Magnetic filtration process, magnetic filtering material, and methods of forming magnetic filtering material

DOEpatents

Taboada-Serrano, Patricia; Tsouris, Constantino; Contescu, Cristian I; McFarlane, Joanna

2013-10-08

The present invention provides magnetically responsive activated carbon, and a method of forming magnetically responsive activated carbon. The method of forming magnetically responsive activated carbon typically includes providing activated carbon in a solution containing ions of ferrite forming elements, wherein at least one of the ferrite forming elements has an oxidation state of +3 and at least a second of the ferrite forming elements has an oxidation state of +2, and increasing pH of the solution to precipitate particles of ferrite that bond to the activated carbon, wherein the activated carbon having the ferrite particles bonded thereto have a positive magnetic susceptibility. The present invention also provides a method of filtering waste water using magnetic activated carbon.

The Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses: Results from W L-Edge Xanes Measurements

NASA Technical Reports Server (NTRS)

Danielson, Lisa R.; Righter, K.; Sutton S.; Newville, M.; Le, L.

2007-01-01

Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted approx. 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies (figure 1) are inconsistent on whether W occurs as W(4+) or W(6+).

Synthesis and characterisation of PuPO4 - a potential analytical standard for EPMA actinide quantification

NASA Astrophysics Data System (ADS)

Wright, K. E.; Popa, K.; Pöml, P.

2018-01-01

Transmutation nuclear fuels contain weight percentage quantities of actinide elements, including Pu, Am and Np. Because of the complex spectra presented by actinide elements using electron probe microanalysis (EPMA), it is necessary to have relatively pure actinide element standards to facilitate overlap correction and accurate quantitation. Synthesis of actinide oxide standards is complicated by their multiple oxidation states, which can result in inhomogeneous standards or standards that are not stable at atmospheric conditions. Synthesis of PuP4 results in a specimen that exhibits stable oxidation-reduction chemistry and is sufficiently homogenous to serve as an EPMA standard. This approach shows promise as a method for producing viable actinide standards for microanalysis.

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

PubMed

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).

A Multireference Density Functional Approach to the Calculation of the Excited States of Uranium Ions

DTIC Science & Technology

2007-03-01

approach. xiv A MULTIREFERENCE DENSITY FUNCTIONAL APPROACH TO THE CALCULATION OF THE EXCITED STATES OF URANIUM IONS I. Introduction Actinide chemistry, in...oxidation state of the uranium atom. Uranium, like most early actinides , can possess a wide range of oxidation states, ranging from +3 to +6, due in part...in predicting the electronic spectra for heavy element compounds. The first difficulty is that relativistic effects for actinides are significant

Using X-ray absorption to probe sulfur oxidation states in complex molecules

NASA Astrophysics Data System (ADS)

Vairavamurthy, A.

1998-10-01

X-ray absorption near-edge structure (XANES) spectroscopy offers an important non-destructive tool for determining oxidation states and for characterizing chemical speciation. The technique was used to experimentally verify the oxidation states of sulfur in different types of complex molecules because there are irregularities and uncertainties in assigning the values traditionally. The usual practice of determining oxidation states involves using a set of conventional rules. The oxidation state is an important control in the chemical speciation of sulfur, ranging from -2 to +6 in its different compounds. Experimental oxidation-state values for various types of sulfur compounds, using their XANES peak-energy positions, were assigned from a scale in which elemental sulfur and sulfate are designated as 0 and +6, respectively. Because these XANES-based values differed considerably from conventionally determined oxidation states for most sulfur compounds, a new term 'oxidation index' was coined to describe them. The experimental values were closer to those conventional values obtained by assigning shared electrons to the more electronegative atoms than to those based on other customary rules for assigning them. Because the oxidation index is distinct and characteristic for each different type of sulfur functionality, it becomes an important parameter for characterizing sulfur species, and for experimentally verifying uncertain oxidation states.

Autothermal reforming catalyst having perovskite structure

DOEpatents

Krumpel, Michael [Naperville, IL; Liu, Di-Jia [Naperville, IL

2009-03-24

The invention addressed two critical issues in fuel processing for fuel cell application, i.e. catalyst cost and operating stability. The existing state-of-the-art fuel reforming catalyst uses Rh and platinum supported over refractory oxide which add significant cost to the fuel cell system. Supported metals agglomerate under elevated temperature during reforming and decrease the catalyst activity. The catalyst is a perovskite oxide or a Ruddlesden-Popper type oxide containing rare-earth elements, catalytically active firs row transition metal elements, and stabilizing elements, such that the catalyst is a single phase in high temperature oxidizing conditions and maintains a primarily perovskite or Ruddlesden-Popper structure under high temperature reducing conditions. The catalyst can also contain alkaline earth dopants, which enhance the catalytic activity of the catalyst, but do not compromise the stability of the perovskite structure.

Periodicity in the Acid-Base Behavior of Oxides and Hydroxides.

ERIC Educational Resources Information Center

Rich, Ronald L.

1985-01-01

Aqueous solubilities of many important hydrous oxides and hydroxides are displayed, for the various elements, as functions primarily of pH. These graphs are then arranged in groups to facilitate studies of the effects of oxidation state, electron structure, and position in the periodic table, along with size and coordination number. (JN)

Correlation among electronegativity, cation polarizability, optical basicity and single bond strength of simple oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dimitrov, Vesselin, E-mail: vesselin@uctm.edu; Komatsu, Takayuki, E-mail: komatsu@mst.nagaokaut.ac.jp

2012-12-15

A suitable relationship between free-cation polarizability and electronegativity of elements in different valence states and with the most common coordination numbers has been searched on the basis of the similarity in physical nature of both quantities. In general, the cation polarizability increases with decreasing element electronegativity. A systematic periodic change in the polarizability against the electronegativity has been observed in the isoelectronic series. It has been found that generally the optical basicity increases and the single bond strength of simple oxides decreases with decreasing the electronegativity. The observed trends have been discussed on the basis of electron donation ability ofmore » the oxide ions and type of chemical bonding in simple oxides. - Graphical abstract: This figure shows the single bond strength of simple oxides as a function of element electronegativity. A remarkable correlation exists between these independently obtained quantities. High values of electronegativity correspond to high values of single bond strength and vice versa. It is obvious that the observed trend in this figure is closely related to the type of chemical bonding in corresponding oxide. Highlights: Black-Right-Pointing-Pointer A suitable relationship between free-cation polarizability and electronegativity of elements was searched. Black-Right-Pointing-Pointer The cation polarizability increases with decreasing element electronegativity. Black-Right-Pointing-Pointer The single bond strength of simple oxides decreases with decreasing the electronegativity. Black-Right-Pointing-Pointer The observed trends were discussed on the basis of type of chemical bonding in simple oxides.« less

Why did Nature choose manganese to make oxygen?

PubMed Central

Armstrong, Fraser A

2007-01-01

This paper discusses the suitability of manganese for its function in catalysing the formation of molecular oxygen from water. Manganese is an abundant element. In terms of its inherent properties, Mn has a particularly rich redox chemistry compared with other d-block elements, with several oxidizing states accessible. The most stable-state Mn2+ behaves like a Group 2 element—it is mobile, weakly complexing, easily taken up by cells and redox-inactive in simple aqueous media. Only in the presence of suitable ligands does Mn2+ become oxidized, so it provides an uncomplicated building unit for the oxygen-evolving centre (OEC). The intermediate oxidation states Mn(III) and Mn(IV) are strongly complexed by O2− and form robust mixed-valence poly-oxo clusters in which the Mn(IV)/Mn(III) ratio can be elevated, one electron at a time, accumulating oxidizing potential and capacity. The OEC is a Mn4CaOx cluster that undergoes sequential oxidations by P680+ at potentials above 1 V, ultimately to a super-oxidized level that includes one Mn(V) or a Mn(IV)-oxyl radical. The latter is powerfully oxidizing and provides the crucial ‘power stroke’ necessary to generate an O–O bond. This leaves a centre still rich in Mn(IV), ensuring a rapid follow-through to O2. PMID:17971329

On the Highest Oxidation States of Metal Elements in MO4 Molecules (M = Fe, Ru, Os, Hs, Sm, and Pu).

PubMed

Huang, Wei; Xu, Wen-Hua; Schwarz, W H E; Li, Jun

2016-05-02

Metal tetraoxygen molecules (MO4, M = Fe, Ru, Os, Hs, Sm, Pu) of all metal atoms M with eight valence electrons are theoretically studied using density functional and correlated wave function approaches. The heavier d-block elements Ru, Os, Hs are confirmed to form stable tetraoxides of Td symmetry in (1)A1 electronic states with empty metal d(0) valence shell and closed-shell O(2-) ligands, while the 3d-, 4f-, and 5f-elements Fe, Sm, and Pu prefer partial occupation of their valence shells and peroxide or superoxide ligands at lower symmetry structures with various spin couplings. The different geometric and electronic structures and chemical bonding types of the six iso-stoichiometric species are explained in terms of atomic orbital energies and orbital radii. The variations found here contribute to our general understanding of the periodic trends of oxidation states across the periodic table.

Oxidation of hydrogen halides to elemental halogens with catalytic molten salt mixtures

DOEpatents

Rohrmann, Charles A.

1978-01-01

A process for oxidizing hydrogen halides by means of a catalytically active molten salt is disclosed. The subject hydrogen halide is contacted with a molten salt containing an oxygen compound of vanadium and alkali metal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen. The reduced vanadium which remains after this contacting is regenerated to the active higher valence state by contacting the spent molten salt with a stream of oxygen-bearing gas.

Pyrometallurgical Extraction of Valuable Elements in Ni-Metal Hydride Battery Electrode Materials

NASA Astrophysics Data System (ADS)

Jiang, Yin-ju; Deng, Yong-chun; Bu, Wen-gang

2015-10-01

Gas selective reduction-oxidation (redox) and melting separation were consecutively applied to electrode materials of AB5-type Ni-metal hydride batteries leading to the production of a Ni-Co alloy and slag enriched with rare earth oxides (REO). In the selective redox process, electrode materials were treated with H2/H2O at 1073 K and 1173 K (800 °C and 900 °C). Active elements such as REs, Al, and Mn were oxidized whereas relatively inert elements such as Ni and Co were transformed into their elemental states in the treated materials. SiO2 and Al2O3 powders were added into the treated materials as fluxes which were then melted at 1823 K (1550 °C) to yield a Ni-Co alloy and a REO-SiO2-Al2O3-MnO slag. The high-purity Ni-Co alloy produced can be used as a raw material for AB5-type hydrogen-storage alloy. The REO content in slag was very high, i.e., 48.51 pct, therefore it can be used to recycle rare earth oxides.

Solid State Carbon Monoxide Sensor

NASA Technical Reports Server (NTRS)

Upchurch, Billy T. (Inventor); Wood, George M. (Inventor); Schryer, David R. (Inventor); Leighty, Bradley D. (Inventor); Oglesby, Donald M. (Inventor); Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); DAmbrosia, Christine M. (Inventor)

1999-01-01

A means for detecting carbon monoxide which utilizes an un-heated catalytic material to oxidize carbon monoxide at ambient temperatures. Because this reaction is exothermic, a thermistor in contact with the catalytic material is used as a sensing element to detect the heat evolved as carbon monoxide is oxidized to carbon dioxide at the catalyst surface, without any heaters or external heating elements for the ambient air or catalytic element material. Upon comparison to a reference thermistor, relative increases in the temperature of the sensing thermistor correspond positively with an increased concentration of carbon monoxide in the ambient medium and are thus used as an indicator of the presence of carbon monoxide.

Accuracy and Precision in Measurements of Biomass Oxidative Ratio and Carbon Oxidation State

NASA Astrophysics Data System (ADS)

Gallagher, M. E.; Masiello, C. A.; Randerson, J. T.; Chadwick, O. A.; Robertson, G. P.

2007-12-01

Ecosystem oxidative ratio (OR) is a critical parameter in the apportionment of anthropogenic CO2 between the terrestrial biosphere and ocean carbon reservoirs. OR is the ratio of O2 to CO2 in gas exchange fluxes between the terrestrial biosphere and atmosphere. Ecosystem OR is linearly related to biomass carbon oxidation state (Cox), a fundamental property of the earth system describing the bonding environment of carbon in molecules. Cox can range from -4 to +4 (CH4 to CO2). Variations in both Cox and OR are driven by photosynthesis, respiration, and decomposition. We are developing several techniques to accurately measure variations in ecosystem Cox and OR; these include elemental analysis, bomb calorimetry, and 13C nuclear magnetic resonance spectroscopy. A previous study, comparing the accuracy and precision of elemental analysis versus bomb calorimetry for pure chemicals, showed that elemental analysis-based measurements are more accurate, while calorimetry- based measurements yield more precise data. However, the limited biochemical range of natural samples makes it possible that calorimetry may ultimately prove most accurate, as well as most cost-effective. Here we examine more closely the accuracy of Cox and OR values generated by calorimetry on a large set of natural biomass samples collected from the Kellogg Biological Station-Long Term Ecological Research (KBS-LTER) site in Michigan.

An Analysis of the Algebraic Method for Balancing Chemical Reactions.

ERIC Educational Resources Information Center

Olson, John A.

1997-01-01

Analyzes the algebraic method for balancing chemical reactions. Introduces a third general condition that involves a balance between the total amount of oxidation and reduction. Requires the specification of oxidation states for all elements throughout the reaction. Describes the general conditions, the mathematical treatment, redox reactions, and…

Natural Variation in the Carbon Oxidation State and Oxidative Ratio of a Deciduous Forest

NASA Astrophysics Data System (ADS)

Masiello, C. A.; Calligan, L. J.; Gallagher, M. E.; Hockaday, W. C.; Robertson, G. P.

2007-12-01

Here we report natural variability in the oxidative ratio (OR) and carbon oxidation state (Cox) of a temperate, deciduous forest measured on an annual basis via elemental analysis of leaf litter. The OR of the terrestrial biosphere is a key component in O2 -based calculations of the biosphere's uptake of fossil fuel CO2 (eg [ Keeling, et al., 1996]). Ecosystem OR has been assumed to be invariant; however, small OR variations may cause significant shifts in the calculated size of the terrestrial biospheric C sink [ Randerson, et al., 2006]. Accurate measurements of OR are necessary for the accurate apportionment of fossil fuel CO2 between the atmosphere, oceans, and terrestrial biosphere. Ecosystem OR is linearly related to Cox, a parameter which can be easily measured via elemental analysis, calorimetry, or solid state nuclear magnetic resonance [ Masiello, et al., 2007]. We are measuring Cox and OR at the three deciduous forest sites within the Kellogg Biological Station NSF LTER (lter.kbs.msu.edu). We report OR from litter collected from three forest sites from 1998-2003, a time series which covers periods of both normal and low precipitation. We also report error introduced in the Cox to OR conversion via a range of plausible assumptions about ecosystem N cycling. Keeling, R. F., et al. (1996), Global and hemispheric CO2 sinks deduced from changes in atmospheric O2 concentration, Nature, 381, 218-221. Masiello, C.A. et al. (in review 2007) Two new approaches for measuring ecosystem carbon oxidation state and oxidative ratio. J.G.R. Biogeosciences. Randerson, J. T., et al. (2006), Is carbon within the global terrestrial biosphere becoming more oxidized? Implications for trends in atmospheric O2, Global Change Biology, 12, 260-271.

Effect of Surface Oxidation on Interfacial Water Structure at a Pyrite (100) Surface as Studied by Molecular Dynamics Simulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Jiaqi; Miller, Jan D.; Dang, Liem X.

2015-06-01

In the first part of this paper, a Scanning Electron Microscopy and contact angle study of a pyrite surface (100) is reported describing the relationship between surface oxidation and the hydrophilic surface state. In addition to these experimental results, the following simulated surface states were examined using Molecular Dynamics Simulation (MDS): fresh unoxidized (100) surface; polysulfide at the (100) surface; elemental sulfur at the (100) surface. Crystal structures for the polysulfide and elemental sulfur at the (100) surface were simulated using Density Functional Theory (DFT) quantum chemical calculations. The well known oxidation mechanism which involves formation of a metal deficientmore » layer was also described with DFT. Our MDS results of the behavior of interfacial water at the fresh and oxidized pyrite (100) surfaces without/with the presence of ferric hydroxide include simulated contact angles, number density distribution for water, water dipole orientation, water residence time, and hydrogen-bonding considerations. The significance of the formation of ferric hydroxide islands in accounting for the corresponding hydrophilic surface state is revealed not only from experimental contact angle measurements but also from simulated contact angle measurements using MDS. The hydrophilic surface state developed at oxidized pyrite surfaces has been described by MDS, on which basis the surface state is explained based on interfacial water structure. The Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences (BES), of the DOE funded work performed by Liem X. Dang. Battelle operates the Pacific Northwest National Laboratory for DOE. The calculations were carried out using computer resources provided by BES.« less

Effect of an in situ Hydrogen Plasma Pre-treatment on the Reduction of GaSb Native oxides Prior to Atomic Layer Deposition

DTIC Science & Technology

2013-04-12

absence of Sb-oxides, a reduction in elemental Sb, and an increase in the Ga2O3 content at the interface. The use of an in situ hydrogen...elemental Sb, and an increase in the Ga2O3 content at the interface. The use of an in situ hydrogen plasma pre-treatment eliminates the need for wet...the +1 state (Ga2O) and the +3 state ( Ga2O3 ), with peak positions found at 530.5 eV (Sb2O4), 20.1 eV (Ga2O), and 20.7 eV ( Ga2O3 ) [11,18]. The AFM image

Lithium metal oxide electrodes for lithium batteries

DOEpatents

Thackeray, Michael M.; Johnson, Christopher S.; Amine, Khalil; Kang, Sun-Ho

2010-06-08

An uncycled preconditioned electrode for a non-aqueous lithium electrochemical cell including a lithium metal oxide having the formula xLi.sub.2-yH.sub.yO.xM'O.sub.2.(1-x)Li.sub.1-zH.sub.zMO.sub.2 in which 0

Rethinking early Earth phosphorus geochemistry

PubMed Central

Pasek, Matthew A.

2008-01-01

Phosphorus is a key biologic element, and a prebiotic pathway leading to its incorporation into biomolecules has been difficult to ascertain. Most potentially prebiotic phosphorylation reactions have relied on orthophosphate as the source of phosphorus. It is suggested here that the geochemistry of phosphorus on the early Earth was instead controlled by reduced oxidation state phosphorus compounds such as phosphite (HPO32−), which are more soluble and reactive than orthophosphates. This reduced oxidation state phosphorus originated from extraterrestrial material that fell during the heavy bombardment period or was produced during impacts, and persisted in the mildly reducing atmosphere. This alternate view of early Earth phosphorus geochemistry provides an unexplored route to the formation of pertinent prebiotic phosphorus compounds, suggests a facile reaction pathway to condensed phosphates, and is consistent with the biochemical usage of reduced oxidation state phosphorus compounds in life today. Possible studies are suggested that may detect reduced oxidation state phosphorus compounds in ancient Archean rocks. PMID:18195373

Rethinking early Earth phosphorus geochemistry.

PubMed

Pasek, Matthew A

2008-01-22

Phosphorus is a key biologic element, and a prebiotic pathway leading to its incorporation into biomolecules has been difficult to ascertain. Most potentially prebiotic phosphorylation reactions have relied on orthophosphate as the source of phosphorus. It is suggested here that the geochemistry of phosphorus on the early Earth was instead controlled by reduced oxidation state phosphorus compounds such as phosphite (HPO(3)(2-)), which are more soluble and reactive than orthophosphates. This reduced oxidation state phosphorus originated from extraterrestrial material that fell during the heavy bombardment period or was produced during impacts, and persisted in the mildly reducing atmosphere. This alternate view of early Earth phosphorus geochemistry provides an unexplored route to the formation of pertinent prebiotic phosphorus compounds, suggests a facile reaction pathway to condensed phosphates, and is consistent with the biochemical usage of reduced oxidation state phosphorus compounds in life today. Possible studies are suggested that may detect reduced oxidation state phosphorus compounds in ancient Archean rocks.

Microanalysis (micro-XRF, micro-XANES, and micro-XRD) of a tertiary sediment using microfocused synchrotron radiation.

PubMed

Denecke, Melissa A; Somogyi, Andrea; Janssens, Koen; Simon, Rolf; Dardenne, Kathy; Noseck, Ulrich

2007-06-01

Micro-focused synchrotron radiation techniques to investigate actinide elements in geological samples are becoming an increasingly used tool in nuclear waste disposal research. In this article, results using mu-focus techniques are presented from a bore core section of a U-rich tertiary sediment collected from Ruprechtov, Czech Republic, a natural analog to nuclear waste repository scenarios in deep geological formations. Different methods are applied to obtain various, complementary information. Elemental and element chemical state distributions are obtained from micro-XRF measurements, oxidation states of As determined from micro-XANES, and the crystalline structure of selected regions are studied by means of micro-XRD. We find that preparation of the thin section created an As oxidation state artifact; it apparently changed the As valence in some regions of the sample. Results support our previously proposed hypothesis of the mechanism for U-enrichment in the sediment. AsFeS coating on framboid Fe nodules in the sediment reduced mobile groundwater-dissolved U(VI) to less-soluble U(IV), thereby immobilizing the uranium in the sediment.

S-containing copolymer as cathode material in poly(ethylene oxide)-based all-solid-state Li-S batteries

NASA Astrophysics Data System (ADS)

Gracia, Ismael; Ben Youcef, Hicham; Judez, Xabier; Oteo, Uxue; Zhang, Heng; Li, Chunmei; Rodriguez-Martinez, Lide M.; Armand, Michel

2018-06-01

Inverse vulcanization copolymers (p(S-DVB)) from the radical polymerization of elemental sulfur and divinylbenzene (DVB) have been studied as cathode active materials in poly(ethylene oxide) (PEO)-based all-solid-state Li-S cells. The Li-S cell comprising the optimized p(S-DVB) cathode (80:20 w/w S/DVB ratio) and lithium bis(fluorosulfonyl)imide/PEO (LiFSI/PEO) electrolyte shows high specific capacity (ca. 800 mAh g-1) and high Coulombic efficiency for 50 cycles. Most importantly, polysulfide (PS) shuttle is highly mitigated due to the strong interactions of PS species with polymer backbone in p(S-DVB). This is demonstrated by the stable cycling of the p(S-DVB)-based cell using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)/PEO electrolyte, where successful charging cannot be achieved even at the first cycle with plain elemental S-based cathode material due to the severe PS shuttle phenomenon. These results suggest that inverse vulcanization copolymers are promising alternatives to elemental sulfur for enhancing the electrochemical performance of PEO-based all-solid-state Li-S cells.

SPECIATION OF MERCURY IN THE PRESENCE OF COAL AND WASTE COMBUSTION FLY ASHES

EPA Science Inventory

The paper gives results of a study that focused on the oxidation of elemental mercury (Hgo) in the presence of both complex, four-component, model fly ashes, and actual coal combustion fly ashes collected from a pilot plant. Steady-state oxidation of Hgo promoted by the four-com...

Webinar on the Removal of Uranium from Drinking Water by Small System Treatment Technology

EPA Science Inventory

Abstract: Radionuclides, such as uranium (U), occur naturally as trace elements in rocks and soils and thus can be found in dissolved forms in ground waters. Uranium has four oxidation states (+3, +4, +5, and +6) and is a very reactive element forming a variety of stable complexe...

Publications - RDF 2000-4 | Alaska Division of Geological & Geophysical

Science.gov Websites

Oxides; Palladium; Platinum; Rare Earth Elements; STATEMAP Project; Trace Metals Top of Page Department Surveys Skip to content State of Alaska myAlaska My Government Resident Business in Alaska Visiting Alaska State Employees DGGS State of Alaska search Alaska Division of Geological & Geophysical

Green Synthesis of Formulated Zinc Oxide Nanoparticles for Chemical Protection of Skin Care and Related Applications

NASA Astrophysics Data System (ADS)

Koppolu, Ramya

Nanomaterials have diversified applications based on the unique properties. These nanoparticles and functionalized nanocomposites have been studied in the health care filed. Nanoparticles are mostly used in sunscreens which are a part of human life. These sunscreens consist of titanium dioxide and zinc oxide nanoparticles. Due to the higher band crevices, they help the skin to protect from ultraviolet rays, for instance, ultraviolet B and ultraviolet A. A series of nanostructured zinc oxide nanoparticles were prepared by cost-effective chemical and bioinspired methods and variables were optimized. Highly stable and spherical zinc oxide nanoparticles were formulated by aloe vera ( Aloe barbadensis) plant extract and avocado (Persea americana Mill) fruit extract. The state-of-the-art instrumentation was used to characterize the morphology, elemental composition, and particle size distribution. X-ray diffraction data indicated highly crystalline and ultrafine nanoparticles were obtained from the colloidal methods. The X-ray photoelectron spectroscopy results showed the chemical state of zinc, carbon, and oxygen atoms were well-indexed and are used as fingerprint identification of the elements. Transmission electron microscopy images show the shape of particles were cubic and fiber shape contingent upon the protecting operators and heat treatment conditions. The toxicity studies of zinc oxide nanoparticles were found to cause an increase in nitric oxide, which is protecting against further oxidative stress and appears to be nontoxic.

Selenium: Element of Contrasts

ERIC Educational Resources Information Center

Goldsmith, Robert H.; And Others

1978-01-01

Reports on recent findings concerning the impact of selenium on human and animal health. In its various oxidation states, different concentrations of selenium may be helpful or detrimental to human health. (CP)

Ion chromatographic determination of sulfur in fuels

NASA Technical Reports Server (NTRS)

Mizisin, C. S.; Kuivinen, D. E.; Otterson, D. A.

1978-01-01

The sulfur content of fuels was determined using an ion chromatograph to measure the sulfate produced by a modified Parr bomb oxidation. Standard Reference Materials from the National Bureau of Standards, of approximately 0.2 + or - 0.004% sulfur, were analyzed resulting in a standard deviation no greater than 0.008. The ion chromatographic method can be applied to conventional fuels as well as shale-oil derived fuels. Other acid forming elements, such as fluorine, chlorine and nitrogen could be determined at the same time, provided that these elements have reached a suitable ionic state during the oxidation of the fuel.

Thermochemistry of rare earth doped uranium oxides LnxU1-xO2-0.5x+y (Ln = La, Y, Nd)

NASA Astrophysics Data System (ADS)

Zhang, Lei; Navrotsky, Alexandra

2015-10-01

Lanthanum, yttrium, and neodymium doped uranium dioxide samples in the fluorite structure have been synthesized, characterized in terms of metal ratio and oxygen content, and their enthalpies of formation measured by high temperature oxide melt solution calorimetry. For oxides doped with 10-50 mol % rare earth (Ln) cations, the formation enthalpies from constituent oxides (LnO1.5, UO2 and UO3 in a reaction not involving oxidation or reduction) become increasingly exothermic with increasing rare earth content, while showing no significant dependence on the varying uranium oxidation state. The oxidation enthalpy of LnxU1-xO2-0.5x+y is similar to that of UO2 to UO3 for all three rare earth doped systems. Though this may suggest that the oxidized uranium in these systems is energetically similar to that in the hexavalent state, thermochemical data alone can not constrain whether the uranium is present as U5+, U6+, or a mixture of oxidation states. The formation enthalpies from elements calculated from the calorimetric data are generally consistent with those from free energy measurements.

Publications - RDF 2016-2 | Alaska Division of Geological & Geophysical

Science.gov Websites

, Major-oxide and trace-element geochemistry of mafic rocks in the Carboniferous Lisburne Group, Ivishak Surveys Skip to content State of Alaska myAlaska My Government Resident Business in Alaska Visiting Alaska State Employees DGGS State of Alaska search Alaska Division of Geological & Geophysical

Selective oxidation of alkanes and/or alkenes to valuable oxygenates

DOEpatents

Lin, Manhua; Pillai, Krishnan S.

2011-02-15

A catalyst, its method of preparation and its use for producing at least one of methacrolein and methacrylic acid, for example, by subjecting isobutane or isobutylene or a mixture thereof to a vapor phase catalytic oxidation in the presence of air or oxygen. In the case where isobutane alone is subjected to a vapor phase catalytic oxidation in the presence of air or oxygen, the product is at least one of isobutylene, methacrolein and methacrylic acid. The catalyst comprises a compound having the formula A.sub.aB.sub.bX.sub.xY.sub.yZ.sub.zO.sub.o wherein A is one or more elements selected from the group of Mo, W and Zr, B is one or more elements selected from the group of Bi, Sb, Se, and Te, X is one or more elements selected from the group of Al, Bi, Ca, Ce, Co, Fe, Ga, Mg, Ni, Nb, Sn, W and Zn, Y is one or more elements selected from the group of Ag, Au, B, Cr, Cs, Cu, K, La, Li, Mg, Mn, Na, Nb, Ni, P, Pb, Rb, Re, Ru, Sn, Te, Ti, V and Zr, and Z is one or more element from the X or Y groups or from the following: As, Ba, Pd, Pt, Sr, or mixtures thereof, and wherein a=1, 0.05

COUPLED IRON CORROSION AND CHROMATE REDUCTION: MECHANISMS FOR SUBSURFACE REMEDIATION

EPA Science Inventory

The reduction of chromium from the Cr(VI) to the Cr- (Ill) state by the presence of elemental, or zero-oxidation-state, iron metal was studied to evaluate the feasibility of such a process for subsurface chromate remediation. Reactions were studied in systems of natural aquifer m...

Fusion of acid oxides for potentially radiation-resistant waste forms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Herrick, C.C.; Penneman, R.A.

1983-02-01

Skull melting of groups VA and VB acid oxides with alkali metal oxides and urania leads to compounds with a good ability to retain radionuclides and establishes immunity to radiation damage. Substitution of neptunium and plutonium for uranium should not diminish these desirable properties. For hexavalent transplutonic elements, even at high oxygen fugacities and oxide activities, acid character losses and the reducing nature of radiation suggest the lower valences (III and IV) will be the stable states. Plutonium becomes the pivotal radionuclide when valence stability in a radiation field is considered.

Chemical bonds and vibrational properties of ordered (U, Np, Pu) mixed oxides

NASA Astrophysics Data System (ADS)

Yang, Yu; Zhang, Ping

2013-01-01

We use density functional theory +U to investigate the chemical bonding characters and vibrational properties of the ordered (U, Np, Pu) mixed oxides (MOXs), UNpO4,NpPuO4, and UPuO4. It is found that the 5f electronic states of different actinide elements keep their localized characters in all three MOXs. The occupied 5f electronic states of different actinide elements do not overlap with each other and tend to distribute over the energy band gap of the other actinide element's 5f states. As a result, the three ordered MOXs all show smaller band gaps than those of the component dioxides, with values of 0.91, 1.47, and 0.19 eV for UNpO4,NpPuO4, and UPuO4, respectively. Through careful charge density analysis, we further show that the U-O and Pu-O bonds in MOXs show more ionic character than in UO2 and PuO2, while the Np-O bonds show more covalent character than in NpO2. The change in covalencies in the chemical bonds leads to vibrational frequencies of oxygen atoms that are different in MOXs.

Design of optimum solid oxide membrane electrolysis cells for metals production

DOE PAGES

Guan, Xiaofei; Pal, Uday B.

2015-12-24

Oxide to metal conversion is one of the most energy-intensive steps in the value chain for metals production. Solid oxide membrane (SOM) electrolysis process provides a general route for directly reducing various metal oxides to their respective metals, alloys, or intermetallics. Because of its lower energy use and ability to use inert anode resulting in zero carbon emission, SOM electrolysis process emerges as a promising technology that can replace the state-of-the-art metals production processes. In this paper, a careful study of the SOM electrolysis process using equivalent DC circuit modeling is performed and correlated to the experimental results. Finally, amore » discussion on relative importance of each resistive element in the circuit and on possible ways of lowering the rate-limiting resistive elements provides a generic guideline for designing optimum SOM electrolysis cells.« less

Estimation of electronegativity values of elements in different valence states.

PubMed

Li, Keyan; Xue, Dongfeng

2006-10-05

The electronegativities of 82 elements in different valence states and with the most common coordination numbers have been quantitatively calculated on the basis of an effective ionic potential defined by the ionization energy and ionic radius. It is found that for a given cation, the electronegativity increases with increasing oxidation state and decreases with increasing coordination number. For the transition-metal cations, the electronegativity of the low-spin state is higher than that of the high-spin state. The ligand field stabilization, the first filling of p orbitals, the transition-metal contraction, and especially the lanthanide contraction are well-reflected by the relative values of our proposed electronegativity. This new scale is useful for us to estimate some quantities (e.g., the Lewis acid strength for the main group elements and the hydration free energy for the first transition series) and predict the structure and property of materials.

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

NASA Astrophysics Data System (ADS)

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 < 0.5 log units) and showing that oxidation state varies as a function of mantle source composition in the Galapagos hotspot system. After correcting back to a common MgO content = 8.0 wt%, the trace element depleted group similar to MORB (ITD), and the group similar to Pinta (WD = high Th/La, Δ7/4, Δ8/4 ratios) show Fe3+/ΣFe ratios within the range of MORB (average ITD = 0.162 ± 0.003 and WD = 0.164 ± 0.006). Another trace element enriched group similar to Sierra Negra and Cerro Azul (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.

Oxidation State of Nakhlites as inferred from Fe-Ti oxide Equilibria and Augite/Melt Europium Partitioning

NASA Technical Reports Server (NTRS)

Makishima, J.; McKay, G.; Le, L.; Miyamoto, M.; Mikouchi, T.

2007-01-01

Recent studies have shown that Martian magmas had wide range of oxygen fugacities (fO2) and that this variation is correlated with the variation of La/Yb ratio and isotopic characteristics of the Martian basalts, shergottite meteorites. The origin of this correlation must have important information about mantle sources and Martian evolution. In order to understand this correlation, it is necessary to know accurate value of oxidation state of other Martian meteorite groups. Nakhlites, cumulate clinopyroxenites, are another major group of Martian meteorites and have distinctly different trace element and isotopic characteristics from shergottites. Thus, estimates of oxidation state of nakhlites will give us important insight into the mantle source in general. Several workers have estimated oxidation state of nakhlites by using Fe-Ti oxide equilibrium. However, Fe-Ti oxides may not record the oxidation state of the parent melt of the nakhlite because it is a late-stage mineral. Furthermore, there is no comprehensive study which analyzed all nakhlite samples at the same time. Therefore, in this study (1) we reduced the uncertainty of the estimate using the same electron microprobe and the same standards under the same condition for Fe-Ti oxide in 6 nakhlites and (2) we also performed crystallization experiments to measure partition coefficients of Eu into pyroxene in the nakhlite system in order to estimate fO2 when the pyroxene core formed (i.e. Eu oxybarometer [e.g. 2,6]).

Method to synthesize and produce thin films by spray pyrolysis

DOEpatents

Squillante, Michael R.

1982-06-22

Forming a film by spraying onto a heated substrate an atomized solution containing the appropriate salt of a constituent element of the film and a highly soluble (i.e., greater than 1 M) organic acid in sufficient amount to reduce the oxidation state of at least one solute element of the spray solution after contacting the heated substrate.

Publications - PDF 98-36A | Alaska Division of Geological & Geophysical

Science.gov Websites

Oxides; Rocks; STATEMAP Project; Trace Elements Top of Page Department of Natural Resources, Division of Surveys Skip to content State of Alaska myAlaska My Government Resident Business in Alaska Visiting Alaska State Employees DGGS State of Alaska search Alaska Division of Geological & Geophysical

Dependence of precipitation of trace elements on pH in standard water

NASA Astrophysics Data System (ADS)

Verma, Shivcharan; Mohanty, Biraja P.; Singh, K. P.; Behera, B. R.; Kumar, Ashok

2018-04-01

The present work aimed to study the dependence of precipitation of trace elements on the pH of solution. A standard solution was prepared by using ultrapure deionized water (18.2 MΩ/cm) as the solvent and 11 water-soluble salts having different elements as solutes. Five samples of different pH values (2 acidic, 2 basic, and 1 neutral) were prepared from this standard solution. Sodium-diethyldithiocarbamate was used as the chelating agent to precipitate the metal ions present in these samples of different pH values. The targets were prepared by collecting these precipitates on mixed cellulose esters filter of 0.4 μm pore size by vacuum filtration. Elemental analysis of these targets was performed by particle-induced X-ray emission (PIXE) using 2.7 MeV protons from the single Dee variable energy cyclotron at Panjab University, Chandigarh, India. PIXE data were analyzed using GUPIXWIN software. For most of the elements, except Hg with oxidation state +2, such as Co, Ni, Zn, Ba, and Cd, a general trend of enhancement in precipitation was observed with the increase in pH. However, for other elements such as V, As, Mo, Ag, and Bi, which have oxidation state other than +2, no definite pattern was observed. Precipitation of Ba and As using this method was negligible at all five pH values. From these results, it can be concluded that the precipitation and recovery of elements depend strongly on the pH of the water sample.

Chemical Properties of Elements 99 and 100 [Einsteinium and Fermium

DOE R&D Accomplishments Database

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

1954-07-23

A description of some of the chemical properties and of the methods used in the separations of elements 99 [Einsteinium] and 100 [Fermium] are given. The new elements exhibit the properties expected for the tenth and eleventh actinide elements. Attempts to produce an oxidation state greater than III of element 99 have been unsuccessful. In normal aqueous media only the III state of element 100 appears to exist. The relative spacings of the elution peaks of the new elements in some separations with ion exchange resin columns are the same as the relative spacings of the homologous lanthanide elements. The results of experiments involving cation exchange resins with very concentrated hydrochloric acid eluant show that the new elements, like the earlier actinides, are more strongly complexed than the lanthanides. The new elements also exist partially as anions in concentrated hydrochloric acid, as do earlier actinide elements, and they may be partially separated from each other by means of ion exchange resins. With some eluants interesting reversals of elution positions are observed in the region Bk-Cf-99-100, indicating complex ion formation involving unusual factors.

The geochemical cycling of trace elements in a biogenic meromictic lake

NASA Astrophysics Data System (ADS)

Balistrieri, Laurie S.; Murray, James W.; Paul, Barbara

1994-10-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d -1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn).

The geochemical cycling of trace elements in a biogenic meromictic lake

USGS Publications Warehouse

Balistrieri, L.S.; Murray, J.W.; Paul, B.

1994-01-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d-1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn). ?? 1994.

The oxidation state, and sulfur and Cu contents of arc magmas: implications for metallogeny

NASA Astrophysics Data System (ADS)

Richards, Jeremy P.

2015-09-01

Global data for measured Fe2O3/FeO ratios and Cu contents in unaltered volcanic and intrusive arc rocks indicate that, on average, they are slightly more oxidized than other magmas derived from depleted upper mantle (such as MORB), but contain similar Cu contents across their compositional ranges. Although Cu scatters to elevated values in some intermediate composition samples, the bulk of the data show a steady but gentle trend to lower concentrations with differentiation, reaching modal values of 50-100 ppm in andesitic rocks. These data suggest that Cu is mildly compatible during partial melting and fractionation processes, likely reflecting minor degrees of sulfide saturation throughout the magmatic cycle. However, the volume of sulfides must be small such that significant proportions of the metal content remain in the magma during fractionation to intermediate compositions. Previous studies have shown that andesitic magmas containing 50 ppm Cu can readily form large porphyry-type Cu deposits upon emplacement in the upper crust. A review of the literature suggests that the elevated oxidation state in the asthenospheric mantle wedge source of arc magmas (ΔFMQ ≈ + 1 ± 1) derives from the subduction of seawater-altered and oxidized oceanic crust, and is transmitted into the mantle wedge via prograde metamorphic dehydration fluids carrying sulfate and other oxidizing components. Progressive hydration and oxidation of the mantle wedge may take up to 10 m.y. to reach a steady state from the onset of subduction, explaining the rarity of porphyry deposits in primitive island arcs, and the late formation of porphyries in continental arc magmatic cycles. Magmas generated from this metasomatized and moderately oxidized mantle source will be hydrous basalts containing high concentrations of sulfur, mainly dissolved as sulfate or sulfite. Some condensed sulfides (melt or minerals) may be present due to the high overall fS2, despite the moderately high oxidation state. These sulfides may retain some highly siderophile elements in the source, but are unlikely to be sufficiently voluminous to significantly affect the budget of more modestly sulfide-compatible and more abundant elements such as Cu and Mo. These primary magmas can therefore be considered to be largely Cu-Mo-undepleted, although highly siderophile elements such as Au and platinum group elements (PGE) may be depleted unless no sulfides remain in the source. The latter condition seems unlikely during active subduction because of the continuous flux of fresh sulfur from the slab, but may occur during post-subduction re-melting (leading to potentially Au-rich post-subduction porphyry and alkalic-type epithermal systems). Lower crustal differentiation of main-stage arc magmas results in some loss of Cu to residual or cumulate sulfides, but again the amount appears to be minor, and does not drastically reduce the Cu content of derivative intermediate-composition melts. Fractionation and devolatilization affect the oxidation state of the magma in competing ways, but, while crystallization and segregation of Fe3 +-rich magnetite can cause reduction in reduced to moderately oxidized evolved magmas, this effect appears to be outweighed by the oxidative effects of degassing reduced or weakly oxidized gaseous species such as H2, H2S, and SIVO2, and preferential solvation and removal of Fe2 + in saline hydrothermal fluids. Consequently, most arc magmatic suites show slight increases in oxidation state during differentiation, reaching typical values of ΔFMQ = + 1 to + 2. This oxidation state is significant, because it corresponds to the transition from dissolved sulfide to sulfate dominance in magmas. It has been shown that Cu and Au solubilities in silicate magma increase up to this level (ΔFMQ ≈ + 1), but while Cu solubility continues to increase at higher oxidation states, Au shows a precipitous drop as sulfide, which solvates Au in the melt, is converted to sulfate. This may explain the somewhat restricted distribution of Au-rich porphyry Cu deposits, but the general association of porphyry Cu deposits with relatively oxidized magmas. Exsolution of a saline, high temperature aqueous fluid enables metals to partition from the magma into a highly mobile volatile phase. Sulfur also partitions strongly into this fluid phase, predominantly as SO2 at ΔFMQ = + 1 to + 2. However, as the fluid cools below 400 °C, SIVO2 disproportionates to form reduced H2S- II and oxidized H2SVIO4. The H2S bonds with metals in solution to precipitate as Cu- and Mo-sulfides, while the H2SO4 (and HCl) generates progressively acidic wallrock alteration (phyllic, argillic, advanced argillic). Gold may precipitate with early Cu/Mo-sulfides, but some may also stay in solution as bisulfide complexes, eventually reaching the epithermal environment. Thus, three components, [S], [H2O], and fO2 work together throughout subduction and arc magmatic processes to transport chalcophile and siderophile metals from the mantle into the upper crust, where they may be concentrated by hydrothermal processes to form ore deposits. These processes are far from 100% efficient, and metals (especially highly siderophile elements such as Au and PGE) may be left behind at various stages of the passage of arc magmas through the lithosphere, where they may form potentially metalliferous source rocks for partial melts and subsequent magmatic-hydrothermal ore deposits generated during later tectonomagmatic events.

Probing the density of states of two-level tunneling systems in silicon oxide films using superconducting lumped element resonators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Skacel, S. T.; Institut für Mikro- und Nanoelektronische Systeme, Karlsruher Institut für Technologie, Hertzstraße 16, D-76187 Karlsruhe; Kaiser, Ch.

2015-01-12

We have investigated dielectric losses in amorphous silicon oxide (a-SiO) thin films under operating conditions of superconducting qubits (mK temperatures and low microwave powers). For this purpose, we have developed a broadband measurement setup employing multiplexed lumped element resonators using a broadband power combiner and a low-noise amplifier. The measured temperature and power dependences of the dielectric losses are in good agreement with those predicted for atomic two-level tunneling systems (TLS). By measuring the losses at different frequencies, we found that the TLS density of states is energy dependent. This had not been seen previously in loss measurements. These resultsmore » contribute to a better understanding of decoherence effects in superconducting qubits and suggest a possibility to minimize TLS-related decoherence by reducing the qubit operation frequency.« less

Effects of point defect concentrations of the reactive element oxides on the oxidation kinetics of pure Ni and Ni-Cr alloys

NASA Astrophysics Data System (ADS)

Yan, Ruey-Fong

The addition of some reactive element oxides, e.g. Ysb2Osb3 or ZrOsb2, has significant effects, e.g. improvement in scale adhesion and reduction in oxidation rate, on the oxidation behavior of chromia and alumina scale forming alloys at high temperatures. However, there is little agreement about how a small addition of an oxygen-active element can cause such profound effects. It was the goal of this project to study the growth kinetics of an oxide scale when different reactive-element oxides were added to pure Ni and Ni-Cr alloys and, consequently, to aid in clarifying the mechanism of reactive element effects. The oxidation kinetics were measured using a thermogravimetric analysis (TGA) method and the material characterization of oxide scale was conducted. The relationship between point defect structures and oxidation kinetics was discussed. The results in this research showed that Ysb2Osb3 and ZrOsb2 exhibited the reactive element effects on the oxidation behaviors of Ni and Ni-Cr alloys. In addition, the point defect concentrations of the reactive element oxide, Ysb2Osb3, were changed by doping of different valent oxides. The modification of point defect concentrations of the reactive element oxide dispersed phases did change the oxidation kinetics of the pure Ni and Ni-Cr alloys containing Ysb2Osb3. These results indicate that the transport properties of the reactive element oxide dispersed phases are one of the important factors in determining the growth rate of an oxide scale.

Modeling of CMOS compatible ring resonator switch with intermediate vanadium oxide as the switching element

NASA Astrophysics Data System (ADS)

Singh, Mandeep; Datta, Arnab

2018-05-01

In this paper, silicon based dual ring resonator with hybrid plasmonic bus waveguides (Cu-SiO2-Si-SiO2-Cu) is investigated for achieving switching in the telecommunication C-band (λ = 1.54-1.553µm). The switch element uses vanadium oxide (VO2) as the switching medium when inserted between the rings in order to tailor transmission from one ring to the other through heating induced phase transition. In this manner, the proposed switch element uses one vanadium oxide medium instead of refractive index tailoring of the whole ring as in the prior reported works and achieves switching response. From two-dimensional finite element analysis we have found that, the proposed switch can achieve maximum extinction ratio of 2.72 dB at λ = 1.5434µm, exclusively by tailoring VO2 phase. Furthermore, impact of aperture width, and gap (separation between the bus waveguide and rings) are investigated to gain insight on the improvement of extinction ratio. From our numerical simulations, we find that free spectral range (FSR) and figure of merit (Q) for OFF and ON states are (173.36 nm, 92.63), and (173.58 nm, 65.39), respectively.

Reduction of Vanadium Oxide (VOx) under High Vacuum Conditions as Investigated by X-Ray Photoelectron Spectroscopy

NASA Astrophysics Data System (ADS)

Chourasia, A.

2015-03-01

Vanadium oxide thin films were formed by depositing thin films of vanadium on quartz substrates and oxidizing them in an atmosphere of oxygen. The deposition was done by the e-beam technique. The oxide films were annealed at different temperatures for different times under high vacuum conditions. The technique of x-ray photoelectron spectroscopy has been employed to study the changes in the oxidation states of vanadium and oxygen in such films. The spectral features in the vanadium 2p, oxygen 1s, and the x-ray excited Auger regions were investigated. The Auger parameter has been utilized to study the changes. The complete oxidation of elemental vanadium to V2O5 was observed to occur at 700°C. At any other temperature, a mixture of oxides consisting of V2O5 and VO2 was observed in the films. Annealing of the films resulted in the gradual loss of oxygen followed by reduction in the oxidation state from +5 to 0. The reduction was observed to depend upon the annealing temperature and the annealing time. Organized Research, TAMU-Commerce.

The New Element Berkelium (Atomic Number 97)

DOE R&D Accomplishments Database

Seaborg, G. T.; Thompson, S. G.; Ghiorso, A.

1950-04-26

An isotope of the element with atomic number 97 has been discovered as a product of the helium-ion bombardment of americium. The name berkelium, symbol Bk, is proposed for element 97. The chemical separation of element 97 from the target material and other reaction products was made by combinations of precipitation and ion exchange adsorption methods making use of its anticipated (III) and (IV) oxidation states and its position as a member of the actinide transition series. The distinctive chemical properties made use of in its separation and the equally distinctive decay properties of the particular isotope constitute the principal evidence for the new element.

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

PubMed Central

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

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

NASA Astrophysics Data System (ADS)

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

2016-12-01

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.

Multiscale model of metal alloy oxidation at grain boundaries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sushko, Maria L.; Alexandrov, Vitali Y.; Schreiber, Daniel K.

2015-06-07

High temperature intergranular oxidation and corrosion of metal alloys is one of the primary causes of materials degradation in nuclear systems. In order to gain insights into grain boundary oxidation processes, a mesoscale metal alloy oxidation model at experimentally relevant length scales is established by combining quantum Density Functional Theory (DFT) and mesoscopic Poisson-Nernst-Planck/classical DFT with predictions focused on Ni alloyed with either Cr or Al. Analysis of species and fluxes at steady-state conditions indicates that the oxidation process involves vacancy-mediated transport of Ni and the minor alloying element to the oxidation front and the formation of stable metal oxides.more » The simulations further demonstrate that the mechanism of oxidation for Ni-5Cr and Ni-4Al is qualitatively different. Intergranular oxidation of Ni-5Cr involves the selective oxidation of the minor element and not matrix Ni, due to slower diffusion of Ni relative to Cr in the alloy and due to the significantly smaller energy gain upon the formation of nickel oxide compared to that of Cr2O3. This essentially one-component oxidation process results in continuous oxide formation and a monotonic Cr vacancy distribution ahead of the oxidation front, peaking at alloy/oxide interface. In contrast, Ni and Al are both oxidized in Ni-4Al forming a mixed spinel NiAl2O4. Different diffusivities of Ni and Al give rise to a complex elemental distribution in the vicinity of the oxidation front. Slower diffusing Ni accumulates in the oxide and metal within 3 nm of the interface, while Al penetrates deeper into the oxide phase. Ni and Al are both depleted from the region 3–10 nm ahead of the oxidation front creating voids. The oxide microstructure is also different. Cr2O3 has a plate-like structure with 1.2 - 1.7 nm wide pores running along the grain boundary, while NiAl2O4 has 1.5 nm wide pores in the direction parallel to the grain boundary and 0.6 nm pores in the perpendicular direction providing an additional pathway for oxygen diffusion through the oxide.« less

Upgrade of the Surface Spectrometer at NEPOMUC for PAES, XPS and STM Investigations

NASA Astrophysics Data System (ADS)

Zimnik, S.; Lippert, F.; Hugenschmidt, C.

2014-04-01

The characterization of the elemental composition of surfaces is of great importance for the understanding of many surface processes, such as surface segregation or oxidation. Positron-annihilation-induced Auger Electron Spectroscopy (PAES) is a powerful technique for gathering information about the elemental composition of only the topmost atomic layer of a sample. The upgraded surface spectrometer at NEPOMUC (NEtron induced POsitron source MUniCh) enables a comprehensive surface analysis with the complementary techniques STM, XPS and PAES. A new X-ray source for X-ray induced photoelectron spectroscopy (XPS) was installed to gather additional information on oxidation states. A new scanning tunneling microscope (STM) is used as a complementary method to investigate with atomic resolution the surface electron density. The combination of PAES, XPS and STM allows the characterization of both the elemental composition, and the surface topology.

Lewis acid catalysis and Green oxidations: sequential tandem oxidation processes induced by Mn-hyperaccumulating plants.

PubMed

Escande, Vincent; Renard, Brice-Loïc; Grison, Claude

2015-04-01

Among the phytotechnologies used for the reclamation of degraded mining sites, phytoextraction aims to diminish the concentration of polluting elements in contaminated soils. However, the biomass resulting from the phytoextraction processes (highly enriched in polluting elements) is too often considered as a problematic waste. The manganese-enriched biomass derived from native Mn-hyperaccumulating plants of New Caledonia was presented here as a valuable source of metallic elements of high interest in chemical catalysis. The preparation of the catalyst Eco-Mn1 and reagent Eco-Mn2 derived from Grevillea exul exul and Grevillea exul rubiginosa was investigated. Their unusual polymetallic compositions allowed to explore new reactivity of low oxidative state of manganese-Mn(II) for Eco-Mn1 and Mn(IV) for Eco-Mn2. Eco-Mn1 was used as a Lewis acid to catalyze the acetalization/elimination of aldehydes into enol ethers with high yields; a new green and stereoselective synthesis of (-)-isopulegol via the carbonyl-ene cyclization of (+)-citronellal was also performed with Eco-Mn1. Eco-Mn2 was used as a mild oxidative reagent and controlled the oxidation of aliphatic alcohols into aldehydes with quantitative yields. Oxidative cleavage was interestingly noticed when Eco-Mn2 was used in the presence of a polyol. Eco-Mn2 allowed direct oxidative iodination of ketones without using iodine, which is strongly discouraged by new environmental legislations. Finally, the combination of the properties in the Eco-Mn catalysts and reagents gave them an unprecedented potential to perform sequential tandem oxidation processes through new green syntheses of p-cymene from (-)-isopulegol and (+)-citronellal; and a new green synthesis of functionalized pyridines by in situ oxidation of 1,4-dihydropyridines.

The role of metals in carcinogenesis: biochemistry and metabolism.

PubMed Central

Jennette, K W

1981-01-01

The oxyanions of vanadium, chromium, molybdenum, arsenic, and selenium are stable forms of these elements in high oxidation states which cross cell membranes using the normal phosphate and/or sulfate transport systems of the cell. Once inside the cell, these oxyanions may sulfuryl transfer reactions. Often the oxyanions serve as alternate enzyme substrates but form ester products which are hydrolytically unstable compared with the sulfate and phosphate esters and, therefore, decompose readily in aqueous solution. Arsenite and selenite are capable of reacting with sulfhydryl groups in proteins. Some cells are able to metabolize redox active oxyanions to forms of the elements in other stable oxidation states. Specific enzymes may be involved in the metabolic processes. The metabolites of these elements may form complexes with small molecules, proteins and nucleic acids which inhibit their ability to function properly. The divalent ions of beryllium, manganese, cobalt, nickel, cadmium, mercury, and lead are stable forms of these elements which may mimic essential divalent ions such as magnesium, calcium, iron, copper, or zinc. These ions may complex small molecules, enzymes, and nucleic acids in such a way that the normal activity of these species is altered. Free radicals may be produced in the presence of these metal ions which damage critical cellular molecules. PMID:7023933

Redox status in a model of cancer stem cells.

PubMed

Zaccarin, Mattia; Bosello-Travain, Valentina; Di Paolo, Maria Luisa; Falda, Marco; Maiorino, Matilde; Miotto, Giovanni; Piccolo, Stefano; Roveri, Antonella; Ursini, Fulvio; Venerando, Rina; Toppo, Stefano

2017-03-01

Reversible oxidation of Cys residues is a crucial element of redox homeostasis and signaling. According to a popular concept in oxidative stress signaling, the oxidation of targets of signals can only take place following an overwhelming of the cellular antioxidant capacity. This concept, however, ignores the activation of feedback mechanisms possibly leading to a paradoxical effect. In a model of cancer stem cells (CSC), stably overexpressing the TAZ oncogene, we observed that the increased formation of oxidants is associated with a globally more reduced state of proteins. Redox proteomics revealed that several proteins, capable of undergoing reversible redox transitions, are indeed more reduced while just few are more oxidized. Among the proteins more oxidized, G6PDH emerges as both more expressed and activated by oxidation. This accounts for the observed more reduced state of the NADPH/NADP + couple. The dynamic redox flux generating this apparently paradoxical effect is rationalized in a computational system biology model highlighting the crucial role of G6PDH activity on the rate of redox transitions eventually leading to the reduction of reversible redox switches. Copyright © 2016 Elsevier Inc. All rights reserved.

Tuning charge transfer in the LaTiO3/RO/LaNiO3 (R = rare-earth) superlattices by the rare-earth oxides interfaces from a first-principles calculation

NASA Astrophysics Data System (ADS)

Yao, Fen; Zhang, Lifang; Meng, Junling; Liu, Xiaojuan; Zhang, Xiong; Zhang, Wenwen; Meng, Jian; Zhang, Hongjie

2018-03-01

We investigate the internal charge transfer at the isopolar interfaces in LaTiO3/RO/LaNiO3 (R = La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu) superlattices by means of density functional theory calculations. The charge transfer from Ti sites to Ni sites in all superlattices is induced by the electronegativity difference between the elements Ti and Ni, and the lanthanide oxides interfaces can modulate the amount of charge transfer. Comparison of the perovskite heterostructures with the different rare-earth interfaces shows that increasing the deviations of bond angles from 180.0° and the oxygen motions near the interfaces enhance charge transfer. The 4f electrons themselves of rare-earth elements have faint influences on charge transfer. In addition, the reasons why our calculated 4f states of Sm and Tm elements disagree with the experimental systems have been provided. It is hoped that all the calculated results could be used to design new functional nanoelectronic devices in perovskite oxides.

The role of electronegativity on the extent of nitridation of group 5 metals as revealed by reactions of tantalum cluster cations with ammonia molecules.

PubMed

Arakawa, Masashi; Ando, Kota; Fujimoto, Shuhei; Mishra, Saurabh; Patwari, G Naresh; Terasaki, Akira

2018-05-10

Reactions of the free tantalum cation, Ta+, and tantalum cluster cations, Tan+ (n = 2-10), with ammonia are presented. The reaction of the monomer cation, Ta+, with two molecules of NH3 leads to the formation of TaN2H2+ along with release of two H2 molecules. The dehydrogenation occurs until the formal oxidation number of the tantalum atom reaches +5. On the other hand, all the tantalum cluster cations, Tan+, react with two molecules of NH3 and form TanN2+ with the release of three H2 molecules. Further exposure to ammonia showed that TanNmH+ and TanNm+ are produced through successive reactions; a pure nitride and three H2 molecules are formed for every other NH3 molecule. The nitridation occurred until the formal oxidation number of the tantalum atoms reaches +5 as in the case of TaN2H2+ in contrast to other group 5 elements, i.e., vanadium and niobium, which have been reported to produce nitrides with lower oxidation states. The present results on small gas-phase metal-nitride clusters show correlation with their bulk properties: tantalum is known to form bulk nitrides in the oxidation states of either +5 (Ta3N5) or +3 (TaN), whereas vanadium and niobium form nitrides in the oxidation state of +3 (VN and NbN). Along with DFT calculations, these findings reveal that nitridation is driven by the electron-donating ability of group 5 elements, i.e., electronegativity of the metal plays a key role in determining the composition of the metal nitrides.

Heptavalent Neptunium in a Gas-Phase Complex: (Np VIIO 3 +)(NO 3 –) 2

DOE PAGES

Dau, Phuong D.; Maurice, Remi; Renault, Eric; ...

2016-09-15

A central goal of chemistry is to achieve ultimate oxidation states, including in gas-phase complexes with no condensed phase perturbations. In the case of the actinide elements, the highest established oxidation states are labile Pu(VII) and somewhat more stable Np(VII). We have synthesized and characterized gas-phase AnO 3(NO 3) 2- complexes for An = U, Np, and Pu by endothermic NO 2 elimination from AnO 2(NO 3) 3-. It was previously demonstrated that the PuO 3+ core of PuO 3(NO 3) 2- has a Pu—O• radical bond such that the oxidation state is Pu(VI); it follows that in UO 3(NOmore » 3) 2- it is the stable U(VI) oxidation state. On the basis of the relatively more facile synthesis of NpO 3(NO 3) 2-, a Np(VII) oxidation state is inferred. This interpretation is substantiated by reactivity of the three complexes: NO 2 spontaneously adds to UO 3(NO 3) 2- and PuO 3(NO 3) 2- but not to NpO 3(NO 3) 2-. This unreactive character is attributed to a Np(VII)O 3+ core with three stable Np=O bonds, this in contrast to reactive U—O• and Pu—O• radical bonds. The computed structures and reaction energies for the three AnO 3(NO 3) 2- support the conclusion that the oxidation states are U(VI), Np(VII), and Pu(VI). These results establish the extreme Np(VII) oxidation state in a gas-phase complex, and demonstrate the inherently greater stability of Np(VII) versus Pu(VII).« less

Concretionary manganese-iron oxides in streams and their usefulness as a sample medium for geochemical prospecting

USGS Publications Warehouse

Nowlan, G.A.

1976-01-01

Correlation studies of 400 samples of sieved stream sediments and 325 samples of fluvial, concretionary Mn-Fe oxides from Maine resulted in the separation of elements into the following categories: (1) elements not scavenged by Mn-Fe oxides - B, Cr, K, Mg, Rb, Sc, Ti, V, and Zr; (2) elements probably not scavenged by Mn-Fe oxides - Ag, Be, Ca, Ga, La, Sb, and Y; (3) elements scavenged weakly by Mn-Fe oxides - Cu, Mo, Pb, and Sr; (4) elements scavenged strongly by Mn oxides - Ba, Cd, Co, Ni, Tl, and Zn; and (5) elements scavenged strongly by Fe oxides - As and In. Studies of the scavenged elements showed that the deviation from the mean is characteristically greater in oxide samples as compared to sieved sediments from the same locality. However, a significant increase in contrast between anomalous and background localities, when oxides are the sample medium, more than offsets the disadvantage of data scatter. The use of oxides as a sampling medium clearly and significantly accentuates anomalous localities. In general, non-ratioed data on oxides give very nearly the same results as data consisting of scavenged elements ratioed to Mn and Fe. However, ratioed data expand the geographic area of specific anomalies. Cd and Zn consistently show strong correlations with concretionary Mn-Fe oxides, but their concentrations in the oxides do not generally show as much contrast between anomalous and background localities as do Cu, Mo, and Pb. These latter elements are strongly scavenged where rocks are mineralized. ?? 1976.

A textural and compositional investigation on the source and timing of iron oxidation and titanium enrichment in high-pressure serpentinites

NASA Astrophysics Data System (ADS)

Crossley, R.; Evans, K. A.; Reddy, S.; Lester, G. W.

2016-12-01

The redox state, quantity and composition of subduction zone fluids influence the transport and precipitation of elements including those which are redox-sensitive, of economic importance such as Cu, Au and Ag, and those considered to be immobile, which include Fe3+. However, subduction zone fluids remain poorly understood. The redox state of Fe in high-pressure ultramafic rocks, which host a significant proportion of Fe3+, can be used to provide an insight into Fe cycling and constrain the composition and possible source of subduction zone fluids. In this work, we use a combination of oxide mineral textures, mineral parageneses, mineral composition data, and whole rock geochemistry of high-pressure retrogressed ultramafic rocks from the Zermatt-Saas Zone to constrain the distribution and oxidation state of iron, and to provide insights on the nature of fluids at depth within subduction zones. Oxide minerals host the bulk of the iron, particularly Fe3+. The increase in mode of magnetite during initial retrogression is most consistent with oxidation of existing iron via the infiltration of an oxidising fluids since it is difficult to reconcile addition of Fe3+ with the known limited solubility of this species. In addition, fluid-mediated or mechanical mixing with other lithologies in the slab could introduce elements and alter the bulk composition of serpentinites. However, the high Ti content of one sample cannot be explained by simple mixing of a depleted mantle protolith with the nearby Allalin gabbros, and provides the tantalising possibility that Ti, an element generally perceived as immobile, has been added to the rock. While we cannot completely exclude the possibility of pre-subduction Ti addition, textural analysis of Ti-rich minerals suggest mobilisation of Ti during subduction on at least a centimetre scale. If Ti addition has occurred, then the introduction of Fe3+, also generally considered to be immobile, cannot be disregarded. The Al-rich nature of the sample may be consistent with aluminosilicate complexing as the transport vector for Ti and/or Fe3+.

Chemical depth profiles of the GaAs/native oxide interface

NASA Technical Reports Server (NTRS)

Grunthaner, P. J.; Vasquez, R. P.; Grunthaner, F. J.

1980-01-01

The final-state oxidation products and their distribution in thin native oxides (30-40 A) on GaAs have been studied using X-ray photoelectron spectroscopy in conjunction with chemical depth profiling. Extended room-temperature-oxidation conditions have been chosen to allow the native oxide to attain its equilibrium composition and structure. The work emphasizes the use of chemical depth-profiling methods which make it possible to examine the variation in chemical reactivity of the oxide structure. A minimum of two distinct regions of Ga2O3 with differing chemical reactivity is observed. Chemical shift data indicate the presence of As2O3 in the oxide together with an elemental As overlayer at the interface. A change in relative charge transfer between oxygen and both arsenic and gallium-oxide species is observed in the region of the interface.

Trace and surface analysis of ceramic layers of solid oxide fuel cells by mass spectrometry.

PubMed

Becker, J S; Breuer, U; Westheide, J; Saprykin, A I; Holzbrecher, H; Nickel, H; Dietze, H J

1996-06-01

For the trace analysis of impurities in thick ceramic layers of a solid oxide fuel cell (SOFC) sensitive solid-state mass spectrometric methods, such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and radiofrequency glow discharge mass spectrometry (rf-GDMS) have been developed and used. In order to quantify the analytical results of LA-ICP-MS, the relative sensitivity coefficients of elements in a La(0.6)Sr(0.35)MnO(3) matrix have been determined using synthetic standards. Secondary ion mass spectrometry (SIMS) - as a surface analytical method - has been used to characterize the element distribution and diffusion profiles of matrix elements on the interface of a perovskite/Y-stabilized ZrO(2) layer. The application of different mass spectrometric methods for process control in the preparation of ceramic layers for the SOFC is described.

Chemistry of peroxide compounds

NASA Technical Reports Server (NTRS)

Volnov, I. I.

1981-01-01

The history of Soviet research from 1866 to 1967 on peroxide compounds is reviewed. This research dealt mainly with peroxide kinetics, reactivity and characteristics, peroxide production processes, and more recently with superoxides and ozonides and emphasis on the higher oxides of group 1 and 2 elements. Solid state fluidized bed synthesis and production of high purity products based on the relative solubilities of the initial, intermediate, and final compounds and elements in liquid ammonia are discussed.

Photoelectron Spectroscopy for Identification of Chemical States

NASA Technical Reports Server (NTRS)

Novakov, T.

1971-01-01

The technique of X-ray photoelectron spectroscopy and the fundamental electronic interactions constituting the basis of the method will be discussed. The method provides information about chemical states ("oxidation states") of atoms in molecules. In addition, quantitative elemental analysis can be performed using the same method. On the basis of this information identification of chemical species is possible. Examples of applications are discussed with particular references to the study of smog particulate matter.

Design of a Molecular Memory Device: The Electron Transfer Shift Register Memory

NASA Technical Reports Server (NTRS)

Beratan, D.

1993-01-01

A molecular shift register memory at the molecular level is described. The memory elements consist of molecules can exit in either an oxidized or reduced state and the bits are shifted between the cells with photoinduced electron transfer reactions.

Study of the Reactive-element Effect in Oxidation of Fe-cr Alloys Using Transverse Section Analytical Electron Microscopy

NASA Technical Reports Server (NTRS)

King, W. E.; Ethridge, E. C.

1985-01-01

The role of trace additions of reactive elements like Y, Ce, Th, or Hf to Cr bearing alloys was studied by applying a new developed technique of transverse section analytical electron microscopy. This reactive-element effect improves the high temperature oxidation resistance of alloys by strongly reducing the high temperature oxidation rate and enhancing the adhesion of the oxide scale, however, the mechanisms for this important effect remain largely unknown. It is indicated that the presence of yttrium affects the oxidation of Fe-Cr-Y alloys in at least two ways. The reactive element alters the growth mechanism of the oxide scale as evidenced by the marked influence of the reactive element on the oxide scale microstructure. The present results also suggest that reactive-element intermetallic compounds, which internally oxidize in the metal during oxidation, act as sinks for excess vacancies thus inhibiting vacancy condensation at the scale-metal interface and possibly enhancing scale adhesion.

Oxygen Fugacity at High Pressure: Equations of State of Metal-Oxide Pairs

NASA Technical Reports Server (NTRS)

Campbell A. J.; Danielson, L.; Righter, K.; Wang, Y.; Davidson, G.; Wang, Y.

2006-01-01

Oxygen fugacity (fO2) varies by orders of magnitude in nature, and can induce profound changes in the chemical state of a substance, and also in the chemical equilibrium of multicomponent systems. One prominent area in high pressure geochemistry, in which fO2 is widely recognized as a principal controlling factor, is that of metal-silicate partitioning of siderophile trace elements (e.g., [1]). Numerous experiments have shown that high pressures and temperatures can significantly affect metal/silicate partitioning of siderophile and moderately siderophile elements. Parameterization of these experimental results over P, T, X, and fO2 can allow the observed siderophile element composition of the mantle to be associated with particular thermodynamic conditions [2]. However, this is best done only if quantitative control exists over each thermodynamic variable relevant to the experiments. The fO2 values for many of these partitioning experiments were determined relative to a particular metal-oxide buffer (e.g., Fe-FeO (IW), Ni-NiO (NNO), Co-CoO, Re-ReO2 (RRO)), but the parameterization of all experimental results is weakened by the fact that the pressure-induced relative changes between these buffer systems are imprecisely known.

Synthesis of visible-light responsive graphene oxide/TiO(2) composites with p/n heterojunction.

PubMed

Chen, Chao; Cai, Weimin; Long, Mingce; Zhou, Baoxue; Wu, Yahui; Wu, Deyong; Feng, Yujie

2010-11-23

Graphene oxide/TiO(2) composites were prepared by using TiCl(3) and graphene oxide as reactants. The concentration of graphene oxide in starting solution played an important role in photoelectronic and photocatalytic performance of graphene oxide/TiO(2) composites. Either a p-type or n-type semiconductor was formed by graphene oxide in graphene oxide/TiO(2) composites. These semiconductors could be excited by visible light with wavelengths longer than 510 nm and acted as sensitizer in graphene oxide/TiO(2) composites. Visible-light driven photocatalytic performance of graphene oxide/TiO(2) composites in degradation of methyl orange was also studied. Crystalline quality and chemical states of carbon elements from graphene oxide in graphene oxide/TiO(2) composites depended on the concentration of graphene oxide in the starting solution. This study shows a possible way to fabricate graphene oxide/semiconductor composites with different properties by using a tunable semiconductor conductivity type of graphene oxide.

Average oxidation state of carbon in proteins

PubMed Central

Dick, Jeffrey M.

2014-01-01

The formal oxidation state of carbon atoms in organic molecules depends on the covalent structure. In proteins, the average oxidation state of carbon (ZC) can be calculated as an elemental ratio from the chemical formula. To investigate oxidation–reduction (redox) patterns, groups of proteins from different subcellular locations and phylogenetic groups were selected for comparison. Extracellular proteins of yeast have a relatively high oxidation state of carbon, corresponding with oxidizing conditions outside of the cell. However, an inverse relationship between ZC and redox potential occurs between the endoplasmic reticulum and cytoplasm. This trend provides support for the hypothesis that protein transport and turnover are ultimately coupled to the maintenance of different glutathione redox potentials in subcellular compartments. There are broad changes in ZC in whole-genome protein compositions in microbes from different environments, and in Rubisco homologues, lower ZC tends to occur in organisms with higher optimal growth temperature. Energetic costs calculated from thermodynamic models are consistent with the notion that thermophilic organisms exhibit molecular adaptation to not only high temperature but also the reducing nature of many hydrothermal fluids. Further characterization of the material requirements of protein metabolism in terms of the chemical conditions of cells and environments may help to reveal other linkages among biochemical processes with implications for changes on evolutionary time scales. PMID:25165594

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

USGS Publications Warehouse

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 with the fire had an OR of 1.091 (??0.003). Fire appears to be a major factor driving the soil C pool to higher oxidation states and lower OR values. Episodic fluxes caused by disturbances like fire may have substantially different ORs from ecosystem respiration fluxes and therefore should be better quantified to reduce uncertainties associated with our understanding of the global atmospheric carbon budget. Copyright 2009 by the American Geophysical Union.

Multiscale model of metal alloy oxidation at grain boundaries

NASA Astrophysics Data System (ADS)

Sushko, Maria L.; Alexandrov, Vitaly; Schreiber, Daniel K.; Rosso, Kevin M.; Bruemmer, Stephen M.

2015-06-01

High temperature intergranular oxidation and corrosion of metal alloys is one of the primary causes of materials degradation in nuclear systems. In order to gain insights into grain boundary oxidation processes, a mesoscale metal alloy oxidation model is established by combining quantum Density Functional Theory (DFT) and mesoscopic Poisson-Nernst-Planck/classical DFT with predictions focused on Ni alloyed with either Cr or Al. Analysis of species and fluxes at steady-state conditions indicates that the oxidation process involves vacancy-mediated transport of Ni and the minor alloying element to the oxidation front and the formation of stable metal oxides. The simulations further demonstrate that the mechanism of oxidation for Ni-5Cr and Ni-4Al is qualitatively different. Intergranular oxidation of Ni-5Cr involves the selective oxidation of the minor element and not matrix Ni, due to slower diffusion of Ni relative to Cr in the alloy and due to the significantly smaller energy gain upon the formation of nickel oxide compared to that of Cr2O3. This essentially one-component oxidation process results in continuous oxide formation and a monotonic Cr vacancy distribution ahead of the oxidation front, peaking at alloy/oxide interface. In contrast, Ni and Al are both oxidized in Ni-4Al forming a mixed spinel NiAl2O4. Different diffusivities of Ni and Al give rise to a complex elemental distribution in the vicinity of the oxidation front. Slower diffusing Ni accumulates in the oxide and metal within 3 nm of the interface, while Al penetrates deeper into the oxide phase. Ni and Al are both depleted from the region 3-10 nm ahead of the oxidation front creating voids. The oxide microstructure is also different. Cr2O3 has a plate-like structure with 1.2-1.7 nm wide pores running along the grain boundary, while NiAl2O4 has 1.5 nm wide pores in the direction parallel to the grain boundary and 0.6 nm pores in the perpendicular direction providing an additional pathway for oxygen diffusion through the oxide. The proposed theoretical methodology provides a framework for modeling metal alloy oxidation processes from first principles and on the experimentally relevant length scales.

Multiscale model of metal alloy oxidation at grain boundaries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sushko, Maria L., E-mail: maria.sushko@pnnl.gov; Alexandrov, Vitaly; Schreiber, Daniel K.

2015-06-07

High temperature intergranular oxidation and corrosion of metal alloys is one of the primary causes of materials degradation in nuclear systems. In order to gain insights into grain boundary oxidation processes, a mesoscale metal alloy oxidation model is established by combining quantum Density Functional Theory (DFT) and mesoscopic Poisson-Nernst-Planck/classical DFT with predictions focused on Ni alloyed with either Cr or Al. Analysis of species and fluxes at steady-state conditions indicates that the oxidation process involves vacancy-mediated transport of Ni and the minor alloying element to the oxidation front and the formation of stable metal oxides. The simulations further demonstrate thatmore » the mechanism of oxidation for Ni-5Cr and Ni-4Al is qualitatively different. Intergranular oxidation of Ni-5Cr involves the selective oxidation of the minor element and not matrix Ni, due to slower diffusion of Ni relative to Cr in the alloy and due to the significantly smaller energy gain upon the formation of nickel oxide compared to that of Cr{sub 2}O{sub 3}. This essentially one-component oxidation process results in continuous oxide formation and a monotonic Cr vacancy distribution ahead of the oxidation front, peaking at alloy/oxide interface. In contrast, Ni and Al are both oxidized in Ni-4Al forming a mixed spinel NiAl{sub 2}O{sub 4}. Different diffusivities of Ni and Al give rise to a complex elemental distribution in the vicinity of the oxidation front. Slower diffusing Ni accumulates in the oxide and metal within 3 nm of the interface, while Al penetrates deeper into the oxide phase. Ni and Al are both depleted from the region 3–10 nm ahead of the oxidation front creating voids. The oxide microstructure is also different. Cr{sub 2}O{sub 3} has a plate-like structure with 1.2–1.7 nm wide pores running along the grain boundary, while NiAl{sub 2}O{sub 4} has 1.5 nm wide pores in the direction parallel to the grain boundary and 0.6 nm pores in the perpendicular direction providing an additional pathway for oxygen diffusion through the oxide. The proposed theoretical methodology provides a framework for modeling metal alloy oxidation processes from first principles and on the experimentally relevant length scales.« less

The effects of trace element content on pyrite oxidation rates

NASA Astrophysics Data System (ADS)

Gregory, D. D.; Lyons, T.; Cliff, J. B.; Perea, D. E.; Johnson, A.; Romaniello, S. J.; Large, R. R.

2017-12-01

Pyrite acts as both an important source and sink for many different metals and metalloids in the environment, including many that are toxic. Oxidation of pyrite can release these elements while at the same time producing significant amounts of sulfuric acid. Such issues are common in the vicinity of abandoned mines and smelters, but, as pyrite is a common accessory mineral in many different lithologies, significant pyrite oxidation can occur whenever pyritic rocks are exposed to oxygenated water or the atmosphere. Accelerated exposure to oxygen can occur during deforestation, fracking for petroleum, and construction projects. Geochemical models for pyrite oxidation can help us develop strategies to mitigate these deleterious effects. An important component of these models is an accurate pyrite oxidation rate; however, current pyrite oxidation rates have been determined using relatively pure pyrite. Natural pyrite is rarely pure and has a wide range of trace element concentrations that may affect the oxidation rate. Furthermore, the position of trace elements within the mineral lattice can also affect the oxidation rate. For example, elements such as Ni and Co, which substitute into the pyrite lattice, are thought to stabilize the lattice and thus prevent pyrite oxidation. Alternatively, trace elements that are held within inclusions of other minerals could form a galvanic cell with the surrounding pyrite, thus enhancing pyrite oxidation rates. In this study, we present preliminary analyses from three different pyrite oxidation experiments each using natural pyrite with different trace element compositions. These results show that the pyrite with the highest trace element concentration has approximately an order of magnitude higher oxidation rate compared to the lowest trace element sample. To further elucidate the mechanisms, we employed microanalytical techniques to investigate how the trace elements are held within the pyrite. LA-ICPMS was used to determine the variability of trace element content from the pyrite samples. These data were then used to select areas of interest for NanoSIMS analyses, which in turn was used to select areas for TEM and APT. These analyses show that the trace element content of pyrite can be highly variable, which may significantly affect the rate of pyrite oxidation.

Mechanisms of neptunium redox reactions in nitric acid solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chatterjee, Sayandev; Bryan, Samuel A.; Casella, Amanda J.

First transuranium element neptunium (Np) exhibits complicated behavior in acidic solutions because it can adopt wide range of oxidation states typically from +3 to +6 and coordinate large variety of ligands. In particular, accurate determination of Np redox potentials in nitric acid solutions is challenging due to overlapping chemical and electrochemical reactions leading to significant experimental uncertainties. Furthermore, over past decades spectrophotometry has been extensively applied to identify and characterize Np solution species in different oxidation states. However, relevant spectral database of Np in nitric acid solutions that can serve for the reference purposes has yet to be established duemore » to the experimental difficulty to isolate and stabilize Np species in pure oxidation states without compromising solution optical properties. This work demonstrates that combination of voltammetry and controlled-potential in situ thin-layer spectropotentiometry overcomes these challenges so that Np species in pure +3, +4, +5, or +6 oxidation states were electrochemically generated in the systematically varied 0.1 – 5 M nitric acid solutions, and corresponding vis-NIR spectral signatures were obtained. In situ optical monitoring of the interconversion between adjacent Np oxidation states resulted in elucidation of the mechanisms of the involved redox reactions, in-depth understanding of the relative stability of the Np oxidation states, and allowed benchmarking of the redox potentials of the NpO22+/NpO2+, NpO2+/Np4+ and Np4+/Np3+ couples. Notably, the NpO2+/Np4+ couple was distinguished from the proximal Np4+/Np3+ process overcoming previous concerns and challenges encountered in accurate determination of the respective potentials.« less

Bolide impacts and the oxidation state of carbon in the earth's early atmosphere

NASA Technical Reports Server (NTRS)

Kasting, James F.

1990-01-01

A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean.

A finite element analysis modeling tool for solid oxide fuel cell development: coupled electrochemistry, thermal and flow analysis in MARC®

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khaleel, Mohammad A.; Lin, Zijing; Singh, Prabhakar

2004-05-03

A 3D simulation tool for modeling solid oxide fuel cells is described. The tool combines the versatility and efficiency of a commercial finite element analysis code, MARC{reg_sign}, with an in-house developed robust and flexible electrochemical (EC) module. Based upon characteristic parameters obtained experimentally and assigned by the user, the EC module calculates the current density distribution, heat generation, and fuel and oxidant species concentration, taking the temperature profile provided by MARC{reg_sign} and operating conditions such as the fuel and oxidant flow rate and the total stack output voltage or current as the input. MARC{reg_sign} performs flow and thermal analyses basedmore » on the initial and boundary thermal and flow conditions and the heat generation calculated by the EC module. The main coupling between MARC{reg_sign} and EC is for MARC{reg_sign} to supply the temperature field to EC and for EC to give the heat generation profile to MARC{reg_sign}. The loosely coupled, iterative scheme is advantageous in terms of memory requirement, numerical stability and computational efficiency. The coupling is iterated to self-consistency for a steady-state solution. Sample results for steady states as well as the startup process for stacks with different flow designs are presented to illustrate the modeling capability and numerical performance characteristic of the simulation tool.« less

Benzyl Alcohol-Mediated Versatile Method to Fabricate Nonstoichiometric Metal Oxide Nanostructures.

PubMed

Qamar, Mohammad; Adam, Alaaldin; Azad, Abdul-Majeed; Kim, Yong-Wah

2017-11-22

Nanostructured metal oxides with cationic or anionic deficiency find applications in a wide range of technological areas including the energy sector and environment. However, a facile route to prepare such materials in bulk with acceptable reproducibility is still lacking; many synthesis techniques are still only bench-top and cannot be easily scaled-up. Here, we report that the benzyl alcohol (BA)-mediated method is capable of producing a host of nanostructured metal oxides (MO x , where M = Ti, Zn, Ce, Sn, In, Ga, or Fe) with inherent nonstoichiometry. It employs multifunctional BA as a solvent, a reducing agent, and a structure-directing agent. Depending on the oxidation states of metal, elemental or nonstoichiometric oxide forms are obtained. Augmented photoelectrochemical oxidation of water under visible light by some of these nonstoichiometric oxides highlights the versatility of the BA-mediated synthesis protocol.

Dithia[3.3]paracyclophane-based monometal ruthenium acetylide complexes: synthesis, characterization and substituent effects.

PubMed

Zhu, Xingxun; Ou, Yaping; Zhang, Jing; Xia, Jian-Long; Yin, Jun; Yu, Guang-Ao; Liu, Sheng Hua

2013-05-21

A series of dithia[3.3]metaparacyclophane-based monometal ruthenium acetylide complexes have been synthesized. All of the complexes have been fully characterised by NMR spectrometry, X-ray crystallography and elemental analyses. At the same time, their basic optical properties, such as UV/Vis absorption spectra, and electrochemical properties have been determined. (1)H NMR and X-ray crystal structure studies reveal that there are intramolecular C-H···π interactions in these ruthenium complexes, in both solution and solid states. Electrochemical studies reveal that the substituted groups on the dithia[3.3]paracyclophane ring can clearly affect the oxidation activities of the ruthenium center by way of the intramolecular C-H···π interaction. In addition, electron-donating groups facilitate the oxidation of the ruthenium center compared with electron-deficient groups. UV/Vis absorption and IR spectra of some complexes in neutral and oxidized states also have been studied. IR spectra studies indicated that the substituents in the cyclophane have some effects on the ν(C≡C) bands of these complexes in the neutral state and little effect on ν(C≡C) of these complexes in the oxidized state.

Degradation of the electrical characteristics of MOS structures with erbium, gadolinium, and dysprosium oxides under the effect of an electric field

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shalimova, M. B., E-mail: shamb@samsu.ru; Sachuk, N. V.

2015-08-15

The degradation of the characteristics of silicon metal-oxide-semiconductor (MOS) structures with oxides of rare-earth elements under the effect of electric fields with intensities of 0.1–4 MV/cm during the course of electroforming is studied. A specific feature of electroforming consists in the possibility of multiple switching of the structures from the insulating state to the low-resistivity one and back. The temporal characteristics of the degradation of MOS structures during the course of electroforming are exponential. The current-voltage characteristics follow the power law in the range of 0.2–3 V; the effect of an electric field brings about a variation in the distributionmore » of the energy density of traps responsible for currents limited by space charge. It is established that multiple cycles of electroforming lead to an increase in the density of surface states at the Si-oxide interface and to a variation in the energy position of the trap levels, which affects the charge state of the traps.« less

High-temperature sorbent method for removal of sulfur-containing gases from gaseous mixtures

DOEpatents

Young, J.E.; Jalan, V.M.

1982-07-07

A copper oxide-zinc oxide mixture is used as a sorbent for removing hydrogen sulfide and other sulfur containing gases at high temperatures from a gaseous fuel mixture. This high-temperature sorbent is especially useful for preparing fuel gases for high temperature fuel cells. The copper oxide is initially reduced in a preconditioning step to elemental copper and is present in a highly dispersed state throughout the zinc oxide which serves as a support as well as adding to the sulfur sorbtion capacity. The spent sorbent is regenerated by high-temperature treatment with an air fuel, air steam mixture followed by hydrogen reduction to remove and recover the sulfur.

High-temperature sorbent method for removal of sulfur containing gases from gaseous mixtures

DOEpatents

Young, J.E.; Jalan, V.M.

1984-06-19

A copper oxide-zinc oxide mixture is used as a sorbent for removing hydrogen sulfide and other sulfur containing gases at high temperatures from a gaseous fuel mixture. This high-temperature sorbent is especially useful for preparing fuel gases for high temperature fuel cells. The copper oxide is initially reduced in a preconditioning step to elemental copper and is present in a highly dispersed state throughout the zinc oxide which serves as a support as well as adding to the sulfur sorption capacity. The spent sorbent is regenerated by high-temperature treatment with an air fuel, air steam mixture followed by hydrogen reduction to remove and recover the sulfur.

High-temperature sorbent method for removal of sulfur containing gases from gaseous mixtures

DOEpatents

Young, John E.; Jalan, Vinod M.

1984-01-01

A copper oxide-zinc oxide mixture is used as a sorbent for removing hydrogen sulfide and other sulfur containing gases at high temperatures from a gaseous fuel mixture. This high-temperature sorbent is especially useful for preparing fuel gases for high temperature fuel cells. The copper oxide is initially reduced in a preconditioning step to elemental copper and is present in a highly dispersed state throughout the zinc oxide which serves as a support as well as adding to the sulfur sorption capacity. The spent sorbent is regenerated by high-temperature treatment with an air fuel, air steam mixture followed by hydrogen reduction to remove and recover the sulfur.

Generally applicable fed-batch culture concept based on the detection of metabolic state by on-line balancing.

PubMed

Jobé, Anna Marya; Herwig, Christoph; Surzyn, Martin; Walker, Bernhard; Marison, Ian; von Stockar, Urs

2003-06-20

In many microorganisms, flux limitations in oxidative metabolism lead to the formation of overflow metabolites even under fully aerobic conditions. This can be avoided if the specific growth rate is controlled at a low enough value. This is usually accomplished by controlling the substrate feeding profile in a fed-batch process. The present work proposes a control concept which is based on the on-line detection of metabolic state by on-line calculation of mass and elemental balances. The advantages of this method are: 1) the check of measurement consistency based on all of the available measurements, 2) the minimum requirement of a priori knowledge of metabolism, and 3) the exclusive use of simple and established on-line techniques which do not require direct measurement of the metabolite in question. The control concept has been linked to a simple adaptive controller and applied to fed-batch cultures of S. cerevisiae and E. coli, organisms which express different overflow metabolites, ethanol and acetic acid, respectively. Oxidative and oxidoreductive states of S. cerevisiae and E. coli cultures were detected with high precision. As demonstrated by the formation of acetic acid in E. coli cultures, metabolic states could be correctly distinguished for systems for which traditional methods, such as respiratory quotient (RQ), are insensitive. Hence, it could be shown that the control concept allowed avoidance of overflow metabolite formation and operation at maximum oxidative biomass productivity and oxidative conversion of substrate into biomass. Based on mass and elemental balances, the proposed method additionally provides a richness of additional information, such as yield coefficients and estimation of concentrations and specific conversion rates. These data certainly help the operator to additionally evaluate the state of the process on-line. Copyright 2003 Wiley Periodicals, Inc. Biotechnol Bioeng 82: 627-639, 2003.

Transcriptional activation of transposable elements in mouse zygotes is independent of Tet3-mediated 5-methylcytosine oxidation.

PubMed

Inoue, Azusa; Matoba, Shogo; Zhang, Yi

2012-12-01

The methylation state of the paternal genome is rapidly reprogrammed shortly after fertilization. Recent studies have revealed that loss of 5-methylcytosine (5mC) in zygotes correlates with appearance of 5-hydroxymethylcytosine (5hmC), 5-formylcytosine (5fC), and 5-carboxylcytosine (5caC). This process is mediated by Tet3 and the 5mC oxidation products generated in zygotes are gradually lost during preimplantation development through a replication-dependent dilution process. Despite these findings, the biological significance of Tet3-mediated oxidation of 5mC to 5hmC/5fC/5caC in zygotes is unknown. DNA methylation plays an important role in silencing gene expression including the repression of transposable elements (TEs). Given that the activation of TEs during preimplantation development correlates with loss of DNA methylation, it is believed that paternal DNA demethylation may have an important role in TE activation. Here we examined this hypothesis and found that Tet3-mediated 5mC oxidation does not have a significant contribution to TE activation. We show that the expression of LINE-1 (long interspersed nucleotide element 1) and ERVL (endogenous retroviruses class III) are activated from both paternal and maternal genomes in zygotes. Inhibition of 5mC oxidation by siRNA-mediated depletion of Tet3 affected neither TE activation, nor global transcription in zygotes. Thus, our study provides the first evidence demonstrating that activation of both TEs and global transcription in zygotes are independent of Tet3-mediated 5mC oxidation.

A Unified Approach to the Study of Chemical Reactions in Freshman Chemistry.

ERIC Educational Resources Information Center

Cassen, T.; DuBois, Thomas D.

1982-01-01

Provides rationale and objectives for presenting chemical reactions in a unified, logical six-stage approach rather than a piecemeal approach. Stages discussed include: introduction, stable electronic configurations and stable oxidation states, reactions between two free elements, ion transfer/proton transfer reactions, double displacement…

Lasing of a Solid-State Active Element Based on Anodized Aluminum Oxide Film Doped with Rhodamine 6G

NASA Astrophysics Data System (ADS)

Shelkovnikov, V. V.; Lyubas, G. A.; Korotaev, S. V.; Kopylova, T. N.; Tel'minov, E. N.; Gadirov, R. M.; Nikonova, E. N.; Nikonov, S. Yu.; Solodova, T. A.; Novikov, V. A.

2017-04-01

Spectral-luminescent and lasing characteristics of rhodamine 6G in porous aluminum oxide films anodized under various conditions are investigated. Lasing is obtained without external resonator in the longitudinal scheme under excitation by the second harmonic of Nd3+:YAG-laser radiation. The threshold pump power densities are in the range 3.5-15 MW/cm2 depending on the anodizing conditions. Wherein, the lasing line narrows down from 12 to 5 nm.

Process for oxidation of hydrogen halides to elemental halogens

DOEpatents

Lyke, Stephen E.

1992-01-01

An improved process for generating an elemental halogen selected from chlorine, bromine or iodine, from a corresponding hydrogen halide by absorbing a molten salt mixture, which includes sulfur, alkali metals and oxygen with a sulfur to metal molar ratio between 0.9 and 1.1 and includes a dissolved oxygen compound capable of reacting with hydrogen halide to produce elemental halogen, into a porous, relatively inert substrate to produce a substrate-supported salt mixture. Thereafter, the substrate-supported salt mixture is contacted (stage 1) with a hydrogen halide while maintaining the substrate-supported salt mixture during the contacting at an elevated temperature sufficient to sustain a reaction between the oxygen compound and the hydrogen halide to produce a gaseous elemental halogen product. This is followed by purging the substrate-supported salt mixture with steam (stage 2) thereby recovering any unreacted hydrogen halide and additional elemental halogen for recycle to stage 1. The dissolved oxygen compound is regenerated in a high temperature (stage 3) and an optical intermediate temperature stage (stage 4) by contacting the substrate-supported salt mixture with a gas containing oxygen whereby the dissolved oxygen compound in the substrate-supported salt mixture is regenerated by being oxidized to a higher valence state.

Investigation of processes controlling summertime gaseous elemental mercury oxidation at midlatitudinal marine, coastal, and inland sites

NASA Astrophysics Data System (ADS)

Ye, Zhuyun; Mao, Huiting; Lin, Che-Jen; Kim, Su Youn

2016-07-01

A box model incorporating a state-of-the-art chemical mechanism for atmospheric mercury (Hg) cycling was developed to investigate the oxidation of gaseous elemental mercury (GEM) at three locations in the northeastern United States: Appledore Island (AI; marine), Thompson Farm (TF; coastal, rural), and Pack Monadnock (PM; inland, rural, elevated). The chemical mechanism in this box model included the most up-to-date Hg and halogen chemistry. As a result, the box model was able to simulate reasonably the observed diurnal cycles of gaseous oxidized mercury (GOM) and chemical speciation bearing distinct differences between the three sites. In agreement with observations, simulated GOM diurnal cycles at AI and TF showed significant daytime peaks in the afternoon and nighttime minimums compared to flat GOM diurnal cycles at PM. Moreover, significant differences in the magnitude of GOM diurnal amplitude (AI > TF > PM) were captured in modeled results. At the coastal and inland sites, GEM oxidation was predominated by O3 and OH, contributing 80-99 % of total GOM production during daytime. H2O2-initiated GEM oxidation was significant (˜ 33 % of the total GOM) at the inland site during nighttime. In the marine boundary layer (MBL) atmosphere, Br and BrO became dominant GEM oxidants, with mixing ratios reaching 0.1 and 1 pptv, respectively, and contributing ˜ 70 % of the total GOM production during midday, while O3 dominated GEM oxidation (50-90 % of GOM production) over the remaining day when Br and BrO mixing ratios were diminished. The majority of HgBr produced from GEM+Br was oxidized by NO2 and HO2 to form brominated GOM species. Relative humidity and products of the CH3O2+BrO reaction possibly significantly affected the mixing ratios of Br or BrO radicals and subsequently GOM formation. Gas-particle partitioning could potentially be important in the production of GOM as well as Br and BrO at the marine site.

Electrochemistry with double electrical layers in frictional interaction metal-polymer tribolink

NASA Astrophysics Data System (ADS)

Volchenko, N. A.; Krasin, P. S.; Volchenko, D. A.; Voznyi, A. V.

2018-03-01

The materials of the article illustrate the estimation of the energy loading of a metal friction element in a “metal-electrolyte-polymer” friction pair while forming various types of double electrical layers with the release of its thermal stabilization state. The rapidity of the processes of oxidation and reduction of the working surfaces of friction pairs during their electrothermomechanical frictional interaction leaves an imprint on all other additional processes that subsequently lead to the thermostabilizing and steady state of the metal friction element. Depending on the type of a brake device, the metal friction element has a different metal consumption and the temperature range varies. In addition, it is shown that the materials of the friction pair play an important role in the formation of electric tribosystems, namely: chemical elements that make up the materials, their valence, and the predominant type of intrinsic conductivity, as well as the sign of the electric charge of the friction pair elements that determines the laws of triboelectricity. Thus, an in-depth approach to the evaluation of the thermal stabilization state of a metal element in a “metal-electrolyte” friction pair is shown due to double electric layers that promote the emergence of current densities of different directions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mammen, Nisha; Spanu, Leonardo; Tyo, Eric C.

Having the ability to tune the oxidation state of Cu nanoparticles is essential for their utility as catalysts. The degree of oxidation that maximizes product yield and selectivity is known to vary, depending on the particular reaction. Using first principles calculations and XANES measurements, we show that for subnanometer sizes in the gas phase, smaller Cu clusters are more resistant to oxidation. However, this trend is reversed upon deposition on an alumina support. We are able to explain this result in terms of strong cluster-support interactions, which differ significantly for the oxidized and elemental clusters. The stable cluster phases alsomore » feature novel oxygen stoichiometries. Our results suggest that one can tune the degree of oxidation of Cu catalysts by optimizing not just their size, but also the support they are deposited on.« less

Stable singlet carbenes as mimics for transition metal centers

PubMed Central

Martin, David; Soleilhavoup, Michele

2011-01-01

This perspective summarizes recent results, which demonstrate that stable carbenes can activate small molecules (CO, H2, NH3 and P4) and stabilize highly reactive intermediates (main group elements in the zero oxidation state and paramagnetic species). These two tasks were previously exclusive for transition metal complexes. PMID:21743834

Reduced As Components in Highly Oxidized Environments: Evidence from Full Spectral XANES Imaging using the Maia Massively Parallel Detector

DOE Office of Scientific and Technical Information (OSTI.GOV)

Etschmann, B.; Ryan, C; Brugger, J

2010-01-01

Synchrotron X-ray fluorescence (SXRF) and X-ray absorption spectroscopy (XAS) have become standard tools to measure element concentration, distribution at micrometer- to nanometer-scale, and speciation (e.g., nature of host phase; oxidation state) in inhomogeneous geomaterials. The new Maia X-ray detector system provides a quantum leap for the method in terms of data acquisition rate. It is now possible to rapidly collect fully quantitative maps of the distribution of major and trace elements at micrometer spatial resolution over areas as large as 1 x 5 cm{sup 2}. Fast data acquisition rates also open the way to X-ray absorption near-edge structure (XANES) imaging,more » in which spectroscopic information is available at each pixel in the map. These capabilities are critical for studying inhomogeneous Earth materials. Using a 96-element prototype Maia detector, we imaged thin sections of an oxidized pisolitic regolith (2 x 4.5 mm{sup 2} at 2.5 x 2.5 {micro}m{sup 2} pixel size) and a metamorphosed, sedimentary exhalative Mn-Fe ore (3.3 x 4 mm{sup 2} at 1.25 x 5 {micro}m{sup 2}). In both cases, As K-edge XANES imaging reveals localized occurrence of reduced As in parts of these oxidized samples, which would have been difficult to recognize using traditional approaches.« less

Occurrences, uses, and properties of chromium.

PubMed

Barnhart, J

1997-08-01

Chromium is the 21st most abundant element in the Earth's crust with a mean concentration in United States soils of about 40 mg/kg. Although it exists in several oxidation states, the zero, trivalent, and hexavalent states are the most important in commercial products and the environment. Nearly all naturally occurring chromium is in the trivalent state, usually in combination with iron or other metal oxides. Although only about 15% of the chromium mined is used in the manufacture of chemicals, most applications of chromium utilize the chemistry of chromium. For instance, the "stainless" nature of stainless steel is due to the chemical properties of the chromium oxides which form on the surface of the alloy. Similarly, the protective properties of chrome plating of metals, chromated copper arsenate (CCA) treatment of wood, and chrome tanning of leather are all dependent on chromium chemistry. The key to these uses is that under typical environmental and biological conditions of pH and oxidation-reduction potential, the most stable form of chromium is the trivalent oxide. This form has very low solubility and low reactivity resulting in low mobility in the environment and low toxicity in living organisms. In this paper the chemical properties of chromium are discussed for the major commercial products in the context of the Eh-pH diagram for chromium. Copyright 1997 Academic Press.

A physiologically based kinetic model for bacterial sulfide oxidation.

PubMed

Klok, Johannes B M; de Graaff, Marco; van den Bosch, Pim L F; Boelee, Nadine C; Keesman, Karel J; Janssen, Albert J H

2013-02-01

In the biotechnological process for hydrogen sulfide removal from gas streams, a variety of oxidation products can be formed. Under natron-alkaline conditions, sulfide is oxidized by haloalkaliphilic sulfide oxidizing bacteria via flavocytochrome c oxidoreductase. From previous studies, it was concluded that the oxidation-reduction state of cytochrome c is a direct measure for the bacterial end-product formation. Given this physiological feature, incorporation of the oxidation state of cytochrome c in a mathematical model for the bacterial oxidation kinetics will yield a physiologically based model structure. This paper presents a physiologically based model, describing the dynamic formation of the various end-products in the biodesulfurization process. It consists of three elements: 1) Michaelis-Menten kinetics combined with 2) a cytochrome c driven mechanism describing 3) the rate determining enzymes of the respiratory system of haloalkaliphilic sulfide oxidizing bacteria. The proposed model is successfully validated against independent data obtained from biological respiration tests and bench scale gas-lift reactor experiments. The results demonstrate that the model is a powerful tool to describe product formation for haloalkaliphilic biomass under dynamic conditions. The model predicts a maximum S⁰ formation of about 98 mol%. A future challenge is the optimization of this bioprocess by improving the dissolved oxygen control strategy and reactor design. Copyright © 2012 Elsevier Ltd. All rights reserved.

Novel polyoxometalate silica nano-sized spheres: efficient catalysts for olefin oxidation and the deep desulfurization process.

PubMed

Nogueira, Lucie S; Ribeiro, Susana; Granadeiro, Carlos M; Pereira, Eulália; Feio, Gabriel; Cunha-Silva, Luís; Balula, Salete S

2014-07-07

A novel method to prepare silica nano-sized particles incorporating polyoxometalates was developed leading to a new efficient heterogeneous oxidative catalyst. Zinc-substituted polyoxotungstate [PW11Zn(H2O)O39](5-) (PW11Zn) was encapsulated into silica nanoparticles using a cross-linked organic-inorganic core, performed through successive spontaneous reactions in water. The potassium salt of PW11Zn and the composite formed, PW11Zn-APTES@SiO2, were characterized by a myriad of solid-state methods such as FT-IR, FT-Raman, (31)P and (13)C CP/MAS solid-state NMR, elemental analysis and SEM-EDS, confirming the integrity of the PW11Zn structure immobilized in the silica nanoparticles. The new composite has shown to be a versatile catalyst for the oxidation of olefins and also to catalyze the desulfurization of a model oil using H2O2 as the oxidant and acetonitrile as the solvent. The novel composite material was capable of being recycled without significant loss of activity and maintaining its structural stability for consecutive desulfurization and olefin oxidative cycles.

Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pacold, J. I.; Lukens, W. W.; Booth, C. H.

Nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. We find significant variationsmore » among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. The resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.« less

Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pacold, J. I.; Lukens, W. W.; Booth, C. H.

We report that nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. Wemore » find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. Lastly, the resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.« less

Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing

DOE PAGES

Pacold, J. I.; Lukens, W. W.; Booth, C. H.; ...

2016-05-18

We report that nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. Wemore » find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. Lastly, the resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.« less

Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing

NASA Astrophysics Data System (ADS)

Pacold, J. I.; Lukens, W. W.; Booth, C. H.; Shuh, D. K.; Knight, K. B.; Eppich, G. R.; Holliday, K. S.

2016-05-01

Nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. We find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. The resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.

Early Diagenesis of Trace Elements in Modern Fjord Sediments of the High Arctic

NASA Astrophysics Data System (ADS)

Herbert, L.; Riedinger, N.; Aller, R. C.; Jørgensen, B. B.; Wehrmann, L.

2017-12-01

Marine sediments are critical repositories for elements that are only available at trace concentrations in seawater, such as Fe, Mn, Co, Ni, As, Mo, and U. The behavior of these trace elements in the sediment is governed by a dynamic interplay of diagenetic reactions involving organic carbon, Fe and Mn oxides, and sulfur phases. In the Arctic fjords of Svalbard, glacial meltwater delivers large amounts of reactive Fe and Mn oxides to the sediment, while organic carbon is deposited episodically and diluted by lithogenic material. These conditions result in pronounced Fe and Mn cycling, which in turn drives other diagenetic processes such as rapid sulfide oxidation. These conditions make the Svalbard fjords ideal sites for investigating trace element diagenesis because they allow resolution of the interconnections between Fe and Mn dynamics and trace element cycling. In August 2016, we collected sediment cores from three Svalbard fjords and analyzed trace elements in the pore water and solid sediment over the top meter. Initial results reveal the dynamic nature of these fjords, which are dominated by non-steady state processes and episodic events such as meltwater pulses and phytoplankton blooms. Within this system, the distribution of As appears to be strongly linked to the Fe cycle, while Co and Ni follow Mn; thus, these three elements may be released from the sediment through diffusion and bioturbation along with Fe and Mn. The pore water profiles of U and Mo indicate removal processes that are independent from Fe or Mn, and which are rather unexpected given the apparent diagenetic conditions. Our results will help elucidate the processes controlling trace element cycling in a dynamic, glacially impacted environment and will ultimately contribute to our understanding of the role of fjords in the biogeochemical cycling of trace elements in a rapidly changing Arctic Ocean.

Stress generation in thermally grown oxide films. [oxide scale spalling from superalloy substrates

NASA Technical Reports Server (NTRS)

Kumnick, A. J.; Ebert, L. J.

1981-01-01

A three dimensional finite element analysis was conducted, using the ANSYS computer program, of the stress state in a thin oxide film thermally formed on a rectangular piece of NiCrAl alloy. The analytical results indicate a very high compressive stress in the lateral directions of the film (approximately 6200 MPa), and tensile stresses in the metal substrate that ranged from essentially zero to about 55 MPa. It was found further that the intensity of the analytically determined average stresses could be approximated reasonably well by the modification of an equation developed previously by Oxx for stresses induced into bodies by thermal gradients.

Tracing iron-carbon redox from surface to core

NASA Astrophysics Data System (ADS)

McCammon, C. A.; Cerantola, V.; Bykova, E.; Kupenko, I.; Bykov, M.; Chumakov, A. I.; Rüffer, R.; Dubrovinsky, L. S.

2017-12-01

Numerous redox reactions separate the Earth's oxidised surface from its reduced core. Many involve iron, the Earth's most abundant element and the mantle's most abundant transition element. Most iron redox reactions (although not all) also involve other elements, including carbon, where iron-carbon interactions drive a number of important processes within the Earth, for example diamond formation. Many of the Earth's redox boundaries are sharp, much like the seismic properties that define them, for example between the lower mantle and the core. Other regions that appear seismically homogeneous, for example the lower mantle, harbour a wealth of reactions between oxidised and reduced phases of iron and carbon. We have undertaken many experiments at high pressure and high temperature on phases containing iron and carbon using synchrotron-based X-rays to probe structures and iron oxidation states. Results demonstrate the dominant role that crystal structures play in determining the stable oxidation states of iron and carbon, even when oxygen fugacity (and common sense) would suggest otherwise. Iron in bridgmanite, for example, occurs predominantly in its oxidised form (ferric iron) throughout the lower mantle, despite the inferred reducing conditions. Newly discovered structures of iron carbonate also stabilise ferric iron, while simultaneously reducing some carbon to diamond to balance charge. Other high-pressure iron carbonates appear to be associated with the emerging zoo of iron oxide phases, involving transitions between ferrous and ferric iron through the exchange of oxygen. The presentation will trace redox relations between iron and carbon from the Earth's surface to its core, with an emphasis on recent experimental results.

Casting of superconducting composite materials (M-4)

NASA Technical Reports Server (NTRS)

Togano, Kazumasa

1993-01-01

An aluminum-lead-bismuth alloy is a flexible alloy and is promising for easily workable embedded-type, filament-dispersed superconducting wire material. It is difficult to produce homogeneous ingots of this material because it is easily separated into elements when melted on Earth due to the large specific gravity differences. In this experiment, a homogeneous alloy will first be produced in molten state in microgravity. It will then be returned to Earth and processed into a wire or tape form. It will then be dispersed as the second phase in micro texture form into the primary phase of aluminum. Superconducting wire material with high-critical-magnetic-field characteristics will be produced. The texture of the material will be observed, and its performance will be evaluated. In addition to the above alloy, a four-element alloy will be produced from silver, a rare Earth element, barium, and copper. The alloys will be oxidized and drawn into wire after being returned to Earth. The materials are expected to be forerunners in obtaining superconducting wire materials from oxide superconductors.

Diversity of Chemical Bonding and Oxidation States in MS 4 Molecules of Group 8 Elements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Wei; Jiang, Ning; Schwarz, W. H. Eugen

The geometric and electronic ground-state structures 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 and correlated wave-function approaches. The MS 4 species are compared to analogous MO 4 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)S 4 and (Ru,Os,Hs)O 4, whereas low MOS=II appears in high- spin septet D 2d species Fe(S 2) 2 and (slightly excited) metastable Fe(O 2) 2. The ground states of all other moleculesmore » have intermediate MOS values, containing S 2-, S 2 2-, S2 1- (and resp. O 2--, O 1-, O 2 2-, O 2 1-) ligands, bonded by ionic, covalent and correlative contributions.« less

Creation of Novel Solid-Solution Alloy Nanoparticles on the Basis of Density-of-States Engineering by Interelement Fusion.

PubMed

Kobayashi, Hirokazu; Kusada, Kohei; Kitagawa, Hiroshi

2015-06-16

Currently 118 known elements are represented in the periodic table. Of these 118 elements, only about 80 elements are stable, nonradioactive, and widely available for our society. From the viewpoint of the "elements strategy", we need to make full use of the 80 elements to bring out their latent ability and create innovative materials. Furthermore, there is a strong demand that the use of rare or toxic elements be reduced or replaced while their important properties are retained. Advanced science and technology could create higher-performance materials even while replacing or reducing minor or harmful elements through the combination of more abundant elements. The properties of elements are correlated directly with their electronic states. In a solid, the magnitude of the density of states (DOS) at the Fermi level affects the physical and chemical properties. In the present age, more attention has been paid to improving the properties of materials by means of alloying elements. In particular, the solid-solution-type alloy is advantageous because the properties can be continuously controlled by tuning the compositions and/or combinations of the constituent elements. However, the majority of bulk alloys are of the phase-separated type under ambient conditions, where constituent elements are immiscible with each other. To overcome the challenge of the bulk-phase metallurgical aspects, we have focused on the nanosize effect and developed methods involving "nonequilibrium synthesis" or "a process of hydrogen absorption/desorption". We propose a new concept of "density-of-states engineering" for the design of materials having the most desirable and suitable properties by means of "interelement fusion". In this Account, we describe novel solid-solution alloys of Pd-Pt, Ag-Rh, and Pd-Ru systems in which the constituent elements are immiscible in the bulk state. The homogeneous solid-solution alloys of Pd and Pt were created from Pd core/Pt shell nanoparticles using a hydrogen absorption/desorption process as a trigger. Several atom percent replacements of Pd with Pt atoms resulted in a significantly enhanced hydrogen absorption capacity compared with Pd nanoparticles. AgxRh1-x and PdxRu1-x solid-solution alloy nanoparticles were also developed by nonequilibrium synthesis based on a polyol method. The AgxRh1-x nanoparticles demonstrated hydrogen storage properties, although pure metal nanoparticles of each constituent element do not adsorb hydrogen. AgxRh1-x is therefore considered to possess a similar electronic structure to Pd as a synthetic pseudo-palladium. The PdxRu1-x nanoparticles showed enhanced catalytic activity for CO oxidation, with the highest catalytic activity found using the equimolar Pd0.5Ru0.5 nanoparticles. The catalytic activity of the Pd0.5Ru0.5 nanoparticles exceeds that of the widely used and best-performing Ru catalysts for CO oxidation and is also higher than that of neighboring Rh on the periodic table. Our present work provides a guiding principle for the design of a suitable DOS shape according to the intended physical and/or chemical properties and a method for the development of novel solid-solution alloys.

Direct formation of element chlorides from the corresponding element oxides through microwave-assisted carbohydrochlorination reactions.

PubMed

Nordschild, Simon; Auner, Norbert

2008-01-01

A series of technically and economically important element chlorides-such as SiCl4, BCl3, AlCl3, FeCl2, PCl3 and TiCl4-was synthesized through reactions between hydrogen chloride and the corresponding element oxides in the presence of different carbon sources with microwave assistance. This process route was optimized for demonstration purposes for tetrachlorosilane formation and successfully demonstrates the broad applicability of various silicon oxide-containing minerals and materials for carbohydrochlorination. The chlorination reaction occurs at lower temperatures than with conventional heating in a tubular oven, with substantially shorter reaction times and in better yields: quantitatively in the case of tetrachlorosilane, based on the silicon content of the starting material. The experimental procedure is very simple and provides basic information about the suitability of element compounds, especially element oxides, for carbohydrochlorination. According to the general reaction sequence element oxide-->element-->element chloride used in today's technology, this one-step carbohydrochlorination with hydrogen chloride is considerably more efficient, particularly in terms of energy input and reaction times, avoiding the isolation of the pure elements required for chlorination to give the element chlorides with use of the more corrosive and toxic chlorine gas.

Design and Fabrication of Oxygen/RP-2 Multi-Element Oxidizer-Rich Staged Combustion Thrust Chamber Injectors

NASA Technical Reports Server (NTRS)

Garcia, C. P.; Medina, C. R.; Protz, C. S.; Kenny, R. J.; Kelly, G. W.; Casiano, M. J.; Hulka, J. R.; Richardson, B. R.

2016-01-01

As part of the Combustion Stability Tool Development project funded by the Air Force Space and Missile Systems Center, the NASA Marshall Space Flight Center was contracted to assemble and hot-fire test a multi-element integrated test article demonstrating combustion characteristics of an oxygen/hydrocarbon propellant oxidizer-rich staged-combustion engine thrust chamber. Such a test article simulates flow through the main injectors of oxygen/kerosene oxidizer-rich staged combustion engines such as the Russian RD-180 or NK-33 engines, or future U.S.-built engine systems such as the Aerojet-Rocketdyne AR-1 engine or the Hydrocarbon Boost program demonstration engine. On the current project, several configurations of new main injectors were considered for the thrust chamber assembly of the integrated test article. All the injector elements were of the gas-centered swirl coaxial type, similar to those used on the Russian oxidizer-rich staged-combustion rocket engines. In such elements, oxidizer-rich combustion products from the preburner/turbine exhaust flow through a straight tube, and fuel exiting from the combustion chamber and nozzle regenerative cooling circuits is injected near the exit of the oxidizer tube through tangentially oriented orifices that impart a swirl motion such that the fuel flows along the wall of the oxidizer tube in a thin film. In some elements there is an orifice at the inlet to the oxidizer tube, and in some elements there is a sleeve or "shield" inside the oxidizer tube where the fuel enters. In the current project, several variations of element geometries were created, including element size (i.e., number of elements or pattern density), the distance from the exit of the sleeve to the injector face, the width of the gap between the oxidizer tube inner wall and the outer wall of the sleeve, and excluding the sleeve entirely. This paper discusses the design rationale for each of these element variations, including hydraulic, structural, thermal, combustion performance, and combustion stability considerations. This paper also discusses the fabrication and assembly of the injector components, including the injector body/interpropellant plate, the additive manufactured GRCop-84 faceplate, and the pieces that make up the injector elements including the oxidizer tube, an inlet to the oxidizer tube, and a facenut that includes the fuel tangential inlets and forms the initial recessed volume where oxidizer and fuel first interact. Hot-fire test results of these main injector designs in an integrated test article that includes an oxidizer-rich preburner are described in companion papers at this JANNAF meeting.

The Role of Hydrous Slab Melts in the Sulfur Content, Metal Content, and Oxidation State of Primitive Arc Magmas in the Southern Cascades

NASA Astrophysics Data System (ADS)

Muth, M.; Wallace, P. J.; Walowski, K. J.

2017-12-01

Arc magmas have an oxidized signature (higher Fe3+/∑Fe) relative to MORB. This oxidized signature could be developed during crustal differentiation or be derived from slab components such as hydrous melts and ­fluids. Previous work in the Lassen region of the Cascade arc shows evidence for the addition of a hydrous slab component to the mantle wedge beneath the southern Cascades [1]. Here we investigate whether this hydrous slab component is linked to the oxidation state of primitive magmas using the sulfur, metal, and trace element concentrations of olivine-hosted melt inclusions. Melt inclusions were selected from the tephra of three cinder cones in Lassen volcanic field and analyzed for trace elements and metals (Cu, Zn, Sn) using LA-ICPMS and for major elements, S, and Cl using EMPA. Sulfur concentrations in individual melt inclusions range from 900 to 2200 ppm. Cu, Zn, and Sn concentrations in individual melt inclusions range from 17 to 167 ppm, 65 to 127 ppm, and 0.4 to 1.4 ppm, respectively. Average sulfur concentrations are different for each of the three cinder cones, and individual melt inclusion S/Dy values correlate well with Sr/Nd values. This is an indication that, like other volatiles, sulfur is supplied to the mantle wedge by a slab-derived component. To assess whether this sulfur-carrying slab component affects the oxidation state of the mantle wedge during melting, we used estimates of sulfur content at sulfide saturation to place a minimum bound on fO2 values for the primitive magmas at each cinder cone. These values range from QFM to QFM + 1.5. Despite this wide range of fO2 values, the concentrations of Cu and other metals are low relative to values predicted by partial melting of the mantle wedge during relatively oxidized (greater than QFM + 1.3) conditions [2], and do not vary systematically with indicators of slab component addition such as Sr/Nd. This suggests that metals are not derived from the slab component and/or that residual sulfide is present during melting across the wide range of fO2 values. This observation is also consistent with the addition of a sulfur-carrying slab component to the mantle wedge. Future work will compare these observations to direct measurement of Fe3+/∑Fe and S6+/∑S using XANES. [1] Walowski et al. 2016, EPSL. [2] Lee et al. 2012, Science.

Chelation and stabilization of berkelium in oxidation state +IV

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deblonde, Gauthier J. -P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B.

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, in this work, 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 withmore » neighbouring trivalent actinides americium, curium and californium (Cf). The corresponding Cf(III)-ligand-protein ternary adduct was characterized by X-ray diffraction analysis. Finally, 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.« less

Chelation and stabilization of berkelium in oxidation state +IV

DOE PAGES

Deblonde, Gauthier J. -P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B.; ...

2017-04-10

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, in this work, 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 withmore » neighbouring trivalent actinides americium, curium and californium (Cf). The corresponding Cf(III)-ligand-protein ternary adduct was characterized by X-ray diffraction analysis. Finally, 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.« less

Expanding frontiers in materials chemistry and physics with multiple anions.

PubMed

Kageyama, Hiroshi; Hayashi, Katsuro; Maeda, Kazuhiko; Attfield, J Paul; Hiroi, Zenji; Rondinelli, James M; Poeppelmeier, Kenneth R

2018-02-22

During the last century, inorganic oxide compounds laid foundations for materials synthesis, characterization, and technology translation by adding new functions into devices previously dominated by main-group element semiconductor compounds. Today, compounds with multiple anions beyond the single-oxide ion, such as oxyhalides and oxyhydrides, offer a new materials platform from which superior functionality may arise. Here we review the recent progress, status, and future prospects and challenges facing the development and deployment of mixed-anion compounds, focusing mainly on oxide-derived materials. We devote attention to the crucial roles that multiple anions play during synthesis, characterization, and in the physical properties of these materials. We discuss the opportunities enabled by recent advances in synthetic approaches for design of both local and overall structure, state-of-the-art characterization techniques to distinguish unique structural and chemical states, and chemical/physical properties emerging from the synergy of multiple anions for catalysis, energy conversion, and electronic materials.

Positron states and annihilation characteristics of surface-trapped positrons at the oxidized Cu(110) surface

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Olenga, Antoine; Weiss, A. H.

2013-03-01

The process by which oxide layers are formed on metal surfaces is still not well understood. In this work we present the results of theoretical studies of positron states and annihilation characteristics of surface-trapped positrons at the oxidized Cu(110) surface. An ab-initio investigation of stability and associated electronic properties of different adsorption phases of oxygen on Cu(110) has been performed on the basis of density functional theory and using DMOl3 code. The changes in the positron work function and the surface dipole moment when oxygen atoms occupy on-surface and sub-surface sites have been attributed to charge redistribution within the first two layers, buckling effects within each layer and interlayer expansion. The computed positron binding energy, positron surface state wave function, and annihilation probabilities of surface trapped positrons with relevant core electrons demonstrate their sensitivity to oxygen coverage, elemental content, atomic structure of the topmost layers of surfaces, and charge transfer effects. Theoretical results are compared with experimental data obtained from studies of oxidized transition metal surfaces using positron annihilation induced Auger electron spectroscopy. This work was supported in part by the National Science Foundation Grant DMR-0907679.

ADVANCED OXIDATION PROCESSES IN THE TREATMENT OF CONTAMINANT CANDIDATE LIST (CCL) COMPOUNDS

EPA Science Inventory

The current (2nd) Contaminant Candidate List was completed in 2005 by the United States EPA as an update to the Safe Drinking Water Act. The list of 42 chemical contaminants spans a wide array of classes, from pesticides to pharmaceuticals to elements, all of which are anticipate...

77 FR 24392 - Approval and Promulgation of Implementation Plans; Tennessee; Regional Haze State Implementation...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-04-24

... located across a broad geographic area and emit fine particles (e.g., sulfates, nitrates, organic carbon, elemental carbon, and soil dust), and their precursors (e.g., sulfur dioxide (SO 2 ), nitrogen oxides (NO X... 13045, Protection of Children From Environmental Health Risks and Safety Risks Protection of Children...

Facilitating atmosphere oxidation through mantle convection

NASA Astrophysics Data System (ADS)

Lee, K. K. M.; Gu, T.; Creasy, N.; Li, M.; McCammon, C. A.; Girard, J.

2017-12-01

Earth's mantle connects the surface with the deep interior through convection, and the evolution of its redox state will affect the distribution of siderophile elements, recycling of refractory isotopes, and the oxidation state of the atmosphere through volcanic outgassing. While the rise of oxygen in the atmosphere, i.e., the Great Oxidation Event (GOE) occurred 2.4 billion years ago (Ga), multiple lines of evidence point to oxygen production in the atmosphere well before 2.4 Ga. In contrast to the fluctuations of atmospheric oxygen, vanadium in Archean mantle lithosphere suggests that the mantle redox state has been constant for 3.5 Ga. Indeed, the connection between the redox state of the deep Earth and the atmosphere is enigmatic as is the effect of redox state on mantle dynamics. Here we show a redox-induced density contrast affects mantle convection and may potentially cause the oxidation of the upper mantle. We compressed two synthetic enstatite chondritic samples with identical bulk compositions but formed under different oxygen fugacities (fO2) to lower mantle pressures and temperatures and find Al2O3 forms its own phase separate from the dominant bridgmanite phase in the more reduced composition, in contrast to a more Al-rich, bridgmanite-dominated assemblage for a more oxidized starting composition. As a result, the reduced material is 1-1.5% denser than the oxidized material. Subsequent experiments on other plausible mantle compositions, which differ only in redox state of the starting glass materials, show similar results: distinct mineral assemblages and density contrasts up to 4%. Our geodynamic simulations suggest that such a density contrast causes a rapid ascent and accumulation of oxidized material in the upper mantle, with descent of the denser reduced material to the core-mantle boundary. The resulting heterogeneous redox conditions in Earth's interior may have contributed to the large low-shear velocity provinces in the lower mantle and the rise of oxygen in Earth's atmosphere.

High temperature degradation mechanism of a red phosphor, CaAlSiN3:Eu for solid-state lighting

NASA Astrophysics Data System (ADS)

Oishi, Masatsugu; Shiomi, Shohei; Yamamoto, Takashi; Ueki, Tomoyuki; Kai, Yoichiro; Chichibu, Shigefusa F.; Takatori, Aiko; Kojima, Kazunobu

2017-09-01

Thermal properties of a red phosphor CaAlSiN3:Eu (CASN) at elevated temperatures were evaluated. A heat treatment at 800 °C degraded the photoluminescence property of CASN and caused irreversible changes in both the excitation and emission intensities. The heat treatment in air simultaneously decreased the N elements and increased the O elements. Consequently, the Eu2+ luminescence center was oxidized and CASN lost its photoluminescence property. Although the crystal structure of CASN host was stable even after the heat treatments, the local structure change around the Eu2+ ions is the origin of the thermal degradation of CASN. We found that the heat treatment in N2 atmosphere suppresses the thermal degradation. This is due to the suppression of N evolutions and the incorporation of O elements, which sustains the optically active Eu2+ state.

Application of Developed APCVD Transparent Conducting Oxides and Undercoat Technologies for Economical OLED Lighting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Silverman, Gary S.; Bluhm, Martin; Coffey, James

2011-01-02

Economics is a key factor for application of organic light emitting diodes (OLED) in general lighting relative to OLED flat panel displays that can handle high cost materials such as indium tin oxide (ITO) or Indium zinc oxide (IZO) as the transparent conducting oxide (TCO) on display glass. However, for OLED lighting to penetrate into general illumination, economics and sustainable materials are critical. The issues with ITO have been documented at the DOE SSL R&D and Manufacturing workshops for the last 5 years and the issue is being exaserbated by export controls from China (one of the major sources ofmore » elemental indium). Therefore, ITO is not sustainable because of the fluctuating costs and the United States (US) dependency on other nations such as China. Numerous alternatives to ITO/IZO are being evaluated such as Ag nanoparticles/nanowires, carbon nanotubes, graphene, and other metal oxides. Of these other metal oxides, doped zinc oxide has attracted a lot of attention over the last 10 years. The volume of zinc mined is a factor of 80,000 greater than indium and the US has significant volumes of zinc mined domestically, resulting in the ability for the US to be self-sufficient for this element that can be used in optoelectonic applications. The costs of elemental zinc is over 2 orders of magnitude less than indium, reflecting the relative abundance and availablility of the elements. Arkema Inc. and an international primary glass manufacturing company, which is located in the United States, have developed doped zinc oxide technology for solar control windows. The genesis of this DOE SSL project was to determine if doped zinc oxide technology can be taken from the commodity based window market and translate the technology to OLED lighting. Thus, Arkema Inc. sought out experts, Philips Lighting, Pacific Northwest National Laboratories (PNNL) and National Renewable Research Laboratories (NREL), in OLED devices and brought them into the project. This project had a clear focus on economics and the work plan focused both on doped ZnO process and OLED device structure that would be consistent with the new TCO. The team successfully made 6 inch OLEDs with a serial construction. More process development is required to optimize commercial OLED structures. Feasibility was demonstrated on two different light extraction technologies: 1/4 lambda refractive index matching and high-low-high band pass filter. Process development was also completed on the key precursors for the TCO, which are ready for pilot-plant scale-up. Subsequently, Arkema has developed a cost of ownership model that is consistent with DOE SSL R&D Manufacturing targets as outlined in the DOE SSL R&D Manufacturing 2010 report. The overall outcome of this project was the demonstration that doped zinc oxide can be used for OLED devices without a drop-off in performance while gaining the economic and sustainable benefits of a more readily available TCO. The broad impact of this project, is the facilitation of OLED lighting market penetration into general illumination, resulting in significant energy savings, decreased greenhouse emissions, with no environmental impact issues such as mercury found in Fluorescent technology.« less

Probing Ultrafast Electron Dynamics at Surfaces Using Soft X-Ray Transient Reflectivity Spectroscopy

NASA Astrophysics Data System (ADS)

Baker, L. Robert; Husek, Jakub; Biswas, Somnath; Cirri, Anthony

The ability to probe electron dynamics with surface sensitivity on the ultrafast time scale is critical for understanding processes such as charge separation, injection, and surface trapping that mediate efficiency in catalytic and energy conversion materials. Toward this goal, we have developed a high harmonic generation (HHG) light source for femtosecond soft x-ray reflectivity. Using this light source we investigated the ultrafast carrier dynamics at the surface of single crystalline α-Fe2O3, polycrystalline α-Fe2O3, and the mixed metal oxide, CuFeO2. We have recently demonstrated that CuFeO2 in particular is a selective catalyst for photo-electrochemical CO2 reduction to acetate; however, the role of electronic structure and charge carrier dynamics in mediating catalytic selectivity has not been well understood. Soft x-ray reflectivity measurements probe the M2,3, edges of the 3d transition metals, which provide oxidation and spin state resolution with element specificity. In addition to chemical state specificity, these measurements are also surface sensitive, and by independently simulating the contributions of the real and imaginary components of the complex refractive index, we can differentiate between surface and sub-surface contributions to the excited state spectrum. Accordingly, this work demonstrates the ability to probe ultrafast carrier dynamics in catalytic materials with element and chemical state specificity and with surface sensitivity.

A study on thermal barrier coatings including thermal expansion mismatch and bond coat oxidation

NASA Technical Reports Server (NTRS)

Chang, George C.; Phucharoen, Woraphat; Miller, Robert A.

1986-01-01

The present investigation deals with a plasma-sprayed thermal barrier coating (TBC) intended for high temperature applications to advanced gas turbine blades. Typically, this type of coating system consists of a zirconia-yttria ceramic layer with a nickel-chromium-aluminum bond coat on a superalloy substrate. The problem on hand is a complex one due to the fact that bond coat oxidation and thermal mismatch occur in the TBC. Cracking in the TBC has also been experimentally illustrated. A clearer understanding of the mechanical behavior of the TBC is investigated. The stress states in a model thermal barrier coating as it cools down in air is studied. The powerful finite element method was utilized to model a coating cylindrical specimen. Four successively refined finite element models were developed. Some results obtained using the first two models have been reported previously. The major accomplishment is the successful development of an elastic TBC finite element model known as TBCG with interface geometry between the ceramic layer and the bond coat. An equally important milestone is the near-completion of the new elastic-plastic TBC finite element model called TBCGEP which yielded initial results. Representative results are presented.

EXAFS/XANES studies of plutonium-loaded sodalite/glass waste forms

NASA Astrophysics Data System (ADS)

Richmann, Michael K.; Reed, Donald T.; Kropf, A. Jeremy; Aase, Scott B.; Lewis, Michele A.

2001-09-01

A sodalite/glass ceramic waste form is being developed to immobilize highly radioactive nuclear wastes in chloride form, as part of an electrochemical cleanup process. Two types of simulated waste forms were studied: where the plutonium was alone in an LiCl/KCl matrix and where simulated fission-product elements were added representative of the electrometallurgical treatment process used to recover uranium from spent nuclear fuel also containing plutonium and a variety of fission products. Extended X-ray absorption fine structure spectroscopy (EXAFS) and X-ray absorption near-edge spectroscopy (XANES) studies were performed to determine the location, oxidation state, and particle size of the plutonium within these waste form samples. Plutonium was found to segregate as plutonium(IV) oxide with a crystallite size of at least 4.8 nm in the non-fission-element case and 1.3 nm with fission elements present. No plutonium was observed within the sodalite in the waste form made from the plutonium-loaded LiCl/KCl eutectic salt. Up to 35% of the plutonium in the waste form made from the plutonium-loaded simulated fission-product salt may be segregated with a heavy-element nearest neighbor other than plutonium or occluded internally within the sodalite lattice.

Variation in trace element content of magnetite crystallized from a fractionating sulfide liquid, Sudbury, Canada: Implications for provenance discrimination

NASA Astrophysics Data System (ADS)

Dare, Sarah A. S.; Barnes, Sarah-Jane; Beaudoin, Georges

2012-07-01

Laser ablation ICP-MS analysis has been applied to many accessory minerals in order to understand better the process by which the rock formed and for provenance discrimination. We have determined trace element concentrations of Fe-oxides in massive sulfides that form Ni-Cu-PGE deposits at the base of the Sudbury Igneous Complex in Canada. The samples represent the crystallization products of fractionating sulfide liquids and consist of early-forming Fe-rich monosulfide solution (MSS) cumulates and residual Cu-rich intermediate solid solution (ISS). This study shows that Fe-oxide geochemistry is a sensitive petrogenetic indicator for the degree of fractionation of the sulfide liquid and provides an insight into the partitioning of elements between sulfide and Fe-oxide phases. In addition, it is useful in determining the provenance of detrital Fe-oxide. In a sulfide melt, all lithophile elements (Cr, Ti, V, Al, Mn, Sc, Nb, Ga, Ge, Ta, Hf, W and Zr) are compatible into Fe-oxide. The concentrations of these elements are highest in the early-forming Fe-oxide (titanomagnetite) which crystallized with Fe-rich MSS. Upon the continual crystallization of Fe-oxide from the sulfide liquid, the lithophile elements gradually decrease so that late-forming Fe-oxide (magnetite), which crystallized from the residual Cu-rich liquid, is depleted in these elements. This behavior is in contrast with Fe-oxides that crystallized from a fractionating silicate melt, whereby the concentration of incompatible elements, such as Ti, increases rather than decreases. The behavior of the chalcophile elements in magnetite is largely controlled by the crystallization of the sulfide minerals with only Ni, Co, Zn, Mo, Sn and Pb present above detection limit in magnetite. Nickel, Mo and Co are compatible in Fe-rich MSS and thus the co-crystallizing Fe-oxide is depleted in these elements. In contrast, magnetite that crystallized later from the fractionated liquid with Cu-rich ISS is enriched in Ni, Mo and Co because Fe-rich MSS is absent. The concentrations of Sn and Pb, which are incompatible with Fe-rich MSS, are highest in magnetite that formed from the fractionated Cu-rich liquid. At subsolidus temperatures, ilmenite exsolved from titanomagnetite whereas Al-spinel exsolved from the cores of some magnetite, locally redistributing the trace elements. However, during laser ablation ICP-MS analysis of these Fe-oxides both the magnetite and its exsolution products are ablated so that the analysis represents the original magmatic composition of the Fe-oxide that crystallized from the sulfide melt.

Incorporation mechanisms of actinide elements into the structures of U 6+ phases formed during the oxidation of spent nuclear fuel

NASA Astrophysics Data System (ADS)

Burns, Peter C.; Ewing, Rodney C.; Miller, Mark L.

1997-05-01

Uranyl oxide hydrate and uranyl silicate phases will form due to the corrosion and alteration of spent nuclear fuel under oxidizing conditions in silica-bearing solution. The actinide elements in the spent fuel may be incorporated into the structures of these secondary U6+ phases during the long-term corrosion of the UO 2 in spent fuel. The incorporation of actinide elements into the crystal structures of the alteration products may decrease actinide mobility. The crystal chemistry of the various oxidation states of the actinide elements of environmental concern is examined to identify possible incorporation mechanisms. The substitutions Pu 6+U 6+ and (Pu 5+, Np 5+)U 6+ should readily occur in many U 6+ structures, although structural modification may be required to satisfy local bond-valence requirements. Crystal-chemical characteristics of the U 6+ phases indicate that An 4+ (An: actinide)U 6+ substitution is likely to occur in the sheets of uranyl polyhedra that occur in the structures of the minerals schoepite, [(UO 2) 8O 2(OH) 12](H 2O) 12, ianthinite, [U 24+ (UO 2) 4O 6(OH) 4(H 2O) 4](H 2O) 5, becquerelite, Ca[(UO 2) 3O 2(OH) 3] 2(H 2O) 8, compreignacite, K 2[(UO 2) 3O 2(OH) 3] 2(H 2O) 8, α-uranophane, Ca[(UO 2)(SiO 3OH)] 2(H 2O) 5, and boltwoodite, K(H 2O)[(UO 2)(SiO 4)], all of which are likely to form due to the oxidation and alteration of the UO 2 in spent fuel. The incorporation of An 3+ into the sheets of the structures of α-uranophane and boltwoodite, as well as interlayer sites of various uranyl phases, may occur.

Elemental Redistribution at the Onset of Soil Genesis from Basalt as Measured in a Soil Lysimeter System

NASA Astrophysics Data System (ADS)

Wang, Y.; Umanzor, M.; Alves Meira Neto, A.; Sengupta, A.; Amistadi, M. K.; Root, R.; Troch, P.; Chorover, J.

2017-12-01

Elemental translocation, resulting in enrichment or depletion relative to parent rock, is a consequence of mineral dissolution and precipitation reactions of soil genesis. Accurate measurement of translocation in natural systems is complicated by factors such as parent material heterogeneity and dust deposition. In the present work, a fully controlled and monitored 10° sloping soil lysimeter with known homogeneous initial conditions, was utilized to investigate initial stages of soil genesis from 1 m3 of crushed basalt. Throughout the two-year experiment, periodic irrigation coupled with sensor measurements enabled monitoring of changes in internal moisture states. A total 15-meter water influx resulted in distinct efflux patterns, wetting and drying cycles, as well as high volume water storage. Biological changes, such as algal and grass emergence, were visible on the soil surface, and microbial colonization throughout the profile was measured in a companion study, suggesting that biogeochemical hotspots may have formed. Forensic excavation and sampling of 324 voxels captured the final state heterogeneity of the lysimeter with respect to length and depth. Total elemental concentrations and a five-step sequential extraction (SE) scheme quantified elemental redistributions into operationally-defined pools including exchangeable, poorly-crystalline (hydr)oxides, and crystalline (hydr)oxides. Data were correlated to water flux and storage that was determined from sensor and tracer data over the two years of rock-water interaction; then used to map 2D cross-sections and identify geochemical hotspots. Total and SE Fe concentrations were used to establish a governing mass balance equation, and sub mass balance equations with unique partitioning coefficients of Fe were developed for each SE pool, respectively. The results help to explain elemental (e.g., Fe) lability and redistribution due to physical and geochemical weathering during the initial stages of soil genesis.

Combined catalysts for the combustion of fuel in gas turbines

DOEpatents

Anoshkina, Elvira V.; Laster, Walter R.

2012-11-13

A catalytic oxidation module for a catalytic combustor of a gas turbine engine is provided. The catalytic oxidation module comprises a plurality of spaced apart catalytic elements for receiving a fuel-air mixture over a surface of the catalytic elements. The plurality of catalytic elements includes at least one primary catalytic element comprising a monometallic catalyst and secondary catalytic elements adjacent the primary catalytic element comprising a multi-component catalyst. Ignition of the monometallic catalyst of the primary catalytic element is effective to rapidly increase a temperature within the catalytic oxidation module to a degree sufficient to ignite the multi-component catalyst.

Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(II)

DOE PAGES

Dau, Phuong D.; Shuh, David K.; Sturzbecher-Hoehne, Manuel; ...

2016-07-07

The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which Cf II is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, Cf II(CH 3SO 2) 3-, prepared in the gas phase by reductive elimination of CH 3SO 2 from Cf III(CH 3SO 2) 4-. Comparison with synthesis of the corresponding Sm and Cm complexes revealsmore » reduction of CfIII and SmIII, and no evidence for reduction of Cm III. This reflects the comparative 3+/2+ reduction potentials: Cf 3+ (-1.60 V) ≈ Sm 3+ (-1.55 V) >> Cm 3+ (-3.7 V). Association of O 2 to the divalent complexes is attributed to formation of superoxides, with recovery of the trivalent oxidation state. Lastly, the new gas-phase chemistry of californium, now the heaviest element to have been studied in this manner, provides evidence for Cf II coordination complexes and similar chemistry of Cf and Sm.« less

Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(II)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dau, Phuong D.; Shuh, David K.; Sturzbecher-Hoehne, Manuel

The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which Cf II is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, Cf II(CH 3SO 2) 3-, prepared in the gas phase by reductive elimination of CH 3SO 2 from Cf III(CH 3SO 2) 4-. Comparison with synthesis of the corresponding Sm and Cm complexes revealsmore » reduction of CfIII and SmIII, and no evidence for reduction of Cm III. This reflects the comparative 3+/2+ reduction potentials: Cf 3+ (-1.60 V) ≈ Sm 3+ (-1.55 V) >> Cm 3+ (-3.7 V). Association of O 2 to the divalent complexes is attributed to formation of superoxides, with recovery of the trivalent oxidation state. Lastly, the new gas-phase chemistry of californium, now the heaviest element to have been studied in this manner, provides evidence for Cf II coordination complexes and similar chemistry of Cf and Sm.« less

Thermodynamic Analysis of Oxygen-Enriched Direct Smelting of Jamesonite Concentrate

NASA Astrophysics Data System (ADS)

Zhang, Zhong-Tang; Dai, Xi; Zhang, Wen-Hai

2017-12-01

Thermodynamic analysis of oxygen-enriched direct smelting of jamesonite concentrate is reported in this article. First, the occurrence state of lead, antimony and other metallic elements in the smelting process was investigated theoretically. Then, the verification test was carried out. The results indicate that lead and antimony mainly exist in the alloy in the form of metallic lead and metallic antimony. Simultaneously, lead and antimony were also oxidized into the slag in the form of lead-antimony oxide. Iron and copper could be oxidized into the slag in the form of oxides in addition to combining with antimony in the alloy, while zinc was mainly oxidized into the slag in the form of zinc oxide. The verification test indicates that the main phases in the alloy contain metallic lead, metallic antimony and a small amount of Cu2Sb, FeSb2 intermetallic compounds, and the slag is mainly composed of kirschsteinite, fayalite and zinc oxide, in agreement with the thermodynamic analysis.

Environmental Survey Plans, Fort Sheridan, Sampling and Analysis Plan, Fort Sheridan, Illinois

DTIC Science & Technology

1990-07-01

technique. The flameless AA procedure is based on the absorption of radiation at 253.7 nm by Hg vapor. The Hg is reduced to the elemental state and aerated...desiccator, cupric oxide is added, and the sample is combusted in an induction furnace. The organic carbon content is determined through a calculation in

Chemical evolution of the Earth: Equilibrium or disequilibrium process?

NASA Technical Reports Server (NTRS)

Sato, M.

1985-01-01

To explain the apparent chemical incompatibility of the Earth's core and mantle or the disequilibrium process, various core forming mechanisms have been proposed, i.e., rapid disequilibrium sinking of molten iron, an oxidized core or protocore materials, and meteorite contamination of the upper mantle after separation from the core. Adopting concepts used in steady state thermodynamics, a method is devised for evaluating how elements should distribute stable in the Earth's interior for the present gradients of temperature, pressure, and gravitational acceleration. Thermochemical modeling gives useful insights into the nature of chemical evolution of the Earth without overly speculative assumptions. Further work must be done to reconcile siderophile elements, rare gases, and possible light elements in the outer core.

Comparison of the oxidation state of Fe in comet 81P/Wild 2 and chondritic-porous interplanetary dust particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ogliore, Ryan C.; Butterworth, Anna L.; Fakra, Sirine C.

2010-07-16

The fragile structure of chondritic-porous interplanetary dust particles (CP-IDPs) and their minimal parent-body alteration have led researchers to believe these particles originate in comets rather than asteroids where aqueous and thermal alterations have occurred. The solar elemental abundances and atmospheric entry speed of CP-IDPs also suggest a cometary origin. With the return of the Stardust samples from Jupiter-family comet 81P/Wild 2, this hypothesis can be tested. We have measured the Fe oxidation state of 15 CP-IDPs and 194 Stardust fragments using a synchrotron-based x-ray microprobe. We analyzed {approx}300 ng of Wild 2 material - three orders of magnitude more materialmore » than other analyses comparing Wild 2 and CP-IDPs. The Fe oxidation state of these two samples of material are > 2{sigma} different: the CP-IDPs are more oxidized than the Wild 2 grains. We conclude that comet Wild 2 contains material that formed at a lower oxygen fugacity than the parent-body, or parent bodies, of CP-IDPs. If all Jupiter-family comets are similar, they do not appear to be consistent with the origin of CP-IDPs. However, comets that formed from a different mix of nebular material and are more oxidized than Wild 2 could be the source of CP-IDPs.« less

Method for the removal of elemental mercury from a gas stream

DOEpatents

Mendelsohn, Marshall H.; Huang, Hann-Sheng

1999-01-01

A method is provided to remove elemental mercury from a gas stream by reacting the gas stream with an oxidizing solution to convert the elemental mercury to soluble mercury compounds. Other constituents are also oxidized. The gas stream is then passed through a wet scrubber to remove the mercuric compounds and oxidized constituents.

Method for the removal of elemental mercury from a gas stream

DOEpatents

Mendelsohn, M.H.; Huang, H.S.

1999-05-04

A method is provided to remove elemental mercury from a gas stream by reacting the gas stream with an oxidizing solution to convert the elemental mercury to soluble mercury compounds. Other constituents are also oxidized. The gas stream is then passed through a wet scrubber to remove the mercuric compounds and oxidized constituents. 7 figs.

A suggested periodic table up to Z≤ 172, based on Dirac-Fock calculations on atoms and ions.

PubMed

Pyykkö, Pekka

2011-01-07

Extended Average Level (EAL) Dirac-Fock calculations on atoms and ions agree with earlier work in that a rough shell-filling order for the elements 119-172 is 8s < 5g≤ 8p(1/2) < 6f < 7d < 9s < 9p(1/2) < 8p(3/2). The present Periodic Table develops further that of Fricke, Greiner and Waber [Theor. Chim. Acta 1971, 21, 235] by formally assigning the elements 121-164 to (nlj) slots on the basis of the electron configurations of their ions. Simple estimates are made for likely maximum oxidation states, i, of these elements M in their MX(i) compounds, such as i = 6 for UF(6). Particularly high i are predicted for the 6f elements.

Chemical state and distribution of iodine deposits on 17% Cr/12% Ni steel oxidised in CO 2/CH 3I gas mixtures

NASA Astrophysics Data System (ADS)

Allen, G. C.; Tyler, J. W.

1990-03-01

Iodine-131 is one of the most important volatile fission product elements with respect to radiobiological impact, and the characterisation of its chemical state and distribution on reactor surfaces is required for reactor safety assessments. To this end, duplicate samples of Type 316 (17%Cr/12% Ni) stainless steel oxidised in {CO 2}/{CH 3}I gas mixtures and previously characterised using X-ray photoelectron spectroscopy have been examined using Raman spectroscopy. The aim is to improve our understanding of the way in which iodine is distributed throughout the oxide scale and to identify its chemical state. In this paper we present Raman spectra recorded from a series of stainless steel specimens together with spectra recorded from a number of standard iodine compounds. It is demonstrated that the technique is well suited as a fingerprint method of species identification, can differentiate between the chemical state of iodine as iodide and iodate and can analyse thin oxide films (5-50 nm). Identification of iodine deposits in these oxide films at concentrations of ⩽ 2 at% was not achieved however, there being insufficient iodine present to distinguish any peaks present from the background signal. It is concluded that local concentrations of iodine in oxide inclusions of different composition/morphology on the steel surface does not occur to any extent.

Biogeochemical cycles of carbon, sulfur, and free oxygen in a microbial mat

NASA Astrophysics Data System (ADS)

Canfield, Donald E.; Des Marais, David J.

1993-08-01

Complete budgets for carbon and oxygen have been constructed for cyanobacterial mats dominated by Microcoleus chthonoplastes from the evaporating ponds of a salt works located in Guerrero Negro, Baja California Sur, Mexico. Included in the budget are measured rates of O 2 production, sulfate reduction, and elemental exchange across the mat/brine interface, day and night, at various temperatures and times of the year. We infer from this data the various sinks for O 2, as well as the sources of carbon for primary production. To summarize, although seasonal variability exists, a major percentage of the O 2 produced during the day did not diffuse out of the mat but was used within the mat to oxidize both organic carbon and the sulfide produced by sulfate reduction. At night, most of the O 2 that diffused into the mat was used to oxidize sulfide, with O 2 respiration of minor importance. During the day, the internal mat processes of sulfate reduction and O 2 respiration generated as much or more inorganic carbon (DIC) for primary production as diffusion into the mat. Also, oxygenic photosynthesis was the most important process of carbon fixation, although anoxygenic photosynthesis may have been important at low light levels during some times of the year. At night, the DIC lost from the mat was mostly from sulfate reduction. Elemental fluxes across the mat/brine interface indicated that carbon with an oxidation state of greater than zero was taken up by the mat during the day and liberated from the mat at night. Overall, carbon with an average oxidation state of near zero accumulated in the mat. Both carbon fixation and carbon oxidation rates varied with temperature by a similar amount. These mats are thus closely coupled systems where rapid rates of photosynthesis both require and fuel rapid rates of heterotrophic carbon oxidation.

The formation of FeO-rich pyroxene and enstatite in unequilibrated enstatite chondrites: A petrologic-trace element (SIMS) study

NASA Technical Reports Server (NTRS)

Weisberg, M. K.; Prinz, M.; Fogel, R. A.; Shimizu, N.

1993-01-01

Enstatite (En) chondrites record the most reducing conditions known in the early solar system. Their oxidation state may be the result of condensation in a nebular region having an enhanced C/O ratio, reduction of more oxidized materials in a reducing nebula, reduction during metamorphic reheating in a parent body, or a combination of these events. The presence of more oxidized Fe-rich silicates, two types of En (distinguished by red and blue CL), and the juxtaposition of FeO-rich pyroxenes (Fe-pyx) surrounded by blue En (enstatite) in the UEC's (unequilibrated enstatite chondrites) is intriguing and led to the examination of the question of enstatite chondrite formation. Previously, data was presented on the petrologic-geochemical characteristics of the Fe-pyx and coexisting red and blue En. Here minor and trace element abundances (determined by ion probe-SIMS) on these three types of pyroxenes are reported on in the following meteorites: Kota Kota and LEW87223 (EH3), MAC88136 (EL3), St. Marks (EH4), and Hvittis (EL6). More data are currently being collected.

Biogeochemical Cycling of Fe, S, C, N, and Mo in the 3.2 Ga ocean: Constraints from DXCL-DP Black Shales from Pilbara, Western Australia

NASA Astrophysics Data System (ADS)

Yamaguchi, K. E.; Naraoka, H.; Ikehara, M.; Ito, T.; Kiyokawa, S.

2014-12-01

Records of geochemical cycling of bio-essential, redox-sensitive elements have keys to decipher mysteries of the co-evolution of Earth and life. To obtain insight into biogeochemical cycling of those elements and early evolution of microbial biosphere from high-quality samples, we drilled through Mesoarchean strata in coastal Pilbara (Dixon Island-Cleaverville Drilling Project, see Yamaguchi et al., 2009; Kiyokawa et al., 2012), and obtained 3.2 Ga old drillcores (CL1, CL2, and DX) of sulfide-rich black shales in the Cleaverville Group, Pilbara Supergroup. We conducted a systematic geochemical study involving sequential extractions of Fe, S, C, and N for phase-dependent contents (e.g., pyrite-Fe, reactive-Fe, highly reactive-Fe, unreactive-Fe, pyrite-S, sulfate-S, organic-S, elemental-S, Corg, Ccarb, Norg, and Nclay) and their stable isotope compositions, micro FT-IR and laser Raman spectroscopy for extracted kerogen, in addition to major and trace (redox-sensitive; e.g., Mo) element analysis, for >100 samples. Here we integrate our recent multidisciplinary investigations into the redox state of ocean and nature of microbial biosphere in the ocean 3.2 Ga ago. All of the obtained data are very difficult to explain only by geochemical processes in strictly anoxic environments, where both atmosphere and oceans were completely anoxic, like an environment before the inferred "Great Oxidation Event" when pO2 was lower than 0.00001 PAL (e.g., Holland, 1994). Our extensive data set consistently suggests that oxygenic photosynthesis, bacterial sulfate reduction, and microbially mediated redox-cycling of nitrogen, possibly involving denitrification and N2-fixation, are very likely to have been operating, and may be used as a strong evidence for at least local and temporal existence of oxidized environment as far back as 3.2 Ga ago. Modern-style biogeochemical cycling of Fe, S, C, N, and Mo has been operating since then. The atmosphere-hydrosphere system 3.2 Ga ago would have been sufficiently oxidized to allow redox-cycling of elements during deposition of the sediments, ~800 Ma earlier than commonly thought. Our suggestions have far-reaching and astrobiological implications for earlier evolution of the surface environment, especially redox state, and marine microbial biosphere.

Removable preheater elements improve oxide induction furnace

NASA Technical Reports Server (NTRS)

Leipold, M. H.

1964-01-01

Heat and corrosion resistant preheater elements are used in oxide induction furnaces to raise the temperature to the level for conducting electricity. These preheater elements are then removed and the induction coil energized.

Quantitative X-ray photoelectron spectroscopy-based depth profiling of bioleached arsenopyrite surface by Acidithiobacillus ferrooxidans

NASA Astrophysics Data System (ADS)

Zhu, Tingting; Lu, Xiancai; Liu, Huan; Li, Juan; Zhu, Xiangyu; Lu, Jianjun; Wang, Rucheng

2014-02-01

In supergene environments, microbial activities significantly enhance sulfide oxidation and result in the release of heavy metals, causing serious contamination of soils and waters. As the most commonly encountered arsenic mineral in nature, arsenopyrite (FeAsS) accounts for arsenic contaminants in various environments. In order to investigate the geochemical behavior of arsenic during microbial oxidation of arsenopyrite, (2 3 0) surfaces of arsenopyrite slices were characterized after acidic (pH 2.00) and oxidative decomposition with or without an acidophilic microorganism Acidithiobacillus ferrooxidans. The morphology as well as chemical and elemental depth profiles of the oxidized arsenopyrite surface were investigated by scanning electron microscopy and X-ray photoelectron spectroscopy. With the mediation of bacteria, cell-shaped and acicular pits were observed on the reacted arsenopyrite surface, and the concentration of released arsenic species in solution was 50 times as high as that of the abiotic reaction after 10 days reaction. Fine-scale XPS depth profiles of the reacted arsenopyrite surfaces after both microbial and abiotic oxidation provided insights into the changes in chemical states of the elements in arsenopyrite surface layers. Within the 450 nm surface layer of abiotically oxidized arsenopyrite, Fe(III)-oxides appeared and gradually increased towards the surface, and detectable sulfite and monovalent arsenic appeared above 50 nm. In comparison, higher contents of ferric sulfate, sulfite, and arsenite were found in the surface layer of approximately 3 μm of the microbially oxidized arsenopyrite. Intermediates, such as Fe(III)-AsS and S0, were detectable in the presence of bacteria. Changes of oxidative species derived from XPS depth profiles show the oxidation sequence is Fe > As = S in abiotic oxidation, and Fe > S > As in microbial oxidation. Based on these results, a possible reaction path of microbial oxidation was proposed in a concept model.

Improvement of electrochemical properties and oxidation/reduction behavior of cobalt in positive electrode of Ni-metal hydride battery

NASA Astrophysics Data System (ADS)

Morimoto, Katsuya; Nagashima, Ikuo; Matsui, Masaki; Maki, Hideshi; Mizuhata, Minoru

2018-06-01

The deterioration mechanisms of a Ni-metal hydride (Ni-MH) battery system during operation is investigated. A decrease of the discharge voltage is observed at the early stage of the cycle, which indicates the possible occurrence of an unexpected system shutdown of the battery at low state of charge. Cyclic voltammetry and surface examination are used to investigate the causes of this phenomenon. The elution of elements such as Al and Mn from the metal hydride negative electrodes is shown to affect the oxidation/reduction behavior of Co, the conductive material of the positive electrode. Furthermore, the possible methods to strengthen the conductive network of Co, including pretreatment of the positive electrode, addition of conductive material, and precipitation of the elution elements as insoluble compounds to reduce their effect are also investigated. By combining these strategies, deterioration of the conductive network can be prevented in the early stage.

Materials and methods for the separation of oxygen from air

DOEpatents

MacKay, Richard; Schwartz, Michael; Sammells, Anthony F.

2003-07-15

Metal oxides particularly useful for the manufacture of catalytic membranes for gas-phase oxygen separation processes having the formula: O.sub.5+z where: x and x' are greater than 0; y and y' are greater than 0; x+x' is equal to 2; y+y' is less than or equal to 2; z is a number that makes the metal oxide charge neutral; A is an element selected from the lanthanide elements; A' is an element selected from Be, Mg, Ca, Sr, Ba and Ra; A" is an element selected from the f block lanthanides, Be, Mg, Ca, Sr, Ba and Ra; B is an element selected from the group consisting of Al, Ga, In or mixtures thereof and B" is Co or Mg, with the exception that when B" is Mg, A' and A" are not Mg. The metal oxides are useful for preparation of dense membranes which may be formed from dense thin films of the mixed metal oxide on a porous metal oxide element. The invention also provides methods and catalytic reactors for oxygen separation and oxygen enrichment of oxygen deficient gases which employ mixed conducting metal oxides of the above formula.

Hydrogen sulfide oxidation by a microbial consortium in a recirculation reactor system: sulfur formation under oxygen limitation and removal of phenols.

PubMed

Alcantara, Sergio; Velasco, Antonio; Muñoz, Ana; Cid, Juan; Revah, Sergio; Razo-Flores, Elías

2004-02-01

Wastewater from petroleum refining may contain a number of undesirable contaminants including sulfides, phenolic compounds, and ammonia. The concentrations of these compounds must be reduced to acceptable levels before discharge. Sulfur formation and the effect of selected phenolic compounds on the sulfide oxidation were studied in autotrophic aerobic cultures. A recirculation reactor system was implemented to improve the elemental sulfur recovery. The relation between oxygen and sulfide was determined calculating the O2/S2- loading rates (Q(O2)/Q(S)2- = Rmt), which adequately defined the operation conditions to control the sulfide oxidation. Sulfur-producing steady states were achieved at Rmt ranging from 0.5 to 1.5. The maximum sulfur formation occurred at Rmt of 0.5 where 85% of the total sulfur added to the reactor as sulfide was transformed to elemental sulfur and 90% of it was recovered from the bottom of the reactor. Sulfide was completely oxidized to sulfate (Rmt of 2) in a stirred tank reactor, even when a mixture of phenolic compounds was present in the medium. Microcosm experiments showed that carbon dioxide production increased in the presence of the phenols, suggesting that these compounds were oxidized and that they may have been used as carbon and energy source by heterotrophic microorganisms present in the consortium.

Direct determination of oxidation state of gold deposits in metal-reducing bacterium Shewanella algae using X-ray absorption near-edge structure spectroscopy (XANES).

PubMed

Konishi, Yasuhiro; Tsukiyama, Takeshi; Saitoh, Norizoh; Nomura, Toshiyuki; Nagamine, Shinsuke; Takahashi, Yoshio; Uruga, Tomoya

2007-06-01

X-ray absorption near-edge structure spectroscopy (XANES) was successfully employed to determine the gold valence in the metal-reducing bacterium Shewanella algae after exposure to a 1 mM aqueous HAuCl4 solution for 10-120 min. XANES spectra revealed the oxidation state of gold in the bacterial cells to be Au(0) without any contribution from Au(III), demonstrating that S. algae cells can reduce AuCl4- ions to elemental gold. Transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) analysis confirmed that gold nanoparticles 5-15 nm in size were deposited in the periplasmic space of the bacterial cells; a preferable, cell surface location for the easy recovery of biogenic nanoparticles.

The reactive element effect of yttrium and yttrium silicon on high temperature oxidation of NiCrAl coating

NASA Astrophysics Data System (ADS)

Ramandhany, S.; Sugiarti, E.; Desiati, R. D.; Martides, E.; Junianto, E.; Prawara, B.; Sukarto, A.; Tjahjono, A.

2018-03-01

The microstructure formed on the bond coat affects the oxidation resistance, particularly the formation of a protective oxide layer. The adhesion of bond coat and TGO increased significantly by addition of reactive element. In the present work, the effect of yttrium and yttrium silicon as reactive element (RE) on NiCrAl coating was investigated. The NiCrAl (without RE) and NiCrAlX (X:Y or YSi) bond coating were deposited on Hastelloy C-276 substrate by High Velocity Oxygen Fuel (HVOF) method. Isothermal oxidation was carried out at 1000 °C for 100 hours. The results showed that the addition of RE could prevent the breakaway oxidation. Therefore, the coating with reactive element were more protective against high temperature oxidation. Furthermore, the oxidation rate of NiCrAlY coating was lower than NiCrAlYSi coating with the total mass change was ±2.394 mg/cm2 after 100 hours of oxidation. The thickness of oxide scale was approximately 1.18 μm consisting of duplex oxide scale of spinel NiCr2O4 in outer scale and protective α-Al2O3 in inner scale.

Sensitivity of trace element pyritization to pyrite oxidation processes

NASA Astrophysics Data System (ADS)

Moreira, Manuel; Díaz, Rut; Mendoza, Ursula; Capilla, Ramses; Böttcher, Michael; Luiza Albuquerque, Ana; Machado, Wilson

2014-05-01

Total trace elements concentration variability in marine sediments has been widely used as a proxy for redox conditions and marine paleoprodutivity. However, partial extraction procedures reduce influences of detrital sedimentary fractions, and information on trace element geochemical partitioning can contribute to provide comprehensive evidences on elemental sensitivity to particular processes. The potential effect of sedimentary pyrite re-oxidative cycling on the degree of trace metal pyritization (DTMP) has not been previously evaluated. This study investigates this effect in 4 sediment cores from the continental shelf under the influence of a tropical upwelling system (Cabo Frio, Brazil). The relation of DTMP with stable isotope signals (δ34SCRS) of chromium reducible sulfur, which becomes lighter in response to intense pyrite re-oxidative cycling in the study area, suggests high (As, Cd and Mn), low (Cu and Zn) or negligible (Cr and Ni) re-oxidation influences. The oldest, pyrite-richer sediments provide an apparent threshold for intense pyrite re-oxidation, after which most trace elements (As, Cd, Zn and Mn) presented more accentuated pyritization. A middle shelf core presented negative correlations of reactive (HCl-soluble) Mn, Cu and Ni with pyrite iron, suggesting Mn oxide (and associated metals) depletion in reaction with pyrite. Results provided evidences for coupled influences from both aerobic and anaerobic oxidative processes on trace elements incorporation into pyrite. Pyrite δ34S signatures under the oxic bottom water from the study area were similar to those from euxinic sedimentary environments, suggesting that pyrite re-oxidative cycling can affect trace element susceptibility to be incorporated and preserved into pyrite in a wide range of sedimentary conditions. The evaluation of trace elements sensitivity to these processes can contribute to improve the use of multiple DTMP data (e.g., as paleoredox proxies). Considering that S re-oxidative cycling is ubiquitous in many sedimentary conditions, such coupled use of DTMP and δ34SCRS proxies can be possibly applied to a large variety of sedimentary environments.

Electrochemical membrane incinerator

DOEpatents

Johnson, Dennis C.; Houk, Linda L.; Feng, Jianren

2001-03-20

Electrochemical incineration of p-benzoquinone was evaluated as a model for the mineralization of carbon in toxic aromatic compounds. A Ti or Pt anode was coated with a film of the oxides of Ti, Ru, Sn and Sb. This quaternary metal oxide film was stable; elemental analysis of the electrolyzed solution indicated the concentration of these metal ions to be 3 .mu.g/L or less. The anode showed good reactivity for the electrochemical incineration of benzoquinone. The use of a dissolved salt matrix as the so-called "supporting electrolyte" was eliminated in favor of a solid-state electrolyte sandwiched between the anode and cathode.

Fundamental aspects of regenerative cerium oxide nanoparticles and their applications in nanobiotechnology

NASA Astrophysics Data System (ADS)

Patil, Swanand D.

Cerium oxide has been used extensively for various applications over the past two decades. The use of cerium oxide nanoparticles is beneficial in present applications and can open avenues for future applications. The present study utilizes the microemulsion technique to synthesize uniformly distributed cerium oxide nanoparticles. The same technique was also used to synthesize cerium oxide nanoparticles doped with trivalent elements (La and Nd). The fundamental study of cerium oxide nanoparticles identified variations in properties as a function of particle size and also due to doping with trivalent elements (La and Nd). It was found that the lattice parameter of cerium oxide nanoparticles increases with decrease in particle size. Also Raman allowed mode shift to lower energies and the peak at 464 cm-1 becomes broader and asymmetric. The size dependent changes in cerium oxide were correlated to increase in oxygen vacancy concentration in the cerium oxide lattice. The doping of cerium oxide nanoparticles with trivalent elements introduces more oxygen vacancies and expands the cerium oxide lattice further (in addition to the lattice expansion due to the size effect). The lattice expansion is greater for La-doped cerium oxide nanoparticles compared to Nd-doping due to the larger ionic radius of La compared to Nd, the lattice expansion is directly proportional to the dopant concentration. The synthesized cerium oxide nanoparticles were used to develop an electrochemical biosensor of hydrogen peroxide (H2O2). The sensor was useful to detect H2O2 concentrations as low as 1muM in water. Also the preliminary testing of the sensor on tomato stem and leaf extracts indicated that the sensor can be used in practical applications such as plant physiological studies etc. The nanomolar concentrations of cerium oxide nanoparticles were also found to be useful in decreasing ROS (reactive oxygen species) mediated cellular damages in various in vitro cell cultures. Cerium oxide nanoparticles reduced the cellular damages to the normal breast epithelial cell line (CRL 8798) induced by X-rays and to the Keratinocyte cell line induced by UV irradiation. Cerium oxide nanoparticles were also found to be neuroprotective to adult rat spinal cord and retinal neurons. We propose that cerium oxide nanoparticles act as free radical scavenger (via redox reactions on its surface) to decrease the ROS induced cellular damages. Additionally, UV-visible spectroscopic studies indicated that cerium oxide nanoparticles possess auto-regenerative property by switching its oxidation state between Ce3+ and Ce4+. The auto-regenerative antioxidant property of these nanoparticles appears to be a key component in all the biological applications discussed in the present study.

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

Toshiba Display Services, a television picture-tube manufacturer in Horseheads, NY, recently was able to meet stringent state regulations to reduce emissions from two of its film applications lines by installing a regenerative catalytic oxidation system. Toshiba officials initially evaluated several technologies to control volatile organic compounds. After deciding that oxidation was the best technology for its facility, the company invited a number of suppliers to submit proposals. Because all of the oxidation technologies considered by Toshiba had the capability to achieve the destruction and removal efficiency requirement, the company combined the second and third decision elements and conducted an in-depthmore » comparison of the initial capital and ongoing operating costs for each proposal. Officials narrowed the field to two systems--the lowest-cost regenerative thermal oxidation system on the market and a regenerative catalytic oxidation system. The company selected St. Louis, Mo.-based Monsanto Enviro-Chem Systems Inc., to install its DynaCycle{reg_sign} regenerative catalytic oxidation system, marking the first Dyna-Cycle installation in a US television picture-tube facility.« less

Pechini process-derived tin oxide and tin oxide-graphite composites for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, R.; Lee, Jim Y.; Liu, Z. L.

The Pechini process [Ceram. Bull. 68 (1989) 1002] is used to obtain fine tin oxide powders that reduce the specific volume change in Li + insertion and extraction reactions. The suitability of these tin oxides as active materials for negative electrodes in lithium-ion batteries is investigated. From elemental analysis, it is found that the templating polymer network is almost completely obliterated after heating at 500 °C. The best tin oxide does not exhibit extensive crystallization of tin atoms even after 30 cycles of alloying and de-alloying reactions with Li. The structure and the specific capacity of the oxides are dependent on the heat treatment and remnants of the polymeric CH network can impose an unfavorable outcome. A capacity of 600 mAh g -1, which is unchanged for 30 cycles, can be obtained from tin oxide heat treated at 1000 °C. Composites of graphite and SnO 2 are also prepared and exhibit synergistic interactions between graphite and tin oxide which are similar to those reported previously [Electrochem. Solid State Lett. 3 (2000) 167].

Indefinitely stable iron(IV) cage complexes formed in water by air oxidation

NASA Astrophysics Data System (ADS)

Tomyn, Stefania; Shylin, Sergii I.; Bykov, Dmytro; Ksenofontov, Vadim; Gumienna-Kontecka, Elzbieta; Bon, Volodymyr; Fritsky, Igor O.

2017-01-01

In nature, iron, the fourth most abundant element of the Earth's crust, occurs in its stable forms either as the native metal or in its compounds in the +2 or +3 (low-valent) oxidation states. High-valent iron (+4, +5, +6) compounds are not formed spontaneously at ambient conditions, and the ones obtained synthetically appear to be unstable in polar organic solvents, especially aqueous solutions, and this is what limits their studies and use. Here we describe unprecedented iron(IV) hexahydrazide clathrochelate complexes that are assembled in alkaline aqueous media from iron(III) salts, oxalodihydrazide and formaldehyde in the course of a metal-templated reaction accompanied by air oxidation. The complexes can exist indefinitely at ambient conditions without any sign of decomposition in water, nonaqueous solutions and in the solid state. We anticipate that our findings may open a way to aqueous solution and polynuclear high-valent iron chemistry that remains underexplored and presents an important challenge.

Indefinitely stable iron(IV) cage complexes formed in water by air oxidation.

PubMed

Tomyn, Stefania; Shylin, Sergii I; Bykov, Dmytro; Ksenofontov, Vadim; Gumienna-Kontecka, Elzbieta; Bon, Volodymyr; Fritsky, Igor O

2017-01-19

In nature, iron, the fourth most abundant element of the Earth's crust, occurs in its stable forms either as the native metal or in its compounds in the +2 or +3 (low-valent) oxidation states. High-valent iron (+4, +5, +6) compounds are not formed spontaneously at ambient conditions, and the ones obtained synthetically appear to be unstable in polar organic solvents, especially aqueous solutions, and this is what limits their studies and use. Here we describe unprecedented iron(IV) hexahydrazide clathrochelate complexes that are assembled in alkaline aqueous media from iron(III) salts, oxalodihydrazide and formaldehyde in the course of a metal-templated reaction accompanied by air oxidation. The complexes can exist indefinitely at ambient conditions without any sign of decomposition in water, nonaqueous solutions and in the solid state. We anticipate that our findings may open a way to aqueous solution and polynuclear high-valent iron chemistry that remains underexplored and presents an important challenge.

Indefinitely stable iron(IV) cage complexes formed in water by air oxidation

PubMed Central

Tomyn, Stefania; Shylin, Sergii I.; Bykov, Dmytro; Ksenofontov, Vadim; Gumienna-Kontecka, Elzbieta; Bon, Volodymyr; Fritsky, Igor O.

2017-01-01

In nature, iron, the fourth most abundant element of the Earth's crust, occurs in its stable forms either as the native metal or in its compounds in the +2 or +3 (low-valent) oxidation states. High-valent iron (+4, +5, +6) compounds are not formed spontaneously at ambient conditions, and the ones obtained synthetically appear to be unstable in polar organic solvents, especially aqueous solutions, and this is what limits their studies and use. Here we describe unprecedented iron(IV) hexahydrazide clathrochelate complexes that are assembled in alkaline aqueous media from iron(III) salts, oxalodihydrazide and formaldehyde in the course of a metal-templated reaction accompanied by air oxidation. The complexes can exist indefinitely at ambient conditions without any sign of decomposition in water, nonaqueous solutions and in the solid state. We anticipate that our findings may open a way to aqueous solution and polynuclear high-valent iron chemistry that remains underexplored and presents an important challenge. PMID:28102364

Understanding the evolution of S- and I-type granitic plutons through analysis of apatite.

NASA Astrophysics Data System (ADS)

Hess, B. L.; Fiege, A.; Tailby, N.

2017-12-01

The major and trace element composition of apatites from the Lachlan fold belt (LFB) S- and I-type granitoids (Australia) and the Central French Massif (CFM) S-type leucogranites (France) were analyzed to investigate their compositional and redox variation. Apatite is a common accessory mineral in magmatic systems that can incorporate a variety of trace elements, including the polyvalent elements sulfur (S), iron (Fe), and manganese (Mn). It was recently discovered that apatite can incorporate three oxidation states of S (S6+, S4+, S2-) into its structure as a function of oxygen fugacity [1]. However, the oxidation states of Mn and Fe in apatite are essentially unknown (2+ and/or 3+). In this study, we collected many electron probe line transects across apatites in several different host phases from a variety of S- and I-type plutons. The F-H-Cl contents of the S- and I-type LFB samples were similar ( 2.9 wt% F, 0.4 wt% Cl, 0.5 wt% OH). The CFM S-types contained virtually no Cl and ranged from near-endmember OH-apatite to near-endmember F-apatite. The apatites of all studied the S- and I-type plutons are characterized by similar ranges of Fe content (<1.5 wt% Fe), while Mn reaches much higher concentrations in the S-type when compared to I-type apatites (<6.5 wt% Mn). The S content of the apatites varies significantly, from <50 ppm S in the LFB S-types, up to 2,000 ppm S in the LFB I-types, and reaching 1,650 ppm S in the CFM S-types. The elevated S contents in the LFB I-type and CFM S-type apatites allowed us to measure the S oxidation states by using X-ray absorption near-edge structure (XANES) spectroscopy. The spectra show variability in S oxidation states ranging from mostly sulfate down to nearly equal S6+/S2- ratios, indicating redox variations during apatite formation. The S-type Mn + Fe content plots in a 1:1 ratio against calcium (Ca) in atoms per formula unit, while the I-type apatites have too low Mn and Fe to show a clear trend. Thus, divalent Mn and Fe probably replace Ca2+ in the S-types' apatite structure, while the incorporation of trivalent Mn or Fe in apatite is rather unlikely. We suggest that Mn and Fe contents in apatite may become a useful tracer of melt evolution once the distributions coefficients are experimentally calibrated. [1] Konecke et al. (2017), Am Mineral

Controlling Hexavalent Americium – A Centerpiece to a Compact Nuclear Fuel Cycle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shafer /Braley, Jenifer; Nash, Kenneth L; Lumetta, Gregg

2014-10-01

Closing the nuclear fuel cycle could be simplified by recovering the actinides U through Am as a group. This could be achieved by converting U, Np, Pu and Am to the hexavalent state. Uranium, Np and Pu are readily oxidized to the hexavalent state. Generation of hexavalent Am in acidic solutions is more difficult, as the standard reduction potential of the Am(VI) /Am(III) couple (+1.68 V in 1 M HClO4) is well outside of the electrochemical stability window of water. While the oxidation and separation of Am has been demonstrated under laboratory conditions, several issues could plague scale up andmore » implementation of this separation with used fuel. Two primary concerns are considered. The first issue concerns the stability of the oxidized Am. The second involves the undesirable co-extraction of tetravalent f-elements with the hexavalent actinides. To address the first concern regarding Am redox instability, Am reduction will be monitored under a variety of different conditions to establish the means of improving the stability of Am(VI) in the organic phase. Identifying the components contributing most significantly to its reduction will allow thoughtful modification of the process. To address the second concern, we propose to apply branched chain extractants to separate hexavalent actinides from tetravalent f-elements. Both branched monoamide and organophosphorus extractants have demonstrated significant selectivity for UO22+ versus Th4+, with separation factors generally on the order of 100. The efforts of this two-pronged research program should represent a significant step forward in the development of aqueous separations approaches designed to recover the U-Am actinides based on the availability of the hexavalent oxidation state. For the purposes of this proposal, separations based on this approach will be called SAn(VI) separations, indicating the Separation of An(VI).« less

Redistribution of iron and titanium in subduction zones: insights from high-pressure serpentinites

NASA Astrophysics Data System (ADS)

Crossley, Rosalind; Evans, Katy; Reddy, Steven; Lester, Gregory

2017-04-01

The redox state, quantity and composition of subduction zone fluids influence the transport and precipitation of elements including those which are redox-sensitive, of economic importance such as Cu, Au and Ag, and those considered to be immobile, which include Fe3+. However, subduction zone fluids remain poorly understood. The redox state of Fe in high-pressure ultramafic rocks, which host a significant proportion of Fe3+, can be used to provide an insight into Fe cycling and constrain the composition of subduction zone fluids. In this work, a combination of the study of oxide and silicate mineral textures, interpretation of mineral parageneses, mineral composition data, and the whole rock geochemistry of high-pressure retrogressed ultramafic rocks from the Zermatt-Saas Zone constrains the distribution of iron and titanium, and oxidation state of iron, to provide constraints on fluids at depth in subduction zones. Oxide minerals host the bulk of the iron, particularly Fe3+. The increase in mode of magnetite during initial retrogression is most consistent with oxidation of existing iron within the samples during the infiltration of an oxidising fluid since it is difficult to reconcile addition of Fe3+ with the known limited solubility of this species. These fluids may be sourced from hybrid samples and/or serpentinites at greater depths. However, high Ti contents are not typical of serpentinites and additionally cannot be accounted for by simple mixing of a depleted mantle protolith with the nearby Allalin gabbro. Titanium-rich samples are suggested to result from fluid-facilitated hybridisation of gabbro and serpentinite protoliths prior to peak metamorphism, and provides the tantalising possibility that Ti, an element generally perceived as immobile, has been added to the rock during this process. If Ti addition has occurred, then the introduction of Fe3+, also generally considered to be immobile, cannot be disregarded. Aluminosilicate complexing could provide a transport vector for Ti where this mechanism of Ti transport is consistent with the Al-rich nature of the sample.

Geochemical, modal, and geochronologic data for 1.4 Ga A-type granitoid intrusions of the conterminous United States

USGS Publications Warehouse

du Bray, Edward A.; Holm-Denoma, Christopher S.; San Juan, Carma A.; Lund, Karen; Premo, Wayne R.; DeWitt, Ed

2015-08-10

In addition, Kisvarsanyi (1972) suggests that iron-copper deposits in the St. Francois Mountains of southeastern Missouri are petrogenetically associated with 1.4 Ga A-type granitoids that occur in that region. Similarly, Dall’Agnol and others (2012) summarize important global associations between A-type granitoid rocks and a variety of important ore deposit types, particularly tin, high-field-strength elements (Zr, Hf, Nb, Ta), rare-earth elements, and iron oxide-copper-gold deposits. Consequently, the need to better understand relations between A-type granitoid rocks, tectonic setting, and magma petrogenesis, as well as their genetic associations with important types of ore deposits, suggests that developing a definitive geochemical, modal, and geochronologic database for these rocks in the conterminous United States is of considerable value.

Single element injector cold flow testing for STME swirl coaxial injector element design

NASA Technical Reports Server (NTRS)

Hulka, J.; Schneider, J. A.

1993-01-01

An oxidizer-swirled coaxial element injector is being investigated for application in the Space Transportation Main Engine (STME). Single element cold flow experiments were conducted to provide characterization of the STME injector element for future analysis, design, and optimization. All tests were conducted to quiescent, ambient backpressure conditions. Spray angle, circumferential spray uniformity, dropsize, and dropsize distribution were measured in water-only and water/nitrogen flows. Rupe mixing efficiency was measured using water/sucrose solution flows with a large grid patternator for simple comparative evaluation of mixing. Factorial designs of experiment were used for statistical evaluation of injector geometrical design features and propellant flow conditions on mixing and atomization. Increasing the free swirl angle of the liquid oxidizer had the greatest influence on increasing the mixing efficiency. The addition of gas assistance had the most significant effect on reducing oxidizer droplet size parameters and increasing droplet size distribution. Increasing the oxidizer injection velocity had the greatest influence for reducing oxidizer droplet size parameters and increasing size distribution for non-gas assisted flows. Single element and multi-element subscale hot fire testing are recommended to verify optimized designs before committing to the STME design.

Advanced Characterization of Rare Earth Elements in Coal Utilization Byproducts

NASA Astrophysics Data System (ADS)

Verba, C.; Scott, M.; Dieterich, M.; Poston, J.; Collins, K.

2016-12-01

Rare earth elements (REE) in various forms (e.g., crystalline mineral phases; adsorbed/absorbed state on and into organic macerals, neoformed glass from flyash or bottom ash) from domestic feedstocks such as coal deposits to coal utilization byproducts (CUB) have the potential to reduce foreign REE dependence and increase domestic resource security. Characterization is critical for understanding environmental risks related to their fate and transport as well as determining the most practical and economical techniques for concentrating the REE and converting them into chemical stocks for manufacturing. Several complementary electron microscopy (SEM-EDS, EPMA-WDS, FIB-SEM, cathodoluminescence, and XRD) and post image processing techniques were used to understand REE transition from coal to CUB. Sites of interest were identified and imaged and respective elemental x-ray maps acquired and montaged. Pixel classification of SEM imagers was completed using image analysis techniques to quantify the distribution of REE associated features. Quantitative elemental analysis of phases were completed using EMPA-WDS followed by FIB-SEM. The FIB-SEM results were reconstructed into 3D volumes and features of interest (e.g. monazite) were analyzed to determine the structure and volumetric estimation of REEs and thus predict detrital REE phases to ICP-MS results. Trace minerals were identified as pyrite, zircon, REE-phosphates' (monazite, xenotime), and barite within the coal tailings. In CUB, amorphous aluminosilicates, iron oxide cenospheres, and calcium oxides were present; monazite appear to be unaltered and unaffected by the combustion process in these samples. Thermal decomposition may have occurred due to presence of detrital zircon and xenotime and subsequent thin Ca-oxide coating enriched in trace REEs.

Elemental Metals or Oxides Distributed on a Carbon Substrate or Self-Supported and the Manufacturing Process Using Graphite Oxide as Template

NASA Technical Reports Server (NTRS)

Hung, Ching-Chen (Inventor)

1999-01-01

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a percursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen. This intermediary product can be further processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

Elemental Metals or Oxides Distributed on a Carbon Substrate or Self-Supported and the Manufacturing Process Using Graphite Oxide as Template

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh (Inventor)

1999-01-01

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen. This intermediary product can be further processed by direct exposure to carbonate-solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

A niobium oxide-tantalum oxide selector-memristor self-aligned nanostack

NASA Astrophysics Data System (ADS)

Diaz Leon, Juan J.; Norris, Kate J.; Yang, J. Joshua; Sevic, John F.; Kobayashi, Nobuhiko P.

2017-03-01

The integration of nonlinear current-voltage selectors and bi-stable memristors is a paramount step for reliable operation of crossbar arrays. In this paper, the self-aligned assembly of a single nanometer-scale device that contains both a selector and a memristor is presented. The two components (i.e., selector and memristor) are vertically assembled via a self-aligned fabrication process combined with electroforming. In designing the device, niobium oxide and tantalum oxide are chosen as materials for selector and memristor, respectively. The formation of niobium oxide is visualized by exploiting the self-limiting reaction between niobium and tantalum oxide; crystalline niobium (di)oxide forms at the interface between metallic niobium and tantalum oxide via electrothermal heating, resulting in a niobium oxide selector self-aligned to a tantalum oxide memristor. A steady-state finite element analysis is used to assess the electrothermal heating expected to occur in the device. Current-voltage measurements and structural/chemical analyses conducted for the virgin device, the electroforming process, and the functional selector-memristor device are presented. The demonstration of a self-aligned, monolithically integrated selector-memristor device would pave a practical pathway to various circuits based on memristors attainable at manufacturing scales.

Bonding of sapphire to sapphire by eutectic mixture of aluminum oxide and zirconium oxide

NASA Technical Reports Server (NTRS)

Deluca, J. J. (Inventor)

1975-01-01

Bonding of an element comprising sapphire, ruby or blue sapphire to another element of such material with a eutectic mixture of aluminum oxide and zirconium oxide is discussed. The bonding mixture may be applied in the form of a distilled water slurry or by electron beam vapor deposition. In one embodiment the eutectic is formed in situ by applying a layer of zirconium oxide and then heating the assembly to a temperature above the eutectic temperature and below the melting point of the material from which the elements are formed. The formation of a sapphire rubidium maser cell utilizing eutectic bonding is shown.

Radioactive ion detector

DOEpatents

Bower, Kenneth E.; Weeks, Donald R.

1997-01-01

Apparatus for detecting the presence, in aqueous media, of substances which emit alpha and/or beta radiation and determining the oxidation state of these radioactive substances, that is, whether they are in cationic or anionic form. In one embodiment, a sensor assembly has two elements, one comprised of an ion-exchange material which binds cations and the other comprised of an ion-exchange material which binds anions. Each ion-exchange element is further comprised of a scintillation plastic and a photocurrent generator. When a radioactive substance to which the sensor is exposed binds to either element and emits alpha or beta particles, photons produced in the scintillation plastic illuminate the photocurrent generator of that element. Sensing apparatus senses generator output and thereby indicates whether cationic species or anionic species or both are present and also provides an indication of species quantity.

Radioactive ion detector

DOEpatents

Bower, K.E.; Weeks, D.R.

1997-08-12

Apparatus for detecting the presence, in aqueous media, of substances which emit alpha and/or beta radiation and determining the oxidation state of these radioactive substances, that is, whether they are in cationic or anionic form. In one embodiment, a sensor assembly has two elements, one comprised of an ion-exchange material which binds cations and the other comprised of an ion-exchange material which binds anions. Each ion-exchange element is further comprised of a scintillation plastic and a photocurrent generator. When a radioactive substance to which the sensor is exposed binds to either element and emits alpha or beta particles, photons produced in the scintillation plastic illuminate the photocurrent generator of that element. Sensing apparatus senses generator output and thereby indicates whether cationic species or anionic species or both are present and also provides an indication of species quantity. 2 figs.

Biological X-ray absorption spectroscopy (BioXAS): a valuable tool for the study of trace elements in the life sciences.

PubMed

Strange, Richard W; Feiters, Martin C

2008-10-01

Using X-ray absorption spectroscopy (XAS) the binding modes (type and number of ligands, distances and geometry) and oxidation states of metals and other trace elements in crystalline as well as non-crystalline samples can be revealed. The method may be applied to biological systems as a 'stand-alone' technique, but it is particularly powerful when used alongside other X-ray and spectroscopic techniques and computational approaches. In this review, we highlight how biological XAS is being used in concert with crystallography, spectroscopy and computational chemistry to study metalloproteins in crystals, and report recent applications on relatively rare trace elements utilised by living organisms and metals involved in neurodegenerative diseases.

Liquid fuel injection elements for rocket engines

NASA Technical Reports Server (NTRS)

Cox, George B., Jr. (Inventor)

1993-01-01

Thrust chambers for liquid propellant rocket engines include three principal components. One of these components is an injector which contains a plurality of injection elements to meter the flow of propellants at a predetermined rate, and fuel to oxidizer mixture ratio, to introduce the mixture into the combustion chamber, and to cause them to be atomized within the combustion chamber so that even combustion takes place. Evolving from these injectors are tube injectors. These tube injectors have injection elements for injecting the oxidizer into the combustion chamber. The oxidizer and fuel must be metered at predetermined rates and mixture ratios in order to mix them within the combustion chamber so that combustion takes place smoothly and completely. Hence tube injectors are subject to improvement. An injection element for a liquid propellant rocket engine of the bipropellant type is provided which includes tangential fuel metering orifices, and a plurality of oxidizer tube injection elements whose injection tubes are also provided with tangential oxidizer entry slots and internal reed valves.

Publications - RDF 2005-5 | Alaska Division of Geological & Geophysical

Science.gov Websites

content DGGS RDF 2005-5 Publication Details Title: Major-oxide, minor-oxide, and trace-element geochemical ., and Lessard, R.R., 2005, Major-oxide, minor-oxide, and trace-element geochemical data from rocks ; Zinc; Zirconium Top of Page Department of Natural Resources, Division of Geological & Geophysical

Synthesis of Au microwires by selective oxidation of Au–W thin-film composition spreads

PubMed Central

Hamann, Sven; Brunken, Hayo; Salomon, Steffen; Meyer, Robert; Savan, Alan; Ludwig, Alfred

2013-01-01

We report on the stress-induced growth of Au microwires out of a surrounding Au–W matrix by selective oxidation, in view of a possible application as ‘micro-Velcro’. The Au wires are extruded due to the high compressive stress in the tungsten oxide formed by oxidation of elemental W. The samples were fabricated as a thin-film materials library using combinatorial sputter deposition followed by thermal oxidation. Sizes and shapes of the Au microwires were investigated as a function of the W to Au ratio. The coherence length and stress state of the Au microwires were related to their shape and plastic deformation. Depending on the composition of the Au–W precursor, the oxidized samples showed regions with differently shaped Au microwires. The Au48W52 composition yielded wires with the maximum length to diameter ratio due to the high compressive stress in the tungsten oxide matrix. The values of wire length (35 μm) and diameter (2 μm) achieved at the Au48W52 composition are suitable for micro-Velcro applications. PMID:27877561

Roadside Accumulation of Pt, Pd, Rh and Other Trace Elements From Automobiles: Catalytic Converter Attrition and Platinum-Group Element Mobility in the Roadside Environment.

NASA Astrophysics Data System (ADS)

Ely, J. C.; Dahlheimer, S. R.; Neal, C. R.

2003-12-01

Elemental abundances of Pt, Pd and Rh have been documented across the industrialized world in roadside environments due to attrition of automotive catalytic converters (Zereini and Alt, 2000, Anthropogenic PGE Emissions, Springer, 308pp; Ely et al., 2001, EnvSci&Tech, 35:3816-3822; Whiteley and Murray, 2003, SciTotEnv, in press). In our ongoing study, the highest reported roadside Pt abundance 1.8 ppm has been found immediately adjacent to the road at a field site in South Bend, IN, USA. Furthermore, initial studies show positive correlations of Pt, Pd and Rh with some trace elements (Ni, Cu, Zn and Pb), which has been confirmed by further analysis for these and other elements (Ce, Cr). It has been demonstrated that elements such as Ce are present in catalytic converters at concentrations of 100's ppm to 3-wt.%. These elements are also being attrited with Pt, Pd and Rh and aerially transported and deposited. Our field site was established next to US-933 adjacent to the Notre Dame campus. Areas were cleared of the top 2-4 cm of soil (removing surficial Pt, Pd and Rh) at 1, 5, 10 and 50 meters from the roadside. Within 3 months the 1-meter site contained 67% of the initial Rh and Pt concentrations and 100% of the initial Pd concentration. The sites at 5, 10 and 50 meters showed similar results, in some cases exceeding the initial concentrations. After 6 months the concentrations of Pt, Pd and Rh were all within error of the initial concentrations, indicating steady state abundances had probably been reached. Grass samples from each site showed that washed vs. unwashed samples were within error of each other, and there may be a slight enrichment (approx. 1 ppb) in the grasses of Pd and Pt, but this enrichment was independent of distance from the road. The steady-state situation suggests that the PGEs are being removed from the immediate roadside environment, which requires that the metals are being oxidized and/or complexed in such a way to facilitate transport. The environmental effects of such processes are unknown, but Pt complexes are known carcinogens. Electron microprobe and SEM analysis are being used to isolate particles using these surrogate trace elements in an ongoing effort to determine the oxidation state (using XANES) of Pt, Pd and Rh in the natural environment.

Distribution and speciation of trace elements in iron and manganese oxide cave deposits

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frierdich, Andrew J.; Catalano, Jeffrey G.

2012-10-24

Fe and Mn oxide minerals control the distribution and speciation of heavy metals and trace elements in soils and aquatic systems through chemical mechanisms involving adsorption, incorporation, and electron transfer. The Pautler Cave System in Southwest Illinois, an analog to other temperate carbonate-hosted karst systems, contains Fe and Mn oxide minerals that form in multiple depositional environments and have high concentrations of associated trace elements. Synchrotron-based micro-scanning X-ray fluorescence ({mu}-SXRF) shows unique spatial distributions of Fe, Mn, and trace elements in mineral samples. Profile maps of Mn oxide cave stream pebble coatings show Fe- and As-rich laminations, indicating dynamic redoxmore » conditions in the cave stream. {mu}-SXRF maps demonstrate that Ni, Cu, and Zn correlate primarily with Mn whereas As correlates with both Mn and Fe; As is more enriched in the Fe phase. Zn is concentrated in the periphery of Mn oxide stream pebble coatings, and may be an indication of recent anthropogenic surface activity. X-ray absorption fine structure spectroscopy measurements reveal that As(V) occurs as surface complexes on Mn and Fe oxides whereas Zn(II) associated with Mn oxides is adsorbed to the basal planes of phyllomanganates in a tetrahedral coordination. Co(III) and Se(IV) are also observed to be associated with Mn oxides. The observation of Fe, Mn, and trace element banding in Mn oxide cave stream pebble coatings suggests that these materials are sensitive to and document aqueous redox conditions, similar to ferromanganese nodules in soils and in marine and freshwater sediments. Furthermore, speciation and distribution measurements indicate that these minerals scavenge trace elements and limit the transport of micronutrients and contaminants in karst aquifer systems while also potentially recording changes in anthropogenic surface activity and land-use.« less

Behaviour of niobium during early Earth’s differentiation: insights from its local structure and oxidation state in silicate melts at high pressure

NASA Astrophysics Data System (ADS)

Sanloup, C.; Cochain, B.; de Grouchy, C.; Glazyrin, K.; Konôpkova, Z.; Liermann, H.-P.; Kantor, I.; Torchio, R.; Mathon, O.; Irifune, T.

2018-02-01

Niobium (Nb) is one of the key trace elements used to understand Earth’s formation and differentiation, and is remarkable for its deficiency relative to tantalum in terrestrial rocks compared to the building chondritic blocks. In this context, the local environment of Nb in silica-rich melts and glasses is studied by in situ x-ray absorption spectroscopy (XAS) at high pressure (P) up to 9.3 GPa and 1350 K using resistive-heating diamond-anvil cells. Nb is slightly less oxidized in the melt (intermediate valence between  +4 and  +5) than in the glass (+5), an effect evidenced from the shift of the Nb-edge towards lower energies. Changes in the pre-edge features are also observed between melt and glass states, consistently with the observed changes in oxidation state although likely enhanced by temperature (T) effects. The oxidation state of Nb is not affected by pressure neither in the molten nor glassy states, and remains constant in the investigated P-range. The Nb-O coordination number is constant and equal to 6.3+/-0.4 below 5 GPa, and only progressively increases up to 7.1+/-0.4 at 9.3 GPa, the maximum P investigated. If these findings were to similarly apply to basaltic melts, that would rule out the hypothesis of Nb/Ta fractionation during early silicate Earth’s differentiation, thus reinforcing the alternative hypothesis of fractionation during core formation on reduced pre-planetary bodies.

Characterization of interfacial reactions and oxide films on 316L stainless steel in various simulated PWR primary water environments

NASA Astrophysics Data System (ADS)

Chen, Junjie; Xiao, Qian; Lu, Zhanpeng; Ru, Xiangkun; Peng, Hao; Xiong, Qi; Li, Hongjuan

2017-06-01

The effect of water chemistry on the electrochemical and oxidizing behaviors of 316L SS was investigated in hydrogenated, deaerated and oxygenated PWR primary water at 310 °C. Water chemistry significantly influenced the electrochemical impedance spectroscopy parameters. The highest charge-transfer resistance and oxide-film resistance occurred in oxygenated water. The highest electric double-layer capacitance and constant phase element of the oxide film were in hydrogenated water. The oxide films formed in deaerated and hydrogenated environments were similar in composition but different in morphology. An oxide film with spinel outer particles and a compact and Cr-rich inner layer was formed in both hydrogenated and deaerated water. Larger and more loosely distributed outer oxide particles were formed in deaerated water. In oxygenated water, an oxide film with hematite outer particles and a porous and Ni-rich inner layer was formed. The reaction kinetics parameters obtained by electrochemical impedance spectroscopy measurements and oxidation film properties relating to the steady or quasi-steady state conditions in the time-period of measurements could provide fundamental information for understanding stress corrosion cracking processes and controlling parameters.

Nutrient and trace-element enrichment of Coeur d'Alene Lake, Idaho

USGS Publications Warehouse

Woods, P.F.; Beckwith, M.A.

1996-01-01

The limnological characteristics and geochemistry of lakebed sediments in Coeur d'Alene Lake, a 129-square-kilometer, natural lake in northern Idaho, were assessed during 1991-92 because of the possible interaction of nutrient enrichment with the highly enriched trace-element concentrations stored in the lakebed. The lake was classified as oligotrophic during 1991-92 on the basis of annual geometric mean concentrations, in micrograms per liter, of total phosphorus (4.1), total nitrogen (247), and chlorophyll-a (0.54). Despite its oligotrophy, the lake developed a substantial hypolimnetic dissolved-oxygen deficit in both years during the later stage of thermal stratification. The lake's current trophic state of oligotrophic differs from the mesotrophic ranking it received in 1975 during the National Eutrophication Survey. The shift in trophic state was consistent with nutrient-load reductions that have occurred within the lake's 9,690-square-kilometer drainage basin since the early 1970's. Approximately 85 percent of the lakebed's surface area was highly enriched in antimony, arsenic, cadmium, lead, mercury, silver, and zinc. Mean total concentrations, in milligrams per kilogram, for cadmium, lead, and zinc in the enriched lakebed sediments were, respectively, 62, 1,900, and 3,600. In contrast, the concentrations of cadmium, lead, and zinc in unenriched lakebed sediments in the lake's southern end were, respec- tively, 2.8, 24, and 110 milligrams per kilogram. The vast majority of the trace elements in the surficial and subsurface sediments were associated with ferric oxides, not sulfides as previously postulated. Under reducing conditions, such as within as anoxic hypolimnon, the ferric oxide- associated trace elements would be readily soluble and available for release into the overlying water column. (USGS)

Persistent bacterial infections, antibiotic tolerance, and the oxidative stress response

PubMed Central

Grant, Sarah Schmidt; Hung, Deborah T.

2013-01-01

Certain bacterial pathogens are able to evade the host immune system and persist within the human host. The consequences of persistent bacterial infections potentially include increased morbidity and mortality from the infection itself as well as an increased risk of dissemination of disease. Eradication of persistent infections is difficult, often requiring prolonged or repeated courses of antibiotics. During persistent infections, a population or subpopulation of bacteria exists that is refractory to traditional antibiotics, possibly in a non-replicating or metabolically altered state. This review highlights the clinical significance of persistent infections and discusses different in vitro models used to investigate the altered physiology of bacteria during persistent infections. We specifically focus on recent work establishing increased protection against oxidative stress as a key element of the altered physiologic state across different in vitro models and pathogens. PMID:23563389

Hydrogen pickup mechanism of zirconium alloys

NASA Astrophysics Data System (ADS)

Couet, Adrien

Although the optimization of zirconium based alloys has led to significant improvements in hydrogen pickup and corrosion resistance, the mechanisms by which such alloy improvements occur are still not well understood. In an effort to understand such mechanisms, a systematic study of the alloy effect on hydrogen pickup is conducted, using advanced characterization techniques to rationalize precise measurements of hydrogen pickup. The hydrogen pick-up fraction is accurately measured for a specially designed set of commercial and model alloys to investigate the effects of alloying elements, microstructure and corrosion kinetics on hydrogen uptake. Two different techniques to measure hydrogen concentrations were used: a destructive technique, Vacuum Hot Extraction, and a non-destructive one, Cold Neutron Prompt Gamma Activation Analysis. The results indicate that hydrogen pickup varies not only from alloy to alloy but also during the corrosion process for a given alloy. For instance Zircaloy type alloys show high hydrogen pickup fraction and sub-parabolic oxidation kinetics whereas ZrNb alloys show lower hydrogen pickup fraction and close to parabolic oxidation kinetics. Hypothesis is made that hydrogen pickup result from the need to balance charge during the corrosion reaction, such that the pickup of hydrogen is directly related to (and indivisible of) the corrosion mechanism and decreases when the rate of electron transport or oxide electronic conductivity sigmao xe through the protective oxide increases. According to this hypothesis, alloying elements (either in solid solution or in precipitates) embedded in the oxide as well as space charge variations in the oxide would impact the hydrogen pick-up fraction by modifying sigmaox e, which drives oxidation and hydriding kinetics. Dedicated experiments and modelling were performed to assess and validate these hypotheses. In-situ electrochemical impedance spectroscopy (EIS) experiments were performed on Zircaloy-4 tubes to directly measure the evolution of sigma oxe as function of exposure time. The results show that sigmao xe decreases as function of exposure time and that its variations are directly correlated to the instantaneous hydrogen pickup fraction variations. The electron transport through the oxide layer is thus altered as the oxide grows, reasons for which are yet to be exactly determined. Preliminary results also show that sigma oxe of ZrNb alloys would be much higher compared with Zircaloy-4. Thus, it is confirmed that sigmaox e is a key parameter in the hydrogen and oxidation mechanism. Because the mechanism whereby alloying elements are incorporated into the oxide layer is critical to changing sigmao xe, the evolution of the oxidation state of two common alloying elements, Fe and Nb, when incorporated into the growing oxide layers is investigated using X-Ray Absorption Near-Edge Spectroscopy (XANES) using micro-beam synchrotron radiation on cross sectional oxide samples. The results show that the oxidation of both Fe and Nb is delayed in the oxide layer compared to that of Zr, and that this oxidation delay is related to the variations of the instantaneous hydrogen pick-up fraction with exposure time. The evolution of Nb oxidation as function of oxide depth is also compatible with space charge compensation in the oxide and with an increase in sigmaox e of ZrNb alloys compared to Zircaloys. Finally, various successively complex models from the well-known Wagner oxidation theory to the more complex effect of space charge on oxidation kinetics have been developed. The general purpose of the modeling effort is to provide a rationale for the sub-parabolic oxidation kinetics and demonstrate the correlation with hydrogen pickup fraction. It is directly demonstrated that parabolic oxidation kinetics is associated with high sigmao xe and low space charges in the oxide whereas sub-parabolic oxidation kinetics is associated with lower sigmaox e and higher space charge in the oxide. All these observations helped us to propose a general corrosion mechanism of zirconium alloys involving both oxidation and hydrogen pickup mechanism to better understand and predict the effect of alloying additions on the behavior of zirconium alloys.

Solid solutions of gadolinium doped zinc oxide nanorods by combined microwave-ultrasonic irradiation assisted crystallization

NASA Astrophysics Data System (ADS)

Kiani, Armin; Dastafkan, Kamran; Obeydavi, Ali; Rahimi, Mohammad

2017-12-01

Nanocrystalline solid solutions consisting of un-doped and gadolinium doped zinc oxide nanorods were fabricated by a modified sol-gel process utilizing combined ultrasonic-microwave irradiations. Polyvinylpyrrolidone, diethylene glycol, and triethylenetetramine respectively as capping, structure directing, and complexing agents were used under ultrasound dynamic aging and microwave heating to obtain crystalline nanorods. Crystalline phase monitoring, lattice parameters and variation, morphology and shape, elemental analysis, functional groups, reducibility, and the oxidation state of emerged species were examined by PXRD, FESEM, TEM, EDX, FTIR, micro Raman, H2-TPR, and EPR techniques. Results have verified that irradiation mechanism of gelation and crystallization reduces the reaction time, augments the crystal quality, and formation of hexagonal close pack structure of Wurtzite morphology. Besides, dissolution of gadolinium within host lattice involves lattice deformation, unit cell distortion, and angular position variation. Structure related shape and growth along with compositional purity were observed through microscopic and spectroscopic surveys. Furthermore, TPR and EPR studies elucidated more detailed behavior upon exposure to the exerted irradiations and subsequent air-annealing including the formed oxidation states and electron trapping centers, presence of gadolinium, zinc, and oxygen disarrays and defects, as well as alteration in the host unit cell via gadolinium addition.

Photoelectronic Properties of Ternary Niobium Oxides.

DTIC Science & Technology

1980-09-01

K . /Dwi ght ,. 1 d N0,OO0l4-77-C-0387 B . PERFORMING ORGAbi)ATi0N NAME AND ADZRESS 10. PROGRAM ELEMENT. PROIECT. TASK00 Po soArn odAREA a WORK UNIT...Kershaw, R.; Dwight, K .; Wold, A. J. Solid State Chem., 1979, 27, 307. 6. Salmon, 0. N.*J. Phys. Chem., 1961, 65, 550. 7. Koenitzer, J.; Khazai, B ...Ann. Rev. Phys. Chem., 197F, 29, 189. 10. Hormadaly, J.; Subbarao , S. N.; Kershaw, R.; Dwight, K .; Wold, A. J. Solid State Chem., to be published. 1.1

NOVEL OXIDANT FOR ELEMENTAL MERCURY CONTROL FROM FLUE GAS

EPA Science Inventory

A novel economical oxidant has been developed for elemental mercury (Hg(0)) removal from coal-fired boilers. The oxidant was rigorously tested in a lab-scale fixed-bed system with the Norit America's FGD activated carbon (DOE's benchmark sorbent) in a typical PRB subbituminous/l...

[Removal Characteristics of Elemental Mercury by Mn-Ce/molecular Sieve].

PubMed

Tan, Zeng-qiang; Niu, Guo-ping; Chen, Xiao-wen; An, Zhen

2015-06-01

The impregnation method was used to support molecular sieve with active manganese and cerium components to obtain a composite molecular sieve catalyst. The mercury removal performance of the catalyst was studied with a bench-scale setup. XPS analysis was used to characterize the sample before and after the modification in order to study the changes in the active components of the catalyst prepared. The results showed that the catalyst carrying manganese and cerium components had higher oxidation ability of elemental mercury in the temperature range of 300 degrees C - 450 degrees C, especially at 450 degrees C, the oxidation efficiency of elemental mercury was kept above 80%. The catalyst had more functional groups that were conducive to the oxidation of elemental mercury, and the mercury removal mainly depended on the chemical adsorption. The SO2 and NO in flue gas could inhibit the oxidation of elemental mercury to certain extent.

Data-driven exploration of copper mineralogy and its application to Earth's near-surface oxidation

NASA Astrophysics Data System (ADS)

Morrison, S. M.; Eleish, A.; Runyon, S.; Prabhu, A.; Fox, P. A.; Ralph, J.; Golden, J. J.; Downs, R. T.; Liu, C.; Meyer, M.; Hazen, R. M.

2017-12-01

Earth's atmospheric composition has changed radically throughout geologic history.1,2 The oxidation of our atmosphere, driven by biology, began with the Great Oxidation Event (GOE) 2.5 Ga and has heavily influenced Earth's near surface mineralogy. Therefore, temporal trends in mineral occurrence elucidate large and small scale geologic and biologic processes. Cu, and other first-row transition elements, are of particular interest due to their variation in valance state and sensitivity to ƒO2. Widespread formation of oxidized Cu mineral species (Cu2+) would not have been possible prior to the GOE and we have found that the proportion of oxidized Cu minerals increased steadily with the increase in atmospheric O2 on Earth's surface (see Fig. 1). To better characterize the changes in Cu mineralogy through time, we have employed advanced analytical and visualization methods. These techniques rely on large and growing mineral databases (e.g., rruff.info, mindat.org, earthchem.org, usgs.gov) and allow us to quantify and visualize multi-dimensional trends.5

Selenium as a versatile center in fluorescence probe for the redox cycle between HClO oxidative stress and H2S repair.

PubMed

Lou, Zhangrong; Li, Peng; Han, Keli

2015-01-01

Selenium is a biologically important trace element and acts as an active center of glutathione peroxidase (GPx). GPx is the important antioxidant enzyme to protect organisms from oxidative damage via catalyzing the reaction between ROS and glutathione (GSH). Mimicking the oxidation-reduction cycles of the versatile selenium core in GPx, we can develop fluorescence probes to detect oxidation and reduction events in living systems. The cellular redox balance between hypochloric acid (HClO) and hydrogen sulfide (H2S) has broad implications in human health and diseases, such as Alzheimer's disease (AD). Therefore, to further investigate the roles of this redox balance and understand the pathogenesis of neurodegenerative diseases, it is necessary to detect the redox state between HClO and H2S in real time. We have developed a reversible fluorescence probe MPhSe-BOD for imaging of the redox cycle between HClO and H2S based on oxidation and reduction of selenide in living cells.

High Performance Oxides-Based Thermoelectric Materials

NASA Astrophysics Data System (ADS)

Ren, Guangkun; Lan, Jinle; Zeng, Chengcheng; Liu, Yaochun; Zhan, Bin; Butt, Sajid; Lin, Yuan-Hua; Nan, Ce-Wen

2015-01-01

Thermoelectric materials have attracted much attention due to their applications in waste-heat recovery, power generation, and solid state cooling. In comparison with thermoelectric alloys, oxide semiconductors, which are thermally and chemically stable in air at high temperature, are regarded as the candidates for high-temperature thermoelectric applications. However, their figure-of-merit ZT value has remained low, around 0.1-0.4 for more than 20 years. The poor performance in oxides is ascribed to the low electrical conductivity and high thermal conductivity. Since the electrical transport properties in these thermoelectric oxides are strongly correlated, it is difficult to improve both the thermoelectric power and electrical conductivity simultaneously by conventional methods. This review summarizes recent progresses on high-performance oxide-based thermoelectric bulk-materials including n-type ZnO, SrTiO3, and In2O3, and p-type Ca3Co4O9, BiCuSeO, and NiO, enhanced by heavy-element doping, band engineering and nanostructuring.

Use of chemical mechanical polishing in micromachining

DOEpatents

Nasby, Robert D.; Hetherington, Dale L.; Sniegowski, Jeffry J.; McWhorter, Paul J.; Apblett, Christopher A.

1998-01-01

A process for removing topography effects during fabrication of micromachines. A sacrificial oxide layer is deposited over a level containing functional elements with etched valleys between the elements such that the sacrificial layer has sufficient thickness to fill the valleys and extend in thickness upwards to the extent that the lowest point on the upper surface of the oxide layer is at least as high as the top surface of the functional elements in the covered level. The sacrificial oxide layer is then polished down and planarized by chemical-mechanical polishing. Another layer of functional elements is then formed upon this new planarized surface.

Theory of superconductivity in oxides. Final technical report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, P.W.

1988-05-18

Progress was made towards a final theory of high-Tc superconductivity. The key elements are the work on normal-state properties and the actual mechanism for Tc. With the understanding (ZA) of the large anisotropy and other transport properties in the normal state, the model is uniquely determined: one must have one version or another of a holon-spinon quantum-fluid state, which is not a normal Fermi liquid. And with the recognition (HWA) of the large-repulsion holon-holon interactions, the author has the first way of thinking quantitatively about the superconducting state. Work on the pure Heisenberg system, which is related but not necessarilymore » crucial to understanding the superconducting properties is described.« less

Modern Material Analysis Instruments Add a New Dimension to Materials Characterization and Failure Analysis

NASA Technical Reports Server (NTRS)

Panda, Binayak

2009-01-01

Modern analytical tools can yield invaluable results during materials characterization and failure analysis. Scanning electron microscopes (SEMs) provide significant analytical capabilities, including angstrom-level resolution. These systems can be equipped with a silicon drift detector (SDD) for very fast yet precise analytical mapping of phases, as well as electron back-scattered diffraction (EBSD) units to map grain orientations, chambers that admit large samples, variable pressure for wet samples, and quantitative analysis software to examine phases. Advanced solid-state electronics have also improved surface and bulk analysis instruments: Secondary ion mass spectroscopy (SIMS) can quantitatively determine and map light elements such as hydrogen, lithium, and boron - with their isotopes. Its high sensitivity detects impurities at parts per billion (ppb) levels. X-ray photo-electron spectroscopy (XPS) can determine oxidation states of elements, as well as identifying polymers and measuring film thicknesses on coated composites. This technique is also known as electron spectroscopy for chemical analysis (ESCA). Scanning Auger electron spectroscopy (SAM) combines surface sensitivity, spatial lateral resolution (10 nm), and depth profiling capabilities to describe elemental compositions of near and below surface regions down to the chemical state of an atom.

Sulfur formation by steady-state continuous cultures of a sulfoxidizing consortium and Thiobacillus thioparus ATCC 23645.

PubMed

Alcántara, S; Velasco, A; Revah, S

2004-10-01

The elemental sulfur formation by the partial oxidation of thiosulfate by both a sulfoxidizing consortium and by Thiobacillus thioparus ATCC 23645 was studied under aerobic conditions in chemostat. Steady state was attained with essentially total conversion to sulfate when the dissolved oxygen concentration was 5 mgO2 l(-1) and below a dilution rate (D) of 3.0 d(-1)for the consortium and 0.9 d(-1) for T thioparus. The consortium formed elemental sulfur in steady state under oxygen limitation. Fifty percent of the theoretical elemental sulfur yield was obtained with a dissolved oxygen concentration of 0.2 mgO2 l(-1). Growth of T thioparus was negatively affected with a concentration below 1.9 mgO2 l(-1). Consortium yield from batch cultures was 2.1 g(-1) (protein) mol(-1) (thiosulfate), which was comparable with the values obtained in the chemostat at dilution rates of 0.4 d(-1) and 1.2 d(-1). The consortium showed a maximum degradation rate of 0.105 g(thiosulfate) g(-1) (protein) min(-1) and a saturation rate for S2O3(2-) of 1.9 mM.

Assessing the oxidation states and structural stability of the Ce analogue of brannerite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aluri, Esther Rani; Bachiu, Lisa M.; Grosvenor, Andrew P.

2017-07-04

The Ce-containing analogue of brannerite (ie, UTi2O6) was previously considered to be stoichiometric (ie, CeTi2O6); however, it has recently been determined that the material is O deficient. This oxygen-deficient material has been suggested to be charged balanced by the presence of a minor concentration of Ce3+ or by the A-site being cation deficient with the Ce oxidation state being 4+. A variety of Ti-containing oxides (including brannerite) have been investigated as potential nuclear wasteforms, and it is necessary to understand the electronic structure of a proposed nuclear wasteform material as well as how the structure responds to radiation from incorporatedmore » waste elements. The radiation resistance of a material can be simulated by ion implantation. The objective of this study was to confirm the Ce oxidation state in the cation- and oxygen-deficient material (ie, Ce0.94Ti2O6 - δ) and to determine how radiation damage affects this material. X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge spectroscopy were used to study Ce0.94Ti2O6 - δ before and after being implanted with 2 MeV Au- ions. Analysis of the Ce 3d XPS spectra from the as-synthesized samples by using a previously developed fitting method has unequivocally shown that Ce adopts both 4+ (major) and 3+ (minor) oxidation states, which was confirmed by examination of magnetic susceptibility data. Analysis of XPS and X-ray absorption near-edge spectroscopy spectra from ion-implanted materials showed that both Ce and Ti were reduced because of radiation damage and that the local coordination environments of the cations are greatly affected by radiation damage.« less

Method for combined removal of mercury and nitrogen oxides from off-gas streams

DOEpatents

Mendelsohn, Marshall H [Downers Grove, IL; Livengood, C David [Lockport, IL

2006-10-10

A method for removing elemental Hg and nitric oxide simultaneously from a gas stream is provided whereby the gas stream is reacted with gaseous chlorinated compound to convert the elemental mercury to soluble mercury compounds and the nitric oxide to nitrogen dioxide. The method works to remove either mercury or nitrogen oxide in the absence or presence of each other.

Oxidation of hydrogen halides to elemental halogens

DOEpatents

Rohrmann, Charles A.; Fullam, Harold T.

1985-01-01

A process for oxidizing hydrogen halides having substantially no sulfur impurities by means of a catalytically active molten salt is disclosed. A mixture of the subject hydrogen halide and an oxygen bearing gas is contacted with a molten salt containing an oxidizing catalyst and alkali metal normal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen and substantially free of sulfur oxide gases.

Ferroelectric capacitor with reduced imprint

DOEpatents

Evans, Jr., Joseph T.; Warren, William L.; Tuttle, Bruce A.; Dimos, Duane B.; Pike, Gordon E.

1997-01-01

An improved ferroelectric capacitor exhibiting reduced imprint effects in comparison to prior art capacitors. A capacitor according to the present invention includes top and bottom electrodes and a ferroelectric layer sandwiched between the top and bottom electrodes, the ferroelectric layer comprising a perovskite structure of the chemical composition ABO.sub.3 wherein the B-site comprises first and second elements and a dopant element that has an oxidation state greater than +4. The concentration of the dopant is sufficient to reduce shifts in the coercive voltage of the capacitor with time. In the preferred embodiment of the present invention, the ferroelectric element comprises Pb in the A-site, and the first and second elements are Zr and Ti, respectively. The preferred dopant is chosen from the group consisting of Niobium, Tantalum, and Tungsten. In the preferred embodiment of the present invention, the dopant occupies between 1 and 8% of the B-sites.

Oxidation corrosion resistant superalloys and coatings

NASA Technical Reports Server (NTRS)

Jackson, Melvin R. (Inventor); Rairden, III, John R. (Inventor)

1978-01-01

An article of manufacture having improved high temperature oxidation and corrosion resistance comprising: (a) a superalloy substrate containing a carbide reinforcing phase, and (b) a coating consisting of chromium, aluminum, carbon, at least one element selected from iron, cobalt or nickel, and optionally an element selected from yttrium or the rare earth elements.

Oxidation corrosion resistant superalloys and coatings

NASA Technical Reports Server (NTRS)

Jackson, Melvin R. (Inventor); Rairden, III, John R. (Inventor)

1980-01-01

An article of manufacture having improved high temperature oxidation and corrosion resistance comprising: (a) a superalloy substrate containing a carbide reinforcing phase, and (b) a coating consisting of chromium, aluminum, carbon, at least one element selected from iron, cobalt or nickel, and optionally an element selected from yttrium or the rare earth elements.

New functionalities in abundant element oxides: ubiquitous element strategy

PubMed Central

Hosono, Hideo; Hayashi, Katsuro; Kamiya, Toshio; Atou, Toshiyuki; Susaki, Tomofumi

2011-01-01

While most ceramics are composed of ubiquitous elements (the ten most abundant elements within the Earth's crust), many advanced materials are based on rare elements. A ‘rare-element crisis’ is approaching owing to the imbalance between the limited supply of rare elements and the increasing demand. Therefore, we propose a ‘ubiquitous element strategy’ for materials research, which aims to apply abundant elements in a variety of innovative applications. Creation of innovative oxide materials and devices based on conventional ceramics is one specific challenge. This review describes the concept of ubiquitous element strategy and gives some highlights of our recent research on the synthesis of electronic, thermionic and structural materials using ubiquitous elements. PMID:27877391

Timing the oxidation of Earth's crust: Evidence from big data records of manganese mineralization

NASA Astrophysics Data System (ADS)

Hummer, D. R.; Golden, J. J.; Hystad, G.; Downs, R. T.; Eleish, A.; Liu, C.; Ralph, J.; Morrison, S.; Meyer, M.; Hazen, R. M.

2017-12-01

A great deal of work has focused on unravelling the oxygenation of Earth's early atmosphere and oceans, which took place during and after the Great Oxidation Event (1). Recently, field and experimental methods have also been used to examine the timing of mantle oxidation, especially near subduction zones (2). However, very little information is available on the timing of crustal oxidation. To examine the oxidation of Earth's shallow crust, we analyzed records of manganese (Mn) mineral occurrences across geologic time from a database of 2666 mineral-locality data pairs (mindat.org as of 20 Nov. 2015) that had associated geologic ages in the literature. Manganese is a redox-sensitive transition element with oxidation states of +2, +3, and +4, whose average oxidation state in the geologic record can be used as a proxy for the oxygenation of the shallow crust, where Mn mineralization typically occurs. Analysis revealed that Mn mineralization older than 600 Ma contained mostly Mn2+ mineral species, with isolated localities containing Mn3+ and Mn4+ species. During the Phanerozoic, the average oxidation state of Mn follows the same trend as reconstructions of atmospheric oxygen (3), but on a 66+1 Myr delay (as calculated using a least squares fitting procedure). This contrasts with a delay of hundreds of millions of years for the oxidation of molybdenum, which forms much deeper in the crust (4). We interpret these time lags as the time necessary to equilibrate various crustal depths to atmospheric oxygen fugacity through infiltration of oxidizing fluids and tectonic mixing processes. Analysis of other redox-sensitive transition metals (such as Cr, V, and Fe) using big data techniques may reveal a strategy for timing the oxidation of different portions of Earth's crust. (1) T.W. Lyons, C.T. Reinhard, N.J. Planavsky, Nature 506, 307-315 (2014). (2) M. Brounce, et al. Geology 43, 775-778 (2015). (3) N.M. Bergman, T.M. Lenton, A.J. Watson, Am. J. Sci. 304, 397-437 (2004). (4) J.J. Golden, et al. EPSL 366, 1-5 (2013).

Microwave Detection of Chemical Agents: A Review

DTIC Science & Technology

1986-06-01

Health (NIOSH).8’l1 This instrument was designed to detect acetonitrile, acetaldehyde , acetone, carbonyl sulfide, ethanol, ethylene oxide , isopropyl...absolute temperature mij - the dipole matrix element connecting the upper and lower energy states vo = the absorption line center v - transition...from multiple reflections through the cell. The Q of a cavity is defined as the electro - magnetic energy in the cavity divided by the energy lost per

Use of chemical mechanical polishing in micromachining

DOEpatents

Nasby, R.D.; Hetherington, D.L.; Sniegowski, J.J.; McWhorter, P.J.; Apblett, C.A.

1998-09-08

A process for removing topography effects during fabrication of micromachines. A sacrificial oxide layer is deposited over a level containing functional elements with etched valleys between the elements such that the sacrificial layer has sufficient thickness to fill the valleys and extend in thickness upwards to the extent that the lowest point on the upper surface of the oxide layer is at least as high as the top surface of the functional elements in the covered level. The sacrificial oxide layer is then polished down and planarized by chemical-mechanical polishing. Another layer of functional elements is then formed upon this new planarized surface. 4 figs.

Association of Serum Concentration of Different Trace Elements with Biomarkers of Systemic Oxidant Status in Dairy Cattle.

PubMed

Abuelo, Angel; Hernandez, Joaquín; Alves-Nores, Víctor; Benedito, José L; Castillo, Cristina

2016-12-01

There has been some recent criticism about the reliability of the assays commonly used to measure oxidant status in cattle, because some recent publications suggested that the concentration of different trace elements influences the results of these assays. The aim of this study was to test the correlation in 502 bovine serum samples between the concentration of several trace elements (Br, Co, Cr, Cu, Fe, I, Mn, Mo, Ni, Se, Sr, V and Zn) and markers of oxidant status (reactive oxygen species (ROS) and total serum antioxidant capacity (SAC)). The Oxidative Stress index (OSi) was also calculated as ROS/SAC. Some significant correlations were found, although weak (|ρ| < 0.50). Therefore, the relationships observed might be attributed to the different pro- and antioxidant effect of the different elements rather than to the assays detecting these elements instead of the oxidised molecules or total antioxidant potential, respectively. The OSi was poorly correlated (|ρ| ≤ 0.36) with the concentration of the studied trace elements, and therefore, its use is recommended to assess shifts in the systemic redox balance.

Trace elements are associated with urinary 8-hydroxy-2'-deoxyguanosine level: a case study of college students in Guangzhou, China.

PubMed

Lu, Shaoyou; Ren, Lu; Fang, Jianzhang; Ji, Jiajia; Liu, Guihua; Zhang, Jianqing; Zhang, Huimin; Luo, Ruorong; Lin, Kai; Fan, Ruifang

2016-05-01

Many trace heavy elements are carcinogenic and increase the incidence of cancer. However, a comprehensive study of the correlation between multiple trace elements and DNA oxidative damage is still lacking. The aim of this study is to investigate the relationships between the body burden of multiple trace elements and DNA oxidative stress in college students in Guangzhou, China. Seventeen trace elements in urine samples were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Urinary 8-hydroxy-2'-deoxyguanosine (8-OHdG), a biomarker of DNA oxidative stress, was also measured using liquid chromatography tandem mass spectrometer (LC-MS/MS). The concentrations of six essential elements including manganese (Mn), copper (Cu), nickel (Ni), selenium (Se), strontium (Sr), and molybdenum (Mo), and five non-essential elements including arsenic (As), cadmium (Cd), aluminum (Al), stibium (Sb), and thallium (Tl), were found to be significantly correlated with urinary 8-OHdG levels. Moreover, urinary levels of Ni, Se, Mo, As, Sr, and Tl were strongly significantly correlated with 8-OHdG (P < 0.01) concentration. Environmental exposure and dietary intake of these trace elements may play important roles in DNA oxidative damage in the population of Guangzhou, China.

Tissue-Specific Regulation of the Contents and Correlations of Mineral Elements in Hens by Zinc Oxide Nanoparticles.

PubMed

Zhao, Yong; Feng, Yan-Ni; Li, Lan; Zhang, Hong-Fu; Zhang, Yu-Na; Zhang, Peng-Fei; Liu, Xin-Qi; Zhang, Wei-Dong; Huang, Ting-Ting; Zhao, Li; Shen, Wei; Hao, Zhi-Hui

2017-06-01

Due to their small size, zinc oxide (ZnO) nanoparticles (NPs) are readily absorbed and easily cross biological barriers, which make them promising candidates as diet additives. However, some studies have reported that ZnO NPs cause toxicity; therefore, their safety and potency as diet additives for farm animals should be established. This study was the first to fully evaluate the effects of ZnO NPs on the homeostasis of eight elements in seven organs/tissues. The regulation of element homeostasis was found to be organ specific with no influence on oxidation status, anti-oxidation capability, or organ damage. ZnO NPs may specifically regulate the homeostasis of mineral elements and affect the following correlations: (1) between the element content in each organ and the concentration of Zn used in ZnSO 4 or ZnO NP treatments; (2) between ZnO NP and ZnSO 4 treatments for the same element in each organ; and (3) between elements (in each organ in ZnSO 4 or ZnO NP treatments) in layers' organs/tissues. The use of ZnO NPs as diet additives for animals should be implemented cautiously because, among other uncertainties, they may affect mineral element content.

A stable silicon(0) compound with a Si=Si double bond.

PubMed

Wang, Yuzhong; Xie, Yaoming; Wei, Pingrong; King, R Bruce; Schaefer, Henry F; von R Schleyer, Paul; Robinson, Gregory H

2008-08-22

Dative, or nonoxidative, ligand coordination is common in transition metal complexes; however, this bonding motif is rare in compounds of main group elements in the formal oxidation state of zero. Here, we report that the potassium graphite reduction of the neutral hypervalent silicon-carbene complex L:SiCl4 {where L: is:C[N(2,6-Pri2-C6H3)CH]2 and Pri is isopropyl} produces L:(Cl)Si-Si(Cl):L, a carbene-stabilized bis-silylene, and L:Si=Si:L, a carbene-stabilized diatomic silicon molecule with the Si atoms in the formal oxidation state of zero. The Si-Si bond distance of 2.2294 +/- 0.0011 (standard deviation) angstroms in L:Si=Si:L is consistent with a Si=Si double bond. Complementary computational studies confirm the nature of the bonding in L:(Cl)Si-Si(Cl):L and L:Si=Si:L.

Electrical characteristics and thermal stability of HfO{sub 2} metal-oxide-semiconductor capacitors fabricated on clean reconstructed GaSb surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miyata, Noriyuki, E-mail: nori.miyata@aist.go.jp; Mori, Takahiro; Yasuda, Tetsuji

2014-06-09

HfO{sub 2}/GaSb interfaces fabricated by high-vacuum HfO{sub 2} deposition on clean reconstructed GaSb surfaces were examined to explore a thermally stable GaSb metal-oxide-semiconductor structure with low interface-state density (D{sub it}). Interface Sb-O bonds were electrically and thermally unstable, and post-metallization annealing at temperatures higher than 200 °C was required to stabilize the HfO{sub 2}/GaSb interfaces. However, the annealing led to large D{sub it} in the upper-half band gap. We propose that the decomposition products that are associated with elemental Sb atoms act as interface states, since a clear correlation between the D{sub it} and the Sb coverage on the initial GaSbmore » surfaces was observed.« less

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

PubMed

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.

Interplay of water and reactive elements in oxidation of alumina-forming alloys.

PubMed

Mortazavi, N; Geers, C; Esmaily, M; Babic, V; Sattari, M; Lindgren, K; Malmberg, P; Jönsson, B; Halvarsson, M; Svensson, J E; Panas, I; Johansson, L G

2018-06-11

High-temperature alloys are crucial to many important technologies that underpin our civilization. All these materials rely on forming an external oxide layer (scale) for corrosion protection. Despite decades of research on oxide scale growth, many open questions remain, including the crucial role of the so-called reactive elements and water. Here, we reveal the hitherto unknown interplay between reactive elements and water during alumina scale growth, causing a metastable 'messy' nano-structured alumina layer to form. We propose that reactive-element-decorated, hydroxylated interfaces between alumina nanograins enable water to access an inner cathode in the bottom of the scale, at odds with the established scale growth scenario. As evidence, hydride-nanodomains and reactive element/hydrogen (deuterium) co-variation are observed in the alumina scale. The defect-rich alumina subsequently recrystallizes to form a protective scale. First-principles modelling is also performed to validate the RE effect. Our findings open up promising avenues in oxidation research and suggest ways to improve alloy properties.

Sulfur isotopic evidence for the origin of elemental sulfur in gas hydrate-bearing sediments of the northern South China Sea

NASA Astrophysics Data System (ADS)

Lin, Zhiyong; Sun, Xiaoming; Strauss, Harald; Lu, Yang; Xu, Li; Lu, Hongfeng; Teichert, Barbara M. A.; Peckmann, Jörn

2017-04-01

Elemental sulfur is a common intermediate in the sulfur cycle and contributes significantly to the fractionation of stable sulfur isotopes in different reservoirs in shelfal marine sediments (e.g., Canfield and Thamdrup, 1994). However, no study dedicated to the isotopic composition of elemental sulfur in seep environments has been conducted to the best of our knowledge, thus limiting further insight into the biochemical pathways involving elemental sulfur in such environments. In this study, elemental sulfur and pyrite were extracted from the sediment of a 200-m long gas hydrate-bearing core, which was obtained from the gas hydrate drilling expedition to the northern South China Sea in 2013 (Zhang et al., 2015). The sulfur isotopic composition of elemental sulfur was found to vary from -16 to +23 per mill, and pyrite yielded values ranging from -34 to +18 per mill. Interestingly, elemental sulfur revealed higher 34S contents (up to 30 per mill) than the associated pyrite in most sediment layers. Since elemental sulfur is only produced during oxidative pathways in the sulfur cycle, the studied elemental sulfur apparently represents the oxidation product of hydrogen sulfide by various electron acceptors such as Mn(IV) oxides or Fe(III) oxides (e.g., Thamdrup et al., 1993; Yao and Millero, 1996). Since there is little sulfur isotope fractionation for oxidative processes (Fry et al., 1986), the enrichment of elemental sulfur in 34S points to a pool of hydrogen sulfide depleted in 32S, which is best interpreted to result from sulfate-driven anaerobic oxidation of methane. References: Canfield D.E. and Thamdrup B. (1994) The production of 34S-depleted sulfide during bacterial disproportionation of elemental sulfur. Science 266, 1973. Fry B., Cox J., Gest H. and Hayer J.M. (1986) Discrimination between 34S and32S during bacterial metabolism of inorganic sulfur compounds. J. Bacteriol. 165, 328-330. Thamdrup B., Finster K., Hansen W. and Bak F. (1993) Bacterial disproportionation of elemental sulfur coupled to chemical reduction of iron and manganese. Appl. Env. Microbiol. 59, 101-108. Yao W. and Millero F.J. (1996) Oxidation of hydrogen sulfide by hydrous Fe(III) oxides in seawater. Mar. Chem. 52, 1-16. Zhang G., Liang J., Lu J.A., Yang S., Zhang M., Holland M., Schultheiss P., Su X., Sha Z., Xu H., Gong Y., Fu S., Wang L. and Kuang Z. (2015) Geological features, controlling factors and potential prospects of the gas hydrate occurrence in the east part of the Pearl River Mouth Basin, South China Sea. Mar. Pet. Geol. 67, 356-367.

Microstructure, ferromagnetic and photoluminescence properties of ITO and Cr doped ITO nanoparticles using solid state reaction

NASA Astrophysics Data System (ADS)

Babu, S. Harinath; Kaleemulla, S.; Rao, N. Madhusudhana; Rao, G. Venugopal; Krishnamoorthi, C.

2016-11-01

Indium-tin-oxide (ITO) (In0.95Sn0.05)2O3 and Cr doped indium-tin-oxide (In0.90Sn0.05Cr0.05)2O3 nanoparticles were prepared using simple low cost solid state reaction method and characterized by different techniques to study their structural, optical and magnetic properties. Microstructures, surface morphology, crystallite size of the nanoparticles were studied using X-ray diffractometer (XRD), field emission scanning electron microscope (FE-SEM). From these methods it was found that the particles were about 45 nm. Chemical composition and valence states of the nanoparticles were studied using energy dispersive analysis of X-rays (EDAX) and X-ray photoelectron spectroscopy (XPS). From these techniques it was observed that the elements of indium, tin, chromium and oxygen were present in the system in appropriate ratios and they were in +3, +4, +3 and -2 oxidation states. Raman studies confirmed that the nanoparticle were free from unintentional impurities. Two broad emission peaks were observed at 330 nm and 460 nm when excited wavelength of 300 nm. Magnetic studies were carried out at 300 K and 100 K using vibrating sample magnetometer (VSM) and found that the ITO nanoparticles were ferromagnetic at 100 K and 300 K. Where-as the room temperature ferromagnetism completely disappeared in Cr doped ITO nanoparticles at 100 K and 300 K.

Oxidation state inherited from the magma source and implications for mineralization: Late Jurassic to Early Cretaceous granitoids, Central Lhasa subterrane, Tibet

NASA Astrophysics Data System (ADS)

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 exploration context for the west Central Lhasa subterrane, features indicative of potential fertility might include more oxidized, positive ɛHf(t), young rocks (<130 Ma).

Self-assembly of a tetrahedral 58-nuclear barium vanadium oxide cluster.

PubMed

Kastner, Katharina; Puscher, Bianka; Streb, Carsten

2013-01-07

We report the synthesis and characterization of a molecular barium vanadium oxide cluster featuring high nuclearity and high symmetry. The tetrameric, 2.3 nm cluster H(5)[Ba(10)(NMP)(14)(H(2)O)(8)[V(12)O(33)](4)Br] is based on a bromide-centred, octahedral barium scaffold which is capped by four previously unknown [V(12)O(33)](6-) clusters in a tetrahedral fashion. The compound represents the largest polyoxovanadate-based heterometallic cluster known to date. The cluster is formed in organic solution and it is suggested that the bulky N-methyl-2-pyrrolidone (NMP) solvent ligands allow the isolation of this giant molecule and prevent further condensation to a solid-state metal oxide. The cluster is fully characterized using single-crystal XRD, elemental analysis, ESI mass spectrometry and other spectroscopic techniques.

Biogeochemical cycles of carbon, sulfur, and free oxygen in a microbial mat

NASA Technical Reports Server (NTRS)

Canfield, Donald E.; Des Marais, David J.

1993-01-01

Complete budgets for carbon and oxygen have been constructed for cyanobacterial mats dominated by Microcoleus chthonoplastes from the evaporating ponds of a salt works. We infer from the data the various sinks for O2 as well as the sources of carbon for primary production. Although seasonal variability exists, a major percentage of the O2 produced during the day did not diffuse out of the mat but was used within the mat to oxidize both organic carbon and the sulfide produced by sulfate reduction. At night, most of the O2 that diffused into the mat was used to oxidize sulfide, with O2 respiration of minor importance. During the day, the internal mat processes of sulfate reduction and O2 respiration generated as much or more inorganic carbon (DIC) for primary production as diffusion into the mat. Oxygenic photosynthesis was the most important process of carbon fixation. At night, the DIC lost from the mat was mostly from sulfate reduction. Elemental fluxes across the mat/brine interface indicated that carbon with an oxidation state of greater than zero was taken up by the mat during the day and liberated from the mat at night. Overall, carbon with an average oxidation state of near zero accumulated in the mat. Both carbon fixation and carbon oxidation rates varied with temperature by a similar amount.

Acidithiobacillus caldus Sulfur Oxidation Model Based on Transcriptome Analysis between the Wild Type and Sulfur Oxygenase Reductase Defective Mutant

PubMed Central

Chen, Linxu; Ren, Yilin; Lin, Jianqun; Liu, Xiangmei; Pang, Xin; Lin, Jianqiang

2012-01-01

Background Acidithiobacillus caldus (A. caldus) is widely used in bio-leaching. It gains energy and electrons from oxidation of elemental sulfur and reduced inorganic sulfur compounds (RISCs) for carbon dioxide fixation and growth. Genomic analyses suggest that its sulfur oxidation system involves a truncated sulfur oxidation (Sox) system (omitting SoxCD), non-Sox sulfur oxidation system similar to the sulfur oxidation in A. ferrooxidans, and sulfur oxygenase reductase (SOR). The complexity of the sulfur oxidation system of A. caldus generates a big obstacle on the research of its sulfur oxidation mechanism. However, the development of genetic manipulation method for A. caldus in recent years provides powerful tools for constructing genetic mutants to study the sulfur oxidation system. Results An A. caldus mutant lacking the sulfur oxygenase reductase gene (sor) was created and its growth abilities were measured in media using elemental sulfur (S0) and tetrathionate (K2S4O6) as the substrates, respectively. Then, comparative transcriptome analysis (microarrays and real-time quantitative PCR) of the wild type and the Δsor mutant in S0 and K2S4O6 media were employed to detect the differentially expressed genes involved in sulfur oxidation. SOR was concluded to oxidize the cytoplasmic elemental sulfur, but could not couple the sulfur oxidation with the electron transfer chain or substrate-level phosphorylation. Other elemental sulfur oxidation pathways including sulfur diooxygenase (SDO) and heterodisulfide reductase (HDR), the truncated Sox pathway, and the S4I pathway for hydrolysis of tetrathionate and oxidation of thiosulfate in A. caldus are proposed according to expression patterns of sulfur oxidation genes and growth abilities of the wild type and the mutant in different substrates media. Conclusion An integrated sulfur oxidation model with various sulfur oxidation pathways of A. caldus is proposed and the features of this model are summarized. PMID:22984393

Molybdenum Valence in Basaltic Silicate Melts

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Righter, K.; Newville, M.; Sutton, S.; Pando, K.

2010-01-01

The moderately siderophile element molybdenum has been used as an indicator in planetary differentiation processes, and is particularly relevant to core formation [for example, 1-6]. However, models that apply experimental data to an equilibrium differentiation scenario infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Partitioning behavior of molybdenum, a multivalent element with a transition near the J02 of interest for core formation (IW-2) will be sensitive to changes in JO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo6+ can be either octahedrally or tetrahedrally coordinated. Here we present first XANES measurements of Mo valence in basaltic run products at a range of P, T, and JO2 and further quantify the valence transition of Mo.

Encapsulation of high temperature thermoelectric modules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Salvador, James R.; Sakamoto, Jeffrey; Park, Youngsam

A method of encapsulating a thermoelectric device and its associated thermoelectric elements in an inert atmosphere and a thermoelectric device fabricated by such method are described. These thermoelectric devices may be intended for use under conditions which would otherwise promote oxidation of the thermoelectric elements. The capsule is formed by securing a suitably-sized thin-walled strip of oxidation-resistant metal to the ceramic substrates which support the thermoelectric elements. The thin-walled metal strip is positioned to enclose the edges of the thermoelectric device and is secured to the substrates using gap-filling materials. The strip, substrates and gap-filling materials cooperatively encapsulate the thermoelectricmore » elements and exclude oxygen and water vapor from atmospheric air so that the elements may be maintained in an inert, non-oxidizing environment.« less

Oxide-based method of making compound semiconductor films and making related electronic devices

DOEpatents

Kapur, Vijay K.; Basol, Bulent M.; Leidholm, Craig R.; Roe, Robert A.

2000-01-01

A method for forming a compound film includes the steps of preparing a source material, depositing the source material on a base and forming a preparatory film from the source material, heating the preparatory film in a suitable atmosphere to form a precursor film, and providing suitable material to said precursor film to form the compound film. The source material includes oxide-containing particles including Group IB and IIIA elements. The precursor film includes non-oxide Group IB and IIIA elements. The compound film includes a Group IB-IIIA-VIA compound. The oxides may constitute greater than about 95 molar percent of the Group IB elements and greater than about 95 molar percent of the Group IIIA elements in the source material. Similarly, non-oxides may constitute greater than about 95 molar percent of the Group IB elements and greater than about 95 molar percent of the Group IIIA elements in the precursor film. The molar ratio of Group IB to Group IIIA elements in the source material may be greater than about 0.6 and less than about 1.0, or substantially greater that 1.0, in which case this ratio in the compound film may be reduced to greater than about 0.6 and less than about 1.0. The source material may be prepared as an ink from particles in powder form. The oxide-containing particles may include a dopant, as may the compound film. Compound films including a Group IIB-IVA-VA compound may be substituted using appropriate substitutions in the method. The method, also, is applicable to fabrication of solar cells and other electronic devices.

Method for production of magnesium

DOEpatents

Diaz, Alexander F.; Howard, Jack B.; Modestino, Anthony J.; Peters, William A.

1998-01-01

A continuous process for the production of elemental magnesium is described. Magnesium is made from magnesium oxide and a light hydrocarbon gas. In the process, a feed stream of the magnesium oxide and gas is continuously fed into a reaction zone. There the magnesium oxide and gas are reacted at a temperature of about 1400.degree. C. or greater in the reaction zone to provide a continuous product stream of reaction products, which include elemental magnesium. The product stream is continuously quenched after leaving the reaction zone, and the elemental magnesium is separated from other reaction products.

Method for production of magnesium

DOEpatents

Diaz, A.F.; Howard, J.B.; Modestino, A.J.; Peters, W.A.

1998-07-21

A continuous process for the production of elemental magnesium is described. Magnesium is made from magnesium oxide and a light hydrocarbon gas. In the process, a feed stream of the magnesium oxide and gas is continuously fed into a reaction zone. There the magnesium oxide and gas are reacted at a temperature of about 1400 C or greater in the reaction zone to provide a continuous product stream of reaction products, which include elemental magnesium. The product stream is continuously quenched after leaving the reaction zone, and the elemental magnesium is separated from other reaction products. 12 figs.

Thermal stability and reduction of iron oxide nanowires at moderate temperatures.

PubMed

Paolone, Annalisa; Angelucci, Marco; Panero, Stefania; Betti, Maria Grazia; Mariani, Carlo

2014-01-01

The thermal stability of iron oxide nanowires, which were obtained with a hard template method and are promising elements of Li-ion based batteries, has been investigated by means of thermogravimetry, infrared and photoemission spectroscopy measurements. The chemical state of the nanowires is typical of the Fe2O3 phase and the stoichiometry changes towards a Fe3O4 phase by annealing above 440 K. The shape and morphology of the nanowires is not modified by moderate thermal treatment, as imaged by scanning electron microscopy. This complementary spectroscopy-microscopy study allows to assess the temperature limits of these Fe2O3 nanowires during operation, malfunctioning or abuse in advanced Li-ion based batteries.

Enrichment mechanisms of tellurium in ferromanganese crusts

NASA Astrophysics Data System (ADS)

Sakaguchi, A.; Sugiyama, T.; Usui, A.; Takahashi, Y.

2012-04-01

Marine ferromanganese crusts (FMCs) consist of iron (Fe) hydroxides and manganese (Mn) oxides with various minor and trace elements. Especially for tellurium (Te), which is recognized as one of the rare metals, it has been reported that this element is concentrated about 105 times in FMCs compared with earth's crust, and the host phase might be Fe (oxy)hydroxide (Hein et al., 2003). Actually, in our previous study, the high concentration of Te in very surface layers of FMCs was found from the top to halfway down of a seamount in the Pacific Ocean. However, the concentration of Te in surface layers through the seamount showed good correlation with that of Mn instead of Fe. In this study, we attempted to clarify the enrichment mechanism of Te in FMCs with some methods including X-ray absorption fine structure (XAFS) technique for synthesised /natural samples. Seventeen FMC samples were collected from the Takuyo-Daigo seamount, from 950 m (summit) to 3000 m in water depth, with hyper-dolphin (remotely operated vehicle) equipped with live video camera and manipulators. The growth rates of all FMC samples were estimated to be about 3 mm/Ma. Very surface layer (less than 1 mm) of all FMC was analyzed with XRD and XAFS to confirm the mineral composition and speciation of Te. Furthermore, to serve as an aid to clarify the adsorption mechanism of Te on FMCs, distribution coefficients (Kd) and oxidation states were determined through the adsorption experiments of Te(IV) and Te(VI) on ferrihydrite and δ-MnO2. In all the experiments, pH and ionic strength were adjusted to pH 7.5 and 0.7 M, respectively. The oxidation state of Te in water phase was determined with HPLC-ICP-MS. As for the analysis of oxidation and adsorption states on the solid phase, XAFS was employed. The major mineral composition of Fe and Mn had no significant variation through the water depth of Takuyo-Daigo seamount. The oxidation state of Te in all samples showed hexavalent, and there was no significant difference of adsorption state independent of the DO, salinity and temperature in water. It has been reported that Te exists as tetravalent and hexavalent in sea water of the Pacific Ocean (Nozaki, 1996). Thus, it can be said that the Te in sea water is oxidised and incorporated into FMCs. As a result of the adsorption experiments in laboratory, the Kd of Te on ferrihydrite was larger than that of δ-MnO2, and Te(IV) was adsorbed to a larger degree than Te(VI) on both minerals. The adsorption experiments of Te(IV) on δ-MnO2 showed that the solid phase has only hexavalent Te, although the water phase has both tetra and hexavalent species of Te. Te(IV) on ferrihydrite was not oxidized to Te(VI). From these results, it can be suggested that Te(IV) was oxidized by δ-MnO2 and would be adsorbed onto ferrihydrite. Actually, the results of double-cell adsorption experiments support this hypothesis. The detail of our results and discussion will be given in the presentation.

Electron spectroscopy imaging and surface defect configuration of zinc oxide nanostructures under different annealing ambient

NASA Astrophysics Data System (ADS)

Ann, Ling Chuo; Mahmud, Shahrom; Bakhori, Siti Khadijah Mohd

2013-01-01

In this study, electron spectroscopy imaging was used to visualize the elemental distribution of zinc oxide nanopowder. Surface modification in zinc oxide was done through annealing treatment and type of surface defect was also inferred from the electron spectroscopy imaging investigation. The micrographs revealed the non-stoichiometric distribution of the elements in the unannealed samples. Annealing the samples in nitrogen and oxygen ambient at 700 °C would alter the density of the elements in the samples as a result of removal or absorption of oxygen. The electrical measurement showed that nitrogen annealing treatment improved surface electrical conductivity, whereas oxygen treatment showed an adverse effect. Observed change in the photoluminescence green emission suggested that oxygen vacancies play a significant role as surface defects. Structural investigation carried out through X-ray diffraction revealed the polycrystalline nature of both zinc oxide samples with hexagonal phase whereby annealing process increased the crystallinity of both zinc oxide specimens. Due to the different morphologies of the two types of zinc oxide nanopowders, X-ray diffraction results showed different stress levels in their structures and the annealing treatment give significant effect to the structural stress. Electron spectroscopy imaging was a useful technique to identify the elemental distribution as well as oxygen defect in zinc oxide nanopowder.

Recent advances in f-element separations based on a new method for the production of pentavalent americium in acidic solution

DOE PAGES

Mincher, Bruce J.; Schmitt, Nicholas C.; Schuetz, Brian K.; ...

2015-03-11

The peroxydisulfate anion has long been used for the preparation of hexavalent americium (Am VI) from the normally stable Am III valence state in mildly acidic solutions. However, there has been no satisfactory means to directly prepare the pentavalent state (Am V) in that medium. Some early literature reports indicated that the peroxydisulfate oxidation was incomplete, and silver ion catalysis in conjunction with peroxydisulfate became accepted as the means to ensure quantitative generation of Am VI. Incomplete oxidation would be expected to leave residual Am III, or to produce Am V in treated solutions. However, until recently, the use ofmore » peroxydisulfate as an Am V reagent has not been reported. Here, parameters influencing the oxidation were investigated, including peroxydisulfate and acid concentration, temperature, duration of oxidative treatment, and the presence of higher concentrations of other redox active metals such as plutonium. Using optimized conditions determined here, quantitative Am V was prepared in an acidic solution and the UV/Vis extinction coefficients of the Am V 513 nm peak were measured over a range of nitric acid concentrations. Furthermore, the utility of Am V for separations from the lanthanides and curium by solvent extraction, organic column chromatography and inorganic ion exchangers was also investigated.« less

Band gap tuning in transition metal oxides by site-specific substitution

DOEpatents

Lee, Ho Nyung; Chisholm, Jr., Matthew F; Jellison, Jr., Gerald Earle; Singh, David J; Choi, Woo Seok

2013-12-24

A transition metal oxide insulator composition having a tuned band gap includes a transition metal oxide having a perovskite or a perovskite-like crystalline structure. The transition metal oxide includes at least one first element selected form the group of Bi, Ca, Ba, Sr, Li, Na, Mg, K, Pb, and Pr; and at least one second element selected from the group of Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Hf, Ta, W, Re, Os, Ir, and Pt. At least one correlated insulator is integrated into the crystalline structure, including REMO.sub.3, wherein RE is at least one Rare Earth element, and wherein M is at least one element selected from the group of Co, V, Cr, Ni, Mn, and Fe. The composition is characterized by a band gap of less of 4.5 eV.

Arsenic Exposure and Toxicology: A Historical Perspective

PubMed Central

Hughes, Michael F.; Beck, Barbara D.; Chen, Yu; Lewis, Ari S.; Thomas, David J.

2011-01-01

The metalloid arsenic is a natural environmental contaminant to which humans are routinely exposed in food, water, air, and soil. Arsenic has a long history of use as a homicidal agent, but in the past 100 years arsenic, has been used as a pesticide, a chemotherapeutic agent and a constituent of consumer products. In some areas of the world, high levels of arsenic are naturally present in drinking water and are a toxicological concern. There are several structural forms and oxidation states of arsenic because it forms alloys with metals and covalent bonds with hydrogen, oxygen, carbon, and other elements. Environmentally relevant forms of arsenic are inorganic and organic existing in the trivalent or pentavalent state. Metabolism of arsenic, catalyzed by arsenic (+3 oxidation state) methyltransferase, is a sequential process of reduction from pentavalency to trivalency followed by oxidative methylation back to pentavalency. Trivalent arsenic is generally more toxicologically potent than pentavalent arsenic. Acute effects of arsenic range from gastrointestinal distress to death. Depending on the dose, chronic arsenic exposure may affect several major organ systems. A major concern of ingested arsenic is cancer, primarily of skin, bladder, and lung. The mode of action of arsenic for its disease endpoints is currently under study. Two key areas are the interaction of trivalent arsenicals with sulfur in proteins and the ability of arsenic to generate oxidative stress. With advances in technology and the recent development of animal models for arsenic carcinogenicity, understanding of the toxicology of arsenic will continue to improve. PMID:21750349

Surface conditions of Nitinol wires, tubing, and as-cast alloys. The effect of chemical etching, aging in boiling water, and heat treatment.

PubMed

Shabalovskaya, S A; Anderegg, J; Laab, F; Thiel, P A; Rondelli, G

2003-04-15

The surface conditions of Nitinol wires and tubing were evaluated with the use of X-ray photoelectron spectroscopy, high-resolution Auger spectroscopy, electron backscattering, and scanning-electron microscopy. Samples were studied in the as-received state as well as after chemical etching, aging in boiling water, and heat treatment, and compared to a mechanically polished 600-grit-finish Nitinol surface treated similarly. General regularities in surface behavior induced by the examined surface treatments are similar for wires, tubing, and studied as-cast alloy, though certain differences in surface Ni concentration were observed. Nitinol wires and tubing from various suppliers demonstrated great variability in Ni surface concentration (0.5-15 at.%) and Ti/Ni ratio (0.4-35). The wires in the as-received state, with the exception of those with a black oxide originating in the processing procedure, revealed nickel and titanium on the surface in both elemental and oxidized states, indicating a nonpassive surface. Shape-setting heat treatment at 500 degrees C for 15 min resulted in tremendous increase in the surface Ni concentration and complete Ni oxidation. Preliminary chemical etching and boiling in water successfully prevented surface enrichment in Ni, initially resulting from heat treatment. A stoichiometric uniformly amorphous TiO(2) oxide generated during chemical etching and aging in boiling water was reconstructed at 700 degrees C, revealing rutile structure. Copyright 2003 Wiley Periodicals, Inc.

Trace Elements in Manganese Minerals as Potential Biosignatures on Mars

NASA Astrophysics Data System (ADS)

Lanza, N.; Clegg, S. M.; Cousin, A.; Forni, O.; Kirk, M. F.; Lamm, S. N.; Ollila, A.; Wiens, R. C.

2017-12-01

Observations from the Curiosity rover in Gale crater, Mars have shown the presence of high abundances of manganese (>3 wt% MnO) within sedimentary rocks throughout the traverse. Such high Mn abundances point to the past presence of abundant liquid water and strongly oxidizing conditions. On Earth, these types of environments are almost always habitable and are frequently inhabited by microbes. Given its close association with life and habitable environments on Earth, manganese has long been considered a potential biosignature for Mars. However, high concentrations of martian Mn have only recently been observed. In addition to the observations in Gale crater, high abundances of Mn have also been observed in Endeavor crater by the Opportunity rover and in the paired martian meteorites NWA 7034 and 7533 (`Black Beauty'), suggesting that Mn deposits may be more widespread on Mars than previously thought. The goal of this work is to determine whether there are unique signatures from rover payload instruments that can distinguish Mn-rich deposits as biogenic in origin (i.e., produced by life) from abiogenic Mn deposits. Importantly, Mn-oxides are known to scavenge trace metals from water because of their surface charge properties. We hypothesize that the presence and abundance of specific trace elements are the critical, distinguishing evidence for identifying the biogenic origin of Mn-bearing materials. A suite of natural rocks containing Mn-rich minerals with a range of Mn redox states was selected for analysis with laser-induced breakdown spectroscopy (LIBS). Samples with a biogenic origin had mixed valence redox states between Mn3+ and Mn4+ as inferred by mineralogy. Trace elements Ba, Li, Sr, and Rb were quantified and the presence or absence of Zn and Cu was ascertained by examining key LIBS peaks. Results show that samples with a known microbial origin had moderate Mn abundances >30 wt% MnO and higher Li and Ba. These results suggest that high Mn abundance alone is not sufficient evidence of a biosignatures. However, the presence of trace elements may help to infer the redox state of Mn, which may in turn point to samples that are more likely to have a biogenic origin.

Acid Sulfate Alteration in Gusev Crater, Mars

NASA Technical Reports Server (NTRS)

Morris, R. V.; Ming, D. W.; Catalano, J. G.

2016-01-01

The Mars Exploration Rover (MER) Spirit landed on the Gusev Crater plains west of the Columbia Hills in January, 2004, during the Martian summer (sol 0; sol = 1 Martian day = 24 hr 40 min). Spirit explored the Columbia Hills of Gusev Crater in the vicinity of Home Plate at the onset on its second winter (sol approximately 900) until the onset of its fourth winter (sol approximately 2170). At that time, Spirit became mired in a deposit of fined-grained and sulfate-rich soil with dust-covered solar panels and unfavorable pointing of the solar arrays toward the sun. Spirit has not communicated with the Earth since sol 2210 (January, 2011). Like its twin rover Opportunity, which landed on the opposite side of Mars at Meridiani Planum, Spirit has an Alpha Particle X-Ray Spectrometer (APXS) instrument for chemical analyses and a Moessbauer spectrometer (MB) for measurement of iron redox state, mineralogical speciation, and quantitative distribution among oxidation (Fe(3+)/sigma Fe) and coordination (octahedral versus tetrahedral) states and mineralogical speciation (e.g., olivine, pyroxene, ilmenite, carbonate, and sulfate). The concentration of SO3 in Gusev rocks and soils varies from approximately 1 to approximately 34 wt%. Because the APXS instrument does not detect low atomic number elements (e.g., H and C), major-element oxide concentrations are normalized to sum to 100 wt%, i.e., contributions of H2O, CO2, NO2, etc. to the bulk composition care not considered. The majority of Gusev samples have approximately 6 plus or minus 5 wt% SO3, but there is a group of samples with high SO3 concentrations (approximately 30 wt%) and high total iron concentrations (approximately 20 wt%). There is also a group with low total Fe and SO3 concentrations that is also characterized by high SiO2 concentrations (greater than 70 wt%). The trend labeled "Basaltic Soil" is interpreted as mixtures in variable proportions between unaltered igneous material and oxidized and SO3-rich basaltic dust. The Moessbauer parameters are not definitive for mineralogical speciation (other than octahedrally-coordinated Fe(3+) but are consistent with a schwertmannite-like phase (i.e., a nanophase ferric oxide). The high oxidation state and values of Moessbauer parameters (center shift and quadrupole splitting) for the high-SO3 samples imply ferric sulfate (i.e., oxidized sulfur), although the hydration state cannot be constrained. In no case is there an excess of SO3 over available cations (i.e., no evidence for elemental sulfur), and Fe sulfide (pyrite) has been detected in only one Gusev sample. The presence of both high-SiO2 (and low total iron and SO3) and high SO3 (and high total iron as ferric sulfate) can be accommodated by a two-step geochemical model developed with the Geochemist's Workbench. (1) Step 1 is anoxic acid sulfate leaching of Martian basalt at high water-to rock ratios (greater than 70). The result is a high-SiO2 residue0, and anoxic conditions are required to solubilize Fe as Fe(2+). (2) Step 2 is the oxic precipitation of sulfate salts from the leachate. Oxic conditions are required to produce the high concentrations of ferric sulfate with minor Mg-sulfates and no detectable Fe(2+)-sulfates.

Elemental ratio measurements of organic compounds using aerosol mass spectrometry: characterization, improved calibration, and implications

DOE PAGES

Canagaratna, M. R.; Jimenez, J. L.; Kroll, J. H.; ...

2014-07-31

Elemental compositions of organic aerosol (OA) particles provide useful constraints on OA sources, chemical evolution, and effects. The Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is widely used to measure OA elemental composition. This study evaluates AMS measurements of atomic oxygen-to-carbon (O : C), hydrogen-to-carbon (H : C), organic mass-to-organic carbon (OM : OC), and carbon oxidation state (OS C) for a vastly expanded laboratory dataset of multifunctional oxidized OA standards. For the expanded standard dataset, the "Aiken-Explicit" method (Aiken et al., 2008), which uses experimentally measured ion intensities at all ions to determine elemental ratios, reproduces known molecular Omore » : C and H : C ratio values within 20% (average absolute value of relative errors) and 12% respectively. The more commonly used "Aiken-Ambient" method, which uses empirically estimated H 2O + and CO + ion intensities to avoid gas phase air interferences at these ions, reproduces O : C and H : C of multifunctional oxidized species within 28% and 14% of known values. These values are systematically biased low, however, with larger biases observed for alcohols and simple diacids. A detailed examination of the H 2O +, CO +, and CO 2 + fragments in the high-resolution mass spectra of the standard compounds indicates that the Aiken-Ambient method underestimates the CO + and H 2O + produced from many oxidized species. Combined AMS-vacuum ultraviolet (VUV) ionization measurements indicate that these ions are produced by dehydration and decarboxylation on the AMS vaporizer (usually operated at 600 °C). Thermal decomposition is observed to be efficient at vaporizer temperatures down to 200 °C. These results are used together to develop an "Improved-Ambient" elemental analysis method for AMS spectra measured in air. The Improved-Ambient method reduces the systematic biases and reproduces O : C (H : C) ratios of individual oxidized standards within 28% (13%) of the known molecular values. The error in Improved-Ambient O : C and H : C values is smaller (12% and 4% respectively) for synthetic mixtures of the oxidized organic standards, which are more representative of the complex mix of species present in ambient OA. For ambient OA, the Improved-Ambient method produces O : C (H : C) values that are 27% (11%) larger than previously published Aiken-Ambient values; a corresponding increase of 9% is observed for OM : OC values. These results imply that ambient OA has a higher relative oxygen content than previously estimated. The OS C values calculated for ambient OA by the two methods agree well, however (average relative difference of 0.06 OS C units). This indicates that OS C is a more robust metric of oxidation than O : C, likely since OS C is not affected by hydration or dehydration, either in the atmosphere or during analysis.« less

Resistive switching in TiO2 nanocolumn arrays electrochemically grown

NASA Astrophysics Data System (ADS)

Marik, M.; Mozalev, A.; Hubalek, J.; Bendova, M.

2017-04-01

Resistive switching in metal oxides, especially in TiO2, has been intensively investigated for potential application in non-volatile memory microdevices. As one of the working mechanisms, a conducting filament consisting of a substoichiometric oxide phase is created within the oxide layer. With the aim of investigating the filament formation in spatially confined elements, we fabricate arrays of self-ordered TiO2 nanocolumns by porous-anodic-alumina (PAA)-assisted anodizing, incorporate them into solid-state microdevices, study their electron transport properties, and reveal that this anodizing approach is suitable for growing TiO2 nanostructures exhibiting resistive switching. The electrical properties and resistive switching behavior are both dependent on the electrolytic formation conditions, influencing the concentration and distribution of oxygen vacancies in the nanocolumn material during the film growth. Therefore, the PAA-assisted TiO2 nanocolumn arrays can be considered as a platform for investigating various phenomena related to resistive switching in valve metal oxides at the nanoscale.

Development of Perovskite-Type Materials for Thermoelectric Application.

PubMed

Wu, Tingjun; Gao, Peng

2018-06-12

Oxide perovskite materials have a long history of being investigated for thermoelectric applications. Compared to the state-of-the-art tin and lead chalcogenides, these perovskite compounds have advantages of low toxicity, eco-friendliness, and high elemental abundance. However, because of low electrical conductivity and high thermal conductivity, the total thermoelectric performance of oxide perovskites is relatively poor. Variety of methods were used to enhance the TE properties of oxide perovskite materials, such as doping, inducing oxygen vacancy, embedding crystal imperfection, and so on. Recently, hybrid perovskite materials started to draw attention for thermoelectric application. Due to the low thermal conductivity and high Seebeck coefficient feature of hybrid perovskites materials, they can be promising thermoelectric materials and hold the potential for the application of wearable energy generators and cooling devices. This mini-review will build a bridge between oxide perovskites and burgeoning hybrid halide perovskites in the research of thermoelectric properties with an aim to further enhance the relevant performance of perovskite-type materials.

Bioconjugated graphene oxide hydrogel as an effective adsorbent for cationic dyes removal.

PubMed

Soleimani, Khadijeh; Tehrani, Abbas Dadkhah; Adeli, Mohsen

2018-01-01

In this study, graphene oxide - cellulose nanowhiskers nanocomposite hydrogel was easily synthesized through covalent functionalization of cellulose nanowhiskers with graphene oxide via a facile approach. The nitrene chemistry applied for covalent functionalization of graphene oxide sheets. The surface morphology and chemical structure of the nanocomposite hydrogel were characterized by FTIR, TGA, Raman, XRD, elemental analysis and SEM. The UV/Visible absorption spectrum revealed that the obtained porous nanocomposite hydrogel can efficiently remove cationic dyes such as methylene blue (MB) and Rhodamine B (RhB) from wastewater with high absorption power. The adsorption process showed that 100% of MB and 90% of RhB have been removed and the equilibrium state has been reached in 15min for low concentration solutions in accordance with the pseudo-second-order model. Moreover, the sample exhibited stable performance after being used several times. High adsorption capacity and easy recovery are the efficient factors making these materials as good adsorbent for water pollutants and wastewater treatment. Copyright © 2017 Elsevier Inc. All rights reserved.

High-throughput technology for novel SO2 oxidation catalysts

PubMed Central

Loskyll, Jonas; Stoewe, Klaus; Maier, Wilhelm F

2011-01-01

We review the state of the art and explain the need for better SO2 oxidation catalysts for the production of sulfuric acid. A high-throughput technology has been developed for the study of potential catalysts in the oxidation of SO2 to SO3. High-throughput methods are reviewed and the problems encountered with their adaptation to the corrosive conditions of SO2 oxidation are described. We show that while emissivity-corrected infrared thermography (ecIRT) can be used for primary screening, it is prone to errors because of the large variations in the emissivity of the catalyst surface. UV-visible (UV-Vis) spectrometry was selected instead as a reliable analysis method of monitoring the SO2 conversion. Installing plain sugar absorbents at reactor outlets proved valuable for the detection and quantitative removal of SO3 from the product gas before the UV-Vis analysis. We also overview some elements used for prescreening and those remaining after the screening of the first catalyst generations. PMID:27877427

Transuranic Computational Chemistry.

PubMed

Kaltsoyannis, Nikolas

2018-02-26

Recent developments in the chemistry of the transuranic elements are surveyed, with particular emphasis on computational contributions. Examples are drawn from molecular coordination and organometallic chemistry, and from the study of extended solid systems. The role of the metal valence orbitals in covalent bonding is a particular focus, especially the consequences of the stabilization of the 5f orbitals as the actinide series is traversed. The fledgling chemistry of transuranic elements in the +II oxidation state is highlighted. Throughout, the symbiotic interplay of experimental and computational studies is emphasized; the extraordinary challenges of experimental transuranic chemistry afford computational chemistry a particularly valuable role at the frontier of the periodic table. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

X-Ray Fluorescence (XRF) to identify chemical analysis of minerals in Buton island, SE Sulawesi, Indonesia

NASA Astrophysics Data System (ADS)

Jamaluddin; Darwis, A.; Massinai, M. A.

2018-02-01

Asbuton as natural rock asphalt consists of a granular material; usually limestone or sandstone. In its natural state, it contains bitumen intimately dispersed throughout its mass, while the remainder of the material is a solid mineral matter. This research was conducted in Sorowalio, Buton Regency, Southeast Sulawesi province, Indonesia. This study aims to determine the content and the percentage of minerals contained in the rocks by using X-Ray Fluorescence (XRF). The method of research is a preliminary survey, sampling and laboratory analysis. XRF reports chemical composition, including Si (quartz) and Ca (calcite). The results indicate the content and the percentage of element dominate the rock sample is Fe2O3, MgO, CaO, and SiO2. Research results using XRF show that there are four metal oxide dominant elements. Hematite (Fe2O3) is dominant in all locations of sampling. Magnesium oxide (MgO) has the highest levels found in sample number six and the lowest is in sample number five. Silicates (SiO) has the highest levels at sample number six and the lowest in sample number seven. Calcium oxide (CaO) is dominant in all sampling locations. The sample of asbuton contains 37.90% asphalt, 43.28% carbonate, and18.82% other minerals.

Valence State Partitioning of Cr and V Between Pyroxene - Melt: Estimates of Oxygen Fugacity for Martian Basalt QUE 94201

NASA Technical Reports Server (NTRS)

Karner, J. M.; Papike, J. J.; Shearer, C. K.; McKay, G.; Le, L.; Burger, P.

2007-01-01

Several studies, using different oxybarometers, have suggested that the variation of fO2 in martian basalts spans about 3 log units from approx. IW-1 to IW+2. The relatively oxidized basalts (e.g., pyroxene-phyric Shergotty) are enriched in incompatible elements, while the relatively reduced basalts (e.g., olivine-phyric Y980459) are depleted in incompatible elements. A popular interpretation of the above observations is that the martian mantle contains two reservoirs; 1) oxidized and enriched, and 2) reduced and depleted. The basalts are thus thought to represent mixing between these two reservoirs. Recently, Shearer et al. determined the fO2 of primitive olivine-phyric basalt Y980459 to be IW+0.9 using the partitioning of V between olivine and melt. In applying this technique to other basalts, Shearer et al. concluded that the martian mantle shergottite source was depleted and varied only slightly in fO2 (IW to IW+1). Thus the more oxidized, enriched basalts had assimilated a crustal component on their path to the martian surface. In this study we attempt to address the above debate on martian mantle fO2 using the partitioning of Cr and V into pyroxene in pyroxene-phyric basalt QUE 94201.

GaAs metal-oxide-semiconductor based non-volatile flash memory devices with InAs quantum dots as charge storage nodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Islam, Sk Masiul, E-mail: masiulelt@gmail.com; Chowdhury, Sisir; Sarkar, Krishnendu

2015-06-24

Ultra-thin InP passivated GaAs metal-oxide-semiconductor based non-volatile flash memory devices were fabricated using InAs quantum dots (QDs) as charge storing elements by metal organic chemical vapor deposition technique to study the efficacy of the QDs as charge storage elements. The grown QDs were embedded between two high-k dielectric such as HfO{sub 2} and ZrO{sub 2}, which were used for tunneling and control oxide layers, respectively. The size and density of the QDs were found to be 5 nm and 1.8×10{sup 11} cm{sup −2}, respectively. The device with a structure Metal/ZrO{sub 2}/InAs QDs/HfO{sub 2}/GaAs/Metal shows maximum memory window equivalent to 6.87 V. Themore » device also exhibits low leakage current density of the order of 10{sup −6} A/cm{sup 2} and reasonably good charge retention characteristics. The low value of leakage current in the fabricated memory device is attributed to the Coulomb blockade effect influenced by quantum confinement as well as reduction of interface trap states by ultra-thin InP passivation on GaAs prior to HfO{sub 2} deposition.« less

Amorphous semiconducting and conducting transparent metal oxide thin films and production thereof

DOEpatents

Perkins, John; Van Hest, Marinus Franciscus Antonius Maria; Ginley, David; Taylor, Matthew; Neuman, George A.; Luten, Henry A.; Forgette, Jeffrey A.; Anderson, John S.

2010-07-13

Metal oxide thin films and production thereof are disclosed. An exemplary method of producing a metal oxide thin film may comprise introducing at least two metallic elements and oxygen into a process chamber to form a metal oxide. The method may also comprise depositing the metal oxide on a substrate in the process chamber. The method may also comprise simultaneously controlling a ratio of the at least two metallic elements and a stoichiometry of the oxygen during deposition. Exemplary amorphous metal oxide thin films produced according to the methods herein may exhibit highly transparent properties, highly conductive properties, and/or other opto-electronic properties.

Effect of reactive element oxide coating on the high temperature oxidation behaviour of FeCrAl alloys

NASA Astrophysics Data System (ADS)

Cueff, R.; Buscail, H.; Caudron, E.; Riffard, F.; Issartel, C.; El Messki, S.

2004-05-01

The influence of yttrium oxide coating (processed by the sol-gel method) on the oxidation behaviour of a commercial FeCrAl alloy (Kanthal A1) has been investigated during isothermal exposures in air at 1373 K. The scale growth kinetics of the uncoated alloy obey a parabolic rate law during the whole oxidation test, whereas the kinetic curves of the Y-coated specimen exhibit an initial transient stage for the first few hours, followed by a parabolic regime. The yttrium sol-gel coating deposited on the bare alloy does not provide the beneficial effect usually ascribed to reactive elements. No oxidation rate improvement of the coated alloy is observed, the parabolic rate constant values are strictly identical for both specimens. In situ X-ray diffraction reveals a marked influence of the reactive element on the composition of the oxide scale. The oxide layer formed on the yttrium-coated specimen comprised, in addition to α-alumina which is the main oxide also identified on the bare specimen, the presence of yttrium aluminates (YAlO 3, Y 3Al 5O 12) located in the outermost part of the layer.

Preliminary estimates of the quantities of rare-earth elements contained in selected products and in imports of semimanufactured products to the United States, 2010

USGS Publications Warehouse

Bleiwas, Donald I.; Gambogi, Joseph

2013-01-01

Rare-earth elements (REEs) are contained in a wide range of products of economic and strategic importance to the Nation. The REEs may or may not represent a significant component of that product by mass, value, or volume; however, in many cases, the embedded REEs are critical for the device’s function. Domestic sources of primary supply and the manufacturing facilities to produce products are inadequate to meet U.S. requirements; therefore, a significant percentage of the supply of REEs and the products that contain them are imported to the United States. In 2011, mines in China produced roughly 97 percent of the world’s supply of REEs, and the country’s production of these elements will likely dominate global supply until at least 2020. Preliminary estimates of the types and amount of rare-earth elements, reported as oxides, in semimanufactured form and the amounts used for electric vehicle batteries, catalytic converters, computers, and other applications were developed to provide a perspective on the Nation’s use of these elements. The amount of rare-earth metals recovered from recycling, remanufacturing, and reuse is negligible when the tonnage of products that contain REEs deposited in landfills and retained in storage is considered. Under favorable market conditions, the recovery of REEs from obsolete products could potentially displace a portion of the supply from primary sources.

Evolution of the atomic order and valence state of rare-earth atoms and uranium in a new carbon-metal composite—diphthalocyanine pyrolysate C64H32N16 Me ( Me = Y, La, Ce, Eu, and U)

NASA Astrophysics Data System (ADS)

Sovestnov, A. E.; Kapustin, V. K.; Tikhonov, V. I.; Fomin, E. V.; Chernenkov, Yu. P.

2014-08-01

The structure of a metal-carbon composite formed by the pyrolysis of diphthalocyanine of some rare-earth elements (Y, La, Ce, Eu) and uranium in the temperature range T ann = 800-1700°C has been investigated for the first time by the methods of X-ray diffraction analysis and X-ray line shift. It has been shown that, in the general case, the studied pyrolysates consist of three phases. One phase corresponds to the structure of graphite. The second phase corresponds to nitrides, carbides, and oxides of basic metal elements with a crystallite size ranging from 5 to 100 nm. The third phase is amorphous or consisting of crystallites with a size of ˜1 nm. It has been found that all the basic elements (Y, La, Ce, Eu, U) and incorporated iodine atoms in the third phase are in a chemically bound state. The previously unobserved electronic configurations have been revealed for europium. The possibility of including not only atoms of elements forming diphthalocyanine but also other elements (for example, iodine) in the composite structure is of interest, in particular, for the creation of a thermally, chemically, and radiation resistant metal-carbon matrix for the radioactive waste storage.

Contaminants from Cretaceous Black Shale Part 1: Natural weathering processes controlling contaminant cycling in Mancos Shale, southwestern United States, with emphasis on salinity and selenium

USGS Publications Warehouse

Tuttle, Michele L.W.; Fahy, Juli W.; Elliott, John G.; Grauch, Richard I.; Stillings, Lisa L.

2013-01-01

Soils derived from black shale can accumulate high concentrations of elements of environmental concern, especially in regions with semiarid to arid climates. One such region is the Colorado River basin in the southwestern United States where contaminants pose a threat to agriculture, municipal water supplies, endangered aquatic species, and water-quality commitments to Mexico. Exposures of Cretaceous Mancos Shale (MS) in the upper basin are a major contributor of salinity and selenium in the Colorado River. Here, we examine the roles of geology, climate, and alluviation on contaminant cycling (emphasis on salinity and Se) during weathering of MS in a Colorado River tributary watershed. Stage I (incipient weathering) began perhaps as long ago as 20 ka when lowering of groundwater resulted in oxidation of pyrite and organic matter. This process formed gypsum and soluble organic matter that persist in the unsaturated, weathered shale today. Enrichment of Se observed in laterally persistent ferric oxide layers likely is due to selenite adsorption onto the oxides that formed during fluctuating redox conditions at the water table. Stage II weathering (pedogenesis) is marked by a significant decrease in bulk density and increase in porosity as shale disaggregates to soil. Rainfall dissolves calcite and thenardite (Na2SO4) at the surface, infiltrates to about 1 m, and precipitates gypsum during evaporation. Gypsum formation (estimated 390 kg m−2) enriches soil moisture in Na and residual SO4. Transpiration of this moisture to the surface or exposure of subsurface soil (slumping) produces more thenardite. Most Se remains in the soil as selenite adsorbed to ferric oxides, however, some oxidizes to selenate and, during wetter conditions is transported with soil moisture to depths below 3 m. Coupled with little rainfall, relatively insoluble gypsum, and the translocation of soluble Se downward, MS landscapes will be a significant nonpoint source of salinity and Se to the Colorado River well into the future. Other trace elements weathering from MS that are often of environmental concern include U and Mo, which mimic Se in their behavior; As, Co, Cr, Cu, Ni, and Pb, which show little redistribution; and Cd, Sb, V, and Zn, which accumulate in Stage I shale, but are lost to varying degrees from upper soil intervals. None of these trace elements have been reported previously as contaminants in the study area.

Influence of residual elements in lead on oxygen- and hydrogen-gassing rates of lead-acid batteries

NASA Astrophysics Data System (ADS)

Lam, L. T.; Ceylan, H.; Haigh, N. P.; Lwin, T.; Rand, D. A. J.

Raw lead materials contain many residual elements. With respect to setting 'safe' levels for these elements, each country has its own standard, but the majority of the present specifications for the lead used to prepare battery oxide apply to flooded batteries that employ antimonial grids. In these batteries, the antimony in the positive and negative grids dominates gassing characteristics so that the influence of residual elements is of little importance. This is, however, not the case for valve-regulated lead-acid (VRLA) batteries, which use antimony-free grids and less sulfuric acid solution. Thus, it is necessary to specify 'acceptable' levels of residual elements for the production of VRLA batteries. In this study, 17 elements are examined, namely: antimony, arsenic, bismuth, cadmium, chromium, cobalt, copper, germanium, iron, manganese, nickel, selenium, silver, tellurium, thallium, tin, and zinc. The following strategy has been formulated to determine the acceptable levels: (i) selection of a control oxide; (ii) determination of critical float, hydrogen and oxygen currents; (iii) establishment of a screening plan for the elements; (iv) development of a statistical method for analysis of the experimental results. The critical values of the float, hydrogen and oxygen currents are calculated from a field survey of battery failure data. The values serve as a base-line for comparison with the corresponding measured currents from cells using positive and negative plates produced either from the control oxide or from oxide doped with different levels of the 17 elements in combination. The latter levels are determined by means of a screening plan which is based on the Plackett-Burman experimental design. Following this systematic and thorough exercise, two specifications are proposed for the purity of the lead to be used in oxide production for VRLA technology.

Fabrication and Testing of a Tubular Thermoelectric Module Based on Oxide Elements

NASA Astrophysics Data System (ADS)

Merkulov, O. V.; Politov, B. V.; Chesnokov, K. Yu.; Markov, A. A.; Leonidov, I. A.; Patrakeev, M. V.

2018-02-01

A thermoelectric module with a tubular design, considered as particularly promising for energy recovery from hot exhaust gases of vehicles was fabricated and successfully tested under laboratory condition. The module included 24 functional oxide elements synthesized by conventional methods. Elements of p-type were made of cobalt-based oxide Ca2.7Bi0.3Co4O9, while n-type elements were produced from manganese-based oxide CaMn0.95Ta0.05O3. The module was assembled using silver paste and clamping mechanisms, with the thermoelectric elements electrically connected in series by metal plates (copper, silver) and placed around the hot tube. The output power of 138 mW was achieved under a temperature gradient of 430°C with a hot side temperature of 514°C. The tested module is characterized by an advantageous manufacturing factor of 0.87 at the contact resistance of 0.44 Ω, but a relatively low output power density per volume and per mass. Possible means by which the module's operational characteristics could be improved are considered.

Impact of iron redox chemistry on nuclear waste disposal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pearce, Carolyn I.; Rosso, Kevin M.; Pattrick, Richard

For the safe disposal of nuclear waste, the ability to predict the changes in oxidation states of redox active actinide elements and fission products, such as U, Pu, Tc and Np is a key factor in determining their long term mobility. Both in the Geological Disposal Facility (GDF) near-field and in the far-field subsurface environment, the oxidation states of radionuclides are closely tied to changes in the redox condition of other elements in the subsurface such as iron. Iron pervades all aspects of the waste package environment, from the steel in the waste containers, through corrosion products, to the ironmore » minerals present in the host rock. Over the long period required for nuclear waste disposal, the chemical conditions of the subsurface waste package will vary along the entire continuum from oxidizing to reducing conditions. This variability leads to the expectation that redox-active components such as Fe oxides can undergo phase transformations or dissolution; to understand and quantify such a system with respect to potential impacts on waste package integrity and radionuclide fate is clearly a serious challenge. Traditional GDF performance assessment models currently rely upon surface adsorption or single phase solubility experiments and do not deal with the incorporation of radionuclides into specific crystallographic sites within the evolving Fe phases. In this chapter, we focus on the iron-bearing phases that are likely to be present in both the near and far-field of a GDF, examining their potential for redox activity and interaction with radionuclides. To support this, thermodynamic and molecular modelling is particularly important in predicting radionuclide behaviour in the presence of Fe-phases. Examination of radionuclide contamination of the natural environment provides further evidence of the importance of Fe-phases in far-field processes; these can be augmented by experimental and analogue studies.« less

Elucidating ultrafast electron dynamics at surfaces using extreme ultraviolet (XUV) reflection-absorption spectroscopy.

PubMed

Biswas, Somnath; Husek, Jakub; Baker, L Robert

2018-04-24

Here we review the recent development of extreme ultraviolet reflection-absorption (XUV-RA) spectroscopy. This method combines the benefits of X-ray absorption spectroscopy, such as element, oxidation, and spin state specificity, with surface sensitivity and ultrafast time resolution, having a probe depth of only a few nm and an instrument response less than 100 fs. Using this technique we investigated the ultrafast electron dynamics at a hematite (α-Fe2O3) surface. Surface electron trapping and small polaron formation both occur in 660 fs following photoexcitation. These kinetics are independent of surface morphology indicating that electron trapping is not mediated by defects. Instead, small polaron formation is proposed as the likely driving force for surface electron trapping. We also show that in Fe2O3, Co3O4, and NiO, band gap excitation promotes electron transfer from O 2p valence band states to metal 3d conduction band states. In addition to detecting the photoexcited electron at the metal M2,3-edge, the valence band hole is directly observed as transient signal at the O L1-edge. The size of the resulting charge transfer exciton is on the order of a single metal-oxygen bond length. Spectral shifts at the O L1-edge correlate with metal-oxygen bond covalency, confirming the relationship between valence band hybridization and the overpotential for water oxidation. These examples demonstrate the unique ability to measure ultrafast electron dynamics with element and chemical state resolution using XUV-RA spectroscopy. Accordingly, this method is poised to play an important role to reveal chemical details of previously unseen surface electron dynamics.

Pathogenic mechanisms in systemic lupus erythematosus.

PubMed

Perl, Andras

2010-02-01

Systemic lupus erythematosus (SLE) is a chronic inflammatory disease characterized by the dysfunction of T cells, B cells, and dendritic cells and by the production of antinuclear autoantibodies. This editorial provides a synopsis of newly discovered genetic factors and signaling pathways in lupus pathogenesis that are documented in 11 state-of-the-art reviews and original articles. Mitochondrial hyperpolarization underlies mitochondrial dysfunction, depletion of ATP, oxidative stress, abnormal activation, and death signal processing in lupus T cells. The mammalian target of rapamycin, which is a sensor of the mitochondrial transmembrane potential, has been successfully targeted for treatment of SLE with rapamycin or sirolimus in both patients and animal models. Inhibition of oxidative stress, nitric oxide production, expression of endogenous retroviral and repetitive elements such as HRES-1, the long interspersed nuclear elements 1, Trex1, interferon alpha (IFN-alpha), toll-like receptors 7 and 9 (TLR-7/9), high-mobility group B1 protein, extracellular signal-regulated kinase, DNA methyl transferase 1, histone deacetylase, spleen tyrosine kinase, proteasome function, lysosome function, endosome recycling, actin cytoskeleton formation, the nuclear factor kappa B pathway, and activation of cytotoxic T cells showed efficacy in animal models of lupus. Although B cell depletion and blockade of anti-DNA antibodies and T-B cell interaction have shown success in animal models, human studies are currently ongoing to establish the value of several target molecules for treatment of patients with lupus. Ongoing oxidative stress and inflammation lead to accelerated atherosclerosis that emerged as a significant cause of mortality in SLE.

The environmental consequences of the oil shale utilization in Jordan: The effect of combustion processes

NASA Astrophysics Data System (ADS)

El-Hasan, Tayel

2015-04-01

The geochemical analysis of the upper Cretaceous organic rich oil shale of El-Lajjoun revealed that it contains considerable concentrations of trace element when compared to the average world shale. The aim of this study was to deduce the effect of various combustion processes on the geochemical and mineralogical characteristics of the produced ashes.The oil shale powder samples were burned under Aerobic Combustion Process (ACP) at 700˚C, 850˚C and 1000˚C respectively, beside the anaerobic (pyrolysis) combustion process (PCP) at 600, 650, 700, 750 and 800˚C respectively.The ashes produced from the (ACP) caused almost all major oxides contents to increase with increasing burning temperature, particularly SiO2 and CaO were nearly doubled at temperature 1000 ˚C. Moreover, trace elements showed the same trend where ashes at higher temperatures (i.e. 1000 ˚C) have doubled its contents of trace elements such as Cr, Ni, Zn, Cu and U. This was reflected through enrichment of calcite and quartz beside the anhydrite as the main mineral phases in the ACP ashes. As for the PCP ash show similar trend but relatively with lower concentrations as evident from its lowerEnrichment Factor (EF) values. This might be due to the higher organic matter remained in the PCP ashes compared with ACP ashes. However, PCP is more likely associated with toxic Cd and Asgasses as evident from their lowerconcentrations in the ashes.Moreover, recent results using the synchrotron-based XANES technique confirm that toxic elements are found in higher oxidation state due to ACP. The investigation was concerned on As and Cr. Thechromium in the original shales was in the form of Cr (III) and then it was converted to Cr(VI) in the ashes due of the ACP. Similarly, As (III) the XANES results showed that it was converted into As(V) too. These findingsare alarming and should be taken seriously. Because elements with higher oxidation states became more mobile, thus they can easily leached from the ash tailing into the nearby water resources. The most important species is Cr(VI) because itis easily leachable and very harmful species. It could cause pollution to surface and ground water resources.Therefore, allot of concerns should be paid on the ongoing oil shale utilization enterprises due to its pollution potential.Further investigation regarding the speciation of vanadium and cadmium are on the way.

URANIUM OXIDE-CONTAINING FUEL ELEMENT COMPOSITION AND METHOD OF MAKING SAME

DOEpatents

Handwerk, J.H.; Noland, R.A.; Walker, D.E.

1957-09-10

In the past, bodies formed of a mixture of uranium dioxide and aluminum powder have been used in fuel elements; however, these mixtures were found not to be suitable when exposed to temperatures of about 600 deg C, because at such high temperatures the fuel elements were distorted. If uranosic oxide, U/sub 3/O/sub 8/, is substituted for UO/sub 2/, the mechanical properties are not impaired when these materials are used at about 600 deg C and no distortion takes place. The uranosic oxide and aluminum, both in powder form, are first mixed, and after a homogeneous mixture has been obtained, are shaped into fuel elements by extrusion at elevated temperature. Magnesium powder may be used in place of the aluminum.

Effect of additives on the volatility of elements in a DC arc during the atomic emission analysis of nickel(II) oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zolotareva, N.I.; Kuzyakov, Yu.Ya.; Khlystova, A.D.

1986-10-20

The authors have studied the effect of traditional halogenating additives, AgCl, CdF/sub 2/, PTFE and that of an effective additive they have selected, ZnF/sub 2/, on the volatility of impurity elements, viz. tungsten, molybdenum, titanium, and zirconium from nickel (II) oxide, and determined the constants for the average relative volatility of the elements by the method of Kantor and Pungor. The results have been used to lower the limits of detection of the impurities cited in nickel(II) oxide.

Distribution and size fractionation of elemental sulfur in aqueous environments: The Chesapeake Bay and Mid-Atlantic Ridge

NASA Astrophysics Data System (ADS)

Findlay, Alyssa J.; Gartman, Amy; MacDonald, Daniel J.; Hanson, Thomas E.; Shaw, Timothy J.; Luther, George W.

2014-10-01

Elemental sulfur is an important intermediate of sulfide oxidation and may be produced via abiotic and biotic pathways. In this study the concentration and size fractionation of elemental sulfur were measured in two different sulfidic marine environments: the Chesapeake Bay and buoyant hydrothermal vent plumes along the Mid-Atlantic Ridge. Nanoparticulate sulfur (<0.2 μm) was found to comprise up to 90% of the total elemental sulfur in anoxic deep waters of the Chesapeake Bay. These data were compared with previous studies of elemental sulfur, and represent one of the few reports of nanoparticulate elemental sulfur in the environment. Additionally, a strain of phototrophic sulfide oxidizing bacteria isolated from the Chesapeake Bay was shown to produce elemental sulfur as a product of sulfide oxidation. Elemental sulfur concentrations are also presented from buoyant hydrothermal vent plumes located along the Mid-Atlantic Ridge. In the Mid-Atlantic Ridge plume, S0 concentrations up to 33 μM were measured in the first meter of rising plumes at three different vent sites, and nanoparticulate S0 was up to 44% of total elemental sulfur present.

The role of extremophile in the redox reaction of Fe and As relating with the formation of secondary phase mineral in extreme environment, Norris Geyser Basin, Yellowstone National Park, USA

NASA Astrophysics Data System (ADS)

Koo, T. H.; Kim, J. Y.; Park, K. R.; Jung, D. H.; Geesey, G. G.; Kim, J. W.

2015-12-01

Redox reaction associated with microbial elemental respiration is a ubiquitous process in sediments and suspended particles at various temperatures or pH/Eh conditions. Particularly, changes in elemental redox states (structural or dissolved elemental form) induced by microbial respiration result in the unexpected biogeochemical reactions in the light of biotic/abiotic mineralization. The objective of the present study is, therefore to investigate the secondary phase mineralization through a-/biogeochemical Fe and As redox cycling in the acido-hyperhtermal Norris Geyser Basin (NGB) in Yellowstone National Park, USA, typical of the extreme condition. X-ray diffraction, scanning electron microscope with energy dispersive x-ray spectroscopy, X-ray absorption near edge structure, inductively coupled plasma-atomic emission spectrometer and liquid chromatography with ICP-mass spectroscopy with filtrated supernatant were performed for the mineralogical and hydro-geochemical analysis. The clay slurry collected from the active hot-spring of the NGB area (pH=3.5 and Temperature=78 ℃) was incubated with ("enrichment") or without the growth medium ("natural"). The control was prepared in the same condition except adding the glutaraldehyde to eliminate the microbial activity. The secondary phase mineral formation of the oxidative phase of Fe and As, and K identified as 'Pharmacosiderite' only appeared in the enrichment set suggesting a role of extremophiles in the mineral formation. The considerable population of Fe-oxidizer (Metallosphera yellowstonensis MK-1) and As-oxidizer (Sulfurihydrogenibium sp.) was measured by phylogenetic analysis in the present study area. The inhibition of As-oxidation in the low pH conditions was reported in the previous study, however the As-redox reaction was observed and consequently, precipitated the Pharmacosiderite only in the enrichment set suggesting a biotic mineralization. The present study collectively suggests that the microbial activity may bypass the chemical or thermodynamical reaction barriers and promote the secondary phase mineral formation through the elemental respiration. The possible biotic/abiotic mechanism or process in mineral alteration/formation in extreme environment will be discussed.

Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

McSkimming, Alex; Su, Jing; Cheisson, Thibault

Separations of f-block elements are a critical aspect of nuclear waste processing. Redox-based separations offer promise, but challenges remain in stabilizing and differentiating actinides in high oxidation states. The investigation of new ligand types that provide thermodynamic stabilization to high-valent actinides is essential for expanding their fundamental chemistry and to elaborate new separation techniques and storage methods. We report herein the preparation and characterization of Th and U complexes of the pyridyl-hydroxylamine ligand, N-tert-butyl-N-(pyridin-2-yl)hydroxylamine (pyNO–). Electrochemical studies performed on the homoleptic complexes [M(pyNO) 4] (M = Th, U) revealed significant stabilization of the U complex upon one-electron oxidation. The saltmore » [U(pyNO) 4] + was isolated by chemical oxidation of [U(pyNO) 4]; spectroscopic and computational data support assignment as a U V cation.« less

Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure

DOE PAGES

McSkimming, Alex; Su, Jing; Cheisson, Thibault; ...

2018-03-23

Separations of f-block elements are a critical aspect of nuclear waste processing. Redox-based separations offer promise, but challenges remain in stabilizing and differentiating actinides in high oxidation states. The investigation of new ligand types that provide thermodynamic stabilization to high-valent actinides is essential for expanding their fundamental chemistry and to elaborate new separation techniques and storage methods. We report herein the preparation and characterization of Th and U complexes of the pyridyl-hydroxylamine ligand, N-tert-butyl-N-(pyridin-2-yl)hydroxylamine (pyNO–). Electrochemical studies performed on the homoleptic complexes [M(pyNO) 4] (M = Th, U) revealed significant stabilization of the U complex upon one-electron oxidation. The saltmore » [U(pyNO) 4] + was isolated by chemical oxidation of [U(pyNO) 4]; spectroscopic and computational data support assignment as a U V cation.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robinson, Ian; Clark, Jesse; Harder, Ross

Materials are generally classified by a phase diagram which displays their properties as a function of external state variables, typically temperature and pressure. A new dimension that is relatively unexplored is time: a rich variety of new materials can become accessible in the transient period following laser excitation from the ground state. The timescale of nanoseconds to femtoseconds, is ripe for investigation using x-ray free-electron laser (XFEL) methods. There is no shortage of materials suitable for time-resolved materials-science exploration. Oxides alone represent most of the minerals making up the Earth's crust, catalysts, ferroelectrics, corrosion products and electronically ordered materials suchmore » as superconductors, to name a few. Some of the elements have metastable phase diagrams with predicted new phases. There are some examples known already: an oxide 'hidden phase' living only nanoseconds and an electronically ordered excited phase of fullerene C 60, lasting only femtoseconds. In a completely general way, optically excited states of materials can be probed with Bragg coherent diffraction imaging, both below the damage threshold and in the destructive regime. Lastly, prospective methods for carrying out such XFEL experiments are discussed.« less

Spatial distribution pattern of vanadium in hydric landscapes

NASA Astrophysics Data System (ADS)

Fiedler, Sabine; Breuer, Jörn; Palmer, Iris; Berger, Jochen

2010-05-01

The geochemical behavior of the trace element vanadium (V) is strongly influenced by its oxidation state (+2 to +5). Consequently, oxidation/reduction reactions play an important role in controlling the mobilization and immobilization of V in soils. Translocation processes of V within soil profiles (pedons), including podzolization and clay illuviation, are well-documented. With regard to its lateral redistribution in landscapes, V is widely regarded as being immobile. Our investigation focused on the fate of V along a moisture gradient in different temperate humid spruce forest ecosystems in Southwest Germany (MAP 1,200-1,600 mm, MAT 6°C). The areas under investigation are characterized by lateral water flow, caused by a physically pre-weathered periglacial layer with poor water-permeability characteristics at the interface between pedo- and lithosphere. We selected different catenas derived from sandstone, gneiss, and granite, respectively. The soil associations occur along moderately inclined slopes and include common forest soils of three redox categories: an anaerobic Histosol, oxic Cambisols, and Stagnosols with an intermediate redox state. The soils are linked to each other by the lateral subsurface transport of solutes, which allows the investigation of the horizontal (i.e. within pedons) and lateral redistribution (i.e. between pedons) of the redox-sensitive elements V and iron (Fe). The redox potential of V and Fe in different soil depths along the hydrological pathway was both measured in the field and subsequently analyzed in 48 soil horizons to deduce the total content of V and Fe using aqua-regia digestion and element spectrometry (ICP-OES and ICP-MS). The different parent materials result in significant differences in V content. The V content in the sandstone soils (0.2 - 30 mg kg-1) was lower than the V content in granite and gneiss soils (up to 75 and 100 mg kg-1, respectively). Our results demonstrate that V is a highly mobile element in hydric landscapes. Independent from the parent material, we found a distinct spatial pattern of V, which reflected that of the local redox environment: Horizons/pedons with oxic conditions revealed a positive correlation between V content and Fe content. In this case, iron oxides act as an important sink for dissolved V which originated from other locations of the catena. Poorly drained soils, such as Stagnosols for example, promote both Fe and V reduction, which is coupled to their removal from the pedons by leaching. It can be demonstrated that the element-specific Eh window for differential reduction is very narrow. The spatial distribution of both elements shows that high V contents are often associated with low Fe contents. It is therefore assumed that a reducing environment promotes Fe3+ reduction, while maintaining while maintaining V stable.

Sulfur cycling in an iron oxide-dominated, dynamic marine depositional system: The Argentine continental margin

NASA Astrophysics Data System (ADS)

Riedinger, Natascha; Brunner, Benjamin; Krastel, Sebastian; Arnold, Gail L.; Wehrmann, Laura M.; Formolo, Michael J.; Beck, Antje; Bates, Steven M.; Henkel, Susann; Kasten, Sabine; Lyons, Timothy W.

2017-05-01

The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates. Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT). Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydr)oxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur. Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron monosulfide phases meters below the SMT demonstrates that in sulfide-limited systems metastable sulfur constituents are not readily converted to pyrite but can be buried to deeper sediment depths. Our data show that in non-steady state systems, redox zones do not occur in sequence but can reappear or proceed in inverse sequence throughout the sediment column, causing similar mineral alteration processes to occur at the same time at different sediment depths.

Roles of Cationic and Elemental Calcium in the Electro-Reduction of Solid Metal Oxides in Molten Calcium Chloride

NASA Astrophysics Data System (ADS)

Qiu, Guohong; Jiang, Kai; Ma, Meng; Wang, Dihua; Jin, Xianbo; Chen, George Z.

2007-06-01

Previous work, mainly from this research group, is re-visited on electrochemical reduction of solid metal oxides, in the form of compacted powder, in molten CaCl2, aiming at further understanding of the roles of cationic and elemental calcium. The discussion focuses on six aspects: 1.) debate on two mechanisms proposed in the literature, i. e. electro-metallothermic reduction and electro-reduction (or electro-deoxidation), for the electrolytic removal of oxygen from solid metals or metal oxides in molten CaCl2; 2.) novel metallic cavity working electrodes for electrochemical investigations of compacted metal oxide powders in high temperature molten salts assisted by a quartz sealed Ag/AgCl reference electrode (650 ºC- 950 ºC); 3.) influence of elemental calcium on the background current observed during electrolysis of solid metal oxides in molten CaCl2; 4.) electrochemical insertion/ inclusion of cationic calcium into solid metal oxides; 5.) typical features of cyclic voltammetry and chronoamperometry (potentiostatic electrolysis) of metal oxide powders in molten CaCl2; and 6.) some kinetic considerations on the electrolytic removal of oxygen.

Baseline Geochemical Data for Medical Researchers in Kentucky

NASA Astrophysics Data System (ADS)

Anderson, W.

2017-12-01

According to the Centers for Disease Control, Kentucky has the highest cancer incidence and death rates in the country. New efforts by geochemists and medical researchers are examining ways to diagnose the origin and sources of carcinogenesis. In an effort to determine if naturally occurring geochemical or mineral elements contributes to the cancer causation, the Kentucky Geological Survey has established a Minerals and Geochemical Database that is available to medical researchers for examination of baseline geochemistry and determine if naturally occurring mineral or chemical elements contribute to the high rate of cancers in the state. Cancer causation is complex, so if natural sources can be accounted for, then researchers can focus on the true causation. Naturally occurring minerals, metals and elements occur in many parts of the state, and their presence is valuable for evaluating causation. For example, some data in the database contain maps showing (a) statewide elemental geochemistry, (b) areas of black shale oxidation occurrence, which releases metals in soil and surface waters, (c) some clay deposits in the state that can contain high content of rare earth elements, and (d) site-specific uranium occurrences. Knowing the locations of major ore deposits in the state can also provide information related to mineral and chemical anomalies, such as for base metals and mercury. Radionuclide data in soil and water analyses are limited, so future research may involve obtaining more analyses to determine radon potential. This database also contains information on faulting and geology in the state. Although the metals content of trees may not seem relevant, the ash and humus content of degraded trees affects soil, stream sediment and water geochemistry. Many rural homes heat with wood, releasing metals into the surrounding biosphere. Stressed vegetation techniques can be used to explore for ore deposits and look for high metal contents in soils and rocks. These naturally occurring elements could be used for baseline information related to new collaborative research that integrates medicine, geology, forestry, and botany to predict metal contents of stream sediments, soil residuum, trees, plants, and forest cover and determine their relation to carcinogenesis.

Smart tungsten alloys as a material for the first wall of a future fusion power plant

NASA Astrophysics Data System (ADS)

Litnovsky, A.; Wegener, T.; Klein, F.; Linsmeier, Ch.; Rasinski, M.; Kreter, A.; Unterberg, B.; Coenen, J. W.; Du, H.; Mayer, J.; Garcia-Rosales, C.; Calvo, A.; Ordas, N.

2017-06-01

Tungsten is currently deemed as a promising plasma-facing material (PFM) for the future power plant DEMO. In the case of an accident, air can get into contact with PFMs during the air ingress. The temperature of PFMs can rise up to 1200 °C due to nuclear decay heat in the case of damaged coolant supply. Heated neutron-activated tungsten forms a volatile radioactive oxide which can be mobilized into the atmosphere. New self-passivating ‘smart’ alloys can adjust their properties to the environment. During plasma operation the preferential sputtering of lighter alloying elements will leave an almost pure tungsten surface facing the plasma. During an accident the alloying elements in the bulk are forming oxides thus protecting tungsten from mobilization. Good plasma performance and the suppression of oxidation are required for smart alloys. Bulk tungsten (W)-chroimum (Cr)-titanium (Ti) alloys were exposed together with pure tungsten (W) samples to the steady-state deuterium plasma under identical conditions in the linear plasma device PSI 2. The temperature of the samples was ~576 °C-715 °C, the energy of impinging ions was 210 eV matching well the conditions expected at the first wall of DEMO. Weight loss measurements demonstrated similar mass decrease of smart alloys and pure tungsten samples. The oxidation of exposed samples has proven no effect of plasma exposure on the oxidation resistance. The W-Cr-Ti alloy demonstrated advantageous 3-fold lower mass gain due to oxidation than that of pure tungsten. New yttrium (Y)-containing thin film systems are demonstrating superior performance in comparison to that of W-Cr-Ti systems and of pure W. The oxidation rate constant of W-Cr-Y thin film is 105 times less than that of pure tungsten. However, the detected reactivity of the bulk smart alloy in humid atmosphere is calling for a further improvement.

Transition metals in superheat melts

NASA Technical Reports Server (NTRS)

Jakes, Petr; Wolfbauer, Michael-Patrick

1993-01-01

A series of experiments with silicate melts doped with transition element oxides was carried out at atmospheric pressures of inert gas at temperatures exceeding liquidus. As predicted from the shape of fO2 buffer curves in T-fO2 diagrams the reducing conditions for a particular oxide-metal pair can be achieved through the T increase if the released oxygen is continuously removed. Experimental studies suggest that transition metals such as Cr or V behave as siderophile elements at temperatures exceeding liquidus temperatures if the system is not buffered by the presence of other oxide of more siderophile element. For example the presence of FeO prevents the reduction of Cr2O3. The sequence of decreasing siderophility of transition elements at superheat conditions (Mo, Ni, Fe, Cr) matches the decreasing degree of depletion of siderophile elements in mantle rocks as compared to chondrites.

Bolide impacts and the oxidation state of carbon in the Earth's early atmosphere

NASA Technical Reports Server (NTRS)

Kasting, J. F.

1992-01-01

A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of Earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the Moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of Earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean. Specifically, high atmospheric CO/CO2 ratios are possible if either: (1) the climate was cool (like today's climate), so that hydration of dissolved CO to formate was slow, or (2) the formate formed from CO was efficiently converted into volatile, reduced carbon compounds, such as methane. A high atmospheric CO/CO2 ratio may have helped to facilitate prebiotic synthesis by enhancing the production rates of hydrogen cyanide and formaldehyde. Formaldehyde may have been produced even more efficiently by photochemical reduction of bicarbonate and formate in Fe(++)-rich surface waters.

Cerium anomaly at microscale in fossils.

PubMed

Gueriau, Pierre; Mocuta, Cristian; Bertrand, Loïc

2015-09-01

Patterns in rare earth element (REE) concentrations are essential instruments to assess geochemical processes in Earth and environmental sciences. Excursions in the "cerium anomaly" are widely used to inform on past redox conditions in sediments. This proxy resources to the specificity of cerium to adopt both the +III and +IV oxidation states, while most rare earths are purely trivalent and share very similar reactivity and transport properties. In practical terms, the level of cerium anomaly is established through elemental point quantification and profiling. All these models rely on a supposed homogeneity of the cerium oxidation state within the samples. However, this has never been demonstrated, whereas the cerium concentration can significantly vary within a sample, as shown for fossils, which would vastly complicate interpretation of REE patterns. Here, we report direct micrometric mapping of Ce speciation through synchrotron X-ray absorption spectroscopy and production of local rare earth patterns in paleontological fossil tissues through X-ray fluorescence mapping. The sensitivity of the approach is demonstrated on well-preserved fishes and crustaceans from the Late Cretaceous (ca. 95 million years (Myr) old). The presence of Ce under the +IV form within the fossil tissues is attributed to slightly oxidative local conditions of burial and agrees well with the limited negative cerium anomaly observed in REE patterns. The [Ce(IV)]/[Ce(tot)] ratio appears remarkably stable at the microscale within each fossil and is similar between fossils from the locality. Speciation maps were obtained from an original combination of synchrotron microbeam X-ray fluorescence, absorption spectroscopy, and diffraction, together with light and electron microscopy. This work also highlights the need for more systematic studies of cerium geochemistry at the microscale in paleontological contexts, in particular across fossil histologies.

How low does iron go? Chasing the active species in fe-catalyzed cross-coupling reactions.

PubMed

Bedford, Robin B

2015-05-19

The catalytic cross-coupling reactions of organic halides or related substrates with organometallic nucleophiles form the cornerstone of many carbon-carbon bond-forming processes. While palladium-based catalysts typically mediate such reactions, there are increasing concerns about the long-term sustainability of palladium in synthesis. This is due to the high cost of palladium, coupled with its low natural abundance, environmentally deleterious extraction (∼6 g of metal are produced per ton of ore), toxicity, and competition for its use from the automotive and consumer electronics sectors. Therefore, there is a growing interest in replacing palladium-based catalysts with those incorporating more earth-abundant elements. With its low cost, high natural abundance, and low toxicity, iron makes a particularly appealing alternative, and accordingly, the development of iron-catalyzed cross-coupling is undergoing explosive growth. However, our understanding of the mechanisms that underpin the iron-based catalytic cycles is still very much in its infancy. Mechanistic insight into catalytic reactions is not only academically important but also allows us to maximize the efficiency of processes or even to develop entirely new transformations. Key to the development of robust mechanistic models for cross-coupling is knowing the lowest oxidation state in the cycle. Once this is established, we can explore subsequent redox processes and build the catalytic manifold. Until we know with confidence what the lowest oxidation state is, any cycles proposed are largely just guesswork. To date, Fe(-II), Fe(-I), Fe(0), Fe(I), and Fe(II) have been proposed as contenders for the lowest-oxidation-state species in the cycle in iron-catalyzed cross-coupling; the aim of this Account is to pull together the various pieces of evidence in support, or otherwise, of each of these suggestions in turn. There currently exists no direct evidence that oxidation states below Fe(0) are active in the catalytic cycle. Meanwhile, the reactivity required of the lowest-oxidation-state species has been observed with model compounds in higher oxidation states, implying that there is no need to invoke such low oxidation states. While subzero-valent complexes do indeed act as effective precatalysts, it is important to recognize that this tells us that they are efficiently converted to an active catalyst but says nothing about the oxidation states of the species in the catalytic cycle. Zero-valent heterogeneous iron nanoparticles can be formed under typical catalytic conditions, but there is no evidence to suggest that homogeneous Fe(0) complexes can be produced under comparable conditions. It seems likely that the zero-valent nanoparticles act as a reservoir for soluble higher-oxidation-state species. Fe(II) complexes can certainly be formed under catalytically relevant conditions, and when bulky nucleophilic coupling partners are exploited, potential intermediates can be isolated. However, the bulky reagents act as poor proxies for most nucleophiles used in cross-coupling, as they give Fe(II) organometallic intermediates that are kinetically stabilized with respect to reductive elimination. When more realistic substrates are exploited, reduction or disproportionation to Fe(I) is widely observed, and while it still has not been conclusively proved, this oxidation state currently represents a likely candidate for the lowest one active in many iron-catalyzed cross-coupling processes.

Process for producing metal compounds from graphite oxide

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh (Inventor)

2000-01-01

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen This intermediary product can be flier processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

Process for Producing Metal Compounds from Graphite Oxide

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh (Inventor)

2000-01-01

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon. metal. chloride. and oxygen This intermediary product can be flier processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon. metal carbonate. and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide: b) in an inert environment to produce metal oxide on carbon substrate: c) in a reducing environment. to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

Organic and Aqueous Redox Speciation of Cu(III) Periodate Oxidized Transuranium Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCann, Kevin; Sinkov, Sergey I.; Lumetta, Gregg J.

A hexavalent group actinide separation process could streamline used nuclear fuel recycle and waste management. The limiting factor to such a process compatible with current fuel dissolution practices is obtaining and maintaining hexavalent Am, in molar nitric acid due to the high reduction potential of the Am(VI)/Am(III) couple (1.68 V vs SCE). Two strong oxidants, sodium bismuthate and Cu(III) periodate, have demonstrated quantitative oxidation of Am under molar acid conditions and better than 50% recovery by diamyl amylphosphonate (DAAP) is possible under these same conditions. This work considers the use of Cu(III) periodate to oxidize Np(V) to Np(VI) and Pu(IV)more » to Pu(VI) and recover these elements by extraction with DAAP. A metal:oxidant ratio of 1:1.2 and 1:3 was necessary to quantitatively oxidize Np(V) and Pu(IV), respectively, to the hexavalent state. Extraction of hexavalent Np, Pu, and Am by 1 M DAAP in n-dodecane was measured using UV-Vis [Pu(VI), Am (VI)] and NIR [Np(VI)]. Distribution values of Am(VI) were found to match previous tracer level studies. The organic phase spectra of Np, Pu, and Am are presented and molar absorptivities are calculated for characteristic peaks. Hexavalent Pu was found to be stable in the organic phase while Np(VI) showed some reduction to Np(V) and Am was present as Am(III), Am(V), and Am(VI) species in aqueous and organic phases during the extraction experiments. These results demonstrate, for the first time, the ability to recover macroscopic amounts of americium that would be present during fuel reprocessing and are the first characterization of Am organic phase oxidation state speciation relevant to a hexavalent group actinide separation process under acidic conditions.« less

Computational Design of Flat-Band Material.

PubMed

Hase, I; Yanagisawa, T; Kawashima, K

2018-02-26

Quantum mechanics states that hopping integral between local orbitals makes the energy band dispersive. However, in some special cases, there are bands with no dispersion due to quantum interference. These bands are called as flat band. Many models having flat band have been proposed, and many interesting physical properties are predicted. However, no real compound having flat band has been found yet despite the 25 years of vigorous researches. We have found that some pyrochlore oxides have quasi-flat band just below the Fermi level by first principles calculation. Moreover, their valence bands are well described by a tight-binding model of pyrochlore lattice with isotropic nearest neighbor hopping integral. This model belongs to a class of Mielke model, whose ground state is known to be ferromagnetic with appropriate carrier doping and on-site repulsive Coulomb interaction. We have also performed a spin-polarized band calculation for the hole-doped system from first principles and found that the ground state is ferromagnetic for some doping region. Interestingly, these compounds do not include magnetic element, such as transition metal and rare-earth elements.

Computational Design of Flat-Band Material

NASA Astrophysics Data System (ADS)

Hase, I.; Yanagisawa, T.; Kawashima, K.

2018-02-01

Quantum mechanics states that hopping integral between local orbitals makes the energy band dispersive. However, in some special cases, there are bands with no dispersion due to quantum interference. These bands are called as flat band. Many models having flat band have been proposed, and many interesting physical properties are predicted. However, no real compound having flat band has been found yet despite the 25 years of vigorous researches. We have found that some pyrochlore oxides have quasi-flat band just below the Fermi level by first principles calculation. Moreover, their valence bands are well described by a tight-binding model of pyrochlore lattice with isotropic nearest neighbor hopping integral. This model belongs to a class of Mielke model, whose ground state is known to be ferromagnetic with appropriate carrier doping and on-site repulsive Coulomb interaction. We have also performed a spin-polarized band calculation for the hole-doped system from first principles and found that the ground state is ferromagnetic for some doping region. Interestingly, these compounds do not include magnetic element, such as transition metal and rare-earth elements.

A memristor-based nonvolatile latch circuit

NASA Astrophysics Data System (ADS)

Robinett, Warren; Pickett, Matthew; Borghetti, Julien; Xia, Qiangfei; Snider, Gregory S.; Medeiros-Ribeiro, Gilberto; Williams, R. Stanley

2010-06-01

Memristive devices, which exhibit a dynamical conductance state that depends on the excitation history, can be used as nonvolatile memory elements by storing information as different conductance states. We describe the implementation of a nonvolatile synchronous flip-flop circuit that uses a nanoscale memristive device as the nonvolatile memory element. Controlled testing of the circuit demonstrated successful state storage and restoration, with an error rate of 0.1%, during 1000 power loss events. These results indicate that integration of digital logic devices and memristors could open the way for nonvolatile computation with applications in small platforms that rely on intermittent power sources. This demonstrated feasibility of tight integration of memristors with CMOS (complementary metal-oxide-semiconductor) circuitry challenges the traditional memory hierarchy, in which nonvolatile memory is only available as a large, slow, monolithic block at the bottom of the hierarchy. In contrast, the nonvolatile, memristor-based memory cell can be fast, fine-grained and small, and is compatible with conventional CMOS electronics. This threatens to upset the traditional memory hierarchy, and may open up new architectural possibilities beyond it.

Modeling of selected ceramic processing parameters employed in the fabrication of 238PuO 2 fuel pellets

DOE PAGES

Brockman, R. A.; Kramer, D. P.; Barklay, C. D.; ...

2011-10-01

Recent deep space missions utilize the thermal output of the radioisotope plutonium-238 as the fuel in the thermal to electrical power system. Since the application of plutonium in its elemental state has several disadvantages, the fuel employed in these deep space power systems is typically in the oxide form such as plutonium-238 dioxide ( 238PuO 2). As an oxide, the processing of the plutonium dioxide into fuel pellets is performed via ''classical'' ceramic processing unit operations such as sieving of the powder, pressing, sintering, etc. Modeling of these unit operations can be beneficial in the understanding and control of processingmore » parameters with the goal of further enhancing the desired characteristics of the 238PuO 2 fuel pellets. A finite element model has been used to help identify the time-temperature-stress profile within a pellet during a furnace operation taking into account that 238PuO 2 itself has a significant thermal output. The results of the modeling efforts will be discussed.« less

Sulfur oxidation to sulfate coupled with electron transfer to electrodes by Desulfuromonas strain TZ1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, T; Bain, TS; Barlett, MA

2014-01-02

Microbial oxidation of elemental sulfur with an electrode serving as the electron acceptor is of interest because this may play an important role in the recovery of electrons from sulfidic wastes and for current production in marine benthic microbial fuel cells. Enrichments initiated with a marine sediment inoculum, with elemental sulfur as the electron donor and a positively poised (+300 mV versus Ag/AgCl) anode as the electron acceptor, yielded an anode biofilm with a diversity of micro-organisms, including Thiobacillus, Sulfurimonas, Pseudomonas, Clostridium and Desulfuromonas species. Further enrichment of the anode biofilm inoculum in medium with elemental sulfur as the electronmore » donor and Fe(III) oxide as the electron acceptor, followed by isolation in solidified sulfur/Fe(III) medium yielded a strain of Desulfuromonas, designated strain TZ1. Strain TZ1 effectively oxidized elemental sulfur to sulfate with an anode serving as the sole electron acceptor, at rates faster than Desulfobulbus propionicus, the only other organism in pure culture previously shown to oxidize S with current production. The abundance of Desulfuromonas species enriched on the anodes of marine benthic fuel cells has previously been interpreted as acetate oxidation driving current production, but the results presented here suggest that sulfur-driven current production is a likely alternative.« less

State of the Haze: The Causes and Consequences of a Hydrocarbon-rich Neoarchean Atmosphere

NASA Astrophysics Data System (ADS)

Zerkle, A.; Izon, G. J.; Claire, M.

2016-12-01

Atmospheric oxygen is thought to have rose irreversibly during the Great Oxidation Event (GOE) 2.4 billion-years-ago, though recent evidence shows that dynamic planetary transitions were also occurring prior to the oxidation of the atmosphere. We've recently documented perturbations in the reducing Neoarchean atmosphere, whereby the planet was periodically enshrouded in a CH4-rich haze. This scenario is based on coupled C- and S-isotope records from two continents, spanning a period of 200 million years [1-3]. A re-evaluation of these data at high resolution alongside additional proxies for trace element and nutrient analyses reveals that haze formed geologically rapidly, as a transient response to top-down stimulation of the biosphere. Net methane fluxes were ultimately controlled by the relative availability of organic-carbon and sulfate, with methanogenesis able to out-pace anaerobic methane oxidation in the low sulfate world of the Neoarchean. In addition, elevated CH4 flux to the atmosphere would have accelerated planetary hydrogen loss, expediting planetary oxidation and paving the way for the GOE [4]. These records suggest that the Neoarchean likely represented a unique state of the Earth System where links between the sulfur and methane cycles played a pivotal role in planetary oxidation and the contingent biological innovations that followed. [1] Zerkle et al. (2012) Nature Geoscience; [2] Farquhar et al. (2013) PNAS; [3] Izon et al. (2015) EPSL; [4] Izon et al. (in review).

Complete phase diagram of rare-earth nickelates from first-principles

NASA Astrophysics Data System (ADS)

Varignon, Julien; Grisolia, Mathieu N.; Íñiguez, Jorge; Barthélémy, Agnès; Bibes, Manuel

2017-12-01

The structural, electronic and magnetic properties of AMO3 perovskite oxides, where M is a 3d transition metal, are highly sensitive to the geometry of the bonds between the metal-d and oxygen-p ions (through octahedra rotations and distortions) and to their level of covalence. This is particularly true in rare-earth nickelates RNiO3 that display a metal-insulator transition with complex spin orders tunable by the rare-earth size, and are on the border line between dominantly ionic (lighter elements) and covalent characters (heavier elements). Accordingly, computing their ground state is challenging and a complete theoretical description of their rich phase diagram is still missing. Here, using first-principles simulations, we successfully describe the electronic and magnetic experimental ground state of nickelates. We show that the insulating phase is characterized by a split of the electronic states of the two Ni sites (i.e., resembling low-spin 4+ and high-spin 2+) with a concomitant shift of the oxygen-2p orbitals toward the depleted Ni cations. Therefore, from the point of view of the charge, the two Ni sites appear nearly identical whereas they are in fact distinct. Performing such calculations for several nickelates, we built a theoretical phase diagram that reproduces all their key features, namely a systematic dependence of the metal-insulator transition with the rare-earth size and the crossover between a second to first order transition for R = Pr and Nd. Finally, our results hint at strategies to control the electronic and magnetic phases of perovskite oxides by fine tuning of the level of covalence.

Structural and elemental analysis of bottom sediments from the Paraíba do Sul River (SE, Brazil) by analytical microscopy

NASA Astrophysics Data System (ADS)

Miguens, Flávio Costa; Oliveira, Martha Lima de; Ferreira, Amanda de Oliveira; Barbosa, Laís Rodrigues; Melo, Edésio José Tenório de; Carvalho, Carlos Eduardo Veiga de

2016-03-01

The Paraíba do Sul River (PSR) is a medium-sized river that flows through the Minas Gerais, São Paulo and Rio de Janeiro Brazilian states the three most developed states in Brazil. Industrial parks and cities have historically been established along the river basin. The waters of PSR are used in agriculture, industry and human consumption of over 20 million people, including Rio de Janeiro City. Furthermore, the river receives effluent from these activities: agricultural runoff, industrial waste, and domestic sewage. Therefore, PSR has been considered polluted, particularly by heavy metals. In order to assess heavy metals in bottom sediments grains of the PSR, to infer their elemental composition, and to characterize individual sediment grains morphology, a non-destructive methodology - X-ray microanalyses (Scanning Electron Microscope coupled to Energy Dispersive X-rays Spectrometer/SEM/EDS) - was used. Heavy metals - Cr, Mn, Ni, Cu, Zn, Zr, Ag, Ba, Au, La, Ce, Nd, Th, Y, Sn, Os and Pb - were detected by SEM/EDS in bottom sediment grains from PSR, predominantly in grains with equivalent diameter ≤10 μm. They occurred as silicates, oxides (hydro-oxides), sulfides, carbonates, sulfates, phosphates and chlorides. All detected heavy metals occurred as, at least, one kind of soluble metal compound, mainly due to ionic exchange from silicates, with the exception of Ag, which was chloride, sulfate or metallic as Os, Au and Pb. These results corroborate heavy metal PSR pollution and food chain risk, considering that near-shore continental shelf is free of heavy metals contamination. Our results also give support to the hypothesis that the PSR estuary can act as a trap for these elements.

Speciated Elemental and Isotopic Characterization of Atmospheric Aerosols - Recent Advances

NASA Astrophysics Data System (ADS)

Shafer, M.; Majestic, B.; Schauer, J.

2007-12-01

Detailed elemental, isotopic, and chemical speciation analysis of aerosol particulate matter (PM) can provide valuable information on PM sources, atmospheric processing, and climate forcing. Certain PM sources may best be resolved using trace metal signatures, and elemental and isotopic fingerprints can supplement and enhance molecular maker analysis of PM for source apportionment modeling. In the search for toxicologically relevant components of PM, health studies are increasingly demanding more comprehensive characterization schemes. It is also clear that total metal analysis is at best a poor surrogate for the bioavailable component, and analytical techniques that address the labile component or specific chemical species are needed. Recent sampling and analytical developments advanced by the project team have facilitated comprehensive characterization of even very small masses of atmospheric PM. Historically; this level of detail was rarely achieved due to limitations in analytical sensitivity and a lack of awareness concerning the potential for contamination. These advances have enabled the coupling of advanced chemical characterization to vital field sampling approaches that typically supply only very limited PM mass; e.g. (1) particle size-resolved sampling; (2) personal sampler collections; and (3) fine temporal scale sampling. The analytical tools that our research group is applying include: (1) sector field (high-resolution-HR) ICP-MS, (2) liquid waveguide long-path spectrophotometry (LWG-LPS), and (3) synchrotron x-ray absorption spectroscopy (sXAS). When coupled with an efficient and validated solubilization method, the HR-ICP-MS can provide quantitative elemental information on over 50 elements in microgram quantities of PM. The high mass resolution and enhanced signal-to-noise of HR-ICP-MS significantly advance data quality and quantity over that possible with traditional quadrupole ICP-MS. The LWG-LPS system enables an assessment of the soluble/labile components of PM, while simultaneously providing critical oxidation state speciation data. Importantly, the LWG- LPS can be deployed in a semi-real-time configuration to probe fine temporal scale variations in atmospheric processing or sources of PM. The sXAS is providing complementary oxidation state speciation of bulk PM. Using examples from our research; we will illustrate the capabilities and applications of these new methods.

In situ X-ray diffraction contribution to the study of reactive element oxide coating effect on the high temperature oxidation behaviour of FeCrAl alloys

NASA Astrophysics Data System (ADS)

Cueff, R.; Buscail, H.; Caudron, E.; Riffard, F.; Issartel, C.; Perrier, S.; El Messki, S.

2004-11-01

The influence of yttrium oxide coating (processed by sol-gel method) on the oxidation behaviour of a commercial FeCrAl alloy (Kanthal A1) has been investigated during isothermal exposures in air at 1373K. The scale growth kinetic of the uncoated alloy obeys a parabolic rate law during the whole oxidation test whereas the kinetic curve of the Y-coated specimen exhibits an initial transient stage during the first hours, followed by a parabolic regime. The yttrium sol-gel coating deposited on the bare alloy does not conduct to the beneficial effect usually ascribed to the reactive elements. No oxidation rate improvement of the coated alloy is observed, the parabolic rate constants values are strictly identical for the both specimens. In situ X-ray diffraction reveals a marked influence of the reactive element on the composition of the oxide scale. The oxide layer formed on the yttrium-coated specimen revealed, in addition to α-alumina which is the main oxide also identified on the bare specimen, the presence of yttrium aluminates (YAlO{3}, Y{3}Al{5}O{12}) located in the outermost part of the layer.

Friction and surface chemistry of some ferrous-base metallic glasses

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1982-01-01

The friction properties of some ferrous-base metallic glasses were measured both in argon and in vacuum to a temperature of 350 C. The alloy surfaces were also analyzed with X-ray photoelectron spectroscopy to identify the compounds and elements present on the surface. The results of the investigation indicate that even when the surfaces of the amorphous alloys, or metallic glasses, are atomically clean, bulk contaminants such as boric oxide and silicon dioxide diffuse to the surfaces. Friction measurements in both argon and vacuum indicate that the alloys exhibit higher coefficients of friction in the crystalline state than they do in the amorphous state.

Ligand field splittings in core level transitions for transition metal (TM) oxides: Tanabe-Sugano diagrams and (TM) dangling bonds in vacated O-atom defects

NASA Astrophysics Data System (ADS)

Lucovsky, Gerry; Wu, Kun; Pappas, Brian; Whitten, Jerry

2013-04-01

Defect states in the forbidden band-gap below the conduction band edge are active as electron traps in nano-grain high-) transition metal (TM) oxides with thickness >0.3 nm, e.g., ZrO2 and HfO2. These oxides have received considerable attention as gate-dielectrics in complementary metal oxide semiconductor (CMOS) devices, and more recently are emerging as candidates for charge storage and memory devices. To provide a theoretical basis for device functionality, ab-initio many-electron theory is combined with X-ray absorption spectroscopy (XAS) to study O K edge and TM core level transitions. These studies identify ligand field splittings (ΔLF) for defect state features,. When compared with those obtained from O-atom and TM-atom core spectroscopic transitions, this provides direct information about defect state sun-nm bonding arrangements. comparisons are made for (i) elemental TiO2 and Ti2O3 with different formal ionic charges, Ti4+ and Ti3+ and for (ii) Magneli Phase alloys, TinO2n-1, n is an integer 9>=n>3, and (TiO2)x(HfO2)1-x alloys. The alloys display multi-valent behavior from (i) different ionic-charge states, (ii} local bond-strain, and (iii) metallic hopping transport. The intrinsic bonding defects in TM oxides are identified as pairs of singly occupied dangling bonds. For 6-fold coordinated Ti-oxides defect excited states in 2nd derivative O K pre-edge spectra are essentially the same as single Ti-atom d2 transitions in Tanabe-Sugano (T-S) diagrams. O-vacated site defects in 8-fold coordinated ZrO2 and HfO2 are described by d8 T-S diagrams. T-S defect state ordering and splittings are functions of the coordination and symmetry of vacated site bordering TM atoms. ΔLF values from the analysis of T-S diagrams indicate medium range order (MRO) extending to 3rd and 4th nearest-neighbor (NN) TM-atoms. Values are different for 6-fold Ti, and 8-fold ZrO2 and HfO2, and scale inversely with differences in respective formal ionic radii. O-vacated site bonding defects in TM nano-grain oxides are qualitatively similar to vacant-site defects in non-crystalline SiO2 and GeO2 for ulta-thin films, < 0.2 nm thick, and yield similar performance in MOSCAPs on Ge substrates heralding applications in aggressively-scale CMOS devices.

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

PubMed

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 make the π*(M═O) orbitals accessible to the addition of electrons. This result is consistent with previous extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) data that reveal that the Tc(V) is "pulled" into the -α1 framework and that may facilitate the reduction of Tc(V)O-α1 and stabilize lower Tc oxidation states. This study highlights the inequivalency of the two sites, and their impact on the chemical properties of the Tc substituted in these positions.

Superconducting structure

DOEpatents

Kwon, Chuhee; Jia, Quanxi; Foltyn, Stephen R.

2003-04-01

A superconductive structure including a dielectric oxide substrate, a thin buffer layer of a superconducting material thereon; and, a layer of a rare earth-barium-copper oxide superconducting film thereon the thin layer of yttrium-barium-copper oxide, the rare earth selected from the group consisting of samarium, gadolinium, ytterbium, erbium, neodymium, dysprosium, holmium, lutetium, a combination of more than one element from the rare earth group and a combination of one or more elements from the rare earth group with yttrium, the buffer layer of superconducting material characterized as having chemical and structural compatibility with the dielectric oxide substrate and the rare earth-barium-copper oxide superconducting film is provided.

Superconducting Structure

DOEpatents

Kwon, Chuhee; Jia, Quanxi; Foltyn, Stephen R.

2005-09-13

A superconductive structure including a dielectric oxide substrate, a thin buffer layer of a superconducting material thereon; and, a layer of a rare earth-barium-copper oxide superconducting film thereon the thin layer of yttrium-barium-copper oxide, the rare earth selected from the group consisting of samarium, gadolinium, ytterbium, erbium, neodymium, dysprosium, holmium, lutetium, a combination of more than one element from the rare earth group and a combination of one or more elements from the rare earth group with yttrium, the buffer layer of superconducting material characterized as having chemical and structural compatibility with the dielectric oxide substrate and the rare earth-barium-copper oxide superconducting film is provided.

Noncontact evaluation for interface states by photocarrier counting

NASA Astrophysics Data System (ADS)

Furuta, Masaaki; Shimizu, Kojiro; Maeta, Takahiro; Miyashita, Moriya; Izunome, Koji; Kubota, Hiroshi

2018-03-01

We have developed a noncontact measurement method that enables in-line measurement and does not have any test element group (TEG) formation. In this method, the number of photocarriers excited from the interface states are counted which is called “photocarrier counting”, and then the energy distribution of the interface states density (D it) is evaluated by spectral light excitation. In our previous experiment, the method used was a preliminary contact measurement method at the oxide on top of the Si wafer. We developed, at this time, a D it measurement method as a noncontact measurement with a gap between the probes and the wafer. The shallow trench isolation (STI) sidewall has more localized interface states than the region under the gate electrode. We demonstrate the noncontact measurement of trapped carriers from interface states using wafers of three different crystal plane orientations. The demonstration will pave the way for evaluating STI sidewall interface states in future studies.

The elements of life and medicines

PubMed Central

Chellan, Prinessa; Sadler, Peter J

2015-01-01

Which elements are essential for human life? Here we make an element-by-element journey through the periodic table and attempt to assess whether elements are essential or not, and if they are, whether there is a relevant code for them in the human genome. There are many difficulties such as the human biochemistry of several so-called essential elements is not well understood, and it is not clear how we should classify elements that are involved in the destruction of invading microorganisms, or elements which are essential for microorganisms with which we live in symbiosis. In general, genes do not code for the elements themselves, but for specific chemical species, i.e. for the element, its oxidation state, type and number of coordinated ligands, and the coordination geometry. Today, the biological periodic table is in a position somewhat similar to Mendeleev's chemical periodic table of 1869: there are gaps and we need to do more research to fill them. The periodic table also offers potential for novel therapeutic and diagnostic agents, based on not only essential elements, but also non-essential elements, and on radionuclides. Although the potential for inorganic chemistry in medicine was realized more than 2000 years ago, this area of research is still in its infancy. Future advances in the design of inorganic drugs require more knowledge of their mechanism of action, including target sites and metabolism. Temporal speciation of elements in their biological environments at the atomic level is a major challenge, for which new methods are urgently needed. PMID:25666066

The elements of life and medicines.

PubMed

Chellan, Prinessa; Sadler, Peter J

2015-03-13

Which elements are essential for human life? Here we make an element-by-element journey through the periodic table and attempt to assess whether elements are essential or not, and if they are, whether there is a relevant code for them in the human genome. There are many difficulties such as the human biochemistry of several so-called essential elements is not well understood, and it is not clear how we should classify elements that are involved in the destruction of invading microorganisms, or elements which are essential for microorganisms with which we live in symbiosis. In general, genes do not code for the elements themselves, but for specific chemical species, i.e. for the element, its oxidation state, type and number of coordinated ligands, and the coordination geometry. Today, the biological periodic table is in a position somewhat similar to Mendeleev's chemical periodic table of 1869: there are gaps and we need to do more research to fill them. The periodic table also offers potential for novel therapeutic and diagnostic agents, based on not only essential elements, but also non-essential elements, and on radionuclides. Although the potential for inorganic chemistry in medicine was realized more than 2000 years ago, this area of research is still in its infancy. Future advances in the design of inorganic drugs require more knowledge of their mechanism of action, including target sites and metabolism. Temporal speciation of elements in their biological environments at the atomic level is a major challenge, for which new methods are urgently needed.

A study to investigate the chemical stability of gallium phosphate oxide/gallium arsenide phosphide

NASA Technical Reports Server (NTRS)

Kuhlman, G. J.

1979-01-01

The elemental composition with depth into the oxide films was examined using secondary ion mass spectrometry. Results indicate that the layers are arsenic-deficient through the bulk of the oxide and arsenic-rich near both the oxide surface and the oxide-semiconductor interface region. Phosphorus is incorporated into the oxide in an approximately uniform manner. The MIS capacitor structures exhibited deep-depletion characteristics and hysteresis indicative of electron trapping at the oxide-semiconductor interface. Post-oxidation annealing of the films in argon or nitrogen generally results in slightly increased dielectric leakage currents and decreased C-V hysteresis effects, and is associated with arsenic loss at the oxide surface. The results of bias-temperature stress experiments indicate that the major instability effects are due to changes in the electron trapping behavior. No changes were observed in the elemental profiles following electrical stressing, indicating that the grown films are chemically stable under device operating conditions.

Method of removing and recovering elemental sulfur from highly reducing gas streams containing sulfur gases

DOEpatents

Gangwal, Santosh K.; Nikolopoulos, Apostolos A.; Dorchak, Thomas P.; Dorchak, Mary Anne

2005-11-08

A method is provided for removal of sulfur gases and recovery of elemental sulfur from sulfur gas containing supply streams, such as syngas or coal gas, by contacting the supply stream with a catalyst, that is either an activated carbon or an oxide based catalyst, and an oxidant, such as sulfur dioxide, in a reaction medium such as molten sulfur, to convert the sulfur gases in the supply stream to elemental sulfur, and recovering the elemental sulfur by separation from the reaction medium.

NEUTRONIC REACTOR FUEL ELEMENT

DOEpatents

Shackleford, M.H.

1958-12-16

A fuel element possessing good stability and heat conducting properties is described. The fuel element comprises an outer tube formed of material selected from the group consisting of stainhess steel, V, Ti. Mo. or Zr, a fuel tube concentrically fitting within the outer tube and containing an oxide of an isotope selected from the group consisting of U/sup 235/, U/sup 233/, and Pu/sup 239/, and a hollow, porous core concentrically fitting within the fuel tube and formed of an oxide of an element selected from the group consisting of Mg, Be, and Zr.

NOVEL OXIDANT FOR ELEMENTAL MERCURY CONTROL FROM FLUE GAS

EPA Science Inventory

The primary objective of this study is to develop and test advanced noncarbonaceous solid sorbent materials suitable for removing the elemental form of mercury from power plant emissions. An efficient and cost-effective novel Hg(0) oxidant was evaluated in a lab-scale fixed-bed ...

Chromium Oxidation State in Planetary Basalts: Oxygen Fugacity Indicator and Critical Variable for Cr-Spinel Stability

NASA Technical Reports Server (NTRS)

Bell, A. S.; Burger, P. V.; Le, Loan; Papike, J. J.; Jone, J.; Shearer, C. K.

2014-01-01

Cr is a ubiquitous and relatively abundant minor element in basaltic, planetary magmas. At the reduced oxidation states (

Technological pretreatment of the synchysite non-oxidized ore

NASA Astrophysics Data System (ADS)

Munkhtsetseg, B.; Burmaa, G.

2013-06-01

Mongolia has rich deposits of rare, precious, and poly-metallic ores. Nowadays, it is important to research separation of rare earth elements oxides concentrates from the ores, analyze their unique physical chemical characteristics, and purified it. Our investigation on raw materials focuses on rare earth non-oxidized ores. Main mineral in this rock sample is Synchysite (LnCa(CO3)2F. We did technological and thermal pretreatment: direct sulphurization (H2SO4), sulphurization with subsequent roasting (800°C+H2SO4), sulphurization prior to roasting (H2SO4+650°C). Sulphurization method based on dissolution of rare earth mineral into sulfuric acid (93%) according to the reaction. The amount of rare earth element oxides is almost 10 times greater (29.16%) after direct sulphurization process, almost 8 times greater (21.14%) after sulphurization with subsequent roasting, and almost 20 times greater (44.62%) after sulphurization prior to roasting process. After those technological pretreatment raw material's micro elements Thorium and Uranium contents are reduced as follows: H2SO4>800°C+H2SO4>H2SO4+650°C. These results show that cerium group rare earth elements have very good solubility in water at +2°C temperature and decreasing micro elements content uranium and thorium good pretreatment condition is prior to roasting (H2SO4+650°C) of synchysite non-oxidized ore.

High quality transparent conducting oxide thin films

DOEpatents

Gessert, Timothy A.; Duenow, Joel N.; Barnes, Teresa; Coutts, Timothy J.

2012-08-28

A transparent conducting oxide (TCO) film comprising: a TCO layer, and dopants selected from the elements consisting of Vanadium, Molybdenum, Tantalum, Niobium, Antimony, Titanium, Zirconium, and Hafnium, wherein the elements are n-type dopants; and wherein the transparent conducting oxide is characterized by an improved electron mobility of about 42 cm.sup.2/V-sec while simultaneously maintaining a high carrier density of .about.4.4e.times.10.sup.20 cm.sup.-3.

Simple Hydrogen Plasma Doping Process of Amorphous Indium Gallium Zinc Oxide-Based Phototransistors for Visible Light Detection.

PubMed

Kang, Byung Ha; Kim, Won-Gi; Chung, Jusung; Lee, Jin Hyeok; Kim, Hyun Jae

2018-02-28

A homojunction-structured amorphous indium gallium zinc oxide (a-IGZO) phototransistor that can detect visible light is reported. The key element of this technology is an absorption layer composed of hydrogen-doped a-IGZO. This absorption layer is fabricated by simple hydrogen plasma doping, and subgap states are induced by increasing the amount of hydrogen impurities. These subgap states, which lead to a higher number of photoexcited carriers and aggravate the instability under negative bias illumination stress, enabled the detection of a wide range of visible light (400-700 nm). The optimal condition of the hydrogen-doped absorption layer (HAL) is fabricated at a hydrogen partial pressure ratio of 2%. As a result, the optimized a-IGZO phototransistor with the HAL exhibits a high photoresponsivity of 1932.6 A/W, a photosensitivity of 3.85 × 10 6 , and a detectivity of 6.93 × 10 11 Jones under 635 nm light illumination.

REDUCTION OF INORGANIC COMPOUNDS WITH MOLECULAR HYDROGEN BY MICROCOCCUS LACTILYTICUS I.

PubMed Central

Woolfolk, C. A.; Whiteley, H. R.

1962-01-01

Woolfolk, C. A. (University of Washington, Seattle) and H. R. Whiteley. Reduction of inorganic compounds with molecular hydrogen by Micrococcus lactilyticus. I. Stoichiometry with compounds of arsenic, selenium, tellurium, transition and other elements. J. Bacteriol. 84:647–658. 1962.—Extracts of Micrococcus lactilyticus (Veillonella alcalescens) oxidize molecular hydrogen at the expense of certain compounds of arsenic, bismuth, selenium, tellurium, lead, thallium, vanadium, manganese, iron, copper, molybdenum, tungsten, osmium, ruthenium, gold, silver, and uranium, as well as molecular oxygen. Chemical and manometric data indicate that the following reductions are essentially quantitative: arsenate to arsenite, pentavalent and trivalent bismuth to the free element, selenite via elemental selenium to selenide, tellurate and tellurite to tellurium, lead dioxide and manganese dioxide to the divalent state, ferric to ferrous iron, osmium tetroxide to osmate ion, osmium dioxide and trivalent osmium to the metal, uranyl uranium to the tetravalent state, vanadate to the level of vanadyl, and polymolybdate ions to molybdenum blues with an average valence for molybdenum of +5. The results of a study of certain other hydrogenase-containing bacteria with respect to their ability to carry out some of the same reactions are also presented. PMID:14001842

The cyclic oxidation resistance at 1200 C of beta-NiAl, FeAl, and CoAl alloys with selected third element additions

NASA Technical Reports Server (NTRS)

Barrett, C. A.; Titran, R. H.

1992-01-01

The intermetallic compounds Beta-NiAl, FeAl, and CoAl were tested in cyclic oxidation with selected third element alloy additions. Tests in static air for 200 1-hr cycles at 1200 C indicated by specific weight change/time data and x-ray diffraction analysis that the 5 at percent alloy additions did not significantly improve the oxidation resistance over the alumina forming baseline alloys without the additions. Many of the alloy additions were actually deleterious. Ta and Nb were the only alloy additions that actually altered the nature of the oxide(s) formed and still maintained the oxidation resistance of the protective alumina scale.

Elemental ratio measurements of organic compounds using aerosol mass spectrometry: characterization, improved calibration, and implications

NASA Astrophysics Data System (ADS)

Canagaratna, M. R.; Jimenez, J. L.; Kroll, J. H.; Chen, Q.; Kessler, S. H.; Massoli, P.; Hildebrandt Ruiz, L.; Fortner, E.; Williams, L. R.; Wilson, K. R.; Surratt, J. D.; Donahue, N. M.; Jayne, J. T.; Worsnop, D. R.

2014-07-01

Elemental compositions of organic aerosol (OA) particles provide useful constraints on OA sources, chemical evolution, and effects. The Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is widely used to measure OA elemental composition. This study evaluates AMS measurements of atomic oxygen-to-carbon (O : C), hydrogen-to-carbon (H : C), organic mass-to-organic carbon (OM : OC), and carbon oxidation state (OSC) for a vastly expanded laboratory dataset of multifunctional oxidized OA standards. For the expanded standard dataset, the "Aiken-Explicit" method (Aiken et al., 2008), which uses experimentally measured ion intensities at all ions to determine elemental ratios, reproduces known molecular O : C and H : C ratio values within 20% (average absolute value of relative errors) and 12% respectively. The more commonly used "Aiken-Ambient" method, which uses empirically estimated H2O+ and CO+ ion intensities to avoid gas phase air interferences at these ions, reproduces O : C and H : C of multifunctional oxidized species within 28% and 14% of known values. These values are systematically biased low, however, with larger biases observed for alcohols and simple diacids. A detailed examination of the H2O+, CO+, and CO2+ fragments in the high-resolution mass spectra of the standard compounds indicates that the Aiken-Ambient method underestimates the CO+ and H2O+ produced from many oxidized species. Combined AMS-vacuum ultraviolet (VUV) ionization measurements indicate that these ions are produced by dehydration and decarboxylation on the AMS vaporizer (usually operated at 600 °C). Thermal decomposition is observed to be efficient at vaporizer temperatures down to 200 °C. These results are used together to develop an "Improved-Ambient" elemental analysis method for AMS spectra measured in air. The Improved-Ambient method reduces the systematic biases and reproduces O : C (H : C) ratios of individual oxidized standards within 28% (13%) of the known molecular values. The error in Improved-Ambient O : C and H : C values is smaller (12% and 4% respectively) for synthetic mixtures of the oxidized organic standards, which are more representative of the complex mix of species present in ambient OA. For ambient OA, the Improved-Ambient method produces O : C (H : C) values that are 27% (11%) larger than previously published Aiken-Ambient values; a corresponding increase of 9% is observed for OM : OC values. These results imply that ambient OA has a higher relative oxygen content than previously estimated. The OSC values calculated for ambient OA by the two methods agree well, however (average relative difference of 0.06 OSC units). This indicates that OSC is a more robust metric of oxidation than O : C, likely since OSC is not affected by hydration or dehydration, either in the atmosphere or during analysis.

Elemental ratio measurements of organic compounds using aerosol mass spectrometry: Characterization, improved calibration, and implications

DOE PAGES

Canagaratna, M. R.; Jimenez, J. L.; Kroll, J. H.; ...

2015-01-12

Elemental compositions of organic aerosol (OA) particles provide useful constraints on OA sources, chemical evolution, and effects. The Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is widely used to measure OA elemental composition. This study evaluates AMS measurements of atomic oxygen-to-carbon (O : C), hydrogen-to-carbon (H : C), and organic mass-to-organic carbon (OM : OC) ratios, and of carbon oxidation state (OS C) for a vastly expanded laboratory data set of multifunctional oxidized OA standards. For the expanded standard data set, the method introduced by Aiken et al. (2008), which uses experimentally measured ion intensities at all ions to determinemore » elemental ratios (referred to here as "Aiken-Explicit"), reproduces known O : C and H : C ratio values within 20% (average absolute value of relative errors) and 12%, respectively. The more commonly used method, which uses empirically estimated H 2O + and CO + ion intensities to avoid gas phase air interferences at these ions (referred to here as "Aiken-Ambient"), reproduces O : C and H : C of multifunctional oxidized species within 28 and 14% of known values. The values from the latter method are systematically biased low, however, with larger biases observed for alcohols and simple diacids. A detailed examination of the H 2O +, CO +, and CO 2 + fragments in the high-resolution mass spectra of the standard compounds indicates that the Aiken-Ambient method underestimates the CO + and especially H 2O + produced from many oxidized species. Combined AMS–vacuum ultraviolet (VUV) ionization measurements indicate that these ions are produced by dehydration and decarboxylation on the AMS vaporizer (usually operated at 600 °C). Thermal decomposition is observed to be efficient at vaporizer temperatures down to 200 °C. These results are used together to develop an "Improved-Ambient" elemental analysis method for AMS spectra measured in air. The Improved-Ambient method uses specific ion fragments as markers to correct for molecular functionality-dependent systematic biases and reproduces known O : C (H : C) ratios of individual oxidized standards within 28% (13%) of the known molecular values. The error in Improved-Ambient O : C (H : C) values is smaller for theoretical standard mixtures of the oxidized organic standards, which are more representative of the complex mix of species present in ambient OA. For ambient OA, the Improved-Ambient method produces O : C (H : C) values that are 27% (11%) larger than previously published Aiken-Ambient values; a corresponding increase of 9% is observed for OM : OC values. These results imply that ambient OA has a higher relative oxygen content than previously estimated. The OS C values calculated for ambient OA by the two methods agree well, however (average relative difference of 0.06 OS C units). This indicates that OS C is a more robust metric of oxidation than O : C, likely since OS C is not affected by hydration or dehydration, either in the atmosphere or during analysis.« less

Advanced High Temperature Coating Systems Beyond Current State of the Art Systems.

DTIC Science & Technology

1986-04-15

cobalt and chromium rich oxides. The A120 3 scales developed on the NiCrAl and CoCrAI alloys doped with yttrium or hafnium were relatively flat and...third element such as Cr is present in the alloy. Chromium acts as a getter which prevents oxygen from entering the alloy, so A12 0 3 tends to develop...or Cr doped alumina. Yttrium is isovalent with aluminum so it is not expected to alter the intrinsic defect structure of alumina, however

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zarkesh, Ryan A.; Foster, Michael E.; Ichimura, Andrew S.

The ability to tune the steric envelope through redox events post-synthetically or in tandem with other chemical processes is a powerful tool that could assist in enabling new catalytic methodologies and understanding potential pitfalls in ligand design. The α-diimine ligand, dmp-BIAN, exhibits the peculiar and previously unreported feature of varying steric profiles depending on oxidation state when paired with a main group element. A study of the factors that give rise to this behaviour as well as its impact on the incorporation of other ligands is performed.

Information storage at the molecular level - The design of a molecular shift register memory

NASA Technical Reports Server (NTRS)

Beratan, David N.; Onuchic, Jose Nelson; Hopfield, J. J.

1989-01-01

The control of electron transfer rates is discussed and a molecular shift register memory at the molecular level is described. The memory elements are made up of molecules which can exist in either an oxidized or reduced state and the bits can be shifted between the cells with photoinduced electron transfer reactions. The device integrates designed molecules onto a VLSI substrate. A control structure to modify the flow of information along a shift register is indicated schematically.

Simultaneous Detection of Electronic Structure Changes from Two Elements of a Bifunctional Catalyst Using Wavelength-Dispersive X-ray Emission Spectroscopy and in situ Electrochemistry

PubMed Central

Gul, Sheraz; Desmond Ng, Jia Wei; Alonso-Mori, Roberto; Kern, Jan; Sokaras, Dimosthenis; Anzenberg, Eitan; Lassalle-Kaiser, Benedikt; Gorlin, Yelena; Weng, Tsu-Chien; Zwart, Petrus H.; Zhang, Jin Z.; Bergmann, Uwe; Yachandra, Vittal K.; Jaramillo, Thomas F.; Yano, Junko

2015-01-01

Multielectron catalytic reactions, such as water oxidation, nitrogen reduction, or hydrogen production in enzymes and inorganic catalysts often involve multimetallic clusters. In these systems, the reaction takes place between metals or metals and ligands to facilitate charge transfer, bond formation/breaking, substrate binding, and release of products. In this study, we present a method to detect X-ray emission signals from multiple elements simultaneously, which allows for the study of charge transfer and the sequential chemistry occurring between elements. Kβ X-ray emission spectroscopy (XES) probes charge and spin states of metals as well as their ligand environment. A wavelength-dispersive spectrometer based on the von Hamos geometry was used to disperse Kβ signals of multiple elements onto a position detector, enabling an XES spectrum to be measured in a single-shot mode. This overcomes the scanning needs of the scanning spectrometers, providing data free from temporal and normalization errors and therefore ideal to follow sequential chemistry at multiple sites. We have applied this method to study MnOx-based bifunctional electrocatalysts for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). In particular, we investigated the effects of adding a secondary element, Ni, to form MnNiOx and its impact on the chemical states and catalytic activity, by tracking the redox characteristics of each element upon sweeping the electrode potential. The detection scheme we describe here is general and can be applied to time-resolved studies of materials consisting of multiple elements, to follow the dynamics of catalytic and electron transfer reactions. PMID:25747045

Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry.

PubMed

Gul, Sheraz; Ng, Jia Wei Desmond; Alonso-Mori, Roberto; Kern, Jan; Sokaras, Dimosthenis; Anzenberg, Eitan; Lassalle-Kaiser, Benedikt; Gorlin, Yelena; Weng, Tsu-Chien; Zwart, Petrus H; Zhang, Jin Z; Bergmann, Uwe; Yachandra, Vittal K; Jaramillo, Thomas F; Yano, Junko

2015-04-14

Multielectron catalytic reactions, such as water oxidation, nitrogen reduction, or hydrogen production in enzymes and inorganic catalysts often involve multimetallic clusters. In these systems, the reaction takes place between metals or metals and ligands to facilitate charge transfer, bond formation/breaking, substrate binding, and release of products. In this study, we present a method to detect X-ray emission signals from multiple elements simultaneously, which allows for the study of charge transfer and the sequential chemistry occurring between elements. Kβ X-ray emission spectroscopy (XES) probes charge and spin states of metals as well as their ligand environment. A wavelength-dispersive spectrometer based on the von Hamos geometry was used to disperse Kβ signals of multiple elements onto a position detector, enabling an XES spectrum to be measured in a single-shot mode. This overcomes the scanning needs of the scanning spectrometers, providing data free from temporal and normalization errors and therefore ideal to follow sequential chemistry at multiple sites. We have applied this method to study MnOx-based bifunctional electrocatalysts for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). In particular, we investigated the effects of adding a secondary element, Ni, to form MnNiOx and its impact on the chemical states and catalytic activity, by tracking the redox characteristics of each element upon sweeping the electrode potential. The detection scheme we describe here is general and can be applied to time-resolved studies of materials consisting of multiple elements, to follow the dynamics of catalytic and electron transfer reactions.

Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry

DOE PAGES

Gul, Sheraz; Ng, Jia Wei Desmond; Alonso-Mori, Roberto; ...

2015-02-25

Multielectron catalytic reactions, such as water oxidation, nitrogen reduction, or hydrogen production in enzymes and inorganic catalysts often involve multimetallic clusters. In these systems, the reaction takes place between metals or metals and ligands to facilitate charge transfer, bond formation/breaking, substrate binding, and release of products. In this study, we present a method to detect X-ray emission signals from multiple elements simultaneously, which allows for the study of charge transfer and the sequential chemistry occurring between elements. Kβ X-ray emission spectroscopy (XES) probes charge and spin states of metals as well as their ligand environment. A wavelength-dispersive spectrometer based onmore » the von Hamos geometry was used to disperse Kβ signals of multiple elements onto a position detector, enabling an XES spectrum to be measured in a single-shot mode. This overcomes the scanning needs of the scanning spectrometers, providing data free from temporal and normalization errors and therefore ideal to follow sequential chemistry at multiple sites. We have applied this method to study MnOx-based bifunctional electrocatalysts for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). In particular, we investigated the effects of adding a secondary element, Ni, to form MnNiOx and its impact on the chemical states and catalytic activity, by tracking the redox characteristics of each element upon sweeping the electrode potential. In conclusion, the detection scheme we describe here is general and can be applied to time-resolved studies of materials consisting of multiple elements, to follow the dynamics of catalytic and electron transfer reactions.« less

Design and Simulation of Optically Actuated Bistable MEMS

NASA Astrophysics Data System (ADS)

Lucas, Thomas; Moiseeva, Evgeniya; Harnett, Cindy

2012-02-01

In this project, bistable three-dimensional MEMS actuators are designed to be optically switched between stable states for biological research applications. The structure is a strained rectangular frame created with stress-mismatched metal-oxide bilayers. The devices curl into an arc in one of two directions tangent to the substrate, and can switch orientation when regions are selectively heated. The heating is powered by infrared laser, and localized with patterned infrared-resonant gold nanoparticles on critical regions. The enhanced energy absorption on selected areas provides switching control and heightened response to narrow-band infrared light. Coventorware has been used for finite element analysis of the system. The numerical simulations indicate that it has two local minimum states with extremely rapid transition time (<<0.1 s) when the structure is thermally deformed. Actuation at laser power and thermal limits compatible with physiological applications will enable microfluidic pumping elements and fundamental studies of tissue response to three-dimensional mechanical stimuli, artificial-muscle based pumps and other biomedical devices triggered by tissue-permeant infrared light.

Effect of high-energy electron irradiation in an electron microscope column on fluorides of alkaline earth elements (CaF2, SrF2, and BaF2)

NASA Astrophysics Data System (ADS)

Nikolaichik, V. I.; Sobolev, B. P.; Zaporozhets, M. A.; Avilov, A. S.

2012-03-01

The effect of high-energy (150 eV) electron irradiation in an electron microscope column on crystals of fluorides of alkaline earth elements CaF2, SrF2, and BaF2 is studied. During structural investigations by electron diffraction and electron microscopy, the electron irradiation causes chemical changes in MF2 crystals such as the desorption of fluorine and the accumulation of oxygen in the irradiated area with the formation of oxide MO. The fluorine desorption rate increases significantly when the electron-beam density exceeds the threshold value of ˜2 × 103 pA/cm2). In BaF2 samples, the transformation of BaO into Ba(OH)2 was observed when irradiation stopped. The renewal of irradiation is accompanied by the inverse transformation of Ba(OH)2 into BaO. In the initial stage of irradiation of all MF2 compounds, the oxide phase is in the single-crystal state with a lattice highly matched with the MF2 matrix. When the irradiation dose is increased, the oxide phase passes to the polycrystalline phase. Gaseous products of MF2 destruction (in the form of bubbles several nanometers in diameter) form a rectangular array with a period of ˜20 nm in the sample.

Calculated power distribution of a thermionic, beryllium oxide reflected, fast-spectrum reactor

NASA Technical Reports Server (NTRS)

Mayo, W.; Lantz, E.

1973-01-01

A procedure is developed and used to calculate the detailed power distribution in the fuel elements next to a beryllium oxide reflector of a fast-spectrum, thermionic reactor. The results of the calculations show that, although the average power density in these outer fuel elements is not far from the core average, the power density at the very edge of the fuel closest to the beryllium oxide is about 1.8 times the core avearge.

PROCESS FOR PRODUCTION OF URANIUM HEXAFLUORIDE

DOEpatents

Fowler, R.D.

1958-11-01

A process is described for the manufacture of uranium bexafluoride which consists in contacting an oxide of uranium simultaneously with elemental carbon and elemental fluorine at an elevated temperature, using a proportion of the carbon to the oxide about 50% in excess of that theoretically required to combine with f the oxygen as C0/.sub 2/. The process has the advantage that the uranium oxide is reduced by tbe carbon aad converted to the hexafluoride in a single operation.

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E [Ames, IA; Terpstra, Robert L [Ames, IA

2012-06-12

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomized particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E.; Terpstra, Robert L.

2010-04-20

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomized particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.

Influence of Minor Alloying Elements on Selective Oxidation and Reactive Wetting of CMnSi TRIP Steel during Hot Dip Galvanizing

NASA Astrophysics Data System (ADS)

Cho, Lawrence; Kim, Myung Soo; Kim, Young Ha; De Cooman, Bruno C.

2014-09-01

The influence of the addition of minor alloying elements on the selective oxidation and the reactive wetting of CMnSi transformation-induced plasticity (TRIP) steels was studied by means of galvanizing simulator tests. Five TRIP steels containing small alloying additions of Cr, Ni, Ti, Cu, and Sn were investigated. After intercritical annealing (IA) at 1093 K (820 °C) in a N2 + 5 pct H2 gas atmosphere with a dew point of 213 K (-60 °C), two types of oxides were formed on the strip surface: Mn-rich xMnO·SiO2 ( x > 1.5) and Si-rich xMnO·SiO2 ( x < 0.3) oxides. The addition of the minor alloying elements changed the morphology of the Si-rich oxides from a continuous film to discrete islands and this improved the wettability by molten Zn. The improved wetting effect of the minor alloying elements was attributed to an increased area fraction of the surface where the oxides were thinner, enabling a direct unhindered reaction between Fe and the Al in the liquid Zn and the formation of the inhibition layer during the hot dip galvanizing. The addition of a small amount of Sn is shown to significantly decrease the density of Zn-coating defects on CMnSi TRIP steels.

Long-distance electron transport occurs globally in marine sediments

NASA Astrophysics Data System (ADS)

Burdorf, Laurine D. W.; Tramper, Anton; Seitaj, Dorina; Meire, Lorenz; Hidalgo-Martinez, Silvia; Zetsche, Eva-Maria; Boschker, Henricus T. S.; Meysman, Filip J. R.

2017-02-01

Recently, long filamentous bacteria have been reported conducting electrons over centimetre distances in marine sediments. These so-called cable bacteria perform an electrogenic form of sulfur oxidation, whereby long-distance electron transport links sulfide oxidation in deeper sediment horizons to oxygen reduction in the upper millimetres of the sediment. Electrogenic sulfur oxidation exerts a strong impact on the local sediment biogeochemistry, but it is currently unknown how prevalent the process is within the seafloor. Here we provide a state-of-the-art assessment of its global distribution by combining new field observations with previous reports from the literature. This synthesis demonstrates that electrogenic sulfur oxidation, and hence microbial long-distance electron transport, is a widespread phenomenon in the present-day seafloor. The process is found in coastal sediments within different climate zones (off the Netherlands, Greenland, the USA, Australia) and thrives on a range of different coastal habitats (estuaries, salt marshes, mangroves, coastal hypoxic basins, intertidal flats). The combination of a widespread occurrence and a strong local geochemical imprint suggests that electrogenic sulfur oxidation could be an important, and hitherto overlooked, component of the marine cycle of carbon, sulfur and other elements.

Imprinted Oxide and MIP/Oxide Hybrid Nanomaterials for Chemical Sensors †

PubMed Central

2018-01-01

The oxides of transition, post-transition and rare-earth metals have a long history of robust and fast responsive recognition elements for electronic, optical, and gravimetric devices. A wide range of applications successfully utilized pristine or doped metal oxides and polymer-oxide hybrids as nanostructured recognition elements for the detection of biologically relevant molecules, harmful organic substances, and drugs as well as for the investigative process control applications. An overview of the selected recognition applications of molecularly imprinted sol-gel phases, metal oxides and hybrid nanomaterials composed of molecularly imprinted polymers (MIP) and metal oxides is presented herein. The formation and fabrication processes for imprinted sol-gel layers, metal oxides, MIP-coated oxide nanoparticles and other MIP/oxide nanohybrids are discussed along with their applications in monitoring bioorganic analytes and processes. The sensor characteristics such as dynamic detection range and limit of detection are compared as the performance criterion and the miniaturization and commercialization possibilities are critically discussed. PMID:29677107

Imprinted Oxide and MIP/Oxide Hybrid Nanomaterials for Chemical Sensors †.

PubMed

Afzal, Adeel; Dickert, Franz L

2018-04-20

The oxides of transition, post-transition and rare-earth metals have a long history of robust and fast responsive recognition elements for electronic, optical, and gravimetric devices. A wide range of applications successfully utilized pristine or doped metal oxides and polymer-oxide hybrids as nanostructured recognition elements for the detection of biologically relevant molecules, harmful organic substances, and drugs as well as for the investigative process control applications. An overview of the selected recognition applications of molecularly imprinted sol-gel phases, metal oxides and hybrid nanomaterials composed of molecularly imprinted polymers (MIP) and metal oxides is presented herein. The formation and fabrication processes for imprinted sol-gel layers, metal oxides, MIP-coated oxide nanoparticles and other MIP/oxide nanohybrids are discussed along with their applications in monitoring bioorganic analytes and processes. The sensor characteristics such as dynamic detection range and limit of detection are compared as the performance criterion and the miniaturization and commercialization possibilities are critically discussed.

Finite element analysis of the tetragonal to monoclinic phase transformation during oxidation of zirconium alloys

NASA Astrophysics Data System (ADS)

Platt, P.; Frankel, P.; Gass, M.; Howells, R.; Preuss, M.

2014-11-01

Corrosion is a key limiting factor in the degradation of zirconium alloys in light water reactors. Developing a mechanistic understanding of the corrosion process offers a route towards improving safety and efficiency as demand increases for higher burn-up of fuel. Oxides formed on zirconium alloys are composed of both monoclinic and meta-stable tetragonal phases, and are subject to a number of potential mechanical degradation mechanisms. The work presented investigates the link between the tetragonal to monoclinic oxide phase transformation and degradation of the protective character of the oxide layer. To achieve this, Abaqus finite element analysis of the oxide phase transformation has been carried out. Study of the change in transformation strain energy shows how relaxation of oxidation induced stress and fast fracture at the metal-oxide interface could destabilise the tetragonal phase. Central to this is the identification of the transformation variant most likely to form, and understanding why twinning of the transformed grain is likely to occur. Development of transformation strain tensors and analysis of the strain components allows some separation of dilatation and shear effects. Maximum principal stress is used as an indication of fracture in the surrounding oxide layer. Study of the stress distributions shows the way oxide fracture is likely to occur and the differing effects of dilatation and shape change. Comparison with literature provides qualitative validation of the finite element simulations.

Selenium Alleviates Oxidative Stress and Lung Damage Induced by Aluminum Chloride in Adult Rats: Biochemical and Histological Approach.

PubMed

Ghorbel, Imen; Elwej, Awatef; Chaabane, Mariem; Jamoussi, Kamel; Mnif, Hela; Boudawara, Tahia; Zeghal, Najiba

2017-03-01

Our study pertains to the potential ability of selenium, used as a nutritional supplement, to alleviate oxidative stress induced by aluminum chloride in the lung tissue. Rats have received during 21 days either aluminum chloride (AlCl 3 ) (400 ppm) via drinking water, AlCl 3 associated with Na 2 SeO 3 (0.5 mg/kg of diet), or only Na 2 SeO 3 . Exposure of rats to AlCl 3 induced lung oxidative stress with an increase of malondialdehyde, hydrogen peroxide, and protein carbonyls levels. An alteration of lactate dehydrogenase activities and antioxidant redox status, enzymatic (catalase, superoxide dismutase, and glutathione peroxidase), and non-enzymatic (non-protein thiols, glutathione, metallothionein, and vitamin C) was also observed. These biochemical modifications were substantiated by histopathological data showing alveolar edema, a large number of hemosiderin-laden macrophages, and emphysema. Se supplementation attenuated the levels of oxidative stress by restoring antioxidant state and improved lung histological damage. Our results revealed that Se, a trace element with antioxidant properties, was effective in preventing lung damage.

High resolution photoemission investigation: The oxidation of W

NASA Astrophysics Data System (ADS)

Morar, J. F.; Himpsel, F. J.; Hughes, G. J.; Jordan, J. L.; McFeely, F. R.; Hollinge, G.

High resolution photoemission measurements of surface oxide layers on tungsten has revealed a set of well resolved core level shifts characteristic of individual metal oxidation states. Measurement and analysis of this type of data can provide specific and quantitative chemical information about surface oxides. The formation of bonds between transition metals and strongly electronegative elements such as oxygen and fluorine results in charge transfer with the effect of shifting the metal core electron binding energies. The magnitude of such shifts depends primarily on two factors; the amount of charge transfer and the screening ability of the metals electrons. The size of core-level shifts tend to increase with additional charge transfer and be decreased by screening. In the case of tungsten the amount of screening should be a function of oxygen content since the oxygen ties up free electrons which are effective at screening. A continuous change in the tungsten core level shifts is observed with increasing oxygen content, i.e., as the screening changes from that characteristic of a metal screened to that characteristic of an insulator unscreened.

New alloys to conserve critical elements. [replacing chromium in steels

NASA Technical Reports Server (NTRS)

Stephens, J. R.

1978-01-01

Previous studies and surveys on availability of domestic reserves have shown that chromium is a most critical element within the U.S. metal industry. More precisely, the bulk of chromium is consumed in the production of stainless steels, specifically Type 304 stainless steel (304SS) which contains 18% Cr. The present paper deals with means of reducing chromium in commercial stainless steels by substituting more abundant or less expensive elements with the intent of maintaining the properties of 304SS. The discussion focuses on some of the oxidation and corrosion properties of new substitute stainless steels with only 12% Cr, which represents a potential saving of 33% of the chromium consumed in the production of 304SS. The alloying elements substituted for Cr in 304SS are selected according to their potential for protective oxide formation during high-temperature oxidation; these are Al, Si, Ti, Y, and misch metal which is 99.7% rare-earth metals containing 50 to 55% cerium. Other alloying elements to impart corrosion resistance are Mn, Mo, and V.

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E; Rieken, Joel

2013-12-10

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with an introduced reactive species than does the alloying element and wherein one or more atomizing parameters is/are modified to controllably reduce the amount of the reactive species, such as oxygen, introduced into the atomized particles so as to reduce anneal times and improve reaction (conversion) to the desired strengthening dispersoids in the matrix. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies are made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.

BONDING ALUMINUM METALS

DOEpatents

Noland, R.A.; Walker, D.E.

1961-06-13

A process is given for bonding aluminum to aluminum. Silicon powder is applied to at least one of the two surfaces of the two elements to be bonded, the two elements are assembled and rubbed against each other at room temperature whereby any oxide film is ruptured by the silicon crystals in the interface; thereafter heat and pressure are applied whereby an aluminum-silicon alloy is formed, squeezed out from the interface together with any oxide film, and the elements are bonded.

Stable mineral recrystallization in low temperature aqueous systems: A critical review

NASA Astrophysics Data System (ADS)

Gorski, Christopher A.; Fantle, Matthew S.

2017-02-01

Minerals may undergo recrystallization reactions in low temperature (<100 °C) aqueous systems, during which they exchange isotopes and trace elements with the dissolved reservoir without undergoing overt structural, bulk compositional, or morphological changes. These interfacial reactions, which are often referred to in the literature as "atom exchange" and herein as "stable mineral recrystallization", have important implications for the use of isotopic and elemental proxies to interpret past temperatures, oxidation states, and aqueous chemistries on Earth. The reactions are also significant for modern environments, including engineered systems, as they imply that mineral lattices may be substantially more open to exchanging toxic elements and radionuclides with coexisting solutions than previously thought. To date, observations of stable mineral recrystallization are distributed among several disciplines, and no work has attempted to review their findings comprehensively. Accordingly, this review article presents laboratory evidence for stable mineral recrystallization, describes data collection and interpretation strategies, summarizes similar recrystallization systematics observed in multiple studies, explores the potential occurrence of stable mineral recrystallization in natural systems, and discusses possible mechanisms by which stable mineral recrystallization occurs. The review focuses primarily on carbonates, sulfates, and iron oxides because these minerals have been studied most extensively to date. The review concludes by presenting key questions that should be addressed in this field to further understand and account for stable mineral recrystallization in natural and engineered aqueous systems at low temperatures.

Metal oxide nanoparticle-modified graphene oxide for removal of elemental mercury.

PubMed

Liu, Yuxi; Chen, Gang; Tian, Chong; Gupta, Rajender; Wang, Xiaogang; Zeng, Hongbo

2018-06-05

Mercury is an extremely toxic element that is primarily released by anthropogenic activities and natural sources. Controlling Hg emissions, especially from coal combustion flue gas, is of practical importance in protecting the environment and preventing human health risks. In the present work, three metal oxides (MnO 2 , CuO, and ZnO) were loaded on graphene oxide (GO) sorbents (designated as MnO 2 -GO, CuO-GO, and ZnO-GO). All three adsorbents were successfully synthesized and were well characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results indicated that the metal oxide nanoparticles (NPs) successfully decorated the GO. The elemental Hg adsorption capabilities of the three sorbents were subsequently evaluated using an in-house built setup for cold vapour atomic fluorescence spectrophotometry (CVAFS) with argon as the carrier gas for mercury detection. The testing temperature ranged from 50°C to 200°C at intervals of 50°C. MnO 2 -GO showed an excel lent Hg 0 adsorption capacity via chemisorption from 50 to 150°C and a mercury removal efficiency as high as 85% at 200°C, indicating that the MnO 2 -NP-modified GO is applicable for enhancing gas-phase elemental mercury removal. However, neither CuO-GO nor ZnO-GO performed well. This work provides useful insights into the development of novel sorbent materials for the elemental mercury removal from flue gases.

Low TCR nanocomposite strain gages

NASA Technical Reports Server (NTRS)

Gregory, Otto J. (Inventor); Chen, Ximing (Inventor)

2012-01-01

A high temperature thin film strain gage sensor capable of functioning at temperatures above 1400.degree. C. The sensor contains a substrate, a nanocomposite film comprised of an indium tin oxide alloy, zinc oxide doped with alumina or other oxide semiconductor and a refractory metal selected from the group consisting of Pt, Pd, Rh, Ni, W, Ir, NiCrAlY and NiCoCrAlY deposited onto the substrate to form an active strain element. The strain element being responsive to an applied force.

Element Distribution in the Oxygen-Rich Side-Blow Bath Smelting of a Low-Grade Bismuth-Lead Concentrate

NASA Astrophysics Data System (ADS)

Yang, Tianzu; Xiao, Hui; Chen, Lin; Chen, Wei; Liu, Weifeng; Zhang, Duchao

2018-03-01

Oxygen-rich side-blow bath smelting (OSBS) technology offers an efficient method for processing complex bismuth-lead concentrates; however, the element distributions in the process remain unclear. This work determined the distributions of elements, i.e., bismuth, lead, silver, copper, arsenic and antimony, in an industrial-scale OSBS process. The feed, oxidized slag and final products were collected from the respective sampling points and analyzed. For the oxidative smelting process, 65% of bismuth and 76% of silver in the concentrate report to the metal alloy, whereas less lead reports to the metal ( 31%) than the oxidized slag ( 44%). Approximately 50% of copper enters the matte, while more than 63% of arsenic and antimony report to the slag. For the reductive smelting process, less than 4.5% of bismuth, lead, silver and copper in the oxidized slag enter the reduced slag, indicating high recoveries of these metal values.

Element Distribution in the Oxygen-Rich Side-Blow Bath Smelting of a Low-Grade Bismuth-Lead Concentrate

NASA Astrophysics Data System (ADS)

Yang, Tianzu; Xiao, Hui; Chen, Lin; Chen, Wei; Liu, Weifeng; Zhang, Duchao

2018-06-01

Oxygen-rich side-blow bath smelting (OSBS) technology offers an efficient method for processing complex bismuth-lead concentrates; however, the element distributions in the process remain unclear. This work determined the distributions of elements, i.e., bismuth, lead, silver, copper, arsenic and antimony, in an industrial-scale OSBS process. The feed, oxidized slag and final products were collected from the respective sampling points and analyzed. For the oxidative smelting process, 65% of bismuth and 76% of silver in the concentrate report to the metal alloy, whereas less lead reports to the metal ( 31%) than the oxidized slag ( 44%). Approximately 50% of copper enters the matte, while more than 63% of arsenic and antimony report to the slag. For the reductive smelting process, less than 4.5% of bismuth, lead, silver and copper in the oxidized slag enter the reduced slag, indicating high recoveries of these metal values.

Oxidation and methylation of dissolved elemental mercury by anaerobic bacteria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Haiyan; Lin, Hui; Zheng, Wang

2013-08-04

Methylmercury is a neurotoxin that poses significant health risks to humans. Some anaerobic sulphate- and iron-reducing bacteria can methylate oxidized forms of mercury, generating methylmercury1-4. One strain of sulphate-reducing bacteria (Desulfovibrio desulfuricans ND132) can also methylate elemental mercury5. The prevalence of this trait among different bacterial strains and species remains unclear, however. Here, we compare the ability of two strains of the sulphate-reducing bacterium Desulfovibrio and one strain of the iron-reducing bacterium Geobacter to oxidise and methylate elemental mercury in a series of laboratory incubations. Experiments were carried out under dark, anaerobic conditions, in the presence of environmentally-relevant concentrations ofmore » elemental mercury. We report differences in the ability of these organisms to oxidise and methylate elemental mercury. In line with recent findings5, we show that Desulfovibrio desulfuricans ND132 can both oxidise and methylate elemental mercury. However, the rate of methylation of elemental mercury is only about one third the rate of methylation of oxidized mercury. We also show that Desulfovibrio alaskensis G20 can oxidise, but not methylate, elemental mercury. Geobacter sulfurreducens PCA is able to oxidise and methylate elemental mercury in the presence of cysteine. We suggest that the activity of methylating and non-methylating bacteria may together enhance the formation of methylmercury in anaerobic environments.« less

Determination of oxidation state of iron in normal and pathologically altered human aortic valves

NASA Astrophysics Data System (ADS)

Czapla-Masztafiak, J.; Lis, G. J.; Gajda, M.; Jasek, E.; Czubek, U.; Bolechała, F.; Borca, C.; Kwiatek, W. M.

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 Fe3+ 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 Fe3+ 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.

Tracking hydrothermal alteration and mineralization in rock-forming and accessory minerals from the Lyon Mountain Granite and related iron oxide apatite (IOA) ores from the Adirondack Mountains, New York State

NASA Astrophysics Data System (ADS)

Buchanan, A.; Hanchar, J. M.; Steele-MacInnis, M. J.; Crowley, J. L.; Valley, P. M.; Fisher, C. M.; Fedo, C.; Piccoli, P. M.; Fournelle, J.

2012-12-01

The Lyon Mountain granite (LMG) is located in the northeastern Adirondack Mountains in New York State and hosts several low-titanium iron oxide apatite (IOA) ore deposits. The ores are predominately hosted by perthite bearing granite, which has been extensively altered to albite and microcline granite by Na and K metasomatism. This alteration results in several distinct groups of rocks that are dominated by either K or Na addition and a group composed of mixed Na and K addition. The different groups of altered perthite also lie on a trend suggestive of addition of Fe to each, consistent with a secondary mineralization origin. Previous work showed that the host rocks of the IOA ores have zircon with ~1150 Ma cores and 1060-1050 Ma rims and whole grains. This study aims to further constrain the timing of LMG emplacement, subsequent hydrothermal alteration, and Fe mineralization through geochemical analysis of the major, minor, and accessory phases and geochronology of accessory phases. SIMS analyses of zircon from several of the IOA ores reveal at least two periods of growth after LMG magmatism, at 1039 +/- 4.4 Ma and 1016 +/- 7 Ma to 1000 +/- 9 Ma. In situ EMPA and LA-ICPMS trace element analyses of the zircon rims and cores reveal that in two samples the zircon rims are enriched in rare earth elements (REE) compared to their cores, potentially pointing to a hydrothermal origin. Apatite has unusually high REE and Y concentrations (some total REE2O3 > 20 wt. % oxide and up to 8 wt. % oxide Y2O3), as does titanite, which allowed for the in situ analysis of Sm-Nd in apatite and titanite by LA-MC-ICP-MS. Initial Nd isotopic composition of both ore and host rock apatite and host rock titanite are consistent with published Adirondack initial Nd whole rock data, suggesting a local source for REE in these ores. EMPA and LA-ICPMS trace-element analyses of the major rock-forming minerals indicate that the feldspar have undergone Na-metasomatism and are depleted in REEs, perhaps signifying the "local source" and the mechanism of the REE enrichment in the LMG apatite in the IOA ores and host rocks. In contrast, the minor- and trace-element compositions of the other major rock-forming minerals (e.g., clinopyroxene and fayalite) as well as the zircon, and fluorite in the LMG have average igneous granitic trace- and minor-element compositions. To better understand the timing and origin of these post ~1050 Ma events, U-Pb ID-TIMS dating of apatite and titanite, and in situ LA-MC-ICPMS Sm-Nd analysis were done on the ore and host rock samples. Apatite dates range from 1050 to 850 Ma and titanite dates range from ~1015 to 970 Ma. There is significant age variation within samples and within grains. Titanite does not have sufficient spread for accurate Sm-Nd isochron dating and two ore-apatite samples have homogenous initial Nd isotopic and Sm-Nd elemental ratios, precluding calculation of Sm-Nd dates. A third ore sample shows a large spread in Sm-Nd and yields a Sm-Nd isochron date of ~850 Ma, in close agreement with U-Pb apatite dates. The Sm-Nd isochron and U-Pb apatite dates may reflect cooling recorded in these minerals or a younger hydrothermal mineralization event.

A prototype hybrid 7π quinone-fused 1,3,2-dithiazolyl radical.

PubMed

Decken, A; Mailman, A; Passmore, J; Rautiainen, J M; Scherer, W; Scheidt, E-W

2011-01-28

Reaction of 1,4-naphthoquinone and SNSMF(6) (M = As, Sb) in SO(2) solution in a 1 : 2 molar ratio led to the naphthoquinone fused 1,3,2-dithiazolylium salts, 3MF(6) quantitatively by multinuclear NMR (87% isolated yield of 3SbF(6)) via the cycloaddition and oxidative dehydrogenation chemistry of SNS(+) with formation of NH(4)SbF(6) and S(8). The product 3SbF(6) was fully characterized by IR, Raman, multinuclear {(1)H, (13)C, (14)N} NMR, elemental analysis, cyclic voltammetry and single crystal X-ray crystallography. The reduction of 3SbF(6) with ferrocene (Cp(2)Fe) in refluxing acetonitrile (CH(3)CN) led to the first isolation of a fused quinone-thiazyl radical, 3˙ in 73% yield. The prototype hybrid quinone-thiazyl radical 3˙ was fully characterized by IR, Raman microscopy, EI-MS, elemental analysis, solution and solid state EPR, magnetic susceptibility (2-370 K) and was found to form π*-π* dimers in the solid state as determined by single crystal X-ray crystallography. Furthermore, the thermal decomposition of 3˙ led to a novel quinone-fused 1,2,3,4-tetrathiine, 10 (x = 2) and the known 1,2,5-thiadiazole, 11. The energetics of the cycloadditon and oxidative dehydrogenation chemistry of SNS(+) and 1,4-naphthoquinone leading to 3SbF(6) were estimated in the gas phase and SO(2) solution by DFT calculations (PBE0/6-311G(d)) and lattice enthalpies obtained by the volume based thermodynamic (VBT) approach in the solid state. The gas phase ion energetics (ionization potential (IP) and electron affinity (EA)) of 3˙ are compared to related 1,3,2- and 1,2,3-dithiazolyl radicals.

Apollo 15 green glass - Compositional distribution and petrogenesis

NASA Technical Reports Server (NTRS)

Steele, Alison M.; Colson, Russell O.; Korotev, Randy L.; Haskin, Larry A.

1992-01-01

We have characterized a comprehensive suite of individual green-glass beads from Apollo 15 soil to determine interelement behavior and to constrain petrogenetic relationships. We analyzed 365 particles for trace elements by instrumental neutron activation analysis and analyzed 52 of them, selected to cover the compositional ranges observed for trace elements, for major elements by electron microprobe analysis. We confirm the observation of Delano (1979) that the beads comprise discrete compositional groups, although two of the groups he defined are further split on the basis of trace-element compositions. Each of the resulting seven groups has distinct average rare-earth abundances. The coherence between major- and trace-element data was masked in previous studies by imprecision, correlated error, and nonrepresentative sampling of the different groups. Most of the compositional characteristics of the green glasses can be explained by a model for batch equilibrium melting of a nearly homogeneous, ultramafic source region, when the complicating effects of high pressure and low oxygen fugacity are taken into account. The previously puzzling behavior of Ni and Co as apparently incompatible elements may arise from partial reduction of those elements to the zero oxidation state, resulting in low mineral/melt partition coefficients. The model also offers explanations for why the green glasses form boomerang-shaped trends on many two-element variation diagrams and why certain compositions (Groups A and D) are more abundant than glasses with other compositions.

Materials science in the time domain using Bragg coherent diffraction imaging

DOE PAGES

Robinson, Ian; Clark, Jesse; Harder, Ross

2016-03-14

Materials are generally classified by a phase diagram which displays their properties as a function of external state variables, typically temperature and pressure. A new dimension that is relatively unexplored is time: a rich variety of new materials can become accessible in the transient period following laser excitation from the ground state. The timescale of nanoseconds to femtoseconds, is ripe for investigation using x-ray free-electron laser (XFEL) methods. There is no shortage of materials suitable for time-resolved materials-science exploration. Oxides alone represent most of the minerals making up the Earth's crust, catalysts, ferroelectrics, corrosion products and electronically ordered materials suchmore » as superconductors, to name a few. Some of the elements have metastable phase diagrams with predicted new phases. There are some examples known already: an oxide 'hidden phase' living only nanoseconds and an electronically ordered excited phase of fullerene C 60, lasting only femtoseconds. In a completely general way, optically excited states of materials can be probed with Bragg coherent diffraction imaging, both below the damage threshold and in the destructive regime. Lastly, prospective methods for carrying out such XFEL experiments are discussed.« less

Natural circular dichroism in non-resonant x-ray emission

NASA Astrophysics Data System (ADS)

Vahtras, Olav; Ågren, Hans; Carravetta, Vincenzo

1997-03-01

The possibility of observing natural circular dichroism in non-resonant x-ray emission spectroscopy is investigated by means of simulations of the chiral molecules twisted ethylene, propylene oxide and trans-1, 2-dimethylcyclopropane, in a two-step model and at the SCF level, with or without relaxation of the core-hole states. We observe both a chemical and an element dependence of the phenomenon and also an effect of electron relaxation. However, the latter is much less crucial than for circular dichroism in x-ray absorption. The calculations indicate that, at least for the decay of the carbon core-hole states, the effect could be detectable with the present or soon to be available experimental equipment.

The phase state at high temperatures in the MOX-SiO 2 system

NASA Astrophysics Data System (ADS)

Nakamichi, S.; Kato, M.; Sunaoshi, T.; Uchida, T.; Morimoto, K.; Kashimura, M.; Kihara, Y.

2009-06-01

Influence of impurity Si on microstructure in a plutonium and uranium mixed oxide (MOX), which is used for fast breeder reactor fuel, was investigated, and phase state in 25% SiO 2 - (U 0.7Pu 0.3)O 2 was observed as a function of oxygen chemical potential. Compounds composed of Pu and Si with other elements were observed at grain boundaries of the MOX parent phase in the specimens after annealing. These compounds were not observed in the grain interior and the MOX phase was not affected significantly by impurity Si. It was found that the compounds tended to form more observably with decreasing O/M ratio and with increasing annealing temperatures.

Application of sludge-based carbonaceous materials in a hybrid water treatment process based on adsorption and catalytic wet air oxidation.

PubMed

Julcour Lebigue, Carine; Andriantsiferana, Caroline; N'Guessan Krou; Ayral, Catherine; Mohamed, Elham; Wilhelm, Anne-Marie; Delmas, Henri; Le Coq, Laurence; Gerente, Claire; Smith, Karl M; Pullket, Suangusa; Fowler, Geoffrey D; Graham, Nigel J D

2010-12-01

This paper describes a preliminary evaluation of the performance of carbonaceous materials prepared from sewage sludges (SBCMs) in a hybrid water treatment process based on adsorption and catalytic wet air oxidation; phenol was used as the model pollutant. Three different sewage sludges were treated by either carbonisation or steam activation, and the physico-chemical properties of the resultant carbonaceous materials (e.g. hardness, BET surface area, ash and elemental content, surface chemistry) were evaluated and compared with a commercial reference activated carbon (PICA F22). The adsorption capacity for phenol of the SBCMs was greater than suggested by their BET surface area, but less than F22; a steam activated, dewatered raw sludge (SA_DRAW) had the greatest adsorption capacity of the SBCMs in the investigated range of concentrations (<0.05 mol L(-1)). In batch oxidation tests, the SBCMs demonstrated catalytic behaviour arising from their substrate adsorptivity and metal content. Recycling of SA_DRAW in successive oxidations led to significant structural attrition and a hardened SA_DRAW was evaluated, but found to be unsatisfactory during the oxidation step. In a combined adsorption-oxidation sequence, both the PICA carbon and a selected SBCM showed deterioration in phenol adsorption after oxidative regeneration, but a steady state performance was reached after 2 or 3 cycles. Copyright © 2010 Elsevier Ltd. All rights reserved.

Numerical modelling of methane oxidation efficiency and coupled water-gas-heat reactive transfer in a sloping landfill cover.

PubMed

Feng, S; Ng, C W W; Leung, A K; Liu, H W

2017-10-01

Microbial aerobic methane oxidation in unsaturated landfill cover involves coupled water, gas and heat reactive transfer. The coupled process is complex and its influence on methane oxidation efficiency is not clear, especially in steep covers where spatial variations of water, gas and heat are significant. In this study, two-dimensional finite element numerical simulations were carried out to evaluate the performance of unsaturated sloping cover. The numerical model was calibrated using a set of flume model test data, and was then subsequently used for parametric study. A new method that considers transient changes of methane concentration during the estimation of the methane oxidation efficiency was proposed and compared against existing methods. It was found that a steeper cover had a lower oxidation efficiency due to enhanced downslope water flow, during which desaturation of soil promoted gas transport and hence landfill gas emission. This effect was magnified as the cover angle and landfill gas generation rate at the bottom of the cover increased. Assuming the steady-state methane concentration in a cover would result in a non-conservative overestimation of oxidation efficiency, especially when a steep cover was subjected to rainfall infiltration. By considering the transient methane concentration, the newly-modified method can give a more accurate oxidation efficiency. Copyright © 2017. Published by Elsevier Ltd.

Charge transfer in rectifying oxide heterostructures and oxide access elements in ReRAM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stefanovich, G. B.; Pergament, A. L.; Boriskov, P. P.

2016-05-15

The main aspects of the synthesis and experimental research of oxide diode heterostructures are discussed with respect to their use as selector diodes, i.e., access elements in oxide resistive memory. It is shown that charge transfer in these materials differs significantly from the conduction mechanism in p–n junctions based on conventional semiconductors (Si, Ge, A{sup III}–B{sup V}), and the model should take into account the electronic properties of oxides, primarily the low carrier drift mobility. It is found that an increase in the forward current requires an oxide with a small band gap (<1.3 eV) in the heterostructure composition. Heterostructuresmore » with Zn, In–Zn (IZO), Ti, Ni, and Cu oxides are studied; it is found that the CuO–IZO heterojunction has the highest forward current density (10{sup 4} A/cm{sup 2}).« less

Anchoring transition metal elements on graphene-like ZnO monolayer by CO molecule to obtain spin gapless semiconductor

NASA Astrophysics Data System (ADS)

Lei, Jie; Xu, Ming-Chun; Hu, Shu-Jun

2017-09-01

Graphene-like zinc oxide monolayer (g-ZnO) is a newfound two-dimensional material. Here we utilize the transition metal (TM) elements (Cr, Mn, Fe, Co, Ni, and Cu) to functionalize the g-ZnO with the aim of designing novel spintronics materials by using first-principles calculations. Our results show that although the adsorption of TM atoms can endow g-ZnO with magnetization and impurity states in the bandgap, the interaction between TM elements and g-ZnO is weak. We found that the attachment of CO molecule on TM is able to stabilize the TM elements on g-ZnO based on the 'donation and back-donation' mechanism. As a result, the adsorption energy of the CO-TM complex on g-ZnO is as high as 1.41-2.11 eV. Furthermore, the incorporation of CO molecule modulates the magnetic and electronic properties of the TM-decorated g-ZnO. In particular, the CO-Mn-g-ZnO is predicted to be a spin gapless semiconductor.

Diffusion of Redox-Sensitive Elements in Basalt at Different Oxygen Fugacities

NASA Technical Reports Server (NTRS)

Szumila, I.; Trail, D.; Danielson, L. R.

2017-01-01

The terrestrial planets and moons of our solar system have differentiated over a range of oxygen fugacity conditions. Basalts formed from magmas on the Earth cover a range of more oxidized states (from approximately IW (iron wustite) plus 2 to approximately FMQ (fayalite-magnetite-quartz) plus 3) than crustal rocks from Mars (IW to approximately IW plus 3), and basalts from the Moon are more reduced than both, ranging from IW to IW minus 2. The small body Vesta differentiated around IW minus 4. Characterization of redox sensitive elements' diffusivities will offer insight into behavior of these elements as a function of f (fugacity of) O2 for these planetary bodies. Here, we report a systematic study of the diffusion of redox-sensitive elements in basaltic melts with varying oxygen fugacities (fO2) for trace elements, V, Nb, W, Mo, La, Ce, Pr, Sm, Eu, Gd, Ta, and W. Since fO2 is an intensive variable that is different for the reservoirs of various planets and moons in our solar system, it is important to characterize how changes in redox states will affect diffusion. We conducted experiments in a piston cylinder device at 1300 degrees Centigrade and 1 gigapascal, at the University of Rochester and NASA Johnson Space Center. We buffered some experiments at Ru-RuO2 (FMQ plus 6.00), and conducted other experiments within either a graphite or Mo capsule, which corresponds to fO2s of either FMQ minus1.2, or FMQ minus 3.00, respectively. Characterizing the diffusivities of redox sensitive elements at different fO2s is important because some elements, like Eu, have varying valence states, such as Eu (sup 2 plus) and Eu (sup 3 plus). Differences in charge and ion radii may lead to differences in diffusivities within silicate melts. This could, lead to formation of a Eu anomaly by diffusion, the magnitude of which may be controlled by the fO2. Characterization of trace element diffusion is also important in understanding trace element fractionation. We found, during the course of our investigation, that not only did the diffusivities of the redox sensitive elements change with fO2, but that the diffusivities of all other analyzed elements also changed. This indicates that not only do changes in valence influence trace elements diffusivities but that the structure of melt may have changed with varying oxygen fugacity, probably due to changes in the speciation of the major element Fe.

Petrology and In Situ Trace Element Chemistry of a Suite of R Chondrites

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Peng, Z. X.; Torrano, Z. A.

2015-01-01

Rumuruti (R) chondrites are characterized by low chondrule/matrix modal ratios, high oxidation state, small mean chondrule size, abundant sulfides and low metal contents, and are of petrologic types 3 to 6 [1, 2]. LAP 04840 (R5, [3]) and MIL 11207 (R6), contain the high-T hydrous phases amphibole and mica [3, 4]; not all equilibrated R chondrites contain these [2]. R chondrites thus can provide evidence on whether there are compositional effects caused by high-T, high-fluid metamorphism of nebular materials. We are investigating a suite of R chondrites of diverse petrologic grades to further understand the nature of the metamorphic processes that engendered them [5]. We report on our petrological studies, plus preliminary in situ analyses of trace elements in amphibole-bearing R chondrites.

Innovative instrumentation for mineralogical and elemental analyses of solid extraterrestrial surfaces: The Backscatter Moessbauer Spectrometer/X Ray Fluorescence analyzer (BaMS/XRF)

NASA Technical Reports Server (NTRS)

Shelfer, T. D.; Morris, Richard V.; Nguyen, T.; Agresti, D. G.; Wills, E. L.

1994-01-01

We have developed a four-detector research-grade backscatter Moessbauer spectrometer (BaMS) instrument with low resolution x-ray fluorescence analysis (XRF) capability. A flight-qualified instrument based on this design would be suitable for use on missions to the surfaces of solid solar-system objects (Moon, Mars, asteroids, etc.). Target specifications for the flight instrument are as follows: mass less than 500 g; volumes less than 300 cu cm; and power less than 2 W. The BaMS/XRF instrument would provide data on the oxidation state of iron and its distribution among iron-bearing mineralogies and elemental composition information. This data is a primary concern for the characterization of extraterrestrial surface materials.

Oxidation States of Grim Glasses in EET79001 Based on Vanadium Valence

NASA Technical Reports Server (NTRS)

Sutton, S. R.; Rao, M. N.; Nyquist, L. E.

2010-01-01

Gas-rich impact-melt (GRIM) glasses in SNC meteorites are very rich in Martian atmospheric noble gases and sulfur suggesting a possible occurrence of regolith-derived secondary mineral assemblages in these samples. Previously, we have studied two GRIM glasses, 506 and 507, from EET79001 Lith A and Lith B, respectively, for elemental abundances and spatial distribution of sulfur using EMPA (WDS) and FE-SEM (EDS) techniques and for sulfur-speciation using K-edge XANES techniques. These elemental and FE-SEM micro-graph data at several locations in the GRIM glasses from Shergotty (DBS), Zagami 994 and EET79001, Lith B showed that FeO and SO3 are positively correlated (SO3 represents a mixture of sulfide and sulfate). FE-SEM (EDS) study revealed that the sulfur-rich pockets in these glasses contain numerous micron-sized iron-sulfide (Fe-S) globules sequestered throughout the volume. However, in some areas (though less frequently), we detected significant Fe-S-O signals suggesting the occurrence of iron sulfate. These GRIM glasses were studied by K-edge microXANES techniques for sulfur speciation in association with iron in sulfur-rich areas. In both samples, we found the sulfur speciation dominated by sulfide with minor oxidized sulfur mixed in with various proportions. The abundance of oxidized sulfur was greater in 506 than in 507. Based on these results, we hypothesize that sulfur initially existed as sulfate in the glass precursor materials and, on shock-impact melting of the precursor materials producing these glasses, the oxidized sulfur was reduced to predominately sulfide. In order to further test this hypothesis, we have used microXANES to measure the valence states of vanadium in GRIM glasses from Lith A and Lith B to complement and compare with previous analogous measurements on Lith C (note: 506 and 507 contain the largest amounts of martian atmospheric gases but the gas-contents in Lith C measured by are unknown). Vanadium is ideal for addressing this re-dox issue because it has multiple valence states and is a well-studied element. Ferrous-dominated iron valences determined by microXANES on the Lith A and Lith B glasses provide little redox sensitivity. Vanadium valence measurements for impact glass in Lith C at three different locations yielded valence values of 3.1, 3.2 and 3.4 with inferred fO2 values of IW-0.7, IW-0.1 and IW+0.7, respectively. This range of oxygen-fugacity values is understandable because the glasses are shock-molten impact glasses which are heterogeneous in nature. Oxygen fugacity values obtained from the analysis of Fe-Ti oxides and Eu partitioning in pyroxenes from EET79001 Lith A and Lith B (host lithologies) were in the range of IW+0.3 to IW+1.9 suggesting that V in the Lith C impact glass was reduced in the impact process. Here, we examine whether the 506 from Lith A and 507 from Lith B GRIM glasses yield similar or different fO2 values from those of Lith C using the vanadium K-edge microXANES technique.

Water and the oxidation state of subduction zone magmas.

PubMed

Kelley, Katherine A; Cottrell, Elizabeth

2009-07-31

Mantle oxygen fugacity exerts a primary control on mass exchange between Earth's surface and interior at subduction zones, but the major factors controlling mantle oxygen fugacity (such as volatiles and phase assemblages) and how tectonic cycles drive its secular evolution are still debated. We present integrated measurements of redox-sensitive ratios of oxidized iron to total iron (Fe3+/SigmaFe), determined with Fe K-edge micro-x-ray absorption near-edge structure spectroscopy, and pre-eruptive magmatic H2O contents of a global sampling of primitive undegassed basaltic glasses and melt inclusions covering a range of plate tectonic settings. Magmatic Fe3+/SigmaFe ratios increase toward subduction zones (at ridges, 0.13 to 0.17; at back arcs, 0.15 to 0.19; and at arcs, 0.18 to 0.32) and correlate linearly with H2O content and element tracers of slab-derived fluids. These observations indicate a direct link between mass transfer from the subducted plate and oxidation of the mantle wedge.

Flow of essential elements in subcellular fractions during oxidative stress.

PubMed

Lago, Larissa; Nunes, Emilene A; Vigato, Aryane A; Souza, Vanessa C O; Barbosa, Fernando; Sato, João R; Batista, Bruno L; Cerchiaro, Giselle

2017-02-01

Essential trace elements are commonly found in altered concentrations in the brains of patients with neurodegenerative diseases. Many studies in trace metal determination and quantification are conducted in tissue, cell culture or whole brain. In the present investigation, we determined by ICP-MS Fe, Cu, Zn, Ca, Se, Co, Cr, Mg, and Mn in organelles (mitochondria, nuclei) and whole motor neuron cell cultured in vitro. We performed experiments using two ways to access oxidative stress: cell treatments with H 2 O 2 or Aβ-42 peptide in its oligomeric form. Both treatments caused accumulation of markers of oxidative stress, such as oxidized proteins and lipids, and alteration in DNA. Regarding trace elements, cells treated with H 2 O 2 showed higher levels of Zn and lower levels of Ca in nuclei when compared to control cells with no oxidative treatments. On the other hand, cells treated with Aβ-42 peptide in its oligomeric form showed higher levels of Mg, Ca, Fe and Zn in nuclei when compared to control cells. These differences showed that metal flux in cell organelles during an intrinsic external oxidative condition (H 2 O 2 treatment) are different from an intrinsic external neurodegenerative treatment.

The role of oxidative damage in poor scalp health: ramifications to causality and associated hair growth.

PubMed

Schwartz, J R; Henry, J P; Kerr, K M; Mizoguchi, H; Li, L

2015-12-01

The oxidative stress element of unhealthy scalp leads to compromised pre-emergent hair formation and poorly formed hair as it grows. Only cosmetic solutions can minimize the impact of unhealthy hair and to achieve healthy looking and feeling hair, the scalp health must be normalized first. The objectives of this research were to both investigate whether oxidative stress was a relevant aetiological element in scalp dandruff and seborrhoeic dermatitis and whether scalp condition affects the quality of hair that grows from it. Further, this research was designed to determine whether an effective anti-dandruff shampoo would repair and protect the scalp and pre-emergent hair from oxidative stress. This study demonstrated that oxidative stress is an aetiological element relevant to the dandruff condition and that a potentiated ZPT shampoo effectively improves scalp condition, including a reduction in oxidative stress. The compromised hair condition associated with dandruff is concomitantly improved when the scalp condition is improved. It appears that there is a direct link between hair quality and scalp health. © 2015 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Application of Degenerately Doped Metal Oxides in the Study of Photoinduced Interfacial Electron Transfer.

PubMed

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.

Solid oxide fuel cells fueled with reducible oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chuang, Steven S.; Fan, Liang Shih

A direct-electrochemical-oxidation fuel cell for generating electrical energy includes a cathode provided with an electrochemical-reduction catalyst that promotes formation of oxygen ions from an oxygen-containing source at the cathode, a solid-state reduced metal, a solid-state anode provided with an electrochemical-oxidation catalyst that promotes direct electrochemical oxidation of the solid-state reduced metal in the presence of the oxygen ions to produce electrical energy, and an electrolyte disposed to transmit the oxygen ions from the cathode to the solid-state anode. A method of operating a solid oxide fuel cell includes providing a direct-electrochemical-oxidation fuel cell comprising a solid-state reduced metal, oxidizing themore » solid-state reduced metal in the presence of oxygen ions through direct-electrochemical-oxidation to obtain a solid-state reducible metal oxide, and reducing the solid-state reducible metal oxide to obtain the solid-state reduced metal.« less

Application of Developed APCVD Transparent Conducting Oxides and Undercoat Technologies for Economical OLED Lighting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martin Bluhm; James Coffey; Roman Korotkov

2011-01-02

Economics is a key factor for application of organic light emitting diodes (OLED) in general lighting relative to OLED flat panel displays that can handle high cost materials such as indium tin oxide (ITO) or Indium zinc oxide (IZO) as the transparent conducting oxide (TCO) on display glass. However, for OLED lighting to penetrate into general illumination, economics and sustainable materials are critical. The issues with ITO have been documented at the DOE SSL R&D and Manufacturing workshops for the last 5 years and the issue is being exacerbated by export controls from China (one of the major sources ofmore » elemental indium). Therefore, ITO is not sustainable because of the fluctuating costs and the United States (US) dependency on other nations such as China. Numerous alternatives to ITO/IZO are being evaluated such as Ag nanoparticles/nanowires, carbon nanotubes, graphene, and other metal oxides. Of these other metal oxides, doped zinc oxide has attracted a lot of attention over the last 10 years. The volume of zinc mined is a factor of 80,000 greater than indium and the US has significant volumes of zinc mined domestically, resulting in the ability for the US to be self-sufficient for this element that can be used in optoelectronic applications. The costs of elemental zinc is over 2 orders of magnitude less than indium, reflecting the relative abundance and availability of the elements. Arkema Inc. and an international primary glass manufacturing company, which is located in the United States, have developed doped zinc oxide technology for solar control windows. The genesis of this DOE SSL project was to determine if doped zinc oxide technology can be taken from the commodity based window market and translate the technology to OLED lighting. Thus, Arkema Inc. sought out experts, Philips Lighting, Pacific Northwest National Laboratories (PNNL) and National Renewable Research Laboratories (NREL), in OLED devices and brought them into the project. This project had a clear focus on economics and the work plan focused both on doped ZnO process and OLED device structure that would be consistent with the new TCO. The team successfully made 6 inch OLEDs with a serial construction. More process development is required to optimize commercial OLED structures. Feasibility was demonstrated on two different light extraction technologies: 1/4 lambda refractive index matching and high-low-high band pass filter. Process development was also completed on the key precursors for the TCO, which are ready for pilot-plant scale-up. Subsequently, Arkema has developed a cost of ownership model that is consistent with DOE SSL R&D Manufacturing targets as outlined in the DOE SSL R&D Manufacturing 2010 report. The overall outcome of this project was the demonstration that doped zinc oxide can be used for OLED devices without a drop-off in performance while gaining the economic and sustainable benefits of a more readily available TCO. The broad impact of this project, is the facilitation of OLED lighting market penetration into general illumination, resulting in significant energy savings, decreased greenhouse emissions, with no environmental impact issues such as mercury found in Fluorescent technology. The primary objective of this project was to develop a commercially viable process for 'Substrates' (Substrate/ undercoat/ TCO topcoat) to be used in production of OLED devices (lamps/luminaries/modules). This project focused on using Arkema's recently developed doped ZnO technology for the Fenestration industry and applying the technology to the OLED lighting industry. The secondary objective was the use of undercoat technology to improve light extraction from the OLED device. In optical fields and window applications, technology has been developed to mitigate reflection losses by selecting appropriate thicknesses and refractive indices of coatings applied either below or above the functional layer of interest. This technology has been proven and implemented in the fenestration industry for more than 15 years. Successful completion of this project would provide doped ZnO coated on inexpensive soda lime glass resulting in a significantly lower cost relative to the current ITO coated Flat Panel Display Glass substrates. Additional benefits will be a more consistent TCO that does not need an activation step with better optical performance. Clearly, this will serve to enhance penetration of OLED technologies into the lighting market.« less

Biosynthesis of nanoparticles of metals and metalloids by basidiomycetes. Preparation of gold nanoparticles by using purified fungal phenol oxidases.

PubMed

Vetchinkina, Elena P; Loshchinina, Ekaterina A; Vodolazov, Ilya R; Kursky, Viktor F; Dykman, Lev A; Nikitina, Valentina E

2017-02-01

The work shows the ability of cultured Basidiomycetes of different taxonomic groups-Lentinus edodes, Pleurotus ostreatus, Ganoderma lucidum, and Grifola frondosa-to recover gold, silver, selenium, and silicon, to elemental state with nanoparticles formation. It examines the effect of these metal and metalloid compounds on the parameters of growth and accumulation of biomass; the optimal cultivation conditions and concentrations of the studied ion-containing compounds for recovery of nanoparticles have been identified. Using the techniques of transmission electron microscopy, dynamic light scattering, X-ray fluorescence and X-ray phase analysis, the degrees of oxidation of the bioreduced elements, the ζ-potential of colloidal solutions uniformity, size, shape, and location of the nanoparticles in the culture fluid, as well as on the surface and the inside of filamentous hyphae have been determined. The study has found the part played by homogeneous chromatographically pure fungal phenol-oxidizing enzymes (laccases, tyrosinases, and Mn-peroxidases) in the recovery mechanism with formation of electrostatically stabilized colloidal solutions. A hypothetical mechanism of gold(III) reduction from HAuCl 4 to gold(0) by phenol oxidases with gold nanoparticles formation of different shapes and sizes has been introduced.

Photocatalytic degradation of sunscreen active ingredients mediated by nanostructured materials

NASA Astrophysics Data System (ADS)

Soto-Vazquez, Loraine

Water scarcity and pollution are environmental issues with terrible consequences. In recent years several pharmaceutical and personal care products, such as sunscreen active ingredients, have been detected in different water matrices. Its recalcitrant behavior in the environment has caused controversies and generated countless questions about its safety. During this research, we employed an advanced oxidation process (photocatalysis) to degrade sunscreen active ingredients. For this study, we used a 3x3 system, evaluating three photocatalysts and three different contaminants. From the three catalysts employed, two of them were synthesized. ZnO nanoparticles were obtained using zinc acetate dihydrated as the precursor, and TiO2 nanowires were synthesized from titanium tetrachloride precursor. The third catalyst employed (namely, P25) was obtained commercially. The synthesized photocatalysts were characterized in terms of the morphology, elemental composition, crystalline structure, elemental oxidation states, vibrational modes and surface area, using SEM-EDS, XRD, XPS, Raman spectroscopy and BET measurements, respectively. The photocatalysts were employed during the study of the degradation of p-aminobenzoic acid, phenylbenzimidazole sulfonic acid, and benzophenone-4. In all the cases, at least 50% degradation was achieved. P25 showed degradation efficiencies above 90%, and from the nine systems, 7 of them degraded at least 86%.

Segregation Phenomena in Size-Selected Bimetallic CuNi Nanoparticle Catalysts

DOE PAGES

Pielsticker, Lukas; Zegkinoglou, Ioannis; Divins, Nuria J.; ...

2017-10-25

Surface segregation, restructuring, and sintering phenomena in size-selected copper–nickel nanoparticles (NPs) supported on silicon dioxide substrates were systematically investigated as a function of temperature, chemical state, and reactive gas environment. Using near-ambient pressure (NAP-XPS) and ultrahigh vacuum X-ray photoelectron spectroscopy (XPS), we showed that nickel tends to segregate to the surface of the NPs at elevated temperatures in oxygen- or hydrogen-containing atmospheres. It was found that the NP pretreatment, gaseous environment, and oxide formation free energy are the main driving forces of the restructuring and segregation trends observed, overshadowing the role of the surface free energy. The depth profile ofmore » the elemental composition of the particles was determined under operando CO 2 hydrogenation conditions by varying the energy of the X-ray beam. The temperature dependence of the chemical state of the two metals was systematically studied, revealing the high stability of nickel oxides on the NPs and the important role of high valence oxidation states in the segregation behavior. Atomic force microscopy (AFM) studies revealed a remarkable stability of the NPs against sintering at temperatures as high as 700 °C. The results provide new insights into the complex interplay of the various factors which affect alloy formation and segregation phenomena in bimetallic NP systems, often in ways different from those previously known for their bulk counterparts. In conclusion, this leads to new routes for tuning the surface composition of nanocatalysts, for example, through plasma and annealing pretreatments.« less

Dispersoid reinforced alloy powder and method of making

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, Iver E.; Terpstra, Robert L.

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomizedmore » particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.« less

Dispersoid reinforced alloy powder and method of making

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, Iver E.; Terpstra, Robert L.

2017-10-10

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomizedmore » particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.« less

Sulfide oxidation under chemolithoautotrophic denitrifying conditions.

PubMed

Cardoso, Ricardo Beristain; Sierra-Alvarez, Reyes; Rowlette, Pieter; Flores, Elias Razo; Gómez, Jorge; Field, Jim A

2006-12-20

Chemolithoautotrophic denitrifying microorganisms oxidize reduced inorganic sulfur compounds coupled to the reduction of nitrate as an electron acceptor. These denitrifiers can be applied to the removal of nitrogen and/or sulfur contamination from wastewater, groundwater, and gaseous streams. This study investigated the physiology and kinetics of chemolithotrophic denitrification by an enrichment culture utilizing hydrogen sulfide, elemental sulfur, or thiosulfate as electron donor. Complete oxidation of sulfide to sulfate was observed when nitrate was supplemented at concentrations equal or exceeding the stoichiometric requirement. In contrast, sulfide was only partially oxidized to elemental sulfur when nitrate concentrations were limiting. Sulfide was found to inhibit chemolithotrophic sulfoxidation, decreasing rates by approximately 21-fold when the sulfide concentration increased from 2.5 to 10.0 mM, respectively. Addition of low levels of acetate (0.5 mM) enhanced denitrification and sulfate formation, suggesting that acetate was utilized as a carbon source by chemolithotrophic denitrifiers. The results of this study indicate the potential of chemolithotrophic denitrification for the removal of hydrogen sulfide. The sulfide/nitrate ratio can be used to control the fate of sulfide oxidation to either elemental sulfur or sulfate. Copyright 2006 Wiley Periodicals, Inc.

The effect and influence of cis-ligands on the electronic and oxidizing properties of nonheme oxoiron biomimetics. A density functional study.

PubMed

de Visser, Sam P; Nam, Wonwoo

2008-12-18

Density functional theory studies on the nature of the cis effect and cis influence of ligands on oxoiron nonheme complexes have been performed. A detailed analysis of the electronic and oxidizing properties of [Fe(IV)O(TPA)L](+) with L = F(-), Cl(-), and Br(-) and TPA = tris-(2-pyridylmethyl)amine are presented and compared with [Fe(IV)O(TPA)NCCH(3)](2+). The calculations show that the electronic cis effect is determined by favorable orbital overlap between first-row elements with the metal, which are missing between the metal and second- and third-row elements. As a consequence, the metal 3d block is split into a one-below-two set of orbitals with L = Cl(-) and Br(-), and the HOMO/LUMO energy gap is widened with respect to the system with L = F(-). However, this larger HOMO/LUMO gap does not lead to large differences in electron affinities of the complexes. Moreover, a quantum mechanical analysis of the binding of the ligand shows that it is built up from a large electric field effect of the ligand on the oxoiron species and a much smaller quantum mechanical effect due to orbital overlap. These contributions are of similar strength for the three tested halogen cis ligands and result in similar reactivity patterns with substrates. The calculations show that [Fe(IV)O(TPA)L](+) with L = F(-), Cl(-), and Br(-) have closely lying triplet and quintet spin states, but only the quintet spin state is reactive with substrates. Therefore, the efficiency of the oxidant will be determined by the triplet-quintet spin state crossing of the reaction. The reaction of styrene with a doubly charged reactant, that is, [Fe(V)O(TPA)L](2+) with L = F(-), Cl(-), and Br(-) or [Fe(V)O(TPA)NCCH(3)](3+), leads to an initial electron transfer from the substrate to the metal followed by a highly exothermic epoxidation mechanism. These reactivity differences are mainly determined by the overall charge of the system rather than the nature of the cis ligand.

The redox state of the mantle during and just after core formation.

PubMed

Frost, D J; Mann, U; Asahara, Y; Rubie, D C

2008-11-28

Siderophile elements are depleted in the Earth's mantle, relative to chondritic meteorites, as a result of equilibration with core-forming Fe-rich metal. Measurements of metal-silicate partition coefficients show that mantle depletions of slightly siderophile elements (e.g. Cr, V) must have occurred at more reducing conditions than those inferred from the current mantle FeO content. This implies that the oxidation state (i.e. FeO content) of the mantle increased with time as accretion proceeded. The oxygen fugacity of the present-day upper mantle is several orders of magnitude higher than the level imposed by equilibrium with core-forming Fe metal. This results from an increase in the Fe2O3 content of the mantle that probably occurred in the first 1Ga of the Earth's history. Here we explore fractionation mechanisms that could have caused mantle FeO and Fe2O3 contents to increase while the oxidation state of accreting material remained constant (homogeneous accretion). Using measured metal-silicate partition coefficients for O and Si, we have modelled core-mantle equilibration in a magma ocean that became progressively deeper as accretion proceeded. The model indicates that the mantle would have become gradually oxidized as a result of Si entering the core. However, the increase in mantle FeO content and oxygen fugacity is limited by the fact that O also partitions into the core at high temperatures, which lowers the FeO content of the mantle. (Mg,Fe)(Al,Si)O3 perovskite, the dominant lower mantle mineral, has a strong affinity for Fe2O3 even in the presence of metallic Fe. As the upper mantle would have been poor in Fe2O3 during core formation, FeO would have disproportionated to produce Fe2O3 (in perovskite) and Fe metal. Loss of some disproportionated Fe metal to the core would have enriched the remaining mantle in Fe2O3 and, if the entire mantle was then homogenized, the oxygen fugacity of the upper mantle would have been raised to its present-day level.

Thermal oxidation of single crystal aluminum antimonide and materials having the same

DOEpatents

Sherohman, John William; Yee, Jick Hong; Coombs, III, Arthur William; Wu, Kuang Jen J.

2012-12-25

In one embodiment, a method for forming a non-conductive crystalline oxide layer on an AlSb crystal includes heat treating an AlSb crystal in a partial vacuum atmosphere at a temperature conducive for air adsorbed molecules to desorb, surface molecule groups to decompose, and elemental Sb to evaporate from a surface of the AlSb crystal and exposing the AlSb crystal to an atmosphere comprising oxygen to form a crystalline oxide layer on the surface of the AlSb crystal. In another embodiment, a method for forming a non-conductive crystalline oxide layer on an AlSb crystal includes heat treating an AlSb crystal in a non-oxidizing atmosphere at a temperature conducive for decomposition of an amorphous oxidized surface layer and evaporation of elemental Sb from the AlSb crystal surface and forming stable oxides of Al and Sb from residual surface oxygen to form a crystalline oxide layer on the surface of the AlSb crystal.

Influence of frequency on the structure of zirconium oxide coatings deposited from aqueous electrolytes under microplasma oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gubaidulina, Tatiana A., E-mail: goub2002@mail.ru; Sergeev, Viktor P., E-mail: vserg@mail.tomsknet.ru; Fedorischeva, Marina V., E-mail: fmw@ispms.tsc.ru

2015-10-27

The work describes the microplasma oxidation (MPO) of zirconium surface resulting in the formation of zirconium oxide Zr-Al-Nb-O. We have used novel power supply to deposit oxide ceramic coatings by MPO and studied the effect of current density on the phase structure of oxide ceramic coatings. The size of microcracks in the coatings was determined at different frequencies. We have also used EVO50c scanning election microscope with an attachment for elemental analysis to study the morphology and elemental composition of oxide ceramic coating. In addition, we have established the influence of the frequency on the phase composition of the coating:more » at the frequency of 2500 Hz, the fraction of monoclinic phase was 18%, while the fraction of tetragonal phase amounted to 72%. The oxide ceramic coating produced at 250 Hz contained 38% of monoclinic phase and 62% of tetragonal phase; in addition, it had no buildups and craters.« less

Photochemical oxidation and changes in molecular composition of organic aerosol in the regional context

NASA Astrophysics Data System (ADS)

Robinson, Allen L.; Donahue, Neil M.; Rogge, Wolfgang F.

2006-02-01

This paper presents evidence that condensed-phase organic compounds are significantly oxidized in regional air masses and in locations affected by regional transport, especially during the summer. The core of the paper examines a large data set of ambient organic aerosol concentrations for removal of reactive compounds relative to less-reactive compounds. The approach allows visualization of both photochemistry and mixing of emissions from multiple sources in order to differentiate between the two phenomena. The focus is on hopanes and alkenoic acids, important markers for motor vehicle and cooking emissions. Ambient data from Pittsburgh, PA and the Southeastern United States contain evidence for significant photochemical oxidation of these compounds in the summertime. There is a strong seasonal pattern in the ratio of different hopanes to elemental carbon consistent with oxidation. In addition, measurements at rural sites indicate that hopanes are severely depleted in the regional air mass during the summer. Alkenoic acids also appear to be photochemically oxidized during the summertime; however, the oxidation rate appears to be much slower than that inferred from laboratory experiments. The significance of photochemistry is supported by rudimentary calculations which indicate substantial oxidation by OH radicals and ozone on a time scale of a few days or so, comparable to time scales for regional transport. Oxidation is non-linear; therefore it represents a very substantial complication to linear source apportionment techniques such as the Chemical Mass Balance model.

Early diagenetic partial oxidation of organic matter and sulfides in the Middle Pennsylvanian (Desmoinesian) Excello Shale Member of the Fort Scott Limestone and equivalents, northern Midcontinent region, USA

USGS Publications Warehouse

Hatch, J.R.; Leventhal, M.S.

1997-01-01

A process of early diagenetic partial oxidation of organic matter and sulfides has altered the chemical composition of the Middle Pennsylvanian Excello Shale Member of the Fort Scott Limestone and equivalents in the northern Midcontinent region. This process was identified by comparison of organic carbon contents, Rock-Eval hydrogen indices, organic carbon ??13C and element compositions of core and surface mine samples of the Excello Shale Member with analyses of three other underlying and overlying organic-matter-rich marine shales (offshore shale lithofacies) from southern Iowa, northern Missouri, eastern Kansas and northeastern Oklahoma. The end product of the partial oxidation process is shale with relatively low contents of hydrogen-poor, C13-enriched organic matter, lower contents of sulfur and sulfide-forming elements, and relatively unchanged contents of phosphorus and many trace elements (e.g. Cr, Ni, and V). However, because of lower organic carbon contents, element/organic carbon ratios are greatly increased. The partial oxidation process apparently took place during subaerial exposure of the overlying marine carbonate member (Blackjack Creek Member of the Fort Scott Limestone) following a marine regression when meteoric waters percolated down to the level of the Excello muds allowing oxidation of organic matter and sulfides. This hypothesis is supported by earlier workers, who have identified meteoric carbonate cements within, and soil horizons at the top of the Blackjack Creek Member. The period of oxidation is constrained in that organic matter and sulfides in the Little Osage Shale Member of the Fort Scott Limestone and equivalents (immediately overlying the Blackjack Creek Member) appear unaltered. Similar alteration of other shales in the Middle and Upper Pennsylvanian sections may be local to regional in extent and would depend on the extent and duration of the marine regression and be influenced by local variations in permeability and topography. The partial oxidation process has likely led to a redistribution of sulfur and sulfide-forming elements into other organic-rich lithologies in the section. The altered/oxidized shales are nongenerative with respect to hydrocarbon generation.

Effect of Alloying Elements, Water Vapor Content, and Temperature on the Oxidation of Interstitial-Free Steels

NASA Astrophysics Data System (ADS)

Zhang, Z. T.; Sohn, I. R.; Pettit, F. S.; Meier, G. H.; Sridhar, S.

2009-08-01

The present study is an investigation of the surface and subsurface oxidation of Mn solid-solution-strengthened interstitial-free (IF) steels with the objective of elucidating the surface evolution before coating. Thermogravimetric (TG) analysis was carried out under 95 vol pct Ar + 5 vol pct (H2 + H2O) atmospheres with P_{{{text{H}}2 {text{O}}}} /P_{{{text{H}}2 }} ranging from 0.01 to 0.13 and temperatures ranging from 800 °C to 843 °C. Post-exposure characterization was carried out through scanning electron microscopy (SEM)/energy-dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and glancing-angle X-ray diffraction (XRD) to study the external and internal oxide evolution. The oxidation proceeds as a combination of the internal and external formation of Mn oxides. Decreasing the P_{{{text{H}}2 {text{O}}}} /P_{{{text{H}}2 }} ratios or temperature has the effect of decreasing the amount of oxidation, which is a combination of internal and external oxidation controlled by solid-state oxygen and manganese diffusion, respectively. External oxides are not continuous; they are instead concentrated near the intersection of alloy grain boundaries with the external surface. Internal oxides are concentrated along the grain boundaries. The effects of Sb (0.03 wt pct), B (10 ppm), P (0.04 and 0.08 wt pct), and Si (0.06 to 1.5 wt pct) on the oxidation were investigated. It is found that small amounts of Sb and B have a significant effect on decreasing both the external and internal oxidation, whereas Si and P increase the external and internal oxidation.

Mobility of major and trace elements in a coupled groundwater-surface water system: Merced River, CA

NASA Astrophysics Data System (ADS)

Wildman, R. A.; Domagalski, J. L.; Hering, J. G.

2004-12-01

Trace element transport in coupled surface water/groundwater systems is controlled not only by advective flow, but also by redox reactions that affect the partitioning of various elements between mobile and immobile phases. These processes have been examined in the context of a field project conducted by the U.S. Geological Survey (USGS) as part of the National Water-Quality Assessment (NAWQA) program. The Merced River flows out of Yosemite National Park and the Sierra Nevada foothills and into California's Central Valley, where it joins the San Joaquin River. Our field site is approximately twenty river kilometers from the confluence with the San Joaquin River. This deep alluvial plain has minimal topography. Agricultural development characterizes the land surrounding this reach of river; consequently, the hydrology is heavily influenced by irrigation. Riverbed groundwater samples were collected from ten wells aligned in two transects across the river located approximately 100 m apart. The wells were sampled from depths of 0.5 m, 1 m, and 3 m below the sediment-water interface. Groundwater flowpath samples were taken from wells positioned on a path perpendicular to the river and located 100 m, 500 m, and 1000 m from the river. The saturated groundwater system exists from 7 to 40 m below the surface and is confined below by a clay layer. Each well location samples from 3-5 depths in this surface aquifer. Samples were collected in December 2003, March-April, June-July, and October 2004. This served to provide an evenly-spaced sampling frequency over the course of a year, and also to allow observation of trends coinciding with the onset of winter, the spring runoff, and early and late summer irrigation. An initial survey of the elements in the riverbed samples was conducted using Inductively-Coupled Plasma Mass Spectrometry (ICP-MS). Elements for further study were selected based on variability in this survey, either with respect to depth or location, as well as to cover a range of expected geochemical behaviors. Further ICP-MS measurements focused on eight elements: strontium, barium, uranium, molybdenum, manganese, iron, phosphorus, and bromine. Bromine is a conservative tracer. Molybdenum, manganese, and iron will precipitate when oxidized, and uranium will precipitate when reduced. Strontium and barium are not redox-active but may be affected by dissolution-precipitation and sorption reactions. Phosphorus is a nutrient that will cycle actively in areas of biological productivity. Generally, these elements appear to behave as expected based on physical waterflow and assumed redox conditions. The two transects of wells across the river bracket a zone of known denitrification, which implies that sediment conditions favor oxidation upriver and reduction downriver. This trend is borne out both by the redox-sensitive elements at each transect, and by the strontium and barium, which bind to precipitated iron and manganese oxides in oxidizing conditions and are released into the dissolved state in reducing conditions. The flowpath samples appear to be enriched in strontium, phosphorus, and bromine when compared to the riverbed samples, and they are depleted in manganese and iron.

Elemental ratio measurements of organic compounds using aerosol mass spectrometry: characterization, improved calibration, and implications

NASA Astrophysics Data System (ADS)

Canagaratna, M. R.; Jimenez, J. L.; Kroll, J. H.; Chen, Q.; Kessler, S. H.; Massoli, P.; Hildebrandt Ruiz, L.; Fortner, E.; Williams, L. R.; Wilson, K. R.; Surratt, J. D.; Donahue, N. M.; Jayne, J. T.; Worsnop, D. R.

2015-01-01

Elemental compositions of organic aerosol (OA) particles provide useful constraints on OA sources, chemical evolution, and effects. The Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is widely used to measure OA elemental composition. This study evaluates AMS measurements of atomic oxygen-to-carbon (O : C), hydrogen-to-carbon (H : C), and organic mass-to-organic carbon (OM : OC) ratios, and of carbon oxidation state (OS C) for a vastly expanded laboratory data set of multifunctional oxidized OA standards. For the expanded standard data set, the method introduced by Aiken et al. (2008), which uses experimentally measured ion intensities at all ions to determine elemental ratios (referred to here as "Aiken-Explicit"), reproduces known O : C and H : C ratio values within 20% (average absolute value of relative errors) and 12%, respectively. The more commonly used method, which uses empirically estimated H2O+ and CO+ ion intensities to avoid gas phase air interferences at these ions (referred to here as "Aiken-Ambient"), reproduces O : C and H : C of multifunctional oxidized species within 28 and 14% of known values. The values from the latter method are systematically biased low, however, with larger biases observed for alcohols and simple diacids. A detailed examination of the H2O+, CO+, and CO2+ fragments in the high-resolution mass spectra of the standard compounds indicates that the Aiken-Ambient method underestimates the CO+ and especially H2O+ produced from many oxidized species. Combined AMS-vacuum ultraviolet (VUV) ionization measurements indicate that these ions are produced by dehydration and decarboxylation on the AMS vaporizer (usually operated at 600 °C). Thermal decomposition is observed to be efficient at vaporizer temperatures down to 200 °C. These results are used together to develop an "Improved-Ambient" elemental analysis method for AMS spectra measured in air. The Improved-Ambient method uses specific ion fragments as markers to correct for molecular functionality-dependent systematic biases and reproduces known O : C (H : C) ratios of individual oxidized standards within 28% (13%) of the known molecular values. The error in Improved-Ambient O : C (H : C) values is smaller for theoretical standard mixtures of the oxidized organic standards, which are more representative of the complex mix of species present in ambient OA. For ambient OA, the Improved-Ambient method produces O : C (H : C) values that are 27% (11%) larger than previously published Aiken-Ambient values; a corresponding increase of 9% is observed for OM : OC values. These results imply that ambient OA has a higher relative oxygen content than previously estimated. The OS C values calculated for ambient OA by the two methods agree well, however (average relative difference of 0.06 OS C units). This indicates that OS C is a more robust metric of oxidation than O : C, likely since OS C is not affected by hydration or dehydration, either in the atmosphere or during analysis.

Trace elements and oxidative stress levels in the blood of painters in Lagos, Nigeria: occupational survey and health concern.

PubMed

Awodele, Olufunsho; Akinyede, Akin; Babawale, Omotola Opeyemi; Coker, Herbert A Babatunde; Akintonwa, Alade

2013-06-01

Adverse effects attributed to exposure to paints are currently a concern because of the continued widespread use of paint containing trace elements. Thus, occupational survey amongst painters in Lagos and determination of trace elements and oxidative stress parameters were carried out. Descriptive cross-sectional survey was done using a standardized questionnaire to obtain job safety-related information. Forty-eight percent of the painters were aware of hazards associated with painting and 52 % of these workers were aware of the necessary precautionary measures during painting. There were no significant differences (p ≥ 0.05) between the levels of trace elements in the blood of painters and the control subjects. However, there was a significance increase (p ≤ 0.0001) in the level of malondialdehyde and a decrease (p ≤ 0.001) in the levels of reduced glutathione, superoxide dismutase, and catalase of the painters compared to the control. An increase in oxidative stress parameters may not only be due to trace element concentrations, but also the painters' exposure to some petrochemical solvents during mixing of paints.

Reversible capture and release of Cl 2 and Br 2 with a redox-active metal–organic framework

DOE PAGES

Tulchinsky, Yuri; Hendon, Christopher H.; Lomachenko, Kirill A.; ...

2017-03-28

Extreme toxicity, corrosiveness, and volatility pose serious challenges for the safe storage and transportation of elemental chlorine and bromine, which play critical roles in the chemical industry. Solid materials capable of forming stable nonvolatile compounds upon reaction with elemental halogens may partially mitigate these challenges by allowing safe halogen release on demand. Here we demonstrate that elemental halogens quantitatively oxidize coordinatively unsaturated Co(II) ions in a robust azolate metal-organic framework (MOF) to produce stable and safe-to-handle Co(III) materials featuring terminal Co(III)-halogen bonds. Thermal treatment of the oxidized MOF causes homolytic cleavage of the Co(III)-halogen bonds, reduction to Co(II), and concomitantmore » release of elemental halogens. The reversible chemical storage and thermal release of elemental halogens occur with no significant losses of structural integrity, as the parent cobaltous MOF retains its crystallinity and porosity even after three oxidation/reduction cycles. Finally, these results highlight a material operating via redox mechanism that may find utility in the storage and capture of other noxious and corrosive gases.« less

Development of phase analysis methods of impurity elements in alloys based on iron and nickel

NASA Astrophysics Data System (ADS)

Andreeva, N. A.; Anuchkin, S. N.; Volchenkova, V. A.; Kazenas, E. K.; Penkina, T. N.; Fomina, A. A.

2018-04-01

Using the method of AES with ICP, new methods have been developed for quantifying the content of various forms of existence of impurity elements: Al-Al2O3; Zr-ZrO2 in alloys based on iron (Fe-Sn) and nickel (Ni-Sn). Open systems were used to dissolve Al and Zr. To translate difficult-to-open aluminum oxides (corundum) and zirconium oxide (baddeleyite) into the solution, accelerated techniques were developed using the microwave system Mars 5. To confirm the completeness of the dissolution of oxides, a classical scheme of alloy fusion with alkali metal salts was used. Optimal analytical parameters for determining the elements: Al and Zr were chosen. The influence of matrix elements (iron and nickel) and methods of its elimination were studied. This made it possible to determine the elements in a wide concentration range from 1 • 10-3 to n% Al and from 1 • 10-4 to n% Zr without preliminary separation of the matrix with good metrological characteristics. The relative standard deviation (Sr) does not exceed 0,2. The separate determination of the contents of aluminum and aluminium oxide in the model melt of Fe-Sn-Al2O3 and zirconium and zirconium oxide in the Ni-Sn-ZrO2 model melt allowed us to estimate the number of nanoparticles participating in the heterophase interaction with tin and retired to the interface in the form of ensembles and the number of nanoparticles present in the melt and affecting the crystallization process and the structure of the metal.

Thorium/U systematics of Precambrian deep-sea pelagic balck shales: implications for redox state of the early atmosphere

NASA Astrophysics Data System (ADS)

Jia, Y.; McCulloch, M.; Charlotte, A.

2003-12-01

To address the question of the redox state of the Precambrian atmosphere-hydrosphere system via sediments requires measurement of redox sensitive trace elements, and inter-element ratios, in deep water black shales with a chemical sedimentary "hydrogenic" component. This approach is endorsed by recent progress in research of redox-sensitive trace metals records in late Proterozoic and Phanerozoic sedimentary rocks, which has provided important clues to how the redox state of depositional environments has changed over time. Many conventional studies, in contrast, have been on first cycle volcanogenic turbidites with a minimal hydrogenic input (Taylor and McLennan, 1995). Accordingly, we have analyzed the redox-sensitive, trace element compositions of the 2.1 Ga black shales in Birimian Blet, West Africa, and the 2.7 Ga Archean counterparts in Timmins, Canada, Tati Belt, Botswana, and Kanowna District, Western Australia. These pyrite-bearing black shales, which were originally argillaceous sediments containing organic matter and low in thermal maturity, were primarily deposited in the deep-sea pelagic environments. Th/U ratios are lower in the Proterozoic shales (0.38-0.82, average 0.67), and Archean shales (0.47-3.65, average 2.43) relative to "conventional" Archean upper crust (3.8), PAAS (4.7), or average upper continental crust (3.8). Calculated U concentrations from hydrogenic component are between 0.90 and 2.45 in the Proterozoic shales, and range from 0.06 to 0.96 for the Archean black shales. Given the conservative behavior of Th in the sedimentary cycle, variably low Th/U ratios in these Precambrian black shales signify that U6+, soluble in oxidized surface waters, was reduced to insoluble U4+ in reducing bottom waters, as in the contemporary Black Sea. The results are consistent with a locally to globally oxidized atmosphere-shallow hydrosphere pre-2.0 Ga. Taylor, S.R., and McLennan, S.C., 1995. The geochemical evolution of the continental crust: Reviews of Geophysics, v. 33. p. 241-265.

On the formation of molecules and solid-state compounds from the AGB to the PN phases

NASA Astrophysics Data System (ADS)

García-Hernández, D. A.; Manchado, A.

2016-07-01

During the asymptoyic giant branch (AGB) phase, different elements are dredge- up to the stellar surface depending on progenitor mass and metallicity. When the mass loss increases at the end of the AGB, a circumstellar dust shell is formed, where different (C-rich or O-rich) molecules and solid-state compounds are formed. These are further processed in the transition phase between AGB stars and planetary nebulae (PNe) to create more complex organic molecules and inorganic solid-state compounds (e.g., polycyclic aromatic hydrocarbons, fullerenes, and graphene precursors in C-rich environments and oxides and crystalline silicates in O-rich ones). We present an observational review of the different molecules and solid-state materials that are formed from the AGB to the PN phases. We focus on the formation routes of complex fullerene (and fullerene-based) molecules as well as on the level of dust processing depending on metallicity.

Arsenic, Antimony, Chromium, and Thallium Speciation in Water and Sediment Samples with the LC-ICP-MS Technique

PubMed Central

Jabłońska-Czapla, Magdalena

2015-01-01

Chemical speciation is a very important subject in the environmental protection, toxicology, and chemical analytics due to the fact that toxicity, availability, and reactivity of trace elements depend on the chemical forms in which these elements occur. Research on low analyte levels, particularly in complex matrix samples, requires more and more advanced and sophisticated analytical methods and techniques. The latest trends in this field concern the so-called hyphenated techniques. Arsenic, antimony, chromium, and (underestimated) thallium attract the closest attention of toxicologists and analysts. The properties of those elements depend on the oxidation state in which they occur. The aim of the following paper is to answer the question why the speciation analytics is so important. The paper also provides numerous examples of the hyphenated technique usage (e.g., the LC-ICP-MS application in the speciation analysis of chromium, antimony, arsenic, or thallium in water and bottom sediment samples). An important issue addressed is the preparation of environmental samples for speciation analysis. PMID:25873962

Memory switches based on metal oxide thin films

NASA Technical Reports Server (NTRS)

Ramesham, Rajeshuni (Inventor); Thakoor, Anilkumar P. (Inventor); Lambe, John J. (Inventor)

1990-01-01

MnO.sub.2-x thin films (12) exhibit irreversible memory switching (28) with an OFF/ON resistance ratio of at least about 10.sup.3 and the tailorability of ON state (20) resistance. Such films are potentially extremely useful as a connection element in a variety of microelectronic circuits and arrays (24). Such films provide a pre-tailored, finite, non-volatile resistive element at a desired place in an electric circuit, which can be electrically turned OFF (22) or disconnected as desired, by application of an electrical pulse. Microswitch structures (10) constitute the thin film element, contacted by a pair of separate electrodes (16a, 16b) and have a finite, pre-selected ON resistance which is ideally suited, for example, as a programmable binary synaptic connection for electronic implementation of neural network architectures. The MnO.sub.2-x microswitch is non-volatile, patternable, insensitive to ultraviolet light, and adherent to a variety of insulating substrates (14), such as glass and silicon dioxide-coated silicon substrates.

Static ferroelectric memory transistor having improved data retention

DOEpatents

Evans, Jr., Joseph T.; Warren, William L.; Tuttle, Bruce A.

1996-01-01

An improved ferroelectric FET structure in which the ferroelectric layer is doped to reduce retention loss. A ferroelectric FET according to the present invention includes a semiconductor layer having first and second contacts thereon, the first and second contacts being separated from one another. The ferroelectric FET also includes a bottom electrode and a ferroelectric layer which is sandwiched between the semiconductor layer and the bottom electrode. The ferroelectric layer is constructed from a perovskite structure of the chemical composition ABO.sub.3 wherein the B site comprises first and second elements and a dopant element that has an oxidation state greater than +4 in sufficient concentration to impede shifts in the resistance measured between the first and second contacts with time. The ferroelectric FET structure preferably comprises Pb in the A-site. The first and second elements are preferably Zr and Ti, respectively. The preferred B-site dopants are Niobium, Tantalum, and Tungsten at concentrations between 1% and 8%.

Efficient growth of HTS films with volatile elements

DOEpatents

Siegal, M.P.; Overmyer, D.L.; Dominguez, F.

1998-12-22

A system is disclosed for applying a volatile element-HTS layer, such as Tl-HTS, to a substrate in a multiple zone furnace, said method includes heating at higher temperature, in one zone of the furnace, a substrate and adjacent first source of Tl-HTS material, to sublimate Tl-oxide from the source to the substrate; and heating at lower temperature, in a separate zone of the furnace, a second source of Tl-oxide to replenish the first source of Tl-oxide from the second source. 3 figs.

Applying the Ce-in-zircon oxygen geobarometer to diverse silicic magmatic systems

NASA Astrophysics Data System (ADS)

Claiborne, L. L.; Miller, C. F.

2012-12-01

Zircon provides information on age, temperature, and composition of the magma from which it grew. In systems such as Mount St. Helens, where zircon is not coeval with the rest of the crystal cargo, it provides the only accessible record of the extended history of the magmatic system, including cycles of intrusion, crystallization and rejuvenation beneath an active volcano (Claiborne et al., 2010). The rare earth elements, which are present in measureable quantities in zircon, provide information about the composition of the magma from which zircon grew. Unique among the generally trivalent rare earth elements, cerium can exist as either trivalent or tetravalent, depending on the oxidation state of the magma. The tetravalent ion is highly compatible in zircon, in the site that usually hosts tetravalent zirconium, and so the amount of Cerium in zircon relative (relative to what would be expected of trivalent Ce) depends the oxidation state of the magma from which it grew. Trail et al. (2011) proposed a calibration based on experimental data that uses the Ce anomaly in zircon as a direct proxy for magma oxidation (fugacity), describing the relationship between Ce in zircon and magma oxygen fugacity as ln(Ce/Ce*)D = (0.1156±0.0050)xln(fO2)+(13860±708)/T-(6.125±0.484). For systems like Mount St. Helens, where the major minerals record only events in the hundreds to thousands of years leading to eruption, (including the Fe-Ti oxides traditionally relied upon for records of oxidation state of the magmas), this presents a novel approach for understanding more extended histories of oxidation of magmas in the tens and hundreds of thousands of years of magmatism at a volcanic center. This calibration also promises to help us better constrain conditions of crystallization in intrusive portions of volcanic systems, as well as plutonic bodes. We apply this new oxygen geobarometer to natural volcanic and plutonic zircons from a variety of tectonic settings, and compare to existing indicators of oxidation state for each system, as available. Zircons included this study are from Mount St. Helens (ΔNNO +1.5 log units; Smith, 1984), the Peach Spring Tuff and Spirit Mountain Batholith (sphene-bearing, silicic, Miocene-aged rocks from the Colorado River Extensional Corridor), Alid Volcano in Eritrea, and rhyolites and granites from Iceland. Median log fO2 for these systems, calculated from the Cerium anomaly in zircons following Trail et al. (2011) using temperatures from Ti-in-zircon thermometry (Ferry and Watson, 2007) are as follows: Alid -12 bars (ΔNNO +3 log units) at 750 degrees C; Iceland -11 bars (ΔNNO +3 log units) at 800 degrees C; Mount St. Helens -8.6 bars (ΔNNO +6 log units) at 750 degrees C; Peach Spring Tuff -3.4 (ΔNNO +10 log units) at 830 degrees C. While ubiquitous sphene in the Spirit Mountain granites suggest relatively high fO2, calculations based on the cerium anomaly in zircon suggest median log fO2 of >0 at 770 degrees C, which is certainly erroneous. While median values for our natural zircons are, for the most part, above expected fugacities for each system when compared with other indicators, and extreme values for each system are almost certainly erroneous, many are within expected values for terrestrial magmas and they vary relative to one another as might be expected given the magma types and tectonic settings.

The oxidation state of Hadean magmas and implications for early Earth's atmosphere.

PubMed

Trail, Dustin; Watson, E Bruce; Tailby, Nicholas D

2011-11-30

Magmatic outgassing of volatiles from Earth's interior probably played a critical part in determining the composition of the earliest atmosphere, more than 4,000 million years (Myr) ago. Given an elemental inventory of hydrogen, carbon, nitrogen, oxygen and sulphur, the identity of molecular species in gaseous volcanic emanations depends critically on the pressure (fugacity) of oxygen. Reduced melts having oxygen fugacities close to that defined by the iron-wüstite buffer would yield volatile species such as CH(4), H(2), H(2)S, NH(3) and CO, whereas melts close to the fayalite-magnetite-quartz buffer would be similar to present-day conditions and would be dominated by H(2)O, CO(2), SO(2) and N(2) (refs 1-4). Direct constraints on the oxidation state of terrestrial magmas before 3,850 Myr before present (that is, the Hadean eon) are tenuous because the rock record is sparse or absent. Samples from this earliest period of Earth's history are limited to igneous detrital zircons that pre-date the known rock record, with ages approaching ∼4,400 Myr (refs 5-8). Here we report a redox-sensitive calibration to determine the oxidation state of Hadean magmatic melts that is based on the incorporation of cerium into zircon crystals. We find that the melts have average oxygen fugacities that are consistent with an oxidation state defined by the fayalite-magnetite-quartz buffer, similar to present-day conditions. Moreover, selected Hadean zircons (having chemical characteristics consistent with crystallization specifically from mantle-derived melts) suggest oxygen fugacities similar to those of Archaean and present-day mantle-derived lavas as early as ∼4,350 Myr before present. These results suggest that outgassing of Earth's interior later than ∼200 Myr into the history of Solar System formation would not have resulted in a reducing atmosphere.

Adsorption of uranium composites onto saltrock oxides - experimental and theoretical study.

PubMed

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.

Pulsed—Laser Deposition Of Oxide Thin Films And Laser—Induced Breakdown Spectroscopy Of Multi—Element Materials

NASA Astrophysics Data System (ADS)

Pedarnig, Johannes D.

2010-10-01

New results of the Linz group on pulsed—laser deposition (PLD) of oxide thin films and on laser—induced breakdown spectroscopy (LIBS) of multi-element materials are reported. High-Tc superconducting (HTS) films with enhanced critical current density Jc are produced by laser ablation of novel nano-composite ceramic targets. The targets contain insulating nano-particles that are embedded into the YBa2Cu3O7 matrix. Epitaxial double-layers of lithium-doped and aluminum-doped ZnO are deposited on r-cut sapphire substrates. Acoustic over-modes in the GHz range are excited by piezoelectric actuation of layers. Smooth films of rare-earth doped glass are produced by F2—laser ablation. The transport properties of HTS thin films are modified by light—ion irradiation. Thin film nano—patterning is achieved by masked ion beam irradiation. LIBS is employed to analyze trace elements in industrial iron oxide powder and reference polymer materials. Various trace elements of ppm concentration are measured in the UV/VIS and vacuum-UV spectral range. Quantitative LIBS analysis of major components in oxide materials is performed by calibration-free methods.

Dissolved Rare Earth Elements in the US GEOTRACES North Atlantic Section

NASA Astrophysics Data System (ADS)

Shiller, A. M.

2016-12-01

The rare earth elements (REEs) are a unique chemical set wherein there are systematic changes in geochemical behavior across the series. Furthermore, while most REEs are in the +III oxidation state, Ce and Eu can be in other oxidation states leading to distinct characteristics of those elements. Thus, the geochemical properties of the REEs make them particularly useful tools for inquiring into various geochemical processes. As part of the US GEOTRACES effort, we determined dissolved REEs and Y at 32 stations across the North Atlantic during US cruises GT10 and GT11 along a meridional transect from Lisbon to the Cape Verde Islands and a zonal transect from Cape Cod to the Mauritanian coast. While profiles are similar to previous reports, the high spatial resolution of the section allows for better elucidation of processes. Light rare earths (LREEs) show removal in the upper water column with a minimum at the chlorophyll maximum. LREE concentrations then increase into the oxygen minimum followed by a slight decrease and fairly constant concentrations in the mid-water column followed by an increase into the deep and bottom waters. Heavy rare earths (HREEs) show a more monotonic increase with depth. We also take advantage of a previously published water mass analysis for the section to estimate that most of the deep water changes can be explained by conservative mixing of waters with different pre-formed REE concentrations. Nonetheless, the pattern of LREE shallow water removal followed by regeneration, possible re-scavenging, and then deep water input is still preserved. Other features of note include an increase in LREEs in the strong oxygen minimum zone off Mauritania, consistent with an association of REE cycling with the redox cycles of Fe and Mn. Also along the eastern margin, but below the oxygen minimum, a small but distinct increase in the cerium and europium anomalies is observed, consistent with terrigenous input. In hydrothermally influenced waters along the mid-Atlantic Ridge, there are increases in Ce/Ce*, Eu/Eu*, and Y/Ho but a decrease in Nd/Yb and in REE concentrations. Surface water distributions are more consistent with elements influenced by margin inputs than with atmospheric input.

Rare Earth and other Chemical Elements Accumulation in Vines of Fogo Island (Cape Verde)

NASA Astrophysics Data System (ADS)

Marques, Rosa; Prudêncio, Maria Isabel; Rocha, Fernando; Dias, Maria Isabel; Franco, Dulce

2017-04-01

The Fogo Island is the fourth bigger island of the Cape Verde (central Atlantic Ocean). This archipelago is located 570 kilometres off the coast of West Africa, and is characterized by a semi-arid climate. The volcanic soils of the caldera of this island, with an active volcanism during historical times, have been used for viticulture. The study of uptake of chemical elements by vines - absorption and translocation to grapes - grown in soils developed on alkaline pyroclasts is the main goal of this work. The concentrations of 27 chemical elements in bark, leafs and grapes of two vines, as well as in the corresponding soils (< 2 mm) were determined by instrumental neutron activation analysis. Irradiations of milled samples and standards were made in the core grid of the Portuguese Research Reactor (CTN/IST, Bobadela). The distribution patterns of the enrichment factors (EF) in the different parts of the plants are similar for the two sampling sites. Significant EF were found for the majority of the chemical elements studied, in the several parts of the plants, particularly in grapes where Cr, As, Sb and U are accumulated (EF > 50). The bioavailable fraction of Cr and As in these soils may be due to the low percentage of iron oxides (particularly in the form of nanoparticles), which play an important role in the retention of these elements. The factors responsible for the phytoavailability of Sb in soils and its uptake by plants it's still poorly known. Although the Sb concentrations in earth's crust are low, higher concentrations of this element in soils may be related with hydrothermal and volcanic processes. Also, the temperature may influence the accumulation of Sb in plants, with an increase of the Sb uptake by plants at higher temperatures, due to an increased desorption rate of Sb from soil particles. Concerning U, its mobility and dispersion in soils is controlled by its oxidation state, its adsorption capacity in clay minerals or iron oxides, and the ability to form more or less soluble complexes. Although U concentrations in these volcanic soils are low, there is a fraction available for absorption and accumulation by grapes. Concerning the rare earth elements (REE), it should be noted that the light REE are not enriched in any part of the vines studied, and only the heavy REE are enriched in grapes (EF = 20-50); this can be explained by the preferential uptake of the heavy REE, after primary minerals breakdown and the formation of more soluble compounds. The significant accumulation of several chemical elements found in grapes of Fogo Island can be mainly explained by a geogenic origin.

Nuclear Forensics and Radiochemistry: Chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rundberg, Robert S.

The chemical behavior of radioactive elements can differ from conventional wisdom because the number of atoms can be unusually small. Kinetic effects and unusual oxidation states are phenomena that make radiochemistry different from conventional analytic chemistry. The procedures developed at Los Alamos are designed to minimize these effects and provide reproducible results over a wide range of sample types. The analysis of nuclear debris has the additional complication of chemical fractionation and the incorporation of environmental contaminants. These are dealt with through the use of three component isotope ratios and the use of appropriate end members.

METHOD OF SEPARATING PLUTONIUM FROM LANTHANUM FLUORIDE CARRIER

DOEpatents

Watt, G.W.; Goeckermann, R.H.

1958-06-10

An improvement in oxidation-reduction type methods of separating plutoniunn from elements associated with it in a neutron-irradiated uranium solution is described. The method relates to the separating of plutonium from lanthanum ions in an aqueous 0.5 to 2.5 N nitric acid solution by 'treating the solution, at room temperature, with ammonium sulfite in an amount sufficient to reduce the hexavalent plutonium present to a lower valence state, and then treating the solution with H/sub 2/O/sub 2/ thereby forming a tetravalent plutonium peroxide precipitate.

MS-CASPT2 study of hole transfer in guanine-indole complexes using the generalized Mulliken-Hush method: effective two-state treatment.

PubMed

Butchosa, C; Simon, S; Blancafort, L; Voityuk, A

2012-07-12

Because hole transfer from nucleobases to amino acid residues in DNA-protein complexes can prevent oxidative damage of DNA in living cells, computational modeling of the process is of high interest. We performed MS-CASPT2 calculations of several model structures of π-stacked guanine and indole and derived electron-transfer (ET) parameters for these systems using the generalized Mulliken-Hush (GMH) method. We show that the two-state model commonly applied to treat thermal ET between adjacent donor and acceptor is of limited use for the considered systems because of the small gap between the ground and first excited states in the indole radical cation. The ET parameters obtained within the two-state GMH scheme can deviate significantly from the corresponding matrix elements of the two-state effective Hamiltonian based on the GMH treatment of three adiabatic states. The computed values of diabatic energies and electronic couplings provide benchmarks to assess the performance of less sophisticated computational methods.

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

PubMed

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 these catalysts.

Surface film effects on drop tube undercooling studies

NASA Technical Reports Server (NTRS)

Ethridge, E. C.; Kaukler, W. F.

1986-01-01

The effects of various gaseous atmospheric constituents on drop-tube solidified samples of elemental metals were examined from a microstructural standpoint. All specimens were prepared from the purest available elements, so effects of impurities should not account for the observed effects. The drop-tube gas has a definite effect on the sample microstructure. Most dramatically, the sample cooling rate is effected. Some samples receive sufficient cooling to solidify in free fall while others do not, splating at the end of the drop tube in the sample catcher. Gases are selectively absorbed into the sample. Upon solidification gas can become less soluble and as a result forms voids within the sample. The general oxidation/reduction characteristics of the gas also affect sample microstructures. In general, under the more favorable experimental conditions including reducing atmospheric conditions and superheatings, examination of sample microstructures indicates that nucleation has been suppressed. This is indicated by underlying uniform dendrite spacings throughout the sample and with a single dendrite orientation through most of the sample. The samples were annealed yielding a few large grains and single or bi-crystal samples were commonly formed. This was especially true of samples that were inadvertently greatly superheated. This is in contrast with results from a previous study in which surface oxides were stable and contained numerous sites of nucleation. The number of nucleation events depends upon the surface state of the specimen as determined by the atmosphere and is consistent with theoretical expectations based upon the thermodynamic stability of surface oxide films. Oxide-free specimens are characterized by shiny surfaces, with no observable features under the scanning electron microscope at 5000X.

Recycling of high purity selenium from CIGS solar cell waste materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gustafsson, Anna M.K., E-mail: anna.gustafsson@chalmers.se; Foreman, Mark R.StJ.; Ekberg, Christian

Highlights: • A new method for recycling of selenium from CIGS solar cell materials is presented. • Separation of selenium as selenium dioxide after heating in oxygen atmosphere. • Complete selenium separation after oxidation of <63 μm particles at 800 °C for 1 h. • After reduction of selenium dioxide the selenium purity was higher than 99.999 wt%. - Abstract: Copper indium gallium diselenide (CIGS) is a promising material in thin film solar cell production. To make CIGS solar cells more competitive, both economically and environmentally, in comparison to other energy sources, methods for recycling are needed. In addition tomore » the generally high price of the material, significant amounts of the metals are lost in the manufacturing process. The feasibility of recycling selenium from CIGS through oxidation at elevated temperatures was therefore examined. During oxidation gaseous selenium dioxide was formed and could be separated from the other elements, which remained in solid state. Upon cooling, the selenium dioxide sublimes and can be collected as crystals. After oxidation for 1 h at 800 °C all of the selenium was separated from the CIGS material. Two different reduction methods for reduction of the selenium dioxide to selenium were tested. In the first reduction method an organic molecule was used as the reducing agent in a Riley reaction. In the second reduction method sulphur dioxide gas was used. Both methods resulted in high purity selenium. This proves that the studied selenium separation method could be the first step in a recycling process aimed at the complete separation and recovery of high purity elements from CIGS.« less

Novel catalytic properties of quadruple perovskites

PubMed Central

Yamada, Ikuya

2017-01-01

ABSTRACT Quadruple perovskite oxides AA′3 B 4O12 demonstrate a rich variety of structural and electronic properties. A large number of constituent elements for A/A′/B-site cations can be introduced using the ultra-high-pressure synthesis method. Development of novel functional materials consisting of earth-abundant elements plays a crucial role in current materials science. In this paper, functional properties, especially oxygen reaction catalysis, for quadruple perovskite oxides CaCu3Fe4O12 and AMn7O12 (A = Ca, La) composed of earth-abundant elements are reviewed. PMID:28970864

Investigation of (Ti-Zr-Hf-V-Nb)N Multicomponent Nanostructured Coatings before and after Thermal Annealing by Nuclear Physics Methods of Analysis

NASA Astrophysics Data System (ADS)

Pogrebnjak, A. D.; Beresnev, V. M.; Bondar', A. V.; Kaverin, M. V.; Ponomarev, A. G.

2013-10-01

(Ti-Zr-Hf-V-Nb)N multicomponent nanostructured coatings with thickness of 1.0-1.4 μm synthesized by the method of cathode arc-vapor deposition at temperatures of 250-300°С are investigated by various mutually complementary methods of elemental structural analysis using slow positron beams (SPB), proton microbeam based particle-induced x-ray emission (μ-PIXE), energy-dispersive x-ray spectroscopy (EDS) and scanning electron microscopy (SEM) analyses based on electron micro- and nanobeams, x-ray diffraction (XRD) method of phase structural analysis, and the "a-sin2φ" method of measuring a stressed-strained state (x-ray tensometry). The elemental composition, microstructure, residual stress in nanograins, profiles of defect and atom distributions with depth and over the coating surface in 3D-representation are studied for these coatings, and their phase composition, severely strained state, and composition of coatings before and after annealing at Tann = 600°С for annealing time τ = 30 min are investigated. It is demonstrated that the oxidation resistance of the examined coatings can be significantly increased by high-temperature annealing that leads to the formation of elastic severely strained compression state of the coating. Redistribution of elements and defects, their segregation near the interface boundaries and around grains and subgrains in the process of thermostimulated diffusion, and termination of spinodal segregation without considerable change of the average nanograin size are revealed.

A facile method to synthesize boron-doped Ni/Fe alloy nano-chains as electrocatalyst for water oxidation

NASA Astrophysics Data System (ADS)

Yang, Yisu; Zhuang, Linzhou; Lin, Rijia; Li, Mengran; Xu, Xiaoyong; Rufford, Thomas E.; Zhu, Zhonghua

2017-05-01

We report a novel magnetic field assisted chemical reduction method for the synthesis of boron-doped Ni/Fe nano-chains as promising catalysts for the oxygen evolution reaction (OER). The boron-doped Ni/Fe nano-chains were synthesised in a one step process at room temperature using NaBH4 as a reducing agent. The addition of boron reduced the magnetic moment of the intermediate synthesis products and produced nano-chains with a high specific surface area of 73.4 m2 g-1. The boron-doped Ni/Fe nano-chains exhibited catalytic performance superior to state-of-the-art Ba0.5Sr0.5Co0.8Fe0.2O3-δ perovskite and RuO2 noble metal oxide catalysts. The mass normalized activity of the boron-doped Ni/Fe nano-chains measured at an overpotential of 0.35 V was 64.0 A g-1, with a Tafel slope of only 40 mV dec-1. The excellent performance of the boron-doped Ni/Fe nano-chains can be attributed to the uniform elemental distribution and highly amorphous structure of the B-doped nano-chains. These results provide new insights into the effect of doping transition-metal based OER catalysts with non-metallic elements. The study demonstrates a facile approach to prepare transition metal nano-chains using magnetic field assisted chemical reduction method as cheap and highly active catalysts for electrochemical water oxidation.

Control of Sulfidogenesis Through Bio-oxidation of H 2S Coupled to (per)chlorate Reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gregoire, Patrick; Engelbrektson, Anna; Hubbard, Christopher G.

2014-04-04

Here, we investigate H 2S attenuation by dissimilatory perchlorate-reducing bacteria (DPRB). All DPRB tested oxidized H 2S coupled to (per)chlorate reduction without sustaining growth. H 2S was preferentially utilized over organic electron donors resulting in an enriched (34S)-elemental sulfur product. Electron microscopy revealed elemental sulfur production in the cytoplasm and on the cell surface of the DPRB Azospira suillum. We also propose a novel hybrid enzymatic-abiotic mechanism for H 2S oxidation similar to that recently proposed for nitrate-dependent Fe(II) oxidation. The results of this study have implications for the control of biosouring and biocorrosion in a range of industrial environments.

Oxidative elemental cycling under the low O2 Eoarchean atmosphere

PubMed Central

Frei, Robert; Crowe, Sean A.; Bau, Michael; Polat, Ali; Fowle, David A.; Døssing, Lasse N.

2016-01-01

The Great Oxidation Event signals the first large-scale oxygenation of the atmosphere roughly 2.4 Gyr ago. Geochemical signals diagnostic of oxidative weathering, however, extend as far back as 3.3–2.9 Gyr ago. 3.8–3.7 Gyr old rocks from Isua, Greenland stand as a deep time outpost, recording information on Earth’s earliest surface chemistry and the low oxygen primordial biosphere. Here we find fractionated Cr isotopes, relative to the igneous silicate Earth reservoir, in metamorphosed banded iron formations (BIFs) from Isua that indicate oxidative Cr cycling 3.8–3.7 Gyr ago. Elevated U/Th ratios in these BIFs relative to the contemporary crust, also signal oxidative mobilization of U. We suggest that reactive oxygen species were present in the Eoarchean surface environment, under a very low oxygen atmosphere, inducing oxidative elemental cycling during the deposition of the Isua BIFs and possibly supporting early aerobic biology. PMID:26864443

Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings.

PubMed

Wooles, Ashley J; Mills, David P; Tuna, Floriana; McInnes, Eric J L; Law, Gareth T W; Fuller, Adam J; Kremer, Felipe; Ridgway, Mark; Lewis, William; Gagliardi, Laura; Vlaisavljevich, Bess; Liddle, Stephen T

2018-05-29

Despite the fact that non-aqueous uranium chemistry is over 60 years old, most polarised-covalent uranium-element multiple bonds involve formal uranium oxidation states IV, V, and VI. The paucity of uranium(III) congeners is because, in common with metal-ligand multiple bonding generally, such linkages involve strongly donating, charge-loaded ligands that bind best to electron-poor metals and inherently promote disproportionation of uranium(III). Here, we report the synthesis of hexauranium-methanediide nanometre-scale rings. Combined experimental and computational studies suggest overall the presence of formal uranium(III) and (IV) ions, though electron delocalisation in this Kramers system cannot be definitively ruled out, and the resulting polarised-covalent U = C bonds are supported by iodide and δ-bonded arene bridges. The arenes provide reservoirs that accommodate charge, thus avoiding inter-electronic repulsion that would destabilise these low oxidation state metal-ligand multiple bonds. Using arenes as electronic buffers could constitute a general synthetic strategy by which to stabilise otherwise inherently unstable metal-ligand linkages.

Virus Removal by Biogenic Cerium

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Gusseme, B.; Du Laing, G; Hennebel, T

2010-01-01

The rare earth element cerium has been known to exert antifungal and antibacterial properties in the oxidation states +III and +IV. This study reports on an innovative strategy for virus removal in drinking water by the combination of Ce(III) on a bacterial carrier matrix. The biogenic cerium (bio-Ce) was produced by addition of aqueous Ce(III) to actively growing cultures of either freshwater manganese-oxidizing bacteria (MOB) Leptothrix discophora or Pseudomonas putida MnB29. X-ray absorption spectroscopy results indicated that Ce remained in its trivalent state on the bacterial surface. The spectra were consistent with Ce(III) ions associated with the phosphoryl groups ofmore » the bacterial cell wall. In disinfection assays using a bacteriophage as model, it was demonstrated that bio-Ce exhibited antiviral properties. A 4.4 log decrease of the phage was observed after 2 h of contact with 50 mg L{sup -1} bio-Ce. Given the fact that virus removal with 50 mg L{sup -1} Ce(III) as CeNO{sub 3} was lower, the presence of the bacterial carrier matrix in bio-Ce significantly enhanced virus removal.« less

Separation of uranium from (U, Th)O 2 and (U, Pu)O 2 by solid state reactions route

NASA Astrophysics Data System (ADS)

Keskar, Meera; Mudher, K. D. Singh; Venugopal, V.

2005-01-01

Solid state reactions of UO 2, ThO 2, PuO 2 and their mixed oxides (U, Th)O 2 and (U, Pu)O 2 were carried out with sodium nitrate upto 900 °C, to study the formation of various phases at different temperatures, which are amenable for easy dissolution and separation of the actinide elements in dilute acid. Products formed by reacting unsintered as well as sintered UO 2 with NaNO 3 above 500 °C were readily soluble in 2 M HNO 3, whereas ThO 2 and PuO 2 did not react with NaNO 3 to form any soluble products. Thus reactions of mixed oxides (U, Th)O 2 and (U, Pu)O 2 with NaNO 3 were carried out to study the quantitative separation of U from (U, Th)O 2 and (U, Pu)O 2. X-ray diffraction, X-ray fluorescence, thermal analysis and chemical analysis techniques were used for the characterization of the products formed during the reactions.

Interfaces in Oxides Formed on NiAlCr Doped with Y, Hf, Ti, and B

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boll, Torben; Unocic, Kinga A.; Pint, Bruce A.

Abstract This study applies atom probe tomography (APT) to analyze the oxide scales formed on model NiAlCr alloys doped with Hf, Y, Ti, and B. Due to its ability to measure small amounts of alloying elements in the oxide matrix and its ability to quantify segregation, t he technique offers a possibility for detailed studies of the dopant’s fate during high-temperature oxidation. Three model NiAlCr alloys with different additions of Hf, Y, Ti, and B were prepared and oxidized in O 2at 1,100°C for 100 h. All specimens showed an outer region consisting of different spinel oxides with relativelymore » small grains and the protective Al 2O 3-oxide layer below. APT analyses focused mainly on this protective oxide layer. In all the investigated samples segregation of both Hf and Y to the oxide grain boundaries was observed and quantified. Neither B nor Ti were observed in the alumina grains or at the analyzed interfaces. The processes of formation of oxide scales and segregation of the alloying elements are discussed. The experimental challenges of the oxide analyses by APT are also addressed.« less

Interfaces in Oxides Formed on NiAlCr Doped with Y, Hf, Ti, and B

DOE PAGES

Boll, Torben; Unocic, Kinga A.; Pint, Bruce A.; ...

2017-03-20

Abstract This study applies atom probe tomography (APT) to analyze the oxide scales formed on model NiAlCr alloys doped with Hf, Y, Ti, and B. Due to its ability to measure small amounts of alloying elements in the oxide matrix and its ability to quantify segregation, t he technique offers a possibility for detailed studies of the dopant’s fate during high-temperature oxidation. Three model NiAlCr alloys with different additions of Hf, Y, Ti, and B were prepared and oxidized in O 2at 1,100°C for 100 h. All specimens showed an outer region consisting of different spinel oxides with relativelymore » small grains and the protective Al 2O 3-oxide layer below. APT analyses focused mainly on this protective oxide layer. In all the investigated samples segregation of both Hf and Y to the oxide grain boundaries was observed and quantified. Neither B nor Ti were observed in the alumina grains or at the analyzed interfaces. The processes of formation of oxide scales and segregation of the alloying elements are discussed. The experimental challenges of the oxide analyses by APT are also addressed.« less

Comparison of the quantitative determination of soil organic carbon in coastal wetlands containing reduced forms of Fe and S

NASA Astrophysics Data System (ADS)

Passos, Tassia R. G.; Artur, Adriana G.; Nóbrega, Gabriel N.; Otero, Xosé L.; Ferreira, Tiago O.

2016-06-01

The performance of the Walkley-Black wet oxidation chemical method for soil organic carbon (SOC) determination in coastal wetland soils (mangroves, coastal lagoons, and hypersaline tidal flats) was evaluated in the state of Ceará along the semiarid coast of Brazil, assessing pyrite oxidation and its effects on soil C stock (SCS) quantification. SOC determined by the chemical oxidation method (CWB) was compared to that assessed by means of a standard elemental analyzer (CEA) for surficial samples (<30 cm depth) from the three wetland settings. The pyrite fraction was quantified in various steps of the chemical oxidation method, evaluating the effects of pyrite oxidation. Regardless of the method used, and consistent with site-specific physicochemical conditions, higher pyrite and SOC contents were recorded in the mangroves, whereas lower values were found in the other settings. CWB values were higher than CEA values. Significant differences in SCS calculations based on CWB and CEA were recorded for the coastal lagoons and hypersaline tidal flats. Nevertheless, the CWB and CEA values were strongly correlated, indicating that the wet oxidation chemical method can be used in such settings. In contrast, the absence of correlation for the mangroves provides evidence of the inadequacy of this method for these soils. Air drying and oxidation decrease the pyrite content, with larger effects rooted in oxidation. Thus, the wet oxidation chemical method is not recommended for mangrove soils, but seems appropriate for SOC/SCS quantification in hypersaline tidal flat and coastal lagoon soils characterized by lower pyrite contents.

Potentially toxic elements (PTEs) in soils from the surroundings of the Trans-Amazonian Highway, Brazil.

PubMed

de Souza, Edna Santos; Fernandes, Antonio Rodrigues; de Souza Braz, Anderson Martins; Sabino, Lorena Lira Leite; Alleoni, Luís Reynaldo Ferracciú

2015-01-01

The Trans-Amazonian Highway (TAH) is located in the northern region of Brazil, comprising a border region where agricultural, mining, and logging activities are the main activities responsible for fostering economic development, in addition to large hydroelectric plants. Such activities lead to environmental contamination by potentially toxic elements (PTEs). Environmental monitoring is only possible through the determination of element contents under natural conditions. Many extraction methods have been proposed to determine PTEs' bioavailability in the soil; however, there is no consensus about which extractor is most suitable. In this study, we determined the contents of PTEs in soils in the surroundings of TAH after mineral extraction with diethylenetriaminepentaacetic acid-triethanolamine (DTPA-TEA), Mehlich I, and Mehlich III solutions. Soil samples were collected in areas of natural vegetation in the vicinity of TAH in the state of Pará, Brazil. Chemical attributes and particle size were determined, besides concentrations of Fe, Al, Mn, and Ti by sulfuric acid digestion, Si after alkaline solution attack, and poorly crystalline Fe, Al, and "free" Fe oxides. Mehlich III solution extracted greater contents from Fe, Al, and Pb as compared to Mehlich I and DTPA-TEA and similar contents from Cd, Mn, Zn, and Cu. Significant correlations were found between concentrations of PTEs and the contents of Fe and Mn oxides as well as organic carbon and soil cation exchange capacity. Contents of Cu, Mn, Fe, and Zn by the three methods were positively correlated.

Kinetics of dissolution of thorium and uranium doped britholite ceramics

NASA Astrophysics Data System (ADS)

Dacheux, N.; Du Fou de Kerdaniel, E.; Clavier, N.; Podor, R.; Aupiais, J.; Szenknect, S.

2010-09-01

In the field of immobilization of actinides in phosphate-based ceramics, several thorium and uranium doped britholite samples were submitted to leaching tests. The normalized dissolution rates determined for several pH values, temperatures and acidic media from the calcium release range from 4.7 × 10 -2 g m -2 d -1 to 21.6 g m -2 d -1. Their comparison with that determined for phosphorus, thorium and uranium revealed that the dissolution is clearly incongruent for all the conditions examined. Whatever the leaching solution considered, calcium and phosphorus elements were always released with higher RL values than the other elements (Nd, Th, U). Simultaneously, thorium was found to quickly precipitate as alteration product, leading to diffusion phenomena for uranium. For all the media considered, the uranium release is higher than that of thorium, probably due to its oxidation from tetravalent oxidation state to uranyl. Moreover, the evaluation of the partial order related to proton concentration and the apparent energy of activation suggest that the reaction of dissolution is probably controlled by surface chemical reactions occurring at the solid/liquid interface. Finally, comparative leaching tests performed in sulphuric acid solutions revealed a significant influence of such media on the chemical durability of the leached pellets, leading to higher normalized dissolution rates for all the elements considered. On the basis of the results of chemical speciation, this difference was mainly explained in the light of higher complexion constants by sulfate ions compared to nitrate, chloride and phosphate.

Dechlorination of polychlorinated biphenyls by iron and its oxides.

PubMed

Sun, Yifei; Liu, Xiaoyuan; Kainuma, Masashi; Wang, Wei; Takaoka, Masaki; Takeda, Nobuo

2015-10-01

The decomposition efficiency of polychlorinated biphenyls (PCBs) was determined using elemental iron (Fe) and three iron (hydr)oxides, i.e., α-Fe2O3, Fe3O4, and α-FeOOH, as catalysts. The experiments were performed using four distinct PCB congeners (PCB-209, PCB-153, and the coplanar PCB-167 and PCB-77) at temperatures ranging from 180 °C to 380 °C and under an inert, oxidizing or reducing atmosphere composed of N2, N2+O2, or N2+H2. From these three options N2 showed to provide the best reaction atmosphere. Among the iron compounds tested, Fe3O4 showed the highest activity for decomposing PCBs. The decomposition efficiencies of PCB-209, PCB-167, PCB-153, and PCB-77 by Fe3O4 in an N2 atmosphere at 230 °C were 88.5%, 82.5%, 69.9%, and 66.4%, respectively. Other inorganic chlorine (Cl) products which were measured by the amount of inorganic Cl ions represented 82.5% and 76.1% of the reaction products, showing that ring cleavage of PCBs was the main elimination process. Moreover, the dechlorination did not require a particular hydrogen donor. We used X-ray photoelectron spectroscopy to analyze the elemental distribution at the catalyst's surface. The O/Fe ratio influenced upon the decomposition efficiency of PCBs: the lower this ratio, the higher the decomposition efficiency. X-ray absorption near edge structure spectra showed that α-Fe2O3 effectively worked as a catalyst, while Fe3O4 and α-FeOOH were consumed as reactants, as their final state is different from their initial state. Finally, a decomposition pathway was postulated in which the Cl atoms in ortho-positions were more difficult to eliminate than those in the para- or meta-positions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Nanocolumnar Crystalline Vanadium Oxide-Molybdenum Oxide Antireflective Smart Thin Films with Superior Nanomechanical Properties.

PubMed

Dey, Arjun; Nayak, Manish Kumar; Esther, A Carmel Mary; Pradeepkumar, Maurya Sandeep; Porwal, Deeksha; Gupta, A K; Bera, Parthasarathi; Barshilia, Harish C; Mukhopadhyay, Anoop Kumar; Pandey, Ajoy Kumar; Khan, Kallol; Bhattacharya, Manjima; Kumar, D Raghavendra; Sridhara, N; Sharma, Anand Kumar

2016-11-17

Vanadium oxide-molybdenum oxide (VO-MO) thin (21-475 nm) films were grown on quartz and silicon substrates by pulsed RF magnetron sputtering technique by altering the RF power from 100 to 600 W. Crystalline VO-MO thin films showed the mixed phases of vanadium oxides e.g., V 2 O 5 , V 2 O 3 and VO 2 along with MoO 3 . Reversible or smart transition was found to occur just above the room temperature i.e., at ~45-50 °C. The VO-MO films deposited on quartz showed a gradual decrease in transmittance with increase in film thickness. But, the VO-MO films on silicon exhibited reflectance that was significantly lower than that of the substrate. Further, the effect of low temperature (i.e., 100 °C) vacuum (10 -5 mbar) annealing on optical properties e.g., solar absorptance, transmittance and reflectance as well as the optical constants e.g., optical band gap, refractive index and extinction coefficient were studied. Sheet resistance, oxidation state and nanomechanical properties e.g., nanohardness and elastic modulus of the VO-MO thin films were also investigated in as-deposited condition as well as after the vacuum annealing treatment. Finally, the combination of the nanoindentation technique and the finite element modeling (FEM) was employed to investigate yield stress and von Mises stress distribution of the VO-MO thin films.

Nanocolumnar Crystalline Vanadium Oxide-Molybdenum Oxide Antireflective Smart Thin Films with Superior Nanomechanical Properties

NASA Astrophysics Data System (ADS)

Dey, Arjun; Nayak, Manish Kumar; Esther, A. Carmel Mary; Pradeepkumar, Maurya Sandeep; Porwal, Deeksha; Gupta, A. K.; Bera, Parthasarathi; Barshilia, Harish C.; Mukhopadhyay, Anoop Kumar; Pandey, Ajoy Kumar; Khan, Kallol; Bhattacharya, Manjima; Kumar, D. Raghavendra; Sridhara, N.; Sharma, Anand Kumar

2016-11-01

Vanadium oxide-molybdenum oxide (VO-MO) thin (21-475 nm) films were grown on quartz and silicon substrates by pulsed RF magnetron sputtering technique by altering the RF power from 100 to 600 W. Crystalline VO-MO thin films showed the mixed phases of vanadium oxides e.g., V2O5, V2O3 and VO2 along with MoO3. Reversible or smart transition was found to occur just above the room temperature i.e., at ~45-50 °C. The VO-MO films deposited on quartz showed a gradual decrease in transmittance with increase in film thickness. But, the VO-MO films on silicon exhibited reflectance that was significantly lower than that of the substrate. Further, the effect of low temperature (i.e., 100 °C) vacuum (10-5 mbar) annealing on optical properties e.g., solar absorptance, transmittance and reflectance as well as the optical constants e.g., optical band gap, refractive index and extinction coefficient were studied. Sheet resistance, oxidation state and nanomechanical properties e.g., nanohardness and elastic modulus of the VO-MO thin films were also investigated in as-deposited condition as well as after the vacuum annealing treatment. Finally, the combination of the nanoindentation technique and the finite element modeling (FEM) was employed to investigate yield stress and von Mises stress distribution of the VO-MO thin films.

Surface characterization of implant materials c.p. Ti, Ti-6Al-7Nb and Ti-6Al-4V with different pretreatments.

PubMed

Sittig, C; Textor, M; Spencer, N D; Wieland, M; Vallotton, P H

1999-01-01

The biocompatibility of commercially pure titanium and its alloys is closely related to their surface properties, with both the composition of the protecting oxide film and the surface topography playing an important role. Surfaces of commercially pure titanium and of the two alloys Ti-6Al-7Nb and Ti-6Al-4V (wt %) have been investigated following three different pretreatments: polishing, nitric acid passivation and pickling in nitric acid-hydrogen fluoride. Nitric acid treatment is found to substantially reduce the concentration of surface contaminants present after polishing. The natural 4-6 nm thick oxide layer on commercially pure titanium is composed of titanium oxide in different oxidation states (TiO2, Ti2O3 and TiO), while for the alloys, aluminium and niobium or vanadium are additionally present in oxidized form (Al2O3, Nb2O5 or V-oxides). The concentrations of the alloying elements at the surface are shown to be strongly dependent on the pretreatment process. While pickling increases the surface roughness of both commercially pure titanium and the alloys, different mechanisms appear to be involved. In the case of commercially pure titanium, the dissolution rate depends on grain orientation, whereas in the case of the two alloys, selective alpha-phase dissolution and enrichment of the beta-phase appears to occur. Copyright 1999 Kluwer Academic Publishers

A Comprehensive Review of One-Dimensional Metal-Oxide Nanostructure Photodetectors

PubMed Central

Zhai, Tianyou; Fang, Xiaosheng; Liao, Meiyong; Xu, Xijin; Zeng, Haibo; Yoshio, Bando; Golberg, Dmitri

2009-01-01

One-dimensional (1D) metal-oxide nanostructures are ideal systems for exploring a large number of novel phenomena at the nanoscale and investigating size and dimensionality dependence of nanostructure properties for potential applications. The construction and integration of photodetectors or optical switches based on such nanostructures with tailored geometries have rapidly advanced in recent years. Active 1D nanostructure photodetector elements can be configured either as resistors whose conductions are altered by a charge-transfer process or as field-effect transistors (FET) whose properties can be controlled by applying appropriate potentials onto the gates. Functionalizing the structure surfaces offers another avenue for expanding the sensor capabilities. This article provides a comprehensive review on the state-of-the-art research activities in the photodetector field. It mainly focuses on the metal oxide 1D nanostructures such as ZnO, SnO2, Cu2O, Ga2O3, Fe2O3, In2O3, CdO, CeO2, and their photoresponses. The review begins with a survey of quasi 1D metal-oxide semiconductor nanostructures and the photodetector principle, then shows the recent progresses on several kinds of important metal-oxide nanostructures and their photoresponses and briefly presents some additional prospective metal-oxide 1D nanomaterials. Finally, the review is concluded with some perspectives and outlook on the future developments in this area. PMID:22454597

Electron Source in Photoinduced Hydrogen Production on Pt-supported TiO Particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perkins, Craig L.; Henderson, Michael A.; McCready, David E.

2001-01-18

Abe et al. illuminated an aqueous suspension of TiO/Pt with a Hg arc lamp and observed H production in the absence of O production. An unspecified elemental analysis excluded carbonaceous contaminants, and the source of the electron donor was concluded to be Ti+ cations. We can suggest at least three more likely (than Ti) sources for their mysterious electron donor: (1)an overlooked inorganic species, (2) Ti, and/or (3)organic impurities. The authors excluded the latter in their paper, but we view this conclusion as suspect given the lack of information on the limits of detection of the carbon assay, and themore » fact that the choice of argon(thermal conductivity= 41.33 x 10-6 cal cm-2s-1 (C cm-1)-1)3 as a carrier gas in their thermal conductivity detector4 probably precluded the observation of CO (thermal conductivity= 37.61 x 10-6 cal cm-2s-1 (C cm-1)-1)3, which is a common product of organic photochemical oxidations. No mention is made of an analysis for inorganic impurities. It is widely accepted that nanometer scale TiO particles can have significant fractions of undercoordinated Ti sites which can be easily oxidized to Ti, the highest valence of Ti observed in condensed phases. Here we point out that oxidation of Ti to Ti is much more physically realistic than oxidation of Ti to Ti. Removal of a fifth electron from titanium requires {approx}56 eV5.Ti, if it were to be generated in a solid oxide, would extract an electron from the valence band composed mainly of oxygen 2s and 2p states rather than remain in the 5 valence state. This unrealistically high oxidation state seems even more unlikely given the fact that at the room temperatures used in the authors' reactions Ti would have been generated and remained at the surface (at room temperature the diffusion of Ti cations in TiO is minimal), and the fact that the surface Madelung potential is smaller than that of the bulk6.« less

The effects of Fe-oxidizing microorganisms on post-biostimulation permeability reduction and oxidative processes at the Rifle IFRC site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chan, Clara Sze-Yue

2015-07-02

Fe oxidation and biomineral formation is important in aquifers because the highly-reactive oxides can control the mobility of nutrients (e.g. phosphate, C) and metals (e.g. arsenic, uranium). Mineral formation also has the potential to affect hydrology, depending on the volume and distribution in pore spaces. In this exploratory study, we sought to understand how microbial Fe-oxidizers and their biominerals affect, and are affected by groundwater flow. As part of work at the Rifle aquifer in Colorado, we initially hypothesized that Fe-oxidizers were contributing to aquifer clogging problems associated with enhanced bioremediation. To demonstrate the presence of Fe-oxidizers in the Riflemore » aquifer, we enriched FeOM from groundwater samples, and isolated two novel chemolithotrophic, microaerophilic Fe-oxidizing Betaproteobacteria, Hydrogenophaga sp. P101 and Curvibacter sp. CD03. To image cells and biominerals in the context of pores, we developed a “micro-aquifer,” a sand-filled flow-through culture chamber that allows for imaging of sediment pore space with multiphoton confocal microscopy. Fe oxide biofilms formed on sand grains, demonstrating that FeOM produce Fe oxide sand coatings. Fe coatings are common on aquifer sands, and tend to sequester contaminants; however, it has never previously been shown that microbes are responsible for their formation. In contrast to our original hypothesis, the biominerals did not clog the mini-aquifer. Instead, Fe biofilm distribution was dynamic: they grew as coatings, then periodically sloughed off sand grains, with some flocs later caught in pore throats. This has implications for physical hydrology, including pore scale architecture, and element transport. The sloughing of coatings likely prevents the biominerals from clogging wells and aquifers, at least initially. Although attached biomineral coatings sequester Fe-associated elements (e.g. P, As, C, U), when biominerals detach, these elements are transported as particles through the aquifer. Our work shows that microbial mineralization impacts in aquifers are dynamic, and that the fate and transport of biomineral-associated elements depend not only on geochemical conditions, but also physical pore-scale processes.« less

Phase Behavior and Equations of State of the Actinide Oxides

NASA Astrophysics Data System (ADS)

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.

Efficient Suppression of Defects and Charge Trapping in High Density In-Sn-Zn-O Thin Film Transistor Prepared using Microwave-Assisted Sputter.

PubMed

Goh, Youngin; Ahn, Jaehan; Lee, Jeong Rak; Park, Wan Woo; Ko Park, Sang-Hee; Jeon, Sanghun

2017-10-25

Amorphous oxide semiconductor-based thin film transistors (TFTs) have been considered as excellent switching elements for driving active-matrix organic light-emitting diodes (AMOLED) owing to their high mobility and process compatibility. However, oxide semiconductors have inherent defects, causing fast transient charge trapping and device instability. For the next-generation displays such as flexible, wearable, or transparent displays, an active semiconductor layer with ultrahigh mobility and high reliability at low deposition temperature is required. Therefore, we introduced high density plasma microwave-assisted (MWA) sputtering method as a promising deposition tool for the formation of high density and high-performance oxide semiconductor films. In this paper, we present the effect of the MWA sputtering method on the defects and fast charge trapping in In-Sn-Zn-O (ITZO) TFTs using various AC device characterization methodologies including fast I-V, pulsed I-V, transient current, low frequency noise, and discharge current analysis. Using these methods, we were able to analyze the charge trapping mechanism and intrinsic electrical characteristics, and extract the subgap density of the states of oxide TFTs quantitatively. In comparison to conventional sputtered ITZO, high density plasma MWA-sputtered ITZO exhibits outstanding electrical performance, negligible charge trapping characteristics and low subgap density of states. High-density plasma MWA sputtering method has high deposition rate even at low working pressure and control the ion bombardment energy, resulting in forming low defect generation in ITZO and presenting high performance ITZO TFT. We expect the proposed high density plasma sputtering method to be applicable to a wide range of oxide semiconductor device applications.

Luminescent hybrid lanthanide sulfates and lanthanide sulfonate-carboxylates with 1,10-phenanthroline involving in-situ oxidation of 2-mercaptonbenzoic acid

NASA Astrophysics Data System (ADS)

Zhong, Jie-Cen; Wan, Fang; Sun, Yan-Qiong; Chen, Yi-Ping

2015-01-01

A series of lanthanide sulfates and lanthanide sulfonate-carboxylates, [Ln2(phen)2(SO4)3(H2O)2]n (I:Ln=Nd(1a), Sm(1b), Eu(1c), phen=1,10-phenanthroline) and [Ln(phen)(2-SBA)(BZA)]n (II: Ln=Sm(2a), Eu(2b), Dy(2c), 2-SBA=2-sulfobenzoate, BZA=benzoate) have been hydrothermally synthesized from lanthanide oxide, 2-mercaptonbenzoic acid with phen as auxiliary ligand and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, TG analyses and luminescence spectroscopy. Interestingly, SO4 2 - anions in I came from the in situ deep oxidation of thiol groups of 2-mercaptonbenzoic acid while 2-sulfobenzoate and benzoate ligands in II from the middle oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. Compounds I are organic-inorganic hybrid lanthanide sulfates, which have rare one-dimensional column-like structures. Complexes II are binuclear lanthanide sulfonate-carboxylates with 2-sulfobenzoate and benzoate as bridges and 1,10-phenanthroline as terminal. Photoluminescence studies reveal that complexes I and II exhibit strong lanthanide characteristic emission bands in the solid state at room temperature.

SO2 Adsorption on CeO2(100) and CeO2(111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mullins, David R.

2016-09-13

The adsorption and reaction of sulfur dioxide, SO2, was studied on oxidized and reduced CeOX(100) and compared to previous results on CeOX(111). SO2 adsorbs on oxidized CeO2(100) as sulfite, SO32-, at 200 K and sulfite is the only adsorbate observed on the surface at any temperature. The sulfite desorbs monotonically from 200 to 700 K. The adsorption and desorption of SO2 does not result in any change in the Ce4+ oxidation state. SO2 also adsorbs as sulfite on reduced CeO1.7(100) at 200 K. There is also a small amount of elemental sulfur, S0, formed. As the sample is heated themore » sulfite decomposes into sulfide, S2-. Roughly 25 % of the adsorbed S either desorbs or diffuses into the bulk of the reduced ceria. The decomposition, and resulting formation of S2- and O2-, re-oxidize some of the Ce3+ to Ce4+. Unlike what has been observed following the adsorption and reaction of many other molecules, the adsorption and reaction of SO2 is virtually identical on CeOX(100) and CeOX(111).« less

TRACE ELEMENT ANALYSES OF URANIUM MATERIALS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beals, D; Charles Shick, C

The Savannah River National Laboratory (SRNL) has developed an analytical method to measure many trace elements in a variety of uranium materials at the high part-per-billion (ppb) to low part-per-million (ppm) levels using matrix removal and analysis by quadrapole ICP-MS. Over 35 elements were measured in uranium oxides, acetate, ore and metal. Replicate analyses of samples did provide precise results however none of the materials was certified for trace element content thus no measure of the accuracy could be made. The DOE New Brunswick Laboratory (NBL) does provide a Certified Reference Material (CRM) that has provisional values for a seriesmore » of trace elements. The NBL CRM were purchased and analyzed to determine the accuracy of the method for the analysis of trace elements in uranium oxide. These results are presented and discussed in the following paper.« less

Effect of processing conditions on microstructural features in Mn–Si sintered steels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oro, Raquel, E-mail: raqueld@chalmers.se; Hryha, Eduard, E-mail: hryha@chalmers.se; Campos, Mónica, E-mail: campos@ing.uc3m.es

2014-09-15

Sintering of steels containing oxidation sensitive elements is possible if such elements are alloyed with others which present lower affinity for oxygen. In this work, a master alloy powder containing Fe–Mn–Si–C, specifically designed to create a liquid phase during sintering, has been used for such purpose. The effect of processing conditions such as sintering temperature and atmosphere was studied with the aim of describing the microstructural evolution as well as the morphology and distribution of oxides in the sintered material, evaluating the potential detrimental effect of such oxides on mechanical properties. Chemical analyses, metallography and fractography studies combined with X-raymore » photoelectron spectroscopy analyses on the fracture surfaces were used to reveal the main mechanism of fracture and their correlation with the chemical composition of the different fracture surfaces. The results indicate that the main mechanism of failure in these steels is brittle fracture in the surrounding of the original master alloy particles due to degradation of grain boundaries by the presence of oxide inclusions. Mn–Si oxide inclusions were observed on intergranular decohesive facets. The use of reducing atmospheres and high sintering temperatures reduces the amount and size of such oxide inclusions. Besides, high heating and cooling rates reduce significantly the final oxygen content in the sintered material. A model for microstructure development and oxide evolution during different stages of sintering is proposed, considering the fact that when the master alloy melts, the liquid formed can dissolve some of the oxides as well as the surface of the surrounding iron base particles. - Highlights: • Oxide distribution in steels containing oxidation-sensitive elements • Mn, Si introduced in a master alloy powder, mixed with a base iron powder • Selective oxidation of Mn and Si on iron grain boundaries • Decohesive fracture caused by degradation of grain boundaries by oxide inclusions • Reducing agents efficient at low temperatures critical for avoiding oxide inclusions.« less

The apparent absence of chemical sensitivity in the 4d and 5d X-ray absorption spectroscopy of uranium compounds

DOE PAGES

Tobin, J. G.

2013-05-03

X-ray absorption spectroscopy (XAS) and related derivative measurements have been used to demonstrate that the Pu 5f states are strongly relativistic and have a 5f occupation number near 5. Owing to the success in this regime, it has been argued that the XAS measurements should be a powerful tool to probe 5f occupation variation, both as a function of elemental nature (actinide atomic number) and as a function of physical and chemical perturbation, e.g., oxidation state. We show that XAS and its related measurements fail in this latter aspect for a wide variety of uranium compounds and materials. Possible causesmore » will be discussed.« less

Geochemistry of the Nsuta Mn deposit in Ghana: Implications for the Paleoproterozoic atmosphere and ocean chemistry

NASA Astrophysics Data System (ADS)

Goto, K. T.; Ito, T.; Suzuki, K.; Kashiwabara, T.; Takaya, Y.; Shimoda, G.; Nozaki, T.; Kiyokawa, S.; Tetteh, G. M.; Nyame, F. K.

2013-12-01

Oxygenation of the atmosphere and oceans has influenced the evolution of ocean chemistry and diversification of early life. A number of large manganese (Mn) deposits are distributed in the Paleoproterozoic sedimentary successions that were formed during the great oxidation event (GOE) around 2.4-2.2 Ga (Meynard, 2010). Due to the high redox potential of Mn, occurrences of Mn deposits have been regarded as important evidence for a highly oxidized environment during the Paleoproterozoic (Kirschvink et al., 2000). Furthermore, because Mn oxides strongly adsorb various elements, including bioessential elements such as Mo, formation of large Mn deposits may have affected the seawater chemical composition and ecology during the Paleoproterozoic. However, the genesis of each Mn deposit is poorly constrained, and the relationships among the formation of Mn deposits, the evolution of atmospheric and ocean chemistry, and the diversification of early life are still ambiguous. In this study, we report the Re-Os isotope compositions, rare earth element (REE) compositions, and abundance of manganophile elements in the Mn carbonate ore and host sedimentary rock samples collected from the Nsuta Mn deposit of the Birimian Supergroup, Ghana. The Nsuta deposit is one of the largest Paleoproterozoic Mn deposits, although its genesis remains controversial (Melcher et al., 1995; Mucke et al., 1999). The composite Re-Os isochron age (2149 × 130 Ma) of the Mn carbonate and sedimentary rock samples was consistent with the depositional age of the sedimentary rocks (~2.2 Ga) presumed from the U-Pb zircon age of volcanic rocks (Hirdes and Davis, 1998), suggesting that the timing of Mn ore deposition was almost equivalent to the host rock sedimentation. The PAAS-normalized REE pattern showed a positive Eu anomaly in all samples and a positive Ce anomaly only in the Mn carbonate ore. These REE patterns indicate the possible contribution of Eu-enriched fluids derived from hydrothermal activity and Ce enrichment due to the oxidation of Ce(III) by Mn(IV) during an ore formation. Among the manganophile elements, merely Mo is enriched in the Mn carbonate ore compared with the host sedimentary rocks. The profile of manganophile elements was similar to that of modern hydrothermal Mn oxide (Kuhn et al., 2003), although the exact Mo concentration was much lower. These geochemical lines of evidence provide the following plausible genetic model for the Nsuta deposits: (1) Mn(II) was derived from hydrothermal vents, (2) Mn(II) was oxidized to Mn(IV) oxide by the oxygenated seawater, (3) the precipitation of Mn oxide is almost concurrent with the deposition of the host sedimentary rocks, (4) Mn oxide was diagenetically transformed to be a Mn carbonate ore. The geochemical features of the Nsuta deposits suggest that, as in the present oxic oceans, Mn oxide was a potential sink for several trace elements in the Paleoproterozoic oceans. The low-Mo concentration in the Mn carbonate ore probably reflects the large difference between the chemical compositions of Paleoproterozoic and present seawater, implying the prevalence of reduced marine conditions even during the GOE (Scott et al., 2008)

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

NASA Astrophysics Data System (ADS)

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 determined S apatite-melt partitioning coefficient debatable. Upon calibration over a range of geologically relevant T-P-X-fO2-fS2, S-in-apatite can serve as a powerful oxybarometer to quantify fO2.

Quantification of rare earth elements using laser-induced breakdown spectroscopy

DOE PAGES

Martin, Madhavi; Martin, Rodger C.; Allman, Steve; ...

2015-10-21

In this paper, a study of the optical emission as a function of concentration of laser-ablated yttrium (Y) and of six rare earth elements, europium (Eu), gadolinium (Gd), lanthanum (La), praseodymium (Pr), neodymium (Nd), and samarium (Sm), has been evaluated using the laser-induced breakdown spectroscopy (LIBS) technique. Statistical methodology using multivariate analysis has been used to obtain the sampling errors, coefficient of regression, calibration, and cross-validation of measurements as they relate to the LIBS analysis in graphite-matrix pellets that were doped with elements at several concentrations. Each element (in oxide form) was mixed in the graphite matrix in percentages rangingmore » from 1% to 50% by weight and the LIBS spectra obtained for each composition as well as for pure oxide samples. Finally, a single pellet was mixed with all the elements in equal oxide masses to determine if we can identify the elemental peaks in a mixed pellet. This dataset is relevant for future application to studies of fission product content and distribution in irradiated nuclear fuels. These results demonstrate that LIBS technique is inherently well suited for the future challenge of in situ analysis of nuclear materials. Finally, these studies also show that LIBS spectral analysis using statistical methodology can provide quantitative results and suggest an approach in future to the far more challenging multielemental analysis of ~ 20 primary elements in high-burnup nuclear reactor fuel.« less

PROCESS OF PRODUCING Cm$sup 244$ AND Cm$sup 24$$sup 5$

DOEpatents

Manning, W.M.; Studier, M.H.; Diamond, H.; Fields, P.R.

1958-11-01

A process is presented for producing Cm and Cm/sup 245/. The first step of the process consists in subjecting Pu/sup 2339/ to a high neutron flux and subsequently dissolving the irradiated material in HCl. The plutonium is then oxidized to at least the tetravalent state and the solution is contacted with an anion exchange resin, causing the plutonium values to be absorbed while the fission products and transplutonium elements remain in the effluent solution. The effluent solution is then contacted with a cation exchange resin causing the transplutonium, values to be absorbed while the fission products remain in solution. The cation exchange resin is then contacted with an aqueous citrate solution and tbe transplutonium elements are thereby differentially eluted in order of decreasing atomic weight, allowing collection of the desired fractions.

[The bonding mechanisms of base metals for metal-ceramic crown microstructure analysis of bonding agent and gold bond between porcelain and base metals].

PubMed

Wang, C C; Hsu, C S

1996-06-01

The use of base metal alloys for porcelain fused to a metal crown and bridges has increased recently because of lower price, high hardness, high tensile strength and high elastic modulus. The addition of beryllium to base metal alloys increased fluidity and improved casting fitness. Beryllium also controlled surface oxidation and bonding strength. The bonding agent and gold bonding agent also affected the bonding strength between porcelain and metal alloys. Four commercially available ceramic base alloys were studied (two alloys contained beryllium element, another two did not). The purpose of this investigation was to study the microstructure between porcelain matrix, bonding agent and alloy matrix interfaces. A scanning electron micro-probe analyzer and energy dispersive X-ray spectroscopy (EDXS) were used to study the distribution of elements (Ni, Cr, Mo, Cu, O, Si, Sn, Al) in four base alloys. The following results were obtained: 1. The thickness of the oxidized layer of Rexillium III alloy and Unitbond alloy (contained beryllium) was thinner than Unibond alloy and Wiron 88 alloy (no beryllium). 2. The thickness of the oxidized layer of alloys in air (10 minutes and 30 minutes) was thinner in Unitbond (2.45 microns and 3.80 microns) and thicker in Wiron 88 (4.39 microns and 5.96 microns). 3. The thickness of the oxidized layer occurring for a duration of ten minutes (in vaccum) showed that the Rexillium III alloy was the thinnest (1.93 microns), and Wiron 88 alloy was the thickest (2.30 microns). But in thirty minutes (vacuum), Unitbond alloy was the thinnest (3.37 microns), and Wiron 88 alloy was the thickest (5.51 microns). 4. The intensity of Cr elements was increased obviously near the interface between Unitbond alloy, Wiron 88 alloy (no beryllium) and oxidized layer, but the intensity of Ni and Mo elements was slightly increased. The intensity of Cr element was not increased markedly between Rexillium III alloy, Unitbond alloy (beryllium) and oxidized layer. 5. A white-grayish oxidized layer appeared at the metal-ceramic interfaces but the thickness of oxidized layer was not obviously different. 6. The use of bonding agent at metal-ceramic interface leads to the deposition of many Sn elements at about 40 microns range within the porcelain surface. 7. Second interaction phases at the porcelain layer appeared when gold bonding agent was used, and a 50-100 microns microleakage occurred at the metal-ceramic interface.

Publications - RDF 2008-1 v. 1.0.1 | Alaska Division of Geological &

Science.gov Websites

main content DGGS RDF 2008-1 v. 1.0.1 Publication Details Title: Major-oxide, minor-oxide, and trace , S.E., and Jing, L., 2008, Major-oxide, minor-oxide, and trace-element geochemical data from rocks and Birch Creek; Hope Creek; Idaho Creek; Major Oxides; McManus Creek; Montana Creek; Polar Creek; Pool

Investigation of the Effect of Alloying Elements and Water Vapor Contents on the Oxidation and Decarburization of Transformation-Induced Plasticity Steels

NASA Astrophysics Data System (ADS)

Zhang, Z. T.; Sohn, I. R.; Pettit, F. S.; Meier, G. H.; Sridhar, S.

2009-08-01

The present research deals with an investigation of the effect of alloying element additions (Si, P, and Sb) and water vapor content ({{{{{P}}_{{{{H}}_{ 2} {{O}}}} } {{{P}}_{{{{H}}_{ 2} }} }}} = 0.01{{ to }}0.13}) on the oxidation and decarburization behavior of transformation-induced plasticity (TRIP) steels in a gas mixture of 95 vol pct argon and 5 vol pct hydrogen/steam, by thermogravimetry (TG). The oxidation proceeds primarily as an internal oxidation front in the TRIP steels, but a thin external scale on the order of a micrometer thickness exists and is comprised primarily of fayalite ((Mn,Fe)2SiO4) and ((MnO) x (FeO)1- x . The oxidation products are distributed near the surface and along grain boundaries. A comparison between calculated and measured oxidation curves indicated that the oxidation and decarburization are independent. The results for TRIP steels, both with and without an Sb addition, indicate that increasing Si and P contents accelerate, whereas Sb addition suppresses, both decarburization and oxidation rates. Water vapor content has no obvious effect on decarburization but has a pronounced effect on oxidation, and decreasing water vapor content decreases the oxidation rates.

Catalysts for the selective oxidation of hydrogen sulfide to sulfur

DOEpatents

Srinivas, Girish; Bai, Chuansheng

2000-08-08

This invention provides catalysts for the oxidation of hydrogen sulfide. In particular, the invention provides catalysts for the partial oxidation of hydrogen sulfide to elemental sulfur and water. The catalytically active component of the catalyst comprises a mixture of metal oxides containing titanium oxide and one or more metal oxides which can be selected from the group of metal oxides or mixtures of metal oxides of transition metals or lanthanide metals. Preferred metal oxides for combination with TiO.sub.2 in the catalysts of this invention include oxides of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Hf, Ta, W, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Catalysts which comprise a homogeneous mixture of titanium oxide and niobium (Nb) oxide are also provided. A preferred method for preparing the precursor homogenous mixture of metal hydroxides is by coprecipitation of titanium hydroxide with one or more other selected metal hydroxides. Catalysts of this invention have improved activity and/or selectivity for elemental sulfur production. Further improvements of activity and/or selectivity can be obtained by introducing relatively low amounts (up to about 5 mol %)of a promoter metal oxide (preferably of metals other than titanium and that of the selected second metal oxide) into the homogeneous metal/titanium oxide catalysts of this invention.

EXTRACTION AND QUANTITATIVE ANALYSIS OF ELEMENTAL SULFUR FROM SULFIDE MINERAL SURFACES BY HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY. (R826189)

EPA Science Inventory

A simple method for the quantitative determination of elemental sulfur on oxidized sulfide minerals is described. Extraction of elemental sulfur in perchloroethylene and subsequent analysis with high-performance liquid chromatography were used to ascertain the total elemental ...

Thiosulfate oxidation by Thiomicrospira thermophila: metabolic flexibility in response to ambient geochemistry

PubMed Central

Houghton, J.L.; Foustoukos, D.; Flynn, T.M.; Vetriani, C.; Bradley, A.S.; Fike, D.A.

2017-01-01

Summary Previous studies of the stoichiometry of thiosulfate oxidation by colorless sulfur bacteria have failed to demonstrate mass balance of sulfur, indicating that unidentified oxidized products must be present. Here we present reaction stoichiometry and kinetics under variable pH conditions during the growth of Thiomicrospira thermophila strain EPR85, isolated from diffuse hydrothermal fluids at the East Pacific Rise. At pH 8.0, thiosulfate is stoichiometrically converted to sulfate. At lower pH, the products of thiosulfate oxidation are extracellular elemental sulfur and sulfate. We were able to replicate previous experiments and identify the missing sulfur as tetrathionate, consistent with previous reports of the activity of thiosulfate dehydrogenase. Tetrathionate was formed under slightly acidic conditions. Genomic DNA from T. thermophila strain EPR85 contains genes homologous to those in the Sox pathway (soxAXYZBCDL), as well as rhodanese and thiosulfate dehydrogenase. No other sulfur oxidizing bacteria containing sox(CD)2 genes have been reported to produce extracellular elemental sulfur. If the apparent modified Sox pathway we observe in T. thermophila is present in marine Thiobacillus and Thiomicrospira species, production of extracellular elemental sulfur may be biogeochemically important in marine sulfur cycling. PMID:26914243

Thiosulfate oxidation by Thiomicrospira thermophila: Metabolic flexibility in response to ambient geochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Houghton, J. L.; Foustoukos, D. I.; Flynn, T. M.

Previous studies of the stoichiometry of thiosulfate oxidation by colorless sulfur bacteria have failed to demonstrate mass balance of sulfur, indicating that unidentified oxidized products must be present. Here the reaction stoichiometry and kinetics under variable pH conditions during the growth of Thiomicrospira thermophila strain EPR85, isolated from diffuse hydrothermal fluids at the East Pacific Rise, is presented. At pH 8.0, thiosulfate was stoichiometrically converted to sulfate. At lower pH, the products of thiosulfate oxidation were extracellular elemental sulfur and sulfate. Here, we were able to replicate previous experiments and identify the missing sulfur as tetrathionate, consistent with previous reportsmore » of the activity of thiosulfate dehydrogenase. Tetrathionate was formed under slightly acidic conditions. Genomic DNA from T. thermophila strain EPR85 contains genes homologous to those in the Sox pathway ( soxAXYZBCDL), as well as rhodanese and thiosulfate dehydrogenase. No other sulfur oxidizing bacteria containing sox(CD)2 genes have been reported to produce extracellular elemental sulfur. If the apparent modified Sox pathway we observed in T. thermophila is present in marine Thiobacillus and Thiomicrospira species, production of extracellular elemental sulfur may be biogeochemically important in marine sulfur cycling.« less

Thiosulfate oxidation by Thiomicrospira thermophila: Metabolic flexibility in response to ambient geochemistry

DOE PAGES

Houghton, J. L.; Foustoukos, D. I.; Flynn, T. M.; ...

2016-03-21

Previous studies of the stoichiometry of thiosulfate oxidation by colorless sulfur bacteria have failed to demonstrate mass balance of sulfur, indicating that unidentified oxidized products must be present. Here the reaction stoichiometry and kinetics under variable pH conditions during the growth of Thiomicrospira thermophila strain EPR85, isolated from diffuse hydrothermal fluids at the East Pacific Rise, is presented. At pH 8.0, thiosulfate was stoichiometrically converted to sulfate. At lower pH, the products of thiosulfate oxidation were extracellular elemental sulfur and sulfate. Here, we were able to replicate previous experiments and identify the missing sulfur as tetrathionate, consistent with previous reportsmore » of the activity of thiosulfate dehydrogenase. Tetrathionate was formed under slightly acidic conditions. Genomic DNA from T. thermophila strain EPR85 contains genes homologous to those in the Sox pathway ( soxAXYZBCDL), as well as rhodanese and thiosulfate dehydrogenase. No other sulfur oxidizing bacteria containing sox(CD)2 genes have been reported to produce extracellular elemental sulfur. If the apparent modified Sox pathway we observed in T. thermophila is present in marine Thiobacillus and Thiomicrospira species, production of extracellular elemental sulfur may be biogeochemically important in marine sulfur cycling.« less

Metal-silicate partitioning and the light element in the core (Invited)

NASA Astrophysics Data System (ADS)

Wood, B. J.; Wade, J.; Tuff, J.

2009-12-01

Most attempts to constrain the concentrations of “light” elements in the Earth’s core rely either on cosmochemical arguments or on arguments based on the densities and equations of state of Fe-alloys containing the element of concern. Despite its utility, the latter approach yields a wide range of permissible compositions and hence weak constraints. The major problem with the cosmochemical approach is that the abundances in the bulk Earth of all the candidate “light” elements- H, C, O, Si and S are highly uncertain because of their volatile behavior during planetary accretion. In contrast, refractory elements appear to be in approximately CI chondritic relative abundances in the Earth. This leads to the potential for using the partitioning of refractory siderophile elements between the mantle and core to constrain the concentrations of light elements in the core. Recent experimental metal-silicate partitioning data, coupled with mantle abundances of refractory siderophile elements (e.g. Wade and Wood, EPSL v.236, 78—95,2005; Kegler et. al. EPSL v.268, 28-40,2008) have shown that the core segregated from the mantle under high pressure conditions (~40 GPa). If a wide range of elements, from very siderophile, (e.g. Mo) through moderately (Ni, Co, W) to weakly siderophile (V, Cr, Nb, Si) are considered, the Earth also appears to have become more oxidized during accretion. Metal-silicate partitioning of some elements is also sensitive to the light element content of the metal. For example, Nb and W partitioning depend strongly on carbon, Mo on silicon and Cr on sulfur. Given the measured mantle abundances of the refractory elements, these observations enable the Si and C contents of the core to be constrained at ~5% and <2% respectively while partitioning is consistent with a cosmochemically-estimated S content of ~2%.

ANSYS duplicate finite-element checker routine

NASA Technical Reports Server (NTRS)

Ortega, R.

1995-01-01

An ANSYS finite-element code routine to check for duplicated elements within the volume of a three-dimensional (3D) finite-element mesh was developed. The routine developed is used for checking floating elements within a mesh, identically duplicated elements, and intersecting elements with a common face. A space shuttle main engine alternate turbopump development high pressure oxidizer turbopump finite-element model check using the developed subroutine is discussed. Finally, recommendations are provided for duplicate element checking of 3D finite-element models.

Synergy of iron and copper oxides in the catalytic formation of PCDD/Fs from 2-monochlorophenol.

PubMed

Potter, Phillip M; Guan, Xia; Lomnicki, Slawomir M

2018-07-01

Transition metal oxides present in waste incineration systems have the ability to catalyze the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) through surface reactions involving organic dioxin precursors. However, studies have concentrated on the catalytic effects of individual transition metal oxides, while the complex elemental composition of fly ash introduces the possibility of synergistic or inhibiting effects between multiple, catalytically active components. In this study, we have tested fly ash surrogates containing different ratios (by weight) of iron (III) oxide and copper (II) oxide. Such Fe 2 O 3 /CuO mixed-oxide surrogates (in the Fe:Cu ratio of 3.5, 0.9 and 0.2 ) were used to study the cooperative effects between two transition metals that are present in high concentrations in most combustion systems and are known to individually catalyze the formation of PCDD/Fs. The presence of both iron and copper oxides increased the oxidative power of the fly ash surrogates in oxygen rich conditions and led to extremely high PCDD/F yields under pyrolytic conditions (up to >5% yield) from 2-monochlorophenol precursor. PCDD/F congener profiles from the mixed oxide samples are similar to results obtained from only CuO, however the total PCDD/F yield increases with increasing Fe 2 O 3 content. Careful analysis of the reaction products and changes to the oxidation states of active metals indicate the CuO surface sites are centers for reaction while the Fe 2 O 3 is affecting the bonds in CuO and increasing the ability of copper centers to form surface-bound radicals that are precursors to PCDD/Fs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Evidence for the remobilisation of transuranic elements in the terrestrial environment.

PubMed

Hursthouse, A S; Livens, F R

1993-09-01

The transuranium elements, Np, Pu and Am discharged from the BNFL fuel reprocessing plant at Sellafield have accumulated in the local environment. The processes responsible for their dispersal rely both on physical transportation and their chemical reactivity. The transuranics have a complex chemistry, with multiple oxidation states and a strongly polarising character. In the environment, the particle active III/IV and more mobile VNI oxidation state groups are important and govern their geochemical behaviour and subsequent dispersal.Studies of the behaviour of the transuranics, particularly Pu, in the Irish Sea, have shown that the majority of the radionuclides in the liquid effluent discharged from Sellafield, quickly becomes associated with the marine sediments. Their dispersal and distribution in the environment is then governed primarily by the movement of particulate material and for some sites it has been suggested that sediment profiles preserve the historical record of discharges from the plant.In tidally inundated soils, radionuclide levels are greatly enhanced. These soils are water-logged for long periods of the year, are strongly anoxic and accretion rate are very low. The distribution of Np, Pu and Am in the soil suggests that simple sedimentary accumulation mechanism cannot provide an adequate explanation for the profiles observed. From preliminary studies of soil pore water composition and detailed analysis of the variation of isotopic ratios in the soil cores, it is apparent that a small but significant component of the radionuclide inventory is mobile. In addition, it is clear that the mechanisms responsible for this mobility allows differentiation between the transuranium nuclides.

Acid pre-treatment method for in situ ore leaching

DOEpatents

Mallon, R.G.; Braun, R.L.

1975-10-28

An acid leaching method is described for the recovery of a desired element from a subterranean rubblized body of primary ore containing the element and also having associated therewith a carbonate mineral wherein the rubblized ore body is flooded with an aqueous acidic solution in order to release carbon dioxide from the associated carbonate mineral. After a substantial portion of the available carbon dioxide is released and removed from the ore body, as by venting to the atmosphere, an oxidizing gas is introduced into the flooded, rubblized ore to oxidize the ore and form an acid leach solution effective in the presence of the dissolved oxidizing gas to dissolve the ore and cause the desired element to go into solution. The leach solution is then circulated to the surface where the metal values are recovered therefrom.

Mercury Emission Measurement in Coal-Fired Boilers by Continuous Mercury Monitor and Ontario Hydro Method

NASA Astrophysics Data System (ADS)

Zhu, Yanqun; Zhou, Jinsong; He, Sheng; Cai, Xiaoshu; Hu, Changxin; Zheng, Jianming; Zhang, Le; Luo, Zhongyang; Cen, Kefa

2007-06-01

The mercury emission control approach attaches more importance. The accurate measurement of mercury speciation is a first step. Because OH method (accepted method) can't provide the real-time data and 2-week time for results attained, it's high time to seek on line mercury continuous emission monitors(Hg-CEM). Firstly, the gaseous elemental and oxidized mercury were conducted to measure using OH and CEM method under normal operation conditions of PC boiler after ESP, the results between two methods show good consistency. Secondly, through ESP, gaseous oxidized mercury decrease a little and particulate mercury reduce a little bit, but the elemental mercury is just the opposite. Besides, the WFGD system achieved to gaseous oxidized mercury removal of 53.4%, gaseous overall mercury and elemental mercury are 37.1% and 22.1%, respectively.

Iron aluminide useful as electrical resistance heating elements

DOEpatents

Sikka, V.K.; Deevi, S.C.; Fleischhauer, G.S.; Hajaligol, M.R.; Lilly, A.C. Jr.

1997-04-15

The invention relates generally to aluminum containing iron-base alloys useful as electrical resistance heating elements. The aluminum containing iron-base alloys have improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The alloy has an entirely ferritic microstructure which is free of austenite and includes, in weight %, over 4% Al, {<=}1% Cr and either {>=}0.05% Zr or ZrO{sub 2} stringers extending perpendicular to an exposed surface of the heating element or {>=}0.1% oxide dispersoid particles. The alloy can contain 14-32% Al, {<=}2% Ti, {<=}2% Mo, {<=}1% Zr, {<=}1% C, {<=}0.1% B, {<=}30% oxide dispersoid and/or electrically insulating or electrically conductive covalent ceramic particles, {<=}1% rare earth metal, {<=}1% oxygen, {<=}3% Cu, balance Fe. 64 figs.

Structure of the Deactive State of Mammalian Respiratory Complex I.

PubMed

Blaza, James N; Vinothkumar, Kutti R; Hirst, Judy

2018-02-06

Complex I (NADH:ubiquinone oxidoreductase) is central to energy metabolism in mammalian mitochondria. It couples NADH oxidation by ubiquinone to proton transport across the energy-conserving inner membrane, catalyzing respiration and driving ATP synthesis. In the absence of substrates, active complex I gradually enters a pronounced resting or deactive state. The active-deactive transition occurs during ischemia and is crucial for controlling how respiration recovers upon reperfusion. Here, we set a highly active preparation of Bos taurus complex I into the biochemically defined deactive state, and used single-particle electron cryomicroscopy to determine its structure to 4.1 Å resolution. We show that the deactive state arises when critical structural elements that form the ubiquinone-binding site become disordered, and we propose reactivation is induced when substrate binding to the NADH-reduced enzyme templates their reordering. Our structure both rationalizes biochemical data on the deactive state and offers new insights into its physiological and cellular roles. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Volatilization of oxides during oxidation of some superalloys at 1200 C

NASA Technical Reports Server (NTRS)

Zaplatynsky, I.

1977-01-01

Volatilization of oxides during cyclic oxidation of commercial Nichrome, Inconel 750, Rene 41, Stellite 6B, and GE-1541 was studied at 1200 C in static air. Quantitative analysis of oxide vapor deposits revealed that oxides of tungsten, molybdenum, niobium, manganese, and chromium volatilized preferentially from the oxide scales. Aluminum and silicon were not detected in vapor deposits. For all the alloys except GE-1541 chromium was found to be the main metallic element in the oxide scales.

Volatilization of oxides during oxidation of some superalloys at 1200 C

NASA Technical Reports Server (NTRS)

Zaplatynsky, I.

1977-01-01

Volatilization of oxides during cyclic oxidation of commercial Nichrome, Inconel 750, Rene 41, Stellite 6B, and GE-1541 was studied at 1200 C in static air. Quantitative analysis of oxide vapor deposits revealed that oxides of tungsten, molybdenum, niobium, manganese, and chromium volatilized preferentially from the oxide scales. Aluminum and silicon were not detected in vapor deposits. For all the alloys except GE-1541, chromium was found to be the main metallic element in the oxide scales.

The effect of melt composition on metal-silicate partitioning of siderophile elements and constraints on core formation in the angrite parent body

NASA Astrophysics Data System (ADS)

Steenstra, E. S.; Sitabi, A. B.; Lin, Y. H.; Rai, N.; Knibbe, J. S.; Berndt, J.; Matveev, S.; van Westrenen, W.

2017-09-01

We present 275 new metal-silicate partition coefficients for P, S, V, Cr, Mn, Co, Ni, Ge, Mo, and W obtained at moderate P (1.5 GPa) and high T (1683-1883 K). We investigate the effect of silicate melt composition using four end member silicate melt compositions. We identify possible silicate melt dependencies of the metal-silicate partitioning of lower valence elements Ni, Ge and V, elements that are usually assumed to remain unaffected by changes in silicate melt composition. Results for the other elements are consistent with the dependence of their metal-silicate partition coefficients on the individual major oxide components of the silicate melt composition suggested by recently reported parameterizations and theoretical considerations. Using multiple linear regression, we parameterize compiled metal-silicate partitioning results including our new data and report revised expressions that predict their metal-silicate partitioning behavior as a function of P-T-X-fO2. We apply these results to constrain the conditions that prevailed during core formation in the angrite parent body (APB). Our results suggest the siderophile element depletions in angrite meteorites are consistent with a CV bulk composition and constrain APB core formation to have occurred at mildly reducing conditions of 1.4 ± 0.5 log units below the iron-wüstite buffer (ΔIW), corresponding to a APB core mass of 18 ± 11%. The core mass range is constrained to 21 ± 8 mass% if light elements (S and/or C) are assumed to reside in the APB core. Incorporation of light elements in the APB core does not yield significantly different redox states for APB core-mantle differentiation. The inferred redox state is in excellent agreement with independent fO2 estimates recorded by pyroxene and olivine in angrites.

Oxidative Addition and Reductive Elimination at Main-Group Element Centers.

PubMed

Chu, Terry; Nikonov, Georgii I

2018-04-11

Oxidative addition and reductive elimination are key steps in a wide variety of catalytic reactions mediated by transition-metal complexes. Historically, this reactivity has been considered to be the exclusive domain of d-block elements. However, this paradigm has changed in recent years with the demonstration of transition-metal-like reactivity by main-group compounds. This Review highlights the substantial progress achieved in the past decade for the activation of robust single bonds by main-group compounds and the more recently realized activation of multiple bonds by these elements. We also discuss the significant discovery of reversible activation of single bonds and distinct examples of reductive elimination at main-group element centers. The review consists of three major parts, starting with oxidative addition of single bonds, proceeding to cleavage of multiple bonds, and culminated by the discussion of reversible bond activation and reductive elimination. Within each subsection, the discussion is arranged according to the type of bond being cleaved or formed and considers elements from the left to the right of each period and down each group of the periodic table. The majority of results discussed in this Review come from the past decade; however, earlier reports are also included to ensure completeness.

Tension-Compression Fatigue of an Oxide/Oxide Ceramic Matrix Composite at Elevated Temperature in Air and Steam Environments

DTIC Science & Technology

2015-03-26

method has been successfully used with several materials such as silicon carbide fiber - silicon carbide matrix ( SiC / SiC ) CMCs with carbon and boron...elements [14]. These advanced ceramics include oxides, nitrides and carbides of silicon , aluminum, titanium, and zirconium [12]. One of the most...oxides over silicon carbide and other non-oxide materials. In fact, it is the inherent stability of oxides in oxidizing environments which originally

Reactive Gaseous Mercury Formation Over The North Pacific Ocean: Influence Of Environmental Parameters On Elemental Mercury Oxidation In The Marine Boundary Layer

NASA Astrophysics Data System (ADS)

Laurier, F. J.

2002-12-01

Global mercury models have identified wet and dry particle deposition and evasion of dissolved gaseous mercury from the ocean and from land as key controls over global mercury cycling (1,2). Recent ocean studies (3,4) however, have indicated that estimated mercury evasion rates from the ocean substantially exceed estimated deposition. Oxidized reactive gaseous mercury species (RGHg) are now known to play a major role in the global mercury cycle (2,5). RGHg species are water-soluble, exhibit a much shorter atmospheric lifetime than elemental mercury, and contribute to a large extent to atmospheric mercury deposition (2,3,6). Although recent global mercury models have accounted for the dry deposition of RGHg derived from point source emissions (6,7), the formation and deposition of RGHg in remote areas have not been incorporated. We suggest that the oxidation of elemental mercury over the ocean, by gas phase or heterogeneous reactions, is an important part the global mercury cycle. In agreement with previous studies (3,8,9) our recent data from atmospheric collections over the North Pacific Ocean support the notion of enhanced oxidation in the marine boundary layer. Our results show an inverse correlation between RGHg production and ozone, and a diurnal cycle with highest concentrations during periods of highest UV irradiation. In addition, the relationship between RGHg and other parameters measured during the cruise will be discussed. Our results clearly show that RGHg deposition to the ocean must be an important Hg source, and a crucial part of the global Hg cycle. (1) Mason R.P., Fitzgerald W.F., and Morel F.M.M. (1994), The biogeochemical cycling of elemental mercury: Anthropogenic influences, Geochim. Cosmochim. Acta, 58: 3191-3198 (2) Shia R.L., Seigneur C., Pai P., Ko M., and Sze N.-D. (1999), Global simulation of atmospheric mercury concentrations and deposition fluxes, J. Geophy. Res., 104(D19), 23, 747-23, 760 (3) Mason, R.P., Lawson N.M., and Sheu G.-R. (2001), Mercury in the Atlantic Ocean: factors controlling air-sea exchange of mercury and its distribution in the upper water, Deep-Sea Res. II, 2829-2853 (4) Lamborg, C.H., Rolfus K.R., and Fitzgerald W.F. (1999), The atmospheric cycling and air-sea exchange of mercury species in the south and equatorial Atlantic Ocean, Deep-Sea Res. II, 957-977 (5) Lindberg S.E., Brooks S., Lin C.-J., Scott K. J., Landis M. S., Stevens R.K., Goodsite M., and Richter A. (2002), Dynamic oxidation of gaseous mercury in the arctic troposphere at polar sunrise, Environ. Sci. Technol., 1245-1256 (6) Bullock O.R. (2000), Modeling assessment of transport and deposition patterns of anthropogenic mercury air emissions in the United States and Canada, Sci Total Environ., 259(1-3), 145-157 (7) Xu X., Yang X., Miller d.R., Helble J.J., and Carley R.J. (2000), a regional scale modelling study of atmospheric transport and formation of mercury. II. Simulation results for the northeast United states, Atmos. Environ., 34: 4945-4955 (8) Sheu G.-R. (2001), Speciation and distribution of atmospheric mercury: Significance of reactive gaseous mercury in the global mercury cycle. PhD. thesis, University of Maryland, College park, pp. 170 (9) Guentzel J.L., Landing W.M., Gill G.A., and Pollman C.D. (2001), Processes influencing rainfall deposition of mercury in Florida, Environ. Sci. Technol., 35: 863-873

Robust adaptive control for a hybrid solid oxide fuel cell system

NASA Astrophysics Data System (ADS)

Snyder, Steven

2011-12-01

Solid oxide fuel cells (SOFCs) are electrochemical energy conversion devices. They offer a number of advantages beyond those of most other fuel cells due to their high operating temperature (800-1000°C), such as internal reforming, heat as a byproduct, and faster reaction kinetics without precious metal catalysts. Mitigating fuel starvation and improving load-following capabilities of SOFC systems are conflicting control objectives. However, this can be resolved by the hybridization of the system with an energy storage device, such as an ultra-capacitor. In this thesis, a steady-state property of the SOFC is combined with an input-shaping method in order to address the issue of fuel starvation. Simultaneously, an overall adaptive system control strategy is employed to manage the energy sharing between the elements as well as to maintain the state-of-charge of the energy storage device. The adaptive control method is robust to errors in the fuel cell's fuel supply system and guarantees that the fuel cell current and ultra-capacitor state-of-charge approach their target values and remain uniformly, ultimately bounded about these target values. Parameter saturation is employed to guarantee boundedness of the parameters. The controller is validated through hardware-in-the-loop experiments as well as computer simulations.

Potential contaminants at a dredged spoil placement site, Charles City County, Virginia, as revealed by sequential extraction

PubMed Central

Tang, Jianwu; Whittecar, G Richard; Johannesson, Karen H; Daniels, W Lee

2004-01-01

Backfills of dredged sediments onto a former sand and gravel mine site in Charles City County, VA may have the potential to contaminate local groundwater. To evaluate the mobility of trace elements and to identify the potential contaminants from the dredged sediments, a sequential extraction scheme was used to partition trace elements associated with the sediments from the local aquifer and the dredged sediments into five fractions: exchangeable, acidic, reducible, oxidizable, and residual phases. Sequential extractions indicate that, for most of the trace elements examined, the residual phases account for the largest proportion of the total concentrations, and their total extractable fractions are mainly from reducible and oxidizable phases. Only Cd, Pb, and Zn have an appreciable extractable proportion from the acidic phase in the filled dredged sediments. Our groundwater monitoring data suggest that the dredged sediments are mainly subject to a decrease in pH and a series of oxidation reactions, when exposed to the atmosphere. Because the trace elements released by carbonate dissolution and the oxidation (e.g., organic matter degradation, iron sulfide and, ammonia oxidation) are subsequently immobilized by sorption to iron, manganese, and aluminum oxides, no potential contaminants to local groundwater are expected by addition of the dredged sediments to this site.

Solid oxide fuel cell with single material for electrodes and interconnect

DOEpatents

McPheeters, Charles C.; Nelson, Paul A.; Dees, Dennis W.

1994-01-01

A solid oxide fuel cell having a plurality of individual cells. A solid oxide fuel cell has an anode and a cathode with electrolyte disposed therebetween, and the anode, cathode and interconnect elements are comprised of substantially one material.

TRACE ELEMENT BINDING DURING STRUCTURAL TRANSFORMATION IN IRON OXIDES

EPA Science Inventory

Iron (hydr)oxides often control the mobility of inorganic contaminants in soils and sediments. A poorly ordered form of ferrihydrite is commonly produced during rapid oxidation of ferrous iron at sharp redox fronts encountered during discharge of anoxic/suboxic waters into terre...

Aluminum powder metallurgy processing

NASA Astrophysics Data System (ADS)

Flumerfelt, Joel Fredrick

In recent years, the aluminum powder industry has expanded into non-aerospace applications. However, the alumina and aluminum hydroxide in the surface oxide film on aluminum powder require high cost powder processing routes. A driving force for this research is to broaden the knowledge base about aluminum powder metallurgy to provide ideas for fabricating low cost aluminum powder components. The objective of this dissertation is to explore the hypothesis that there is a strong linkage between gas atomization processing conditions, as-atomized aluminum powder characteristics, and the consolidation methodology required to make components from aluminum powder. The hypothesis was tested with pure aluminum powders produced by commercial air atomization commercial inert gas atomization and gas atomization reaction synthesis (GARS). The commercial atomization methods are bench marks of current aluminum powder technology. The GARS process is a laboratory scale inert gas atomization facility. A benefit of using pure aluminum powders is an unambiguous interpretation of the results without considering the effects of alloy elements. A comparison of the GARS aluminum powders with the commercial aluminum powders showed the former to exhibit superior powder characteristics. The powders were compared in terms of size and shape, bulk chemistry, surface oxide chemistry and structure, and oxide film thickness. Minimum explosive concentration measurements assessed the dependence of explosibility hazard on surface area, oxide film thickness, and gas atomization processing conditions. The GARS aluminum powders were exposed to different relative humidity levels, demonstrating the effect of atmospheric conditions on post-atomization oxidation of aluminum powder. An Al-Ti-Y GARS alloy exposed in ambient air at different temperatures revealed the effect of reactive alloy elements on post-atomization powder oxidation. The pure aluminum powders were consolidated by two different routes, a conventional consolidation process for fabricating aerospace components with aluminum powder and a proposed alternative. The consolidation procedures were compared by evaluating the consolidated microstructures and the corresponding mechanical properties. A low temperature solid state sintering experiment demonstrated that tap densified GARS aluminum powders can form sintering necks between contacting powder particles, unlike the total resistance to sintering of commercial air atomization aluminum powder.

Calcite and dolomite in intrusive carbonatites. II. Trace-element variations

NASA Astrophysics Data System (ADS)

Chakhmouradian, Anton R.; Reguir, Ekaterina P.; Couëslan, Christopher; Yang, Panseok

2016-04-01

The composition of calcite and dolomite from several carbonatite complexes (including a large set of petrographically diverse samples from the Aley complex in Canada) was studied by electron-microprobe analysis and laser-ablation inductively-coupled-plasma mass-spectrometry to identify the extent of substitution of rare-earth and other trace elements in these minerals and the effects of different igneous and postmagmatic processes on their composition. Analysis of the newly acquired and published data shows that the contents of rare-earth elements (REE) and certain REE ratios in magmatic calcite and dolomite are controlled by crystal fractionation of fluorapatite, monazite and, possibly, other minerals. Enrichment in REE observed in some samples (up to ~2000 ppm in calcite) cannot be accounted for by coupled substitutions involving Na, P or As. At Aley, the REE abundances and chondrite-normalized (La/Yb)cn ratios in carbonates decrease with progressive fractionation. Sequestration of heavy REE from carbonatitic magma by calcic garnet may be responsible for a steeply sloping "exponential" pattern and lowered Ce/Ce* ratios of calcite from Magnet Cove (USA) and other localities. Alternatively, the low levels of Ce and Mn in these samples could result from preferential removal of these elements by Ce4+- and Mn3+-bearing minerals (such as cerianite and spinels) at increasing f(O2) in the magma. The distribution of large-ion lithophile elements (LILE = Sr, Ba and Pb) in rock-forming carbonates also shows trends indicative of crystal fractionation effects (e.g., concomitant depletion in Ba + Pb at Aley, or Sr + Ba at Kerimasi), although the phases responsible for these variations cannot be identified unambiguously at present. Overall, element ratios sensitive to the redox state of the magma and its complexing characteristics (Eu/Eu*, Ce/Ce* and Y/Ho) are least variable and in both primary calcite and dolomite, approach the average chondritic values. In consanguineous rocks, calcite invariably has higher REE and LILE levels than dolomite. Hydrothermal reworking of carbonatites does not produce a unique geochemical fingerprint, leading instead to a variety of evolutionary trends that range from light-REE and LILE enrichment (Turiy Mys, Russia) to heavy-REE enrichment and LILE depletion (Bear Lodge, USA). These differences clearly attest to variations in the chemistry of carbonatitic fluids and, consequently, their ability to mobilize specific trace elements from earlier-crystallized minerals. An important telltale indicator of hydrothermal reworking is deviation from the primary, chondrite-like REE ratios (in particular, Y/Ho and Eu/Eu*), accompanied by a variety of other compositional changes depending on the redox state of the fluid (e.g., depletion of carbonates in Mn owing to its oxidation and sequestration by secondary oxides). The effect of supergene processes was studied on a single sample from Bear Lodge, which shows extreme depletion in Mn and Ce (both due to oxidation), coupled with enrichment in Pb and U, possibly reflecting an increased availability of Pb2+ and (UO2)2+ species in the system. On the basis of these findings, several avenues for future research can be outlined: (1) structural mechanisms of REE uptake by carbonates; (2) partitioning of REE and LILE between cogenetic calcite and dolomite; (3) the effects of fluorapatite, phlogopite and pyrochlore fractionation on the LILE budget of magmatic carbonates; (4) the cause(s) of coupled Mn-Ce depletion in some primary calcite; and (5) relations between fluid chemistry and compositional changes in hydrothermal carbonates.

Ternary arsenides ATt{sub 3}As{sub 3} (A=K, Rb; Tt=Ge, Sn) with layered structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khatun, Mansura; Stoyko, Stanislav S.; Mar, Arthur, E-mail: arthur.mar@ualberta.ca

2016-06-15

The four ternary arsenides ATt{sub 3}As{sub 3} (A=K, Rb; Tt=Ge, Sn) were obtained by reaction of the elements at 600–650 °C. They adopt an orthorhombic structure (space group Pnma, Z=4, with cell parameters ranging from a=9.9931(11) Å, b=3.7664(4) Å, c=18.607(2) Å for KGe{sub 3}As{sub 3} to a=10.3211(11) Å, b=4.0917(4) Å, c=19.570(2) Å for RbSn{sub 3}As{sub 3}) containing corrugated [Tt{sub 3}As{sub 3}] layers built from Tt-centred trigonal pyramids and tetrahedra forming five-membered rings decorated with As handles. They can be considered to be Zintl phases with Tt atoms in +4, +3, and +1 oxidation states. Band structure calculations predict that thesemore » compounds are semiconductors with narrow band gaps (0.71 eV in KGe{sub 3}As{sub 3}, 0.50 eV in KSn{sub 3}As{sub 3}). - Graphical abstract: Ternary arsenides ATt{sub 3}As{sub 3} (A=K, Rb; Tt=Ge, Sn) contain corrugated layers with Tt atoms in three different oxidation states and are narrow band gap semiconductors. Display Omitted - Highlights: • ATt{sub 3}As{sub 3} (A=K, Rb; Tt=Ge, Sn) contains Tt atoms in three oxidation states. • The structure differs from NaGe{sub 3}P{sub 3} in terms of layer stacking arrangement. • The compounds are predicted to be narrow band gap semiconductors.« less

Comparison of Nickel XANES Spectra and Elemental Maps from a Ureilite, a LL3.8 Ordinary Chondrite, Two Carbonaceous Chondrites and Two Large Cluster IDPs

NASA Technical Reports Server (NTRS)

Wirick, S.; Flynn, G. J.; Sutton, S.; Zolensky, M. E.

2014-01-01

Nickel in the extraterrestrial world is commonly found in both Fe-Ni sulfide and Fe-Ni met-al forms [1] and in the pure metal state in the interior of iron meteorites where it is not easily oxidized. Ni is also found in olivine, pyroxene and glasses and in some melts the partitioning of Ni between the olivines and glass is controlled by the amount of S in the melt [2]. Its most common valence state is Ni(2+) but Ni also occurs as Ni(0), Ni(+), and Ni(3+) and rarely as Ni(2-), Ni(1-) and Ni(4+) [3]. It's valence state in olivines is Ni(2+) in octa-hedral coordination on the M1 site and rarely on the M2 site.[4]. The chemical sensitivity of X-ray absorp-tion near-edge structure (XANES) spectroscopy is well established and can be used to determine not only va-lence states but also coordination sites [5]. We report here Ni XANES spectroscopy and elemental maps collected from 2 carbonaceous chondrites, 2 large clus-ter IDPs, 1 ureilite and 1 LL3 orginary chondrite.Using XANES it may be possible to find a common trait in the large cluster IDPs that will also be found in mete-orite samples.

Improving the electrical contact at a Pt/TiO2 nanowire interface by selective application of focused femtosecond laser irradiation

NASA Astrophysics Data System (ADS)

Xing, Songling; Lin, Luchan; Zou, Guisheng; Liu, Lei; Peng, Peng; Wu, Aiping; Duley, Walter W.; Zhou, Y. Norman

2017-10-01

In this paper, we show that tightly focused femtosecond laser irradiation is effective in improving nanojoining of an oxide nanowire (NW) (TiO2) to a metal electrode (Pt), and how this process can be used to modify contact states. Enhanced chemical bondings are created due to localized plasmonically enhanced optical absorption at the Pt/TiO2 interface as confirmed by finite element simulations of the localized field distribution during irradiation. Nano Auger electron spectroscopy shows that the resulting heterojunction is depleted in oxygen, suggesting that a TiO2-x layer is formed between the Pt electrode and the TiO2 NW. The presence of this redox layer at the metal/oxide interface plays an important role in decreasing the Schottky barrier height and in facilitating chemical bonding. After laser irradiation at the cathode for 10 s at a fluence of 5.02 mJ cm-2, the Pt/TiO2 NW/Pt structure displays different electrical properties under forward and reverse bias voltage, respectively. The creation of this asymmetric electrical characteristic shows the way in which modification of the electronic interface by laser engineering can replace the electroforming process in resistive switching devices and how it can be used to control contact states in a metal/oxide interface.

Improving the electrical contact at a Pt/TiO2 nanowire interface by selective application of focused femtosecond laser irradiation.

PubMed

Xing, Songling; Lin, Luchan; Zou, Guisheng; Liu, Lei; Peng, Peng; Wu, Aiping; Duley, Walter W; Zhou, Y Norman

2017-10-06

In this paper, we show that tightly focused femtosecond laser irradiation is effective in improving nanojoining of an oxide nanowire (NW) (TiO 2 ) to a metal electrode (Pt), and how this process can be used to modify contact states. Enhanced chemical bondings are created due to localized plasmonically enhanced optical absorption at the Pt/TiO 2 interface as confirmed by finite element simulations of the localized field distribution during irradiation. Nano Auger electron spectroscopy shows that the resulting heterojunction is depleted in oxygen, suggesting that a TiO 2-x layer is formed between the Pt electrode and the TiO 2 NW. The presence of this redox layer at the metal/oxide interface plays an important role in decreasing the Schottky barrier height and in facilitating chemical bonding. After laser irradiation at the cathode for 10 s at a fluence of 5.02 mJ cm -2 , the Pt/TiO 2 NW/Pt structure displays different electrical properties under forward and reverse bias voltage, respectively. The creation of this asymmetric electrical characteristic shows the way in which modification of the electronic interface by laser engineering can replace the electroforming process in resistive switching devices and how it can be used to control contact states in a metal/oxide interface.

Rapid solid-state metathesis route to transition-metal doped titanias

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coleman, Nathaniel; Perera, Sujith; Gillan, Edward G., E-mail: edward-gillan@uiowa.edu

2015-12-15

Rapid solid-state metathesis (SSM) reactions are often short-lived highly exothermic reactions that yield a molten alkali halide salt that aids in product growth and crystallization. SSM reactions may also produce kinetically stabilized structures due to the short (seconds) reaction times. This report describes the investigation of rapid SSM reactions in the synthesis of transition-metal doped titanias (M–TiO{sub 2}). The dopant targeted compositions were ten mol percent and based on elemental analysis, many of the M–TiO{sub 2} samples were close to this targeted level. Based on surface analysis, some samples showed large enrichment in surface dopant content, particularly chromium and manganesemore » doped samples. Due to the highly exothermic nature of these reactions, rutile structured TiO{sub 2} was observed in all cases. The M–TiO{sub 2} samples are visible colored and show magnetic and optical properties consistent with the dopant in an oxide environment. UV and visible photocatalytic experiments with these visibly colored rutile M–TiO{sub 2} powders showed that many of them are strongly absorbent for methylene blue dye and degrade the dye under both UV and visible light illumination. This work may open up SSM reactions as an alternate non-thermodynamic reaction strategy for dopant incorporation into a wide range of oxide and non-oxides.« less

The thermal conductivity of mixed fuel U xPu 1-xO 2: molecular dynamics simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xiang-Yang; Cooper, Michael William Donald; Stanek, Christopher Richard

2015-10-16

Mixed oxides (MOX), in the context of nuclear fuels, are a mixture of the oxides of heavy actinide elements such as uranium, plutonium and thorium. The interest in the UO 2-PuO 2 system arises from the fact that these oxides are used both in fast breeder reactors (FBRs) as well as in pressurized water reactors (PWRs). The thermal conductivity of UO 2 fuel is an important material property that affects fuel performance since it is the key parameter determining the temperature distribution in the fuel, thus governing, e.g., dimensional changes due to thermal expansion, fission gas release rates, etc. Formore » this reason it is important to understand the thermal conductivity of MOX fuel and how it differs from UO 2. Here, molecular dynamics (MD) simulations are carried out to determine quantitatively, the effect of mixing on the thermal conductivity of U xPu 1-xO 2, as a function of PuO 2 concentrations, for a range of temperatures, 300 – 1500 K. The results will be used to develop enhanced continuum thermal conductivity models for MARMOT and BISON by INL. These models express the thermal conductivity as a function of microstructure state-variables, thus enabling thermal conductivity models with closer connection to the physical state of the fuel.« less

Role of alloying elements in adhesive transfer and friction of copper-base alloys

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1978-01-01

Sliding friction experiments were conducted in a vacuum with binary-copper alloy riders sliding against a conventional bearing-steel surface with normal residual oxides present. The binary alloys contained 1 atomic percent of various alloying elements. Auger spectroscopy analysis was used to monitor the adhesive transfer of the copper alloys to the bearing-steel surface. A relation was found to exist between adhesive transfer and the reaction potential and free energy of formation of the alloying element in the copper. The more chemically active the element and the more stable its oxide, the greater was the adhesive transfer and wear of the copper alloy. Transfer occurred in all the alloys except copper-gold after relatively few (25) passes across the steel surface.

Stability of Fe-Cr alloy interconnects under CH 4-H 2O atmosphere for SOFCs

NASA Astrophysics Data System (ADS)

Horita, Teruhisa; Xiong, Yueping; Yamaji, Katsuhiko; Sakai, Natsuko; Yokokawa, Harumi

The chemical stability of Fe-Cr alloys (ZMG232 and SUS430) was examined under humidified CH 4 gases at 1073 K to simulate the real anode atmosphere in SOFC operation. Surface microstructure change and oxide scale layer formation were observed on the oxidized Fe-Cr alloy surfaces. The main reaction products were Mn-Cr-(Fe) spinels for both alloys. Secondary ion mass spectrometry (SIMS) was applied to measure the elemental distribution of minor and major elements around the oxide scale/alloy interface. A high concentration of Mn on the oxide scale surface suggested the fast diffusion of Mn in the oxide scale to form the spinels. Annealing in CH 4-H 2O made the oxide scale thicker with duration time on the alloy surface. The parabolic growth rates ( kp) of oxide scale layer were evaluated from the thickness of oxide scales by secondary ion mass spectrometry (SIMS) depth profiles, which were calculated to the following: kp=6.25×10 -6 μm 2/s for SUS430 and kp=4.42×10 -6 μm 2/s for ZMG232. The electrical conductivity of oxidized alloys showed the semi-conductor temperature dependence for both alloys. The electrical conductivity of oxidized ZMG232 alloy was higher than that of oxidized SUS430.

FUSED REACTOR FUELS

DOEpatents

Mayer, S.W.

1962-11-13

This invention relates to a nuciear reactor fuel composition comprising (1) from about 0.01 to about 50 wt.% based on the total weight of said composition of at least one element selected from the class consisting of uranium, thorium, and plutonium, wherein said eiement is present in the form of at least one component selected from the class consisting of oxides, halides, and salts of oxygenated anions, with components comprising (2) at least one member selected from the class consisting of (a) sulfur, wherein the sulfur is in the form of at least one entity selected irom the class consisting of oxides of sulfur, metal sulfates, metal sulfites, metal halosulfonates, and acids of sulfur, (b) halogen, wherein said halogen is in the form of at least one compound selected from the class of metal halides, metal halosulfonates, and metal halophosphates, (c) phosphorus, wherein said phosphorus is in the form of at least one constituent selected from the class consisting of oxides of phosphorus, metal phosphates, metal phosphites, and metal halophosphates, (d) at least one oxide of a member selected from the class consisting of a metal and a metalloid wherein said oxide is free from an oxide of said element in (1); wherein the amount of at least one member selected from the class consisting of halogen and sulfur is at least about one at.% based on the amount of the sum of said sulfur, halogen, and phosphorus atom in said composition; and wherein the amount of said 2(a), 2(b) and 2(c) components in said composition which are free from said elements of uranium, thorium, arid plutonium, is at least about 60 wt.% based on the combined weight of the components of said composition which are free from said elements of uranium, thorium, and plutonium. (AEC)

Structure and thermodynamics of uranium-containing iron garnets

NASA Astrophysics Data System (ADS)

Guo, Xiaofeng; Navrotsky, Alexandra; Kukkadapu, Ravi K.; Engelhard, Mark H.; Lanzirotti, Antonio; Newville, Matthew; Ilton, Eugene S.; Sutton, Stephen R.; Xu, Hongwu

2016-09-01

Use of crystalline garnet as a waste form phase appears to be advantageous for accommodating actinides from nuclear waste. Previous studies show that large amounts of uranium (U) and its analogues such as cerium (Ce) and thorium (Th) can be incorporated into the garnet structure. In this study, we synthesized U loaded garnet phases, Ca3UxZr2-xFe3O12 (x = 0.5-0.7), along with the endmember phase, Ca3(Zr2)SiFe3+2O12, for comparison. The oxidation states of U were determined by X-ray photoelectron and absorption spectroscopies, revealing the presence of mixed pentavalent and hexavalent uranium in the phases with x = 0.6 and 0.7. The oxidation states and coordination environments of Fe were measured using transmission 57Fe-Mössbauer spectroscopy, which shows that all iron is tetrahedrally coordinated Fe3+. U substitution had a significant effect on local environments, the extent of U substitution within this range had a minimal effect on the structure, and unlike in the x = 0 sample, Fe exists in two different environments in the substituted garnets. The enthalpies of formation of garnet phases from constituent oxides and elements were first time determined by high temperature oxide melt solution calorimetry. The results indicate that these substituted garnets are thermodynamically stable under reducing conditions. Our structural and thermodynamic analysis further provides explanation for the formation of natural uranium garnet, elbrusite-(Zr), and supports the potential use of Ca3UxZr2-xFe3O12 as viable waste form phases for U and other actinides.

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

NASA Technical Reports Server (NTRS)

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 refined in further experiments.

Oxides having high energy densities

DOEpatents

Ceder, Gerbrand; Kang, Kisuk

2013-09-10

Certain disclosed embodiments generally relate to oxide materials having relatively high energy and/or power densities. Various aspects of the embodiments are directed to oxide materials having a structure B.sub.i(M.sub.jY.sub.k)O.sub.2, for example, a structure Li.sub.j(Ni.sub.jY.sub.k)O.sub.2 such as Li(Ni.sub.0.5Mn.sub.0.5)O.sub.2. In this structure, Y represents one or more atoms, each independently selected from the group consisting of alkaline earth metals, transition metals, Group 14 elements, Group 15, or Group 16 elements. In some embodiments, such an oxide material may have an O3 crystal structure, and/or a layered structure such that the oxide comprises a plurality of first, repeating atomic planes comprising Li, and a plurality of second, repeating atomic planes comprising Ni and/or Y.

Electronically conductive perovskite-based oxide nanoparticles and films for optical sensing applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ohodnicki, Jr., Paul R; Schultz, Andrew M

2015-04-28

The disclosure relates to a method of detecting a change in a chemical composition by contacting a electronically conducting perovskite-based metal oxide material with a monitored stream, illuminating the electronically conducting perovskite-based metal oxide with incident light, collecting exiting light, monitoring an optical signal based on a comparison of the incident light and the exiting light, and detecting a shift in the optical signal. The electronically conducting perovskite-based metal oxide has a perovskite-based crystal structure and an electronic conductivity of at least 10.sup.-1 S/cm, where parameters are specified at the gas stream temperature. The electronically conducting perovskite-based metal oxide hasmore » an empirical formula A.sub.xB.sub.yO.sub.3-.delta., where A is at least a first element at the A-site, B is at least a second element at the B-site, and where 0.8« less

Analytical Transmission Electron Microscopy Studies on Copper-Alumina Interfaces.

DTIC Science & Technology

1999-06-01

association with alumina, such as, copper, aluminum, chromium, silver, and gold . In particular, copper has been chosen because of its excellent...similar results in variance. However, the oxide calculation program assumes that all elements are 100% oxidized with no monoatomic species or mixed oxide

Graphene oxide windows for in situ environmental cell photoelectron spectroscopy.

PubMed

Kolmakov, Andrei; Dikin, Dmitriy A; Cote, Laura J; Huang, Jiaxing; Abyaneh, Majid Kazemian; Amati, Matteo; Gregoratti, Luca; Günther, Sebastian; Kiskinova, Maya

2011-08-28

The performance of new materials and devices often depends on processes taking place at the interface between an active solid element and the environment (such as air, water or other fluids). Understanding and controlling such interfacial processes require surface-specific spectroscopic information acquired under real-world operating conditions, which can be challenging because standard approaches such as X-ray photoelectron spectroscopy generally require high-vacuum conditions. The state-of-the-art approach to this problem relies on unique and expensive apparatus including electron analysers coupled with sophisticated differentially pumped lenses. Here, we develop a simple environmental cell with graphene oxide windows that are transparent to low-energy electrons (down to 400 eV), and demonstrate the feasibility of X-ray photoelectron spectroscopy measurements on model samples such as gold nanoparticles and aqueous salt solution placed on the back side of a window. These proof-of-principle results show the potential of using graphene oxide, graphene and other emerging ultrathin membrane windows for the fabrication of low-cost, single-use environmental cells compatible with commercial X-ray and Auger microprobes as well as scanning or transmission electron microscopes.

Using Temperature-Dependent Phenomena at Oxide Surfaces for Species Recognition in Chemical Sensing.

NASA Astrophysics Data System (ADS)

Semancik, Steve; Meier, Douglas; Evju, Jon; Benkstein, Kurt; Boger, Zvi; Montgomery, Chip

2006-03-01

Nanostructured films of SnO2 and TiO2 have been deposited on elements in MEMS arrays to fabricate solid state conductometric gas microsensors. The multilevel platforms within an array, called microhotplates, are individually addressable for localized temperature control and measurement of sensing film electrical conductance. Temperature variations of the microhotplates are employed in thermally-activated CVD oxide film growth, and for rapid temperature-programmed operation of the microsensors. Analytical information on environmental gas phase composition is produced temporally as purposeful thermal fluctuations provide energetic and kinetic control of surface reaction and adsorption/desorption phenomena. Resulting modulations of oxide adsorbate populations cause changing charge transfer behavior and measurable conductance responses. Rich data streams from different sensing films in the arrays have been analyzed by Artificial Neural Networks (ANN) to successfully recognize low concentration species in mixed gases. We illustrate capabilities of the approach and technology in the homeland security area, where dangerous chemicals (TICs, CWSs and CWAs) have been detected at 10-100 ppb levels in interference-spiked air backgrounds.

Recovery of fissile materials from nuclear wastes

DOEpatents

Forsberg, Charles W.

1999-01-01

A process for recovering fissile materials such as uranium, and plutonium, and rare earth elements, from complex waste feed material, and converting the remaining wastes into a waste glass suitable for storage or disposal. The waste feed is mixed with a dissolution glass formed of lead oxide and boron oxide resulting in oxidation, dehalogenation, and dissolution of metal oxides. Carbon is added to remove lead oxide, and a boron oxide fusion melt is produced. The fusion melt is essentially devoid of organic materials and halogens, and is easily and rapidly dissolved in nitric acid. After dissolution, uranium, plutonium and rare earth elements are separated from the acid and recovered by processes such as PUREX or ion exchange. The remaining acid waste stream is vitrified to produce a waste glass suitable for storage or disposal. Potential waste feed materials include plutonium scrap and residue, miscellaneous spent nuclear fuel, and uranium fissile wastes. The initial feed materials may contain mixtures of metals, ceramics, amorphous solids, halides, organic material and other carbon-containing material.

Process for growing a film epitaxially upon an oxide surface and structures formed with the process

DOEpatents

McKee, Rodney Allen; Walker, Frederick Joseph

1998-01-01

A process and structure wherein a film comprised of a perovskite or a spinel is built epitaxially upon a surface, such as an alkaline earth oxide surface, involves the epitaxial build up of alternating constituent metal oxide planes of the perovskite or spinel. The first layer of metal oxide built upon the surface includes a metal element which provides a small cation in the crystalline structure of the perovskite or spinel, and the second layer of metal oxide built upon the surface includes a metal element which provides a large cation in the crystalline structure of the perovskite or spinel. The layering sequence involved in the film build up reduces problems which would otherwise result from the interfacial electrostatics at the first atomic layers, and these oxides can be stabilized as commensurate thin films at a unit cell thickness or grown with high crystal quality to thicknesses of 0.5-0.7 .mu.m for optical device applications.

Process for growing a film epitaxially upon an oxide surface and structures formed with the process

DOEpatents

McKee, Rodney A.; Walker, Frederick J.

1995-01-01

A process and structure wherein a film comprised of a perovskite or a spinel is built epitaxially upon a surface, such as an alkaline earth oxide surface, involves the epitaxial build up of alternating constituent metal oxide planes of the perovskite or spinel. The first layer of metal oxide built upon the surface includes a metal element which provides a small cation in the crystalline structure of the perovskite or spinel, and the second layer of metal oxide built upon the surface includes a metal element which provides a large cation in the crystalline structure of the perovskite or spinel. The layering sequence involved in the film build up reduces problems which would otherwise result from the interfacial electrostatics at the first atomic layers, and these oxides can be stabilized as commensurate thin films at a unit cell thickness or grown with high crystal quality to thicknesses of 0.5-0.7 .mu.m for optical device applications.

Inhibition of growth of S. epidermidis by hydrothermally synthesized ZnO nanoplates

NASA Astrophysics Data System (ADS)

Abinaya, C.; Mayandi, J.; Osborne, J.; Frost, M.; Ekstrum, C.; Pearce, J. M.

2017-07-01

The antibacterial effect of zinc oxide (ZnO#1) as prepared and annealed (ZnO#2) at 400 °C, Cu doped ZnO (CuZnO), and Ag doped ZnO (AgZnO) nanoplates on Staphylococcus epidermidis was investigated for the inhibition and inactivation of cell growth. The results shows that pure ZnO and doped ZnO samples exhibited antibacterial activity against Staphylococcus epidermidis (S. epidermidis) as compared to tryptic soy broth (TSB). Also it is observed that S. epidermidis was extremely sensitive to treatment with ZnO nanoplates and it is clear that the effect is not purely depend on Cu/Ag. Phase identification of a crystalline material and unit cell dimensions were studied by x-ray powder diffraction (XRD). The scanning electron microscopy (SEM) provides information on sample’s surface topography and the EDX confirms the presence of Zn, O, Cu and Ag. X-ray photo-electron spectroscopy (XPS) was used to analyze the elemental composition and electronic state of the elements that exist within the samples. These studies confirms the formation of nanoplates and the presence of Zn, O, Ag, Cu with the oxidation states  +2, -2, 0 and  +2 respectively. These results indicates promising antibacterial applications of these ZnO-based nanoparticles synthesized with low-cost hydrothermal methods.

Minor elements in lunar olivine as a petrologic indicator

NASA Technical Reports Server (NTRS)

Steele, I. M.; Smith, J. V.

1975-01-01

Accurate electron microprobe analyses (approximately 50 ppm) were made for Al, Ca, Ti, Cr, Mn, and Ni in Mg-rich olivines which may derive from early lunar crust or deeper environments. Low-Ca contents consistently occur only in olivines from dunitic and troctolitic breccia: spinel troctolite and other rock types have high-Ca olivines suggesting derivation by near-surface processes. Rock 15445 has olivine with distinctly low CaO (approximately 0.01 wt.%). Chromium ranges to higher values (max.0.2 oxide wt.%) than for terrestrial harzburgites and lherzolites but is similar to the range in terrestrial komatiites. Divalent chromium may be indicated over trivalent Cr because olivines lack sufficient other elements for charge balance of the latter. NiO values in lunar specimens range from 0.00 to 0.07 wt.% and a weak anticorrelation with Cr2O3 suggests an oxidation state effect. Al2O3 values are mostly below 0.04-wt.% and show no obvious correlation with fragment type. TiO2 values lie below 0.13-wt.% and seem to correlate best with crystallization rate and plagioclase content of the host rock. High values of Al2O3 and TiO2 reported by other workers have not been confirmed, and are probably wrong.

Precision synthesis of colloidal inorganic nanocrystals using metal and metalloid amides

NASA Astrophysics Data System (ADS)

Yarema, Maksym; Caputo, Riccarda; Kovalenko, Maksym V.

2013-08-01

Rational selection of molecular precursors is the key consideration in the synthesis of inorganic nanocrystals and nanoparticles. This review highlights the state-of-the-art and future potential of metal amides as precursors in the solution-phase synthesis of monodisperse colloidal nanocrystals of metals and metal alloys, as well as metal oxides and chalcogenides. We exclusively focus on homoleptic metal and metalloid alkylamides M(NR2)n and silylamides M[N(SiMe3)2]n as predominant choice of element-nitrogen bonded precursors, which are often advantageous to commonly used metal-oxygen and metal-carbon bonded counterparts. In particular, these amides are highly reactive in oxidation, reduction and metathesis reactions; they are oxygen-free, easy-to-make and/or commercially available. A comprehensive literature review is complemented by our theoretical studies on the thermal stability of metal silylamides using molecular dynamics simulations.

Conduction at a ferroelectric interface

DOE PAGES

Marshall, Matthew S. J.; Malashevich, Andrei; Disa, Ankit S.; ...

2014-11-05

Typical logic elements utilizing the field effect rely on the change in carrier concentration due to the field in the channel region of the device. Ferroelectric-field-effect devices provide a nonvolatile version of this effect due to the stable polarization order parameter in the ferroelectric. In this study, we describe an oxide/oxide ferroelectric heterostructure device based on (001)-oriented PbZr₀̣.₂Ti₀.₈O₃-LaNiO₃ where the dominant change in conductivity is a result of a significant mobility change in the interfacial channel region. The effect is confined to a few atomic layers at the interface and is reversible by switching the ferroelectric polarization. More interestingly, inmore » one polarization state, the field effect induces a 1.7 eV shift of the interfacial bands to create a new conducting channel in the interfacial PbO layer of the ferroelectric.« less

Polyanion Driven Antiferromagnetic and Insulating Ground State of Olivine Phosphates: LiMPO4

NASA Astrophysics Data System (ADS)

Jena, Ajit Kumar; Nanda, B. R. K.; Condensed Matter Theory; Computation Team

Through density functional calculations we have investigated the electronic and magnetic properties of LiMPO4, where M is a 3d transition metal element. We find that contrary to many transition metal oxides, in these Olivine phosphates the band gap is originated due to crystal field anisotropy as well as weak O-p - M-d covalent interaction. Both of them are attributed to the presence of PO43- polyanion. The anisotropic crystal field, in the absence of covalent interactions, creates atomically localized non-degenerate M-d states and therefore the gap is a natural outcome. Onsite repulsion, due to strong correlation effect, further enhances the gap. These localized d states favor high-spin configuration which leads to antiferromagnetic ordering due to Hund's coupling. Experimentally observed low Neel temperature of this family of compounds is explained from the DFT obtained spin exchange interaction parameters. Work supported by Nissan Research Program.

METHOD OF MAKING WIRE FUEL ELEMENTS

DOEpatents

Zambrow, J.L.

1960-08-01

A method is given for making a nuclear reactor fuel element in the form of a uranium-bearing wire clad with zirconium. A uranium bar is enclosed in a zirconium sheath which is coated with an oxide of magnesium, beryllium, or zirconium. The sheathed bar is then placed in a steel tube and reduced to the desired diameter by swaging at 800 to 900 deg C, after which the steel and oxide are removed.

Iron aluminide useful as electrical resistance heating elements

DOEpatents

Sikka, Vinod K.; Deevi, Seetharama C.; Fleischhauer, Grier S.; Hajaligol, Mohammad R.; Lilly, Jr., A. Clifton

1997-01-01

The invention relates generally to aluminum containing iron-base alloys useful as electrical resistance heating elements. The aluminum containing iron-base alloys have improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The alloy has an entirely ferritic microstructure which is free of austenite and includes, in weight %, over 4% Al, .ltoreq.1% Cr and either .gtoreq.0.05% Zr or ZrO.sub.2 stringers extending perpendicular to an exposed surface of the heating element or .gtoreq.0.1% oxide dispersoid particles. The alloy can contain 14-32% Al, .ltoreq.2% Ti, .ltoreq.2% Mo, .ltoreq.1% Zr, .ltoreq.1% C, .ltoreq.0.1% B, .ltoreq.30% oxide dispersoid and/or electrically insulating or electrically conductive covalent ceramic particles, .ltoreq.1% rare earth metal, .ltoreq.1% oxygen, .ltoreq.3% Cu, balance Fe.

Iron aluminide useful as electrical resistance heating elements

DOEpatents

Sikka, Vinod K.; Deevi, Seetharama C.; Fleischhauer, Grier S.; Hajaligol, Mohammad R.; Lilly, Jr., A. Clifton

1999-01-01

The invention relates generally to aluminum containing iron-base alloys useful as electrical resistance heating elements. The aluminum containing iron-base alloys have improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The alloy has an entirely ferritic microstructure which is free of austenite and includes, in weight %, over 4% Al, .ltoreq.1% Cr and either .gtoreq.0.05% Zr or ZrO.sub.2 stringers extending perpendicular to an exposed surface of the heating element or .gtoreq.0.1% oxide dispersoid particles. The alloy can contain 14-32% Al, .ltoreq.2% Ti, .ltoreq.2% Mo, .ltoreq.1% Zr, .ltoreq.1% C, .ltoreq.0.1% B, .ltoreq.30% oxide dispersoid and/or electrically insulating or electrically conductive covalent ceramic particles, .ltoreq.1% rare earth metal, .ltoreq.1% oxygen, .ltoreq.3% Cu, balance Fe.

Iron aluminide useful as electrical resistance heating elements

DOEpatents

Sikka, Vinod K.; Deevi, Seetharama C.; Fleischhauer, Grier S.; Hajaligol, Mohammad R.; Lilly, Jr., A. Clifton

2001-01-01

The invention relates generally to aluminum containing iron-base alloys useful as electrical resistance heating elements. The aluminum containing iron-base alloys have improved room temperature ductility, electrical resistivity, cyclic fatigue resistance, high temperature oxidation resistance, low and high temperature strength, and/or resistance to high temperature sagging. The alloy has an entirely ferritic microstructure which is free of austenite and includes, in weight %, over 4% Al, .ltoreq.1% Cr and either .gtoreq.0.05% Zr or ZrO.sub.2 stringers extending perpendicular to an exposed surface of the heating element or .gtoreq.0.1% oxide dispersoid particles. The alloy can contain 14-32% Al, .ltoreq.2% Ti, .ltoreq.2% Mo, .ltoreq.1% Zr, .ltoreq.1% C, .ltoreq.0.1% B, .ltoreq.30% oxide dispersoid and/or electrically insulating or electrically conductive covalent ceramic particles, .ltoreq.1% rare earth metal, .ltoreq.1% oxygen, .ltoreq.3% Cu, balance Fe.

Removal of titanium plates coated with anodic titanium oxide ceramic: retrospective study.

PubMed

Velich, Norbert; Németh, Zsolt; Suba, Csongor; Szabó, György

2002-09-01

Transformation of the surface of metallic titanium with titanium oxides prepared in various ways is a modern procedure. For more than 15 years, the authors have been utilizing fixing elements coated with titanium oxide ceramics, prepared by anodic oxidation and thermal treatment, for purposes of jawbone osteosynthesis. The aim of the authors' work was to assess the extent to which the titanium oxide ceramic coating influences the fate of the plates used for osteosynthesis within the human organism, in regard to the possible need for their removal. During a 5-year period, 108 of 1,396 plates coated with anodic titanium oxide had to be removed for various reasons: plate exposure (47), osteomyelitis (25), palpable swelling and tenderness (21), patient request for psychological reasons (13), or fracture of the plate (2). In none of these 108 cases was metallosis observed, which otherwise is reported relatively frequently in the vicinity of traditional titanium fixing elements, nor was any tissue damage connected with the surface of the plates. The results indicate the favorable properties of the titanium oxide ceramic surface.

Understanding complete oxidation of methane on spinel oxides at a molecular level

DOE PAGES

Tao, Franklin Feng; Shan, Jun-jun; Nguyen, Luan; ...

2015-08-04

It is crucial to develop a catalyst made of earth-abundant elements highly active for a complete oxidation of methane at a relatively low temperature. NiCo 2O 4 consisting of earth-abundant elements which can completely oxidize methane in the temperature range of 350-550 °C. Being a cost-effective catalyst, NiCo 2O 4 exhibits activity higher than precious-metal-based catalysts. Here we report that the higher catalytic activity at the relatively low temperature results from the integration of nickel cations, cobalt cations and surface lattice oxygen atoms/oxygen vacancies at the atomic scale. Finally, in situ studies of complete oxidation of methane on NiCo 2Omore » 4 and theoretical simulations show that methane dissociates to methyl on nickel cations and then couple with surface lattice oxygen atoms to form -CH 3O with a following dehydrogenation to -CH 2O; a following oxidative dehydrogenation forms CHO; CHO is transformed to product molecules through two different sub-pathways including dehydrogenation of OCHO and CO oxidation.« less

Disguised as a Sulfate Reducer: Growth of the Deltaproteobacterium Desulfurivibrio alkaliphilus by Sulfide Oxidation with Nitrate

PubMed Central

Thorup, Casper; Schramm, Andreas

2017-01-01

ABSTRACT This study demonstrates that the deltaproteobacterium Desulfurivibrio alkaliphilus can grow chemolithotrophically by coupling sulfide oxidation to the dissimilatory reduction of nitrate and nitrite to ammonium. Key genes of known sulfide oxidation pathways are absent from the genome of D. alkaliphilus. Instead, the genome contains all of the genes necessary for sulfate reduction, including a gene for a reductive-type dissimilatory bisulfite reductase (DSR). Despite this, growth by sulfate reduction was not observed. Transcriptomic analysis revealed a very high expression level of sulfate-reduction genes during growth by sulfide oxidation, while inhibition experiments with molybdate pointed to elemental sulfur/polysulfides as intermediates. Consequently, we propose that D. alkaliphilus initially oxidizes sulfide to elemental sulfur, which is then either disproportionated, or oxidized by a reversal of the sulfate reduction pathway. This is the first study providing evidence that a reductive-type DSR is involved in a sulfide oxidation pathway. Transcriptome sequencing further suggests that nitrate reduction to ammonium is performed by a novel type of periplasmic nitrate reductase and an unusual membrane-anchored nitrite reductase. PMID:28720728

Reduction in the Band Gap of Manganese-Doped Zinc Oxide: Role of the Oxidation State

NASA Astrophysics Data System (ADS)

Sharma, Sonia; Ramesh, Pranith; Swaminathan, P.

2015-12-01

Manganese-doped zinc oxide powders were synthesized by solid state reaction of the respective oxides. The high-temperature conditions were chosen such that multiple valence states of manganese were doped in the host zinc oxide lattice. Structural characterization was carried out to confirm the doping and to find the maximum amount of manganese that can be incorporated. Diffuse reflectance spectroscopy was used to measure the optical band gap of the doped sample and the lowering with respect to pure ZnO was attributed to the presence of higher oxidation states of manganese. The presence of these oxidation states was confirmed using x-ray photoelectron spectroscopy. The study shows that a solid state reaction is a viable route for synthesizing doped metal oxides with desired optical properties.

RECONDITIONING FUEL ELEMENTS

DOEpatents

Brandt, H.L.

1962-02-20

A process is given for decanning fuel elements that consist of a uranium core, an intermediate section either of bronze, silicon, Al-Si, and uranium silicide layers or of lead, Al-Si, and uranium silicide layers around said core, and an aluminum can bonded to said intermediate section. The aluminum can is dissolved in a solution of sodium hydroxide (9 to 20 wt%) and sodium nitrate (35 to 12 wt %), and the layers of the intermediate section are dissolved in a boiling sodium hydroxide solution of a minimum concentration of 50 wt%. (AEC) A method of selectively reducing plutonium oxides and the rare earth oxides but not uranium oxides is described which comprises placing the oxides in a molten solvent of zinc or cadmium and then adding metallic uranium as a reducing agent. (AEC)

Ni/metal hydride secondary element

DOEpatents

Bauerlein, Peter

2005-04-19

A Ni/metal hydride secondary element having a positive nickel hydroxide electrode, a negative electrode having a hydrogen storage alloy, and an alkaline electrolyte, the positive electrode, provided with a three-dimensional metallic conductive structure, also contains an aluminum compound which is soluble in the electrolyte, in addition to nickel hydroxide and cobalt oxide. The aluminum compound is aluminum hydroxide and/or aluminum oxide, and the mass of the aluminum compound which is present in the positive bulk material mixture is 0.1 to 2% by weight relative to the mass of the nickel hydroxide which is present. In combination with aluminum hydroxide or aluminum oxide, the positive electrode further contains lanthanoid oxidic compounds Y.sub.2 O.sub.3, La.sub.2 O.sub.3 and Ca(OH).sub.2, as well as mixtures of these compounds.

Potential Application of Silica Mineral from Dieng Mountain in Agriculture Sector to Control the Release Rate of Fertilizer Elements

NASA Astrophysics Data System (ADS)

Solihin; Mursito, Anggoro Tri; Dida, Eki N.; Erlangga, Bagus D.; Widodo

2017-07-01

Silica mineral, which comes along with geothermal fluid in Dieng, is a product of erosion, decomposition and dissolution of silicon oxide based mineral, which is followed by precipitation to form silica mineral. This silica cell structure is non crystalline, and it contains 85,60 % silicon oxide, 6.49 volatile elements, and also other oxide elements. Among the direct potential application of this silica is as raw material in slow release fertilizer. Silica in compacted slow release fertilizer is able control the release rate of fertilizer elements. Two type of slow release fertilizer has been made by using silica as the matrix in these slow release fertilizer. The first type is the mixing of ordinary solid fertilizer with Dieng silica, whereas the second one is the mixing of disposal leach water with Dieng silica. The release test shows that both of these modified fertilizers have slow release fertilizer characteristic. The release rate of fertilizer elements (magnesium, potassium, ammonium, and phosphate) can be significantly reduced. The addition of kaolin in the first type of slow release fertilizer makes the release rate of fertilizer elements can be more slowed down. Meanwhile in the second type of slow release fertilizer, the release rate is determined by ratio of silica/hydrogel. The lowest release rate is achieved by sample that has highest ratio of silica/hydrogel.

Synthesis of high T.sub.C superconducting coatings and patterns by melt writing and oxidation of metallic precursor alloys

DOEpatents

Gao, Wei; Vander Sande, John B.

1998-01-01

A method is provided for fabrication of superconducting oxides and superconducting oxide composites and for joining superconductors to other materials. A coating of a molten alloy containing the metallic elements of the oxide is applied to a substrate surface and oxidized to form the superconducting oxide. A material can be contacted to the molten alloy which is subsequently oxidized joining the material to the resulting superconducting oxide coating. Substrates of varied composition and shape can be coated or joined by this method.

Synthesis of high {Tc} superconducting coatings and patterns by melt writing and oxidation of metallic precursor alloys

DOEpatents

Gao, W.; Vander Sande, J.B.

1998-07-28

A method is provided for fabrication of superconducting oxides and superconducting oxide composites and for joining superconductors to other materials. A coating of a molten alloy containing the metallic elements of the oxide is applied to a substrate surface and oxidized to form the superconducting oxide. A material can be contacted to the molten alloy which is subsequently oxidized joining the material to the resulting superconducting oxide coating. Substrates of varied composition and shape can be coated or joined by this method. 5 figs.

Understanding the Intrinsic Electrochemistry of Ni-Rich Layered Cathodes

NASA Astrophysics Data System (ADS)

Sallis, Shawn

The demand for energy is continually increasing overtime and the key to meeting future demand in a sustainable way is with energy storage. Li-ion batteries employing layered transition metal oxide cathodes are one of the most technologically important energy storage technologies. However, current Li-ion batteries are unable to access their full theoretical capacity and suffer from performance limiting degradation over time partially originating from the cathode and partially from the interface with the electrolyte. Understanding the fundamental limitations of layered transition metal oxide cathodes requires a complete understanding of the surface and bulk of the materials in their most delithiated state. In this thesis, we employ LiNi0.8Co0.15Al 0.05O2 (NCA) as a model system for Ni-rich layered oxide cathodes. Unlike its parent compound, LiCoO2, NCA is capable of high states of delithiation with minimal structural transitions. Furthermore, commercially available NCA has little to no transition metals in the Li layer. X-ray spectroscopies are an ideal tool for studying cathodes at high states of delithiation due their elemental selectivity, range of probing depths, and sensitivity to both chemical and electronic state information. The oxidation state of the transition metals at the surface can be probed via X-ray photoelectron spectroscopy (XPS) while both bulk and surface oxidation states as well as changes in metal oxygen bonding can be probed using X-ray absorption spectroscopy (XAS). Using X-ray spectroscopy in tandem with electrochemical, transport and microscopy measurements of the same materials, the impedance growth with increasing delithiation was correlated with the formation of a disordered NiO phase on the surface of NCA which was precipitated by the release of oxygen. Furthermore, the surface degradation was strongly impacted by the type of Li salt used in the electrolyte, with the standard commercial salt LiPF6 suffering from exothermic decomposition at high voltages and temperatures. Substituting LiPF6with LiBF4 suppressed NCA surface degradation and the dissolution of the transition metals into the electrolyte which is responsible for the impedance growth. Even in the most extreme conditions (4.75V vs Li +/Li0 at 60 °C for > 100 hrs) the degradation (i.e. metal reduction) was restricted to the first 10-30 nm and no evidence of oxygen loss was observed in the bulk. However, the transition metal ions were found to cease oxidizing above 4.25 V vs Li+/Li0 despite it being possible to extract 20% more lithium. Using a newly developed high efficiency resonant inelastic x-ray scattering (RIXS) spectrometer to probe the O K-edge of NCA electrodes at various conditions, it was concluded that oxygen participates in the charge compensation at the highest states of delithiation instead of the transition metals. These results are intrinsic to the physical and electronic structure of NCA and appear general to the other layered transition metal oxides currently under consideration for use as cathodes in Li-ion batteries.

Solid oxide fuel cell with single material for electrodes and interconnect

DOEpatents

McPheeters, C.C.; Nelson, P.A.; Dees, D.W.

1994-07-19

A solid oxide fuel cell is described having a plurality of individual cells. A solid oxide fuel cell has an anode and a cathode with electrolyte disposed there between, and the anode, cathode and interconnect elements are comprised of substantially one material. 9 figs.

PRACTICAL APPLICATIONS FROM OBSERVATIONS OF MERCURY OXIDATION AND BINDING MECHANISMS

EPA Science Inventory

This paper describes a bench-scale program at the U.S. EPA. The goals of this program are to (a) isolate individual mechanisms of elemental mercury oxidation and oxidized mercury capture, (b) compete these mechanisms over a broad temperature range to determine which are dominant...