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Sample records for hafnium sulfides

  1. SEPARATING HAFNIUM FROM ZIRCONIUM

    DOEpatents

    Lister, B.A.J.; Duncan, J.F.

    1956-08-21

    A dilute aqueous solution of zirconyl chloride which is 1N to 2N in HCl is passed through a column of a cation exchange resin in acid form thereby absorbing both zirconium and associated hafnium impurity in the mesin. The cation exchange material with the absorbate is then eluted with aqueous sulfuric acid of a O.8N to 1.2N strength. The first portion of the eluate contains the zirconium substantially free of hafnium.

  2. Amphoteric Aqueous Hafnium Cluster Chemistry.

    PubMed

    Goberna-Ferrón, Sara; Park, Deok-Hie; Amador, Jenn M; Keszler, Douglas A; Nyman, May

    2016-05-17

    Selective dissolution of hafnium-peroxo-sulfate films in aqueous tetramethylammonium hydroxide enables extreme UV lithographic patterning of sub-10 nm HfO2 structures. Hafnium speciation under these basic conditions (pH>10), however, is unknown, as studies of hafnium aqueous chemistry have been limited to acid. Here, we report synthesis, crystal growth, and structural characterization of the first polynuclear hydroxo hafnium cluster isolated from base, [TMA]6 [Hf6 (μ-O2 )6 (μ-OH)6 (OH)12 ]⋅38 H2 O. The solution behavior of the cluster, including supramolecular assembly via hydrogen bonding is detailed via small-angle X-ray scattering (SAXS) and electrospray ionization mass spectrometry (ESI-MS). The study opens a new chapter in the aqueous chemistry of hafnium, exemplifying the concept of amphoteric clusters and informing a critical process in single-digit-nm lithography. PMID:27094575

  3. SEPARATING HAFNIUM FROM ZIRCONIUM

    DOEpatents

    Lister, B.A.J.; Duncan, J.F.; Hutcheon, J.M.

    1956-08-21

    Substantially complete separation of zirconium from hafnium may be obtained by elution of ion exchange material, on which compounds of the elements are adsorbed, with an approximately normal solution of sulfuric acid. Preferably the acid concentration is between 0.8 N amd 1.2 N, amd should not exceed 1.5 N;. Increasing the concentration of sulfate ion in the eluting solution by addition of a soluble sulfate, such as sodium sulfate, has been found to be advantageous. The preferred ion exchange materials are sulfonated polystyrene resins such as Dowex 50,'' and are preferably arranged in a column through which the solutions are passed.

  4. SEPARATION OF HAFNIUM FROM ZIRCONIUM

    DOEpatents

    Overholser, L.B.; Barton, C.J. Sr.; Ramsey, J.W.

    1960-05-31

    The separation of hafnium impurities from zirconium can be accomplished by means of organic solvent extraction. The hafnium-containing zirconium feed material is dissolved in an aqueous chloride solution and the resulting solution is contacted with an organic hexone phase, with at least one of the phases containing thiocyanate. The hafnium is extracted into the organic phase while zirconium remains in the aqueous phase. Further recovery of zirconium is effected by stripping the onganic phase with a hydrochloric acid solution and commingling the resulting strip solution with the aqueous feed solution. Hexone is recovered and recycled by means of scrubbing the onganic phase with a sulfuric acid solution to remove the hafnium, and thiocyanate is recovered and recycled by means of neutralizing the effluent streams to obtain ammonium thiocyanate.

  5. Hafnium germanium telluride

    PubMed Central

    Jang, Gyung-Joo; Yun, Hoseop

    2008-01-01

    The title hafnium germanium telluride, HfGeTe4, has been synthesized by the use of a halide flux and structurally characterized by X-ray diffraction. HfGeTe4 is isostructural with stoichiometric ZrGeTe4 and the Hf site in this compound is also fully occupied. The crystal structure of HfGeTe4 adopts a two-dimensional layered structure, each layer being composed of two unique one-dimensional chains of face-sharing Hf-centered bicapped trigonal prisms and corner-sharing Ge-centered tetra­hedra. These layers stack on top of each other to complete the three-dimensional structure with undulating van der Waals gaps. PMID:21202163

  6. Ablation Resistant Zirconium and Hafnium Ceramics

    NASA Technical Reports Server (NTRS)

    Bull, Jeffrey (Inventor); White, Michael J. (Inventor); Kaufman, Larry (Inventor)

    1998-01-01

    High temperature ablation resistant ceramic composites have been made. These ceramics are composites of zirconium diboride and zirconium carbide with silicon carbide, hafnium diboride and hafnium carbide with silicon carbide and ceramic composites which contain mixed diborides and/or carbides of zirconium and hafnium. along with silicon carbide.

  7. Zirconium and hafnium in meteorites

    NASA Technical Reports Server (NTRS)

    Ehmann, W. D.; Chyi, L. L.

    1974-01-01

    The abundances of zirconium and hafnium have been determined in nine stony meteorites by a new, precise neutron-activation technique. The Zr/Hf abundance ratios for the chondrites vary in a rather narrow range, consistent with previously published observations from our group. Replicate analyses of new, carefully selected clean interior samples of the Cl chondrite Orgueil yield mean zirconium and hafnium abundances of 5.2 and 0.10 ppm, respectively. These abundances are lower than we reported earlier for two Cl chondrite samples which we now suspect may have suffered contamination. The new Cl zirconium and hafnium abundances are in closer agreement with predictions based on theories of nucleosynthesis than the earlier data.

  8. Hafnium radioisotope recovery from irradiated tantalum

    DOEpatents

    Taylor, Wayne A.; Jamriska, David J.

    2001-01-01

    Hafnium is recovered from irradiated tantalum by: (a) contacting the irradiated tantalum with at least one acid to obtain a solution of dissolved tantalum; (b) combining an aqueous solution of a calcium compound with the solution of dissolved tantalum to obtain a third combined solution; (c) precipitating hafnium, lanthanide, and insoluble calcium complexes from the third combined solution to obtain a first precipitate; (d) contacting the first precipitate of hafnium, lanthanide and calcium complexes with at least one fluoride ion complexing agent to form a fourth solution; (e) selectively adsorbing lanthanides and calcium from the fourth solution by cationic exchange; (f) separating fluoride ion complexing agent product from hafnium in the fourth solution by adding an aqueous solution of ferric chloride to obtain a second precipitate containing the hafnium and iron; (g) dissolving the second precipitate containing the hafnium and iron in acid to obtain an acid solution of hafnium and iron; (h) selectively adsorbing the iron from the acid solution of hafnium and iron by anionic exchange; (i) drying the ion exchanged hafnium solution to obtain hafnium isotopes. Additionally, if needed to remove residue remaining after the product is dried, dissolution in acid followed by cation exchange, then anion exchange, is performed.

  9. Hafnium carbide formation in oxygen deficient hafnium oxide thin films

    NASA Astrophysics Data System (ADS)

    Rodenbücher, C.; Hildebrandt, E.; Szot, K.; Sharath, S. U.; Kurian, J.; Komissinskiy, P.; Breuer, U.; Waser, R.; Alff, L.

    2016-06-01

    On highly oxygen deficient thin films of hafnium oxide (hafnia, HfO2-x) contaminated with adsorbates of carbon oxides, the formation of hafnium carbide (HfCx) at the surface during vacuum annealing at temperatures as low as 600 °C is reported. Using X-ray photoelectron spectroscopy the evolution of the HfCx surface layer related to a transformation from insulating into metallic state is monitored in situ. In contrast, for fully stoichiometric HfO2 thin films prepared and measured under identical conditions, the formation of HfCx was not detectable suggesting that the enhanced adsorption of carbon oxides on oxygen deficient films provides a carbon source for the carbide formation. This shows that a high concentration of oxygen vacancies in carbon contaminated hafnia lowers considerably the formation energy of hafnium carbide. Thus, the presence of a sufficient amount of residual carbon in resistive random access memory devices might lead to a similar carbide formation within the conducting filaments due to Joule heating.

  10. Silver-hafnium braze alloy

    DOEpatents

    Stephens, Jr., John J.; Hosking, F. Michael; Yost, Frederick G.

    2003-12-16

    A binary allow braze composition has been prepared and used in a bonded article of ceramic-ceramic and ceramic-metal materials. The braze composition comprises greater than approximately 95 wt % silver, greater than approximately 2 wt % hafnium and less than approximately 4.1 wt % hafnium, and less than approximately 0.2 wt % trace elements. The binary braze alloy is used to join a ceramic material to another ceramic material or a ceramic material, such as alumina, quartz, aluminum nitride, silicon nitride, silicon carbide, and mullite, to a metal material, such as iron-based metals, cobalt-based metals, nickel-based metals, molybdenum-based metals, tungsten-based metals, niobium-based metals, and tantalum-based metals. A hermetic bonded article is obtained with a strength greater than 10,000 psi.

  11. Ferroelectricity in undoped hafnium oxide

    NASA Astrophysics Data System (ADS)

    Polakowski, Patrick; Müller, Johannes

    2015-06-01

    We report the observation of ferroelectric characteristics in undoped hafnium oxide thin films in a thickness range of 4-20 nm. The undoped films were fabricated using atomic layer deposition (ALD) and embedded into titanium nitride based metal-insulator-metal (MIM) capacitors for electrical evaluation. Structural as well as electrical evidence for the appearance of a ferroelectric phase in pure hafnium oxide was collected with respect to film thickness and thermal budget applied during titanium nitride electrode formation. Using grazing incidence X-Ray diffraction (GIXRD) analysis, we observed an enhanced suppression of the monoclinic phase fraction in favor of an orthorhombic, potentially, ferroelectric phase with decreasing thickness/grain size and for a titanium nitride electrode formation below crystallization temperature. The electrical presence of ferroelectricity was confirmed using polarization measurements. A remanent polarization Pr of up to 10 μC cm-2 as well as a read/write endurance of 1.6 × 105 cycles was measured for the pure oxide. The experimental results reported here strongly support the intrinsic nature of the ferroelectric phase in hafnium oxide and expand its applicability beyond the doped systems.

  12. Ferroelectricity in undoped hafnium oxide

    SciTech Connect

    Polakowski, Patrick; Müller, Johannes

    2015-06-08

    We report the observation of ferroelectric characteristics in undoped hafnium oxide thin films in a thickness range of 4–20 nm. The undoped films were fabricated using atomic layer deposition (ALD) and embedded into titanium nitride based metal-insulator-metal (MIM) capacitors for electrical evaluation. Structural as well as electrical evidence for the appearance of a ferroelectric phase in pure hafnium oxide was collected with respect to film thickness and thermal budget applied during titanium nitride electrode formation. Using grazing incidence X-Ray diffraction (GIXRD) analysis, we observed an enhanced suppression of the monoclinic phase fraction in favor of an orthorhombic, potentially, ferroelectric phase with decreasing thickness/grain size and for a titanium nitride electrode formation below crystallization temperature. The electrical presence of ferroelectricity was confirmed using polarization measurements. A remanent polarization P{sub r} of up to 10 μC cm{sup −2} as well as a read/write endurance of 1.6 × 10{sup 5} cycles was measured for the pure oxide. The experimental results reported here strongly support the intrinsic nature of the ferroelectric phase in hafnium oxide and expand its applicability beyond the doped systems.

  13. Formulation and method for preparing gels comprising hydrous hafnium oxide

    DOEpatents

    Collins, Jack L; Hunt, Rodney D; Montgomery, Frederick C

    2013-08-06

    Formulations useful for preparing hydrous hafnium oxide gels contain a metal salt including hafnium, an acid, an organic base, and a complexing agent. Methods for preparing gels containing hydrous hafnium oxide include heating a formulation to a temperature sufficient to induce gel formation, where the formulation contains a metal salt including hafnium, an acid, an organic base, and a complexing agent.

  14. Oxidation of Hafnium and Diffusion of Hafnium Atoms in Hexagonal Close-Packed Hafnium; Microscopic Investigations by Perturbed Angular Correlations

    NASA Astrophysics Data System (ADS)

    Dey, Chandi C.

    2012-11-01

    Time-differential perturbed angular correlation (TDPAC) studies in hafnium metal (~5%Zr) have been carried out at different temperatures. It is found that hafnium metal on heating at 873 K continuously for two days in air, transforms partially and abruptly to HfO2 while no component of oxide has been observed for heating up to 773 K and during initial heating at 873 K for 1 day. This result is strikingly different to that expected from the Arrhenius theory. Also, a strong nuclear relaxation effect has been observed at 873 K due to rapid fluctuation of hafnium atoms in hexagonal closepacked (hcp) hafnium. At this temperature, ~ 5% probe nuclei experience static perturbation due to monoclinic HfO2, ~ 50% experience fluctuating interaction, and ~ 5% produce static defect configuration of hcp hafnium. With lowering of temperature, defect configurations of hafnium increase at the cost of fluctuating interaction. An almost total fluctuating interaction observed in hcp hafnium at a temperature much lower than its melting point is another interesting phenomenon.

  15. Thermal Expansion of Hafnium Carbide

    NASA Technical Reports Server (NTRS)

    Grisaffe, Salvatore J.

    1960-01-01

    Since hafnium carbide (HfC) has a melting point of 7029 deg. F, it may have many high-temperature applications. A literature search uncovered very little information about the properties of HfC, and so a program was initiated at the Lewis Research Center to determine some of the physical properties of this material. This note presents the results of the thermal expansion investigation. The thermal-expansion measurements were made with a Gaertner dilatation interferometer calibrated to an accuracy of +/- 1 deg. F. This device indicates expansion by the movement of fringes produced by the cancellation and reinforcement of fixed wave-length light rays which are reflected from the surfaces of two parallel quartz glass disks. The test specimens which separate these disks are three small cones, each approximately 0.20 in. high.

  16. Selenium Sulfide

    MedlinePlus

    Selenium sulfide, an anti-infective agent, relieves itching and flaking of the scalp and removes the dry, ... Selenium sulfide comes in a lotion and is usually applied as a shampoo. As a shampoo, selenium ...

  17. Recovery of hafnium values from loaded extraction solvent

    SciTech Connect

    Abodishish, H.A.

    1989-10-10

    This patent describes an improvement in a process for recovering high purity hafnium hydroxide from a methyl isobutyl ketone organic solvent that is substantially free of sulfate ions and contains hafnium thiocyanate and thiocyanic acid. The improvement comprising reacting the organic solvent with ammonia to produce a reaction product in the form of a methyl isobutyl ketone organic solvent that is substantially free of sulfate ions and contains ammonium thiocyanite solution and hafnium hydroxide; separating the constituents of the reaction product in accordance with their respective specific gravities to produce a hafnium hydroxide sludge as one of the separation products; and removing the liquid component of the sludge to yield a high purity hafnium hydroxide ready for calcination to hafnium oxide.

  18. Percolation conductivity in hafnium sub-oxides

    SciTech Connect

    Islamov, D. R. Gritsenko, V. A.; Cheng, C. H.; Chin, A.

    2014-12-29

    In this study, we demonstrated experimentally that formation of chains and islands of oxygen vacancies in hafnium sub-oxides (HfO{sub x}, x < 2) leads to percolation charge transport in such dielectrics. Basing on the model of Éfros-Shklovskii percolation theory, good quantitative agreement between the experimental and theoretical data of current-voltage characteristics was achieved. Based on the percolation theory suggested model shows that hafnium sub-oxides consist of mixtures of metallic Hf nanoscale clusters of 1–2 nm distributed onto non-stoichiometric HfO{sub x}. It was shown that reported approach might describe low resistance state current-voltage characteristics of resistive memory elements based on HfO{sub x}.

  19. Percolation conductivity in hafnium sub-oxides

    NASA Astrophysics Data System (ADS)

    Islamov, D. R.; Gritsenko, V. A.; Cheng, C. H.; Chin, A.

    2014-12-01

    In this study, we demonstrated experimentally that formation of chains and islands of oxygen vacancies in hafnium sub-oxides (HfOx, x < 2) leads to percolation charge transport in such dielectrics. Basing on the model of Éfros-Shklovskii percolation theory, good quantitative agreement between the experimental and theoretical data of current-voltage characteristics was achieved. Based on the percolation theory suggested model shows that hafnium sub-oxides consist of mixtures of metallic Hf nanoscale clusters of 1-2 nm distributed onto non-stoichiometric HfOx. It was shown that reported approach might describe low resistance state current-voltage characteristics of resistive memory elements based on HfOx.

  20. Selenium Sulfide

    MedlinePlus

    Selenium sulfide comes in a lotion and is usually applied as a shampoo. As a shampoo, selenium sulfide usually is used twice a week for the first ... it is irritating. Rinse off all of the lotion.Do not use this medication on children younger ...

  1. Process of precipitating zirconium or hafnium from spent pickling solutions

    SciTech Connect

    Aguilar, C.L.; Walker, R.G.

    1991-12-31

    This patent describes a process for regenerating a spent, fluoride-containing pickle solution used in the pickling of zirconium or hafnium metal or their alloys. It comprises adding to the spent pickle solution a sufficient amount of sodium sulfate to precipitate sodium zirconium or hafnium fluoride.

  2. Assessing hafnium on hafnia as an oxygen getter

    SciTech Connect

    O'Hara, Andrew; Demkov, Alexander A.; Bersuker, Gennadi

    2014-05-14

    Hafnium dioxide or hafnia is a wide band gap dielectric used in a range of electronic applications from field effect transistors to resistive memory. In many of these applications, it is important to maintain control over oxygen stoichiometry, which can be realized in practice by using a metal layer, specifically hafnium, to getter oxygen from the adjacent dielectric. In this paper, we employ density functional theory to study the thermodynamic stability of an interface between (100)-oriented monoclinic hafnia and hafnium metal. The nudged elastic band method is used to calculate the energy barrier for migration of oxygen from the oxide to the metal. Our investigation shows that the presence of hafnium lowers the formation energy of oxygen vacancies in hafnia, but more importantly the oxidation of hafnium through the migration of oxygen from hafnia is favored energetically.

  3. Selenium sulfide

    Integrated Risk Information System (IRIS)

    Selenium sulfide ; CASRN 7446 - 34 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  4. Hydrogen sulfide

    Integrated Risk Information System (IRIS)

    Hydrogen sulfide ; 7783 - 06 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effec

  5. Carbonyl sulfide

    Integrated Risk Information System (IRIS)

    Carbonyl sulfide ; CASRN 463 - 58 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  6. Uranium-preextraction in zirconium/hafnium separations processs

    SciTech Connect

    Feuling, R.J.

    1990-04-03

    This patent describes an improvement in a process for recovering zirconium values from uranium containing zircon ore. The process comprising a fluidized bed carbochlorination of the zircon ore at 800{degrees}--1250{degrees} C., producing a relatively impure, hafnium-containing zirconium tetrachloride stream and by-product silicon tetrachloride, which silicon tetrachloride by-product is separated by differential condensation, and wherein uranium chloride is volatilized at the ore chlorinator temperature and follows as an impurity in the zirconium-hafnium tetrachloride stream, mixing the zirconium-hafnium tetrachloride with water to produce a zirconium-hafnium oxychloride solution, and removing iron impurities by liquid--liquid iron extraction with a methyl isobutyl ketone extractant.

  7. Hafnium stainless steel absorber rod for control rod

    SciTech Connect

    Charnley, J.E.; Cearley, J.E.; Dixon, R.C.; Izzo, K.R.; Aiello, L.L.

    1989-08-01

    This patent describes an improvement in a control rod having a stainless steel body for enclosing a neutron absorbing poison, the control rod having movement along an axial direction for insertion into and out of a nuclear reactor for controlling a nuclear reaction. The improvement comprising: a piece of hafnium; a piece of stainless steel joined to the hafnium by a thin diffusion interface created by friction welding. The hafnium and the stainless steel oriented serially in the axial direction with the thin diffusion interface disposed normal to the axial direction of the control rod movement; means for confining the hafnium to movement along the axial direction with the control rod; and means for attaching the piece of stainless steel to the remaining portion of the control rod to load the weld therebetween under compression or tension during the control rod movement. Whereby the thin diffusion interface is loaded in tension or compression only upon dynamic movement of the control rod.

  8. Structure of copper-hafnium multilayers

    SciTech Connect

    Clemens, B.M.; Stec, J.P.; Heald, S.M.; Tranquada, J.M.

    1986-01-01

    The structure of copper-hafnium multilayers has been studied as a function of composition modulation wavelength by x-ray diffraction and EXAFS. Sputter deposited samples were produced with composition modulation wavelengths of 1/2, 5, 7, 10, 14, and 20 close packed planes of each constituent per layer. The structure evolved anisotropically from amorphous to crystalline with increasing composition modulation wavelength, with crystalline order first appearing in the growth direction in the 7 monolayer sample. Structural coherence in the growth direction was not observed to extend beyond one elemental layer in any sample, and evidence for a disordered interfacial layer was observed by EXAFS for all samples. Small angle x-ray diffraction showed strong composition modulation for all but the 1/2 monolayer sample. The amorphous interface is the result of reaction during deposition similar to the solid state reaction observed in other systems such as nickel-zirconium.

  9. 40 CFR 421.330 - Applicability: Description of the primary zirconium and hafnium subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... primary zirconium and hafnium subcategory. 421.330 Section 421.330 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Zirconium and Hafnium Subcategory § 421.330 Applicability: Description of the primary zirconium and hafnium subcategory. The provisions of this subpart are applicable to discharges...

  10. 40 CFR 471.90 - Applicability; description of the zirconium-hafnium forming subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... zirconium-hafnium forming subcategory. 471.90 Section 471.90 Protection of Environment ENVIRONMENTAL... METAL POWDERS POINT SOURCE CATEGORY Zirconium-Hafnium Forming Subcategory § 471.90 Applicability; description of the zirconium-hafnium forming subcategory. This subpart applies to discharges of pollutants...

  11. 40 CFR 471.90 - Applicability; description of the zirconium-hafnium forming subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... zirconium-hafnium forming subcategory. 471.90 Section 471.90 Protection of Environment ENVIRONMENTAL... POINT SOURCE CATEGORY Zirconium-Hafnium Forming Subcategory § 471.90 Applicability; description of the zirconium-hafnium forming subcategory. This subpart applies to discharges of pollutants to waters of...

  12. 40 CFR 471.90 - Applicability; description of the zirconium-hafnium forming subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... zirconium-hafnium forming subcategory. 471.90 Section 471.90 Protection of Environment ENVIRONMENTAL... METAL POWDERS POINT SOURCE CATEGORY Zirconium-Hafnium Forming Subcategory § 471.90 Applicability; description of the zirconium-hafnium forming subcategory. This subpart applies to discharges of pollutants...

  13. 40 CFR 421.330 - Applicability: Description of the primary zirconium and hafnium subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... primary zirconium and hafnium subcategory. 421.330 Section 421.330 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Zirconium and Hafnium Subcategory § 421.330 Applicability: Description of the primary zirconium and hafnium subcategory. The provisions of this subpart are applicable to discharges...

  14. 40 CFR 471.90 - Applicability; description of the zirconium-hafnium forming subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... zirconium-hafnium forming subcategory. 471.90 Section 471.90 Protection of Environment ENVIRONMENTAL... METAL POWDERS POINT SOURCE CATEGORY Zirconium-Hafnium Forming Subcategory § 471.90 Applicability; description of the zirconium-hafnium forming subcategory. This subpart applies to discharges of pollutants...

  15. 40 CFR 471.90 - Applicability; description of the zirconium-hafnium forming subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... zirconium-hafnium forming subcategory. 471.90 Section 471.90 Protection of Environment ENVIRONMENTAL... POINT SOURCE CATEGORY Zirconium-Hafnium Forming Subcategory § 471.90 Applicability; description of the zirconium-hafnium forming subcategory. This subpart applies to discharges of pollutants to waters of...

  16. 40 CFR 421.330 - Applicability: Description of the primary zirconium and hafnium subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... primary zirconium and hafnium subcategory. 421.330 Section 421.330 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Zirconium and Hafnium Subcategory § 421.330 Applicability: Description of the primary zirconium and hafnium subcategory. The provisions of this subpart are applicable to discharges...

  17. Hafnium isotope variations in oceanic basalts

    NASA Technical Reports Server (NTRS)

    Patchett, P. J.; Tatsumoto, M.

    1980-01-01

    Hafnium isotope ratios generated by the beta(-) decay of Lu-176 are investigated in volcanic rocks derived from the suboceanic mantle. Hf-176/Hf-177 and Lu/Hf ratios were determined to precisions of 0.01-0.04% and 0.5%, respectively, by routine, low-blank chemistry. The Hf-176/Hf-177 ratio is found to be positively correlated with the Nd-143/Nd-144 ratio and negatively correlated with the Sr-87/Sr-86 and Pb-206/Pb-204 ratios, and to increase southwards along the Iceland-Reykjanes ridge traverse. An approximate bulk earth Hf-176/Hf-177 ratio of 0.28295 is inferred from the bulk earth Nd-143/Nd-144 ratio, which requires a bulk earth Lu/Hf ratio of 0.25, similar to the Juvinas eucrite. Midocean ridge basalts are shown to account for 60% of the range of Hf isotope ratios, and it is suggested that Lu-Hf fractionation is decoupled from Sm-Nd and Rb-Sr fractionation in very trace-element-depleted source regions as a result of partial melting.

  18. Ground-state structures of Hafnium clusters

    SciTech Connect

    Ng, Wei Chun; Yoon, Tiem Leong; Lim, Thong Leng

    2015-04-24

    Hafnium (Hf) is a very large tetra-valence d-block element which is able to form relatively long covalent bond. Researchers are interested to search for substitution to silicon in the semi-conductor industry. We attempt to obtain the ground-state structures of small Hf clusters at both empirical and density-functional theory (DFT) levels. For calculations at the empirical level, charge-optimized many-body functional potential (COMB) is used. The lowest-energy structures are obtained via a novel global-minimum search algorithm known as parallel tempering Monte-Carlo Basin-Hopping and Genetic Algorithm (PTMBHGA). The virtue of using COMB potential for Hf cluster calculation lies in the fact that by including the charge optimization at the valence shells, we can encourage the formation of proper bond hybridization, and thus getting the correct bond order. The obtained structures are further optimized using DFT to ensure a close proximity to the ground-state.

  19. Some properties of RF sputtered hafnium nitride coatings

    NASA Technical Reports Server (NTRS)

    Aron, P. R.; Grill, A.

    1982-01-01

    Hafnium nitride coatings were deposited by reactive RF sputtering from a hafnium target in nitrogen and argon gas mixtures. The rate of deposition, composition, electrical resistivity and complex index of refraction were investigated as a function of target substrate distance and the fraction nitrogen, (fN2) in the sputtering atmosphere. The relative composition of the coatings is independent on fN2 for values above 0.1. The electric resistivity of the hafnium nitride films changes over 8 orders of magnitude when fN2 changes from 0.10 to 0.85. The index of refraction is almost constant at 2.8(1-0.3i) up to fN2 = 0.40 then decreases to 2.1(1 - 0.01i) for higher values of fN2.

  20. Sulfide chemiluminescence detection

    DOEpatents

    Spurlin, Stanford R.; Yeung, Edward S.

    1985-01-01

    A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

  1. Sulfide chemiluminescence detection

    DOEpatents

    Spurlin, S.R.; Yeung, E.S.

    1985-11-26

    A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

  2. Mineral resource of the month: zirconium and hafnium

    USGS Publications Warehouse

    Gambogi, Joseph

    2007-01-01

    Zirconium and hafnium are corrosion-resistant metals that are grouped in the same family as titanium on the periodic table. The two elements commonly occur in oxide and silicate minerals and have significant economic importance in everything from ink, ceramics and golf shoes to nuclear fuel rods.

  3. Article having an improved platinum-aluminum-hafnium protective coating

    NASA Technical Reports Server (NTRS)

    Nagaraj, Bangalore Aswatha (Inventor); Williams, Jeffrey Lawrence (Inventor)

    2005-01-01

    An article protected by a protective coating has a substrate and a protective coating having an outer layer deposited upon the substrate surface and a diffusion zone formed by interdiffusion of the outer layer and the substrate. The protective coating includes platinum, aluminum, no more than about 2 weight percent hafnium, and substantially no silicon. The outer layer is substantially a single phase.

  4. Discovery of gallium, germanium, lutetium, and hafnium isotopes

    SciTech Connect

    Gross, J.L.; Thoennessen, M.

    2012-09-15

    Currently, twenty-eight gallium, thirty-one germanium, thirty-five lutetium, and thirty-six hafnium isotopes have been observed and the discovery of these isotopes is described here. For each isotope a brief synopsis of the first refereed publication, including the production and identification method, is presented.

  5. Corrosion and tribocorrosion of hafnium in simulated body fluids.

    PubMed

    Rituerto Sin, J; Neville, A; Emami, N

    2014-08-01

    Hafnium is a passive metal with good biocompatibility and osteogenesis, however, little is known about its resistance to wear and corrosion in biological environments. The corrosion and tribocorrosion behavior of hafnium and commercially pure (CP) titanium in simulated body fluids were investigated using electrochemical techniques. Cyclic polarization scans and open circuit potential measurements were performed in 0.9% NaCl solution and 25% bovine calf serum solution to assess the effect of organic species on the corrosion behavior of the metal. A pin-on-plate configuration tribometer and a three electrode electrochemical cell were integrated to investigate the tribocorrosion performance of the studied materials. The results showed that hafnium has good corrosion resistance. The corrosion density currents measured in its passive state were lower than those measured in the case of CP titanium; however, it showed a higher tendency to suffer from localized corrosion, which was more acute when imperfections were present on the surface. The electrochemical breakdown of the oxide layer was retarded in the presence of proteins. Tribocorrosion tests showed that hafnium has the ability to quickly repassivate after the oxide layer was damaged; however, it showed higher volumetric loss than CP titanium in equivalent wear-corrosion conditions. © 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 102B: 1157-1164, 2014. PMID:24376175

  6. Hafnium Resonance Parameter Analysis Using Neutron Capture and Transmission Experiments

    SciTech Connect

    MJ Trbovich; DP Barry; RE Slovacck; Y Danon; RC Block; JA Burke; NJ Drindak; G Leinweber; RV Ballad

    2004-10-13

    The focus of this work is to determine resonance parameters for stable hafnium isotopes in the 0.005-200 eV region, with special emphasis on the overlapping {sup 176}Hf and {sup 178}Hf resonances near 8 eV. The large neutron cross section of hafnium, combined with its corrosion resistance and excellent mechanical properties, make it a useful material for controlling nuclear reactions. Experiments measuring neutron capture and transmission were performed at the Rensselaer Polytechnic Institute (RPI) electron linear accelerator (LINAC) using the time of flight method. {sup 6}Li glass scintillation detectors were used for transmission experiments at flight path lengths of 15 and 25 m. Capture experiments were done using a sixteen section NaI(Tl) multiplicity detector at a flight path length of 25 m. These experiments utilized various thicknesses of metallic and isotopically-enriched liquid samples. The liquid samples were designed to provide information on the {sup 176}Hf and {sup 178}Hf contributions to the 8 eV doublet without saturation. Data analysis was done using the R-matrix Bayesian code SAMMY version M6 beta. SAMMY is able to account for experimental resolution effects for each of the experimental setups at the RPI LINAC, and also can correct for multiple scattering effects in neutron capture yield data. The combined capture and transmission data analysis yielded resonance parameters for all hafnium isotopes from 0.005-200 eV. Resonance integrals were calculated along with errors for each hafnium isotope using the NJOY [1] and INTER [2] codes. The isotopic resonance integrals calculated were significantly different than previously published values; however the calculated elemental hafnium resonance integral changed very little.

  7. Hafnium Resonance Parameter Analysis using Neutron Capture and Transmission Experiments

    SciTech Connect

    Trbovich, Michael J.; Barry, Devin P.; Burke, John A.; Drindak, Noel J.; Leinweber, Greg; Ballad, Robert V.; Slovacek, Rudy E.; Danon, Yaron; Block, Robert C.

    2005-05-24

    The focus of this work is to determine resonance parameters for stable hafnium isotopes in the 0.005-200 eV region, with special emphasis on the overlapping 176Hf and 178Hf resonances near 8 eV. The large neutron cross section of hafnium, combined with its corrosion resistance and excellent mechanical properties, make it a useful material for controlling nuclear reactions.Experiments measuring neutron capture and transmission were performed at the Rensselaer Polytechnic Institute (RPI) electron linear accelerator (LINAC) using the time of flight method. 6Li glass scintillation detectors were used for transmission experiments at flight path lengths of 15 and 25 m. Capture experiments were done using a sixteen-section NaI(Tl) multiplicity detector at a flight path length of 25 m. These experiments utilized various thicknesses of metallic and isotopically enriched liquid samples. The liquid samples were designed to provide information on the 176Hf and 178Hf contributions to the 8-eV doublet without saturation.Data analysis was done using the R-matrix Bayesian code SAMMY version M6 beta. SAMMY is able to account for experimental resolution effects for each of the experimental setups at the RPI LINAC, and also can correct for multiple scattering effects in neutron capture yield data. The combined capture and transmission data analysis yielded resonance parameters for all hafnium isotopes from 0.005-200 eV. Resonance integrals were calculated along with errors for each hafnium isotope using the NJOY and INTER codes. The isotopic resonance integrals calculated were significantly different than previously published values; however the calculated elemental hafnium resonance integral changed very little.

  8. Method of purifying zirconium tetrachloride and hafnium tetrachloride in a vapor stream

    SciTech Connect

    Snyder, T.S.; Stolz, R.A.

    1992-04-07

    This patent describes a method of purifying zirconium tetrachloride and hafnium tetrachloride in a vapor stream from a sand chlorinator in which the silicon and metals present in sand fed to the chlorinator are converted to chlorides at temperatures over about 800{degrees} C. It comprises cooling a vapor stream from a sand chlorinator, the vapor stream containing principally silicon tetrachloride, zirconium tetrachloride, and hafnium tetrachloride contaminated with ferric chloride, to a temperature of from about 335{degrees} C to about 600{degrees} C; flowing the vapor stream through a gaseous diffusion separative barrier to produce a silicon tetrachloride-containing vapor stream concentrated in zirconium tetrachloride and hafnium tetrachloride and a silicon tetrachloride-containing vapor stream depleted in zirconium tetrachloride and hafnium tetrachloride; adsorbing the ferric chloride in the separative barrier; and recovering the silicon tetrachloride stream concentrated in zirconium tetrachloride and hafnium tetrachloride separately from the silicon tetrachloride stream depleted in zirconium tetrachloride and hafnium tetrachloride.

  9. Hafnium Resonance Parameter Analysis Using Neutron Capture and Transmission Experiments

    SciTech Connect

    Trbovich, M J; Barry, D P; Slovacek, R E; Danon, Y; Block, R C; Francis, N C; Lubert, M; Burke, J A; Drindak, N J; Lienweber, G; Ballad, R

    2007-02-06

    The focus of this work is to determine the resonance parameters for stable hafnium isotopes in the 0.005 - 200 eV region, with special emphasis on the overlapping {sup 176}Hf and {sup 178}Hf resonances near 8 eV. Accurate hafnium cross sections and resonance parameters are needed in order to quantify the effects of hafnium found in zirconium, a metal commonly used in reactors. The accuracy of the cross sections and the corresponding resonance parameters used in current nuclear analysis tools are rapidly becoming the limiting factor in reducing the overall uncertainty on reactor physics calculations. Experiments measuring neutron capture and transmission are routinely performed at the Rensselaer Polytechnic Institute (RPI) LINAC using the time-of flight technique. {sup 6}Li glass scintillation detectors were used for transmission experiments at flight path lengths of 15 and 25 m, respectively. Capture experiments were performed using a sixteen section NaI multiplicity detector at a flight path length of 25 m. These experiments utilized several thicknesses of metallic and isotope-enriched liquid Hf samples. The liquid Hf samples were designed to provide information on the {sup 176}Hf and {sup 178}Hf contributions to the 8 eV doublet without saturation. Data analyses were performed using the R-matrix Bayesian code SAMMY. A combined capture and transmission data analysis yielded resonance parameters for all hafnium isotopes from 0.005 - 200 eV. Additionally, resonance integrals were calculated, along with errors for each hafnium isotope, using the NJOY and INTER codes. The isotopic resonance integrals calculated were significantly different than previous values. The {sup 176}Hf resonance integral, based on this work, is approximately 73% higher than the ENDF/B-VI value. This is due primarily to the changes to resonance parameters in the 8 eV resonance, the neutron width presented in this work is more than twice that of the previous value. The calculated elemental

  10. Cadmium sulfide membranes

    DOEpatents

    Spanhel, Lubomir; Anderson, Marc A.

    1992-07-07

    A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

  11. Cadmium sulfide membranes

    DOEpatents

    Spanhel, Lubomir; Anderson, Marc A.

    1991-10-22

    A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

  12. Synthesis of Hafnium-Based Ceramic Materials for Ultra-High Temperature Aerospace Applications

    NASA Technical Reports Server (NTRS)

    Johnson, Sylvia; Feldman, Jay

    2004-01-01

    This project involved the synthesis of hafnium (Hf)-based ceramic powders and Hf-based precursor solutions that were suitable for preparation of Hf-based ceramics. The Hf-based ceramic materials of interest in this project were hafnium carbide (with nominal composition HE) and hafnium dioxide (HfO2). The materials were prepared at Georgia Institute of Technology and then supplied to research collaborators Dr. Sylvia Johnson and Dr. Jay Feldman) at NASA Ames Research Center.

  13. Alternative Processing of High Temperature Hafnium and Zirconium Based Materials

    NASA Technical Reports Server (NTRS)

    Gasch, Matthew; Gusman, Michael; Ellerby, Don; Irby, Edward; Johnson, Sylvia M.

    2003-01-01

    The behavior of refractory hafnium and zirconium based materials are being investigated at NASA Ames as part of ongoing research aimed at developing superior heat resistant materials for aerospace applications. Hafnium and zirconium diboride based materials have shown high temperature capabilities in simulated reentry environments indicating that these materials may successfully operate as reusable oxidation resistant components for leading edge applications. Due to the refractory nature of these materials, processing of fine-grained uniform microstructures poses a number of challenges. To better understand the process-property-microstructure relationship, processing of these materials has been carried out with conventional hot pressing in addition to the novel approach of Spark Plasma Sintering (SPS). The two processing methods are compared and contrasted in an evaluation of the sintering behavior of high temperature diboride based materials and preliminary physical and mechanical properties are presented.

  14. Electrochemical Synthesis of Niobium-Hafnium Coatings in Molten Salts

    NASA Astrophysics Data System (ADS)

    Kuznetsov, Sergey A.; Kuznetsova, Svetlana V.

    2007-08-01

    Graphite is widely used in technology because of its unique properties. A drawback of graphite is its low heat resistance in oxidizing atmospheres. To increase its heat resistance, Nb-Hf protective coatings were synthesized. Electrodeposition of niobium coatings on graphite with subsequent precise surface alloying of niobium with hafnium was studied. Electrochemical synthesis of Nb-Hf coatings from molten salt systems containing compounds of niobium and hafnium was used too. It was shown that Nb-Hf coatings with a planar growing front can be obtained if the concentration and therefore the limiting current density of the more electropositive component Nb is kept low. Nb-Hf coatings with a thickness of 20 - 30 μm have been obtained in this way from an NaCl-KCl-K2NbF7 (1 wt%)-K2HfF6 (10 wt%)-NaF (5 wt%) melt, above the limiting current density of niobium deposition.

  15. Process for producing high purity zirconium and hafnium

    SciTech Connect

    Kwon, Y.J.

    1987-05-26

    An improved process is described for producing zirconium or hafnium. The process is of the type wherein a tetrachloride of zirconium or hafnium is reduced by magnesium and the resulting metal is subjected to a distillation treatment. The improvement comprises: introducing magnesium chloride into a combination reduction-distillation vessel. An inner liner with at least one bottom drain opening with the drain opening providing fluid communication between the vessel and the liner. The magnesium chloride is added in a quantity to fill the vessel and the inner liner to a level above the liner bottom drain opening, whereby the magnesium chloride provides a seal which prevents magnesium in the inner liner from flowing out of the inner liner.

  16. Phase transformations in some hafnium-tantalum-titanium-zirconium alloys

    SciTech Connect

    Ohriner, E.K.; Kapoor, D.

    1997-11-01

    Phase transformations in hafnium alloys are of interest as a means of achieving a material which exhibits flow softening and high localized strains during deformation at high strain rates. Hafnium transforms from a body-centered-cubic beta phase to a hexagonal alpha phase upon cooling below 1749{degrees}C. Hafnium-based alloys containing up to 17.5% Ti, up to 17.5% Ta, and up to 7.3% Zr by weight were button-arc melted and, in some cases, hot extruded to obtain a refined grain size. A number of alloys were shown to have beta solvus temperatures in the range of 1100 to 1300{degrees}C and showed evidence of a shear transformation upon water quenching. The Vickers microhardness of the quenched materials are typically above 350 HV as compared to 300 HV or less for materials with an alpha plus beta structure. Quenching dilatometry indicates a martensite start temperature of about 750{degrees}C for the Hf-7.5 Ta-10 Ti-1 Zr alloy and 800{degrees}C or more for the Hf-7.5 Ta-7.5 Ti-1 Zr alloy. Tensile tests at 1 s{sup {minus}1} strain rate show a constant ultimate tensile strength for temperatures up to 600{degrees}C for the above two alloys and a rapid decrease in strength with a further increase in temperature.

  17. Continuous ion exchange separation of zirconium and hafnium

    SciTech Connect

    Begovich, J.M.; Sisson, W.G.

    1981-01-01

    A pressurized continuous annular chromatograph (CAC) has been developed for truly continuous ion exchange preparative separations. This device utilizes a slowly rotating annular bed of sorbent material, fixed multiple feed points, and fixed withdrawal locations. Most of our investigations have been performed with a 28-cm-diam by 60-cm-long CAC, but a larger model has recently been designed and constructed. A detailed study has been made of the separation of copper, nickel, and cobalt components from a simulated carbonate leach liquor of the Caron process for recovering nickel and cobalt from laterite ores. Recent studies have investigated the ion exchange separation of zirconium and hafnium from a sulfate feed solution. Nuclear reactor-grade zirconium, containing < 0.01 wt % hafnium, and hafnium, containing < 1% zirconium, have been continuously prepared using cation exchange resin in the pressurized CAC. This device, because of its continuous feed and product withdrawal, its adaptability to largescale operations, and its ability to separate many components, is expected to make chromatography a more competitive process in the industrial sector.

  18. 40 CFR 421.330 - Applicability: Description of the primary zirconium and hafnium subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... primary zirconium and hafnium subcategory. 421.330 Section 421.330 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Zirconium and Hafnium Subcategory § 421.330 Applicability: Description of the...

  19. 40 CFR 421.330 - Applicability: Description of the primary zirconium and hafnium subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... primary zirconium and hafnium subcategory. 421.330 Section 421.330 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Zirconium and Hafnium Subcategory § 421.330 Applicability: Description of the...

  20. A simple spectrophotometric method for determination of zirconium or hafnium in selected molybdenum-base alloys

    NASA Technical Reports Server (NTRS)

    Dupraw, W. A.

    1972-01-01

    A simple analytical procedure is described for accurately and precisely determining the zirconium or hafnium content of molybdenum-base alloys. The procedure is based on the reaction of the reagent Arsenazo III with zirconium or hafnium in strong hydrochloric acid solution. The colored complexes of zirconium or hafnium are formed in the presence of molybdenum. Titanium or rhenium in the alloy have no adverse effect on the zirconium or hafnium complex at the following levels in the selected aliquot: Mo, 10 mg; Re, 10 mg; Ti, 1 mg. The spectrophotometric measurement of the zirconium or hafnium complex is accomplished without prior separation with a relative standard deviation of 1.3 to 2.7 percent.

  1. The abundances of zirconium and hafnium in the solar system

    NASA Technical Reports Server (NTRS)

    Ganapathy, R.; Papia, G. M.; Grossman, L.

    1976-01-01

    The concentrations of zirconium and hafnium have been determined in the Orgueil, Murchison, Allende, Bruderheim, and Alais meteorites by radiochemical neutron activation analysis. The mean Zr/Hf weight ratio in the first four of these meteorites is 31.3 (plus or minus 2.2), indicating no major fractionation of Zr from Hf. Alais contains anomalously high amounts of many refractory lithophile elements, including Zr and Hf. Orgueil contains 3.1 ppm Zr and 0.11 ppm Hf, corresponding to 9.0 and 0.16 atoms, respectively, relative to 1 million Si atoms.

  2. Radiochemical separation of zirconium and hafnium from other radionuclides.

    PubMed

    Hahn, R B

    1972-11-01

    Radiozirconium and radiohafnium may be separated from all other radionuclides except scandium and protactinium by precipitation with mandelic acid from 5-10 M hydrochloric acid, using commercial zirconyl chloride as carrier. Scandium and protactinium are removed by dissolving the precipitate in sodium carbonate, then adding barium nitrate to precipitate barium carbonate which acts as a scavenger. Zirconium mandelate is finally reprecipitated and the sample weighed and counted in this form. The method was checked by analysing commercial zirconyl chloride and standard rock samples for zirconium and hafnium by neutron-activation analysis. PMID:18961201

  3. Slow DNA Transport through Nanopores in Hafnium Oxide Membranes

    PubMed Central

    Bell, David C.; Cohen-Karni, Tzahi; Rosenstein, Jacob K.; Wanunu, Meni

    2016-01-01

    We present a study of double- and single-stranded DNA transport through nanopores fabricated in ultrathin (2–7 nm thick) free-standing hafnium oxide (HfO2) membranes. The high chemical stability of ultrathin HfO2 enables long-lived experiments with <2 nm diameter pores that last several hours, in which we observe >50 000 DNA translocations with no detectable pore expansion. Mean DNA velocities are slower than velocities through comparable silicon nitride pores, providing evidence that HfO2 nanopores have favorable physicochemical interactions with nucleic acids that can be leveraged to slow down DNA in a nanopore. PMID:24083444

  4. Sulfide Mineralogy and Geochemistry

    NASA Astrophysics Data System (ADS)

    Dilles, John

    2007-02-01

    Reviews in Mineralogy and Geochemistry Series, Volume 61 David J. Vaughan, Editor Geochemical Society and Mineralogical Society of America; ISBN 0-939950-73-1 xiii + 714 pp.; 2006; $40. Sulfide minerals as a class represent important minor rock-forming minerals, but they are generally known as the chief sources of many economic metallic ores. In the past two decades, sulfide research has been extended to include important roles in environmental geology of sulfide weathering and resultant acid mine drainage, as well as in geomicrobiology in which bacteria make use of sulfides for metabolic energy sources. In the latter respect, sulfides played an important role in early evolution of life on Earth and in geochemical cycling of elements in the Earth's crust and hydrosphere.

  5. Formation of hybrid hafnium oxide by applying sacrifacial silicon film

    NASA Astrophysics Data System (ADS)

    Lin, Chiung-Wei; Zheng, Bo-Shen; Huang, Jing-Wei

    2016-01-01

    In the fabrication of hafnium oxide (HfO2)-based metal-insulator-semiconductor (MIS) devices, a sacrificial amorphous silicon (a-Si) film was used as silicon source for facilitating the formation of hafnium silicate (Hf-silicate; HfSiO) between HfO2 and crystallized Si (c-Si). HfSiO can assist in changing the phase of the HfO2 film into the tetragonal phase and achieve high dielectric constant. The combination of HfSiO and HfO2 was named as “Hybrid HfO2”. When this Hybrid HfO2 insulator was applied to MIS devices, it can form a good insulator/semiconductor interface with c-Si. Hybrid HfO2 cannot only suppress the leakage current but also show high dielectric strength. The Hybrid HfO2 film in this work exhibited a high dielectric constant of 25.5 and a high dielectric strength of 17.9 MV/cm.

  6. Changes in the Young Modulus of hafnium oxide thin films

    NASA Astrophysics Data System (ADS)

    Vargas, André Luís Marin; de Araújo Ribeiro, Fabiana; Hübler, Roberto

    2015-12-01

    Hafnium-oxide (HfO2)-based materials have been extensively researched due to their excellent optical and electrical properties. However, the literature data on the mechanical properties of these materials and its preparation for heavy machinery application is very limited. The aim of this work is to deposit hafnium oxide thin films by DC reactive magnetron sputtering with different Young's Modulus from the Ar/O2 concentration variation in the deposition chamber. The thin films were deposited by DC reactive magnetron sputtering with different Ar/O2 gas concentrations in plasma. After deposition, HfOx thin films were characterized through XRD, AFM, RBS and XRF. In this regard, it was observed that the as-deposited HfO2 films were mostly amorphous in the lower Ar/O2 gas ratio and transformed to polycrystalline with monoclinic structure as the Ar/O2 gas ratios grows. RBS technique shows good compromise between the experimental data and the simulated ones. It was possible to tailored the Young Modulus of the films by alter the Ar/O2 content on the deposition chamber without thermal treatment.

  7. Simultaneous determination of tantalum and hafnium in silicates by neutron activation analysis

    USGS Publications Warehouse

    Greenland, L.P.

    1968-01-01

    A neutron activation procedure suitable for the routine determination of tantalum and hafnium in silicates is described. The irradiated sample is fused with sodium peroxide and leached, and the insoluble hydroxides are dissolved in dilute hydrofluoric acid-hydrochloric acid. After LaF3 and AgCl scavenges, tantalum and hafnium are separated by anion exchange. Tantalum is obtained radiochemically pure; 233Pa and 95Zr contaminants in the hafnium fraction are resolved by ??-ray spectrometry. The chemical yield of the procedure is detemined after counting by re-irradiation. Values for the 8 U.S. Geological Survey standard rocks are reported. ?? 1968.

  8. PROCESS OF RECOVERING ZIRCONIUM VALUES FROM HAFNIUM VALUES BY SOLVENT EXTRACTION WITH AN ALKYL PHOSPHATE

    DOEpatents

    Peppard, D.F.

    1960-02-01

    A process of separating hafnium nitrate from zirconium nitrate contained in a nitric acid solution by selectively. extracting the zirconium nitrate with a water-immiscible alkyl phosphate is reported.

  9. On hafnium chelation by EDTA and DTPA for TDPAC experiments

    NASA Astrophysics Data System (ADS)

    Chain, Cecilia Y.; Pasquevich, A. F.

    2010-04-01

    Polyaminocarboxilate chelating agents, like ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA), form stable complexes with many heavy metals ions and are of spread use in the industrial and biomedical field. In this paper, Time Differential Perturbed Angular Correlations (TDPAC) spectroscopy has been used to investigate the formation of Hf-complexes prepared from 181Hf-HfF4 and polyaminocarboxylic acids, by taking into account the possible formation of inorganic compounds. The obtained wet precipitates were measured at room temperature. Different behaviors were observed depending on the ratio fluorine/sodium atoms present in the sample. The obtaining of sodium heptafluorohafnate Na3HfF7 was verified when the ratio F/Na was approximately 1.5 and tridecafluorodihafnate Na5Hf2F13 appeared for relations between 3 and 4. No evidence of hafnium complexation by the polyaminocarboxilic acids was observed.

  10. Growth mode evolution of hafnium oxide by atomic layer deposition

    SciTech Connect

    Nie, Xianglong; Ma, Fei; Ma, Dayan; Xu, Kewei

    2014-01-15

    HfO{sub 2} thin films were deposited using tetrakis-ethylmethylamido hafnium and H{sub 2}O as precursors on silicon by atomic layer deposition (ALD). The morphology and microstructures at different ALD cycles were characterized by atomic force microscopy and high-resolution transmission electron microscopy. Based on the height–height correlation function and power spectral density function, quantitative analysis of surface morphologies was performed. Three characteristic dimensions (ξ{sub 1}, ξ{sub 2}, and ξ{sub 3}) corresponding to three surface structures, islands, local and global fluctuations, were identified. The evolution of ALD growth mode at range of the three critical scales was investigated, respectively. It suggests the transformation of growth mode from quasi two-dimensional layer-by-layer to three-dimensional island for global fluctuations.

  11. Hafnium and Neodymium Isotopes in Atlantic Ocean Waters

    NASA Astrophysics Data System (ADS)

    Rickli, J.; Frank, M.; Halliday, A.

    2007-12-01

    Neodymium isotopic compositions (ICs) have been established as a tracer of water masses in the present and past oceans since the late 1970s. Hafnium isotopes share the capability of tracing water masses and in combination with Nd isotopes provide information on continental weathering regimes. Whereas Nd released during weathering reflects the bulk Nd IC of the weathered lithology, the released Hf is more radiogenic than the weathered lithology. This effect is due to highly variable Lu/Hf--ratios in rock--forming minerals ("zircon effect") and as a consequence physical weathering apparently leads to more congruent weathering of Hf than chemical weathering does. Our understanding of the Hf IC of seawater to date has been derived (with the exception of some as yet unpublished data from the Arctic and Pacific oceans (Zimmermann et al., in prep.)) from ferromanganese crusts and nodules, since Hf concentrations in seawater are low and have until recently hampered direct measurements of Hf IC of seawater. We present IC for the dissolved Hf and Nd in Atlantic seawater. Samples were taken mainly on a transect from the Bay of Biscay to Cape Town (RV Polarstern cruise ANT XXIII/1 in 2005). A few additional samples are from the Labrador Sea and the Drake Passage. Hafnium and Nd were pre--concentrated by iron co--precipitation from 60 to 140 liters of filtered (0.45 μm) seawater. Separation of Hf and Nd followed previously established ion chromatographic procedures. Hafnium and Nd ICs were measured by MC--ICPMS (Nu Plasma) with a 2σ external reproducibility of 0.65 and 0.3 ǎrepsilon--units, respectively. Sample sizes varied but were in most cases larger than 3ng of Hf. Surface seawater as well as deep water samples extending to ~5,000 m, plot on the "seawater array" defined previously from measurements of ferromanganese crusts and nodules. Surface seawater ICs are quite uniform for Hf ranging from ǎrepsilonHf = 0 to +2 at most sampling sites on the Atlantic transect. In the

  12. Plasma-enhanced chemical vapor deposition and characterization of high-permittivity hafnium and zirconium silicate films

    NASA Astrophysics Data System (ADS)

    Kato, Hiromitsu; Nango, Tomohiro; Miyagawa, Takeshi; Katagiri, Takahiro; Seol, Kwang Soo; Ohki, Yoshimichi

    2002-07-01

    Deposition of hafnium silicate films with various hafnium contents was tried by plasma-enhanced chemical vapor deposition using tetraethoxysilane and a hafnium alkoxide. From x-ray photoelectron spectroscopy, the deposited films are confirmed to be silicate with Hf-O-Si bonds but without any Hf-Si bonds. The permittivity calculated from the capacitance of the accumulation layer increases monotonically with an increase in the hafnium content, whereas the optical band gap energy estimated from vacuum ultraviolet absorption spectra decreases. Similar results were obtained from zirconium silicate films deposited using tetraethoxysilane and a zirconium alkoxide. If we compare the films with the same hafnium or zirconium content, the hafnium silicate exhibits a higher permittivity and a larger band gap energy than the zirconium silicate.

  13. Sulfidation of silver nanoparticles

    NASA Astrophysics Data System (ADS)

    Levard, C.; Michel, F. M.; Brown, G. E.

    2010-12-01

    Rapid development of nanotechnologies that exploit the properties of silver nanoparticles (Ag-NPs) raises questions concerning the impact of Ag on the environment. Ag-NPs are currently among the most widely used in the nanotechnology industry and the amount released into the environment is expected to increase along with production (1). When present in geochemical systems, Ag-NPs may undergo a variety of changes due to varying redox, pH, and chemical conditions. Expected changes range from surface modification (e.g., oxidation, sulfidation, chloridation etc.) to complete dissolution and re-precipitation. In this context, the focus of our work is on understanding the behavior of synthetic Ag-NPs with different particle sizes under varying conditions relevant to the environment. Sulfidation of Ag-NPs is of particular interest since it among the processes most likely to occur in aqueous systems, in particular under reducing conditions. Three sizes of Ag-NPs coated with polyvinyl pyrrolidone were produced using the polyol process (2) (7 ±1; 20 ±4, and 40 ±9 nm). Batch solutions containing the different Ag-NPs were subsequently reacted with Na2S solutions of different concentrations. The sulfidation process was followed step-wise for 24 hours and the corrosion products formed were characterized by electron microscopy (TEM/SEM), diffraction (XRD), and photo-electron spectroscopy (XPS). Surface charge (pHPZC) of the products formed during this process was also measured, as were changes in solubility and reactivity. Based on experimental observations we infer that the sulfidation process is the result of dissolution-precipitation and find that: (i) acanthite (Ag2S) is formed as a corrosion product; (ii) Ag-NPs aggregation increased with sulfidation rate; (iii) pHPZC increases with the rate of sulfidation; and (iv) the solubility of the corrosion products formed from sulfidation appears lower than that of non-sulfidated Ag-NPs. We observe size-dependent differences in

  14. SULFIDE METHOD PLUTONIUM SEPARATION

    DOEpatents

    Duffield, R.B.

    1958-08-12

    A process is described for the recovery of plutonium from neutron irradiated uranium solutions. Such a solution is first treated with a soluble sullide, causing precipitation of the plutoniunn and uraniunn values present, along with those impurities which form insoluble sulfides. The precipitate is then treated with a solution of carbonate ions, which will dissolve the uranium and plutonium present while the fission product sulfides remain unaffected. After separation from the residue, this solution may then be treated by any of the usual methods, such as formation of a lanthanum fluoride precipitate, to effect separation of plutoniunn from uranium.

  15. Zinc sulfide liquefaction catalyst

    DOEpatents

    Garg, Diwakar

    1984-01-01

    A process for the liquefaction of carbonaceous material, such as coal, is set forth wherein coal is liquefied in a catalytic solvent refining reaction wherein an activated zinc sulfide catalyst is utilized which is activated by hydrogenation in a coal derived process solvent in the absence of coal.

  16. RF-sputtered silicon and hafnium nitrides - Properties and adhesion to 440C stainless steel

    NASA Technical Reports Server (NTRS)

    Grill, A.; Aron, P. R.

    1983-01-01

    Silicon nitride and hafnium nitride coatings were deposited by reactive RF sputtering on oxidized and unoxidized 440C stainless steel substrates. Sputtering was done in mixtures of argon and nitrogen gases from pressed powder silicon nitride and from hafnium metal targets. Depositions were at two background pressures, 8 and 20 mtorr, and at two different fractions (f) of nitrogen in argon, 0.25 and 0.60, for hafnium nitride and at f = 0.25 for silicon nitride. The coatings and the interface between the coating and substrates were investigated by X-ray diffractometry, scanning electron microscopy, energy dispersive X-ray analysis and Auger electron spectroscopy. A Knoop microhardness of 1650 + or 100 kg/sq mm was measured for hafnium nitride and 3900 + or 500 kg/sq mm for silicon nitride. The friction coefficients between a 440C rider and the coatings were measured under lubricated conditions. Scratch test results demonstrate that the adhesion of hafnium nitride to both oxidized and unoxidized 440C is superior to that of silicon nitride. Oxidized 440C is found to have increased adhesion, to both nitrides, over that of unoxidized 440C.

  17. RF sputtered silicon and hafnium nitrides: Properties and adhesion to 440C stainless steel

    NASA Technical Reports Server (NTRS)

    Grill, A.; Aron, P. R.

    1982-01-01

    Silicon nitride and hafnium nitride coatings were deposited by reactive RF sputtering on oxidized and unoxidized 440C stainless steel substrates. Sputtering was done in mixtures of argon and nitrogen gases from pressed powder silicon nitride and from hafnium metal targets. Depositions were at two background pressures, 8 and 20 mtorr, and at two different fractions (f) of nitrogen in argon, 0.25 and 0.60, for hafnium nitride and at f = 0.25 for silicon nitride. The coatings and the interface between the coating and substrates were investigated by X-ray diffractometry, scanning electron microscopy, energy dispersive X-ray analysis and Auger electron spectroscopy. A Knoop microhardness of 1650 + or - 100 kg/sq mm was measured for hafnium nitride and 3900 + or - 500 kg/sq mm for silicon nitride. The friction coefficients between a 440C rider and the coatings were measured under lubricated conditions. Scratch test results demonstrate that the adhesion of hafnium nitride to both oxidized and unoxidized 440C is superior to that of silicon nitride. Oxidized 440C is found to have increased adhesion, to both nitrides, over that of unoxidized 440C.

  18. Sulfidation kinetics of silver nanoparticles reacted with metal sulfides.

    PubMed

    Thalmann, Basilius; Voegelin, Andreas; Sinnet, Brian; Morgenroth, Eberhard; Kaegi, Ralf

    2014-05-01

    Recent studies have documented that the sulfidation of silver nanoparticles (Ag-NP), possibly released to the environment from consumer products, occurs in anoxic zones of urban wastewater systems and that sulfidized Ag-NP exhibit dramatically reduced toxic effects. However, whether Ag-NP sulfidation also occurs under oxic conditions in the absence of bisulfide has not been addressed, yet. In this study we, therefore, investigated whether metal sulfides that are more resistant toward oxidation than free sulfide, could enable the sulfidation of Ag-NP under oxic conditions. We reacted citrate-stabilized Ag-NP of different sizes (10-100 nm) with freshly precipitated and crystalline CuS and ZnS in oxygenated aqueous suspensions at pH 7.5. The extent of Ag-NP sulfidation was derived from the increase in dissolved Cu(2+) or Zn(2+) over time and linked with results from X-ray absorption spectroscopy (XAS) analysis of selected samples. The sulfidation of Ag-NP followed pseudo first-order kinetics, with rate coefficients increasing with decreasing Ag-NP diameter and increasing metal sulfide concentration and depending on the type (CuS and ZnS) and crystallinity of the reacting metal sulfide. Results from analytical electron microscopy revealed the formation of complex sulfidation patterns that seemed to follow preexisting subgrain boundaries in the pristine Ag-NP. The kinetics of Ag-NP sulfidation observed in this study in combination with reported ZnS and CuS concentrations and predicted Ag-NP concentrations in wastewater and urban surface waters indicate that even under oxic conditions and in the absence of free sulfide, Ag-NP can be transformed into Ag2S within a few hours to days by reaction with metal sulfides. PMID:24678586

  19. Hafnium oxide nanoparticles: toward an in vitro predictive biological effect?

    PubMed Central

    2014-01-01

    Background Hafnium oxide, NBTXR3 nanoparticles were designed for high dose energy deposition within cancer cells when exposed to ionizing radiation. The purpose of this study was to assess the possibility of predicting in vitro the biological effect of NBTXR3 nanoparticles when exposed to ionizing radiation. Methods Cellular uptake of NBTXR3 nanoparticles was assessed in a panel of human cancer cell lines (radioresistant and radiosensitive) by transmission electron microscopy. The radioenhancement of NBTXR3 nanoparticles was measured by the clonogenic survival assay. Results NBTXR3 nanoparticles were taken up by cells in a concentration dependent manner, forming clusters in the cytoplasm. Differential nanoparticle uptake was observed between epithelial and mesenchymal or glioblastoma cell lines. The dose enhancement factor increased with increase NBTXR3 nanoparticle concentration and radiation dose. Beyond a minimum number of clusters per cell, the radioenhancement of NBTXR3 nanoparticles could be estimated from the radiation dose delivered and the radiosensitivity of the cancer cell lines. Conclusions Our preliminary results suggest a predictable in vitro biological effect of NBTXR3 nanoparticles exposed to ionizing radiation. PMID:24981953

  20. Oxidation Effect in Octahedral Hafnium Disulfide Thin Film.

    PubMed

    Chae, Sang Hoon; Jin, Youngjo; Kim, Tae Soo; Chung, Dong Seob; Na, Hyunyeong; Nam, Honggi; Kim, Hyun; Perello, David J; Jeong, Hye Yun; Ly, Thuc Hue; Lee, Young Hee

    2016-01-26

    Atomically smooth van der Waals materials are structurally stable in a monolayer and a few layers but are susceptible to oxygen-rich environments. In particular, recently emerging materials such as black phosphorus and perovskite have revealed stronger environmental sensitivity than other two-dimensional layered materials, often obscuring the interesting intrinsic electronic and optical properties. Unleashing the true potential of these materials requires oxidation-free sample preparation that protects thin flakes from air exposure. Here, we fabricated few-layer hafnium disulfide (HfS2) field effect transistors (FETs) using an integrated vacuum cluster system and study their electronic properties and stability under ambient conditions. By performing all the device fabrication and characterization procedure under an oxygen- and moisture-free environment, we found that few-layer AA-stacking HfS2-FETs display excellent field effect responses (Ion/Ioff ≈ 10(7)) with reduced hysteresis compared to the FETs prepared under ambient conditions. Oxidation of HfS2 occurs uniformly over the entire area, increasing the film thickness by 250% at a prolonged oxidation time of >120 h, while defects on the surface are the preferential initial oxidation sites. We further demonstrated that the stability of the device in air is significantly improved by passivating FETs with BN in a vacuum cluster. PMID:26735305

  1. Electric quadrupole interaction of 100Rh in antimony, hafnium and rhenium

    NASA Astrophysics Data System (ADS)

    Kemp, W. J.; Abiona, A. A.; Kessler, P.; Timmers, H.

    2013-05-01

    Time differential perturbed angular correlation (TDPAC) spectroscopy in beryllium, zinc, rhodium, antimony, hafnium and rhenium was performed with the 100Pd/100Rh probe using four-detector arrays with relative detector orientations of 90° and 180°. The probe was synthesized using the 92Zr(12C,4n)100Pd fusion evaporation reaction, with evaporation residues recoiling into specimens of the metals. The quadrupole coupling constant for 100Rh has been determined for the first time for antimony, hafnium and rhenium, while results for the other elements agree with known values. The coupling constants for the measured hexagonal lattices of the period VI transition metals, hafnium and rhenium, show the same trend with increasing atomic number as those of period V.

  2. Cathodo- and photoluminescence increase in amorphous hafnium oxide under annealing in oxygen

    NASA Astrophysics Data System (ADS)

    Ivanova, E. V.; Zamoryanskaya, M. V.; Pustovarov, V. A.; Aliev, V. Sh.; Gritsenko, V. A.; Yelisseyev, A. P.

    2015-04-01

    Cathodo- and photoluminescence of amorphous nonstoichiometric films of hafnium oxide are studied with the aim to verify the hypothesis that oxygen vacancies are responsible for the luminescence. To produce oxygen vacancies, hafnium oxide was enriched in surplus metal during synthesis. To reduce the oxygen concentration, the film was annealed in oxygen. A qualitative control of the oxygen concentration was carried out by the refractive index. In the initial, almost stoichiometric films we observed a 2.7-eV band in cathodoluminescence. Annealing in oxygen results in a considerable increase in its intensity, as well as in the appearance of new bands at 1.87, 2.14, 3.40, and 3.6 eV. The observed emission bands are supposed to be due to single oxygen vacancies and polyvacancies in hafnium oxide. The luminescence increase under annealing in an oxygen atmosphere may be a result of the emission quenching effect.

  3. Cathodo- and photoluminescence increase in amorphous hafnium oxide under annealing in oxygen

    SciTech Connect

    Ivanova, E. V. Zamoryanskaya, M. V.; Pustovarov, V. A.; Aliev, V. Sh.; Gritsenko, V. A.; Yelisseyev, A. P.

    2015-04-15

    Cathodo- and photoluminescence of amorphous nonstoichiometric films of hafnium oxide are studied with the aim to verify the hypothesis that oxygen vacancies are responsible for the luminescence. To produce oxygen vacancies, hafnium oxide was enriched in surplus metal during synthesis. To reduce the oxygen concentration, the film was annealed in oxygen. A qualitative control of the oxygen concentration was carried out by the refractive index. In the initial, almost stoichiometric films we observed a 2.7-eV band in cathodoluminescence. Annealing in oxygen results in a considerable increase in its intensity, as well as in the appearance of new bands at 1.87, 2.14, 3.40, and 3.6 eV. The observed emission bands are supposed to be due to single oxygen vacancies and polyvacancies in hafnium oxide. The luminescence increase under annealing in an oxygen atmosphere may be a result of the emission quenching effect.

  4. The Hot-Pressing of Hafnium Carbide (Melting Point, 7030 F)

    NASA Technical Reports Server (NTRS)

    Sanders, William A.; Grisaffe, Salvatore J.

    1960-01-01

    An investigation was undertaken to determine the effects of the hot-pressing variables (temperature, pressure, and time) on the density and grain size of hafnium carbide disks. The purpose was to provide information necessary for the production of high-density test shapes for the determination of physical and mechanical properties. Hot-pressing of -325 mesh hafnium carbide powder was accomplished with a hydraulic press and an inductively heated graphite die assembly. The ranges investigated for each variable were as follows: temperature, 3500 to 4870 F; pressure, 1000 to 6030 pounds per square inch; and time, 5 to 60 minutes. Hafnium carbide bodies of approximately 98 percent theoretical density can be produced under the following minimal conditions: 4230 F, 3500 pounds per square inch, and 15 minutes. Further increases in temperature and time resulted only in greater grain size.

  5. Mechanical Effects of Hafnium and Boron Addition to Aluminum Alloy Films for Submicrometer LSI Interconnects

    NASA Astrophysics Data System (ADS)

    Onoda, Hiroshi; Takahashi, Eishi; Kawai, Yasuaki; Madokoro, Shoji; Fukuyo, Hideaki; Sawada, Susumu

    1993-11-01

    This is the first report on the mechanical properties of hafnium- and boron-added Al-Si-Cu alloy film for LSI interconnects. Two to three hundred ppm of hafnium and boron addition into Al-Si-Cu alloy film does not influence the Al alloy properties for metal lines as LSI interconnects, such as its low resistivity, low ohmic contact resistance with Si, and fine-line patterning feasibility. The mechanical properties of the Al alloy film, however, change greatly. Vertical hillock and lateral hillock formation is considerably suppressed during heat treatments used in LSI fabrication processes. Stress-induced void formation is also reduced during aging test at 125°C. These effects due to hafnium and boron addition are considered to be an impurity precipitation effect ihat was confirmed by X-ray diffraction analysis and electron probe microanalysis.

  6. Composition and microstructure of zirconium and hafnium germanates obtained by different chemical routes

    SciTech Connect

    Utkin, A.V. Prokip, V.E.; Baklanova, N.I.

    2014-01-15

    The phase composition and morphology of zirconium and hafnium germanates synthesized by ceramic and co-precipitation routes were studied. The products were characterized using high-temperature X-ray diffraction analysis (XRD), Raman spectroscopy, scanning electron microscopy (SEM) and thermal (TG/DTA) analysis. To investigate the phase composition and stoichiometry of compounds the unit cell parameters were refined by full-profile Rietveld XRD analysis. The morphology of products and its evolution during high-temperature treatment was examined by SEM analysis. It was stated that there is the strong dependence of the phase composition and morphology of products on the preparation route. The ceramic route requires a multi-stage high-temperature treatment to obtain zirconium and hafnium germanates of 95% purity or more. Also, there are strong diffusion limitations to obtain hafnium germanate Hf{sub 3}GeO{sub 8} by ceramic route. On the contrary, the co-precipitation route leads to the formation of nanocrystalline single phase germanates of stoichiometric composition at a relatively low temperatures (less than 1000 °C). The results of quantitative XRD analysis showed the hafnium germanates are stoichiometric compounds in contrast to zirconium germanates that form a set of solid solutions. This distinction may be related to the difference in the ion radii of Zr and Hf. - Graphical abstract: The phase composition and morphology of zirconium and hafnium germanates synthesized by ceramic and co-precipitation routes were studied. It was stated that there is the strong dependence of the phase composition and morphology of products on the preparation route. Display Omitted - Highlights: • Zr and Hf germanates were synthesized by ceramic and co-precipitation routes. • The morphology of products depends on the synthesis parameters. • Zirconium germanates forms a set of solid solutions. • Hafnium germanates are stoichiometric compounds.

  7. Effect of substrate temperature on structural and electrical properties of RF sputtered hafnium oxide thin films

    SciTech Connect

    Das, K. C.; Ghosh, S. P.; Tripathy, N.; Kar, J. P.; Bose, G.; Lee, T.; Myoung, J. M.

    2015-06-24

    In this work hafnium oxide thin films were deposited on p-type silicon substrate by Radio frequency magnetron sputtering at different substrate temperature ranging from room temperature to 300 °C. The structural and electrical properties of the sputtered films were investigated by x-ray diffraction, capacitance-voltage and current-voltage measurements. The XRD results show the formation monoclinic structure of the hafnium oxide thin films. The shifting of C-V curves towards negative voltage side depicts the increase in positive oxide charges with the rise of substrate temperature. Leakage current was found increased, when temperature enhanced from room temperature to 300 °C.

  8. Sulfide detoxification in plant mitochondria.

    PubMed

    Birke, Hannah; Hildebrandt, Tatjana M; Wirtz, Markus; Hell, Rüdiger

    2015-01-01

    In contrast to animals, which release the signal molecule sulfide in small amounts from cysteine and its derivates, phototrophic eukaryotes generate sulfide as an essential intermediate of the sulfur assimilation pathway. Additionally, iron-sulfur cluster turnover and cyanide detoxification might contribute to the release of sulfide in mitochondria. However, sulfide is a potent inhibitor of cytochrome c oxidase in mitochondria. Thus, efficient sulfide detoxification mechanisms are required in mitochondria to ensure adequate energy production and consequently survival of the plant cell. Two enzymes have been recently described to catalyze sulfide detoxification in mitochondria of Arabidopsis thaliana, O-acetylserine(thiol)lyase C (OAS-TL C), and the sulfur dioxygenase (SDO) ethylmalonic encephalopathy protein 1 (ETHE1). Biochemical characterization of sulfide producing and consuming enzymes in mitochondria of plants is fundamental to understand the regulatory network that enables mitochondrial sulfide homeostasis under nonstressed and stressed conditions. In this chapter, we provide established protocols to determine the activity of the sulfide releasing enzyme β-cyanoalanine synthase as well as sulfide-consuming enzymes OAS-TL and SDO. Additionally, we describe a reliable and efficient method to purify OAS-TL proteins from plant material. PMID:25747485

  9. Geothermal hydrogen sulfide removal

    SciTech Connect

    Urban, P.

    1981-04-01

    UOP Sulfox technology successfully removed 500 ppM hydrogen sulfide from simulated mixed phase geothermal waters. The Sulfox process involves air oxidation of hydrogen sulfide using a fixed catalyst bed. The catalyst activity remained stable throughout the life of the program. The product stream composition was selected by controlling pH; low pH favored elemental sulfur, while high pH favored water soluble sulfate and thiosulfate. Operation with liquid water present assured full catalytic activity. Dissolved salts reduced catalyst activity somewhat. Application of Sulfox technology to geothermal waters resulted in a straightforward process. There were no requirements for auxiliary processes such as a chemical plant. Application of the process to various types of geothermal waters is discussed and plans for a field test pilot plant and a schedule for commercialization are outlined.

  10. A reconnaissance ion-probe of hafnium isotopes in zircons

    SciTech Connect

    Kinny, P.D.; Compston, W.; Williams, I.S. )

    1991-03-01

    A SIMS technique for the isotopic analysis of hafnium in zircons using the SHRIMP ion microprobe has been developed, and a precision of typically 0.5{per thousand} (2{sigma}) achieved in the mean reduced {sup 176}Hf/{sup 177}Hf ratio measured at several spots on a single grain. Unfractionated (chondritic) initial Hf isotopic compositions have been measured on a number of Archaean zircon populations. These include the oldest-known terrestrial minerals, the 4.2 Ga-old Mount Narryer detrital zircons, thereby confirming their antiquity. In contrast, positive initial {epsilon}{sub Hf} (relative to the chondritic model composition) has been found in several post-Archaean zircon populations, reflecting the increasing involvement of isotopically evolved depleted mantle sources in the formation of younger crust. The 570 Ma-old Sri Lankan zircon standard SL7 yielded an exceptionally low initial {epsilon}{sub Hf} of {minus}23, implying a metamorphic origin as a reworked product of ancient crust. SHRIMP U-Pb analyses of zircons from Archaean tonalitic gneiss at Watersmeet, Michigan, yield a precise crystallization age of 3636 {plus minus}6 Ma (2{sigma}), and show that a previously reported correlation between {sup 176}Hf/{sup 177}Hf and U-Pb isotopic discordance in bulk zircon samples (Patchett, 1983) was caused by the addition of radiogenic Hf in discrete overgrowths of new zircon ca. 2.7 Ga ago. The original 3.64 Ga grains show no evidence of distrubance to their original (chondritic) Hf isotopic composition. There is presently no evidence for significant isotopic exchange of Hf between zircon and other minerals in crustal rocks.

  11. Biotreatment of refinery spent sulfidic caustics

    SciTech Connect

    Sublette, K.L.; Rajganesh, B.; Woolsey, M.; Plato, A.

    1995-12-31

    Caustics are used in petroleum refinering to remove hydrogen sulfide from various hydrocarbon streams. Spent sulfidic caustics from two Conoco refineries have been successfully biotreated on bench and pilot scale, resulting in neutralization and removal of active sulfides. Sulfides were completely oxidized to sulfate by Thiobacillus denitrificans. Microbial oxidation of sulfide produced acid, which at least partially neutralized the caustic.

  12. "Decarbonization" of an imino N-heterocyclic carbene via triple benzyl migration from hafnium

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An imino N-heterocyclic carbene underwent three sequential benzyl migrations upon reaction with tetrabenzylhafnium, resulting in complete removal of the carbene carbon from the ligand. The resulting eneamido-amidinato hafnium complex showed alkene polymerization activity comparable to that of a prec...

  13. The corrosion behavior of hafnium in high-temperature-water environments

    SciTech Connect

    Rishel, D.M.; Smee, J.D.; Kammenzind, B.F.

    1999-10-01

    The high-temperature-water corrosion performance of hafnium is evaluated. Corrosion kinetic data are used to develop correlations that are a function of time and temperature. The evaluation is based on corrosion tests conducted in out-of-pile autoclaves and in out-of-flux locations of the Advanced Test Reactor (ATR) at temperatures ranging from 288 to 360 C. Similar to the corrosion behavior of unalloyed zirconium, the high-temperature-water corrosion response of hafnium exhibits three corrosion regimes: pretransition, posttransition, and spalling. In the pretransition regime, cubic corrosion kinetics are exhibited, whereas in the posttransition regime, linear corrosion kinetics are exhibited. Because of the scatter in the spalling regime data, it is not reasonable to use a best fit of the data to describe spalling regime corrosion. Data also show that neutron irradiation does not alter the corrosion performance of hafnium. Finally, the data illustrate that the corrosion rate of hafnium is significantly less than that of Zircaloy-2 and Zircaloy-4.

  14. Theoretical Investigation of the Hafnia-Hafnium Interface in RRAM Devices

    NASA Astrophysics Data System (ADS)

    O'Hara, Andrew; Bersuker, Gennadi; Demkov, Alexander

    2014-03-01

    Oxide based resistive-switching memory devices (RRAM) utilizing hafnia (HfO2) as the dielectric serve as an attractive option for embedded non-volatile memory systems. Successful operation requires a degree of oxygen deficiency caused by application of a forming voltage. A recent approach to help facilitate this has been the use of an oxygen gettering layer overlaying hafnia. Using density functional theory (DFT) in the local density approximation (LDA), we construct and study a hafnia-hafnium interface to understand the reducing and gettering properties. With this interface, we compare two routes to the creation of substoichiometric hafnia: formation of oxygen vacancies that leave hafnium unoxidized and migration of oxygen to hafnium to form an extended Frenkel pair (FP). Our work shows that the presence of the interface lowers the vacancy formation energy by 1.1 eV from the bulk value of 7.5 eV. Using the nudged-elastic band method, we show that not only is the formation energy lower for an extended FP, but that the barrier to formation of the shortest such FP is only 1.3 eV implying the favorability of such defects. Finally, we study the diffusion of oxygen in bulk hafnium to learn how the defect would behave after disassociation of the FP.

  15. Synthesis, properties, and structure of potassium titanyl phosphate single crystals doped with hafnium

    SciTech Connect

    Orlova, E. I.; Kharitonova, E. P.; Novikova, N. E. Verin, I. A.; Alekseeva, O. A.; Sorokina, N. I.; Voronkova, V. I.

    2010-05-15

    Single crystals of potassium titanyl phosphate doped with hafnium are grown by spontaneous flux crystallization. Their physical properties are studied, and the structure of three KTi{sub 1-x}Hf{sub x}OPO{sub 4} crystals (x = 0.01, 0.03, and 0.12) is determined. In the crystals studied, hafnium mostly occupies the second titanium position. The doping of KTP crystals with hafnium results in an elongation of K-O bonds in the potassium polyhedra and, as a consequence, in a considerable (by approximately 180 deg. C) decrease in the temperature of ferroelectric phase transition. The magnitude of anomalous permittivity substantially decreases. The electrical conduction in the specimens studied decreases by approximately half an order of magnitude in the low-temperature region but remains almost unchanged in the high-temperature region. Even at minor concentrations, the presence of a hafnium additive in the specimens considerably (by 35%) enhances the intensity of the second harmonic generation of laser radiation.

  16. Hydrogen sulfide intoxication.

    PubMed

    Guidotti, Tee L

    2015-01-01

    Hydrogen sulfide (H2S) is a hazard primarily in the oil and gas industry, agriculture, sewage and animal waste handling, construction (asphalt operations and disturbing marshy terrain), and other settings where organic material decomposes under reducing conditions, and in geothermal operations. It is an insoluble gas, heavier than air, with a very low odor threshold and high toxicity, driven by concentration more than duration of exposure. Toxicity presents in a unique, reliable, and characteristic toxidrome consisting, in ascending order of exposure, of mucosal irritation, especially of the eye ("gas eye"), olfactory paralysis (not to be confused with olfactory fatigue), sudden but reversible loss of consciousness ("knockdown"), pulmonary edema (with an unusually favorable prognosis), and death (probably with apnea contributing). The risk of chronic neurcognitive changes is controversial, with the best evidence at high exposure levels and after knockdowns, which are frequently accompanied by head injury or oxygen deprivation. Treatment cannot be initiated promptly in the prehospital phase, and currently rests primarily on supportive care, hyperbaric oxygen, and nitrite administration. The mechanism of action for sublethal neurotoxicity and knockdown is clearly not inhibition of cytochrome oxidase c, as generally assumed, although this may play a role in overwhelming exposures. High levels of endogenous sulfide are found in the brain, presumably relating to the function of hydrogen sulfide as a gaseous neurotransmitter and immunomodulator. Prevention requires control of exposure and rigorous training to stop doomed rescue attempts attempted without self-contained breathing apparatus, especially in confined spaces, and in sudden release in the oil and gas sector, which result in multiple avoidable deaths. PMID:26563786

  17. Tensile and stress-rupture behavior of hafnium carbide dispersed molybdenum and tungsten base alloy wires

    NASA Technical Reports Server (NTRS)

    Yun, Hee Mann; Titran, Robert H.

    1993-01-01

    The tensile strain rate sensitivity and the stress-rupture strength of Mo-base and W-base alloy wires, 380 microns in diameter, were determined over the temperature range from 1200 K to 1600 K. Three molybdenum alloy wires; Mo + 1.1w/o hafnium carbide (MoHfC), Mo + 25w/o W + 1.1w/o hafnium carbide (MoHfC+25W) and Mo + 45w/o W + 1.1w/o hafnium carbide (MoHfC+45W), and a W + 0.4w/o hafnium carbide (WHfC) tungsten alloy wire were evaluated. The tensile strength of all wires studied was found to have a positive strain rate sensitivity. The strain rate dependency increased with increasing temperature and is associated with grain broadening of the initial fibrous structures. The hafnium carbide dispersed W-base and Mo-base alloys have superior tensile and stress-rupture properties than those without HfC. On a density compensated basis the MoHfC wires exhibit superior tensile and stress-rupture strengths to the WHfC wires up to approximately 1400 K. Addition of tungsten in the Mo-alloy wires was found to increase the long-term stress rupture strength at temperatures above 1400 K. Theoretical calculations indicate that the strength and ductility advantage of the HfC dispersed alloy wires is due to the resistance to recrystallization imparted by the dispersoid.

  18. Field method for sulfide determination

    SciTech Connect

    Wilson, B L; Schwarser, R R; Chukwuenye, C O

    1982-01-01

    A simple and rapid method was developed for determining the total sulfide concentration in water in the field. Direct measurements were made using a silver/sulfide ion selective electrode in conjunction with a double junction reference electrode connected to an Orion Model 407A/F Specific Ion Meter. The method also made use of a sulfide anti-oxidant buffer (SAOB II) which consists of ascorbic acid, sodium hydroxide, and disodium EDTA. Preweighed sodium sulfide crystals were sealed in air tight plastic volumetric flasks which were used in standardization process in the field. Field standards were prepared by adding SAOB II to the flask containing the sulfide crystals and diluting it to the mark with deionized deaerated water. Serial dilutions of the standards were used to prepare standards of lower concentrations. Concentrations as low as 6 ppB were obtained on lake samples with a reproducibility better than +- 10%.

  19. Sulfide Mineral Surfaces

    SciTech Connect

    Rosso, Kevin M.; Vaughan, David J.

    2006-08-01

    The past twenty years or so have seen dramatic development of the experimental and theoretical tools available to study the surfaces of solids at the molecular (?atomic resolution?) scale. On the experimental side, two areas of development well illustrate these advances. The first concerns the high intensity photon sources associated with synchrotron radiation; these have both greatly improved the surface sensitivity and spatial resolution of already established surface spectroscopic and diffraction methods, and enabled the development of new methods for studying surfaces. The second centers on the scanning probe microscopy (SPM) techniques initially developed in the 1980's with the first scanning tunneling microscope (STM) and atomic force microscope (AFM) experiments. The direct 'observation' of individual atoms at surfaces made possible with these methods has truly revolutionized surface science. On the theoretical side, the availability of high performance computers coupled with advances in computational modeling has provided powerful new tools to complement the advances in experiment. Particularly important have been the quantum mechanics based computational approaches such as density functional theory (DFT), which can now be easily used to calculate the equilibrium crystal structures of solids and surfaces from first principles, and to provide insights into their electronic structure. In this chapter, we review current knowledge of sulfide mineral surfaces, beginning with an overview of the principles relevant to the study of the surfaces of all crystalline solids. This includes the thermodynamics of surfaces, the atomic structure of surfaces (surface crystallography and structural stability, adjustments of atoms at the surface through relaxation or reconstruction, surface defects) and the electronic structure of surfaces. We then discuss examples where specific crystal surfaces have been studied, with the main sulfide minerals organized by structure type

  20. Electrobioleaching of base metal sulfides

    NASA Astrophysics Data System (ADS)

    Natarajan, K. A.

    1992-01-01

    Bioleaching of base metal sulfides, such as pyrite, chalcopyrite, and sphalerite, under the influence of applied direct current (DC) potentials is discussed. Contributions toward mineral dissolution from three effects, namely, galvanic, applied potential, and microbiological, are analyzed and compared. Sphalerite could be selectively bioleached in the presence of Thiobacillus ferrooxidans under an applied potential of -500 mV (SCE) from mixed sulfides containing sphalerite, pyrite, and chalcopyrite. Bacterial activity and growth were found to be promoted under electrobioleaching conditions. Probable mechanisms involved in the bioleaching of different sulfides under positive and negative applied potentials are discussed.

  1. A novel method for improving cerussite sulfidization

    NASA Astrophysics Data System (ADS)

    Feng, Qi-cheng; Wen, Shu-ming; Zhao, Wen-juan; Cao, Qin-bo; Lü, Chao

    2016-06-01

    Evaluation of flotation behavior, solution measurements, and surface analyses were performed to investigate the effects of chloride ion addition on the sulfidization of cerussite in this study. Micro-flotation tests indicate that the addition of chloride ions prior to sulfidization can significantly increase the flotation recovery of cerussite, which is attributed to the formation of more lead sulfide species on the mineral surface. Solution measurement results suggest that the addition of chloride ions prior to sulfidization induces the transformation of more sulfide ions from pulp solution onto the mineral surface by the formation of more lead sulfide species. X-ray diffraction and energy-dispersive spectroscopy indicate that more lead sulfide species form on the mineral surface when chloride ions are added prior to sulfidization. These results demonstrate that the addition of chloride ions prior to sulfidization can significantly improve the sulfidization of cerussite, thereby enhancing the flotation performance.

  2. Prevention of sulfide oxidation in sulfide-rich waste rock

    NASA Astrophysics Data System (ADS)

    Nyström, Elsa; Alakangas, Lena

    2015-04-01

    The ability to reduce sulfide oxidation in waste rock after mine closure is a widely researched area, but to reduce and/or inhibit the oxidation during operation is less common. Sulfide-rich (ca 30 % sulfur) waste rock, partially oxidized, was leached during unsaturated laboratory condition. Trace elements such as As and Sb were relatively high in the waste rock while other sulfide-associated elements such as Cu, Pb and Zn were low compared to common sulfide-rich waste rock. Leaching of unsaturated waste rock lowered the pH, from around six down to two, resulting in continuously increasing element concentrations during the leaching period of 272 days. The concentrations of As (65 mg/L), Cu (6.9 mg/L), Sb (1.2 mg/L), Zn (149 mg/L) and S (43 g/L) were strongly elevated at the end of the leaching period. Different alkaline industrial residues such as slag, lime kiln dust and cement kiln dust were added as solid or as liquid to the waste rock in an attempt to inhibit sulfide oxidation through neo-formed phases on sulfide surfaces in order to decrease the mobility of metals and metalloids over longer time scale. This will result in a lower cost and efforts of measures after mine closure. Results from the experiments will be presented.

  3. Apparatus for use in sulfide chemiluminescence detection

    DOEpatents

    Spurlin, S.R.; Yeung, E.S.

    1987-01-06

    A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

  4. Apparatus for use in sulfide chemiluminescence detection

    DOEpatents

    Spurlin, Stanford R.; Yeung, Edward S.

    1987-01-01

    A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

  5. Chemical solution deposition of ferroelectric yttrium-doped hafnium oxide films on platinum electrodes

    SciTech Connect

    Starschich, S.; Griesche, D.; Schneller, T.; Böttger, U.; Waser, R.

    2014-05-19

    Ferroelectric hafnium oxide films were fabricated by chemical solution deposition with a remnant polarization of >13 μC/cm{sup 2}. The samples were prepared with 5.2 mol. % yttrium-doping and the thickness varied from 18 nm to 70 nm. The hafnium oxide layer was integrated into a metal-insulator-metal capacitor using platinum electrodes. Due to the processing procedure, no thickness dependence of the ferroelectric properties was observed. To confirm the ferroelectric nature of the deposited samples, polarization, capacitance, and piezoelectric displacement measurements were performed. However, no evidence of the orthorhombic phase was found which has been proposed to be the non-centrosymmetric, ferroelectric phase in HfO{sub 2}.

  6. Zirconium and hafnium tetrachloride separation by extractive distillation with molten zinc chloride lead chloride solvent

    SciTech Connect

    McLaughlin, D.F.; Stoltz, R.A.

    1988-04-12

    In an extractive distillation method for separating hafniuim tetrachloride from zirconium tetrachloride of the type wherein a mixture of zirconium and hafnium tetrachlorides is introduced into an extractive distillation column, which extractive distillation column has a reboiler connected at the bottom and a reflux condenser connected at the top and wherein a molten salt solvent is circulated into the reflux condenser and through the column to provide a liquid phase, and wherein molten salt solvent containing zirconium tetrachloride is taken from the reboiler and run through a stripper to remove zirconium tetrachloride product from the molten salt solvent and the stripped molten salt solvent is returned to the reflux condenser and hafnium tetrachloride enriched vapor is taken as product from the reflux condenser, the improvement is described comprising: the molten salt having a composition of at least 30 mole percent zinc chloride and at least 10 mole percent of lead chloride.

  7. Electrodeposition of hafnium coatings from molten CsCl-HfCl{sub 4}

    SciTech Connect

    Kuznetsov, S.A.; Glagolevskaya, A.L.; Kuznetsova, S.V.

    1992-04-20

    The electrode processes in the CsCl-HfCl{sub 4} melt were examined by potentiodynamic and potentiostatic methods with the use of P-5827 and PI-50.1.1 potentiostats. The potential sweep rates were varied form 0.005 to 1.0 V/sec. The recorders were KSP-4 and LKD-4-003 potentiometers and a PO-5122 oscillographic polarograph. The electrochemical cell was the traditional one for electrochemical studies. The reference electrode was Ag/NaCl-KCl-AgCl (2 mass %). The mass loss in the hafnium anode was used to determine the anode current yield and the mean degree of oxidation for the hafnium ion entering the melt. The anode products were identified by X-ray methods with a DRON-2 diffractometer and also by thermographic and chemical analysis. 15 refs., 4 figs., 1 tab.

  8. Properties of tungsten-rhenium and tungsten-rhenium with hafnium carbide

    NASA Astrophysics Data System (ADS)

    Leonhardt, Todd

    2009-07-01

    Historically, tungsten-25wt.% rhenium alloy has been manufactured into wire for the thermocouple market, but recent demands for high-temperature structural components have forced the development of novel processing techniques for tungsten-rhenium and tungsten-rhenium with hafnium carbide. With a melting temperature of 3,050°C, and a recrystallization temperature near 1,900°C, tungsten-rhenium alloys are being used in aerospace, temperature measuring, and friction stir welding applications. The mechanical properties and microstructures of tungsten-25wt.% rhenium and tungsten-25wt.% rhenium with hafnium carbide are reported at ambient temperature, 1,371°C, and 1,926°C, after processing by three methods: hot isostatic pressing, swaging, and extrusion.

  9. Hafnium nitride buffer layers for growth of GaN on silicon

    DOEpatents

    Armitage, Robert D.; Weber, Eicke R.

    2005-08-16

    Gallium nitride is grown by plasma-assisted molecular-beam epitaxy on (111) and (001) silicon substrates using hafnium nitride buffer layers. Wurtzite GaN epitaxial layers are obtained on both the (111) and (001) HfN/Si surfaces, with crack-free thickness up to 1.2 {character pullout}m. However, growth on the (001) surface results in nearly stress-free films, suggesting that much thicker crack-free layers could be obtained.

  10. Hafnium- and titanium-coated tungsten powders for kinetic energy penetrators, Phase I, SBIR. Final report

    SciTech Connect

    Williams, B.E.; Stiglich, J.J.

    1992-05-01

    Depleted uranium (DU) is the state-of-the-art material for kinetic energy penetrators used to defeat steel and composite armors. DU alloys, however, are costly to fabricate, handle, and store because of their extremely complex metallurgy and the obvious health considerations associated with the use of uranium. Tungsten composite materials are also used in kinetic energy penetrators, offering easier and safer fabrication, handling, and storage but to date lacking the performance of DU. The mechanisms by which a penetrator defeats an armor are difficult to determine, either experimentally or from first principles. Recent experiments have identified the presence of an adiabatic shear mechanism that appears to be important in the penetration of rolled homogeneous armor (RHA) by DU penetrators. In this program, Ultramet proposed to apply hafnium and titanium coatings to tungsten powder (Wp) particles by chemical vapor deposition (CVD) using an established fluidized-bed powder coating technique. Both hafnium and titanium are known to exhibit the adiabatic shear phenomenon. High strain rate experiments (approx.10 to the 4th power/sec) were performed on Ti(6A1-4V) and hafnium materials in order to establish the presence or absence of this mode of deformation in small cylindrical specimens. In addition, specimens of 2 wt% CVD Hf/Wp and 2 wt% CVD Hf + 8 wt% powder-mixed Hf/Wp were tested at high strain rate conditions (approx. 10 to the 4th power/sec). Tungsten powders, Composites, Chemical Vapor Deposition(CVD), Microstructure, Hafnium, Titanium, Dynamic tests, Strain rate testing, Powder metallurgy.

  11. Thermoelectric Properties of Lanthanum Sulfide

    NASA Technical Reports Server (NTRS)

    Wood, C.; Lockwood, R.; Parker, J. B.; Zoltan, A.; Zoltan, L. D.; Danielson, L.; Raag, V.

    1987-01-01

    Report describes measurement of Seebeck coefficient, electrical resistivity, thermal conductivity, and Hall effect in gamma-phase lanthanum sulfide with composition of La3-x S4. Results of study, part of search for high-temperature thermoelectric energy-conversion materials, indicate this sulfide behaves like extrinsic semiconductor over temperature range of 300 to 1,400 K, with degenerate carrier concentration controlled by stoichiometric ratio of La to S.

  12. Hydrogen Sulfide Oxidation by Myoglobin.

    PubMed

    Bostelaar, Trever; Vitvitsky, Victor; Kumutima, Jacques; Lewis, Brianne E; Yadav, Pramod K; Brunold, Thomas C; Filipovic, Milos; Lehnert, Nicolai; Stemmler, Timothy L; Banerjee, Ruma

    2016-07-13

    Enzymes in the sulfur network generate the signaling molecule, hydrogen sulfide (H2S), from the amino acids cysteine and homocysteine. Since it is toxic at elevated concentrations, cells are equipped to clear H2S. A canonical sulfide oxidation pathway operates in mitochondria, converting H2S to thiosulfate and sulfate. We have recently discovered the ability of ferric hemoglobin to oxidize sulfide to thiosulfate and iron-bound hydropolysulfides. In this study, we report that myoglobin exhibits a similar capacity for sulfide oxidation. We have trapped and characterized iron-bound sulfur intermediates using cryo-mass spectrometry and X-ray absorption spectroscopy. Further support for the postulated intermediates in the chemically challenging conversion of H2S to thiosulfate and iron-bound catenated sulfur products is provided by EPR and resonance Raman spectroscopy in addition to density functional theory computational results. We speculate that the unusual sensitivity of skeletal muscle cytochrome c oxidase to sulfide poisoning in ethylmalonic encephalopathy, resulting from the deficiency in a mitochondrial sulfide oxidation enzyme, might be due to the concentration of H2S by myoglobin in this tissue. PMID:27310035

  13. Radiation effects on the electrical properties of hafnium oxide based MOS capacitors.

    SciTech Connect

    Petrosky, J. C.; McClory, J. W.; Bielejec, Edward Salvador; Foster, J. C.

    2010-10-01

    Hafnium oxide-based MOS capacitors were investigated to determine electrical property response to radiation environments. In situ capacitance versus voltage measurements were analyzed to identify voltage shifting as a result of changes to trapped charge with increasing dose of gamma, neutron, and ion radiation. In situ measurements required investigation and optimization of capacitor fabrication to include dicing, cleaning, metalization, packaging, and wire bonding. A top metal contact of 200 angstroms of titanium followed by 2800 angstroms of gold allowed for repeatable wire bonding and proper electrical response. Gamma and ion irradiations of atomic layer deposited hafnium oxide on silicon devices both resulted in a midgap voltage shift of no more than 0.2 V toward less positive voltages. This shift indicates recombination of radiation induced positive charge with negative trapped charge in the bulk oxide. Silicon ion irradiation caused interface effects in addition to oxide trap effects that resulted in a flatband voltage shift of approximately 0.6 V also toward less positive voltages. Additionally, no bias dependent voltage shifts with gamma irradiation and strong oxide capacitance room temperature annealing after ion irradiation was observed. These characteristics, in addition to the small voltage shifts observed, demonstrate the radiation hardness of hafnium oxide and its applicability for use in space systems.

  14. In vivo and in vitro studies of hafnium-binding to rat serum transferrin.

    PubMed

    Then, G M; Appel, H; Duffield, J; Taylor, D M; Thies, W G

    1986-08-01

    The binding of hafnium to rat serum transferrin was studied using the time differential perturbed angular correlation (TDPAC) technique. Hafnium is interesting as a toxic metal binding to transferrin because it behaves metabolically similarly to plutonium. The isotope 181Hf offers favorable access to the TDPAC-method. Samples were prepared in vivo by intravenous injection of Hf-NTA, Hf-citrate, and Hf-oxalate solutions, respectively, into Sprague-Dawley rats and in vitro by adding Hf-NTA solution to fresh rat serum. In both cases two specific electric quadrupole interactions were observed, which correspond to two well-defined binding configurations. They may be attributed to the N-terminal and the C-terminal binding site in the transferrin molecule. The 181Hf-distribution between these two binding states depends on pH, salt and hafnium concentrations, temperature, and incubation time. With a fast TDPAC-setup of four BaF2-detectors a time resolution of about 600 ps could be achieved. The specific binding configurations of 181Hf and the comparatively slow relaxation times lead to spectra of considerable accuracy. PMID:3746294

  15. In vivo and in vitro studies of hafnium-binding to rat serum transferrin

    SciTech Connect

    Then, G.M.; Appel, H.; Duffield, J.; Taylor, D.M.; Thies, W.G.

    1986-08-01

    The binding of hafnium to rat serum transferrin was studied using the time differential perturbed angular correlation (TDPAC) technique. Hafnium is interesting as a toxic metal binding to transferrin because it behaves metabolically similarly to plutonium. The isotope 181Hf offers favorable access to the TDPAC-method. Samples were prepared in vivo by intravenous injection of Hf-NTA, Hf-citrate, and Hf-oxalate solutions, respectively, into Sprague-Dawley rats and in vitro by adding Hf-NTA solution to fresh rat serum. In both cases two specific electric quadrupole interactions were observed, which correspond to two well-defined binding configurations. They may be attributed to the N-terminal and the C-terminal binding site in the transferrin molecule. The 181Hf-distribution between these two binding states depends on pH, salt and hafnium concentrations, temperature, and incubation time. With a fast TDPAC-setup of four BaF2-detectors a time resolution of about 600 ps could be achieved. The specific binding configurations of 181Hf and the comparatively slow relaxation times lead to spectra of considerable accuracy.

  16. On the phase formation of sputtered hafnium oxide and oxynitride films

    NASA Astrophysics Data System (ADS)

    Sarakinos, K.; Music, D.; Mráz, S.; to Baben, M.; Jiang, K.; Nahif, F.; Braun, A.; Zilkens, C.; Konstantinidis, S.; Renaux, F.; Cossement, D.; Munnik, F.; Schneider, J. M.

    2010-07-01

    Hafnium oxynitride films are deposited from a Hf target employing direct current magnetron sputtering in an Ar-O2-N2 atmosphere. It is shown that the presence of N2 allows for the stabilization of the transition zone between the metallic and the compound sputtering mode enabling deposition of films at well defined conditions of target coverage by varying the O2 partial pressure. Plasma analysis reveals that this experimental strategy facilitates control over the flux of the O- ions which are generated on the oxidized target surface and accelerated by the negative target potential toward the growing film. An arrangement that enables film growth without O- ion bombardment is also implemented. Moreover, stabilization of the transition sputtering zone and control of the O- ion flux without N2 addition is achieved employing high power pulsed magnetron sputtering. Structural characterization of the deposited films unambiguously proves that the phase formation of hafnium oxide and hafnium oxynitride films with the crystal structure of HfO2 is independent from the O- bombardment conditions. Experimental and theoretical data indicate that the presence of vacancies and/or the substitution of O by N atoms in the nonmetal sublattice favor the formation of the cubic and/or the tetragonal HfO2 crystal structure at the expense of the monoclinic HfO2 one.

  17. On the phase formation of sputtered hafnium oxide and oxynitride films

    SciTech Connect

    Sarakinos, K.; Music, D.; Mraz, S.; Baben, M. to; Jiang, K.; Nahif, F.; Braun, A.; Zilkens, C.; Schneider, J. M.; Konstantinidis, S.; Renaux, F.; Cossement, D.; Munnik, F.

    2010-07-15

    Hafnium oxynitride films are deposited from a Hf target employing direct current magnetron sputtering in an Ar-O{sub 2}-N{sub 2} atmosphere. It is shown that the presence of N{sub 2} allows for the stabilization of the transition zone between the metallic and the compound sputtering mode enabling deposition of films at well defined conditions of target coverage by varying the O{sub 2} partial pressure. Plasma analysis reveals that this experimental strategy facilitates control over the flux of the O{sup -} ions which are generated on the oxidized target surface and accelerated by the negative target potential toward the growing film. An arrangement that enables film growth without O{sup -} ion bombardment is also implemented. Moreover, stabilization of the transition sputtering zone and control of the O{sup -} ion flux without N{sub 2} addition is achieved employing high power pulsed magnetron sputtering. Structural characterization of the deposited films unambiguously proves that the phase formation of hafnium oxide and hafnium oxynitride films with the crystal structure of HfO{sub 2} is independent from the O{sup -} bombardment conditions. Experimental and theoretical data indicate that the presence of vacancies and/or the substitution of O by N atoms in the nonmetal sublattice favor the formation of the cubic and/or the tetragonal HfO{sub 2} crystal structure at the expense of the monoclinic HfO{sub 2} one.

  18. RF sputtered silicon and hafnium nitrides as applied to 440C steel

    NASA Technical Reports Server (NTRS)

    Grill, A.; Aron, P. R.

    1984-01-01

    Silicon nitride and hafnium nitride coatings were deposited on oxidized and unoxidized 440C stainless steel substrates. Sputtering was done in mixtures of argon and nitrogen gases from pressed powder silicon nitride and from hafnium metal targets. The coatings and the interface between the coating and substrate were investigated by X-ray diffractometry, scanning electron microscopy, energy dispersive X-ray analysis and Auger electron spectroscopy. Oxide was found at all interfaces with an interface width of at least 600 A for the oxidized substrates and at least 300 A for the unoxidized substrates. Scratch test results demonstrate that the adhesion of hafnium nitride to both oxidized and unoxidized 440C is superior to that of silicon nitride. Oxidized 440C is found to have increased adhesion, to both nitrides, over that of unoxidized 440C. Coatings of both nitrides deposited at 8 mtorr were found to have increased adhesion to both oxidized and unoxidized 440C over those deposited at 20 mtorr.

  19. Oxygen and nitrogen diffusion in α-hafnium from first principles

    SciTech Connect

    O'Hara, Andrew; Demkov, Alexander A.

    2014-05-26

    We use a combination of density functional theory and multistate diffusion formalism to analyze the diffusion of oxygen and nitrogen in technologically important hafnium metal. Comparing the local density approximation and the Perdew-Burke-Ernzerhof version of the generalized gradient approximation, we find that a better description of the hafnium lattice in the latter results in the correct sequence of stable and transition states for oxygen interstitials leading to essentially quantitative agreement with experiment. For oxygen diffusion, we find an isotropic temperature-dependent diffusion coefficient of D=0.082e{sup −2.04/k{sub B}T}cm{sup 2}s{sup −1} utilizing interstitial sites with hexahedral and octahedral coordination. For the diffusivity of nitrogen, we find that an additional stable interstitial site, the crowdion site, exists and that the diffusion coefficient is D=0.15e{sup −2.68/k{sub B}T}cm{sup 2}s{sup −1}. Our results also reproduce the experimental observation that nitrogen diffusivity is lower than that of oxygen in hafnium.

  20. Inhaled Hydrogen Sulfide

    PubMed Central

    Volpato, Gian Paolo; Searles, Robert; Yu, Binglan; Scherrer-Crosbie, Marielle; Bloch, Kenneth D.; Ichinose, Fumito; Zapol, Warren M.

    2010-01-01

    Background Breathing hydrogen sulfide (H2S) has been reported to induce a suspended animation–like state with hypothermia and a concomitant metabolic reduction in rodents. However, the impact of H2S breathing on cardiovascular function remains incompletely understood. In this study, the authors investigated the cardiovascular and metabolic effects of inhaled H2S in a murine model. Methods The impact of breathing H2S on cardiovascular function was examined using telemetry and echocardiography in awake mice. The effects of breathing H2S on carbon dioxide production and oxygen consumption were measured at room temperature and in a warmed environment. Results Breathing H2S at 80 parts per million by volume at 27°C ambient temperature for 6 h markedly reduced heart rate, core body temperature, respiratory rate, and physical activity, whereas blood pressure remained unchanged. Echocardiography demonstrated that H2S exposure decreased both heart rate and cardiac output but preserved stroke volume. Breathing H2S for 6 h at 35°C ambient temperature (to prevent hypothermia) decreased heart rate, physical activity, respiratory rate, and cardiac output without altering stroke volume or body temperature. H2S breathing seems to induce bradycardia by depressing sinus node activity. Breathing H2S for 30 min decreased whole body oxygen consumption and carbon dioxide production at either 27° or 35°C ambient temperature. Both parameters returned to baseline levels within 10 min after the cessation of H2S breathing. Conclusions Inhalation of H2S at either 27° or 35°C reversibly depresses cardiovascular function without changing blood pressure in mice. Breathing H2S also induces a rapidly reversible reduction of metabolic rate at either body temperature. PMID:18362598

  1. Sulfur and sulfides in chondrules

    NASA Astrophysics Data System (ADS)

    Marrocchi, Yves; Libourel, Guy

    2013-10-01

    The nature and distribution of sulfides within type I PO, POP and PP chondrules of the carbonaceous chondrite Vigarano (CV3) have been studied by secondary electron microscopy and electron microprobe. They occur predominantly as spheroidal blebs composed entirely of low-Ni iron sulfide (troilite, FeS) or troilite + magnetite but in less abundance in association with metallic Fe-Ni beads in opaque assemblages. Troilites are mainly located within the low-Ca pyroxene outer zone and their amounts increase with the abundance of low-Ca pyroxene within chondrules, suggesting co-crystallization of troilite and low-Ca pyroxene during high-temperature events. We show that sulfur concentration and sulfide occurrence in chondrules obey high temperature sulfur solubility and saturation laws. Depending on the fS2 and fO2 of the surrounding gas and on the melt composition, mainly the FeO content, sulfur dissolved in chondrule melts may eventually reach a concentration limit, the sulfur content at sulfide saturation (SCSS), at which an immiscible iron sulfide liquid separates from the silicate melt. The occurrence of both a silicate melt and an immiscible iron sulfide liquid is further supported by the non-wetting behavior of sulfides on silicate phases in chondrules due to the high interfacial tension between their precursor iron-sulfide liquid droplets and the surrounding silicate melt during the high temperature chondrule-forming event. The evolution of chondrule melts from PO to PP towards more silicic compositions, very likely due to high PSiO(g) of the surrounding nebular gas, induces saturation of FeS at much lower S content in PP than in PO chondrules, leading to the co-crystallization of iron sulfides and low-Ca pyroxenes. Conditions of co-saturation of low-Ca pyroxene and FeS are only achieved in non canonical environments characterized by high partial pressures of sulfur and SiO and redox conditions more oxidizing than IW-3. Fe and S mass balance calculations also

  2. Mechanistic chemical perspective of hydrogen sulfide signaling.

    PubMed

    Nagy, Péter

    2015-01-01

    Hydrogen sulfide is now a well-appreciated master regulator in a diverse array of physiological processes. However, as a consequence of the rapid growth of the area, sulfide biology suffers from an increasing number of controversial observations and interpretations. A better understanding of the underlying molecular pathways of sulfide's actions is key to reconcile controversial issues, which calls for rigorous chemical/biochemical investigations. Protein sulfhydration and coordination/redox chemical interactions of sulfide with heme proteins are the two most extensively studied pathways in sulfide biochemistry. These pathways are important mediators of protein functions, generate bioactive sulfide metabolites, contribute to sulfide storage/trafficking and carry antioxidant functions. In addition, inorganic polysulfides, which are oxidative sulfide metabolites, are increasingly recognized as important players in sulfide biology. This chapter provides an overview of our mechanistic perspective on the reactions that govern (i) sulfide's bioavailability (including the delicate enzyme machineries that orchestrate sulfide production and consumption and the roles of the large sulfide-storing pools as biological buffers), (ii) biological significance and mechanisms of persulfide formation (including the reduction of disulfides, condensation with sulfenic acids, oxidation of thiols with polysulfides and radical-mediated pathways), (iii) coordination and redox chemical interactions of sulfide with heme proteins (including cytochrome c oxidase, hemoglobins, myoglobins and peroxidases), and (iv) the chemistry of polysulfides. PMID:25725513

  3. Sulfide Stability of Planetary Basalts

    NASA Technical Reports Server (NTRS)

    Caiazza, C. M.; Righter, K.; Gibson, E. K., Jr.; Chesley, J. T.; Ruiz, J.

    2004-01-01

    The isotopic system, 187Re 187Os, can be used to determine the role of crust and mantle in magma genesis. In order to apply the system to natural samples, we must understand variations in Re/Os concentrations. It is thought that low [Os] and [Re] in basalts can be attributed to sulfide (FeS) saturation, as Re behaves incompatibly to high degrees of evolution until sulfide saturation occurs [1]. Previous work has shown that lunar basalts are sulfide under-saturated, and mid-ocean ridge, ocean-island and Martian (shergottites) basalts are saturated [2,3]. However, little is known about arc basalts. In this study, basaltic rocks were analyzed across the Trans-Mexican Volcanic Belt.

  4. A Reaction Involving Oxygen and Metal Sulfides.

    ERIC Educational Resources Information Center

    Hill, William D. Jr.

    1986-01-01

    Describes a procedure for oxygen generation by thermal decomposition of potassium chlorate in presence of manganese dioxide, reacted with various sulfides. Provides a table of sample product yields for various sulfides. (JM)

  5. 30 CFR 250.604 - Hydrogen sulfide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.604 Section 250.604...-Workover Operations § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined...

  6. 30 CFR 250.808 - Hydrogen sulfide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 2 2013-07-01 2013-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or...

  7. 30 CFR 250.808 - Hydrogen sulfide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 2 2012-07-01 2012-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or...

  8. 30 CFR 250.808 - Hydrogen sulfide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 2 2014-07-01 2014-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or...

  9. 30 CFR 250.504 - Hydrogen sulfide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.504 Section 250.504...-Completion Operations § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined...

  10. Nanostructured metal sulfides for energy storage.

    PubMed

    Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

    2014-09-01

    Advanced electrodes with a high energy density at high power are urgently needed for high-performance energy storage devices, including lithium-ion batteries (LIBs) and supercapacitors (SCs), to fulfil the requirements of future electrochemical power sources for applications such as in hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles. Metal sulfides with unique physical and chemical properties, as well as high specific capacity/capacitance, which are typically multiple times higher than that of the carbon/graphite-based materials, are currently studied as promising electrode materials. However, the implementation of these sulfide electrodes in practical applications is hindered by their inferior rate performance and cycling stability. Nanostructures offering the advantages of high surface-to-volume ratios, favourable transport properties, and high freedom for the volume change upon ion insertion/extraction and other reactions, present an opportunity to build next-generation LIBs and SCs. Thus, the development of novel concepts in material research to achieve new nanostructures paves the way for improved electrochemical performance. Herein, we summarize recent advances in nanostructured metal sulfides, such as iron sulfides, copper sulfides, cobalt sulfides, nickel sulfides, manganese sulfides, molybdenum sulfides, tin sulfides, with zero-, one-, two-, and three-dimensional morphologies for LIB and SC applications. In addition, the recently emerged concept of incorporating conductive matrices, especially graphene, with metal sulfide nanomaterials will also be highlighted. Finally, some remarks are made on the challenges and perspectives for the future development of metal sulfide-based LIB and SC devices. PMID:25073046

  11. 30 CFR 250.808 - Hydrogen sulfide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.808 Section 250.808... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Production Safety Systems § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of...

  12. 30 CFR 250.604 - Hydrogen sulfide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.604 Section 250.604... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Workover Operations § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or...

  13. 30 CFR 250.504 - Hydrogen sulfide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.504 Section 250.504... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Completion Operations § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or...

  14. 30 CFR 250.490 - Hydrogen sulfide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 2 2014-07-01 2014-07-01 false Hydrogen sulfide. 250.490 Section 250.490 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL AND GAS AND SULPHUR OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Drilling Operations Hydrogen Sulfide § 250.490 Hydrogen sulfide. (a)...

  15. Long period gratings coated with hafnium oxide by plasma-enhanced atomic layer deposition for refractive index measurements.

    PubMed

    Melo, Luis; Burton, Geoff; Kubik, Philip; Wild, Peter

    2016-04-01

    Long period gratings (LPGs) are coated with hafnium oxide using plasma-enhanced atomic layer deposition (PEALD) to increase the sensitivity of these devices to the refractive index of the surrounding medium. PEALD allows deposition at low temperatures which reduces thermal degradation of UV-written LPGs. Depositions targeting three different coating thicknesses are investigated: 30 nm, 50 nm and 70 nm. Coating thickness measurements taken by scanning electron microscopy of the optical fibers confirm deposition of uniform coatings. The performance of the coated LPGs shows that deposition of hafnium oxide on LPGs induces two-step transition behavior of the cladding modes. PMID:27137052

  16. Determination of Ideal Broth Formulations Needed to Prepare Hydrous Hafnium Oxide Microspheres via the Internal Gelation Process

    SciTech Connect

    Collins, Jack Lee; Hunt, Rodney Dale; Simmerman, S. G.

    2009-02-01

    A simple test-tube methodology was used to determine optimum process parameters for preparing hydrous hafnium oxide microspheres by the internal gelation process. Broth formulations of hafnyl chloride [HfOCl{sub 2}], hexamethylenetetramine, and urea were found that can be used to prepare hydrous hafnium oxide gel spheres in the temperature range of 70-90 C. A few gel-forming runs were made in which microspheres were prepared with some of these formulations in order to equate the test-tube gelation times with actual gelation times. These preparations confirmed that the test-tube methodology is reliable for determining the ideal broths.

  17. Multimode resistive switching in nanoscale hafnium oxide stack as studied by atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Hou, Y.; Celano, U.; Goux, L.; Liu, L.; Degraeve, R.; Cheng, Y.; Kang, J.; Jurczak, M.; Vandervorst, W.

    2016-07-01

    The nanoscale resistive switching in hafnium oxide stack is investigated by the conductive atomic force microscopy (C-AFM). The initial oxide stack is insulating and electrical stress from the C-AFM tip induces nanometric conductive filaments. Multimode resistive switching can be observed in consecutive operation cycles at one spot. The different modes are interpreted in the framework of a low defect quantum point contact theory. The model implies that the optimization of the conductive filament active region is crucial for the future application of nanoscale resistive switching devices.

  18. Aluminum depletion in komatiites and garnet fractionation in the early Archean mantle: Hafnium isotopic constraints

    SciTech Connect

    Gruau, G. Universite de Rennes ); Chauvel, C.; Arndt, N.T. ); Cornichet, J. )

    1990-11-01

    Hafnium isotopic compositions were measured in Al-depleted and Al-enriched komatiites from the 3,450 Ma old Barberton greenstone belt, southern Africa. All samples have initial {var epsilon}{sub Hf} values close to zero. Such values are at variance with the strongly negative or positive values that should be observed if these rocks came from old garnet-depleted or garnet-enriched layers, such as may have formed during the solidification of an ancient terrestrial magma ocean. The garnet fractionation observed in komatiites probably took place during the melting event.

  19. Periodic alignment of Si quantum dots on hafnium oxide coated single wall carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Olmedo, Mario; Martinez-Morales, Alfredo A.; Liu, Gang; Yengel, Emre; Ozkan, Cengiz S.; Lau, Chun Ning; Ozkan, Mihrimah; Liu, Jianlin

    2009-03-01

    We demonstrate a bottom up approach for the aligned epitaxial growth of Si quantum dots (QDs) on one-dimensional (1D) hafnium oxide (HfO2) ridges created by the growth of HfO2 thin film on single wall carbon nanotubes. This growth process creates a high strain 1D ridge on the HfO2 film, which favors the formation of Si seeds over the surrounding flat HfO2 area. Periodic alignment of Si QDs on the 1D HfO2 ridge was observed, which can be controlled by varying different growth conditions, such as growth temperature, growth time, and disilane flow rate.

  20. SULFIDE PRECIPITATION OF HEAVY METALS

    EPA Science Inventory

    The research program was initiated with the objective of evaluating a new process, the sulfide precipitation of heavy metals from industrial wastewaters. The process was expected to effect a more complete removal of heavy metals than conventional lime processing because of the mu...

  1. p-Chlorophenyl methyl sulfide

    Integrated Risk Information System (IRIS)

    p - Chlorophenyl methyl sulfide ; CASRN 123 - 09 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for N

  2. Transition metal sulfide loaded catalyst

    DOEpatents

    Maroni, Victor A.; Iton, Lennox E.; Pasterczyk, James W.; Winterer, Markus; Krause, Theodore R.

    1994-01-01

    A zeolite based catalyst for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C.sub.2 + hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

  3. Platinum metals magmatic sulfide ores.

    PubMed

    Naldrett, A J; Duke, J M

    1980-06-27

    Platinum-group elements (PGE) are mined predominantly from deposits that have formed by the segregation of molten iron-nickel-copper sulfides from silicate magmas. The absolute concentrations of PGE in sulfides from different deposits vary over a range of five orders of magnitude, whereas those of other chalcophile elements vary by factors of only 2 to 100. However, the relative proportions of the different PGE in a given deposit are systematically related to the nature of the parent magma. The absolute and relative concentrations of PGE in magmatic sulfides are explained in terms of the degree of partial melting of mantle peridotite required to produce the parent magma and the processes of batch equilibration and fractional segregation of sulfides. The Republic of South Africa and the U.S.S.R. together possess more than 97 percent of the world PGE reserves, but significant undeveloped resources occur in North America. The Stillwater complex in Montana is perhaps the most important example. PMID:17796685

  4. Microstructure and optical properties of Pr3+-doped hafnium silicate films

    PubMed Central

    2013-01-01

    In this study, we report on the evolution of the microstructure and photoluminescence properties of Pr3+-doped hafnium silicate thin films as a function of annealing temperature (TA). The composition and microstructure of the films were characterized by means of Rutherford backscattering spectrometry, spectroscopic ellipsometry, Fourier transform infrared absorption, and X-ray diffraction, while the emission properties have been studied by means of photoluminescence (PL) and PL excitation (PLE) spectroscopies. It was observed that a post-annealing treatment favors the phase separation in hafnium silicate matrix being more evident at 950°C. The HfO2 phase demonstrates a pronounced crystallization in tetragonal phase upon 950°C annealing. Pr3+ emission appeared at TA = 950°C, and the highest efficiency of Pr3+ ion emission was detected upon a thermal treatment at 1,000°C. Analysis of the PLE spectra reveals an efficient energy transfer from matrix defects towards Pr3+ ions. It is considered that oxygen vacancies act as effective Pr3+ sensitizer. Finally, a PL study of undoped HfO2 and HfSiOx matrices is performed to evidence the energy transfer. PMID:23336520

  5. Effect of reactive magnetron sputtering parameters on structural and electrical properties of hafnium oxide thin films

    NASA Astrophysics Data System (ADS)

    Szymańska, Magdalena; Gierałtowska, Sylwia; Wachnicki, Łukasz; Grobelny, Marcin; Makowska, Katarzyna; Mroczyński, Robert

    2014-05-01

    The purpose of this work was to compare the structural and electrical properties of magnetron sputtered hafnium oxide (HfOx) and hafnium oxynitride (HfOxNy) thin films. A careful analysis of the influence of deposition process parameters, among them: pressure in the reactor chamber, Ar and O2 flow rate, power applied to the reactor chamber and deposition time, on electro-physical properties of HfOx and HfOxNy layers has been performed. In the course of this work we performed number of experiments by means of Taguchi's orthogonal arrays approach. Such a method allowed for the determination of dielectric layers properties depending on process parameters with relatively low amount of experiments. Moreover, the effects of post-deposition annealing on electrical characteristics of metal-insulator-semiconductor (MIS) structures with HfOx or HfOxNy gate dielectric and its structural properties have also been reported. Investigated hafnia thin films were characterized by means of spectroscopic ellipsometry (SE), electrical characteristics measurements, atomic force microscopy (AFM), X-ray diffraction spectroscopy (XRD) and Rutherford backscattering spectrometry (RBS).

  6. Processing and properties of extruded tungsten-hafnium and tungsten-steel composites

    SciTech Connect

    Ohriner, E.K.; Sikka, V.K.; Kapoor, D.

    1995-02-01

    The purpose of this study was to evaluate the processing behavior and properties of tungsten-hafnium (W-Hf) and W-steel composites produced by hot extrusion of canned powders. The W-Hf composite was consolidated by extrusion of blended powders with preheat temperatures over the temperature range of 1100 to 1400{degrees}C. All extrusions produced fully dense material which exhibits elongation of the tungsten phase within the hafnium matrix. The flow stress, as characterized by the extrusion constant, decreases with increasing temperature up to 1300{degrees}C and increases substantially at 1400{degrees}C as significant quantities of intermetallic phase are formed during preheating. The room-temperature (RT) hardness and compressive yield stress increase modestly with increased extrusion ratio and are not affected by extrusion temperature in the range 1100 to 1300{degrees}C. The microstructures are essentially fully recrystallized at the 1300{degrees}C preheat temperature and partially recrystallized at lower temperatures. Additionally, a mixture of tungsten and steel powder was consolidated to full density by hot extrusion at a 1000{degrees}C preheat temperature and a reduction ratio of 4.2. Increased reduction of the W-steel composite results in increased RT hardness.

  7. Hafnium hydroxide complexation and solubility: The impact of hydrolysis reactions on the disposition of weapons-grade plutonium

    SciTech Connect

    Cerefice, G.; Draye, M.; Noyes, K.; Czerwinski, K.

    1999-07-01

    The stability constants for the complexation of hafnium by hydroxide ions is investigated by potentiometric titration over a range of ionic strengths (I{sub m} = 0.1 to 6.6 molal). The stability constants are determined from the titration data using the HYPERQUAD suite of programs. The stability constants at infinite dilution are determined using the Specific Ion Interaction Theory from the stability constants determined by titration. The solubility product of Hf(OH){sub 4} (s) is determined in 0.1 M NaClO{sub 4} by measuring the total hafnium in solution that is in equilibrium with an excess of hafnium hydroxide solid under an argon atmosphere. The total Hf concentration is determined by ICP-AES. The solubility product is determined using the stability constants measured for the Hf hydrolysis products in 0.1 M NaClO{sub 4}. The precipitate examined is confirmed to be a hydroxide by IR spectroscopy. For Hf(OH){sub 4} (s) in 0.1 M NaClO{sub 4}, the solubility product is log K{sub sp} (Hf(OH){sub 4} (s)) = {minus}51.8 {+-} 0.5. The solubility and stability constants determined are used, along with literature values for plutonium solubility and complexation constants, to examine the behavior of hafnium and plutonium under the conditions expected at Yucca Mountain.

  8. Preparation and properties of electrically conducting ceramics based on indium oxide-rare earth oxides-hafnium oxides

    SciTech Connect

    Marchant, D.D.; Bates, J.L.

    1983-09-01

    Electrically conducting refractory oxides based on adding indium oxide to rare earth-stabilized hafnium oxide are being studied for use in magnetohydrodynamic (MHD) generators, fuel cells, and thermoelectric generators. The use of indium oxide generally increases the electrical conductivity. The results of measurements of the electrical conductivity and data on corrosion resistance in molten salts are presented.

  9. Marine diagenesis of hydrothermal sulfide

    SciTech Connect

    Moammar, M.O.

    1985-01-01

    An attempt is made to discuss the artificial and natural oxidation and hydrolysis of hydrothermal sulfide upon interaction with normal seawater. Synthetic and natural ferrosphalerite particles used in kinetic oxidation and hydrolysis studies in seawater develop dense, crystalline coatings consisting of ordered and ferrimagnetic delta-(Fe, Zn)OOH. Due to the formation of this reactive diffusion barrier, the release of Zn into solution decreases rapidly, and sulfide oxidation is reduced to a low rate determined by the diffusion of oxygen through the oxyhydroxide film. This also acts as an efficient solvent for ions such as Zn/sup 2 +/, Ca/sup 2 +/, and possibly Cd/sup 2 +/, which contribute to the stabilization of the delta-FeOOH structure. The oxidation of sulfide occurs in many seafloor spreading areas, such as 21/sup 0/N on the East Pacific Ridge. In these areas the old surface of the sulfide chimneys are found to be covered by an orange stain, and sediment near the base of nonactive vents is also found to consist of what has been referred to as amorphous iron oxide and hydroxide. This thesis also discusses the exceedingly low solubility of zinc in seawater, from delta-(Fe, Zn)OOH and the analogous phase (zinc-ferrihydroxide) and the zinc exchange minerals, 10-A manganate and montmorillonite. The concentrations of all four are of the same magnitude (16, 36.4, and 12 nM, respectively) as the zinc concentration in deep ocean water (approx. 10 nM), which suggests that manganates and montmorillonite with iron oxyhydroxides control zinc concentration in the deep ocean.

  10. Sulfide-Driven Microbial Electrosynthesis

    SciTech Connect

    Gong, YM; Ebrahim, A; Feist, AM; Embree, M; Zhang, T; Lovley, D; Zengler, K

    2013-01-01

    Microbial electrosynthesis, the conversion of carbon dioxide to organic molecules using electricity, has recently been demonstrated for acetogenic microorganisms, such as Sporomusa ovata. The energy for reduction of carbon dioxide originates from the hydrolysis of water on the anode, requiring a sufficiently low potential. Here we evaluate the use of sulfide as an electron source for microbial electrosynthesis. Abiotically oxidation of sulfide on the anode yields two electrons. The oxidation product, elemental sulfur, can be further oxidized to sulfate by Desulfobulbus propionicus, generating six additional electrons in the process. The eight electrons generated from the combined abiotic and biotic steps were used to reduce carbon dioxide to acetate on a graphite cathode by Sporomusa ovata at a rate of 24.8 mmol/day.m(2). Using a strain of Desulfuromonas as biocatalyst on the anode resulted in an acetate production rate of 49.9 mmol/day.m(2), with a Coulombic efficiency of over 90%. These results demonstrate that sulfide can serve effectively as an alternative electron donor for microbial electrosynthesis.

  11. 30 CFR 250.504 - Hydrogen sulfide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 2 2013-07-01 2013-07-01 false Hydrogen sulfide. 250.504 Section 250.504... § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of...

  12. 30 CFR 250.604 - Hydrogen sulfide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 2 2014-07-01 2014-07-01 false Hydrogen sulfide. 250.604 Section 250.604... § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of...

  13. 30 CFR 250.504 - Hydrogen sulfide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 2 2012-07-01 2012-07-01 false Hydrogen sulfide. 250.504 Section 250.504... § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of...

  14. 30 CFR 250.604 - Hydrogen sulfide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 2 2012-07-01 2012-07-01 false Hydrogen sulfide. 250.604 Section 250.604... § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of...

  15. 30 CFR 250.604 - Hydrogen sulfide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 2 2013-07-01 2013-07-01 false Hydrogen sulfide. 250.604 Section 250.604... § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of...

  16. 30 CFR 250.504 - Hydrogen sulfide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 2 2014-07-01 2014-07-01 false Hydrogen sulfide. 250.504 Section 250.504... § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined in § 250.490 of...

  17. Effect of hafnium doping on density of states in dual-target magnetron co-sputtering HfZnSnO thin film transistors

    SciTech Connect

    Huang, Chuan-Xin; Li, Jun Fu, Yi-Zhou; Jiang, Xue-Yin; Zhang, Jian-Hua; Zhang, Zhi-Lin

    2015-11-23

    This study investigates the effect of hafnium doping on the density of states (DOSs) in HfZnSnO thin film transistors fabricated by dual-target magnetron co-sputtering system. The DOSs is extracted by temperature-dependent field-effect measurements, and they decrease from 1.1 × 10{sup 17} to 4.6 × 10{sup 16 }eV/cm{sup 3} with increasing the hafnium concentrations. The behavior of DOSs for the increasing hafnium concentration HfZnSnO thin film transistors can be confirmed by both the reduction of ΔV{sub T} under bias stress and the trapping charges calculated by capacitance voltage measurements. It suggests that the reduction in DOSs due to the hafnium doping is closely related with the bias stability and thermal stability.

  18. Rapid Synthesis of Nonstoichiometric Lanthanum Sulfide

    NASA Technical Reports Server (NTRS)

    Matsuda, S.; Shapiro, E.; Danielson, L.; Hardister, H.

    1987-01-01

    New process relatively fast and simple. Improved method of synthesizing nonstoichiometric lanthanum sulfide faster and simpler. Product purer because some of prior sources of contamination eliminated.

  19. Stress-rupture strength and microstructural stability of tungsten-hafnium-carbon-wire reinforced superalloy composites

    NASA Technical Reports Server (NTRS)

    Petrasek, D. W.; Signorelli, R. A.

    1974-01-01

    Tungsten-hafnium-carbon - superalloy composites were found to be potentially useful for turbine blade applications on the basis of stress-rupture strength. The 100- and 1000-hr rupture strengths calculated for 70 vol. % fiber composites based on test data at 1090C (2000F) were 420 and 280 MN/m2 (61,000 and 41,000 psi, respectively). The investigation indicated that, with better quality fibers, composites having 100- and 1000-hr rupture strengths of 570 and 370 MN/m2 (82,000 and 54,000 psi, respectively), may be obtained. Metallographic studies indicated sufficient fiber-matrix compatibility for 1000 hr or more at 1090C (2000F).

  20. Composition effects on mechanical properties of tungsten-rhenium-hafnium-carbon alloys

    NASA Technical Reports Server (NTRS)

    Witzke, W. R.

    1973-01-01

    The mechanical properties of rod and sheet fabricated from arc melted W-4Re-Hf-C alloys containing up to about 0.8 mol percent hafnium carbide (HfC) were evaluated in the as-worked condition. The DBTT's of electropolished bend and tensile specimens were independent of HfC content in this range but dependent on excess Hf or C above that required for stoichiometric HfC. Low temperature ductility was a maximum at Hf contents slightly in excess of stoichiometric. Variations in high temperature strength were also dependent on excess Hf and C. Maximum creep strengthening also occurred at Hf contents in excess of stoichiometric. Analysis of extracted second phase particles indicated that creep strength was reduced by increasing WC content in the HfC particles.

  1. Density and surface tension of melts of zirconium and hafnium fluorides with lithium fluoride

    SciTech Connect

    Katyshev, S.F.; Artemov, V.V.; Desyatnik, V.N.

    1988-06-01

    A study was conducted to determine the temperature dependence of the density and surface tension of melts of LiF-ZrF/sub 4/ and LiF-HfF/sub 4/. Density and surface tension were determined by the method of maximum pressure in an argon bubble. On the basis of experimental data over the entire concentration range the molar volumes and their relative deviations from the additive molar volumes were calculated for 1100/sup 0/K. The positive deviations of the molar volumes from additivity in the LiF-HfF/sub 4/ system (22.45%) were greater than in the LiF-ZrF/sub 4/ system (15.75%). This indicated that the reaction with lithium fluoride is intensified with the switch to the hafnium fluoride. Results also demonstrated that the fluorides are surface-active components in the molten mixtures.

  2. Cesium hafnium chloride: A high light yield, non-hygroscopic cubic crystal scintillator for gamma spectroscopy

    SciTech Connect

    Burger, Arnold; Rowe, Emmanuel; Groza, Michael; Morales Figueroa, Kristle; Cherepy, Nerine J.; Beck, Patrick R.; Hunter, Steven; Payne, Stephen A.

    2015-10-05

    We report on the scintillation properties of Cs{sub 2}HfCl{sub 6} (cesium hafnium chloride or CHC) as an example of a little-known class of non-hygroscopic compounds having the generic cubic crystal structure of K{sub 2}PtCl{sub 6}. The crystals are easily growable from the melt using the Bridgman method with minimal precursor treatments or purification. CHC scintillation is centered at 400 nm, with a principal decay time of 4.37 μs and a light yield of up to 54 000 photons/MeV when measured using a silicon CCD photodetector. The light yield is the highest ever reported for an undoped crystal, and CHC also exhibits excellent light yield nonproportionality. These desirable properties allowed us to build and test CHC gamma-ray spectrometers providing energy resolution of 3.3% at 662 keV.

  3. Hafnium dioxide as a dielectric for highly-sensitive waveguide-coupled surface plasmon resonance sensors

    NASA Astrophysics Data System (ADS)

    Tiwari, Kunal; Sharma, Suresh C.; Hozhabri, Nader

    2016-04-01

    Hafnium dioxide has been recognized as an excellent dielectric for microelectronics. However, its usefulness for the surface plasmon based sensors has not yet been tested. Here we investigate its usefulness for waveguide-coupled bi-metallic surface plasmon resonance sensors. Several Ag/HfO2/Au multilayer structure sensors were fabricated and evaluated by optical measurements and computer simulations. The resulting data establish correlations between the growth parameters and sensor performance. The sensor sensitivity to refractive index of analytes is determined to be S n = /∂ θ SPR ∂ n ≥ 4 7 0 . The sensitivity data are supported by simulations, which also predict 314 nm for the evanescent field decay length in air.

  4. Sub-10 nm low current resistive switching behavior in hafnium oxide stack

    NASA Astrophysics Data System (ADS)

    Hou, Y.; Celano, U.; Goux, L.; Liu, L.; Fantini, A.; Degraeve, R.; Youssef, A.; Xu, Z.; Cheng, Y.; Kang, J.; Jurczak, M.; Vandervorst, W.

    2016-03-01

    In this letter, a tip-induced cell relying on the conductive atomic force microscope is proposed. It is verified as a referable replica of an integrated resistive random access memory (RRAM) device. On the basis of this cell, the functionality of sub-10 nm resistive switching is confirmed in hafnium oxide stack. Moreover, the low current switching behavior in the sub-10 nm dimension is found to be more pronounced than that of a 50 × 50 nm2 device. It shows better ON/OFF ratio and low leakage current. The enhanced memory performance is ascribed to a change in the shape of the conductive filament as the device dimensions are reduced to sub-10 nm. Therefore, device downscaling provides a promising approach for the resistance optimization that benefits the RRAM array design.

  5. The effect of twinning on the work hardening behavior in Hafnium

    SciTech Connect

    Cerreta, E. K.; Gray, G. T. , III; Yablinsky, C.

    2004-01-01

    In many HCP metals, both twinning and slip are known to be important modes of deformation. However, the interaction of the two mechanisms and their effect on work hardening is not well understood. In hafnium, twinning and work hardening rates increase with increasing strain, increasing strain rate, and decreasing temperature. At low strains and strain rates and at higher temperatures, slip dominates deformation and rates of work hardening are relatively lower. To characterize the interaction of slip and twinning, Hf specimens were prestrained quasi-statically in compression at 77K, creating specimens that were heavily twinned. These specimens were subsequently reloaded at room temperature. Twinning within the microstructures was characterized optically and using transmission electron microscopy. The interaction of slip with the twins was investigated as a function of prestrain and correlated with the observed rates of work hardening.

  6. Periodic alignment of Si quantum dots on hafnium oxide coated single wall carbon nanotubes

    SciTech Connect

    Olmedo, Mario; Martinez-Morales, Alfredo A.; Ozkan, Mihrimah; Liu Jianlin; Liu Gang; Lau, C.N.; Yengel, Emre; Ozkan, Cengiz S.

    2009-03-23

    We demonstrate a bottom up approach for the aligned epitaxial growth of Si quantum dots (QDs) on one-dimensional (1D) hafnium oxide (HfO{sub 2}) ridges created by the growth of HfO{sub 2} thin film on single wall carbon nanotubes. This growth process creates a high strain 1D ridge on the HfO{sub 2} film, which favors the formation of Si seeds over the surrounding flat HfO{sub 2} area. Periodic alignment of Si QDs on the 1D HfO{sub 2} ridge was observed, which can be controlled by varying different growth conditions, such as growth temperature, growth time, and disilane flow rate.

  7. High-k (k=30) amorphous hafnium oxide films from high rate room temperature deposition

    SciTech Connect

    Li, Flora M.; Bayer, Bernhard C.; Hofmann, Stephan; Milne, William I.; Flewitt, Andrew J.; Dutson, James D.; Wakeham, Steve J.; Thwaites, Mike J.

    2011-06-20

    Amorphous hafnium oxide (HfO{sub x}) is deposited by sputtering while achieving a very high k{approx}30. Structural characterization suggests that the high k is a consequence of a previously unreported cubiclike short range order in the amorphous HfO{sub x} (cubic k{approx}30). The films also possess a high electrical resistivity of 10{sup 14} {Omega} cm, a breakdown strength of 3 MV cm{sup -1}, and an optical gap of 6.0 eV. Deposition at room temperature and a high deposition rate ({approx}25 nm min{sup -1}) makes these high-k amorphous HfO{sub x} films highly advantageous for plastic electronics and high throughput manufacturing.

  8. Episodic growth of the Gondwana supercontinent from hafnium and oxygen isotopes in zircon.

    PubMed

    Kemp, A I S; Hawkesworth, C J; Paterson, B A; Kinny, P D

    2006-02-01

    It is thought that continental crust existed as early as 150 million years after planetary accretion, but assessing the rates and processes of subsequent crustal growth requires linking the apparently contradictory information from the igneous and sedimentary rock records. For example, the striking global peaks in juvenile igneous activity 2.7, 1.9 and 1.2 Gyr ago imply rapid crustal generation in response to the emplacement of mantle 'super-plumes', rather than by the continuous process of subduction. Yet uncertainties persist over whether these age peaks are artefacts of selective preservation, and over how to reconcile episodic crust formation with the smooth crustal evolution curves inferred from neodymium isotope variations of sedimentary rocks. Detrital zircons encapsulate a more representative record of igneous events than the exposed geology and their hafnium isotope ratios reflect the time since the source of the parental magmas separated from the mantle. These 'model' ages are only meaningful if the host magma lacked a mixed or sedimentary source component, but the latter can be diagnosed by oxygen isotopes, which are strongly fractionated by rock-hydrosphere interactions. Here we report the first study that integrates hafnium and oxygen isotopes, all measured in situ on the same, precisely dated detrital zircon grains. The data reveal that crust generation in part of Gondwana was limited to major pulses at 1.9 and 3.3 Gyr ago, and that the zircons crystallized during repeated reworking of crust formed at these times. The implication is that the mechanisms of crust formation differed from those of crustal differentiation in ancient orogenic belts. PMID:16452978

  9. Molybdenum sulfide/carbide catalysts

    DOEpatents

    Alonso, Gabriel; Chianelli, Russell R.; Fuentes, Sergio; Torres, Brenda

    2007-05-29

    The present invention provides methods of synthesizing molybdenum disulfide (MoS.sub.2) and carbon-containing molybdenum disulfide (MoS.sub.2-xC.sub.x) catalysts that exhibit improved catalytic activity for hydrotreating reactions involving hydrodesulfurization, hydrodenitrogenation, and hydrogenation. The present invention also concerns the resulting catalysts. Furthermore, the invention concerns the promotion of these catalysts with Co, Ni, Fe, and/or Ru sulfides to create catalysts with greater activity, for hydrotreating reactions, than conventional catalysts such as cobalt molybdate on alumina support.

  10. Preparation of amorphous sulfide sieves

    DOEpatents

    Siadati, Mohammad H.; Alonso, Gabriel; Chianelli, Russell R.

    2006-11-07

    The present invention involves methods and compositions for synthesizing catalysts/porous materials. In some embodiments, the resulting materials are amorphous sulfide sieves that can be mass-produced for a variety of uses. In some embodiments, methods of the invention concern any suitable precursor (such as thiomolybdate salt) that is exposed to a high pressure pre-compaction, if need be. For instance, in some cases the final bulk shape (but highly porous) may be same as the original bulk shape. The compacted/uncompacted precursor is then subjected to an open-flow hot isostatic pressing, which causes the precursor to decompose and convert to a highly porous material/catalyst.

  11. 40 CFR 425.03 - Sulfide analytical methods and applicability.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Provisions § 425.03 Sulfide analytical methods and applicability. (a) The potassium ferricyanide titration... the potassium ferricyanide titration method for the determination of sulfide in wastewaters...

  12. Synthesis and Optical Properties of Sulfide Nanoparticles Prepared in Dimethylsulfoxide

    SciTech Connect

    Li, Yuebin; Ma, Lun; Zhang, Xing; Joly, Alan G.; Liu, Zuli; Chen, Wei

    2008-11-01

    Many methods have been reported for the formation of sulfide nanoparticles by the reaction of metallic salts with sulfide chemical sources in aqueous solutions or organic solvents. Here, we report the formation of sulfide nanoparticles in dimethylsulfoxide (DMSO) by boiling metallic salts without sulfide sources. The sulfide sources are generated from the boiling of DMSO and react with metallic salts to form sulfide nanoparticles. In this method DMSO functions as a solvent and a sulfide source as well as a stabilizer for the formation of the nanoparticles. The recipe is simple and economical making sulfide nanoparticles formed in this way readily available for many potential applications.

  13. Response of sulfide:quinone oxidoreductase to sulfide exposure in the echiuran worm Urechis unicinctus.

    PubMed

    Ma, Yu-Bin; Zhang, Zhi-Feng; Shao, Ming-Yu; Kang, Kyoung-Ho; Shi, Xiao-Li; Dong, Ying-Ping; Li, Jin-Long

    2012-04-01

    Sulfide is a natural, widely distributed, poisonous substance, and sulfide:quinone oxidoreductase (SQR) is responsible for the initial oxidation of sulfide in mitochondria. In this study, we examined the response of SQR to sulfide exposure (25, 50, and 150 μM) at mRNA, protein, and enzyme activity levels in the body wall and hindgut of the echiuran worm Urechis unicinctus, a benthic organism living in marine sediments. The results revealed SQR mRNA expression during sulfide exposure in the body wall and hindgut increased in a time- and concentration-dependent manner that increased significantly at 12 h and continuously increased with time. At the protein level, SQR expression in the two tissues showed a time-dependent relationship that increased significantly at 12 h in 50 μM sulfide and 6 h in 150 μM, and then continued to increase with time while no significant increase appeared after 25 μM sulfide exposure. SQR enzyme activity in both tissues increased significantly in a time-dependent manner after 50 μM sulfide exposure. We concluded that SQR expression could be induced by sulfide exposure and that the two tissues studied have dissimilar sulfide metabolic patterns. A U. unicinctus sulfide-induced detoxification mechanism was also discussed. PMID:21997848

  14. Variation in Sulfide Tolerance of Photosystem II in Phylogenetically Diverse Cyanobacteria from Sulfidic Habitats

    PubMed Central

    Miller, Scott R.; Bebout, Brad M.

    2004-01-01

    Physiological and molecular phylogenetic approaches were used to investigate variation among 12 cyanobacterial strains in their tolerance of sulfide, an inhibitor of oxygenic photosynthesis. Cyanobacteria from sulfidic habitats were found to be phylogenetically diverse and exhibited an approximately 50-fold variation in photosystem II performance in the presence of sulfide. Whereas the degree of tolerance was positively correlated with sulfide levels in the environment, a strain's phenotype could not be predicted from the tolerance of its closest relatives. These observations suggest that sulfide tolerance is a dynamic trait primarily shaped by environmental variation. Despite differences in absolute tolerance, similarities among strains in the effects of sulfide on chlorophyll fluorescence induction indicated a common mode of toxicity. Based on similarities with treatments known to disrupt the oxygen-evolving complex, it was concluded that sulfide toxicity resulted from inhibition of the donor side of photosystem II. PMID:14766549

  15. Variation in sulfide tolerance of photosystem II in phylogenetically diverse cyanobacteria from sulfidic habitats

    NASA Technical Reports Server (NTRS)

    Miller, Scott R.; Bebout, Brad M.

    2004-01-01

    Physiological and molecular phylogenetic approaches were used to investigate variation among 12 cyanobacterial strains in their tolerance of sulfide, an inhibitor of oxygenic photosynthesis. Cyanobacteria from sulfidic habitats were found to be phylogenetically diverse and exhibited an approximately 50-fold variation in photosystem II performance in the presence of sulfide. Whereas the degree of tolerance was positively correlated with sulfide levels in the environment, a strain's phenotype could not be predicted from the tolerance of its closest relatives. These observations suggest that sulfide tolerance is a dynamic trait primarily shaped by environmental variation. Despite differences in absolute tolerance, similarities among strains in the effects of sulfide on chlorophyll fluorescence induction indicated a common mode of toxicity. Based on similarities with treatments known to disrupt the oxygen-evolving complex, it was concluded that sulfide toxicity resulted from inhibition of the donor side of photosystem II.

  16. Catalyst and process for oxidizing hydrogen sulfide

    SciTech Connect

    Hass, R.H.; Fullerton; Ward, J.W.; Yorba, L.

    1984-04-24

    Catalysts comprising bismuth and vanadium components are highly active and stable, especially in the presence of water vapor, for oxidizing hydrogen sulfide to sulfur or SO/sub 2/. Such catalysts have been found to be especially active for the conversion of hydrogen sulfide to sulfur by reaction with oxygen or SO/sub 2/.

  17. New biologically active hydrogen sulfide donors.

    PubMed

    Roger, Thomas; Raynaud, Francoise; Bouillaud, Frédéric; Ransy, Céline; Simonet, Serge; Crespo, Christine; Bourguignon, Marie-Pierre; Villeneuve, Nicole; Vilaine, Jean-Paul; Artaud, Isabelle; Galardon, Erwan

    2013-11-25

    Generous donors: The dithioperoxyanhydrides (CH3 COS)2 , (PhCOS)2 , CH3 COSSCO2 Me and PhCOSSCO2 Me act as thiol-activated hydrogen sulfide donors in aqueous buffer solution. The most efficient donor (CH3 COS)2 can induce a biological response in cells, and advantageously replace hydrogen sulfide in ex vivo vascular studies. PMID:24115650

  18. 30 CFR 250.808 - Hydrogen sulfide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF OCEAN ENERGY MANAGEMENT, REGULATION, AND ENFORCEMENT, DEPARTMENT OF THE... Safety Systems § 250.808 Hydrogen sulfide. Production operations in zones known to contain...

  19. Ammonia and hydrogen sulfide removal using biochar

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Reducing ammonia and hydrogen sulfide emissions from livestock facilities is an important issue for many communities and livestock producers. Ammonia has been regarded as odorous, precursor for particulate matter (PM), and contributed to livestock mortality. Hydrogen sulfide is highly toxic at elev...

  20. Weathering of sulfides on Mars

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.; Fisher, Duncan S.

    1987-01-01

    Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produce degradation products in the Martian regolith. By analogy and terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni, and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato-and hydroxo-complex ions and sols formed gossan above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite), and silica (opal). Underlying groundwater, now permafrost contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates, and phyllosilicates during dust storms on Mars.

  1. Percutaneous absorption of selenium sulfide

    SciTech Connect

    Farley, J.; Skelly, E.M.; Weber, C.B.

    1986-01-01

    The purpose of this study was to determine selenium levels in the urine of Tinea patients before and after overnight application of a 2.5% selenium sulfide lotion. Selenium was measured by atomic absorption spectroscopy (AAS). Hydride generation and carbon rod atomization were studied. It was concluded from this study that selenium is absorbed through intact skin. Selenium is then excreted, at least partially, in urine, for at least a week following treatment. The data show that absorption and excretion of selenium vary on an individual basis. Selenium levels in urine following a single application of selenium sulfide lotion do not indicate that toxic amounts of selenium are being absorbed. Repeated treatments with SeS/sub 2/ result in selenium concentrations in urine which are significantly higher than normal. Significant matrix effects are observed in the carbon rod atomization of urine samples for selenium determinations, even in the presence of a matrix modifier such as nickel. The method of standard additions is required to obtain accurate results in the direct determination of selenium in urine by carbon rod AAS.

  2. Characterization of low dimensional molybdenum sulfide nanostructures

    SciTech Connect

    Camacho-Bragado, G. Alejandra; Elechiguerra, Jose Luis; Yacaman, Miguel Jose

    2008-03-15

    It is presented a detailed structural characterization of a nanostructured form of molybdenum disulfide. The material consists of a layer of highly textured molybdenum sulfide growing off a molybdenum dioxide core. The structure and chemical composition of the synthesized nanostructured sulfide was compared to two well-known forms of molybdenum disulfide, i.e. a commercial molybdenite sample and a poorly crystalline sulfide. X-ray diffraction, high-resolution electron microscopy and electron diffraction showed that the material reported here presents crystalline nanodomains with a crystal structure corresponding to the 2H polytype of molybdenum disulfide. X-ray photoelectron spectroscopy was used to demonstrate the differences between our sulfide and other materials such as amorphous MoS{sub 3}, oxysulfides and poorly crystalline MoS{sub 2}, corroborating the molybdenite-2H stacking in this form of sulfide. The material under study showed a high proportion of crystalline planes different from the basal plane.

  3. Synthesis of magnetic rhenium sulfide composite nanoparticles

    NASA Astrophysics Data System (ADS)

    Tang, Naimei; Tu, Weixia

    2009-10-01

    Rhenium sulfide nanoparticles are associated with magnetic iron oxide through coprecipitation of iron salts with tetramethylammonium hydroxide. Sizes of the formed magnetic rhenium sulfide composite particles are in the range 5.5-12.5 nm. X-ray diffraction and energy-dispersive analysis of X-rays spectra demonstrate the coexistence of Fe 3O 4 and ReS 2 in the composite particle, which confirm the formation of the magnetic rhenium sulfide composite nanoparticles. The association of rhenium sulfide with iron oxide not only keeps electronic state and composition of the rhenium sulfide nanoparticles, but also introduces magnetism with the level of 24.1 emu g -1 at 14 kOe. Surface modification with monocarboxyl-terminated poly(ethylene glycol) (MPEG-COOH) has the role of deaggregating the composite nanoparticles to be with average hydrodynamic size of 27.3 nm and improving the dispersion and the stability of the composite nanoparticles in water.

  4. Hydrogen sulfide pollution in wastewater treatment facilities

    SciTech Connect

    AlDhowalia, K.H. )

    1987-01-01

    The hydrogen sulfide (H{sub 2}S) found in wastewater collection systems and wastewater treatment facilities results from the bacterial reduction of the sulfate ion (SO{sub 4}). Hydrogen sulfide is a gas that occurs both in the sewer atmosphere and as a dissolved gas in the wastewater. When raw wastewater first enters the wastewater treatment facility by gravity most of the hydrogen sulfide is in the gaseous phase and will escape into the atmosphere at the inlet structures. Also some of the dissolved hydrogen sulfide will be released at points of turbulance such as at drops in flow, flumes, or aeration chambers. Several factors can cause excessive hydrogen sulfide concentrations in a sewerage system. These include septic sewage, long flow times in the sewerage system, high temperatures, flat sewer grades, and poor ventilation. These factors are discussed in this paper.

  5. Ion-bombardment-induced reduction in vacancies and its enhanced effect on conductivity and reflectivity in hafnium nitride films

    NASA Astrophysics Data System (ADS)

    Gu, Zhiqing; Wang, Jiafu; Hu, Chaoquan; Zhang, Xiaobo; Dang, Jianchen; Zhang, Sam; Gao, Jing; Wang, Xiaoyi; Chen, Hong; Zheng, Weitao

    2016-08-01

    Although the role of ion bombardment on electrical conductivity and optical reflectivity of transition metal nitrides films was reported previously, the results were controversial and the mechanism was not yet well explored. Here, we show that proper ion bombardment, induced by applying the negative bias voltage ( V b), significantly improves the electrical conductivity and optical reflectivity in rocksalt hafnium nitride films regardless of level of stoichiometry (i.e., in both near-stoichiometric HfN1.04 and over-stoichiometric HfN1.17 films). The observed improvement arises from the increase in the concentration of free electrons and the relaxation time as a result of reduction in nitrogen and hafnium vacancies in the films. Furthermore, HfN1.17 films have always much lower electrical conductivity and infrared reflectance than HfN1.04 films for a given V b, owing to more hafnium vacancies because of larger composition deviation from HfN exact stoichiometry (N:Hf = 1:1). These new insights are supported by good agreement between experimental results and theoretical calculations.

  6. Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase.

    PubMed

    Mishanina, Tatiana V; Yadav, Pramod K; Ballou, David P; Banerjee, Ruma

    2015-10-01

    The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be -123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation. PMID:26318450

  7. Primordial Xenon in Allende Sulfides

    NASA Astrophysics Data System (ADS)

    Lee, J. T.; Manuel, O. K.

    1995-09-01

    The Allende C3V carbonaceous chondrite incorporated isotopically anomalous components of several medium-heavy elements (Z=36-62) from nucleosynthesis [1]. Isotopically distinct Xe (Z=54) has been found in grains ranging from several _ to a few mm in size. Diamond [2] is the host of Xe that is enriched in isotopes produced by the very rapid p- and r-processes in a supernova explosion [3]. Silicon carbide [4] is the host of Xe that is enriched in the middle isotopes, 128-132Xe, produced by slow neutron capture [3] before a star reaches the supernova stage. The present study was undertaken to identify the isotopic composition of primitive Xe initially trapped in sulfides of the Allende meteorite. Two FeS mineral separates were analyzed by stepwise heating. One sample was first irradiated in a neutron flux to generate a tracer isotope, 131*Xe, by the 130Te(n, gamma beta-)131*Xe reaction. The release pattern of this tracer isotope, 131*Xe, closely paralleled the release of primordial 132Xe up to 950 degrees C, when the sulfide melted and released the bulk of its trapped Xe (Figure 1). The Xe released from both samples at 950 deg C was terrestrial in isotopic composition, except for enrichments from spallogenic and radiogenic components (Figure 2). From the results of this and earlier analyses of Xe in meteoritic FeS [5, 6, 7], we conclude that terrestrial-type Xe was dominant in the central region of the protoplanetary nebula, and it remains a major component in the FeS of diverse meteorites and in the terrestrial planets that are rich in Fe, S [8]. References: [1] Begemann F. (1993) Origin and Evolution of the Elements (N. Prantzos et al., eds.), 518-527, Cambridge Univ. [2] Lewis R. S. and Anders E. (1988) LPS XIX, 679-680. [3] Burbidge et al. (1957) Rev. Modern Phys., 29, 547-650. [4] Tang M. and Anders E. (1988) GCA, 52, 1235-1244. [5] Niemeyer S. (1979) GCA, 43, 843-860. [6] Lewis et al. (1979) GCA, 43, 1743-1752. [7] Hwaung G. and Manuel O. K. (1982) Nature, 299

  8. Mantle derived economic sulfide mineralization?

    NASA Astrophysics Data System (ADS)

    Krivolutskaya, Nadezda; Gongalskiy, Bronislav; Svirskaya, Natalia

    2014-05-01

    Sulfide ores of the unique Pt-Cu-Ni Noril'sk deposits are characterized by heavy sulfur isotopic composition (d34S = 6-18 ‰ ; Grinenko, 1985). These data are traditionally explained by the crustal contamination of the mantle melts by Devonian sedimentary rocks with anhydrites at certain depths or in a chamber of crystallization (Naldrett, 1992; Li et al., 2009). However, data on the distribution of major and trace elements and isotopic composition (their eNd, 87Sr/86Sr, d34S) in the contact zones of the intrusions with the host rocks are at variance with any significant in-situ contamination. Moreover , the mechanism of the "digestion" of this high-temperature material (Tm = 1430ºC) by the lower temperature magma (1250ºC) has never been analyzed and questioned. Our pioneering data on the sulfur radiogenic isotopes in the anhydrite are in conflict with the hypothesis that this mineral could serve as a sulfur source for the Noril'sk ores. The fact that the average composition of the intrusions is independent on the stratigraphic setting of these intrusions, which can be hosted by limestone, sandstone, and/or basalt, provides further support for the idea that no assimilation took place at the depths of the chambers in which the melts crystallized.The reason for the heavy sulfur isotopic composition of ores in the Noril'sk district is still uncertain. Last data obtained on the sulfur isotopic composition of basalts and ores from some intrusions in the Taimyr Peninsula likely provide a clue to this problem. The highest d34S values in rocks of all of the trap formations were detected in the Gudchikhinsky picrites (d34S = +8,7; Ripley et al., 2003) formed from a primitive mantle magma. They are geochemically similar to the rocks from the Dyumtaleysky Massif (d34S = 12.2; Krivolutskaya and Gongalsky, 2013) which crystallized from a primitive mantle-derived magma (with no Ta-Nb and Pb anomalies and high Gd/Yb ratio) too. This intrusion comprises economic important

  9. Structural studies in limestone sulfidation

    SciTech Connect

    Fenouil, L.A.; Lynn, S.

    1993-05-01

    This study investigates the sulfidation of limestone at high temperatures (700--900{degree}C) as the first step in the design of a High-Temperature Coal-Gas Clean-Up system using millimeter-size limestone particles. Several workers have found that the rate of this reaction significantly decreases after an initial 10 to 15% conversion of CaCO{sub 3} to CaS. The present work attempts to explain this feature. It is first established that millimeter-size limestone particles do not sinter at temperatures up to the CaCO{sub 3} calcination point (899{degree}C at 1.03 bar CO{sub 2} partial pressure). It is then shown that CaS sinters rapidly at 750 to 900{degree}C if CO{sub 2} is present in the gas phase. Scanning Electron Microscope (SEM) photographs and Electron Dispersive Spectroscopy (EDS) data reveal that the CaS product layer sinters and forms a quasi-impermeable coating around the CaCO{sub 3} grains that greatly hinders more H{sub 2}S from reaching the still unreacted parts of the stone. Moreover, most of the pores initially present within the limestone structure begin to disappear or, at least, are significantly reduced in size. From then on, subsequent conversion is limited by diffusion of H{sub 2}S through the CaS layer, possibly by S{sup 2{minus}} ionic diffusion. The kinetics is then adequately described by a shrinking-core model, in which a sharp front of completely converted limestone is assumed to progress toward the center of the pellet. Finally, experimental evidence and computer simulations using simple sintering models suggest that the CaS sintering, responsible for the sharp decrease in the sulfidation rate, is surface-diffusion controlled.

  10. REMOVAL AND RECOVERY OF SULFIDE FROM TANNERY WASTEWATER

    EPA Science Inventory

    Recovery of sulfide from tannery waste was accomplished through acidification with sulfuric acid in a closed system and removing hydrogen sulfide formed by blowing with air. Sulfide was then absorbed in caustic solution to produce re-usable sodium sulfide/sulfhydrate liquor for t...

  11. Microbial control of hydrogen sulfide production

    SciTech Connect

    Montgomery, A.D.; Bhupathiraju, V.K.; Wofford, N.; McInerney, M.J.

    1995-12-31

    A sulfide-resistant strain of Thiobacillus denitrificans, strain F, prevented the accumulation of sulfide by Desulfovibrio desulfuricans when both organisms were grown in liquid medium. The wild-type strain of T. denitrificans did not prevent the accumulation of sulfide produced by D. desulfuricans. Strain F also prevented the accumulation of sulfide by a mixed population of sulfate-reducing bacteria enriched from an oil field brine. Fermentation balances showed that strain F stoichiometrically oxidized the sulfide produced by D. desulfuricans and the oil field brine enrichment to sulfate. The ability of a strain F to control sulfide production in an experimental system of cores and formation water from the Redfield, Iowa, natural gas storage facility was also investigated. A stable, sulfide-producing biofilm was established in two separate core systems, one of which was inoculated with strain F while the other core system (control) was treated in an identical manner, but was not inoculated with strain F. When formation water with 10 mM acetate and 5 mM nitrate was injected into both core systems, the effluent sulfide concentrations in the control core system ranged from 200 to 460 {mu}M. In the test core system inoculated with strain F, the effluent sulfide concentrations were lower, ranging from 70 to 110 {mu}M. In order to determine whether strain F could control sulfide production under optimal conditions for sulfate-reducing bacteria, the electron donor was changed to lactate and inorganic nutrients (nitrogen and phosphate sources) were added to the formation water. When nutrient-supplemented formation water with 3.1 mM lactate and 10 mM nitrate was used, the effluent sulfide concentrations of the control core system initially increased to about 3,800 {mu}M, and then decreased to about 1,100 {mu}M after 5 weeks. However, in the test core system inoculated with strain F, the effluent sulfide concentrations were much lower, 160 to 330 {mu}M.

  12. Nanostructured lead sulfide: synthesis, structure and properties

    NASA Astrophysics Data System (ADS)

    Sadovnikov, S. I.; Gusev, A. I.; Rempel, A. A.

    2016-07-01

    The theoretical and experimental results of recent studies dealing with nanostructured lead sulfide are summarized and analyzed. The key methods for the synthesis of nanostructured lead sulfide are described. The crystal structure of PbS in nanopowders and nanofilms is discussed. The influence of the size of nanostructure elements on the optical and thermal properties of lead sulfide is considered. The dependence of the band gap of PbS on the nanoparticle (crystallite) size for powders and films is illustrated. The bibliography includes 222 references.

  13. Removal of methanethiol, dimethyl sulfide, dimethyl disulfide, and hydrogen sulfide from contaminated air by Thiobacillus thioparus TK-m

    SciTech Connect

    Kanagawa, T.; Mikami, E.

    1989-03-01

    Methanethiol, dimethyl sulfide, dimethyl disulfide, and hydrogen sulfide were efficiently removed from contaminated air by Thiobacillus thioparus TK-m and oxidized to sulfate stoichiometrically. More than 99.99% of dimethyl sulfide was removed when the load was less than 4.0 g of dimethyl sulfide per g (dry cell weight) per day.

  14. Formation of Copper Sulfide Artifacts During Electrolytic Dissolution of Steel

    NASA Astrophysics Data System (ADS)

    Tan, Jia; Pistorius, P. Chris

    2013-06-01

    Based on equilibrium considerations, copper sulfide is not expected to form in manganese-containing steel, yet previous workers reported finding copper sulfide in transmission electron microscope samples which had been prepared by electropolishing. It is proposed that copper sulfide can form during electrolytic dissolution because of the much greater stability of copper sulfide relative to manganese sulfide in contact with an electrolyte containing copper and manganese cations. This mechanism has been demonstrated with aluminum-killed steel samples.

  15. Ridding Groundwater of Hydrogen Sulfide. Part 1.

    ERIC Educational Resources Information Center

    Lochrane, Thomas G.

    1979-01-01

    This article is the first in a series reviewing the problems associated with hydrogen sulfide in drinking water sources. Discussion centers on identification of a cost-effective balance between aeration and chlorination treatment operations. (AS)

  16. Photooxidation of methyl sulfide, ethyl sulfide, and methanethiol

    SciTech Connect

    Grosjean, D.

    1984-06-01

    Products of sunlight-irradiated mixtures of oxides of nitrogen and alkyl sulfides (RSR, R = CH/sub 3/, C/sub 2/H/sub 5/) and methanethiol (CH/sub 3/SH) in air include formaldehyde (R = CH/sub 3/), acetaldehyde and PAN (R = C/sub 2/H/sub 5/), sulfur dioxide, and alkyl nitrates (RONO/sub 2/) as well as particulate alkanesulfonic acids (RSO/sub 2/OH) and inorganic sulfate. The nature and yields of gaseous and particulate products are discussed in terms of OH-initiated reaction pathways, including C-S bond scission, and subsequent reactions of alkythiyl radicals (RS), including those leading to photolabile RSNO and stable RSNO/sub 2/ products for which indirect evidence is presented. SO/sub 2/ yields are found to vary according to the relative importance of the competing pathways RS + O/sub 2/ (a) and RS + NO/sub 2/ (b), for which a ratio k/sub b/ / k/sub a/ approx. 2 x 10/sup 6/ is derived from data for irradiated RSR-NO/sub x/, RSH-Cl/sub 2/, and RSH-Cl/sub 2/-NO/sub 2/ mixtures.

  17. Temperature effect on electrospinning of nanobelts: the case of hafnium oxide.

    PubMed

    Su, Yurong; Lu, Bingan; Xie, Yizhu; Ma, Ziwei; Liu, Lixin; Zhao, Haiting; Zhang, Jia; Duan, Huigao; Zhang, Hongliang; Li, Jian; Xiong, Yuqing; Xie, Erqing

    2011-07-15

    Electrospinning is a convenient and versatile method for fabricating different kinds of one-dimensional nanostructures such as nanofibres, nanotubes and nanobelts. Environmental parameters have a great influence on the electrospinning nanostructure. Here we report a new method to fabricate hafnium oxide (HfO(2)) nanobelts. HfO(2) nanobelts were prepared by electrospinning a sol-gel solution with the implementation of heating and subsequent calcination treatment. We investigate the temperature dependence of the products by scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and energy-dispersive x-ray (EDX) spectroscopy. The heating temperature of spinning ambient is found to be crucial to the formation of HfO(2) nanobelts. By tuning the temperature, the morphological transformation of HfO(2) from nanowires to nanobelts was achieved. It was found that the rapid evaporation of solvent played an important role in the formation process of HfO(2) nanobelts. It is shown that nanobelts can only be obtained with the temperature higher than 50 °C and they are in the high quality monoclinic phase. A possible growth mechanism of the nanobelts based on phase separation is proposed. The enhanced photoluminescence (PL) of HfO(2):Eu(3+) nanobelts is also illustrated. PMID:21659687

  18. Low temperature structural phase transition in hafnium and zirconium tetrafluoride trihydrates

    NASA Astrophysics Data System (ADS)

    Dey, S. K.; Dey, C. C.; Saha, S.

    2016-04-01

    From time-differential perturbed angular correlation (TDPAC) measurements, the monoclinic and triclinic crystal structures in hafnium and zirconium tetrafluoride trihydrates are found to be present simultaneously in both the compounds. From previous TDPAC and XRD investigations, a monoclinic crystal structure for HfF4·3H2O but, for its analogues zirconium compound, a triclinic structure was reported. Contrary to earlier reports, the triclinic fraction in HfF4·3H2O is found to be maximum (80%) at room temperature. In fact, the triclinic crystal structure of HfF4·3H2O is reported here which was not known prior to this report. In ZrF4·3H2O, a strong signal (80-90%) for the triclinic structure is found at room temperature while the monoclinic fraction appears as a weak signal (10-15%). Structural phase transitions in these trihydrate compounds have been observed in the temperature range 298-333 K.

  19. Recoil Induced Room Temperature Stable Frenkel Pairs in a-Hafnium Upon Thermal Neutron Capture

    NASA Astrophysics Data System (ADS)

    Butz, Tilman; Das, Satyendra K.; Dey, Chandi C.; Ghoshal, Shamik

    2013-11-01

    Ultrapure hafnium metal (110 ppm zirconium) was neutron activated with a thermal neutron flux of 6:6 · 1012 cm-2s-1 in order to obtain 181Hf for subsequent time differential perturbed angular correlation (TDPAC) experiments using the nuclear probe 181Hf(β-) 181Ta. Apart from the expected nuclear quadrupole interaction (NQI) signal for a hexagonal close-packed (hcp) metal, three further discrete NQIs were observed with a few percent fraction each. The TDPAC spectra were recorded for up to 11 half lives with extreme statistical accuracy. The fitted parameters vary slightly within the temperature range between 248 K and 373 K. The signals corresponding to the three additional sites completely disappear after `annealing' at 453 K for one minute. Based on the symmetry of the additional NQIs and their temperature dependencies, they are tentatively attributed to Frenkel pairs produced by recoil due to the emission of a prompt 5:694 MeV -ray following thermal neutron capture and reported by the nuclear probe in three different positions. These Frenkel pairs are stable up to at least 373 K.

  20. Carrier Transport at Metal/Amorphous Hafnium-Indium-Zinc Oxide Interfaces.

    PubMed

    Kim, Seoungjun; Gil, Youngun; Choi, Youngran; Kim, Kyoung-Kook; Yun, Hyung Joong; Son, Byoungchul; Choi, Chel-Jong; Kim, Hyunsoo

    2015-10-14

    In this paper, the carrier transport mechanism at the metal/amorphous hafnium-indium-zinc oxide (a-HIZO) interface was investigated. The contact properties were found to be predominantly affected by the degree of interfacial reaction between the metals and a-HIZO; that is, a higher tendency to form metal oxide phases leads to excellent Ohmic contact via tunneling, which is associated with the generated donor-like oxygen vacancies. In this case, the Schottky-Mott theory is not applicable. Meanwhile, metals that do not form interfacial metal oxide, such as Pd, follow the Schottky-Mott theory, which results in rectifying Schottky behavior. The Schottky characteristics of the Pd contact to a-HIZO can be explained in terms of the barrier inhomogeneity model, which yields a mean barrier height of 1.40 eV and a standard deviation of 0.14 eV. The work function of a-HIZO could therefore be estimated as 3.7 eV, which is in good agreement with the ultraviolet photoelectron spectroscopy (3.68 eV). Our findings will be useful for establishing a strategy to form Ohmic or Schottky contacts to a-HIZO films, which will be essential for fabricating reliable high-performance electronic devices. PMID:26411354

  1. Measurement and Simulation of Thermal Conductivity of Hafnium-Aluminum Thermal Neutron Absorber Material

    NASA Astrophysics Data System (ADS)

    Guillen, Donna Post; Harris, William H.

    2016-05-01

    A metal matrix composite (MMC) material composed of hafnium aluminide (Al3Hf) intermetallic particles in an aluminum matrix has been identified as a promising material for fast flux irradiation testing applications. This material can filter thermal neutrons while simultaneously providing high rates of conductive cooling for experiment capsules. The purpose of this work is to investigate effects of Hf-Al material composition and neutron irradiation on thermophysical properties, which were measured before and after irradiation. When performing differential scanning calorimetry (DSC) on the irradiated specimens, a large exotherm corresponding to material annealment was observed. Therefore, a test procedure was developed to perform DSC and laser flash analysis (LFA) to obtain the specific heat and thermal diffusivity of pre- and post-annealment specimens. This paper presents the thermal properties for three states of the MMC material: (1) unirradiated, (2) as-irradiated, and (3) irradiated and annealed. Microstructure-property relationships were obtained for the thermal conductivity. These relationships are useful for designing components from this material to operate in irradiation environments. The ability of this material to effectively conduct heat as a function of temperature, volume fraction Al3Hf, radiation damage, and annealing is assessed using the MOOSE suite of computational tools.

  2. Tailoring the index of refraction of nanocrystalline hafnium oxide thin films

    SciTech Connect

    Vargas, Mirella; Murphy, N. R.; Ramana, C. V.

    2014-03-10

    Hafnium oxide (HfO{sub 2}) films were grown by sputter-deposition by varying the growth temperature (T{sub s} = 25–700 °C). HfO{sub 2} films grown at T{sub s} < 200 °C were amorphous, while those grown at T{sub s} ≥ 200 °C were monoclinic, nanocrystalline with (1{sup ¯}11) texturing. X-ray reflectivity (XRR) analyses indicate that the film-density (ρ) increases with increasing T{sub s}. The index of refraction (n) profiles derived from spectroscopic ellipsometry analyses follow the Cauchy dispersion relation. Lorentz-Lorenz analysis (n{sub (λ)} = 550 nm) and optical-model adopted agree well with the XRR data/analyses. A direct T{sub s}-ρ-n relationship suggests that tailoring the optical quality is possible by tuning T{sub s} and the microstructure of HfO{sub 2} films.

  3. Effect of nitrogen containing plasmas on interface stability of hafnium oxide ultrathin films on Si (100)

    NASA Astrophysics Data System (ADS)

    Chen, P.; Bhandari, H. B.; Klein, T. M.

    2004-08-01

    Hafnium oxide dielectric thin films were deposited by metalorganic chemical vapor deposition with Hf (IV) t-butoxide and either an O2, N2, or N2O plasma in a 1:1 ratio with helium. Films approximately 5nm thick were analyzed using angle-resolved x-ray photoelectron spectroscopy (XPS) and variable angle ellipsometry before and after heat treatment in an ultrahigh vacuum up to 470°C. Interdiffusion and/or reaction of the film with the silicon substrate, as measured by an increase in thickness and an increase in Si-O type bonding at the interface was most apparent with O2 plasma deposited films and least observed with N2 plasma deposited films. Also, the Hf (4f) XPS peak shifts toward higher binding energy after anneals for the N2 and N2O plasma deposited films indicates further oxidation of the film. In contrast, oxygen plasma deposited films do not exhibit a Hf (4f) peak shift. These results provide evidence that high-κ film/substrate stability may be controlled by applying appropriate plasma chemistry.

  4. Coordination compounds of hafnium(IV) with some N-substituted derivatives of unsaturated hydroxamic acids

    SciTech Connect

    Stratulat, A.A.; Batyr, D.G.

    1987-05-01

    Coordination compounds of hafnium(IV) with N-o(or m)-X-phenylacryl- and methacrylhydroxamic acids with the general formula (Hf/XC/sub 6/H/sub 4/-N(O)-C(O)-R//sub 4/), where X = 4-CH/sub 3/, H, 4-Cl, 4-Br, 4-CH/sub 3/C(O), 4-CH=CH/sub 2/, 4-CH/sub 3/OC(O), 3-CH/sub 3/, 3-Cl, and 3-Br, and R = CH=CH/sub 2/ and C(CH/sub 3/)=CH/sub 2/, have been synthesized and characterized. The type of coordination of the organic ligands and the structure of the complexes have been established on the basis of the data from IR, electronic, and PMR spectra. It has been shown that the complexation process involves the replacement of the proton of the hydroxyl group of the hydroxamic grouping by a metal ion and the coordination of the oxygen atom of the carbonyl group. The coordination compounds obtained have been assigned a square-antiprismatic structure. The introduction of a methyl radical into the vinyl grouping R results in a significant increase in the strength of the complex.

  5. Compounds between the dioxides of hafnium and zirconium and the oxides of strontium and barium

    SciTech Connect

    Gerasimyuk, G.I.; Lopato, L.M.; Shevchenko, A.V.; Zaitseva, Z.A.

    1985-12-01

    The goal of the paper is the synthesis and study of the properties of compounds in the system HfO/sub 2/ (ZrO2)-SrO(BaO). These compounds form in the region of high alkaline-earth content. The phase composition of the samples was studied by x-ray and petrographic analyses on a DRON-1.5 unit at room temperature. It was established from the studies that, independent of the means of sample preparation, there form on interaction of the dioxides of hafnium and zirconium with the oxides of strontium in the region of high SrO content the compounds Sr/sub 4/HF/sub 3/O/sub 10/, Sr/sub 4/Zr/sub 3/O/sub 10/, Sr/sub 3/Hf/sub 2/O/sub 7/, Sr/sub 3/Zr/sub 2/O/sub 7/, Sr/sub 2/HfO/sub 4/, and Sr/sub 2/ZrO/sub 4/. The unit-cell parameters and crystal-optical characteristics of the compounds synthesized were determined.

  6. Investigation of crystallization processes from hafnium silicate powders prepared from an oxychloride sol-gel

    SciTech Connect

    McGilvery, Catriona M.; De Gendt, S; Payzant, E Andrew; Craven, A J; MacKenzie, M; McComb, D W

    2012-01-01

    Hafnium oxide and silicate materials are now incorporated into working CMOS devices, however the crystallisation mechanism is still poorly understood. In particular, addition of SiO2 to HfO2 has been shown to increase the crystallisation temperature of HfO2 hence allowing it to remain amorphous under current processing conditions. Building on earlier work we here investigate bulk HfxSi1-xO2 samples to determine the effect of SiO2 on the crystallisation pathway. Techniques such as XRD, HTXRD, thermal analysis techniques and TEM are used. It is found that the addition of SiO2 has very little affect on the crystallisation path at temperatures below 900 C but at higher temperatures a second t-HfO2 phase nucleates and is stabilised due to the strain of the surrounding amorphous SiO2 material. With an increase in SiO2 content the temperature at which this nucleation and stabilisation occurs is increased. The effect of strain has implications for inhibiting the crystallisation of the high-k layer, reduction of grain boundaries and hence diffusion, reduction of formation of interface layers and the possibility of stabilising t-HfO2 rather than m-HfO2 hence increasing the dielectric of the layer.

  7. Dry Sliding Wear Behavior of Hafnium-Based Bulk Metallic Glass at Room and Elevated Temperatures

    NASA Astrophysics Data System (ADS)

    Keshri, Anup Kumar; Behl, Lovish; Lahiri, Debrupa; Dulikravich, George S.; Agarwal, Arvind

    2016-07-01

    Dry sliding wear behavior of hafnium-based bulk metallic glass was studied at two loads (5 and 15 N) and two temperatures (298 and 673 K) using aluminum oxide (Al2O3) ball as a wear counterpart. At 5 N load, wear reduced by ~71% on increasing the temperature from 298 to 673 K. At a higher load of 15 N, the weight loss reduction was much lower (45%) on increasing the temperature from 298 to 673 K. Decreased wear weight loss on increasing the temperature was attributed to the increased hardness of the Hf-based metallic glass at high temperatures. Micro-hardness of the alloy at 293 K was found to be 636 Hv, which gradually increased to 655 Hv on annealing at 673 K. Improvement in the hardness at elevated temperature is attributed to: (1) free volume annihilation, (2) surface oxide formation and (3) nano-crystallites precipitation. Reduced wear at elevated temperature resulted in smaller volume of debris generation that restricted three-body wear to obtain lower coefficient of friction (COF) (0.25-0.35) compared to COF (0.65-0.75) at room temperature.

  8. Electron-beam-evaporated thin films of hafnium dioxide for fabricating electronic devices

    SciTech Connect

    Xiao, Zhigang; Kisslinger, Kim

    2015-06-17

    Thin films of hafnium dioxide (HfO2) are widely used as the gate oxide in fabricating integrated circuits because of their high dielectric constants. In this paper, the authors report the growth of thin films of HfO2 using e-beam evaporation, and the fabrication of complementary metal-oxide semiconductor (CMOS) integrated circuits using this HfO2 thin film as the gate oxide. The authors analyzed the thin films using high-resolution transmission electron microscopy and electron diffraction, thereby demonstrating that the e-beam-evaporation-grown HfO2 film has a polycrystalline structure and forms an excellent interface with silicon. Accordingly, we fabricated 31-stage CMOS ring oscillator to test the quality of the HfO2 thin film as the gate oxide, and obtained excellent rail-to-rail oscillation waveforms from it, denoting that the HfO2 thin film functioned very well as the gate oxide.

  9. Electron-beam-evaporated thin films of hafnium dioxide for fabricating electronic devices

    DOE PAGESBeta

    Xiao, Zhigang; Kisslinger, Kim

    2015-06-17

    Thin films of hafnium dioxide (HfO2) are widely used as the gate oxide in fabricating integrated circuits because of their high dielectric constants. In this paper, the authors report the growth of thin films of HfO2 using e-beam evaporation, and the fabrication of complementary metal-oxide semiconductor (CMOS) integrated circuits using this HfO2 thin film as the gate oxide. The authors analyzed the thin films using high-resolution transmission electron microscopy and electron diffraction, thereby demonstrating that the e-beam-evaporation-grown HfO2 film has a polycrystalline structure and forms an excellent interface with silicon. Accordingly, we fabricated 31-stage CMOS ring oscillator to test themore » quality of the HfO2 thin film as the gate oxide, and obtained excellent rail-to-rail oscillation waveforms from it, denoting that the HfO2 thin film functioned very well as the gate oxide.« less

  10. Unique erosion features of hafnium cathode in atmospheric pressure arcs of air, nitrogen and oxygen

    NASA Astrophysics Data System (ADS)

    Ghorui, S.; Meher, K. C.; Kar, R.; Tiwari, N.; Sahasrabudhe, S. N.

    2016-07-01

    Experimental investigation of cathode erosion in atmospheric pressure hafnium-electrode plasma torches is reported under different plasma environments along with the results of numerical simulation. Air, nitrogen and oxygen are the plasma gases considered. Distinct differences in the erosion features in different plasmas are brought out. Cathode images exhibiting a degree of erosion and measured erosion rates are presented in detail as a function of time of arc operation and arc current. Physical erosion rates are determined using high precision balance. The changes in the surface microstructures are investigated through scanning electron microscopy (SEM). Evolution of cathode chemistry is determined using energy dispersive x-ray spectroscopy (EDX). Numerical simulation with proper consideration of the plasma effects is performed for all the plasma gases. The important role of electromagnetic body forces in shaping the flow field and the distribution of pressure in the region is explored. It is shown that the mutual interaction between fluid dynamic and electromagnetic body forces may self-consistently evolve a situation of an extremely low cathode erosion rate.

  11. Facing-target mid-frequency magnetron reactive sputtered hafnium oxide film: Morphology and electrical properties

    NASA Astrophysics Data System (ADS)

    Zhang, Yu; Xu, Jun; Wang, You-Nian; Choi, Chi Kyu; Zhou, Da-Yu

    2016-03-01

    Amorphous hafnium dioxide (HfO2) film was prepared on Si (100) by facing-target mid-frequency reactive magnetron sputtering under different oxygen/argon gas ratio at room temperature with high purity Hf target. 3D surface profiler results showed that the deposition rates of HfO2 thin film under different O2/Ar gas ratio remain unchanged, indicating that the facing target midfrequency magnetron sputtering system provides effective approach to eliminate target poisoning phenomenon which is generally occurred in reactive sputtering procedure. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) demonstrated that the gradual reduction of oxygen vacancy concentration and the densification of deposited film structure with the increase of oxygen/argon (O2/Ar) gas flow ratio. Atomic force microscopy (AFM) analysis suggested that the surface of the as-deposited HfO2 thin film tends to be smoother, the root-meansquare roughness (RMS) reduced from 0.876 nm to 0.333 nm while O2/Ar gas flow ratio increased from 1/4 to 1/1. Current-Voltage measurements of MOS capacitor based on Au/HfO2/Si structure indicated that the leakage current density of HfO2 thin films decreased by increasing of oxygen partial pressure, which resulted in the variations of pore size and oxygen vacancy concentration in deposited thin films. Based on the above characterization results the leakage current mechanism for all samples was discussed systematically.

  12. Ion-assisted deposition of moisture-stable hafnium oxide films for ultraviolet applications

    NASA Astrophysics Data System (ADS)

    Jensen, Traci R.; Warren, John; Johnson,, Robert L., Jr.

    2002-06-01

    A design-of-experiments statistical approach was taken to determine the optimum ion gun operating parameters for the deposition of moisture-stable, low-absorbing hafnium oxide films by ion-assisted electron-beam evaporation. Factors identified as affecting the quality of hafnia films were chamber pressure, deposition rate, ion gun source gas composition, and ion gun current. Both oxygen and argon were used as source gases. High and low levels of the factors were chosen on the basis of our experience with the operating range of the system, and we made a series of 24 runs with all possible combinations of these factors. From a statistical analysis of the data, we find that the best films are obtained with a 1:1 mixture of argon and oxygen, 3-3.5 x 10-4 Torr chamber pressure, 0.3-nm/s deposition rate, and 0.5-A ion gun current. X-ray diffraction measurements show that the ion-assisted films exhibit a partial monoclinic crystalline structure, whereas the unassisted films are amorphous.

  13. Upper critical field of copper molybdenum sulfide

    NASA Technical Reports Server (NTRS)

    Alterovitz, S. A.; Woollam, J. A.

    1978-01-01

    The upper critical field of sintered and sputtered copper molybdenum sulfide Cu(x)Mo6S8 was measured and found to exceed the Werthamer, Helfand, and Hohenberg (1966) value for a type II superconductor characterized by dirty limit, weak isotropic electron phonon coupling, and no paramagnetic limiting. It is suggested that the enhancement results from anisotropy or clean limit or both. Other ternary molybdenum sulfides appear to show similar anomalies.

  14. Effect of Nitrate on Biogenic Sulfide Production

    PubMed Central

    Jenneman, Gary E.; McInerney, M. J.; Knapp, Roy M.

    1986-01-01

    The addition of 59 mM nitrate inhibited biogenic sulfide production in dilute sewage sludge (10% [vol/vol]) amended with 20 mM sulfate and either acetate, glucose, or hydrogen as electron donors. Similar results were found when pond sediment or oil field brines served as the inoculum. Sulfide production was inhibited for periods of at least 6 months and was accompanied by the oxidation of resazurin from its colorless reduced state to its pink oxidized state. Lower amounts of nitrate (6 or 20 mM) and increased amounts of sewage sludge resulted in only transient inhibition of sulfide production. The addition of 156 mM sulfate to bottles with 59 mM nitrate and 10% (vol/vol) sewage sludge or pond sediment resulted in sulfide production. Nitrate, nitrite, and nitrous oxide were detected during periods where sulfide production was inhibited, whereas nitrate, nitrite, and nitrous oxide were below detectable levels at the time sulfide production began. The oxidation of resazurin was attributed to an increase in nitrous oxide which persisted in concentration of about 1.0 mM for up to 5 months. The numbers of sulfate-reducing organisms decreased from 106 CFU ml−1 sludge to less than detectable levels after prolonged incubation of oxidized bottles. The addition of 10 mM glucose to oxidized bottles after 14.5 weeks of incubation resulted in rereduction of the resazurin and subsequent sulfide production. The prolonged inhibition of sulfide production was attributed to an increase in oxidation-reduction potential due to biogenic production of nitrous oxide, which appeared to have a cytotoxic effect on sulfate-reducing populations. PMID:16347078

  15. The Search for Interstellar Sulfide Grains

    NASA Technical Reports Server (NTRS)

    Keller, Lindsay P.; Messenger, Scott

    2010-01-01

    The lifecycle of sulfur in the galaxy is poorly understood. Fe-sulfide grains are abundant in early solar system materials (e.g. meteorites and comets) and S is highly depleted from the gas phase in cold, dense molecular cloud environments. In stark contrast, sulfur is essentially undepleted from the gas phase in the diffuse interstellar medium, indicating that little sulfur is incorporated into solid grains in this environment. It is widely believed that sulfur is not a component of interstellar dust grains. This is a rather puzzling observation unless Fe-sulfides are not produced in significant quantities in stellar outflows, or their lifetime in the ISM is very short due to rapid destruction. Fe sulfide grains are ubiquitous in cometary samples where they are the dominant host of sulfur. The Fe-sulfides (primarily pyrrhotite; Fe(1-x)S) are common, both as discrete 0.5-10 micron-sized grains and as fine (5-10 nm) nanophase inclusions within amorphous silicate grains. Cometary dust particles contain high abundances of well-preserved presolar silicates and organic matter and we have suggested that they should contain presolar sulfides as well. This hypothesis is supported by the observation of abundant Fe-sulfides grains in dust around pre- and post-main sequence stars inferred from astronomical spectra showing a broad 23 micron IR feature due to FeS. Fe-sulfide grains also occur as inclusions in bona fide circumstellar amorphous silicate grains and as inclusions within deuterium-rich organic matter in cometary dust samples. Our irradiation experiments show that FeS is far more resistant to radiation damage than silicates. Consequently, we expect that Fe sulfide stardust should be as abundant as silicate stardust in solar system materials.

  16. Catalytic dehydroxylation of phenols. [Metal sulfides

    SciTech Connect

    Pieters, W.J.M.

    1984-05-29

    Phenolic compounds are dehydroxylated in the vapor phase by contacting with a reducing atmosphere substantially comprising hydrogen sulfide as the reducing agent in the presence of a sulfur-tolerant metal sulfide catalyst. The additional presence of hydrogen gas helps to desulfurize the catalyst and maintain catalytic activity. The process is useful in the treatment of phenolic naphtha fractions present in coal liquids, produced by pyrolysis or direct coal liquefaction.

  17. Microbiological Leaching of Metallic Sulfides

    PubMed Central

    Razzell, W. E.; Trussell, P. C.

    1963-01-01

    The percentage of chalcopyrite leached in percolators by Thiobacillus ferrooxidans was dependent on the surface area of the ore but not on the amount. Typical examples of ore leaching, which demonstrate the role of the bacteria, are presented. In stationary fermentations, changes in KH2PO4 concentration above or below 0.1% decreased copper leaching as did reduction in the MgSO4·7H2O and increase in the (NH4)2SO4 concentration. Bacterial leaching of chalcopyrite was more effective than nonbiological leaching with ferric sulfate; ferric sulfate appeared to retard biological leaching, but this effect was likely caused by formation of an insoluble copper-iron complex. Ferrous sulfate and sodium chloride singly accentuated both bacterial and nonbiological leaching of chalcocite but jointly depressed bacterial action. Sodium chloride appeared to block bacterial iron oxidation without interfering with sulfide oxidation. Bacterial leaching of millerite, bornite, and chalcocite was greatest at pH 2.5. The economics of leaching a number of British Columbia ore bodies was discussed. PMID:16349627

  18. Hydrogen Sulfide as a Gasotransmitter

    PubMed Central

    Gadalla, Moataz M.; Snyder, Solomon H.

    2010-01-01

    Nitric oxide (NO) and carbon monoxide (CO) are well established as messenger molecules throughout the body, gasotransmitters, based on striking alterations in mice lacking the appropriate biosynthetic enzymes. Hydrogen sulfide (H2S) is even more chemically reactive, but till recently there was little definitive evidence for its physiologic formation. Cystathionine β-synthase (CBS, EC 4.2.1.22), and Cystathionine γ-lyase (CSE; EC 4.4.1.1), also known as cytathionase, can generate H2S from cyst(e)ine. Very recent studies with mice lacking these enzymes have established that CSE is responsible for H2S formation in the periphery, while in the brain CBS is the biosynthetic enzyme. Endothelial-derived relaxing factor (EDRF) activity is reduced 80% in the mesenteric artery of mice with deletion of CSE, establishing H2S as a major physiologic EDRF. H2S appears to signal predominantly by S-sulfhydrating cysteines in its target proteins, analogous to S-nitrosylation by NO. Whereas S-nitrosylation typically inhibits enzymes, S-sulfhydration activates them. S-nitrosylation basally affects 1–2% of its target proteins, while 10–25% of H2S target proteins are S-sulfhydrated. In summary, H2S appears to be a physiologic gasotransmitter of comparable importance to NO and CO. PMID:20067586

  19. Hydrogen sulfide and translational medicine

    PubMed Central

    Guo, Wei; Cheng, Ze-yu; Zhu, Yi-zhun

    2013-01-01

    Hydrogen sulfide (H2S) along with carbon monoxide and nitric oxide is an important signaling molecule that has undergone large numbers of fundamental investigations. H2S is involved in various physiological activities associated with the regulation of homeostasis, vascular contractility, pro- and anti-inflammatory activities, as well as pro- and anti-apoptotic activities etc. However, the actions of H2S are influenced by its concentration, reaction time, and cell/disease types. Therefore, H2S is a signaling molecule without definite effect. The use of existing H2S donors is limited because of the instant release and short lifetime of H2S. Thus, translational medicine involving the sustained and controlled release of H2S is of great value for both scientific and clinical uses. H2S donation can be manipulated by different ways, including where H2S is given, how H2S is donated, or the specific structures of H2S-releasing drugs and H2S donor molecules. This review briefly summarizes recent progress in research on the physiological and pathological functions of H2S and H2S-releasing drugs, and suggests hope for future investigations. PMID:24096643

  20. Sulfide response analysis for sulfide control using a pS electrode in sulfate reducing bioreactors.

    PubMed

    Villa-Gomez, D K; Cassidy, J; Keesman, K J; Sampaio, R; Lens, P N L

    2014-03-01

    Step changes in the organic loading rate (OLR) through variations in the influent chemical oxygen demand (CODin) concentration or in the hydraulic retention time (HRT) at constant COD/SO4(2-) ratio (0.67) were applied to create sulfide responses for the design of a sulfide control in sulfate reducing bioreactors. The sulfide was measured using a sulfide ion selective electrode (pS) and the values obtained were used to calculate proportional-integral-derivative (PID) controller parameters. The experiments were performed in an inverse fluidized bed bioreactor with automated operation using the LabVIEW software version 2009(®). A rapid response and high sulfide increment was obtained through a stepwise increase in the CODin concentration, while a stepwise decrease to the HRT exhibited a slower response with smaller sulfide increment. Irrespective of the way the OLR was decreased, the pS response showed a time-varying behavior due to sulfide accumulation (HRT change) or utilization of substrate sources that were not accounted for (CODin change). The pS electrode response, however, showed to be informative for applications in sulfate reducing bioreactors. Nevertheless, the recorded pS values need to be corrected for pH variations and high sulfide concentrations (>200 mg/L). PMID:24361702

  1. NEAR-CONTINUOUS MEASUREMENT OF HYDROGEN SULFIDE AND CARBONYL SULFIDE BY AN AUTOMATIC GAS CHROMATOGRAPH

    EPA Science Inventory

    An automatic gas chromatograph with a flame photometric detector that samples and analyzes hydrogen sulfide and carbonyl sulfide at 30-s intervals is described. Temperature programming was used to elute trace amounts of carbon disulfide present in each injection from a Supelpak-S...

  2. Emission stability enhancement of a tip-type carbon-nanotube-based field emitter via hafnium interlayer deposition and thermal treatment

    NASA Astrophysics Data System (ADS)

    Kim, Jong-Pil; Chang, Han-Beet; Kim, Bu-Jong; Park, Jin-Seok

    2012-03-01

    Carbon nanotubes (CNTs) were deposited on a tip-type tungsten substrate via electrophoretic deposition, in which a hafnium thin film was used as an interlayer. The long-term (up to 24 h) emission stability of the CNT-based field emitter was remarkably enhanced when the hafnium interlayer was coated and thermally treated. This is attributed to the enhanced adhesion between the substrate and the CNTs. An x-ray photoelectron spectroscopy study and nano-scratch measurement provided a convincing evidence of the increase in the adhesive force.

  3. In-Pile Experiment of a New Hafnium Aluminide Composite Material to Enable Fast Neutron Testing in the Advanced Test Reactor

    SciTech Connect

    Donna Post Guillen; Douglas L. Porter; James R. Parry; Heng Ban

    2010-06-01

    A new hafnium aluminide composite material is being developed as a key component in a Boosted Fast Flux Loop (BFFL) system designed to provide fast neutron flux test capability in the Advanced Test Reactor. An absorber block comprised of hafnium aluminide (Al3Hf) particles (~23% by volume) dispersed in an aluminum matrix can absorb thermal neutrons and transfer heat from the experiment to pressurized water cooling channels. However, the thermophysical properties, such as thermal conductivity, of this material and the effect of irradiation are not known. This paper describes the design of an in-pile experiment to obtain such data to enable design and optimization of the BFFL neutron filter.

  4. Continuous measurement of dissolved sulfide in sewer systems.

    PubMed

    Sutherland-Stacey, L; Corrie, S; Neethling, A; Johnson, I; Gutierrez, O; Dexter, R; Yuan, Z; Keller, J; Hamilton, G

    2008-01-01

    Sulfides are particularly problematic in the sewage industry. Hydrogen sulfide causes corrosion of concrete infrastructure, is dangerous at high concentrations and is foul smelling at low concentrations. Despite the importance of sulfide monitoring there is no commercially available system to quantify sulfide in waste water. In this article we report on our use of an in situ spectrometer to quantify bisulfide in waste water and additional analysis with a pH probe to calculate total dissolved sulfide. Our results show it is possible to use existing commercially available and field proven sensors to measure sulfide to mg/l levels continuously with little operator intervention and no sample preparation. PMID:18309215

  5. Process for producing cadmium sulfide on a cadmium telluride surface

    DOEpatents

    Levi, Dean H.; Nelson, Art J.; Ahrenkiel, Richard K.

    1996-01-01

    A process for producing a layer of cadmium sulfide on a cadmium telluride surface to be employed in a photovoltaic device. The process comprises providing a cadmium telluride surface which is exposed to a hydrogen sulfide plasma at an exposure flow rate, an exposure time and an exposure temperature sufficient to permit reaction between the hydrogen sulfide and cadmium telluride to thereby form a cadmium sulfide layer on the cadmium telluride surface and accomplish passivation. In addition to passivation, a heterojunction at the interface of the cadmium sulfide and the cadmium telluride can be formed when the layer of cadmium sulfide formed on the cadmium telluride is of sufficient thickness.

  6. Animal adaptations for tolerance and exploitation of poisonous sulfide.

    PubMed

    Grieshaber, M K; Völkel, S

    1998-01-01

    Many aquatic animal species can survive sulfide exposure to some extent through oxidation of the sulfide, which results mainly in thiosulfate. In several species, sulfide oxidation is localized in the mitochondria and is accompanied by ATP synthesis. In addition, blood-based and intracellular compounds can augment sulfide oxidation. The formation of thiosulfate requires oxygen, which results in an increase in oxygen consumption of some species. If not all sulfide is detoxified, cytochrome C oxidase is inhibited. Under these conditions, a sulfide-dependent anaerobic energy metabolism commences. PMID:9558453

  7. Hafnium isotope evidence for a transition in the dynamics of continental growth 3.2 Gyr ago.

    PubMed

    Næraa, T; Scherstén, A; Rosing, M T; Kemp, A I S; Hoffmann, J E; Kokfelt, T F; Whitehouse, M J

    2012-05-31

    Earth's lithosphere probably experienced an evolution towards the modern plate tectonic regime, owing to secular changes in mantle temperature. Radiogenic isotope variations are interpreted as evidence for the declining rates of continental crustal growth over time, with some estimates suggesting that over 70% of the present continental crustal reservoir was extracted by the end of the Archaean eon. Patterns of crustal growth and reworking in rocks younger than three billion years (Gyr) are thought to reflect the assembly and break-up of supercontinents by Wilson cycle processes and mark an important change in lithosphere dynamics. In southern West Greenland numerous studies have, however, argued for subduction settings and crust growth by arc accretion back to 3.8 Gyr ago, suggesting that modern-day tectonic regimes operated during the formation of the earliest crustal rock record. Here we report in situ uranium-lead, hafnium and oxygen isotope data from zircons of basement rocks in southern West Greenland across the critical time period during which modern-like tectonic regimes could have initiated. Our data show pronounced differences in the hafnium isotope-time patterns across this interval, requiring changes in the characteristics of the magmatic protolith. The observations suggest that 3.9-3.5-Gyr-old rocks differentiated from a >3.9-Gyr-old source reservoir with a chondritic to slightly depleted hafnium isotope composition. In contrast, rocks formed after 3.2 Gyr ago register the first additions of juvenile depleted material (that is, new mantle-derived crust) since 3.9 Gyr ago, and are characterized by striking shifts in hafnium isotope ratios similar to those shown by Phanerozoic subduction-related orogens. These data suggest a transitional period 3.5-3.2 Gyr ago from an ancient (3.9-3.5 Gyr old) crustal evolutionary regime unlike that of modern plate tectonics to a geodynamic setting after 3.2 Gyr ago that involved juvenile crust generation by plate

  8. Effect of nitrogen on tensile properties and structures of T-111 (tantalum, 8 percent tungsten, 2 percent hafnium) tubing

    NASA Technical Reports Server (NTRS)

    Buzzard, R. J.; Metroka, R. R.

    1973-01-01

    The effect of controlled nitrogen additions was evaluated on the mechanical properties of T-111 (Ta-8W-2Hf) fuel pin cladding material proposed for use in a lithium-cooled nuclear reactor concept. Additions of 80 to 1125 ppm nitrogen resulted in increased strengthening of T-111 tubular section test specimens at temperatures of 25 to 1200 C. Homogeneous distributions of up to 500 ppm nitrogen did not seriously decrease tensile ductility. Both single and two-phase microstructures, with hafnium nitride as the second phase, were evaluated in this study.

  9. Hydrogen Sulfide Inhibits Amyloid Formation

    PubMed Central

    2015-01-01

    Amyloid fibrils are large aggregates of misfolded proteins, which are often associated with various neurodegenerative diseases such as Alzheimer’s, Parkinson’s, Huntington’s, and vascular dementia. The amount of hydrogen sulfide (H2S) is known to be significantly reduced in the brain tissue of people diagnosed with Alzheimer’s disease relative to that of healthy individuals. These findings prompted us to investigate the effects of H2S on the formation of amyloids in vitro using a model fibrillogenic protein hen egg white lysozyme (HEWL). HEWL forms typical β-sheet rich fibrils during the course of 70 min at low pH and high temperatures. The addition of H2S completely inhibits the formation of β-sheet and amyloid fibrils, as revealed by deep UV resonance Raman (DUVRR) spectroscopy and ThT fluorescence. Nonresonance Raman spectroscopy shows that disulfide bonds undergo significant rearrangements in the presence of H2S. Raman bands corresponding to disulfide (RSSR) vibrational modes in the 550–500 cm–1 spectral range decrease in intensity and are accompanied by the appearance of a new 490 cm–1 band assigned to the trisulfide group (RSSSR) based on the comparison with model compounds. The formation of RSSSR was proven further using a reaction with TCEP reduction agent and LC-MS analysis of the products. Intrinsic tryptophan fluorescence study shows a strong denaturation of HEWL containing trisulfide bonds. The presented evidence indicates that H2S causes the formation of trisulfide bridges, which destabilizes HEWL structure, preventing protein fibrillation. As a result, small spherical aggregates of unordered protein form, which exhibit no cytotoxicity by contrast with HEWL fibrils. PMID:25545790

  10. Stratospheric carbonyl sulfide (OCS) burden

    NASA Astrophysics Data System (ADS)

    Kloss, Corinna; Walker, Kaley A.; Deshler, Terry; von Hobe, Marc

    2015-04-01

    An estimation of the global stratospheric burden of carbonyl sulfide (OCS) calculated using satellite based measurements from the Atmospheric Chemistry Experiment - Fourier Transform Spectrometer (ACE-FTS) will be presented. OCS is the most abundant sulfur containing gas in the atmosphere in the absence of volcanic eruptions. With a long lifetime of 2-6 years it reaches the stratosphere where it is photolyzed and the sulfur oxidized and condensed to aerosols, contributing to the stratospheric aerosol layer. The aerosol layer is the one factor of the middle-atmosphere with a direct impact on the Earth's climate by scattering incoming solar radiation back to space. Therefore it is crucial to understand and estimate the different processes and abundances of the species contributing to the aerosol layer. However, the exact amount of OCS in the stratosphere has not been quantified yet. A study on the OCS mixing ratio distribution based on ACE-FTS data has already been made by Barkley et al. (2008), also giving an estimation for the total atmospheric OCS mass. ACE-FTS is an infrared solar occultation spectrometer providing high- resolution profile observations since 2004. In the scope of this work the focus lies on the stratospheric OCS burden, calculated by integrating the ACE profiles. A global overview on the stratospheric OCS amount in the past and present based on the ACE data as well as a look at regional and seasonal variability will be given. Furthermore, the results of this work will be useful for further studies on OCS fluxes and lifetimes, and in quantifying the contribution of OCS to the global stratospheric sulfur burden. Barkley et al., 2008, Geophys. Res. Lett., 35, L14810.

  11. Electronic States of Hafnium and Vanadium oxide in Silicon Gate Stack Structure

    NASA Astrophysics Data System (ADS)

    Zhu, Chiyu; Tang, Fu; Liu, Xin; Yang, Jialing; Nemanich, Robert

    2010-03-01

    Vanadium oxide (VO2) is a narrow band gap material with a metal-insulator transition (MIT) at less than 100C. Hafnium oxide (HfO2) is currently the preferred high-k material for gate dielectrics. To utilize VO2 in a charge storage device, it is necessary to understand the band relationships between VO2, HfO2, and Si substrate. In this study, a 2nm thick VO2 layer is embedded in a dielectric stack structure between an oxidized n-type Si(100) surface and a 2nm HfO2 layer. The in situ experiments are carried out in an UHV multi-chamber system. After each growth step, the surface is characterized using XPS and UPS. After the initial plasma cleaning and oxidation treatment the Si substrate displayed essentially flat bands at the surface. After deposition of the VO2 layer, the Si 2p peak shifted to lower binding energy, and the Si 2p associated with the SiO2 layer also was shifted, indicating an internal field in the SiO2. The VO2 valence band maximum (VBM) was identified at 0.6 eV below the Fermi level (EF). This ultra thin VO2 exhibits the metal-insulator transition at a temperature higher than thicker films. As a comparison, a 100nm thick film of VO2 on Si showed a MIT at 60C. After the HfO2 deposition, the Si 2p substrate feature returned to the initial value indicating a return to flat band conditions. The UPS indicated the VBM of HfO2 at 4.0 eV below EF. This work is supported by the NSF (DMR-0805353).

  12. Phase Engineering of 2D Tin Sulfides.

    PubMed

    Mutlu, Zafer; Wu, Ryan J; Wickramaratne, Darshana; Shahrezaei, Sina; Liu, Chueh; Temiz, Selcuk; Patalano, Andrew; Ozkan, Mihrimah; Lake, Roger K; Mkhoyan, K A; Ozkan, Cengiz S

    2016-06-01

    Tin sulfides can exist in a variety of phases and polytypes due to the different oxidation states of Sn. A subset of these phases and polytypes take the form of layered 2D structures that give rise to a wide host of electronic and optical properties. Hence, achieving control over the phase, polytype, and thickness of tin sulfides is necessary to utilize this wide range of properties exhibited by the compound. This study reports on phase-selective growth of both hexagonal tin (IV) sulfide SnS2 and orthorhombic tin (II) sulfide SnS crystals with diameters of over tens of microns on SiO2 substrates through atmospheric pressure vapor-phase method in a conventional horizontal quartz tube furnace with SnO2 and S powders as the source materials. Detailed characterization of each phase of tin sulfide crystals is performed using various microscopy and spectroscopy methods, and the results are corroborated by ab initio density functional theory calculations. PMID:27099950

  13. Uniform yolk-shell iron sulfide-carbon nanospheres for superior sodium-iron sulfide batteries.

    PubMed

    Wang, Yun-Xiao; Yang, Jianping; Chou, Shu-Lei; Liu, Hua Kun; Zhang, Wei-Xian; Zhao, Dongyuan; Dou, Shi Xue

    2015-01-01

    Sodium-metal sulfide battery holds great promise for sustainable and cost-effective applications. Nevertheless, achieving high capacity and cycling stability remains a great challenge. Here, uniform yolk-shell iron sulfide-carbon nanospheres have been synthesized as cathode materials for the emerging sodium sulfide battery to achieve remarkable capacity of ∼ 545 mA h g(-1) over 100 cycles at 0.2 C (100 mA g(-1)), delivering ultrahigh energy density of ∼ 438 Wh kg(-1). The proven conversion reaction between sodium and iron sulfide results in high capacity but severe volume changes. Nanostructural design, including of nanosized iron sulfide yolks (∼ 170 nm) with porous carbon shells (∼ 30 nm) and extra void space (∼ 20 nm) in between, has been used to achieve excellent cycling performance without sacrificing capacity. This sustainable sodium-iron sulfide battery is a promising candidate for stationary energy storage. Furthermore, this spatially confined sulfuration strategy offers a general method for other yolk-shell metal sulfide-carbon composites. PMID:26507613

  14. Uniform yolk-shell iron sulfide-carbon nanospheres for superior sodium-iron sulfide batteries

    NASA Astrophysics Data System (ADS)

    Wang, Yun-Xiao; Yang, Jianping; Chou, Shu-Lei; Liu, Hua Kun; Zhang, Wei-Xian; Zhao, Dongyuan; Dou, Shi Xue

    2015-10-01

    Sodium-metal sulfide battery holds great promise for sustainable and cost-effective applications. Nevertheless, achieving high capacity and cycling stability remains a great challenge. Here, uniform yolk-shell iron sulfide-carbon nanospheres have been synthesized as cathode materials for the emerging sodium sulfide battery to achieve remarkable capacity of ~545 mA h g-1 over 100 cycles at 0.2 C (100 mA g-1), delivering ultrahigh energy density of ~438 Wh kg-1. The proven conversion reaction between sodium and iron sulfide results in high capacity but severe volume changes. Nanostructural design, including of nanosized iron sulfide yolks (~170 nm) with porous carbon shells (~30 nm) and extra void space (~20 nm) in between, has been used to achieve excellent cycling performance without sacrificing capacity. This sustainable sodium-iron sulfide battery is a promising candidate for stationary energy storage. Furthermore, this spatially confined sulfuration strategy offers a general method for other yolk-shell metal sulfide-carbon composites.

  15. Labile sulfide and sulfite in phytochelatin complexes

    SciTech Connect

    Eannetta, N.T.; Steffens, J.C. )

    1989-04-01

    Heavy metals such as cadmium induce tomato cell cultures to synthesize the metal binding polypeptides ({gamma}-Glu-Cys){sub 3} and ({gamma}-Glu-Cys){sub 4}-Gly (phytochelatins). Tomato cells selected for growth on normally lethal concentrations of CdCl{sub 2} synthesize higher quantities of these polypeptides. Cd{sup r} cells are not cross-resistant to other heavy metals, and recent work suggests that metal detoxification by these peptides may be Cd-specific. The occurrence of labile sulfur as a component of the metal complex raises questions concerning possible functions of phytochelatins besides that of Cd binding. The presence of acid-labile sulfide ion in phytochelatin complexes has been reported by several groups. We report the additional finding that labile sulfite is also present in these complexes and in higher amounts than sulfide. Sulfide and sulfite are both released from the metal binding complex by acidification or by treatment with EDTA.

  16. Preparation of silver-activated zinc sulfide thin films

    NASA Technical Reports Server (NTRS)

    Feldman, C.; Swindells, F. E.

    1968-01-01

    Silver improves luminescence and reduces contamination of zinc sulfide phosphors. The silver is added after the zinc sulfide phosphors are deposited in thin films by vapor evaporation, but before calcining, by immersion in a solution of silver salt.

  17. Hydrogen sulfide to the rescue in obstructive kidney injury

    PubMed Central

    Kasinath, Balakuntalam S.

    2014-01-01

    Hydrogen sulfide is a gasotransmitter with far reaching effects on cell function. Studies show that depending on the context hydrogen sulfide can function as an ameliorative agent or as a mediator of kidney injury. PMID:24875544

  18. Mechanisms of hydrogen sulfide removal with steel making slag.

    PubMed

    Kim, Kyunghoi; Asaoka, Satoshi; Yamamoto, Tamiji; Hayakawa, Shinjiro; Takeda, Kazuhiko; Katayama, Misaki; Onoue, Takasumi

    2012-09-18

    In the present study, we experimentally investigated the removal of hydrogen sulfide using steel-making slag (SMS) and clarified the mechanism of hydrogen sulfide removal with the SMS. The results proved that SMS is able to remove hydrogen sulfide dissolved in water, and the maximum removal amount of hydrogen sulfide per unit weight of the SMS for 8 days was estimated to be 37.5 mg S/g. The removal processes of hydrogen sulfide were not only adsorption onto the SMS, but oxidation and precipitation as sulfur. The chemical forms of sulfide adsorbed onto the SMS were estimated to be sulfur and manganese sulfide in the ratio of 81% and 19%, respectively. It is demonstrated here that the SMS is a promising material to remediate organically enriched coastal sediments in terms of removal of hydrogen sulfide. Furthermore, using SMS is expected to contribute to development of a recycling-oriented society. PMID:22894171

  19. Evolution of sulfide mineralization on Mars

    SciTech Connect

    Burns, R.G.; Fisher, D.S. )

    1990-08-30

    The presence of komatiitic igneous rocks on Marks, based on geochemical evidence from SNC meteorites and Viking X ray fluorescence analyses of the regolith, suggests that massive and disseminated iron sulfide mineralization occurs near the Martian surface. Analogies are drawn between possible ultramafic Fe-Ni sulfides on Mars and terrestrial pyrrhotite-pentlandite ore deposits associated with Archean komatiites formed during early crustal development on Earth. Partial melting of the mantle as a result of high radiogenic heat production then, extrusion of turbulent high-temperature ultramafic lavas, segregation of immiscible FeS melts during cooling, gravitational settling and fractional crystallization of sulfide minerals in magma chambers or lava flows produced massive and disseminated sulfide mineralization associated with terrestrial komatiites. Comparable processes probably occurred on Mars where, on account of the inferred higher Fe/(Fe + Mg) ratio of the X ray mantle (estimated to contain {approximately}4.5 wt % S), iron-rich basaltic magmas were produced by partial melting at depths and temperatures exceeding 165 km and 1,400{degree}C, respectively. Adiabatic diapiric emplacement of these iron-rich, very low viscosity basaltic melts transported significant concentrations of dissolved sulfur as S{sup 2{minus}} and HS{sup {minus}} from the mantle. Ensuing sulfide mineralization may have been either thinly disseminated within ultramafic lavas erupting over large areas of Mars or concentrated locally at the base of structural depressions. Cumulate ore deposits several meters thick may occur at the base of intrusions or in near-surface magma chambers. The evidence for insignificant plate tectonic activity on Mars and minimal interactions of Martian mantle with crust, hydrosphere and atmosphere has restricted the evolution of sulfide ore deposits there.

  20. Surface modifications of steels to improve corrosion resistance in sulfidizing-oxidizing environments

    NASA Astrophysics Data System (ADS)

    Behrani, Vikas

    Industrial and power generation processes employ units like boilers and gasifiers to burn sulfur containing fuels to produce steam and syn gas (H 2 and CO), which can generate electricity using turbines and fuel cells. These units often operate under environments containing gases such as H 2S, SO2, O2 etc, which can attack the metallic structure and impose serious problems of corrosion. Corrosion control in high temperature sulfur bearing environments is a challenging problem requiring information on local gaseous species at the surface of alloy and mechanisms of degradation in these environments. Coatings have proved to be a better alternative for improving corrosion resistance without compromising the bulk mechanical properties. Changes in process conditions may result in thermal and/or environment cycling between oxidizing and sulfidizing environments at the alloy surface, which can damage the protective scale formed on the alloy surface, leading to increase in corrosion rates. Objective of this study was to understand the effect of fluctuating environments on corrosion kinetics of carbon steels and develop diffusion based coatings to mitigate the high temperatures corrosion under these conditions. More specifically, the focus was: (1) to characterize the local gaseous environments at the surface of alloys in boilers; (2) optimizing diffusion coatings parameters for carbon steel; (3) understand the underlying failure mechanisms in cyclic environments; (4) to improve aluminide coating behavior by co-deposition of reactive elements such as Yttrium and Hafnium; (5) to formulate a plausible mechanism of coating growth and effects of alloying elements on corrosion; and (6) to understand the spallation behavior of scale by measuring stresses in the scales. The understanding of coating mechanism and effects of fluctuating gaseous environments provides information for designing materials with more reliable performance. The study also investigates the mechanism behind

  1. Modeling of Sulfide Microenvironments on Mars

    NASA Technical Reports Server (NTRS)

    Schwenzer, S. P.; Bridges, J. C.; McAdam, A.; Steer, E. D.; Conrad, P. G.; Kelley, S. P.; Wiens, R. C.; Mangold, N.; Grotzinger, J.; Eigenbrode, J. L.; Franz, H. B.; Sutter, B.

    2016-01-01

    Yellowknife Bay (YKB; sol 124-198) is the second site that the Mars Science Laboratory Rover Curiosity investigated in detail on its mission in Gale Crater. YKB represents lake bed sediments from an overall neutral pH, low salinity environment, with a mineralogical composition which includes Ca-sulfates, Fe oxide/hydroxides, Fe-sulfides, amorphous material, and trioctahedral phyllosilicates. We investigate whether sulfide alteration could be associated with ancient habitable microenvironments in the Gale mudstones. Some textural evidence for such alteration may be pre-sent in the nodules present in the mudstone.

  2. Reviewing sulfidation corrosion—Yesterday and today

    NASA Astrophysics Data System (ADS)

    Bornstein, Norman S.

    1996-11-01

    At one time, sulfidation corrosion threatened to severely limit the use of gas turbines in marine applications, markedly reduce the life of industrial gas turbines, and affect the performance of aircraft engines. Today, gas turbine engines drive U.S. naval ships, produce electricity, and power aircraft. However, the problem of sulfidation corrosion has not disappeared. The rapid rate of degradation of airfoil materials in the presence of condensed sulfates is still a concern for gas turbine engines that operate in industrial and marine environments.

  3. Classification of polytype structures of zinc sulfide

    SciTech Connect

    Laptev, V.I.

    1994-12-31

    It is suggested that the existing classification of polytype structures of zinc sulfide be supplemented with an additional criterion: the characteristic of regular point systems (Wyckoff positions) including their type, number, and multiplicity. The consideration of the Wyckoff positions allowed the establishment of construction principles of known polytype series of different symmetries and the systematization (for the first time) of the polytypes with the same number of differently packed layers. the classification suggested for polytype structures of zinc sulfide is compact and provides a basis for creating search systems. The classification table obtained can also be used for numerous silicon carbide polytypes. 8 refs., 4 tabs.

  4. Sol-gel processing of metal sulfides

    NASA Astrophysics Data System (ADS)

    Stanic, Vesha

    Metal sulfides were synthesised via a sol-gel process using various metal alkoxides and hydrogen sulfide in toluene. Colloidal gels were prepared from germanium ethoxide, germanium isopropoxide, zinc tert-butoxide and tungsten (VI) ethoxide, whereas colloidal powder was produced from tungsten (V) dichloride ethoxide. Special precautions were necessary to protect the reaction mixture from water contamination which produced metal oxides. Results indicated that the main source of water is the hydrogen sulfide gas. In addition, synthesis of metal sulfides from a mixture of metal oxide and sulfide was demonstrated by the example of monoclinic germanium disulfide. It was produced by reaction of the sol-gel product with sulfur. Heat treatment of the sol-gel product and sulfur yielded single phase GeSsb2. The sol-gel prepared materials and their heat treated products were characterized by various methods. A chemical kinetics study of the functional groups -OR, -SH and Ssp{2-} was carried out for the sol-gel processing of GeSsb2 from of hydrogen sulfide and two different alkoxides, germanium ethoxide and germanium isopropoxide. The study was performed for different concentrations of precursors at different molar ratios and temperatures. The results indicate that the proposed reaction mechanism was simplified under appropriate reaction conditions. Experimentally determined rate constants of thiolysis and condensations demonstrate that thiolysis is slow and that condensations are fast steps, regardless of the studied reaction conditions. A study of the temperature effect on the reaction rate constant shows that it increases with temperature in accord with both Arrhenius law and transition-state theory. Activation energies, Esba, and activation parameters DeltaSsp{ddagger}, DeltaHsp{ddagger} and DeltaGsp{ddagger}, were determined for thiolysis and condensation reactions. The potentiometric tiration method was used for quantitative determination of germanium sulfide and

  5. Acute inhalation toxicity of carbonyl sulfide

    SciTech Connect

    Benson, J.M.; Hahn, F.F.; Barr, E.B.

    1995-12-01

    Carbonyl sulfide (COS), a colorless gas, is a side product of industrial procedures sure as coal hydrogenation and gasification. It is structurally related to and is a metabolite of carbon disulfide. COS is metabolized in the body by carbonic anhydrase to hydrogen sulfide (H{sub 2}S), which is thought to be responsible for COS toxicity. No threshold limit value for COS has been established. Results of these studies indicate COS (with an LC{sub 50} of 590 ppm) is slightly less acutely toxic than H{sub 2}S (LC{sub 50} of 440 ppm).

  6. Method for inhibiting oxidation of metal sulfide-containing material

    DOEpatents

    Elsetinow, Alicia; Borda, Michael J.; Schoonen, Martin A.; Strongin, Daniel R.

    2006-12-26

    The present invention provides means for inhibiting the oxidation of a metal sulfide-containing material, such as ore mine waste rock or metal sulfide taiulings, by coating the metal sulfide-containing material with an oxidation-inhibiting two-tail lipid coating (12) thereon, thereby inhibiting oxidation of the metal sulfide-containing material in acid mine drainage conditions. The lipids may be selected from phospholipids, sphingolipids, glycolipids and combinations thereof.

  7. Membrane for hydrogen recovery from streams containing hydrogen sulfide

    DOEpatents

    Agarwal, Pradeep K.

    2007-01-16

    A membrane for hydrogen recovery from streams containing hydrogen sulfide is provided. The membrane comprises a substrate, a hydrogen permeable first membrane layer deposited on the substrate, and a second membrane layer deposited on the first layer. The second layer contains sulfides of transition metals and positioned on the on a feed side of the hydrogen sulfide stream. The present invention also includes a method for the direct decomposition of hydrogen sulfide to hydrogen and sulfur.

  8. Gondwanan basement terranes of the Variscan-Appalachian orogen: Baltican, Saharan and West African hafnium isotopic fingerprints in Avalonia, Iberia and the Armorican Terranes

    NASA Astrophysics Data System (ADS)

    Henderson, Bonnie J.; Collins, William Joseph; Murphy, James Brendan; Gutierrez-Alonso, Gabriel; Hand, Martin

    2016-06-01

    Iberia, Avalonia and the "Armorican" terranes form key constituents of the Variscan-Appalachian orogen, but their Neoproterozoic origins along the northern Gondwanan margin continue to be strongly debated. Here, we present a new detrital zircon U-Pb-Hf dataset from Neoproterozoic-Silurian sedimentary sequences in NW Iberia and Avalonia, in conjunction with the comprehensive existing datasets from potential source cratons, to demonstrate that the provenance of each terrane is relatively simple and can be traced back to three major cratons. The enigmatic Tonian-Stenian detrital zircons in autochthonous Iberian rocks were derived from the Saharan metacraton in the latest Neoproterozoic-early Cambrian. Avalonia is commonly considered to have been derived from the Amazonian margin of Gondwana, but the hafnium isotopic characteristics of the detrital zircon grains in early Neoproterozoic rocks bear much stronger similarities to Baltica. The hafnium isotopic array also suggests the early Avalonian oceanic arc was built on a sliver of "Grenvillian-type crust" (~ 2.0-1.0 Ga) possibly of Baltican affinity at ~ 800 Ma, prior to accretion with a continental margin at ~ 640 Ma. The Upper Allochthon of Iberia is frequently linked to the West African Craton in the late Neoproterozoic-early Cambrian, however the hafnium isotopic array presented here does not support this connection; rather it is more similar to the hafnium array from Avalonia. The Armorican terranes have strong detrital zircon isotopic links to the West African Craton during the late Neoproterozoic-Cambrian.

  9. Hydrotreating with catalysts comprising mixtures of an amorphous sulfide or trivalent chromium and microcrystallites of molybdenum sulfide or tungsten sulfide

    SciTech Connect

    Jacobson, A.J.; Ho, T.C.; Chianelli, R.R.; Steger, J.J.; Montagna, A.A.

    1989-03-14

    A process is described for hydrorefining a hydrocarbon feed to reduce the contents of nitrogen compounds and sulfur compounds in the feed which comprises contacting the feed at an elevated temperature of at least about 150/sup 0/C and in the presence of hydrogen with a catalyst consisting essentially of a mixture of (i) an amorphous sulfide of trivalent chromium and (ii) microcrystallities of a metal sulfide of a metal selected from the group consisting of Mo, W and mixture thereof, the contacting occurring for a time sufficient to hydrorefine at least a portion of the feed. The patent also describes a process for improving the oxidation stability of a nitrogen and sulfur containing lube oil feed which comprises contacting the feed at an elevated temperature of at least about 150/sup 0/C and in the presence of hydrogen with a catalyst consisting essentially of a mixture of (i) an amorphous sulfide of trivalent chromium and (ii) microcrystallities of metal sulfides of a metal selected from the group consisting of Mo, W and mixture thereof, the contacting occurring for a time sufficient to improve the oxidation stability of the lube oil feed.

  10. 21 CFR 872.1870 - Sulfide detection device.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...) MEDICAL DEVICES DENTAL DEVICES Diagnostic Devices § 872.1870 Sulfide detection device. (a) Identification. A sulfide detection device is a device consisting of an AC-powered control unit, probe handle, probe... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Sulfide detection device. 872.1870 Section...

  11. 21 CFR 872.1870 - Sulfide detection device.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...) MEDICAL DEVICES DENTAL DEVICES Diagnostic Devices § 872.1870 Sulfide detection device. (a) Identification. A sulfide detection device is a device consisting of an AC-powered control unit, probe handle, probe... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Sulfide detection device. 872.1870 Section...

  12. 21 CFR 872.1870 - Sulfide detection device.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...) MEDICAL DEVICES DENTAL DEVICES Diagnostic Devices § 872.1870 Sulfide detection device. (a) Identification. A sulfide detection device is a device consisting of an AC-powered control unit, probe handle, probe... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Sulfide detection device. 872.1870 Section...

  13. The effect of sulfide inhibition on the ANAMMOX process.

    PubMed

    Jin, Ren-Cun; Yang, Guang-Feng; Zhang, Qian-Qian; Ma, Chun; Yu, Jin-Jin; Xing, Bao-Shan

    2013-03-01

    The feasibility of anaerobic ammonium oxidation (ANAMMOX) process to treat wastewaters containing sulfide was studied in this work. Serum bottles were used as experimental containers in batch tests to analyze the short-term response of the ANAMMOX process under sulfide stress. The IC(50) of sulfide-S for ANAMMOX biomass was substrates-dependent and was calculated to be 264 mg L(-1) at an initial total nitrogen level of 200 mg L(-1) (molar ratio of ammonium and nitrite was 1:1). The long-term effects and the performance recovery under sulfide stress were continuously monitored and evaluated in an upflow anaerobic sludge blanket reactor. The performance of the ANAMMOX system was halved at an sulfide-S level of 32 mg L(-1) within 13 days; however, the nitrogen removal rate (NRR) decreased by only 17.2% within 18 days at an sulfide-S concentration of 40 mg L(-1) after long-time acclimatization of sludge in the presence of sulfide. The ANAMMOX performance recovered under sulfide-S level of 8 mg L(-1) with a steady NRR increasing speed, linear relationship between the NRR and operation time. The synchronic reduce in the specific ANAMMOX activity and the biomass extended the apparent doubling time of the nitrogen removal capacity and decreased biomass growth rate. PMID:23273856

  14. Hafnium dioxide gate dielectrics, metal gate electrodes, and phenomena occurring at their interfaces

    NASA Astrophysics Data System (ADS)

    Schaeffer, James Kenyon, III

    As metal-oxide-semiconductor field-effect transistor (MOSFET) gate lengths scale down below 45 nm, the gate oxide thickness approaches 1 nm equivalent oxide thickness. At this thickness, conventional silicon dioxide (SiO 2) gate dielectrics suffer from excessive gate leakage. Higher permittivity dielectrics are required to counter the increase in gate leakage. Hafnium dioxide (HfO2) has emerged as a promising dielectric candidate. HfO2 films deposited using metal organic chemical vapor deposition are being studied to determine the impact of process and annealing conditions on the physical and electrical properties of the gate dielectric. This study indicates that deposition and annealing temperatures influence the microstructure, density, impurity concentration, chemical environment of the impurities, and band-gap of the HfO2 dielectric. Correlations of the electrical and physical properties of the films indicate that impurities in the form of segregated carbon clusters, and low HfO2 density are detrimental to the leakage properties of the gate dielectric. Additionally, as the HfO2 thickness scales, the additional series capacitance due to poly-silicon depletion plays a larger roll in reducing the total gate capacitance. To solve this problem, high performance bulk MOSFETs will require dual metal gate electrodes possessing work functions near the silicon band edges for optimized drive current. This investigation evaluates TiN, Ta-Si-N, Ti-Al-N, WN, TaN, TaSi, Ir and IrO2 electrodes as candidate electrodes on HfO2 dielectrics. The metal-dielectric compatibility was studied by annealing the gate stacks at different temperatures. The physical stability and effective work functions of metal electrodes on HfO2 are discussed. Finally, Fermi level pinning of the metal is a barrier to identifying materials with appropriate threshold voltages. The contributions to the Fermi level pinning of platinum electrodes on HfO2 gate dielectrics are investigated by examining the

  15. Deposition and characterization of titanium dioxide and hafnium dioxide thin films for high dielectric applications

    NASA Astrophysics Data System (ADS)

    Yoon, Meeyoung

    The industry's demand for higher integrated circuit density and performance has forced the gate dielectric layer thickness to decrease rapidly. The use of conventional SiO2 films as gate oxide is reaching its limit due to the rapid increase in tunneling current. Therefore, a need for a high dielectric material to produce large oxide capacitance and low leakage current has emerged. Metal-oxides such as titanium dioxide (TiO2) and hafnium dioxide (HfO2) are attractive candidates for gate dielectrics due to their electrical and physical properties suitable for high dielectric applications. MOCVD of TiO2 using titanium isopropoxide (TTIP) precursor on p-type Si(100) has been studied. Insertion of a TiO x buffer layer, formed by depositing metallic Ti followed by oxidation, at the TiO2/Si interface has reduced the carbon contamination in the TiO2 film. Elemental Ti films, analyzed by in-situ AES, were found to grow according to Stranski-Krastanov mode on Si(100). Carbon-free, stoichiometric TiO2 films were successfully produced on Si(100) without any parasitic SiO2 layers at the TiO 2/Si interface. Electron-beam deposition of HfO2 films on Si(100) has also been investigated in this work. HfO2 films are formed by depositing elemental Hf on Si(100) and then oxidizing it either in O2 or O 3. XPS results reveal that with oxidation Hf(4f) peak shifts +3.45eV with 02 and +3.65eV with O3 oxidation. LEED and AFM studies show that the initially ordered crystalline Hf becomes disordered after oxidation. The thermodynamic stability of HfO2 films on Si has been studied using a unique test-bed structure of Hf/O3/Si. Post-Oxidation of Layer Deposition (POLD) has been employed to produce HfO2 films with a desired thickness. XPS results indicate that stoichiometric HfO 2 films were successfully produced using the POLD process. The investigation of the growth and thin film properties of TiO 2 and HfO2 using oxygen and ozone has laid a foundation for the application of these metal

  16. The energy landscape of glassy dynamics on the amorphous hafnium diboride surface

    SciTech Connect

    Nguyen, Duc; Girolami, Gregory S.; Mallek, Justin; Cloud, Andrew N.; Abelson, John R.; Lyding, Joseph; Gruebele, Martin

    2014-11-28

    Direct visualization of the dynamics of structural glasses and amorphous solids on the sub-nanometer scale provides rich information unavailable from bulk or conventional single molecule techniques. We study the surface of hafnium diboride, a conductive ultrahigh temperature ceramic material that can be grown in amorphous films. Our scanning tunneling movies have a second-to-hour dynamic range and single-point current measurements extend that to the millisecond-to-minute time scale. On the a-HfB{sub 2} glass surface, two-state hopping of 1–2 nm diameter cooperatively rearranging regions or “clusters” occurs from sub-milliseconds to hours. We characterize individual clusters in detail through high-resolution (<0.5 nm) imaging, scanning tunneling spectroscopy and voltage modulation, ruling out individual atoms, diffusing adsorbates, or pinned charges as the origin of the observed two-state hopping. Smaller clusters are more likely to hop, larger ones are more likely to be immobile. HfB{sub 2} has a very high bulk glass transition temperature T{sub g}, and we observe no three-state hopping or sequential two-state hopping previously seen on lower T{sub g} glass surfaces. The electronic density of states of clusters does not change when they hop up or down, allowing us to calibrate an accurate relative z-axis scale. By directly measuring and histogramming single cluster vertical displacements, we can reconstruct the local free energy landscape of individual clusters, complete with activation barrier height, a reaction coordinate in nanometers, and the shape of the free energy landscape basins between which hopping occurs. The experimental images are consistent with the compact shape of α-relaxors predicted by random first order transition theory, whereas the rapid hopping rate, even taking less confined motion at the surface into account, is consistent with β-relaxations. We make a proposal of how “mixed” features can show up in surface dynamics of glasses.

  17. The Molecular Frame Electric Dipole Moment and Hyperfine Interactions in Hafnium Fluoride, HfF

    NASA Astrophysics Data System (ADS)

    Le, Anh; Steimle, Timothy C.; Skripnikov, Leonid; Titov, Anatoly V.

    2013-06-01

    The identification of HfF^{+} as a possible candidate for a d_{e}} measurement has stimulated new interest in the spectroscopy of both HfF^{+} and neutral HfF. Studies of the neutral are relevant because photoionization schemes can be used to produce the cations. More importantly, computational methodologies used to predict the electronic wavefunction of HfF^{+} can be effectively assessed by making a comparison of predicted and experimental properties of the neutral, which are more readily determinable. The (1,0)[17.9]2.5 -X^{2}Δ_{3/2} band of hafnium monofluoride (HfF) has been recorded using high-resolution laser-induced fluorescence spectroscopy both field-free and in the presence of a static electric field. The field-free spectra of ^{177}HfF, ^{179}HfF, and ^{180}HfF were model to generate a set of fine and hyperfine parameters for the X^{2}Δ_{3/2} (v=0) and [17.9]2.5 (v=1) states. The observed optical Stark shifts for the ^{180}HfF isotopologue were analyzed to produce the molecular frame electric dipole moments of 1.66(1)D and 0.419(7)D for the X^{2}Δ_{3/2} and [17.9]2.5 states, respectively. A two-step ab initio calculation consisting of a two-component generalized relativistic effective core potential calculation (GRECP) followed by a restoration of the proper four-component wavefunction was performed to predict the properties of ground state HfF. B. J. Barker, I. O. Antonov, V. E. Bondybey, and M. C. Heaven, J. Chem. Phys., 134, 201102 (2011). K. C. Cossel, D. N. Gresh, L. C. Sinclair, T. Coffey, L. V. Skripnikov, A. N. Petrov, N. S. Mosyagin, A. V. Titov, R. W. Field, E. R. Meyer, E. A. Cornell and J. Ye, Chem. Phys. Lett., 546, 1 (2012). M. Grau, A. E. Leanhardt, H. Loh, L. C. Sinclair, R. P. Stutz, T. S. Yahn, and E. A. Cornell, J. Mol. Spectroc., 272, 32 (2012). H. Loh, R. P. Stutz, T. S. Yahn, H. Looser, R. W. Field, and E. A. Cornell, J. Mol. Spectroc.,276-277, 49 (2012).

  18. Charge trapping characterization methodology for the evaluation of hafnium-based gate dielectric film systems

    NASA Astrophysics Data System (ADS)

    Young, Chadwin Delin

    Scaling of advanced CMOS device dimensions, as set forth for future technology nodes by the International Technology Roadmap for Semiconductors (ITRS), will require reduction of the equivalent oxide thickness (EOT) of gate dielectrics below a point that can be physically realized using silicon dioxide. In order to continue EOT scaling below ˜1.5nm and reduce gate leakage current, higher dielectric constant materials will be needed to replace SiO2. Hafnium-based dielectrics are being widely investigated as potential candidates for the gate dielectric application. Their charge trapping characteristics were identified as a primary issue preventing the introduction of Hf-based materials into CMOS technology, potentially causing threshold voltage instability and mobility degradation. Several measurement techniques can be used to study and quantify charge trapping: Capacitance-Voltage (C-V) hysteresis, alternating stress and sense Vfb/Vt instability, charge pumping (CP), and fast transient Id-Vg (FT) measurement. The two most promising techniques are CP and FT measurements. Fixed-amplitude (FA) CP can measure interface state densities, while variable-amplitude (VA) CP can measure trap densities in the high-kappa bulk. In the FT measurement, the shift of the Id -Vg curves generated by the up and down swing of a trapezoidal pulse (i.e., DeltaVt) corresponds to the amount of the trapped charge. By using these two measurement approaches on varying physical thicknesses of Hf-based gate dielectric stacks, the impact of interfacial and bulk high-kappa charge-trapping properties on device performance (i.e., mobility) was investigated. Fixed-amplitude CP gives low interface state densities for all depositions indicating good interface passivation, whereas VA CP and FT shows large trap densities in the bulk of the high-kappa layer. Results demonstrate that the bulk trapping in the high-kappa film contributes to the degradation of device performance. Using fast transient

  19. Hafnium and neodymium isotope composition of seawater and filtered particles from the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Stichel, T.; Frank, M.; Haley, B. A.; Rickli, J.; Venchiarutti, C.

    2009-12-01

    Radiogenic hafnium (Hf) and neodymium (Nd) isotopes have been used as tracers for past continental weathering regimes and ocean circulation. To date, however, there are only very few data available on dissolved Hf isotope compositions in present-day seawater and there is a complete lack of particulate data. During expedition ANTXXIV/3 (February to April 2008) we collected particulate samples (> 0.8 µm), which were obtained by filtrations of 270-700 liters of water. The samples were separated from the filters, completely dissolved, and purified for Nd and Hf isotope determination by TIMS and MC-ICPMS, respectively. In addition, we collected filtered (0.45 µm) seawater samples (20-120 liters) to determine the dissolved isotopic composition of Hf and Nd. The Hf isotope composition of the particulate fraction in the Drake Passage ranged from 0 to -28 ɛHf and is thus similar to that observed in core top sediments from the entire Southern Ocean in a previous study. The most unradiogenic and isotopically homogenous Hf isotope compositions in our study were found near the Antarctic Peninsula. Most of the stations north of the Southern Antarctic Circumpolar Front (SACC) show a large variation in ɛHf between 0 and -23 within the water column of one station and between the stations. The locations at which these Hf isotope compositions were measured are mostly far away from the potential source areas. Nd, in contrast, was nearly absent throughout the entire sample set and the only measurable ɛNd data ranged from 0 to -7, which is in good agreement with the sediment data in that area. The dissolved seawater isotopic compositions of both Hf and Nd show only minor variance (ɛHf = 4.2 to 4.7 and ɛNd = -8.8 to -7.6, respectively). These patterns in Hf isotopes and the nearly complete absence of Nd indicates that the particulate fraction does not contain a lot of terrigeneous material but is almost entirely dominated by biogenic opal. The homogenous and relatively radiogenic

  20. Formation of selenide, sulfide or mixed selenide-sulfide films on metal or metal coated substrates

    DOEpatents

    Eser, Erten; Fields, Shannon

    2012-05-01

    A process and composition for preventing cracking in composite structures comprising a metal coated substrate and a selenide, sulfide or mixed selenide sulfide film. Specifically, cracking is prevented in the coating of molybdenum coated substrates upon which a copper, indium-gallium diselenide (CIGS) film is deposited. Cracking is inhibited by adding a Se passivating amount of oxygen to the Mo and limiting the amount of Se deposited on the Mo coating.

  1. The diagenesis of carbohydrates by hydrogen sulfide

    NASA Astrophysics Data System (ADS)

    Mango, Frank D.

    1983-08-01

    Carbohydrates react with hydrogen sulfide under low temperature (100° to 200°C) yielding a variety of organosulfur compounds including thiophenes, thiols, sulfides and sulfones. A polymer is also produced, whose elemental composition is within the range of natural coals. When reductive dehydration is carried out in the presence of hydrocarbon, organosulfur compounds are formed in the carbon number range of the hydrocarbon used. In these processes, an active hydrogen transfer catalyst is produced which facilitates the passage of hydrogen between normal paraffins and saccharide units, distributing sulfur between these two families primarily in the form of thiophene rings. The simplicity of these systems - H 2S, carbohydrates, H 2O, hydrocarbon - and the facility of the chemistry would suggest that the carbohydrates and hydrogen sulfide may be important agents in the diagenetic processes leading to petroleum and coal. Carbohydrate reduction by hydrogen sulfide may constitute an important route through which certain organosulfur compounds found in petroleum and coal entered these materials in early diagenesis.

  2. REACTION PROCESSES OF ARSENIC IN SULFIDIC SOLUTIONS

    EPA Science Inventory

    The fate of arsenic in the environment is fundamentally linked to its speciation. Arsenic in aerobic environments is predominantly arsenate, however under reducing conditions arsenite species dominate. In anoxic or sulfidic environments thioarsenite ((As(OH)x(SH)yz-) species alon...

  3. Monitoring sulfide and sulfate-reducing bacteria

    SciTech Connect

    Tanner, R.S.

    1995-12-31

    Simple yet precise and accurate methods for monitoring sulfate-reducing bacteria (SRB) and sulfide remain useful for the study of bacterial souring and corrosion. Test kits are available to measure sulfide in field samples. A more precise methylene blue sulfide assay for both field and laboratory studies is described here. Improved media, compared to that in API RP-38, for enumeration of SRB have been formulated. One of these, API-RST, contained cysteine (1.1 mM) as a reducing agent, which may be a confounding source of sulfide. While cysteine was required for rapid enumeration of SRB from environmental samples, the concentration of cysteine in medium could be reduced to 0.4 mM. It was also determined that elevated levels of yeast extract (>1 g/liter) could interfere with enumeration of SRB from environmental samples. The API-RST medium was modified to a RST-11 medium. Other changes in medium composition, in addition to reduction of cysteine, included reduction of the concentration of phosphate from 3.4 mM to 2.2 mM, reduction of the concentration of ferrous iron from 0.8 mM to 0.5 mM and preparation of a stock mineral solution to ease medium preparation. SRB from environmental samples could be enumerated in a week in this medium.

  4. Comparison of Hydrogen Sulfide Analysis Techniques

    ERIC Educational Resources Information Center

    Bethea, Robert M.

    1973-01-01

    A summary and critique of common methods of hydrogen sulfide analysis is presented. Procedures described are: reflectance from silver plates and lead acetate-coated tiles, lead acetate and mercuric chloride paper tapes, sodium nitroprusside and methylene blue wet chemical methods, infrared spectrophotometry, and gas chromatography. (BL)

  5. Sulfide as a signaling molecule in autophagy

    PubMed Central

    Gotor, Cecilia; García, Irene; Crespo, José L.; Romero, Luis C.

    2013-01-01

    Hydrogen sulfide is already recognized as an important signaling molecule in mammalian systems, and emerging data suggest that H2S is a signaling molecule just as important as nitric oxide (NO) and H2O2 in plants. Although sulfide is generated in chloroplasts and mitochondria, it is present predominantly in the charged HS- form due to the basic pH inside both organelles, thus requiring an active transporter, which is yet to be identified, to be released. In Arabidopsis, we found that the cytosolic L-cysteine desulfhydrase DES1 is involved in the degradation of cysteine, and therefore responsible for the generation of H2S in this cellular compartment. DES1 deficiency leads to the induction of autophagy. Moreover, we have demonstrated that sulfide in particular exerts a general effect on autophagy through negative regulation, in a way unrelated to nutrient deficiency. The mechanisms of H2S action and its molecular targets are largely unknown, although in animal systems, protein S-sulfhydration has been proposed as a mechanism for sulfide-mediated signaling. PMID:23328265

  6. New Sulfide Derivatives of Vegetable Oils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Vegetable oils containing sulfide group were synthesized using a UV initiated thiol-ene reaction. The reaction involved addition of butyl thiol to the double bonds of the vegetable oil without the presence of a solvent. The effects of temperature, reaction time, type of vegetable oil, thiol to veg...

  7. Platinum metals in magmatic sulfide ores

    USGS Publications Warehouse

    Naldrett, A.J.; Duke, J.M.

    1980-01-01

    Platinum-group elements (PGE) are mined predominantly from deposits that have formed by the segregation of molten iron-nickel-copper sulfides from silicate magmas. The absolute concentrations of PGE in sulfides from different deposits vary over a range of five orders of magnitude, whereas those of other chalcophile elements vary by factors of only 2 to 100. However, the relative proportions of the different PGE in a given deposit are systematically related to the nature of the parent magma. The absolute and relative concentrations of PGE in magmatic sulfides are explained in terms of the degree of partial melting of mantle peridotite required to produce the parent magma and the processes of batch equilibration and fractional segregation of sulfides. The Republic of South Africa and the U.S.S.R. together possess more than 97 percent of the world PGE reserves, but significant undeveloped resources occur in North America. The Stillwater complex in Montana is perhaps the most important example. Copyright ?? 1980 AAAS.

  8. 30 CFR 250.490 - Hydrogen sulfide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... black lettering as follows: Letter height Wording 12 inches Danger. Poisonous Gas. Hydrogen Sulfide. 7... well-control techniques to prevent formation fracturing in an open hole within the pressure limits of... designed consistent with the anticipated depth, conditions of the hole, and reservoir environment to...

  9. Atomic layer deposition of metal sulfide materials.

    PubMed

    Dasgupta, Neil P; Meng, Xiangbo; Elam, Jeffrey W; Martinson, Alex B F

    2015-02-17

    CONSPECTUS: The field of nanoscience is delivering increasingly intricate yet elegant geometric structures incorporating an ever-expanding palette of materials. Atomic layer deposition (ALD) is a powerful driver of this field, providing exceptionally conformal coatings spanning the periodic table and atomic-scale precision independent of substrate geometry. This versatility is intrinsic to ALD and results from sequential and self-limiting surface reactions. This characteristic facilitates digital synthesis, in which the film grows linearly with the number of reaction cycles. While the majority of ALD processes identified to date produce metal oxides, novel applications in areas such as energy storage, catalysis, and nanophotonics are motivating interest in sulfide materials. Recent progress in ALD of sulfides has expanded the diversity of accessible materials as well as a more complete understanding of the unique chalcogenide surface chemistry. ALD of sulfide materials typically uses metalorganic precursors and hydrogen sulfide (H2S). As in oxide ALD, the precursor chemistry is critical to controlling both the film growth and properties including roughness, crystallinity, and impurity levels. By modification of the precursor sequence, multicomponent sulfides have been deposited, although challenges remain because of the higher propensity for cation exchange reactions, greater diffusion rates, and unintentional annealing of this more labile class of materials. A deeper understanding of these surface chemical reactions has been achieved through a combination of in situ studies and quantum-chemical calculations. As this understanding matures, so does our ability to deterministically tailor film properties to new applications and more sophisticated devices. This Account highlights the attributes of ALD chemistry that are unique to metal sulfides and surveys recent applications of these materials in photovoltaics, energy storage, and photonics. Within each application

  10. Method of washing hydrogen sulfide from coke oven gas by the ammonium sulfide method

    SciTech Connect

    Ritter, H.

    1985-05-21

    An improved coke oven gas washing process for removing hydrogen sulfide is proposed wherein the coke oven gas is treated in a hydrogen sulfide scrubber by counterflow with an aqueous ammonia wash water. A stream of aqueous weak ammonia liquor is cooled and sprayed through nozzles in the mid-region of the hydrogen sulfide scrubber. A quantity of aqueous ammonia liquor, corresponding to the quantity which is sprayed through the said nozzles, is withdrawn from the hydrogen sulfide scrubber at a level below the nozzles and is introduced into the top of the said hydrogen sulfide scrubber. Ammonia vapor released at the nozzles has a higher partial pressure than the ammonia partial pressure of the coke oven gas in the region of the nozzle. The aqueous ammonia liquor from the deacidifier is the source of the cooled aqueous ammonia liquor which is introduced through the nozzles. A portion of the aqueous ammonia liquor from the deacidifier is introduced directly into the top of the hydrogen sulfide scrubber as a portion of the required aqueous ammonia wash water.

  11. Oxygen Demand of Fresh and Stored Sulfide Solutions and Sulfide-Rich Constructed Wetland Effluent.

    PubMed

    Chan, Carolyn; Farahbakhsh, Khosrow

    2015-08-01

    This study investigated the contribution of hydrogen sulfide to biological oxygen demand (BOD5) and chemical oxygen demand (COD) in wastewater effluents, and documented the effect of storage times and conditions on the BOD5 and COD of pH-adjusted sodium sulfide solutions as well as graywater wetland effluent. Initial COD measurements of sulfide solutions were 84-89% of the theoretical oxygen demand (ThOD), 1.996 mg O2/mg S, whereas unseeded BOD5 measurements were 55-77%. For sulfide solutions, all storage conditions led to declines of >15% (COD, BOD5), and >31% (sulfide). For wetland effluent, storage without headspace was effective in reducing COD losses (3.7%), compared to storage with headspace (17%), and affected changes in turbidity, UVA-254 and pH. The results suggest that storage times and conditions should be controlled and reported when reporting BOD5 and COD of sulfide-rich samples. Wetland models representing sulfate reduction as a method of COD removal may need to be reconsidered. PMID:26237688

  12. New treatment for sulfide-laden tannery waste

    SciTech Connect

    Berberich, S.

    1984-02-01

    A new treatment for tannery wastes containing toxic sulfide has been developed using anaerobic microorganisms that thrive alongside sulfide compounds. The new system, using an anaerobic reactor, transforms sulfide-laden tannery wastes into inert matter, methane, and material (including sulfide) readily digested in an aerobic polishing step. An industrial scale-up of the anaerobic reactor could digest between 60-70% of tannery pollutants. The new treatment offers leather tanneries and other industries that generate high-sulfide waste a cheaper way to meet federal water pollution guidelines.

  13. Study on the sulfidation behavior of smithsonite

    NASA Astrophysics Data System (ADS)

    Wu, Dandan; Wen, Shuming; Deng, Jiushuai; Liu, Jian; Mao, Yingbo

    2015-02-01

    Zinc extraction from low-grade mineral resources of oxidized zinc has recently become a focus of study. Sulfidation is an important process in oxidized ore flotation. In this study, the influence of sulfur ion adsorption on smithsonite surface was investigated with the use of zeta potential, inductively coupled plasma (ICP), scanning electron microscope (SEM), and X-ray photoelectron spectroscopic studies. Zeta potential measurements of sodium sulfide showed that sulfur ions were adsorbed onto the surface of pure smithsonite, as evidenced by the increased negative charge and the decrease in the pHIEP of smithsonite from 7.7 to 6 after sodium sulfide treatment. The ICP test revealed the gradual reduction in sulfur ion adsorption onto the surface of smithsonite in pulp sulfur. After 30 min of absorption, CS in the solution declined from 1000 × 10-6 mol/L to 1.4 × 10-6 mol/L. SEM results showed that the mineral surface was partially changed to ZnS film after sodium sulfide treatment, whereas EDS analysis results showed that 2% S is contained on the smithsonite surface. X-ray photoelectron spectroscopy results indicated the presence of a characteristic signal peak of sulfur ions after sulfidation. Sulfur concentration increased to 11.89%, whereas oxygen concentration decreased from 42.31% to 13.74%. Sulfur ions were not only present during chemical adsorption, but were also incorporated into the crystal lattices of minerals by the exchange reaction between S2- and CO32- ions.

  14. Sulfidization and magnetization above hydrocarbon reservoirs

    SciTech Connect

    Reynolds, R.L.; Goldhaber, M.B.; Tuttle, M.L. )

    1991-03-01

    Geochemical and rock magnetic studies of strata over Cement oil field (Anadarko basin, Oklahoma), Simpson oil field (North Slope basin, Alaska), and the Edwards deep gas trend, south Texas coastal plain, document changes in original magnetizations caused by postdepositional iron sulfide minerals that are, or may be, related to hydrocarbon seepage. At Cement, ferrimagnetic pyrrhotite (Fe{sub 7}S{sub 8}) formed with pyrite and marcasite in Permian red beds. The Fe-S minerals contain isotopically heavy, abiogenic sulfur derived from thermal degradation of petroleum and (or) isotopically light sulfur derived from sulfate-reducing bacteria fed by leaking hydrocarbons. At Simpson, ferrimagnetic greigite (Fe{sub 3}S{sub 4}) dominates magnetizations in Upper Cretaceous nonmarine beds that contain biodegraded oil. Sulfur isotopic data are consistent with, but do not prove, a genetic link between the greigite ({delta}{sup 34}S {gt} +20 per mil) and seepage. In middle Tertiary sandstones of southeast Texas, pyrite and marcasite formed when abiogenic H{sub 2}S migrated upward from deep reservoirs, or when H{sub 2}S was produced at shallow depths by bacteria that utilized organic material dissolved in migrating water from depth. The sulfide minerals replaced detrital magnetite to result in a systematic decrease in magnetic susceptibility toward faults that connect deep petroleum reservoirs to shallow sandstone. The authors results show that abiologic and biologic mechanisms can generate magnetic sulfide minerals in some sulfidic zones of hydrocarbon seepage. The magnetizations in such zones are diminished most commonly by replacement of detrital magnetic minerals with nonmagnetic sulfide minerals or are unchanged if such detrital minerals were originally absent.

  15. Analog Experiments on Sulfide Foams in Magmatic Ore Deposits

    NASA Astrophysics Data System (ADS)

    Leitch, A. M.; Dahn, D.; Zavala, K.

    2009-05-01

    Metal sulfides form as an immiscible phase from silicate magmas. Dynamic mingling and unmingling of the two phases is important for the development of economic deposits: mingling promotes enrichment of the sulfide in valuable metals, and subsequent unmingling generates massive sulfide. Analog experiments were carried out to investigate mingling processes in immiscible systems, using oil, water and small beads to represent magma, sulfide liquid and silicate crystals. Stirring or injection led to the formation of a foam of analog sulfide droplets within an analog silicate framework. We propose that the partial collapse of such a foam explains massive sulfide lenses at the Voisey's Bay magmatic sulfide deposit, and that crystallization of silicate crystals in the remaining foam walls generates 'net-textured' ores. In the experiments, solid particles had a profound effect on unmingling: analog sulfide droplets were stably contained within analog crystal-rich magma and did not coalesce. We therefore suggest that 'net' and 'leopard' textures in disseminated sulfides indicate mingling of sulfide with crystal-poor magma, whereas isolated disseminated patches of sulfide indicate mingling with a crystal-rich magma.

  16. Effect of sulfide on growth of marine bacteria.

    PubMed

    Mirzoyan, Natella; Schreier, Harold J

    2014-04-01

    Severe hypoxia leads to excess production of hydrogen sulfide in marine environments. In this study, we examined the effect of sulfide on growth of four facultative anaerobic marine bacteria in minimal media under anaerobic conditions. The Gram-negative chemolithoautotrophic Marinobacter sp. tolerated sulfide concentrations up to 0.60 mM, with doubling and lag times increasing as a function of increasing sulfide concentration but with no change in maximum culture yields; growth did not occur at 1.2 mM sulfide. Similar results were obtained for the metabolically diverse Gram-negative denitrifying Pseudomonas stutzeri, except that growth occurred at 1.2 mM and culture yields at 0.60 and 1.2 mM sulfide were approximately 10-fold lower than at sulfide concentrations between 0 and 0.30 mM. Increases in doubling and lag times accompanied by an overall 10-fold decrease in maximum culture yields were found for the Gram-negative chemoheterotrophic Vibrio sp. at all sulfide concentrations tested. In contrast, growth of a Gram-positive chemoheterotrophic Bacillus sp. was resistant to all sulfide concentrations tested (0.15-1.2 mM). Our results highlight the variable responses of marine bacteria to sulfide and provide some insight into shifts that may occur in microbial community structure and diversity as a consequence of changes in sulfide levels that are the result of hypoxia. PMID:24609188

  17. Microbial oxidation of mixtures of methylmercaptan and hydrogen sulfide.

    PubMed

    Subramaniyan, A; Kolhatkar, R; Sublette, K L; Beitle, R

    1998-01-01

    Refinery spent-sulfidic caustic, containing only inorganic sulfides, has previously been shown to be amenable to biotreatment with Thiobacillus denitrificans strain F with complete oxidation of sulfides to sulfate. However, many spent caustics contain mercaptans that cannot be metabolized by this strict autotroph. An aerobic enrichment culture was developed from mixed Thiobacilli and activated sludge that was capable of simultaneous oxidation of inorganic sulfide and mercaptans using hydrogen sulfide (H2S) and methylmercaptan (MeSH) gas feeds used to simulate the inorganic and organic sulfur of a spent-sulfidic caustic. The enrichment culture was also capable of biotreatment of an actual mercaptan-containing, spent-sulfidic caustic but at lower rates than predicted by operation on MeSH and H2S fed to the culture in the gas phase, indicating that the caustic contained other inhibitory components. PMID:18576062

  18. Selective chemical dissolution of sulfides: An evaluation of six methods applicable to assaying sulfide-bound nickel

    USGS Publications Warehouse

    Klock, P.R.; Czamanske, G.K.; Foose, M.; Pesek, J.

    1986-01-01

    Six analytical techniques for the selective chemical dissolution of sulfides are compared with the purpose of defining the best method for accurately determining the concentration of sulfide-bound nickel. Synthesized sulfide phases of known elemental content, mixed with well-analyzed silicates, were used to determine the relative and absolute efficiency, based on Ni and Mg recovery, of the techniques. Tested leach-methods purported to dissolve sulfide from silicate phases include: brominated water, brominated water-carbon tetrachloride, nitric-hydrochloric acid, hydrogen peroxide-ammonium citrate, bromine-methanol and hydrogen peroxide-ascorbic acid. Only the hydrogen peroxide-ammonium citrate method did not prove adequate in dissolving the sulfide phases. The remaining five methods dissolved the sulfide phases, but the indicated amount of attack on the silicate portion ranged from 3% to 100%. The bromine-methanol method is recommended for assaying sulfide-Ni deposits when Ni is also present in silicate phases. ?? 1986.

  19. Arsenic speciation in natural sulfidic geothermal waters

    NASA Astrophysics Data System (ADS)

    Keller, Nicole S.; Stefánsson, Andri; Sigfússon, Bergur

    2014-10-01

    The speciation of arsenic in natural sulfidic geothermal waters was studied using chemical analyses and thermodynamic aqueous speciation calculations. Samples were collected in three geothermal systems in Iceland, having contrasting H2S concentrations in the reservoir (high vs. low). The sampled waters contained 7-116 ppb As and <0.01-77.6 ppm H2S with pH of 8.56-9.60. The analytical setup used for the determination of arsenic species (Ion Chromatography-Hydride Generation Atomic Fluorescence Spectrometry, IC-HG-AFS) was field-deployed and the samples analyzed within ∼5 min of sampling in order to prevent changes upon storage, which were shown to be considerable regardless of the sample storage method used. Nine aqueous arsenic species were detected, among others arsenite (HnAsO3n-3), thioarsenite (HnAsS3n-3), arsenate (HnAsO4n-3), monothioarsenate (HnAsSO3n-3), dithioarsenate (HnAsS2O2n-3), trithioarsenate (HnAsS3O) and tetrathioarsenate (HnAsS4n-3). The results of the measured aqueous arsenic speciation in the natural geothermal waters and comparison with thermodynamic calculations reveal that the predominant factors determining the species distribution are sulfide concentration and pH. In alkaline waters with low sulfide concentrations the predominant species are AsIII oxyanions. This can be seen in samples from a liquid-only well, tapping water that is H2S-poor and free of oxygen. At intermediate sulfide concentration AsIII and AsV thio species become important and predominate at high sulfide concentration, as seen in two-phase well waters, which have high H2S concentrations in the reservoir. Upon oxidation, for instance due to mixing of the reservoir fluid with oxygenated water upon ascent to the surface, AsV oxyanions form, as well as AsV thio complexes if the sulfide concentration is intermediate to high. This oxidation process can be seen in samples from hot springs in the Geysir geothermal area. While the thermodynamic modeling allows for a first

  20. Nuclear quadrupole interaction at 181Ta in hafnium dioxide fiber: Time differential perturbed angular correlation measurements and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Banerjee, D.; Das, P.; Guin, R.; Das, S. K.

    2012-09-01

    The thermal behavior of hafnium dioxide fiber has been investigated with the aid of time differential perturbed angular correlation (TDPAC) technique along with XRD and SEM measurements. This study has proved a good thermal stability of the fibrous material up to 1173 K and the fiber loses its crystallinity to a meager extent at 1673 K. No phase transition has been observed up to 1673 K in this fiber. TDPAC parameters for the HfO2 fiber annealed at 1173 K are ωQ=124.6 (3) Mrad/s and η=0.36 (1). These values remain unaltered for the HfO2 fiber annealed even at 1673 K. Electronic structure calculations based on the density functional theory (DFT) for HfO2 doped with tantalum impurity have been performed and the calculated EFG parameters are in reasonable agreement with the experimental values.

  1. Effect of post-deposition annealing on the structural and electrical properties of RF sputtered hafnium oxide thin films

    NASA Astrophysics Data System (ADS)

    Das, K. C.; Ghosh, S. P.; Tripathy, N.; Bose, G.; Kar, J. P.

    2016-02-01

    Hafnium oxide films were deposited on silicon substrates by RF sputtering at room temperature. Post-deposition rapid thermal annealing of the sputtered HfO2 films was carried out in the temperature range of 400°C to 800°C in oxygen ambient. The structural properties ware studied by X-ray diffraction (XRD), where the enhancement in the crystallinity of HfO2 (1¯11) orientation was observed. The Capacitance —Voltage (C-V) and Current density —Voltage (J-V) characteristics of the annealed dielectric film were investigated employing Al/HfO2/Si Metal Oxide Semiconductor (MOS) capacitor structure. The flatband voltage (V fb ) and oxide charge density (Q ox ) were extracted from the high frequency (1 MHz) C-V curve. Leakage current was found to be minimum for the annealing temperature of 600°C.

  2. In situ infrared spectroscopy of hafnium oxide growth on hydrogen-terminated silicon surfaces by atomic layer deposition

    SciTech Connect

    Ho, M.-T.; Wang, Y.; Brewer, R.T.; Wielunski, L.S.; Chabal, Y.J.; Moumen, N.; Boleslawski, M.

    2005-09-26

    The interface formation between HfO{sub 2} and H-terminated Si(111) and Si(100) is studied by in situ infrared absorption spectroscopy during atomic layer deposition using alternating tetrakis-ethylmethylamino hafnium (TEMAH) and deuterium oxide (D{sub 2}O) pulses. The HfO{sub 2} growth is initiated by the reaction of TEMAH with Si-H rather than D{sub 2}O, and there is no evidence for SiO{sub 2} formation at moderate growth temperatures ({approx}100 deg. C). Although Rutherford backscattering shows a linear increase of Hf coverage, direct observations of Si-H, Si-O-Hf, and HfO{sub 2} phonons indicate that five cycles are needed to reach the steady state interface composition of {approx}50% reacted sites. The formation of interfacial SiO{sub 2} ({approx}0.7 nm) is observed after postdeposition annealing at 700 deg. C in ultrapure nitrogen.

  3. Tribo-electrochemical characterization of hafnium multilayer systems deposited on nitride/vanadium nitride AISI 4140 steel

    NASA Astrophysics Data System (ADS)

    Mora, M.; Vera, E.; Aperador, W.

    2016-02-01

    In this work is presented the synergistic behaviour among corrosion/wear (tribocorrosion) of the multilayer coatings hafnium nitride/vanadium nitride [HfN/VN]n. The multilayers were deposited on AISI 4140 steel using the technique of physical vapor deposition PVD magnetron sputtering, the tests were performed using a pin-on-disk tribometer, which has an adapted potentiostat galvanostat with three-electrode electrochemical cell. Tribocorrosive parameters such as: Friction coefficient between the coating and the counter body (100 Cr6 steel ball); Polarization resistance by means of electrochemical impedance spectroscopy technique and corrosion rate by polarization curves were determined. It was observed an increase in the polarization resistance, a decrease in the corrosion rate and a low coefficient of friction in comparison with the substrate, due to an increase on the number of bilayers.

  4. Experimental and first-principles studies on the elastic properties of α-hafnium metal under pressure

    DOE PAGESBeta

    Qi, Xintong; Wang, Xuebing; Chen, Ting; Li, Baosheng

    2016-03-30

    Compressional and shear wave velocities of the α phase of hafnium have been measured up to 10.4 GPa at room temperature using ultrasonic interferometry in a multi-anvil apparatus. A finite strain equation of state analysis yielded Ks0 = 110.4 (5) GPa, G0 = 54.7(5) GPa,Ks0' = 3.7 and G0' = 0.6 for the elastic bulk and shear moduli and their pressure derivatives at ambient conditions. Complementary to the experimental data, the single crystal elastic constants, elastic anisotropy and the unit cell axial ratio c/a of α-hafnium at high pressures were investigated by Density Functional Theory (DFT) based first principles calculations.more » A c/a value of 1.605 is predicted for α-Hf at 40 GPa, which is in excellent agreement with previous experimental results. The low-pressure derivative of the shear modulus observed in our experimental data up to 10 GPa was found to originate from the elastic constant C44 which exhibits negligible pressure dependence within the current experimental pressure range. At higher pressures (>10 GPa), C44 was predicted to soften and the shear wave velocity νS trended to decrease with pressure, which can be interpreted as a precursor to the α-ω transition similar to that observed in other group IV elements (titanium and zirconium). Here, the acoustic velocities, bulk and shear moduli, and the acoustic Debye temperature (θD = 240.1 K) determined from the current experiments were all compared well with those predicted by our theoretical DFT calculations.« less

  5. Sulfide Intrusion and Detoxification in the Seagrass Zostera marina.

    PubMed

    Hasler-Sheetal, Harald; Holmer, Marianne

    2015-01-01

    Gaseous sulfide intrusion into seagrasses growing in sulfidic sediments causes little or no harm to the plant, indicating the presence of an unknown sulfide tolerance or detoxification mechanism. We assessed such mechanism in the seagrass Zostera marina in the laboratory and in the field with scanning electron microscopy coupled to energy dispersive X-ray spectroscopy, chromatographic and spectrophotometric methods, and stable isotope tracing coupled with a mass balance of sulfur compounds. We found that Z. marina detoxified gaseous sediment-derived sulfide through incorporation and that most of the detoxification occurred in underground tissues, where sulfide intrusion was greatest. Elemental sulfur was a major detoxification compound, precipitating on the inner wall of the aerenchyma of underground tissues. Sulfide was metabolized into thiols and entered the plant sulfur metabolism as well as being stored as sulfate throughout the plant. We conclude that avoidance of sulfide exposure by reoxidation of sulfide in the rhizosphere or aerenchyma and tolerance of sulfide intrusion by incorporation of sulfur in the plant are likely major survival strategies of seagrasses in sulfidic sediments. PMID:26030258

  6. Sulfide Intrusion and Detoxification in the Seagrass Zostera marina

    PubMed Central

    Hasler-Sheetal, Harald; Holmer, Marianne

    2015-01-01

    Gaseous sulfide intrusion into seagrasses growing in sulfidic sediments causes little or no harm to the plant, indicating the presence of an unknown sulfide tolerance or detoxification mechanism. We assessed such mechanism in the seagrass Zostera marina in the laboratory and in the field with scanning electron microscopy coupled to energy dispersive X-ray spectroscopy, chromatographic and spectrophotometric methods, and stable isotope tracing coupled with a mass balance of sulfur compounds. We found that Z. marina detoxified gaseous sediment-derived sulfide through incorporation and that most of the detoxification occurred in underground tissues, where sulfide intrusion was greatest. Elemental sulfur was a major detoxification compound, precipitating on the inner wall of the aerenchyma of underground tissues. Sulfide was metabolized into thiols and entered the plant sulfur metabolism as well as being stored as sulfate throughout the plant. We conclude that avoidance of sulfide exposure by reoxidation of sulfide in the rhizosphere or aerenchyma and tolerance of sulfide intrusion by incorporation of sulfur in the plant are likely major survival strategies of seagrasses in sulfidic sediments. PMID:26030258

  7. Enhanced reductive dechlorination of trichloroethylene by sulfidated nanoscale zerovalent iron.

    PubMed

    Rajajayavel, Sai Rajasekar C; Ghoshal, Subhasis

    2015-07-01

    Direct injection of reactive nanoscale zerovalent iron particles (NZVI) is considered to be a promising approach for remediation of aquifers contaminated by chlorinated organic pollutants. In this study we show that the extent of sulfidation of NZVI enhances the rate of dechlorination of trichloroethylene (TCE) compared to that by unamended NZVI, and the enhancement depends on the Fe/S molar ratio. Experiments where TCE was reacted with NZVI sulfidated to different extents (Fe/S molar ratios 0.62-66) showed that the surface-area normalized first-order TCE degradation rate constant increased up to 40 folds compared to non-sulfidated NZVI. Fe/S ratios in the range of 12-25 provided the highest TCE dechlorination rates, and rates decreased at both higher and lower Fe/S. In contrast, sulfidated NZVI exposed to water in the absence of TCE showed significantly lower hydrogen evolution rate (2.75 μmol L(-1) h(-1)) compared to that by an unamended NZVI (6.92 μmol L(-1) h(-1)), indicating that sulfidation of NZVI suppressed corrosion reactions with water. Sulfide (HS(-)) ions reacted rapidly with NZVI and X-ray photoelectron spectroscopy analyses showed formation of a surface layer of FeS and FeS2. We propose that more electrons are preferentially conducted from sulfidated NZVI than from unamended NZVI to TCE, likely because of greater binding of TCE on the reactive sites of the iron sulfide outer layer. Resuspending sulfidated NZVI in sulfide-free or sulfide containing solutions altered the TCE degradation rate constants because of changes in the FeS layer thickness. Sulfidated NZVI maintained its high reactivity in the presence of multiple mono and divalent ions and with polyelectrolyte coatings. Thus, sulfide ions in groundwater can significantly alter NZVI reactivity. PMID:25935369

  8. The Evolution of Sulfide Tolerance in the Cyanobacteria

    NASA Technical Reports Server (NTRS)

    Miller, Scott R.; Bebout, Brad M.; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    Understanding how the function of extant microorganisms has recorded both their evolutionary histories and their past interactions with the environment is a stated goal of astrobiology. We are taking a multidisciplinary approach to investigate the diversification of sulfide tolerance mechanisms in the cyanobacteria, which vary both in their degree of exposure to sulfide and in their capacity to tolerate this inhibitor of photosynthetic electron transport. Since conditions were very reducing during the first part of Earth's history and detrital sulfides have been found in Archean sediments, mechanisms conferring sulfide tolerance may have been important for the evolutionary success of the ancestors of extant cyanobacteria. Two tolerance mechanisms have been identified in this group: (1) resistance of photosystem II, the principal target of sulfide toxicity; and (2) maintenance of the ability to fix carbon despite photosystem II inhibition by utilizing sulfide as an electron donor in photosystem I - dependent, anoxygenic photosynthesis. We are presently collecting comparative data on aspects of sulfide physiology for laboratory clones isolated from a variety of habitats. These data will be analyzed within a phylogenetic framework inferred from molecular sequence data collected for these clones to test how frequently different mechanisms of tolerance have evolved and which tolerance mechanism evolved first. In addition, by analyzing these physiological data together with environmental sulfide data collected from our research sites using microelectrodes, we can also test whether the breadth of an organism's sulfide tolerance can be predicted from the magnitude of variation in environmental sulfide concentration it has experienced in its recent evolutionary past and whether greater average sulfide concentration and/or temporal variability in sulfide favors the evolution of a particular mechanism of sulfide tolerance.

  9. Cadmium zinc sulfide by solution growth

    DOEpatents

    Chen, Wen S.

    1992-05-12

    A process for depositing thin layers of a II-VI compound cadmium zinc sulfide (CdZnS) by an aqueous solution growth technique with quality suitable for high efficiency photovoltaic or other devices which can benefit from the band edge shift resulting from the inclusion of Zn in the sulfide. A first solution comprising CdCl.sub.2 2.5H.sub.2 O, NH.sub.4 Cl, NH.sub.4 OH and ZnCl.sub.2, and a second solution comprising thiourea ((NH.sub.2).sub.2 CS) are combined and placed in a deposition cell, along with a substrate to form a thin i.e. 10 nm film of CdZnS on the substrate. This process can be sequentially repeated with to achieve deposition of independent multiple layers having different Zn concentrations.

  10. Removal of hydrogen sulfide from drilling fluids

    SciTech Connect

    Gilligan Jr., T. J.

    1985-10-22

    The present invention relates to a process for scavenging hydrogen sulfide which frequently becomes entrained in drilling fluid during the course of drilling operations through subterranean formations. The process consists of introducing a solid oxidant in powdered form into the circulating drilling fluid when hydrogen sulfide is encountered. The solid oxidants are selected from the group consisting of calcium hypochlorite (Ca-(OCl)/sub 2/), sodium perborate (NaBO/sub 3/), potassium permanganate (KMnO/sub 4/), and potassium peroxydisulfate (K/sub 2/S/sub 2/O/sub 8/). The solid oxidants are soluble in the drilling fluid, promoting fast and complete scavenging reactions without adversely altering the drilling fluid rheology.

  11. Absorption of carbonyl sulfide in aqueous methyldiethanolamine

    SciTech Connect

    Al-Ghawas, H.A.; Ruiz-Ibanez, G.; Sandall, O.C. )

    1988-01-01

    The absorption of carbonyl sulfide in aqueous methyldiethanolamine (MDEA) was studied over a range of temperatures and MDEA concentrations. MDEA is commonly used for selective absorption of hydrogen sulfide in the presence of carbon dioxide. However, sulfur in the form of COS may also be present and it is necessary that estimates of absorption rates of this compound be made. The objective of this study is to determine the physiochemical properties needed to predict COS absorption rates in aqueous MDEA. Free gas solubility and the diffusivity of COS in MDEA solutions were measured over the temperature range 15 to 40{sup 0}C for MDEA concentrations up to 30 weight per cent using the nitrous oxide analogy method. Solubilities were measured volumetrically in an equilibrium cell and diffusivities were measured using a laminar liquid jet absorber. The kinetics of the reaction between COS and MDEA were studied by measuring absorption rates in a single wetted-sphere absorber.

  12. Speciation of arsenic in sulfidic waters

    PubMed Central

    Wilkin, Richard T; Wallschläger, Dirk; Ford, Robert G

    2003-01-01

    Formation constants for thioarsenite species have been determined in dilute solutions at 25°C, ΣH2S from 10-7.5 to 10-3.0 M, ΣAs from 10-5.6 to 10-4.8 M, and pH 7 and 10. The principal inorganic arsenic species in anoxic aquatic systems are arsenite, As(OH)30, and a mononuclear thioarsenite with an S/As ratio of 3:1. Thioarsenic species with S/As ratios of 1 : 1,2 : 1, and 4 : 1 are lesser components in sulfidic solutions that might be encountered in natural aquatic environments. Thioarsenites dominate arsenic speciation at sulfide concentrations > 10-4.3 M at neutral pH. Conversion from neutral As(OH)30 to anionic thioarsenite species may regulate the transport and fate of arsenic in sulfate-reducing environments by governing sorption and mineral precipitation reactions.

  13. Sulfide stress corrosion cracking of line pipe

    SciTech Connect

    Kimuro, M.; Totsuka, N.; Kurisu, T.; Amano, K.; Matsuyama, J.; Nakai, Y. )

    1989-04-01

    This paper reports the sulfide stress corrosion cracking (SSC) behavior of line pipe steel investigated using the SSC test method in NACE Standard TMO177-77, Testing of Metals for Resistance to Sulfide Stress Cracking at Ambient Temperatures. SSC of base metal can be classified into two types, depending on microstructures. In ferrite-perlite steel, the first crack initiates parallel to the pipe surface and propagates perpendicularly to the axis of stress. In ferrite-bainite steel or low C-bainite steel, the crack initiates at the interface between the bainite particle and the ferrite. With decreasing carbon content, the threshold stress of SSC ({sigma}{sub th}) increases, but in low-carbon steel, the {sigma}{sub th} value of weld seam is lower than that of base metal. SSC of weld seams occurs at the softening zone in the heat-affected zone (HAZ) about 2 to 4 mm away from the fusion line.

  14. Iron-sulfide redox flow batteries

    DOEpatents

    Xia, Guan-Guang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

    2013-12-17

    Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

  15. Iron-sulfide redox flow batteries

    DOEpatents

    Xia, Guanguang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

    2016-06-14

    Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

  16. Single-layer transition metal sulfide catalysts

    DOEpatents

    Thoma, Steven G.

    2011-05-31

    Transition Metal Sulfides (TMS), such as molybdenum disulfide (MoS.sub.2), are the petroleum industry's "workhorse" catalysts for upgrading heavy petroleum feedstocks and removing sulfur, nitrogen and other pollutants from fuels. We have developed an improved synthesis technique to produce SLTMS catalysts, such as molybdenum disulfide, with potentially greater activity and specificity than those currently available. Applications for this technology include heavy feed upgrading, in-situ catalysis, bio-fuel conversion and coal liquefaction.

  17. Hydrogen sulfide prodrugs—a review

    PubMed Central

    Zheng, Yueqin; Ji, Xingyue; Ji, Kaili; Wang, Binghe

    2015-01-01

    Hydrogen sulfide (H2S) is recognized as one of three gasotransmitters together with nitric oxide (NO) and carbon monoxide (CO). As a signaling molecule, H2S plays an important role in physiology and shows great potential in pharmaceutical applications. Along this line, there is a need for the development of H2S prodrugs for various reasons. In this review, we summarize different H2S prodrugs, their chemical properties, and some of their potential therapeutic applications. PMID:26579468

  18. Subsurface heaters with low sulfidation rates

    SciTech Connect

    John, Randy Carl; Vinegar, Harold J

    2013-12-10

    A system for heating a hydrocarbon containing formation includes a heater having an elongated ferromagnetic metal heater section. The heater is located in an opening in a formation. The heater section is configured to heat the hydrocarbon containing formation. The exposed ferromagnetic metal has a sulfidation rate that goes down with increasing temperature of the heater, when the heater is in a selected temperature range.

  19. Hydrogen sulfide prodrugs-a review.

    PubMed

    Zheng, Yueqin; Ji, Xingyue; Ji, Kaili; Wang, Binghe

    2015-09-01

    Hydrogen sulfide (H2S) is recognized as one of three gasotransmitters together with nitric oxide (NO) and carbon monoxide (CO). As a signaling molecule, H2S plays an important role in physiology and shows great potential in pharmaceutical applications. Along this line, there is a need for the development of H2S prodrugs for various reasons. In this review, we summarize different H2S prodrugs, their chemical properties, and some of their potential therapeutic applications. PMID:26579468

  20. Redetermination of piperidinium hydrogen sulfide structure

    NASA Technical Reports Server (NTRS)

    Andras, Maria T.; Hepp, Aloysius F.; Fanwick, Phillip E.; Duraj, Stan A.; Gordon, Edward M.

    1994-01-01

    The presence of adventitious water in a reaction between dicyclopentamethylene thiuram-disulfide (C5H10NCS2)(sub 2) and a picoline solution of tricyclopentadienyl indium(III) (C5H5)(sub 3). It resulted in the formation of piperidinium hydrogen sulfide (C5H13NS). The piperidinium hydrogen sulfide produced in this way was unambiguously characterized by X-ray crystallography. The structure determination showed that the piperidinium hydrogen sulfide crystal (MW = 119.23 g/mol) has an orthorhombic (Pbcm) unit cell whose parameters are: a = 9.818(2), b = 7.3720(1), c = 9.754(1) A, V = 706.0(3) A(exp 3), Z=4. D(sub chi) = 1.122 g cm(exp -3), Mo K(alpha) (lamda = 0.71073), mu= 3.36 cm(exp -1), F(000) = 264.0, T =293 K, R = 0.036 for 343 reflections with F(sub O)(sup 2) greater than 3 sigma (F(sub O)(sup 2)) and 65 variables. The compound consists of (C5H10NH2)(+) cations and (SH)(-) anions with both species residing on crystallographic mirror planes. N-H -- S hydrogen bonding contributes to the interconnection of neighboring piperidinium components of the compound.

  1. Metal sulfide initiators for metal oxide sorbent regeneration

    DOEpatents

    Turk, Brian S.; Gupta, Raghubir P.

    1999-01-01

    A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream.

  2. Metal sulfide initiators for metal oxide sorbent regeneration

    DOEpatents

    Turk, Brian S.; Gupta, Raghubir P.

    2001-01-01

    A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing gas. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream.

  3. Microaeration for hydrogen sulfide removal in UASB reactor.

    PubMed

    Krayzelova, Lucie; Bartacek, Jan; Kolesarova, Nina; Jenicek, Pavel

    2014-11-01

    The removal of hydrogen sulfide from biogas by microaeration was studied in Up-flow Anaerobic Sludge Blanket (UASB) reactors treating synthetic brewery wastewater. A fully anaerobic UASB reactor served as a control while air was dosed into a microaerobic UASB reactor (UMSB). After a year of operation, sulfur balance was described in both reactors. In UASB, sulfur was mainly presented in the effluent as sulfide (49%) and in biogas as hydrogen sulfide (34%). In UMSB, 74% of sulfur was detected in the effluent (41% being sulfide and 33% being elemental sulfur), 10% accumulated in headspace as elemental sulfur and 9% escaped in biogas as hydrogen sulfide. The efficiency of hydrogen sulfide removal in UMSB was on average 73%. Microaeration did not cause any decrease in COD removal or methanogenic activity in UMSB and the elemental sulfur produced by microaeration did not accumulate in granular sludge. PMID:25270045

  4. Process for producing cadmium sulfide on a cadmium telluride surface

    DOEpatents

    Levi, D.H.; Nelson, A.J.; Ahrenkiel, R.K.

    1996-07-30

    A process is described for producing a layer of cadmium sulfide on a cadmium telluride surface to be employed in a photovoltaic device. The process comprises providing a cadmium telluride surface which is exposed to a hydrogen sulfide plasma at an exposure flow rate, an exposure time and an exposure temperature sufficient to permit reaction between the hydrogen sulfide and cadmium telluride to thereby form a cadmium sulfide layer on the cadmium telluride surface and accomplish passivation. In addition to passivation, a heterojunction at the interface of the cadmium sulfide and the cadmium telluride can be formed when the layer of cadmium sulfide formed on the cadmium telluride is of sufficient thickness. 12 figs.

  5. Metal sulfide initiators for metal oxide sorbent regeneration

    DOEpatents

    Turk, B.S.; Gupta, R.P.

    1999-06-22

    A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing gas. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream. 1 fig.

  6. Gold Sulfide Nanoclusters: A Unique Core-in-cage Structure

    SciTech Connect

    Jiang, Deen; Walter, Michael; Dai, Sheng

    2010-01-01

    By using a DFT-based basin-hopping method, we found putative global minima for three gold sulfide nanoclusters, observed in mass spectrometry, that all show a symmetric core-in-cage structure: a metallic Au core inside a cage with S as vertices and Au at the edges. This core-in-cage structure is distinct from bulk gold sulfide. This work fills the knowledge gap regarding the structure of gold sulfide nanoclusters of {approx}1 nm.

  7. Sulfide clean-up of solutions from heavy metal ions

    SciTech Connect

    Kislinskaya, G.E.; Kozachek, N.N.; Krasnova, G.M.; Shenk, N.I.

    1982-09-20

    The object of the present research was to determine the conditions for thorough clean-up of solutions from cadmium or mercury contamination by use of iron sulfide. Results indicated that the shape of the dependence of the degree of extraction of copper with iron sulfide on the pH value is analogous to the curve for cadmium; that is, copper, like cadmium, is precipitated by chemical reaction. In distinction from cadmium and copper, mercury is extracted by iron sulfide both in acid and also in neutral solutions, that is, it is possible to attain a direct ion exchange by reaction. At high pH values, only small amounts of iron go into solution, therefore FeS can be used very rationally for the extraction of both small (about 1 mg/liter), and also of large (about 1 mg/liter) amounts of mercury from solutions, which are nearly neutral. By adding sodium sulfide and a flocculant, one can accelerate the process of mercury precipitation, and also reduce the solution of iron sulfide. In the present case, iron sulfide plays the role of a substrate for the crystallization of mercury sulfide, since in dilute solutions the latter forms poorly filterable colloidal solutions. Thus when one uses fused iron sulfide with addition of sodium sulfide, a high degree of mercury extraction is attained, and the spent sorbent is filtered well.

  8. Limitation of Sulfide Capacity Concept for Molten Slags

    NASA Astrophysics Data System (ADS)

    Jung, In-Ho; Moosavi-Khoonsari, Elmira

    2016-04-01

    The sulfide capacity concept has been widely used in pyrometallurgy to define sulfur removal capacities of slags. Typically, the sulfide capacity is considered to be a unique slag property depending only on temperature regardless of partial pressures of oxygen and sulfur. In the present study, it is demonstrated that sulfide capacities of slags in particular those of Na2O-containing slags can vary with partial pressures of oxygen and sulfur due to large solubility of sulfide in Na2O-containing slag systems.

  9. Evidence supporting biologically mediated sulfide oxidation in hot spring ecosystems

    NASA Astrophysics Data System (ADS)

    Cox, A. D.; Shock, E.

    2011-12-01

    The sulfide concentration of fluids in hydrothermal ecosystems is one of several factors determining the transition to microbial photosynthesis (Cox et al., 2011, Chem. Geol. 280, 344-351). To investigate the loss of sulfide in Yellowstone hot spring systems, measurements of total dissolved sulfide with respect to time were made in incubation experiments conducted on 0.2-micron filtered (killed controls) vs. unfiltered hot spring water at locations with three different pH:sulfide combinations (pH 2.5 with 50 μM sulfide, 5.2 with 5.6 μM sulfide, and 8.3 with 86 μM sulfide). At the higher pH values, the experiments yielded similar rates of sulfide loss in filtered and unfiltered water of approximately 0.8 (pH 5.2) and 7.6 nmol sulfide L-1s-1 (pH 8.3). At the acidic spring, the unfiltered water lost sulfide at a rate 1.6 times that of the filtered water (8.2 vs. 5 nmol sulfide L-1s-1). These results suggest that the pelagic biomass at the pH 5.2 and 8.3 springs may not affect sulfide loss, whereas in the pH 2.5 spring there appears to be an effect. In addition, the incubation of filamentous biomass with unfiltered water increased the rate of sulfide loss by approximately two-fold at a pH of 2.5 (59 vs. 31 nmol L-1s-1; Cox et al., 2011), five-fold at a pH of 5.2 (3.9 vs. 0.8 nmol sulfide L-1s-1), and barely increased the rate of sulfide loss at a pH of 8.3 (9.1 vs. 8.4 nmol sulfide L-1s-1). Sulfide is predominately present as HS- at a pH of 8.3, which may not be taken up as easily by microorganisms as the H2S (aq) that dominates sulfide speciation at pH 2.5 and 5.2. That the loss of sulfide at acidic pH is due to biotic rather than abiotic factors is further supported by studies with whole mat samples that show greater sulfide consumption than killed controls (D'Imperio et al., 2008, AEM 74, 5802-5808). Taken together, the results of these experiments suggest that the majority of sulfide oxidation occurs in the filamentous biomass of hot spring ecosystems, although

  10. Mitochondrial adaptations to utilize hydrogen sulfide for energy and signaling.

    PubMed

    Olson, Kenneth R

    2012-10-01

    Sulfur is a versatile molecule with oxidation states ranging from -2 to +6. From the beginning, sulfur has been inexorably entwined with the evolution of organisms. Reduced sulfur, prevalent in the prebiotic Earth and supplied from interstellar sources, was an integral component of early life as it could provide energy through oxidization, even in a weakly oxidizing environment, and it spontaneously reacted with iron to form iron-sulfur clusters that became the earliest biological catalysts and structural components of cells. The ability to cycle sulfur between reduced and oxidized states may have been key in the great endosymbiotic event that incorporated a sulfide-oxidizing α-protobacteria into a host sulfide-reducing Archea, resulting in the eukaryotic cell. As eukaryotes slowly adapted from a sulfidic and anoxic (euxinic) world to one that was highly oxidizing, numerous mechanisms developed to deal with increasing oxidants; namely, oxygen, and decreasing sulfide. Because there is rarely any reduced sulfur in the present-day environment, sulfur was historically ignored by biologists, except for an occasional report of sulfide toxicity. Twenty-five years ago, it became evident that the organisms in sulfide-rich environments could synthesize ATP from sulfide, 10 years later came the realization that animals might use sulfide as a signaling molecule, and only within the last 4 years did it become apparent that even mammals could derive energy from sulfide generated in the gastrointestinal tract. It has also become evident that, even in the present-day oxic environment, cells can exploit the redox chemistry of sulfide, most notably as a physiological transducer of oxygen availability. This review will examine how the legacy of sulfide metabolism has shaped natural selection and how some of these ancient biochemical pathways are still employed by modern-day eukaryotes. PMID:22430869

  11. Surface reactivity of pyrite and related sulfides

    NASA Astrophysics Data System (ADS)

    Murphy, Riley; Strongin, Daniel R.

    2009-01-01

    Pyrite, FeS 2, commonly referred to as "Fool's gold" is the most common sulfide in the Earth's surface region. Not only is the mineral ubiquitous, but the reactivity of pyrite is of central importance in a devastating environmental issue known as acid mine drainage (AMD) and in beneficial commercial processes such as mineral benefaction, which can range from the desulfurization of coal to the isolation of copper or gold ores. Pyrite has even been postulated to be a key constituent of a prebiotic iron-sulfur world existing at the high pressure and temperature conditions common to hydrothermal vents at the oceanic floor. The development of an atomic level picture of the structure and reactivity of pyrite is paramount to understanding the chemistry of this mineral in these wide-ranging environments. This contribution focuses on research carried out over the past three decades that has used modern surface science tools to understand the reactivity of pyrite surfaces. An understanding of the reactivity of the pyrite surfaces has benefited from studies using a wide range of experimental techniques that range from vacuum-based experiments utilizing electron and photon spectroscopies, and probe microscopy to in situ studies using infra-red spectroscopy. Synchrotron-based techniques that include photoelectron spectroscopy and X-ray absorption spectroscopy have played a large role in both these environments. These techniques have perhaps been the most useful in establishing the structure of the pristine pyrite surface. Related iron sulfides are also briefly introduced in this review including pyrrhotite (Fe xS 1- x) and the dimorph of pyrite, marcasite. The surface reactivity of these sulfides exhibit both similarities and differences to pyrite, and help to bring forward the unique activity of pyrite in both environmentally and technologically important conditions.

  12. Organic Sulfur Gas Production in Sulfidic Caves

    NASA Astrophysics Data System (ADS)

    Stern, L. A.; Engel, A. S.; Bennett, P. C.

    2001-12-01

    Lower Kane Cave, Big Horn Basin, WY, permits access to an environment where anaerobic sulfide-rich groundwater meets the aerobic vadose zone. At this interface microorganisms thrive on diverse metabolic pathways including autotrophic sulfur oxidation, sulfate reduction, and aerobic heterotrophy. Springs introduce groundwater rich in H2S to the cave where it both degasses into the cave atmosphere and is used by chemautotrophic sulfur oxidizing bacteria in the cave spring and stream habitat. The cave atmosphere in the immediate vicinity of the springs has elevated levels of CO2, H2S and methane, mirroring the higher concentration of H2S and methane in the spring water. The high CO2 concentrations are attenuated toward the two main sources of fresh air, the cave entrance and breathing holes at the rear of the cave. Conventional toxic gas monitors permit estimations of H2S concentrations, but they have severe cross sensitivity with other reduced sulfur gases, and thus are inadequate for characterization of sulfur cave gases. However employment of a field-based GC revealed elevated concentrations of carbonyl sulfide in cave atmosphere. Cultures of microorganisms collected from the cave optimized for enriching fermenters and autotrophic and heterophic sulfate reducing bacteria each produced carbonyl sulfide suggesting a biogenic in origin of the COS in addition to H2S. Enrichment cultures also produced methanethiol (methyl mercaptan) and an additional as yet undetermined volatile organic sulfur compound. In culture, the organo-sulfur compounds were less abundant than H2S, whereas in the cave atmosphere the organo-sulfur compounds were the dominant sulfur gases. Thus, these organo-sulfur gases may prove to be important sources of both reduced sulfur and organic carbon to microorganisms living on the cave wall in a subaerial habitat. Moreover groundwater has not yet been recognized as a source of sulfur gases to the atmosphere, but with the abundance of sulfidic

  13. High temperature regenerable hydrogen sulfide removal agents

    DOEpatents

    Copeland, Robert J.

    1993-01-01

    A system for high temperature desulfurization of coal-derived gases using regenerable sorbents. One sorbent is stannic oxide (tin oxide, SnO.sub.2), the other sorbent is a metal oxide or mixed metal oxide such as zinc ferrite (ZnFe.sub.2 O.sub.4). Certain otherwise undesirable by-products, including hydrogen sulfide (H.sub.2 S) and sulfur dioxide (SO.sub.2) are reused by the system, and elemental sulfur is produced in the regeneration reaction. A system for refabricating the sorbent pellets is also described.

  14. 46 CFR 148.285 - Metal sulfide concentrates.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Metal sulfide concentrates. 148.285 Section 148.285... MATERIALS THAT REQUIRE SPECIAL HANDLING Special Requirements for Certain Materials § 148.285 Metal sulfide concentrates. (a) When information given by the shipper under § 148.60 of this part indicates that the...

  15. 46 CFR 148.285 - Metal sulfide concentrates.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Metal sulfide concentrates. 148.285 Section 148.285... MATERIALS THAT REQUIRE SPECIAL HANDLING Special Requirements for Certain Materials § 148.285 Metal sulfide concentrates. (a) When information given by the shipper under § 148.60 of this part indicates that the...

  16. Alternatives to Sulfide Dehairing: Use of Oxidative Agents

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The dehairing of cattle hides with sodium sulfide generates large quantities of waste that are of environmental concern as they have a large biological and chemical oxygen demand. Additionally, sodium sulfide is a potential workplace hazard. We had worked with industry to develop a rapid dehairing...

  17. 46 CFR 148.285 - Metal sulfide concentrates.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Metal sulfide concentrates. 148.285 Section 148.285... concentrates. (a) When information given by the shipper under § 148.60 of this part indicates that the metal sulfide concentrate may generate toxic or flammable gases, the appropriate gas detection equipment...

  18. Normal state properties of the ternary molybdenum sulfides

    NASA Technical Reports Server (NTRS)

    Woollam, J. A.; Alterovitz, S. A.

    1978-01-01

    By making a large number of normal state and superconducting properties measurements, all on the same ternary molybdenum sulfide samples, we obtain values for Fermi surface and superconducting parameters. From these we conclude that sputtered ternary molybdenum sulfides are not completely in the dirty superconductor limit, and that they are d-band metals with a high electron carrier density.

  19. The Hydrolysis of Carbonyl Sulfide at Low Temperature: A Review

    PubMed Central

    Zhao, Shunzheng; Yi, Honghong; Tang, Xiaolong; Jiang, Shanxue; Gao, Fengyu; Zhang, Bowen; Zuo, Yanran; Wang, Zhixiang

    2013-01-01

    Catalytic hydrolysis technology of carbonyl sulfide (COS) at low temperature was reviewed, including the development of catalysts, reaction kinetics, and reaction mechanism of COS hydrolysis. It was indicated that the catalysts are mainly involved metal oxide and activated carbon. The active ingredients which can load on COS hydrolysis catalyst include alkali metal, alkaline earth metal, transition metal oxides, rare earth metal oxides, mixed metal oxides, and nanometal oxides. The catalytic hydrolysis of COS is a first-order reaction with respect to carbonyl sulfide, while the reaction order of water changes as the reaction conditions change. The controlling steps are also different because the reaction conditions such as concentration of carbonyl sulfide, reaction temperature, water-air ratio, and reaction atmosphere are different. The hydrolysis of carbonyl sulfide is base-catalyzed reaction, and the force of the base site has an important effect on the hydrolysis of carbonyl sulfide. PMID:23956697

  20. Physical and microstructural aspects of iron sulfide degradation in concrete

    SciTech Connect

    Schmidt, Thomas; Gallucci, Emanuel; Scrivener, Karen

    2011-03-15

    The microstructural aspects of iron sulfide degradation in dam concrete were investigated by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) in both dam concrete samples and laboratory concrete. The results show that iron sulfide inclusions with a diameter of a few micrometers in the aggregates are reactive and appear to generate expansion first in the aggregates and consequently in the cement paste. The expansion from the iron sulfides is a consequence of the increase in volume of the reaction products formed. The types of iron sulfide present in the aggregate, mainly pyrrhotite (FeS) and pyrite (FeS{sub 2}), show similar reaction behavior in the aggregates. The released sulfate can lead to a secondary ettringite formation in the concrete matrix, but the degradation associated with this appears to be minor. The reaction of the iron sulfides was found to be very slow even when laboratory samples were exposed to elevated temperatures.

  1. DISSOLUTION OF PLUTONIUM CONTAINING CARRIER PRECIPITATE BY CARBONATE METATHESIS AND SEPARATION OF SULFIDE IMPURITIES THEREFROM BY SULFIDE PRECIPITATION

    DOEpatents

    Duffield, R.B.

    1959-07-14

    A process is described for recovering plutonium from foreign products wherein a carrier precipitate of lanthanum fluoride containing plutonium is obtained and includes the steps of dissolving the carrier precipitate in an alkali metal carbonate solution, adding a soluble sulfide, separating the sulfide precipitate, adding an alkali metal hydroxide, separating the resulting precipitate, washing, and dissolving in a strong acid.

  2. The interfacial orientation relationship of oxide nanoparticles in a hafnium-containing oxide dispersion-strengthened austenitic stainless steel

    DOE PAGESBeta

    Miao, Yinbin; Mo, Kun; Cui, Bai; Chen, Wei-Ying; Miller, Michael K.; Powers, Kathy A.; McCreary, Virginia; Gross, David; Almer, Jonathan; Robertson, Ian M.; et al

    2015-01-26

    We report comprehensive investigations on the orientation relationship of the oxide nanoparticles in a hafnium-containing austenitic oxide dispersion-strengthened 316 stainless steel. The phases of the oxide nanoparticles were determined by a combination of scanning transmission electron microscopy–electron dispersive X-ray spectroscopy, atom probe tomography and synchrotron X-ray diffraction to be complex Y–Ti–Hf–O compounds with similar crystal structures, including bixbyite Y2O3, fluorite Y2O3–HfO2 solid solution and pyrochlore (or fluorite) Y2(Ti,Hf)2 - xO7 - x. High resolution transmission electron microscopy was used to characterize the particle–matrix interfaces. Moreover, two different coherency relationships along with one axis-parallel relation between the oxide nanoparticles and themore » steel matrix were found. The size of the nanoparticles significantly influences the orientation relationship. Our results provide insight into the relationship of these nanoparticles with the matrix, which has implications for interpreting material properties as well as responses to radiation.« less

  3. Fiber textures of titanium nitride and hafnium nitride thin films deposited by off-normal incidence magnetron sputtering

    SciTech Connect

    Deniz, D.; Harper, J. M. E.

    2008-09-15

    We studied the development of crystallographic texture in titanium nitride (TiN) and hafnium nitride (HfN) films deposited by off-normal incidence reactive magnetron sputtering at room temperature. Texture measurements were performed by x-ray pole figure analysis of the (111) and (200) diffraction peaks. For a deposition angle of 40 deg. from substrate normal, we obtained TiN biaxial textures for a range of deposition conditions using radio frequency (rf) sputtering. Typically, we find that the <111> orientation is close to the substrate normal and the <100> orientation is close to the direction of the deposition source, showing substantial in-plane alignment. We also introduced a 150 eV ion beam at 55 deg. with respect to substrate normal during rf sputtering of TiN. Ion beam enhancement caused TiN to align its out-of-plane texture along <100> orientation. In this case, (200) planes are slightly tilted with respect to the substrate normal away from the ion beam source, and (111) planes are tilted 50 deg. toward the ion beam source. For comparison, we found that HfN deposited at 40 deg. without ion bombardment has a strong <100> orientation parallel to the substrate normal. These results are consistent with momentum transfer among adatoms and ions followed by an increase in surface diffusion of the adatoms on (200) surfaces. The type of fiber texture results from a competition among texture mechanisms related to surface mobilities of adatoms, geometrical, and directional effects.

  4. Improved Retention Characteristic in Polycrystalline Silicon-Oxide-Hafnium Oxide-Oxide-Silicon-Type Nonvolatile Memory with Robust Tunnel Oxynitride

    NASA Astrophysics Data System (ADS)

    Hsieh, Chih Ren; Lai, Chiung Hui; Lin, Bo Chun; Zheng, Yuan Kai; Chung Lou, Jen; Lin, Gray

    2011-03-01

    In this paper, we present a simple novel process for forming a robust and reliable oxynitride dielectric with a high nitrogen content. It is highly suitable for n-channel metal-oxide-semiconductor field-effect transistor (nMOSFETs) and polycrystalline silicon-oxide-hafnium oxide-oxide-silicon (SOHOS)-type memory applications. The proposed approach is realized by using chemical oxide with ammonia (NH3) nitridation followed by reoxidation with oxygen (O2). The novel oxynitride process is not only compatible with the standard complementary metal-oxide-semiconductor (CMOS) process, but also can ensure the improvement of flash memory with low-cost manufacturing. The characteristics of nMOSFETs and SOHOS-type nonvolatile memories (NVMs) with a robust oxynitride as a gate oxide or tunnel oxide are studied to demonstrate their advantages such as the retardation of the stress-induced trap generation during constant-voltage stress (CVS), the program/erase behaviors, cycling endurance, and data retention. The results indicate that the proposed robust oxynitride is suitable for future nonvolatile flash memory technology application.

  5. Tetra­kis(quinolin-8-olato-κ2 N,O)hafnium(IV) toluene disolvate

    PubMed Central

    Viljoen, J. Augustinus; Visser, Hendrik G.; Roodt, Andreas; Steyn, Maryke

    2009-01-01

    In the title compound, [Hf(C9H6NO)4]·2C7H8, the hafnium metal centre is coordinated by four N,O-donating bidentate quinolin-8-olate ligands arranged to give a square-anti­prismatic coordination polyhedron with a slightly distorted dodeca­hedral geometry. The average Hf—O and Hf—N distances are 2.096 (3) and 2.398 (3) Å, respectively, and the average O—Hf—N bite angle is 70.99 (11)°. The crystal packing is controlled by π–π inter­actions between quinoline ligands of neighbouring mol­ecules and hydrogen-bonding inter­actions. The inter­planar distances vary between 3.138 (1) and 3.208 (2) Å, while the centroid–centroid distances range from 3.576 (1) to 4.074 (1) Å. PMID:21578562

  6. Thermomechanical and Thermochemical Behavior of a Hafnium-20 Percent Tantalum Alloy. Ph.D. Thesis - North Carolina State Univ., Raleigh

    NASA Technical Reports Server (NTRS)

    Howell, J. P.

    1971-01-01

    An investigation was conducted to determine the thermomechanical and thermochemical behavior of a high temperature, oxidation resistant, hafnium-20 percent tantalum alloy. The elastic and shear moduli of this alloy were determined in air up to 1000 C and in vacuum up to 2000 C using a mechanical resonance technique. The internal friction of the alloy was measured up to temperatures greater than 1400 C. Room temperature stress-strain behavior of the oxidized and unoxidized alloy was established. The effect of annealing on the elastic and shear moduli of the extruded rod material was investigated. The martensitic-type phase transformation occurring in the alloy was studied using hot stage metallography and electron microscopy. Static oxidation tests were conducted on the alloy at temperatures from 1000 C to 1700 C with weight gain measurements made as a function of time and temperatures. Surface morphology studies were conducted on the oxide coatings formed at the different temperatures using scanning electron microscopy and X-ray diffraction techniques.

  7. Band alignment of vanadium oxide as an interlayer in a hafnium oxide-silicon gate stack structure

    NASA Astrophysics Data System (ADS)

    Zhu, Chiyu; Kaur, Manpuneet; Tang, Fu; Liu, Xin; Smith, David J.; Nemanich, Robert J.

    2012-10-01

    Vanadium oxide (VO2) is a narrow band gap material (Eg = 0.7 eV) with a thermally induced insulator-metal phase transition at ˜343 K and evidence of an electric field induced transition at T < 343 K. To explore the electronic properties of VO2, a sandwich structure was prepared with a 2 nm VO2 layer embedded between an oxidized Si(100) surface and a 2 nm hafnium oxide (HfO2) layer. The layer structure was confirmed with high resolution transmission electron microscopy. The electronic properties were characterized with x-ray and ultraviolet photoemission spectroscopy, and the band alignment was deduced on both n-type and p-type Si substrates. The valence band offset between VO2 and SiO2 is measured to be 4.0 eV. The valence band offset between HfO2 and VO2 is measured to be ˜3.4 eV. The band relation developed from these results demonstrates the potential for charge storage and switching for the embedded VO2 layer.

  8. Near-ultraviolet absorption annealing in hafnium oxide thin films subjected to continuous-wave laser radiation

    NASA Astrophysics Data System (ADS)

    Papernov, Semyon; Kozlov, Alexei A.; Oliver, James B.; Kessler, Terrance J.; Shvydky, Alexander; Marozas, Brendan

    2014-12-01

    Hafnium oxide (HfO2) is the most frequently used high-index material in multilayer thin-film coatings for high-power laser applications ranging from near-infrared to near-ultraviolet (UV). Absorption in this high-index material is also known to be responsible for nanosecond-pulse laser-damage initiation in multilayers. In this work, modification of the near-UV absorption of HfO2 monolayer films subjected to irradiation by continuous-wave (cw), 355-nm or 351-nm laser light focused to produce power densities of the order of ˜100 kW/cm2 is studied. Up to a 70% reduction in absorption is found in the areas subjected to irradiation. Temporal behavior of absorption is characterized by a rapid initial drop on the few-tens-of-seconds time scale, followed by a longer-term decline to a steady-state level. Absorption maps generated by photothermal heterodyne imaging confirm the permanent character of the observed effect. Nanosecond-pulse, 351-nm and 600-fs, 1053-nm laser-damage tests performed on these cw laser-irradiated areas confirm a reduction of absorption by measuring up to 25% higher damage thresholds. We discuss possible mechanisms responsible for near-UV absorption annealing and damage-threshold improvement resulting from irradiation by near-UV cw laser light.

  9. The interfacial orientation relationship of oxide nanoparticles in a hafnium-containing oxide dispersion-strengthened austenitic stainless steel

    SciTech Connect

    Miao, Yinbin; Mo, Kun; Cui, Bai; Chen, Wei-Ying; Miller, Michael K.; Powers, Kathy A.; McCreary, Virginia; Gross, David; Almer, Jonathan; Robertson, Ian M.; Stubbins, James F.

    2015-01-26

    We report comprehensive investigations on the orientation relationship of the oxide nanoparticles in a hafnium-containing austenitic oxide dispersion-strengthened 316 stainless steel. The phases of the oxide nanoparticles were determined by a combination of scanning transmission electron microscopy–electron dispersive X-ray spectroscopy, atom probe tomography and synchrotron X-ray diffraction to be complex Y–Ti–Hf–O compounds with similar crystal structures, including bixbyite Y2O3, fluorite Y2O3–HfO2 solid solution and pyrochlore (or fluorite) Y2(Ti,Hf)2 - xO7 - x. High resolution transmission electron microscopy was used to characterize the particle–matrix interfaces. Moreover, two different coherency relationships along with one axis-parallel relation between the oxide nanoparticles and the steel matrix were found. The size of the nanoparticles significantly influences the orientation relationship. Our results provide insight into the relationship of these nanoparticles with the matrix, which has implications for interpreting material properties as well as responses to radiation.

  10. The combination self-cleaning effect of trimethylaluminium and tetrakis (dimethyl-amino) hafnium pretreatments on GaAs

    NASA Astrophysics Data System (ADS)

    Cao, Yan-Qiang; Li, Xue-Fei; Li, Ai-Dong; Li, Hui; Wu, Di

    2012-12-01

    The self-cleaning effect of trimethylaluminium (TMA) and tetrakis (dimethyl-amino) hafnium (TDMAH) pretreatments on GaAs substrates was investigated deeply. The chemical states were carefully characterized by the X-ray photoelectron spectroscopy, which demonstrates that the pretreatment before ALD of dielectric films can suppress the formation of native oxides on GaAs substrates effectively. It is found that the combination of TMA and TDMAH pretreatments has better self-cleaning effect than single TMA pretreatment based on a ligand-exchange reaction mechanism between TMA/TDMAH and the native oxide. The transmission electron microscopy images also show a thinnest interlayer thickness of ˜0.2 nm for the TMA + TDMAH pretreated sample. TMA + TDMAH pretreated samples exhibit significantly improved interfacial and electrical properties such as the highest accumulation capacitance, the least stretch-out of capacitance-voltage curves, and the lowest interface trap density. These results indicate that the surface pretreatment by using the combination of TMA and TDMAH pulses may be a promising approach for the realization of high quality GaAs-based transistor devices.

  11. Copper sulfide solid-state electrolytic memory devices

    NASA Astrophysics Data System (ADS)

    You, Liang

    Copper sulfide thin films with electrical switching and memory effect were grown using a chemical vapor reaction apparatus. The formation of copper sulfide film undergoes a process which includes nucleation, growth of nucleation, coalescence into continuous film, and film thickening. The initial phase of the sulfide growth was reaction limited followed by a diffusion limited phase involving out-diffusion of copper. The thin film tends to nucleate and grow at energy favorable sites such as twinning boundary. Sulfidation of polycrystalline copper results in formation of voids at the interface between the copper and its sulfide. (111) copper has the highest sulfidation rate followed by (100) and (110) copper planes. Moreover, the sulfidation rate near the microfabricated plug edge was found to be faster than the rate at the center of the plug. A mechanism based on competing sulfidation sites due to the geometry difference between the plugs' center and their edge is presented to explain this phenomenon. We show for the first time that field-assisted solid-electrolyte copper sulfide thin film device can function as a switch by reversing the voltage polarity between copper and inert metal electrodes through a copper-sulfide layer in planar and vertical structures. The copper oxide at the top of copper sulfide greatly increased the turn-on voltage. The turn-on voltage depends linearly on the film thickness. Copper sulfide devices in micrometer dimension were microfabricated using IC compatible techniques and characterized showing the same switching effect. Electrode contact area effect on switching performance was investigated in term of turn-on voltage, turn-off voltage, on-state resistance and off-state resistance. Four-point resistance measurement unit, Hall Effect and transfer length measurement were also fabricated together with copper sulfide switching devices and they were studied in order to determine the CuxS carrier type, carrier concentration, film resistivity

  12. Amorphous molybdenum sulfides as hydrogen evolution catalysts.

    PubMed

    Morales-Guio, Carlos G; Hu, Xile

    2014-08-19

    Providing energy for a population projected to reach 9 billion people within the middle of this century is one of the most pressing societal issues. Burning fossil fuels at a rate and scale that satisfy our near-term demand will irreversibly damage the living environment. Among the various sources of alternative and CO2-emission-free energies, the sun is the only source that is capable of providing enough energy for the whole world. Sunlight energy, however, is intermittent and requires an efficient storage mechanism. Sunlight-driven water splitting to make hydrogen is widely considered as one of the most attractive methods for solar energy storage. Water splitting needs a hydrogen evolution catalyst to accelerate the rate of hydrogen production and to lower the energy loss in this process. Precious metals such as Pt are superior catalysts, but they are too expensive and scarce for large-scale applications. In this Account, we summarize our recent research on the preparation, characterization, and application of amorphous molybdenum sulfide catalysts for the hydrogen evolution reaction. The catalysts can be synthesized by electrochemical deposition under ambient conditions from readily available and inexpensive precursors. The catalytic activity is among the highest for nonprecious catalysts. For example, at a loading of 0.2 mg/cm(2), the optimal catalyst delivers a current density of 10 mA/cm(2) at an overpotential of 160 mV. The growth mechanism of the electrochemically deposited film catalysts was revealed by an electrochemical quartz microcrystal balance study. While different electrochemical deposition methods produce films with different initial compositions, the active catalysts are the same and are identified as a "MoS(2+x)" species. The activity of the film catalysts can be further promoted by divalent Fe, Co, and Ni ions, and the origins of the promotional effects have been probed. Highly active amorphous molybdenum sulfide particles can also be prepared

  13. Hydrogen sulfide selectivity with carbonyl sulfide removal to less than PPM levels

    SciTech Connect

    Bacon, T.R.; Pearce, R.L.; Foster, W.R. Jr.

    1986-01-01

    Changes in market conditions and plant operating economics require examination of traditional processes and operating practices in gas treating applications for upgrading to more stringent standards of efficiency in order to remain competitive while returning a satisfactory operating profit margin to the company. Anticipated reduction in solvent usage, improvements in Claus sulfur recovery unit performance and lower energy costs induced Ashland's Catlettsburg refinery to convert its entire sulfur removal system from monoethanolamine to methyldiethanolamine. One of the seven product streams being treated required extremely low carbonyl sulfide specifications. When the initial converted operations evidenced a need to improve the carbonyl sulfide removal, GAS/SPEC Tech Service produced an innovative solution which allowed for efficient operation which still achieved these objectives.

  14. Atomic layer deposition of aluminum sulfide thin films using trimethylaluminum and hydrogen sulfide

    SciTech Connect

    Sinha, Soumyadeep; Sarkar, Shaibal K.; Mahuli, Neha

    2015-01-15

    Sequential exposures of trimethylaluminum and hydrogen sulfide are used to deposit aluminum sulfide thin films by atomic layer deposition (ALD) in the temperature ranging from 100 to 200 °C. Growth rate of 1.3 Å per ALD cycle is achieved by in-situ quartz crystal microbalance measurements. It is found that the growth rate per ALD cycle is highly dependent on the purging time between the two precursors. Increased purge time results in higher growth rate. Surface limited chemistry during each ALD half cycle is studied by in-situ Fourier transformed infrared vibration spectroscopy. Time of flight secondary ion-mass spectroscopy measurement is used to confirm elemental composition of the deposited films.

  15. Trap state passivation improved hot-carrier instability by zirconium-doping in hafnium oxide in a nanoscale n-metal-oxide semiconductor-field effect transistors with high-k/metal gate

    NASA Astrophysics Data System (ADS)

    Liu, Hsi-Wen; Chang, Ting-Chang; Tsai, Jyun-Yu; Chen, Ching-En; Liu, Kuan-Ju; Lu, Ying-Hsin; Lin, Chien-Yu; Tseng, Tseung-Yuen; Cheng, Osbert; Huang, Cheng-Tung; Ye, Yi-Han

    2016-04-01

    This work investigates the effect on hot carrier degradation (HCD) of doping zirconium into the hafnium oxide high-k layer in the nanoscale high-k/metal gate n-channel metal-oxide-semiconductor field-effect-transistors. Previous n-metal-oxide semiconductor-field effect transistor studies demonstrated that zirconium-doped hafnium oxide reduces charge trapping and improves positive bias temperature instability. In this work, a clear reduction in HCD is observed with zirconium-doped hafnium oxide because channel hot electron (CHE) trapping in pre-existing high-k bulk defects is the main degradation mechanism. However, this reduced HCD became ineffective at ultra-low temperature, since CHE traps in the deeper bulk defects at ultra-low temperature, while zirconium-doping only passivates shallow bulk defects.

  16. Banded sulfide-magnetite ores of Mauk copper massive sulfide deposit, Central Urals: Composition and genesis

    NASA Astrophysics Data System (ADS)

    Safina, N. P.; Maslennikov, V. V.; Maslennikova, S. P.; Kotlyarov, V. A.; Danyushevsky, L. V.; Large, R. R.; Blinov, I. A.

    2015-05-01

    The results of investigation of metamorphosed sulfide-magnetite ores from the Mauk deposit located within the Main Ural Fault at the junction of Tagil and Magnitogorsk massive sulfide zones are discussed. The ore-hosting sequence comprises metamorphic rocks formed from basalt, carbonaceous and carbonaceous-cherty siltstone, and lenticular serpentinized ultramafic bodies. The ores of the deposit are represented by banded varieties and less frequent breccia. The clastic origin of the banded ore is indicated by load casts at the bottom of sulfide beds, alternation of sulfide and barren beds, and the truncation of the growth zones of pyrite crystals. Pyrite, pyrrhotite, chalcopyrite, sphalerite, and magnetite are the major minerals of the banded ores. The internal structure of the listed minerals testifies to the deep metamorphic recrystallization of primary hydrothermal-sedimentary ores accompanied with deformation. Cubanite, pyrrhotite, mackinawite, greigite, and gold are enclosed in metacrysts of pyrite, magnetite, and chalcopyrite. The accessory minerals of the Pb-Bi-Te, Bi-Te, and Ag-Te systems as well as uraninite have been found at the Mauk deposit for the first time. Magnetite predominantly replaces pyrite and less frequently chalcopyrite, pyrrhotite, and gangue minerals. It was established that the major carriers of As and Co are crystals of metamorphic pyrite. Chalcopyrite is the major carrier of Zn, Sn, Te, Pb, Bi, and Ag. Admixture of Fe and Cu is typical of sphalerite, and Se and Ni are characteristic of pyrrhotite. Ti, V, Mn, Sb, As, Ba, and U are concentrated in magnetite. The banded ores of the Mauk deposit are suggested as having been transformed in several stages: diagenesis, anadiagenesis, epidiagenesis ( t < 300°C), and amphibolite facies metamorphism ( t > 500°C).

  17. Sulfide elimination by intermittent nitrate dosing in sewer sediments.

    PubMed

    Liu, Yanchen; Wu, Chen; Zhou, Xiaohong; Zhu, David Z; Shi, Hanchang

    2015-01-01

    The formation of hydrogen sulfide in biofilms and sediments in sewer systems can cause severe pipe corrosions and health hazards, and requires expensive programs for its prevention. The aim of this study is to propose a new control strategy and the optimal condition for sulfide elimination by intermittent nitrate dosing in sewer sediments. The study was carried out based on lab-scale experiments and batch tests using real sewer sediments. The intermittent nitrate dosing mode and the optimal control condition were investigated. The results indicated that the sulfide-intermittent-elimination strategy by nitrate dosing is advantageous for controlling sulfide accumulation in sewer sediment. The oxidation-reduction potential is a sensitive indicator parameter that can reflect the control effect and the minimum N/S (nitrate/sulfide) ratio with slight excess nitrate is necessary for optimal conditions of efficient sulfide control with lower carbon source loss. The optimal control condition is feasible for the sulfide elimination in sewer systems. PMID:25597685

  18. Stabilization of mercury-containing wastes using sulfide.

    PubMed

    Piao, Haishan; Bishop, Paul L

    2006-02-01

    This paper summarizes the findings of our studies on mercury stabilization using sulfide. Primary stabilization variables such as stabilization pH and sulfide/mercury molar ratio were tested. Mercury stabilization effectiveness was evaluated using the Toxicity Characteristic Leaching Procedure (TCLP) and the constant pH leaching tests. The influence of interfering ions on mercury immobilization was also tested. The experimental results indicate that the sulfide-induced treatment technology is an effective way to minimize mercury leaching. It was found that the most effective mercury stabilization occurs at pH 6 combined with a sulfide/mercury molar ratio of 1. The combined use of increased dosage of sulfide and ferrous ions ([S]/[Hg]=2 and [Fe]/[Hg]=3 at pH=6) can significantly reduce interferences by chloride and/or phosphate during sulfide-induced mercury immobilization. The sulfide-treated waste stabilization efficiency reached 98%, even with exposure of the wastes to high pH leachants. PMID:16099084

  19. Solubility of hydrogen sulfide in n-methylpyrrolidone

    SciTech Connect

    Yarym-Agaev, N.L.; Matvienko, V.G.; Povalyaeva, N.V.

    1980-01-01

    The solubility of hydrogen sulfide in N-methylpyrrolidone was investigated over wide ranges of temperature and pressure. The dynamic variant of the gravimetric method was used at hydrogen sulfide pressures equal to or below atmospheric, and the static variant at higher pressures. In the dynamic variant of the gravimetric method hydrogen sulfide is passed through a known amount of solvent until saturation is reached, and the amount of gas dissolved is found from the weight increase. This method is particularly convenient in studies of highly soluble gases when the solvent has a low vapor pressure. If the vapor pressure of the solvent exceeded this value a correction for entrainment of solvent vapor by undissolved gas was applied. The study showed that the solubility of hydrogen sulfide in N-methylpyrrolidone rose steeply with increase of pressure and decrease of temperature and that it can be used as an effective absorbent of hydrogen sulfide in highly sulfurous natural gas. Since the solubility of hydrogen sulfide under atmospheric pressure is fairly high even at elevated temperatures, effective regeneration of N-methylpyrrolidone is possible by a combination of heating and blowing with an inert gas or by application of vacuum for removal of the hydrogen sulfide.

  20. [Oxidation of sulfide minerals by Thiobacillus ferrooxidans].

    PubMed

    Malakhova, P T; Chebotarev, G M; Kovalenko, E V; Volkov, Iu A

    1981-01-01

    Samples of natural pyrites and sphalerites were subjected to the action of the mineral medium 9K with 1 g of Fe3+ per litre in the presence and in the absence of Thiobacillus ferrooxidans, and incubated at 28 degrees C under the stationary conditions for 30 days. The chemical composition of the solutions was studied after leaching as well as changes of the surfaces of monoliths. The deepest etching of surfaces with the formation of crusts and films of jarosite, limonite and goslarite occurs upon the combined action of bacteria and Fe3+ in regions of a fine-zonal structure enriched with an isomorphous arsenic admixture which are characterized by a defective weak structure. The pyrite and sphalerite from Charmitan with a higher arsenic and iron content were leached more than the pyrite and sphalerite from Kurgashincan. This was also corroborated by chemical analyses of leaching solutions and by monometric studies of crushed sulfide samples. PMID:7219212

  1. Dibenzyl Sulfide Metabolism by White Rot Fungi

    PubMed Central

    Van Hamme, Jonathan D.; Wong, Eddie T.; Dettman, Heather; Gray, Murray R.; Pickard, Michael A.

    2003-01-01

    Microbial metabolism of organosulfur compounds is of interest in the petroleum industry for in-field viscosity reduction and desulfurization. Here, dibenzyl sulfide (DBS) metabolism in white rot fungi was studied. Trametes trogii UAMH 8156, Trametes hirsuta UAMH 8165, Phanerochaete chrysosporium ATCC 24725, Trametes versicolor IFO 30340 (formerly Coriolus sp.), and Tyromyces palustris IFO 30339 all oxidized DBS to dibenzyl sulfoxide prior to oxidation to dibenzyl sulfone. The cytochrome P-450 inhibitor 1-aminobenzotriazole eliminated dibenzyl sulfoxide oxidation. Laccase activity (0.15 U/ml) was detected in the Trametes cultures, and concentrated culture supernatant and pure laccase catalyzed DBS oxidation to dibenzyl sulfoxide more efficiently in the presence of 2,2′-azinobis(3-ethylbenzthiazoline-6-sulfonate) (ABTS) than in its absence. These data suggest that the first oxidation step is catalyzed by extracellular enzymes but that subsequent metabolism is cytochrome P-450 mediated. PMID:12571066

  2. Bioextraction of cobalt from complex metal sulfides

    SciTech Connect

    Thompson, D.L.; Noah, K.S.; Wichlacz, P.L.; Torma, A.E.

    1993-01-01

    The present study has investigated the bioleachability of naturally occurring cobaltite and synthetic cobalt sulfides using 29 pedigree and wild type'' strains of Thiobacillus ferrooxidans. On the basis of a screening test, five strains of bacteria were selected for assessing the effects of leach parameters (pH, ferrous and ferric sulfates, ammonium sulfate, bipotassium hydrogen phosphate, and substrate concentrations) on cobalt extraction from Blackbird Mine ore and concentrate. The mechanisms of cobalt extraction were explained in terms of direct and indirect modes of bacterial activity, and the chemistry involved in these processes was identified. Using various size fractions of a high-grade cobaltite, the kinetic parameters of cobalt extraction were derived for the effect of specific surface area to be V[sub m] = 376 mg dm[sup [minus]3] h[sup [minus]1] and K 1.27 m[sup 2] g[sup [minus]1].

  3. Bioextraction of cobalt from complex metal sulfides

    SciTech Connect

    Thompson, D.L.; Noah, K.S.; Wichlacz, P.L.; Torma, A.E.

    1993-05-01

    The present study has investigated the bioleachability of naturally occurring cobaltite and synthetic cobalt sulfides using 29 pedigree and ``wild type`` strains of Thiobacillus ferrooxidans. On the basis of a screening test, five strains of bacteria were selected for assessing the effects of leach parameters (pH, ferrous and ferric sulfates, ammonium sulfate, bipotassium hydrogen phosphate, and substrate concentrations) on cobalt extraction from Blackbird Mine ore and concentrate. The mechanisms of cobalt extraction were explained in terms of direct and indirect modes of bacterial activity, and the chemistry involved in these processes was identified. Using various size fractions of a high-grade cobaltite, the kinetic parameters of cobalt extraction were derived for the effect of specific surface area to be V{sub m} = 376 mg dm{sup {minus}3} h{sup {minus}1} and K 1.27 m{sup 2} g{sup {minus}1}.

  4. Hydrogen sulfide and polysulfides as signaling molecules.

    PubMed

    Kimura, Hideo

    2015-01-01

    Hydrogen sulfide (H2S) is a familiar toxic gas that smells of rotten eggs. After the identification of endogenous H2S in the mammalian brain two decades ago, studies of this molecule uncovered physiological roles in processes such as neuromodulation, vascular tone regulation, cytoprotection against oxidative stress, angiogenesis, anti-inflammation, and oxygen sensing. Enzymes that produce H2S, such as cystathionine β-synthase, cystathionine γ-lyase, and 3-mercaptopyruvate sulfurtransferase have been studied intensively and well characterized. Polysulfides, which have a higher number of inner sulfur atoms than that in H2S, were recently identified as potential signaling molecules that can activate ion channels, transcription factors, and tumor suppressors with greater potency than that of H2S. This article focuses on our contribution to the discovery of these molecules and their metabolic pathways and mechanisms of action. PMID:25864468

  5. Hydrogen sulfide exposure in an adult male

    PubMed Central

    Doujaiji, Bassam; Al-Tawfiq, Jaffar A.

    2010-01-01

    Hydrogen sulfide (H2S) is responsible for many incidents of occupational toxic exposure, especially in the petroleum industry. The clinical effects of H2S depend on its concentration and the duration of exposure. H2S is immediately fatal when concentrations are over 500-1000 parts per million (ppm) but exposure to lower concentrations, such as 10-500 ppm, can cause various respiratory symptoms that range from rhinitis to acute respiratory failure. H2S may also affect multiple organs, causing temporary or permanent derangements in the nervous, cardiovascular, renal, hepatic, and hematological systems. We present a case of occupational exposure to H2S leading to multi-organ involvement, acute respiratory failure, organizing pneumonia, and shock resembling acute sepsis. The patient also developed mild obstructive and restrictive pulmonary disease and peripheral neuropathy. PMID:20103963

  6. Interactions among sulfide-oxidizing bacteria

    NASA Technical Reports Server (NTRS)

    Poplawski, R.

    1985-01-01

    The responses of different phototrophic bacteria in a competitive experimental system are studied, one in which primary factors such as H2S or light limited photometabolism. Two different types of bacteria shared one limited source of sulfide under specific conditions of light. The selection of a purple and a green sulfur bacteria and the cyanobacterium was based on their physiological similarity and also on the fact that they occur together in microbial mats. They all share anoxygenic photosynthesis, and are thus probably part of an evolutionary continuum of phototrophic organisms that runs from, strictly anaerobic physiology to the ability of some cyanobacteria to shift between anoxygenic bacterial style photosynthesis and the oxygenic kind typical of eukaryotes.

  7. Structure of 4-methylpyridinium Hydrogen Sulfide

    NASA Technical Reports Server (NTRS)

    Andras, Maria T.; Hepp, Aloysius F.; Fanwick, Phillip E.; Martuch, Robert A.; Duraj, Stan A.; Gordon, Edward M.

    1994-01-01

    4-Methylpyridinium hydrogen sulfide, (C6H7NH)HS, M(sub r) = 127.21, consists of C6H7NH(+) cations and HS(-) anions. Z = 2 for the crystal with monoclinic space group Cm (#8), dimensions of a = 8.679(2) A, b = 7.964(1) A, and c = 4.860(2) A, an angle beta of 101.10(2) degrees, and a volume of V = 329.6(3) A(exp 3). R = 0.039 and R(sub w) = 0.048 for 385 reflections with F(sub o)(exp 2) greater than 3 sigma(F(sub o)(exp 2)) and 59 variables. Both the C6H7NH(+) cation and the HS(-) anion lie on crystallographic mirror planes with the N,S, two carbon atoms, and two hydrogen atoms positioned in the planes. The hydrogen atom of the HS(-) anion was not located.

  8. Atmospheric carbonyl sulfide exchange in bog microcosms

    SciTech Connect

    Fried, A.; Klinger, L.F.; Erickson, D.J. III )

    1993-01-22

    Measurements of Carbonyl sulfide (OCS) fluxes were carried out on bog microcosms using chamber sampling and tunable diode laser analysis. Intact bog microcosms (vascular plants, mosses, and peat) removed ambient levels of OCS in the light and dark with rates from [minus]2.4 to [minus]8.1 ng S min[sup [minus]1] m[sup [minus]2]. Peat and peat plus mosses emitted OCS in the light with rates of 17.4 and 10.9 ng S min[sup [minus]1] m[sup [minus]2], respectively. In the dark, the mosses apparently removed OCS at a rate equivalent to the peat emissions. A 3-D numerical tracer model using this data indicated that boreal bog ecosystems remove at most 1% of ambient OCS, not sufficient to account for an observed OCS depletion in boreal air masses. 13 refs., 1 fig., 1 tab.

  9. Hydrogen sulfide and polysulfides as signaling molecules

    PubMed Central

    KIMURA, Hideo

    2015-01-01

    Hydrogen sulfide (H2S) is a familiar toxic gas that smells of rotten eggs. After the identification of endogenous H2S in the mammalian brain two decades ago, studies of this molecule uncovered physiological roles in processes such as neuromodulation, vascular tone regulation, cytoprotection against oxidative stress, angiogenesis, anti-inflammation, and oxygen sensing. Enzymes that produce H2S, such as cystathionine β-synthase, cystathionine γ-lyase, and 3-mercaptopyruvate sulfurtransferase have been studied intensively and well characterized. Polysulfides, which have a higher number of inner sulfur atoms than that in H2S, were recently identified as potential signaling molecules that can activate ion channels, transcription factors, and tumor suppressors with greater potency than that of H2S. This article focuses on our contribution to the discovery of these molecules and their metabolic pathways and mechanisms of action. PMID:25864468

  10. Reactively evaporated films of copper molybdenum sulfide

    NASA Technical Reports Server (NTRS)

    Chi, K. C.; Dillon, R. O.; Bunshah, R. F.; Alterovitz, S.; Woollam, J. A.

    1978-01-01

    Films of superconducting Chevrel-phase copper molybdenum sulfide CuxMo6S8 were deposited on sapphire substrates by reactive evaporation using H2S as the reacting gas. Two superconducting temperatures (10.0 K and 5.0 K) of the films were found, corresponding to two different phases with different copper concentrations. All films were superconducting above 4.2 K and contained Chevrel-phase compound as well as free molybdenum. The critical current was measured as a function of applied field. One sample was found to deviate from the scaling law found for co-evaporated or sputtered samples, which possibly indicates a different pinning mechanism or inhomogeneity of the sample.

  11. Chemical Foundations of Hydrogen Sulfide Biology

    PubMed Central

    Li, Qian; Lancaster, Jack R.

    2013-01-01

    Following nitric oxide (nitrogen monoxide) and carbon monoxide, hydrogen sulfide (or its newer systematic name sulfane, H2S) became the third small molecule that can be both toxic and beneficial depending on the concentration. In spite of its impressive therapeutic potential, the underlying mechanisms for its beneficial effects remain unclear. Any novel mechanism has to obey fundamental chemical principles. H2S chemistry was studied long before its biological relevance was discovered, however, with a few exceptions, these past works have received relatively little attention in the path of exploring the mechanistic conundrum of H2S biological functions. This review calls attention to the basic physical and chemical properties of H2S, focuses on the chemistry between H2S and its three potential biological targets: oxidants, metals and thiol derivatives, discusses the applications of these basics into H2S biology and methodology, and introduces the standard terminology to this youthful field. PMID:23850631

  12. Chemical foundations of hydrogen sulfide biology.

    PubMed

    Li, Qian; Lancaster, Jack R

    2013-11-30

    Following nitric oxide (nitrogen monoxide) and carbon monoxide, hydrogen sulfide (or its newer systematic name sulfane, H2S) became the third small molecule that can be both toxic and beneficial depending on the concentration. In spite of its impressive therapeutic potential, the underlying mechanisms for its beneficial effects remain unclear. Any novel mechanism has to obey fundamental chemical principles. H2S chemistry was studied long before its biological relevance was discovered, however, with a few exceptions, these past works have received relatively little attention in the path of exploring the mechanistic conundrum of H2S biological functions. This review calls attention to the basic physical and chemical properties of H2S, focuses on the chemistry between H2S and its three potential biological targets: oxidants, metals and thiol derivatives, discusses the applications of these basics into H2S biology and methodology, and introduces the standard terminology to this youthful field. PMID:23850631

  13. Lanthanum sulfides as high temperature thermoelectric materials

    NASA Technical Reports Server (NTRS)

    Danielson, L. R.; Matsuda, S.; Raag, V.

    1984-01-01

    Thermoelectric property measurements have been made for the nonstoichiometric lanthanum sulfides, LaS(R) with R in the range 1.33-1.50. The Seebeck coefficients and electrical resistivities increase with temperature from 200 to 1100 C. Power factors (defined as Seebeck coefficient squared divided by electrical resistivity) generally increase both as the temperature is increased and as the compound composition is varied from LaS(1.48) to LaS(1.35). The power factor values combined with estimates of thermal conductivities for LaS(1.38) and LaS(1.4) yield figures of merit greater than 0.0005 at 1000 C.

  14. MODIFICATION OF METHODS 9030 AND 9031 FOR THE ANALYSIS OF SULFIDE BY SPECIFIC ION ELECTRODE

    EPA Science Inventory

    Two OSW SW-846 methods (Method 9030 and 9031) used for the determination of sulfide have been modified to include the use of sulfide specific ion electrodes (SIE). urrently in both methods sulfide is converted to hydrogen sulfide and distilled into a scrubber solution for subsequ...

  15. Optimization of the superconducting phase of hydrogen sulfide

    SciTech Connect

    Degtyarenko, N. N.; Masur, E. A.

    2015-12-15

    The electron and phonon spectra, as well as the densities of electron and phonon states of the SH{sub 3} phase and the stable orthorhombic structure of hydrogen sulfide SH{sub 2}, are calculated for the pressure interval 100–225 GPa. It is found that the I4/mmm phase can be responsible for the superconducting properties of metallic hydrogen sulfide along with the SH{sub 3} phase. Sequential stages for obtaining and conservation of the SH{sub 2} phase are proposed. The properties of two (SH{sub 2} and SH{sub 3}) superconducting phases of hydrogen sulfide are compared.

  16. Integrated thin film cadmium sulfide solar cell module

    NASA Technical Reports Server (NTRS)

    Mickelsen, R. A.; Abbott, D. D.

    1971-01-01

    The design, development, fabrication and tests of flexible integrated thin-film cadmium sulfide solar cells and modules are discussed. The development of low cost and high production rate methods for interconnecting cells into large solar arrays is described. Chromium thin films were applied extensively in the deposited cell structures as a means to: (1) achieve high adherence between the cadmium sulfide films and the vacuum-metallized copper substrates, (2) obtain an ohmic contact to the cadmium sulfide films, and (3) improve the adherence of gold films as grids or contact areas.

  17. Hydrogen and sulfur recovery from hydrogen sulfide wastes

    DOEpatents

    Harkness, John B. L.; Gorski, Anthony J.; Daniels, Edward J.

    1993-01-01

    A process for generating hydrogen and elemental sulfur from hydrogen sulfide waste in which the hydrogen sulfide is associated under plasma conditions and a portion of the hydrogen output is used in a catalytic reduction unit to convert sulfur-containing impurities to hydrogen sulfide for recycle, the process also including the addition of an ionizing gas such as argon to initiate the plasma reaction at lower energy, a preheater for the input to the reactor and an internal adjustable choke in the reactor for enhanced coupling with the microwave energy input.

  18. Hydrogen and sulfur recovery from hydrogen sulfide wastes

    DOEpatents

    Harkness, J.B.L.; Gorski, A.J.; Daniels, E.J.

    1993-05-18

    A process is described for generating hydrogen and elemental sulfur from hydrogen sulfide waste in which the hydrogen sulfide is [dis]associated under plasma conditions and a portion of the hydrogen output is used in a catalytic reduction unit to convert sulfur-containing impurities to hydrogen sulfide for recycle, the process also including the addition of an ionizing gas such as argon to initiate the plasma reaction at lower energy, a preheater for the input to the reactor and an internal adjustable choke in the reactor for enhanced coupling with the microwave energy input.

  19. Use of sulfide-containing liquors for removing mercury from flue gases

    DOEpatents

    Nolan, Paul S.; Downs, William; Bailey, Ralph T.; Vecci, Stanley J.

    2003-01-01

    A method and apparatus for reducing and removing mercury in industrial gases, such as a flue gas, produced by the combustion of fossil fuels, such as coal, adds sulfide ions to the flue gas as it passes through a scrubber. Ideally, the source of these sulfide ions may include at least one of: sulfidic waste water, kraft caustic liquor, kraft carbonate liquor, potassium sulfide, sodium sulfide, and thioacetamide. The sulfide ion source is introduced into the scrubbing liquor as an aqueous sulfide species. The scrubber may be either a wet or dry scrubber for flue gas desulfurization systems.

  20. Use of sulfide-containing liquors for removing mercury from flue gases

    DOEpatents

    Nolan, Paul S.; Downs, William; Bailey, Ralph T.; Vecci, Stanley J.

    2006-05-02

    A method and apparatus for reducing and removing mercury in industrial gases, such as a flue gas, produced by the combustion of fossil fuels, such as coal, adds sulfide ions to the flue gas as it passes through a scrubber. Ideally, the source of these sulfide ions may include at least one of: sulfidic waste water, kraft caustic liquor, kraft carbonate liquor, potassium sulfide, sodium sulfide, and thioacetamide. The sulfide ion source is introduced into the scrubbing liquor as an aqueous sulfide species. The scrubber may be either a wet or dry scrubber for flue gas desulfurization systems.

  1. As-Received, Ozone Cleaned and Ar+ Sputtered Surfaces of Hafnium Oxide Grown by Atomic Layer Deposition and Studied by XPS

    SciTech Connect

    Engelhard, Mark H.; Herman, Jacob A.; Wallace, Robert; Baer, Donald R.

    2012-06-27

    In this study, X-ray photoelectron spectroscopy (XPS) characterization was performed on 47 nm thick hafnium oxide (HfO{sub 2}) films grown by atomic layer deposition using TEMA-Hf/H{sub 2}O at 250 C substrate temperature. HfO{sub 2} is currently being studied as a possible replacement for Silicon Oxide (SiO{sub 2}) as a gate dielectric in electronics transistors. XPS spectra were collected on a Physical Electronics Quantum 2000 Scanning ESCA Microprobe using a monochromatic Al K{sub a} X-ray (1486.7 eV) excitation source. The sample was analyzed under the following conditions: as received, after UV irradiation for five minutes, and after sputter cleaning with 2 kV Ar{sup +} ions for 180 seconds. Survey scans showed carbon, oxygen, and hafnium as the major species in the film, while the only minor species of argon and carbide was detected after sputtering. Adventitious carbon initially composed approximately 18.6 AT% of the surface, but after UV cleaning it was reduced to 2.4 AT%. This demonstrated that that the majority of carbon was due to adventitious carbon. However, after 2 kV Ar{sup +} sputtering there was still only trace amounts of carbon at {approx}1 AT%, Some of this trace carbon is now in the form of a carbide due to the interaction with Ar{sup +} used for sputter cleaning. Furthermore, the stoiciometric ratio of oxygen and hafnium is consistent with a high quality HfO{sub 2} film.

  2. Micro-aeration for hydrogen sulfide removal from biogas

    NASA Astrophysics Data System (ADS)

    Duangmanee, Thanapong

    The presence of sulfur compounds (e.g. protein, sulfate, thiosulfate, sulfite, etc.) in the feed stream generates highly corrosive and odorous hydrogen sulfide during anaerobic digestion. The high sulfide level in the biogas stream is not only poisonous to many novel metal catalysts employed in thermo-catalytic processes but also reduces the quality of methane to produce renewable energy. This study used an innovative, low-maintenance, low-cost biological sulfide removal technology to remove sulfides simultaneously from both gas and liquid phase. ORP (Oxidation-Reduction-Potential) was used as the controlling parameter to precisely regulate air injection to the sulfide oxidizing unit (SOU). The microaeration technique provided just enough oxygen to partially oxidize sulfides to elemental sulfur without inhibiting methanogenesis. The SOU was equipped with a diffuser at the bottom for the dispersion of sulfide-laden biogas and injected air throughout the column. The SOU can be operated as a standalone unit or coupled with an anaerobic digester to simultaneously remove sulfide from the biogas and effluent. The integrated system was capable of reducing hydrogen sulfide in biogas from 2,450 to less than 2 ppmV with minimal sulfate production at the highest available sulfide loading rate of 0.24 kg/m3-day. More than 98% of sulfide removed was recovered as elemental sulfur. However, the standalone SOU was able to operate at high hydrogen sulfide loading of 1.46 kg/m 3-day at inlet sulfide concentration of 3000 ppmV and reduce the off-gas hydrogen sulfide concentrations to less than 10 ppmV. The experiment also revealed that the ORP controlled aeration was sensitive enough to prevent oxygen overdosing (dampening effect) during unexpected surges of aeration. Using generalized linear regression, a model predicting output H2S concentration based on input H2S concentrations, SOU medium heights, and biogas flow rates, was derived. With 95% confidence, output H2S concentration

  3. Enhanced Mantle Conductivity from Sulfides beneath the Sierra Nevada?

    NASA Astrophysics Data System (ADS)

    Park, S. K.

    2002-12-01

    A region of enhanced mantle conductivity (0.03-0.1 S/m) beneath the southern Sierra Nevada, where elevations of over 4000 m are found, has been attributed previously to 3-5% basaltic melt (Park et al., 1996) and to a mix of basaltic and sulfide melt (Ducea and Park, 2000). Because the sulfide melt is assumed to have similar conductivities to its solid counterpart (10,000 S/m), very small amounts (< 0.1%) of sulfide are needed in order to reduce the bulk conductivity from matrix values of about 0.003 S/m or even that of the matrix-basalt melt mix to the values observed. Basaltic melt percentages of less than 1% are needed in the presence of ~0.1% sulfide melt in order to match the observed mantle values. Xenoliths from the Holocene basalts in the Big Pine Volcanic Field contain 0.06-0.4% sulfide, so the estimated values are reasonable. Given the lack of evidence for volumetrically extensive, young (< 10 Ma) basaltic volcanism, calculated residence times of approximately 100 Ka for 3-5% partial melt, the short (about 300 Ka) times needed to develop connected pathways for the basalt, and the young extension of the adjacent Basin and Range province, a mixed melt with both basalt and sulfides seems more reasonable. This conclusion presupposes that the sulfide melt is somehow interconnected in the mantle. Models in which the matrix, the basaltic melt, and the sulfide melt each form interconnected, interlaced networks leads to much higher predictions of mantle conductivity; the sulfide melt fraction must be discontinuous in order to lower bulk conductivity. Petrological studies of sulfide-silicate systems confirm this conclusion; sulfide melts form isolated blebs on the surfaces of olivine within interconnected basaltic melt channels (Holzheid et al., 2000). Simple series-parallel models of ~1% continuous basaltic melt and ~0.01% discontinuous sulfide melt provide bulk conductivities comparable to the observed mantle values. More complicated equivalent media and Hashin

  4. Hafnium dioxide as a passivating layer and diffusive barrier in ZnO/Ag Schottky junctions obtained by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Krajewski, Tomasz A.; Luka, Grzegorz; Gieraltowska, Sylwia; Zakrzewski, Adam J.; Smertenko, Petro S.; Kruszewski, Piotr; Wachnicki, Lukasz; Witkowski, Bartlomiej S.; Lusakowska, Elzbieta; Jakiela, Rafal; Godlewski, Marek; Guziewicz, Elzbieta

    2011-06-01

    This paper reports on ZnO/Ag Schottky junctions obtained by the low temperature atomic layer deposition process. Introducing the thin (from 1.25 to 7.5 nm) layer of hafnium dioxide between the ZnO layer and evaporated Ag Schottky contact improves the rectification ratio to about 105 at 2V. For the ZnO/Ag junctions without the HfO2 interlayer, the rectification ratio is only 102. We assign this effect to the passivation of ZnO surface accumulation layer that is reported for ZnO thin films.

  5. Processing development of 4 tantalum carbide-hafnium carbide and related carbides and borides for extreme environments

    NASA Astrophysics Data System (ADS)

    Gaballa, Osama Gaballa Bahig

    Carbides, nitrides, and borides ceramics are of interest for many applications because of their high melting temperatures and good mechanical properties. Wear-resistant coatings are among the most important applications for these materials. Materials with high wear resistance and high melting temperatures have the potential to produce coatings that resist degradation when subjected to high temperatures and high contact stresses. Among the carbides, Al4SiC4 is a low density (3.03 g/cm3), high melting temperature (>2000°C) compound, characterized by superior oxidation resistance, and high compressive strength. These desirable properties motivated this investigation to (1) obtain high-density Al4SiC4 at lower sintering temperatures by hot pressing, and (2) to enhance its mechanical properties by adding WC and TiC to the Al4SiC4. Also among the carbides, tantalum carbide and hafnium carbide have outstanding hardness; high melting points (3880°C and 3890°C respectively); good resistance to chemical attack, thermal shock, and oxidation; and excellent electronic conductivity. Tantalum hafnium carbide (Ta4HfC 5) is a 4-to-1 ratio of TaC to HfC with an extremely high melting point of 4215 K (3942°C), which is the highest melting point of all currently known compounds. Due to the properties of these carbides, they are considered candidates for extremely high-temperature applications such as rocket nozzles and scramjet components, where the operating temperatures can exceed 3000°C. Sintering bulk components comprised of these carbides is difficult, since sintering typically occurs above 50% of the melting point. Thus, Ta4 HfC5 is difficult to sinter in conventional furnaces or hot presses; furnaces designed for very high temperatures are expensive to purchase and operate. Our research attempted to sinter Ta4HfC5 in a hot press at relatively low temperature by reducing powder particle size and optimizing the powder-handling atmosphere, milling conditions, sintering

  6. Catalytic reduction of CO with hydrogen sulfide. 4. Temperature-programmed desorption of methanethiol on anatase, rutile, and sulfided rutile

    SciTech Connect

    Beck, D.D.; White, J.M.; Ratcliffe, C.T.

    1986-07-03

    The interaction of methanethiol with anatase, rutile, and sulfided rutile was studied by temperature-programmed desorption. Dissociative adsorption occurs on rutile but is insignificant on anatase. Decomposition products are dominated by H/sub 2/ on rutile and by CH/sub 4/ on sulfided rutile. In both cases desorption occurs between 500 and 775 K. The 5- and 4-coordinate sites on the (110) face of rutile are proposed as the active sites for decomposition. The dominance of methane on a sulfided surface is attributed to the relatively large supply of highly mobile surface hydrogen atoms.

  7. Oxidation Characterization of Hafnium-Based Ceramics Fabricated by Hot Pressing and Electric Field-Assisted Sintering

    NASA Technical Reports Server (NTRS)

    Gasch, Matt; Johnson, Sylvia; Marschall, Jochen

    2010-01-01

    Ceramic borides, such as hafnium diboride (HfB2) and zirconium diboride (ZrB2), are members of a family of materials with extremely high melting temperatures referred to as Ultra High Temperature Ceramics (UHTCs). UHTCs constitute a class of promising materials for use in high temperature applications, such as sharp leading edges on future-generation hypersonic flight vehicles, because of their high melting points. The controlled development of microstructure has become important to the processing of UHTCs, with the prospect of improving their mechanical and thermal properties. The improved oxidation resistance of HfB2 has also become important if this material is to be successfully used at temperatures above 2000 C. Furthermore, the use of UHTCs on the leading edges of vehicles traveling at hypersonic speeds will mean exposure to a mixed oxidation environment comprised of both molecular and atomic oxygen. The current study has investigated the high-temperature oxidation behavior of HfB2-based materials in a pure O2 environment, as well as in environments containing different levels of dissociated oxygen (O/O2). Materials were processed by two techniques: conventional hot pressing (HP) and electric field-assisted sintering (FAS). Their oxidation behavior was evaluated in both a tube furnace at 1250 C for 3 hours and in a simulated re-entry environment in the Advanced Heating Facility (AHF) arcjet at NASA Ames Research Center, during a 10-minute exposure to a cold wall heat flux of 250W/sq cm and stagnation pressure of 0.1-0.2 atm. The microstructure of the different materials was characterized before and after oxidation using scanning electron microscopy (SEM).

  8. Characterization of high-k gate dielectrics based on hafnium oxide and titanium oxide for CMOS application

    NASA Astrophysics Data System (ADS)

    Lee, Sanghyun

    Hafnium oxide, Titanium oxide, and ternary alloys with nitrided films of each of the above on Silicon and Germanium substrate were investigated in effort of understanding origins and various factors governing intrinsic band edge defects and interface trapped charges which are crucial to implent the high-k dielectrics into CMOS device below Electrical Equivalent Thickness (EOT) < 1nm. Novel design of atomic scale molecule was applied to achieve superb quality guided by the bond constrain theory. Tetrahedral bonding of Hf and Ti oxide in each Hf/Ti Silicon oxynitride gave the chemical stability upon annealing up to 1100°C. From the spectroscopic and electrical measurements, defect states were suppressed by reducing oxygen vacancy related defect states in Hf/Ti Silicon oxynitride. Conduction and valence band edge defect states were detected and reduced by limiting the thickness of HfO2 to 2 nm which is critical length for forming coherent inter-primitive pi bonding between Hf dpi-O ppi orbitals. As a result, Jahn-Teller d state term splittings were suppressed. The application of ultrathin Hf oxide and Hf Si oxynitride films onto Ge (100) and Ge (111) substrates resulted in the elimination of interfacial transition layer by removing Ge-N and possibly Ge-O bond after 800°C anneal. This could afford re-grown Ge epitaxial layer on top of Ge substrate which dramatically reduced the defect states between Hf Silicon oxynitride and Ge substrate. The gate leakage current for Hf Silicon oxynitride was lower than that on Si substrate.

  9. Silicon Nanowires with High-k Hafnium Oxide Dielectrics for Sensitive Detection of Small Nucleic Acid Oligomers

    PubMed Central

    Dorvel, Brian R.; Reddy, Bobby; Go, Jonghyun; Guevara, Carlos Duarte; Salm, Eric; Alam, Muhammad Ashraful; Bashir, Rashid

    2012-01-01

    Nanobiosensors based on silicon nanowire field effect transistors offer advantages of low cost, label-free detection, and potential for massive parallelization. As a result, these sensors have often been suggested as an attractive option for applications in Point-of-care (POC) medical diagnostics. Unfortunately, a number of performance issues such as gate leakage and current instability due to fluid contact, have prevented widespread adoption of the technology for routine use. High-k dielectrics, such as hafnium oxide (HfO2), have the known ability to address these challenges by passivating the exposed surfaces against destabilizing concerns of ion transport. With these fundamental stability issues addressed, a promising target for POC diagnostics and SiNWFET’s has been small oligonucleotides, more specifically microRNA (miRNA). MicroRNA’s are small RNA oligonucleotides which bind to messenger RNA’s, causing translational repression of proteins, gene silencing, and expressions are typically altered in several forms of cancer. In this paper, we describe a process for fabricating stable HfO2 dielectric based silicon nanowires for biosensing applications. Here we demonstrate sensing of single stranded DNA analogues to their microRNA cousins using miR-10b and miR-21 as templates, both known to be upregulated in breast cancer. We characterize the effect of surface functionalization on device performance using the miR-10b DNA analogue as the target sequence and different molecular weight poly-l-lysine as the functionalization layer. By optimizing the surface functionalization and fabrication protocol, we were able to achieve <100fM detection levels of miR-10b DNA analogue, with a theoretical limit of detection of 1fM. Moreover, the non-complementary DNA target strand, based on miR-21, showed very little response, indicating a highly sensitive and highly selective biosensing platform. PMID:22695179

  10. Micro-PIXE Analysis of Trace Elements in Sulfides

    SciTech Connect

    Hickmott, D.D.; Wetteland, C.; Stimac, J.; Larocque, A.C.L.; Brearley, A.

    2003-08-26

    Micro-scale Proton-induced X-ray Emission (PIXE) of trace elements (TE) in sulfides provides insights into geologic processes including magmatic system evolution, ore forming events, and fluid-flow processes. The Los Alamos nuclear microprobe was used to determine TE concentrations and ratios in sulfides from diverse geologic environments including hydrothermal ore deposits, coal seams, and metamorphic rocks. Pyrrhotite (Po) from silicic volcanics contains high Cu and Ni; Po from the Clear Lake volcanic field has higher Mo than does Po from other volcanic fields. Coal pyrites contain high Cu, As, Se, Mo and Pb, and show high As/Se and Mo/Se in marine influenced sulfides from the Lower Kittanning coal, but not in other marine-influenced coals. Sulfides are amenable to micro-PIXE studies because of the difficulties in obtaining the homogeneous standards required for many other TE microanalytical techniques.

  11. The hydrogen sulfide metabolite trimethylsulfonium is found in human urine

    NASA Astrophysics Data System (ADS)

    Lajin, Bassam; Francesconi, Kevin A.

    2016-06-01

    Hydrogen sulfide is the third and most recently discovered gaseous signaling molecule following nitric oxide and carbon monoxide, playing important roles both in normal physiological conditions and disease progression. The trimethylsulfonium ion (TMS) can result from successive methylation reactions of hydrogen sulfide. No report exists so far about the presence or quantities of TMS in human urine. We developed a method for determining TMS in urine using liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-QQQ), and applied the method to establish the urinary levels of TMS in a group of human volunteers. The measured urinary levels of TMS were in the nanomolar range, which is commensurate with the steady-state tissue concentrations of hydrogen sulfide previously reported in the literature. The developed method can be used in future studies for the quantification of urinary TMS as a potential biomarker for hydrogen sulfide body pools.

  12. 21 CFR 177.2490 - Polyphenylene sulfide resins.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... Sulfur in Organic Compounds,” “Determination of the Inherent Viscosity of Polyphenylene Sulfide,” and... viscosity: 0.13 deciliters per gram. (3) Maximum residual p-dichlorobenzene: 0.8 ppm. (b) Subject to...

  13. 21 CFR 177.2490 - Polyphenylene sulfide resins.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... Sulfur in Organic Compounds,” “Determination of the Inherent Viscosity of Polyphenylene Sulfide,” and... viscosity: 0.13 deciliters per gram. (3) Maximum residual p-dichlorobenzene: 0.8 ppm. (b) Subject to...

  14. 21 CFR 177.2490 - Polyphenylene sulfide resins.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...,” “Determination of the Inherent Viscosity of Polyphenylene Sulfide,” and “Analysis for Dichlorobenzene in Ryton... percent by weight of finished resin. (2) Minimum inherent viscosity: 0.13 deciliters per gram. (3)...

  15. 21 CFR 177.2490 - Polyphenylene sulfide resins.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... Sulfur in Organic Compounds,” “Determination of the Inherent Viscosity of Polyphenylene Sulfide,” and... viscosity: 0.13 deciliters per gram. (3) Maximum residual p-dichlorobenzene: 0.8 ppm. (b) Subject to...

  16. 21 CFR 177.2490 - Polyphenylene sulfide resins.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Sulfur in Organic Compounds,” “Determination of the Inherent Viscosity of Polyphenylene Sulfide,” and... viscosity: 0.13 deciliters per gram. (3) Maximum residual p-dichlorobenzene: 0.8 ppm. (b) Subject to...

  17. An Experiment in Autotrophic Fermentation: Microbial Oxidation of Hydrogen Sulfide.

    ERIC Educational Resources Information Center

    Sublette, Kerry L.

    1989-01-01

    Described is an experiment which uses an autotrophic bacterium to anaerobically oxidize hydrogen sulfide to sulfate in a batch-stirred tank reactor. Discusses background information, experimental procedure, and sample results of this activity. (CW)

  18. TREATMENT OF METAL FINISHING WASTES BY SULFIDE PRECIPITATION

    EPA Science Inventory

    This project involved precipitating heavy metals normally present in metal finishing wastewaters by a novel process which employs ferrous sulfide addition (Sulfex), as well as by conventional treatment using calcium hydroxide for comparison purposes. These studies consisted of la...

  19. Crystallinity of Fe-Ni Sulfides in Carbonaceous Chondrites

    NASA Astrophysics Data System (ADS)

    Zolensky, M. E.; Ohsumi, K.; Mikouchi, T.; Hagiya, K.; Le, L.

    2008-03-01

    We examine the crystallinity and crystal structures of Fe-Ni sulfides in five carbonaceous chondrites - Acfer 094 (CM2), Tagish Lake (C2 ungrouped), Kaidun C1, Bali (CV2/3 oxidized), and Efremovka (CV3 reduced).

  20. 40 CFR 425.03 - Sulfide analytical methods and applicability.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... sulfide in wastewaters discharged by plants operating in all subcategories except the hair save or pulp... by plants operating in the hair save or pulp, non-chrome tan, retan-wet finish subcategory (subpart...

  1. 40 CFR 425.03 - Sulfide analytical methods and applicability.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... sulfide in wastewaters discharged by plants operating in all subcategories except the hair save or pulp... by plants operating in the hair save or pulp, non-chrome tan, retan-wet finish subcategory (subpart...

  2. [Activity of hydrogen sulfide production enzymes in kidneys of rats].

    PubMed

    Mel'nyk, A V; Pentiuk, O O

    2009-01-01

    An experimental research of activity and kinetic descriptions of enzymes participating in formation of hydrogen sulfide in the kidney of rats has been carried out. It was established that cystein, homocystein and thiosulphate are the basic substrates for hydrogen sulfide synthesis. The higest activity for hydrogen sulfide production belongs to thiosulfate-dithiolsulfurtransferase and cysteine aminotransferase, less activity is characteristic of cystathionine beta-synthase and cystathio-nine gamma-lyase. The highest affinity to substrate is registered for thiosulfate-dithiolsulfurtransferase and cystathionine gamma-lyase. It is discovered that the substrate inhibition is typical of all hydrogen sulfide formation enzymes, although this characteristic is the most expressed thiosulfat-dithiolsulfurtransferase. PMID:20387629

  3. The hydrogen sulfide metabolite trimethylsulfonium is found in human urine.

    PubMed

    Lajin, Bassam; Francesconi, Kevin A

    2016-01-01

    Hydrogen sulfide is the third and most recently discovered gaseous signaling molecule following nitric oxide and carbon monoxide, playing important roles both in normal physiological conditions and disease progression. The trimethylsulfonium ion (TMS) can result from successive methylation reactions of hydrogen sulfide. No report exists so far about the presence or quantities of TMS in human urine. We developed a method for determining TMS in urine using liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-QQQ), and applied the method to establish the urinary levels of TMS in a group of human volunteers. The measured urinary levels of TMS were in the nanomolar range, which is commensurate with the steady-state tissue concentrations of hydrogen sulfide previously reported in the literature. The developed method can be used in future studies for the quantification of urinary TMS as a potential biomarker for hydrogen sulfide body pools. PMID:27247020

  4. The hydrogen sulfide metabolite trimethylsulfonium is found in human urine

    PubMed Central

    Lajin, Bassam; Francesconi, Kevin A.

    2016-01-01

    Hydrogen sulfide is the third and most recently discovered gaseous signaling molecule following nitric oxide and carbon monoxide, playing important roles both in normal physiological conditions and disease progression. The trimethylsulfonium ion (TMS) can result from successive methylation reactions of hydrogen sulfide. No report exists so far about the presence or quantities of TMS in human urine. We developed a method for determining TMS in urine using liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-QQQ), and applied the method to establish the urinary levels of TMS in a group of human volunteers. The measured urinary levels of TMS were in the nanomolar range, which is commensurate with the steady-state tissue concentrations of hydrogen sulfide previously reported in the literature. The developed method can be used in future studies for the quantification of urinary TMS as a potential biomarker for hydrogen sulfide body pools. PMID:27247020

  5. A New Preparation Method of Ultrafine Particles of Metallic Sulfides

    NASA Astrophysics Data System (ADS)

    Kaito, Chihiro; Saito, Yoshio; Fujita, Kazuo

    1987-12-01

    Ultrafine particles of metallic sulfides have been produced by the reaction of metal and sulfur vapor. The sulfur vapor was prepared by evaporating sulfur powder from a quartz boat using the atmospheric temperature of either the heated metal or boat. Electron microscopic observation of the particles of Mo3S4 and PbS has shown them to be typical examples of the produced sulfides.

  6. Process for thin film deposition of cadmium sulfide

    DOEpatents

    Muruska, H. Paul; Sansregret, Joseph L.; Young, Archie R.

    1982-01-01

    The present invention teaches a process for depositing layers of cadmium sulfide. The process includes depositing a layer of cadmium oxide by spray pyrolysis of a cadmium salt in an aqueous or organic solvent. The oxide film is then converted into cadmium sulfide by thermal ion exchange of the O.sup.-2 for S.sup.-2 by annealing the oxide layer in gaseous sulfur at elevated temperatures.

  7. Preparation of mesoporous cadmium sulfide nanoparticles with moderate pore size

    SciTech Connect

    Han Zhaohui Zhu, Huaiyong; Shi, Jeffrey; Parkinson, Gordon; Lu, G.Q.

    2007-03-15

    The preparation of cadmium sulfide nanoparticles that have a moderate pore size is reported. This preparation method involves a hydrothermal process that produces a precursor mixture and a following acid treatment of the precursor to get the porous material. The majority of the particles have a pore size close to 20nm, which complements and fills in the gap between the existing cadmium sulfide materials, which usually have a pore size either less than 10nm or are well above 100nm.

  8. Sulfide catalysts for reducing SO2 to elemental sulfur

    DOEpatents

    Jin, Yun; Yu, Qiquan; Chang, Shih-Ger

    2001-01-01

    A highly efficient sulfide catalyst for reducing sulfur dioxide to elemental sulfur, which maximizes the selectivity of elemental sulfur over byproducts and has a high conversion efficiency. Various feed stream contaminants, such as water vapor are well tolerated. Additionally, hydrogen, carbon monoxide, or hydrogen sulfides can be employed as the reducing gases while maintaining high conversion efficiency. This allows a much wider range of uses and higher level of feed stream contaminants than prior art catalysts.

  9. Determination of Hydrogen Sulfide in Fermentation Broths Containing SO21

    PubMed Central

    Acree, T. E.; Sonoff, Elisabeth P.; Splittstoesser, D. F.

    1971-01-01

    A procedure for the determination of hydrogen sulfide in fermentation broths containing up to 100 μg of SO2 per ml is described. The method involves the sparging of H2S from the broth into a cadmium hydroxide absorption solution, the formation of methylene blue from the absorbed sulfide, and the measuring of this color spectrophotometrically. The use of cadmium hydroxide instead of zinc acetate, the common absorbent, substantially reduced the interference of SO2 with the analysis. PMID:5111300

  10. Bioavailability and stability of mercury sulfide in Armuchee (USA) soil

    SciTech Connect

    Han, Fengxiang; Shiyab, Safwan; Su, Yi; Monts, David L.; Waggoner, Charles A.; Matta, Frank B.

    2007-07-01

    Because of the adverse effects of elemental mercury and mercury compounds upon human health, the U.S. Department of Energy (DOE) is engaged in an on-going effort to monitor and remediate mercury-contaminated DOE sites. In order to more cost effectively implement those extensive remediation efforts, it is necessary to obtain an improved understanding of the role that mercury and mercury compounds play in the ecosystem. We have conducted pilot scale experiments to study the bioavailability of mercury sulfide in an Armuchee (eastern US ) soil. The effects of plants and incubation time on chemical stability and bioavailability of HgS under simulated conditions of the ecosystem have been examined, as has the dynamics of the dissolution of mercury sulfide by various extractants. The results show that mercury sulfide in contaminated Armuchee soil was still to some extent bioavailable to plants. After planting, soil mercury sulfide is more easily dissolved by both 4 M and 12 M nitric acid than pure mercury sulfide reagent. Dissolution kinetics of soil mercury sulfide and pure chemical reagent by nitric acid are different. Mercury release by EDTA from HgS-contaminated soil increased with time of reaction and soil mercury level. Chelating chemicals increase the solubility and bioavailability of mercury in HgS-contaminated soil. (authors)

  11. Sulfide as a soil phytotoxin—a review

    PubMed Central

    Lamers, Leon P. M.; Govers, Laura L.; Janssen, Inge C. J. M.; Geurts, Jeroen J. M.; Van der Welle, Marlies E. W.; Van Katwijk, Marieke M.; Van der Heide, Tjisse; Roelofs, Jan G. M.; Smolders, Alfons J. P.

    2013-01-01

    In wetland soils and underwater sediments of marine, brackish and freshwater systems, the strong phytotoxin sulfide may accumulate as a result of microbial reduction of sulfate during anaerobiosis, its level depending on prevailing edaphic conditions. In this review, we compare an extensive body of literature on phytotoxic effects of this reduced sulfur compound in different ecosystem types, and review the effects of sulfide at multiple ecosystem levels: the ecophysiological functioning of individual plants, plant-microbe associations, and community effects including competition and facilitation interactions. Recent publications on multi-species interactions in the rhizosphere show even more complex mechanisms explaining sulfide resistance. It is concluded that sulfide is a potent phytotoxin, profoundly affecting plant fitness and ecosystem functioning in the full range of wetland types including coastal systems, and at several levels. Traditional toxicity testing including hydroponic approaches generally neglect rhizospheric effects, which makes it difficult to extrapolate results to real ecosystem processes. To explain the differential effects of sulfide at the different organizational levels, profound knowledge about the biogeochemical, plant physiological and ecological rhizosphere processes is vital. This information is even more important, as anthropogenic inputs of sulfur into freshwater ecosystems and organic loads into freshwater and marine systems are still much higher than natural levels, and are steeply increasing in Asia. In addition, higher temperatures as a result of global climate change may lead to higher sulfide production rates in shallow waters. PMID:23885259

  12. Sulfide inhibition of and metabolism by cytochrome c oxidase.

    PubMed

    Nicholls, Peter; Marshall, Doug C; Cooper, Chris E; Wilson, Mike T

    2013-10-01

    Hydrogen sulfide (H2S), a classic cytochrome c oxidase inhibitor, is also an in vitro oxidase substrate and an in vivo candidate hormonal ('gasotransmitter') species affecting sleep and hibernation. H2S, nitric oxide (NO) and carbon monoxide (CO) share some common features. All are low-molecular-mass physiological effectors and also oxidase inhibitors, capable of binding more than one enzyme site, and each is an oxidizable 'substrate'. The oxidase oxidizes CO to CO2, NO to nitrite and sulfide to probable persulfide species. Mitochondrial cytochrome c oxidase in an aerobic steady state with ascorbate and cytochrome c is rapidly inhibited by sulfide in a biphasic manner. At least two successive inhibited species are involved, probably partially reduced. The oxidized enzyme, in the absence of turnover, occurs in at least two forms: the 'pulsed' and 'resting' states. The pulsed form reacts aerobically with sulfide to form two intermediates, 'P' and 'F', otherwise involved in the reaction of oxygen with reduced enzyme. Sulfide can directly reduce the oxygen-reactive a3CuB binuclear centre in the pulsed state. The resting enzyme does not undergo such a step, but only a very slow one-electron reduction of the electron-transferring haem a. In final reactivation phases, both the steady-state inhibition of catalysis and the accumulation of P and F states are reversed by slow sulfide oxidation. A model for this complex reaction pattern is presented. PMID:24059525

  13. Nitrite as an antidote for acute hydrogen sulfide intoxication

    SciTech Connect

    Beck, J.F.; Bradbury, C.M.; Connors, A.J.; Donini, J.C.

    1981-11-01

    The detoxification of hydrogen sulfide (H/sub 2/S) by a heme catalyzed oxidation was examined as part of an on-going study of H/sub 2/S toxicity. Interlocking O/sub 2/ absorption and sulfide depletion data indicate that both oxyhemoglobin and methemoglobin are effective catalytic agents. Although the latter is more efficacious, the life time of excess sulfide in the presence of oxygen and either of the above is of the order of minutes. It has also been established that the formation of methemoglobin following nitrite administration occurs preferentially under oxygen poor conditions. Under an atmospheric or oxygen enriched environment, which favors sulfide depletion, the nitrite retards sulfide oxidation. Thus nitrite as an antidote for acute H/sub 2/S intoxication can only be effective within the first few minutes after the exposure, at which time resuscitation and/or ventilation of the victim is likely to produce conditions in which the nitrite actually slows sulfide removal.

  14. Metal Sulfides as Sensing Materials for Chemoresistive Gas Sensors.

    PubMed

    Gaiardo, Andrea; Fabbri, Barbara; Guidi, Vincenzo; Bellutti, Pierluigi; Giberti, Alessio; Gherardi, Sandro; Vanzetti, Lia; Malagù, Cesare; Zonta, Giulia

    2016-01-01

    This work aims at a broad overview of the results obtained with metal-sulfide materials in the field of chemoresistive gas sensing. Indeed, despite the well-known electrical, optical, structural and morphological features previously described in the literature, metal sulfides present lack of investigation for gas sensing applications, a field in which the metal oxides still maintain a leading role owing to their high sensitivity, low cost, small dimensions and simple integration, in spite of the wide assortment of sensing materials. However, despite their great advantages, metal oxides have shown significant drawbacks, which have led to the search for new materials for gas sensing devices. In this work, Cadmium Sulfide and Tin (IV) Sulfide were investigated as functional materials for thick-film chemoresistive gas-sensors fabrication and they were tested both in thermo- and in photo-activation modes. Furthermore, electrical characterization was carried out in order to verify their gas sensing properties and material stability, by comparing the results obtained with metal sulfides to those obtained by using their metal-oxides counterparts. The results highlighted the possibility to use metal sulfides as a novel class of sensing materials, owing to their selectivity to specific compounds, stability, and the possibility to operate at room temperature. PMID:26927120

  15. Trace element-sulfide mineral association in eastern oil shale

    SciTech Connect

    Mason, G.M.

    1989-03-01

    Eastern oil shales including the Chattanooga Shale in Tennessee and the various other time-equivalent black shales in the central portion of the United States represent a major source of hydrocarbons. A primary concern for the development of eastern oil shale and all fossil fuels is the high concentration of sulfide minerals and associated with these materials. The objectives of this study were (1) to evaluate trace elements in sulfide minerals from a Chattanooga Shale core from central Tennessee and (2) establish mineral residence and stratigraphic distribution of selected trace elements. Previous researchers have suggested the residency of the trace elements As, Cu, Cd, Pb, Mo, Ni, and Zn as being sulfide minerals, either as separate distinct phases, inclusions, or isomorphous substitution. The most significant contribution derived from the present study is the direct observation and association of selected trace and minor elements with sulfide minerals. Rather than an indirect or inferred trace element- sulfide mineral association, sulfide mineral phases were isolated allowing the morphology and composition to be directly evaluated. 9 refs., 31 figs., 3 tabs.

  16. Metal Sulfides as Sensing Materials for Chemoresistive Gas Sensors

    PubMed Central

    Gaiardo, Andrea; Fabbri, Barbara; Guidi, Vincenzo; Bellutti, Pierluigi; Giberti, Alessio; Gherardi, Sandro; Vanzetti, Lia; Malagù, Cesare; Zonta, Giulia

    2016-01-01

    This work aims at a broad overview of the results obtained with metal-sulfide materials in the field of chemoresistive gas sensing. Indeed, despite the well-known electrical, optical, structural and morphological features previously described in the literature, metal sulfides present lack of investigation for gas sensing applications, a field in which the metal oxides still maintain a leading role owing to their high sensitivity, low cost, small dimensions and simple integration, in spite of the wide assortment of sensing materials. However, despite their great advantages, metal oxides have shown significant drawbacks, which have led to the search for new materials for gas sensing devices. In this work, Cadmium Sulfide and Tin (IV) Sulfide were investigated as functional materials for thick-film chemoresistive gas-sensors fabrication and they were tested both in thermo- and in photo-activation modes. Furthermore, electrical characterization was carried out in order to verify their gas sensing properties and material stability, by comparing the results obtained with metal sulfides to those obtained by using their metal-oxides counterparts. The results highlighted the possibility to use metal sulfides as a novel class of sensing materials, owing to their selectivity to specific compounds, stability, and the possibility to operate at room temperature. PMID:26927120

  17. Hydrogen sulfide production from subgingival plaque samples.

    PubMed

    Basic, A; Dahlén, G

    2015-10-01

    Periodontitis is a polymicrobial anaerobe infection. Little is known about the dysbiotic microbiota and the role of bacterial metabolites in the disease process. It is suggested that the production of certain waste products in the proteolytic metabolism may work as markers for disease severity. Hydrogen sulfide (H2S) is a gas produced by degradation of proteins in the subgingival pocket. It is highly toxic and believed to have pro-inflammatory properties. We aimed to study H2S production from subgingival plaque samples in relation to disease severity in subjects with natural development of the disease, using a colorimetric method based on bismuth precipitation. In remote areas of northern Thailand, adults with poor oral hygiene habits and a natural development of periodontal disease were examined for their oral health status. H2S production was measured with the bismuth method and subgingival plaque samples were analyzed for the presence of 20 bacterial species with the checkerboard DNA-DNA hybridization technique. In total, 43 subjects were examined (age 40-60 years, mean PI 95 ± 6.6%). Fifty-six percent had moderate periodontal breakdown (CAL > 3 < 7 mm) and 35% had severe periodontal breakdown (CAL > 7 mm) on at least one site. Parvimonas micra, Filifactor alocis, Porphyromonas endodontalis and Fusobacterium nucleatum were frequently detected. H2S production could not be correlated to periodontal disease severity (PPD or CAL at sampled sites) or to a specific bacterial composition. Site 21 had statistically lower production of H2S (p = 0.02) compared to 16 and 46. Betel nut chewers had statistically significant lower H2S production (p = 0.01) than non-chewers. Rapid detection and estimation of subgingival H2S production capacity was easily and reliably tested by the colorimetric bismuth sulfide precipitation method. H2S may be a valuable clinical marker for degradation of proteins in the subgingival pocket. PMID:25280920

  18. Lithium-aluminum/iron sulfide batteries

    NASA Astrophysics Data System (ADS)

    Henriksen, G. L.; Vissers, D. R.

    Lithium-alloy/metal sulfide batteries have been under development at Argonne National Laboratory since 1972. ANL's technology employs a two-phase Li alloy negative electrode, low-melting point LiCl-rich LiCl-LiBr-KBr molten salt electrolyte, and either an FeS or an upper-plateau (UP) FeS 2 positive electrode. These components are assembled in an 'electrolyte-starved' bipolar cell configuration. Use of the multi-phase Li alloy ((α+β)-Li-Al and Li 5Al 5Fe 2) negative electrode provides in situ overcharge tolerance that renders the bipolar design viable. Employing LiCl-rich LiCl-LiBr-KBr electrolyte is 'electrolyte-starved" cells achieves low-burdened cells that possess low area-specific impedance, comparable with that of flooded cells using LiCl-LiBr-KBr eutectic electrolyte. The combination of dense UP FeS 2 electrodes and low-melting electrolyte produces a stable and reversible couple, achieving over 1000 cycles in flooded cells, with high power capabilities. In addition, a new class of stable chalcogenide ceramic/sealant materials was developed. These materials produce high-strength bonds between a variety of metals and ceramics, which make fabrication of lithium/iron sulfide bipolar stacks practical. Bipolar Li-Al/FeS and Li-Al/FeS 2 cells and four-cell stacks using these seals have been built and tested for electric vehicle (EV) applications. When cell performance characteristics are used to model full-scale EV ad hybrid vehicle (HV) batteries, they are projected to meet or exceed the performance requirements for a large variety of EV and HV applications. In 1992, the US Advanced Battery Consortium awarded contracts to ANL and SAFT America to continue the development of the bipolar Li-Al/FeS 2 battery to meet their long-term criteria. Both ANL and sAFT are working together to refine this technology for EV applications and scale it up to larger stacks and fully integrated battery modules.

  19. Airborne measurements of sulfur dioxide, dimethyl sulfide, carbon disulfide, and carbonyl sulfide by isotope dilution gas chromatography/mass spectrometry

    NASA Technical Reports Server (NTRS)

    Bandy, Alan R.; Thornton, Donald C.; Driedger, Arthur R., III

    1993-01-01

    A gas chromatograph/mass spectrometer is described for determining atmospheric sulfur dioxide, carbon disulfide, dimethyl sulfide, and carbonyl sulfide from aircraft and ship platforms. Isotopically labelled variants of each analyte were used as internal standards to achieve high precision. The lower limit of detection for each species for an integration time of 3 min was 1 pptv for sulfur dioxide and dimethyl sulfide and 0.2 pptv for carbon disulfide and carbonyl sulfide. All four species were simultaneously determined with a sample frequency of one sample per 6 min or greater. When only one or two species were determined, a frequency of one sample per 4 min was achieved. Because a calibration is included in each sample, no separate calibration sequence was needed. Instrument warmup was only a few minutes. The instrument was very robust in field deployments, requiring little maintenance.

  20. An intercomparison of aircraft instrumentation for tropospheric measurements of carbonyl sulfide, hydrogen sulfide, and carbon disulfide

    NASA Astrophysics Data System (ADS)

    Gregory, Gerald L.; Davis, Douglas D.; Thornton, Donald C.; Johnson, James E.; Bandy, Alan R.; Saltzman, Eric S.; Andreae, Meinrat O.; Barrick, John D.

    1993-12-01

    This paper reports results of NASA's Chemical Instrumentation and Test Evaluation (CITE 3) during which airborne measurements for carbonyl sulfide (COS), hydrogen sulfide (H2S), and carbon disulfide (CS2) were intercompared. Instrumentation included a gas chromatograph using flame photometric detection (COS, H2S, and CS2), a gas chromatograph using mass spectrometric detection (COS and CS2), a gas chromatograph using fluorination and subsequent SF6 detection via electron capture (COS and CS2), and the Natusch technique (H2S). The measurements were made over the Atlantic Ocean east of North and South America during flights from NASA's Wallops Flight Center, Virginia, and Natal, Brazil, in August/September 1989. Most of the intercomparisons for H2S and CS2 were at mixing ratios <25 pptv and <10 pptv, respectively, with a maximum mixing ratio of about 100 pptv and 50 pptv, respectively. Carbonyl sulfide intercomparisons were at mixing ratios between 400 and 600 pptv. Measurements were intercompared from data bases constructed from time periods of simultaneous or overlapping measurements. Agreement among the COS techniques averaged about 5%, and individual measurements were generally within 10%. For H2S and at mixing ratio >25 pptv, the instruments agreed on average to about 15%. At mixing ratios <25 pptv the agreement was about 5 pptv. For CS2 (mixing ratios <50 pptv), two techniques agreed on average to about 4 pptv, and the third exhibited a bias (relative to the other two) that varied in the range of 3-7 pptv. CS2 mixing ratios over the ocean east of Natal as measured by the gas chromatograph-mass spectrometer technique were only a few pptv and were below the detection limits of the other two techniques. The CITE 3 data are used to estimate the current uncertainty associated with aircraft measurements of COS, H2S, and CS2 in the remote troposphere.

  1. An intercomparison of aircraft instrumentation for tropospheric measurements of carbonyl sulfide, hydrogen sulfide, and carbon disulfide

    NASA Technical Reports Server (NTRS)

    Gregory, Gerald L.; Davis, Douglas D.; Thornton, Donald C.; Johnson, James E.; Bandy, Alan R.; Saltzman, Eric S.; Andreae, Meinrat O.; Barrick, John D.

    1993-01-01

    This paper reports results of NASA's Chemical Instrumentation and Test Evaluation (CITE 3) during which airborne measurements for carbonyl sulfide (COS), hydrogen sulfide (H2S), and carbon disulfide (CS2) were intercompared. Instrumentation included a gas chromatograph using flame photometric detection (COS, H2S, and CS2), a gas chromatograph using mass spectrometric detection (COS) and CS2), a gas chromatograph using fluorination and subsequent SF6 detection via electron capture (COS and CS2), and the Natusch technique (H2S). The measurements were made over the Atlantic Ocean east of North and South America during flights from NASA's Wallops Flight Center, Virginia, and Natal, Brazil, in August/September 1989. Most of the intercomparisons for H2S and CS2 were at mixing ratios less than 25 pptv and less than 10 pptv, respectively, with a maximum mixing ratio of about 100 pptv and 50 pptv, respectively. Carbonyl sulfide intercomparisons were at mixing ratios between 400 and 600 pptv. Measurements were intercompared from data bases constructed from time periods of simultaneous or overlapping measurements. Agreement among the COS techniques averaged about 5%, and individual measurements were generally within 10%. For H2S and at mixing ratio greater than 25 pptv, the instruments agreed on average to about 15%. At mixing ratios less than 25 pptv the agreement was about 5 pptv. For CS2 (mixing ratios less than 50 pptv), two techniques agreed on average to about 4 pptv, and the third exhibited a bias (relative to the other two) that varied in the range of 3-7 pptv. CS2 mixing ratios over the ocean east of Natal as measured by the gas chromatograph-mass spectrometer technique were only a few pptv and were below the detection limits of the other two techniques. The CITE 3 data are used to estimate the current uncertainty associated with aircraft measurements of COS, H2S, and CS2 in the remote troposphere.

  2. Tracing the history of submarine hydrothermal inputs and the significance of hydrothermal hafnium for the seawater budget - A combined Pb-Hf-Nd isotope approach

    USGS Publications Warehouse

    van de Flierdt, T.; Frank, M.; Halliday, A.N.; Hein, J.R.; Hattendorf, B.; Gunther, D.; Kubik, P.W.

    2004-01-01

    Secular variations in the Pb isotopic composition of a mixed hydrogenous-hydrothermal ferromanganese crust from the Bauer Basin in the eastern Equatorial Pacific provide clear evidence for changes in hydrothermal contributions during the past 7 Myr. The nearby Galapagos Rise spreading center provided a strong hydrothermal flux prior to 6.5 Ma. After 6.5 Ma, the Pb became stepwise more radiogenic and more similar to Equatorial Pacific seawater, reflecting the westward shift of spreading to the presently active East Pacific Rise (EPR). A second, previously unrecognized enhanced hydrothermal period occurred between 4.4 and 2.9 Ma, which reflects either off-axis hydrothermal activity in the Bauer Basin or a late-stage pulse of hydrothermal Pb from the then active, but waning Galapagos Rise spreading center. Hafnium isotope time-series of the same mixed hydrogenous-hydrothermal crust show invariant values over the past 7 Myr. Hafnium isotope ratios, as well as Nd isotope ratios obtained for this crust, are identical to that of hydrogenous Equatorial Pacific deep water crusts and clearly indicate that hydrothermal Hf, similar to Nd, does not travel far from submarine vents. Therefore, we suggest that hydrothermal Hf fluxes do not contribute significantly to the global marine Hf budget. ?? 2004 Elsevier B.V. All rights reserved.

  3. Nitrogen sulfide in giant molecular clouds

    NASA Technical Reports Server (NTRS)

    McGonagle, D.; Irvine, W. M.

    1997-01-01

    We report a survey for nitrogen sulfide (NS) toward regions of massive star formation. NS was observed by means of its 2 pi 1/2, J = 3/2 --> 1/2, J = 5/2 --> 3/2, and J = 7/2 --> 5/2 transitions at 69, 115, and 161 GHz, respectively, and was detected toward 12 of 14 giant molecular clouds (GMCs) observed. Analysis of the hyperfine component relative line strengths suggests that NS emission is optically thin toward these sources, with the possible exception of Sgr B2(M). The fractional abundance of NS relative to molecular hydrogen is best defined for the Orion molecular cloud, where it is typically (1-4) x 10(-10), which is about an order of magnitude larger than found by some recent gas-phase chemistry models developed for quiescent clouds. Toward OMC-1, the NS integrated intensity is strongly peaked toward KL, but also extends all along the Orion ridge, resembling the distribution of SO and CH3OH. We have identified a spectral feature seen toward several sources as the ortho-NKK = 4(04) --> 3(13) J = 3 --> 2, fine-structure component of methylene (CH2; cf. Hollis, Jewell, & Lovas). We also report the first detection of the SO+ 2 pi 1/2, J = 3/2 --> 1/2, parity-e transition toward W51(MS) and L134N.

  4. Hydrogen Sulfide and Cellular Redox Homeostasis

    PubMed Central

    Xie, Zhi-Zhong; Liu, Yang; Bian, Jin-Song

    2016-01-01

    Intracellular redox imbalance is mainly caused by overproduction of reactive oxygen species (ROS) or weakness of the natural antioxidant defense system. It is involved in the pathophysiology of a wide array of human diseases. Hydrogen sulfide (H2S) is now recognized as the third “gasotransmitters” and proved to exert a wide range of physiological and cytoprotective functions in the biological systems. Among these functions, the role of H2S in oxidative stress has been one of the main focuses over years. However, the underlying mechanisms for the antioxidant effect of H2S are still poorly comprehended. This review presents an overview of the current understanding of H2S specially focusing on the new understanding and mechanisms of the antioxidant effects of H2S based on recent reports. Both inhibition of ROS generation and stimulation of antioxidants are discussed. H2S-induced S-sulfhydration of key proteins (e.g., p66Shc and Keap1) is also one of the focuses of this review. PMID:26881033

  5. Hydrogen Sulfide Signaling in the Gastrointestinal Tract

    PubMed Central

    2014-01-01

    Abstract Significance: The current literature regarding the effects of the gaseous signal molecule hydrogen sulfide (H2S) in the gastrointestinal system is reviewed. Bacterial, host and pharmaceutical-derived H2S are all considered and presented according to the physiological or pathophysiological effects of the gaseous signal molecule. These subjects include the toxicology of intestinal H2S with emphasis on bacterial-derived H2S, especially from sulfate-reducing bacteria, the role of endogenous and exogenous H2S in intestinal inflammation, and the roles of H2S in gastrointestinal motility, secretion and nociception. Recent Advances: While its pro- and anti-inflammatory, smooth muscle relaxant, prosecretory, and pro- and antinociceptive actions continue to remain the major effects of H2S in this system; recent findings have expanded the potential molecular targets for H2S in the gastrointestinal tract. Critical Issues: Numerous discrepancies remain in the literature, and definitive molecular targets in this system have not been supported by the use of competitive antagonism. Future Directions: Future work will hopefully resolve discrepancies in the literature and identify molecular targets and mechanisms of action for H2S. It is clear from the current literature that the long-appreciated relationship between H2S and the gastrointestinal tract continues to be strong as we endeavor to unravel its mysteries. Antioxid. Redox Signal. 20, 818–830. PMID:23582008

  6. Production and Physiological Effects of Hydrogen Sulfide

    PubMed Central

    2014-01-01

    Abstract Significance: Hydrogen sulfide (H2S) has been recognized as a physiological mediator with a variety of functions. It regulates synaptic transmission, vascular tone, inflammation, transcription, and angiogenesis; protects cells from oxidative stress and ischemia-reperfusion injury; and promotes healing of ulcers. Recent Advances: In addition to cystathionine β-synthase and cystathionine γ-lyase, 3-mercaptopyruvate sulfurtransferase along with cysteine aminotransferase was recently demonstrated to produce H2S. Even in bacteria, H2S produced by these enzymes functions as a defense against antibiotics, suggesting that the cytoprotective effect of H2S is a universal defense mechanism in organisms from bacteria to mammals. Critical Issues: The functional form of H2S—undissociated H2S gas, dissociated HS ion, or some other form of sulfur—has not been identified. Future Directions: The regulation of H2S production by three enzymes may lead to the identification of the physiological signals that are required to release H2S. The identification of the physiological functions of other forms of sulfur may also help understand the biological significance of H2S. Antioxid. Redox Signal. 20, 783–793. PMID:23581969

  7. Nitrogen sulfide in quiescent dark clouds.

    PubMed

    McGonagle, D; Irvine, W M; Ohishi, M

    1994-02-20

    We report the first detection of interstellar nitrogen sulfide (NS) in cold dark clouds. Several components of the 2 pi 1/2, J = 3/2 --> 1/2 and J = 5/2 --> 3/2 transitions were observed in TMC-1 and L134N. The inferred column density for TMC-1 is NNS approximately 8 x 10(12)cm-2 toward the NH3 peak in that cloud, and in L134N is NNS approximately 3 x 10(12)cm-2 toward the position of peak NH3 emission. These values correspond to fractional abundances relative to molecular hydrogen of fNS approximately 8 x 10(-10) for TMC-1, and fNS approximately 6 x 10(-10) for L134N. The NS emission is extended along the TMC-1 ridge and is also extended in L134N. The measured abundances are significantly higher than those predicted by some recent gas phase ion-molecule models. PMID:11539492

  8. Enamel surface changes caused by hydrogen sulfide

    PubMed Central

    Yamaguchi, Takao; Hanabusa, Masao; Hosoya, Noriyasu; Chiba, Toshie; Yoshida, Takumasa; Morito, Akiyuki

    2015-01-01

    Background: Volatile sulfur compounds (VSCs) produced inside the mouth are a well-known cause of halitosis. Recent studies have suggested that VSCs modify the pathology of periodontitis by encouraging the migration of bacterial toxins associated with increased permeability of gingival epithelia, and enhancing the production of matrix metalloproteinases in gingival connective tissue. Nonetheless, the effects on the enamel of direct exposure to VSCs within the oral cavity remain unclear. In the present study, we observed the effects of VSCs in the form of hydrogen sulfide (H2S) on enamel surfaces and determined their effects on restorations. Materials and Methods: Extracted human tooth and bovine tooth samples were divided into the H2S experimental side and the control side. We observed the effects of H2S on enamel surfaces using electron microscopy and conducted a shear test. Results: We found that exposure to H2S obscured the enamel surface's crystal structure. The surface also exhibited coarseness and reticular changes. Shear testing did not reveal any differences in bond strength. Conclusions: Our findings suggested that H2S occurring inside the mouth causes changes to the crystal structure of the enamel surface that can lead to tooth wear, but that it does not diminish the effects of dental bonding in adhesive restorations. PMID:26752833

  9. Signaling Molecules: Hydrogen Sulfide and Polysulfide

    PubMed Central

    2015-01-01

    Abstract Significance: Hydrogen sulfide (H2S) has been recognized as a signaling molecule as well as a cytoprotectant. It modulates neurotransmission, regulates vascular tone, and protects various tissues and organs, including neurons, the heart, and kidneys, from oxidative stress and ischemia-reperfusion injury. H2S is produced from l-cysteine by cystathionine β-synthase (CBS), cystathionine γ-lyase (CSE), and 3-mercaptopyruvate sulfurtransferase (3MST) along with cysteine aminotransferase. Recent Advances: In addition to these enzymes, we recently identified a novel pathway to produce H2S from d-cysteine, which involves d-amino acid oxidase (DAO) along with 3MST. These enzymes are localized in the cytoplasm, mitochondria, and peroxisomes. However, some enzymes translocate to organelles under specific conditions. Moreover, H2S-derived potential signaling molecules such as polysulfides and HSNO have been identified. Critical Issues: The physiological stimulations, which trigger the production of H2S and its derivatives and maintain their local levels, remain unclear. Future Directions: Understanding the regulation of the H2S production and H2S-derived signaling molecules and the specific stimuli that induce their release will provide new insights into the biology of H2S and therapeutic development in diseases involving these substances. Antioxid. Redox Signal. 22, 362–376. PMID:24800864

  10. Mercury Sulfide Dimorphism in Thioarsenate Glasses.

    PubMed

    Kassem, M; Sokolov, A; Cuisset, A; Usuki, T; Khaoulani, S; Masselin, P; Le Coq, D; Neuefeind, J C; Feygenson, M; Hannon, A C; Benmore, C J; Bychkov, E

    2016-06-16

    Crystalline mercury sulfide exists in two drastically different polymorphic forms in different domains of the P,T-diagram: red chain-like insulator α-HgS, stable below 344 °C, and black tetrahedral narrow-band semiconductor β-HgS, stable at higher temperatures. Using pulsed neutron and high-energy X-ray diffraction, we show that these two mercury bonding patterns are present simultaneously in mercury thioarsenate glasses HgS-As2S3. The population and interconnectivity of chain-like and tetrahedral dimorphous forms determine both the structural features and fundamental glass properties (thermal, electronic, etc.). DFT simulations of mercury species and RMC modeling of high-resolution diffraction data provide additional details on local Hg environment and connectivity implying the (HgS2/2)m oligomeric chains (1 ≤ m ≤ 6) are acting as a network former while the HgS4/4-related mixed agglomerated units behave as a modifier. PMID:27214120

  11. Comparison of Carbon XANES Spectra from an Iron Sulfide from Comet Wild 2 with an Iron Sulfide Interplanetary Dust Particle

    NASA Technical Reports Server (NTRS)

    Wirick, S.; Flynn, G. J.; Keller, L. P.; Sanford, S. A.; Zolensky, M. E.; Messenger, Nakamura K.; Jacobsen, C.

    2008-01-01

    Among one of the first particles removed from the aerogel collector from the Stardust sample return mission was an approx. 5 micron sized iron sulfide. The majority of the spectra from 5 different sections of this particle suggests the presence of aliphatic compounds. Due to the heat of capture in the aerogel we initially assumed these aliphatic compounds were not cometary but after comparing these results to a heated iron sulfide interplanetary dust particle (IDP) we believe our initial interpretation of these spectra was not correct. It has been suggested that ice coating on iron sulfides leads to aqueous alteration in IDP clusters which can then lead to the formation of complex organic compounds from unprocessed organics in the IDPs similar to unprocessed organics found in comets [1]. Iron sulfides have been demonstrated to not only transform halogenated aliphatic hydrocarbons but also enhance the bonding of rubber to steel [2,3]. Bromfield and Coville (1997) demonstrated using Xray photoelectron spectroscopy that "the surface enhancement of segregated sulfur to the surface of sulfided precipitated iron catalysts facilitates the formation of a low-dimensional structure of extraordinary properties" [4]. It may be that the iron sulfide acts in some way to protect aliphatic compounds from alteration due to heat.

  12. Geochemistry of the Kalatongke Ni-Cu-(PGE) sulfide deposit, NW China: implications for the formation of magmatic sulfide mineralization in a postcollisional environment

    NASA Astrophysics Data System (ADS)

    Song, Xie-Yan; Li, Xiang-Ren

    2009-04-01

    The Kalatongke (also spelt as Karatungk) Ni-Cu-(platinum-group element, PGE) sulfide deposit, containing 33 Mt sulfide ore with a grade of 0.8 wt.% Ni and 1.3 wt.% Cu, is located in the Eastern Junggar terrane, Northern Xinjiang, NW China. The largest sulfide ore body, which occupies more than 50 vol.% of the intrusion Y1, is dominantly comprised of disseminated sulfide with a massive sulfide inner zone. Economic disseminated sulfides also occur at the base of the intrusions Y2 and Y3. The main host rock types are norite in the lower part and diorite in the upper part of each intrusion. Enrichment in large ion lithophile elements and depletion in heavy rare earth elements relative to mid-ocean ridge basalt indicate that the mafic intrusions were produced from magmas derived from a metasomatized garnet lherzolite mantle. The average grades of the disseminated ores are 0.6 wt.% Ni and 1.1 wt.% Cu, whereas those of the massive ores are 2 wt.% Ni and 8 wt.% Cu. The PGE contents of the disseminated ores (14-69 ppb Pt and 78-162 ppb Pd) are lower than those of the massive ores (120-505 ppb Pt and 30-827 ppb Pd). However, on the basis of 100% sulfide, PGE contents of the massive sulfides are lower than those of the disseminated sulfides. Very high Cu/Pd ratios (>4.5 × 104) indicate that the Kalatongke sulfides segregated from PGE-depleted magma produced by prior sulfide saturation and separation. A negative correlation between the Cu/Pd ratio and the Pd content in 100% sulfide indicates that the PGE content of the sulfide is controlled by both the PGE concentrations in the parental silicate magma and the ratio of the amount of silicate to sulfide magma. The negative correlations between Ir and Pd indicate that the massive sulfides experienced fractionation.

  13. The effects of varying humidity on copper sulfide film formation.

    SciTech Connect

    Mayer, Thomas Michael; Missert, Nancy A.; Barbour, John Charles; Sullivan, John Patrick; Copeland, Robert Guild; Campin, Michael J.

    2004-02-01

    Detailed experiments involving extensive high resolution transmission electron microscopy (TEM) revealed significant microstructural differences between Cu sulfides formed at low and high relative humidity (RH). It was known from prior experiments that the sulfide grows linearly with time at low RH up to a sulfide thickness approaching or exceeding one micron, while the sulfide initially grows linearly with time at high RH then becomes sub-linear at a sulfide thickness less than about 0.2 microns, with the sulfidation rate eventually approaching zero. TEM measurements of the Cu2S morphology revealed that the Cu2S formed at low RH has large sized grains (75 to greater than 150 nm) that are columnar in structure with sharp, abrupt grain boundaries. In contrast, the Cu2S formed at high RH has small equiaxed grains of 20 to 50 nm in size. Importantly, the small grains formed at high RH have highly disordered grain boundaries with a high concentration of nano-voids. Two-dimensional diffusion modeling was performed to determine whether the existence of localized source terms at the Cu/Cu2S interface could be responsible for the suppression of Cu sulfidation at long times at high RH. The models indicated that the existence of static localized source terms would not predict the complete suppression of growth that was observed. Instead, the models suggest that the diffusion of Cu through Cu2S becomes restricted during Cu2S formation at high RH. The leading speculation is that the extensive voiding that exists at grain boundaries in this material greatly reduces the flux of Cu between grains, leading to a reduction in the rate of sulfide film formation. These experiments provide an approach for adding microstructural information to Cu sulfidation rate computer models. In addition to the microstructural studies, new micro-patterned test structures were developed in this LDRD to offer insight into the point defect structure of Cu2S and to permit measurement of surface reaction

  14. Airborne sulfur trace species intercomparison campaign: Sulfur dioxide, dimethylsulfide, hydrogen sulfide, carbon disulfide, and carbonyl sulfide

    NASA Technical Reports Server (NTRS)

    Gregory, Gerald L.; Hoell, James M., Jr.; Davis, Douglas D.

    1991-01-01

    Results from an airborne intercomparison of techniques to measure tropospheric levels of sulfur trace gases are presented. The intercomparison was part of the NASA Global Tropospheric Experiment (GTE) and was conducted during the summer of 1989. The intercomparisons were conducted on the Wallops Electra aircraft during flights from Wallops Island, Virginia, and Natal, Brazil. Sulfur measurements intercompared included sulfur dioxide (SO2), dimethylsulfide (DMS), hydrogen sulfide (H2S), carbon disulfide (CS2), and carbonyl sulfide (OCS). Measurement techniques ranged from filter collection systems with post-flight analyses to mass spectrometer and gas chromatograph systems employing various methods for measuring and identifying the sulfur gases during flight. Sampling schedules for the techniques ranged from integrated collections over periods as long as 50 minutes to one- to three-minute samples every ten or fifteen minutes. Several of the techniques provided measurements of more than one sulfur gas. Instruments employing different detection principles were involved in each of the sulfur intercomparisons. Also included in the intercomparison measurement scenario were a host of supporting measurements (i.e., ozone, nitrogen oxides, carbon monoxide, total sulfur, aerosols, etc.) for purposes of: (1) interpreting results (i.e., correlation of any noted instrument disagreement with the chemical composition of the measurement environment); and (2) providing supporting chemical data to meet CITE-3 science objectives of studying ozone/sulfur photochemistry, diurnal cycles, etc. The results of the intercomparison study are briefly discussed.

  15. Hydrogen sulfide can inhibit and enhance oxygenic photosynthesis in a cyanobacterium from sulfidic springs.

    PubMed

    Klatt, Judith M; Haas, Sebastian; Yilmaz, Pelin; de Beer, Dirk; Polerecky, Lubos

    2015-09-01

    We used microsensors to investigate the combinatory effect of hydrogen sulfide (H2 S) and light on oxygenic photosynthesis in biofilms formed by a cyanobacterium from sulfidic springs. We found that photosynthesis was both positively and negatively affected by H2 S: (i) H2 S accelerated the recovery of photosynthesis after prolonged exposure to darkness and anoxia. We suggest that this is possibly due to regulatory effects of H2 S on photosystem I components and/or on the Calvin cycle. (ii) H2 S concentrations of up to 210 μM temporarily enhanced the photosynthetic rates at low irradiance. Modelling showed that this enhancement is plausibly based on changes in the light-harvesting efficiency. (iii) Above a certain light-dependent concentration threshold H2 S also acted as an inhibitor. Intriguingly, this inhibition was not instant but occurred only after a specific time interval that decreased with increasing light intensity. That photosynthesis is most sensitive to inhibition at high light intensities suggests that H2 S inactivates an intermediate of the oxygen evolving complex that accumulates with increasing light intensity. We discuss the implications of these three effects of H2 S in the context of cyanobacterial photosynthesis under conditions with diurnally fluctuating light and H2 S concentrations, such as those occurring in microbial mats and biofilms. PMID:25630511

  16. Chemical and colloidal aspects of collectorless flotation behavior of sulfide and non-sulfide minerals.

    PubMed

    Aghazadeh, Sajjad; Mousavinezhad, Seyed Kamal; Gharabaghi, Mahdi

    2015-11-01

    Flotation has been widely used for separation of valuable minerals from gangues based on their surface characterizations and differences in hydrophobicity on mineral surfaces. As hydrophobicity of minerals widely differs from each other, their separation by flotation will become easier. Collectors are chemical materials which are supposed to make selectively valuable minerals hydrophobic. In addition, there are some minerals which based on their surface and structural features are intrinsically hydrophobic. However, their hydrophobicities are not strong enough to be floatable in the flotation cell without collectors such as sulfide minerals, coal, stibnite, and so forth. To float these minerals in a flotation cell, their hydrophobicity should be increased in specific conditions. Various parameters including pH, Eh, size distribution, mill types, mineral types, ore characterization, and type of reaction in flotation cells affect the hydrophobicity of minerals. Surface analysis results show that when sulfide minerals experience specific flotation conditions, the reactions on the surface of these minerals increase the amount of sulfur on the surface. These phenomenons improve the hydrophobicity of these minerals due to strong hydrophobic feature of sulfurs. Collectorless flotation reduces chemical material consumption amount, increases flotation selectivity (grade increases), and affects the equipment quantities; however, it can also have negative effects. Some minerals with poor surface floatability can be increased by adding some ions to the flotation system. Depressing undesirable minerals in flotation is another application of collectorless flotation. PMID:26601925

  17. Carbonyl sulfide removal with compost and wood chip biofilters, and in the presence of hydrogen sulfide.

    PubMed

    Sattler, Melanie L; Garrepalli, Divya R; Nawal, Chandraprakash S

    2009-12-01

    Carbonyl sulfide (COS) is an odor-causing compound and hazardous air pollutant emitted frequently from wastewater treatment facilities and chemical and primary metals industries. This study examined the effectiveness of biofiltration in removing COS. Specific objectives were to compare COS removal efficiency for various biofilter media; to determine whether hydrogen sulfide (H2S), which is frequently produced along with COS under anaerobic conditions, adversely impacts COS removal; and to determine the maximum elimination capacity of COS for use in biofilter design. Three laboratory-scale polyvinyl chloride biofilter columns were filled with up to 28 in. of biofilter media (aged compost, fresh compost, wood chips, or a compost/wood chip mixture). Inlet COS ranged from 5 to 46 parts per million (ppm) (0.10-9.0 g/m3 hr). Compost and the compost/wood chip mixture produced higher COS removal efficiencies than wood chips alone. The compost and compost/wood chip mixture had a shorter stabilization times compared with wood chips alone. Fresh versus aged compost did not impact COS removal efficiency. The presence of H2S did not adversely impact COS removal for the concentration ratios tested. The maximum elimination capacity is at least 9 g/m3 hr for COS with compost media. PMID:20066911

  18. Atmospheric measurements of carbonyl sulfide, dimethyl sulfide, and carbon disulfide using the electron capture sulfur detector

    NASA Technical Reports Server (NTRS)

    Johnson, James E.; Bates, Timothy S.

    1993-01-01

    Measurements of atmospheric dimethyl sulfide (DMS), carbonyl sulfide (COS), and carbon disulfide (CS2) were conducted over the Atlantic Ocean on board the NASA Electra aircraft during the Chemical Instrumentation Test and Evaluation (CITE 3) project using the electron capture sulfur detector (ECD-S). The system employed cryogenic preconcentration of air samples, gas chromatographic separation, catalytic fluorination, and electron capture detection. Samples collected for DMS analysis were scrubbed of oxidants with NaOH impregnated glass fiber filters to preconcentration. The detection limits (DL) of the system for COS, DMS, and CS2 were 5, 5, and 2 ppt, respectively. COS concentrations ranged from 404 to 603 ppt with a mean of 489 ppt for measurements over the North Atlantic Ocean (31 deg N to 41 deg N), and from 395 to 437 ppt with a mean of 419 ppt for measurements over the Tropical Atlantic Ocean (11 deg S to 2 deg N). DMS concentrations in the lower marine boundary layer, below 600-m altitude, ranged from below DL to 150 ppt from flights over the North Atlantic, and from 9 to 104 ppt over the Tropical Atlantic. CS2 concentrations ranged from below DL to 29 ppt over the North Atlantic. Almost all CS2 measurements over the Tropical Atlantic were below DL.

  19. Selenium content of sulfide ores related to ophiolites of Greece.

    PubMed

    Economou-Eliopoulos, M; Eliopoulos, D G

    1998-01-01

    Several deposits of sulfide mineralization have been described in the ophiolites of Greece. Based on their mineralogical and chemical composition and the host rocks, two types can be distinguished: (1) the Fe-Cu-Ni-Co type consisting of pyrrhotite, chalcopyrite, Co-pentlandite, pyrite, magnetite + arsenides, +/- chromite, hosted in serpentinites, gabbros or diabases, which have variable geochemical characteristics, and (2) sulfide mineralization of the Cyprus type containing variable proportions of pyrite, chalcopyrite, bornite, and sphalerite. The spatial association with shear zones and fault systems, which is a common feature in both types of mineralization, provided the necessary permeability for the circulation of the responsible mineralized hydrothermal fluids. The selenium (Se) content in representative samples of both types of mineralization from the ophiolites of Pindos (Kondro, Perivoli, and Neropriona), Othrys (Eretria and A. Theodoroi), Veria (Trilofon), and Argolis (Ermioni) shows a wide variation. The highest values of Se (130 to 1900 ppm) were found in massive Fe-Cu sulfide ores from Kondro, in particular the Cu-rich portions (average 1300 ppm Se). The average values of Se for the Othrys sulfides are low (< 40 ppm Se). The Se content in a diabase breccia pipe (50 x 200 m) with disseminated pyrite mineralization (Neropriona) ranges from < 1 to 35 ppm Se. The highest values were noted in strongly altered samples that also exhibited a significant enrichment in platinum (1 ppm Pt). Sulfide mineralization (irregular to lens-like masses and stringers) associated with magnetite, hosted in gabbros exposed in the Perivoli area (Tsouma hill), shows a content ranging from 40 to 350 ppm Se. The distribution of Se in the studied type of the sulfide mineralization may be of genetic significance, indicating that the Se level, which often is much higher than in typical magmatic sulfides related to mafic-ultramafic rocks (average 90-100 ppm Se), may positively affect

  20. Hydrogen sulfide oxidation is coupled to oxidative phosphorylation in mitochondria of Solemya reidi

    SciTech Connect

    Powell, M.A.; Somero, G.N.

    1986-08-01

    Solemya reidi, a gutless clam found in sulfide-rich habitats, contains within its gills bacterial symbionts thought to oxidize sulfur compounds and provide a reduced carbon food source to the clam. However, the initial step or steps in sulfide oxidation occur in the animal tissue, and mitochondria isolated from both gill and symbiont-free foot tissue of the clam coupled the oxidation of sulfide to oxidative phosphorylation (adenosine triphosphate (ATP) synthesis). The ability of Solemya reidi to exploit directly the energy in sulfide for ATP synthesis is unprecedented, and suggests that sulfide-habitat animals that lack bacterial symbionts may also use sulfide as an inorganic energy source.

  1. Hydrogen Sulfide as an Oxygen Sensor

    PubMed Central

    2015-01-01

    Abstract Significance Although oxygen (O2)-sensing cells and tissues have been known for decades, the identity of the O2-sensing mechanism has remained elusive. Evidence is accumulating that O2-dependent metabolism of hydrogen sulfide (H2S) is this enigmatic O2 sensor. Recent Advances The elucidation of biochemical pathways involved in H2S synthesis and metabolism have shown that reciprocal H2S/O2 interactions have been inexorably linked throughout eukaryotic evolution; there are multiple foci by which O2 controls H2S inactivation, and the effects of H2S on downstream signaling events are consistent with those activated by hypoxia. H2S-mediated O2 sensing has been demonstrated in a variety of O2-sensing tissues in vertebrate cardiovascular and respiratory systems, including smooth muscle in systemic and respiratory blood vessels and airways, carotid body, adrenal medulla, and other peripheral as well as central chemoreceptors. Critical Issues Information is now needed on the intracellular location and stoichometry of these signaling processes and how and which downstream effectors are activated by H2S and its metabolites. Future Directions Development of specific inhibitors of H2S metabolism and effector activation as well as cellular organelle-targeted compounds that release H2S in a time- or environmentally controlled way will not only enhance our understanding of this signaling process but also provide direction for future therapeutic applications. Antioxid. Redox Signal. 22, 377–397. “Nothing in Biology Makes Sense Except in the Light of Evolution” —Theodosius Dobzhansky (29) PMID:24801248

  2. Hydrogen Sulfide in Biochemistry and Medicine

    PubMed Central

    Predmore, Benjamin Lee; Lefer, David Joseph

    2012-01-01

    Abstract Significance: An abundance of experimental evidence suggests that hydrogen sulfide (H2S) plays a prominent role in physiology and pathophysiology. Many targets exist for H2S therapy. The molecular targets of H2S include proteins, enzymes, transcription factors, and membrane ion channels. Recent Advances: Novel H2S precursors are being synthesized and discovered that are capable of releasing H2S in a slow and sustained manner. This presents a novel and advantageous approach to H2S therapy for treatment of chronic conditions associated with a decline in endogenous H2S, such as diabetes and cardiovascular disease. Critical Issues: While H2S is cytoprotective at physiological concentrations, it is not universally cytoprotective, as it appears to have pro-apoptotic actions in cancer cells and is well known to be toxic at supraphysiological concentrations. Many of the pleiotropic effects of H2S on health are associated with the inhibition of inflammation and upregulation of prosurvival pathways. The powerful anti-inflammatory, cytoprotective, immunomodulating, and trophic effects of H2S on the vast majority of normal cells seem to be mediated mainly by its actions as an extremely versatile direct and indirect antioxidant and free radical scavenger. While the overall effects of H2S on transformed (i.e., malignant) cells can be characterized as pro-oxidant and pro-apoptotic, they contrast sharply with the cytoprotective effects on most normal cells. Future Directions: H2S has become a molecule of great interest, and several slow-releasing H2S prodrugs are currently under development. We believe that additional agents regulating H2S bioavailability will be developed during the next 10 years. Antioxid. Redox Signal. 17, 119–140. PMID:22432697

  3. Dimethyl sulfide in the Amazon rain forest

    NASA Astrophysics Data System (ADS)

    Jardine, K.; Yañez-Serrano, A. M.; Williams, J.; Kunert, N.; Jardine, A.; Taylor, T.; Abrell, L.; Artaxo, P.; Guenther, A.; Hewitt, C. N.; House, E.; Florentino, A. P.; Manzi, A.; Higuchi, N.; Kesselmeier, J.; Behrendt, T.; Veres, P. R.; Derstroff, B.; Fuentes, J. D.; Martin, S. T.; Andreae, M. O.

    2015-01-01

    Surface-to-atmosphere emissions of dimethyl sulfide (DMS) may impact global climate through the formation of gaseous sulfuric acid, which can yield secondary sulfate aerosols and contribute to new particle formation. While oceans are generally considered the dominant sources of DMS, a shortage of ecosystem observations prevents an accurate analysis of terrestrial DMS sources. Using mass spectrometry, we quantified ambient DMS mixing ratios within and above a primary rainforest ecosystem in the central Amazon Basin in real-time (2010-2011) and at high vertical resolution (2013-2014). Elevated but highly variable DMS mixing ratios were observed within the canopy, showing clear evidence of a net ecosystem source to the atmosphere during both day and night in both the dry and wet seasons. Periods of high DMS mixing ratios lasting up to 8 h (up to 160 parts per trillion (ppt)) often occurred within the canopy and near the surface during many evenings and nights. Daytime gradients showed mixing ratios (up to 80 ppt) peaking near the top of the canopy as well as near the ground following a rain event. The spatial and temporal distribution of DMS suggests that ambient levels and their potential climatic impacts are dominated by local soil and plant emissions. A soil source was confirmed by measurements of DMS emission fluxes from Amazon soils as a function of temperature and soil moisture. Furthermore, light- and temperature-dependent DMS emissions were measured from seven tropical tree species. Our study has important implications for understanding terrestrial DMS sources and their role in coupled land-atmosphere climate feedbacks.

  4. Electrical properties of seafloor massive sulfides

    NASA Astrophysics Data System (ADS)

    Spagnoli, Giovanni; Hannington, Mark; Bairlein, Katharina; Hördt, Andreas; Jegen, Marion; Petersen, Sven; Laurila, Tea

    2016-06-01

    Seafloor massive sulfide (SMS) deposits are increasingly seen as important marine metal resources for the future. A growing number of industrialized nations are involved in the surveying and sampling of such deposits by drilling. Drill ships are expensive and their availability can be limited; seabed drill rigs are a cost-effective alternative and more suitable for obtaining cores for resource evaluation. In order to achieve the objectives of resource evaluations, details are required of the geological, mineralogical, and physical properties of the polymetallic deposits and their host rocks. Electrical properties of the deposits and their ore minerals are distinct from their unmineralized host rocks. Therefore, the use of electrical methods to detect SMS while drilling and recovering drill cores could decrease the costs and accelerate offshore operations by limiting the amount of drilling in unmineralized material. This paper presents new data regarding the electrical properties of SMS cores that can be used in that assessment. Frequency-dependent complex electrical resistivity in the frequency range between 0.002 and 100 Hz was examined in order to potentially discriminate between different types of fresh rocks, alteration and mineralization. Forty mini-cores of SMS and unmineralized host rocks were tested in the laboratory, originating from different tectonic settings such as the intermediate-spreading ridges of the Galapagos and Axial Seamount, and the Pacmanus back-arc basin. The results indicate that there is a clear potential to distinguish between mineralized and non-mineralized samples, with some evidence that even different types of mineralization can be discriminated. This could be achieved using resistivity magnitude alone with appropriate rig-mounted electrical sensors. Exploiting the frequency-dependent behavior of resistivity might amplify the differences and further improve the rock characterization.

  5. Electrical properties of seafloor massive sulfides

    NASA Astrophysics Data System (ADS)

    Spagnoli, Giovanni; Hannington, Mark; Bairlein, Katharina; Hördt, Andreas; Jegen, Marion; Petersen, Sven; Laurila, Tea

    2016-02-01

    Seafloor massive sulfide (SMS) deposits are increasingly seen as important marine metal resources for the future. A growing number of industrialized nations are involved in the surveying and sampling of such deposits by drilling. Drill ships are expensive and their availability can be limited; seabed drill rigs are a cost-effective alternative and more suitable for obtaining cores for resource evaluation. In order to achieve the objectives of resource evaluations, details are required of the geological, mineralogical, and physical properties of the polymetallic deposits and their host rocks. Electrical properties of the deposits and their ore minerals are distinct from their unmineralized host rocks. Therefore, the use of electrical methods to detect SMS while drilling and recovering drill cores could decrease the costs and accelerate offshore operations by limiting the amount of drilling in unmineralized material. This paper presents new data regarding the electrical properties of SMS cores that can be used in that assessment. Frequency-dependent complex electrical resistivity in the frequency range between 0.002 and 100 Hz was examined in order to potentially discriminate between different types of fresh rocks, alteration and mineralization. Forty mini-cores of SMS and unmineralized host rocks were tested in the laboratory, originating from different tectonic settings such as the intermediate-spreading ridges of the Galapagos and Axial Seamount, and the Pacmanus back-arc basin. The results indicate that there is a clear potential to distinguish between mineralized and non-mineralized samples, with some evidence that even different types of mineralization can be discriminated. This could be achieved using resistivity magnitude alone with appropriate rig-mounted electrical sensors. Exploiting the frequency-dependent behavior of resistivity might amplify the differences and further improve the rock characterization.

  6. Chemical dosing for sulfide control in Australia: An industry survey.

    PubMed

    Ganigue, Ramon; Gutierrez, Oriol; Rootsey, Ray; Yuan, Zhiguo

    2011-12-01

    Controlling sulfide (H(2)S) production and emission in sewer systems is critical due to the corrosion and malodour problems that sulfide causes. Chemical dosing is one of the most commonly used measures to mitigate these problems. Many chemicals have been reported to be effective for sulfide control, but the extent of success varies between chemicals and is also dependent on how they are applied. This industry survey aims to summarise the current practice in Australia with the view to assist the water industry to further improve their practices and to identify new research questions. Results showed that dosing is mainly undertaken in pressure mains. Magnesium hydroxide, sodium hydroxide and nitrate are the most commonly used chemicals for sewers with low flows. In comparison, iron salts are preferentially used for sulfide control in large systems. The use of oxygen injection has declined dramatically in the past few years. Chemical dosing is mainly conducted at wet wells and pumping stations, except for oxygen, which is injected into the pipe. The dosing rates are normally linked to the control mechanisms of the chemicals and the dosing locations, with constant or profiled dosing rates usually applied. Finally, key opportunities for improvement are the use of mathematical models for the selection of chemicals and dosing locations, on-line dynamic control of the dosing rates and the development of more cost-effective chemicals for sulfide control. PMID:22018528

  7. Synthesis of arsenic transition metal sulfides and metal arsenides

    SciTech Connect

    Singhal, G.H.; Brown, L.D.; Ryan, D.F.

    1993-12-31

    One of the chief problems in upgrading shale oil is the presence of inherent arsenic which is known to poison downstream catalysts. Highly dispersed transition metal sulfides formed in situ from the decomposition of dithiocarbamate (DTC) complexes of transition metals show excellent potential as dearsenation agents. The authors have studied the reaction of these sulfides with various arsenic compositions and characterized the metal arsenides and arsenic metal sulfides formed as well as the ease of their formation. Thus, the reaction of bis(butyldithiocarbamato)Ni, (NiBuDTC) with model compounds was very facile and gave NiAs, NiAsS, and NiAs2=xSx. In general the effectiveness of the sulfides for dearsenation followed the sequence Ni>Mo{much_gt}Co, while iron sulfides were totally ineffective. Based upon these results, tests were run in autoclaves (as well as a fixed-bed flow-through unit) with NiBuDTC and shale oil having 73 ppm inherent As. Under optimum conditions, dearsenation down to les than 1 ppm was obtained.

  8. Sulfide inclusion chemistry and carbon isotopes of African diamonds

    NASA Astrophysics Data System (ADS)

    Deines, Peter; Harris, J. W.

    1995-08-01

    Significant differences in the composition of sulfide mineral inclusions among diamond suites from Koffiefontein, Orapa, Premier, Roberts Victor, Jagersfontein, Sierra Leone, Star, and Mwadui have been found. The mode of the Ni content of the monosulfide (mss) inclusions lies between 8 and 10 wt%, i.e., between the means for mss from Siberian diamonds with inclusion of the eclogitic (3 wt% Ni) and peridotitic (23 wt% Ni) paragenesis. Considering the Ni/Fe ratios of the diamond mss inclusions and mantle olivines, together with experimental and naturally observed Ni/Fe distribution coefficients, we conclude that less than 20% of the mss inclusions of the African diamonds (mostly from Koffiefontein) could have been in chemical equilibrium with mantle olivine. This observation is in sharp contrast with the reported relative abundance of silicate inclusions in Koffiefontein diamonds (93% peridotitic, 7% eclogitic) and lends support to the proposal that a separate sulfide diamond paragenesis should be recognized. The δ 13C distributions of sulfide containing diamonds differs among kimberlites, however, for each kimberlite sulfide and silicate inclusion containing diamonds cover the same δ 13C range. Sulfides with high Ni concentrations can occur in diamonds of low as well as high 13C content. The current observations, in conjunction with other chemical properties of diamonds suggest that fluid reactions rather than silica melt equilibria may be important in diamond formation. A dominance of fluid processes would have significant implications for the interpretation of the chemical and geochronological record of diamond inclusions.

  9. Species-specific enzymatic tolerance of sulfide toxicity in plant roots.

    PubMed

    Martin, Nicole M; Maricle, Brian R

    2015-03-01

    Toxic effects of sulfide come from a poisoning of a number of enzymes, especially cytochrome c oxidase, which catalyzes the terminal step in mitochondrial aerobic respiration. Despite this, some estuarine plants live in sulfide-rich sediments. We hypothesized estuarine and flooding-tolerant species might be more tolerant of sulfide compared to upland species, and this was tested by measures of root cytochrome c oxidase and alcohol dehydrogenase activities in extracts exposed to sulfide. Enzyme activities were measured in 0, 5, 10, 15, and 20 μM sodium sulfide, and compared among 17 species of plants. Activities of alcohol dehydrogenase and cytochrome c oxidase were both reduced by increasing sulfide concentration, but cytochrome c oxidase was more sensitive to sulfide compared to alcohol dehydrogenase. Activities of cytochrome c oxidase were reduced to near zero at 5-10 μM sulfide whereas alcohol dehydrogenase activities were only reduced by about 50% at 10 μM sulfide. All species were sensitive to increasing sulfide, but to different degrees. Cytochrome c oxidase in flooding-sensitive species was decreased to near zero activity at 5 μM sulfide, whereas activities in some flooding-tolerant species were still detectable until 15 μM sulfide. Cytochrome c oxidase activities in some estuarine species were low even in the absence of sulfide, perhaps an adaptation to avoid sulfide vulnerability in their native, sulfide-rich habitat. This illustrates the potent metabolic effects of sulfide, and this is the first demonstration of varying sensitivities of cytochrome c oxidase to sulfide across organisms, making these data of novel importance. PMID:25635761

  10. Species-specific enzymatic tolerance of sulfide toxicity in plant roots

    PubMed Central

    Martin, Nicole M.; Maricle, Brian R.

    2015-01-01

    Toxic effects of sulfide come from a poisoning of a number of enzymes, especially cytochrome c oxidase, which catalyzes the terminal step in mitochondrial aerobic respiration. Despite this, some estuarine plants live in sulfide-rich sediments. We hypothesized estuarine and flooding-tolerant species might be more tolerant of sulfide compared to upland species, and this was tested by measures of root cytochrome c oxidase and alcohol dehydrogenase activities in extracts exposed to sulfide. Enzyme activities were measured in 0, 5, 10, 15, and 20 µM sodium sulfide, and compared among 17 species of plants. Activities of alcohol dehydrogenase and cytochrome c oxidase were both reduced by increasing sulfide concentration, but cytochrome c oxidase was more sensitive to sulfide compared to alcohol dehydrogenase. Activities of cytochrome c oxidase were reduced to near zero at 5 to 10 µM sulfide whereas alcohol dehydrogenase activities were only reduced by about 50% at 10 µM sulfide. All species were sensitive to increasing sulfide, but to different degrees. Cytochrome c oxidase in flooding-sensitive species was decreased to near zero activity at 5 µM sulfide, whereas activities in some flooding-tolerant species were still detectable until 15 µM sulfide. Cytochrome c oxidase activities in some estuarine species were low even in the absence of sulfide, perhaps an adaptation to avoid sulfide vulnerability in their native, sulfide-rich habitat. This illustrates the potent metabolic effects of sulfide, and this is the first demonstration of varying sensitivities of cytochrome c oxidase to sulfide across organisms, making these data of novel importance. PMID:25635761

  11. Metamorphism, graphite crystallinity, and sulfide anatexis of the Rampura-Agucha massive sulfide deposit, northwestern India

    NASA Astrophysics Data System (ADS)

    Mishra, Biswajit; Bernhardt, Heinz-Jurgen

    2009-02-01

    Located adjacent to the Banded Gneissic Complex, Rampura-Agucha is the only sulfide ore deposit discovered to date within the Precambrian basement gneisses of Rajasthan. The massive Zn-(Pb) sulfide orebody occurs within graphite-biotite-sillimanite schist along with garnet-biotite-sillimanite gneiss, calc-silicate gneisses, amphibolites, and garnet-bearing leucosomes. Plagioclase-hornblende thermometry in amphibolites yielded a peak metamorphic temperature of 720-780°C, whereas temperatures obtained from Fe-Mg exchange between garnet and biotite (580-610°C) in the pelites correspond to postpeak resetting. Thermodynamic considerations of pertinent silicate equilibria, coupled with sphalerite geobarometry, furnished part of a clockwise P- T- t path with peak P- T of ˜6.2 kbar and 780°C, attained during granulite grade metamorphism of the major Zn-rich stratiform sedimentary exhalative deposits orebody and its host rocks. Arsenopyrite composition in the metamorphosed ore yielded a temperature [and log f( S 2)] range of 352°C (-8.2) to 490°C (-4.64), thus indicating its retrograde nature. Contrary to earlier research on the retrogressed nature of graphite, Raman spectroscopic studies on graphite in the metamorphosed ore reveal variable degree of preservation of prograde graphite crystals (490 ± 43°C with a maximum at 593°C). The main orebody is mineralogically simple (sphalerite, pyrite, pyrrhotite, arsenopyrite, galena), deformed and metamorphosed while the Pb-Ag-rich sulfosalt-bearing veins and pods that are irregularly distributed within the hanging wall calc-silicate gneisses show no evidence of deformation and metamorphism. The sulfosalt minerals identified include freibergite, boulangerite, pyrargyrite, stephanite, diaphorite, Mn-jamesonite, Cu-free meneghinite, and semseyite; the last three are reported from Agucha for the first time. Stability relations of Cu-free meneghinite and semseyite in the Pb-Ag-rich ores constrain temperatures at >550°C and

  12. Metallorganic chemical vapor deposition and atomic layer deposition approaches for the growth of hafnium-based thin films from dialkylamide precursors for advanced CMOS gate stack applications

    NASA Astrophysics Data System (ADS)

    Consiglio, Steven P.

    To continue the rapid progress of the semiconductor industry as described by Moore's Law, the feasibility of new material systems for front end of the line (FEOL) process technologies needs to be investigated, since the currently employed polysilicon/SiO2-based transistor system is reaching its fundamental scaling limits. Revolutionary breakthroughs in complementary-metal-oxide-semiconductor (CMOS) technology were recently announced by Intel Corporation and International Business Machines Corporation (IBM), with both organizations revealing significant progress in the implementation of hafnium-based high-k dielectrics along with metal gates. This announcement was heralded by Gordon Moore as "...the biggest change in transistor technology since the introduction of polysilicon gate MOS transistors in the late 1960s." Accordingly, the study described herein focuses on the growth of Hf-based dielectrics and Hf-based metal gates using chemical vapor-based deposition methods, specifically metallorganic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD). A family of Hf source complexes that has received much attention recently due to their desirable properties for implementation in wafer scale manufacturing is the Hf dialkylamide precursors. These precursors are room temperature liquids and possess sufficient volatility and desirable decomposition characteristics for both MOCVD and ALD processing. Another benefit of using these sources is the existence of chemically compatible Si dialkylamide sources as co-precursors for use in Hf silicate growth. The first part of this study investigates properties of MOCVD-deposited HfO2 and HfSixOy using dimethylamido Hf and Si precursor sources using a customized MOCVD reactor. The second part of this study involves a study of wet and dry surface pre-treatments for ALD growth of HfO2 using tetrakis(ethylmethylamido)hafnium in a wafer scale manufacturing environment. The third part of this study is an investigation of

  13. Re-Os geochronology on sulfides from the Tudun Cu-Ni sulfide deposit, Eastern Tianshan, and its geological significance

    NASA Astrophysics Data System (ADS)

    Wang, Minfang; Wang, Wei; Gutzmer, Jens; Liu, Kun; Li, Chao; Michałak, Przemysław P.; Xia, Qinlin; Guo, Xiaonan

    2015-11-01

    The Tudun deposit is a medium-sized Cu-Ni sulfide deposit, located at the westernmost edge of the Huangshan-Jing'erquan Belt in the northern part of Eastern Tianshan, NW China. Sulfide separates including pentlandite, pyrrhotite and chalcopyrite from the Tudun deposit, contain Re, common Os and 187Os ranging from 40.46 to 201.2, 0.8048 to 6.246 and 0.1709 to 0.9977 ppb, respectively. They have very low 187Os/188Os ratios of 1.224-2.352. The sulfides yield a Re-Os isochron age of 270.0 ± 7.5 Ma (MSWD = 1.3), consistent within uncertainty with the SHRIMP zircon U-Pb age for the Tudun mafic intrusion (gabbro) of 280.0 ± 3.0 Ma. The calculated initial 187Os/188Os ratio is 0.533 ± 0.022, and γOs values range from 283 to 307, with a mean of 297, indicating significant crustal contamination of the parent melt prior to sulfide saturation. The Tudun deposit shares the same age and Re-Os isotopic compositions with other orthomagmatic Cu-Ni sulfide deposits in Huangshan-Jing'erquan Belt, suggesting that they have formed in Early Permian.

  14. Sulfidation of Silver Nanoparticles: Natural antidote to their toxicity

    PubMed Central

    Levard, Clément; Hotze, Ernest M.; Colman, Benjamin P.; Truong, Lisa; Yang, X. Y.; Bone, Audrey; Brown, Gordon E.; Tanguay, Robert L.; Di Giulio, Richard T.; Bernhardt, Emily S.; Meyer, Joel N.; Wiesner, Mark R.; Lowry, Gregory V.

    2014-01-01

    Nanomaterials are highly dynamic in biological and environmental media. A critical need for advancing environmental health and safety research for nanomaterials is to identify commonly occurring physical and chemical transformations affecting nanomaterial properties and toxicity. Silver nanoparticles, one of the most ecotoxic and well-studied nanomaterials, readily sulfidize in the environment. Here, we show that very low degrees of sulfidation (0.019 S/Ag mass ratio) universally and significantly decreases the toxicity of silver nanoparticles to four diverse types of aquatic and terrestrial eukaryotic organisms. Toxicity reduction is primarily associated with a decrease in Ag+ availability after sulfidation due to the lower solubility of Ag2S relative to elemental Ag (Ag(0)). We also show that chloride in exposure media determines silver nanoparticle toxicity by controlling the speciation of Ag. These results highlight the need to consider environmental transformation of NPs in assessing their toxicity to accurately portray their potential environmental risks. PMID:24180218

  15. Laser cleaning of sulfide scale on compressor impeller blade

    NASA Astrophysics Data System (ADS)

    Tang, Q. H.; Zhou, D.; Wang, Y. L.; Liu, G. F.

    2015-11-01

    Sulfide scale on the surface of a compressor impeller blade can considerably reduce the impeller performance and its service life. To prepare for subsequent remanufacturing, such as plasma spraying, it needs to be removed completely. In the corrosion process on an FV(520)B stainless steel, sulfide scale is divided into two layers because of different outward diffusion rates of Cr, Ni and Fe. In this paper, the cleaning threshold values of the upper and inner layers and the damage threshold value of the substrate were investigated using a pulsed fiber laser. To obtain experimental evidence, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and 3D surface profilometry were employed to investigate the two kinds of sulfide layers on specimens before, during, and after laser cleaning.

  16. Diverse sulfur metabolisms from two subterranean sulfidic spring systems.

    PubMed

    Rossmassler, Karen; Hanson, Thomas E; Campbell, Barbara J

    2016-08-01

    In sulfidic environments, microbes oxidize reduced sulfur compounds via several pathways. We used metagenomics to investigate sulfur metabolic pathways from microbial mat communities in two subterranean sulfidic streams in Lower Kane Cave, WY, USA and from Glenwood Hot Springs, CO, USA. Both unassembled and targeted recA gene assembly analyses revealed that these streams were dominated by Epsilonproteobacteria and Gammaproteobacteria, including groups related to Sulfurovum, Sulfurospirillum, Thiothrix and an epsilonproteobacterial group with no close cultured relatives. Genes encoding sulfide:quinone oxidoreductase (SQR) were abundant at all sites, but the specific SQR type and the taxonomic affiliation of each type differed between sites. The abundance of thiosulfate oxidation pathway genes (Sox) was not consistent between sites, although overall they were less abundant than SQR genes. Furthermore, the Sox pathway appeared to be incomplete in all samples. This work reveals both variations in sulfur metabolism within and between taxonomic groups found in these systems, and the presence of novel epsilonproteobacterial groups. PMID:27324397

  17. Altered Sulfide (H2S) Metabolism in Ethylmalonic Encephalopathy

    PubMed Central

    Tiranti, Valeria; Zeviani, Massimo

    2013-01-01

    Hydrogen sulfide (sulfide, H2S) is a colorless, water-soluble gas with a typical smell of rotten eggs. In the past, it has been investigated for its role as a potent toxic gas emanating from sewers and swamps or as a by-product of industrial processes. At high concentrations, H2S is a powerful inhibitor of cytochrome c oxidase; in trace amounts, it is an important signaling molecule, like nitric oxide (NO) and carbon monoxide (CO), together termed “gasotransmitters.” This review will cover the physiological role and the pathogenic effects of H2S, focusing on ethylmalonic encephalopathy, a human mitochondrial disorder caused by genetic abnormalities of sulfide metabolism. We will also discuss the options that are now conceivable for preventing genetically driven chronic H2S toxicity, taking into account that a complete understanding of the physiopathology of H2S has still to be achieved. PMID:23284046

  18. Froth flotation of oil-bearing metal sulfide wastes

    SciTech Connect

    Miller, R.L. ); Atwood, R.L.; Ye, Yi )

    1991-01-01

    An industrial wastewater, including plating wastes, is treated with sodium sulfide and ferrous sulfate to form a sulfide-oxide precipitate containing chromium and other toxic metals. Hydrocarbons, in the water, coat the sulfide-oxide particles, impeding metal recovery. Froth flotation, without reagent addition, was found to recover 93.9% of the solids from the sludge with simultaneous rejection of 89% of the water. Methyl isobutyl carbinol (MIBC) improved recovery and potassium amyl xanthate improved both recovery and grade. The process design has wastewater feed (without MIBC) to the rougher circuit. The rougher concentrate is conditioned with MIBC and fed to a cleaner circuit to achieve a high grade concentrate. About 95% of the water is recirculated to the waste treatment plant. 3 refs., 3 figs., 4 tabs.

  19. Froth flotation of oil-bearing metal sulfide wastes

    SciTech Connect

    Miller, R.L.; Atwood, R.L.; Ye, Yi

    1991-12-01

    An industrial wastewater, including plating wastes, is treated with sodium sulfide and ferrous sulfate to form a sulfide-oxide precipitate containing chromium and other toxic metals. Hydrocarbons, in the water, coat the sulfide-oxide particles, impeding metal recovery. Froth flotation, without reagent addition, was found to recover 93.9% of the solids from the sludge with simultaneous rejection of 89% of the water. Methyl isobutyl carbinol (MIBC) improved recovery and potassium amyl xanthate improved both recovery and grade. The process design has wastewater feed (without MIBC) to the rougher circuit. The rougher concentrate is conditioned with MIBC and fed to a cleaner circuit to achieve a high grade concentrate. About 95% of the water is recirculated to the waste treatment plant. 3 refs., 3 figs., 4 tabs.

  20. Thermoelectric properties of non-stoichiometric lanthanum sulfides

    NASA Technical Reports Server (NTRS)

    Shapiro, E.; Danielson, L. R.

    1983-01-01

    The lanthanum sulfides are promising candidate materials for high-efficiency thermoelectric applications at temperatures up to 1300 C. The non-stoichiometric lanthanum sulfides (LaS(x), where x is in the range 1.33-1.50) appear to possess the most favorable thermoelectric properties. The Seebeck coefficient and resistivity vary significantly with composition, so that an optimum value of alpha sq/rho (where alpha is the Seebeck coefficient and rho is the resistivity) can be chosen. The thermal conductivity remains approximately constant with stoichiometry, so a material with an optimum value of alpha sq/rho should possess the optimum figure-of-merit. Data for the Seebeck coefficient and electrical resistivity of non-stoichiometric lanthanum sulfides will be pressed, together with structural properties of these materials.

  1. Denitrifying sulfide removal process on high-salinity wastewaters.

    PubMed

    Liu, Chunshuang; Zhao, Chaocheng; Wang, Aijie; Guo, Yadong; Lee, Duu-Jong

    2015-08-01

    Denitrifying sulfide removal (DSR) process comprising both heterotrophic and autotrophic denitrifiers can simultaneously convert nitrate, sulfide, and acetate into nitrogen gas, elemental sulfur (S(0)), and carbon dioxide, respectively. Sulfide- and nitrate-laden wastewaters at 2-35 g/L NaCl were treated by DSR process. A C/N ratio of 3:1 was proposed to maintain high S(0) conversion rate. The granular sludge with a compact structure and smooth outer surface was formed. The microbial communities of DSR consortium via high-throughput sequencing method suggested that salinity shifts the predominating heterotrophic denitrifiers at <10 g/L NaCl to autotrophic denitrifiers at >10 g/L NaCl. PMID:25773977

  2. Understanding hydrogen sulfide storage: probing conditions for sulfide release from hydrodisulfides.

    PubMed

    Bailey, T Spencer; Zakharov, Lev N; Pluth, Michael D

    2014-07-30

    Hydrogen sulfide (H2S) is an important biological signaling agent that exerts action on numerous (patho)physiological processes. Once generated, H2S can be oxidized to generate reductant-labile sulfane sulfur pools, which include hydrodisulfides/persulfides. Despite the importance of hydrodisulfides in H2S storage and signaling, little is known about the physical properties or chemical reactivity of these compounds. We report here the synthesis, isolation, and characterization (NMR, IR, Raman, HRMS, X-ray) of a small-molecule hydrodisulfide and highlight its reactivity with reductants, nucleophiles, electrophiles, acids, and bases. Our experimental results establish that hydrodisulfides release H2S upon reduction and that deprotonation results in disproportionation to the parent thiol and S(0), thus providing a mechanism for transsulfuration in the sulfane sulfur pool. PMID:25010540

  3. The tropospheric oxidation of dimethyl sulfide: A new source of carbonyl sulfide

    NASA Astrophysics Data System (ADS)

    Barnes, I.; Becker, K. H.; Patroescu, I.

    1994-11-01

    In laboratory investigations of the gas-phase OH initiated oxidation of dimethyl sulfide (DMS: CH3SCH3) at room temperature the formation of SO2, dimethyl sulfoxide (DMSO: CH3SOCH3), and OCS have been observed. A yield of 0.7±0.2% S was measured for OCS. These new results represent a hitherto unknown and quite considerable in situ atmospheric source of OCS. Based on the global DMS source strength as given in the literature and provided that the results from the laboratory study are valid under atmospheric conditions we estimate a contribution in the range 0.10 to 0.28 Tg (OCS) yr-1 from the gas-phase atmospheric photooxidation of DMS to the global OCS budget.

  4. Mathematical model for microbial oxidation of pure lead sulfide by Thiobacillus ferrooxidans.

    PubMed

    Kargi, F

    1989-08-01

    A shrinking-core mathematical model describing bioleaching of lead sulfide is developed considering the deposition of insoluble bio-oxidation products on metal sulfide particle surfaces. Variations in particle size are considered as it affects diffusion limitations. PMID:18588129

  5. IRON SULFIDES IN THE ENVIRONMENT: FORMATION, FATE, AND SIGNIFICANCE TO CONTAMINANT BEHAVIOR

    EPA Science Inventory

    This seminar will cover aspects of the geochemistry of iron sulfides, their formation in sedimentary and aquifer environments, and their roles in sequestering and releasing contaminants. A special emphasis will be placed on the interactions between iron sulfides and arsenic.

  6. Thermodynamics of Complex Sulfide Inclusion Formation in Ca-Treated Al-Killed Structural Steel

    NASA Astrophysics Data System (ADS)

    Guo, Yin-tao; He, Sheng-ping; Chen, Gu-jun; Wang, Qian

    2016-08-01

    Controlling the morphology of the sulfide inclusion is of vital importance in enhancing the properties of structural steel. Long strip-shaped sulfides in hot-rolled steel can spherize when, instead of the inclusion of pure single-phase MnS, the guest is a complex sulfide, such as an oxide-sulfide duplex and a solid-solution sulfide particle. In this study, the inclusions in a commercial rolled structural steel were investigated. Spherical and elongated oxide-sulfide duplex as well as single-phase (Mn,Ca)S solid solution inclusions were observed in the steel. A thermodynamic equilibrium between the oxide and sulfide inclusions was proposed to understand the oxide-sulfide duplex inclusion formation. Based on the equilibrium solidification principle, thermodynamic discussions on inclusion precipitation during the solidification process were performed for both general and resulfurized structural steel. The predicted results of the present study agreed well with the experimental ones.

  7. Thermodynamics of Complex Sulfide Inclusion Formation in Ca-Treated Al-Killed Structural Steel

    NASA Astrophysics Data System (ADS)

    Guo, Yin-tao; He, Sheng-ping; Chen, Gu-jun; Wang, Qian

    2016-05-01

    Controlling the morphology of the sulfide inclusion is of vital importance in enhancing the properties of structural steel. Long strip-shaped sulfides in hot-rolled steel can spherize when, instead of the inclusion of pure single-phase MnS, the guest is a complex sulfide, such as an oxide-sulfide duplex and a solid-solution sulfide particle. In this study, the inclusions in a commercial rolled structural steel were investigated. Spherical and elongated oxide-sulfide duplex as well as single-phase (Mn,Ca)S solid solution inclusions were observed in the steel. A thermodynamic equilibrium between the oxide and sulfide inclusions was proposed to understand the oxide-sulfide duplex inclusion formation. Based on the equilibrium solidification principle, thermodynamic discussions on inclusion precipitation during the solidification process were performed for both general and resulfurized structural steel. The predicted results of the present study agreed well with the experimental ones.

  8. Morphology and thermal studies of zinc sulfide and cadmium sulfide nanoparticles in polyvinyl alcohol matrix

    NASA Astrophysics Data System (ADS)

    Osuntokun, Jejenija; Ajibade, Peter A.

    2016-09-01

    Zn(II) and Cd(II) metal complexes of 1-cyano-1-carboethoxyethylene-2,2-dithiolato-κS,S'-bis(N,N-dimethylthiourea-κS) have been synthesized and characterized with analytical and spectroscopic techniques. The complexes were thermolysed in hexadecylamine at 200 °C to prepare ZnS and CdS nanoparticles. The nanoparticles were characterized with scanning electron microscope (SEM), transmission electron microscope (TEM), and powder X-ray diffraction (p-XRD). TEM images showed spherically shaped nanoparticles, whose sizes are in the range 4.33-7.21 nm for ZnS and 4.95-7.7 nm CdS respectively and XRD confirmed cubic crystalline phases for the nanoparticles. The optical band gap energy evaluated from the absorption spectra are 2.88 eV (430 nm) and 2.81 eV (440 nm) for the ZnS and CdS nanoparticles respectively. The as-prepared metal sulfide nanoparticles were further incorporated into polyvinyl alcohol (PVA) to give ZnS/PVA and CdS/PVA composites. The polymer nanocomposites were studied to investigate their morphology and thermal properties relative to the pure PVA. XRD diffractions indicated that the crystalline phases of the nanoparticles and the sizes in PVA matrices remained unaltered. Infra-red spectra studies revealed interactions between the PVA and the metal sulfide nanoparticles and TGA studies show that the ZnS/PVA and CdS/PVA nanocomposites exhibit better thermal stability than the pure PVA.

  9. Application of Borehole SIP Technique to Sulfide Mineral Exploration

    NASA Astrophysics Data System (ADS)

    Kim, Changryol; Park, Mi Kyung; Park, Samgyu; Sung, Nak Hoon; Shin, Seung Wook

    2016-04-01

    In the study, SIP (Spectral Induced Polarization) well logging probe system was developed to rapidly locate the metal ore bodies with sulfide minerals in the boreholes. The newly developed SIP logging probe employed the non-polarizable electrodes, consisting of zinc chloride (ZnCl2), sodium chloride (NaCl), gypsum (CaSO4·2H2O), and water (H2O), instead of existing copper electrodes, leading to eliminating the EM coupling effect in the IP surveys as much as possible. In addition, the SIP logging system is designed to make measurements down to maximum 500 meters in depth in the boreholes. The SIP well logging was conducted to examine the applicability of the SIP probe system to the boreholes at the ore mine in Jecheon area, Korea. The boreholes used in the SIP logging are known to have penetrated the metal ore bodies with sulfide minerals from the drilling investigations. The ore mine of the study area is the scarn deposits surrounded by the limestone or lime-silicate rocks in Ordovician period. The results of the SIP well logging have shown that the borehole segments with limestone or lime-silicate rocks yielded the insignificant SIP responses while the borehole segments with sulfide minerals (e.g. pyrite) provided the significant phase shifts of the SIP responses. The borehole segments penetrating the metal ore body, so-called cupola, have shown very high response of the phase shift, due to the high contents of the sulfide mineral pyrite. The phase shifts of the SIP response could be used to estimate the grade of the ore bodies since the higher contents of the sulfide minerals, the higher magnitudes of the phase shifts in the SIP responses. It is, therefore, believed that the borehole SIP technique can be applied to investigate the metal ore bodies with sulfide minerals, and that could be used to estimate the ore grades as a supplementary tool in the future.

  10. Hydrogen evolution from water through metal sulfide reactions.

    PubMed

    Saha, Arjun; Raghavachari, Krishnan

    2013-11-28

    Transition metal sulfides play an important catalytic role in many chemical reactions. In this work, we have conducted a careful computational study of the structures, electronic states, and reactivity of metal sulfide cluster anions M2S(X)(-) (M = Mo and W, X = 4-6) using density functional theory. Detailed structural analysis shows that these metal sulfide anions have ground state isomers with two bridging sulfide bonds, notably different in some cases from the corresponding oxides with the same stoichiometry. The chemical reactivity of these metal sulfide anions with water has also been carried out. After a thorough search on the reactive potential energy surface, we propose several competitive, energetically favorable, reaction pathways that lead to the evolution of hydrogen. Selectivity in the initial water addition and subsequent hydrogen migration are found to be the key steps in all the proposed reaction channels. Initial adsorption of water is most favored involving a terminal metal sulfur bond in Mo2S4(-) isomers whereas the most preferred orientation for water addition involves a bridging metal sulfur bond in the case of W2S4(-) and M2S5(-) isomers. In all the lowest energy H2 elimination steps, the interacting hydrogen atoms involve a metal hydride and a metal hydroxide (or thiol) group. We have also observed a higher energy reaction channel where the interacting hydrogen atoms in the H2 elimination step involve a thiol (-SH) and a hydroxyl (-OH) group. For all the reaction pathways, the Mo sulfide reactions involve a higher barrier than the corresponding W analogues. We observe for both metals that reactions of M2S4(-) and M2S5(-) clusters with water to liberate H2 are exothermic and involve modest free energy barriers. However, the reaction of water with M2S6(-) is highly endothermic with a considerable barrier due to saturation of the local bonding environment. PMID:24289348

  11. Vegetation successfully prevents oxidization of sulfide minerals in mine tailings.

    PubMed

    Li, Yang; Sun, Qingye; Zhan, Jing; Yang, Yang; Wang, Dan

    2016-07-15

    The oxidization of metal sulfide in tailings causes acid mine drainage. However, it remains unclear whether vegetation prevents the oxidization of metal sulfides. The oxidization characteristics and microbial indices of the tailings in the presence of various plant species were investigated to explore the effects of vegetation on the oxidization of sulfide minerals in tailings. The pH, reducing sulfur, free iron oxides (Fed), chemical oxygen consumption (COC) and biological oxygen consumption (BOC) were measured. Key iron- and sulfur-oxidizing bacteria (Acidithiobacillus spp., Leptospirillum spp. and Thiobacillus spp.) were quantified using real-time PCR. The results indicate that vegetation growing on tailings can effectively prevent the oxidization of sulfide minerals in tailings. A higher pH and reducing-sulfur content and lower Fed were observed in the 0-30 cm depth interval in the presence of vegetation compared to bare tailings (BT). The COC gradually decreased with depth in all of the soil profiles; specifically, the COC rapidly decreased in the 10-20 cm interval in the presence of vegetation but gradually decreased in the BT profiles. Imperata cylindrica (IC) and Chrysopogon zizanoides (CZ) profiles contained the highest BOC in the 10-20 cm interval. The abundance of key iron- and sulfur-oxidizing bacteria in the vegetated tailings were significantly lower than in the BT; in particular, IC was associated with the lowest iron- and sulfur-oxidizing bacterial abundance. In conclusion, vegetation successfully prevented the oxidization of sulfide minerals in the tailings, and Imperata cylindrica is the most effective in reducing the number of iron- and sulfur-oxidizing bacteria and helped to prevent the oxidization of sulfide minerals in the long term. PMID:27093236

  12. Spectrometric characteristics of cadmium sulfide-based scintillators

    SciTech Connect

    Zdesenko, Y.G.; Nikolaiko, A.S.; Ryzhikov, V.D.; Silin, V.J.

    1985-11-01

    Results of measurements of the time and spectrometric characteristics of CdS(Te) scintillation crystals produced by advanced technology are presented. The possibility of using detectors based on cadmium sulfide for spectrometry of ionizing radiation at a temperature of 300/sup 0/K is shown. The energy resolution of the better specimens is 21% for the 622-keV /sup 137/Cs gamma line. Measurements made confirm the possibility of creating spectrometers based on CdS(Te) and allow it to be hoped that cadmium sulfide detectors can be produced that have the necessary parameters of studying /sup 116/Cd double beta decay.

  13. Non-hydrolytic Sol-gel Synthesis of Tin Sulfides

    NASA Astrophysics Data System (ADS)

    Kaur, Rajvinder

    The non-hydrolytic sol-gel (NHSG) process is an effective low temperature route well known for preparing homogeneous metal oxides. Thermodynamically as well as kinetically favored products, which cannot be prepared with the traditional solid-state routes, can be produced using NHSG. This project is focused on the exploration of NHSG synthesis of binary tin sulfides. In the past few years, metal sulfides have been the subject of significant interest. Much effort has been devoted to understand these materials because of their potential applications in electronic, optical, and superconductor devices.4 Among these materials, tin sulfides are materials of technological importance, which are being explored as semiconductors, anode materials for Li ion batteries, photoconductors, photocatalysts and absorber layer materials in photovoltaic solar cell devices. All of these applications depend upon features like homogeneity, oxidation state, high surface area and purity of the materials. These properties can be difficult to achieve by employing traditional synthetic routes, which require high temperatures due to slow diffusion, limiting the products to thermodynamically stable phases and prohibiting control over properties like particle size and surface area. A variety of low temperature methods are being explored due to the increased demand for such advanced materials. This project is focused on exploring the NHSG approach to synthesize binary tin sulfides, with the main goal of establishing conditions for the targeted synthesis of different tin sulfide polymorphs with controlled particle size. Being non-oxide materials, tin sulfides can be air sensitive, which requires special attention in handling. All reactions were carried out in absence of oxygen. This project explores the reaction of tin halides with thioethers in a dry solvent medium, leading to the formation of tin sulfides. There are a number of synthetic parameters that can be varied for the NHSG approach. A

  14. Radical cations of sulfides and disulfides: An ESR study

    SciTech Connect

    Bonazzola, L.; Michaut, J.P.; Roncin, J.

    1985-09-15

    Exposure of dilute solutions of dimethylsulfide, methanethiol, tetrahydrothiophene, terbutyl and diterbutyl-sulfides, dimethyl-disulfide, and diterbutyldisulfide, in freon at 77 K to /sup 60/Co ..gamma.. rays gave the corresponding cations. From the reported ESR spectra, g tensors were obtained. It was found that both sulfide and disulfide cations exhibit the same g tensor: (g/sub max/ = 2.034 +- 0.002, g/sub int/ = 2.017 +- 0.001, g/sub min/ = 2.001 +- 0.005). From this result it has been shown that the disulfide cation is planar. This finding was supported by fully optimized geometry ab initio calculations.

  15. Superconducting properties of evaporated copper molybdenum sulfide films

    NASA Technical Reports Server (NTRS)

    Woollam, J. A.; Chi, K. C.; Dillon, R. O.; Bunshah, R. F.; Alterovitz, S. A.

    1978-01-01

    Films of copper molybdenum sulfide were produced by coevaporation. Those that were superconducting contained only the ternary compound and free molybdenum. The range of copper content in the ternary compound was as large as that in polycrystalline material, that is, it includes either phase alone, or a mixture of the two phases of this material. This is in contrast with sputtered materials where copper concentration has been limited to a narrower range. The upper critical field and the critical current were measured as functions of external magnetic field, and found to be similar to those of sputtered copper molybdenum sulfide, when the comparison was made for samples having the same amount of copper.

  16. Hydrogen sulfide: physiological properties and therapeutic potential in ischaemia

    PubMed Central

    Bos, Eelke M; van Goor, Harry; Joles, Jaap A; Whiteman, Matthew; Leuvenink, Henri G D

    2015-01-01

    Hydrogen sulfide (H2S) has become a molecule of high interest in recent years, and it is now recognized as the third gasotransmitter in addition to nitric oxide and carbon monoxide. In this review, we discuss the recent literature on the physiology of endogenous and exogenous H2S, focusing upon the protective effects of hydrogen sulfide in models of hypoxia and ischaemia. Linked Articles This article is part of a themed section on Pharmacology of the Gasotransmitters. To view the other articles in this section visit http://dx.doi.org/10.1111/bph.2015.172.issue-6 PMID:25091411

  17. Accessible mixotrophic growth of denitrifying sulfide removal consortium.

    PubMed

    Juang, Ruey-Shin; Wong, Biing-Teo; Lee, Duu-Jong

    2015-06-01

    Nitrate, sulfide and organic matters in wastewaters can be removed simultaneously by denitrifying sulfide removal (DSR) process. Complicated interactions between different microbial groups in the DSR medium render the process design and control difficult to implement. A consortium with DSR activity was grown mixotrophically at varying concentrations of nitrate, acetate or ammonium. The kinetic diagram previously proposed was adopted to quantitatively represent DSR performance with accessible regimes of the diagram being identified. Example on the use of the so-yielded accessible regime was provided. PMID:25795451

  18. Method for direct production of carbon disulfide and hydrogen from hydrocarbons and hydrogen sulfide feedstock

    SciTech Connect

    Miao, Frank Q.; Erekson, Erek James

    1998-12-01

    A method for converting hydrocarbons and hydrogen sulfide to carbon disulfide and hydrogen is provided comprising contacting the hydrocarbons and hydrogen sulfide to a bi-functional catalyst residing in a controlled atmosphere for a time and at a temperature sufficient to produce carbon disulfide and hydrogen. Also provided is a catalyst for converting carbon sulfides and hydrogen sulfides to gasoline range hydrocarbons comprising a mixture containing a zeolite catalyst and a hydrogenating catalyst.

  19. Empirical equations to predict the sulfur content of mafic magmas at sulfide saturation and applications to magmatic sulfide deposits

    NASA Astrophysics Data System (ADS)

    Li, Chusi; Ripley, Edward M.

    2005-03-01

    Empirical equations to predict the sulfur content of a mafic magma at the time of sulfide saturation have been developed based on several sets of published experimental data. The S content at sulfide saturation (SCSS) can be expressed as: ln X_{text S} = 1.229 - 0.74(10^4/T) - 0.021(P) - 0.311 ln X_{{text{FeO}}} - 6.166X_{{text{SiO}}_{text{2}}} - 9.153X_{{text{Na}}_{text{2}} {text{O + K}}_{text{2}} {text{O}}} - 1.914X_{{text{MgO}}} + 6.594X_{{text{FeO}}} where T is in degrees Kelvin, X is mole fraction and P is in kbar. The squared multiple correlation coefficient ( r 2) for the equation is 0.88. Application of the equation to data from sulfide-saturated mid-ocean ridge basalts (MORB) samples show that the SCSS is closely predicted for primitive MORBs, but that accuracy decreases for lower T (<1,130°C) and more evolved MORB samples. This suggests that because the calibrations are based on anhydrous experimental runs done at temperatures of 1,200°C and above, it is not possible to extrapolate them to significantly lower temperatures and hydrous conditions. Because the SCSS of a primitive MORB magma increases with decreasing P, sulfide saturation in MORB appears to be a function of the degree of en route assimilation of S from country rocks as well as the degree of fractional crystallization in shallow staging chambers. Application of the equation to the high- T impact melt sheet that produced the Sudbury Igneous Complex and associated Ni-Cu sulfide ores indicates that sulfide-saturation was reached at 1,500°C, well above the start of orthopyroxene crystallization at 1,190°C. This would permit ample time for the gravitational settling and collection of immiscible sulfide liquid that produced the high-grade ore bodies. The development of a platinum group element (PGE)-enriched layer in the Sonju Lake Intrusion of the Duluth Complex is thought to be due to the attainment of sulfide saturation in the magma after a period of fractional crystallization. Using the

  20. Minimization of germanium penetration, nanocrystal formation, charge storage, and retention in a trilayer memory structure with silicon nitride/hafnium dioxide stack as the tunnel dielectric

    NASA Astrophysics Data System (ADS)

    Ng, T. H.; Chim, W. K.; Choi, W. K.; Ho, V.; Teo, L. W.; Du, A. Y.; Tung, C. H.

    2004-05-01

    Trilayer structures, consisting of a rapid thermal oxide (RTO) layer (2.5 or 5 nm thick) grown on silicon, a sputtered Ge middle layer (3-20 nm thick), and a 50-nm-thick sputtered silicon oxide capping layer, exhibit significant penetration of Ge atoms into the silicon substrate for devices with the smaller (2.5 nm) RTO thickness, resulting in negligible nanocrystal formation and hence no charge storage or memory effect. The Ge penetration is minimized by replacing the RTO layer with a high dielectric constant (high-κ) silicon nitride/hafnium dioxide stack (grown by metalorganic chemical vapor deposition) having a larger physical thickness but smaller equivalent oxide thickness of 1.9 nm. Results show that the high-κ trilayer structure exhibits better charge storage capability (in terms of a lower program voltage) and better charge retention performance as compared to the RTO trilayer structure.

  1. Effects of vacuum ultraviolet and ultraviolet irradiation on ultrathin hafnium-oxide dielectric layers on (100)Si as measured with electron-spin resonance

    SciTech Connect

    Ren, H.; Shohet, J. L.; Cheng, S. L.; Nishi, Y.

    2010-05-10

    The effects of vacuum ultraviolet (VUV) (7.2 eV) and UV (4.9 eV) irradiation on hafnium-oxide dielectric layers were studied with electron-spin resonance to detect defect states. Silicon dangling-bond defects (P{sub b} centers) and positively charged oxygen vacancies (E{sup '} centers) were detected with g-factor fitting. VUV irradiation increases the level of P{sub b} states, while UV decreases the level of P{sub b} states but increases the level of E{sup '} states significantly. Rapid thermal annealing appears to mitigate these effects. Absolute values of the defect-state concentrations are presented.

  2. Comparison of equivalent oxide thickness and electrical properties of atomic layer deposited hafnium zirconate dielectrics with thermal or decoupled plasma nitridation process

    NASA Astrophysics Data System (ADS)

    Chiang, Chen-Kuo; Wu, Chien-Hung; Liu, Chin-Chien; Lin, Jin-Fu; Yang, Chien-Lun; Wu, Jiun-Yuan; Wang, Shui-Jinn

    2012-10-01

    The NH3 thermal annealing and decoupled plasma nitridation (DPN) processes are compared for the equivalent oxide thickness (EOT) scaling of atomic-layer-deposited hafnium zirconate (HfZrO2) gate dielectric. Detailed physical, optical, and electrical characteristics of nitrided HfZrO2 (HfZrON) film are reported. It is found that DPN can yield a thinner SiOx interfacial layer (IL) (about 0.12 nm more in terms of EOT scaling) and a more densified HfZrO2 layer compared to those obtained using NH3 thermal annealing at a 16% nitrogen dose. NH3 thermal nitridation causes a large nitrogen distribution tail at the SiOx IL/Si substrate interface and increases leakage current, which suppresses EOT scalability.

  3. High-energy X-ray detection by hafnium-doped organic-inorganic hybrid scintillators prepared by sol-gel method

    SciTech Connect

    Sun, Yan; Koshimizu, Masanori Yahaba, Natsuna; Asai, Keisuke; Nishikido, Fumihiko; Kishimoto, Shunji; Haruki, Rie

    2014-04-28

    With the aim of enhancing the efficiency with which plastic scintillators detect high-energy X-rays, hafnium-doped organic-inorganic hybrid scintillators were fabricated via a sol-gel method. Transmission electron microscopy of sampled material reveals the presence of Hf{sub x}Si{sub 1−x}O{sub 2} nanoparticles, dispersed in a polymer matrix that constitutes the active material of the X-ray detector. With Hf{sub x}Si{sub 1−x}O{sub 2} nanoparticles incorporated in the polymer matrix, the absorption edge and the luminescence wavelength is shifted, which we attribute to Mie scattering. The detection efficiency for 67.4-keV X-rays in a 0.6-mm-thick piece of this material is two times better than the same thickness of a commercial plastic scintillator-NE142.

  4. Metallic sulfide additives for positive electrode material within a secondary electrochemical cell

    DOEpatents

    Walsh, William J.; McPheeters, Charles C.; Yao, Neng-ping; Koura, Kobuyuki

    1976-01-01

    An improved active material for use within the positive electrode of a secondary electrochemical cell includes a mixture of iron disulfide and a sulfide of a polyvalent metal. Various metal sulfides, particularly sulfides of cobalt, nickel, copper, cerium and manganese, are added in minor weight proportion in respect to iron disulfide for improving the electrode performance and reducing current collector requirements.

  5. Thermochemical hydrogen production via a cycle using barium and sulfur - Reaction between barium sulfide and water

    NASA Technical Reports Server (NTRS)

    Ota, K.; Conger, W. L.

    1977-01-01

    The reaction between barium sulfide and water, a reaction found in several sulfur based thermochemical cycles, was investigated kinetically at 653-866 C. Gaseous products were hydrogen and hydrogen sulfide. The rate determining step for hydrogen formation was a surface reaction between barium sulfide and water. An expression was derived for the rate of hydrogen formation.

  6. MEASURING METAL SULFIDE COMPLEXES IN OXIC RIVER WATERS WITH SQUARE WAVE VOLTAMMETRY. (R825395)

    EPA Science Inventory

    A sulfide identification protocol was developed to quantify specific metal
    sulfides that could exist in river water. Using a series of acid additions,
    nitrogen purges, and voltammetric analyses, metal sulfides were identified and
    semiquantified in three specific gr...

  7. H2S exposure elicits differential expression of candidate genes in fish adapted to sulfidic and non-sulfidic environments.

    PubMed

    Tobler, Michael; Henpita, Chathurika; Bassett, Brandon; Kelley, Joanna L; Shaw, Jennifer H

    2014-09-01

    Disentangling the effects of plasticity, genetic variation, and their interactions on organismal responses to environmental stressors is a key objective in ecological physiology. We quantified the expression of five candidate genes in response to hydrogen sulfide (H2S) exposure in fish (Poecilia mexicana, Poeciliidae) from a naturally sulfide-rich environment as well as an ancestral, non-sulfidic population to test for constitutive and environmentally dependent population differences in gene expression patterns. Common garden raised individuals that had never encountered environmental H2S during their lifetime were subjected to short or long term H2S exposure treatments or respective non-sulfidic controls. The expression of genes involved in responses to H2S toxicity (cytochrome c oxidase, vascular endothelial growth factor, and cytochrome P450-2J6), H2S detoxification (sulfide:quinone oxidoreductase), and endogenous H2S production (cystathionine γ lyase) was determined in both gill and liver tissues by real time PCR. The results indicated complex changes in expression patterns that--depending on the gene--not only differed between organs and populations, but also on the type of H2S exposure. Populations differences, both constitutive and H2S exposure dependent (i.e., plastic), in gene expression were particularly evident for sulfide:quinone oxidoreductase, vascular endothelial growth factor, and to a lesser degree for cytochrome P450-2J6. Our study uncovered putatively adaptive modifications in gene regulation that parallel previously documented adaptive changes in phenotypic traits. PMID:24813672

  8. S/Se In Sulfide Inclusion In Diamond

    NASA Astrophysics Data System (ADS)

    Thomassot, E.; Couffignal, F.; Lorand, J.; Bureau, H.; Cartigny, P.; Harris, J. W.

    2009-05-01

    Sulfides are among the most common minerals found as inclusions in diamonds. Being protected from any alteration after diamond formation, they likely represent the most pristine sulfide sample of mantle rocks. Their chemical composition in major and minor elements (mainly Ni, Cu and Cr), as determined using Electron Probe Micro Analyse (EPMA), is commonly used to determine the rock type in which the diamond formed. Here we propose to apply the same technique to the trace element abundance determination. We performed selenium (Se) on sulfide inclusion in diamonds. The S/Se value could help understanding whether the diamond formed in an eclogitic or peridotitic environment and may also constrain on the magmatic differentiation of diamonds host rock as well as provide a potential surface (hydrothermal) signature in diamond inclusions. A trace element measurement scheme has been developed by EPMA at the CAMPARIS centre (Paris). Se-abundance was obtained using a 30 kV accelerating voltage and 100nA probe current. Total counting time was 800s for peak (1.1 Å ) and 400s for background on both side of peak. Analyses were duplicated by μPIXE using the LPS nuclear microprobe facility (SIS2M CEA Saclay, France). Maps from 30x30 μm2 to 70x70 μm2 were obtained by scanning a 4x4 μm2 proton beam of 3MeV, 600 pA, (0.4 to 2 μC). The two techniques show good agreement and we conclude that EPMA is well suited for accurate and precise Se measurements. We analysed five samples; two monosulfide solid solution (MSS) (Ni>22wt%) typical of the peridotitic paragenesis (P-type), and three Ni-poor sulfides (Ni<7wt%) typical of the eclogitic paragenesis (E-type). In P-type sulfides, Se-content (260 ppm) is significantly higher than previously reported in sulfides from mantle-derived lherzolites (40-160 ppm), pyroxenites (25-45 ppm) or harzburgite. The value of S/Se in MSS is low (˜1400) compared to those of the primitive mantle reservoir (3,300; McDounough et al., 1995 Chemical Geology

  9. Removing hydrogen sulfide from geothermal gases: hypochlorite process reduces hydrogen sulfide emissions to acceptable levels. NTIS tech note

    SciTech Connect

    Not Available

    1981-10-01

    This citation summarizes a one-page announcement of technology available for utilization. A hypochlorite process has been proposed as an alternative to other methods for the removal of hydrogen sulfide from the exhaust gases of geothermal powerplants. An electrolytically-generated sodium hypochlorite solution converts the hydrogen sulfide to water, salt, and sulfur. The hypochlorite process appears to be less expensive than competing processes for most of the cases studied. ...FOR ADDITIONAL INFORMATION: Detailed information about the technology described may be obtained by ordering the NTIS report, order number: DOE/ER/1092-T7, price code: PC A03.

  10. Redox sensitivity of P cycling during marine black shale formation: Dynamics of sulfidic and anoxic, non-sulfidic bottom waters

    NASA Astrophysics Data System (ADS)

    März, C.; Poulton, S. W.; Beckmann, B.; Küster, K.; Wagner, T.; Kasten, S.

    2009-04-01

    A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (about 15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After around 15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H2S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for about 90-100 ka, followed by another period of

  11. Redox sensitivity of P cycling during marine black shale formation: Dynamics of sulfidic and anoxic, non-sulfidic bottom waters

    NASA Astrophysics Data System (ADS)

    März, C.; Poulton, S. W.; Beckmann, B.; Küster, K.; Wagner, T.; Kasten, S.

    2008-08-01

    A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (˜15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After ˜15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H 2S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for ˜90-100 ka, followed by another period of anoxic, non-sulfidic

  12. Dynamics of Withdrawal and Backflow of Sulfide Liquids and the Formation of Magmatic Ni-Cu-PGE Sulfide Deposits: Theory and Analogue Modeling

    NASA Astrophysics Data System (ADS)

    Saumur, B. M.; Cruden, A. R.

    2012-12-01

    Sulfide liquids precipitated from silicate magmas after sulfide saturation represent a volumetrically small portion of magmatic systems, but are responsible for the formation of orthomagmatic Ni-Cu-PGE sulfide deposits. Compared to silicate melts, immiscible magmatic sulfide liquids have lower viscosities (by 1 to 3 orders of magnitude), higher densities ( >1500 kg/m3 higher; also significantly higher than surrounding crust) and lower solidus temperatures (>150°C lower). These properties hinder the withdrawal of sulfide liquid from magma staging chambers and its ascent to higher structural levels, and allow for late-stage mobility and downward percolation along grain boundaries and fractures within wall rocks. Prior to emplacement towards higher crustal levels, sulfide liquid will have a tendency to accumulate and pond at the bottom of staging chambers. Later mobilization and upward or lateral withdrawal of sulfide can occur by viscous entrainment within relatively buoyant (mafic) magma. Analytical solutions (e.g., Blake and Ivey, 1986, JVGR, 27, 153-178) applied to the low viscosities, high densities and the likely relatively high volumetric flow rates (Q) in mafic melt-sulfide liquid systems predicts that significant draw-up of sulfide liquid within mafic magmas can occur at high, yet realistic flow rates (10-1000 m3/s), at reasonable Reynolds (>1000) and Weber numbers (0.07-700). At lower Q and Re draw up is hindered by interfacial tension, as indicated by the low capillary numbers of the system. We evaluate the dynamics of withdrawal and entrainment of sulfide liquid using analogue models scaled to mafic-sulfide system, focusing on flow rates and the viscosity and density ratios between sulfide and mafic magmas, in order to further explore the conditions under which sulfide liquids can be effectively entrained to promote the generation of deposits elsewhere in the magma system. The dynamics of sulfide percolation are analogous to the behavior of dense non

  13. Operational overview of the NASA GTE/CITE 3 airborne instrument intercomparisons for sulfur dioxide, hydrogen sulfide, carbonyl sulfide, dimethyl sulfide, and carbon disulfide

    NASA Technical Reports Server (NTRS)

    Hoell, James M., Jr.; Davis, Douglas D.; Gregory, Gerald L.; Mcneal, Robert J.; Bendura, Richard J.; Drewry, Joseph W.; Barrick, John D.; Kirchhoff, Volker W. J. H.; Motta, Adauto G.; Navarro, Roger L.

    1993-01-01

    This paper reports the overall experimental design and gives a brief overview of results from the third airborne Chemical Instrumentation Test and Evaluation (CITE 3) mission conducted as part of the National Aeronautics and Space Administration's Global Tropospheric Experiment. The primary objective of CITE 3 was to evaluate the capability of instrumentation for airborne measurements of ambient concentrations of SO2, H2S, CS, dimethyl sulfide, and carbonyl sulfide. Ancillary measurements augmented the intercomparison data in order to address the secondary objective of CITE 3 which was to address specific issues related to the budget and photochemistry of tropospheric sulfur species. The CITE 3 mission was conducted on NASA's Wallops Flight Center Electra aircraft and included a ground-based intercomparison of sulfur standards and intercomparison/sulfur science flights conducted from the NASA Wallops Flight Facility, Wallops Island, Virginia, followed by flights from Natal, Brazil. Including the transit flights, CITE 3 included 16 flights encompassing approximately 96 flight hours.

  14. PRODUCTION OF HAFNIUM METAL

    DOEpatents

    Elger, G.W.; Boubel, R.W.

    1963-01-01

    This patent deals with a process of producing pure Hf metal from oxygen- contaminated gaseous Hf chloride. The oxygen compounds in the chioride gas are halogenated by contacting the gas at elevated temperature with Cl/sub 2/ in the presence of C. The Hf chloride, still in gaseous form, is contacted with molten Mg whereby Hf metal is formed and condensed on the Mg. (AEC)

  15. The influence of hydrogen sulfide-to-hydrogen partial pressure ratio on the sulfidization of Pd and 70 mol% Pd–Cu membranes

    SciTech Connect

    Iyoha, O.; Enick, R.M.; Killmeyer, R.P.; Morreale, B.

    2007-11-15

    The influence of H2S-to-H2 partial pressure ratio on the sulfidization of Pd and 70 mol% Pd–Cu membrane alloys was studied using various H2Scontaining gas mixtures. The Pd membranes exposed to various H2S mixtures were in very good agreement with the thermodynamic calculations used in this study, resisting sulfidization when exposed to H2S-to-H2 ratios below the equilibrium value predicted for Pd4S formation, and experiencing sulfidization when exposed to ratios above the equilibrium values. The 70 mol% Pd–Cu membranes, however, exhibited deviations from the predicted values, resisting sulfidization at some conditions close to the equilibrium values at which sulfidization was expected, and experiencing sulfidization at some conditions at which resistance was expected. This phenomenon was attributed to deviations of the Pd–Cu alloy from ideality, probably due to Cu segregation at the membrane surface.

  16. The influence of hydrogen sulfide-to-hydrogen partial pressure ratio on the sulfidization of Pd and 70 mol% Pd-Cu membranes

    SciTech Connect

    Iyoha, O.; Enick, R.M.; Killmeyer, R.P.; Morreale, B.D.

    2007-11-15

    The influence of H2S-to-H2 partial pressure ratio on the sulfidization of Pd and 70 mol% Pd–Cu membrane alloys was studied using various H2S-containing gas mixtures. The Pd membranes exposed to various H2S mixtures were in very good agreement with the thermodynamic calculations used in this study, resisting sulfidization when exposed to H2S-to-H2 ratios below the equilibrium value predicted for Pd4S formation, and experiencing sulfidization when exposed to ratios above the equilibrium values. The 70 mol% Pd–Cu membranes, however, exhibited deviations from the predicted values, resisting sulfidization at some conditions close to the equilibrium values at which sulfidization was expected, and experiencing sulfidization at some conditions at which resistance was expected. This phenomenon was attributed to deviations of the Pd–Cu alloy from ideality, probably due to Cu segregation at the membrane surface.

  17. Hydrotreating catalysts comprising a mixture of a sulfide of a promoter metal, amorphous sulfide of trivalent chromium and microcrystalline molybdenum or tungsten sulfide

    SciTech Connect

    Jacobson, A.J.; Ho, T.C.; Chianelli, R.R.; Steger, J.J.; Montagna, A.A.

    1989-04-25

    A process is described for preparing a catalyst comprising a mixture of (i) an amorphous sulfide of trivalent chromium, (ii) microcrystallites of a metal sulfide of a metal selected from the group consisting of Mo, W, and mixtures thereof, and (iii) a sulfide of at least one promoter metal selected from the group consisting of Ni, Co, Mn, Zn, Cu, mixtures thereof and mixtures thereof with Fe, the process comprising heating a precursor at a temperature of at least about 200/sup 0/C., in the presence of sulfur and under oxygen free conditions for a time sufficient to form the catalyst. The precursor comprises a mixture of (i) a hydrated oxide of trivalent chromium and (ii) a thiometallate salt of the general formula (ML)(Mo/sub y/W/sub 1-y/S/sub 4/) wherein M is one or more of the divalent promoter metals selected from the group consisting of Ni, Co, Mn, Zn, Cu, mixtures thereof and mixtures thereof with Fe, wherein Y is any value ranging from 0 to 1, L is one or more neutral, nitrogen-containing ligands, at least one of which is a chelating polydentate ligand.

  18. DIETARY SUBACUTE TOXICITY OF ETHYLENEBISISOTHIOCYANATE SULFIDE IN THE LABORATORY RAT

    EPA Science Inventory

    Ethylenebisisothiocyanate sulfide (EBIS) was fed to groups of rats at 0, 1, 10, 100, and 1000 ppm for up to 90 days. Only those rats receiving EBIS at 1000 ppm demonstrated a toxic response to the test chemical reflected as a reversible paralysis of the hind legs noted within 8 t...

  19. NATURAL ATTENUATION OF INORGANICS DURING METAL SULFIDE FORMATION

    EPA Science Inventory

    Three different types of experiments will be carried out to investigate metal uptake during iron sulfide formation. These experimental designs were developed to examine the effects of the reactive iron source, and the extent to which nucleation and growth processes influence met...

  20. Synthesis and characterization of sulfide modified vegetable oils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Butanethiol was used in ultraviolet-initiated thiol-ene reaction with canola and corn oils to produce sulfide-modified vegetable oils (SMVO). The crude SMVO product was successfully purified by solvent extraction, vacuum evaporation, and silica gel chromatography. The SMVO products were characterize...

  1. Transformation of two chlorinated fumigants by hydrogen sulfide species

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The chlorinated fumigants chloropicrin and 1,3-dichloropropene (1,3-D) are extensively used to control soilborne pests. Transformation of these two pesticides by hydrogen sulfide species (H2S and HS-) was examined in well-defined anoxic aqueous solutions. Chloropicrin underwent an extremely rapid re...

  2. Solution processed silver sulfide thin films for filament memory applications

    NASA Astrophysics Data System (ADS)

    Yin, Shong

    Filament Memories based on resistive switching have been attracting attention in recent years as a potential replacement for flash memory in CMOS technology and as a potential candidate memory for low-cost, large-area electronics. These memories operate at low voltages with fast switching speeds. These devices are based on ionic conduction through an electrolyte layer and differ fundamentally in operation from conventional flash memory, which is based on the field effect transistor. To facilitate development of this technology, effects of film structure on ionic and electronic conducting properties and the filament formation processes must be studied. In this work, silver sulfide, a mixed ionic-electronic conductor, is used as a model material for studying the solution processing of filament memories, and to study the impact of film structure on conducting and switching properties. Three different solution processing methods are investigated for depositing silver sulfide: sulfidation of elemental silver films, and sintering of two types of silver sulfide nanoparticles. Effects of nanoparticle sintering conditions on electrolyte structured and mixed conducting properties are investigated by a combination of X-ray diffraction, electrical impedance spectroscopy and thermo-gravimetric analysis. Impact of forming voltage and time on filament morphology is examined to provide an overall view of the impact of electrical and material parameters on device operation.

  3. Estimation of bacterial hydrogen sulfide production in vitro.

    PubMed

    Basic, Amina; Blomqvist, Susanne; Carlén, Anette; Dahlén, Gunnar

    2015-01-01

    Oral bacterial hydrogen sulfide (H2S) production was estimated comparing two different colorimetric methods in microtiter plate format. High H2S production was seen for Fusobacterium spp., Treponema denticola, and Prevotella tannerae, associated with periodontal disease. The production differed between the methods indicating that H2S production may follow different pathways. PMID:26130377

  4. Crystallinity of Fe-Ni Sulfides in Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Zolensky, Michael E.; Ohsumi, Kazumasa; Mikouchi, Takashi; Hagiya, Kenji; Le, Loan

    2008-01-01

    The main long-term goal of this research is to understand the physical conditions in the early solar nebula through the detailed characterization of a key class of mineral present in all primitive materials: Fe-Ni sulfides [1&2]. Fe-Ni sulfides can take dozens of structures, depending on the temperature of formation, as well as other physico-chemical factors which are imperfectly understood. Add to this the additional varying factor of Ni content, and we have a potentially sensitive cosmothermometer [3]. Unfortunately, this tool requires exact knowledge of the crystal structure of each grain being considered, and there have been few (none?) studies of the detailed structures of sulfides in chondritic materials. We report here on coordinated compositional and crystallographic investigation of Fe-Ni sulfides in diverse carbonaceous chondrites, initially Acfer 094 (the most primitive CM2 [4]) Tagish Lake (a unique type C2 [5]), a C1 lithology in Kaidun [6], Bali (oxidized CV3 [7]), and Efremovka (reduced CV3 [7]).

  5. PRESERVATION OF SULFIDIC WATERS CONTAINING DISSOLVED AS (III)

    EPA Science Inventory

    Field samples for arsenic analyses are commonly preserved by acidification with hydrochloric or nitric acid. In some suboxic samples, appreciable concentrations of H2S and HS- are observed due to the microbial respiration of sulfate-reducing bacteria. If both As(III) and sulfid...

  6. Alternatives to Sulfide Dehairing: Use of Oxidative Agents

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The dehairing of cattle hides with sodium sulfate generates large quantities of waste that are of environmental concern as they have a large biological and chemical oxygen demand. Additionally, sodium sulfide is a potential workplace hazard. We had worked with industry to develop a rapid dehairing...

  7. CARBONYL SULFIDE INHALATION PRODUCES BRAIN LESIONS IN F344 RATS.

    EPA Science Inventory

    Carbonyl sulfide (COS) is an intermediate in the production of pesticides and herbicides, and is a metabolite of the neurotoxicant carbon disulfide. The potential neurotoxicity of inhaled COS was investigated in F344 rats. Male rats were exposed to 0, 75, 150, 300, or 600 ppm COS...

  8. Carbon-supported and alumina-supported niobium sulfide catalysts

    SciTech Connect

    Allali, N.; Marie, A.M.; Danot, M.

    1995-10-01

    Few studies deal with the properties of niobium sulfide as a hydrodesulfurization catalyst. In this paper, the preparation of carbon-supported niobium sulfide catalysts was optimized concerning (i) the nature of the soluble precursor, (ii) the drying process, and (iii) the sulfurizing treatment, which was always performed under atmospheric pressure but for different H{sub 2}S-based flows and reaction temperatures. The activities of the best samples prepared with niobium oxalate as the impregnation salt, drying at room temperature, and presulfurization with N{sub 2}/H{sub 2}S at 400{degrees}C are superior to that of a supported MoS{sub 2} reference catalyst. Alumina-supported systems can be sulfurized only under more severe conditions (CS{sub 2} under pressure). After optimization of the sulfurization treatment (400{degrees}C, 10 h) the maximum activity obtained is significantly higher than that of a molybdenum sulfide reference catalyst. The catalytic activities of the various catalysts studied are related to their morphological and chemical characteristics using TPR and EXAFS measurements. The work illustrates the importance of the support and the sulfurization method on the genesis of a niobium sulfide active phase. 37 refs., 7 figs., 4 tabs.

  9. Impact of Iron Sulfide Transformation on Trichloroethylene Degradation

    EPA Science Inventory

    Trichloroethylene (TCE) is one of the most common and persistent groundwater contaminants encountered at hazardous waste sites around the world. A growing body of evidence indicates that iron sulfides play an important role in degrading TCE in natural environments and in enginee...

  10. Micelle Mediated Trace Level Sulfide Quantification through Cloud Point Extraction

    PubMed Central

    Devaramani, Samrat; Malingappa, Pandurangappa

    2012-01-01

    A simple cloud point extraction protocol has been proposed for the quantification of sulfide at trace level. The method is based on the reduction of iron (III) to iron (II) by the sulfide and the subsequent complexation of metal ion with nitroso-R salt in alkaline medium. The resulting green-colored complex was extracted through cloud point formation using cationic surfactant, that is, cetylpyridinium chloride, and the obtained surfactant phase was homogenized by ethanol before its absorbance measurement at 710 nm. The reaction variables like metal ion, ligand, surfactant concentration, and medium pH on the cloud point extraction of the metal-ligand complex have been optimized. The interference effect of the common anions and cations was studied. The proposed method has been successfully applied to quantify the trace level sulfide in the leachate samples of the landfill and water samples from bore wells and ponds. The validity of the proposed method has been studied by spiking the samples with known quantities of sulfide as well as comparing with the results obtained by the standard method. PMID:22619597

  11. TREATMENT OF METAL FINISHING WASTES BY USE OF FERROUS SULFIDE

    EPA Science Inventory

    This demonstration was performed to study the operation, performance and economics of a new sulfide precipitation process ('Sulfex'TN), for treating metal finishing wastewaters. The study was performed by Holley Carburetor Division of Colt Industries, with assistance from the Per...

  12. Estimation of bacterial hydrogen sulfide production in vitro

    PubMed Central

    Basic, Amina; Blomqvist, Susanne; Carlén, Anette; Dahlén, Gunnar

    2015-01-01

    Oral bacterial hydrogen sulfide (H2S) production was estimated comparing two different colorimetric methods in microtiter plate format. High H2S production was seen for Fusobacterium spp., Treponema denticola, and Prevotella tannerae, associated with periodontal disease. The production differed between the methods indicating that H2S production may follow different pathways. PMID:26130377

  13. Synthesis and photovoltaic application of coper (I) sulfide nanocrystals

    SciTech Connect

    Wu, Yue; Wadia, Cyrus; Ma, Wanli; Sadtler, Bryce; Alivisatos, A.Paul

    2008-06-24

    We present the rational synthesis of colloidal copper(I) sulfide nanocrystals and demonstrate their application as an active light absorbing component in combination with CdS nanorods to make a solution-processed solar cell with 1.6percent power conversion efficiency on both conventional glass substrates and flexible plastic substrates with stability over a 4 month testing period.

  14. Removal of sulfide, sulfate and sulfite ions by electro coagulation.

    PubMed

    Murugananthan, M; Raju, G Bhaskar; Prabhakar, S

    2004-06-18

    The removal of various species of sulfur from beamhouse of tannery wastewater and also from synthetic samples was studied by electro-flotation technique. Consumable anodes of iron and aluminum and insoluble anode of titanium were tested as anodes. It was found that iron and aluminum anodes were effective for the removal of suspended solids, sulfide, sulfite and sulfate. Progress of simultaneous coagulation of suspended solids during electro-flotation was measured using particle size analysis. Coagulation was found to be essential for effective flotation of suspended solids. Metal ions generated in situ by electrolytic oxidation of anode were found to react with dissolved sulfide ions. Metal sulfides thus formed as colloidal suspension were coagulated and floated simultaneously by hydrogen bubbles generated from cathode. Simultaneous occurrence of precipitation, coagulation and flotation was observed during electro-flotation. X-ray diffraction studies were conducted to identify the nature of sulfide phase formed during electrolytic precipitation. The effect of pH, current density and initial concentration of pollutants was studied and the results are discussed. The removal of sulfite and sulfate ions is explained by zeta-potential measurements. PMID:15177743

  15. DETERMINATION OF HYDROGEN SULFIDE IN REFINERY FUEL GASES

    EPA Science Inventory

    Several widely employed test methods for the iodimetric measurement of hydrogen sulfide in refinery fuel gases are shown to suffer from serious thiol interferences. An absorbing solution consisting of 0.16 M cadmium sulfate/sulfuric acid at pH 3.0 is shown to be effective for the...

  16. ISE Analysis of Hydrogen Sulfide in Cigarette Smoke

    NASA Astrophysics Data System (ADS)

    Li, Guofeng; Polk, Brian J.; Meazell, Liz A.; Hatchett, David W.

    2000-08-01

    Many advanced undergraduate analytical laboratory courses focus on exposing students to various modern instruments. However, students rarely have the opportunity to construct their own analytical tools for solving practical problems. We designed an experiment in which students are required to build their own analytical module, a potentiometric device composed of a Ag/AgCl reference electrode, a Ag/Ag2S ion selective electrode (ISE), and a pH meter used as voltmeter, to determine the amount of hydrogen sulfide in cigarette smoke. Very simple techniques were developed for constructing these electrodes. Cigarette smoke is collected by a gas washing bottle into a 0.1 M NaOH solution. The amount of sulfide in the cigarette smoke solution is analyzed by standard addition of sulfide solution while monitoring the response of the Ag/Ag2S ISE. The collected data are further evaluated using the Gran plot technique to determine the concentration of sulfide in the cigarette smoke solution. The experiment has been successfully incorporated into the lab course Instrumental Analysis at Georgia Institute of Technology. Students enjoy the idea of constructing an analytical tool themselves and applying their classroom knowledge to solve real-life problems. And while learning electrochemistry they also get a chance to visualize the health hazard imposed by cigarette smoking.

  17. Selective Sulfidation of Lead Smelter Slag with Sulfur

    NASA Astrophysics Data System (ADS)

    Han, Junwei; Liu, Wei; Wang, Dawei; Jiao, Fen; Qin, Wenqing

    2016-02-01

    The selective sulfidation of lead smelter slag with sulfur was studied. The effects of temperature, sulfur dosage, carbon, and Na salts additions were investigated based on thermodynamic calculation. The results indicated that more than 96 pct of zinc in the slag could be converted into sulfides. Increasing temperature, sulfur dosage, or Na salts dosage was conducive to the sulfidation of the zinc oxides in the slag. High temperature and excess Na salts would result in the more consumption of carbon and sulfur. Carbon addition not only promoted the selective sulfidation but reduced the sulfur dosage and eliminated the generation of SO2. Iron oxides had a buffering role on the sulfur efficient utilization. The transformation of sphalerite to wurtzite was feasible under reducing condition at high temperature, especially above 1273 K (1000 °C). The growth of ZnS particles largely depended upon the roasting temperature. They were significantly increased when the temperature was above 1273 K (1000 °C), which was attributed to the formation of a liquid phase.

  18. 40 CFR 425.04 - Applicability of sulfide pretreatment standards.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Applicability of sulfide pretreatment standards. 425.04 Section 425.04 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS LEATHER TANNING AND FINISHING POINT SOURCE CATEGORY General...

  19. 40 CFR 425.04 - Applicability of sulfide pretreatment standards.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 31 2013-07-01 2013-07-01 false Applicability of sulfide pretreatment standards. 425.04 Section 425.04 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS (CONTINUED) LEATHER TANNING AND FINISHING POINT SOURCE CATEGORY...

  20. 40 CFR 425.04 - Applicability of sulfide pretreatment standards.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 30 2011-07-01 2011-07-01 false Applicability of sulfide pretreatment standards. 425.04 Section 425.04 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS LEATHER TANNING AND FINISHING POINT SOURCE CATEGORY General...