

    Ramešová, Šárka; Sokolová, Romana; Degano, Ilaria

    2015-01-01

    Highlights: • The oxidation mechanisms of fisetin and quercetin were compared. • The oxidation product of fisetin was identified even if it was not stable. • A benzofuranon derivative is the common oxidation product of flavonols. • Fisetin decomposes in solution during minutes handled in the presence of air. - Abstract: Oxidation of the bioactive flavonoid fisetin was studied under inert atmosphere and under ambient conditions. The presence of fast subsequent chemical reactions following the electron transfer was supported by in situ spectroelectrochemistry and identification of products by HPLC-DAD and HPLC–ESI-MS/MS. In the absence of oxygen, 2,6-dihydroxy-2-(3′,4′-dihydroxybenzoyl)-benzofuran-3(2H)-one was identified as the only oxidation product of fisetin. This product was found also as the main oxidation product in the presence of oxygen. The oxidation pathway leading to formation of a benzofuranone derivative can be considered as common for flavonols containing C2-C3 double bond, C3-OH group and dihydroxy-substituted phenyl moiety in its structure. This product was not stable and decomposed further even in contact with oxygen coming from eluents during chromatography. Two oxidation pathways occur under ambient conditions. DFT calculations support the result.

  13. Visualizing chemical states and defects induced magnetism of graphene oxide by spatially-resolved-X-ray microscopy and spectroscopy.

    Science.gov (United States)

    Wang, Y F; Singh, Shashi B; Limaye, Mukta V; Shao, Y C; Hsieh, S H; Chen, L Y; Hsueh, H C; Wang, H T; Chiou, J W; Yeh, Y C; Chen, C W; Chen, C H; Ray, Sekhar C; Wang, J; Pong, W F; Takagi, Y; Ohigashi, T; Yokoyama, T; Kosugi, N

    2015-10-20

    This investigation studies the various magnetic behaviors of graphene oxide (GO) and reduced graphene oxides (rGOs) and elucidates the relationship between the chemical states that involve defects therein and their magnetic behaviors in GO sheets. Magnetic hysteresis loop reveals that the GO is ferromagnetic whereas photo-thermal moderately reduced graphene oxide (M-rGO) and heavily reduced graphene oxide (H-rGO) gradually become paramagnetic behavior at room temperature. Scanning transmission X-ray microscopy and corresponding X-ray absorption near-edge structure spectroscopy were utilized to investigate thoroughly the variation of the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups, as well as the C 2p(σ*)-derived states in flat and wrinkle regions to clarify the relationship between the spatially-resolved chemical states and the magnetism of GO, M-rGO and H-rGO. The results of X-ray magnetic circular dichroism further support the finding that C 2p(σ*)-derived states are the main origin of the magnetism of GO. Based on experimental results and first-principles calculations, the variation in magnetic behavior from GO to M-rGO and to H-rGO is interpreted, and the origin of ferromagnetism is identified as the C 2p(σ*)-derived states that involve defects/vacancies rather than the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups on GO sheets.

  14. Mechanistic Study of Monodisperse Iron Oxide Nanocrystals ...

    African Journals Online (AJOL)

    To gain better insight into the formation of iron oxide nanocrystals from the solution phase thermal decomposition of iron (III) oleate complex, different reaction conditions including time, heating ramp, as well as concentrations of iron oleate precursor and oleic acid ligand were systematically varied and the resulting ...

  15. Electrochemical studies on vanadium oxides, 9

    International Nuclear Information System (INIS)

    Miura, Takashi; Yamamoto, Masahiro; Takahashi, Hirobumi; Kishi, Tomiya; Nagai, Takashi

    1979-01-01

    The mechanism of the anodic oxidation of various organic compounds-including methanol, formaldehyde, formic acid, ethanol, acetaldehyde and acetic acid-at illuminated vanadium pentoxide (V 2 O 5 ) single crystal electrodes were investigated in aqueous solutions of an H 2 SO 4 -K 2 SO 4 system of about pH 2, in which oxygen evolution from water molecules had previously been confirmed to occur with a current efficiency of about 100%. It was shown that all the organics were oxidized by the so called hole-current doubling mechanism, and that the oxygen evolution reaction, which competed with the above oxidation reaction at the hole-capturing step from the valence band of the electrode, proceeded by the simple hole-capturing mechanism, not followed by an electron injection step into the conduction band. Furthermore, it is considered that chloride ions added to the electrolytes tended to hinder hole-current doubling oxidation owing to their reactivity with the holes at the illuminated V 2 O 5 electrodes. (author)

  16. Triplet-State Dissolved Organic Matter Quantum Yields and Lifetimes from Direct Observation of Aromatic Amine Oxidation.

    Science.gov (United States)

    Schmitt, Markus; Erickson, Paul R; McNeill, Kristopher

    2017-11-21

    Excited triplet state chromophoric dissolved organic matter ( 3 CDOM*) is a short-lived mixture of excited-state species that plays important roles in aquatic photochemical processes. Unlike the study of the triplet states of well-defined molecules, which are amenable to transient absorbance spectroscopy, the study of 3 CDOM* is hampered by it being a complex mixture and its low average intersystem crossing quantum yield (Φ ISC ). This study is an alternative approach to investigating 3 CDOM* using transient absorption laser spectroscopy. The radical cation of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), formed through oxidation by 3 CDOM*, was directly observable by transient absorption spectroscopy and was used to probe basic photophysical properties of 3 CDOM*. Quenching and control experiments verified that TMPD •+ was formed from 3 CDOM* under anoxic conditions. Model triplet sensitizers with a wide range of excited triplet state reduction potentials and CDOM oxidized TMPD at near diffusion-controlled rates. This gives support to the idea that a large cross-section of 3 CDOM* moieties are able to oxidize TMPD and that the complex mixture of 3 CDOM* can be simplified to a single signal. Using the TMPD •+ transient, the natural triplet lifetime and Φ ISC for different DOM isolates and natural waters were quantified; values ranged from 12 to 26 μs and 4.1-7.8%, respectively.

  17. A microstuctural study on accelerated zirconium alloy oxidation

    International Nuclear Information System (INIS)

    Sohn, Seung Bum; Oh, Seung Jun; Jang, Jung Nam; Kim, Yong Soo; Jung, Yong Hwan; Baek, Jong Hyuk; Park, Jung Yong

    2005-01-01

    It has been reported that the effect of thermal redistribution of hydrides across the zirconium metaloxide interface, coupled with thermal feedback on the metal-oxide interface, is a dominating factor in the accelerated oxidation in zirconium alloys cladding PWR fuel. Basically this influence determines characteristic of oxide layer. Influence estimation for corrosion oxide layer due to hydrogen / hydride carried out because of investigation on the kinetic on accelerated oxidation due to hydride precipitation was preceded. Generally, it is known that ZrO 2 tetragonal layer structures play an important role as a barrier layer. So analysing the ZrO 2 monoclinic and tetragonal structure distribution is our main aim. Especially, this study focused on the hydride effects. In other words, the difference of crystal structure distribution between pre-hydrided and without hydrided specimen is just expected results. Experimental results of microstructure at zirconium metal-oxide interface through TEM and EBSD analysis was confirmed

  18. DetOx: a program for determining anomalous scattering factors of mixed-oxidation-state species.

    Science.gov (United States)

    Sutton, Karim J; Barnett, Sarah A; Christensen, Kirsten E; Nowell, Harriott; Thompson, Amber L; Allan, David R; Cooper, Richard I

    2013-01-01

    Overlapping absorption edges will occur when an element is present in multiple oxidation states within a material. DetOx is a program for partitioning overlapping X-ray absorption spectra into contributions from individual atomic species and computing the dependence of the anomalous scattering factors on X-ray energy. It is demonstrated how these results can be used in combination with X-ray diffraction data to determine the oxidation state of ions at specific sites in a mixed-valance material, GaCl(2).

  19. Two-color studies of autoionizing states of small molecules

    International Nuclear Information System (INIS)

    Pratt, S.T.; Dehmer, P.M.; Dehmer, J.L.; Tomkins, F.S.; O'Halloran, M.A.

    1989-01-01

    Two-color, resonantly enhanced multiphoton ionization is proving to be a valuable technique for the study of autoionizing states of small molecules. In this talk, results obtained by combining REMPI, photoelectron spectroscopy, and mass spectrometry will be discussed and will be illustrated by examples from our recent studies of rotational and vibrational autoionization in molecular hydrogen and rotational autoionization in nitric oxide. 2 refs., 1 fig

  20. Studies of physicochemical properties of graphite oxide and thermally exfoliated/reduced graphene oxide

    Directory of Open Access Journals (Sweden)

    Drewniak Sabina Elżbieta

    2015-12-01

    Full Text Available The aim of the experimental research studies was to determine some electrical properties of graphite oxide and thermally exfoliated/reduced graphene oxide. The authors tried to interpret the obtained physicochemical results. For that purpose, both resistance measurements and investigation studies were carried out in order to characterize the samples. The resistance was measured at various temperatures in the course of composition changes of gas atmospheres (which surround the samples. The studies were also supported by such methods as: scanning electron microscopy (SEM, Raman spectroscopy (RS, atomic force microscopy (AFM and thermogravimetry (TG. Moreover, during the experiments also the elemental analyses (EA of the tested samples (graphite oxide and thermally exfoliated/reduced graphene oxide were performed.

  1. Role of the oxidation state of cerium on the ceria surfaces for silicate adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Seo, Jihoon [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Moon, Jinok [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Clean/CMP Technology Team, Memory, Samsung Electronics, Hwaseong (Korea, Republic of); Kim, Joo Hyun; Lee, Kangchun [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Hwang, Junha [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Materials R& D Center, K.C.Tech, Anseong (Korea, Republic of); Yoon, Heesung [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Yi, Dong Kee, E-mail: vitalis@mju.ac.kr [Department of Chemistry, Myongji University, Yongin (Korea, Republic of); Paik, Ungyu, E-mail: upaik@hanyang.ac.kr [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of)

    2016-12-15

    Highlights: • We investigated the role of Ce oxidation state (Ce{sup 3+}/Ce{sup 4+}) on the CeO{sub 2} surfaces for the silicate adsorption. • As the Ce{sup 3+} concentration increased from 19.3 to 27.6%, the surface density of −OH group increased from 0.34 to 0.72 OH/nm{sup 2}. • The Freundlich constant for the relative adsorption capacity (K{sub F}) and adsorption intensity (1/n) indicated that CeO{sub 2} NPs with high Ce{sup 3+} concentration show higher adsorption affinity with silicate ions. - Abstract: In this study, we have investigated the role of the Ce oxidation state (Ce{sup 3+}/Ce{sup 4+}) on the CeO{sub 2} surfaces for silicate adsorption. In aqueous medium, the Ce{sup 3+} sites lead to the formation of −OH groups at the CeO{sub 2} surface through H{sub 2}O dissociation. Silicate ions can adsorb onto the CeO{sub 2} surface through interaction with the −OH groups (−Ce−OH− + −Si−O{sup −} ↔ −Ce−O−Si− + OH{sup −}). As the Ce{sup 3+} concentration increased from 19.3 to 27.6%, the surface density of −OH group increased from 0.34 to 0.72 OH/nm{sup 2}. To evaluate the adsorption behaviors of silicate ions onto CeO{sub 2} NPs, we carried out an adsorption isothermal analysis, and the adsorption isotherm data followed the Freundlich model. The Freundlich constant for the relative adsorption capacity (K{sub F}) and adsorption intensity (1/n) indicated that CeO{sub 2} NPs with high Ce{sup 3+} concentration show higher adsorption affinity with silicate ions. As a result, we have demonstrated that the Ce oxidation state (Ce{sup 3+}/Ce{sup 4+}) on the CeO{sub 2} surface can have a significant influence on the silicate adsorption.

  2. Conformational Toggling of Yeast Iso-1-Cytochrome c in the Oxidized and Reduced States

    Science.gov (United States)

    Yang, Zhongzheng; Zhu, Jing; Ying, Tianlei; Jiang, Xianwang; Zhang, Xu; Wu, Houming; Liu, Maili; Tan, Xiangshi; Cao, Chunyang; Huang, Zhong-Xian

    2011-01-01

    To convert cyt c into a peroxidase-like metalloenzyme, the P71H mutant was designed to introduce a distal histidine. Unexpectedly, its peroxidase activity was found even lower than that of the native, and that the axial ligation of heme iron was changed to His71/His18 in the oxidized state, while to Met80/His18 in the reduced state, characterized by UV-visible, circular dichroism, and resonance Raman spectroscopy. To further probe the functional importance of Pro71 in oxidation state dependent conformational changes occurred in cyt c, the solution structures of P71H mutant in both oxidation states were determined. The structures indicate that the half molecule of cyt c (aa 50–102) presents a kind of “zigzag riveting ruler” structure, residues at certain positions of this region such as Pro71, Lys73 can move a big distance by altering the tertiary structure while maintaining the secondary structures. This finding provides a molecular insight into conformational toggling in different oxidation states of cyt c that is principle significance to its biological functions in electron transfer and apoptosis. Structural analysis also reveals that Pro71 functions as a key hydrophobic patch in the folding of the polypeptide of the region (aa 50–102), to prevent heme pocket from the solvent. PMID:22087268

  3. The effect of cerium valence states at cerium oxide nanoparticle surfaces on cell proliferation

    KAUST Repository

    Naganuma, Tamaki

    2014-05-01

    Understanding and controlling cell proliferation on biomaterial surfaces is critical for scaffold/artificial-niche design in tissue engineering. The mechanism by which underlying integrin ligates with functionalized biomaterials to induce cell proliferation is still not completely understood. In this study, poly-l-lactide (PL) scaffold surfaces were functionalized using layers of cerium oxide nanoparticles (CNPs), which have recently attracted attention for use in therapeutic application due to their catalytic ability of Ce4+ and Ce3+ sites. To isolate the influence of Ce valance states of CNPs on cell proliferation, human mesenchymal stem cells (hMSCs) and osteoblast-like cells (MG63) were cultured on the PL/CNP surfaces with dominant Ce4+ and Ce3+ regions. Despite cell type (hMSCs and MG63 cells), different surface features of Ce4+ and Ce3+ regions clearly promoted and inhibited cell spreading, migration and adhesion behavior, resulting in rapid and slow cell proliferation, respectively. Cell proliferation results of various modified CNPs with different surface charge and hydrophobicity/hydrophilicity, indicate that Ce valence states closely correlated with the specific cell morphologies and cell-material interactions that trigger cell proliferation. This finding suggests that the cell-material interactions, which influence cell proliferation, may be controlled by introduction of metal elements with different valence states onto the biomaterial surface. © 2014 Elsevier Ltd.

  4. XPS studies of the oxide formed on pure Ti

    International Nuclear Information System (INIS)

    Cremery, P.; David, D.; Beranger, G.; Oviedo, C.; Garcia, E.A.

    1980-01-01

    The XPS technique was used to study titanium samples oxidized at 200 ton of pure oxigen at different times and temperatures with the aim of producing variable oxide thicknesses. The thicknesses of different oxigen layers were determined by the nuclear reaction O 16 (d,p) O 17 *. (author) [pt

  5. Studies of Deactivation of Methanol to Formaldehyde Selective Oxidation Catalyst

    DEFF Research Database (Denmark)

    Raun, Kristian Viegaard; Schumann, Max; Høj, Martin

    This work presents a study of the deactivation behavior of Fe-Mo oxide catalyst during selective oxidation of methanol to formaldehyde in a period of 5 days. The structural changes in the catalyst have been investigated in situ for the initial 10 h by Raman spectroscopy, and the structure after 5...

  6. Investigating the capability of ToF-SIMS to determine the oxidation state of Ce

    Science.gov (United States)

    Seed Ahmed, H. A. A.; Swart, H. C.; Kroon, R. E.

    2018-04-01

    The capability of time of flight secondary ion mass spectrometry (ToF-SIMS) to determine the oxidation state of Ce ions doped in a phosphor was investigated. Two samples of SiO2:Ce (4 mol%) with known Ce3+/Ce4+ relative concentrations were subjected to ToF-SIMS measurements. The spectra were very similar and no significant differences in the relative peak intensities were observed that would readily allow one to distinguish Ce3+ from Ce4+. Although ToF-SIMS was therefore not useful to distinguish the charge state of Ce ions doped in this phosphor material, the idea in principle was also tested on two other samples, namely CeF3 and CeF4 These contain Ce as part of the host (i.e. much higher concentration) and are fluorides, which is significant because ToF-SIMS has previously been reported to be able to distinguish Eu2+ from Eu3+ in Eu doped Sr5(PO4)3F phosphor. The spectrum of CeF4 contained a small peak related to Ce4+ which was not observed in the CeF3 spectrum, yet the peak related to the Ce3+ ions was found to be much more intense in the spectrum of CeF4 than CeF3, showing that the ToF-SIMS signals cannot be directly interpreted as retaining the charge state of the ions in the original material. Nevertheless, the significant differences in the Ce-related peaks in the ToF-SIMS spectra from CeF3 and CeF4 show that the charge state of Ce may be distinguished. This study shows that while in principle ToF-SIMS may be used to distinguish the charge state of Ce ions, this depends on the sample and it would not be easy to interpret the spectra without a standard or reference.

  7. The Impact of Environmental Factors in Influencing Epigenetics Related to Oxidative States in the Cardiovascular System

    Directory of Open Access Journals (Sweden)

    Francesco Angelini

    2017-01-01

    Full Text Available Oxidative states exert a significant influence on a wide range of biological and molecular processes and functions. When their balance is shifted towards enhanced amounts of free radicals, pathological phenomena can occur, as the generation of reactive oxygen species (ROS in tissue microenvironment or in the systemic circulation can be detrimental. Epidemic chronic diseases of western societies, such as cardiovascular disease, obesity, and diabetes correlate with the imbalance of redox homeostasis. Current advances in our understanding of epigenetics have revealed a parallel scenario showing the influence of oxidative stress as a major regulator of epigenetic gene regulation via modification of DNA methylation, histones, and microRNAs. This has provided both the biological link and a potential molecular explanation between oxidative stress and cardiovascular/metabolic phenomena. Accordingly, in this review, we will provide current insights on the physiological and pathological impact of changes in oxidative states on cardiovascular disorders, by specifically focusing on the influence of epigenetic regulation. A special emphasis will highlight the effect on epigenetic regulation of human’s current life habits, external and environmental factors, including food intake, tobacco, air pollution, and antioxidant-based approaches. Additionally, the strategy to quantify oxidative states in humans in order to determine which biological marker could best match a subject’s profile will be discussed.

  8. Study of bixin oxidation by ionizing irradiation

    International Nuclear Information System (INIS)

    Fonseca, Thais N.; Teixeira, Paula S.; Moura, Eduardo de; Geraldo, Áurea Beatriz C.

    2017-01-01

    Brazil is the world's largest producer of anatto, followed by Kenya and Peru. The fruit of the annatto tree is constituted by a capsule containing external spines and internal seeds with reddish coloration, providing a natural pigment which is environmentally efficient, being able to replace synthetic pigments and dyes. The active substance of the pigment is Bixin, which is a type of carotenoid which constitutes a greater percentage of pigment in these seeds and has a lipo soluble character. Bixin reacts with NaOH in a saponification reaction giving norbixin, which is water soluble. It is known that the destination of the dye extracted from the fruit is intended for industry, especially the food industry. The culture of annatto tree brings prospects of development in agricultural programs for medium and small producers, which are able to use decadent areas of other crops. In addition to the food sector, new applications for the pigment helps the development of family farming. The pigment extracted from annatto undergoes a natural oxidation; this work aims to evaluate this phenomenon and also the oxidation of the pigment after the irradiation process. This work also evaluates of the how the oxidation process is affected by irradiation and the modifications introduced to irradiated pigments. Irradiated and nonirradiated samples were characterized by thermogravimetry, UV-vis spectrophotometry and infrared spectroscopy (FTIR). The results are then discussed. (author)

  9. Plutonium uptake by the green alga Scenedesmus obliquus (Turp) Kutz, as a function of isotope and oxidation state

    Energy Technology Data Exchange (ETDEWEB)

    Tkacik, M.F.

    1977-01-01

    This study was designed to determine the effect of plutonium chemical valence state on the availability of small concentrations of /sup 238/Pu and /sup 239/Pu to algae. The uptake experiments involved the green alga Scenedesmus obliquus, grown in batch cultures. Plutonium concentrations accumulated by this alga were linearly related to plutonium concentrations. There was no significant difference (rho = 0.05) in algal plutonium accumulations, on a mass basis, of either /sup 238/Pu or /sup 239/Pu in either Pu/sup +4/ or Pu/sup +6/ oxidation state at the concentrations studied.

  10. Plutonium uptake by the green alga Scenedesmus obliquus (Turp) Kutz, as a function of isotope and oxidation state

    International Nuclear Information System (INIS)

    Tkacik, M.F.

    1977-01-01

    This study was designed to determine the effect of plutonium chemical valence state on the availability of small concentrations of 238 Pu and 239 Pu to algae. The uptake experiments involved the green alga Scenedesmus obliquus, grown in batch cultures. Plutonium concentrations accumulated by this alga were linearly related to plutonium concentrations. There was no significant difference (rho = 0.05) in algal plutonium accumulations, on a mass basis, of either 238 Pu or 239 Pu in either Pu +4 or Pu +6 oxidation state at the concentrations studied

  11. Oxidation states of Fe in LaNi1-xFexO3

    International Nuclear Information System (INIS)

    Goeta, A.E.; Falcon, H.; Carbonio, R.

    1994-01-01

    The distribution of oxidation states in perovskites of the type LaA 1-x B x O 3 (A and B transition metal ions) can be ''tailored'' by x variation. In particular, in LaNiO 3 it has been shown that Fe substitution for Ni foces some Ni 3+ into Ni 2+ , while some Fe 3+ changes into the unusual Fe 4+ state. In addition, the existence of mixed oxidation states of Fe and/or Ni in LaNi 1-x Fe x O 3 has been related to its catalytic activity in hydrogen peroxide decomposition. The Fe 4+ population, obtained using Moessbauer spectroscopy, was found to be constant for all the analyzed annealing temperatures for x = 0.25 concentration, where the isomer shift difference for both states is the highest and the catalytic activity is maximum. (orig.)

  12. Facile solid-state synthesis of oxidation-resistant metal nanoparticles at ambient conditions

    Science.gov (United States)

    Lee, Kyu Hyung; Jung, Hyuk Joon; Lee, Ju Hee; Kim, Kyungtae; Lee, Byeongno; Nam, Dohyun; Kim, Chung Man; Jung, Myung-Hwa; Hur, Nam Hwi

    2018-05-01

    A simple and scalable method for the synthesis of metal nanoparticles in the solid-state was developed, which can produce nanoparticles in the absence of solvents. Nanoparticles of coinage metals were synthesized by grinding solid hydrazine and the metal precursors in their acetates and oxides at 25 °C. The silver and gold acetates converted completely within 6 min into Ag and Au nanoparticles, respectively, while complete conversion of the copper acetate to the Cu sub-micrometer particles took about 2 h. Metal oxide precursors were also converted into metal nanoparticles by grinding alone. The resulting particles exhibit distinctive crystalline lattice fringes, indicating the formation of highly crystalline phases. The Cu sub-micrometer particles are better resistant to oxidation and exhibit higher conductivity compared to conventional Cu nanoparticles. This solid-state method was also applied for the synthesis of platinum group metals and intermetallic Cu3Au, which can be further extended to synthesize other metal nanoparticles.

  13. Actinide oxides synthesis in molten chloride. Structural studies and reaction mechanisms

    International Nuclear Information System (INIS)

    Vigier, J.F.

    2012-01-01

    Pyrochemical processes are studied as potential alternatives to hydrochemical processes for spent nuclear fuel treatment. The CEA pyrochemical process led to a molten LiCl-CaCl 2 (30-70% mol) salt at 700 C with solubilized actinides at the oxidation state (III). The study developed in this thesis concerns actinide oxides synthesis in this media for nuclear fuel re-fabrication. This synthesis was done by wet argon sparging. First, this conversion method is described for neodymium (III) and cerium (III) co-conversion. The conversion rates are around 99.9%. The obtained powders contain mixed oxychloride Ce 1-x Nd x OCl as main component, with a small amount of mixed oxide Ce 1-x Nd x O 2-0,5x for the high cerium ratio. A second oxychloride CeIV(Nd 0.7 Ce 0.3 ) III O 3 Cl is obtained in specific conditions and in very low quantity. The structure of this oxychloride is described in this study. The partially oxidative property of the conversion method induces the oxidation of a part of cerium (III) to oxidation state (IV). In the case of uranium (III) conversion by wet argon sparging, all the uranium is oxidized and give the oxide UO 2 as single compound. The conversion rate for this element is over 99.9% in the molten chloride, but significant amount of uranium is lost by volatilization during the conversion. The study shows the oxygen sensitivity of uranium during the conversion, inducing oxidation over the oxidation state (IV), and giving UO 2+x or uranate CaUO 4 . As a consequence, oxygen led to calcium pollution in the precipitate. Finally, the U(III) and Pu(III) co-conversion study shows the highest precipitation sensitivity of uranium (III) in comparison with plutonium (III), responsible of a successive conversion of the two elements, giving an oxide mixture of UO 2 et PuO 2 with quantitative conversion rate. Surprisingly, the conversion of Pu(III) in the same conditions led to a mixture of PuO 2 and PuOCl, characteristic of a partial oxidation from Pu (III) to Pu

  14. Templated electrodeposition of Ag7NO11 nanowires with very high oxidation states of silver

    NARCIS (Netherlands)

    Rodijk, E.J.B.; Maijenburg, A.W.; Maas, M.G.; Blank, David H.A.; ten Elshof, Johan E.

    2011-01-01

    The templated electrodeposition of 200 nm diameter nanowires of the argentic oxynitrate Ag(Ag3O4)2NO3 phase is reported. Their high surface-to-volume ratio and the high average oxidation state of Ag make these wires promising candidates for nanoscale redox processes in which both a high volumetric

  15. Investigation of the oxidation states of Pu isotopes in a hydrochloric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Lee, M.H. [Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, P. O. Box 105, Yuseong, Daejeon 305-353 (Korea, Republic of)], E-mail: mhlee@kaeri.re.kr; Kim, J.Y.; Kim, W.H.; Jung, E.C.; Jee, K.Y. [Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, P. O. Box 105, Yuseong, Daejeon 305-353 (Korea, Republic of)

    2008-12-15

    The characteristics of the oxidation states of Pu in a hydrochloric acid solution were investigated and the results were applied to a separating of Pu isotopes from IAEA reference soils. The oxidation states of Pu(III) and Pu(IV) were prepared by adding hydroxylamine hydrochloride and sodium nitrite to a Pu stock solution, respectively. Also, the oxidation state of Pu(VI) was adjusted with concentrated HNO{sub 3} and HClO{sub 4}. The stability of the various oxidation states of plutonium in a HCl solution with elapsed time after preparation were found to be in the following order: Pu(III){approx}Pu(VI)>Pu(IV)>Pu(V). The chemical recoveries of Pu(IV) in a 9 M HCl solution with an anion exchange resin were similar to those of Pu(VI). This method for the determination of Pu isotopes with an anion exchange resin in a 9 M HCl medium was applied to IAEA reference soils where the activity concentrations of {sup 239,240}Pu and {sup 238}Pu in IAEA-375 and IAEA-326 were consistent with the reference values reported by the IAEA.

  16. Regulation of Ca2+ release from mitochondria by the oxidation-reduction state of pyridine nucleotides

    Science.gov (United States)

    Lehninger, Albert L.; Vercesi, Anibal; Bababunmi, Enitan A.

    1978-01-01

    Mitochondria from normal rat liver and heart, and also Ehrlich tumor cells, respiring on succinate as energy source in the presence of rotenone (to prevent net electron flow to oxygen from the endogenous pyridine nucleotides), rapidly take up Ca2+ and retain it so long as the pyridine nucleotides are kept in the reduced state. When acetoacetate is added to bring the pyridine nucleotides into a more oxidized state, Ca2+ is released to the medium. A subsequent addition of a reductant of the pyridine nucleotides such as β-hydroxybutyrate, glutamate, or isocitrate causes reuptake of the released Ca2+. Successive cycles of Ca2+ release and uptake can be induced by shifting the redox state of the pyridine nucleotides to more oxidized and more reduced states, respectively. Similar observations were made when succinate oxidation was replaced as energy source by ascorbate oxidation or by the hydrolysis of ATP. These and other observations form the basis of a hypothesis for feedback regulation of Ca2+-dependent substrate- or energy-mobilizing enzymatic reactions by the uptake or release of mitochondrial Ca2+, mediated by the cytosolic phosphate potential and the ATP-dependent reduction of mitochondrial pyridine nucleotides by reversal of electron transport. Images PMID:25436

  17. Measurements of the oxidation state and concentration of plutonium in interstitial waters of the Irish Sea

    International Nuclear Information System (INIS)

    Nelson, D.M.; Lovett, M.B.

    1980-01-01

    The question of plutonium movement in interstitial waters resulting from diffusion along concentration gradients or from advective flow is addressed. The results of measurements of both the concentration and the oxidation state of plutonium in interstitial water collected from sediments near the Windscale discharge, in the solid phases of these sediments and in seawater and suspended solids collected at the coring locations are discussed

  18. Ion irradiation studies of oxide ceramics

    International Nuclear Information System (INIS)

    Zinkle, S.J.

    1988-01-01

    This paper presents the initial results of an investigation of the depth-dependent microstructures of three oxide ceramics following ion implantation to moderate doses. The implantations were performed using ion species that occur as cations in the target material; for example, Mg + ions were used for MgO and MgAl 2 O 4 (spinel) irradiations. This minimized chemical effects associated with the implantation and allowed a more direct evaluation to be made of the effects of implanted ions on the microstructure. 11 refs., 14 figs

  19. The Oxidation State of Fe in Glasses from the Galapagos Archipelago: Variable Oxygen Fugacity as a Function of Mantle Source

    Science.gov (United States)

    Peterson, M. E.; Kelley, K. A.; Cottrell, E.; Saal, A. E.; Kurz, M. D.

    2015-12-01

    The oxidation state of the mantle plays an intrinsic role in the magmatic evolution of the Earth. Here we present new μ-XANES measurements of Fe3+/ΣFe ratios (a proxy for ƒO2) in a suite of submarine glasses from the Galapagos Archipelago. Using previously presented major, trace, and volatile elements and isotopic data for 4 groups of glass that come from distinct mantle sources (depleted upper mantle, 2 recycled, and a primitive mantle source) we show that Fe3+/ΣFe ratios vary both with the influence of shallow level processes and with variations in mantle source. Fe3+/ΣFe ratios increase with differentiation (i.e. decreasing MgO), but show a large variation at a given MgO. Progressive degassing of sulfur accompanies decreasing Fe3+/ΣFe ratios, while assimilation of hydrothermally altered crust (as indicated by increasing Sr/Sr*) is shown to increase Fe3+/ΣFe ratios. After taking these processes into account, there is still variability in the Fe3+/ΣFe ratios of the isotopically distinct sample suites studied, yielding a magmatic ƒO2 that ranges from ΔQFM = +0.16 to +0.74 (error ITE = enriched Sr and Pb isotopes) shows evidence of mixing between oxidized and reduced sources (ITE oxidized end-member = 0.177). This suggests that mantle sources in the Galapagos that are thought to contain recycled components (i.e., WD and ITE groups) have distinct oxidation states. The high 3He/4He Fernandina samples (HHe group) are shown to be the most oxidized (ave. 0.175 ± 0.006). With C/3He ratios an order of magnitude greater than MORB this suggests that the primitive mantle is a more carbonated and oxidized source than the depleted upper mantle.

  20. Comparative study of synthesis and reduction methods for graphene oxide

    KAUST Repository

    Alazmi, Amira; Rasul, Shahid; Patole, Shashikant P.; Da Costa, Pedro M. F. J.

    2016-01-01

    Graphene oxide (GO) and reduced graphene oxide (rGO) have congregated much interest as promising active materials for a variety of applications such as electrodes for supercapacitors. Yet, partially given the absence of comparative studies in synthesis methodologies, a lack of understanding persists on how to best tailor these materials. In this work, the effect of using different graphene oxidation-reduction strategies in the structure and chemistry of rGOs is systematically discussed. Two of the most popular oxidation routes in the literature were used to obtain GO. Subsequently, two sets of rGO powders were synthesised employing three different reduction routes, totalling six separate products. It is shown that the extension of the structural rearrangement in rGOs is not just dependent on the reduction step but also on the approach followed for the initial graphite oxidation.

  1. Comparative study of synthesis and reduction methods for graphene oxide

    KAUST Repository

    Alazmi, Amira

    2016-05-14

    Graphene oxide (GO) and reduced graphene oxide (rGO) have congregated much interest as promising active materials for a variety of applications such as electrodes for supercapacitors. Yet, partially given the absence of comparative studies in synthesis methodologies, a lack of understanding persists on how to best tailor these materials. In this work, the effect of using different graphene oxidation-reduction strategies in the structure and chemistry of rGOs is systematically discussed. Two of the most popular oxidation routes in the literature were used to obtain GO. Subsequently, two sets of rGO powders were synthesised employing three different reduction routes, totalling six separate products. It is shown that the extension of the structural rearrangement in rGOs is not just dependent on the reduction step but also on the approach followed for the initial graphite oxidation.

  2. V6O13 films by control of the oxidation state from aqueous precursor to crystalline phase.

    Science.gov (United States)

    Peys, Nick; Ling, Yun; Dewulf, Daan; Gielis, Sven; De Dobbelaere, Christopher; Cuypers, Daniel; Adriaensens, Peter; Van Doorslaer, Sabine; De Gendt, Stefan; Hardy, An; Van Bael, Marlies K

    2013-01-28

    An aqueous deposition process for V(6)O(13) films is developed whereby the vanadium oxidation state is continuously controlled throughout the entire process. In the precursor stage, a controlled wet chemical reduction of the vanadium(V) source with oxalic acid is achieved and monitored by (51)Vanadium Nuclear Magnetic Resonance ((51)V-NMR) and Ultraviolet-Visible (UV-Vis) spectroscopy. The resulting vanadium(IV) species in the aqueous solution are identified as mononuclear citrato-oxovanadate(IV) complexes by Electron Paramagnetic Resonance (EPR) and Fourier Transform Infra-Red (FTIR) spectroscopy. This precursor is successfully employed for the deposition of uniform, thin films. The optimal deposition and annealing conditions for the formation of crystalline V(6)O(13), including the control of the vanadium oxidation state, are determined through an elaborate study of processing temperature and O(2) partial pressure. To ensure a sub 100 nm adjustable film thickness, a non-oxidative intermediate thermal treatment is carried out at the end of each deposition cycle, allowing maximal precursor decomposition while still avoiding V(IV) oxidation. The resulting surface hydrophilicity, indispensable for the homogeneous deposition of the next layer, is explained by an increased surface roughness and the increased availability of surface vanadyl groups. Crystalline V(6)O(13) with a preferential (002) orientation is obtained after a post deposition annealing in a 0.1% O(2) ambient for thin films with a thickness of 20 nm.

  3. Sorption behaviour of well-defined oxidation states

    International Nuclear Information System (INIS)

    Allard, B.; Olofsson, U.; Torstenfelt, B.; Kipatsi, H.

    1983-05-01

    The sorption of the actinides Am(III), Th(IV), Np(V), Pa(V), U(VI) and Pu has been studied as a function of pH (2-12) for two nuclide concentrations (10 -7 -10 -9 M) (only one for Pa and U) in the systems Al 2 0 3 - 0.01 M NaCl0 4 and Si0 2 - 0.01 M NaCl0 4 . Distribution coefficients have been determined by a batch technique after various contact times (6h - 6w) at constant temperature (25degreeC) in systems equilibrated with air. The observed sorption behaviour indicates a predominantly physical adsorption mechanism, where pH of the aqueous phase is the principal chemical parameter of influence. The sorption is highly related to the degree of hydrolysis, with a maximum in the pH-region where neutral species dominate and with a reduction of the sorption under conditions when anionic species (hydroxides or carbonates) would exist in solution. This is particularly the case for U(VI) at pH above 7-8 when anionic carbonate complexes would be formed. Plutonium is predominantly tetravalent under the present conditions, as indicated by the sorption behaviour. (authors)

  4. Exploring routes to tailor the physical and chemical properties of oxides via doping: an STM study

    International Nuclear Information System (INIS)

    Nilius, Niklas

    2015-01-01

    Doping opens fascinating possibilities for tailoring the electronic, optical, magnetic, and chemical properties of oxides. The dopants perturb the intrinsic behavior of the material by generating charge centers for electron transfer into adsorbates, by inducing new energy levels for electronic and optical excitations, and by altering the surface morphology and hence the adsorption and reactivity pattern. Despite a vivid scientific interest, knowledge on doped oxides is limited when compared to semiconductors, which reflects the higher complexity and the insulating nature of many oxides. In fact, atomic-scale studies, aiming at a mechanistic understanding of dopant-related processes, are still scarce.In this article, we review our scanning tunneling microscopy (STM) experiments on thin, crystalline oxide films with a defined doping level. We demonstrate how the impurities alter the surface morphology and produce cationic/anionic vacancies in order to keep the system charge neutral. We discuss how individual dopants can be visualized in the lattice, even if they reside in subsurface layers. By means of STM-conductance and x-ray photoelectron spectroscopy, we determine the electronic impact of dopants, including the energies of their eigen states and local band-bending effects in the host oxide. Electronic transitions between dopant-induced gap states give rise to new optical modes, as detected with STM luminescence spectroscopy. From a chemical perspective, dopants are introduced to improve the redox potential of oxide materials. Electron transfer from Mo-donors, for example, alters the growth behavior of gold and activates O 2 molecules on a wide-gap CaO surface. Such results demonstrate the enormous potential of doped oxides in heterogeneous catalysis. Our experiments address the issue of doping from a fundamental viewpoint, posing questions on the lattice position, charge state, and electron-transfer potential of the impurity ions. Whether doped oxides are

  5. Exploring routes to tailor the physical and chemical properties of oxides via doping: an STM study

    Science.gov (United States)

    Nilius, Niklas

    2015-08-01

    Doping opens fascinating possibilities for tailoring the electronic, optical, magnetic, and chemical properties of oxides. The dopants perturb the intrinsic behavior of the material by generating charge centers for electron transfer into adsorbates, by inducing new energy levels for electronic and optical excitations, and by altering the surface morphology and hence the adsorption and reactivity pattern. Despite a vivid scientific interest, knowledge on doped oxides is limited when compared to semiconductors, which reflects the higher complexity and the insulating nature of many oxides. In fact, atomic-scale studies, aiming at a mechanistic understanding of dopant-related processes, are still scarce. In this article, we review our scanning tunneling microscopy (STM) experiments on thin, crystalline oxide films with a defined doping level. We demonstrate how the impurities alter the surface morphology and produce cationic/anionic vacancies in order to keep the system charge neutral. We discuss how individual dopants can be visualized in the lattice, even if they reside in subsurface layers. By means of STM-conductance and x-ray photoelectron spectroscopy, we determine the electronic impact of dopants, including the energies of their eigen states and local band-bending effects in the host oxide. Electronic transitions between dopant-induced gap states give rise to new optical modes, as detected with STM luminescence spectroscopy. From a chemical perspective, dopants are introduced to improve the redox potential of oxide materials. Electron transfer from Mo-donors, for example, alters the growth behavior of gold and activates O2 molecules on a wide-gap CaO surface. Such results demonstrate the enormous potential of doped oxides in heterogeneous catalysis. Our experiments address the issue of doping from a fundamental viewpoint, posing questions on the lattice position, charge state, and electron-transfer potential of the impurity ions. Whether doped oxides are

  6. Oxidative desulphurization study of gasoline and kerosene. Role of some organic and inorganic oxidants

    Energy Technology Data Exchange (ETDEWEB)

    Shakirullah, M.; Ahmad, Waqas; Ahmad, Imtiaz; Ishaq, M.

    2010-11-15

    Desulphurization of gasoline and kerosene was carried out using organic and inorganic oxidants. Among the organic oxidants used were hydrogen peroxide in combination with acetic acid, formic acid, benzoic acid and butyric acid, while inorganic oxidants used included potassium permanganate and sodium perchlorate. The oxidation of each petroleum oil was carried out in two steps; the first step consisted of oxidation of the feed at moderate temperature and atmospheric pressure while in the second step, the oxidized mixture was extracted with azeotropic mixture of acetonitrile-water. A maximum desulphurization has occurred with NaClO{sub 4} and hydrogen peroxide and acetic acid, which are 68% and 61%, respectively in case of gasoline and 66% and 63%, respectively in case of kerosene oil. The FTIR study of the whole and variously desulphurized gasoline and kerosene was also carried out. The results indicate considerable desulphurization by absence of bands that corresponds to sulphur moieties in NaClO{sub 4} and hydrogen peroxide treated samples. (author)

  7. Kinetic studies of electrochemical generation of Ag(II) ion and catalytic oxidation of selected organics

    International Nuclear Information System (INIS)

    Zawodzinski, C.; Smith, W.H.; Martinez, K.R.

    1993-01-01

    The goal of this research is to develop a method to treat mixed hazardous wastes containing selected organic compounds and heavy metals, including actinide elements. One approach is to destroy the organic via electrochemical oxidation to carbon dioxide, then recover the metal contaminants through normally accepted procedures such as ion exchange, precipitation, etc. The authors have chosen to study the electrochemical oxidation of a simple alcohol, iso-propanol. Much of the recent work reported involved the use of an electron transfer mediator, usually the silver(I)/(II) redox couple. This involved direct electrochemical generation of the mediator at the anode of a divided cell followed by homogeneous reaction of the mediator with the organic compound. In this study the authors have sought to compare the mediated reaction with direct electrochemical oxidation of the organic. In addition to silver(I)/(II) they also looked at the cobalt(II)/(III) redox coupled. In the higher oxidation state both of these metal ions readily hydrolyze in aqueous solution to ultimately form insoluble oxide. The study concluded that in a 6M nitric acid solution at room temperature iso-propanol can be oxidized to carbon dioxide and acetic acid. Acetic acid is a stable intermediate and resists further oxidation. The presence of Co(III) enhances the rate or efficiency of the reaction

  8. Origin of deep subgap states in amorphous indium gallium zinc oxide: Chemically disordered coordination of oxygen

    International Nuclear Information System (INIS)

    Sallis, S.; Williams, D. S.; Butler, K. T.; Walsh, A.; Quackenbush, N. F.; Junda, M.; Podraza, N. J.; Fischer, D. A.; Woicik, J. C.; White, B. E.; Piper, L. F. J.

    2014-01-01

    The origin of the deep subgap states in amorphous indium gallium zinc oxide (a-IGZO), whether intrinsic to the amorphous structure or not, has serious implications for the development of p-type transparent amorphous oxide semiconductors. We report that the deep subgap feature in a-IGZO originates from local variations in the oxygen coordination and not from oxygen vacancies. This is shown by the positive correlation between oxygen composition and subgap intensity as observed with X-ray photoelectron spectroscopy. We also demonstrate that the subgap feature is not intrinsic to the amorphous phase because the deep subgap feature can be removed by low-temperature annealing in a reducing environment. Atomistic calculations of a-IGZO reveal that the subgap state originates from certain oxygen environments associated with the disorder. Specifically, the subgap states originate from oxygen environments with a lower coordination number and/or a larger metal-oxygen separation.

  9. Origin of deep subgap states in amorphous indium gallium zinc oxide: Chemically disordered coordination of oxygen

    Energy Technology Data Exchange (ETDEWEB)

    Sallis, S.; Williams, D. S. [Materials Science and Engineering, Binghamton University, Binghamton, New York 13902 (United States); Butler, K. T.; Walsh, A. [Center for Sustainable Technologies and Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (United Kingdom); Quackenbush, N. F. [Department of Physics, Applied Physics, and Astronomy, Binghamton University, Binghamton, New York 13902 (United States); Junda, M.; Podraza, N. J. [Department of Physics and Astronomy, University of Toledo, Toledo, Ohio 43606 (United States); Fischer, D. A.; Woicik, J. C. [Materials Science and Engineering Laboratory, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); White, B. E.; Piper, L. F. J., E-mail: lpiper@binghamton.edu [Department of Physics, Applied Physics, and Astronomy, Binghamton University, Binghamton, New York 13902 (United States); Materials Science and Engineering, Binghamton University, Binghamton, New York 13902 (United States)

    2014-06-09

    The origin of the deep subgap states in amorphous indium gallium zinc oxide (a-IGZO), whether intrinsic to the amorphous structure or not, has serious implications for the development of p-type transparent amorphous oxide semiconductors. We report that the deep subgap feature in a-IGZO originates from local variations in the oxygen coordination and not from oxygen vacancies. This is shown by the positive correlation between oxygen composition and subgap intensity as observed with X-ray photoelectron spectroscopy. We also demonstrate that the subgap feature is not intrinsic to the amorphous phase because the deep subgap feature can be removed by low-temperature annealing in a reducing environment. Atomistic calculations of a-IGZO reveal that the subgap state originates from certain oxygen environments associated with the disorder. Specifically, the subgap states originate from oxygen environments with a lower coordination number and/or a larger metal-oxygen separation.

  10. Laboratory Oxidation Stability Study on B10 Biodiesel Blends

    Energy Technology Data Exchange (ETDEWEB)

    Engelen, B. [and others

    2013-11-15

    A laboratory oxidation stability study has been completed jointly by CONCAWE and DGMK on three biodiesel blends containing 10% v/v (B10) Fatty Acid Methyl Ester (FAME). The results of the study are compared to measurements from an in-vehicle storage stability study on similar B10 diesel fuels that had been conducted previously in a Joint Industry Study. This laboratory study monitored the oxidation stability of the three B10 blends during six weeks of laboratory storage under ambient (25C) and elevated temperature (43C) conditions. Various test methods were used to monitor oxidation stability changes in the B10 diesel fuel blends including electrical conductivity, viscosity, Rancimat oxidation stability (EN 15751), PetroOxy oxidation stability (EN 16091), acid number (EN 14104), Delta Total Acid Number (Delta TAN), and peroxide number (ISO 3960). Elemental analyses by ICP were also completed on the FAME and B10 blends at the start and end of the laboratory study. The concentrations of dissolved metals were very low in all cases except for silicon which was found to be between about 600-700 ppb in the B10 blends. A limited study was also conducted on one neat FAME sample (B100) to investigate the effect of air/oxygen exposure on the rate of decrease in oxidation stability.

  11. Preparation and study of properties of dispersed graphene oxide

    Directory of Open Access Journals (Sweden)

    Evgeniya Seliverstova

    2015-09-01

    Full Text Available Ability of graphene oxide to form stable dispersion in organic solvents was studied in this work. As it was shown, sonication of graphene leads to the decreas of the particle size. Stability of prepared graphene dispersions was studied upon measurements of distribution of number of the particles via size and change of optical density of the solutions with time. It was found that graphene oxide forms a more stable dispersion in tetrahydrofuran and dimethylformamide than in chloroform and acetone.

  12. Method of isolation of traces of americium by using the +6 oxidation state properties

    International Nuclear Information System (INIS)

    Kwinta, Jean; Michel, Jean-Jacques

    1969-05-01

    The authors present a method to separate traces of americium from a solution containing fission products and actinides. This method comprises the following steps: firstly, the oxidation of americium at the +6 state by ammonium persulfate and carrying over of actinides and III and IV lanthanides by lanthanum fluoride; secondly, the reduction by hydrazine of the oxidized americium and carrying over of the reduced americium by lutetium fluoride; and thirdly, the americium-lutetium separation by selective extractions either with di 2 ethyl hexyl phosphoric acid, or by fractionated elution on an anionic resin column by a mixture of nitric acid and methanol [fr

  13. High pressure structural studies on nanophase praseodymium oxide

    International Nuclear Information System (INIS)

    Saranya, L.; Chandra Shekar, N.V.; Amirthapandian, S.; Hussain, Shamima; Arulraj, A.; Sahu, P. Ch.

    2014-01-01

    The phase stability of nanocrystalline Pr 2 O 3 has been investigated under pressure by in-situ high pressure X-ray diffraction using Mao-Bell type diamond anvil cell. The ambient structure and phase of the praseodymium oxide have been resolved unambiguously using x-ray diffraction, SEM and TEM techniques. Under the action of pressure the cubic phase of the system is retained up to 15 GPa. This is unusual as other isostructural rare earth oxides show structural transformations even at lower pressures. From the best fit to the P–V data with the Murnaghan equation of state yields a bulk modulus of 171 GPa

  14. Comparative studies of MOS-gate/oxide-passivated AlGaAs/InGaAs pHEMTs by using ozone water oxidation technique

    International Nuclear Information System (INIS)

    Lee, Ching-Sung; Hung, Chun-Tse; Chou, Bo-Yi; Hsu, Wei-Chou; Liu, Han-Yin; Ho, Chiu-Sheng; Lai, Ying-Nan

    2012-01-01

    Al 0.22 Ga 0.78 As/In 0.24 Ga 0.76 As pseudomorphic high-electron-mobility transistors (pHEMTs) with metal-oxide-semiconductor (MOS)-gate structure or oxide passivation by using ozone water oxidation treatment have been comprehensively investigated. Annihilated surface states, enhanced gate insulating property and improved device gain have been achieved by the devised MOS-gate structure and oxide passivation. The present MOS-gated or oxide-passivated pHEMTs have demonstrated superior device performances, including superior breakdown, device gain, noise figure, high-frequency characteristics and power performance. Temperature-dependent device characteristics of the present designs at 300–450 K are also studied. (paper)

  15. SIMS and TEM study on oxide characteristics of Zircaloy

    International Nuclear Information System (INIS)

    Jung, Y. H.; Baek, J. H.; Kim, S. J.; Kim, K. H.; Choi, B. K.; Jung, Y. H.

    1998-01-01

    Long-term corrosion test, SIMS analysis, and TEM study were carried out to investigate the corrosion characteristics and corrosion mechanism of Zircaloy-4 in LiOH solution. The corrosion tests were performed in alkali solutions at 350 deg C for 500days. SIMS analysis was performed for the specimens prepared to have an equal oxide thickness to measure the cation content. TEM studies on the samples formed in various alkali solutions were also conducted. Based on the corrosion test, SIMS analysis, and TEM study, the cation is considered to control the corrosion in LiOH solution and its effect is dependent on the concentration of alkali and the oxide thickness. The slight acceleration of corrosion rate at a low concentration is thought to be caused by the cation incorporation into oxide while the significant acceleration at a high concentration is due to the transformation of oxide microstructure that would be induced by the cation incorporation

  16. Mossbauer studies of high-Tc oxides

    International Nuclear Information System (INIS)

    Shinjo, T.; Nasu, S.

    1989-01-01

    Mossbauer spectroscopy has been known as one of the useful experimental tools in fundamental solid state physics. Main parameters which the authors obtain from Mossbauer spectra are: isomer shift, quadrupole interaction, magnetic hyperfine interaction, and recoilless fraction. An electronic structure of the relevant atom is argued from the value of isomer shift and in usual ionic cases the valance state can be determined unambiguously. If a magnetic hyperfine splitting is observed, it is helpful for confirming the existence of magnetic order. From the temperature dependence of hyperfine field, the magnetic transition temperatures is estimated

  17. Non steady-state model for dry oxidation of nuclear wastes metallic containers in long term interim storage conditions

    International Nuclear Information System (INIS)

    Bertrand, Nathalie; Desgranges, Clara; Poquillon, Dominique; Monceau, Daniel

    2006-01-01

    oxidation tests. In a second step, in order to increase the reliability of the long term extrapolations from basic models, a non-steady state numerical model able to take into account several elementary steps is built. The aim is to get a more reliable tool to describe mechanisms that control oxide scale growth in this specific low temperature range. The paper has the following contains: Experimental results; Growth kinetics; Scale morphology; A basic model for kinetics of oxidation; Conclusion of the experimental study; EKINOX: Estimation KINetics OXidation: an advanced model; General description; Equations in the model; Results; Future developments; Conclusion. To summarize, the basic model consists in some extrapolations of available experimental data in the temperature range of interest following simple analytical laws deduced from classical oxidation theories. This leads to a very small oxide scale and thus to the loss of very small amounts of metal even for extrapolations to over 100 years. However, the reliability of this kind of basic models is very poor since it is based on the assumption that a single elementary process controls the oxidation rate. Indeed in the temperature range concerned by long term interim deposit of waste containers, several mechanisms can control the oxidation rate. A numerical model able to take in consideration several growth mechanisms is now in progress. At this stage of development, the originality of the proposed advanced model consists in explicitly calculating the vacancy profiles and treating these as non-conservative species. It is based on an original numerical treatment to correctly and easily describe elimination of vacancies at the metal/oxide interface and thus relative motion between the substrate lattice and the oxide one, even for non-stationary states. It can treat Wagner's model but without the quasi-steady state 'hypothesis or also take into account a partial control of the oxidation process by interfacial reaction. In

  18. Solid-phase extraction of plutonium in various oxidation states from simulated groundwater using N-benzoylphenylhydroxylamine

    International Nuclear Information System (INIS)

    Perevalov, S.A.; Malofeeva, G.I.; Kuzovkina, E.V.; Spivakov, B.Ya.

    2013-01-01

    Solid-phase extraction of plutonium in different individual and mixed oxidation states from simulated groundwater (pH 8.5) was studied. The extraction of plutonium species was carried out in a dynamic mode using DIAPAK C16 cartridges modified by N-benzoylphenylhydroxylamine (BPHA). It was shown that the extent of recovery depends on the oxidation state of plutonium. The extraction of Pu(IV) was at the level of 98-99% regardless of the volume and flow-rate of the sample solution. Pu(V) was extracted by 90-95% and 75-80% from 10- and 100-mL aliquots of the samples, respectively, whereas the extraction of Pu(VI) did not exceed 45-50%. An equimolar mixture of Pu(IV), Pu(V), and Pu(VI) was extracted by 74%. The distribution coefficients (K d ) and kinetic exchange capacities (S) of plutonium in various oxidation states were measured. It was found that during the sorption process, Pu(V) was reduced to Pu(IV) by 80-90% after an hour-long contact with the solid phase. Pu(VI) is reduced to Pu(V) by 34% and to Pu(IV) by 55%. In the case of mixed-valent solution of plutonium, only Pu(V) and Pu(IV) were found in the effluents. (author)

  19. Corrosion mechanisms of zirconium alloys - study of the initial oxidation kinetics and of the mechanical behaviour of the metal/oxide system

    International Nuclear Information System (INIS)

    Parise, M.

    1996-12-01

    Nuclear fuel claddings are made of zirconium alloys. The conditions of use lead the cladding oxidize outside. The so-formed layers behaves like a thermal barrier and prevents from using oxidized claddings with an oxide thickness larger than 100 μm. The oxidation kinetic is approximately cubic for oxide thicknesses smaller than about 2μm, linear beyond. A kinetic model has been proposed which estimates the post-transition growth rate from the kinetic parameters of the pre-transition state and morphological features of post-transition layers. This work aims at providing the necessary elements to validate this model and studying the layers around the kinetic transition, in order to determine whether the oxidation mechanisms before and after the transition are similar. Thicknesses of the 50 - 500 nm range of the oxide layers are measured by an optical method; pre-transition kinetics are thus precisely determined. The effect of the composition, the thermal treatment and the presence of oxygen in solid solution is studied. The morphological and crystallographic study of the layers show that they exhibit a lot of similarities before and after the kinetic transition. The results concerning the kinetic aspects and the morphology of the post-transition layers point out that the proposed model leads to realistic post-transition growth rates. Furthermore, the kinetic transition corresponds to the appearance of cracks in the oxide layer. The mechanical behaviour of the metal/oxide system has been modelled at different scales. When the specific behaviours of the metal and the oxide are taken into account together with the interface geometry, radial stresses appear, which are high enough to locally open cracks. The appearance and localization of cracks depend on both the interface geometry and the stress distribution in the metal/oxide system. (author)

  20. General regularity of the oxidation potential variations and high oxidation states in the second half of the actinide series

    International Nuclear Information System (INIS)

    Spitsyn, V.I.; Vokhmin, V.G.; Ionova, G.V.; Pershina, V.G.

    1984-01-01

    Oxidation potentials (OP) PHI(4/3), PHI(5/3), PHI(6/3), PHI(5/4) and PHI(6/5) are calculated for the members of the actinide series. A semiemperic relation combining OP with explicit terms for ground level energies of actinide ions in Russell-Saunders approximation as well as known values of formal OP relative to the normal hydrogen electrode potential are used as an extrapolation function. It is shown that an increase of PHI(4/3) OP which occurs after Bsub(k) explains a low stability of the oxidation state 4 in solutions for actinides of the second half of the series. PHI(5/3) and PHI(5/4) OP in the section starting with Cm have the minimum at Cf. PHI(6/3) OP for Cm, Bk, Cf and Es are practically the same but for Cm, Bk and Es they are smaller than PHI(5/3) OP. A principle possibility of Bk(6), Cf(6) and Es(6) preparation is shown

  1. The Effect of Precursor Ligands and Oxidation State in the Synthesis of Bimetallic Nano-Alloys

    KAUST Repository

    LaGrow, Alec P.

    2015-05-12

    The characteristics of bimetallic nanomaterials are dictated by their size, shape and elemental distribution. Solution synthesis is widely utilized to form nanomaterials, such as nanoparticles, with controlled size and shape. However, the effects of variables on the characteristics of bimetallic nanomaterials are not completely understood. In this study, we used a continuous-flow synthetic strategy to explore the effects of the ligands and the oxidation state of a metal precursor in a shape-controlled synthesis on the final shape of the nanomaterials and the elemental distribution within the alloy. We demonstrate that this strategy can tune the size of monodisperse PtM (M=Ni or Cu) alloy nanocrystals ranging from 3 to 16 nm with an octahedral shape using acetylacetonate or halide precursors of Pt(II), Pt(IV) and Ni or Cu (II). The nanoparticles formed from halide precursors showed an enrichment of platinum on their surfaces, and the bromides could oxidatively etch the nanoparticles during synthesis with the O2/Br- pair. The two nanocrystal precursors can be uti-lized independently and can control the size with a trend of Pt(acac)2

  2. In situ oxidation state profiling of nickel hexacyanoferrate derivatized electrodes using line-imaging Raman spectroscopy and multivariate calibration

    International Nuclear Information System (INIS)

    Haight, S.M.; Schwartz, D.T.

    1999-01-01

    Metal hexacyanoferrate compounds show promise as electrochemically switchable ion exchange materials for use in the cleanup of radioactive wastes such as those found in storage basins and underground tanks at the Department of Energy's Hanford Nuclear Reservation. Reported is the use of line-imaging Raman spectroscopy for the in situ determination of oxidation state profiles in nickel hexacyanoferrate derivatized electrodes under potential control in an electrochemical cell. Line-imaging Raman spectroscopy is used to collect 256 contiguous Raman spectra every ∼5 microm from thin films (ca. 80 nm) formed by electrochemical derivatization of nickel electrodes. The cyanide stretching region of the Raman spectrum of the film is shown to be sensitive to iron oxidation state and is modeled by both univariate and multivariate correlations. Although both correlations fit the calibration set well, the multivariate (principle component regression or PCR) model's predictions of oxidation state are less sensitive to noise in the spectrum, yielding a much smoother oxidation state profile than the univariate model. Oxidation state profiles with spatial resolution of approximately 5 microm are shown for a nickel hexacyanoferrate derivatized electrode in reduced, intermediate, and oxidized states. In situ oxidation state profiles indicate that the 647.1 nm laser illumination photo-oxidizes the derivatized electrodes. This observation is confirmed using photoelectrochemical methods

  3. A study on the utilization of chromic oxide wastes

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Seung Woong; Kim, Chi Kwon; Hwang, Seon Kook; Kim, Byung Gyu; Son, Jeong Soo; Nam, Chul Woo [Korea Inst. of Geology Mining and Materials, Taejon (Korea, Republic of)

    1995-12-01

    This study was carried out to develop the optimum process for recovering precious and valuable metals from chrome oxide wastes. The following subjects such as, (1) feasibility on the recovery of precious and valuable metals, (2) recovery rate of precious and valuable metals, (3) purification of extracted precious and valuable metals, and (4) environmental aspects of recovery process, were investigated and the main results are as follows. (1) With Sem analysis of chrome oxide wastes, it was found that combustion process for eliminating oil and water in wastes, was necessary. (2) After leaching chrome oxide wastes with nitric acid and aqua regia, silver and gold were effectively separated and recovered. But a lot of silver and gold were remaining in the leaching residue. It was considered that chrome oxide powder was coated with organic materials during polishing stage and their products were insoluble in acidic solution. (3) The optimum process for separation and recovery of precious metal and production of new chrome oxide is consist of several process such as perchloric acid leaching, recovery of silver chloride, cementation for gold, reduction of chrome ion, and production of pure chrome oxide. (4) For separating chrome compound from the chrome oxide waste occurred in stainless steel polishing process, alkali roasting process was suggested. (author). 18 refs., 29 figs., 11 tabs.

  4. Study of the Rancimat test method in measuring the oxidation stability of biodiesel ester and blends

    Energy Technology Data Exchange (ETDEWEB)

    Berthiaume, D.; Tremblay, A. [Oleotek Inc., Thetford Mines, PQ (Canada)

    2006-11-15

    This paper provided details of a study conducted to examine the oxidation stability of biodiesel blends. The study tested samples of canola oil, soybean oil, fish oil, yellow grease, and tallow. The EN 14112 (Rancimat) method was used to compare oxidation stability results obtained in previous tests conducted in the United States and Europe. The aim of the study was also to evaluate the influence of peroxide value (PV), acid value (AV) and feedstock source on the the oxidative stability of different samples. The study also evaluated the possibility of developing a validated test method developed from the EN 14112 methods to specifically consider biodiesel blends. Results of the study indicated that the Rancimat method was not suitable for measuring the oxidation stability of biodiesels blended with petrodiesels. No direct correlation between oxidative stability and PV or AV was observed. It was concluded that fatty acid distribution was not a principal factor in causing changes in oxidation stability. 22 refs., 3 tabs., 1 fig.

  5. Fuel cells: spectroscopic studies in the electrocatalysis of alcohol oxidation

    OpenAIRE

    Iwasita Teresa

    2002-01-01

    Modern spectroscopic methods are useful for elucidating complex electrochemical mechanisms as those occurring during the oxidation of small organic molecules (CH3OH, HCOH, HCOOH). In the present paper it is shown the use of spectroscopic methods to study the oxidation of alcohols on platinum or Pt-based binary electrodes. These reactions are of importance in conexion with the development of anode systems for use in fuel cells. Mass spectrometry and FT infrared spectroscopy allow to establishi...

  6. Characterization of Interface State in Silicon Carbide Metal Oxide Semiconductor Capacitors

    Science.gov (United States)

    Kao, Wei-Chieh

    Silicon carbide (SiC) has always been considered as an excellent material for high temperature and high power devices. Since SiC is the only compound semiconductor whose native oxide is silicon dioxide (SiO2), it puts SiC in a unique position. Although SiC metal oxide semiconductor (MOS) technology has made significant progress in recent years, there are still a number of issues to be overcome before more commercial SiC devices can enter the market. The prevailing issues surrounding SiC MOSFET devices are the low channel mobility, the low quality of the oxide layer and the high interface state density at the SiC/SiO2 interface. Consequently, there is a need for research to be performed in order to have a better understanding of the factors causing the poor SiC/SiO2 interface properties. In this work, we investigated the generation lifetime in SiC materials by using the pulsed metal oxide semiconductor (MOS) capacitor method and measured the interface state density distribution at the SiC/SiO2 interface by using the conductance measurement and the high-low frequency capacitance technique. These measurement techniques have been performed on n-type and p-type SiC MOS capacitors. In the course of our investigation, we observed fast interface states at semiconductor-dielectric interfaces in SiC MOS capacitors that underwent three different interface passivation processes, such states were detected in the nitrided samples but not observed in PSG-passivated samples. This result indicate that the lack of fast states at PSG-passivated interface is one of the main reasons for higher channel mobility in PSG MOSFETs. In addition, the effect of mobile ions in the oxide on the response time of interface states has been investigated. In the last chapter we propose additional methods of investigation that can help elucidate the origin of the particular interface states, enabling a more complete understanding of the SiC/SiO2 material system.

  7. A magnetic route to measure the average oxidation state of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS).

    Science.gov (United States)

    Shen, Xiong-Fei; Ding, Yun-Shuang; Liu, Jia; Han, Zhao-Hui; Budnick, Joseph I; Hines, William A; Suib, Steven L

    2005-05-04

    A magnetic route has been applied for measurement of the average oxidation state (AOS) of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS). The method gives AOS measurement results in good agreement with titration methods. A maximum analysis deviation error of +/-7% is obtained from 10 sample measurements. The magnetic method is able to (1) confirm the presence of mixed-valent manganese and (2) evaluate AOS and the spin states of d electrons of both single oxidation state and mixed-valent state Mn in manganese oxides. In addition, the magnetic method may be extended to (1) determine AOS of Mn in manganese oxide OMS with dopant "diamagnetic" ions, such as reducible V5+ (3d0) ions, which is inappropriate for the titration method due to interference of redox reactions between these dopant ions and titration reagents, such as KMnO4, (2) evaluate the dopant "paramagnetic" ions that are present as clusters or in the OMS framework, and (3) determine AOS of other mixed-valent/single oxidation state ion systems, such as Mo3+(3d3)-Mo4+(3d2) systems and Fe3+ in FeCl3.

  8. Mn K-edge XANES spectroscopy of photosynthetic water oxidation enzyme in the S0-, S1-, S2- and S3-states induced by flash excitation

    International Nuclear Information System (INIS)

    Ono, Taka-aki; Noguchi, Takumi; Inoue, Yorinao; Kusunoki, Masami; Matsushita, Tadashi; Oyanagi, Hiroyuki.

    1993-01-01

    Electronic and structural rearrangement of the Mn-cluster during the four step oxidation of water in photosynthetic oxygen evolution was studied by XANES spectroscopy. The Mn K-edge energy of the spectrum was changed with flash number to show a clear quadruple oscillation, indicating a periodic change in oxidation and electronic state of the Mn-cluster depending on Joliot and Kok's oxygen clock. (author)

  9. Conductivity study of nitrogen-doped calcium zinc oxide prepared by spray pyrolysis

    International Nuclear Information System (INIS)

    Hsu, Yu-Ting; Lan, Wen-How; Huang, Kai-Feng; Lin, Jia-Ching; Chang, Kuo-Jen

    2016-01-01

    In this study, the spray pyrolysis method was used to prepare unintentionally doped and nitrogen-doped calcium zinc oxide films by using zinc acetate, calcium nitrate precursor, and ammonium acetate precursor. Morphological and structural analyses were conducted using scanning electron microscopy and X-ray diffraction. The results indicated that film grain size decreased as the nitrogen doping was increased. Both calcium oxide and zinc oxide structures were identified in the unintentionally doped calcium zinc oxide. When nitrogen doping was introduced, the film mainly exhibited a zinc oxide structure with preferred (002) and (101) orientations. The concentration and mobility were investigated using a Hall measurement system. P-type films with a mobility and concentration of 10.6 cm"2 V"−"1 s"−"1 and 2.8×10"1"7 cm"−"3, respectively, were obtained. Moreover, according to a temperature-dependent conductivity analysis, an acceptor state with activation energy 0.266 eV dominated the p-type conduction for the unintentionally doped calcium zinc oxide. By contrast, a grain boundary with a barrier height of 0.274–0.292 eV dominated the hole conduction for the nitrogen-doped calcium zinc oxide films.

  10. Theoretical aspects of studies of oxide and semiconductor surfaces using low energy positrons

    Science.gov (United States)

    Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

    2011-01-01

    This paper presents the results of a theoretical study of positron surface and bulk states and annihilation characteristics of surface trapped positrons at the oxidized Cu(100) single crystal and at both As- and Ga-rich reconstructed GaAs(100) surfaces. The variations in atomic structure and chemical composition of the topmost layers of the surfaces associated with oxidation and reconstructions and the charge redistribution at the surfaces are found to affect localization and spatial extent of the positron surface-state wave functions. The computed positron binding energy, work function, and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the surfaces. Theoretical positron annihilation probabilities with relevant core electrons computed for the oxidized Cu(100) surface and the As- and Ga-rich reconstructed GaAs(100) surfaces are compared with experimental ones estimated from the positron annihilation induced Auger peak intensities measured from these surfaces.

  11. Petrology of chromite in ureilites: Deconvolution of primary oxidation states and secondary reduction processes

    Science.gov (United States)

    Goodrich, Cyrena Anne; Harlow, George E.; Van Orman, James A.; Sutton, Stephen R.; Jercinovic, Michael J.; Mikouchi, Takashi

    2014-06-01

    Ureilites are ultramafic achondrites thought to be residues of partial melting on a carbon-rich asteroid. They show a trend of FeO-variation (olivine Fo from ∼74 to 95) that suggests variation in oxidation state. Whether this variation was established during high-temperature igneous processing on the ureilite parent body (UPB), or preserved from nebular precursors, is a subject of debate. The behavior of chromium in ureilites offers a way to assess redox conditions during their formation and address this issue, independent of Fo. We conducted a petrographic and mineral compositional study of occurrences of chromite (Cr-rich spinel) in ureilites, aimed at determining the origin of the chromite in each occurrence and using primary occurrences to constrain models of ureilite petrogenesis. Chromite was studied in LEW 88774 (Fo 74.2), NWA 766 (Fo 76.7), NWA 3109 (Fo 76.3), HaH 064 (Fo 77.5), LAP 03587 (Fo 74.9), CMS 04048 (Fo 76.4), LAP 02382 (Fo 78.6) and EET 96328 (Fo 85.2). Chromite occurs in LEW 88774 (∼5 vol.%), NWA 766 (event involved initial elevation of T (to 1300-1400 °C), followed by rapid decompression and drop in T (to exclusively in low-Fo samples supports the interpretation that the ureilite FeO-variation was established during igneous processing on the UPB.

  12. Solid state chemistry of rare earth oxides. Final report, September 1, 1950--July 31, 1977

    International Nuclear Information System (INIS)

    Eyring, L.

    1977-07-01

    Work under Contract E(11-1)-1109 and its antecedents has been primarily for the purpose of obtaining detailed thermodynamic, kinetic and structural information on the complex rare earth oxides of praseodymium and terbium. These systems exhibit homologous series of ordered phases, order-disorder transformations, wide-range nonstoichiometric phases, chemical hysteresis in two-phase regions and many other solid state reaction phenomena. Fluorite-related materials of importance to ERDA occur as nuclear fuels, radiation power sources, insulators and solid electrolytes. The rare earth oxides serve directly as model systems for such similar materials and, in a more general sense, they serve as models of solids in general since they exhibit nearly the full range of solid state properties

  13. Hemoglobin redux: combining neutron and X-ray diffraction with mass spectrometry to analyse the quaternary state of oxidized hemoglobins

    Energy Technology Data Exchange (ETDEWEB)

    Mueser, Timothy C., E-mail: timothy.mueser@utoledo.edu; Griffith, Wendell P. [Department of Chemistry, University of Toledo, Toledo, OH 43606 (United States); Kovalevsky, Andrey Y. [Bioscience Division, MS M888, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Guo, Jingshu; Seaver, Sean [Department of Chemistry, University of Toledo, Toledo, OH 43606 (United States); Langan, Paul [Department of Chemistry, University of Toledo, Toledo, OH 43606 (United States); Bioscience Division, MS M888, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Hanson, B. Leif [Department of Chemistry, University of Toledo, Toledo, OH 43606 (United States)

    2010-11-01

    X-ray and neutron diffraction studies of cyanomethemoglobin are being used to evaluate the structural waters within the dimer–dimer interface involved in quaternary-state transitions. Improvements in neutron diffraction instrumentation are affording the opportunity to re-examine the structures of vertebrate hemoglobins and to interrogate proton and solvent position changes between the different quaternary states of the protein. For hemoglobins of unknown primary sequence, structural studies of cyanomethemoglobin (CNmetHb) are being used to help to resolve sequence ambiguity in the mass spectra. These studies have also provided additional structural evidence for the involvement of oxidized hemoglobin in the process of erythrocyte senescence. X-ray crystal studies of Tibetan snow leopard CNmetHb have shown that this protein crystallizes in the B state, a structure with a more open dyad, which possibly has relevance to RBC band 3 protein binding and erythrocyte senescence. R-state equine CNmetHb crystal studies elaborate the solvent differences in the switch and hinge region compared with a human deoxyhemoglobin T-state neutron structure. Lastly, comparison of histidine protonation between the T and R state should enumerate the Bohr-effect protons.

  14. SIMS studies of oxide growth on beta-NiAl

    Science.gov (United States)

    Mitchell, D. F.; Prescott, R.; Graham, M. J.; Doychak, J.

    1992-01-01

    This paper reports on a study of the growth of aluminum oxide on beta-NiAl at temperatures up to 1200 C. The scales have been formed in two-stage experiments using O2-16 and O2-18 gases, and the various isotopic species have been located by direct imaging using SIMS. Supplementary information on oxide morphologies and structures has been obtained by SEM. SIMS images and depth profiles indicate where oxidation has taken place predominantly by cation or anion diffusion at different stages of the growth process. The way in which the presence of small amounts of reactive elements can affect scale growth is also considered. These results help to provide an improved understanding of the mechanism of alumina scale formation, which is of benefit in the development of oxidation-resistant alloys and intermetallics for service at high temperatures.

  15. Solid State Electrochemical Sensors for Nitrogen Oxide (NOx) Detection in Lean Exhaust Gases

    OpenAIRE

    Rheaume, Jonathan Michael

    2010-01-01

    Solid state electrochemical sensors that measure nitrogen oxides (NOx) in lean exhaust have been investigated in order to help meet future on-board diagnostic (OBD) regulations for diesel vehicles. This impedancemetric detection technology consists of a planar, single cell sensor design with various sensing electrode materials and yttria-stabilized zirconia (YSZ) as the electrolyte. No reference to ambient air is required. An impedance analysis method yields a signal that is proportional to t...

  16. Arsenic (+3 oxidation state) methyltransferase and the inorganic arsenic methylation phenotype

    International Nuclear Information System (INIS)

    Li Jiaxin; Waters, Stephen B.; Drobna, Zuzana; Devesa, Vicenta; Styblo, Miroslav; Thomas, David J.

    2005-01-01

    Inorganic arsenic is enzymatically methylated; hence, its ingestion results in exposure to the parent compound and various methylated arsenicals. Both experimental and epidemiological evidences suggest that some of the adverse health effects associated with chronic exposure to inorganic arsenic may be mediated by these methylated metabolites. If i As methylation is an activation process, then the phenotype for inorganic arsenic methylation may determine risk associated with exposure to this metalloid. We examined inorganic arsenic methylation phenotypes and arsenic (+3 oxidation state) methyltransferase genotypes in four species: three that methylate inorganic arsenic (human (Homo sapiens), rat (Rattus norwegicus), and mouse (Mus musculus)) and one that does not methylate inorganic arsenic (chimpanzee, Pan troglodytes). The predicted protein products from arsenic (+3 oxidation state) methyltransferase are similar in size for rat (369 amino acid residues), mouse (376 residues), and human (375 residues). By comparison, a 275-nucleotide deletion beginning at nucleotide 612 in the chimpanzee gene sequence causes a frameshift that leads to a nonsense mutation for a premature stop codon after amino acid 205. The null phenotype for inorganic arsenic methylation in the chimpanzee is likely due to the deletion in the gene for arsenic (+3 oxidation state) methyltransferase that yields an inactive truncated protein. This lineage-specific loss of function caused by the deletion event must have occurred in the Pan lineage after Homo-Pan divergence about 5 million years ago

  17. Single Crystal Growth of Pure Co3+ Oxidation State Material LaSrCoO4

    Directory of Open Access Journals (Sweden)

    Hanjie Guo

    2016-08-01

    Full Text Available We report on the single crystal growth of the single-layer perovskite cobaltate LaSrCoO4 that was grown by the optical floating zone method using high oxygen pressures. Phase purity and single crystallinity were confirmed by X-ray diffraction techniques. The pure Co3+ oxidation state was confirmed by X-ray absorbtion spectroscopy measurements. A transition to a spin glass state is observed at ∼7 K in magnetic susceptibility and specific heat measurements.

  18. A Study on the Oxidative-dissolution Leaching of Fission Product Oxides in the carbonate solution

    International Nuclear Information System (INIS)

    Lee, Eil Hee; Kim, Kwang Wook; Lim, Jae Gwan; Chung, Dong Yong; Yang, Han Beom; Joe, Kih Soo; Seo, Heui Seung; Kim, Yeon Hwa; Lee, Se Yoon

    2009-07-01

    This study was carried out to investigate the characteristics of an oxidativedissolution leaching of FP co-dissolved with U in a carbonate solution of Na 2 CO 3 - H 2 O 2 and (NH 4 ) 2 CO 3 -H 2 O 2 , respectively. Simulated FP-oxides which contained 12 components have been added to the solution to examine their oxidative dissolution characteristics. It was found that H 2 O 2 was an effective oxidant to minimize the dissolution of FP in a carbonate solution. In 0.5M Na 2 CO 3 -0.5M H 2 O 2 and 0.5M (NH 4 ) 2 CO 3 -0.5M H 2 O 2 solution, some elements such as Re, Te, Cs and Mo seem to be dissolved together with U. It is revealed that dissolution rates of Re, Te and Cs are high (completely dissolved within 10∼20 minutes) due to their high solubility in Na 2 CO 3 and (NH 4 ) 2 CO 3 solution regardless of the addition of H 2 O 2 , and independent of the concentrations of Na 2 CO 3 and H 2 O 2 . However, Mo was slowly dissolved by an oxidative dissolution with H 2 O 2 . It is found that the most important factor for the oxidative dissolution of FP is the pH of the solution and an effective oxidative dissolution is achieved at a pH between 10∼12 for Na 2 CO 3 and a pH between 9∼10 for (NH 4 ) 2 CO 3 , respectively, in order to minimize the dissolution of FP

  19. Structural basis of protein oxidation resistance: a lysozyme study.

    Directory of Open Access Journals (Sweden)

    Marion Girod

    Full Text Available Accumulation of oxidative damage in proteins correlates with aging since it can cause irreversible and progressive degeneration of almost all cellular functions. Apparently, native protein structures have evolved intrinsic resistance to oxidation since perfectly folded proteins are, by large most robust. Here we explore the structural basis of protein resistance to radiation-induced oxidation using chicken egg white lysozyme in the native and misfolded form. We study the differential resistance to oxidative damage of six different parts of native and misfolded lysozyme by a targeted tandem/mass spectrometry approach of its tryptic fragments. The decay of the amount of each lysozyme fragment with increasing radiation dose is found to be a two steps process, characterized by a double exponential evolution of their amounts: the first one can be largely attributed to oxidation of specific amino acids, while the second one corresponds to further degradation of the protein. By correlating these results to the structural parameters computed from molecular dynamics (MD simulations, we find the protein parts with increased root-mean-square deviation (RMSD to be more susceptible to modifications. In addition, involvement of amino acid side-chains in hydrogen bonds has a protective effect against oxidation Increased exposure to solvent of individual amino acid side chains correlates with high susceptibility to oxidative and other modifications like side chain fragmentation. Generally, while none of the structural parameters alone can account for the fate of peptides during radiation, together they provide an insight into the relationship between protein structure and susceptibility to oxidation.

  20. Atomic scale imaging of competing polar states in a Ruddlesden–Popper layered oxide

    Science.gov (United States)

    Stone, Greg; Ophus, Colin; Birol, Turan; Ciston, Jim; Lee, Che-Hui; Wang, Ke; Fennie, Craig J.; Schlom, Darrell G.; Alem, Nasim; Gopalan, Venkatraman

    2016-01-01

    Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden–Popper (RP), An+1BnO3n+1, thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Srn+1TinO3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases. We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure. PMID:27578622

  1. Atomic scale imaging of competing polar states in a Ruddlesden-Popper layered oxide.

    Science.gov (United States)

    Stone, Greg; Ophus, Colin; Birol, Turan; Ciston, Jim; Lee, Che-Hui; Wang, Ke; Fennie, Craig J; Schlom, Darrell G; Alem, Nasim; Gopalan, Venkatraman

    2016-08-31

    Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden-Popper (RP), An+1BnO3n+1, thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Srn+1TinO3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases. We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure.

  2. 3 and 4 oxidation state element solubilities in borosilicate glasses. Implement to actinides in nuclear glasses

    International Nuclear Information System (INIS)

    Cachia, J.N.

    2005-12-01

    In order to ensure optimal radionuclides containment, the knowledge of the actinide loading limits in nuclear waste glasses and also the comprehension of the solubilization mechanisms of these elements are essential. A first part of this manuscript deals with the study of the differences in solubility of the tri and tetravalent elements (actinides and surrogates) particularly in function of the melting temperature. The results obtained indicate that trivalent elements (La, Gd, Nd, Am, Cm) exhibit a higher solubility than tetravalent elements (Hf, Th, Pu). Consequently, it was planned to reduce plutonium at the oxidation state (III), the later being essentially tetravalent in borosilicate glasses. An innovating reduction process of multi-valent elements (cerium, plutonium) using silicon nitride has been developed in a second part of this work. Reduced plutonium-bearing glasses synthesized by Si 3 N 4 addition made it possible to double the plutonium solubility from 2 to 4 wt% at 1200 deg C. A structural approach to investigate the differences between tri and tetravalent elements was finally undertaken. These investigations were carried out by X-rays Absorption Spectroscopy (EXAFS) and NMR. Trivalent rare earth and actinide elements seem to behave as network modifiers while tetravalent elements rather present true intermediaries' behaviour. (author)

  3. Positronium formation studies in crystalline molecular complexes: Triphenylphosphine oxide - Acetanilide

    Science.gov (United States)

    Oliveira, F. C.; Denadai, A. M. L.; Guerra, L. D. L.; Fulgêncio, F. H.; Windmöller, D.; Santos, G. C.; Fernandes, N. G.; Yoshida, M. I.; Donnici, C. L.; Magalhães, W. F.; Machado, J. C.

    2013-04-01

    Hydrogen bond formation in the triphenylphosphine oxide (TPPO), acetanilide (ACN) supramolecular heterosynton system, named [TPPO0.5·ACN0.5], has been studied by Positron Annihilation Lifetime Spectroscopy (PALS) and supported by several analytical techniques. In toluene solution, Isothermal Titration Calorimetry (ITC) presented a 1:1 stoichiometry and indicated that the complexation process is driven by entropy, with low enthalpy contribution. X-ray structure determination showed the existence of a three-dimensional network of hydrogen bonds, allowing also the confirmation of the existence of a 1:1 crystalline molecular complex in solid state. The results of thermal analysis (TGA, DTA and DSC) and FTIR spectroscopy showed that the interactions in the complex are relatively weaker than those found in pure precursors, leading to a higher positronium formation probability at [TPPO0.5·ACN0.5]. These weak interactions in the complex enhance the possibility of the n- and π-electrons to interact with positrons and consequently, the probability of positronium formation is higher. Through the present work is shown that PALS is a sensible powerful tool to investigate intermolecular interactions in solid heterosynton supramolecular systems.

  4. Enhanced catalytic hydrogenation activity of Ni/reduced graphene oxide nanocomposite prepared by a solid-state method

    Science.gov (United States)

    Li, Yizhao; Cao, Yali; Jia, Dianzeng

    2018-01-01

    A simple solid-state method has been applied to synthesize Ni/reduced graphene oxide (Ni/rGO) nanocomposite under ambient condition. Ni nanoparticles with size of 10-30 nm supported on reduced graphene oxide (rGO) nanosheets are obtained through one-pot solid-state co-reduction among nickel chloride, graphene oxide, and sodium borohydride. The Ni/rGO nanohybrid shows enhanced catalytic activity toward the reduction of p-nitrophenol (PNP) into p-aminophenol compared with Ni nanoparticles. The results of kinetic research display that the pseudo-first-order rate constant for hydrogenation reaction of PNP with Ni/rGO nanocomposite is 7.66 × 10-3 s-1, which is higher than that of Ni nanoparticles (4.48 × 10-3 s-1). It also presents superior turnover frequency (TOF, 5.36 h-1) and lower activation energy ( E a, 29.65 kJ mol-1) in the hydrogenation of PNP with Ni/rGO nanocomposite. Furthermore, composite catalyst can be magnetically separated and reused for five cycles. The large surface area and high electron transfer property of rGO support are beneficial for good catalytic performance of Ni/rGO nanocomposite. Our study demonstrates a simple approach to fabricate metal-rGO heterogeneous nanostructures with advanced functions.

  5. Example of uranium(IV) insertion within a macrocyclic crown ether with coexistence of the metal in two oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Bombieri, G; De Paoli, G [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi; Immirzi, A

    1978-01-01

    Reaction of UCl/sub 4/ with 18-crown-6 in tetrahydrofuran yields (UCl/sub 4/)/sub 3/ (18-crown-6)/sub 2/ which on recrystallization in nitromethane, gives a partially oxidized and hydrolyzed product whose structure has been investigated by X-ray diffraction. The compound crystallizes in the orthorhombic system. The cell contains eight UCl/sub 3//sup +/ cations each inserted within a crown molecule and four (UO/sub 2/Cl/sub 3/(OH)(H/sub 2/O))/sup 2 -/anions having a pentagonal bipyramidal structure. Four solvated nitromethane molecules are also present. The compound represents one of the very few examples in which uranium exists in two oxidation states, and the first example in which its insertion within a crown macrocycle has been proved by an X-ray diffraction study.

  6. Hydrogen incorporation and radiation induced dynamics in metal-oxide-silicon structures. A study using nuclear reaction analysis

    International Nuclear Information System (INIS)

    Briere, M.A.

    1993-07-01

    Resonant nuclear reaction analysis, using the 1 H( 15 N, αγ) 12 C reaction at 6.4 MeV, has been successfully applied to the investigation of hydrogen incorporation and radiation induced migration in metal-oxide-silicon structures. A preliminary study of the influence of processing parameters on the H content of thermal oxides, with and without gate material present, has been performed. It is found that the dominant source of hydrogen in Al gate devices and dry oxides is often contamination, likely in the form of adsorbed water vapor, formed upon exposure to room air after removal from the oxidation furnace. Concentrations of hydrogen in the bulk oxide as high as 3 10 20 cm -3 (Al gate), and as low as 1 10 18 cm -3 (poly Si-gate) have been observed. Hydrogen accumulation at the Si-SiO 2 interface has been reproducibly demonstrated for as-oxidized samples, as well as for oxides exposed to H 2 containing atmospheres during subsequent thermal processing. The migration of hydrogen, from the bulk oxide to the silicon-oxide interface during NRA, has been observed and intensively investigated. A direct correlation between the hydrogen content of the bulk oxide and the radiation generated oxide charges and interface states is presented. These data provide strong support for the important role of hydrogen in determining the radiation sensitivity of electronic devices. (orig.)

  7. System Tb-Fe-O: thermodynamic properties of ternary oxides using solid-state electrochemical cells

    International Nuclear Information System (INIS)

    Rakshit, S.K.; Parida, S.C.; Dash, S.; Singh, Ziley; Prasad, R.; Venugopal, V.

    2003-01-01

    The standard molar Gibbs free energies of formation of TbFeO 3 (s) and Tb 3 Fe 5 O 12 (s) have been determined using solid-state electrochemical cell employing different solid electrolytes. The reversible emfs of the following solid-state electrochemical cells have been measured in the temperature range 1050≤T/K≤1250. Cell (I):(-)Pt/{TbFeO 3 (s)+Tb 2 O 3 (s)+Fe(s)}//YDT/CSZ//{Fe(s)+Fe 0.95 O(s)}/Pt(+))) (Cell (II):(-)Pt/{Fe(s)+Fe 0.95 O(s)}//CSZ//{TbFeO 3 (s)+Tb 3 Fe 5 O 12 (s)+Fe 3 O 4 (s)}/Pt(+) The oxygen chemical potentials corresponding to the three-phase equilibria involving the ternary oxides have been computed from the emf data. The standard molar Gibbs free energies of formation of solid TbFeO 3 and Tb 3 Fe 5 O 12 calculated by the least-squares regression analysis of the data obtained in the present study are given by {Δ f G compfn m (TbFeO 3 ,s)/(kJ·mol -1 )±3.2}=-1357.5+0.2531·(T/K); (1050≤T/K≤1548);))and({Δ f G compfn m (Tb 3 Fe 5 O 12 ,s)/(kJ·mol -1 )±3.5}=-4901.7+ 0.9997·(T/K); (1050≤T/K≤1250).)) The uncertainty estimates for Δ f G compfn m include the standard deviation in the emf and uncertainty in the data taken from the literature. Based on the thermodynamic information, oxygen potential diagram and chemical potential diagrams were computed for the system Tb-Fe-O at T=1250 K

  8. Rare oxidation states of group V metal compounds generated by radiolysis in non aqueous solvents: experimental and theoretical study. Attempts for synthesis of heterometallic complexes containing niobium and uranium or thorium

    International Nuclear Information System (INIS)

    Le Motais, B.

    1986-02-01

    Mononuclear and binuclear complexes of group V trivalent metals (V, Nb, Ta), coordinated with γ-picolin molecules and chlorine atoms, have been oxidized or reduced, respectively by the radical-ions CH 2 Cl 2 + or CH 3 CN - radiolytically generated in free-oxygen dichloromethane or acetonitrile. The mechanism of these reactions have been established from kinetic, spectroscopic data and in some cases, from EPR measurements and theoretical SWXα calculations. Some preliminary results about the reaction occurring between Cp 2 Nb-(CO)H and Cp 2 'M(CH 3 ) 2 (M=U or Th) (Cp = eta 5 - C 5 H 5 ; Cp = eta 5 - (C 5 (CH 3 ) 5 ) are also reported [fr

  9. Speciation of the oxidation states of plutonium in aqueous solutions by UV/Vis spectroscopy, CE-ICP-MS and CE-RIMS

    International Nuclear Information System (INIS)

    Buerger, S.; Banik, N.L.; Buda, R.A.; Kratz, J.V.; Kuczewski, B.; Trautmann, N.

    2007-01-01

    For the speciation of the plutonium oxidation states in aqueous solutions, the online coupling of capillary electrophoresis (CE) with inductively coupled plasma mass spectrometry (ICP-MS) has been developed. Depending on the radius/electrical charge ratio, the oxidation states III, IV, V, and VI of plutonium are separated by CE, based on the different migration times through the capillary and are detected by ICP-MS. The detection limit is 20 ppb, i.e. 10 9 -10 10 atoms (10 -12 -10 -13 g) for one oxidation state with an uncertainty of the reproducibility of the migration times of ≤ 1% and ≤ 5% for the peak area. The redox kinetics of the different plutonium oxidation states in the presence of humic substances (humic and fulvic acid) have been studied. A relatively rapid reduction of Pu(VI) (10 to 1000 h) in contact with Gorleben fulvic or Aldrich humic acid could be observed, depending on the pH of the solution. Furthermore, at pH=1, a reduction to Pu(III) and Pu(IV) in a mixture of all four oxidation states in contact with Gorleben fulvic acid after one month has been observed. In order to improve the sensitivity of the CE method, the offline coupling of CE to resonance ionization mass spectrometry (RIMS) has been explored. First applications of this new speciation method are presented. (orig.)

  10. Synchrotron Micro-XANES Measurements of Vanadium Oxidation State in Glasses as a Function of Oxygen Fugacity: Experimental Calibration of Data Relevant to Partition Coefficient Determination

    Science.gov (United States)

    Delaney, J. S.; Sutton, S. R.; Newville, M.; Jones, J. H.; Hanson, B.; Dyar, M. D.; Schreiber, H.

    2000-01-01

    Oxidation state microanalyses for V in glass have been made by calibrating XANES spectral features with optical spectroscopic measurements. The oxidation state change with fugacity of O2 will strongly influence partitioning results.

  11. A study of oxidative stress in paucibacillary and multibacillary leprosy

    Directory of Open Access Journals (Sweden)

    Jyothi P

    2008-01-01

    Full Text Available Background: The study and assessment of oxidative stress plays a significant role in the arena of leprosy treatment. Once the presence of oxidative stress is proved, antioxidant supplements can be provided to reduce tissue injury and deformity. Aim: To study oxidative stress in paucibacillary (PB and multibacillary (MB leprosy and to compare it with that in a control group. Methods: Fifty-eight untreated leprosy patients (23 PB and 35 MB cases were studied and compared with 58 healthy controls. Superoxide dismutase (SOD level as a measure of antioxidant status; malondialdehyde (MDA level, an indicator of lipid peroxidation; and MDA/SOD ratio, an index of oxidative stress were estimated in the serum. Results: The SOD level was decreased in leprosy patients, especially in MB leprosy. The MDA level was increased in PB and MB leprosy. The MDA/SOD ratio was significantly elevated in MB patients. There was a steady increase in this ratio along the spectrum from tuberculoid to lepromatous leprosy (LL. Conclusion: There is increased oxidative stress in MB leprosy, especially in LL. This warrants antioxidant supplements to prevent tissue injury.

  12. Chemical state analysis of oxidation products on steel surface by conversion electron Moessbauer spectrometry

    International Nuclear Information System (INIS)

    Ujihira, Yusuke; Nomura, Kiyoshi

    1978-01-01

    The polished NT-70H steel (Fe: 95.97%, C: 0.56%, diameter: 5 cm, thickness: 0.5 cm) was immersed in deionized water or in solutions containing (0.25 -- 0.5) M of chloride, sulfate and nitrate ions. The chemical states of oxidation products of iron on the surface were identified through the analysis of conversion electron Moessbauer spectra (CEMS). CEMS of the steel surface, which had been dipped in deionized water, revealed that γ-FeOOH was formed on the surface. The thickness of γ-FeOOH layer increased with the increase of the duration of dipping. Dissolved oxygen in the solution played an essential role in the oxidation of iron to γ-FeOOH. Oxidation product of iron dipped in the 0.5 M sodium chloride solution was identified as γ-FeOOH. Amorphous paramagnetic iron (III) compound tended to form in the presence of hydrogen peroxide or ammonium ions in the solutions. The increase of alkalinity of the solution up to pH 12 suppressed the oxidation rate and assisted the formation of green rust, which was confirmed by the appearance of the quadrupole splitting peaks of the green rust. In the 0.25 M sodium sulfate solution, oxidation of the steel surface proceeded slowly and the quadrupole splitting peaks of Fe(OH) 2 were seen in the CEMS. The peak intensity of Fe(OH) 2 gradually decreased and that of γ-FeOOH increased by the extension of immersion of steel in the solution. Magnetite (Fe 3 O 4 ) layer was developed beneath the γ-FeOOH layer, when steel was dipped in 0.5 M sodium nitrate solution. However, the peaks of Fe 3 O 4 were not seen on CEMS of steel surface immersed in 0.5 M ammonium nitrate solution. Thus, applying the feasibility of CEMS for the characterization of oxidated compounds of iron on the steel surface formed by the immersion in solutions, the oxidation mechanism of the steel surface was discussed based upon the results of chemical state analyses. (author)

  13. Salt-stone Oxidation Study: Leaching Method - 13092

    International Nuclear Information System (INIS)

    Langton, C.A.; Stefanko, D.B.; Burns, H.H.

    2013-01-01

    Cementitious waste forms can be designed to chemically stabilize selected contaminants, such as Tc +7 and Cr +6 , by chemically reduction to lower valance states, Tc +4 and Cr +3 , respectively, and precipitation of these species in alkaline media as low solubility solid phases. Data for oxidation of this type of cementitious waste form cured under field conditions as a function of time is required for predicting the performance of the waste form and disposal facility. The rate of oxidation (oxidation front advancement) is an important parameter for predicting performance because the solubilities of some radionuclide contaminants, e.g., technetium, are a function of the oxidation state. A non-radioactive experiment was designed for quantifying the oxidation front advancement using chromium, as an approximate redox-sensitive surrogate (Cr +6 / Cr +3 ) for technetium (Tc +7 / Tc +4 ). Nonradioactive cementitious waste forms were prepared in the laboratory and cured under both laboratory and 'field conditions'. Laboratory conditions were ambient temperature and sealed sample containers. Field conditions were approximated by curing samples in open containers which were placed inside a plastic container stored outdoors at SRS. The container had a lid and was instrumented with temperature and humidity probes. Sub-samples as thin as 0.2 mm were taken as a function of distance from the exposed surface of the as-cast sample. The sub-samples were leached and the leachates were analyzed for chromium, nitrate, nitrite and sodium. Nitrate, nitrite, and sodium concentrations were used to provide baseline data because these species are not chemically retained in the waste form matrix to any significant extent and are not redox sensitive. 'Effective' oxidation fronts for Cr were measured for samples containing 1000, 500 and 20 mg/kg Cr added as soluble sodium chromate, Na 2 CrO 4 . For a sample cured for 129 days under field conditions, leachable Cr (assumed to be the oxidized

  14. Salt-stone Oxidation Study: Leaching Method - 13092

    Energy Technology Data Exchange (ETDEWEB)

    Langton, C.A.; Stefanko, D.B.; Burns, H.H. [Savannah River National Laboratory, Savannah River Remediation, LLC, Savannah River Site, Aiken, SC 29808 (United States)

    2013-07-01

    Cementitious waste forms can be designed to chemically stabilize selected contaminants, such as Tc{sup +7} and Cr{sup +6}, by chemically reduction to lower valance states, Tc{sup +4} and Cr{sup +3}, respectively, and precipitation of these species in alkaline media as low solubility solid phases. Data for oxidation of this type of cementitious waste form cured under field conditions as a function of time is required for predicting the performance of the waste form and disposal facility. The rate of oxidation (oxidation front advancement) is an important parameter for predicting performance because the solubilities of some radionuclide contaminants, e.g., technetium, are a function of the oxidation state. A non-radioactive experiment was designed for quantifying the oxidation front advancement using chromium, as an approximate redox-sensitive surrogate (Cr{sup +6} / Cr{sup +3}) for technetium (Tc{sup +7} / Tc{sup +4}). Nonradioactive cementitious waste forms were prepared in the laboratory and cured under both laboratory and 'field conditions'. Laboratory conditions were ambient temperature and sealed sample containers. Field conditions were approximated by curing samples in open containers which were placed inside a plastic container stored outdoors at SRS. The container had a lid and was instrumented with temperature and humidity probes. Sub-samples as thin as 0.2 mm were taken as a function of distance from the exposed surface of the as-cast sample. The sub-samples were leached and the leachates were analyzed for chromium, nitrate, nitrite and sodium. Nitrate, nitrite, and sodium concentrations were used to provide baseline data because these species are not chemically retained in the waste form matrix to any significant extent and are not redox sensitive. 'Effective' oxidation fronts for Cr were measured for samples containing 1000, 500 and 20 mg/kg Cr added as soluble sodium chromate, Na{sub 2}CrO{sub 4}. For a sample cured for 129 days

  15. The initial growth of complex oxides : study and manipulation

    NARCIS (Netherlands)

    Rijnders, Augustinus J.H.M.

    2001-01-01

    In this thesis, the initial growth stage, i.e., nucleation and growth of the first few unit cell layers, of complex oxides was studied in real time during pulsed laser deposition (PLD). These studies were performed at their optimal epitaxial growth conditions, i.e., high temperature and high oxygen

  16. In situ X-ray powder diffraction studies of the synthesis of graphene oxide and formation of reduced graphene oxide

    International Nuclear Information System (INIS)

    Storm, Mie Møller; Johnsen, Rune E.; Norby, Poul

    2016-01-01

    Graphene oxide (GO) and reduced graphene oxide (rGO) are important materials in a wide range of fields. The modified Hummers methods, for synthesizing GO, and subsequent thermal reduction to rGO, are often employed for production of rGO. However, the mechanism behinds these syntheses methods are still unclear. We present an in situ X-ray diffraction study of the synthesis of GO and thermal reduction of GO. The X-ray diffraction revealed that the Hummers method includes an intercalation state and finally formation of additional crystalline material. The formation of GO is observed during both the intercalation and the crystallization stage. During thermal reduction of GO three stages were observed: GO, a disordered stage, and the rGO stage. The appearance of these stages depends on the heating ramp. The aim of this study is to provide deeper insight into the chemical and physical processes during the syntheses. - Graphical abstract: In situ X-ray diffraction results for of the modified Hummers synthesis and the thermal reduction of graphene oxide, revealing three stages for both syntheses as well as new GO diffraction peaks and unidentified crystalline material for the Hummers synthesis and a disordered stage for the thermal reduction of graphene oxide. Display Omitted - Highlights: • Hummers synthesis consists of three stages: dissolution, intercalation and crystal. • GO is produced early on during the synthesis and display new diffraction peaks. • An unidentified triclinic phase is observed for the Hummers synthesis. • Thermal reduction of GO display three stages: GO, a disordered stage and rGO. • In situ XRD indicate reformation of rGO even for fast heated thermal reduction.

  17. In situ X-ray powder diffraction studies of the synthesis of graphene oxide and formation of reduced graphene oxide

    Energy Technology Data Exchange (ETDEWEB)

    Storm, Mie Møller, E-mail: mmst@dtu.dk; Johnsen, Rune E.; Norby, Poul

    2016-08-15

    Graphene oxide (GO) and reduced graphene oxide (rGO) are important materials in a wide range of fields. The modified Hummers methods, for synthesizing GO, and subsequent thermal reduction to rGO, are often employed for production of rGO. However, the mechanism behinds these syntheses methods are still unclear. We present an in situ X-ray diffraction study of the synthesis of GO and thermal reduction of GO. The X-ray diffraction revealed that the Hummers method includes an intercalation state and finally formation of additional crystalline material. The formation of GO is observed during both the intercalation and the crystallization stage. During thermal reduction of GO three stages were observed: GO, a disordered stage, and the rGO stage. The appearance of these stages depends on the heating ramp. The aim of this study is to provide deeper insight into the chemical and physical processes during the syntheses. - Graphical abstract: In situ X-ray diffraction results for of the modified Hummers synthesis and the thermal reduction of graphene oxide, revealing three stages for both syntheses as well as new GO diffraction peaks and unidentified crystalline material for the Hummers synthesis and a disordered stage for the thermal reduction of graphene oxide. Display Omitted - Highlights: • Hummers synthesis consists of three stages: dissolution, intercalation and crystal. • GO is produced early on during the synthesis and display new diffraction peaks. • An unidentified triclinic phase is observed for the Hummers synthesis. • Thermal reduction of GO display three stages: GO, a disordered stage and rGO. • In situ XRD indicate reformation of rGO even for fast heated thermal reduction.

  18. Experimental and Kinetic Modeling Study of Methanol Ignition and Oxidation at High Pressure

    DEFF Research Database (Denmark)

    Aranda, V.; Christensen, J. M.; Alzueta, Maria

    2013-01-01

    A detailed chemical kinetic model for oxidation of CH3OH at high pressure and intermediate temperatures has been developed and validated experimentally. Ab initio calculations and Rice–Ramsperger–Kassel–Marcus/transition state theory (RRKM/TST) analysis were used to obtain rate coefficients for CH...... the conditions studied, the onset temperature for methanol oxidation was not dependent on the stoichiometry, whereas increasing pressure shifted the ignition temperature toward lower values. Model predictions of the present experimental results, as well as rapid compression machine data from the literature, were...

  19. Bringing the State Back into Terrorism Studies

    OpenAIRE

    Blakeley, Ruth

    2007-01-01

    Orthodox terrorism studies tend to focus on the activities of illiberal nonstate actors against the liberal democratic states in the North. It thus excludes state terrorism, which is one of a number of repressive tools that great powers from the North have used extensively in the global South in\\ud the service of foreign policy objectives. I establish the reasons for the absence of state terrorism from orthodox accounts of terrorism and argue that critical–normative approaches could help to o...

  20. The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis

    Science.gov (United States)

    Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S.

    2017-10-01

    Nanosized Ir-black (3 nm) and Ir-oxide (5 nm) oxygen evolution electrocatalysts showing high performance in polymer electrolyte membrane (PEM) water electrolysis based on Aquivion® short-side chain ionomer membrane are investigated to understand the role of the Ir oxidation state on the electrocatalytic activity and stability. Despite the smaller mean crystallite size, the Ir-black electrocatalyst shows significantly lower initial performance than the Ir-oxide. During operation at high current density, the Ir-black shows a decrease of cell potential with time whereas the Ir-oxide catalyst shows increasing cell potential resulting in a degradation rate of about 10 μV/h, approaching 1000 h. The unusual behaviour of the Ir-black results from the oxidation of metallic Ir to IrOx. The Ir-oxide catalyst shows instead a hydrated structure on the surface and a negative shift of about 0.5 eV for the Ir 4f binding energy after 1000 h electrolysis operation. This corresponds to the formation of a sub-stoichiometric Ir-oxide on the surface. These results indicate that a hydrated IrO2 with high oxidation state on the surface is favourable in decreasing the oxygen evolution overpotential. Modifications of the Ir chemical oxidation state during operation can affect significantly the catalytic activity and durability of the electrolysis system.

  1. The New York State optometry workforce study.

    Science.gov (United States)

    Soroka, Mort

    2012-04-01

    This study presents an analysis of the current optometry workforce, both as a unique profession and more broadly within the context of all eye care providers (optometry and ophthalmology) in New York State. The supply and distribution of eye care practitioners provides useful information for policy makers while providing insights as to the impact of the one optometry school within the state. Several databases were employed and a web based survey was developed for completion by all optometrists. The questionnaire included demographic data, whether they were actively practicing in New York State or any other state, were they full time or part time, their primary mode of practice, or if they provided care within institutional settings. Access to care was gauged by the respondents' availability for appointments during evenings or weekends. Access to eye care services in New York State has improved significantly during the past 30 years as the supply of optometrists increased. Before this study was conducted it was generally believed that there were more optometrists than ophthalmologists in every state of the nation except New York, Maryland and the District of Columbia. Findings of this study demonstrate there are 37% more optometrists in New York State than ophthalmologists and more evenly distributed as optometrists are located in almost every county of the state. Sixteen counties have no ophthalmologists. This is attributed to the presence of the College of Optometry established in 1971. More than 60% of all optometrists in the state are SUNY College of Optometry graduates.

  2. Study of optics anisotropy of niobium oxide

    International Nuclear Information System (INIS)

    Ferreira, N.G.; Decker, F.; Fracastoro-Decker, M.

    1988-01-01

    This work shows the use of ''in-situ'' optical techniques in electrochemical experiments to determine the refractive indexes of an anisotropic film. ''In situ'' reflectance measurements allow to study the behavior of a film during its growth process: in our case, since Nb 2 O 5 films are anisotropic only in the presence of an electric field, an ''in-situ'' technique is the only one appropriate to detect this phenomenon. (author) [pt

  3. Positron lifetime studies on thorium oxide powders

    International Nuclear Information System (INIS)

    Upadhyaya, D.D.; Muraleedharan, R.V.; Sharma, B.D.

    1982-01-01

    Positron lifetime spectra have been studied for ThO 2 powders, calcined at different temperatures and having different particle sizes. Three lifetime components could be resolved, the longest component being of low intensity. An observed strong dependence on the particle size of the annihilation process and the variation of positronium diffusion constant is explained on the basis of defect density variations in these powders. (author)

  4. Introducing a Simple Equation to Express Oxidation States as an Alternative to Using Rules Associated with Words Alone

    Science.gov (United States)

    Minkiewicz, Piotr; Darewicz, Malgorzata; Iwaniak, Anna

    2018-01-01

    A simple equation to calculate the oxidation states (oxidation numbers) of individual atoms in molecules and ions may be introduced instead of rules associated with words alone. The equation includes two of three categories of bonds, classified as proposed by Goodstein: number of bonds with more electronegative atoms and number of bonds with less…

  5. Manganese oxide phases and morphologies: A study on calcination temperature and atmospheric dependence

    Directory of Open Access Journals (Sweden)

    Matthias Augustin

    2015-01-01

    Full Text Available Manganese oxides are one of the most important groups of materials in energy storage science. In order to fully leverage their application potential, precise control of their properties such as particle size, surface area and Mnx+ oxidation state is required. Here, Mn3O4 and Mn5O8 nanoparticles as well as mesoporous α-Mn2O3 particles were synthesized by calcination of Mn(II glycolate nanoparticles obtained through an economical route based on a polyol synthesis. The preparation of the different manganese oxides via one route facilitates assigning actual structure–property relationships. The oxidation process related to the different MnOx species was observed by in situ X-ray diffraction (XRD measurements showing time- and temperature-dependent phase transformations occurring during oxidation of the Mn(II glycolate precursor to α-Mn2O3 via Mn3O4 and Mn5O8 in O2 atmosphere. Detailed structural and morphological investigations using transmission electron microscopy (TEM and powder XRD revealed the dependence of the lattice constants and particle sizes of the MnOx species on the calcination temperature and the presence of an oxidizing or neutral atmosphere. Furthermore, to demonstrate the application potential of the synthesized MnOx species, we studied their catalytic activity for the oxygen reduction reaction in aprotic media. Linear sweep voltammetry revealed the best performance for the mesoporous α-Mn2O3 species.

  6. SOLID STATE ENERGY CONVERSION ALLIANCE (SECA) SOLID OXIDE FUEL CELL PROGRAM

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen Minh; Jim Powers

    2003-10-01

    This report summarizes the work performed for April 2003--September 2003 reporting period under Cooperative Agreement DE-FC26-01NT41245 for the U.S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled ''Solid State Energy Conversion Alliance (SECA) Solid oxide Fuel Cell Program''. During this reporting period, the conceptual system design activity was completed. The system design, including strategies for startup, normal operation and shutdown, was defined. Sealant and stack materials for the solid oxide fuel cell (SOFC) stack were identified which are capable of meeting the thermal cycling and degradation requirements. A cell module was tested which achieved a stable performance of 0.238 W/cm{sup 2} at 95% fuel utilization. The external fuel processor design was completed and fabrication begun. Several other advances were made on various aspects of the SOFC system, which are detailed in this report.

  7. SOLID STATE ENERGY CONVERSION ALLIANCE (SECA) SOLID OXIDE FUEL CELL PROGRAM

    Energy Technology Data Exchange (ETDEWEB)

    Unknown

    2003-06-01

    This report summarizes the progress made during the September 2001-March 2002 reporting period under Cooperative Agreement DE-FC26-01NT41245 for the U. S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled ''Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program''. The program focuses on the development of a low-cost, high-performance 3-to-10-kW solid oxide fuel cell (SOFC) system suitable for a broad spectrum of power-generation applications. The overall objective of the program is to demonstrate a modular SOFC system that can be configured to create highly efficient, cost-competitive, and environmentally benign power plants tailored to specific markets. When fully developed, the system will meet the efficiency, performance, life, and cost goals for future commercial power plants.

  8. The study of very high spin states

    International Nuclear Information System (INIS)

    Nolan, P.J.

    1992-01-01

    Some examples are given of the study of very high spin states that decay by discrete line gamma-ray emission. States up to spin 70(h/2π) have been seen in superdeformed bands. In other bands with normal deformation the limit is near 50(h/2π). (Author)

  9. Marijuana: A Study of State Policies & Penalties.

    Science.gov (United States)

    Peat, Marwick, Mitchell and Co., Columbia, MD.

    This study is a comprehensive analysis of issues concerning marijuana that are of importance to state policy makers. It reviews the medical, legal, and historical dimensions of marijuana use and examines the range of policy approaches toward marijuana possession and use which state officials have considered. Attention is directed to the experience…

  10. Study of Pentaquark States at LHCb

    CERN Document Server

    Yang, Zhenwei

    2016-01-01

    The observation of the two resonances consistent with charmonium-like pentaquark states, Pc(4380)+ and Pc(4450)+, by the LHCb collaboration inspires enthusiasm in particle physics. This article briefly reports about the observation and the experimental study of the pentaquark states by the LHCb collaboration

  11. High pressure structural studies on nanophase praseodymium oxide

    Energy Technology Data Exchange (ETDEWEB)

    Saranya, L. [Jamal Mohamed College, Tiruchirapalli 620020, Tamil Nadu (India); Chandra Shekar, N.V., E-mail: chandru@igcar.gov.in [Condensed Matter Physics Division, Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu (India); Amirthapandian, S. [Materials Physics Division, Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu (India); Hussain, Shamima [UGC-DAE-CSR node, Kokilamedu 603103, Tamil Nadu (India); Arulraj, A.; Sahu, P. Ch. [Condensed Matter Physics Division, Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu (India)

    2014-09-15

    The phase stability of nanocrystalline Pr{sub 2}O{sub 3} has been investigated under pressure by in-situ high pressure X-ray diffraction using Mao-Bell type diamond anvil cell. The ambient structure and phase of the praseodymium oxide have been resolved unambiguously using x-ray diffraction, SEM and TEM techniques. Under the action of pressure the cubic phase of the system is retained up to 15 GPa. This is unusual as other isostructural rare earth oxides show structural transformations even at lower pressures. From the best fit to the P–V data with the Murnaghan equation of state yields a bulk modulus of 171 GPa.

  12. Surface State Capture Cross-Section at the Interface between Silicon and Hafnium Oxide

    Directory of Open Access Journals (Sweden)

    Fu-Chien Chiu

    2013-01-01

    Full Text Available The interfacial properties between silicon and hafnium oxide (HfO2 are explored by the gated-diode method and the subthreshold measurement. The density of interface-trapped charges, the current induced by surface defect centers, the surface recombination velocity, and the surface state capture cross-section are obtained in this work. Among the interfacial properties, the surface state capture cross-section is approximately constant even if the postdeposition annealing condition is changed. This effective capture cross-section of surface states is about 2.4 × 10−15 cm2, which may be an inherent nature in the HfO2/Si interface.

  13. Control of lipid oxidation during exercise: role of energy state and mitochondrial factors

    DEFF Research Database (Denmark)

    Sahlin, K; Harris, R C

    2008-01-01

    Despite considerable progress during recent years our understanding of how lipid oxidation (LOx) is controlled during exercise remains incomplete. This review focuses on the role of mitochondria and energy state in the control of LOx. LOx increases in parallel with increased energy demand up...... to an exercise intensity of about 50-60% of VO(2max) after which the contribution of lipid decreases. The switch from lipid to carbohydrate (CHO) is of energetic advantage due to the increased ATP/O(2) yield. In the low-intensity domain (energy state will stimulate both LOx...... during high-intensity exercise. Another potential mechanism, suggested in this review, is that Acyl-CoA synthetase (ACS), an initial step in LCFA catabolism, functions as a regulator of LOx. ACS activity is suggested to be under control of CoASH and energy state. Furthermore, evidence exists...

  14. Optically induced bistable states in metal/tunnel-oxide/semiconductor /MTOS/ junctions

    Science.gov (United States)

    Lai, S. K.; Dressendorfer, P. V.; Ma, T. P.; Barker, R. C.

    1981-01-01

    A new switching phenomenon in metal-oxide semiconductor tunnel junction has been discovered. With a sufficiently large negative bias applied to the electrode, incident visible light of intensity greater than about 1 microW/sq cm causes the reverse-biased junction to switch from a low-current to a high-current state. It is believed that hot-electron-induced impact ionization provides the positive feedback necessary for switching, and causes the junction to remain in its high-current state after the optical excitation is removed. The junction may be switched back to the low-current state electrically. The basic junction characteristics have been measured, and a simple model for the switching phenomenon has been developed.

  15. XPS study of surface state of novel perovskite system Dy{sub 0.5}Sr{sub 0.5}Co{sub 0.8}Fe{sub 0.2}O{sub 3-δ} as cathode for solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Kautkar, Pranay R.; Acharya, Smita A., E-mail: saha275@yahoo.com; Tumram, Priya V. [Depatment of Physics, Rashtrasant Tukadoji Maharaj Nagpur University Campus, Nagpur-440033 (India); Deshpande, U. P. [UGC-DAE Consortium for scientific Research, University Campus, Khandwa Road, Indore-452001, Madhya Pradesh,India (India)

    2016-05-06

    In the present attempt,novel perovskite oxide Dy{sub 0.5}Sr{sub 0.5}Co{sub 0.8}Fe{sub 0.2}O{sub 3–δ} (DSCF) as cathode material has been synthesized by an Ethylene glycol-citrate combined sol-gel combustion route. Orthorhombic symmetry structure is confirmed by X-ray diffraction (XRD) and data is well fitted using Rietveld refinement by Full-Prof software suite. Chemical natureof surface of DSCF has been analyzed by using X-ray photoelectron spectroscopy (XPS). XPS result shows that Dy ions are in +3 oxidation state and Sr in +2 states. However Co2p and Fe2p spectra indicates partial change in oxidation state from Co3+/Fe3+ to Co4+/Fe4+. These attribute to develop active sites on the surface for oxygen ions. O1s XPS spectra shows two oxygen peaks relatedto lattice oxygen in perovskite and absorbed oxygen in oxygen vacancy are detected. O1s spectra demonstrate the existence of adsorbed oxygen species on the surface of DSCF oxide which is quite beneficial for intermediate temperature of Solid Oxide Fuel Cell.

  16. Evolution of the Oxidation State of the Earth's Mantle: Challenges of High Pressure Quenching

    Science.gov (United States)

    Danielson, L. R.; Righter, K.; Keller, L.; Christoffersen, R.; Rahman, Z.

    2015-01-01

    The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3+ at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. Experiments of more mafic compositions and at higher pressures commonly form a polyphase quench intergrowth composed primarily of pyroxenes, with interstitial glass which hosts nearly all of the more volatile minor elements. In our previous experiments on shergottite compositions, variable fO2, T, and P is less than 4 GPa, Fe3+/TotFe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3+/TotFe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3+. Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Experiments with Knippa basalt as the starting composition were conducted at 1-8 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products from 7-8 GPa quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal Fe3+/2+. A number of different approaches have been employed to produce glassy samples that can be measured by EELS and XANES. A more intermediate andesite was used in one experiment, and decompression during quenching was attempted after, but both resulted in a finer grained polyphase texture. Experiments are currently underway to test different capsule materials may affect quench texture. A preliminary experiment using liquid nitrogen to greatly enhance the rate of cooling of the assembly has also been attempted and this technique will be

  17. High-energy photoemission studies of oxide interfaces

    Science.gov (United States)

    Claessen, Ralph

    2015-03-01

    The interfaces of complex oxide heterostructures can host novel quantum phases not existing in the bulk of the constituents, with the high-mobility 2D electron system (2DES) in LaAlO3/SrTiO3 (LAO/STO) representing a prominent example. Despite extensive research the origin of the 2DES and its unusual properties - including the supposed coexistence of superconductivity and ferromagnetism - are still a matter of intense debate. Photoelectron spectroscopy, recently extended into the soft (SX-ARPES) and hard (HAXPES) X-ray regime, is a powerful method to provide detailed insight into the electronic structure of these heterostructures and, in particular, of the buried interface. This includes the identification of the orbital character of the 2DES as well as the determination of vital band structure information, such as band alignment, band bending, and even k-resolved band dispersions and Fermi surface topology. Moreover, resonant photoemission at the Ti L-edge reveals the existence of two different species of Ti 3d states, localized and itinerant, which can be distinguished and identified by their different resonance behavior. The role of oxygen vacancies is studied by controlled in-situ oxidation, which allows us to vary the composition from fully stoichiometric to strongly O-deficient. By comparison to free STO surfaces we can thus demonstrate that the metallicity of the heteointerfaces is intrinsic, i . e . it persists even in the absence of O defects. I will discuss our photoemission results on LAO/STO heterostructures in both (100) and (111) orientation as well as on the related system γ-Al2O3/STO(100), which also hosts a 2DES with an even higher mobility. Work in collaboration with J. Mannhart (MPI-FKF, Stuttgart), N. Pryds (TU Denmark), G. Rijnders (U Twente), S. Suga (U Osaka), M. Giorgoi (BESSY, HZB), W. Drube (DESY Photon Science), V.N. Strocov (Swiss Light Source), J. Denlinger (Advanced Light Source, LBNL), and T.-L. Lee (Diamond Light Source). Support by

  18. Experimental study on oxidation and combustion characteristics of sodium droplets

    International Nuclear Information System (INIS)

    Zhang Zhigang; Sun Shubin; Liu Chongchong; Tang Yexin

    2015-01-01

    In the operation of the sodium-cooled fast reactor, the accident caused by the leakage and combustion of liquid sodium is common and frequent. In this paper, the oxidation and combustion characteristics of sodium droplets were studied by carrying out the experiments of the oxidation and combustion under different conditions of initial temperatures (140-370℃) of the sodium droplets and oxygen concentrations (4%-21%). The oxidation and combustion behaviors were visualized by a set of combustion apparatus of sodium droplet and a high speed camera. The experiment results show that the columnar oxides grow longer as the initial temperature of sodium droplet and oxygen concentration become lower. Under the same oxygen concentration condition, the sodium droplet with the higher initial temperature is easier to ignite and burn. When the initial temperature of sodium droplet is below 200℃, it is very difficult to ignite. If there is a turbulence damaging the oxide layer on the surface, the sodium droplet will also burn gradually. When the initial temperature ranges from 140℃ to 370℃ and the oxygen fraction is equal to or higher than 12%, the sodium droplet could burn completely and the maximum combustion temperature could roughly reach 600-800℃. When the oxygen concentration is below 12%, the sodium droplet could not burn completely and the highest combustion temperature is below 600℃. The results are helpful to the research on the columnar flow and spray sodium fire. (authors)

  19. Study on thermodynamic properties of actinoid oxides

    Energy Technology Data Exchange (ETDEWEB)

    Tsuji, Toshihide; Miyajima, Nobuyoshi; Kato, Tetsuya; Ochida, Manabu [Nagoya Univ. (Japan). School of Engineering; Mumomura, Tadasumi; Yamashita, Toshiyuki; Nitani, Noriko; Ouchi, Kinji

    1996-01-01

    Since long-life transuranium elements (TRU) accumulate associated with a progress of high-burnup of fuel, TRU quenching in a reactor or an accelerator has been examined in Japan. To design a fuel for TRU quenching, thermal expansion is an important thermal parameter along with thermal capacity and heat transfer coefficient. Here, lattice constants of PuO{sub 2} ThO{sub 2}, UO{sub 2} and NpO{sub 2} were investigated by high temperature X-ray diffraction, showing that the lattice constants of these dioxides but UO{sub 2} obtained in this study were well coincident with Tailor`s values. The linear expansion coefficients for ThO{sub 2}, UO{sub 2} and PuO{sub 2} agreed with TPRC data and that of NpO{sub 2} with Fahey`s measurement. The linear expansion coefficient of NpO{sub 2} was found to be temperature dependent as well as other three dioxides. Those values were in inverse proportion to their melting points in a higher temperature range, whereas in a lower temperature one, the coefficient of UO{sub 2} was larger than those of NpO{sub 2} and PuO{sub 2}. Therefore, such abnormal behavior of the coefficient in a low temperature range was considered to be related to the lower Debye temperature of UO{sub 2} compared with the other dioxides. (M.N.)

  20. State of dog's metabolism in the remote period after the oxide tritium influence

    International Nuclear Information System (INIS)

    Kalistratova, V.S.; Tishchenko, G.S.; Bortnik, L.A.; Nisimov, P.G.; Romanova, I.B.

    2000-01-01

    Influence of tritium oxide on the metabolism by some indices of lipid metabolism (common lipids, β-lipoproteins, cholesterin), protein metabolism (cholinesterase) and carbohydrate metabolism (blood sugar) was studied. It was established that the introduction into organism of tritium oxide in the quantities, which could form lethal and sublethal doses of internal radiation, provoked the main changes of values of mentioned indices of metabolism. The character of metabolism changes in the remote period allows to judge about the development of sclerosis processes which can be the result of radiation-stipulated acceleration of organism aging [ru

  1. Pulse radiolysis study on oxidation reactions of gallic acid

    International Nuclear Information System (INIS)

    Dwibedy, P.; Dey, G.R.; Naik, D.B.; Kishore, Kamal

    1998-01-01

    Reactions of OH . /O - and other oxidising radicals viz. N 3 . , Br 2 .- , Cl 2 .- with gallic acid (GA) have been studied at various pHs. At pH 6.8, OH . radicals react with GA giving an adduct which in turn reacts with the parent GA to give a dimeric species. At pH 9.7, the initial OH adduct formed is able to oxidize GA to give a semi-oxidised species. At pH 12 and ∼ 13.6, OH . /O .- radicals directly bring about oxidation of GA. (author)

  2. ONIOM Studies of Esterification at Oxidized Carbon Nanotube Tips

    Energy Technology Data Exchange (ETDEWEB)

    Contreras-Torres, F F; Basiuk, V A [Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, Circuito Exterior C.U., A. Postal 70-543, 04510 Mexico D. F. (Mexico)

    2007-03-15

    Esterification of oxidized carbon nanotubes (CNTs) can open a new route for the separation of zigzag and armchair nanotubes. We studied theoretically (by using hybrid DFT within the ONIOM embedding protocol) the reactions of monocarboxy-substituted oxidized tips of zigzag and armchair single-walled CNTs (SWCNTs) with methanol. According to the calculated values of activation energy, Gibbs free-activation barriers, and enthalpies of formation for the SWCNT-(COOH)H5 models, the zigzag nanotube isomer is more reactive as compared to its armchair counterpart. For other models we obtained variable results.

  3. Fuel cells: spectroscopic studies in the electrocatalysis of alcohol oxidation

    Directory of Open Access Journals (Sweden)

    Iwasita Teresa

    2002-01-01

    Full Text Available Modern spectroscopic methods are useful for elucidating complex electrochemical mechanisms as those occurring during the oxidation of small organic molecules (CH3OH, HCOH, HCOOH. In the present paper it is shown the use of spectroscopic methods to study the oxidation of alcohols on platinum or Pt-based binary electrodes. These reactions are of importance in conexion with the development of anode systems for use in fuel cells. Mass spectrometry and FT infrared spectroscopy allow to establishing the reaction intermediates and products and the dependence of the amount of species on the applied potential. FTIR and scanning tunneling microscopy contribute to understand the effects of the surface structure on the rate of reaction. Examples are presented for methanol and ethanol oxidation at pure and modified Pt catalysts.

  4. Global analysis of genetic variation in human arsenic (+ 3 oxidation state) methyltransferase (AS3MT)

    International Nuclear Information System (INIS)

    Fujihara, Junko; Soejima, Mikiko; Yasuda, Toshihiro; Koda, Yoshiro; Agusa, Tetsuro; Kunito, Takashi; Tongu, Miki; Yamada, Takaya; Takeshita, Haruo

    2010-01-01

    Human arsenic (+ 3 oxidation state) methyltransferase (AS3MT) is known to catalyze the methylation of arsenite. The objective of this study was to investigate the diversity of the AS3MT gene at the global level. The distribution of 18 single nucleotide polymorphisms (SNPs) in AS3MT was performed in 827 individuals from 10 populations (Japanese, Korean, Chinese, Mongolian, Tibetans, Sri Lankan Tamils, Sri Lankan Sinhalese, Nepal Tamangs, Ovambo, and Ghanaian). In the African populations, the A allele in A6144T was not observed; the allele frequencies of C35587 were much lower than those in other populations; the allele frequencies of A37616 and C37950 were relatively higher than those in other populations. Among Asian populations, Mongolians showed a different genotype distribution pattern. A lower C3963 and T6144 frequencies were observed, and, in the C37616A and T37950C polymorphism, the Mongolian population showed higher A37616 and C37950 allele frequencies than other Asian populations, similarly to the African populations. A total of 66 haplotypes were observed in the Ovambo, 48, in the Ghanaian, 99, in the Japanese, 103, in the Korean, 103, in the South Chinese, 20, in the Sri Lankan Tamil, 12, in the Sri Lankan Sinhalese, 21, in the Nepal Tamang, 50, in the Tibetan, and 45, in the Mongolian populations. The D' values between the SNP pairs were extremely high in the Sri Lankan Sinhalese population. Relatively higher D' values were observed in Mongolian and Sri Lankan Tamil populations. Network analysis showed two clusters that may have different origins, African and Asians (Chinese and/or Japanese). The present study is the first to demonstrate the existence of genetic heterogeneity in a world wide distribution of 18 SNPs in AS3MT.

  5. Determination of Model Kinetics for Forced Unsteady State Operation of Catalytic CH4 Oxidation

    Directory of Open Access Journals (Sweden)

    Effendy Mohammad

    2016-01-01

    Full Text Available The catalytic oxidation of methane for abating the emission vented from coal mine or natural gas transportation has been known as most reliable method. A reverse flow reactor operation has been widely used to oxidize this methane emission due to its capability for autothermal operation and heat production. The design of the reverse flow reactor requires a proper kinetic rate expression, which should be developed based on the operating condition. The kinetic rate obtained in the steady state condition cannot be applied for designing the reactor operated under unsteady state condition. Therefore, new approach to develop the dynamic kinetic rate expression becomes indispensable, particularly for periodic operation such as reverse flow reactor. This paper presents a novel method to develop the kinetic rate expression applied for unsteady state operation. The model reaction of the catalytic methane oxidation over Pt/-Al2O3 catalyst was used with kinetic parameter determined from laboratory experiments. The reactor used was a fixed bed, once-through operation, with a composition modulation in the feed gas. The switching time was set at 3 min by varying the feed concentration, feed flow rate, and reaction temperature. The concentrations of methane in the feed and product were measured and analysed using gas chromatography. The steady state condition for obtaining the kinetic rate expression was taken as a base case and as a way to judge its appropriateness to be applied for dynamic system. A Langmuir-Hinshelwood reaction rate model was developed. The time period during one cycle was divided into some segments, depending on the ratio of CH4/O2. The experimental result shows that there were kinetic regimes occur during one cycle: kinetic regime controlled by intrinsic surface reaction and kinetic regime controlled by external diffusion. The kinetic rate obtained in the steady state operation was not appropriate when applied for unsteady state operation

  6. Positron studies of metal-oxide-semiconductor structures

    Science.gov (United States)

    Au, H. L.; Asoka-Kumar, P.; Nielsen, B.; Lynn, K. G.

    1993-03-01

    Positron annihilation spectroscopy provides a new probe to study the properties of interface traps in metal-oxide semiconductors (MOS). Using positrons, we have examined the behavior of the interface traps as a function of gate bias. We propose a simple model to explain the positron annihilation spectra from the interface region of a MOS capacitor.

  7. Study of oxide facing at silicone detectors of ionization detectors

    International Nuclear Information System (INIS)

    Kopestansky, J.; Tykva, R.

    1999-01-01

    Formation of oxide facing on silicone in discrete phases of technological preparation of detectors and interaction of gold (aluminium) steamed with SiO x layer were studied. The homogeneity of Au and Si) x layers and interface Au-SiO x and SiO x -Si were examined. The methods SIMS, and partially XPS, AES and RBS were used

  8. Physical and electrochemical study of cobalt oxide nano- and microparticles

    Energy Technology Data Exchange (ETDEWEB)

    Alburquenque, D. [Dpto. de Química de los Materiales, USACh, Av. L.B.O.‘Higgins 3363, 9170022 Santiago (Chile); Dpto. de Metalurgia, USACh, Av. Ecuador 3469, 9170124, Santiago (Chile); Vargas, E. [Dpto. de Física, USACh and CEDENNA, Av. Ecuador 3493, 9170124 Santiago (Chile); Dpto. de Metalurgia, USACh, Av. Ecuador 3469, 9170124, Santiago (Chile); Denardin, J.C.; Escrig, J. [Dpto. de Física, USACh and CEDENNA, Av. Ecuador 3493, 9170124 Santiago (Chile); Marco, J.F. [Instituto de Química Física “Rocasolano”, CSIC, c/Serrano 119, 28006 Madrid (Spain); Ortiz, J. [Dpto. de Química de los Materiales, USACh, Av. L.B.O.‘Higgins 3363, 9170022 Santiago (Chile); Gautier, J.L., E-mail: juan.gautier@usach.cl [Dpto. de Química de los Materiales, USACh, Av. L.B.O.‘Higgins 3363, 9170022 Santiago (Chile)

    2014-07-01

    Cobalt oxide nanocrystals of size 17–21 nm were synthesized by a simple reaction between cobalt acetate (II) and dodecylamine. On the other hand, micrometric Co{sub 3}O{sub 4} was prepared using the ceramic method. The structural examination of these materials was performed using powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM and HRTEM). XRD studies showed that the oxides were pure, well-crystallized, spinel cubic phases with a-cell parameter of 0.8049 nm and 0.8069 nm for the nano and micro-oxide, respectively. The average particle size was 19 nm (nano-oxide) and 1250 μm (micro-oxide). Morphological studies carried out by SEM and TEM analyses have shown the presence of octahedral particles in both cases. Bulk and surface properties investigated by X-ray photoelectron spectroscopy (XPS), point zero charge (pzc), FTIR and cyclic voltammetry indicated that there were no significant differences in the composition on both materials. The magnetic behavior of the samples was determined using a vibrating sample magnetometer. The compounds showed paramagnetic character and no coercivity and remanence in all cases. Galvanostatic measurements of electrodes formed with nanocrystals showed better performance than those built with micrometric particles. - Highlights: • Spinel Co{sub 3}O{sub 4} nanoparticles and microparticles with same structure but with different cell parameters, particle size and surface area were synthesized. • Oxide nanoparticles showed better electrochemical behavior than micrometric ones due to area effect.

  9. Quantitative chemical state XPS analysis of first row transition metals, oxides and hydroxides

    Energy Technology Data Exchange (ETDEWEB)

    Biesinger, M C; Payne, B P; McIntryre, N S [Department of Chemistry, University of Western Ontario, London, Ontario, N6A 5B7 (Canada); Hart, B R; Lau, L Wm [Surface Science Western, Room G1, Western Science Centre, University of Western Ontario, London, Ontario, N6A 5B7 (Canada); Grosvenor, A P [Department of Chemistry, Gunning/Lemieux Chemistry Centre, University of Alberta, Edmonton, Alberta, T6G 2G2 (Canada); Smart, R StC [ACeSSS, Applied Centre for Structural and Synchrotron Studies, University of South Australia, Mawson Lakes, SA 5095 (Australia)], E-mail: biesingr@uwo.ca

    2008-03-15

    Practical quantitative chemical state X-ray photoelectron spectroscopy (XPS) analysis of first row transition metals, oxides and hydroxides is challenging due to the complexity of their M 2p spectra. Complex multiplet splitting, shake-up and plasmon loss structure can play a role in the interpretation of the chemical states present. This paper will show practical curve fitting procedures for the quantitative measurement of different chemical states for metal oxides and hydroxides from a survey of transition metals. It will also discuss some of the limitations and pitfalls present as well as give practical examples of their successful use. These curve-fitting procedures are based on 1) standard spectra from quality reference samples, 2) a survey of appropriate literature databases and/or a compilation of literature references, 3) fitting of multiplet split spectra based on spectra of numerous reference materials and theoretical modelling, 4) spectral subtractions routines, again using reference spectra, and 5) specific literature references where fitting procedures are available.

  10. Quantitative chemical state XPS analysis of first row transition metals, oxides and hydroxides

    International Nuclear Information System (INIS)

    Biesinger, M C; Payne, B P; McIntryre, N S; Hart, B R; Lau, L Wm; Grosvenor, A P; Smart, R StC

    2008-01-01

    Practical quantitative chemical state X-ray photoelectron spectroscopy (XPS) analysis of first row transition metals, oxides and hydroxides is challenging due to the complexity of their M 2p spectra. Complex multiplet splitting, shake-up and plasmon loss structure can play a role in the interpretation of the chemical states present. This paper will show practical curve fitting procedures for the quantitative measurement of different chemical states for metal oxides and hydroxides from a survey of transition metals. It will also discuss some of the limitations and pitfalls present as well as give practical examples of their successful use. These curve-fitting procedures are based on 1) standard spectra from quality reference samples, 2) a survey of appropriate literature databases and/or a compilation of literature references, 3) fitting of multiplet split spectra based on spectra of numerous reference materials and theoretical modelling, 4) spectral subtractions routines, again using reference spectra, and 5) specific literature references where fitting procedures are available

  11. Studies of high coverage oxidation of the Cu(100) surface using low energy positrons

    Science.gov (United States)

    Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

    2012-02-01

    The study of oxidation of single crystal metal surfaces is important in understanding the corrosive and catalytic processes associated with thin film metal oxides. The structures formed on oxidized transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which result from the diffusion of oxygen into subsurface regions. In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. The results of calculations of positron binding energy, positron work function, and annihilation characteristics of surface trapped positrons with relevant core electrons as function of oxygen coverage are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES).

  12. Solid-state electrochromic cell with anodic iridium oxide film electrodes

    International Nuclear Information System (INIS)

    Dautremont-Smith, W.C.; Beni, G.; Schiavone, L.M.; Shay, J.L.

    1979-01-01

    A new solid-state electrochromic cell has been fabricated using an anodic iridium oxide film (AIROF) display electrode. The cell has the symmetric sandwich structure AIROFvertical-barNafionvertical-barAIROF, with the Nafion solid electrolyte opacified by an in situ precipitation technique. A symmetric square-wave voltage of 1.5 V amplitude produces clearly perceivable color changes from pale to dark blue-gray in approx. =1 sec when viewed in diffuse reflection. Good open-circuit optical memory is exhibited:

  13. First-Principles Study of Structure Property Relationships of Monolayer (Hydroxy)Oxide-Metal Bifunctional Electrocatalysts

    DEFF Research Database (Denmark)

    Zeng, Zhenhua; Kubal, Joseph; Greeley, Jeffrey Philip

    2015-01-01

    step towards accurate identification and prediction of a variety of oxide/electrode interfacial structure-properties relationships, but also provides the foundation for rational design and control of ‘targeted active phases’ at catalytic interfaces. The successful design of bifunctional......In the present study, on the basis of detailed density functional theory (DFT) calculations, and using Ni hydroxy(oxide) films on Pt(111) and Au(111) electrodes as model systems, we describe a detailed structural and electrocatalytic analysis of hydrogen evolution (HER) at three-phase boundaries...... under alkaline electrochemical conditions. We demonstrate that the structure and oxidation state of the films can be systematically tuned by changing the applied electrode potential and/or the nature of substrates. Structural features determined from the theoretical calculations provide a wealth...

  14. High-Resolution Electron Energy Loss Studies of Oxygen, Hydrogen, Nitrogen, Nitric Oxide, and Nitrous Oxide Adsorption on Germanium Surfaces.

    Science.gov (United States)

    Entringer, Anthony G.

    The first high resolution electron energy loss spectroscopy (HREELS) studies of the oxidation and nitridation of germanium surfaces are reported. Both single crystal Ge(111) and disordered surfaces were studied. Surfaces were exposed to H, O_2, NO, N _2O, and N, after cleaning in ultra-high vacuum. The Ge surfaces were found to be non-reactive to molecular hydrogen (H_2) at room temperature. Exposure to atomic hydrogen (H) resulted hydrogen adsorption as demonstrated by the presence of Ge-H vibrational modes. The HREEL spectrum of the native oxide of Ge characteristic of nu -GeO_2 was obtained by heating the oxide to 200^circC. Three peaks were observed at 33, 62, and 106 meV for molecular oxygen (O_2) adsorbed on clean Ge(111) at room temperature. These peaks are indicative of dissociative bonding and a dominant Ge-O-Ge bridge structure. Subsequent hydrogen exposure resulted in a shift of the Ge-H stretch from its isolated value of 247 meV to 267 meV, indicative of a dominant +3 oxidation state. A high density of dangling bonds and defects and deeper oxygen penetration at the amorphous Ge surface result in a dilute bridge structure with a predominant +1 oxidation state for similar exposures. Molecules of N_2O decompose at the surfaces to desorbed N_2 molecules and chemisorbed oxygen atoms. In contrast, both oxygen and nitrogen are detected at the surfaces following exposure to NO molecules. Both NO and N_2O appear to dissociate and bond at the top surface layer. Molecular nitrogen (N_2) does not react with the Ge surfaces, however, a precursor Ge nitride is observed at room temperature following exposure to nitrogen atoms and ions. Removal of oxygen by heating of the NO-exposed surface to 550^circC enabled the identification of the Ge-N vibrational modes. These modes show a structure similar to that of germanium nitride. This spectrum is also identical to that of the N-exposed surface heated to 550^circC. Surface phonon modes of the narrow-gap semiconducting

  15. Metabolomic profiles of arsenic (+3 oxidation state) methyltransferase knockout mice: Effect of sex and arsenic exposure

    Science.gov (United States)

    Huang, Madelyn C.; Douillet, Christelle; Su, Mingming; Zhou, Kejun; Wu, Tao; Chen, Wenlian; Galanko, Joseph A.; Drobná, Zuzana; Saunders, R. Jesse; Martin, Elizabeth; Fry, Rebecca C.; Jia, Wei; Stýblo, Miroslav

    2016-01-01

    Arsenic (+3 oxidation state) methyltransferase (As3mt) is the key enzyme in the pathway for methylation of inorganic arsenic (iAs). Altered As3mt expression and AS3MT polymorphism have been linked to changes in iAs metabolism and in susceptibility to iAs toxicity in laboratory models and in humans. As3mt-knockout mice have been used to study the association between iAs metabolism and adverse effects of iAs exposure. However, little is known about systemic changes in metabolism of these mice and how these changes lead to their increased susceptibility to iAs toxicity. Here, we compared plasma and urinary metabolomes of male and female wild-type (WT) and As3mt-KO (KO) C57BL6 mice and examined metabolomic shifts associated with iAs exposure in drinking water. Surprisingly, exposure to 1 ppm As elicited only small changes in the metabolite profiles of either WT or KO mice. In contrast, comparisons of KO mice with WT mice revealed significant differences in plasma and urinary metabolites associated with lipid (phosphatidylcholines, cytidine, acyl-carnitine), amino acid (hippuric acid, acetylglycine, urea), and carbohydrate (L-sorbose, galactonic acid, gluconic acid) metabolism. Notably, most of these differences were sex-specific. Sex-specific differences were also found between WT and KO mice in plasma triglyceride and lipoprotein cholesterol levels. Some of the differentially changed metabolites (phosphatidylcholines, carnosine, and sarcosine) are substrates or products of reactions catalyzed by other methyltransferases. These results suggest that As3mt KO alters major metabolic pathways in a sex-specific manner, independent of iAs treatment, and that As3mt may be involved in other cellular processes beyond iAs methylation. PMID:26883664

  16. N-Oxide-N-oxide interactions and Cl...Cl halogen bonds in pentachloropyridine N-oxide: the many-body approach to interactions in the crystal state.

    Science.gov (United States)

    Wzgarda-Raj, Kinga; Rybarczyk-Pirek, Agnieszka J; Wojtulewski, Sławomir; Palusiak, Marcin

    2018-02-01

    Pentachloropyridine N-oxide, C 5 Cl 5 NO, crystallizes in the monoclinic space group P2 1 /c. In the crystal structure, molecules are linked by C-Cl...Cl halogen bonds into infinite ribbons extending along the crystallographic [100] direction. These molecular aggregates are further stabilized by very short intermolecular N-oxide-N-oxide interactions into herringbone motifs. Computations based on quantum chemistry methods allowed for a more detailed description of the N-oxide-N-oxide interactions and Cl...Cl halogen bonds. For this purpose, Hirshfeld surface analysis and the many-body approach to interaction energy were applied.

  17. Studies on mixed metal oxides solid solutions as heterogeneous catalysts

    Directory of Open Access Journals (Sweden)

    H. R. Arandiyan

    2009-03-01

    Full Text Available In this work, a series of perovskite-type mixed oxide LaMo xV1-xO3+δ powder catalysts (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, and 1.0, with 0.5 < δ < 1.5, prepared by the sol-gel process and calcined at 750ºC, provide an attractive and effective alternative means of synthesizing materials with better control of morphology. Structures of resins obtained during the gel formation process by FT-IR spectroscopy and XRD analysis showed that all the LaMo xV1-xO3+δ samples are single phase perovskite-type solid solutions. The surface area (BET between 2.5 - 5.0 m²/g (x = 0.1 and 1.0 respectively increases with increasing Mo ratio in the samples. They show high purity, good chemical homogeneity, and lower calcinations temperatures as compared with the solid-state chemistry route. SEM coupled to EDS and thermogravimetric analysis/differential thermal analyses (TGA/DTA have been carried out in order to evaluate the homogeneity of the catalyst. Finally, the experimental studies show that the calcination temperature and Mo content exhibited a significant influence on catalytic activity. Among the LaMo xV1-xO3+δ samples, LaMo0.7V0.3O4.2 showed the best catalytic activity for the topic reaction and the best activity and stability for ethane reforming at 850ºC under 8 bar.

  18. Evaluating chemical extraction techniques for the determination of uranium oxidation state in reduced aquifer sediments

    Science.gov (United States)

    Stoliker, Deborah L.; Campbell, Kate M.; Fox, Patricia M.; Singer, David M.; Kaviani, Nazila; Carey, Minna; Peck, Nicole E.; Barger, John R.; Kent, Douglas B.; Davis, James A.

    2013-01-01

    Extraction techniques utilizing high pH and (bi)carbonate concentrations were evaluated for their efficacy in determining the oxidation state of uranium (U) in reduced sediments collected from Rifle, CO. Differences in dissolved concentrations between oxic and anoxic extractions have been proposed as a means to quantify the U(VI) and U(IV) content of sediments. An additional step was added to anoxic extractions using a strong anion exchange resin to separate dissolved U(IV) and U(VI). X-ray spectroscopy showed that U(IV) in the sediments was present as polymerized precipitates similar to uraninite and/or less ordered U(IV), referred to as non-uraninite U(IV) species associated with biomass (NUSAB). Extractions of sediment containing both uraninite and NUSAB displayed higher dissolved uranium concentrations under oxic than anoxic conditions while extractions of sediment dominated by NUSAB resulted in identical dissolved U concentrations. Dissolved U(IV) was rapidly oxidized under anoxic conditions in all experiments. Uraninite reacted minimally under anoxic conditions but thermodynamic calculations show that its propensity to oxidize is sensitive to solution chemistry and sediment mineralogy. A universal method for quantification of U(IV) and U(VI) in sediments has not yet been developed but the chemical extractions, when combined with solid-phase characterization, have a narrow range of applicability for sediments without U(VI).

  19. Study of Oxide Formation on Alloy 800 by Potentiostatic Polarization

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Chong Hun [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Momenib, M.; Wren, C. J. [University of Western Ontario, London (Canada)

    2015-10-15

    The objectives of study are to investigate the effect of potential on oxide formation and conversion on alloy 800 under potentiostatic conditions. For this study we have focused primarily on corrosion at pH{sub 25.}deg. C8.4. The results presented in Figures 1 show that in the range from -0.8 V{sub SCE} to +0.2 V{sub SCE} there are four potential regions having distinctly different short- and long-term characteristics in the log |i| vs. log t and Q vs. t plots. At a potential below -0.8 V{sub SCE}, the current becomes cathodic immediately (< 10 s) upon polarization, indicating negligible metal oxidation and hence is not of interest. In nuclear power plants, it is used for steam generator tubing in pressurized water reactors (PWRs), including Canadian Deuterium Uranium (CANDU) reactors. However, failures resulting from localized corrosion such as pitting, crevice and stress corrosion cracking (SCC) have been observed in the service environments. There exists still considerable controversy over the type of oxide that can be formed and the mechanism of oxide formation on Alloy 800.

  20. Graphene oxide and adsorption of chloroform: A density functional study

    Energy Technology Data Exchange (ETDEWEB)

    Kuisma, Elena; Hansson, C. Fredrik; Lindberg, Th. Benjamin; Gillberg, Christoffer A.; Idh, Sebastian; Schröder, Elsebeth, E-mail: schroder@chalmers.se [Quantum Device Physics Laboratory, Microtechnology and Nanoscience (MC2), Chalmers University of Technology, SE-412 96 Göteborg (Sweden)

    2016-05-14

    Chlorinated hydrocarbon compounds are of environmental concerns, since they are toxic to humans and other mammals, and are widespread, and exposure is hard to avoid. Understanding and improving methods to reduce the amount of the substances are important. We present an atomic-scale calculational study of the adsorption of chlorine-based substance chloroform (CHCl{sub 3}) on graphene oxide, as a step in estimating the capacity of graphene oxide for filtering out such substances, e.g., from drinking water. The calculations are based on density functional theory, and the recently developed consistent-exchange functional for the van der Waals density-functional method is employed. We obtain values of the chloroform adsorption energy varying from roughly 0.2 to 0.4 eV per molecule. This is comparable to previously found results for chloroform adsorbed directly on clean graphene, using similar calculations. In a wet environment, like filters for drinking water, the graphene will not stay clean and will likely oxidize, and thus adsorption onto graphene oxide, rather than clean graphene, is a more relevant process to study.

  1. Heritability of Biomarkers of Oxidized Lipoproteins: Twin Pair Study.

    Science.gov (United States)

    Rao, Fangwen; Schork, Andrew J; Maihofer, Adam X; Nievergelt, Caroline M; Marcovina, Santica M; Miller, Elizabeth R; Witztum, Joseph L; O'Connor, Daniel T; Tsimikas, Sotirios

    2015-07-01

    To determine whether biomarkers of oxidized lipoproteins are genetically determined. Lipoprotein(a) (Lp[a]) is a heritable risk factor and carrier of oxidized phospholipids (OxPL). We measured oxidized phospholipids on apolipoprotein B-containing lipoproteins (OxPL-apoB), Lp(a), IgG, and IgM autoantibodies to malondialdehyde-modified low-density lipoprotein, copper oxidized low-density lipoprotein, and apoB-immune complexes in 386 monozygotic and dizygotic twins to estimate trait heritability (h(2)) and determine specific genetic effects among traits. A genome-wide linkage study followed by genetic association was performed. The h(2) (scale: 0-1) for Lp(a) was 0.91±0.01 and for OxPL-apoB 0.87±0.02, which were higher than physiological, inflammatory, or lipid traits. h(2) of IgM malondialdehyde-modified low-density lipoprotein, copper oxidized low-density lipoprotein, and apoB-immune complexes were 0.69±0.04, 0.67±0.05, and 0.80±0.03, respectively, and for IgG malondialdehyde-modified low-density lipoprotein, copper oxidized low-density lipoprotein, and apoB-immune complexes 0.62±0.05, 0.52±0.06, and 0.53±0.06, respectively. There was an inverse correlation between the major apo(a) isoform and OxPL-apoB (R=-0.49; Plipoprotein and copper oxidized low-density lipoprotein, and apoB-immune complexes. Sib-pair genetic linkage of the Lp(a) trait revealed that single nucleotide polymorphism rs10455872 was significantly associated with OxPL-apoB after adjusting for Lp(a). OxPL-apoB and other biomarkers of oxidized lipoproteins are highly heritable cardiovascular risk factors that suggest novel genetic origins of atherothrombosis. © 2015 American Heart Association, Inc.

  2. A comparison study between ZnO nanorods coated with graphene oxide and reduced graphene oxide

    International Nuclear Information System (INIS)

    Ding, Jijun; Wang, Minqiang; Deng, Jianping; Gao, Weiyin; Yang, Zhi; Ran, Chenxin; Zhang, Xiangyu

    2014-01-01

    Highlights: • Optical properties between ZnO-GO and ZnO-RGO composites were compared. • Photoluminescence quenching was observed in ZnO-GO composites. • We obtained enhanced photoluminescence in ZnO-RGO composites. -- Abstract: ZnO nanorods (ZnO NRs) coated with graphene oxide (ZnO-GO) and reduced graphene oxide sheets (ZnO-RGO) were prepared on indium tin oxide (ITO) substrates. The crystal structures, morphology and optical properties were analyzed by using X-ray diffraction (XRD) pattern, scanning electron microscopy (SEM) images, absorption spectra and photoluminescence (PL) spectra, respectively. A comparison between PL properties from ZnO-GO and ZnO-RGO were studied. Results indicated that the peak at 442 nm and a broad band at 450–600 nm of ZnO NRs show PL quenching after coating with GO sheets. As coating with RGO sheets, the extent of PL quenching increases. It is interesting to note that as ZnO NRs coated with RGO sheets, the intensity of PL peak at 390 nm significantly increased. The enhanced PL emission research in ZnO-RGO is directed toward development of the “nextgeneration” optoelectronics devices related with graphene materials

  3. Nanoscale probing of bandgap states on oxide particles using electron energy-loss spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Qianlang [School for the Engineering of Matter, Transport and Energy, Arizona State University, 85287 AZ (United States); March, Katia [Laboratoire de Physique des Solides, Bâtiment 510, Université Paris-Sud, 91405 Orsay Cedex (France); Crozier, Peter A., E-mail: CROZIER@asu.edu [School for the Engineering of Matter, Transport and Energy, Arizona State University, 85287 AZ (United States)

    2017-07-15

    Surface and near-surface electronic states were probed with nanometer spatial resolution in MgO and TiO{sub 2} anatase nanoparticles using ultra-high energy resolution electron energy-loss spectroscopy (EELS) coupled to a scanning transmission electron microscope (STEM). This combination allows the surface electronic structure determined with spectroscopy to be correlated with nanoparticle size, morphology, facet etc. By acquiring the spectra in aloof beam mode, radiation damage to the surface can be significantly reduced while maintaining the nanometer spatial resolution. MgO and TiO{sub 2} showed very different bandgap features associated with the surface/sub-surface layer of the nanoparticles. Spectral simulations based on dielectric theory and density of states models showed that a plateau feature found in the pre-bandgap region in the spectra from (100) surfaces of 60 nm MgO nanocubes is consistent with a thin hydroxide surface layer. The spectroscopy shows that this hydroxide species gives rise to a broad filled surface state at 1.1 eV above the MgO valence band. At the surfaces of TiO{sub 2} nanoparticles, pronounced peaks were observed in the bandgap region, which could not be well fitted to defect states. In this case, the high refractive index and large particle size may make Cherenkov or guided light modes the likely causes of the peaks. - Highlights: • Bandgap states detected with aloof beam monochromated EELS on oxide nanoparticle surfaces. • Dielectric theory applied to simulate the spectra and interpret surface structure. • Density of states models also be employed to understand the surface electronic structure. • In MgO, one states associate with water species was found close to the valence band edge. • In anatase, two mid-gap states associated with point defects were found.

  4. Adsorption of CO, CO2, H2, and H2O on titania surfaces with different oxidation states

    International Nuclear Information System (INIS)

    Raupp, G.B.; Dumesic, J.A.

    1985-01-01

    The adsorptive properties of titania surfaces with different oxidation states were proved by temperature-programmed desorption (TPD) of CO, H 2 , CO 2 , and H 2 O. Auger electron spectroscopy and X-ray photoelectron spectroscopy revealed that vacuum annealing an oxidized titanium foil at temperatures from 300 to 800 K was an effective means of systematically varying the average surface oxidation state from Ti 4+ to Ti 2+ . Carbon monoxide weakly adsorbed (desorption energy of 44-49 kJ x mol -1 ) in a carbonyl fashion on coordinatively unsaturated cation sites. Titania surfaces were inert with respect to H 2 adsorption and dissociation. Carbon dioxide adsorbed in a linear molecular fashion. Water adsorbed both molecularly and dissociatively. Results are discussed in terms of the role of titania oxidation state in CO hydrogenation over titania-supported metal catalysts. 74 references, 7 figures

  5. Contribution to the study of ruthenium fluorides, oxyfluorides and oxides

    International Nuclear Information System (INIS)

    Corbin, Odile.

    1982-08-01

    Studies on the dry processing of spent fuels reveal a poor ruthenium decontamination of plutonium. For a better understanding of this result a study of ruthenium fluorides, oxyfluorides and oxides is carried out here as follows: - bibliographical review; - thermochromatographic identification of the number and nature of compounds formed by fluorination of microquantities of ruthenium; - confirmation of the thermochromatographic results by two other analytical methods: thermogravimetry and infrared spectroscopy [fr

  6. Chemical states of fission products in irradiated uranium-plutonium mixed oxide fuel

    International Nuclear Information System (INIS)

    Kurosaki, Ken; Uno, Masayoshi; Yamanaka, Shinsuke

    1999-01-01

    The chemical states of fission products (FPs) in irradiated uranium-plutonium mixed oxide (MOX) fuel for the light water reactor (LWR) were estimated by thermodynamic equilibrium calculations on system of fuel and FPs by using ChemSage program. A stoichiometric MOX containing 6.1 wt. percent PuO 2 was taken as a loading fuel. The variation of chemical states of FPs was calculated as a function of oxygen potential. Some pieces of information obtained by the calculation were compared with the results of the post-irradiation examination (PIE) of UO 2 fuel. It was confirmed that the multicomponent and multiphase thermodynamic equilibrium calculation between fuel and FPs system was an effective tool for understanding the behavior of FPs in fuel. (author)

  7. Origin of major donor states in In–Ga–Zn oxide

    Energy Technology Data Exchange (ETDEWEB)

    Nakashima, Motoki; Oota, Masashi; Ishihara, Noritaka; Nonaka, Yusuke; Hirohashi, Takuya; Takahashi, Masahiro; Yamazaki, Shunpei [Semiconductor Energy Laboratory Co., Ltd., 398 Hase, Atsugi, Kanagawa 243-0036 (Japan); Obonai, Toshimitsu; Hosaka, Yasuharu; Koezuka, Junichi [Advanced Film Device Inc., 161-2 Masuzuka, Tsuga-machi, Tochigi, Tochigi 328-0114 (Japan)

    2014-12-07

    To clarify the origin of the major donor states in indium gallium zinc oxide (IGZO), we report measurement results and an analysis of several physical properties of IGZO thin films. Specifically, the concentration of H atoms and O vacancies (V{sub O}), carrier concentration, and conductivity are investigated by hard X-ray photoelectron spectroscopy, secondary ion mass spectroscopy, thermal desorption spectroscopy, and Hall effect measurements. The results of these experiments suggest that the origin of major donor states is H occupancy of V{sub O} sites. Furthermore, we use first-principles calculations to investigate the influence of the coexistence of V{sub O} and H in crystalline InGaO{sub 3}(ZnO){sub m} (m = 1). The results indicate that when H is trapped in V{sub O}, a stable complex is created that serves as a shallow-level donor.

  8. Solid-State Electrochromic Device Consisting of Amorphous WO3 and Various Thin Oxide Layers

    Science.gov (United States)

    Shizukuishi, Makoto; Shimizu, Isamu; Inoue, Eiichi

    1980-11-01

    A mixed oxide containing Cr2O3 was introduced into an amorphous WO3 solid-state electrochromic device (ECD) in order to improve its colour memory effect. The electrochromic characteristics were greatly affected by the chemical constituents of a dielectric layer on the a-WO3 layer. Particularly, long memory effect and low power dissipation were attained in a solid-state ECD consisting of a-WO3 and Cr2O3\\cdotV2O5(50 wt.%). Some electrochromic characteristics of the a-WO3/Cr2O3\\cdotV2O5 ECD and the role of V2O5 were investigated.

  9. Long-living positron and positronium states in zeolites and microcrystalline oxides

    International Nuclear Information System (INIS)

    Kajcsos, Zs.; Liszkay, L.; Varga, L.; Lohonyai, L.; Lazar, K.

    1995-01-01

    Positron annihilation (PA) investigation were performed on zeolites (X, Y and ZSM-5) and on microcrystalline MgO, Al 2 O 3 and SiO 2 , providing long lifetime components attributed to o-Ps atoms. In addition to the positron lifetime (LT) measurements, the energy distribution (ED) of the annihilation gamma radiation spectrum was recorded in the 30 keV - 1.5 MeV range for different samples and was compared to reference distributions for Si and GaAs samples, where no long-living Ps states are formed. Apart from the strong correlation with the water content in the samples, the positron data collected testify much more pronounced positronium hosting features for powders of the mentioned oxides than for zeolites. Positron LT spectroscopy combined with recording of the ED of the annihilation radiation provides reliable information on the forming of long living 3γ states. (author) 15 refs.; 4 figs

  10. Probing the transition state region in catalytic CO oxidation on Ru

    Energy Technology Data Exchange (ETDEWEB)

    Ostrom, H. [Stockholm Univ. (Sweden); Oberg, H. [Stockholm Univ. (Sweden); Xin, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); LaRue, J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Beye, M. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Dell' Angela, M. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Gladh, J. [Stockholm Univ. (Sweden); Ng, M. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Sellberg, J. A. [Stockholm Univ. (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States); Kaya, S. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Mercurio, G. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Nordlund, D. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Hantschmann, M. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Hieke, F. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Kuhn, D. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Schlotter, W. F. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Dakovski, G. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Turner, J. J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Minitti, M. P. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Mitra, A. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Moeller, S. P. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Fohlisch, A. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Univ. Potsdam, Potsdam (Germany); Wolf, M. [Fritz-Haber Institute of the Max-Planck-Society, Berlin (Germany); Wurth, W. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); DESY Photon Science, Hamburg (Germany); Persson, M. [The Univ. of Liverpool, Liverpool (United Kingdom); Norskov, J. K. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Abild-Pedersen, F. [Stanford Univ., Stanford, CA (United States); Ogasawara, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Pettersson, L. G. M. [Stockholm Univ. (Sweden); Nilsson, A. [Stockholm Univ. (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

    2015-02-12

    Femtosecond x-ray laser pulses are used to probe the CO oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and O on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC–O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.

  11. Oxidative stress markers in hypertensive states of pregnancy: preterm and term disease.

    Directory of Open Access Journals (Sweden)

    Lesia Olha Kurlak

    2014-08-01

    Full Text Available Discussion continues as to whether de novo hypertension in pregnancy with significant proteinuria (pre-eclampsia; PE and non-proteinuric new hypertension (gestational hypertension; GH are parts of the same disease spectrum or represent different conditions. Non-pregnant hypertension, pregnancy and PE are all associated with oxidative stress. We have established a 6 weeks post-partum clinic for women who experienced a hypertensive pregnancy. We hypothesized that PE and GH could be distinguished by markers of oxidative stress; thiobarbituric acid reactive substances (TBARS and antioxidants (ferric ion reducing ability of plasma; FRAP. Since the severity of PE and GH is greater pre-term, we also compared pre-term and term disease. Fifty-eight women had term PE, 23 pre-term PE, 60 had term GH and 6 pre-term GH, 11 pre-existing (essential hypertension (EH without PE. Limited data were available from normotensive pregnancies (n=7 and non-pregnant controls (n=14. There were no differences in postpartum TBARS or FRAP between hypertensive states; TBARS (P=0.001 and FRAP (P=0.009 were lower in plasma of non-pregnant controls compared to recently-pregnant women. Interestingly FRAP was higher in preterm than term GH (P=0.013. In PE and GH, TBARS correlated with low density lipoprotein (LDL-cholesterol (P=0.036; this association strengthened with inclusion of EH ((P=0.011. The 10 year Framingham index for cardiovascular risk was positively associated with TBARS (P=0.003.Oxidative stress profiles do not differ between hypertensive states but appear to distinguish between recently-pregnant and non-pregnant states. This suggests that pregnancy may alter vascular integrity with changes remaining 6 weeks postpartum. LDL-cholesterol is a known determinant of oxidative stress in cardiovascular disease and we have shown this association to be present in hypertensive pregnancy further emphasizing that such a pregnancy may be revealing a pre-existing cardiovascular

  12. Obesity-Associated Oxidative Stress: Strategies Finalized to Improve Redox State

    Directory of Open Access Journals (Sweden)

    Valeria Gasperi

    2013-05-01

    Full Text Available Obesity represents a major risk factor for a plethora of severe diseases, including diabetes, cardiovascular disease, non-alcoholic fatty liver disease, and cancer. It is often accompanied by an increased risk of mortality and, in the case of non-fatal health problems, the quality of life is impaired because of associated conditions, including sleep apnea, respiratory problems, osteoarthritis, and infertility. Recent evidence suggests that oxidative stress may be the mechanistic link between obesity and related complications. In obese patients, antioxidant defenses are lower than normal weight counterparts and their levels inversely correlate with central adiposity; obesity is also characterized by enhanced levels of reactive oxygen or nitrogen species. Inadequacy of antioxidant defenses probably relies on different factors: obese individuals may have a lower intake of antioxidant- and phytochemical-rich foods, such as fruits, vegetables, and legumes; otherwise, consumption of antioxidant nutrients is normal, but obese individuals may have an increased utilization of these molecules, likewise to that reported in diabetic patients and smokers. Also inadequate physical activity may account for a decreased antioxidant state. In this review, we describe current concepts in the meaning of obesity as a state of chronic oxidative stress and the potential interventions to improve redox balance.

  13. Obesity-Associated Oxidative Stress: Strategies Finalized to Improve Redox State

    Science.gov (United States)

    Savini, Isabella; Catani, Maria Valeria; Evangelista, Daniela; Gasperi, Valeria; Avigliano, Luciana

    2013-01-01

    Obesity represents a major risk factor for a plethora of severe diseases, including diabetes, cardiovascular disease, non-alcoholic fatty liver disease, and cancer. It is often accompanied by an increased risk of mortality and, in the case of non-fatal health problems, the quality of life is impaired because of associated conditions, including sleep apnea, respiratory problems, osteoarthritis, and infertility. Recent evidence suggests that oxidative stress may be the mechanistic link between obesity and related complications. In obese patients, antioxidant defenses are lower than normal weight counterparts and their levels inversely correlate with central adiposity; obesity is also characterized by enhanced levels of reactive oxygen or nitrogen species. Inadequacy of antioxidant defenses probably relies on different factors: obese individuals may have a lower intake of antioxidant- and phytochemical-rich foods, such as fruits, vegetables, and legumes; otherwise, consumption of antioxidant nutrients is normal, but obese individuals may have an increased utilization of these molecules, likewise to that reported in diabetic patients and smokers. Also inadequate physical activity may account for a decreased antioxidant state. In this review, we describe current concepts in the meaning of obesity as a state of chronic oxidative stress and the potential interventions to improve redox balance. PMID:23698776

  14. Influence of Structure and Charge State on the Mechanism of CO Oxidation on Gold Clusters

    Science.gov (United States)

    Johnson, Grant; Burgel, Christian; Reilly, Nelly; Mitric, Roland; Kimble, Michele; Tyo, Eric; Castleman, A. W.; Bonacic-Koutecky, Vlasta

    2008-05-01

    Gas-phase reactivity experiments and high level theoretical calculations have been employed to study the interaction of both positively and negatively charged gold oxide clusters with carbon monoxide (CO). We demonstrate that for negatively charged clusters CO is oxidized to CO2 by an Eley-Ridel-like (ER-) mechanism involving the attack of CO on oxygen rather than gold. In contrast, for positively charged clusters, the oxidation reaction may also occur by a Langmuir-Hinshelwood-like (LH-) mechanism involving the initial binding of CO to a gold atom followed by subsequent migration to an oxygen site. The LH mechanism is made possible through the large energy gain associated with the adsorption of two CO molecules onto cationic gold clusters. Structure-reactivity relationships are also established which demonstrate that terminally bound oxygen atoms are the most active sites for CO oxidation. Bridge bonded oxygen atoms and molecularly bound O2 units are shown to be inert. We also establish an inverse relationship between the binding energy of CO to gold clusters and the energy of the clusters lowest unoccupied molecular orbital (LUMO).

  15. Final Report for research grant "Development of Methods for High Specific Activity Labeling of Biomolecules Using Astatine-211 in Different Oxidation States"

    Energy Technology Data Exchange (ETDEWEB)

    Wilbur, D. Scott [Univ. of Washington, Seattle, WA (United States)

    2011-12-14

    The overall objective of this research effort was to develop methods for labeling biomolecules with higher oxidation state species of At-211. This was to be done in an effort to develop reagents that had higher in vivo stability than the present carbon-bonded At-211-labeled compounds. We were unsuccessful in that effort, as none of the approaches studied provided reagents that were stable to in vivo deastatination. However, we gained a lot of information about At-211 in higher oxidation states. The studies proved to be very difficult as small changes in pH and other conditions appeared to change the nature of the species that obtained (by HPLC retention time analyses), with many of the species being unidentifiable. The fact that there are no stable isotopes of astatine, and the chemistry of the nearest halogen iodine is quite different, made it very difficult to interpret results of some experiments. With that said, we believe that a lot of valuable information was obtained from the studies. The research effort evaluated: (1) methods for chemical oxidation of At-211, (2) approaches to chelation of oxidized At-211, and (3) approaches to oxidation of astatophenyl compounds. A major hurdle that had to be surmounted to conduct the research was the development of HPLC conditions to separate and identify the various oxidized species formed. Attempts to develop conditions for separation of iodine and astatine species by normal and reversed-phase TLC and ITLC were not successful. However, we were successful in developing conditions (from a large number of attempts) to separate oxidized forms of iodine ([I-125]iodide, [I-125]iodate and [I-125]periodate) and astatine ([At-211]astatide, [At-211]astatate, [At-211]perastatate, and several unidentified At-211 species). Information on the basic oxidation and characterization of At-211 species is provided under Objective 1. Conditions were developed to obtain new At-211 labeling method where At-211 is chelated with the DOTA and

  16. MECHANISTIC STUDY OF COLCHICINE’s ELECTROCHEMICAL OXIDATION

    International Nuclear Information System (INIS)

    Bodoki, Ede; Chira, Ruxandra; Zaharia, Valentin; Săndulescu, Robert

    2015-01-01

    Colchicine, as one of the most ancient drugs of human kind, is still in the focal point of the current research due to its multimodal mechanism of action. The elucidation of colchicine’s still unknown redox properties may play an important role in deciphering its beneficial and harmful implications over the human body. Therefore, a systematic mechanistic study of colchicine’s oxidation has been undertaken by electrochemistry coupled to mass spectrometry using two different types of electrolytic cells, in order to clarify the existing inconsistencies with respect to this topic. At around 1 V vs. Pd/H 2 , initiated by a one-electron transfer, the oxidation of colchicine sets off leading to a cation radical, whose further oxidation may evolve on several different pathways. The main product of the anodic electrochemical reaction, regardless of the carrier solution’s pH is represented by a 7-hydroxy derivative of colchicine. At more anodic potentials (above 1.4 V vs. Pd/H 2 ) compounds arising from epoxidation and/or multiple hydroxylation occur. No di- or tridemethylated quinone structures, as previously suggested in the literature for the electrolytic oxidation of colchicine, has been detected in the mass spectra.

  17. Molecular modeling studies of oleate adsorption on iron oxides

    Energy Technology Data Exchange (ETDEWEB)

    Rath, Swagat S. [CSIR-Institute of Minerals and Materials Technology, Bhubaneswar (India); Sinha, Nishant [Accelrys K.K, Bengaluru (India); Sahoo, Hrushikesh [CSIR-Institute of Minerals and Materials Technology, Bhubaneswar (India); Das, Bisweswar, E-mail: bdas@immt.res.in [CSIR-Institute of Minerals and Materials Technology, Bhubaneswar (India); Mishra, Barada Kanta [CSIR-Institute of Minerals and Materials Technology, Bhubaneswar (India)

    2014-03-01

    Graphical abstract: - Highlights: • Plane wave periodic DFT study of oleate-iron oxide interaction. • Magnetite-oleate complex is more stable than hematite and goethite. • Flotation recovery of magnetite is more compared to the other two oxides. - Abstract: Comparative studies of oleate interaction with hematite, magnetite and goethite using density functional calculations are presented. The approach is illustrated by carrying out geometric optimization of oleate on the stable and most exposed planes of hematite, magnetite, and goethite. Interaction energies for oleate-mineral surface have been determined, based on which, magnetite is found to be forming the most stable complex with oleate. Trend as obtained from the quantum chemical calculations has been validated by contact angle measurements and flotation studies on hematite, magnetite and goethite with sodium oleate at different pH and collector concentrations.

  18. Molecular modeling studies of oleate adsorption on iron oxides

    International Nuclear Information System (INIS)

    Rath, Swagat S.; Sinha, Nishant; Sahoo, Hrushikesh; Das, Bisweswar; Mishra, Barada Kanta

    2014-01-01

    Graphical abstract: - Highlights: • Plane wave periodic DFT study of oleate-iron oxide interaction. • Magnetite-oleate complex is more stable than hematite and goethite. • Flotation recovery of magnetite is more compared to the other two oxides. - Abstract: Comparative studies of oleate interaction with hematite, magnetite and goethite using density functional calculations are presented. The approach is illustrated by carrying out geometric optimization of oleate on the stable and most exposed planes of hematite, magnetite, and goethite. Interaction energies for oleate-mineral surface have been determined, based on which, magnetite is found to be forming the most stable complex with oleate. Trend as obtained from the quantum chemical calculations has been validated by contact angle measurements and flotation studies on hematite, magnetite and goethite with sodium oleate at different pH and collector concentrations

  19. Kinetic Study of Hydroxyl and Sulfate Radical-Mediated Oxidation of Pharmaceuticals in Wastewater Effluents.

    Science.gov (United States)

    Lian, Lushi; Yao, Bo; Hou, Shaodong; Fang, Jingyun; Yan, Shuwen; Song, Weihua

    2017-03-07

    Advanced oxidation processes (AOPs), such as hydroxyl radical (HO • )- and sulfate radical (SO 4 •- )-mediated oxidation, are alternatives for the attenuation of pharmaceuticals and personal care products (PPCPs) in wastewater effluents. However, the kinetics of these reactions needs to be investigated. In this study, kinetic models for 15 PPCPs were built to predict the degradation of PPCPs in both HO • - and SO 4 •- -mediated oxidation. In the UV/H 2 O 2 process, a simplified kinetic model involving only steady state concentrations of HO • and its biomolecular reaction rate constants is suitable for predicting the removal of PPCPs, indicating the dominant role of HO • in the removal of PPCPs. In the UV/K 2 S 2 O 8 process, the calculated steady state concentrations of CO 3 •- and bromine radicals (Br • , Br 2 •- and BrCl •- ) were 600-fold and 1-2 orders of magnitude higher than the concentrations of SO 4 •- , respectively. The kinetic model, involving both SO 4 •- and CO 3 •- as reactive species, was more accurate for predicting the removal of the 9 PPCPs, except for salbutamol and nitroimidazoles. The steric and ionic effects of organic matter toward SO 4 •- could lead to overestimations of the removal efficiencies of the SO 4 •- -mediated oxidation of nitroimidazoles in wastewater effluents.

  20. Oxidation of tertiary amines by cytochrome p450-kinetic isotope effect as a spin-state reactivity probe.

    Science.gov (United States)

    Li, Chunsen; Wu, Wei; Cho, Kyung-Bin; Shaik, Sason

    2009-08-24

    Two types of tertiary amine oxidation processes, namely, N-dealkylation and N-oxygenation, by compound I (Cpd I) of cytochrome P450 are studied theoretically using hybrid DFT calculations. All the calculations show that both N-dealkylation and N-oxygenation of trimethylamine (TMA) proceed preferentially from the low-spin (LS) state of Cpd I. Indeed, the computed kinetic isotope effects (KIEs) for the rate-controlling hydrogen abstraction step of dealkylation show that only the KIE(LS) fits the experimental datum, whereas the corresponding value for the high-spin (HS) process is much higher. These results second those published before for N,N-dimethylaniline (DMA), and as such, they further confirm the conclusion drawn then that KIEs can be a sensitive probe of spin state reactivity. The ferric-carbinolamine of TMA decomposes most likely in a non-enzymatic reaction since the Fe-O bond dissociation energy (BDE) is negative. The computational results reveal that in the reverse reaction of N-oxygenation, the N-oxide of aromatic amine can serve as a better oxygen donor than that of aliphatic amine to generate Cpd I. This capability of the N-oxo derivatives of aromatic amines to transfer oxygen to the heme, and thereby generate Cpd I, is in good accord with experimental data previously reported.

  1. High resolution studies of barium Rydberg states

    International Nuclear Information System (INIS)

    Eliel, E.R.

    1982-01-01

    The subtle structure of Rydberg states of barium with orbital angular momentum 0, 1, 2 and 3 is investigated. Some aspects of atomic theory for a configuration with two valence electrons are reviewed. The Multi Channel Quantum Defect Theory (MQDT) is concisely introduced as a convenient way to describe interactions between Rydberg series. Three high-resolution UV studies are presented. The first two, presenting results on a transition in indium and europium serve as an illustration of the frequency doubling technique. The third study is of hyperfine structure and isotope shifts in low-lying p states in Sr and Ba. An extensive study of the 6snp and 6snf Rydberg states of barium is presented with particular emphasis on the 6snf states. It is shown that the level structure cannot be fully explained with the model introduced earlier. Rather an effective two-body spin-orbit interaction has to be introduced to account for the observed splittings, illustrating that high resolution studies on Rydberg states offer an unique opportunity to determine the importance of such effects. Finally, the 6sns and 6snd series are considered. The hyperfine induced isotope shift in the simple excitation spectra to 6sns 1 S 0 is discussed and attention is paid to series perturbers. It is shown that level mixing parameters can easily be extracted from the experimental data. (Auth.)

  2. Water Sorption and Gamma Radiolysis Studies for Uranium Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Icenhour, A.S.

    2002-02-27

    During the development of a standard for the safe, long-term storage of {sup 233}U-containing materials, several areas were identified that needed additional experimental studies. These studies were related to the perceived potential for the radiolytic generation of large pressures or explosive concentrations of gases in storage containers. This report documents the results of studies on the sorption of water by various uranium oxides and on the gamma radiolysis of uranium oxides containing various amounts of sorbed moisture. In all of the experiments, {sup 238}U was used as a surrogate for the {sup 233}U. For the water sorption experiments, uranium oxide samples were prepared and exposed to known levels of humidity to establish the water uptake rate. Subsequently, the amount of water removed was studied by heating samples in a oven at fixed temperatures and by thermogravimetric analysis (TGA)/differential thermal analysis (DTA). It was demonstrated that heating at 650 C adequately removes all moisture from the samples. Uranium-238 oxides were irradiated in a {sup 60}Co source and in the high-gamma-radiation fields provided by spent nuclear fuel elements of the High Flux Isotope Reactor. For hydrated samples of UO{sub 3}, H{sub 2} was the primary gas produced; but the total gas pressure increase reached steady value of about 10 psi. This production appears to be a function of the dose and the amount of water present. Oxygen in the hydrated UO{sub 3} sample atmosphere was typically depleted, and no significant pressure rise was observed. Heat treatment of the UO{sub 3} {center_dot} xH{sub 2}O at 650 C would result in conversion to U{sub 3}O{sub 8} and eliminate the H{sub 2} production. For all of the U{sub 3}O{sub 8} samples loaded in air and irradiated with gamma radiation, a pressure decrease was seen and little, if any, H{sub 2} was produced--even for samples with up to 9 wt % moisture content. Hence, these results demonstrated that the efforts to remove trace

  3. Mechanistic interaction study of thin oxide dielectric with conducting organic electrode

    International Nuclear Information System (INIS)

    Sharma, Himani; Sethi, Kanika; Raj, P. Markondeya; Gerhardt, R.A.; Tummala, Rao

    2012-01-01

    Highlights: ► Thin film-oxide dielectric-organic electrode interface studies for investigating the leakage mechanism. ► XPS to elucidate chemical-structural changes on dielectric oxide surface. ► Correlates structural characterization data with capacitor leakage current and impedance spectroscopy characteristics. - Abstract: This paper aims at understanding the interaction of intrinsic conducting polymer, PEDT, with ALD-deposited Al 2 O 3 and thermally oxidized Ta 2 O 5 dielectrics, and the underlying mechanisms for increase in leakage currents in PEDT-based capacitors. Conducting polymers offer several advantages as electrodes for high surface area capacitors because of their lower resistance, self-healing and enhanced conformality. However, capacitors with in situ polymerized PEDT show poor electrical properties that are attributed to the interfacial interaction between the organic electrode and the oxide dielectric. This study focuses on characterizing these interactions. A combination of compositional, structural and electrical characterization techniques was applied to polymer-solid-state-capacitor to understand the interfacial chemical behavior and dielectric property deterioration of alumina and tantalum-oxide films. XPS and impedance studies were employed to understand the stiochiometric and compositional changes that occur in the dielectric film on interaction with in situ deposited PEDT. Based on the observations from several complimentary techniques, it is concluded that tantalum-pentoxide has more resistance towards chemical interaction with in situ polymerized PEDT. The thermally oxidized Ta 2 O 5 -PEDT system showed leakage current of 280 nA μF −1 at 3 V with a breakdown voltage of 30 V. On the other hand, Al 2 O 3 -PEDT capacitor showed leakage current of 50 μA μF −1 and a breakdown voltage of 40 V. The study reports direct evidence for the mechanism of resistivity drop in alumina dielectric with in situ polymerized PEDT electrode.

  4. An unusual high-spin ground state of Co3+ in octahedral coordination in brownmillerite-type cobalt oxide.

    Science.gov (United States)

    Istomin, S Ya; Tyablikov, O A; Kazakov, S M; Antipov, E V; Kurbakov, A I; Tsirlin, A A; Hollmann, N; Chin, Y Y; Lin, H-J; Chen, C T; Tanaka, A; Tjeng, L H; Hu, Z

    2015-06-21

    The crystal and magnetic structures of brownmillerite-like Sr(2)Co(1.2)Ga(0.8)O(5) with a stable Co(3+) oxidation state at both octahedral and tetrahedral sites are refined using neutron powder diffraction data collected at 2 K (S.G. Icmm, a = 5.6148(6) Å, b = 15.702(2) Å, c = 5.4543(6) Å; R(wp) = 0.0339, R(p) = 0.0443, χ(2) = 0.775). The very large tetragonal distortion of CoO(6) octahedra (1.9591(4) Å for Co-O(eq) and 2.257(6) Å for Co-O(ax)) could be beneficial for the stabilization of the long-sought intermediate-spin state of Co(3+) in perovskite-type oxides. However, the large magnetic moment of octahedral Co(3+) (3.82(7)μ(B)) indicates the conventional high-spin state of Co(3+) ions, which is further supported by the results of a combined theoretical and experimental soft X-ray absorption spectroscopy study at the Co-L(2,3) edges on Sr(2)Co(1.2)Ga(0.8)O(5). A high-spin ground state of Co(3+) in Sr(2)Co(1.2)Ga(0.8)O(5) resulted in much lower in comparison with a LaCoO(3) linear thermal expansion coefficient of 13.1 ppm K(-1) (298-1073 K) determined from high-temperature X-ray powder diffraction data collected in air.

  5. Cellulose nanofibril/reduced graphene oxide/carbon nanotube hybrid aerogels for highly flexible and all-solid-state supercapacitors

    Science.gov (United States)

    Qifeng Zheng; Zhiyong Cai; Zhenqiang Ma; Shaoqin Gong

    2015-01-01

    A novel type of highly flexible and all-solid-state supercapacitor that uses cellulose nanofibril (CNF)/reduced graphene oxide (RGO)/carbon nanotube (CNT) hybrid aerogels as electrodes and H2SO4 poly (vinyl alcohol) PVA gel as the electrolyte was developed and is reported here. These flexible solid-state supercapacitors...

  6. The GC/AED studies on the reactions of sulfur mustard with oxidants

    International Nuclear Information System (INIS)

    Popiel, StanisIaw; Witkiewicz, Zygfryd; Szewczuk, Aleksander

    2005-01-01

    A gas chromatograph coupled with an atomic emission detector was used to identify and to determine the products formed on oxidation of sulfur mustard. The oxidation rate and the resulting oxidates were studied in relation to oxidant type and reaction medium parameters. Hydrogen peroxide, sodium hypochlorite, sodium perborate, potassium monopercarbonate, ammonium peroxydisulfate, potassium peroxymonosulfate (oxone), and tert-butyl peroxide were used as oxidants. Oxidations were run in aqueous media or in solvents of varying polarities. The oxidation rate was found to be strongly related to oxidant type: potassium peroxymonosulfate (oxone) and sodium hypochlorite were fast-acting oxidants; sodium perborate, hydrogen peroxide, ammonium peroxydisulfate, and sodium monopercarbonate were moderate oxidants; tert-butyl peroxide was the slowest-acting oxidant. In non-aqueous solvents, the oxidation rate was strongly related to solvent polarity. The higher the solvent polarity, the faster the oxidation rate. In the acid and neutral media, the mustard oxidation rates were comparable. In the alkaline medium, oxidation was evidently slower. A suitable choice of the initial oxidant-to-mustard concentration ratio allowed to control the type of the resulting mustard oxidates. As the pH of the reaction medium was increased, the reaction of elimination of hydrogen chloride from mustard oxidates becomes more and more intensive

  7. Healthy Dietary Patterns and Oxidative Stress as Measured by Fluorescent Oxidation Products in Nurses’ Health Study

    Directory of Open Access Journals (Sweden)

    Seungyoun Jung

    2016-09-01

    Full Text Available Healthy diets may lower oxidative stress and risk of chronic diseases. However, no previous studies examined associations between diet and fluorescent oxidation products (FlOP, a global marker of oxidative stress. We evaluated associations between healthy eating patterns (Alternative Healthy Eating Index (AHEI, Dietary Approach to Stop Hypertension (DASH, and Alternate Mediterranean Diet (aMED and FlOP, measured at three excitation/emission wavelengths (FlOP_360, FlOP_320, FlOP_400 from 2021 blood samples collected from 1688 women within the Nurses’ Health Study. AHEI, DASH, and aMED scores were significantly positively associated with FlOP_360 and FlOP_320 concentrations (p-trend ≤ 0.04, but not associated with FlOP_400. Among specific food groups that contribute to these diet scores, significantly positive associations were observed with legumes and vegetables for FlOP_360, vegetables and fruits for FlOP_320, and legumes and alcohol for FlOP_400. Inverse associations were observed with nuts, sweets or desserts, and olive oil for FlOP_360, nuts for FlOP_320 and sweets or desserts for FlOP_400 (all p-trend ≤ 0.05. However, FlOP variation due to diet was small compared to overall FlOP variation. In conclusion, AHEI, DASH, and aMED scores were unexpectedly positively, but weakly, associated with FlOP_360 and FlOP_320. However, these findings should be interpreted cautiously as the determinants of FlOP concentrations are not fully understood.

  8. Healthy Dietary Patterns and Oxidative Stress as Measured by Fluorescent Oxidation Products in Nurses' Health Study.

    Science.gov (United States)

    Jung, Seungyoun; Smith-Warner, Stephanie A; Willett, Walter C; Wang, Molin; Wu, Tianying; Jensen, Majken; Hankinson, Susan E; Eliassen, A Heather

    2016-09-21

    Healthy diets may lower oxidative stress and risk of chronic diseases. However, no previous studies examined associations between diet and fluorescent oxidation products (FlOP), a global marker of oxidative stress. We evaluated associations between healthy eating patterns (Alternative Healthy Eating Index (AHEI), Dietary Approach to Stop Hypertension (DASH), and Alternate Mediterranean Diet (aMED)) and FlOP, measured at three excitation/emission wavelengths (FlOP_360, FlOP_320, FlOP_400) from 2021 blood samples collected from 1688 women within the Nurses' Health Study. AHEI, DASH, and aMED scores were significantly positively associated with FlOP_360 and FlOP_320 concentrations ( p -trend ≤ 0.04), but not associated with FlOP_400. Among specific food groups that contribute to these diet scores, significantly positive associations were observed with legumes and vegetables for FlOP_360, vegetables and fruits for FlOP_320, and legumes and alcohol for FlOP_400. Inverse associations were observed with nuts, sweets or desserts, and olive oil for FlOP_360, nuts for FlOP_320 and sweets or desserts for FlOP_400 (all p -trend ≤ 0.05). However, FlOP variation due to diet was small compared to overall FlOP variation. In conclusion, AHEI, DASH, and aMED scores were unexpectedly positively, but weakly, associated with FlOP_360 and FlOP_320. However, these findings should be interpreted cautiously as the determinants of FlOP concentrations are not fully understood.

  9. Thermochemical study of MoS2 oxidation

    International Nuclear Information System (INIS)

    Filimonov, D.S.; Topor, N.D.; Kesler, Ya.A.

    1990-01-01

    Thermochemical studies of oxidation processes of metallic molybdenum, sulfur, molybdenum disulfide under different conditions in microcalorimeter are conducted. Values of thermal effects which are used to calculate standard formation enthalpy of MoS 2 and which correlate well are obtained. Δ f H 0 (MoS 2 ,298.15 K) recommended value constitutes (-223.0±16.7) kJ/mol

  10. Study of comportment of trioctylphosphine oxide by coat slight chromatography

    International Nuclear Information System (INIS)

    Meddour, Laaldja; Azzouz Abdelkrim

    1996-04-01

    The synthesis and characterisation process of the extractant agent 'Trioctylphosphine oxide' (TOPO) are not very developped in the literature. However, in order to identify this agent (TOPO) in its synthesis process, we attempt several analysis methods. The coat slight chromatography proves the simple and accessible method, that explains the choice of this study. In the present work, we have analysed the TOPO by coat slight chromatography with the intention of finding a better solvent

  11. Quantum State-Resolved Collision Dynamics of Nitric Oxide at Ionic Liquid and Molten Metal Surfaces

    Science.gov (United States)

    Zutz, Amelia Marie

    Detailed molecular scale interactions at the gas-liquid interface are explored with quantum state-to-state resolved scattering of a jet-cooled beam of NO(2pi1/2; N = 0) from ionic liquid and molten metal surfaces. The scattered distributions are probed via laser-induced fluorescence methods, which yield rotational and spin-orbit state populations that elucidate the dynamics of energy transfer at the gas-liquid interface. These collision dynamics are explored as a function of incident collision energy, surface temperature, scattering angle, and liquid identity, all of which are found to substantially affect the degree of rotational, electronic and vibrational excitation of NO via collisions at the liquid surface. Rotational distributions observed reveal two distinct scattering pathways, (i) molecules that trap, thermalize and eventually desorb from the surface (trapping-desorption, TD), and (ii) those that undergo prompt recoil (impulsive scattering, IS) prior to complete equilibration with the liquid surface. Thermally desorbing NO molecules are found to have rotational temperatures close to, but slightly cooler than the surface temperature, indicative of rotational dependent sticking probabilities on liquid surfaces. Nitric oxide is a radical with multiple low-lying electronic states that serves as an ideal candidate for exploring nonadiabatic state-changing collision dynamics at the gas-liquid interface, which induce significant excitation from ground (2pi1/2) to excited (2pi 3/2) spin-orbit states. Molecular beam scattering of supersonically cooled NO from hot molten metals (Ga and Au, Ts = 300 - 1400 K) is also explored, which provide preliminary evidence for vibrational excitation of NO mediated by thermally populated electron-hole pairs in the hot, conducting liquid metals. The results highlight the presence of electronically nonadiabatic effects and build toward a more complete characterization of energy transfer dynamics at gas-liquid interfaces.

  12. Studies on yttrium oxide coatings for corrosion protection against molten uranium

    International Nuclear Information System (INIS)

    Chakravarthy, Y.; Bhandari, Subhankar; Pragatheeswaran; Thiyagarajan, T.K.; Ananthapadmanabhan, P.V.; Das, A.K.; Kumar, Jay; Kutty, T.R.G.

    2012-01-01

    Yttrium oxide is resistant to corrosion by molten uranium and its alloys. Yttrium oxide is recommended as a protective oxide layer on graphite and metal components used for melting and processing uranium and its alloys. This paper presents studies on the efficacy of plasma sprayed yttrium oxide coatings for barrier applications against molten uranium

  13. Optical studies of multiply excited states

    International Nuclear Information System (INIS)

    Mannervik, S.

    1989-01-01

    Optical studies of multiply-excited states are reviewed with emphasis on emission spectroscopy. From optical measurements, properties such as excitation energies, lifetimes and autoionization widths can be determined with high accuracy, which constitutes a challenge for modern computational methods. This article mainly covers work on two-, three- and four-electron systems, but also sodium-like quartet systems. Furthermore, some comments are given on bound multiply-excited states in negative ions. Fine structure effects on transition wavelengths and lifetimes (autoionization) are discussed. In particular, the most recent experimental and theoretical studies of multiply-excited states are covered. Some remaining problems, which require further attention, are discussed in more detail. (orig.) With 228 refs

  14. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries.

    Science.gov (United States)

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-12-23

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn 4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g -1 based on solid-state redox reaction of oxide ions.

  15. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

    Science.gov (United States)

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-01-01

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions. PMID:28008955

  16. Combinatorial study of zinc tin oxide thin-film transistors

    Science.gov (United States)

    McDowell, M. G.; Sanderson, R. J.; Hill, I. G.

    2008-01-01

    Groups of thin-film transistors using a zinc tin oxide semiconductor layer have been fabricated via a combinatorial rf sputtering technique. The ZnO :SnO2 ratio of the film varies as a function of position on the sample, from pure ZnO to SnO2, allowing for a study of zinc tin oxide transistor performance as a function of channel stoichiometry. The devices were found to have mobilities ranging from 2to12cm2/Vs, with two peaks in mobility in devices at ZnO fractions of 0.80±0.03 and 0.25±0.05, and on/off ratios as high as 107. Transistors composed predominantly of SnO2 were found to exhibit light sensitivity which affected both the on/off ratios and threshold voltages of these devices.

  17. Study of oxidation stability of Jatropha curcas biodiesel/ diesel blends

    Energy Technology Data Exchange (ETDEWEB)

    Jain, Siddharth; Sharma, M.P. [Biofuel Research Laboratory, Alternate Hydro Energy Centre, Indian Institute of Technology Roorkee, Uttarakhand- 247667 (India)

    2011-07-01

    Biodiesel production is undergoing rapid technological reforms in industries and academia. This has become more obvious and relevant since the recent increase in the petroleum prices and the growing awareness relating to the environmental consequences of the fuel overdependency. However, the possibilities of production of biodiesel from edible oil resources in India is almost impossible, as primary need is to first meet the demand of edible oil that is already imported therefore it is essential to explore non-edible seed oils, like Jatropha curcas and Pongamia as biodiesel raw materials. The oxidation stability of biodiesel from Jatropha curcas oil is very poor. Therefore the aim of the present paper is to study the oxidation stability of Jatropha curcas biodiesel/ diesel blend. Also the effectiveness of various antioxidants is checked with respect to various blends of biodiesel with diesel.

  18. Studies on Thermal Oxidation Stability of Aviation Lubricating Oils

    Directory of Open Access Journals (Sweden)

    Wu Nan

    2017-01-01

    Full Text Available Simulating the operating condition of aviation engine via autoclave experiment of high temperature and pressure, we studied the physic-chemical property of poly-α-olefin base oil samples mixed with antioxidants of 2,6-di-tert-butyl-4-methylphenol and p,p’-diisooctyl diphenylamine at different temperature. The mechanism of degradation of PAO aviation lubricating oil was analyzed according to the oxidized products by modern analytical instruments. The results showed that the aviation lubricating oil produced a large number of low molecule compounds while increasing the temperature, and resulted in the viscosity decreasing and acid value increasing which indicated that the thermal oxidation of the oil sample underwent a radical process.

  19. Pulse radiolysis study of one electron oxidation of riboflavin

    International Nuclear Information System (INIS)

    Kishore, K.; Moorthy, P.N.; Guha, S.N.

    1991-01-01

    One electron oxidation of riboflavin (Rf) has been studied using various oxidising species such as Cl 2 -. , SO 4 -. and OH radicals. The transient species produced by the reaction of SO 4 -. with riboflavin gave spectra with λ m at 680 and 640 nm at pHs 4 and 7.1 respectively with a pK a at ∼ 6. Cl 2 -. radicals reacted with riboflavin to give a transient spectrum with λ m at 570 nm. The possibility of two sites viz. C-8 methyl group and the extended π-ring system of the molecule for oxidation reaction are discussed. The reaction of Cl 2 -. with riboflavin is an equilibrium from which the redox potential for the Rf +. /Rf couple has been evaluated to be 2.28 V vs NHE. OH radicals reacted with riboflavin to give a transient spectrum attributable to a mixture of species produced by addition or abstraction reactions. (author)

  20. Study of Plasma Electrolytic Oxidation Coatings on Aluminum Composites

    Directory of Open Access Journals (Sweden)

    Leonid Agureev

    2018-06-01

    Full Text Available Coatings, with a thickness of up to 75 µm, were formed by plasma electrolytic oxidation (PEO under the alternating current electrical mode in a silicate-alkaline electrolyte on aluminum composites without additives and alloyed with copper (1–4.5%. The coatings’ structure was analyzed by scanning electron microscopy, X-ray microanalysis, X-ray photoelectron spectroscopy, nuclear backscattering spectrometry, and XRD analysis. The coatings formed for 60 min were characterized by excessive aluminum content and the presence of low-temperature modifications of alumina γ-Al2O3 and η-Al2O3. The coatings formed for 180 min additionally contained high-temperature corundum α-Al2O3, and aluminum inclusions were absent. The electrochemical behavior of coated composites and uncoated ones in 3% NaCl was studied. Alloyage of aluminum composites with copper increased the corrosion current density. Plasma electrolytic oxidation reduced it several times.

  1. Deodorization optimization of Camelina sativa oil: Oxidative and sensory studies

    DEFF Research Database (Denmark)

    Hrastar, Robert; Cheong, Ling‐Zhi; Xu, Xuebing

    2011-01-01

    [peroxide value (PV), p‐anisidine value (p‐AV), γ‐tocopherol (γ‐T) and oxidative stability (OS)]. Additionally, sensory evaluation was performed. RSM analysis showed a significant effect of deodorization temperature and to a lesser extent, deodorization steam flow and time on removal of oxidative compounds....... In the present study RSM and principal component analysis (PCA) were used to optimize bench‐scale deodorization of CO. Mathematical models were generated through multiple regressions with backward elimination, describing the effects of process parameters (temperature, steam flow, time) on oil quality indicators......, flavour and odour. PCA of chemical and sensory results showed that deodorization temperature affected the sensory properties in the samples. The best conditions for removing undesirable flavour and odour were achieved by using a deodorization temperature of 195–210°C....

  2. Lithium ion behavior in lithium oxide by neutron scattering studies

    International Nuclear Information System (INIS)

    Ishii, Yoshinobu; Morii, Yukio; Katano, Susumu; Watanabe, Hitoshi; Funahashi, Satoru; Ohno, Hideo; Nicklow, R.M.

    1992-01-01

    Lithium ion behavior in lithium oxide, Li 2 O, was studied in the temperature range from 293 K to 1120 K by the High-Resolution Powder Diffractometer (HRPD) installed in the JRR-3M. The diffraction patterns were analyzed with the RIETAN program. At room temperature, the thermal parameters related to the mean square of the amplitude of vibration of the lithium and the oxygen ions were 6 x 10 -21 m 2 and 4 x 10 -21 m 2 , respectively. AT 1120 K the thermal parameter of the lithium ion was 34 x 10 -21 m 2 . On the other hand, the parameter of the oxygen ion was 16 x 10 -21 m 2 . Inelastic neutron scattering studies for the lithium oxide single crystal were also carried out on the triple-axis neutron spectrometers installed at the JRR-2 and the HFIR. Although the value of a phonon energy of a transverse acoustic mode (Σ 3 ) at zone boundary was 30.6 meV at room temperature, this value was decreased to 25.1 meV at 700 K. This large softening was caused by anharmonicity of the crystal potential of lithium oxide. (author)

  3. Kinetic Studies on State of the Art Solid Oxide Cells

    DEFF Research Database (Denmark)

    Njodzefon, Jean-Claude; Graves, Christopher R.; Hjelm, Johan

    2014-01-01

    of the technology, cell optimization and eventual commercialisation requires a sound understanding of the mechanisms that affect performance and stability. These mechanisms depend on operation conditions like temperature, gas composition, fuel utilisation and current load as well as on gradients along cell...

  4. Kinetic Studies on State of the Art Solid Oxide Cells

    DEFF Research Database (Denmark)

    Njodzefon, Jean-Claude; Graves, Christopher R.; Mogensen, Mogens Bjerg

    2016-01-01

    /steam fuel split into two processes with opposing temperature behavior in the reformate fuels. An 87.5 % reduction in active electrode area diminishes the gas conversion impedance in the hydrogen/steam fuel at high fuel flow rates. In both reformates, the second and third lowest frequency processes merged...

  5. Remote Sensing the Thermosphere's State Using Emissions From Carbon Dioxide and Nitric Oxide

    Science.gov (United States)

    Weimer, D. R.; Mlynczak, M. G.; Doornbos, E.

    2017-12-01

    Measurements of emissions from nitric oxide and carbon dioxide in the thermosphere have strong correlations with properties that are very useful to the determination of thermospheric densities. We have compared emissions measured with the Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) instrument on the Thermosphere Ionosphere Mesosphere Energetics and Dynamics (TIMED) satellite with neutral density measurements from the Challenging Mini-satellite Payload (CHAMP), the Gravity Recovery and Climate Experiment (GRACE), the Ocean Circulation Explorer (GOCE), and the three Swarm satellites, spanning a time period of over 15 years. It has been found that nitric oxide emissions match changes in the exospheric temperatures that have been derived from the densities through use of the Naval Reasearch Laboratory Mass Spectrometer, Incoherent Scatter Radar Extended Model (NRLMSISE-00) thermosphere model. Similarly, our results indicate that the carbon dioxide emissions have annual and semiannual oscillations that correlate with changes in the amount of oxygen in the thermosphere, also determined by use of the NRLMSISE-00 model. These annual and semi-annual variations are found to have irregular amplitudes and phases, which make them very difficult to accurately predict. Prediction of exospheric temperatures through the use of geomagnetic indices also tends to be inexact. Therefore, it would be possible and very useful to use measurements of the thermosphere's infrared emissions for real-time tracking of the thermosphere's state, so that more accurate calculations of the density may be obtained.

  6. Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen Minh

    2006-07-31

    This report summarizes the work performed for Phase I (October 2001 - August 2006) under Cooperative Agreement DE-FC26-01NT41245 for the U. S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled 'Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program'. The program focuses on the development of a low-cost, high-performance 3-to-10-kW solid oxide fuel cell (SOFC) system suitable for a broad spectrum of power-generation applications. During Phase I of the program significant progress has been made in the area of SOFC technology. A high-efficiency low-cost system was designed and supporting technology developed such as fuel processing, controls, thermal management, and power electronics. Phase I culminated in the successful demonstration of a prototype system that achieved a peak efficiency of 41%, a high-volume cost of $724/kW, a peak power of 5.4 kW, and a degradation rate of 1.8% per 500 hours. . An improved prototype system was designed, assembled, and delivered to DOE/NETL at the end of the program. This prototype achieved an extraordinary peak efficiency of 49.6%.

  7. Oxidation states by X-ray fluorescence and electron probe microanalysis techniques

    International Nuclear Information System (INIS)

    Vazquez, Cristina; Riveros, J.A.

    1987-01-01

    Many years ago, several studies showed the effect of a chemical state in X-ray spectra. The effect, however, has rarely been utilized in quantitative chemical analysis. The purpose of this work is to show observed shifts due to different chemical states in iron compounds. (Author) [es

  8. Determination of oxidation state of iron in normal and pathologically altered human aortic valves

    Energy Technology Data Exchange (ETDEWEB)

    Czapla-Masztafiak, J. [Institute of Nuclear Physics PAN, Radzikowskiego 152, 31-342 Kraków (Poland); Lis, G.J.; Gajda, M.; Jasek, E. [Department of Histology, Jagiellonian University Medical College, Kopernika 7, 31-034 Kraków (Poland); Czubek, U. [Department of Coronary Disease, Jagiellonian University Medical College, John Paul II Hospital, Prądnicka 80, 31-202 Kraków (Poland); Bolechała, F. [Department of Forensic Medicine, Jagiellonian University Medical College, Grzegórzecka 16, 31-531 Kraków (Poland); Borca, C. [Swiss Light Source, Paul Scherrer Institute, 5232 Villigen PSI (Switzerland); Kwiatek, W.M. [Institute of Nuclear Physics PAN, Radzikowskiego 152, 31-342 Kraków (Poland)

    2015-12-01

    In order to investigate changes in chemical state of iron in normal and pathologically altered human aortic valves X-ray absorption spectroscopy was applied. Since Fe is suspected to play detrimental role in aortic valve stenosis pathogenesis the oxidation state of this element has been determined. The experimental material consisted of 10 μm sections of valves excised during routine surgery and from autopsies. The experiment was performed at the MicroXAS beamline of the SLS synchrotron facility in Villigen (Switzerland). The Fe K-edge XANES spectra obtained from tissue samples were carefully analyzed and compared with the spectra of reference compounds containing iron in various chemical structures. The analysis of absorption edge position and shape of the spectra revealed that both chemical forms of iron are presented in valve tissue but Fe{sup 3+} is the predominant form. Small shift of the absorption edge toward higher energy in the spectra from stenotic valve samples indicates higher content of the Fe{sup 3+} form in pathological tissue. Such a phenomenon suggests the role of Fenton reaction and reactive oxygen species in the etiology of aortic valve stenosis. The comparison of pre-edge regions of XANES spectra for control and stenotic valve tissue confirmed no differences in local symmetry or spin state of iron in analyzed samples.

  9. Coherent diffractive imaging of solid state reactions in zinc oxide crystals

    Science.gov (United States)

    Leake, Steven J.; Harder, Ross; Robinson, Ian K.

    2011-11-01

    We investigated the doping of zinc oxide (ZnO) microcrystals with iron and nickel via in situ coherent x-ray diffractive imaging (CXDI) in vacuum. Evaporated thin metal films were deposited onto the ZnO microcrystals. A single crystal was selected and tracked through annealing cycles. A solid state reaction was observed in both iron and nickel experiments using CXDI. A combination of the shrink wrap and guided hybrid-input-output phasing methods were applied to retrieve the electron density. The resolution was 33 nm (half order) determined via the phase retrieval transfer function. The resulting images are nevertheless sensitive to sub-angstrom displacements. The exterior of the microcrystal was found to degrade dramatically. The annealing of ZnO microcrystals coated with metal thin films proved an unsuitable doping method. In addition the observed defect structure of one crystal was attributed to the presence of an array of defects and was found to change upon annealing.

  10. Oxidation-state distribution of plutonium in surface and subsurface waters at Thule, northwest Greenland

    DEFF Research Database (Denmark)

    McMahon, C.A.; Vintró, L.L.; Mitchell, P.I.

    2000-01-01

    (V, VI) (mean, 68 +/- 6%; n = 6), with little if any distinction apparent between surface and bottom waters. Further, the oxidation state distribution at stations close to the accident site is similar to that measured at Upernavik, remote from this site. It is also similar to the distribution observed...... in shelf waters at midlatitudes, suggesting that the underlying processes controlling plutonium speciation are insensitive to temperature over the range 0-25 degrees C. Measurements using tangential-flow ultrafiltration indicate that virtually all of the plutonium (including the fraction in a reduced...... chemical form) is present as fully dissolved species. Most of this plutonium would seem to be of weapons fallout origin, as the mean Pu-238/Pu-239,Pu-240 activity ratio in the water column (dissolved phase) at Thule (0.06 +/- 0.02; n = 10) is similar to the global fallout ratio at this latitude...

  11. State-of-the-art technologies of gallium oxide power devices

    Science.gov (United States)

    Higashiwaki, Masataka; Kuramata, Akito; Murakami, Hisashi; Kumagai, Yoshinao

    2017-08-01

    Gallium oxide (Ga2 O3 ) has gained increased attention for power devices due to its superior material properties and the availability of economical device-quality native substrates. This review illustrates recent advances in Ga2 O3 device technologies, beginning with an overview of the social circumstances that motivate the development of new-generation switching devices. Following an introduction to the material properties of Ga2 O3 from the viewpoint of power electronics, growth technologies of Ga2 O3 bulk single crystals and epitaxial thin films are discussed. The fabrication and performance of state-of-the-art Ga2 O3 transistors and diodes are then described. We conclude by identifying the directions and challenges of Ga2 O3 power device development in the near future.

  12. Coordination and Oxidation States of Iron Incorporated in Mesoporous MCM41

    International Nuclear Information System (INIS)

    Lazar, K.; Pal-Borbely, G.; Szegedi, A.; Beyer, H. K.

    2002-01-01

    Mesoporous Fe-MCM41 samples (Si/Fe=25) were synthesized and characterized under evacuation and reducing/oxidizing treatments by in situ FTIR and Moessbauer spectroscopies. Both Fe(II) and Fe(III) located in low coordination states in top layers of pore walls exhibit Lewis acidity and may participate in Fe(III) ↔ Fe(II) processes at low temperatures (570 K). Furthermore, Fe(III) ↔ Fe(II) cycles can be achieved and repeated with participation of the full amount of iron at higher temperatures (670 K). The accompanying formation of oxygen vacancies and restoration of the structure in the reverse process does not result in extended damages; the MCM41 structure retains its stability under the conditions applied.

  13. Study of the tunnelling initiated leakage current through the carbon nanotube embedded gate oxide in metal oxide semiconductor structures

    International Nuclear Information System (INIS)

    Chakraborty, Gargi; Sarkar, C K; Lu, X B; Dai, J Y

    2008-01-01

    The tunnelling currents through the gate dielectric partly embedded with semiconducting single-wall carbon nanotubes in a silicon metal-oxide-semiconductor (MOS) structure have been investigated. The application of the gate voltage to such an MOS device results in the band bending at the interface of the partly embedded oxide dielectric and the surface of the silicon, initiating tunnelling through the gate oxide responsible for the gate leakage current whenever the thickness of the oxide is scaled. A model for silicon MOS structures, where carbon nanotubes are confined in a narrow layer embedded in the gate dielectric, is proposed to investigate the direct and the Fowler-Nordheim (FN) tunnelling currents of such systems. The idea of embedding such elements in the gate oxide is to assess the possibility for charge storage for memory device applications. Comparing the FN tunnelling onset voltage between the pure gate oxide and the gate oxide embedded with carbon nanotubes, it is found that the onset voltage decreases with the introduction of the nanotubes. The direct tunnelling current has also been studied at very low gate bias, for the thin oxide MOS structure which plays an important role in scaling down the MOS transistors. The FN tunnelling current has also been studied with varying nanotube diameter

  14. First principles studies of complex oxide surfaces and interfaces

    International Nuclear Information System (INIS)

    Noguera, Claudine; Finocchi, Fabio; Goniakowski, Jacek

    2004-01-01

    Oxides enter our everyday life and exhibit an impressive variety of physical and chemical properties. The understanding of their behaviour, which is often determined by the electronic and atomic structures of their surfaces and interfaces, is a key question in many fields, such as geology, environmental chemistry, catalysis, thermal coatings, microelectronics, and bioengineering. In the last decade, first principles methods, mainly those based on the density functional theory, have been frequently applied to study complex oxide surfaces and interfaces, complementing the experimental observations. In this work, we discuss some of these contributions, with emphasis on several issues that are especially important when dealing with oxides: the local electronic structure at interfaces, and its connection with chemical reactivity; the charge redistribution and the bonding variations, in relation to screening properties; and the possibility of bridging the gap between model and real systems by taking into account the chemical environments and the effect of finite temperatures, and by performing simulations on systems of an adequate (large) size

  15. Brain oxidative metabolism of the newborn dog: correlation between 31P NMR spectroscopy and pyridine nucleotide redox state.

    Science.gov (United States)

    Mayevsky, A; Nioka, S; Subramanian, V H; Chance, B

    1988-04-01

    The effects of both anoxia and short- and long-term hypoxia on brain oxidative metabolism were studied in newborn dogs. Oxidative metabolism was evaluated by two independent measures: in vivo continuous monitoring of mitochondrial NADH redox state and energy stores as calculated from the phosphocreatine (PCr)/Pi levels measured by 31P nuclear magnetic resonance (NMR) spectroscopy. The hemodynamic response to low oxygen supply was further evaluated by measuring the changes in the reflected light intensity at 366 nm (the excitation wavelength for NADH). The animal underwent surgery and was prepared for monitoring of the two signals (NADH and PCr/Pi). It was then placed inside a Phosphoenergetics 260-80 NMR spectrometer magnet with a 31-cm bore. Each animal (1-21 days old) was exposed to short-term anoxia or hypoxia as well as to long-term hypoxia (1-2 h). The results can be summarized as follow: (a) In the normoxic brain, the ratio between PCr and Pi was greater than 1 (1.2-1.4), while under hypoxia or asphyxia a significant decrease that was correlated to the FiO2 levels was recorded. (b) A clear correlation was found between the decrease in PCr/Pi values and the increased NADH redox state developed under decreased O2 supply to the brain. (c) Exposing the animal to moderately long-term hypoxia led to a stabilized low-energy state of the brain with a good recovery after rebreathing normal air. (d) Under long-term and severe hypoxia, the microcirculatory autoregulatory mechanism was damaged and massive vasoconstriction was optically recorded simultaneously with a significant decrease in PCr/Pi values.(ABSTRACT TRUNCATED AT 250 WORDS)

  16. Study of the pelletizing process zirconium oxide and zircon sand

    International Nuclear Information System (INIS)

    Seo, E.S.M.; Paschoal, J.O.A.; Acevedo, M.T.P.

    1990-12-01

    The study of the process to obtain zirconium tetrachloride under development at IPEN, can be divide into two steps: pelletizing and chlorination. Pelletizing is an important step in the overall process as it facilitates greater contact between the particles and permits the production of pellets with dimensional uniformity and mechanical strength. In this paper, the results of the study of pelletizing zirconium oxide and zircon sand are presented. The influence of some variables related to the process and the equipment on the physical characteristics of the pellets are discussed. (author)

  17. Oxidation State of Iron in the Izu-Bonin Arc Initial Magma and Its Influence Factors

    Science.gov (United States)

    Li, H.; Arculus, R. J.; Brandl, P. A.; Hamada, M.; Savov, I. P.; Zhu, S.; Hickey-Vargas, R.; Tepley, F. J., III; Meffre, S.; Yogodzinski, G. M.; McCarthy, A.; Barth, A. P.; Kanayama, K.; Kusano, Y.; Sun, W.

    2014-12-01

    The redox state of mantle-derived magmas is a controversial issue, especially whether island arc basalts are more oxidized than those from mid-ocean ridges. Usually, arc magmas have higher Fe3+/Fe2+ and calculated oxygen fugacity (fO2) than mid-ocean ridge basalts (MORB). It is the high fO2 of arc magma that apparently delays onset of sulfide fractionation and sequestration of precious/base metals thereby facilitating the formation of many giant gold-copper deposits typically associated with subduction zones. But due to a paucity of Fe3+/Fe2+ data for primary mantle-derived arc magmas, the cause for high fO2 of these magma types is still controversial; causes may include inter alia subduction-released oxidized material addition to the mantle wedge source of arc magma, partial melting of subducted slab, and redox changes occurring during ascent of the magma. Fortunately, IODP expedition 351 drilling at IODP Site U1438 in the Amami-Sankaku Basin of the northwestern Philipine Sea, adjacent to the proto-Izu-Bonin Arc at the Kyushu-Palau Ridge (KPR), recovered not only volcaniclastics derived from the inception of Izu-Bonin Mariana (IBM) arc in the Eocene, but also similar materials for the Arc's subsequent evolution through to the Late Oligocene and abandonment of the KPR as a remnant arc. Samples of the pre-Arc oceanic crustal basement were also recovered enabling us to determine the fO2of the mantle preceding arc inception. As the oxidation state of iron in basaltic glass directly relates to the fO2 , the Fe3+/∑Fe ratio [Fe3+/(Fe3++ Fe2+)] of basaltic glass are quantified by synchrotron-facilitated micro X-ray Absorption Near Edge Structure (XANES) spectroscopy to reflect its fO2. Fe K-edge µ-XANES spectra were recorded in fluorescence mode at Beamline 15U1, Shanghai Synchrotron Radiation Facility (SSRF). Synthetic silicate glass with known Fe3+/∑Fe ratio was used in data handling. The experimental results as well as preliminary data from IODP Expedition 351

  18. Identification of the iron oxidation state and coordination geometry in iron oxide- and zeolite-based catalysts using pre-edge XAS analysis.

    Science.gov (United States)

    Boubnov, Alexey; Lichtenberg, Henning; Mangold, Stefan; Grunwaldt, Jan Dierk

    2015-03-01

    Analysis of the oxidation state and coordination geometry using pre-edge analysis is attractive for heterogeneous catalysis and materials science, especially for in situ and time-resolved studies or highly diluted systems. In the present study, focus is laid on iron-based catalysts. First a systematic investigation of the pre-edge region of the Fe K-edge using staurolite, FePO4, FeO and α-Fe2O3 as reference compounds for tetrahedral Fe(2+), tetrahedral Fe(3+), octahedral Fe(2+) and octahedral Fe(3+), respectively, is reported. In particular, high-resolution and conventional X-ray absorption spectra are compared, considering that in heterogeneous catalysis and material science a compromise between high-quality spectroscopic data acquisition and simultaneous analysis of functional properties is required. Results, which were obtained from reference spectra acquired with different resolution and quality, demonstrate that this analysis is also applicable to conventionally recorded pre-edge data. For this purpose, subtraction of the edge onset is preferentially carried out using an arctangent and a first-degree polynomial, independent of the resolution and quality of the data. For both standard and high-resolution data, multiplet analysis of pre-edge features has limitations due to weak transitions that cannot be identified. On the other hand, an arbitrary empirical peak fitting assists the analysis in that non-local transitions can be isolated. The analysis of the oxidation state and coordination geometry of the Fe sites using a variogram-based method is shown to be effective for standard-resolution data and leads to the same results as for high-resolution spectra. This method, validated by analysing spectra of reference compounds and their well defined mixtures, is finally applied to track structural changes in a 1% Fe/Al2O3 and a 0.5% Fe/BEA zeolite catalyst during reduction in 5% H2/He. The results, hardly accessible by other techniques, show that Fe(3+) is

  19. The oxidation state of Fe in glasses from the Kerguelen Large Igneous Province: Evidence for the changing oxidation state of the Indian Ocean Basin

    Science.gov (United States)

    Peterson, M. E.; Stolper, E.; Brounce, M. N.; Eiler, J. M.; Wallace, P. J.

    2017-12-01

    Oxygen fugacity (ƒO2) is a thermodynamic property of silicate magmas that can be influenced by volcanic processes such as melting, crystal fractionation, and degassing. Lavas erupted as part of large igneous provinces (LIPs) may reflect the impingement of mantle plumes on the lithosphere, and thus could provide constraints on the ƒO2 of plumes responsible for generation of LIPs. The Kerguelen plateau was emplaced during the break up of Gondwana and the initial opening of the Indian Ocean. Elevated 207Pb/204Pb and 208Pb/204Pb ratios at low 206Pb/204Pb suggests that continental lithosphere from Gondwana is present in the asthenosphere of this region. The Sr-Nd-Pb-He isotopic compositions of the Kerguelen lavas are variable and have been used to infer that the mantle sources of these lavas reflect contributions from the depleted upper mantle, a common plume component, and the EM1 mantle component (perhaps recycled lower continental crust; e.g. Frey et al., 2002). The ƒO2 of the lavas of the Kerguelen LIP may thus reflect mixing of the upper mantle (i.e., near QFM), the plume component, and continental crust. We present new μ-XANES measurements of Fe3+/ΣFe ratios in a suite of 21 submarine glasses from Kerguelen. Over a narrow range in MgO (6.5-7.5 wt%), these glasses have Fe3+/ΣFe ratios of 0.16-0.18, corresponding to an ƒO2 of QFM+0.23 to +0.38 (at 1 atm, 1200°C). The H2O/Ce and Cl/K ratios of these glasses suggest that they did not assimilate significant amounts of altered oceanic crust. Also, S-FeOT variations indicate that the magmas are near sulfide saturation. These lavas were erupted in 1000 m of water, precluding significant loss of S to a vapor phase. At a given MgO content, samples from Kerguelen have similar to higher Fe3+/ΣFe ratios than the average values found in samples from along the Indian mid-ocean ridge, which could indicate a more oxidized mantle source. In addition, increases in Fe3+/ΣFe ratios of the Kerguelen samples, over a narrow

  20. Oxidative stress markers, cognitive functions, and psychosocial functioning in bipolar disorder: an empirical cross-sectional study.

    Science.gov (United States)

    Aydemir, Ömer; Çubukçuoğlu, Zeynep; Erdin, Soner; Taş, Cumhur; Onur, Ece; Berk, Michael

    2014-01-01

    This study aimed to evaluate the relationship between oxidative stress markers and cognitive functions and domains of psychosocial functioning in bipolar disorder. Oxidative stress markers, cognitive functions, and domains of psychosocial functioning were evaluated in 51 patients with bipolar disorder who were in remission. Correlation analyses between these parameters were calculated with data controlled for duration of illness and number of episodes. There was no statistically significant correlation between oxidative stress markers and cognitive functions. In terms of psychosocial functioning, significant correlations were found between malondialdehyde and sense of stigmatization (r = -0.502); household activities and superoxide dismutase (r = 0.501); participation in social activities and nitric oxide (r = 0.414); hobbies and leisure time activities and total glutathione (r = -0.567), superoxide dismutase (r = 0.667), and neurotrophin 4 (r = 0.450); and taking initiative and self-sufficiency and superoxide dismutase (r = 0.597). There was no correlation between other domains of psychosocial functioning and oxidative stress markers. These results imply that oxidative stress markers do not appear to correlate clearly with cognitive impairment and reduced psychosocial functioning. However, there were some associations between selected oxidative markers and activity-oriented functional markers. This may represent a true negative association, or may be an artifact of oxidative stress being a state rather than a trait marker.

  1. Oxidative stress markers, cognitive functions, and psychosocial functioning in bipolar disorder: an empirical cross-sectional study

    Directory of Open Access Journals (Sweden)

    Ömer Aydemir

    2014-12-01

    Full Text Available Objective: This study aimed to evaluate the relationship between oxidative stress markers and cognitive functions and domains of psychosocial functioning in bipolar disorder. Methods: Oxidative stress markers, cognitive functions, and domains of psychosocial functioning were evaluated in 51 patients with bipolar disorder who were in remission. Correlation analyses between these parameters were calculated with data controlled for duration of illness and number of episodes. Results: There was no statistically significant correlation between oxidative stress markers and cognitive functions. In terms of psychosocial functioning, significant correlations were found between malondialdehyde and sense of stigmatization (r = -0.502; household activities and superoxide dismutase (r = 0.501; participation in social activities and nitric oxide (r = 0.414; hobbies and leisure time activities and total glutathione (r = -0.567, superoxide dismutase (r = 0.667, and neurotrophin 4 (r = 0.450; and taking initiative and self-sufficiency and superoxide dismutase (r = 0.597. There was no correlation between other domains of psychosocial functioning and oxidative stress markers. Conclusion: These results imply that oxidative stress markers do not appear to correlate clearly with cognitive impairment and reduced psychosocial functioning. However, there were some associations between selected oxidative markers and activity-oriented functional markers. This may represent a true negative association, or may be an artifact of oxidative stress being a state rather than a trait marker.

  2. Kinetic studies of sulfide mineral oxidation and xanthate adsorption

    Science.gov (United States)

    Mendiratta, Neeraj K.

    2000-10-01

    Sulfide minerals are a major source of metals; however, certain sulfide minerals, such as pyrite and pyrrhotite, are less desirable. Froth flotation is a commonly used separation technique, which requires the use of several reagents to float and depress different sulfide minerals. Xanthate, a thiol collector, has gained immense usage in sulfide minerals flotation. However, some sulfides are naturally hydrophobic and may float without a collector. Iron sulfides, such as pyrite and pyrrhotite, are few of the most abundant minerals, yet economically insignificant. Their existence with other sulfide minerals leads to an inefficient separation process as well as environmental problems, such as acid mine drainage during mining and processing and SO 2 emissions during smelting process. A part of the present study is focused on understanding their behavior, which leads to undesired flotation and difficulties in separation. The major reasons for the undesired flotation are attributed to the collectorless hydrophobicity and the activation with heavy metal ions. To better understand the collectorless hydrophobicity of pyrite, Electrochemical Impedance Spectroscopy (EIS) of freshly fractured pyrite electrodes was used to study the oxidation and reduction of the mineral. The EIS results showed that the rate of reaction increases with oxidation and reduction. At moderate oxidizing potentials, the rate of reaction is too slow to replenish hydrophilic iron species leaving hydrophobic sulfur species on the surface. However, at higher potentials, iron species are replaced fast enough to depress its flotation. Effects of pH and polishing were also explored using EIS. Besides collectorless hydrophobicity, the activation of pyrrhotite with nickel ions and interaction with xanthate ions makes the separation more difficult. DETA and SO2 are commonly used as pyrrhotite depressants; however, the mechanism is not very well understood. Contact angle measurements, cyclic voltammetry and Tafel

  3. Ab initio study of perovskite type oxide materials for solid oxide fuel cells

    Science.gov (United States)

    Lee, Yueh-Lin

    2011-12-01

    Perovskite type oxides form a family of materials of significant interest for cathodes and electrolytes of solid oxide fuel cells (SOFCs). These perovskites not only are active catalysts for surface oxygen reduction (OR) reactions but also allow incorporating the spilt oxygen monomers into their bulk, an unusual and poorly understood catalytic mechanism that couples surface and bulk properties. The OR mechanisms can be influenced strongly by defects in perovskite oxides, composition, and surface defect structures. This thesis work initiates a first step in developing a general strategy based on first-principles calculations for detailed control of oxygen vacancy content, transport rates of surface and bulk oxygen species, and surface/interfacial reaction kinetics. Ab initio density functional theory methods are used to model properties relevant for the OR reactions on SOFC cathodes. Three main research thrusts, which focus on bulk defect chemistry, surface defect structures and surface energetics, and surface catalytic properties, are carried to investigate different level of material chemistry for improved understanding of key physics/factors that govern SOFC cathode OR activity. In the study of bulk defect chemistry, an ab initio based defect model is developed for modeling defect chemistry of LaMnO 3 under SOFC conditions. The model suggests an important role for defect interactions, which are typically excluded in previous defect models. In the study of surface defect structures and surface energetics, it is shown that defect energies change dramatically (1˜2 eV lower) from bulk values near surfaces. Based on the existing bulk defect model with the calculated ab initio surface defect energetics, we predict the (001) MnO 2 surface oxygen vacancy concentration of (La0.9Sr0.1 )MnO3 is about 5˜6 order magnitude higher than that of the bulk under typical SOFC conditions. Finally, for surface catalytic properties, we show that area specific resistance, oxygen

  4. Ultrathin reduced graphene oxide films as transparent top-contacts for light switchable solid-state molecular junctions

    DEFF Research Database (Denmark)

    Li, Tao; Jevric, Martyn; Hauptmann, Jonas Rahlf

    2013-01-01

    A new type of solid-state molecular junction is introduced, which employs reduced graphene oxide as a transparent top contact that permits a self-assembled molecular monolayer to be photoswitched in situ, while simultaneously enabling charge-transport measurements across the molecules. The electr......A new type of solid-state molecular junction is introduced, which employs reduced graphene oxide as a transparent top contact that permits a self-assembled molecular monolayer to be photoswitched in situ, while simultaneously enabling charge-transport measurements across the molecules...

  5. Studies of Heterogenous Palladium and Related Catalysts for Aerobic Oxidation of Primary Alcohols

    Science.gov (United States)

    Ahmed, Maaz S.

    alcohol solvent and the surface of the catalyst: (listed in order of strength) lone pair-surface (heterocyclic primary alcohols) > pi-surface (aryl primary alcohols) > van der Waals-surface (alkyl primary alcohols). These interactions were previously underappreciated in condensed phase heterogeneously catalyzed aerobic oxidations. Bi and Te serve as synergistic promoters that enhance both the rate and yield of the reactions relative to reactions employing Pd alone or Pd in combination with Bi or with Te as the sole promoter. We report X-ray absorption spectroscopic studies of the heterogenous catalyst. These methods show that the promoters undergo oxidation in preference to Pd, maintaining the Pd surface in the active metallic state and preventing inhibition by surface Pd-oxide formation. The data also suggest formation of a Pd-Te alloy phase that modifies the electronic properties of the Pd catalyst. Collectively, these results provide valuable insights into the synergistic benefits of multiple promoters in heterogeneous catalytic oxidation reactions.

  6. Eco-friendly wood-based solid-state flexible supercapacitors from wood transverse section slice and reduced graphene oxide

    Science.gov (United States)

    Lv, Shaoyi; Fu, Feng; Wang, Siqun; Huang, Jingda; Hu, La

    2015-07-01

    An interesting wood-based all-solid-state supercapacitor is produced using reduced graphene oxide (RGO) coated on wood transverse section slice (WTSS) as electrode material by means of a low-cost, eco-friendly, and simple method for the first time. The RGO-coated WTSS electrode has a porous 3D honeycomb framework due to the hierarchical cellular structure of the WTSS substrate and can function as an electrolyte reservoir. This special construction endows this novel electrode with good areal capacitance (102 mF cm-2) and excellent cyclic stability (capacitance retention of 98.9% after 5000 cycles). In addition, the supercapacitors exhibit good mechanical flexibility and preserve almost constant capacitive behavior under different bending conditions. Our study introduces a new and eco-friendly material design for electrodes in future flexible energy storage devices that closely resemble natural materials. [Figure not available: see fulltext.

  7. Iron oxides as pedoenvironmental indicators: state of the art, answers and questions (Philippe Duchaufour Medal Lecture)

    Science.gov (United States)

    Torrent, J.

    2012-04-01

    The colour and magnetic properties of soils largely reflect the content and mineralogy of their iron oxides, which in turn relate to the physical, chemical and biological characteristics of the soil environment. For more than 50 years, soil mineralogists and chemists have collected data for iron oxides in soils formed in widely different environments and tried to understand the complex nature of the different suites and formation pathways for these minerals via laboratory experiments. The discovery of ferrihydrite —the poorly crystalline precursor of most Fe oxides— in 1971, and the recognition of its common presence in soils, raised interest in deciphering the environmental factors that affect its transformation into goethite and hematite, the two most abundant crystalline iron oxides in soil. Field observations were consistent with laboratory experiments in which temperature, water activity, pH, foreign ions and organic matter were found to play a key role in the crystallization of ferrihydrite. Thus, the hematite/(hematite + goethite) ratio increased with increasing temperature and also with the likelihood of seasonal soil drying. Exploiting this ratio as a (pedo)environment indicator is, however, not devoid of problems derived from insufficient knowledge of the interactions between the influential chemical variables, difficulties in quantifying the two minerals and changes brought about by reductive dissolution. Soil formation usually leads to magnetic enhancement as a result of the production of magnetite and/or maghemite, which are ferrimagnetic iron oxides, and, possibly, an ordered ferrimagnetic ferrihydrite, as suggested by recent laboratory experiments. The concentration of pedogenic ferrimagnets as estimated via proxies such as magnetic susceptibility or frequency-dependent magnetic susceptibility has been found to relate to climate variables [particularly (paleo)rainfall] in many studies reported over the last 30 years. However, extracting accurate

  8. Analytical study of doubly excited ridge states

    International Nuclear Information System (INIS)

    Wong, H.Y.

    1988-01-01

    Two different non-separable problems are explored and analyzed. Non-perturbative methods need to be used to handle them, as the competing forces involved in these problems are equally strong and do not yield to a perturbative analysis. The first one is the study of doubly excited ridge states of atoms, in which two electrons are comparably excited. An analytical wavefunction for such states is introduced and is used to solve the two-electron Hamiltonian in the pair coordinates called hyperspherical coordinates variationally. The correlation between the electrons is built in analytically into the structure of the wavefunction. Sequences of ridge states out to very high excitation are computed and are organized as Rydberg series converging to the double ionization limit. Numerical results of such states in He and H - are compared with other theoretical calculations where available. The second problem is the analysis of the photodetachment of negative ions in an electric field via the frame transformation theory. The presence of the electron field requires a transformation from spherical to cylindrical symmetry for the outgoing photoelectron. This gives an oscillatory modulating factor as the effect of the electric field on cross-sections. All of this work is derived analytically in a general form applicable to the photodetachment of any negative ion. The expressions are applied to H - and S - for illustration

  9. An initial applications study of ceria-gadolinia solid oxide fuel cells: V. 1

    Energy Technology Data Exchange (ETDEWEB)

    Bauen, A.; Hart, D.; Mould, B.

    1998-11-01

    Fuel cells are categorised by their electrolytes, and the solid oxide fuel cell is so called because its electrolyte consists of a solid ceramic oxide. Commonly this has been a form of zirconia, though other materials are now being considered for their different electrical properties. One of these, ceria doped with gadolinia, shows promise for use in lower temperature regimes than zirconia, and may open up different areas of a future market for consideration. This report considers the opportunities for ceria-gadolinia solid oxide fuel cell systems by comparing them with the application requirements in markets where fuel cells may have potential. The advantages and disadvantages of the technology are analysed, together with the state of the art in research and development. The direction in which research effort needs to move to address some of the issues is assessed. The report then draws conclusions regarding the potential of ceria-gadolinia in solid oxide fuel cell systems and in the energy markets as a whole. It should be noted that while this report is an applications study, some technology assessment has been included. Much of this is found in Volume 2. (author)

  10. One-electron oxidations of ferrocenes: a pulse radiolysis study

    International Nuclear Information System (INIS)

    Faraggi, Moshe; Weinraub, Dany; Broitman, Federico; DeFelippis, M.R.; Klapper, M.H.

    1988-01-01

    Using the pulse radiolysis technique we have studied the oxidation by various inorganic radicals of four water soluble ferrocene derivatives, hydroxyethyl, dimethylaminomethyl, monocarboxylic acid and dicarboxylic acid. We report the second order rate constants for these reactions, the stabilities and spectral properties of the ferrocinium products, and the electrochemically determined ferrocinium/ferrocene redox potentials. We also present preliminary estimates of tyrosine and tryptophan radical redox potentials obtained with the dicarboxylic acid ferrocene derivative as reference, and we discuss the relationship between redox potential differences and the reactivities of the ferrocenes with the inorganic radicals. (author)

  11. Electroencephalogram, cognitive state, psychological disorders, clinical symptom, and oxidative stress in horticulture farmers exposed to organophosphate pesticides.

    Science.gov (United States)

    Bayrami, Mansour; Hashemi, Touraj; Malekirad, Ali Akbar; Ashayeri, Hassan; Faraji, Fardin; Abdollahi, Mohammad

    2012-02-01

    The aim of this paper was to study the toxicity of organophosphate (OP) pesticides in exposed farmers for electroencephalography, cognitive state, psychological disorders, clinical symptom, oxidative stress, acetylcholinesterase, and DNA damage. A comparative cross-sectional analysis was carried out in 40 horticulture farmers who were exposed to OPs in comparison to a control group containing 40 healthy subjects with the same age and sex and education level. Lipid peroxidation (LPO), superoxide dismutase (SOD), catalase, glutathione peroxidase, DNA damage, total antioxidant capacity (TAC), total thiol molecules, and acetylcholinesterase (AChE) activity were measured in the blood of subjects. Clinical examination and complete blood test were undertaken in order to record any abnormal sign or symptoms. Cognitive function, psychological symptoms, and psychological distress were examined and recorded. Comparing with controls, the farmers showed higher blood levels of SOD and LPO while their TAC decreased. Farmers showed clinical symptoms such as eczema, breathing muscle weakness, nausea, and saliva secretion. Regarding cognitive function, the orientation, registration, attention and calculation, recall, and language were not significantly different in farmers and controls. Among examinations for psychological distress, only labeled somatization was significantly higher in farmers. The present findings indicate that oxidative stress and inhibition of AChE can be seen in chronically OP-exposed people but incidence of neuropsychological disorders seems a complex multivariate phenomenon that might be seen in long-term high-dose exposure situations. Use of supplementary antioxidants would be useful in the treatment of farmers.

  12. Diversity of Chemical Bonding and Oxidation States in MS 4 Molecules of Group 8 Elements

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Wei [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Jiang, Ning [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Schwarz, W. H. Eugen [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Physical and Theoretical Chemistry, University of Siegen, Siegen 57068 Germany; Yang, Ping [Theoretical Division, Los Alamos National Laboratory, Los Alamos New Mexico 87545 USA; Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland Washington 953002 USA; Li, Jun [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland Washington 953002 USA

    2017-07-11

    The geometric and electronic ground-state structures of six MS4 molecules (M = group-8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density-functional and correlated wave-function approaches. The MS4 species are compared to analogous MO4 species recently investi-gated (Inorg. Chem. 2016, 55: 4616). Metal oxidation state (MOS) of high value VIII appears in low- spin singlet Td geometric species (Os,Hs)S4 and (Ru,Os,Hs)O4, whereas low MOS=II appears in high- spin septet D2d species Fe(S2)2 and (slightly excited) metastable Fe(O2)2. The ground states of all other molecules have intermediate MOS values, containing S2-, S22-, S21- (and resp. O2--, O1-, O22-, O21-) ligands, bonded by ionic, covalent and correlative contributions.

  13. Actinide Oxidation State and O/M Ratio in Hypostoichiometric Uranium-Plutonium-Americium U0.750Pu0.246Am0.004O2-x Mixed Oxides.

    Science.gov (United States)

    Vauchy, Romain; Belin, Renaud C; Robisson, Anne-Charlotte; Lebreton, Florent; Aufore, Laurence; Scheinost, Andreas C; Martin, Philippe M

    2016-03-07

    Innovative americium-bearing uranium-plutonium mixed oxides U1-yPuyO2-x are envisioned as nuclear fuel for sodium-cooled fast neutron reactors (SFRs). The oxygen-to-metal (O/M) ratio, directly related to the oxidation state of cations, affects many of the fuel properties. Thus, a thorough knowledge of its variation with the sintering conditions is essential. The aim of this work is to follow the oxidation state of uranium, plutonium, and americium, and so the O/M ratio, in U0.750Pu0.246Am0.004O2-x samples sintered for 4 h at 2023 K in various Ar + 5% H2 + z vpm H2O (z = ∼ 15, ∼ 90, and ∼ 200) gas mixtures. The O/M ratios were determined by gravimetry, XAS, and XRD and evidenced a partial oxidation of the samples at room temperature. Finally, by comparing XANES and EXAFS results to that of a previous study, we demonstrate that the presence of uranium does not influence the interactions between americium and plutonium and that the differences in the O/M ratio between the investigated conditions is controlled by the reduction of plutonium. We also discuss the role of the homogeneity of cation distribution, as determined by EPMA, on the mechanisms involved in the reduction process.

  14. Solid state oxidation of phenols to quinones with sodium perborate on wet montmorillonite K10

    Energy Technology Data Exchange (ETDEWEB)

    Hashemi, Mohammed M.; Eftekhari-Sis, Bagher; Khalili, Behzad; Karimi-Jaberi, Zahed [Sharif University of Technology, Tehran (Iran, Islamic Republic of). Dept. of Chemistry]. E-mail: mhashemi@sharif.edu

    2005-09-15

    Phenols were oxidized to quinones using sodium perborate (SPB) on wet montmorillonite as oxidant. The reaction was carried out at ambient temperature on the solid phase under solvent free conditions. (author)

  15. Solid state oxidation of phenols to quinones with sodium perborate on wet montmorillonite K10

    International Nuclear Information System (INIS)

    Hashemi, Mohammed M.; Eftekhari-Sis, Bagher; Khalili, Behzad; Karimi-Jaberi, Zahed

    2005-01-01

    Phenols were oxidized to quinones using sodium perborate (SPB) on wet montmorillonite as oxidant. The reaction was carried out at ambient temperature on the solid phase under solvent free conditions. (author)

  16. Study on the serum oxidative stress status in silicosis patients

    African Journals Online (AJOL)

    Administrator

    2011-09-07

    Sep 7, 2011 ... oxidative stress parameters were investigated in silicosis patients and controls group. 128 silicosis ... to help clinicians to further delineate the role of oxidative- stress .... in age, working duration smoking, total cholesterol, ALT,.

  17. Thermo-oxidative degradation study of melt-processed polyethylene and its blend with polyamide using time-resolved rheometry

    CSIR Research Space (South Africa)

    Salehiyan, Reza

    2017-05-01

    Full Text Available Time-resolved mechanical spectroscopy (TRMS) was conducted to study the thermo-oxidative degradation of linear low density polyethylene (LLDPE) samples with different thermal histories and their blends with a polyamide (PA6) in the melt state. Neat...

  18. [Studies on the oxidation reaction of octanol-2 with nitric acid by infrared spectroscopy].

    Science.gov (United States)

    Zhang, G; Zhao, G; Wang, Y; Zhang, Q; Zhang, S; Lu, F

    1998-04-01

    In this paper, the reaction process of oxidation of octanol-2 with nitric acid has been studied by IR spectroscopy. It is found that the main components of non-sapoifiable matter are different in different oxidation degrees. The relation between oxidation products and the amount of nitric acid are investigated,the reaction mechanism has also been studied. Experimental results show that the oxidation process of octanol-2 is as follows: first, octanol-2 is oxidated to octanone-2, or to nitrate, nitrite and nitrile copmpounds, then these compounds are reoxidated to caproic acid in the meantime some by-products, such as valeric, enanthic acids are also found in oxidated products.

  19. Electronic States of High-k Oxides in Gate Stack Structures

    Science.gov (United States)

    Zhu, Chiyu

    In this dissertation, in-situ X-ray and ultraviolet photoemission spectroscopy have been employed to study the interface chemistry and electronic structure of potential high-k gate stack materials. In these gate stack materials, HfO2 and La2O3 are selected as high-k dielectrics, VO2 and ZnO serve as potential channel layer materials. The gate stack structures have been prepared using a reactive electron beam system and a plasma enhanced atomic layer deposition system. Three interrelated issues represent the central themes of the research: 1) the interface band alignment, 2) candidate high-k materials, and 3) band bending, internal electric fields, and charge transfer. 1) The most highlighted issue is the band alignment of specific high-k structures. Band alignment relationships were deduced by analysis of XPS and UPS spectra for three different structures: a) HfO2/VO2/SiO2/Si, b) HfO 2-La2O3/ZnO/SiO2/Si, and c) HfO 2/VO2/ HfO2/SiO2/Si. The valence band offset of HfO2/VO2, ZnO/SiO2 and HfO 2/SiO2 are determined to be 3.4 +/- 0.1, 1.5 +/- 0.1, and 0.7 +/- 0.1 eV. The valence band offset between HfO2-La2O3 and ZnO was almost negligible. Two band alignment models, the electron affinity model and the charge neutrality level model, are discussed. The results show the charge neutrality model is preferred to describe these structures. 2) High-k candidate materials were studied through comparison of pure Hf oxide, pure La oxide, and alloyed Hf-La oxide films. An issue with the application of pure HfO2 is crystallization which may increase the leakage current in gate stack structures. An issue with the application of pure La2O3 is the presence of carbon contamination in the film. Our study shows that the alloyed Hf-La oxide films exhibit an amorphous structure along with reduced carbon contamination. 3) Band bending and internal electric fields in the gate stack structure were observed by XPS and UPS and indicate the charge transfer during the growth and process. The oxygen

  20. Study of coal oxidation by charged particle activation analysis

    International Nuclear Information System (INIS)

    Schlyer, D.J.; Wolf, A.P.

    1980-01-01

    It has been possible, using the technique of changed particle activation analysis, to follow the time course of the oxidation of coal exposed to air. The kinetics have been studied and seem to be consistent with a rapid initial uptake of oxygen containing molecules followed by slow diffusion into the surface of the coal particles. In this latter regard a study has been undertaken to study the depth profile of the oxygen into the coal particle surface. The depth of penetration of the activating particle is determined by the incident energy and therefore, by comparison to the appropriate standards, the depth profile may be determined either by varying the incident energy or by varying the particle size. Both approaches have been used and give consistent results. The depth to which a significant amount of oxygen penetrates varies from about 3 μm for very high rank coals to about 20 μm for low rank coals. This diffusion depth seems to be related to the porosity of the coals. A model for the low temperature air oxidation of coal has been developed to explain the results from the above mentioned experiments

  1. Uranium Immobilization through Fe(II) bio-oxidation: A Column study

    Energy Technology Data Exchange (ETDEWEB)

    Coates, John D.

    2009-09-14

    Current research on the bioremediation of heavy metals and radionuclides is focused on the ability of reducing organisms to use these metals as alternative electron acceptors in the absence of oxygen and thus precipitate them out of solution. However, many aspects of this proposed scheme need to be resolved, not the least of which is the time frame of the treatment process. Once treatment is complete and the electron donor addition is halted, the system will ultimately revert back to an oxic state and potentially result in the abiotic reoxidation and remobilization of the immobilized metals. In addition, the possibility exists that the presence of more electropositive electron acceptors such as nitrate or oxygen will also stimulate the biological oxidation and remobilization of these contaminants. The selective nitrate-dependent biooxidation of added Fe(II) may offer an effective means of “capping off” and completing the attenuation of these contaminants in a reducing environment making the contaminants less accessible to abiotic and biotic reactions and allowing the system to naturally revert to an oxic state. Our previous DOE-NABIR funded studies demonstrated that radionuclides such as uranium and cobalt are rapidly removed from solution during the biogenic formation of Fe(III)-oxides. In the case of uranium, X-ray spectroscopy analysis indicated that the uranium was in the hexavalent form (normally soluble) and was bound to the precipitated Fe(III)-oxides thus demonstrating the bioremediative potential of this process. We also demonstrated that nitrate-dependent Fe(II)- oxidizing bacteria are prevalent in the sediment and groundwater samples collected from sites 1 and 2 and the background site of the NABIR FRC in Oakridge, TN. However, all of these studies were performed in batch experiments in the laboratory with pure cultures and although a significant amount was learned about the microbiology of nitrate-dependent bio-oxidation of Fe(II), the effects of

  2. Internal photoemission study on charge trapping behavior in rapid thermal oxides on strained-Si/SiGe heterolayers

    International Nuclear Information System (INIS)

    Bera, M.K.; Mahata, C.; Bhattacharya, S.; Chakraborty, A.K.; Armstrong, B.M.; Gamble, H.S.; Maiti, C.K.

    2008-01-01

    A comparative study on the nature of defects and their relationship to charge trapping with enhanced photosensitivity has been investigated through magnetic resonance and internal photoemission (IPE) experiments for rapid thermal grown oxides (RTO) on strained-Si/Si 0.8 Ge 0.2 and on co-processed bulk-Si (1 0 0) substrates. Both the band and defect-related electronic states were characterized through EPR, IPE, C-V and I-V measurements under UV-illumination. Surface chemical characterization of as-grown ultrathin oxides (5-7 nm) has been performed using high-resolution XPS. Enhancement in Ge-segregation with increasing oxidation temperature is reported. Comparative studies on interface properties and leakage current behavior of rapid thermal oxides have also been studied through fabricating metal-oxide-semiconductor capacitor structures. A degraded electrical property with increasing oxidation temperature is reported. Constant voltage stressing (CVS) in the range of 5.5-7 V was used to study the breakdown characteristics of different samples. We observe a distinguishably different time-to-breakdown (t bd ) phenomenon for bulk-Si and strained-Si/SiGe samples. Whereas the oxide on bulk-Si shows a typical breakdown behavior, the RTO grown oxide on strained-Si/SiGe samples showed a quasi-or soft-breakdown with lower t bd value. It may be pointed out that quasi-breakdown may be a stronger reliability limiting factor for strained-Si/SiGe devices in the oxide thickness range studied

  3. Hydrophobic matrix-free graphene-oxide composites with isotropic and nematic states

    Science.gov (United States)

    Wåhlander, Martin; Nilsson, Fritjof; Carlmark, Anna; Gedde, Ulf W.; Edmondson, Steve; Malmström, Eva

    2016-08-01

    We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been immobilised on anionic GO and subsequently grafted with hydrophobic polymer grafts. Dense grafts of PBA, PBMA and PMMA with a wide range of average graft lengths (MW: 1-440 kDa) were polymerised by surface-initiated controlled radical precipitation polymerisation from the statistical MI. The surface modification is designed similarly to bimodal graft systems, where the cationic MI generates nanoparticle repulsion, similar to dense short grafts, while the long grafts offer miscibility in non-polar environments and cohesion. The state-of-the-art dispersions of grafted GO were in the isotropic state. Transparent and translucent matrix-free GO-composites could be melt-processed directly using only grafted GO. After processing, birefringence due to nematic alignment of grafted GO was observed as a single giant Maltese cross, 3.4 cm across. Permeability models for composites containing aligned 2D-fillers were developed, which were compared with the experimental oxygen permeability data and found to be consistent with isotropic or nematic states. The storage modulus of the matrix-free GO-composites increased with GO content (50% increase at 0.67 wt%), while the significant increases in the thermal stability (up to 130 °C) and the glass transition temperature (up to 17 °C) were dependent on graft length. The tuneable matrix-free GO-composites with rapid thermo-responsive shape-memory effects are promising candidates for a vast range of applications, especially selective membranes and sensors.We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been

  4. Alkylselenite-catalyzed Oxidative Carbonylation of Amines: Density Functional Theory Study

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Sun; Kim, Hoon Sik; Cheong, Minserk [Kyung Hee Univ., Seoul (Korea, Republic of)

    2012-11-15

    Ureas and carbamates have been conventionally produced by the reaction of amines with phosgene. However, phosgenation processes raise severe environmental concerns, which are attributed to the toxicity of phosgene and the formation of corrosive hydrogen chloride as a co-product. The considerable industrial interest in replacing current phosgene-based processes prompted several methods using non-phosgene routes including carbonylation of amines or nitro compounds and carbomethoxylation of amines with dialkylcarbonates. Among these, catalytic oxidative carbonylation of an amine in the presence of alcohol has been studied most extensively. Catalytic systems based on precious metals such as Rh and Pd are commonly used for this purpose, but most of these catalytic systems suffer from either low reactivity or severe reaction conditions such as high temperature and pressures. In conclusion, the facile change of selenium oxidation state by CO and O{sub 2} might be the main reason for the activity of the selenium catalyst for this reaction.

  5. Alkylselenite-catalyzed Oxidative Carbonylation of Amines: Density Functional Theory Study

    International Nuclear Information System (INIS)

    Hwang, Sun; Kim, Hoon Sik; Cheong, Minserk

    2012-01-01

    Ureas and carbamates have been conventionally produced by the reaction of amines with phosgene. However, phosgenation processes raise severe environmental concerns, which are attributed to the toxicity of phosgene and the formation of corrosive hydrogen chloride as a co-product. The considerable industrial interest in replacing current phosgene-based processes prompted several methods using non-phosgene routes including carbonylation of amines or nitro compounds and carbomethoxylation of amines with dialkylcarbonates. Among these, catalytic oxidative carbonylation of an amine in the presence of alcohol has been studied most extensively. Catalytic systems based on precious metals such as Rh and Pd are commonly used for this purpose, but most of these catalytic systems suffer from either low reactivity or severe reaction conditions such as high temperature and pressures. In conclusion, the facile change of selenium oxidation state by CO and O 2 might be the main reason for the activity of the selenium catalyst for this reaction

  6. XPS study of vanadium surface oxidation by oxygen ion bombardment

    Czech Academy of Sciences Publication Activity Database

    Alov, N.; Kutsko, D.; Spirovová, Ilona; Bastl, Zdeněk

    2006-01-01

    Roč. 600, č. 8 (2006), s. 1628-1631 ISSN 0039-6028 R&D Projects: GA ČR GA104/04/0467 Institutional research plan: CEZ:AV0Z40400503 Keywords : vanadium oxide * oxide film * ion-beam oxidation * X-ray photoelectron spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.880, year: 2006

  7. The stability study of myristyl dimethyl amine oxide as an amphoteric ...

    African Journals Online (AJOL)

    The stability study of myristyl dimethyl amine oxide as an amphoteric surfactant in strong oxidant media containing 5 % m/m sodium hypochlorite through measurement of decomposing rate using high performance liquid chromatography and two phase titration.

  8. Studies of colossal magnetoresistive oxides with radioactive isotopes

    CERN Document Server

    CERN. Geneva. ISOLDE and Neutron Time-of-Flight Experiments Committee; Amaral, V S; Araújo, J P; Butz, T; Correia, J G; Dubourdieu, C; Habermeier, H U; Lourenço, A A; Marques, J G; Da Silva, M F A; Senateur, J P; Soares, J C; Sousa, J B; Suryan, R; Tokura, Y; Tavares, P B; Tomioka, Y; Tröger, W; Vantomme, A; Vieira, J M; Wahl, U; Weiss, F P; INTC

    2000-01-01

    We propose to study Colossal Magnetoresistive (CMR) oxides with several nuclear techniques, which use radioactive elements at ISOLDE. Our aim is to provide local and element selective information on some of the doping mechanisms that rule electronic interactions and magnetoresistance, in a complementary way to the use of conventional characterisation techniques. Three main topics are proposed: \\\\ \\\\ a) Studies of local [charge and] structural modifications in antiferromagnetic LaMnO$_{3+ \\delta}$ and La$_{1-x}$R$_{x}$MnO$_{3}$ with R=Ca and Cd, doped ferromagnetic systems with competing interactions: - research on the lattice site and electronic characterisation of the doping element. \\\\ \\\\ b) Studies of self doped La$_{x}$R$_{1-x}$MnO$_{3+\\delta}$ systems, with oxygen and cation non-stoichiometry: -learning the role of defects in the optimisation of magnetoresistive properties. \\\\ \\\\ c) Probing the disorder and quenched random field effects in the vicinity of the charge or orbital Ordered/Ferromagnetic phase...

  9. Studies of Colossal Magnetoresistive Oxides with Radioactive Isotopes

    CERN Multimedia

    2002-01-01

    We propose to study Colossal Magnetoresistive (CMR) oxides with several nuclear techniques, which use radioactive elements at ISOLDE. Our aim is to provide local and element selective information on some of the doping mechanisms that rule electronic interactions and magneto- resistance, in a complementary way to the use of conventional characterisation techniques. Three main topics are proposed: \\\\ \\\\ a) Studies of local [charge and] structural modifications in antiferromagnetic LaMnO$_{3+\\delta}$ and La$_{1-x}$R$_{x}$MnO$_{3}$ with R=Ca and Cd, doped ferromagnetic systems with competing interactions: - research on the lattice site and electronic characterisation of the doping element. \\\\ \\\\ b) Studies of self doped La$_{x}$R$_{1-x}$MnO$_{3+\\delta}$ systems, with oxygen and cation non- stoichiometry: - learning the role of defects in the optimisation of magnetoresestive properties. \\\\ \\\\ c) Probing the disorder and quenched random field effects in the vicinity of the charge or orbital Ordered/Ferromagnetic p...

  10. A study on the oxidation behavior of uranium

    International Nuclear Information System (INIS)

    Kim, Tae Kook; Kang, Kweon Ho; Kim, Kil Jeang; Kang, Il Sik; Jung, Kyung Whan

    1998-03-01

    When storing depleted uranium wastes, careful handling is required due to their very high oxidation rates. To determine the oxidation mechanism and oxidation rate of depleted uranium wastes, the most important factors to be considered in their treatment, an experiment was carried out by varying the heating rates of the Air-Controlled Oxidizer. The experiment, showed that depleted uranium wastes are pulverized after complete oxidation because of the density difference and then converted to UO 2 , U 3 O 7 , U 3 O 8 . The grain size of pulverized powder decrease with increased temperature. (author). 30 refs., 5 tabs., 28 figs

  11. Study of the oxidation kinetics of the MA 956 superalloy

    International Nuclear Information System (INIS)

    Garcia-Alonso, M.C.; Gonzalez-Carrasco, J.L.; Escudero, M.L.

    1998-01-01

    This work deals with the oxidation kinetics of the MA 956 superalloy in the temperature range of 800-1,200 degree centigree for up to 200 h exposure. During oxidation the alloy develops a fine, compact and very well adhered α-alumina layer, the thickness of which increases with increasing time and temperature. The oxidation kinetics obeys a sub parabolic type behaviour. The scale growth seems to occur by two different oxidation mechanisms; above 1,050 degree centigree, the oxidation process would be controlled by α-alumina, and below 900 degree centigree by γ-alumina. (Author) 17 refs

  12. Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

    Energy Technology Data Exchange (ETDEWEB)

    Yamaura, Kazunari, E-mail: YAMAURA.Kazunari@nims.go.jp [Superconducting Properties Unit, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Graduate School of Chemical Sciences and Engineering, Hokkaido University, North 10 West 8, Kita-ku, Sapporo, Hokkaido 060-0810 (Japan)

    2016-04-15

    High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO{sub 3}, LiOsO{sub 3}, and Na{sub 2}OsO{sub 4}, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal–insulator transition in NaOsO{sub 3}, a ferroelectric-like transition in LiOsO{sub 3}, and high-temperature ferrimagnetism driven by a local structural distortion in Ca{sub 2}FeOsO{sub 6} may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices. - Graphical Abstract: Flux-grown crystals of NaOsO{sub 3} under high-pressure and high-temperature conditions in a belt-type apparatus. The crystal shows a magnetically driven metal–insulator transition at a temperature of 410 K. - Highlights: • Short review of high-pressure crystal growth of solid-state osmium oxides. • Wide variety of magnetic properties of solid-state osmium oxides. • Perovskite and related dense structures stabilized at 3–17 GPa.

  13. Pu oxidation state distributions in suspensions of the Mont Terri Opalinus Clay isolate Sporomusa sp. MT-2.99

    Energy Technology Data Exchange (ETDEWEB)

    Moll, Henry [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biogeochemistry; Cherkouk, Andrea [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). HZDR Young Investigator Group; Bok, Frank [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

    2017-06-01

    The time-dependent {sup 242}Pu oxidation state distribution in the presence of Sporomusa sp. cells as a function of pH with or without Na-pyruvate was analyzed. In all cases, the presence of bacterial cells enhanced removal of Pu from solution and accelerated Pu interaction reactions, e.g. biosorption and bioreduction.

  14. Pu oxidation state distributions in suspensions of the Mont Terri Opalinus Clay isolate Sporomusa sp. MT-2.99

    International Nuclear Information System (INIS)

    Moll, Henry; Cherkouk, Andrea; Bok, Frank

    2017-01-01

    The time-dependent "2"4"2Pu oxidation state distribution in the presence of Sporomusa sp. cells as a function of pH with or without Na-pyruvate was analyzed. In all cases, the presence of bacterial cells enhanced removal of Pu from solution and accelerated Pu interaction reactions, e.g. biosorption and bioreduction.

  15. Oxide nanomaterials: synthetic developments, mechanistic studies, and technological innovations.

    Science.gov (United States)

    Patzke, Greta R; Zhou, Ying; Kontic, Roman; Conrad, Franziska

    2011-01-24

    Oxide nanomaterials are indispensable for nanotechnological innovations, because they combine an infinite variety of structural motifs and properties with manifold morphological features. Given that new oxide materials are almost reported on a daily basis, considerable synthetic and technological work remains to be done to fully exploit this ever increasing family of compounds for innovative nano-applications. This calls for reliable and scalable preparative approaches to oxide nanomaterials and their development remains a challenge for many complex nanostructured oxides. Oxide nanomaterials with special physicochemical features and unusual morphologies are still difficult to access by classic synthetic pathways. The limitless options for creating nano-oxide building blocks open up new technological perspectives with the potential to revolutionize areas ranging from data processing to biocatalysis. Oxide nanotechnology of the 21st century thus needs a strong interplay of preparative creativity, analytical skills, and new ideas for synergistic implementations. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. A DMS kinetic study of the boron oxides vapor in the combustion front of SHS system Mo + B

    International Nuclear Information System (INIS)

    Kashireninov, O.E.; Yuranov, I.A.

    1994-01-01

    The distribution of the boron oxides vapor in the combustion wave of the SHS system Mo + B has been studied by the dynamic mass spectrometry technique (DMS) to test the thermodynamically based hypothesis for the key role of gas-phase transport in solid-state combustion. The molecular beam sampling of the gases over the burning tablet was performed by a stationary probe cone from the moving combustion wave. Ion currents of boron oxides were recorded at 10--20 ms intervals that afforded spatial resolution of 0.1--0.2 mm. It has been found that the distribution of the boron oxides vapor pressure along the combustion wave corresponds to the known zones of preheating, reaction, and postcombustion. The rapid increase of B 2 O 2 pressure takes place in the preheating zone as a result of the reaction B(s) + B 2 O 3 (g) = B 2 O 2 (g). Boron oxides are not observed over the reaction zone because of their complete decay in the reaction with Mo(s) to form molybdenum boride(s). The appearance The appearance of boron oxide vapors over the postcombustion zone is due to the evaporation of B 2 O 3 (l). The effective kinetic parameters are estimated from the data obtained. The results show that solid-state combustion of the Mo + B system proceeds predominantly through formation of gas-phase boron oxides

  17. Experimental kinetic study and modeling of calcium oxide carbonation

    International Nuclear Information System (INIS)

    Rouchon, L.

    2012-01-01

    Anthropogenic carbon dioxide (CO 2 ) emissions, major contributors to the greenhouse effect, are considered as the main cause of global warming. So, decrease of CO 2 emitted by large industrial combustion sources or power plants, is an important scientific goal. One of the approaches is based on CO 2 separation and capture from flue gas, followed by sequestration in a wide range of geological formations. In this aim, CO 2 is captured by sorbents like calcium oxide (CaO) in multi-cycle process of carbonation/de-carbonation. However, it was shown that the most important limitations of such process are related to the reversibility of reaction. CaO rapidly loses activity towards CO 2 , so the maximum extent of carbonation decreases as long as the number of cycles increases. In order to well understand the processes and parameters influencing the capture capacity of CaO-based sorbents, it appears important to get details on the kinetic law governing the reaction, which have not been really studied up to now. To investigate this reaction, CaO carbonation kinetics was followed by means of thermogravimetric analysis (TGA) on divided materials. Special care was given to the validation of the usual kinetic assumptions such as steady state and rate-determining step assumptions. The aim was to obtain a model describing the reaction in order to explain the influence of intensive variables such as carbonation temperature and CO 2 partial pressure. TGA curves obtained under isothermal and isobaric conditions showed an induction period linked to the nucleation process and a strong slowing down of the reaction rate once a given fractional conversion was reached. Both phenomena were observed to depend on carbonation temperature and CO 2 partial pressure. To explain these results, the evolution of texture and microstructure of the solid during the reaction was regarded as essential. Reaction at the grain scale induces a volume increase from CaO to CaCO 3 which causes a change in the

  18. Shock compression of strongly correlated oxides: A liquid-regime equation of state for cerium(IV) oxide

    Science.gov (United States)

    Weck, Philippe F.; Cochrane, Kyle R.; Root, Seth; Lane, J. Matthew D.; Shulenburger, Luke; Carpenter, John H.; Sjostrom, Travis; Mattsson, Thomas R.; Vogler, Tracy J.

    2018-03-01

    The shock Hugoniot for full-density and porous CeO2 was investigated in the liquid regime using ab initio molecular dynamics (AIMD) simulations with Erpenbeck's approach based on the Rankine-Hugoniot jump conditions. The phase space was sampled by carrying out NVT simulations for isotherms between 6000 and 100 000 K and densities ranging from ρ =2.5 to 20 g /cm3 . The impact of on-site Coulomb interaction corrections +U on the equation of state (EOS) obtained from AIMD simulations was assessed by direct comparison with results from standard density functional theory simulations. Classical molecular dynamics (CMD) simulations were also performed to model atomic-scale shock compression of larger porous CeO2 models. Results from AIMD and CMD compression simulations compare favorably with Z-machine shock data to 525 GPa and gas-gun data to 109 GPa for porous CeO2 samples. Using results from AIMD simulations, an accurate liquid-regime Mie-Grüneisen EOS was built for CeO2. In addition, a revised multiphase SESAME-type EOS was constrained using AIMD results and experimental data generated in this work. This study demonstrates the necessity of acquiring data in the porous regime to increase the reliability of existing analytical EOS models.

  19. Conditioning of Si-interfaces by wet-chemical oxidation: Electronic interface properties study by surface photovoltage measurements

    International Nuclear Information System (INIS)

    Angermann, Heike

    2014-01-01

    Highlights: • Determination of electronic interface properties by contact-less surface photovoltage (SPV) technique. • Systematic correlations of substrate morphology and surface electronic properties. • Optimization of surface pre-treatment for flat, saw damage etched, and textured Si solar cell substrates. • Ultra-thin passivating Si oxide layers with low densities of rechargeable states by wet-chemical oxidation and subsequent annealing. • Environmentally acceptable processes, utilizing hot water, diluted HCl, or ozone low cost alternative to current approaches with concentrated chemicals. • The effect of optimized wet-chemical pre-treatments can be preserved during subsequent layer deposition. - Abstract: The field-modulated surface photovoltage (SPV) method, a very surface sensitive technique, was utilized to determine electronic interface properties on wet-chemically oxidized and etched silicon (Si) interfaces. The influence of preparation-induced surface micro-roughness and un-stoichiometric oxides on the resulting the surface charge, energetic distribution D it (E), and density D it,min of rechargeable states was studied by simultaneous, spectroscopic ellipsometry (SE) measurements on polished Si(111) and Si(100) substrates. Based on previous findings and new research, a study of conventional and newly developed wet-chemical oxidation methods was established, correlating the interactions between involved oxidizing and etching solutions and the initial substrate morphology to the final surface conditioning. It is shown, which sequences of wet-chemical oxidation and oxide removal, have to be combined in order to achieve atomically smooth, hydrogen terminated surfaces, as well as ultra-thin oxide layers with low densities of rechargeable states on flat, saw damage etched, and textured Si substrates, as commonly applied in silicon device and solar cell manufacturing. These conventional strategies for wet-chemical pre-treatment are mainly based on

  20. Oxidation state inherited from the magma source and implications for mineralization: Late Jurassic to Early Cretaceous granitoids, Central Lhasa subterrane, Tibet

    Science.gov (United States)

    Cao, MingJian; Qin, KeZhang; Li, GuangMing; Evans, Noreen J.; McInnes, Brent I. A.; Li, JinXiang; Zhao, JunXing

    2018-03-01

    Arc magmas are more oxidized than mid-ocean ridge basalts; however, there is continuing debate as to whether this higher oxidation state is inherited from the source magma or developed during late-stage magmatic differentiation processes. Well-constrained Late Jurassic to Early Cretaceous arc-related intermediate to felsic rocks derived from distinct magma sources provide us with a good opportunity to resolve this enigma. A series of granitoids from the western Central Lhasa subterrane were analyzed for whole-rock magnetic susceptibility, Fe2O3/FeO ratios, and trace elements in zircon. Compared to Late Jurassic samples (1.8 ± 2.0 × 10-4 emu g-1 oe-1, Fe3+/Fetotal = 0.32 ± 0.07, zircon Ce4+/Ce3+* = 15.0 ± 13.4), Early Cretaceous rocks show higher whole-rock magnetic susceptibility (5.8 ± 2.5 × 10-4 emu g-1 oe-1), Fe3+/Fetotal ratios (0.43 ± 0.04), and zircon Ce4+/Ce3+* values (23.9 ± 22.3). In addition, positive correlations among whole-rock magnetic susceptibility, Fe3+/Fetotal ratios, and zircon Ce4+/Ce3+* reveal a slight increase in oxidation state from fO2 = QFM to NNO in the Late Jurassic to fO2 = ˜NNO in the Early Cretaceous. Obvious linear correlation between oxidation indices (whole-rock magnetic susceptibility, zircon Ce4+/Ce3+*) and source signatures (zircon ɛHf(t), TDM C ages) indicates that the oxidation state was predominantly inherited from the source with only a minor contribution from magmatic differentiation. Thus, the sources for both the Late Jurassic and Early Cretaceous rocks were probably influenced by mantle wedge-derived magma, contributing to the increased fO2. Compared to ore-forming rocks at giant porphyry Cu deposits, the relatively low oxidation state (QFM to NNO) and negative ɛHf(t) (-16 to 0) of the studied granitoids implies relative infertility. However, this study demonstrates two potential fast and effective indices ( fO2 and ɛHf(t)) to evaluate the fertility of granitoids for porphyry-style mineralization. In an

  1. Influence of de-hulled rapeseed roasting on the physicochemical composition and oxidative state of oil

    International Nuclear Information System (INIS)

    Rękas, A.; Siger, A.; Wroniak, M.; Ścibisz, I.; Derewiaka, D.; Anders, A.

    2017-01-01

    The effect of roasting time on the contents of bioactive compounds (tocopherols, phytosterols, phenolic compounds), antioxidant capacity and physicochemical properties of rapeseed oil pressed from de-hulled seeds was investigated. The de-hulled seeds were roasted at a temperature of 165 °C for 20, 40, 60, 80, and 100 min. The results of this study show that a roasting pre-treatment led to a gradual increase in canolol content (from 1.34 to 117.33 mg/100 g), total phytosterols (from 573.51 to 609.86 mg/100 g) and total carotenoids (0.82 to 2.41 mg/100 g), while only slight changes in the contents of tocopherols were noted. With the increase in roasting time a gradual increase in oxidative stability (from 4.27 to 6.85 h), and antioxidant capacity, seen mainly in the hydrophilic fraction of oil (from 0.32 to 2.30 mmol TEAC/l) was found. Although roasting resulted in the formation of primary and secondary oxidation products, the quality parameters of oils were within Codex Alimentarius limits. [es

  2. Study of molybdenum oxide by means of Perturbed Angular Correlations (PAC) and Mössbauer spectroscopy

    CERN Multimedia

    Among transition-metal oxides, the molybdenum oxide compounds are particularly attractive due to the structural (2D) anisotropy and to the ability of the molybdenum ion to change its oxidation state. These properties make it suitable for applications on, e.g., chemical sensors, solar cells, catalytic and optoelectronic devices. At ISOLDE we aim studying the incorporation of selected dopants by ion implantation, using the nuclear techniques of Perturbed Angular Correlations (PAC) and Mössbauer spectroscopy (MS). Both techniques make use of highly diluted radioactive probe nuclei, which interact – as atomic-sized tips – with the host atoms and defects. The objectives of this project are to study at the atomic scale the probe’s local environment, its electronic configuration and polarization, the probe’s lattice sites, point defects and its recombination dynamics. In the case of e-$\\gamma$ PAC, the electron mobility on the host can be further studied, e.g., as a function of temperature.

  3. Radiolysis study of the oxidation of a vitamin K model compound in ethanolic solution

    International Nuclear Information System (INIS)

    Fackir, L.; Jore, D.; Gardes-Albert, M.; Ferradini, C.; Acher, F.; Azerad, R.

    1993-01-01

    It seems that the biological action of vitamin K (with its important role in carboxylating processes) may involve monoelectronic exchanges. Therefore radical mechanisms of a vitamin K model molecule KHp have been studied in ethanolic solution by mean of steady state radiolysis method. The oxidation of KHp by H 3 C-CH(OH)OO . model peroxyl radicals leads to the formation of a 'dimeric' form of vitamin K. The superoxide anions seem not to be reactive towards KHp in the chosen irradiation conditions

  4. A structural study of ceramic oxides by X-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Akhtar, M.J.

    1995-01-01

    A detailed structural study of ceramic oxides is presented by employing X-ray Absorption Spectroscopy (XAS). In the present work X-ray Absorption Near Edge Structure (XANES) is used for the investigation of valence state of metal cations; whereas, Extended X-ray Absorption Fine Structure EXAFS) is employed for the determination for bond lengths, coordination numbers and nature of the elements present in the near neighbour shells surrounding the absorbing atom. These results show that local environment of dopant and host cations are different; and this variation in local structure depends on the nature and concentration of the dopant ions. (author)

  5. Diethyl Phthalate Causes Oxidative Stress: An in Vitro Study

    Directory of Open Access Journals (Sweden)

    Heena Prajapati

    2014-03-01

    Full Text Available Background: Phthalates are a group of multifunctional chemicals. Diethyl phthalate (DEP is one of the most frequently used phthalates in solvents and fixatives for numerous industrial products. Method: The present experiment was designed to assess oxidative stress, if any, caused by diethyl phthalate. For this the homogenates of liver and kidney were treated with different concentrations ( 10-40 µg/mL of DEP. 10% liver and kidney homogenates were prepared in phosphate buffered saline and used for estimation of lipid peroxidation.In final step lipid peroxidation and total protein content were analyzed. Results: The result revealed significant and dose - dependent increase in lipid peroxidation, whereas protein content reduced significantly. Maximum increase in LPO and decrease in protein content was observed at 40 µg/mL of DEP concentration. Conclusion: From this study, it can be concluded that different concentrations of DEP leads to dose- dependent significant increase in lipid peroxidation and decrease protein content.So at the different concentration of DEP cause oxidative stress.

  6. Molecular beam studies of oxide reduction by atomic hydrogen

    International Nuclear Information System (INIS)

    Olander, D.R.

    1978-01-01

    The graphite and oxide internals of a CTR are susceptible to chemical corrosion as well as to physical degradation by high-energy particles. Reactions of thermal atomic hydrogen with oxides are being studied. The hydrogen used is at thermal energy (0.22 eV). Typical data are reported for the H/UO 2 system. The reaction probability is plotted as a function of solid temperature at fixed beam intensity and moculation frequency. The reaction probability increases from low temperature to a high-temperature plateau at about 1300 0 C. Here the reaction rate is limited solely by the sticking probability of H on the surface; about one in seven of the incident atoms is chemisorbed by the surface and ultimately returns to the gas phase as water vapor. A reaction model comprising sticking, recombination to H 2 , solution and diffusion of H in the bulk of the UO 2 , surface reaction of adsorbed H with lattice oxygen atoms to produce the hydroxyl radical, and production of water is constructed. The rate constants for the elementary steps in the mechanism are tabulated. 2 figures, 2 tables

  7. Enhanced piezoelectricity of monolayer phosphorene oxides: a theoretical study.

    Science.gov (United States)

    Yin, Huabing; Zheng, Guang-Ping; Gao, Jingwei; Wang, Yuanxu; Ma, Yuchen

    2017-10-18

    Two-dimensional (2D) piezoelectric materials have potential applications in miniaturized sensors and energy conversion devices. In this work, using first-principles simulations at different scales, we systematically study the electronic structures and piezoelectricity of a series of 2D monolayer phosphorene oxides (POs). Our calculations show that the monolayer POs have tunable band gaps along with remarkable piezoelectric properties. The calculated piezoelectric coefficient d 11 of 54 pm V -1 in POs is much larger than those of 2D transition metal dichalcogenide monolayers and the widely used bulk α-quartz and AlN, and almost reaches the level of the piezoelectric effect in recently discovered 2D GeS. Furthermore, two other considerable piezoelectric coefficients, i.e., d 31 and d 26 with values of -10 pm V -1 and 21 pm V -1 , respectively, are predicted in some monolayer POs. We also examine the correlation between the piezoelectric coefficients and energy stability. The enhancement of piezoelectricity for monolayer phosphorene by oxidation will broaden the applications of phosphorene and phosphorene derivatives in nano-sized electronic and piezotronic devices.

  8. Valence state of Mn in Ca-doped LaMnO3 studied by high-resolution Mn K ß emission spectroscopy

    NARCIS (Netherlands)

    Tyson, T.A.; Qian, Q.; Kao, C.-C.; Rueff, J.-P.; Groot, F.M.F. de; Croft, M.; Cheong, S.-W.; Greenblatt, M.; Subramanian, M.A.

    1999-01-01

    Mn K ß x-ray emission spectra provide a direct method to probe the effective spin state and charge density on the Mn atom and is used in an experimental study of a class of Mn oxides. Specifically, the Mn K ß line positions and detailed spectral shapes depend on the oxidation and the spin state of

  9. Experimental studies of oxidic molten corium-vessel steel interaction

    International Nuclear Information System (INIS)

    Bechta, S.V.; Khabensky, V.B.; Vitol, S.A.; Krushinov, E.V.; Lopukh, D.B.; Petrov, Yu.B.; Petchenkov, A.Yu.; Kulagin, I.V.; Granovsky, V.S.; Kovtunova, S.V.; Martinov, V.V.; Gusarov, V.V.

    2001-01-01

    The experimental results of molten corium-steel specimen interaction with molten corium on the 'Rasplav-2' test facility are presented. In the experiments, cooled vessel steel specimens positioned on the molten pool bottom and uncooled ones lowered into the molten pool were tested. Interaction processes were studied for different corium compositions, melt superheating and in alternative (inert and air) overlying atmosphere. Hypotheses were put forward explaining the observed phenomena and interaction mechanisms. The studies presented in the paper were aimed at the detection of different corium-steel interaction mechanisms. Therefore certain identified phenomena are more typical of the ex-vessel localization conditions than of the in-vessel corium retention. Primarily, this can be referred to the phenomena of low-temperature molten corium-vessel steel interaction in oxidizing atmosphere

  10. Experimental studies of oxidic molten corium-vessel steel interaction

    Energy Technology Data Exchange (ETDEWEB)

    Bechta, S.V. E-mail: niti-npc@sbor.net; Khabensky, V.B.; Vitol, S.A.; Krushinov, E.V.; Lopukh, D.B.; Petrov, Yu.B.; Petchenkov, A.Yu.; Kulagin, I.V.; Granovsky, V.S.; Kovtunova, S.V.; Martinov, V.V.; Gusarov, V.V

    2001-12-01

    The experimental results of molten corium-steel specimen interaction with molten corium on the 'Rasplav-2' test facility are presented. In the experiments, cooled vessel steel specimens positioned on the molten pool bottom and uncooled ones lowered into the molten pool were tested. Interaction processes were studied for different corium compositions, melt superheating and in alternative (inert and air) overlying atmosphere. Hypotheses were put forward explaining the observed phenomena and interaction mechanisms. The studies presented in the paper were aimed at the detection of different corium-steel interaction mechanisms. Therefore certain identified phenomena are more typical of the ex-vessel localization conditions than of the in-vessel corium retention. Primarily, this can be referred to the phenomena of low-temperature molten corium-vessel steel interaction in oxidizing atmosphere.

  11. Preliminary design study of a large scale graphite oxidation loop

    International Nuclear Information System (INIS)

    Epel, L.G.; Majeski, S.J.; Schweitzer, D.G.; Sheehan, T.V.

    1979-08-01

    A preliminary design study of a large scale graphite oxidation loop was performed in order to assess feasibility and to estimate capital costs. The nominal design operates at 50 atmospheres helium and 1800 F with a graphite specimen 30 inches long and 10 inches in diameter. It was determined that a simple single walled design was not practical at this time because of a lack of commercially available thick walled high temperature alloys. Two alternative concepts, at reduced operating pressure, were investigated. Both were found to be readily fabricable to operate at 1800 F and capital cost estimates for these are included. A design concept, which is outside the scope of this study, was briefly considered

  12. Defect studies in copper-based p-type transparent conducting oxides

    Science.gov (United States)

    Ameena, Fnu

    Among other intrinsic open-volume defects, copper vacancy (VCu) has been theoretically identified as the major acceptor in p-type Cu-based semiconducting transparent oxides, which has potential as low-cost photovoltaic absorbers in semi-transparent solar cells. A series of positron annihilation experiments with pure Cu, Cu2O, and CuO presented strong presence of VCu and its complexes in the copper oxides. The lifetime data also showed that the density of VCu was becoming higher as the oxidation state of Cu increased which was consistent with the decrease in the formation energy of VCu. Doppler broadening measurements further indicated that electrons with low momentum made more contribution to the contributed as pure Cu oxidizes to copper oxides. The metastable defects are known to be generated in Cu2O upon illumination and it has been known to affect the performance of Cu2O-based hetero-junctions used in solar cells. The metastable effect was studied using positron annihilation lifetime spectroscopy and its data showed the change in the defect population upon light exposure and the minimal effect of light-induced electron density increase in the bulk of materials to the average lifetime of the positrons. The change in the defect population is concluded to be related to the dissociation and association of VCu -- V Cu complexes. For example, the shorter lifetime under light was ascribed to the annihilation with smaller size vacancies, which explains the dissociation of the complexes with light illumination. Doppler broadening of the annihilation was independent of light illumination, which suggested that the chemical nature of the defects remained without change upon their dissociation and association -- only the size distribution of copper vacancies varied. The delafossite metal oxides, CuMIIIO2 are emerging wide-bandgap p-type semiconductors. In this research, the formation energies of structural vacancies are calculated using Van Vechten cavity model as an attempt

  13. Studies on the biological oxidation - The oxidation of ascorbic acid (vitamin C) in biological fluids

    OpenAIRE

    Guzmán Barrón, E. S.; Guzmán Barrón, Alberto; Klemperer, Friedrich

    2014-01-01

    Biological fluids can be divided according to their behavior toward ascorbic acid into two groups: those having an inhibitory mechanism that protects the ascorbic acid oxidation, and those lacking this mechanism. Animal fluids and some of vegetable origin (those containing dosables amounts of ascorbic acid) corresponding to the first group. Ascorbic acid is protected from oxidation in the fluids by the action of copper catalyst. Fluids from plants (those that contain very little ascorbic acid...

  14. Waste management state-of-the-art review for mixed-oxide fuel fabrication facilities

    International Nuclear Information System (INIS)

    Woodsum, H.C.; Goodman, J.

    1977-11-01

    This report provides a state-of-the-art review of the waste management for mixed-oxide (MOX) fuel fabrication facilities. The intent of this report is to focus on those processes and regulatory issues which have a direct bearing on existing and anticipated future management of transuranic (TRU) wastes from a commercial MOX fuel fabrication faciity. Recent government agency actions are reviewed with regard to their impact on existing and projected waste management regulations; and it is concluded that acceleration in the development of regulations, standards, and criteria is one of the most important factors in the implementation of improved MOX plant waste management techniques. ERDA development programs pertaining to the management of TRU wastes have been reviewed and many promising methods for volume reduction of both solid and liquid wastes are discussed. For solid wastes, these methods include compaction, shredding and baling, combustion, acid digestion, and decontamination by electropolishing or by electrolytic treatment. For liquid wastes, treatment options include evaporation, drying, calcination, flocculation, ion exchange, filtration, reverse osmosis, combustion (of combustible organics), and bioprocessing. Based on this review, it is recommended that ERDA continue with its combustible solid waste volume reduction program and complete these development activities by 1979. Following this, a critical evaluation of solid waste volume reduction techniques should be made to select the most promising systems for a commercial MOX fuel facility

  15. Oxidation state of uranium in metamict and annealed zircon: near-infrared spectroscopic quantitative analysis

    CERN Document Server

    Zhang Ming; Ewing, R C

    2003-01-01

    Radiation and thermally induced changes in the oxidation state of uranium in metamict zircon have been systematically analysed, for the first time, using polarized near-infrared spectroscopy. The results showed that in damaged zircon U ions in crystalline domains exhibited relatively sharp, anisotropic signals from tetravalent and pentavalent U ions in crystalline domains (U sub c sub r sub y sub s sub t sub a sub l sup 4 sup + and U sub c sub r sub y sub s sub t sub a sub l sup 5 sup +). The linewidths and peak positions of the 4834 cm sup - sup 1 band (U sub c sub r sub y sub s sub t sub a sub l sup 4 sup + , E || c) and the 6668 cm sup - sup 1 band (U sub c sub r sub y sub s sub t sub a sub l sup 5 sup + , E perp. c) are a non-linear function of the self-radiation dose. They reach nearly constant values at doses greater than approx 3.5 x 10 sup 1 sup 8 alpha-events g sup - sup 1. Quantitative analysis of U sub c sub r sub y sub s sub t sub a sub l sup 4 sup + and U sub c sub r sub y sub s sub t sub a sub l...

  16. Carbonate-linked poly(ethylene oxide) polymer electrolytes towards high performance solid state lithium batteries

    International Nuclear Information System (INIS)

    He, Weisheng; Cui, Zili; Liu, Xiaochen; Cui, Yanyan; Chai, Jingchao; Zhou, Xinhong; Liu, Zhihong; Cui, Guanglei

    2017-01-01

    The classic poly(ethylene oxide) (PEO) based solid polymer electrolyte suffers from poor ionic conductivity of ambient temperature, low lithium ion transference number and relatively narrow electrochemical window (<4.0 V vs. Li + /Li). Herein, the carbonate-linked PEO solid polymer such as poly(diethylene glycol carbonate) (PDEC) and poly(triethylene glycol carbonate) (PTEC) were explored to find out the feasibility of resolving above issues. It was proven that the optimized ionic conductivity of PTEC based electrolyte reached up to 1.12 × 10 −5 S cm −1 at 25 °C with a decent lithium ion transference number of 0.39 and a wide electrochemical window about 4.5 V vs. Li + /Li. In addition, the PTEC based Li/LiFePO 4 cell could be reversibly charged and discharged at 0.05 C-rates at ambient temperature. Moreover, the higher voltage Li/LiFe 0.2 Mn 0.8 PO 4 cell (cutoff voltage 4.35 V) possessed considerable rate capability and excellent cycling performance even at ambient temperature. Therefore, these carbonate-linked PEO electrolytes were demonstrated to be fascinating candidates for the next generation solid state lithium batteries simultaneously with high energy and high safety.

  17. Adsorption of uranium composites onto saltrock oxides - experimental and theoretical study.

    Science.gov (United States)

    Ivanova, Bojidarka; Spiteller, Michael

    2014-09-01

    The study encompassed experimental mass spectrometric and theoretical quantum chemical studies on adsorption of uranium species in different oxidation states of the metal ion, and oxides of UxOy(n+) type, where x = 1 or 3, y = 2 or 8, and n = 0, 1 or 2 onto nanosize-particles of saltrock oxides MO (M = Mg(II), Ca(II), Ni(II), Co(II), Sr(II) or Ba(II)), M2Oy (M = Au(III) or Ag(I), y = 3 or 1) silicates 3Al2O3.2SiO2, natural kaolinite (Al2O2·2SiO2·2H2O), illite (K0.78Ca0.02Na0.02(Mg0.34Al1.69Fe(III)0.02)[Si3.35Al0.65]O10(OH)2·nH2O), CaSiO3, 3MgO·4SiO2,H2O, and M(1)M(2)(SiO4)X2 (M(1) = M(2) = Al or M(1) = K, M(2) = Al, X = F or Cl), respectively. The UV-MALDI-Orbitrap mass spectrometry was utilized in solid-state and semi-liquid colloidal state, involving the laser ablation at λex = 337.2 nm. The theoretical modeling and experimental design was based on chemical-, physico-chemical, physical and biological processes involving uranium species under environmental conditions. Therefore, the results reported are crucial for quality control and monitoring programs for assessment of radionuclide migration. They impact significantly the methodology for evaluation of human health risk from radioactive contamination. The study has importance for understanding the coordination and red-ox chemistry of uranium compounds as well. Due to the double nature of uranium between rare element and superconductivity like materials as well as variety of oxidation states ∈ (+1)-(+6), the there remain challenging areas for theoretical and experimental research, which are of significant importance for management of nuclear fuel cycles and waste storage. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Study on emission characteristics and reduction strategy of nitrous oxide during wastewater treatment by different processes.

    Science.gov (United States)

    Sun, Shichang; Bao, Zhiyuan; Sun, Dezhi

    2015-03-01

    Given the inexorable increase in global wastewater treatment, increasing amounts of nitrous oxide are expected to be emitted from wastewater treatment plants and released to the atmosphere. It has become imperative to study the emission and control of nitrous oxide in the various wastewater treatment processes currently in use. In the present investigation, the emission characteristics and the factors affecting the release of nitrous oxide were studied via full- and pilot-scale experiments in anoxic-oxic, sequencing batch reactor and oxidation ditch processes. We propose an optimal treatment process and relative strategy for nitrous oxide reduction. Our results show that both the bio-nitrifying and bio-denitrifying treatment units in wastewater treatment plants are the predominant sites for nitrous oxide production in each process, while the aerated treatment units are the critical sources for nitrous oxide emission. Compared with the emission of nitrous oxide from the anoxic-oxic (1.37% of N-influent) and sequencing batch reactor (2.69% of N-influent) processes, much less nitrous oxide (0.25% of N-influent) is emitted from the oxidation ditch process, which we determined as the optimal wastewater treatment process for nitrous oxide reduction, given the current technologies. Nitrous oxide emissions differed with various operating parameters. Controlling the dissolved oxygen concentration at a proper level during nitrification and denitrification and enhancing the utilization rate of organic carbon in the influent for denitrification are the two critical methods for nitrous oxide reduction in the various processes considered.

  19. Thulium oxide fuel characterization study: Part 3, Procedures

    International Nuclear Information System (INIS)

    Nelson, C.A.; Anderson, R.W.; Talbot, M.; Bierds, W.

    1970-06-01

    Procedures are presented for the following: Tm 2 O 3 -Yb 2 O 3 pseudo - binary phase diagram tests; compatibility tests; thulium-170 oxide dose rate measurements; preparation of Tm 2 O 3 wafers; SRL thulium and/or ytterbium oxide powder reprocessing for sintering; cold pressing and sintering thulium oxide wafers; preparation of thulium and/or ytterbium oxide powder via precipitation with oxalic acid, ammonium oxalate, urea and methyl oxalate; determination of the total surface area of rare earth oxide powders; determining oxygen in thulia - thulia/ytterbia for the purpose of determining metal-to-oxygen ratios; and determination of the impact resistance to fines generation of sintered rare earth oxide

  20. Study of oxidation behaviour of Zr-based bulk amorphous alloy Zr 65 ...

    Indian Academy of Sciences (India)

    The oxidation behaviour of Zr-based bulk amorphous alloy Zr65Cu17.5Ni10Al7.5 has been studied in air environment at various temperatures in the temperature range 591–684 K using a thermogravimetric analyser (TGA). The oxidation kinetics of the alloy in the amorphous phase obeys the parabolic rate law for oxidation ...

  1. Graphene oxide and reduced graphene oxide studied by the XRD, TEM and electron spectroscopy methods

    International Nuclear Information System (INIS)

    Stobinski, L.; Lesiak, B.; Malolepszy, A.; Mazurkiewicz, M.; Mierzwa, B.; Zemek, J.; Jiricek, P.; Bieloshapka, I.

    2014-01-01

    Highlights: • Graphene oxide (FL-GOc) and reduced graphene oxide (FL-RGOc): XRD, TEM, XPS, REELS. • FL-GOc: stacking nanostructure—22 × 6 nm (DxH), 0.9 nm layers separation (XRD). • FL-RGOc: stacking nanostructure—8 × 1 nm (DxH), 0.4 nm layers separation (XRD). • Reduction: oxygen group degradation, decreasing distance between graphene layers. • Number of graphene layers in stacking nanostructure: 6–7 (FL-GOc), 2–3 (FL-RGOc). - Abstract: The commercial and synthesised few-layer graphene oxide, prepared using oxidation reactions, and few-layer reduced graphene oxide samples were structurally and chemically investigated by the X-ray diffraction (XRD), transmission electron microscopy (TEM) and electron spectroscopy methods, i.e. X-ray photoelectron spectroscopy (XPS) and reflection electron energy loss spectroscopy (REELS). The commercial graphene oxide (FL-GOc) shows a stacking nanostructure of about 22 × 6 nm average diameter by height with the distance of 0.9 nm between 6-7 graphene layers, whereas the respective reduced graphene oxide (FL-RGOc)—about 8 × 1 nm average diameter by height stacking nanostructure with the distance of 0.4 nm between 2-3 graphene layers (XRD). The REELS results are consistent with those by the XRD indicating 8 (FL-GOc) and 4 layers (FL-RGOc). In graphene oxide and reduced graphene oxide prepared from the graphite the REELS indicates 8–11 and 7–10 layers. All graphene oxide samples show the C/O ratio of 2.1–2.3, 26.5–32.1 at% of C sp 3 bonds and high content of functional oxygen groups (hydroxyl—C-OH, epoxy—C-O-C, carbonyl—C=O, carboxyl—C-OOH, water) (XPS). Reduction increases the C/O ratio to 2.8–10.3, decreases C sp 3 content to 11.4–20.3 at% and also the content of C-O-C and C=O groups, accompanied by increasing content of C-OH and C-OOH groups. Formation of additional amount of water due to functional oxygen group reduction leads to layer delamination. Removing of functional oxygen groups

  2. Numerical Study of the Simultaneous Oxidation of NO and SO2 by Ozone

    Science.gov (United States)

    Li, Bo; Zhao, Jinyang; Lu, Junfu

    2015-01-01

    This study used two kinetic mechanisms to evaluate the oxidation processes of NO and SO2 by ozone. The performance of the two models was assessed by comparisons with experimental results from previous studies. The first kinetic mechanism was a combined model developed by the author that consisted of 50 species and 172 reactions. The second mechanism consisted of 23 species and 63 reactions. Simulation results of both of the two models show under predictions compared with experimental data. The results showed that the optimized reaction temperature for NO with O3 ranged from 100~200 °C. At higher temperatures, O3 decomposed to O2 and O, which resulted in a decrease of the NO conversion rate. When the mole ratio of O3/NO was greater than 1, products with a higher oxidation state (such as NO3, N2O5) were formed. The reactions between O3 and SO2 were weak; as such, it was difficult for O3 to oxidize SO2. PMID:25642689

  3. Polydatin administration improves serum biochemical parameters and oxidative stress markers during chronic alcoholism: a pilot study.

    Science.gov (United States)

    Pace, Maria Caterina; Passavanti, Maria Beatrice; Aurilio, Caterina; Sansone, Pasquale; Aurilio, Rossella; DE Maria, Salvatore; Lama, Stefania; Federico, Alessandro; Ravagnan, Gianpietro; Caraglia, Michele; Stiuso, Paola

    2015-01-01

    Polydatin, a hydroxystilbene derived from the rhizome of Polygonum cuspidatum, elicits hepatoprotective and neuroprotective effects through its anti-oxidant properties. The present study aimed to determine the effects of oral administration of polydatin in alcoholic patients in order to improve liver biochemical parameters, serum oxidative stress and mental state. We enrolled 20 chronic alcoholic patients hospitalized for rehabilitative therapy. The patients were divided into two groups receiving the following treatment regimes for two weeks: administration of an anti-oxidant nutritional supplement containing glutathione and vitamin C (group 1), or glutathione, vitamin C and polydatin (group 2). The results of the present study show that elevated plasma aspartate aminotransferase and alanine aminotransferase levels in patients after two weeks of alcohol withdrawal were significantly reduced by polydatin (group 2), when compared to group 1. Polydatin also significantly reduced lipid peroxidation levels. Finally, our preliminary data resulting from the analysis of the Mini-Mental Status suggest that polydatin improves cognitive performance. Daily dietary administration of polydatin should be considered for prevention and treatment of liver disease and cognitive impairment in alcoholic patients. Copyright © 2015 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

  4. The protonation state around TyrD/TyrD• in photosystem II is reflected in its biphasic oxidation kinetics.

    Science.gov (United States)

    Sjöholm, Johannes; Ho, Felix; Ahmadova, Nigar; Brinkert, Katharina; Hammarström, Leif; Mamedov, Fikret; Styring, Stenbjörn

    2017-02-01

    The tyrosine residue D2-Tyr160 (Tyr D ) in photosystem II (PSII) can be oxidized through charge equilibrium with the oxygen evolving complex in PSII. The kinetics of the electron transfer from Tyr D has been followed using time-resolved EPR spectroscopy after triggering the oxidation of pre-reduced Tyr D by a short laser flash. After its oxidation Tyr D is observed as a neutral radical (Tyr D • ) indicating that the oxidation is coupled to a deprotonation event. The redox state of Tyr D was reported to be determined by the two water positions identified in the crystal structure of PSII [Saito et al. (2013) Proc. Natl. Acad. Sci. USA 110, 7690]. To assess the mechanism of the proton coupled electron transfer of Tyr D the oxidation kinetics has been followed in the presence of deuterated buffers, thereby resolving the kinetic isotope effect (KIE) of Tyr D oxidation at different H/D concentrations. Two kinetic phases of Tyr D oxidation - the fast phase (msec-sec time range) and the slow phase (tens of seconds time range) were resolved as was previously reported [Vass and Styring (1991) Biochemistry 30, 830]. In the presence of deuterated buffers the kinetics was significantly slower compared to normal buffers. Furthermore, although the kinetics were faster at both high pH and pD values the observed KIE was found to be similar (~2.4) over the whole pL range investigated. We assign the fast and slow oxidation phases to two populations of PSII centers with different water positions, proximal and distal respectively, and discuss possible deprotonation events in the vicinity of Tyr D . Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Native oxide formation on pentagonal copper nanowires: A TEM study

    Science.gov (United States)

    Hajimammadov, Rashad; Mohl, Melinda; Kordas, Krisztian

    2018-06-01

    Hydrothermally synthesized copper nanowires were allowed to oxidize in air at room temperature and 30% constant humidity for the period of 22 days. The growth of native oxide layer was followed up by high-resolution transmission electron microscopy and diffraction to reveal and understand the kinetics of the oxidation process. Copper oxides appear in the form of differently oriented crystalline phases around the metallic core as a shell-like layer (Cu2O) and as nanoscopic islands (CuO) on the top of that. Time dependent oxide thickness data suggests that oxidation follows the field-assisted growth model at the beginning of the process, as practically immediately an oxide layer of ∼2.8 nm thickness develops on the surface. However, after this initial rapid growth, the local field attenuates and the classical parabolic diffusion limited growth plays the main role in the oxidation. Because of the single crystal facets on the side surface of penta-twinned Cu nanowires, the oxidation rate in the diffusion limited regime is lower than in polycrystalline films.

  6. Rapid Synthesis of Lead Oxide Nanorods by One-step Solid-state Chemical Reaction at Room Temperature

    Institute of Scientific and Technical Information of China (English)

    CAO, Ya-Li(曹亚丽); JIA, Dian-Zeng(贾殿赠); LIU, Lang(刘浪); LUO, Jian-Min(骆建敏)

    2004-01-01

    A simple and facile method was reported to synthesize lead oxide nanorods. Nanorods of lead oxide were obtained directly from grinding solid metal salt and sodium hydroxide in agate mortar with the assistance of a suitable nonionic surfactant in only one step, which is different from the result of hydroxide in solution. The product has been characterized by XRD, TEM and SEM. The formation mechanism of rod-like morphology is discussed and the surfactant plays an important soft-template role in modifying the interface of solid-state reaction and according process of rod-formation.

  7. Oxidative stress and redox state-regulating enzymes have prognostic relevance in diffuse large B-cell lymphoma

    Directory of Open Access Journals (Sweden)

    Peroja Pekka

    2012-03-01

    Full Text Available Abstract Background Oxidative stress and redox-regulating enzymes may have roles both in lymphomagenesis and resistance to lymphoma therapy. Previous studies from the pre-rituximab era suggest that antioxidant enzyme expression is related to prognosis in diffuse large B-cell lymphoma (DLBCL, although these results cannot be extrapolated to patient populations undergoing modern treatment modalities. In this study we assessed expression of the oxidative stress markers 8-hydroxydeoxyguanosine (8-OHdG and nitrotyrosine and the antioxidant enzymes thioredoxin (Trx, manganese superoxide dismutase (MnSOD and glutamate-cysteine ligase (GCL via immunohistochemistry in 106 patients with DLBCL. All patients were treated with CHOP-like therapy combined with rituximab. Immunostaining results were correlated with progression-free survival, disease-specific survival and traditional prognostic factors of DLBCL. Results Strong 8-OHdG immunostaining intensity was associated with extranodal involvement (p = 0.00002, a high International Prognostic Index (p = 0.002 and strong Trx (p = 0.011 and GCL (p = 0.0003 expression. Strong Trx staining intensity was associated with poor progression-free survival (p = 0.046 and poor disease-specific survival (p = 0.015. Strong GCL immunostaining intensity predicted poor progression-free survival (p = 0.049. Patients with either strong Trx or strong nitrotyrosine expression showed significantly poorer progression-free survival (p = 0.003 and disease-specific survival (p = 0.031 compared with the other patients. Conclusions The redox state-regulating enzymes GCL and Trx are promising markers in the evaluation of DLBCL prognosis in the era of modern immunochemotherapy.

  8. Monte Carlo study of double exchange interaction in manganese oxide

    Energy Technology Data Exchange (ETDEWEB)

    Naa, Christian Fredy, E-mail: chris@cphys.fi.itb.ac.id [Physics Department, Faculty of Mathematics and Natural Science, Institut Teknologi Bandung, Jalan Ganesha 10 Bandung (Indonesia); Unité de Dynamique et Structure des Matérioux Moléculaires, Université Littoral Côte d’Opale, Maison de la Reserche Blaise Pascal 50, rue Ferdinand Buisson, Calais, France email (France); Suprijadi,, E-mail: supri@fi.itb.ac.id; Viridi, Sparisoma, E-mail: dudung@fi.itb.ac.id; Djamal, Mitra, E-mail: mitra@fi.itb.ac.id [Physics Department, Faculty of Mathematics and Natural Science, Institut Teknologi Bandung, Jalan Ganesha 10 Bandung (Indonesia); Fasquelle, Didier, E-mail: didier.fasquelle@univ-littoral.fr [Unité de Dynamique et Structure des Matérioux Moléculaires, Université Littoral Côte d’Opale, Maison de la Reserche Blaise Pascal 50, rue Ferdinand Buisson, Calais, France email (France)

    2015-09-30

    In this paper we study the magnetoresistance properties attributed by double exchange (DE) interaction in manganese oxide by Monte Carlo simulation. We construct a model based on mixed-valence Mn{sup 3+} and Mn{sup 4+} on the general system of Re{sub 2/3}Ae{sub 1/3}MnO{sub 3} in two dimensional system. The conduction mechanism is based on probability of e{sub g} electrons hopping from Mn{sup 3+} to Mn{sup 4+}. The resistivity dependence on temperature and the external magnetic field are presented and the validity with related experimental results are discussed. We use the resistivity power law to fit our data on metallic region and basic activated behavior on insulator region. On metallic region, we found our result agree well with the quantum theory of DE interaction. From general arguments, we found our simulation agree qualitatively with experimental results.

  9. Comparative DEMS study on the electrochemical oxidation of carbon blacks

    DEFF Research Database (Denmark)

    Ashton, Sean James; Arenz, Matthias

    2012-01-01

    Publication year: 2012 Source:Journal of Power Sources, Volume 217 Sean J. Ashton, Matthias Arenz The intention of the study presented here is to compare the electrochemical oxidation tendencies of a pristine Ketjen Black EC300 high surface area (HSA) carbon black, and four graphitised counterparts...... heat-treated between 2100 and 3200 °C, such as those typically used as corrosion resistant carbon (CRC) supports for polymer electrolyte membrane fuel cell (PEMFC) catalysts. A methodology combining cyclic voltammetry (CV) and differential electrochemical mass spectrometry (DEMS) is used, which allows......; however, CRC samples graphitised =2800 °C did not exhibit this same behaviour. Highlights ¿ We quantitatively determine electrooxidation of carbon support materials. ¿ We can distinguish between the total and partial electrooxidation. ¿ Non or mildly heat treated carbon forms passivating layer. ¿ Heat...

  10. Study of the discontinuous dissolution of uranium oxides

    International Nuclear Information System (INIS)

    Bueno, L.A.O.; Floh, B.; Araujo, J.A. de.

    1978-01-01

    Dissolution studies of UO 2 and U 3 O 8 particles and pellets in nitric acid were carried out to find the best flowsheet conditions for treatment of irradiated materials. All experiments were accomplished with unirradiated oxides at room-and boiling point temperature of the nitric acid solutions, the acid molarity ranging from 1 up to 12M in stoichiometric-and (100% up to 300%) excess conditions. The UO 2 (10g) and U 3 O 8 (10g) are easily dissolved (10 and 50s), respectively, at boiling point of 6M nitric acid solution. At the same conditions compacted pellets are dissolved in 29 min (U 3 O 8 =5g) and in 330 min (UO 2 =20g) [pt

  11. Investigation of electrochemical behaviour and structure of oxide films on Ni60Nb40 alloy in amorphous and crystalline states

    International Nuclear Information System (INIS)

    Tomashov, N.D.; Skvortsova, I.B.; Gorodetskij, A.E.; Bogomolov, D.B.

    1987-01-01

    Electrochemical properties of Ni 60 Nb 40 alloy in amorphous and crystalline states as well as structure of oxide films forming during anode polarization in electrolytes on the surface of this alloy in both its states are investigated. It is stated that increased passive ability of Ni 60 Nb 40 alloys in amorphous state and high efficiency of chlorine evolution (2 n NaCl+HCl up to pH=0) anode process in comparison with crystalline state are defined by increased homogeneity and uniformity of passive films forming on amorphous alloy and their increased electron conductivity, that is in direct dependence on different structure of passive films forming on alloys in amorphous and crystalline states

  12. Assigning Oxidation States to Organic Compounds via Predictions from X-Ray Photoelectron Spectroscopy: A Discussion of Approaches and Recommended Improvements

    Science.gov (United States)

    Gupta, Vipul; Ganegoda, Hasitha; Engelhard, Mark H.; Terry, Jeff; Linford, Matthew R.

    2014-01-01

    The traditional assignment of oxidation states to organic molecules is problematic. Accordingly, in 1999, Calzaferri proposed a simple and elegant solution that is based on the similar electronegativities of carbon and hydrogen: hydrogen would be assigned an oxidation state of zero when bonded to carbon. Here, we show that X-ray photoelectron…

  13. Piper sarmentosum increases nitric oxide production in oxidative stress: a study on human umbilical vein endothelial cells.

    Science.gov (United States)

    Ugusman, Azizah; Zakaria, Zaiton; Hui, Chua Kien; Nordin, Nor Anita Megat Mohd

    2010-07-01

    Nitric oxide produced by endothelial nitric oxide synthase (eNOS) possesses multiple anti-atherosclerotic properties. Hence, enhanced expression of eNOS and increased Nitric oxide levels may protect against the development of atherosclerosis. Piper sarmentosum is a tropical plant with antioxidant and anti-inflammatory activities. This study aimed to investigate the effects of Piper sarmentosum on the eNOS and Nitric oxide pathway in cultured human umbilical vein endothelial cells (HUVECs). HUVECS WERE DIVIDED INTO FOUR GROUPS: control, treatment with 180 microM hydrogen peroxide (H(2)O(2)), treatment with 150 microg/mL aqueous extract of Piper sarmentosum, and concomitant treatment with aqueous extract of PS and H(2)O(2) for 24 hours. Subsequently, HUVECs were harvested and eNOS mRNA expression was determined using qPCR. The eNOS protein level was measured using ELISA, and the eNOS activity and Nitric oxide level were determined by the Griess reaction. Human umbilical vein endothelial cells treated with aqueous extract of Piper sarmentosum showed a marked induction of Nitric oxide. Treatment with PS also resulted in increased eNOS mRNA expression, eNOS protein level and eNOS activity in HUVECs. Aqueous extract of Piper sarmentosum may improve endothelial function by promoting NO production in HUVECs.

  14. Piper sarmentosum increases nitric oxide production in oxidative stress: a study on human umbilical vein endothelial cells

    Directory of Open Access Journals (Sweden)

    Azizah Ugusman

    2010-01-01

    Full Text Available OBJECTIVE: Nitric oxide produced by endothelial nitric oxide synthase (eNOS possesses multiple anti-atherosclerotic properties. Hence, enhanced expression of eNOS and increased Nitric oxide levels may protect against the development of atherosclerosis. Piper sarmentosum is a tropical plant with antioxidant and anti-inflammatory activities. This study aimed to investigate the effects of Piper sarmentosum on the eNOS and Nitric oxide pathway in cultured human umbilical vein endothelial cells (HUVECs. METHODS: HUVECs were divided into four groups: control, treatment with 180 μM hydrogen peroxide (H2O2, treatment with 150 μg/mL aqueous extract of Piper sarmentosum, and concomitant treatment with aqueous extract of PS and H2O2 for 24 hours. Subsequently, HUVECs were harvested and eNOS mRNA expression was determined using qPCR. The eNOS protein level was measured using ELISA, and the eNOS activity and Nitric oxide level were determined by the Griess reaction. RESULTS: Human umbilical vein endothelial cells treated with aqueous extract of Piper sarmentosum showed a marked induction of Nitric oxide. Treatment with PS also resulted in increased eNOS mRNA expression, eNOS protein level and eNOS activity in HUVECs. CONCLUSION: Aqueous extract of Piper sarmentosum may improve endothelial function by promoting NO production in HUVECs.

  15. AUTOFLUORESCENCE IN PRIMARY RAINBOW TROUT HEPATOCYTES INTERFERES WITH MEASUREMENT OF OXIDATIVE ACTIVITY VIA THE EXOGENOUS PROBE, DCF, BUT PROVIDES INTRINSIC MEASURE OF CELLULAR OXIDATIVE STATE

    Science.gov (United States)

    The compound 2', 7'-dichlorodihydrofluoroscein diacetate is a probe commonly used to detect oxidative activity in live cells. Studies were undertaken to measure reactive oxygen species generated in freshly isolated rainbow trout hepatocytes exposed to a variety of redox cycling c...

  16. Sulfur diffusion in dacitic melt at various oxidation states: Implications for volcanic degassing

    Science.gov (United States)

    Lierenfeld, Matthias Bernhard; Zajacz, Zoltán; Bachmann, Olivier; Ulmer, Peter

    2018-04-01

    The diffusivity of S in a hydrous dacitic melt (4.5-6.0 wt.% H2O) has been investigated in the temperature (T) and pressure (P) range of 950 °C to 1100 °C and 200 to 250 MPa, respectively. Three series of experiments were conducted at relatively low oxygen fugacity (fO2) conditions [0.8 log units below fayalite-magnetite-quartz equilibrium (FMQ -0.8); referred to as "low fO2"] and high fO2 conditions (FMQ +2.5; referred to as "high fO2") to determine if the diffusivity of S is affected by its oxidation state and speciation. Sulfur concentration profiles were measured by electron microprobe and the diffusion coefficient (D) was calculated by fitting these profiles. Sulfur diffusion is approximately one order of magnitude faster when S is dominantly present as sulfide species (low fO2) in comparison to the sulfate dominated experiments (high fO2). The following Arrhenian equations were obtained for high and low fO2 conditions at 200 MPa: high fO2: D = 10-5.92±0.86 * exp ({-137.3±21.5 kJ/mol}/{RT}) low fO2: D = 10-5.18±1.39 * exp ({-125.7±34.4 kJ/mol}/{RT}) where D is the average diffusion coefficient in m2 s-1, R is the gas constant in 8.3144 J mol-1 K-1 and T is the temperature in K. Our results demonstrate for the first time in natural melts that S diffusion is strongly sensitive to fO2. Our S diffusivities under low fO2 conditions are only slightly slower of those found for H2O, suggesting that S can be rather efficiently purged from reduced dacitic melts during volcanic eruptions. However, for more oxidized systems (e.g. subduction zones), S diffusion will be much slower and will hinder equilibrium syn-eruptive degassing during rapid decompression. Therefore, we conclude that the "excess" measured during many explosive volcanic eruptions in arcs is dominantly derived from S-rich bubble accumulation in the eruptible portion of the magma reservoir.

  17. Study on atmospheric aerosols in Khartoum state

    International Nuclear Information System (INIS)

    Albadwai, K. A.

    2012-09-01

    This study is primarily conducted to evaluate air pollution with chemical contaminants and to determine their possible sources in Khartoum State. Air samples representing areas with heavy traffic ( Algorashi and Burri) and industrial area ( Kafoory) were collected with the aid of gent SFU sampler and analysed for Ti, Zn, Fe, Br and Pb in both fine ( PM2.5) and particulate ( PM10) fractions of aerosol using an energy dispersive X RF. On the average, the results obtained in Kafoory were 349.43 (Ti), 594.15 (Fe), 681.25 9 (Zn), 284.18 (Br) and 299.13 (Pb) μg/m 2 for PM10; and the result obtained were 685.33 (Ti), 376.93 (Fe), 187.05 (Zn), 477.13 (Br), and 263.7 (Pb) μg/m 2 for PM2.5. Based on particle size, Zn is more concentration in PM10 whereas Ti in PM2.5. In general, the level contamination was high in particulate fraction (PM10) relative to fine fraction which is typical characteristic of desert environments. The Pb/Br ratio found to be greater than natural value (0.386) in both fractions and reveals a similar distribution trends which indicates that the air in Khartoum state is polluted with these elements and probably due to the sue of leaded fuel.(Author)

  18. Application of Degenerately Doped Metal Oxides in the Study of Photoinduced Interfacial Electron Transfer.

    Science.gov (United States)

    Farnum, Byron H; Morseth, Zachary A; Brennaman, M Kyle; Papanikolas, John M; Meyer, Thomas J

    2015-06-18

    Degenerately doped In2O3:Sn semiconductor nanoparticles (nanoITO) have been used to study the photoinduced interfacial electron-transfer reactivity of surface-bound [Ru(II)(bpy)2(4,4'-(PO3H2)2-bpy)](2+) (RuP(2+)) molecules as a function of driving force over a range of 1.8 eV. The metallic properties of the ITO nanoparticles, present within an interconnected mesoporous film, allowed for the driving force to be tuned by controlling their Fermi level with an external bias while their optical transparency allowed for transient absorption spectroscopy to be used to monitor electron-transfer kinetics. Photoinduced electron transfer from excited-state -RuP(2+*) molecules to nanoITO was found to be dependent on applied bias and competitive with nonradiative energy transfer to nanoITO. Back electron transfer from nanoITO to oxidized -RuP(3+) was also dependent on the applied bias but without complication from inter- or intraparticle electron diffusion in the oxide nanoparticles. Analysis of the electron injection kinetics as a function of driving force using Marcus-Gerischer theory resulted in an experimental estimate of the reorganization energy for the excited-state -RuP(3+/2+*) redox couple of λ* = 0.83 eV and an electronic coupling matrix element, arising from electronic wave function overlap between the donor orbital in the molecule and the acceptor orbital(s) in the nanoITO electrode, of Hab = 20-45 cm(-1). Similar analysis of the back electron-transfer kinetics yielded λ = 0.56 eV for the ground-state -RuP(3+/2+) redox couple and Hab = 2-4 cm(-1). The use of these wide band gap, degenerately doped materials provides a unique experimental approach for investigating single-site electron transfer at the surface of oxide nanoparticles.

  19. A DFT study of permanganate oxidation of toluene and its ortho-nitroderivatives.

    Science.gov (United States)

    Adamczyk, Paweł; Wijker, Reto S; Hofstetter, Thomas B; Paneth, Piotr

    2014-02-01

    Calculations of alternative oxidation pathways of toluene and its ortho-substituted nitro derivatives by permanganate anion have been performed. The competition between methyl group and ring oxidation has been addressed. Acceptable results have been obtained using IEFPCM/B3LYP/6-31+G(d,p) calculations with zero-point (ZPC) and thermal corrections, as validated by comparison with the experimental data. It has been shown that ring oxidation reactions proceed via relatively early transition states that become quite unsymmetrical for reactions involving ortho-nitrosubstituted derivatives. Transition states for the hydrogen atom abstraction reactions, on the other hand, are late. All favored reactions are characterized by the Gibbs free energy of activation, ΔG(≠), of about 25 kcal mol(-1). Methyl group oxidations are exothermic by about 20 kcal mol(-1) while ring oxidations are around thermoneutrality.

  20. Thermogravimetric study of oxidation of a PdCr alloy used for high-temperature sensors

    Science.gov (United States)

    Boyd, Darwin L.; Zeller, Mary V.

    1994-01-01

    In this study, the oxidation of Pd-13 weight percent Cr, a candidate alloy for high-temperature strain gages, was investigated by thermogravimetry. Although the bulk alloy exhibits linear electrical resistivity versus temperature and stable resistivity at elevated temperatures, problems attributed to oxidation occur when this material is fabricated into strain gages. In this work, isothermal thermogravimetry (TG) was used to study the oxidation kinetics. Results indicate that the oxidation of Pd-13 weight percent Cr was approximately parabolic in time at 600 C but exhibited greater passivation from 700 to 900 C. At 1100 C, the oxidation rate again increased.

  1. Neotectonic studies in the northeastern United States

    International Nuclear Information System (INIS)

    The definitions of contemporary regional and local stress regimes which explain neotectonism are based on data derived from (1) gross crustal patterns suggested by plate tectonic theory, (2) vertical crustal movements, (3) earthquake focal mechanism solutions, which usually lack known geologic control at (focal) depths of concern, (4) instrumental measurements which, for all practical purposes, are near-surface measurements, (5) and the character and orientation of Quaternary (surficial) geologic features. It has been suggested that principal stress vectors vary widely within regions and reflect the interaction of whatever stress mechanisms are present at a particular locale as imposed on particular rock media. Recent studies on the tectonism of northern and southeastern New York state are summarized and interpretations of the available data are offered which present an explanation for the observed neotectonism. (author)

  2. Treatment of β-Thalassemia/Hemoglobin E with Antioxidant Cocktails Results in Decreased Oxidative Stress, Increased Hemoglobin Concentration, and Improvement of the Hypercoagulable State

    Directory of Open Access Journals (Sweden)

    Orn-uma Yanpanitch

    2015-01-01

    Full Text Available Studies on the antioxidant treatment for thalassemia have reported variable outcomes. However, treatment of thalassemia with a combination of hydrophobic and hydrophilic antioxidants and an iron chelator has not been studied. This study investigated the effects of antioxidant cocktails for the treatment of β-thalassemia/hemoglobin E (HbE, which is the most common form of β-thalassemia in Southeast Asia. Sixty patients were divided into two groups receiving N-acetylcysteine, deferiprone, and either curcuminoids (CUR or vitamin E (Vit-E, and their hematological parameters, iron load, oxidative stress, and blood coagulation potential were evaluated. Patients were classified as responders if they showed the improvements of the markers of iron load and oxidative stress, otherwise as nonresponders. During treatment, the responders in both groups had significantly decreased iron load, oxidative stress, and coagulation potential and significantly increased antioxidant capacity and hemoglobin concentration. The significantly maximum increase (P<0.01 in hemoglobin concentration was 11% at month 4 in CUR group responders and 10% at month 10 in Vit-E group responders. In conclusion, the two antioxidant cocktails can improve anemia, iron overload, oxidative stress, and hypercoagulable state in β-thalassemia/HbE.

  3. A comprehensive experimental and modeling study of isobutene oxidation

    KAUST Repository

    Zhou, Chong-Wen

    2016-03-17

    Isobutene is an important intermediate in the pyrolysis and oxidation of higher-order branched alkanes, and it is also a component of commercial gasolines. To better understand its combustion characteristics, a series of ignition delay time (IDT) and laminar flame speed (LFS) measurements have been performed. In addition, flow reactor speciation data recorded for the pyrolysis and oxidation of isobutene is also reported. Predictions of an updated kinetic model described herein are compared with each of these data sets, as well as with existing jet-stirred reactor (JSR) species measurements. IDTs of isobutene oxidation were measured in four different shock tubes and in two rapid compression machines (RCMs) under conditions of relevance to practical combustors. The combination of shock tube and RCM data greatly expands the range of available validation data for isobutene oxidation models to pressures of 50 atm and temperatures in the range 666–1715 K. Isobutene flame speeds were measured experimentally at 1 atm and at unburned gas temperatures of 298–398 K over a wide range of equivalence ratios. For the flame speed results, there was good agreement between different facilities and the current model in the fuel-rich region. Ab initio chemical kinetics calculations were carried out to calculate rate constants for important reactions such as H-atom abstraction by hydroxyl and hydroperoxyl radicals and the decomposition of 2-methylallyl radicals. A comprehensive chemical kinetic mechanism has been developed to describe the combustion of isobutene and is validated by comparison to the presently considered experimental measurements. Important reactions, highlighted via flux and sensitivity analyses, include: (a) hydrogen atom abstraction from isobutene by hydroxyl and hydroperoxyl radicals, and molecular oxygen; (b) radical–radical recombination reactions, including 2-methylallyl radical self-recombination, the recombination of 2-methylallyl radicals with

  4. Oxidative stabilization of polyacrylonitrile nanofibers and carbon nanofibers containing graphene oxide (GO: a spectroscopic and electrochemical study

    Directory of Open Access Journals (Sweden)

    İlknur Gergin

    2017-08-01

    Full Text Available In this study, a precursor for carbon nanofibers (CNF was fabricated via electrospinning and carbonized through a thermal process. Before carbonization, oxidative stabilization should be applied, and the oxidation mechanism also plays an important role during carbonization. Thus, the understanding of the oxidation mechanism is an essential part of the production of CNF. The oxidation process of polyacrylonitrile was studied and nanofiber webs containing graphene oxide (GO are obtained to improve the electrochemical properties of CNF. Structural and morphological characterizations of the webs are carried out by using attenuated total reflectance Fourier transform infrared spectroscopy and Raman spectroscopy, scanning electron microscopy, atomic force microscopy and transmission electron microscopy. Mechanical tests are performed with a dynamic mechanical analyzer, and thermal studies are conducted by using thermogravimetric analysis. Electrochemical impedance spectroscopy, and cyclic voltammetry are used to investigate capacitive behavior of the products. The proposed equivalent circuit model was consistent with charge-transfer processes taking place at interior pores filled with electrolyte.

  5. Oxidation-reduction reactions. Overview and implications for repository studies

    International Nuclear Information System (INIS)

    Apted, Michael J.; Arthur, Randolph C.; Sasamoto, Hiroshi; Yui, Mikazu; Iwatsuki, Teruki

    2001-02-01

    The purpose of this report is to provide a survey and review on oxidation-reduction ('redox') reactions, with particular emphasis on implications for disposal of high-level waste (HLW) in deep geological formations. As an overview, the focus is on basic principles, problems, and proposed research related specifically to the assessment of redox for a HLW repository in Japan. For a more comprehensive treatment of redox and the myriad associated issues, the reader is directed to the cited textbooks used as primary references in this report. Low redox conditions in deep geological formations is a key assumption in the 'Second Progress Report on Research and Development for the Geological Disposal of HLW in Japan' (hereafter called H12'). The release behavior of multi-valent radioelements (e.g., Tc, Se, U, Pu, Np), as well as daughter radioelements of these radioelements, from a deep geological repository are sensitively related to redox conditions. Furthermore, the performance of certain barrier materials, such as overpack and buffer, may be impacted by redox conditions. Given this importance, this report summarizes some key topics for future technical studies supporting site characterization and repository performance as follows: To fully test the conceptual models for system Eh, it will be necessary to measure and evaluate trace element and isotopic information of both coexisting groundwater and reactive minerals of candidate rocks. Because of importance of volatile species (e.g., O 2 , H 2 etc.) in redox reactions, and given the high total pressure of a repository located 500 to 1000 meter deep, laboratory investigations of redox will necessarily require use of pressurized test devices that can fully simulate repository conditions. The stability (redox capacity) of the repository system with respect to potential changes in redox boundary condition induced by oxidizing waters intrusion should be established experimentally. An overall conceptual model that unifies

  6. Trace methane oxidation studied in several Euryarchaeota under diverse conditions

    Directory of Open Access Journals (Sweden)

    James J. Moran

    2005-01-01

    Full Text Available We used 13C-labeled methane to document the extent of trace methane oxidation by Archaeoglobus fulgidus, Archaeoglobus lithotrophicus, Archaeoglobus profundus, Methanobacterium thermoautotrophicum, Methanosarcina barkeri and Methanosarcina acetivorans. The results indicate trace methane oxidation during growth varied among different species and among methanogen cultures grown on different substrates. The extent of trace methane oxidation by Mb. thermoautotrophicum (0.05 ± 0.04%, ± 2 standard deviations of the methane produced during growth was less than that by M. barkeri (0.15 ± 0.04%, grown under similar conditions with H2 and CO2. Methanosarcina acetivorans oxidized more methane during growth on trimethylamine (0.36 ± 0.05% than during growth on methanol (0.07 ± 0.03%. This may indicate that, in M. acetivorans, either a methyltransferase related to growth on trimethylamine plays a role in methane oxidation, or that methanol is an intermediate of methane oxidation. Addition of possible electron acceptors (O2, NO3–, SO22–, SO32– or H2 to the headspace did not substantially enhance or diminish methane oxidation in M. acetivorans cultures. Separate growth experiments with FAD and NAD+ showed that inclusion of these electron carriers also did not enhance methane oxidation. Our results suggest trace methane oxidized during methanogenesis cannot be coupled to the reduction of these electron acceptors in pure cultures, and that the mechanism by which methane is oxidized in methanogens is independent of H2 concentration. In contrast to the methanogens, species of the sulfate-reducing genus Archaeoglobus did not significantly oxidize methane during growth (oxidizing 0.003 ± 0.01% of the methane provided to A. fulgidus, 0.002 ± 0.009% to A. lithotrophicus and 0.003 ± 0.02% to A. profundus. Lack of observable methane oxidation in the three Archaeoglobus species examined may indicate that methyl-coenzyme M reductase, which is not present in

  7. Study of oxide/metal/oxide thin films for transparent electronics and solar cells applications by spectroscopic ellipsometry

    Directory of Open Access Journals (Sweden)

    Mihaela Girtan

    2017-05-01

    Full Text Available A comprehensive study of a class of Oxide/Metal/Oxide (Oxide = ITO, AZO, TiO2 and Bi2O3, Metal = Au thin films was done by correlating the spectrophotometric studies with the ellispometric models. Films were deposited by successive sputtering from metallic targets In:Sn, Zn:Al, Ti and Bi in reactive atmosphere (for the oxide films and respective inert atmosphere (for the metallic Au interlayer films on glass substrates. The measurements of optical constants n—the refractive index and k—the extinction coefficient, at different incident photon energies for single oxide films and also for the three layers films oxide/metal/oxide samples were made using the spectroscopic ellipsometry (SE technique. The ellipsometry modelling process was coupled with the recorded transmission spectra data of a double beam spectrophotometer and the best fitting parameters were obtained not only by fitting the n and k experimental data with the dispersion fitting curves as usual is practiced in the most reported data in literature, but also by comparing the calculated the transmission coefficient from ellipsometry with the experimental values obtained from direct spectrophotometry measurements. In this way the best dispersion model was deduced for each sample. Very good correlations were obtained for the other different thin films characteristics such as the films thickness, optical band gap and electrical resistivity obtained by other measurements and calculation techniques. The ellipsometric modelling, can hence give the possibility in the future to predict, by ellipsometric simulations, the proper device architecture in function of the preferred optical and electrical properties.

  8. Tin Oxide Nanowires: The Influence of Trap States on Ultrafast Carrier Relaxation

    Directory of Open Access Journals (Sweden)

    Zervos Matthew

    2009-01-01

    Full Text Available Abstract We have studied the optical properties and carrier dynamics in SnO2nanowires (NWs with an average radius of 50 nm that were grown via the vapor–liquid solid method. Transient differential absorption measurements have been employed to investigate the ultrafast relaxation dynamics of photogenerated carriers in the SnO2NWs. Steady state transmission measurements revealed that the band gap of these NWs is 3.77 eV and contains two broad absorption bands. The first is located below the band edge (shallow traps and the second near the center of the band gap (deep traps. Both of these absorption bands seem to play a crucial role in the relaxation of the photogenerated carriers. Time resolved measurements suggest that the photogenerated carriers take a few picoseconds to move into the shallow trap states whereas they take ~70 ps to move from the shallow to the deep trap states. Furthermore the recombination process of electrons in these trap states with holes in the valence band takes ~2 ns. Auger recombination appears to be important at the highest fluence used in this study (500 μJ/cm2; however, it has negligible effect for fluences below 50 μJ/cm2. The Auger coefficient for the SnO2NWs was estimated to be 7.5 ± 2.5 × 10−31 cm6/s.

  9. Enzyme phylogenies as markers for the oxidation state of the environment: the case of respiratory arsenate reductase and related enzymes.

    Science.gov (United States)

    Duval, Simon; Ducluzeau, Anne-Lise; Nitschke, Wolfgang; Schoepp-Cothenet, Barbara

    2008-07-16

    Phylogenies of certain bioenergetic enzymes have proved to be useful tools for deducing evolutionary ancestry of bioenergetic pathways and their relationship to geochemical parameters of the environment. Our previous phylogenetic analysis of arsenite oxidase, the molybdopterin enzyme responsible for the biological oxidation of arsenite to arsenate, indicated its probable emergence prior to the Archaea/Bacteria split more than 3 billion years ago, in line with the geochemical fact that arsenite was present in biological habitats on the early Earth. Respiratory arsenate reductase (Arr), another molybdopterin enzyme involved in microbial arsenic metabolism, serves as terminal oxidase, and is thus situated at the opposite end of bioenergetic electron transfer chains as compared to arsenite oxidase. The evolutionary history of the Arr-enzyme has not been studied in detail so far. We performed a genomic search of genes related to arrA coding for the molybdopterin subunit. The multiple alignment of the retrieved sequences served to reconstruct a neighbor-joining phylogeny of Arr and closely related enzymes. Our analysis confirmed the previously proposed proximity of Arr to the cluster of polysulfide/thiosulfate reductases but also unravels a hitherto unrecognized clade even more closely related to Arr. The obtained phylogeny strongly suggests that Arr originated after the Bacteria/Archaea divergence in the domain Bacteria, and was subsequently laterally distributed within this domain. It further more indicates that, as a result of accumulation of arsenate in the environment, an enzyme related to polysulfide reductase and not to arsenite oxidase has evolved into Arr. These findings are paleogeochemically rationalized by the fact that the accumulation of arsenate over arsenite required the increase in oxidation state of the environment brought about by oxygenic photosynthesis.

  10. Source-dependent and source-independent controls on plutonium oxidation state and colloid associations in groundwater.

    Science.gov (United States)

    Buesseler, Ken O; Kaplan, Daniel I; Dai, Minhan; Pike, Steven

    2009-03-01

    Plutonium (Pu) was characterized for its isotopic composition, oxidation states, and association with colloids in groundwater samples near disposal basins in F-Area of the Savannah River Site and compared to similar samples collected six years earlier. Two sources of Pu were identified, the disposal basins, which contained a 24Pu/l39Pu isotopic signature consistent with weapons grade Pu, and 244Cm, a cocontaminant that is a progenitor radionuclide of 24Pu. 24Pu that originated primarily from 244Cm tended to be appreciably more oxidized (Pu(V/VI)), less associated with colloids (approximately 1 kDa - 0.2 microm), and more mobile than 239Pu, as suggested by our prior studies at this site. This is not evidence of isotope fractionation but rather "source-dependent" controls on 240Pu speciation which are processes that are not at equilibrium, i.e., processes that appear kinetically hindered. There were also "source-independent" controls on 239Pu speciation, which are those processes that follow thermodynamic equilibrium with their surroundings. For example, a groundwater pH increase in one well from 4.1 in 1998 to 6.1 in 2004 resulted in an order of magnitude decrease in groundwater 239Pu concentrations. Similarly, the fraction of 239Pu in the reduced Pu(III/IV) and colloidal forms increased systematically with decreases in redox condition in 2004 vs 1998. This research demonstrates the importance of source-dependent and source-independent controls on Pu speciation which would impact Pu mobility during changes in hydrological, chemical, or biological conditions on both seasonal and decadal time scales, and over short spatial scales. This implies more dynamic shifts in Pu speciation, colloids association, and transport in groundwater than commonly believed.

  11. The lack of effects of zinc and nitric oxide in initial state of pilocarpine-induced seizures.

    Science.gov (United States)

    Noyan, Behzat; Jensen, Morten Skovgaard; Danscher, Gorm

    2007-07-01

    In this study we investigated whether intracerebroventricular (i.c.v.) injection of L-NAME (a nitric oxide synthase inhibitor) or CaEDTA (an extracellular zinc chelator) or the combination of the two could affect the initial phase of pilocarpine induced (2 h) seizures. Two groups of rats were used. Animals from both groups were given with i.c.v. injections of either saline (10 microl), L-NAME (150 microg/10 microl), CaEDTA (100 mM/10 microl) or L-NAME and CaEDTA. One group received pilocarpine HCl (380 mg/kg i.p.) the other served as control. Pilocarpine HCl was injected intraperitoneally 10 min later. The behavior of the animals was observed for 2h and the intensity of their seizures was scored. The rats were then sacrificed and their brains were removed and analyzed for zinc ions by using the immersion autometallography and the TSQ fluorescence staining. All the animals which received pilocarpine HCl developed seizures. Despite treatment with L-NAME and/or CaEDTA we found that the latency and the intensity of seizures were similar in both groups investigated. The distribution of stainable zinc ions and the intensity of staining in hippocampus were not affected by pilocarpine and found unchanged after L-NAME and/or CaEDTA injections in both the control animals and the pilocarpine treated animals. The data suggest that the nitric oxide system and zinc ions do not affect pilocarpine-induced seizures in their initial state.

  12. In situ X-ray studies of film cathodes for solid oxide fuel cells

    International Nuclear Information System (INIS)

    Fuoss, Paul; Chang, Kee-Chul; You, Hoydoo

    2013-01-01

    Highlights: •Synchrotron X-rays are used to study in operando the structural and chemical changes of LSM and LSCF film cathodes during half-cell operations. •A-site and B-site cations actively segregate or desegregate on the changes of temperature, pO 2 , and electrochemical potential. •Chemical lattice expansions show that oxygen-cathode interface is the primary source of rate-limiting processes. •The surface and subsurface of the LSM and LSCF films have different oxidation-states due to vacancy concentration changes. •Liquid-phase infiltration and coarsening processes of cathode materials into porous YSZ electrolyte backbone were monitored by USAXS. -- Abstract: Synchrotron-based X-ray techniques have been used to study in situ the structural and chemical changes of film cathodes during half-cell operations. The X-ray techniques used include X-ray reflectivity (XR), total-reflection X-ray fluorescence (TXRF), high-resolution diffraction (HRD), ultra-small angle X-ray scattering (USAXS). The epitaxial thin film model cathodes for XR, TXRF, and HRD measurements are made by pulse laser deposition and porous film cathodes for USAX measurements are made by screen printing technique. The experimental results reviewed here include A-site and B-site segregations, lattice expansion, oxidation-state changes during cell operations and liquid-phase infiltration and coarsening of cathode to electrolyte backbone

  13. Oxidation-state distribution of plutonium in surface and subsurface waters at Thule, northwest Greenland

    International Nuclear Information System (INIS)

    McMahon, C.A.; Leon Vintro, L.; Mitchell, P.I.; Dahlgaard, H.

    2000-01-01

    The speciation of plutonium in Arctic waters sampled on the northwest Greenland shelf in August 1997 is discussed in this paper. Specifically, we report the results of analyses carried out on seawater sampled (a) close to the Thule air base where, in 1968, a US military aircraft carrying four nuclear weapons crashed on sea ice, releasing kilogram quantities of plutonium to the snow pack and underlying seabed sediments, and (b) at a reference station (Upernavik) located ∼400 km to the south. The data show that most of the plutonium in the dissolved phase at Thule is in the form of Pu(V, VI) (mean: 68±6%; n=6), with little if any distinction apparent between surface and bottom waters. Further, the oxidation state distribution at stations close to the accident site is similar to that measured at Upernavik, remote from this site. It is also similar to the distribution observed in shelf waters at mid-latitudes, suggesting that the underlying processes controlling plutonium speciation are insensitive to temperature over the range 0-25 deg. C. Measurements using tangential-flow ultrafiltration indicate that virtually all of the plutonium (including the fraction in a reduced chemical form) is present as fully dissolved species. Most of this plutonium would seem to be of weapons fallout origin, as the mean 238 Pu/ 239,240 Pu activity ratio in the water column (dissolved phase) at Thule (0.06±0.02; n=10) is similar to the global fallout ratio at this latitude (∼0.04). Thus, there is little evidence of weapons-grade plutonium in the water column at Thule at the present time

  14. The changing face of lower tropospheric sulfur oxides in the United States

    Directory of Open Access Journals (Sweden)

    G. M. Hidy

    2016-12-01

    Full Text Available Abstract Sulfur oxides, sulfur dioxide and airborne sulfate, SOx, are short-lived species in the troposphere whose concentrations in air and precipitation have changed dramatically in association with fossil fuel combustion. The historic rise in concentration is coincident with the era of the so-called “Anthropocene.” Unlike concentrations of long-lived species such as carbon dioxide, atmospheric SOx in the United States (US peaked between 1970 and 2005 then declined. The rise and fall of SOx is traced by comparing national data on emission changes, ambient concentrations, and precipitation sulfate from prior to World War II to the present. Surface SOx concentrations and precipitation sulfate have decreased with emissions in most parts of the US after the late 1970s. Continued reduction toward a natural “background” condition has depended on aggressive management of anthropogenic emission sources. Annual average ambient concentrations of SO2 and SO4 have become more uniform across the US at levels of 1–3 ppbv and 0.3–3 µg/m3, respectively. Precipitation SO4 has a nominal concentration generally less than 0.5 mg/L. The effective lifetime of SOx in the troposphere is a few days. This duration limits the spatial extent of emission source influence of SOx to regional scales, wherein spatial gradients in species concentrations lead to variations in human exposure and impacts on vulnerable terrestrial and aquatic ecosystems. The effects of domestic emission reductions on SOx levels are moderated by intra- and intercontinental transport of SOx from Canada, Mexico, Asia and elsewhere. The trends in tropospheric SOx concentrations illustrate the results of more than a century of rising public awareness and action to progressively reduce a US environmental risk, accomplished with advances in energy production technology that have maintained economic well-being.

  15. Study of water vapour adsorption kinetics on aluminium oxide materials

    Science.gov (United States)

    Livanova, Alesya; Meshcheryakov, Evgeniy; Reshetnikov, Sergey; Kurzina, Irina

    2017-11-01

    Adsorbents on the basis of active aluminum oxide are still of demand on the adsorbent-driers market. Despite comprehensive research of alumina adsorbents, and currently is an urgent task to improve their various characteristics, and especially the task of increasing the sorption capacity. In the present work kinetics of the processes of water vapours' adsorption at room temperature on the surface of desiccant samples has been studied. It was obtained on the basis of bayerite and pseudoboehmite experimentally. The samples of pseudoboehmite modified with sodium and potassium ions were taken as study objects. The influence of an adsorbent's grain size on the kinetics of water vapours' adsorption was studied. The 0.125-0.25 mm and 0.5-1.0 mm fractions of this sample were used. It has been revealed that the saturation water vapor fine powder (0.125-0.25 mm) is almost twofold faster in comparison with the sample of fraction 0.5-1.0 mm due to the decrease in diffusion resistance in the pores of the samples when moving from the sample of larger fraction to the fine-dispersed sample. It has been established that the adsorption capacity of the pseudoboehmite samples, modified by alkaline ions, is higher by ˜40 %, than for the original samples on the basis of bayerite and pseudoboehmite.

  16. Determination of Pu Oxidation states in the HCl Media Using with UV-Visible Absorption Spectroscopic Techniques

    International Nuclear Information System (INIS)

    Lee, Myung Ho; Suh, Mu Yeol; Park, Kyoung Kyun; Park, Yeong Jae; Kim, Won Ho

    2006-01-01

    The spectroscopic characteristics of Pu (III, IV, V, VI) in the HCl media were investigated by measuring Pu oxidation states using a UV-Vis-NIR spectrophotometer (400-1200 nm) after adjusting Pu oxidation states with oxidation/reduction reagents. Pu in stock solution was reduced to Pu(III) with NH 2 OH · HCl, and oxidized to Pu(IV) and Pu(VI) with NaNO 2 and HCIO 4 , respectively. Also, Pu(V) was adjusted in the Pu(VI) solution with NH 2 OH · HCl. The major absorption peaks of Pu (IV) and Pu(III) were measured in the 470 nm and 600 nm, respectively. The major absorption peaks of Pu (VI) and Pu(V) were measured in the 830 nm and 1135 nm, respectively. There was not found to be significant changes of UV-V is absorption spectra for Pu(III), Pu(IV) and Pu(VI) with aging time, except that an unstable Pu(V) immediately reduced to Pu(III).

  17. Thermodynamic properties of ternary oxides in the system Ba-Fe-O using solid-state electrochemical cells with oxide and fluoride ion conducting electrolytes

    Science.gov (United States)

    Rakshit, S. K.; Parida, S. C.; Singh, Ziley; Prasad, R.; Venugopal, V.

    2004-04-01

    The standard molar Gibbs energy of formations of BaFe 12O 19(s), BaFe 2O 4(s), Ba 2Fe 2O 5(s), Ba 3Fe 2O 6(s) and Ba 5Fe 2O 8(s) have been determined using solid-state electrochemical technique employing CaF 2(s) as an electrolyte. The reversible e.m.f. values have been measured in the temperature range from 970 to 1151 K. The oxygen chemical potential corresponding to three phase equilibria involving technologically important compound BaFe 12O 19(s) has been determined using solid-state electrochemical technique employing CSZ as an electrolyte from 1048 to 1221 K. The values of Δ fGm0( T) for the above ternary oxides are given by ΔfG m0( BaFe12O19, s)/ kJ mol -1(±0.6)=-5431.3+1.5317 (T/ K) (970⩽T/ K⩽1151) ΔfG m0( BaFe2O4, s)/ kJ mol -1(±1.3)=-1461.4+0.3745 (T/ K) (970⩽T/ K⩽1151) ΔfG m0( Ba2Fe2O5, s)/ kJ mol -1(±1.4)=-2038.3+0.4433 (T/ K) (970⩽T/ K⩽1149) ΔfG m0( Ba3Fe2O6, s)/ kJ mol -1(±1.5)=-2700.1+0.6090 (T/ K) (969⩽T/ K⩽1150) and ΔfG m0( Ba5Fe2O8, s)/ kJ mol -1(±1.6)=-3984.1+0.9300 (T/ K) (973⩽T/ K⩽1150) The uncertainty estimates for Δ fGm0 includes the standard deviation in the e.m.f. and uncertainty in the data taken from the literature. An isothermal oxygen potential diagram for the system Ba-Fe-O was constructed at 1100 K based on the thermodynamic data obtained in this study.

  18. A Semi-Analytical Extraction Method for Interface and Bulk Density of States in Metal Oxide Thin-Film Transistors.

    Science.gov (United States)

    Chen, Weifeng; Wu, Weijing; Zhou, Lei; Xu, Miao; Wang, Lei; Ning, Honglong; Peng, Junbiao

    2018-03-11

    A semi-analytical extraction method of interface and bulk density of states (DOS) is proposed by using the low-frequency capacitance-voltage characteristics and current-voltage characteristics of indium zinc oxide thin-film transistors (IZO TFTs). In this work, an exponential potential distribution along the depth direction of the active layer is assumed and confirmed by numerical solution of Poisson's equation followed by device simulation. The interface DOS is obtained as a superposition of constant deep states and exponential tail states. Moreover, it is shown that the bulk DOS may be represented by the superposition of exponential deep states and exponential tail states. The extracted values of bulk DOS and interface DOS are further verified by comparing the measured transfer and output characteristics of IZO TFTs with the simulation results by a 2D device simulator ATLAS (Silvaco). As a result, the proposed extraction method may be useful for diagnosing and characterising metal oxide TFTs since it is fast to extract interface and bulk density of states (DOS) simultaneously.

  19. A Semi-Analytical Extraction Method for Interface and Bulk Density of States in Metal Oxide Thin-Film Transistors

    Directory of Open Access Journals (Sweden)

    Weifeng Chen

    2018-03-01

    Full Text Available A semi-analytical extraction method of interface and bulk density of states (DOS is proposed by using the low-frequency capacitance–voltage characteristics and current–voltage characteristics of indium zinc oxide thin-film transistors (IZO TFTs. In this work, an exponential potential distribution along the depth direction of the active layer is assumed and confirmed by numerical solution of Poisson’s equation followed by device simulation. The interface DOS is obtained as a superposition of constant deep states and exponential tail states. Moreover, it is shown that the bulk DOS may be represented by the superposition of exponential deep states and exponential tail states. The extracted values of bulk DOS and interface DOS are further verified by comparing the measured transfer and output characteristics of IZO TFTs with the simulation results by a 2D device simulator ATLAS (Silvaco. As a result, the proposed extraction method may be useful for diagnosing and characterising metal oxide TFTs since it is fast to extract interface and bulk density of states (DOS simultaneously.

  20. An X-ray absorption near-edge structure (XANES) study of the Sn L_3 edge in zirconium alloy oxide films formed during autoclave corrosion

    International Nuclear Information System (INIS)

    Hulme, Helen; Baxter, Felicity; Babu, R. Prasath; Denecke, Melissa A.; Gass, Mhairi; Steuwer, Axel; Norén, Katarina; Carlson, Stefan; Preuss, Michael

    2016-01-01

    Highlights: • Characterisation of tin speciation in zirconium alloy metal and oxide films using Sn L_3-XANES. • Chemical environment of tin in Zircaloy-4 and ZIRLO™ oxide films shown to be similar. • Tin in the oxide films is present in both the di- and tetravalent states and oxidises progressively with oxide-layer growth. - Abstract: Application of Sn L_3-XANES to study the oxidation state of alloying additions of tin (1–1.2 wt%) in <2 μm oxide layers formed on nuclear grade zirconium alloy has been demonstrated. Data obtained for metallic and corroded ZIRLO™ (1 wt% Sn) and Zircaloy-4 (1.2 wt% Sn) indicate tin has a similar chemical speciation in both metal alloys but this differs in the oxidised surface layers. By recording XANES at various incident angles to vary the photon penetration depth and amount of the oxide layer probed in the measurement, the authors found evidence that the oxidation of tin progresses with increasing oxide thickness.

  1. 2-22 Study of Oxidation/reduction Volatilization Technology

    Institute of Scientific and Technical Information of China (English)

    Tan; Cunmin[1; Cao; Shiwei[1; Tian; Yuan[1; Qin; Zhi[1

    2015-01-01

    As an advanced dry head-end processing of spent fuel reprocessing, the oxidation-reduction volatilization technology will use for pulverizing uranium oxide ceramic pellets, decladding, and removal of most of volatile and semi-volatile fission elements, 3H, 14C, Kr, Xe, I, Cs, Ru and Tc, from fuel prior to main treatment process. The AIROX and ORIOX process, including circulation of oxidation in oxygen atmosphere and reduction in hydrogen atmosphere, researched on international at present, is considered to be the first choice for head-end processing.

  2. Study of the oxidation kinetics of the nickel-molybdenum alloy

    International Nuclear Information System (INIS)

    Gouillon, Marie-Josephe

    1974-01-01

    This research thesis reports the study of the oxidation of a nickel-molybdenum alloy in the high-nickel-content part of this alloy. After a bibliographical study on the both metals, the author proposes a physical model based on observed phenomena and based on experimental results. Based on a thermodynamic study, the author compares the stability of the different oxides which may be formed, and reports a prediction of oxides obtained on the alloy during oxidation. Qualitative and quantitative studies have been performed by scanning electron microscopy coupled with electronic microprobe analysis to investigate morphological characteristics on oxidation films. A kinetic study by thermogravimetry shows a decrease of the alloy oxidation rate with respect to that of pure nickel at temperatures lower than 800 degrees C. This result is interpreted by the intervention of two opposed diffusion phenomena which act against each other [fr

  3. Studies on Optical and Electrical Properties of Hafnium Oxide Nanoparticles

    Science.gov (United States)

    Jayaraman, Venkatachalam; Sagadevan, Suresh; Sudhakar, Rajesh

    2017-07-01

    In this paper, the synthesis and physico-chemical properties of hafnium oxide nanoparticles (HfO2 NPs) are analyzed and reported. The synthesis was carried out by the precipitation route by using hafnium tetrachloride (HfCl4) as precursor material with potassium hydroxide (KOH) dissolved in Millipore water. In the precipitation technique, the chemical reaction is comparatively simple, low-cost and non-toxic compared to other synthetic methods. The synthesized HfO2 NPs were characterized by using powder x-ray diffraction (PXRD), ultraviolet-visible (UV-Vis) spectroscopy, Raman analysis, and high-resolution transmission electron microscopy (HRTEM). The monoclinic structure of the HfO2 NPs was resolved utilizing x-ray diffraction (XRD). The optical properties were studied from the UV-Vis absorption spectrum. The optical band gap of the HfO2NPs was observed to be 5.1 eV. The Raman spectrum shows the presence of HfO2 NPs. The HRTEM image showed that the HfO2 NPs were of spherical shape with an average particle size of around 28 nm. The energy-dispersive x-ray spectroscopy (EDS) spectrum obviously demonstrated the presence of HfO2 NPs. Analysis and studies on the dielectric properties of the HfO2 NPs such as the dielectric constant, the dielectric loss, and alternating current (AC) conductivity were carried out at varying frequencies and temperatures.

  4. Nuclear quadrupole resonance applied for arsenic oxide study

    International Nuclear Information System (INIS)

    Correia, J.A.S.

    1991-04-01

    The objectives of this study are mounting a pulsed Nuclear Quadrupole Resonance (NQR) building a flow cryostat capable of varying the temperature continuously from 77 K to 340 K and using the spectrometer and the cryostat to study the polycrystalline arsenic oxide. The spin-lattice relaxation time (T 1 ), the spin-spin relaxation time (T 2 ) and the resonance frequency are obtained as a function of temperature. These data are obtained in 77 to 330 K interval. The relaxation times are obtained using the spin echo technique. The spin echo phenomenon is due to refocusing spins, when a 180 0 C pulse is applied after a 90 0 C pulse. The spin-lattice relaxation time is obtained using the plot of echo amplitude versus the repetition time. The spin-spin relaxation time is obtained using the plot of echo amplitude versus the separation between the 90 0 C - 180 0 C pulses. The theory developed by Bayer is used to explain the spin-lattice relaxation time and the frequency temperature dependence. The spin-spin relaxation time is discussed using the Bloch equations. (author)

  5. A numerical study of threshold states

    International Nuclear Information System (INIS)

    Ata, M.S.; Grama, C.; Grama, N.; Hategan, C.

    1979-01-01

    There are some experimental evidences of charged particle threshold states. On the statistical background of levels, some simple structures were observed in excitation spectrum. They occur near the coulombian threshold and have a large reduced width for the decay in the threshold channel. These states were identified as charged cluster threshold states. Such threshold states were observed in sup(15,16,17,18)O, sup(18,19)F, sup(19,20)Ne, sup(24)Mg, sup(32)S. The types of clusters involved were d, t, 3 He, α and even 12 C. They were observed in heavy-ions transfer reactions in the residual nucleus as strong excited levels. The charged particle threshold states occur as simple structures at high excitation energy. They could be interesting both from nuclear structure as well as nuclear reaction mechanism point of view. They could be excited as simple structures both in compound and residual nucleus. (author)

  6. First-principles study of nitric oxide oxidation on Pt(111) versus Pt overlayer on 3d transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Arevalo, Ryan Lacdao [Department of Precision Science and Technology and Applied Physics, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan); Escaño, Mary Clare Sison [Graduate School of Engineering, University of Fukui, 3-9-1 Bunkyo, Fukui 910-8507 (Japan); Kasai, Hideaki, E-mail: kasai@dyn.ap.eng.osaka-u.ac.jp [Department of Precision Science and Technology and Applied Physics, Center for Atomic and Molecular Technologies, and Center for Continuing Professional Development, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan)

    2015-03-15

    Catalytic oxidation of NO to NO{sub 2} is a significant research interest for improving the quality of air through exhaust gas purification systems. In this paper, the authors studied this reaction on pure Pt and Pt overlayer on 3d transition metals using kinetic Monte Carlo simulations coupled with density functional theory based first principles calculations. The authors found that on the Pt(111) surface, NO oxidation proceeds via the Eley–Rideal mechanism, with O{sub 2} dissociative adsorption as the rate-determining step. The oxidation path via the Langmuir–Hinshelwood mechanism is very slow and does not significantly contribute to the overall reaction. However, in the Pt overlayer systems, the oxidation of NO on the surface is more thermodynamically and kinetically favorable compared to pure Pt. These findings are attributed to the weaker binding of O and NO on the Pt overlayer systems and the binding configuration of NO{sub 2} that promotes easier N-O bond formation. These results present insights for designing affordable and efficient catalysts for NO oxidation.

  7. Surface morphology study on chromium oxide growth on Cr films by Nd-YAG laser oxidation process

    International Nuclear Information System (INIS)

    Dong Qizhi; Hu Jiandong; Guo Zuoxing; Lian Jianshe; Chen Jiwei; Chen Bo

    2002-01-01

    Grain sized (60-100 nm) Cr 2 O 3 thin films were prepared on Cr thin film surfaces by Nd-YAG laser photothermal oxidation process. Surface morphology study showed crack-free short plateau-like oxide films formed. Increase of dislocation density after pulsed laser irradiation was found. Thin film external surfaces, grain boundaries and dislocations are main paths of laser surface oxidation. Pinning and sealing of grain boundary was the reason that deeper oxidation did not produce. Grain growth and agglomeration of Cr sub-layer yielded tensile stress on the surface Cr 2 O 3 thin film. It was the reason that short plateau-like surface morphology formed and cracks appeared sometimes. In oxygen annealing at 700 deg. C, grain boundaries were considered not to be pinned at the surface, mixture diffusion was main mechanism in growth of oxide. Compression stress development in whole film led to extrusion of grains that was the reason that multiple appearances such as pyramid-like and nutshell-like morphology formed