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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. 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 ...

  19. 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}.

  20. 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.

  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. 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.

  3. 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.

  4. 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.

  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. 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.

  14. 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.

  15. 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.

  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. 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

  2. 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

  3. 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.

  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. 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

  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. 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.

  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. 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

  17. 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.

  18. 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.

  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. 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.

  2. 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.

  3. 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.

  4. 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.

  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. 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

  8. 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.

  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. 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.

  13. 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.

  14. "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...

  15. 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.

  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. 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.

  6. 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.

  7. 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}.

  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. 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.

  10. 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.

  11. 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.

  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. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  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. 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...

  11. 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...

  12. 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...

  13. 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

  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. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  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. 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

  3. 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.

  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. 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.

  6. 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).

  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. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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).

  5. 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.

  6. 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.

  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. 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.

  12. 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...

  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

    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.

  15. 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

  16. 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...

  17. 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/.

  18. 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

  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. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  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. 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

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 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

  18. 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

  19. 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

  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. 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.

  3. 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.

  4. 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

  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. 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

  7. 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.

  8. 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

  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

    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.

  14. 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

  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. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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).

  5. 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

  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. 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.

  9. 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.

  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...