Polyethylene glycol coated CoFe{sub 2}O{sub 4} nanoparticles: A potential spinel ferrite for biomedical applications

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

Humbe, Ashok V.; Birajdar, Shankar D.; Jadhav, K. M., E-mail: drjadhavkm@gmail.com

2015-06-24

The structural and magnetic properties of the polyethylene glycol (PEG) coated cobalt spinel ferrite (CoFe{sub 2}O{sub 4}) nanoparticles have been reported in the present study. CoFe{sub 2}O{sub 4} nanoparticles were prepared by sol-gel auto-combustion method using citric acid + ethylene glycol as a fuel. The prepared powder of cobalt ferrite nanoparticles was annealed at 600°C for 6h and used for further study. The structural characterization of CoFe{sub 2}O{sub 4} nanoparticles were carried out by X-ray diffraction technique. The X-ray analysis confirmed the formation of single phase cubic spinel structure. The crystallite size, Lattice constant and X-ray density of the PEGmore » coated CoFe{sub 2}O{sub 4} nanoparticles were calculated by using XRD data. The presence of PEG on CoFe{sub 2}O{sub 4} nanoparticles and reduced agglomeration in the CoFe{sub 2}O{sub 4} nanoparticles were revealed by SEM studies. The magnetic properties were studied by pulse field hysteresis loop tracer technique at a room temperature. The magnetic parameters such as saturation magnetization, remanence magnetization, coercivity etc have been obtained. These magnetic parameters were get decreased by PEG coating.« less

Intra- and interparticle magnetism of cobalt-doped iron-oxide nanoparticles encapsulated in a synthetic ferritin cage

NASA Astrophysics Data System (ADS)

Skoropata, E.; Desautels, R. D.; Falvo, E.; Ceci, P.; Kasyutich, O.; Freeland, J. W.; van Lierop, J.

2014-11-01

We present an in-depth examination of the composition and magnetism of cobalt (Co2 +)-doped iron-oxide nanoparticles encapsulated in Pyrococcus furiosus ferritin shells. We show that the Co2 + dopant ions were incorporated into the γ -Fe2O3/Fe3O4 core, with small paramagnetic-like clusters likely residing on the surface of the nanoparticle that were observed for all cobalt-doped samples. In addition, element-specific characterization using Mössbauer spectroscopy and polarized x-ray absorption indicated that Co2 + was incorporated exclusively into the octahedral B sites of the spinel-oxide nanoparticle. Comparable superparamagnetic blocking temperatures, coercivities, and effective anisotropies were obtained for 7%, 10%, and 12% cobalt-doped nanoparticles, and were only slightly reduced for 3% cobalt, indicating a strong effect of cobalt incorporation, with a lesser effect of cobalt content. Due to the regular particle size and separation that result from the use of the ferritin cage, a comparison of the effects of interparticle interactions on the disordered assembly of nanoparticles was also obtained that indicated significantly different behaviors between undoped and cobalt-doped nanoparticles.

Structure and electrical properties of Cu-doped Mn-Co-O spinel prepared via soft chemistry and its application in intermediate-temperature solid oxide fuel cell interconnects

NASA Astrophysics Data System (ADS)

Brylewski, T.; Kruk, A.; Bobruk, M.; Adamczyk, A.; Partyka, J.; Rutkowski, P.

2016-11-01

The study describes CuxMn1.25-0.5xCo1.75-0.5xO4 (x = 0, 0.1, 0.3 and 0.5) spinels synthesized using EDTA gel processes in order to optimize the performance of high-quality spinel protective-conducting films deposited on steel interconnects. The powders obtained after 12 h of calcination in air at 1073 K are solely cubic spinels. Sintering these spinels for 12 h in air at 1423 K also leads to the formation of small amounts of CoO, Mn2O3 or CuO; the type of phase depends on the quantity of copper introduced into the manganese-cobalt lattice. The highest electrical conductivity at 1073 K is observed for Cu0.3Mn1.1Co1.6O4 (162 S·cm-1), which is closely correlated with the lowest activation energy of conduction over the entire temperature range (373≤T≤1073 K); the lowest conductivity is measured for Mn1.25Co1.75O4 (84 Sṡcm-1). The study confirms the suitability of the Cu0.3Mn1.1Co1.6O4 spinel as a potential material for the preparation of protective-conducting coatings on the surface of the DIN 50049 ferritic steel applied in IT-SOFC interconnects. The area-specific resistance of coated steel is 0.08 Ω·cm2, which is lower than that of bare steel after 300 h of oxidation at 1073 K. Cr vaporization tests show that the Cu0.3Mn1.1Co1.6O4 coating is efficient at blocking the outward diffusion of chromium.

Micro-XANES Measurements on Experimental Spinels and the Oxidation State of Vanadium in Spinel-Melt Pairs

NASA Technical Reports Server (NTRS)

Righter, K.; Sutton, S.R.; Newville, M.

2004-01-01

Spinel can be a significant host phase for V as well as other transition metals such as Ni and Co. However, vanadium has multiple oxidation states V(2+), V(3+), V(4+) or V(5+) at oxygen fugacities relevant to natural systems. We do know that D(V) spinel/melt is correlated with V and TiO2 content and fO2, but the uncertainty of the oxidation state under the range of natural conditions has made elusive a thorough understanding of D(V) spinel/melt. For example, V(3+) is likely to be stable in spinels, based on exchange with Al in experiments in the CaO-MgO-Al2O3-SiO2 system. On the other hand, it has been argued that V(4+) will be stable across the range of natural oxygen fugacities in nature. In order to gain a better understanding of D(V) spinel/melt we have equilibrated spinel-melt pairs at controlled oxygen fugacities, between HM to NNO, where V is present in the spinel at natural levels (approx. 300 ppm V). These spinel-melt pairs were analyzed using micro-XANES at the Advanced Photon Source at Argonne National Laboratory. The new results will be used together with spinel compositional data (Ti, V content) and oxygen fugacity, to unravel the effects of these variables on D(V) spinel/melt.

Impedance spectroscopy and electric modulus behavior of Molybdenum doped Cobalt-Zinc ferrite

NASA Astrophysics Data System (ADS)

Pradhan, A. K.; Nath, T. K.; Saha, S.

2017-07-01

The complex impedance spectroscopy and the electric modulus of Mo doped Cobalt-Zinc inverse spinel ferrite has been investigated in detail. The conventional ceramic technique has been used to prepare the CZMO. The HRXRD technique has been used to study the structural analysis which confirms the inverse spinel structure of the material and also suggest the material have Fd3m space group. The complex impedance spectroscopic data and the electric modulus formalism have been used to understand the dielectric relaxation and conduction process. The contribution of grain and grain boundary in the electrical conduction process of CZMO has been confirmed from the Cole-Cole plot. The activation energy is calculated from both the IS (Impedance Spectroscopy) and electric modulus formalism and found to be nearly same for the materials.

XANES and Mg isotopic analyses of spinels in Ca-Al-rich inclusions: Evidence for formation under oxidizing conditions

NASA Astrophysics Data System (ADS)

Paque, J. M.; Sutton, S. R.; Simon, S. B.; Beckett, J. R.; Burnett, D. S.; Grossman, L.; Yurimoto, H.; Itoh, S.; Connolly, H. C.

2013-10-01

Ti valence measurements in MgAl2O4 spinel from calcium-aluminum-rich inclusions (CAIs) by X-ray absorption near-edge structure (XANES) spectroscopy show that many spinels have predominantly tetravalent Ti, regardless of host phases. The average spinel in Allende type B1 inclusion TS34 has 87% Ti+4. Most spinels in fluffy type A (FTA) inclusions also have high Ti valence. In contrast, the rims of some spinels in TS34 and spinel grain cores in two Vigarano type B inclusions have larger amounts of trivalent titanium. Spinels from TS34 have approximately equal amounts of divalent and trivalent vanadium. Based on experiments conducted on CAI-like compositions over a range of redox conditions, both clinopyroxene and spinel should be Ti+3-rich if they equilibrated with CAI liquids under near-solar oxygen fugacities. In igneous inclusions, the seeming paradox of high-valence spinels coexisting with low-valence clinopyroxene can be explained either by transient oxidizing conditions accompanying low-pressure evaporation or by equilibration of spinel with relict Ti+4-rich phases (e.g., perovskite) prior to or during melting. Ion probe analyses of large spinel grains in TS34 show that they are enriched in heavy Mg, with an average Δ25Mg of 4.25 ± 0.028‰, consistent with formation of the spinel from an evaporating liquid. Δ25Mg shows small, but significant, variation, both within individual spinels and between spinel and adjacent melilite hosts. The Δ25Mg data are most simply explained by the low-pressure evaporation model, but this model has difficulty explaining the high Ti+4 concentrations in spinel.

Cobalt-manganese-based spinels as multifunctional materials that unify catalytic water oxidation and oxygen reduction reactions.

PubMed

Menezes, Prashanth W; Indra, Arindam; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Strasser, Peter; Driess, Matthias

2015-01-01

Recently, there has been much interest in the design and development of affordable and highly efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts that can resolve the pivotal issues that concern solar fuels, fuel cells, and rechargeable metal-air batteries. Here we present the synthesis and application of porous CoMn2 O4 and MnCo2 O4 spinel microspheres as highly efficient multifunctional catalysts that unify the electrochemical OER with oxidant-driven and photocatalytic water oxidation as well as the ORR. The porous materials were prepared by the thermal degradation of the respective carbonate precursors at 400 °C. The as-prepared spinels display excellent performances in electrochemical OER for the cubic MnCo2 O4 phase in comparison to the tetragonal CoMn2 O4 material in an alkaline medium. Moreover, the oxidant-driven and photocatalytic water oxidations were performed and they exhibited a similar trend in activity to that of the electrochemical OER. Remarkably, the situation is reversed in ORR catalysis, that is, the oxygen reduction activity and stability of the tetragonal CoMn2 O4 catalyst outperformed that of cubic MnCo2 O4 and rivals that of benchmark Pt catalysts. The superior catalytic performance and the remarkable stability of the unifying materials are attributed to their unique porous and robust microspherical morphology and the intrinsic structural features of the spinels. Moreover, the facile access to these high-performance materials enables a reliable and cost-effective production on a large scale for industrial applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Spinel-integrated P2-type Layered Composite: High-rate Cathode for Sodium-ion Batteries

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

Zheng, Jianming; Yan, Pengfei; Kan, Wang Hay

2016-01-14

Sodium-ion batteries (SIB) are being intensively investigated, owing to the natural abundance and low cost of Na resources. However, the SIBs still suffer from poor rate capability due to the large ionic radius of Na+ ion and the significant kinetic barrier to Na+-ion transport. Here, we present an Fd-3m spinel-integrated P2-type layered composite (P2 + Fd-3m) material as a high-rate cathode for SIBs. The P2 + Fd-3m composite material Na0.50Ni1/6Co1/6Mn2/3O2 shows significantly enhanced discharge capacity, energy density, and rate capability as compared to the pure P2-type counterpart. The composite delivers a high capacity of 85 mA h g-1 when dischargingmore » at a very high current density of 1500 mA g-1 (10C rate) between 2.0 and 4.5 V, validating it as a promising cathode candidate for high-power SIBs. The superior performance is ascribed to the improved kinetics in the presence of the integrated-spinel phase, which facilitates fast electron transport to coordinate with the timely Na+-ion insertion/extraction. The findings of this work also shed light on the importance of developing lattice doping, surface coating, and electrolyte additives to further improve the structural and interfacial stability of P2-type cathode materials and fully realize their practical applications in sodium-ion batteries.« less

Spinel: where did it go?

NASA Astrophysics Data System (ADS)

Roy, Donald W.

1997-11-01

Polycrystalline magnesium aluminum oxide, transparent from 200 nanometers to 6 microns, offers a unique combination of optical and physical properties. A superior dome and window material in respect to rain and particle erosion, solar radiation, high temperatures and humidity; it is resistant to attack by strong acids, sea water, and jet fuels. Although it had been qualified for, and designed into several advanced UV/visible/IR optical systems, production of hot-pressed Spinel was stopped at Alpha Optical Systems in 1993 by the parent company Coors Ceramics. Development efforts on cold-pressed/sinter/HIP Spinel at RCS Technologies are reportedly stalemated at the present time. Therefore, there is no known significant effort directed toward the development of polycrystalline Spinel. however, the author is in contact with both domestic and foreign laboratories which have expressed a desire to develop the technology for transparent Spinel. Renewed development may begin during calendar year 1997. Because of the apparent continuing significant interest in Spinel this paper will review the properties of Spinel and will compare the most significant properties of Spinel with sapphire and aluminum oxynitride. The limitations of competing manufacturing processes, will be mentioned. Grinding and polishing considerations will be reviewed in respect to maximizing optical and structural properties.

SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Beederman, M.; Vogler, S.; Hyman, H.H.

1959-07-14

The separation of rathenium from a rathenium containing aqueous solution is described. The separation is accomplished by adding sodium nitrite, silver nitrate and ozone to the ruthenium containing aqueous solution to form ruthenium tetroxide and ihen volatilizing off the ruthenium tetroxide.

Study of structural phase transformation and hysteresis behavior of inverse-spinel α-ferrite nanoparticles synthesized by co-precipitation method

NASA Astrophysics Data System (ADS)

Dabagh, Shadab; Chaudhary, Kashif; Haider, Zuhaib; Ali, Jalil

2018-03-01

Substitution of cobalt (Co2+) ions in cobalt ferrite (CoFe2O4) with copper (Cu2+) and aluminum (Al3+) ions allows variations in their electric and magnetic properties which can be optimized for specific applications. In this article, synthesis of inverse-spinel Co1-xCuxFe2-xAlxO4 (0.0 ≤ x ≤ 0.8) nanoparticles by substituting Cu2+ and Al3+ ions in CoFe2O4 via co-precipitation method is reported. By controlling copper and aluminum (Cu-Al) substituent ratio, the magnetic moment and coercivity of synthesized cobalt ferrite nanoparticles is optimized. The role of substituents on the structure, particle size, morphology, and magnetic properties of nano-crystalline ferrite is investigated. The Co1-xCuxFe2-xAlxO4 (0.0 ≤ x≤ 0.8) nanoparticles with crystallite size in the range of 23.1-26.5 nm are observed, 26.5 nm for x = 0.0-23.1 nm for x = 0.8. The inverse-spinel structure of synthesized Co1-xCuxFe2-xAlxO4 (0.0 ≤ x ≤ 0.8) nano-particles is confirmed by characteristic vibrational bands at tetrahedral and octahedral sites using Fourier transform infrared spectroscopy. A decreases in coercive field and magnetic moment is observed as Cu-Al contents are increased (x = 0.0-0.8). The positive anisotropy of synthesized particles Co1-xCuxFe2-xAlxO4 (0.0 ≤ x ≤ 0.8) is obtained in the range 1.96 × 105 J/m3 for x = 0.0 to 0.29 × 105 J/m3 for x = 0.8.

Structural, dielectric and magnetic properties of nickel substituted cobalt ferrite nanoparticles: Effect of nickel concentration

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

Velhal, Ninad B.; Patil, Narayan D.; Puri, Vijaya R., E-mail: vijayapuri1@gmail.com

2015-09-15

Nickel substituted cobalt ferrite nanoparticles with composition Co{sub 1−x}Ni{sub x}Fe{sub 2}O{sub 4} (0.0 ≤ x ≤ 1.0) was synthesized using simple, low temperature auto combustion method. The X-ray diffraction patterns reveal the formation of cubic phase spinel structure. The crystallite size varies from 30-44 nm with the nickel content. Porous and agglomerated morphology of the bulk sample was displayed in the scanning electron microscopy. Micro Raman spectroscopy reveals continuous shift of E{sub g} and E{sub g}(2) stokes line up to 0.8 Ni substitution. The dispersion behavior of the dielectric constant with frequency and the semicircle nature of the impedance spectramore » show the cobalt nickel ferrite to have high resistance. The ferromagnetic nature is observed in all the samples, however, the maximum saturation magnetization was achieved by the 0.4 Ni substituted cobalt ferrite, which is up to the 92.87 emu/gm at 30K.« less

Preparation and microwave absorbing properties of carbon/cobalt ferromagnetic composites.

PubMed

Li, Wangchang; Qiao, Xiaojing; Zhao, Hui; Wang, Shuman; Ren, Qingguo

2013-02-01

Carbon/cobalt ferromagnetic light composites with high performance of microwave absorbing properties were prepared by hydrothermal method using starch and hollow cobalt ferrites. It was concluded that after carbonization the spinel structure ferrites changed to Co3Fe7 alloys and the temperature of graphitization was significantly decreased for the catalytic of CoFe2O4/Co3Fe7. The increase of carbon content, and exist of CoFe2O4/Co3Fe7 heightened the microwave absorbing properties. Electromagnetic parameters were tested with 40% of the titled materials and 60% of paraffin wax composites by using HP8722ES vector network analyzer. The reflection was also simulated through transmission line theory. The microwave absorbers exhibited a maximum reflection loss -43 dB and the electromagnetic wave absorption less than -10 dB was found to exceed 3.0 GHz between 11.6 GHz and 15 GHz for an absorber thickness of 2 mm.

Hydrotalcite-derived cobalt-aluminum mixed oxide catalysts for toluene combustion

NASA Astrophysics Data System (ADS)

Białas, Anna; Mazur, Michal; Natkański, Piotr; Dudek, Barbara; Kozak, Marek; Wach, Anna; Kuśtrowski, Piotr

2016-01-01

Hydrotalcite-like compounds (HTlcs) containing cobalt and aluminum (intended Co/Al molar ratio = 3.0) were coprecipitated at 30, 50 and 70 °C. Their crystallinity, which was confirmed by powder X-ray diffraction, increased with the precipitation temperature. Furthermore, HTlcs with various cobalt contents were prepared at 70 °C. Thermogravimetric analysis showed that HTlcs were transformed into stable oxides at 550 °C. The decrease in the crystallite size of the formed spinels with the increase in the precipitation temperature was observed. Low temperature sorption of nitrogen revealed meso-macroporous nature of the oxides with extended interparticle porosity. Aluminum segregated on the samples surface, which contained various amounts of lattice and adsorbed/electrophilic oxygen as detected by X-ray electron spectroscopy. The high ratio of lattice to adsorbed/electrophilic oxygen found for the sample with Co/Al = 3:1 caused that it turned out to be the most efficient catalyst in the total oxidation of toluene (50% conversion at 257 °C).

A new class of cyclometalated ruthenium sensitizers of the type ĈNN for efficient dye-sensitized solar cells.

PubMed

Kim, Jeum-Jong; Choi, Hyunbong; Paek, Sanghyun; Kim, Chulwoo; Lim, Kimin; Ju, Myung-Jong; Kang, Hong Seok; Kang, Moon-Sung; Ko, Jaejung

2011-11-21

A new class of cyclometalated ruthenium sensitizers incorporating a ĈNN ligand and conjugated 2,2'-bipyridine in the ancillary ligand have been designed and synthesized. The photovoltaic performance of JK-206 using an electrolyte containing 0.6 M 1,2-dimethyl-3-propylimidazolium iodide, 0.05 M I(2), 0.1 M LiI, and 0.5 M tert-butylpyridine in CH(3)CN gave a short-circuit photocurrent density of 19.63 mA cm(-2), an open-circuit voltage of 0.74 V, and a fill factor of 0.72, affording an overall conversion efficiency of 10.39%. The efficiency is the highest one reported for dye-sensitized solar cells based on the cyclometalated ruthenium sensitizer of the type ĈNN. Moreover, the same device using a polymer gel electrolyte exhibited a remarkable stability under 1000 h of light soaking at 60 °C, retaining 91% of the initial efficiency of 7.14%.

IR-doped ruthenium oxide catalyst for oxygen evolution

NASA Technical Reports Server (NTRS)

Valdez, Thomas I. (Inventor); Narayanan, Sekharipuram R. (Inventor)

2012-01-01

A method for preparing a metal-doped ruthenium oxide material by heating a mixture of a doping metal and a source of ruthenium under an inert atmosphere. In some embodiments, the doping metal is in the form of iridium black or lead powder, and the source of ruthenium is a powdered ruthenium oxide. An iridium-doped or lead-doped ruthenium oxide material can perform as an oxygen evolution catalyst and can be fabricated into electrodes for electrolysis cells.

Ruthenium-catalyzed insertion of adjacent diol carbon atoms into C-C bonds: Entry to type II polyketides.

PubMed

Bender, Matthias; Turnbull, Ben W H; Ambler, Brett R; Krische, Michael J

2017-08-25

Current catalytic processes involving carbon-carbon bond activation rely on π-unsaturated coupling partners. Exploiting the concept of transfer hydrogenative coupling, we report a ruthenium(0)-catalyzed cycloaddition of benzocyclobutenones that functionalizes two adjacent saturated diol carbon-hydrogen bonds. These regio- and diastereoselective processes enable convergent construction of type II polyketide substructures. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

A new lithium-rich anti-spinel in Li–O–Br system

DOE PAGES

Zhang, J.; Zhu, J.; Wang, L.; ...

2015-05-11

In spinel-type materials currently known, the divalent anions are arranged in a closed-pack lattice and cations of various valences occupy some or all of the tetrahedral and octahedral sites. We report here the first discovery of an ‘‘electronically inverted’’ antispinel. Furthermore, the new material, crystallized in a defect spinel structure, was obtained from the dehydration of Li 5Br(OH) 4 under moderate pressure and temperature conditions.

Characterization And Dissolution Properties Of Ruthenium Oxides

EPA Science Inventory

Ruthenium oxides (RuO₂•1.10H₂O and RuO₂) have been synthesized by forced hydrolysis and oxidation of ruthenium chloride. The resulting materials were extensively characterized to determine the crystallinity, surface area, and ruthenium oxidation ...

Design of organic dyes and cobalt polypyridine redox mediators for high-efficiency dye-sensitized solar cells.

PubMed

Feldt, Sandra M; Gibson, Elizabeth A; Gabrielsson, Erik; Sun, Licheng; Boschloo, Gerrit; Hagfeldt, Anders

2010-11-24

Dye-sensitized solar cells (DSCs) with cobalt-based mediators with efficiencies surpassing the record for DSCs with iodide-free electrolytes were developed by selecting a suitable combination of a cobalt polypyridine complex and an organic sensitizer. The effect of the steric properties of two triphenylamine-based organic sensitizers and a series of cobalt polypyridine redox mediators on the overall device performance in DSCs as well as on transport and recombination processes in these devices was compared. The recombination and mass-transport limitations that, previously, have been found to limit the performance of these mediators were avoided by matching the properties of the dye and the cobalt redox mediator. Organic dyes with higher extinction coefficients than the standard ruthenium sensitizers were employed in DSCs in combination with outer-sphere redox mediators, enabling thinner TiO(2) films to be used. Recombination was reduced further by introducing insulating butoxyl chains on the dye rather than on the cobalt redox mediator, enabling redox couples with higher diffusion coefficients and more suitable redox potential to be used, simultaneously improving the photocurrent and photovoltage of the device. Optimization of DSCs sensitized with a triphenylamine-based organic dye in combination with tris(2,2'-bipyridyl)cobalt(II/III) yielded solar cells with overall conversion efficiencies of 6.7% and open-circuit potentials of more than 0.9 V under 1000 W m(-2) AM1.5 G illumination. Excellent performance was also found under low light intensity indoor conditions.

Volatile-rich komatiitic and picritic melt inclusions in Cr-spinel beach sand from Gorgona Island, Colombia

NASA Astrophysics Data System (ADS)

Shimizu, K.; Shimizu, N.; Suzuki, K.; Tatsumi, Y.; Komiya, T.; Maruyama, S.

2007-12-01

Volatile content of komatiite is a key to constrain thermal evolution of the deep Earth. We report volatile contents with major and trace element compositions of melt inclusions (MIs) in chromian spinel (Cr-spinel) from beach sands of Gorgona Island, Colombia. Gorgona Island is ~90 Ma volcanic island, where picrites and the world-youngest komatiites occur. As Cr-spinel is dense and rigid oxide mineral that crystallizes only at early stages of crystallization, it is considered to be a superior container for retaining primitive melt, even including volatiles. Volatile (H2O, CO2, S, F and Cl) and trace element (K2O, Sr, Y, Zr, Nb, Ba, La, Ce, Sm, Dy, Yb) compositions of ~80 MIs were analyzed by SIMS (Cameca-1280 and 3f, respectively) at WHOI. MIs in the Cr-spinel from Gorgona Is. are classified into three types by their host Cr-spinel compositions such as low-Ti (P-type), high-Ti with high-Cr# (BK-type) and high-Ti with low-Cr# (K-type). MIs of P-type, BK-type and K-type are mostly in compositional ranges of picrite, high TiO2 komatiite (some basalt) and low TiO2 komatiite in Gorgona Island, respectively. Water content of P-type MIs is variable, ranging from 0.05 to 0.9 wt%, whereas those of BK and K-type MIs are limited (< 0.1 wt%). On the other hand, CO2 contents of BK-type and K- type MIs are highly scattered (40 to 4200 ppm), whereas that of P-type is relatively constant at ~200 ppm. All MIs with high CO2 content (>500 ppm) do not contain (shrinkage) bubbles and many of them are low in K2O. H2O/K2O, CO2/K2O, S/K2O and F/K2O ratios are positively correlated with Y/Sr ratios, indicating degassing trends of melt at crystallization, magma mixing and/or assimilation. Undegassed H2O/K2O, CO2/K2O, S/K2O and F/K2O ratios of komatiitic (picritic) melt are estimated to be ~10 (~40), ~80 (n.d.), ~7(~3) and ~1(~0.5), respectively, which are much higher than those estimated for the depleted source mantle of the MORB [1.6, 0.7, 1.6 and 0.2, respectively; Salters, V. & Stracke

Microwave magnetic properties of spinel ferrite films deposited by one-step electrochemical method

NASA Astrophysics Data System (ADS)

Zhang, Yao; Yuan, Lixin; Zhang, Xiaozhi; Zhang, Jie; Yue, Zhenxing; Li, Longtu

2017-07-01

Spinel ferrites have been widely used in microwave devices due to their excellent electromagnetic properties. In this study, two kinds of spinel ferrite films, Fe3O4 and Co xFe3-xO4, were grown on Pt(111)/Ti/SiO2/Si substrates by one-step electrochemical deposition method. The XRD and SEM characterizations demonstrated that the orientation of the ferrite films changed from (111) to (100) with the increase of depositing time. The cobalt content within Co xFe3-xO4 films was studied in detail by EDS analysis. The ferromagnetic resonance (FMR) responses of the ferrite films were measured by the flip-chip method using a vector network analyzer (VNA). It showed that the FMR frequency of Fe3O4 films reached to 10.5 GHz under an out-plane magnetic field of 5 kOe, while it reached to 27 GHz under an in-plane magnetic field of 5 kOe for Co xFe3-xO4 films. Meanwhile, whether the magnetic field was applied parallelly or perpendicularly, the resonant peaks were increased linearly with increasing the magnetic field, indicating that the films are promising candidates for applications in tunable wave-absorbing materials or other tunable frequency devices.

A Metal-Organic Framework Derived Porous Cobalt Manganese Oxide Bifunctional Electrocatalyst for Hybrid Na-Air/Seawater Batteries.

PubMed

Abirami, Mari; Hwang, Soo Min; Yang, Juchan; Senthilkumar, Sirugaloor Thangavel; Kim, Junsoo; Go, Woo-Seok; Senthilkumar, Baskar; Song, Hyun-Kon; Kim, Youngsik

2016-12-07

Spinel-structured transition metal oxides are promising non-precious-metal electrocatalysts for oxygen electrocatalysis in rechargeable metal-air batteries. We applied porous cobalt manganese oxide (CMO) nanocubes as the cathode electrocatalyst in rechargeable seawater batteries, which are a hybrid-type Na-air battery with an open-structured cathode and a seawater catholyte. The porous CMO nanocubes were synthesized by the pyrolysis of a Prussian blue analogue, Mn 3 [Co(CN) 6 ] 2 ·nH 2 O, during air-annealing, which generated numerous pores between the final spinel-type CMO nanoparticles. The porous CMO electrocatalyst improved the redox reactions, such as the oxygen evolution/reduction reactions, at the cathode in the seawater batteries. The battery that used CMO displayed a voltage gap of ∼0.53 V, relatively small compared to that of the batteries employing commercial Pt/C (∼0.64 V) and Ir/C (∼0.73 V) nanoparticles and without any catalyst (∼1.05 V) at the initial cycle. This improved performance was due to the large surface area (catalytically active sites) and the high oxidation states of the randomly distributed Co and Mn cations in the CMO. Using a hard carbon anode, the Na-metal-free seawater battery exhibited a good cycle performance with an average discharge voltage of ∼2.7 V and a discharge capacity of ∼190 mAh g -1 hard carbon during 100 cycles (energy efficiencies of 74-79%).

Ruthenium-catalyzed regioselective allylic amination of 2,3,3-trifluoroallylic carbonates.

PubMed

Isobe, Shin-Ichi; Terasaki, Shou; Hanakawa, Taisyun; Mizuno, Shota; Kawatsura, Motoi

2017-04-05

We demonstrated the ruthenium-catalyzed allylic amination of 2,3,3-trifluoroallylic carbonates with several types of amines. The reactions proceeded with several types of amines, and succeeded in obtaining polyfluorinated terminal alkenes possessing branched allylic amines as a single regioisomer.

Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide

NASA Astrophysics Data System (ADS)

Cabán-Acevedo, Miguel; Stone, Michael L.; Schmidt, J. R.; Thomas, Joseph G.; Ding, Qi; Chang, Hung-Chih; Tsai, Meng-Lin; He-Hau, Jr.; Jin, Song

2015-12-01

The scalable and sustainable production of hydrogen fuel through water splitting demands efficient and robust Earth-abundant catalysts for the hydrogen evolution reaction (HER). Building on promising metal compounds with high HER catalytic activity, such as pyrite structure cobalt disulphide (CoS2), and substituting non-metal elements to tune the hydrogen adsorption free energy could lead to further improvements in catalytic activity. Here we present a combined theoretical and experimental study to establish ternary pyrite-type cobalt phosphosulphide (CoPS) as a high-performance Earth-abundant catalyst for electrochemical and photoelectrochemical hydrogen production. Nanostructured CoPS electrodes achieved a geometrical catalytic current density of 10 mA cm-2 at overpotentials as low as 48 mV, with outstanding long-term operational stability. Integrated photocathodes of CoPS on n+-p-p+ silicon micropyramids achieved photocurrents up to 35 mA cm-2 at 0 V versus the reversible hydrogen electrode (RHE), onset photovoltages as high as 450 mV versus RHE, and the most efficient solar-driven hydrogen generation from Earth-abundant systems.

Mg-Spinel-rich lithology at crater Endymion in the lunar nearside

NASA Astrophysics Data System (ADS)

Bhattacharya, Satadru; Chauhan, Prakash; Ajai, A.

2012-07-01

The recent discovery of a Mg-Spinel-rich lithology at the inner ring of Mare Moscoviense (a farside mare) by [1, 2] based on the analysis of high-resolution Moon Mineralogy Mapper (M3) data from Chandrayaan-1, has stimulated interest in studying and identifying more and more such rock types across the lunar surface as spinel-rich lithologies and OOS (Orthopyroxene-Olivine-Spinel) suites of rocks hold the key to understand the deeper crustal composition and processes of the Moon. The genesis of this spinel-rich rare and unusual lithology on the lunar surface is yet to be understood by the lunar scientists. [3-6] has reported the occurrence of Mg-Spinel-rich lithology at the central peaks of crater Theophilus. The Mg-spinel-rich lithology at Theophilus is found to occur in association with mafic-free plagioclase and associated with lesser exposures of pyroxene and olivine-bearing materials. In a very recent work, [7] has identified Mg-spinel rich lithology at the floor of crater Copernicus. Very recently [8] has reported presence of Mg-spinel-rich lithology at the central peak of crater Tycho in association with olivine, crystalline plagioclase and high-Ca pyroxenes. All these detections are restricted within very small areal extents. Here, we report a new identification of this Mg-spinel-rich lithology at the rim of crater Endymion situated near the northeast limb of the Moon at the nearside using high-resolution M3 data. In Endymion, Mg-spinel-rich lithology occurs in close association with orthopyroxene-olivine assemblages and therefore represent OOS lithological suite of rocks. Spectral signature of Mg-spinel-rich lithology at the rim of crater Endymion: Spectra of Mg-spinel lacks 1000-nm absorption feature and is characterised by a strong absorption near 2000 nm arising due to the small amounts of Fe2+ in the tetrahedral crystallographic site of the mineral. Spectral signature of Mg-spinel-rich lithology, as obtained from the southern rim of crater Endymion

SOLVENT EXTRACTION OF RUTHENIUM

DOEpatents

Hyman, H.H.; Leader, G.R.

1959-07-14

The separation of rathenium from aqueous solutions by solvent extraction is described. According to the invention, a nitrite selected from the group consisting of alkali nitrite and alkaline earth nitrite in an equimolecular quantity with regard to the quantity of rathenium present is added to an aqueous solution containing ruthenium tetrantrate to form a ruthenium complex. Adding an organic solvent such as ethyl ether to the resulting mixture selectively extracts the rathenium complex.

Protic NNN and NCN Pincer-Type Ruthenium Complexes Featuring (Trifluoromethyl)pyrazole Arms: Synthesis and Application to Catalytic Hydrogen Evolution from Formic Acid.

PubMed

Nakahara, Yoshiko; Toda, Tatsuro; Matsunami, Asuka; Kayaki, Yoshihito; Kuwata, Shigeki

2018-01-04

NNN and NCN pincer-type ruthenium(II) complexes featuring two protic pyrazol-3-yl arms with a trifluoromethyl (CF 3 ) group at the 5-position were synthesized and structurally characterized to evaluate the impact of the substitution on the properties and catalysis. The increased Brønsted acidity by the highly electron-withdrawing CF 3 pendants was demonstrated by protonation-deprotonation experiments. By contrast, the IR spectra of the carbonyl derivatives as well as the cyclic voltammogram indicated that the electron density of the ruthenium atom is negligibly influenced by the CF 3 group. Catalysis of these complexes in the decomposition of formic acid to dihydrogen and carbon dioxide was also examined. The NNN pincer-type complex 1 a with the CF 3 group exhibited a higher catalytic activity than the tBu-substituted analogue 1 b. In addition, the bis(CF 3 -pyrazolato) ammine derivative 4 catalyzed the reaction even in the absence of base additives. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Platinum-ruthenium-palladium fuel cell electrocatalyst

DOEpatents

Gorer, Alexander

2006-02-07

A catalyst suitable for use in a fuel cell, especially as an anode catalyst, that contains platinum at a concentration that is between about 20 and about 60 atomic percent, ruthenium at a concentration that is between about 20 and about 60 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having an atomic ratio of platinum to ruthenium that is between about 0.7 and about 1.2. Alternatively, the catalyst may contain platinum at a concentration that is between about 25 and about 50 atomic percent, ruthenium at a concentration that is between about 25 and about 55 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having a difference between the concentrations of ruthenium and platinum that is no greater than about 20 atomic percent.

A New Spinel-Olivine Oxybarometer: Near-Liquidus Partitioning of V between Olivine-Melt, Spinel-Melt, and Spinel-Olivine in Martian Basalt Composition Y980459 as a Function of Oxygen Fugacity

NASA Technical Reports Server (NTRS)

Papike, J. J.; Le, L.; Burger, P. V.; Shearer, C. K.; Bell, A. S.; Jones, J.

2013-01-01

Our research on valence state partitioning began in 2005 with a review of Cr, Fe, Ti, and V partitioning among crystallographic sites in olivine, pyroxene, and spinel [1]. That paper was followed by several on QUE94201 melt composition and specifically on Cr, V, and Eu partitioning between pyroxene and melt [2-5]. This paper represents the continuation of our examination of the partitioning of multivalent V between olivine, spinel, and melt in martian olivine-phyric basalts of Y980459 composition [6, 7]. Here we introduce a new, potentially powerful oxybarometer, V partitioning between spinel and olivine, which can be used when no melt is preserved in the meteorite. The bulk composition of QUE94201 was ideal for our study of martian pyroxene-phyric basalts and specifically the partitioning between pyroxene-melt for Cr, V, and Eu. Likewise, bulk composition Y980459 is ideal for the study of martian olivine-phyric basalts and specifically for olivine-melt, spinel-melt, and spinel-olivine partitioning of V as a function of oxygen fugacity.

Closed system oxygen isotope redistribution in igneous CAIs upon spinel dissolution

NASA Astrophysics Data System (ADS)

Aléon, Jérôme

2018-01-01

In several Calcium-Aluminum-rich Inclusions (CAIs) from the CV3 chondrites Allende and Efremovka, representative of the most common igneous CAI types (type A, type B and Fractionated with Unknown Nuclear isotopic anomalies, FUN), the relationship between 16O-excesses and TiO2 content in pyroxene indicates that the latter commonly begins to crystallize with a near-terrestrial 16O-poor composition and becomes 16O-enriched during crystallization, reaching a near-solar composition. Mass balance calculations were performed to investigate the contribution of spinel to this 16O-enrichment. It is found that a back-reaction of early-crystallized 16O-rich spinel with a silicate partial melt having undergone a 16O-depletion is consistent with the O isotopic evolution of CAI minerals during magmatic crystallization. Dissolution of spinel explains the O isotopic composition (16O-excess and extent of mass fractionation) of pyroxene as well as that of primary anorthite/dmisteinbergite and possibly that of the last melilite crystallizing immediately before pyroxene. It requires that igneous CAIs behaved as closed-systems relative to oxygen from nebular gas during a significant fraction of their cooling history, contrary to the common assumption that CAI partial melts constantly equilibrated with gas. The mineralogical control on O isotopes in igneous CAIs is thus simply explained by a single 16O-depletion during magmatic crystallization. This 16O-depletion occurred in an early stage of the thermal history, after the crystallization of spinel, i.e. in the temperature range for melilite crystallization/partial melting and did not require multiple, complex or late isotope exchange. More experimental work is however required to deduce the protoplanetary disk conditions associated with this 16O-depletion.

Cobalt poisoning

MedlinePlus

... This type of implant is an artificial hip socket that is created by fitting a metal ball ... particles (ions) can get released into the hip socket and sometimes the bloodstream, causing cobalt toxicity. This ...

An Integrated, Layered-Spinel Composite Cathode for Energy Storage Applications

NASA Technical Reports Server (NTRS)

Hagh, Nader; Skandan, Ganesh

2012-01-01

At low operating temperatures, commercially available electrode materials for lithium-ion batteries do not fully meet the energy and power requirements for NASA fs exploration activities. The composite cathode under development is projected to provide the required energy and power densities at low temperatures and its usage will considerably reduce the overall volume and weight of the battery pack. The newly developed composite electrode material can provide superior electrochemical performance relative to a commercially available lithium cobalt system. One advantage of using a composite cathode is its higher energy density, which can lead to smaller and lighter battery packs. In the current program, different series of layered-spinel composite materials with at least two different systems in an integrated structure were synthesized, and the volumetric and gravimetric energy densities were evaluated. In an integrated network of a composite electrode, the effect of the combined structures is to enhance the capacity and power capabilities of the material to levels greater than what is possible in current state-of-the-art cathode systems. The main objective of the current program is to implement a novel cathode material that meets NASA fs low temperature energy density requirements. An important feature of the composite cathode is that it has at least two components (e.g., layered and spinel) that are structurally integrated. The layered material by itself is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated, thereby delivering a large amount of energy with stable cycling. A key aspect of the innovation has been the development of a scalable process to produce submicronand micron-scale particles of these composite materials. An additional advantage of using such a composite electrode material is its low irreversible loss (.5%), which is primarily due to the unique activation

NNP-Type Pincer Imidazolylphosphine Ruthenium Complexes: Efficient Base-Free Hydrogenation of Aromatic and Aliphatic Nitriles under Mild Conditions.

PubMed

Adam, Rosa; Alberico, Elisabetta; Baumann, Wolfgang; Drexler, Hans-Joachim; Jackstell, Ralf; Junge, Henrik; Beller, Matthias

2016-03-24

A series of seven novel N(Im)N(H)P-type pincer imidazolylphosphine ruthenium complexes has been synthesized and fully characterized. The use of hydrogenation of benzonitrile as a benchmark test identified [RuHCl(CO)(N(Im)N(H) P(tBu))] as the most active catalyst. With its stable Ru-BH4 analogue, in which chloride is replaced by BH4, a broad range of (hetero)aromatic and aliphatic nitriles, including industrially interesting adiponitrile, has been hydrogenated under mild and base-free conditions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Partitioning of Ni, Co and V between Spinel-Structured Oxides and Silicate Melts: Importance of Spinel Composition

NASA Technical Reports Server (NTRS)

Righter, K.; Leeman, W. P.; Hervig, R. L.

2006-01-01

Partitioning of Ni, Co and V between Cr-rich spinels and basaltic melt has been studied experimentally between 1150 and 1325 C, and at controlled oxygen fugacity from the Co-CoO buffer to slightly above the hematite magnetite buffer. These new results, together with new Ni, Co and V analyses of experimental run products from Leeman [Leeman, W.P., 1974. Experimental determination of the partitioning of divalent cations between olivine and basaltic liquid, Pt. II. PhD thesis, Univ. Oregon, 231 - 337.], show that experimentally determined spinel melt partition coefficients (D) are dependent upon temperature (T), oxygen fugacity (fO2) and spinel composition. In particular, partition coefficients determined on doped systems are higher than those in natural (undoped) systems, perhaps due to changing activity coefficients over the composition range defined by the experimental data. Using our new results and published runs (n =85), we obtain a multilinear regression equation that predicts experimental D(V) values as a function of T, fO2, concentration of V in melt and spinel composition. This equation allows prediction of D(V) spinel/melt values for natural mafic liquids at relevant crystallization conditions. Similarly, D(Ni) and D(Co) values can be inferred from our experiments at redox conditions approaching the QFM buffer, temperatures of 1150 to 1250 C and spinel composition (early Cr-bearing and later Ti-magnetite) appropriate for basic magma differentiation. When coupled with major element modelling of liquid lines of descent, these values (D(Ni) sp/melt=10 and D(Co) sp/melt=5) closely reproduce the compositional variation observed in komatiite, mid-ocean ridge basalt (MORB), ocean island basalt (OIB) and basalt to rhyolite suites.

Spinel Ferrite Core–Shell Nanostructures by a Versatile Solvothermal Seed-Mediated Growth Approach and Study of Their Nanointerfaces

DOE PAGES

Sanna Angotzi, Marco; Musinu, Anna; Mameli, Valentina; ...

2017-07-23

An easy, low-cost, repeatable seed-mediated growth approach in solvothermal condition has been proposed to synthesize bimagnetic spinel ferrite core–shell heterostructures in the 10–20 nm particle size range. Cobalt ferrite and manganese ferrite nanoparticles (CoFe 2O 4 and MnFe 2O 4) have been coated with isostructural spinel ferrites like maghemite/magnetite, MnFe 2O 4, and CoFe 2O 4 with similar cell parameters to create different heterostructures. The conventional study of the structure, morphology, and composition has been combined with advanced techniques in order to achieve details on the interface at the nanoscale level. Clear evidence of the heterostructure formation have been obtainedmore » (i) indirectly by comparing the 57Fe Mössbauer spectra of the core–shell samples and an ad hoc mechanical mixture and (ii) directly by mapping the nanoparticles’ chemical composition by electron energy loss spectroscopy (EELS) and energy-dispersive X-ray spectroscopy (EDX) in the scanning transmission electron microscopy mode (STEM). Additionally, chemical-sensitive electron tomography in STEM-EDX mode has been applied in order to obtain detailed 3D images with a sub-nanometer spatial resolution.« less

Spinel Ferrite Core–Shell Nanostructures by a Versatile Solvothermal Seed-Mediated Growth Approach and Study of Their Nanointerfaces

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

Sanna Angotzi, Marco; Musinu, Anna; Mameli, Valentina

An easy, low-cost, repeatable seed-mediated growth approach in solvothermal condition has been proposed to synthesize bimagnetic spinel ferrite core–shell heterostructures in the 10–20 nm particle size range. Cobalt ferrite and manganese ferrite nanoparticles (CoFe 2O 4 and MnFe 2O 4) have been coated with isostructural spinel ferrites like maghemite/magnetite, MnFe 2O 4, and CoFe 2O 4 with similar cell parameters to create different heterostructures. The conventional study of the structure, morphology, and composition has been combined with advanced techniques in order to achieve details on the interface at the nanoscale level. Clear evidence of the heterostructure formation have been obtainedmore » (i) indirectly by comparing the 57Fe Mössbauer spectra of the core–shell samples and an ad hoc mechanical mixture and (ii) directly by mapping the nanoparticles’ chemical composition by electron energy loss spectroscopy (EELS) and energy-dispersive X-ray spectroscopy (EDX) in the scanning transmission electron microscopy mode (STEM). Additionally, chemical-sensitive electron tomography in STEM-EDX mode has been applied in order to obtain detailed 3D images with a sub-nanometer spatial resolution.« less

Scale up of large ALON® and spinel windows

NASA Astrophysics Data System (ADS)

Goldman, Lee M.; Kashalikar, Uday; Ramisetty, Mohan; Jha, Santosh; Sastri, Suri

2017-05-01

Aluminum Oxynitride (ALON® Transparent Ceramic) and Magnesia Aluminate Spinel (Spinel) combine broadband transparency with excellent mechanical properties. Their cubic structure means that they are transparent in their polycrystalline form, allowing them to be manufactured by conventional powder processing techniques. Surmet has scaled up its ALON® production capability to produce and deliver windows as large as 4.4 sq ft. We have also produced our first 6 sq ft window. We are in the process of producing 7 sq ft ALON® window blanks for armor applications; and scale up to even larger, high optical quality blanks for Recce window applications is underway. Surmet also produces spinel for customers that require superior transmission at the longer wavelengths in the mid wave infra-red (MWIR). Spinel windows have been limited to smaller sizes than have been achieved with ALON. To date the largest spinel window produced is 11x18-in, and windows 14x20-in size are currently in process. Surmet is now scaling up its spinel processing capability to produce high quality window blanks as large as 19x27-in for sensor applications.

Ruthenium red-induced bundling of bacterial cell division protein, FtsZ.

PubMed

Santra, Manas Kumar; Beuria, Tushar K; Banerjee, Abhijit; Panda, Dulal

2004-06-18

The assembly of FtsZ plays a major role in bacterial cell division, and it is thought that the assembly dynamics of FtsZ is a finely regulated process. Here, we show that ruthenium red is able to modulate FtsZ assembly in vitro. In contrast to the inhibitory effects of ruthenium red on microtubule polymerization, we found that a substoichiometric concentration of ruthenium red strongly increased the light-scattering signal of FtsZ assembly. Further, sedimentable polymer mass was increased by 1.5- and 2-fold in the presence of 2 and 10 microm ruthenium red, respectively. In addition, ruthenium red strongly reduced the GTPase activity and prevented dilution-induced disassembly of FtsZ polymers. Electron microscopic analysis showed that 4-10 microm of ruthenium red produced thick bundles of FtsZ polymers. The significant increase in the light-scattering signal and pelletable polymer mass in the presence of ruthenium red seemed to be due to the bundling of FtsZ protofilaments into larger polymers rather than the actual increase in the level of polymeric FtsZ. Furthermore, ruthenium red was found to copolymerize with FtsZ, and the copolymerization of substoichiometric amounts of ruthenium red with FtsZ polymers promoted cooperative assembly of FtsZ that produced large bundles. Calcium inhibited the binding of ruthenium red to FtsZ. However, a concentration of calcium 1000-fold higher than that of ruthenium red was required to produce similar effects on FtsZ assembly. Ruthenium red strongly modulated FtsZ polymerization, suggesting the presence of an important regulatory site on FtsZ and suggesting that a natural ligand, which mimics the action of ruthenium red, may regulate the assembly of FtsZ in bacteria.

Highly sensitive catalytic spectrophotometric determination of ruthenium

NASA Astrophysics Data System (ADS)

Naik, Radhey M.; Srivastava, Abhishek; Prasad, Surendra

2008-01-01

A new and highly sensitive catalytic kinetic method (CKM) for the determination of ruthenium(III) has been established based on its catalytic effect on the oxidation of L-phenylalanine ( L-Pheala) by KMnO 4 in highly alkaline medium. The reaction has been followed spectrophotometrically by measuring the decrease in the absorbance at 526 nm. The proposed CKM is based on the fixed time procedure under optimum reaction conditions. It relies on the linear relationship where the change in the absorbance (Δ At) versus added Ru(III) amounts in the range of 0.101-2.526 ng ml -1 is plotted. Under the optimum conditions, the sensitivity of the proposed method, i.e. the limit of detection corresponding to 5 min is 0.08 ng ml -1, and decreases with increased time of analysis. The method is featured with good accuracy and reproducibility for ruthenium(III) determination. The ruthenium(III) has also been determined in presence of several interfering and non-interfering cations, anions and polyaminocarboxylates. No foreign ions interfered in the determination ruthenium(III) up to 20-fold higher concentration of foreign ions. In addition to standard solutions analysis, this method was successfully applied for the quantitative determination of ruthenium(III) in drinking water samples. The method is highly sensitive, selective and very stable. A review of recently published catalytic spectrophotometric methods for the determination of ruthenium(III) has also been presented for comparison.

Dipole defects in MgAl2O4 spinel crystals

NASA Astrophysics Data System (ADS)

Ayres, F.; de Souza, S. S.; Blak, A. R.

In order to study defects of dipole origin in normal and inverse spinel structures, Thermally Stimulated Depolarisation Current (TSDC) measurements have been carried out in MgAl2O4 spinel crystals doped with Fe, Cr, Mn and Co. The TSDC spectrum of the as-received sample labelled R shows two bands at 160K and 290K. Temperatures above 700K destroy the 290K band and γ-irradiation up to 1,500kGy restores the peak. In another sample labelled UC, the 290K band, of dipole origin, is only detected after γ-irradiation. The dipole origin of the 160K band has already been verified. This band is affected neither by γ-irradiation nor by thermal treatment. The reduction of the 290K band is observed when heating the samples between 350K and 480K for three minutes at each temperature. The correlation between the thermal reduction of the 290K band and the study of V-centres in MgAl2O4 spinels indicates the possible attribution of the band to V-type centres.

Agonist-stimulated cobalt uptake provides selective visualization of neurons expressing AMPA- or kainate-type glutamate receptors in the retina.

PubMed

Pourcho, Roberta G; Qin, Pu; Goebel, Dennis J; Fyk-Kolodziej, Bozena

2002-12-16

Fast-acting excitatory neurotransmission in the retina is mediated primarily by glutamate, acting at alpha-amino-3-hydroxy-5-methyl-4-isoxazole propionic acid (AMPA) -selective and kainate-selective receptors. To localize these sites of action, cat retinas were stimulated with either AMPA or kainate and processed for histochemical visualization of cobalt uptake through calcium-permeable channels. Treatment with both agonists resulted in staining of A- and B-type horizontal cells and several types of OFF cone bipolar cells; there was no evidence for staining of ON cone bipolar cells or rod bipolar cells. The subpopulations of OFF cone bipolar cells differed in their responses with two distinct types that stained heavily with cobalt after exposure to AMPA and three different types that were preferentially labeled after exposure to kainate. Although many amacrine and ganglion cells appeared to respond to both agonists, AII amacrine cells were stained after stimulation by AMPA but not by kainate. The OFF cone bipolar cells that exhibit AMPA-stimulated cobalt uptake were found to have a high level of correspondence with cells that show immunocytochemical staining for the AMPA-selective glutamate receptor subunits GluR1 and GluR2/3. Similarly, the cone bipolar cells exhibiting kainate-stimulated cobalt uptake resemble those that are immunoreactive for the kainate subunit GluR5. The results indicate that, whereas many retinal neurons express both AMPA and kainate receptors, AII amacrine cells and subpopulations of OFF cone bipolar cells are limited to the expression of either AMPA or kainate receptors. This differential expression may contribute to the unique character of transmission by these cell types. Copyright 2002 Wiley-Liss, Inc.

An improved soft-chemistry approach to the preparation of spinel powders

NASA Astrophysics Data System (ADS)

Cook, Ronald

2007-04-01

Spinel powders for the production of transparent polycrystalline ceramic windows have been produced using a number of traditional ceramic and sol-gel methods. We have demonstrated that magnesium aluminate spinel powders produced from the reaction of organo-magnesium compounds with surface modified boehmite precursors can be used to produce high quality transparent spinel parts. In previous work, the spinel powders were prepared by the reaction of surface-modified boehmite nanoparticles with magnesium acetylacetonate. While the magnesium acetylacetonate can produce small quantities of high quality spinel powders, it use for large scale production of spinel powders is problematic. Through a thermodynamic analysis we have identified a new high-purity, low-cost, low-toxicity organomagnesium compound that reacts the with surface modified boehmite nanoparticles to produce a spinel precursor. The magnesium doped precursor readily transforms into pure phase spinel at temperature between 900°C and 1200°C.

High-temperature X-ray diffraction study of crystallization and phase segregation on spinel-type lithium manganese oxides

NASA Astrophysics Data System (ADS)

Komaba, Shinichi; Yabuuchi, Naoaki; Ikemoto, Sachi

2010-01-01

To study crystallization process of spinel-type Li 1+xMn 2-xO 4, in-situ high-temperature X-ray diffraction technique (HT-XRD) was utilized for the mixture consisting of Li 2CO 3 and Mn 2O 3 as starting material in the temperature range of 25-700 °C. In-situ HT-XRD analysis directly revealed that crystallization process of Li 1+xMn 2-xO 4 was significantly affected by the difference in the Li/Mn molar ratio in the precursor. Single phase of stoichiometric LiMn 2O 4 formed at 700 °C. The formation of single phase of spinel was achieved at the lower temperature than the stoichiometric sample as Li/Mn molar ratio in the precursor increased. Lattice parameter of the stoichiometric LiMn 2O 4 at 25 °C was 8.24 Å and expanded to 8.31 Å at 700 °C, which corresponds to the approximately 3% expansion in the unit cell volume. From the slope of the lattice parameter change as a function of temperatures, linear thermal expansion coefficient of the stoichiometric LiMn 2O 4 was calculated to be 1.2×10 -5 °C -1 in this temperature range. When the Li/Mn molar ratio in Li 1+xMn 2-xO 4 increased ( x > 0.1), the spinel phase segregated into the Li 1+yMn 2-yO 4 ( x > y) and Li 2MnO 3 during heating, which involved the oxygen loss from the materials. During the cooling process from 700 °C, and the segregated phase merged into Li 1+xMn 2-xO 4 with oxygen incorporation. Such trend directly observed by in-situ HT-XRD was supported by thermal gravimetric analysis as reversible weight (oxygen) loss/gain at higher temperature (500-700 °C).

Experimental crystallization of chrome spinel in FAMOUS basalt 527-1-1

NASA Astrophysics Data System (ADS)

Fisk, Martin R.; Bence, A. E.

1980-06-01

FAMOUS basalt 527-1-1 (a high-Mg oceanic pillow basalt) has three generations of spinel which can be distinguished petrographically and chemically. The first generation (Group I) have reaction coronas and are high in Al 2O 3. The second generation (Group II) have no reaction coronas and are high in Cr 2O 3 and the third generation (Group III) are small, late-stage spinels with intermediate Al 2O 3 and Cr 2O 3. Experimental synthesis of spinels from fused rock powder of this basalt was carried out at temperatures of 1175-1270°C and oxygen fugacities of 10 -5.5 to 10 -10 atm at 1 atm pressure. Spinel is the liquidus phase at oxygen fugacities of 10 -8.5 atm and higher but it does not crystallize at any temperature at oxygen fugacities less than 10 -9.5. The composition of our spinels synthesized at 1230-1250°C and 10 -9 atm f O 2 are most similar to the high-Cr spinels (Group II) found in the rock. Spinels synthesized at 1200°C and 10 -8.5 atm O 2 are chemically similar to the Group III spinels in 527-1-1. We did not synthesize spinel at any temperature or oxygen fugacity that are similar to the high-Al (Group I) spinel found in 527-1-1. These results indicate that the high-Cr (Group II) spinel is the liquidus phase in 527-1-1 at low pressure and Group III spinel crystallize below the liquidus (˜1200°C) after eruption of the basalt on the sea floor. The high-Al spinel (Group I) could have crystallized at high pressure or from a magma enriched in Al and perhaps Mg compared to 527-1-1.

History of development of polycrystalline optical spinel in the U.S.

NASA Astrophysics Data System (ADS)

Harris, Daniel C.

2005-05-01

Optical quality polycrystalline spinel (MgAl2O4) has been sought as a visible- and infrared-transmitting material since the 1960s because of its potential for transparent armor and durable sensor windows. Its physical properties were known from synthetic crystals available since ~1950 from Linde Air Products. In the late 1960s, methods to process powder into transparent, polycrystalline spinel were investigated at North Carolina State University, General Electric Co., AVCO, and Westinghouse, mainly with Government support. The leading figure in the development of polycrystalline spinel was Don Roy, who began work on spinel at Coors Ceramics around 1970, initially for transparent armor. In the late 1970s, both Coors Ceramics and Raytheon Research Division were funded to make spinel for the infrared dome of the Advanced Short-Range Air-to-Air Missile, an application that disappeared by 1980. In the late 1980s, there was another burst of activity when spinel was a candidate for the Stinger Missile. By 1990, Raytheon had dropped spinel and the material was spun off by Coors Ceramics to Alpha Optical Systems, whose technical effort was led by Don Roy. With low commercial sales potential for spinel, Alpha was dissolved in 1993. RCS Technologies took over a Government contract seeking 200-mm spinel domes for the Harrier aircraft, but this effort ended in 1996 and RCS was dissolved. In 1998, the Army enlisted TA&T to make spinel for transparent armor. Other potential applications appeared and TA&T received numerous Government development contracts. Demand for the still-unavailable spinel drew Surmet to begin development in 2002. In early 2005, spinel is under active development at TA&T and Surmet.

Metalorganic Chemical Vapor Deposition of Ruthenium-Doped Diamond like Carbon Films

NASA Technical Reports Server (NTRS)

Sunkara, M. K.; Ueno, M.; Lian, G.; Dickey, E. C.

2001-01-01

We investigated metalorganic precursor deposition using a Microwave Electron Cyclotron Resonance (ECR) plasma for depositing metal-doped diamondlike carbon films. Specifically, the deposition of ruthenium doped diamondlike carbon films was investigated using the decomposition of a novel ruthenium precursor, Bis(ethylcyclopentadienyl)-ruthenium (Ru(C5H4C2H5)2). The ruthenium precursor was introduced close to the substrate stage. The substrate was independently biased using an applied RF power. Films were characterized using Fourier Transform Infrared Spectroscopy (FTIR), Transmission Electron Microscopy (TEM) and Four Point Probe. The conductivity of the films deposited using ruthenium precursor showed strong dependency on the deposition parameters such as pressure. Ruthenium doped sample showed the presence of diamond crystallites with an average size of approx. 3 nm while un-doped diamondlike carbon sample showed the presence of diamond crystallites with an average size of 11 nm. TEM results showed that ruthenium was atomically dispersed within the amorphous carbon network in the films.

Identification of a New Spinel-Rich Lunar Rock Type by the Moon Mineralogy Mapper (M (sup 3))

NASA Technical Reports Server (NTRS)

Pieters, C. M.; Boardman, J.; Buratti, B.; Clark, R.; Combe, J. P.; Green, R.; Goswami, J. N.; Head, J. W., III; Hicks, M.; Isaacson, P.;

Temperature dependent and applied field strength dependent magnetic study of cobalt nickel ferrite nano particles: Synthesized by an environmentally benign method

NASA Astrophysics Data System (ADS)

Sontu, Uday Bhasker; G, Narsinga Rao; Chou, F. C.; M, V. Ramana Reddy

2018-04-01

Spinel ferrites have come a long way in their versatile applications. The ever growing applications of these materials demand detailed study of material properties and environmental considerations in their synthesis. In this article, we report the effect of temperature and applied magnetic field strength on the magnetic behavior of the cobalt nickel ferrite nano powder samples. Basic structural properties of spinel ferrite nano particles, that are synthesized by an environmentally benign method of auto combustion, are characterized through XRD, TEM, RAMAN spectroscopy. Diffuse Reflectance Spectroscopy (DRS) is done to understand the nickel substitution effect on the optical properties of cobalt ferrite nano particles. Thermo magnetic studies using SQUID in the temperature range 5 K to 400 K and room temperature (300 K) VSM studies are performed on these samples. Fields of 0Oe (no applied field: ZF), 1 kOe (for ZFC and FC curves), 5 kOe (0.5 T), 50 kOe (5T) (for M-H loop study) are used to study the magnetic behavior of these nano particles. The XRD,TEM analysis suggest 40 nm crystallites that show changes in the cation distribution and phase changes in the spinel structure with nickel substitution. Raman micrographs support phase purity changes and cation redistributions with nickel substitution. Diffuse reflectance study on powder samples suggests two band gap values for nickel rich compounds. The Magnetic study of these sample nano particles show varied magnetic properties from that of hard magnetic, positive multi axial anisotropy and single-magnetic-domain structures at 5 K temperature to soft magnetic core shell like structures at 300 K temperature. Nickel substitution effect is non monotonous. Blocking temperature of all the samples is found to be higher than the values suggested in the literature.

METABOLISM OF RUTHENIUM IN THE RAT. Technical Documentary Report

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

Traynor, J.E.; Leeper, S.W.

1961-12-01

Seventeen Sprague-Dawley rats were injected intramuscularly and intraperitoneally with ruthenium-106. The amount of this isotope was determined daily for 5 weeks in the urine and feces. Animals were sacrificed at intervals and the various organs were analyzed for ruthenium. It was noted from this experiment that the pathways of absorption, metabolism, and excretion are dependent on the route of administration of ruthenium. (auth)

DFT studies on H 2O adsorption and its effect on CO oxidation over spinel Co 3O 4 (110) surface

NASA Astrophysics Data System (ADS)

Xu, Xiang Lan; Li, Jun Qian

2011-12-01

Adsorption of H2O and its effect on CO oxidation over spinel Co3O4 (110) surface were studied by density functional theory calculations. H2O is adsorbed favorably at the octahedral cobalt (Cooct) site through O atom on the surface. Hydrogen bonding interaction between 1s orbitals of H atoms in H2O and the 2p orbitals of surface active oxygen sites plays a key role for H2O adsorption. The inhibition effect of H2O adsorption on the CO oxidation over the surfaces is attributed to the competition between H2O and CO molecules for the surface twofold coordinated oxygen site.

The Record of Meteorite Infall During the Jurassic as Derived from Chrome-Spinel Grains

NASA Astrophysics Data System (ADS)

Caplan, C.; Huss, G. R.; Schmitz, B.; Nagashima, K.

2017-12-01

We study sediment-dispersed chrome-spinels in the stratigraphic record to determine how the types and amounts of meteorites falling to Earth have changed over time. The parent meteorite type of chrome-spinel grains can be determined using characteristic elemental and O-isotope compositions. In this study, we present data on grains from the Jurassic period ( 160 Ma). The Jurassic was chosen because of the possibility of discovering remnants from the breakup of the Baptistina asteroid family estimated to have occurred 160 Ma (+30, -20 Myr) (Bottke et al., 2007). Chrome-spinel grains derived from 400 kg of condensed limestone near Carcabuey, Spain were measured for their chemical compositions by electron microprobe, and their O-isotope compositions were measured by ion microprobe at the University of Hawai'i. Initial results show that 43% of the grains come from ordinary chondrites (OCs) and 18% from known types of achondrites. The remaining grains are extraterrestrial, as shown by their O-isotopes, but have not yet been classified. Some may represent material that is not currently falling on Earth. Meteorites falling on Earth today are 90.6% OCs and 7.1% achondrites. The Jurassic samples show a lower percentage of chrome-spinels from OCs (even though OCs are chrome-spinel rich). Other time periods also show meteorite abundances that are different than today. About 466 Ma there was an overwhelming influx of L-chondritic material (>99% of infalling material), due to the breakup of the L-chondrite parent body (Schmitz et al., 2001). One million years prior to the breakup, 56% of the infalling meteorites were OCs and 44% were achondrites (Heck et al., 2017). A new study suggests that 80% of the material falling in the Early Cretaceous (145-133 Ma) were from OCs and 10% were from achondrites (Schmitz et al., 2017). With just a few windows into Earth's past, we are already seeing significant changes in the mixture of materials that have fallen to Earth throughout time.

Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

NASA Technical Reports Server (NTRS)

Valdez, Thomas I.; Narayan, Sri R.; Billings, Keith J.

2011-01-01

NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

Cobalt.

PubMed

Fowler, Joseph F

2016-01-01

Cobalt has been a recognized allergen capable of causing contact dermatitis for decades. Why, therefore, has it been named 2016 "Allergen of the Year"? Simply put, new information has come to light in the last few years regarding potential sources of exposure to this metallic substance. In addition to reviewing some background on our previous understanding of cobalt exposures, this article will highlight the recently recognized need to consider leather as a major site of cobalt and the visual cues suggesting the presence of cobalt in jewelry. In addition, a chemical spot test for cobalt now allows us to better identify its presence in suspect materials.

Conformal ALON® and spinel windows

NASA Astrophysics Data System (ADS)

Goldman, Lee M.; Smith, Mark; Ramisetty, Mohan; Jha, Santosh; Sastri, Suri

2017-05-01

The requirements for modern aircraft based reconnaissance systems are driving the need for conformal windows for future sensor systems. However, limitations on optical systems and the ability to produce windows in complex geometries currently limit the geometry of existing windows and window assemblies to faceted assemblies of flat windows. ALON consists primarily of aluminum and oxygen, similar to that of alumina, with a small amount of nitrogen added to help stabilize the cubic gamma-AlON phase. ALON's chemical similarity to alumina, translates into a robust manufacturing process. This ease of processing has allowed Surmet to produce ALON windows and domes in a wide variety of geometries and sizes. Spinel (MgAl2O4) contains equal molar amounts of MgO and Al2O3, and is a cubic material, that transmits further into the Infrared than ALON. Spinel is produced via powder processing techniques similar to those used to produce ALON. Surmet is now applying the lessons learned with ALON to produce conformal spinel windows and domes as well.

Occurrence of chromian, hercynitic spinel ("pleonaste") in Apollo-14 samples and its petrologic implications

USGS Publications Warehouse

Roedder, E.; Weiblen, P.W.

1972-01-01

Many isolated grains of a reddish pleonaste-type spinel occur in fines and metabreccia samples, particularly 14 319. Electron microprobe analyses (104) of spinels and their associated phases include 58 of pleonaste which show Mg/(Mg + Fe) 0.44-0.62 and Cr/(Cr + Al) 0.017-0.134 (atomic), plus minor amounts of other ions, and differ greatly from almost all previously recorded lunar spinels; almost no spinels of intermediate composition were found. Two types of compositional zoning exist: a diffuse primary one with cores lower in Ti, and a narrow secondary one from reaction with matrix yielding rims higher in Cr, Ti, and Mn. At contacts with breccia matrix there is a narrow corona of almost pure plagioclase (An80-An94), free of opaque minerals and pyroxene. Two types of solid inclusions found in the pleonaste are calcic plagioclase, and tiny spherical masses of nickel-rich sulfide. Similar pleonaste occurs in crystalline rock clasts, mainly with plagioclase; one clast (A) consists only of coarse olivine, plagioclase, and pleonaste, with granulated grain boundaries suggestive of deformation. From composition and texture, this clast is one possible candidate for the mafic cumulate counterpart of the "anorthositic" crust. Another clast (B), also made solely of olivine, plagioclase and pleonaste, is itself a breccia. These data suggest a two-stage brecciation process: 1) disruption (probably pre-Imbrian) of a deep-seated pleonaste-bearing source rock like A and reconsolidation to form a breccia without addition of pyroxene, ilmenite or other minerals; and 2) disruption of this breccia to yield breccia clast B which was then incorporated into the Fra Mauro formation. ?? 1972.

Spinel and post-spinel phase assemblages in Zn 2TiO 4: an experimental and theoretical study

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

Zhang, Yanyao; Liu, Xi; Shieh, Sean R.

Zn2TiO4 spinel (Zn2TiO4-Sp) was synthesized by a solid-state reaction method (1573 K, room P and 72 h) and quasi-hydrostatically compressed to ~24 GPa using a DAC coupled with a synchrotron X-ray radiation (ambient T). We found that the Zn2TiO4-Sp was stable up to ~21 GPa and transformed to another phase at higher P. With some theoretical simulations, we revealed that this high-P phase adopted the CaTi2O4-type structure (Zn2TiO4-CT). Additionally, the isothermal bulk modulus (KT) of the Zn2TiO4-Sp was experimentally obtained as 156.0(44) GPa and theoretically obtained as 159.1(4) GPa, with its first pressure derivative K'TKT' as 3.8(6) and 4.37(4), respectively.more » The volumetric and axial isothermal bulk moduli of the Zn2TiO4-CT were theoretically obtained as KT = 150(2) GPa (K'TKT' = 5.4(2); for the volume), KT-a = 173(2) GPa (K'T-aKT-a' = 3.9(1); for the a-axis), KT-b = 74(2) GPa (K'T-bKT-b' = 7.0(2); for the b-axis), and KT-c = 365(8) GPa (K'T-cKT-c' = 1.5(4); for the c-axis), indicating a strong elastic anisotropy. The Zn2TiO4-CT was found as ~10.0 % denser than the Zn2TiO4-Sp at ambient conditions. The spinel and post-spinel phase assemblages for the Zn2TiO4 composition at high T have been deduced as Zn2TiO4-Sp, ZnTiO3-ilmenite + ZnO-wurtzite, ZnTiO3-ilmenite + ZnO-rock salt, ZnTiO3-perovskite + ZnO-rock salt, and Zn2TiO4-CT as P increases, which presumably implies a potential stability field for a CT-type Mg2SiO4 at very high P.« less

CO 2-rich komatiitic melt inclusions in Cr-spinels within beach sand from Gorgona Island, Colombia

NASA Astrophysics Data System (ADS)

Shimizu, Kenji; Shimizu, Nobumichi; Komiya, Tsuyoshi; Suzuki, Katsuhiko; Maruyama, Shigenori; Tatsumi, Yoshiyuki

2009-10-01

The volatile content of komatiite is a key to constrain the thermal and chemical evolution of the deep Earth. We report the volatile contents with major and trace element compositions of ~ 80 melt inclusions in chromian spinels (Cr-spinels) from beach sands on Gorgona Island, Colombia. Gorgona Island is a ~ 90 Ma volcanic island, where picrites and the youngest komatiites known on the Earth are present. Melt inclusions are classified into three types on the basis of their host Cr-spinel compositions: low Ti (P type), high Ti with high Cr # (K1 type) and high Ti with low Cr # (K2 type). Chemical variations of melt inclusions in the Cr-spinels cover all of the island's lava types. P-type inclusions mainly occur in the picrites, K1-type in high-TiO 2 komatiites (some enriched basalts: E-basalts) and K2-type in low-TiO 2 komatiites. The H 2O and CO 2 contents of melt inclusions within Cr-spinels from the beach sand are highly variable (H 2O: 0.03-0.9 wt.%; CO 2: 40-4000 ppm). Evaluation of volatile content is not entirely successful because of compositional alterations of the original melt by degassing, seawater/brine assimilation and post-entrapment modification of certain elements and volatiles. However, the occurrence of many melt inclusions with low H 2O/K 2O ratios indicates that H 2O/K 2O of Gorgona komatiite is not much different from that of modern mid-oceanic ridge basalt (MORB) or oceanic island basalt. Trend of CO 2/Nb and Zr/Y ratios, accounted for by two-component mixing between the least degassed primary komatiite and low-CO 2/Nb evolved basalt, allow us to estimate a primary CO 2/Nb ratio of 4000 ± 2200 or a CO 2 content of 0.16 ± 0.09 wt.%. The determined CO 2/Nb ratio is unusually high, compared to that of MORB (530). Although the presence of CO 2 in the Gorgona komatiite does not affect the magma generation temperature, CO 2 degassing may have contributed to the eruption of high-density magmas. High CO 2/Nb and the relatively anhydrous nature of

Metal oxide films on metal

DOEpatents

Wu, Xin D.; Tiwari, Prabhat

1995-01-01

A structure including a thin film of a conductive alkaline earth metal oxide selected from the group consisting of strontium ruthenium trioxide, calcium ruthenium trioxide, barium ruthenium trioxide, lanthanum-strontium cobalt oxide or mixed alkaline earth ruthenium trioxides thereof upon a thin film of a noble metal such as platinum is provided.

Synthesis of magnesium aluminate spinel by periclase and alumina chlorination

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

Orosco, Pablo, E-mail: porosco@unsl.edu.ar; Facultad de Química, Bioquímica y Farmacia, Universidad Nacional de San Luis Chacabuco y Pedernera, San Luis; Barbosa, Lucía

2014-11-15

Highlights: • Use of chlorination for the synthesis of magnesium aluminate spinel. • The reagents used were alumina, periclase and chlorine. • Isothermal and non-isothermal assays were performed in air and Cl{sub 2}–N{sub 2} flows. • The chlorination produced magnesium aluminate spinel at 700 °C. • Selectivity of the chlorination reaction to obtain spinel is very high. - Abstract: A pyrometallurgical route for the synthesis of magnesium aluminate spinel by thermal treatment of a mechanical mixture containing 29 wt% MgO (periclase) and 71 wt% Al{sub 2}O{sub 3} (alumina) in chlorine atmosphere was developed and the results were compared with thosemore » obtained by calcining the same mixture of oxides in air atmosphere. Isothermal and non-isothermal assays were performed in an experimental piece of equipment adapted to work in corrosive atmospheres. Both reagents and products were analyzed by differential thermal analysis (DTA), X-ray diffraction (XRD) and X-ray fluorescence (XRF). Thermal treatment in Cl{sub 2} atmosphere of the MgO–Al{sub 2}O{sub 3} mixture produces magnesium aluminate spinel at 700 °C, while in air, magnesium spinel is generated at 930 °C. The synthesis reaction of magnesium aluminate spinel was complete at 800 °C.« less

Compositional dependence of elastic moduli for transition-metal oxide spinels

NASA Astrophysics Data System (ADS)

Reichmann, H. J.; Jacobsen, S. D.; Boffa Ballaran, T.

2012-12-01

Spinel phases (AB2O4) are common non-silicate oxides in the Earth's crust and upper mantle. A characteristic of this mineral group is the ability to host a wide range of transition metals. Here we summarize the influence of transition metals (Fe, Zn, and Mn) on the pressure dependence of elastic moduli of related spinels (magnetite, gahnite, and franklinite) using GHz-ultrasonic interferometry. Measurements were carried out up to 10 GPa in diamond-anvil cells using hydrostatic pressure media. Transition metals with unfilled 3d orbitals strongly influence the elastic properties of spinels. Franklinite (Zn,Mn)Fe2O4 and magnetite Fe3O4 with transition metals on both A and B cation sites exhibit pressure-induced mode softening of C44, whereas C44 of gahnite(ZnAl2O4) and spinel (MgAl2O4) exhibit positive pressure derivatives of the shear moduli. Spinels with two transition elements tend to undergo phase changes at a lower pressure than those with none or only one transition metal. Along the Mn-Zn solid solution, the variation of moduli with composition is non-linear, and a mid-range franklinite composition studied here shows a minimum in C44 compared with either end-member: MnFe2O 4 or ZnFe2O4. In general, the linear variation of sound velocity with density (Birch's Law) is followed by spinels, however spinels containing only one or no transition metals follow a distinct slope from those containing transition metals on both A and B sites. The Cauchy relation, 0.5(C12 - C44) = P is fulfilled by spinels with only one or no transition metals, suggesting that that Coulomb interactions dominate. Spinels with two transition metals fail to meet the Cauchy relation, indicating strong directional dependence and covalent character of bonding. The bonding character of transition metals is crucial to understanding the elastic behavior of natural and synthetic spinel solid solutions containing transition metals.

Lunar Cordierite-Spinel Troctolite: Igneous History, and Volatiles

NASA Astrophysics Data System (ADS)

Treiman, A. H.; Gross, J.

2012-03-01

Apollo sample 15295,101 contains a cordierite spinel troctolite (Marvin et al., 1989). The cordierite is volatile-free, at least by EMP — more precise analyses are in progress. The troctolite may be a partial melt of a spinel-rich igneous cumulate.

Mononuclear ruthenium(III) complexes containing chelating thiosemicarbazones: Synthesis, characterization and catalytic property

NASA Astrophysics Data System (ADS)

Raja, N.; Ramesh, R.

2010-02-01

Mononuclear ruthenium(III) complexes of the type [RuX(EPh 3) 2(L)] (E = P or As; X = Cl or Br; L = dibasic terdentate dehydroacetic acid thiosemicarbazones) have been synthesized from the reaction of thiosemicarbazone ligands with ruthenium(III) precursors, [RuX 3(EPh 3) 3] (where E = P, X = Cl; E = As, X = Cl or Br) and [RuBr 3(PPh 3) 2(CH 3OH)] in benzene. The compositions of the complexes have been established by elemental analysis, magnetic susceptibility measurement, FT-IR, UV-vis and EPR spectral data. These complexes are paramagnetic and show intense d-d and charge transfer transitions in dichloromethane. The complexes show rhombic EPR spectra at LNT which are typical of low-spin distorted octahedral ruthenium(III) species. All the complexes are redox active and display an irreversible metal centered redox processes. Complex [RuCl(PPh 3) 2(DHA-PTSC)] ( 5) was used as catalyst for transfer hydrogenation of ketones in the presence of isopropanol/KOH and was found to be the active species.

Dating exhumed peridotite with spinel (U-Th)/He chronometry

NASA Astrophysics Data System (ADS)

Cooperdock, Emily H. G.; Stockli, Daniel F.

2018-05-01

The timing of cooling and exhumation of mantle peridotites in oceanic and continental settings has been challenging to determine using traditional geo- and thermochronometric techniques. Hence, the timing of the exhumation of mantle rocks to the Earth's surface at mid-ocean ridges, rifted and passive continental margins, and within continental volcanic and orogenic systems has remained largely elusive or only loosely constrained by relative age bracketing. Magmatic spinel [(Mg, Fe)(Al,Cr)2O4] is a ubiquitous primary mineral phase in mantle peridotites and is often the only primary mineral phase to survive surface weathering and serpentinization. This work explores spinel (U-Th)/He thermochronology as a novel tool to directly date the exhumation and cooling history of spinel-bearing mantle peridotite. Samples were chosen from a range of tectonic and petrologic settings, including a mid-ocean ridge abyssal peridotite (ODP Leg 209), an orogenic tectonic sliver of sub-continental mantle (Lherz massif, France), and a volcanic-rock hosted mantle xenolith (Green Knobs, NM). Spinel grains were selected based on grain size and morphology, screened for internal homogeneity using X-ray computed tomography, and air abraded to eliminate effects of alpha ejection/implantation. These case studies yield spinel He age results that are reproducible and generally in good agreement with independent age constraints. For ODP Leg 209, a spinel He age of 1.1 ± 0.3 Ma (2 SE) (n = 8) is consistent with independent U-Pb and magnetic anomaly ages for the exhumation of oceanic crust by detachment faulting along this segment of the slow-spreading ridge. Spinel from the Lherz massif yield He ages from 60-70 Ma (n = 3), which correspond well with independent thermochronometric constraints for cooling associated with Pyrenean collisional exhumation. Spinel from a mantle xenolith within a previously undated kimberlite diatreme at Green Knobs, New Mexico, generate a reproducible mean He age of 11

Untangling the History of Oceanic Peridotites Using Spinel Oxybarometry

NASA Astrophysics Data System (ADS)

Birner, S.; Warren, J. M.; Cottrell, E.; Davis, F. A.

2014-12-01

Comprehensive knowledge of the oxygen fugacity of the upper mantle is critical to understanding the processes associated with melt production, interaction, and extraction. Thus, it is important to understand how fO2 changes during a peridotite's thermal and petrologic history in the asthenospheric and lithospheric mantle, as metamorphic subsolidus reequilibration can result in changes to recorded fO2. A case study of Tongan forearc peridotites highlights the heterogeneity seen in mantle peridotites. We analyzed two dredges located 250 km apart along the trench: one dredge ranges in fO2 from 0.5 to 1 log unit above the QFM buffer, similar to analyses of supra-subduction zone xenoliths (e.g. Brandon and Draper, 1996; Wood and Virgo, 1989) while the other dredge ranges from QFM-0.75 to QFM+0.25 and exhibits high spinel Cr# (ranging from 0.45 to 0.75). Systematics between fO2, Ti concentration, olivine forsterite content, and Cr# within each dredge allow us to differentiate between the effects of melt extraction, melt interaction, and cooling. Because the spinel oxybarometry equation is dependent on temperature, it is important to be able to accurately determine the temperature recorded by peridotites. Though many geothermometers are available for mantle rocks, we assert that geothermometers based on Fe-Mg exchange between olivine and spinel are the most applicable to fO2 calculations, because the oxygen fugacity recorded by a mantle assemblage is primarily controlled by this exchange. Additionally, preliminary analyses of diffusion profiles across olivine-spinel grain boundaries provide insight into the cooling of peridotite in the oceanic lithosphere and its effects on oxygen fugacity. Mg-Fe exchange between olivine and spinel is controlled by the distribution coefficient, KD, which is dependent on both temperature and the proportion of Cr to other trivalent cations in spinel. We see an increase in olivine forsterite content towards the olivine-spinel interface

Cobalt recycling in the United States in 1998

USGS Publications Warehouse

Shedd, Kim B.

2002-01-01

This report is one of a series of reports on metals recycling. It defines and quantifies the 1998 flow of cobalt-bearing materials in the United States, from imports and stock releases through consumption and disposition, with particular emphasis on the recycling of industrial scrap (new scrap) and used products (old scrap). Because of cobalt?s many and diverse uses, numerous types of scrap were available for recycling by a wide variety of processes. In 1998, an estimated 32 percent of U.S. cobalt supply was derived from scrap. The ratio of cobalt consumed from new scrap to that from old scrap was estimated to be 50:50. Of all the cobalt in old scrap available for recycling, an estimated 68 percent was either consumed in the United States or exported to be recycled.

Photoelectrochemical and theoretical investigations of spinel type ferrites (MxFe3-xO4) for water splitting: a mini-review

NASA Astrophysics Data System (ADS)

Taffa, Dereje H.; Dillert, Ralf; Ulpe, Anna C.; Bauerfeind, Katharina C. L.; Bredow, Thomas; Bahnemann, Detlef W.; Wark, Michael

2017-01-01

Solar-assisted water splitting using photoelectrochemical cells (PECs) is one of the promising pathways for the production of hydrogen for renewable energy storage. The nature of the semiconductor material is the primary factor that controls the overall energy conversion efficiency. Finding semiconductor materials with appropriate semiconducting properties (stability, efficient charge separation and transport, abundant, visible light absorption) is still a challenge for developing materials for solar water splitting. Owing to the suitable bandgap for visible light harvesting and the abundance of iron-based oxide semiconductors, they are promising candidates for PECs and have received much research attention. Spinel ferrites are subclasses of iron oxides derived from the classical magnetite (FeIIFe2IIIO4) in which the FeII is replaced by one (some cases two) additional divalent metals. They are generally denoted as MxFe3-xO4 (M=Ca, Mg, Zn, Co, Ni, Mn, and so on) and mostly crystallize in spinel or inverse spinel structures. In this mini review, we present the current state of research in spinel ferrites as photoelectrode materials for PECs application. Strategies to improve energy conversion efficiency (nanostructuring, surface modification, and heterostructuring) will be presented. Furthermore, theoretical findings related to the electronic structure, bandgap, and magnetic properties will be presented and compared with experimental results.

Study of structural and magnetic properties of cobalt ferrite nanoparticles sintered at different temperature

NASA Astrophysics Data System (ADS)

Kumari, Mukesh; Bhatnagar, Mukesh Chander

2018-05-01

Cobalt ferrite (CFO) has been synthesized in the form of nanoparticles (NPs) through sol-gel auto-combustion method. The prepared NPs of CFO were sintered for four hours at various temperatures from 300°C to 900°C. The physical properties of the sintered samples have been optimized using X-ray diffraction (XRD), Raman spectroscopy and physical properties measurement system (PPMS). The XRD and Raman studies have confirmed the cubic spinel phase formation of CFO NPs. XRD results showed that as we increase the sintering temperature the crystallite size of particles increases. Whereas the magnetic studies revealed that the saturation magnetization (MS) increases while the coercivity (HC) of nanoparticles decreases with increase of sintering temperature.

Empirical constraints on partitioning of platinum group elements between Cr-spinel and primitive terrestrial magmas

NASA Astrophysics Data System (ADS)

Park, Jung-Woo; Kamenetsky, Vadim; Campbell, Ian; Park, Gyuseung; Hanski, Eero; Pushkarev, Evgeny

2017-11-01

Recent experimental studies and in situ LA-ICP-MS analysis on natural Cr-spinel have shown that Rh and IPGEs (Ir-group platinum group elements: Ru, Ir, Os) are enriched in the lattice of Cr-spinel. However, the factors controlling the partitioning behaviour of these elements are not well constrained. In this study, we report the Rh, IPGE, and trace element contents in primitive Cr-spinel, measured by LA-ICP-MS, from nine volcanic suites covering various tectonic settings including island arc picrites, boninites, large igneous province picrites and mid-ocean ridge basalts. The aim is to understand the factors controlling the enrichment of Rh and IPGEs in Cr-spinels, to estimate empirical partition coefficients between Cr-spinel and silicate melts, and to investigate the role of Cr-spinel fractional crystallization on the PGE geochemistry of primitive magmas during the early stages of fractional crystallization. There are systematic differences in trace elements, Rh and IPGEs in Cr-spinels from arc-related magmas (Arc Group Cr-spinel), intraplate magmas (Intraplate Group Cr-spinel), and mid-ocean ridge magmas (MORB Group Cr-spinel). Arc Group Cr-spinels are systematically enriched in Sc, Co and Mn and depleted in Ni compared to the MORB Group Cr-spinels. Intraplate Group Cr-spinels are distinguished from the Arc Group Cr-spinels by their high Ni contents. Both the Arc and Intraplate Group Cr-spinels have total Rh and IPGE contents of 22-689 ppb whereas the MORB Group Cr-spinels are depleted in Rh and IPGE (total < 20 ppb). Palladium and Pt contents are below detection limit for all of the studied Cr-spinels (<1-5 ppb). The time-resolved spectra of LA-ICP-MS data for Cr-spinels mostly show constant count rates for trace element and Rh and IPGEs, suggesting homogeneous distribution of these elements in Cr-spinels. The PGE spikes observed in several Cr-spinels were interpreted to be PGE-bearing mineral inclusions and excluded from calculating the PGE contents of the Cr-spinels

Integrated thick-film nanostructures based on spinel ceramics

PubMed Central

2014-01-01

Integrated temperature-humidity-sensitive thick-film structures based on spinel-type semiconducting ceramics of different chemical compositions and magnesium aluminate ceramics were prepared and studied. It is shown that temperature-sensitive thick-film structures possess good electrophysical characteristics in the region from 298 to 358 K. The change of electrical resistance in integrated thick-film structures is 1 order, but these elements are stable in time and can be successfully used for sensor applications. PMID:24670141

Synthesis and magnetic properties of cobalt-iron/cobalt-ferrite soft/hard magnetic core/shell nanowires

NASA Astrophysics Data System (ADS)

Leandro Londoño-Calderón, César; Moscoso-Londoño, Oscar; Muraca, Diego; Arzuza, Luis; Carvalho, Peterson; Pirota, Kleber Roberto; Knobel, Marcelo; Pampillo, Laura Gabriela; Martínez-García, Ricardo

2017-06-01

A straightforward method for the synthesis of CoFe2.7/CoFe2O4 core/shell nanowires is described. The proposed method starts with a conventional pulsed electrodeposition procedure on alumina nanoporous template. The obtained CoFe2.7 nanowires are released from the template and allowed to oxidize at room conditions over several weeks. The effects of partial oxidation on the structural and magnetic properties were studied by x-ray spectrometry, magnetometry, and scanning and transmission electron microscopy. The results indicate that the final nanowires are composed of 5 nm iron-cobalt alloy nanoparticles. Releasing the nanowires at room conditions promoted surface oxidation of the nanoparticles and created a CoFe2O4 shell spinel-like structure. The shell avoids internal oxidation and promotes the formation of bi-magnetic soft/hard magnetic core/shell nanowires. The magnetic properties of both the initial single-phase CoFe2.7 nanowires and the final core/shell nanowires, reveal that the changes in the properties from the array are due to the oxidation more than effects associated with released processes (disorder and agglomeration).

Synthesis and magnetic properties of cobalt-iron/cobalt-ferrite soft/hard magnetic core/shell nanowires.

PubMed

Londoño-Calderón, César Leandro; Moscoso-Londoño, Oscar; Muraca, Diego; Arzuza, Luis; Carvalho, Peterson; Pirota, Kleber Roberto; Knobel, Marcelo; Pampillo, Laura Gabriela; Martínez-García, Ricardo

2017-06-16

A straightforward method for the synthesis of CoFe 2.7 /CoFe 2 O 4 core/shell nanowires is described. The proposed method starts with a conventional pulsed electrodeposition procedure on alumina nanoporous template. The obtained CoFe 2.7 nanowires are released from the template and allowed to oxidize at room conditions over several weeks. The effects of partial oxidation on the structural and magnetic properties were studied by x-ray spectrometry, magnetometry, and scanning and transmission electron microscopy. The results indicate that the final nanowires are composed of 5 nm iron-cobalt alloy nanoparticles. Releasing the nanowires at room conditions promoted surface oxidation of the nanoparticles and created a CoFe 2 O 4 shell spinel-like structure. The shell avoids internal oxidation and promotes the formation of bi-magnetic soft/hard magnetic core/shell nanowires. The magnetic properties of both the initial single-phase CoFe 2.7 nanowires and the final core/shell nanowires, reveal that the changes in the properties from the array are due to the oxidation more than effects associated with released processes (disorder and agglomeration).

Thermodynamic properties of gaseous ruthenium species.

PubMed

Miradji, Faoulat; Souvi, Sidi; Cantrel, Laurent; Louis, Florent; Vallet, Valérie

2015-05-21

The review of thermodynamic data of ruthenium oxides reveals large uncertainties in some of the standard enthalpies of formation, motivating the use of high-level relativistic correlated quantum chemical methods to reduce the level of discrepancies. The reaction energies leading to the formation of ruthenium oxides RuO, RuO2, RuO3, and RuO4 have been calculated for a series of reactions. The combination of different quantum chemical methods has been investigated [DFT, CASSCF, MRCI, CASPT2, CCSD(T)] in order to predict the geometrical parameters, the energetics including electronic correlation and spin-orbit coupling. The most suitable method for ruthenium compounds is the use of TPSSh-5%HF for geometry optimization, followed by CCSD(T) with complete basis set (CBS) extrapolations for the calculation of the total electronic energies. SO-CASSCF seems to be accurate enough to estimate spin-orbit coupling contributions to the ground-state electronic energies. This methodology yields very accurate standard enthalpies of formations of all species, which are either in excellent agreement with the most reliable experimental data or provide an improved estimate for the others. These new data will be implemented in the thermodynamical databases that are used by the ASTEC code (accident source term evaluation code) to build models of ruthenium chemistry behavior in severe nuclear accident conditions. The paper also discusses the nature of the chemical bonds both from molecular orbital and topological view points.

Structure-reactivity relationships in the hydrogenation of carbon dioxide with ruthenium complexes bearing pyridinylazolato ligands.

PubMed

Muller, Keven; Sun, Yu; Heimermann, Andreas; Menges, Fabian; Niedner-Schatteburg, Gereon; van Wüllen, Christoph; Thiel, Werner R

2013-06-10

Pyridinylazolato (N-N') ruthenium(II) complexes of the type [(N-N')RuCl(PMe3)3] have been obtained in high yields by treating the corresponding functionalised azolylpyridines with [RuCl2 (PMe3)4] in the presence of a base. (15)N NMR spectroscopy was used to elucidate the electronic influence of the substituents attached to the azolyl ring. The findings are in agreement with slight differences in the bond lengths of the ruthenium complexes. Furthermore, the electronic nature of the azolate moiety modulates the catalytic activity of the ruthenium complexes in the hydrogenation of carbon dioxide under supercritical conditions and in the transfer hydrogenation of acetophenone. DFT calculations were performed to shed light on the mechanism of the hydrogenation of carbon dioxide and to clarify the impact of the electronic nature of the pyridinylazolate ligands. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of PVP-stabilized ruthenium colloids with low boiling point alcohols.

PubMed

Zhang, Yuqing; Yu, Jiulong; Niu, Haijun; Liu, Hanfan

2007-09-15

A route to the preparation of poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized ruthenium colloids by refluxing ruthenium(III) chloride in low boiling point alcohols was developed. Deep purple colloids with shuttle-like ruthenium particles were also synthesized. XPS measurement verified the nanoparticles were in the metallic state. The morphology of metal nanoparticles was characterized by UV-visible absorption spectrophotometry, TEM and XRD.

Effects of cobalt in nickel-base superalloys

NASA Technical Reports Server (NTRS)

Tien, J. K.; Jarrett, R. N.

1983-01-01

The role of cobalt in a representative wrought nickel-base superalloy was determined. The results show cobalt affecting the solubility of elements in the gamma matrix, resulting in enhanced gamma' volume fraction, in the stabilization of MC-type carbides, and in the stabilization of sigma phase. In the particular alloy studied, these microstructural and microchemistry changes are insufficient in extent to impact on tensile strength, yield strength, and in the ductilities. Depending on the heat treatment, creep and stress rupture resistance can be cobalt sensitive. In the coarse grain, fully solutioned and aged condition, all of the alloy's 17% cobalt can be replaced by nickel without deleteriously affecting this resistance. In the fine grain, partially solutioned and aged condition, this resistance is deleteriously affected only when one-half or more of the initial cobalt content is removed. The structure and property results are discussed with respect to existing theories and with respect to other recent and earlier findings on the impact of cobalt, if any, on the performance of nickel-base superalloys.

Electrochemically synthesized nanocrystalline spinel thin film for high performance supercapacitor

NASA Astrophysics Data System (ADS)

Gupta, Vinay; Gupta, Shubhra; Miura, Norio

Spinels are not known for their supercapacitive nature. Here, we have explored electrochemically synthesized nanostructured NiCo 2O 4 spinel thin-film electrode for electrochemical supercapacitors. The nanostructured NiCo 2O 4 spinel thin film exhibited a high specific capacitance value of 580 F g -1 and an energy density of 32 Wh kg -1 at the power density of 4 kW kg -1, accompanying with good cyclic stability.

Comparison effects and electron spin resonance studies of α-Fe2O4 spinel type ferrite nanoparticles.

PubMed

Bayrakdar, H; Yalçın, O; Cengiz, U; Özüm, S; Anigi, E; Topel, O

2014-11-11

α-Fe2O4 spinel type ferrite nanoparticles have been synthesized by cetyltrimethylammonium bromide (CTAB) and ethylenediaminetetraacetic acid (EDTA) assisted hydrothermal route by using NaOH solution. Electron spin resonance (ESR/EPR) measurements of α-Fe2O4 nanoparticles have been performed by a conventional x-band spectrometer at room temperature. The comparison effect of nanoparticles prepared by using CTAB and EDTA in different α-doping on the structural and morphological properties have been investigated in detail. The effect of EDTA-assisted synthesis for α-Fe2O4 nanoparticles are refined, and thus the spectroscopic g-factor are detected by using ESR signals. These samples can be considered as great benefits for magnetic recording media, electromagnetic and drug delivery applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Method for thermal processing alumina-enriched spinel single crystals

DOEpatents

Jantzen, Carol M.

1995-01-01

A process for age-hardening alumina-rich magnesium aluminum spinel to obtain the desired combination of characteristics of hardness, clarity, flexural strength and toughness comprises selection of the time-temperature pair for isothermal heating followed by quenching. The time-temperature pair is selected from the region wherein the precipitate groups have the characteristics sought. The single crystal spinel is isothermally heated and will, if heated long enough pass from its single phase through two pre-precipitates and two metastable precipitates to a stable secondary phase precipitate within the spinel matrix. Quenching is done slowly at first to avoid thermal shock, then rapidly.

Regional Variations in Composition of Cr-spinel Xenocrysts From Kimberlite

NASA Astrophysics Data System (ADS)

Schulze, D. J.

2001-05-01

Important information on the composition of the upper mantle can be obtained by studying mantle xenocrysts in kimberlite, especially in situations in which intact mantle xenoliths are rare to absent. Spinel-group minerals are especially useful as they can coexist with garnet or represent regions of the mantle shallower than garnet-facies rocks, and chromites can exist in rocks too Al-depleted to form garnet. Xenolith studies have shown that along most typical cratonic geothermal gradients, the maximum Cr/(Cr+Al) (cr#) of spinel coexisting with garnet is 0.88. Cr-spinels with cr# > 0.88 are from Al-depleted rocks or from assemblages in which Al is partitioned into another phase (e.g., metasomatic phlogopite). Approximately 2500 Cr-spinel xenocrysts from 36 kimberlites in southern Africa and North America have been analysed (and some published data used) and evaluated, primarily in terms of cr# and Fe2/(Fe2+Mg) (fe#). Differences from pipe to pipe within and between cratons reflect variations in geologic history and fertility/depletion, only some of which can be related to mantle age. Within southern Africa, pipe average values of spinel xenocryst cr# are highest on the Kaapvaal Craton (0.80-0.89) where fe# varies from 0.36 to 0.47. Suites from the craton margin (e.g., in Lesotho) indicate a less depleted mantle (cr# = 0.75-0.80), similar to those from the Zimbabwe Craton (Orapa and Letlhakane, cr# = 0.80-0.81). Jwaneng (Kaapvaal Craton) is similar to the Zimbabwe Craton pipes (cr# = 0.83). Off-craton South African suites (Kalkput and Rietfontein) have lower cr# (0.72-0.75). Most southern African suites contain a significant population of Cr-spinel with cr# > 0.88 (including off-craton Rietfontein) except Liqhobong on the craton margin in Lesotho. Cr-spinel suites from North American kimberlites are quite different, with most suites being significantly more aluminous than African populations. Most Kirkland Lake kimberlites on the Superior Craton have a very

Cobalt treatment does not prevent glomerular morphological alterations in type 1 diabetic rats.

PubMed

Singh, Gaaminepreet; Krishan, Pawan

2018-06-02

Early renal morphological alterations including glomerular hypertrophy and mesangial expansion occur in diabetic kidney disease and correlate with various clinical manifestations of diabetes. The present study was designed to investigate the influence of pharmacological modulation of HIF-1α (hypoxia inducible factor-1 alpha) protein levels, on these glomerular changes in rodent model of type 1 diabetes. Male wistar rats were made diabetic (Streptozotocin 45 mg/kg; i.p.) and afterwards treated with HIF activator cobalt chloride for 4 weeks. Renal function was assessed by serum creatinine, albumin, proteinuria levels, oxidative stress: reduced glutathione levels and catalase activity, and renal tissue HIF-1α protein levels were determined by ELISA assay. Histological analysis of kidney sections was done by haematoxylin and eosin (glomeruli diameter), periodic acid Schiff (mesangial expansion and glomerulosclerosis) and sirius red (fibrosis, tubular dilation) staining. Diabetes rats displayed reduced serum albumin levels, marked proteinuria, lower kidney reduced glutathione content, glomerular hypertrophy, glomerulosclerosis, mesangial expansion, tubular dilation and renal fibrosis. Cobalt chloride treatment normalised renal HIF-1α protein levels, reduced development of proteinuria and tubulo-interstitial fibrosis, but the glomerular morphological alterations such as glomerulosclerosis, mesangial expansion, increased glomerular diameter and tubular vacoulations were not abrogated in diabetic kidneys. Glomerular morphological abnormalities might precede the development of proteinuria and renal fibrosis in experimental model of type 1 diabetes. Pharmacological modulation of renal HIF-1α protein levels does not influence glomerular and tubular dilatory changes in diabetic kidney disease.

Cobalt-Doped Perovskite-Type Oxide LaMnO3 as Bifunctional Oxygen Catalysts for Hybrid Lithium-Oxygen Batteries.

PubMed

Liu, Xiao; Gong, Hao; Wang, Tao; Guo, Hu; Song, Li; Xia, Wei; Gao, Bin; Jiang, Zhongyi; Feng, Linfei; He, Jianping

2018-03-02

Perovskite-type oxides based on rare-earth metals containing lanthanum manganate are promising catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte. Perovskite-type LaMnO 3 shows excellent ORR performance, but poor OER activity. To improve the OER performance of LaMnO 3 , the element cobalt is doped into perovskite-type LaMnO 3 through a sol-gel method followed by a calcination process. To assess electrocatalytic activities for the ORR and OER, a series of LaMn 1-x Co x O 3 (x=0, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5) perovskite oxides were synthesized. The results indicate that the amount of doped cobalt has a significant effect on the catalytic performance of LaMn 1-x Co x O 3 . If x=0.3, LaMn 0.7 Co 0.3 O 3 not only shows a tolerable electrocatalytic activity for the ORR, but also exhibits a great improvement (>200 mV) on the catalytic activity for the OER; this indicates that the doping of cobalt is an effective approach to improve the OER performance of LaMnO 3 . Furthermore, the results demonstrate that LaMn 0.7 Co 0.3 O 3 is a promising cost-effective bifunctional catalyst with high performance in the ORR and OER for application in hybrid Li-O 2 batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Epitaxially stabilized iridium spinel oxide without cations in the tetrahedral site

NASA Astrophysics Data System (ADS)

Kuriyama, Hiromichi; Matsuno, Jobu; Niitaka, Seiji; Uchida, Masaya; Hashizume, Daisuke; Nakao, Aiko; Sugimoto, Kunihisa; Ohsumi, Hiroyuki; Takata, Masaki; Takagi, Hidenori

2010-05-01

Single-crystalline thin film of an iridium dioxide polymorph Ir2O4 has been fabricated by the pulsed laser deposition of LixIr2O4 precursor and the subsequent Li-deintercalation using soft chemistry. Ir2O4 crystallizes in a spinel (AB2O4) without A cations in the tetrahedral site, which is isostructural to λ-MnO2. Ir ions form a pyrochlore sublattice, which is known to give rise to a strong geometrical frustration. This Ir spinel was found to be a narrow gap insulator, in remarkable contrast to the metallic ground state of rutile-type IrO2. We argue that an interplay of a strong spin-orbit coupling and a Coulomb repulsion gives rise to an insulating ground state as in a layered perovskite Sr2IrO4.

Fluid-related modifications of Cr-spinel and olivine from ophiolitic peridotites by contact metamorphism of granitic intrusions in the Ablah area, Saudi Arabia

NASA Astrophysics Data System (ADS)

Ahmed, Ahmed Hassan; Surour, Adel Abdullah

2016-05-01

The Ablah serpentinized peridotites and overlying layered metagabbros represent an allochthonous piece of a dismembered ophiolite in the southern Hijaz terrane that belongs to the Neoproterozoic Arabian Shield in Saudi Arabia. On both sides, the ophiolite is bounded by wider domains of granitic intrusions and volcano-sedimentary successions, all together follow a N-S trend. The protolith of the Ablah serpentinized peridotites is mainly harzburgite which is partly or totally serpentinized. Carbonate veins of variable sizes invade and hydrate the serpentinized peridotites. Away from the contact with the granitic intrusions, fresh primary (igneous) olivine and Cr-spinel are preserved in the partly serpentinized peridotites. These relict primary minerals are used to infer their tectonic setting of formation as a nascent spreading center rock association of mid-ocean ridge or back-arc basin setting. Based on the re-distribution of elements related to different thermal effects, three patterns of Cr-spinel modification can be defined. The first pattern can be followed in the partly serpentinized peridotites where Cr-spinel displays simple zoning that is characterized by sharp contact between primary Al-rich cores and secondary Fe3+-rich rims. These cores and rims are homogeneous and show progressive decrease in Mg, Al and Cr, but with remarkable increase in Fe3+ and Fe2+ toward the rims. Mineral assemblage in equilibrium with this type of Cr-spinel is primary olivine + antigorite + chlorite ± talc ± chrysotile. The second pattern of Cr-spinel modification is represented by homogeneous weakly zoned Cr-rich spinel with no distinct sharp contacts between Cr-rich cores and magnetite rims. Cr-spinel cores of this type are rich in Cr and Fe2+, and poor in Mg, Al and Fe3+. The mineral assemblage in equilibrium with this Cr-spinel type is Fe-rich olivine + antigorite + enstatite + chlorite + tremolite + anthophyllite ± talc. The third pattern is defined by pervasive

Synthetic and natural chromium-bearing spinels: an optical spectroscopy study

NASA Astrophysics Data System (ADS)

Taran, M. N.; Parisi, F.; Lenaz, D.; Vishnevskyy, A. A.

2014-09-01

Four samples of synthetic chromium-bearing spinels of (Mg, Fe2+)(Cr, Fe3+)2O4 composition and four samples of natural spinels of predominantly (Mg, Fe2+)(Al, Cr)2O4 composition were studied at ambient conditions by means of optical absorption spectroscopy. Synthetic end-member MgCr2O4 spinel was also studied at pressures up to ca. 10 GPa. In both synthetic and natural samples, chromium is present predominantly as octahedral Cr3+ seen in the spectra as two broad intense absorption bands in the visible range caused by the electronic spin-allowed 4 A 2 g → 4 T 2 g and 4 A 2 g → 4 T 1 g transitions (U- and Y-band, respectively). A distinct doublet structure of the Y-band in both synthetic and natural spinels is related to trigonal distortion of the octahedral site in the spinel structure. A small, if any, splitting of the U-band can only be resolved at curve-fitting analysis. In all synthetic high-chromium spinels, a couple of relatively narrow and weak bands of the spin-allowed transitions 4 A 2 g → 2 E g and 4 A 2 g → 2 T 1 g of Cr3+, intensified by exchange-coupled interaction between Cr3+ and Fe3+ at neighboring octahedral sites of the structure, appear at ~14,400 and ~15,100 cm-1. A vague broad band in the range from ca. 15,000 to 12,000 cm-1 in synthetic spinels is tentatively attributed to IVCr2+ + VICr3+ → IVCr3+ + VICr2+ intervalence charge-transfer transition. Iron, mainly as octahedral Fe3+, causes intense high-energy absorption edge in near UV-range (ligand-metal charge-transfer O2- → Fe3+, Fe2+ transitions). As tetrahedral Fe2+, it appears as a strong infrared absorption band at around 4,850 cm-1 caused by electronic spin-allowed 5 E → 5 T 2 transitions of IVFe2+. From the composition shift of the U-band in natural and synthetic MgCr2O4 spinels, the coefficient of local structural relaxation around Cr3+ in spinel MgAl2O4-MgCr2O4 system was evaluated as ~0.56(4), one of the lowest among (Al, Cr)O6 polyhedra known so far. The octahedral modulus

PROCESS FOR DECONTAMINATING THORIUM AND URANIUM WITH RESPECT TO RUTHENIUM

DOEpatents

Meservey, A.A.; Rainey, R.H.

1959-10-20

The control of ruthenium extraction in solvent-extraction processing of neutron-irradiated thorium is presented. Ruthenium is rendered organic-insoluble by the provision of sulfite or bisulfite ions in the aqueous feed solution. As a result the ruthenium remains in the aqueous phase along with other fission product and protactinium values, thorium and uranium values being extracted into the organic phase. This process is particularly applicable to the use of a nitrate-ion-deficient aqueous feed solution and to the use of tributyl phosphate as the organic extractant.

Method for thermal processing alumina-enriched spinel single crystals

DOEpatents

Jantzen, C.M.

1995-05-09

A process for age-hardening alumina-rich magnesium aluminum spinel to obtain the desired combination of characteristics of hardness, clarity, flexural strength and toughness comprises selection of the time-temperature pair for isothermal heating followed by quenching. The time-temperature pair is selected from the region wherein the precipitate groups have the characteristics sought. The single crystal spinel is isothermally heated and will, if heated long enough pass from its single phase through two pre-precipitates and two metastable precipitates to a stable secondary phase precipitate within the spinel matrix. Quenching is done slowly at first to avoid thermal shock, then rapidly. 12 figs.

Spinel-olivine-pryoxene equilibrium iron isotopic fractionation and applications to natural peridotites

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

Roskosz, Mathieu; Sio, Corliss K. I.; Dauphas, Nicolas

2015-11-15

Eight spinel-group minerals were synthesized by a flux-growth method producing spinels with varying composition and Fe3+/Fe-tot ratios. The mean force constants of iron bonds in these minerals were determined by synchrotron nuclear resonant inelastic X-ray scattering (NRIXS) in order to determine the reduced isotopic partition function ratios (beta-factors) of these spinels. The mean force constants are strongly dependent on the Fe3+/Fe-tot of the spinel but are independent, or weakly dependent on other structural and compositional parameters. From our spectroscopic data, it is found that a single redox-dependent calibration line accounts for the effects of Fe3+/Fe-tot on the beta-factors of spinels.more » This calibration successfully describes the equilibrium Fe isotopes fractionation factors between spinels and silicates (olivine and pyroxenes). Our predictions are in excellent agreement with independent determinations for the equilibrium Fe isotopic fractionations for the magnetite- fayalite and the magnetite-hedenbergite couples. Our calibration applies to the entire range of Fe3+/Fe-tot ratios found in natural spinels and provides a basis for interpreting iron isotopic variations documented in mantle peridotites. Except for a few exceptions, most of the samples measured so far are in isotopic disequilibrium, reflecting metasomatism and partial melting processes.« less

Manufacturing process scale-up of optical grade transparent spinel ceramic at ArmorLine Corporation

NASA Astrophysics Data System (ADS)

Spilman, Joseph; Voyles, John; Nick, Joseph; Shaffer, Lawrence

2013-06-01

While transparent Spinel ceramic's mechanical and optical characteristics are ideal for many Ultraviolet (UV), visible, Short-Wave Infrared (SWIR), Mid-Wave Infrared (MWIR), and multispectral sensor window applications, commercial adoption of the material has been hampered because the material has historically been available in relatively small sizes (one square foot per window or less), low volumes, unreliable supply, and with unreliable quality. Recent efforts, most notably by Technology Assessment and Transfer (TA and T), have scaled-up manufacturing processes and demonstrated the capability to produce larger windows on the order of two square feet, but with limited output not suitable for production type programs. ArmorLine Corporation licensed the hot-pressed Spinel manufacturing know-how of TA and T in 2009 with the goal of building the world's first dedicated full-scale Spinel production facility, enabling the supply of a reliable and sufficient volume of large Transparent Armor and Optical Grade Spinel plates. With over $20 million of private investment by J.F. Lehman and Company, ArmorLine has installed and commissioned the largest vacuum hot press in the world, the largest high-temperature/high-pressure hot isostatic press in the world, and supporting manufacturing processes within 75,000 square feet of manufacturing space. ArmorLine's equipment is capable of producing window blanks as large as 50" x 30" and the facility is capable of producing substantial volumes of material with its Lean configuration and 24/7 operation. Initial production capability was achieved in 2012. ArmorLine will discuss the challenges that were encountered during scale-up of the manufacturing processes, ArmorLine Optical Grade Spinel optical performance, and provide an overview of the facility and its capabilities.

Blood doping by cobalt. Should we measure cobalt in athletes?

PubMed

Lippi, Giuseppe; Franchini, Massimo; Guidi, Gian Cesare

2006-07-24

Blood doping is commonplace in competitive athletes who seek to enhance their aerobic performances through illicit techniques. Cobalt, a naturally-occurring element with properties similar to those of iron and nickel, induces a marked and stable polycythemic response through a more efficient transcription of the erythropoietin gene. Although little information is available so far on cobalt metabolism, reference value ranges or supplementation in athletes, there is emerging evidence that cobalt is used as a supplement and increased serum concentrations are occasionally observed in athletes. Therefore, given the athlete's connatural inclination to experiment with innovative, unfair and potentially unhealthy doping techniques, cobalt administration might soon become the most suited complement or surrogate for erythropoiesis-stimulating substances. Nevertheless, cobalt administration is not free from unsafe consequences, which involve toxic effects on heart, liver, kidney, thyroid and cancer promotion. Cobalt is easily purchasable, inexpensive and not currently comprehended within the World Anti-Doping Agency prohibited list. Moreover, available techniques for measuring whole blood, serum, plasma or urinary cobalt involve analytic approaches which are currently not practical for antidoping laboratories. Thus more research on cobalt metabolism in athletes is compelling, along with implementation of effective strategies to unmask this potentially deleterious doping practice.

A RELICT Spinel Grain in an Allende Ferromagnesian Chondrule

NASA Astrophysics Data System (ADS)

Misawa, K.; Fujita, T.; Kitamura, M.; Nakamura, N.; Yurimoto, H.

1993-07-01

It is suggested that one of the refractory lithophile precursors in CV-CO chondrules was a hightemperature condensate from the nebular gas and was related to Ca,Al-rich inclusions (CAIs) [1-3]. However, little is known about refractory siderophile precursors in chondrules [4]. Allende barred olivine chondrule R-11 consists mainly of olivine (Fa(sub)7- 18), pyroxene (En(sub)93Fs(sub)1Wo(sub)6, En(sub)66Fs(sub)1Wo(sub)33), plagioclase (An(sub)80), Fe-poor spinel, and alkali-rich glass. The CI- chondrite normalized REE pattern of the chondrule, excluding a spinel grain, are fractionated, HREEdepleted (4.6-7.8 x CI) with a large positive Yb anomaly. The REE abundances are hump-shaped functions of elemental volatility, moderately refractory REE-enriched, suggesting that the refractory lithophile precursor component of R-11 could be a condensate from the nebular gas and related to Group 11 CAIs [1,2]. An interior portion of spinel is almost Fe-free, but in an outer zone (2040 micrometers in width) FeO contents increase rapidly. TiO(sub)2, Cr(sub)2O(sub)3, and V(sub)2O(sub)3 contents in core spinel are less than 0.5%, which is different from the V-rich nature of spinel in fluffy Type A CAIs [5]. The Fe-Mg zoning of spinel may have been generated by diffusional emplacement of Mg and Fe during chondrule-forming events. The spinel contains silicate inclusions and tiny metallic grains. The largest silicate inclusion is composed of Al,Ti-rich pyroxene and Ak 40 melilite. One of the submicrometersized grains was analyzed by SEM-EDS and found to be composed of refractory Pt-group metals with minor amounts of Fe and Ni. This is the first occurrence of refractory Pt-group metal nuggets in a ferromagnesian chondrule from the Allende meteorite. Tungsten, Os, Ir, Mo, and Ru are enriched 2-6 x 10^5 relative to CIs, and abundances of Pt and Rh decrease 2-10 x 10^4 with increasing volatility. In addition, abundances of Fe and Ni in the nugget are equal to or less than that CI chondrites

The response of cobalt-free Udimet 700 type alloy to modified heat treatments

NASA Technical Reports Server (NTRS)

Harf, F. H.

1986-01-01

A superalloy based on Udimet 700, in which all of the cobalt was replaced by nickel, was prepared from hot isostatically pressed prealloyed powders. This material was given various heat treatments consisting of partial solutioning and aging in a sequence of four different temperatures. Comparisons were made of microstructures and mechanical properties. Best results were obtained by partially solutioning at 1145 deg C and aging through a sequence of 870, 1030, 650 and 760 deg C. This heat treatment also provided significantly improved properties for wrought material of the same composition. The results suggest that cobalt free Udimet 700 should be considered as a substitute for Udimet 700 with the standard 17 percent cobalt content.

The response of cobalt-free Udimet 700 type alloy to modified heat treatments

NASA Technical Reports Server (NTRS)

Harf, F. H.

1985-01-01

A superalloy based on Udimet 700, in which all of the cobalt was replaced by nickel, was prepared from hot isostatically pressed prealloyed powders. This material was given various heat treatments consisting of partial solutioning and aging in a sequence of four different temperatures. Comparisons were made of microstructures and mechanical properties. Best results were obtained by partially solutioning at 1145 deg C and aging through a sequence of 870, 1030, 650 and 760 deg C. This heat treatment also provided significantly improved properties for wrought material of the same composition. The results suggest that cobalt free Udimet 700 should be considered as a substitute for Udimet 700 with the standard 17 percent cobalt content.

Cordierite-spinel troctolite, a new magnesium-rich lithology from the lunar highlands.

PubMed

Marvin, U B; Carey, J W; Lindstrom, M M

1989-02-17

A clast of spinel troctolite containing 8 percent cordierite (Mg(2)Al(4)Si(5)O(18)) has been identified among the constituents of Apollo 15 regolith breccia 15295. The cordierite and associated anorthite, forsteritic olivine, and pleonaste spinel represent a new, Mg-rich lunar highlands lithology that formed by metamorphism of an igneous spinel cumulate. The cordierite-forsterite pair in the assemblage is stable at a maximum pressure of 2.5 kilobars, equivalent to a depth of 50 kilometers, or 10 kilometers above the lunar crust-mantle boundary. The occurrence of the clast indicates that spinel cumulates are a more important constituent of the lower lunar crust than has been recognized. The rarity of cordierite-spinel troctolite among lunar rock samples suggests that it is excavated only by large impact events, such as the one that formed the adjacent Imbrium Basin.

Cotectic proportions of olivine and spinel in olivine-tholeiitic basalt and evaluation of pre-eruptive processes

USGS Publications Warehouse

Roeder, Peter; Gofton, Emma; Thornber, Carl

2006-01-01

The volume %, distribution, texture and composition of coexisting olivine, Cr-spinel and glass has been determined in quenched lava samples from Hawaii, Iceland and mid-oceanic ridges. The volume ratio of olivine to spinel varies from 60 to 2800 and samples with >0·02% spinel have a volume ratio of olivine to spinel of approximately 100. A plot of wt % MgO vs ppm Cr for natural and experimental basaltic glasses suggests that the general trend of the glasses can be explained by the crystallization of a cotectic ratio of olivine to spinel of about 100. One group of samples has an olivine to spinel ratio of approximately 100, with skeletal olivine phenocrysts and small (<50 μm) spinel crystals that tend to be spatially associated with the olivine phenocrysts. The large number of spinel crystals included within olivine phenocrysts is thought to be due to skeletal olivine phenocrysts coming into physical contact with spinel by synneusis during the chaotic conditions of ascent and extrusion. A second group of samples tend to have large olivine phenocrysts relatively free of included spinel, a few large (>100 μm) spinel crystals that show evidence of two stages of growth, and a volume ratio of olivine to spinel of 100 to well over 1000. The olivine and spinel in this group have crystallized more slowly with little physical interaction, and show evidence that they have accumulated in a magma chamber.

Blood doping by cobalt. Should we measure cobalt in athletes?

PubMed Central

Lippi, Giuseppe; Franchini, Massimo; Guidi, Gian Cesare

2006-01-01

Background Blood doping is commonplace in competitive athletes who seek to enhance their aerobic performances through illicit techniques. Presentation of the hypothesis Cobalt, a naturally-occurring element with properties similar to those of iron and nickel, induces a marked and stable polycythemic response through a more efficient transcription of the erythropoietin gene. Testing the hypothesis Although little information is available so far on cobalt metabolism, reference value ranges or supplementation in athletes, there is emerging evidence that cobalt is used as a supplement and increased serum concentrations are occasionally observed in athletes. Therefore, given the athlete's connatural inclination to experiment with innovative, unfair and potentially unhealthy doping techniques, cobalt administration might soon become the most suited complement or surrogate for erythropoiesis-stimulating substances. Nevertheless, cobalt administration is not free from unsafe consequences, which involve toxic effects on heart, liver, kidney, thyroid and cancer promotion. Implications of the hypothesis Cobalt is easily purchasable, inexpensive and not currently comprehended within the World Anti-Doping Agency prohibited list. Moreover, available techniques for measuring whole blood, serum, plasma or urinary cobalt involve analytic approaches which are currently not practical for antidoping laboratories. Thus more research on cobalt metabolism in athletes is compelling, along with implementation of effective strategies to unmask this potentially deleterious doping practice PMID:16863591

Graphene/Ruthenium Active Species Aerogel as Electrode for Supercapacitor Applications

PubMed Central

Gigot, Arnaud; Fontana, Marco; Pirri, Candido Fabrizio; Rivolo, Paola

2017-01-01

Ruthenium active species containing Ruthenium Sulphide (RuS2) is synthesized together with a self-assembled reduced graphene oxide (RGO) aerogel by a one-pot hydrothermal synthesis. Ruthenium Chloride and L-Cysteine are used as reactants. The hydrothermal synthesis of the innovative hybrid material occurs at 180 °C for 12 h, by using water as solvent. The structure and morphology of the hybrid material are fully characterized by Raman, XRD, XPS, FESEM and TEM. The XRD and diffraction pattern obtained by TEM display an amorphous nanostructure of RuS2 on RGO crystallized flakes. The specific capacitance measured in planar configuration in 1 M NaCl electrolyte at 5 mV s−1 is 238 F g−1. This supercapacitor electrode also exhibits perfect cyclic stability without loss of the specific capacitance after 15,000 cycles. In summary, the RGO/Ruthenium active species hybrid material demonstrates remarkable properties for use as active material for supercapacitor applications. PMID:29301192

Graphene/Ruthenium Active Species Aerogel as Electrode for Supercapacitor Applications.

PubMed

Gigot, Arnaud; Fontana, Marco; Pirri, Candido Fabrizio; Rivolo, Paola

2017-12-30

Ruthenium active species containing Ruthenium Sulphide (RuS₂) is synthesized together with a self-assembled reduced graphene oxide (RGO) aerogel by a one-pot hydrothermal synthesis. Ruthenium Chloride and L-Cysteine are used as reactants. The hydrothermal synthesis of the innovative hybrid material occurs at 180 °C for 12 h, by using water as solvent. The structure and morphology of the hybrid material are fully characterized by Raman, XRD, XPS, FESEM and TEM. The XRD and diffraction pattern obtained by TEM display an amorphous nanostructure of RuS₂ on RGO crystallized flakes. The specific capacitance measured in planar configuration in 1 M NaCl electrolyte at 5 mV s -1 is 238 F g -1 . This supercapacitor electrode also exhibits perfect cyclic stability without loss of the specific capacitance after 15,000 cycles. In summary, the RGO/Ruthenium active species hybrid material demonstrates remarkable properties for use as active material for supercapacitor applications.

IR spectroscopic determination of OH defects in spinel group minerals

NASA Astrophysics Data System (ADS)

Halmer, M. M.; Libowitzky, E.; Beran, A.

2003-04-01

Previous experimental studies showed that spinel phases, likely to occur in the transition zone of the Earth's mantle, contain essential amounts of water in form of OH groups. The g-Mg_2SiO_4 phase is reported to contain 27000 wt.ppm H_2O. The corresponding IR spectrum shows very broad absorption bands centered at 3645 and 3345cm-1 with a shoulder at 3120cm-1 (Kohlstedt et al., 1996). Thus, it is evident that under high-pressure conditions the spinel structure is capable to incorporate OH groups. Up to present, hydrogen contents of spinels from upper Earth's mantle and from crustal occurrences have not been reported in the literature. It is the aim of this study to prove the presence of OH defects in spinels of naturally occurring paragenesis and to develop some ideas on the structural incorporation mode based on promising results obtained from synthetic phases. Highly disordered non-stoichiometric Verneuil-grown MgAl spinels are characterized by two significant bands centered at 3355cm-1 and 3510cm-1, which show variations in band intensities. Synthetic H_ high-temperature treated intermediate compounds in the spinel-magnesioferrite (MgFe_2O_4), spinel-hercynite (FeAl2O4) and spinel-franklinite (ZnFe2O4) system from Andreozzi et al. (2001) indicate variable behavior. Whereas some of the spectra, which may be also correlated to d-d transitions of IVFe2+ (Skogby and Halenius, 2003) show broad absorptions in the 3500-3100cm-1 range, a pure MgAl2O4 end member sample is characterized by a rather sharp mode at 3450cm-1. Naturally occurring gahnite crystals (ZnAl2O_4) show significantly broad absorption band at 3400cm-1, which resembles some of the bands of the former synthetic samples. Based on the calibration of Libowitzky and Rossman (1997) the analytical H_2O content of the natural gahnite sample was determined to 580 wt.ppm. The position of the absorption bands implies weak hydrogen bonding of the OH defects in the spinel structure. This work was partly supported by

Biphase Cobalt-Manganese Oxide with High Capacity and Rate Performance for Aqueous Sodium-Ion Electrochemical Energy Storage

DOE PAGES

Shan, Xiaoqiang; Charles, Daniel S.; Xu, Wenqian; ...

2017-11-22

Manganese-based metal oxide electrode materials are of great importance in electrochemical energy storage for their favorable redox behavior, low cost and environmental-friendliness. However, their storage capacity and cycle life in aqueous Na-ion electrolytes is not satisfactory. In this paper, we report the development of a bi-phase cobalt-manganese oxide (Co-Mn-O) nanostructured electrode material, comprised of a layered MnO 2.H 2O birnessite phase and a (Co 0.83Mn 0.13Va 0.04)tetra(Co 0.38Mn 1.62) octaO 3.72 (Va: vacancy; tetra: tetrahedral sites; octa: octahedral sites) spinel phase, verified by neutron total scattering and pair distribution function analyses. The bi-phase Co-Mn-O material demonstrates an excellent storage capacitymore » towards Na-ions in an aqueous electrolyte (121 mA h g -1 at a scan rate of 1 mV s -1 in the half-cell and 81 mA h g -1 at a current density of 2 A g -1 after 5000 cycles in full-cells), as well as high rate performance (57 mA h g -1 a rate of 360 C). Electro-kinetic analysis and in situ X-ray diffraction measurements further confirm that the synergistic interaction between the spinel and layered phases, as well as the vacancy of the tetrahedral sites of spinel phase, contribute to the improved capacity and rate performance of the Co-Mn-O material by facilitating both diffusion-limited redox and capacitive charge storage processes.« less

Biphase Cobalt-Manganese Oxide with High Capacity and Rate Performance for Aqueous Sodium-Ion Electrochemical Energy Storage

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

Shan, Xiaoqiang; Charles, Daniel S.; Xu, Wenqian

Manganese-based metal oxide electrode materials are of great importance in electrochemical energy storage for their favorable redox behavior, low cost and environmental-friendliness. However, their storage capacity and cycle life in aqueous Na-ion electrolytes is not satisfactory. In this paper, we report the development of a bi-phase cobalt-manganese oxide (Co-Mn-O) nanostructured electrode material, comprised of a layered MnO 2.H 2O birnessite phase and a (Co 0.83Mn 0.13Va 0.04)tetra(Co 0.38Mn 1.62) octaO 3.72 (Va: vacancy; tetra: tetrahedral sites; octa: octahedral sites) spinel phase, verified by neutron total scattering and pair distribution function analyses. The bi-phase Co-Mn-O material demonstrates an excellent storage capacitymore » towards Na-ions in an aqueous electrolyte (121 mA h g -1 at a scan rate of 1 mV s -1 in the half-cell and 81 mA h g -1 at a current density of 2 A g -1 after 5000 cycles in full-cells), as well as high rate performance (57 mA h g -1 a rate of 360 C). Electro-kinetic analysis and in situ X-ray diffraction measurements further confirm that the synergistic interaction between the spinel and layered phases, as well as the vacancy of the tetrahedral sites of spinel phase, contribute to the improved capacity and rate performance of the Co-Mn-O material by facilitating both diffusion-limited redox and capacitive charge storage processes.« less

Evidence of exchange-coupled behavior in chromium-cobalt ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Tanbir, Kamar; Sharma, Lalit Kumar; Aakash; Singh, Rakesh Kumar; Choubey, Ravi Kant; Mukherjee, Samrat

2018-06-01

Cr doped cobalt ferrite nanoparticles were synthesized with the generic formula Co1-xCrxFe2O4 (x = 0, 0.05, 0.15, 0.25) through standard chemical co-precipitation method. XRD studies confirmed the pure spinel cubic structure belonging to Fd 3 bar m space group. From the Williamson-Hall plots, crystallite sizes were found to lie within the range (42 ± 1) nm for the different doped samples. The lattice parameter was found to decrease linearly with increase in the concentration of Cr3+ ion. The magnetic behavior of the samples was determined by M-H studies at 300 K, field cooled (5 T) at 5 K and temperature dependent studies. The M-H at 300 K show soft magnetic behavior whereas the M-H plots at 5 K predict the existence of in-homogeneity of the exchange interactions due to strong exchange coupling between the spins at the core and the surface of the nanoparticles.

Origin of spinel-rich chondrules and inclusions in carbonaceous and ordinary chondrites

NASA Technical Reports Server (NTRS)

Kornacki, A. S.; Fegley, B., Jr.

1984-01-01

The evaluation of three models of the origin of spinel-rich chondrules and inclusions presented here includes new calculations of the major-element refractory mineral condensation sequence from a gas of solar composition over a wide pressure interval. Condensation calculations show that spinel-rich chondrules did not crystallize from metastable liquid condensates, and that spinel-rich inclusions are not aggregates of refractory nebular condensates. It is proposed that spinel-rich objects are fractionated distillation residues of small aggregates of primitive dust that lost Ca, Si-rich partial melts by evaporation, ablation, or splashing during collisions. This model also explains why spinel-rich chondrules and inclusions (1) are usually smaller than melilite-rich chondrules and inclusions; (2) often have highly fractionated trace-element compositions; and (3) usually do not contain Pt-metal nuggets even when they are more enriched in the Pt-group metals than nugget-bearing melilite-rich objects.

Cr diffusion in MgAl2O4 synthetic spinels: preliminary results

NASA Astrophysics Data System (ADS)

Freda, C.; Celata, B.; Andreozzi, G.; Perinelli, C.; Misiti, V.

2012-04-01

Chromian spinel is an accessory phase common in crustal and mantle rocks, including peridotites, gabbros and basalts. Spinel, it has been identified as one of the most effective, sensible, and versatile petrogenetic indicator in mafic and ultramafic rock systems due to the strict interdependence between its physico-chemical properties (chemical composition, cation configuration etc.) and genetic conditions (temperature, pressure, and chemical characteristics of the system). In particular, studies on intra- and inter-crystalline Mg-Fe2+, Cr-Al exchange demonstrated the close relationship between spinel composition and both degree of partial melting and equilibrium temperature of spinel-peridotites. Moreover, studies focused on the chemical zoning of Mg-Fe2+ and/or Cr-Al components in spinel have been used, combined with a diffusion model, to provide quantitative information on peridotites and gabbros pressure-temperature paths and on deformation mechanisms. Although these potentials, most of the experimental studies have been performed on spinels hosting a limited content of divalent iron (sensu stricto, MgAl2O4), whereas the scarce studies on Cr-Al inter-diffusion coefficient have been performed at 3-7 GPa as pressure boundary condition. In order to contribute to the understanding of processes occurring in the lithospheric mantle, we have initiated an experimental research project aiming at determining the Cr-Al inter-diffusion in spinel at 2 GPa pressure and temperature ranging from 1100 to 1250 °C. The experiments were performed in a end-loaded piston cylinder by using a 19 mm assembly and graphite-Pt double capsules. As starting materials we used synthetic Mg-Al spinel (200-300 μm in size) and Cr2O3 powder. Microanalyses of experimental charge were performed on polished carbon-coated mounts by electronic microprobe. Line elemental analyses were made perpendicular to the contact surface between Cr2O3 powder and spinel, at interval of 2 μm. By processing these

Nickel stabilization efficiency of aluminate and ferrite spinels and their leaching behavior.

PubMed

Shih, Kaimin; White, Tim; Leckie, James O

2006-09-01

Stabilization efficiencies of spinel-based construction ceramics incorporating simulated nickel-laden waste sludge were evaluated and the leaching behavior of products investigated. To simulate the process of immobilization, nickel oxide was mixed alternatively with gamma-alumina, kaolinite, and hematite. These tailoring precursors are commonly used to prepare construction ceramics in the building industry. After sintering from 600 to 1480 degrees C at 3 h, the nickel aluminate spinel (NiAl204) and the nickel ferrite spinel (NiFe204) crystallized with the ferrite spinel formation commencing about 200-300 degrees C lower than for the aluminate spinel. All the precursors showed high nickel incorporation efficiencies when sintered at temperatures greater than 1250 degrees C. Prolonged leach tests (up to 26 days) of product phases were carried out using a pH 2.9 acetic acid solution, and the spinel products were invariably superior to nickel oxide for immobilization over longer leaching periods. The leaching behavior of NiAl2O4 was consistent with congruent dissolution without significant reprecipitation, but for NiFe2O4, ferric hydroxide precipitation was evident. The major leaching reaction of sintered kaolinite-based products was the dissolution of cristobalite rather than NiAl2O4. This study demonstrated the feasibility of transforming nickel-laden sludge into spinel phases with the use of readily available and inexpensive ceramic raw materials, and the successful reduction of metal mobility under acidic environments.

Unique atom hyper-kagome order in Na4Ir3O8 and in low-symmetry spinel modifications.

PubMed

Talanov, V M; Shirokov, V B; Talanov, M V

2015-05-01

Group-theoretical and thermodynamic methods of the Landau theory of phase transitions are used to investigate the hyper-kagome atomic order in structures of ordered spinels and a spinel-like Na4Ir3O8 crystal. The formation of an atom hyper-kagome sublattice in Na4Ir3O8 is described theoretically on the basis of the archetype (hypothetical parent structure/phase) concept. The archetype structure of Na4Ir3O8 has a spinel-like structure (space group Fd\\bar 3m) and composition [Na1/2Ir3/2](16d)[Na3/2](16c)O(32e)4. The critical order parameter which induces hypothetical phase transition has been stated. It is shown that the derived structure of Na4Ir3O8 is formed as a result of the displacements of Na, Ir and O atoms, and ordering of Na, Ir and O atoms, ordering dxy, dxz, dyz orbitals as well. Ordering of all atoms takes place according to the type 1:3. Ir and Na atoms form an intriguing atom order: a network of corner-shared Ir triangles called a hyper-kagome lattice. The Ir atoms form nanoclusters which are named decagons. The existence of hyper-kagome lattices in six types of ordered spinel structures is predicted theoretically. The structure mechanisms of the formation of the predicted hyper-kagome atom order in some ordered spinel phases are established. For a number of cases typical diagrams of possible crystal phase states are built in the framework of the Landau theory of phase transitions. Thermodynamical conditions of hyper-kagome order formation are discussed by means of these diagrams. The proposed theory is in accordance with experimental data.

Oceanization of the lithospheric mantle: the study case of the spinel peridotites from Monte Maggiore (Corsica, France).

NASA Astrophysics Data System (ADS)

Piccardo, G. B.

2009-04-01

The Monte Maggiore peridotite body, cropping out within the Alpine Corsica metamorphic belt, is an ophiolite massif derived from the more internal setting of the Jurassic Ligurian Tethys basin. It is mostly composed by spinel and plagioclase peridotites that are cut by MORB gabbroic dykes. The spinel peridotites, similarly to other ophiolitic peridotites from the Internal Ligurides, have been considered, on the basis of their low abundance of fusible components, low Si and high Mg contents, as refractory residua after MORB-type partial melting related to the formation of the Jurassic basin (e.g. Rampone et al., 1997). Recent studies (e.g. Müntener & Piccardo 2003; Rampone et al. 2008) have evidenced that these depleted spinel peridotites show diffuse melt-rock interaction micro-textures and contrasting bulk vs. mineral chemistry features which cannot be simply reconciled with partial melting. Accordingly, these peridotites have been recognized as reactive peridotites, formed by interaction of pristine peridotites with melts percolating by porous flow. Geochemical data have evidenced the depleted MORB signature of the percolating melts. Recent field studies at Monte Maggiore (Piccardo, 2007; Piccardo & Guarnieri, 2009), have revealed: 1) the presence and local abundance of pyroxenite-bearing, cpx-rich spinel lherzolites and 2) the replacement relationships of the reactive peridotites on the pyroxenite-bearing lherzolite rock-types. The pyroxenite-veined spinel lherzolites record a composite history of subsolidus evolution under lithospheric P-T conditions, thus indicating their provenance from the sub-continental lithospheric mantle. Accordingly, the pristine sub-continental mantle protoliths were infiltrated by MORB melts and transformed by melt-rock interaction to reactive spinel peridotites and refertilized by melt impregnation to plagioclase-enriched peridotites. Available isotopic data on the Mt. Maggiore spinel and plagioclase peridotites and gabbroic rocks

Toxicology and pharmacology of some ruthenium compounds: Vascular smooth muscle relaxation by nitrosyl derivatives of ruthenium and iridium.

PubMed

Kruszyna, H; Kruszyna, R; Hurst, J; Smith, R P

1980-07-01

A series of compounds were synthesized from ruthenium trichloride, and their ip LD50s were determined in mice: pentamminenitrosylruthenium(II) chloride, 8.9; chloronitrobis(2,2'-dipyridyl)ruthenium(II), 55;dichlorobis(2,2'-dipyridyl)ruthenium(II), 63; ruthenium trichloride, 108; and potassium pentachloronitrosylruthenate(II), 127 mg/kg. The two bis-bipyridyl complexes produced death in convulsions within minutes, whereas the remaining compounds resulted in long, debilitating courses with death occurring in 4-7d. When given in massive overdoses, however, the compounds with inorganic ligands also produced rapid convulsive death in mice, and when given iv to anesthetized cats, they produced respiratory arrest. The major toxic effects of all the complexes appeared to be due to the metal and not to its associated ligands. Only complexes having nitrosyl ligand specifically relaxed vascular smooth muscle. Potassium pentabromoiridate(III) also relaxed rabbit aortic strips that had been contracted by adrenergic agonists, but potassium pentachloroiridate(III) did not. None of the complexes was as active as nitroprusside in relaxing aortic strips or in decreasing arterial blood pressure in cats. No compound tested was as potent as cisplatin in antitumor activity. The pentamminenitrosylruthenium(II) complex also relaxed guinea pig ileum and frog rectus abdominus when these isolated muscles had been contracted by acetylcho line. It appears that these organoruthenium compounds may produce death in central respiratory arrest, as do the inorganic complexes when given iv or ip in massive overdoses. In minimally lethal doses, the complexes with inorganic ligands may affect a variety of contractile tissues, perhaps by a general mechanism involving Ca. These complexes are apt to be generally cytotoxic as well.

Transparent magnesium aluminate spinel: a prospective biomaterial for esthetic orthodontic brackets.

PubMed

Krishnan, Manu; Tiwari, Brijesh; Seema, Saraswathy; Kalra, Namitha; Biswas, Papiya; Rajeswari, Kotikalapudi; Suresh, Madireddy Buchi; Johnson, Roy; Gokhale, Nitin M; Iyer, Satish R; Londhe, Sanjay; Arora, Vimal; Tripathi, Rajendra P

2014-11-01

Adult orthodontics is recently gaining popularity due to its importance in esthetics, oral and general health. However, none of the currently available alumina or zirconia based ceramic orthodontic brackets meet the esthetic demands of adult patients. Inherent hexagonal lattice structure and associated birefringence limits the visible light transmission in polycrystalline alumina and make them appear white and non transparent. Hence focus of the present study was to assess the feasibility of using magnesium aluminate (MgAl2O4) spinel; a member of the transparent ceramic family for esthetic orthodontic brackets. Transparent spinel specimens were developed from commercially available white spinel powder through colloidal shaping followed by pressureless sintering and hot isostatic pressing at optimum conditions of temperature and pressure. Samples were characterized for chemical composition, phases, density, hardness, flexural strength, fracture toughness and optical transmission. Biocompatibility was evaluated with in-vitro cell line experiments for cytotoxicity, apoptosis and genotoxicity. Results showed that transparent spinel samples had requisite physico-chemical, mechanical, optical and excellent biocompatibility for fabricating orthodontic brackets. Transparent spinel developed through this method demonstrated its possibility as a prospective biomaterial for developing esthetic orthodontic brackets.

Photoisomerization of ruthenium(ii) aquo complexes: mechanistic insights and application development.

PubMed

Hirahara, Masanari; Yagi, Masayuki

2017-03-21

Ruthenium(ii) complexes with polypyridyl ligands have been extensively studied as promising functional molecules due to their unique photochemical and photophysical properties as well as redox properties. In this context, we report the photoisomerization of distal-[Ru(tpy)(pynp)OH 2 ] 2+ (d-1) (tpy = 2,2';6',2''-terpyridine, pynp = 2-(2-pyridyl)-1,8-naphthyridine) to proximal-[Ru(tpy)(pynp)OH 2 ] 2+ (p-1), which has not been previously characterized for polypyridyl ruthenium(ii) aquo complexes. Herein, we review recent progress made by our group on the mechanistic insights and application developments related to the photoisomerization of polypyridyl ruthenium(ii) aquo complexes. We report a new strategic synthesis of dinuclear ruthenium(ii) complexes that can act as an active water oxidation catalyst, as well as the development of unique visible-light-responsive giant vesicles, both of which were achieved based on photoisomerization.

Magnetization and anisotropy of cobalt ferrite thin films

NASA Astrophysics Data System (ADS)

Eskandari, F.; Porter, S. B.; Venkatesan, M.; Kameli, P.; Rode, K.; Coey, J. M. D.

2017-12-01

The magnetization of thin films of cobalt ferrite frequently falls far below the bulk value of 455 kA m-1 , which corresponds to an inverse cation distribution in the spinel structure with a significant orbital moment of about 0.6 μB that is associated with the octahedrally coordinated Co2+ ions. The orbital moment is responsible for the magnetostriction and magnetocrystalline anisotropy and its sensitivity to imposed strain. We have systematically investigated the structure and magnetism of films produced by pulsed-laser deposition on different substrates (Ti O2 , MgO, MgA l2O4 , SrTi O3 , LSAT, LaAl O3 ) and as a function of temperature (500 -700 °C) and oxygen pressure (10-4-10 Pa ) . Magnetization at room-temperature ranges from 60 to 440 kA m-1 , and uniaxial substrate-induced anisotropy ranges from +220 kJ m-3 for films on deposited on MgO (100) to -2100 kJ m-3 for films deposited on MgA l2O4 (100), where the room-temperature anisotropy field reaches 14 T. No rearrangement of high-spin Fe3+ and Co2+ cations on tetrahedral and octahedral sites can reduce the magnetization below the bulk value, but a switch from Fe3+ and Co2+ to Fe2+ and low-spin Co3+ on octahedral sites will reduce the low-temperature magnetization to 120 kA m-1 , and a consequent reduction of Curie temperature can bring the room-temperature value to near zero. Possible reasons for the appearance of low-spin cobalt in the thin films are discussed.

Precise ruthenium fission product isotopic analysis using dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS)

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

Brown, Christopher F.; Dresel, P. Evan; Geiszler, Keith N.

2006-05-09

99Tc is a subsurface contaminant of interest at numerous federal, industrial, and international facilities. However, as a mono-isotopic fission product, 99Tc lacks the ability to be used as a signature to differentiate between the different waste disposal pathways that could have contributed to subsurface contamination at these facilities. Ruthenium fission-product isotopes are attractive analogues for the characterization of 99Tc sources because of their direct similarity to technetium with regard to subsurface mobility, and their large fission yields and low natural background concentrations. We developed an inductively coupled plasma mass spectrometry (ICP-MS) method capable of measuring ruthenium isotopes in groundwater samplesmore » and extracts of vadose zone sediments. Samples were analyzed directly on a Perkin Elmer ELAN DRC II ICP-MS after a single pass through a 1-ml bed volume of Dowex AG 50W-X8 100-200 mesh cation exchange resin. Precise ruthenium isotopic ratio measurements were achieved using a low-flow Meinhard-type nebulizer and long sample acquisition times (150,000 ms). Relative standard deviations of triplicate replicates were maintained at less than 0.5% when the total ruthenium solution concentration was 0.1 ng/ml or higher. Further work was performed to minimize the impact caused by mass interferences using the dynamic reaction cell (DRC) with O2 as the reaction gas. The aqueous concentrations of 96Mo and 96Zr were reduced by more than 99.7% in the reaction cell prior to injection of the sample into the mass analyzer quadrupole. The DRC was used in combination with stable-mass correction to quantitatively analyze samples containing up to 2-orders of magnitude more zirconium and molybdenum than ruthenium. The analytical approach documented herein provides an efficient and cost-effective way to precisely measure ruthenium isotopes and quantitate total ruthenium (natural vs. fission-product) in aqueous matrixes.« less

Thermobarometry for spinel lherzolite xenoliths in alkali basalts

NASA Astrophysics Data System (ADS)

Ozawa, Kazuhito; Youbi, Nasrrddine; Boumehdi, Moulay Ahmed; Nagahara, Hiroko

2016-04-01

Application of geothermobarometers to peridotite xenoliths has been providing very useful information on thermal and chemical structure of lithospheric or asthenospheric mantle at the time of almost instantaneous sampling by the host magmas, based on which various thermal (e.g., McKenzie et al., 2005), chemical (e.g., Griffin et al., 2003), and rheological (e.g., Ave Lallemant et al., 1980) models of lithosphere have been constructed. Geothermobarometry for garnet or plagioclase-bearing lithologies provide accurate pressure estimation, but this is not the case for the spinel peridotites, which are frequently sampled from Phanerozoic provinces in various tectonic environments (Nixon and Davies, 1987). There are several geobarometers proposed for spinel lherzolite, such as single pyroxene geothermobarometer (Mercier, 1980) and geothermobarometer based on Ca exchange between olivine and clinopyroxene (Köhler and Brey, 1990), but they have essential problems and it is usually believed that appropriated barometers do not exist for spinel lherzolites (O'Reilly et al., 1997; Medaris et al., 1999). It is thus imperative to develop reliable barometry for spinel peridotite xenoliths. We have developed barometry for spinel peridotite xenoliths by exploiting small differences in pressure dependence in relevant reactions, whose calibration was made through careful evaluation of volume changes of the reactions. This is augmented with higher levels of care in application of barometer by choosing mineral domains and their chemical components that are in equilibrium as close as possible. This is necessary because such barometry is very sensitive to changes in chemical composition induced by transient state of the system possibly owing to pressure and temperature changes as well as chemical modification, forming chemical heterogeneity or zoning frequently reported from various mantle xenoliths (Smith, 1999). Thus very carful treatment of heterogeneity, which might be trivial for

Cobalt, manganese, and iron near the Hawaiian Islands: A potential concentrating mechanism for cobalt within a cyclonic eddy and implications for the hybrid-type trace metals

NASA Astrophysics Data System (ADS)

Noble, Abigail E.; Saito, Mak A.; Maiti, Kanchan; Benitez-Nelson, Claudia R.

2008-05-01

The vertical distributions of cobalt, iron, and manganese in the water column were studied during the E-Flux Program (E-Flux II and III), which focused on the biogeochemistry of cold-core cyclonic eddies that form in the lee of the Hawaiian Islands. During E-Flux II (January 2005) and E-Flux III (March 2005), 17 stations were sampled for cobalt ( n=147), all of which demonstrated nutrient-like depletion in surface waters. During E-Flux III, two depth profiles collected from within a mesoscale cold-core eddy, Cyclone Opal, revealed small distinct maxima in cobalt at ˜100 m depth and a larger inventory of cobalt within the eddy. We hypothesize that this was due to a cobalt concentrating effect within the eddy, where upwelled cobalt was subsequently associated with sinking particulate organic carbon (POC) via biological activity and was released at a depth coincident with nearly complete POC remineralization [Benitez-Nelson, C., Bidigare, R.R., Dickey, T.D., Landry, M.R., Leonard, C.L., Brown, S.L., Nencioli, F., Rii, Y.M., Maiti, K., Becker, J.W., Bibby, T.S., Black, W., Cai, W.J., Carlson, C.A., Chen, F., Kuwahara, V.S., Mahaffey, C., McAndrew, P.M., Quay, P.D., Rappe, M.S., Selph, K.E., Simmons, M.P., Yang, E.J., 2007. Mesoscale eddies drive increased silica export in the subtropical Pacific Ocean. Science 316, 1017-1020]. There is also evidence for the formation of a correlation between cobalt and soluble reactive phosphorus during E-Flux III relative to the E-Flux II cruise that we suggest is due to increased productivity, implying a minimum threshold of primary production below which cobalt-phosphate coupling does not occur. Dissolved iron was measured in E-Flux II and found in somewhat elevated concentrations (˜0.5 nM) in surface waters relative to the iron depleted waters of the surrounding Pacific [Fitzwater, S.E., Coale, K.H., Gordon, M.R., Johnson, K.S., Ondrusek, M.E., 1996. Iron deficiency and phytoplankton growth in the equatorial Pacific. Deep

The inhibition of mitochondrial calcium transport by lanthanides and Ruthenium Red

PubMed Central

Reed, Ken C.; Bygrave, Fyfe L.

1974-01-01

An EGTA (ethanedioxybis(ethylamine)tetra-acetic acid)-quench technique was developed for measuring initial rates of 45Ca2+ transport by rat liver mitochondria. This method was used in conjunction with studies of Ca2+-stimulated respiration to examine the mechanisms of inhibition of Ca2+ transport by the lanthanides and Ruthenium Red. Ruthenium Red inhibits Ca2+ transport non-competitively with Ki 3×10−8m; there are 0.08nmol of carrier-specific binding sites/mg of protein. The inhibition by La3+ is competitive (Ki=2×10−8m); the concentration of lanthanide-sensitive sites is less than 0.001nmol/mg of protein. A further difference between their modes of action is that lanthanide inhibition diminishes with time whereas that by Ruthenium Red does not. Binding studies showed that both classes of inhibitor bind to a relatively large number of external sites (probably identical with the `low-affinity' Ca2+-binding sites). La3+ competes with Ruthenium Red for most of these sites, but a small fraction of the bound Ruthenium Red (less than 2nmol/mg of protein) is not displaced by La3+. The results are discussed briefly in relation to possible models for a Ca2+ carrier. PMID:4375957

Pt-Doped NiFe₂O₄ Spinel as a Highly Efficient Catalyst for H₂ Selective Catalytic Reduction of NO at Room Temperature.

PubMed

Sun, Wei; Qiao, Kai; Liu, Ji-Yuan; Cao, Li-Mei; Gong, Xue-Qing; Yang, Ji

2016-04-11

H2 selective catalytic reduction (H2-SCR) has been proposed as a promising technology for controlling NOx emission because hydrogen is clean and does not emit greenhouse gases. We demonstrate that Pt doped into a nickel ferrite spinel structure can afford a high catalytic activity of H2-SCR. A superior NO conversion of 96% can be achieved by employing a novel NiFe1.95Pt0.05O4 spinel-type catalyst at 60 °C. This novel catalyst is different from traditional H2-SCR catalysts, which focus on the role of metallic Pt species and neglect the effect of oxidized Pt states in the reduction of NO. The obtained Raman and XPS spectra indicate that Pt in the spinel lattice has different valence states with Pt(2+) occupying the tetrahedral sites and Pt(4+) residing in the octahedral ones. These oxidation states of Pt enhance the back-donation process, and the lack of filling electrons of the 5d band causes Pt to more readily hybridize with the 5σ orbital of the NO molecule, especially for octahedral Pt(4+), which enhances the NO chemisorption on the Pt sites. We also performed DFT calculations to confirm the enhancement of adsorption of NO onto Pt sites when doped into the Ni-Fe spinel structure. The prepared Pt/Ni-Fe catalysts indicate that increasing the dispersity of Pt on the surfaces of the individual Ni-Fe spinel-type catalysts can efficiently promote the H2-SCR activity. Our demonstration provides new insight into designing advanced catalysts for H2-SCR.

On the cobalt and cobalt oxide electrodeposition from a glyceline deep eutectic solvent.

PubMed

Sakita, Alan M P; Della Noce, Rodrigo; Fugivara, Cecílio S; Benedetti, Assis V

2016-09-14

The electrodeposition of cobalt and cobalt oxides from a glyceline deep eutectic solvent is reported. Cyclic voltammetry, chronoamperometry, scanning electron microscopy, and Raman spectroscopy are employed to study the Co deposition processes. Surface analysis reveals that metallic cobalt is deposited at potentials less negative than the current peak potential whereas cobalt oxides are detected and electrochemically observed when the deposition is done at more negative potentials. i-t transients are analyzed by applying the Scharifker and Hills (SH) theoretical model. It is concluded that cobalt deposition occurs via a progressive nucleation and growth mechanism for concentrations higher than 0.05 mol L -1 cobalt ions. For concentrations ≤0.025 mol L -1 cobalt ions and low overpotentials, the mechanism changes to instantaneous nucleation. The i m -t m relationships of the SH model are used to determine the values of the kinetic parameters and the cobalt ion diffusion coefficient.

Ruthenium-Catalyzed Aerobic Oxidation of Amines.

PubMed

Ray, Ritwika; Hazari, Arijit Singha; Lahiri, Goutam Kumar; Maiti, Debabrata

2018-01-18

Amine oxidation is one of the fundamental reactions in organic synthesis as it leads to a variety of value-added products such as oximes, nitriles, imines, and amides among many others. These products comprise the key N-containing building blocks in the modern chemical industry, and such transformations, when achieved in the presence of molecular oxygen without using stoichiometric oxidants, are much preferred as they circumvent the production of unwanted wastes. In parallel, the versatility of ruthenium catalysts in various oxidative transformations is well-documented. Herein, this review focuses on aerobic oxidation of amines specifically by using ruthenium catalysts and highlights the major achievements in this direction and challenges that still need to be addressed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recommendation of ruthenium source for sludge batch flowsheet studies

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

Woodham, W.

Included herein is a preliminary analysis of previously-generated data from sludge batches 7a, 7b, 8, and 9 sludge simulant and real-waste testing, performed to recommend a form of ruthenium for future sludge batch simulant testing under the nitric-formic flowsheet. Focus is given to reactions present in the Sludge Receipt and Adjustment Tank cycle, given that this cycle historically produces the most changes in chemical composition during Chemical Process Cell processing. Data is presented and analyzed for several runs performed under the nitric-formic flowsheet, with consideration given to effects on the production of hydrogen gas, nitrous oxide gas, consumption of formate,more » conversion of nitrite to nitrate, and the removal and recovery of mercury during processing. Additionally, a brief discussion is given to the effect of ruthenium source selection under the nitric-glycolic flowsheet. An analysis of data generated from scaled demonstration testing, sludge batch 9 qualification testing, and antifoam degradation testing under the nitric-glycolic flowsheet is presented. Experimental parameters of interest under the nitric-glycolic flowsheet include N2O production, glycolate destruction, conversion of glycolate to formate and oxalate, and the conversion of nitrite to nitrate. To date, the number of real-waste experiments that have been performed under the nitric-glycolic flowsheet is insufficient to provide a complete understanding of the effects of ruthenium source selection in simulant experiments with regard to fidelity to real-waste testing. Therefore, a determination of comparability between the two ruthenium sources as employed under the nitric-glycolic flowsheet is made based on available data in order to inform ruthenium source selection for future testing under the nitric-glycolic flowsheet.« less

C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex.

PubMed

Man, Wai-Lun; Xie, Jianhui; Pan, Yi; Lam, William W Y; Kwong, Hoi-Ki; Ip, Kwok-Wa; Yiu, Shek-Man; Lau, Kai-Chung; Lau, Tai-Chu

2013-04-17

We report experimental and computational studies of the facile oxidative C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex. We provide evidence that the initial step involves nucleophilic attack of aniline at the nitrido ligand of the ruthenium complex, which is followed by proton and electron transfer to afford a (salen)ruthenium(II) diazonium intermediate. This intermediate then undergoes unimolecular decomposition to generate benzene and N2.

Potential for cobalt recovery from lateritic ores in Europe

NASA Astrophysics Data System (ADS)

Herrington, R.

2012-04-01

Cobalt is one of the 'critical metals' identified under the EU Raw Materials Initiative. Annually the global mine production of cobalt is around 55,000 tonnes,with Europe's industries consuming around 30% of that figure. Currently Europe produces around 27 tonnes of cobalt from mines in Finland although new capacity is planned. Co-bearing nickel laterite ores being mined in Greece, Macedonia and Kosovo where the cobalt is currently not being recovered (ores have typical analyses of 0.055% Co and >1% Ni,). These ores are currently treated directly in pyrometallurgical plants to recover the contained nickel and this process means there is no separate cobalt product produced. Hydrometallurgical treatment of mineralogically suitable laterite ores can recover the cobalt; for example Cuba recovers 3,500 tonnes of cobalt from its laterite mining operations, which are of a similar scale to the current European operations. Implementation of hydrometallurgical techniques is in its infancy in Europe with one deposit in Turkey planning to use atmospheric heap leaching to recover nickel and copper from oxide-dominated ores. More widespread implementation of these methods to mineralogically suitable ore types could unlock the highly significant undeveloped resources (with metal contents >0.04% Co and >1% Ni), which have been defined throughout the Balkans eastwards into Turkey. At a conservative estimate, this region has the potential to supply up to 30% of the EU cobalt requirements.

Cobalt release from inexpensive jewellery: has the use of cobalt replaced nickel following regulatory intervention?

PubMed

Thyssen, Jacob Pontoppidan; Jellesen, Morten S; Menné, Torkil; Lidén, Carola; Julander, Anneli; Møller, Per; Johansen, Jeanne Duus

2010-08-01

Before the introduction of the EU Nickel Directive, concern was raised that manufacturers of jewellery might turn from the use of nickel to cobalt following the regulatory intervention on nickel exposure. The aim was to study 354 consumer items using the cobalt spot test. Cobalt release was assessed to obtain a risk estimate of cobalt allergy and dermatitis in consumers who would wear the jewellery. The cobalt spot test was used to assess cobalt release from all items. Microstructural characterization was made using scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS). Cobalt release was found in 4 (1.1%) of 354 items. All these had a dark appearance. SEM/EDS was performed on the four dark appearing items which showed tin-cobalt plating on these. This study showed that only a minority of inexpensive jewellery purchased in Denmark released cobalt when analysed with the cobalt spot test. As fashion trends fluctuate and we found cobalt release from dark appearing jewellery, cobalt release from consumer items should be monitored in the future. Industries may not be fully aware of the potential cobalt allergy problem.

Nonproductive events in ring-closing metathesis using ruthenium catalysts.

PubMed

Stewart, Ian C; Keitz, Benjamin K; Kuhn, Kevin M; Thomas, Renee M; Grubbs, Robert H

2010-06-30

The relative TONs of productive and nonproductive metathesis reactions of diethyl diallylmalonate are compared for eight different ruthenium-based catalysts. Nonproductive cross metathesis is proposed to involve a chain-carrying ruthenium methylidene. A second more-challenging substrate (dimethyl allylmethylallylmalonate) that forms a trisubstituted olefin product is used to further delineate the effect of catalyst structure on the relative efficiencies of these processes. A steric model is proposed to explain the observed trends.

COBALT FOLLICULITIS

PubMed Central

Sidell, Chester M.; Erickson, J. Gordon; McCleary, Jack E.

1958-01-01

Clinical observations in 60 cases of folliculitis or pronounced activation of acne in patients taking cobalt led to conclusion that the development or aggravation of the dermal lesions were owing to ingestion of the metal. The dermal manifestations abated when use of cobalt was discontinued. Active acne is considered a contraindication to the use of vitamin-iron-mineral supplements containing cobalt. Short courses of antibiotics in addition to regular acne regimen helped shorten the course of the eruption. ImagesFigure 1. PMID:13489508

Determination of the spinel group end-members based on electron microprobe analyses

NASA Astrophysics Data System (ADS)

Ferracutti, Gabriela R.; Gargiulo, M. Florencia; Ganuza, M. Luján; Bjerg, Ernesto A.; Castro, Silvia M.

2015-04-01

The spinel group minerals have been the focus of many studies, not only because of their economic interest, but also due to the fact that they are very useful as petrogenetic indicators. The application End-Members Generator (EMG) allows to establish, based on electron microprobe analyses (EMPA), the 19 end-members of the spinel group: MgAl2O4 (Spinel sensu stricto, s.s.), FeAl2O4 (Hercynite), MnAl2O4 (Galaxite), ZnAl2O4 (Gahnite), MgFe2O4 (Magnesioferrite), Fe3O4 (Magnetite), MnFe2O4 (Jacobsite), ZnFe2O4 (Franklinite), NiFe2O4 (Trevorite), MgCr2O4 (Magnesiochromite), FeCr2O4 (Chromite), MnCr2O4 (Manganochromite), ZnCr2O4 (Zincochromite), NiCr2O4 (Nichromite), MgV2O4 (Magnesiocoulsonite), FeV2O4 (Coulsonite), MnV2O4 (Vuorelainenite), Mg2TiO4 (Qandilite) and Fe2TiO4 (Ulvöspinel). EMG is an application that does not require an installation process and was created with the purpose of performing calculations to obtain: cation proportions (per formula unit, p.f.u.), end-members of the spinel group, redistribution proportions for the corresponding end-members in the Magnetite prism or Ulvöspinel prism and a data validation section to check the results. EMG accepts .csv data files and the results obtained can be used to represent a given dataset with the SpinelViz program or any other 2D and/or 3D graph plotting software.

New type of in-gap states at a spinel/perovskite interface: combined resonant soft x-ray photoemission spectroscopy and first-principles study.

NASA Astrophysics Data System (ADS)

Borisov, Vladislav; Schuetz, Philipp; Pfaff, Florian; Scheiderer, Philipp; Dudy, Lenart; Zapf, Michael; Gabel, Judith; Christensen, Dennis Valbjorn; Chen, Yunzhong; Pryds, Nini; Strocov, Vladimir; Rogalev, Victor; Schlueter, Christoph; Lee, Tien-Lin; Jeschke, Harald O.; Valenti, Roser; Sing, Michael; Claessen, Ralph

Oxygen vacancies in oxide heterostructures create a plethora of electronic phenomena not observed in the stoichiometric systems. In this talk we will discuss the presence of a new type of in-gap states at the spinel/perovskite γ-Al2O3/SrTiO3 interface, as observed in soft x-ray resonant photoemission spectroscopy. Based on ab initio calculations and crystal-field analysis of different atomic environments, we identify the origin of this behavior and we argue on the possible origin of the extraordinarily high electron mobility measured in this heterostructure. This work was financially supported by the Deutsche Forschungsgemeinschaft SFB/TR 49 and SFB 1170.

Investigation of Synthetic Mg(1.3)V(1.7)O4 Spinel with MgO Inclusions: Case Study of a Spinel with an Apparently occupied Interstitial Site

NASA Technical Reports Server (NTRS)

Uchida, Hinako; Righter, Kevin; Lavina, Barbara; Nowell, Matthew M.; Wright, Stuart I.; Downs, Robert T.; Yang, Hexiong

2007-01-01

A magnesium vanadate spinel crystal, ideally MgV2O4, synthesized at 1 bar, 1200 C and equilibrated under FMQ + 1.3 log f(sub o2) condition, was investigated using single-crystal X-ray diffraction, electron microprobe, and electron backscatter (EBSD). The initial X-ray structure refinements gave tetrahedral and octahedral site occupancies, along with the presence of 0.053 apfu Mg at an interstitial octahedral site . Back-scattered electron (BSE) images and electron microprobe analyses revealed the existence of an Mg-rich phase in the spinel matrix, which was too small (less than or equal to 3microns) for an accurate chemical determination. The EBSD analysis combined with X-ray energy dispersive spectroscop[y (XEDS) suggested that the Mg-rich inclusions are periclase oriented coherently with the spinel matrix. The final structure refinements were optimized by subtracting the X-ray intensity contributions (approx. 9%) of periclase reflections, which eliminated the interstitial Mg. This study provides insight into possible origins of refined interstitial cations reported in the the literature for spinel, and points to the difficulty of using only X-ray diffraction data to distinguish a spinel with interstitial cations from one with coherently oriented MgO inclusions.

Using ruthenium sawhorse based decarboxylation to produce industrial materials from oleic acid

USDA-ARS?s Scientific Manuscript database

Ruthenium catalyzed isomerization and decarboxylation of 9-cis-octadecenoic acid are reported as part of the effort to produce valuable industrial materials from biobased sources. Initial studies have demonstrated the efficacy of ruthenium sawhorse materials and further mechanistic studies uncovered...

Platinum-ruthenium-nickel fuel cell electrocatalyst

DOEpatents

Gorer, Alexander

2005-07-26

A catalyst suitable for use in a fuel cell, especially as an anode catalyst, that contains platinum, ruthenium, and nickel, wherein the nickel is at a concentration that is less than about 10 atomic percent.

Advances in spinel optical quality, size/shape capacity, and applications

NASA Astrophysics Data System (ADS)

Roy, Donald W.; Martin, Gay G., Jr.

1992-12-01

Polycrystalline MgAl2O4 Spinel, transparent from two hundred nanometers to six microns, offers a unique combination of optical and physical properties. A superior dome and window material with respect to rain and particle erosion, solar radiation, high temperatures and humidity, it is resistant to attack by strong acids, alkali solutions, sea water and jet fuels. Residual microporosity from the powder process used for fabricating Spinel which previously limited the use of Spinel to thin wall thicknesses and small sizes, has been significantly reduced by advanced hot press and hot isostatic press (HIP) technology. It is now possible to manufacture high quality shallow domes up to seven inches in diameter with a two tenths inch thick wall thickness. Eight inch diameter flat windows have been produced for an advanced missile system. Proof of process near hemispherical 8 inch dome blanks have been fabricated. Recent measurements of refractive index, homogeneity, scatter and surface roughness are available for design purposes. Improvement in the optical quality and in size/shape capability along with several successful prototype tests demonstrate that Spinel is ready for inclusion in appropriate production systems.

A New Type of Metal-Binding Site in Cobalt- And Zinc-Containing Adenylate Kinases Isolated From Sulfate-Reducers D. Gigas And D. Desulfuricans ATCC 27774

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

Gavel, O.Y.; Bursakov, S.A.; Rocco, G.Di

2009-05-18

Adenylate kinase (AK) mediates the reversible transfer of phosphate groups between the adenylate nucleotides and contributes to the maintenance of their constant cellular level, necessary for energy metabolism and nucleic acid synthesis. The AK were purified from crude extracts of two sulfate-reducing bacteria (SRB), Desulfovibrio (D.) gigas NCIB 9332 and Desulfovibrio desulfuricans ATCC 27774, and biochemically and spectroscopically characterized in the native and fully cobalt- or zinc-substituted forms. These are the first reported adenylate kinases that bind either zinc or cobalt and are related to the subgroup of metal-containing AK found, in most cases, in Gram-positive bacteria. The electronic absorptionmore » spectrum is consistent with tetrahedral coordinated cobalt, predominantly via sulfur ligands, and is supported by EPR. The involvement of three cysteines in cobalt or zinc coordination was confirmed by chemical methods. Extended X-ray absorption fine structure (EXAFS) indicate that cobalt or zinc are bound by three cysteine residues and one histidine in the metal-binding site of the 'LID' domain. The sequence {sup 129}Cys-X{sub 5}-His-X{sub 15}-Cys-X{sub 2}-Cys of the AK from D. gigas is involved in metal coordination and represents a new type of binding motif that differs from other known zinc-binding sites of AK. Cobalt and zinc play a structural role in stabilizing the LID domain.« less

Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise

ERIC Educational Resources Information Center

Rapp, Teresa L.; Phillips, Susan R.; Dmochowski, Ivan J.

2016-01-01

The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, lightdriven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes…

Cordierite-spinel troctolite, a new magnesium-rich lithology from the lunar highlands

NASA Technical Reports Server (NTRS)

Marvin, Ursula B.; Carey, J. William; Lindstrom, Marilyn M.

1989-01-01

A clast of spineltroctolite containing 8 percent cordierite (Mg2,Al4Si5O18) has been identified among the constituents of Apollo 15 regolith breccia 15295. The cordierite and associated anorthite, forsteritic olivine, and pleonaste spinel represent a new, Mg-rich lunar highlands lithology that formed by metamorphism of an igneous spinel cumulate. The cordierite-forsterite pair in the assemblage is stable at a maximum pressure of 2.5 kilobars, equivalent to a depth of 50 kilometers, or 10 kilometers above the lunar crust-mantle boundary. The occurrence of the clast indicates that spinel cumulates are a more important constituent of the lower lunar crust than has been recognized. The rarity of cordierite-spinel troctolite among lunar rock samples suggests that it is excavated only by large impact events, such as the one that formed the adjacent Imbrium Basin.

Static and dynamic cyclic oxidation of 12 nickel-, cobalt-, and iron-base high-temperature alloys

NASA Technical Reports Server (NTRS)

Barrett, C. A.; Johnston, J. R.; Sanders, W. A.

1978-01-01

Twelve typical high-temperature nickel-, cobalt-, and iron-base alloys were tested by 1 hr cyclic exposures at 1038, 1093, and 1149 C and 0.05 hr exposures at 1093 C. The alloys were tested in both a dynamic burner rig at Mach 0.3 gas flow and in static air furnace for times up to 100 hr. The alloys were evaluated in terms of specific weight loss as a function of time, and X-ray diffraction analysis and metallographic examination of the posttest specimens. A method previously developed was used to estimate specific metal weight loss from the specific weight change of the sample. The alloys were then ranked on this basis. The burner-rig test was more severe than a comparable furnace test and resulted in an increased tendency for oxide spalling due to volatility of Cr in the protective scale and the more drastic cooling due to the air-blast quench of the samples. Increased cycle frequency also increased the tendency to spall for a given test exposure. The behavior of the alloys in both types of tests was related to their composition and their tendency to form scales. The alloys with the best overall behavior formed alpha-Al2O3 aluminate spinels.

Nickel/ruthenium catalyst and method for aqueous phase reactions

DOEpatents

Elliott, Douglas C.; Sealock, John L.

1998-01-01

A method of hydrogenation using a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional ruthenium metal deposited onto the support in a second dispersed phase. The additional ruthenium metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase thereby increasing the life time of the catalyst during hydrogenation reactions.

Metal-metal interactions in linear tri-, penta-, hepta-, and nona-nuclear ruthenium string complexes.

PubMed

Niskanen, Mika; Hirva, Pipsa; Haukka, Matti

2012-05-01

Density functional theory (DFT) methodology was used to examine the structural properties of linear metal string complexes: [Ru(3)(dpa)(4)X(2)] (X = Cl(-), CN(-), NCS(-), dpa = dipyridylamine(-)), [Ru(5)(tpda)(4)Cl(2)], and hypothetical, not yet synthesized complexes [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] (tpda = tri-α-pyridyldiamine(2-), tpta = tetra-α-pyridyltriamine(3-), ppta = penta-α-pyridyltetraamine(4-)). Our specific focus was on the two longest structures and on comparison of the string complexes and unsupported ruthenium backboned chain complexes, which have weaker ruthenium-ruthenium interactions. The electronic structures were studied with the aid of visualized frontier molecular orbitals, and Bader's quantum theory of atoms in molecules (QTAIM) was used to study the interactions between ruthenium atoms. The electron density was found to be highest and distributed most evenly between the ruthenium atoms in the hypothetical [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] string complexes.

Recent advances in ruthenium complex-based light-driven water oxidation catalysts.

PubMed

Xue, Long-Xin; Meng, Ting-Ting; Yang, Wei; Wang, Ke-Zhi

2015-11-01

The light driven splitting of water is one of the most attractive approaches for direct conversion of solar energy into chemical energy in the future. Ruthenium complexes as the water oxidation catalysts (WOCs) and light sensitizers have attracted increasing attention, and have made a great progress. This mini-review highlights recent progress on ruthenium complex-based photochemical and photoelectrochemical water oxidation catalysts. The recent representative examples of these ruthenium complexes that are in homogeneous solution or immobilized on solid electrodes, are surveyed. In particular, special attention has been paid on the supramolecular dyads with photosensitizer and WOC being covalently hold together, and grafted onto the solid electrode. Copyright © 2015 Elsevier B.V. All rights reserved.

Progress in doping of ruthenium silicide (Ru2Si3)

NASA Technical Reports Server (NTRS)

Vining, C. B.; Allevato, C. E.

1992-01-01

Ruthenium silicide is currently under development as a promising thermoelectric material suitable for space power applications. Key to realizing the potentially high figure of merit values of this material is the development of appropriate doping techniques. In this study, manganese and iridium have been identified as useful p- and n-type dopants, respectively. Resistivity values have been reduced by more than 3 orders of magnitude. Anomalous Hall effect results, however, complicate interpretation of some of the results and further effort is required to achieve optimum doping levels.

Analytical Description of Degradation-Relaxation Transformations in Nanoinhomogeneous Spinel Ceramics.

PubMed

Shpotyuk, O; Brunner, M; Hadzaman, I; Balitska, V; Klym, H

2016-12-01

Mathematical models of degradation-relaxation kinetics are considered for jammed thick-film systems composed of screen-printed spinel Cu 0.1 Ni 0.1 Co 1.6 Mn 1.2 O 4 and conductive Ag or Ag-Pd alloys. Structurally intrinsic nanoinhomogeneous ceramics due to Ag and Ag-Pd diffusing agents embedded in a spinel phase environment are shown to define governing kinetics of thermally induced degradation under 170 °C obeying an obvious non-exponential behavior in a negative relative resistance drift. The characteristic stretched-to-compressed exponential crossover is detected for degradation-relaxation kinetics in thick-film systems with conductive contacts made of Ag-Pd and Ag alloys. Under essential migration of a conductive phase, Ag penetrates thick-film spinel ceramics via a considerable two-step diffusing process.

Observation of longitudinal spin-Seebeck effect in cobalt-ferrite epitaxial thin films

NASA Astrophysics Data System (ADS)

Niizeki, Tomohiko; Kikkawa, Takashi; Uchida, Ken-ichi; Oka, Mineto; Suzuki, Kazuya Z.; Yanagihara, Hideto; Kita, Eiji; Saitoh, Eiji

2015-05-01

The longitudinal spin-Seebeck effect (LSSE) has been investigated in cobalt ferrite (CFO), an exceptionally hard magnetic spinel ferrite. A bilayer of a polycrystalline Pt and an epitaxially-strained CFO(110) exhibiting an in-plane uniaxial anisotropy was prepared by reactive rf sputtering technique. Thermally generated spin voltage in the CFO layer was measured via the inverse spin-Hall effect in the Pt layer. External-magnetic-field (H) dependence of the LSSE voltage (VLSSE) in the Pt/CFO(110) sample with H ∥ [001] was found to exhibit a hysteresis loop with a high squareness ratio and high coercivity, while that with H ∥ [ 1 1 ¯ 0 ] shows a nearly closed loop, reflecting the different anisotropies induced by the epitaxial strain. The magnitude of VLSSE has a linear relationship with the temperature difference (ΔT), giving the relatively large VLSSE /ΔT of about 3 μV/K for CFO(110) which was kept even at zero external field.

Method of microbially producing metal gallate spinel nano-objects, and compositions produced thereby

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

Duty, Chad E.; Jellison, Jr., Gerald E.; Love, Lonnie J.

A method of forming a metal gallate spinel structure that includes mixing a divalent metal-containing salt and a gallium-containing salt in solution with fermentative or thermophilic bacteria. In the process, the bacteria nucleate metal gallate spinel nano-objects from the divalent metal-containing salt and the gallium-containing salt without requiring reduction of a metal in the solution. The metal gallate spinel structures, as well as light-emitting structures in which they are incorporated, are also described.

Influence of cobalt and manganese content on the dehydrogenation capacity and kinetics of air-exposed LaNi 5+ x-type alloys in solid gas and electrochemical reactions

NASA Astrophysics Data System (ADS)

Raekelboom, E.; Cuevas, F.; Knosp, B.; Percheron-Guégan, A.

The effect of cobalt and manganese content on the dehydrogenation properties of air-exposed MmB 5+ x-type (Mm = mischmetal; B = Ni, Al, Co and Mn) alloys was investigated both in solid gas and electrochemical reactions. The cobalt and manganese content were varied separately while keeping constant the plateau pressure of the hydrides. The increase of the cobalt content leads to a decrease of the hydrogen capacity whereas the manganese content has no much effect. In solid gas reactions, the kinetics were found to be limited by the hydrogen diffusion through the surface oxidation layer. As for the electrochemistry, the kinetics are limited by a corrosion layer formed in alkaline medium. The desorption rates for both processes increase as the cobalt or manganese content decreases. This is thought to be due to an enhancement of the hydrogen diffusivity through the oxidation layer. As a result, a low cobalt or manganese content in MmB 5+ x alloys is found to be beneficial for the hydrogen desorption kinetics in both processes.

Opposite correlations between cation disordering and amorphization resistance in spinels versus pyrochlores

PubMed Central

Uberuaga, Blas Pedro; Tang, Ming; Jiang, Chao; Valdez, James A.; Smith, Roger; Wang, Yongqiang; Sickafus, Kurt E.

2015-01-01

Understanding and predicting radiation damage evolution in complex materials is crucial for developing next-generation nuclear energy sources. Here, using a combination of ion beam irradiation, transmission electron microscopy and X-ray diffraction, we show that, contrary to the behaviour observed in pyrochlores, the amorphization resistance of spinel compounds correlates directly with the energy to disorder the structure. Using a combination of atomistic simulation techniques, we ascribe this behaviour to structural defects on the cation sublattice that are present in spinel but not in pyrochlore. Specifically, because of these structural defects, there are kinetic pathways for the relaxation of disorder in spinel that are absent in pyrochlore. This leads to a direct correlation between amorphization resistance and disordering energetics in spinel, the opposite of that observed in pyrochlores. These results provide new insight into the origins of amorphization resistance in complex oxides beyond fluorite derivatives. PMID:26510750

Opposite correlations between cation disordering and amorphization resistance in spinels versus pyrochlores.

PubMed

Uberuaga, Blas Pedro; Tang, Ming; Jiang, Chao; Valdez, James A; Smith, Roger; Wang, Yongqiang; Sickafus, Kurt E

2015-10-29

Understanding and predicting radiation damage evolution in complex materials is crucial for developing next-generation nuclear energy sources. Here, using a combination of ion beam irradiation, transmission electron microscopy and X-ray diffraction, we show that, contrary to the behaviour observed in pyrochlores, the amorphization resistance of spinel compounds correlates directly with the energy to disorder the structure. Using a combination of atomistic simulation techniques, we ascribe this behaviour to structural defects on the cation sublattice that are present in spinel but not in pyrochlore. Specifically, because of these structural defects, there are kinetic pathways for the relaxation of disorder in spinel that are absent in pyrochlore. This leads to a direct correlation between amorphization resistance and disordering energetics in spinel, the opposite of that observed in pyrochlores. These results provide new insight into the origins of amorphization resistance in complex oxides beyond fluorite derivatives.

Spinel Co3O4 nanomaterials for efficient and stable large area carbon-based printed perovskite solar cells.

PubMed

Bashir, Amna; Shukla, Sudhanshu; Lew, Jia Haur; Shukla, Shashwat; Bruno, Annalisa; Gupta, Disha; Baikie, Tom; Patidar, Rahul; Akhter, Zareen; Priyadarshi, Anish; Mathews, Nripan; Mhaisalkar, Subodh G

2018-02-01

Carbon based perovskite solar cells (PSCs) are fabricated through easily scalable screen printing techniques, using abundant and cheap carbon to replace the hole transport material (HTM) and the gold electrode further reduces costs, and carbon acts as a moisture repellent that helps in maintaining the stability of the underlying perovskite active layer. An inorganic interlayer of spinel cobaltite oxides (Co 3 O 4 ) can greatly enhance the carbon based PSC performance by suppressing charge recombination and extracting holes efficiently. The main focus of this research work is to investigate the effectiveness of Co 3 O 4 spinel oxide as the hole transporting interlayer for carbon based perovskite solar cells (PSCs). In these types of PSCs, the power conversion efficiency (PCE) is restricted by the charge carrier transport and recombination processes at the carbon-perovskite interface. The spinel Co 3 O 4 nanoparticles are synthesized using the chemical precipitation method, and characterized by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and UV-Vis spectroscopy. A screen printed thin layer of p-type inorganic spinel Co 3 O 4 in carbon PSCs provides a better-energy level matching, superior efficiency, and stability. Compared to standard carbon PSCs (PCE of 11.25%) an improved PCE of 13.27% with long-term stability, up to 2500 hours under ambient conditions, is achieved. Finally, the fabrication of a monolithic perovskite module is demonstrated, having an active area of 70 cm 2 and showing a power conversion efficiency of >11% with virtually no hysteresis. This indicates that Co 3 O 4 is a promising interlayer for efficient and stable large area carbon PSCs.

Nickel/ruthenium catalyst and method for aqueous phase reactions

DOEpatents

Elliott, D.C.; Sealock, J.L.

1998-09-29

A method of hydrogenation is described using a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional ruthenium metal deposited onto the support in a second dispersed phase. The additional ruthenium metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase thereby increasing the life time of the catalyst during hydrogenation reactions. 2 figs.

Mechanical properties of nanocrystalline cobalt

NASA Astrophysics Data System (ADS)

Karimpoor, Amir A.; Erb, Uwe

2006-05-01

Due to their excellent wear and corrosion properties, nanocrystalline cobalt and several cobalt alloys made by electrodeposition are currently being developed as environmentally benign replacement coatings for hard chromium electrodeposits. The focus of this study is on the mechanical properties of nanocrystalline cobalt, which are currently not well understood. A comparison is presented for hardness, tensile properties, Charpy impact properties and fracture surface analysis of both nanocrystalline (grain size: 12 nm) and conventional polycrystalline (grain size: 4.8 m) cobalt. It is shown that the hardness and tensile strength of nanocrystalline cobalt is 2-3 times higher than for polycrystalline cobalt. However, in contrast to other nanocrystalline materials tested previously, nanocrystalline cobalt retains considerable ductility with elongation to fracture values up to 7%.

Analysis of the Fragmentation of AlON and Spinel Under Ballistic Impact

DTIC Science & Technology

2013-05-01

Suite 1204, Arlington VA 22202-4302. Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to a penalty...PAGES 11 19a. NAME OF RESPONSIBLE PERSON a. REPORT unclassified b. ABSTRACT unclassified c. THIS PAGE unclassified Standard Form 298 (Rev. 8-98...penetration could not be clearly observed with the other types of spinel tested. This finding corresponds to the lower residual penetration and lower

Solvothermal Synthesis of Magnetic Spinel Ferrites

PubMed Central

Rafienia, Mohammad; Bigham, Ashkan; Hassanzadeh-Tabrizi, Seyed Ali

2018-01-01

At present, solvothermal fabrication method has widely been applied in the synthesis of spinel ferrite nanoparticles (SFNs), which is mainly because of its great advantages such as precise control over size, shape distribution, and high crystallinity that do not require postannealing treatment. Among various SFNs, Fe3O4 nanoparticles have attracted tremendous attention because of their favorable physical and structural properties which are advantageous, especially in biomedical applications, among which the vast application of these materials as targeted drug delivery systems, hyperthermia, and imaging agents in cancer therapy can be mentioned. The main focus of this study is to present an introduction to solvothermal method and key synthesis parameters of SFNs through this synthesis route. Moreover, most recent progress on the potential applications of Fe3O4 nanoparticles as the most important compound among the spinel ferrites family members is discussed. PMID:29928636

Tin-decorated ruthenium nanoparticles: a way to tune selectivity in hydrogenation reaction

NASA Astrophysics Data System (ADS)

Bonnefille, Eric; Novio, Fernando; Gutmann, Torsten; Poteau, Romuald; Lecante, Pierre; Jumas, Jean-Claude; Philippot, Karine; Chaudret, Bruno

2014-07-01

Two series of ruthenium nanoparticles stabilized either by a polymer (polyvinylpyrrolidone; Ru/PVP) or a ligand (bisdiphenylphosphinobutane; Ru/dppb) were reacted with tributyltin hydride [(n-C4H9)3SnH] leading to tin-decorated ruthenium nanoparticles, Ru/PVP/Sn and Ru/dppb/Sn. The Sn/Ru molar ratio was varied in order to study the influence of the surface tin content on the properties of these new nanoparticles, by comparison with Ru/PVP and Ru/dppb. Besides HRTEM and WAXS analyses, spectroscopic techniques (IR, NMR and Mössbauer) combined with theoretical calculations and a simple catalytic test (styrene hydrogenation) allowed us to evidence the formation of μ3-bridging ``SnR'' groups on the ruthenium surface as well as to rationalize their influence on surface chemistry and catalytic activity.Two series of ruthenium nanoparticles stabilized either by a polymer (polyvinylpyrrolidone; Ru/PVP) or a ligand (bisdiphenylphosphinobutane; Ru/dppb) were reacted with tributyltin hydride [(n-C4H9)3SnH] leading to tin-decorated ruthenium nanoparticles, Ru/PVP/Sn and Ru/dppb/Sn. The Sn/Ru molar ratio was varied in order to study the influence of the surface tin content on the properties of these new nanoparticles, by comparison with Ru/PVP and Ru/dppb. Besides HRTEM and WAXS analyses, spectroscopic techniques (IR, NMR and Mössbauer) combined with theoretical calculations and a simple catalytic test (styrene hydrogenation) allowed us to evidence the formation of μ3-bridging ``SnR'' groups on the ruthenium surface as well as to rationalize their influence on surface chemistry and catalytic activity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr00791c

Nature of the lithospheric mantle beneath the Arabian Shield and genesis of Al-spinel micropods: Evidence from the mantle xenoliths of Harrat Kishb, Western Saudi Arabia

NASA Astrophysics Data System (ADS)

Ahmed, Ahmed H.; Moghazi, Abdel Kader M.; Moufti, Mohamed R.; Dawood, Yehia H.; Ali, Kamal A.

2016-01-01

The Harrat Kishb area of western Saudi Arabia is part of the Cenozoic volcanic fields in the western margin of the Arabian Shield. Numerous fresh ultramafic xenoliths are entrained in the basanite lava of Harrat Kishb, providing an opportunity to study the nature and petrogenetic processes involved in the evolution of the lithospheric mantle beneath the Arabian Shield. Based on the petrological characteristics and mineralogical compositions, the majority of the mantle xenoliths ( 92%) are peridotites (lherzolites and pyroxene-bearing harzburgites); the remaining xenoliths ( 8%) are unusual spinel-rich wehrlites containing black Al-spinel micropods. The two types of mantle xenoliths display magmatic protogranular texture. The peridotite xenoliths have high bulk-rock Mg#, high forsterite (Fo90-Fo92) and NiO (0.24-0.46 wt.%) contents of olivine, high clinopyroxene Mg# (0.91-0.93), variable spinel Cr# (0.10-0.49, atomic ratio), and approximately flat chondrite-normalized REE patterns. These features indicate that the peridotite xenoliths represent residues after variable degrees of melt extraction from fertile mantle. The estimated P (9-16 kbar) and T (877-1227 °C) as well as the oxidation state (ΔlogfO2 = - 3.38 to - 0.22) under which these peridotite xenoliths originated are consistent with formation conditions similar to most sub-arc abyssal-type peridotites worldwide. The spinel-rich wehrlite xenoliths have an unusual amount ( 30 vol.%) of Al-spinel as peculiar micropods with very minor Cr2O3 content (< 1 wt.%). Olivines of the spinel-rich wehrlites have low-average Fo (Fo81) and NiO (0.18 wt.%) contents, low-average cpx Mg# (0.79), high average cpx Al2O3 content (8.46 wt.%), and very low-average spinel Cr# (0.01). These features characterize early mantle cumulates from a picritic melt fraction produced by low degrees of partial melting of a garnet-bearing mantle source. The relatively high Na2O and Al2O3 contents of cpx suggest that the spinel-rich wehrlites are

Zinc Isotopic Compositions of Spinel Peridotites

NASA Astrophysics Data System (ADS)

Chen, S.; Huang, F.

2015-12-01

Zn isotope geochemistry has shown great potential in exploring planetary differentiation and volatilization history [1,2,3,4]. However, the zinc isotopic composition of the mantle and its fractionation mechanism in high-temperature processes are still unclear. In order to understand Zn isotope composition of the mantle, here we measured Zn isotope data for mantle rocks and minerals, including coexisting olivine, orthopyroxene (Opx), clinopyroxene (Cpx) and spinel from peridotite xenoliths in the Hannuoba (China), Vitim (Siberia), Tariat (central Mongolia), and Dariganga (SE Mongolia). As an accessary mineral, spinels in our study have high Zn contents (500-1400 ppm), accounting for 18%-40% of the total Zn budget in peridotites. Spinels have higher δ66Zn ranging from 0.17 to 0.30‰ than other mantle minerals. For most samples, the δ66Zn of olivines vary from -0.03‰ to 0.19‰, indistinguishable to the value of the coexisting Opx (0.05‰ to 0.20‰). However, we also observed large fractionation between these two minerals, which may reflect disequilibrium fractionation due to kinetic processes. Finally, δ66Zn for peridotites are 0.12-0.21‰, slightly lighter than that of basalts (~0.25±0.05‰), revealing that Zn isotopes can be slightly fractionated during mantle melting. [1] Luck et al., (2005) Geochimica Cosmo Acta, 69, 5351-5363. [2] Paniello et al., (2012) Nature, 490, 376-379. [3] Chen et al., (2013) Meteoritics Planet Sci, 48, 2441-2450. [4] Day and Moynier, (2014) Phil. Transac. of the Royal Society B, 372, 20130259

Complex of transferrin with ruthenium for medical applications

DOEpatents

Richards, Powell; Srivastava, Suresh C.; Meinken, George E.

1984-05-15

A novel Ruthenium-transferrin complex, prepared by reacting iron-free human transferrin dissolved in a sodium acetate solution at pH 7 with ruthenium by heating at about 40.degree. C. for about 2 hours, and purifying said complex by means of gel chromotography with pH 7 sodium acetate as eluent. The mono- or di-metal complex produced can be used in nuclear medicine in the diagnosis and/or treatment of tumors and abscesses. Comparative results with Ga-67-citrate, which is the most widely used tumor-localizing agent in nuclear medicine, indicate increased sensitivity of detection and greater tumor uptake with the Ru-transferrin complex.

Structural and Mössbauer analysis of pure and Ce-Dy doped cobalt ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Hashim, Mohd.; Meena, Sher Singh; Kumar, Shalendra; Ahmed, Ateeq; Bhatt, Pramod

2018-05-01

Ce and Dy doped Cobalt ferrites with the chemical composition CoCexDyxFe2-2xO4 (x = 0.00 and 0.04) were synthesized via the chemical route using citrate-gel auto-combustion method. The structural analysis has been carried out with the help of x-ray diffraction (XRD). Formation of spinel cubic structure of the ferrites was confirmed by XRD analysis. Mössbauer spectra were recorded for both samples at room temperature. Presence of the well resolved sextet spectra corresponding to A and B sub-lattice clearly shows that both the samples have ferrimagnetic ordering at room temperature. Isomer shift observed from fitting of the Mössbauer spectra infers that Fe3+ ions are in high valence state. The decrease in the hyperfine field due to the doping of Ce and Dy clearly showed that magnetic interactions diluted due to the doping of Ce and Dy ions.

Steric and Electronic Effects of Bidentate Phosphine Ligands on Ruthenium(II)-Catalyzed Hydrogenation of Carbon Dioxide.

PubMed

Zhang, Pan; Ni, Shao-Fei; Dang, Li

2016-09-20

The reactivity difference between the hydrogenation of CO2 catalyzed by various ruthenium bidentate phosphine complexes was explored by DFT. In addition to the ligand dmpe (Me2 PCH2 CH2 PMe2 ), which was studied experimentally previously, a more bulky diphosphine ligand, dmpp (Me2 PCH2 CH2 CH2 PMe2 ), together with a more electron-withdrawing diphosphine ligand, PN(Me) P (Me2 PCH2 N(Me) CH2 PMe2 ), have been studied theoretically to analyze the steric and electronic effects on these catalyzed reactions. Results show that all of the most favorable pathways for the hydrogenation of CO2 catalyzed by bidentate phosphine ruthenium dihydride complexes undergo three major steps: cis-trans isomerization of ruthenium dihydride complex, CO2 insertion into the Ru-H bond, and H2 insertion into the ruthenium formate ion. Of these steps, CO2 insertion into the Ru-H bond has the lowest barrier compared with the other two steps in each preferred pathway. For the hydrogenation of CO2 catalyzed by ruthenium complexes of dmpe and dmpp, cis-trans isomerization of ruthenium dihydride complex has a similar barrier to that of H2 insertion into the ruthenium formate ion. However, in the reaction catalyzed by the PN(Me) PRu complex, cis-trans isomerization of the ruthenium dihydride complex has a lower barrier than H2 insertion into the ruthenium formate ion. These results suggest that the steric effect caused by the change of the outer sphere of the diphosphine ligand on the reaction is not clear, although the electronic effect is significant to cis-trans isomerization and H2 insertion. This finding refreshes understanding of the mechanism and provides necessary insights for ligand design in transition-metal-catalyzed CO2 transformation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A promising new thermoelectric material - Ruthenium silicide

NASA Technical Reports Server (NTRS)

Vining, Cronin B.; Mccormack, Joseph A.; Zoltan, Andrew; Zoltan, Leslie D.

1991-01-01

Experimental and theoretical efforts directed toward increasing thermoelectric figure of merit values by a factor of 2 or 3 have been encouraging in several respects. An accurate and detailed theoretical model developed for n-type silicon-germanium (SiGe) indicates that ZT values several times higher than currently available are expected under certain conditions. These new, high ZT materials are expected to be significantly different from SiGe, but not unreasonably so. Several promising candidate materials have been identified which may meet the conditions required by theory. One such candidate, ruthenium silicide, currently under development at JPL, has been estimated to have the potential to exhibit figure of merit values 4 times higher than conventional SiGe materials. Recent results are summarized.

High density nonmagnetic cobalt in thin films

NASA Astrophysics Data System (ADS)

Banu, Nasrin; Singh, Surendra; Basu, Saibal; Roy, Anupam; Movva, Hema C. P.; Lauter, V.; Satpati, B.; Dev, B. N.

2018-05-01

Recently high density (HD) nonmagnetic cobalt has been discovered in a nanoscale cobalt thin film, grown on Si(111) single crystal. This form of cobalt is not only nonmagnetic but also superconducting. These promising results have encouraged further investigations of the growth of the nonmagnetic (NM) phase of cobalt. In the original investigation, the cobalt film had a natural cobalt oxide at the top. We have investigated whether the growth of HD NM cobalt layers in the thin film depends on (i) a capping layer on the cobalt film, (ii) the thickness of the cobalt film and (iii) the nature of the substrate on which the cobalt film is grown. The results of such investigations indicate that for cobalt films capped with a thin gold layer, and for various film thicknesses, HD NM cobalt layers are formed. However, instead of a Si substrate, when the cobalt films are grown on oxide substrates, such as silicon oxide or cobalt oxide, HD NM cobalt layers are not formed. The difference is attributed to the nature—crystalline or amorphous—of the substrate.

Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility.

PubMed

Li, H F; Zhou, F Y; Li, L; Zheng, Y F

2016-04-19

In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co-Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10(-6) cm(3)·g(-1)-1.29 × 10(-6) cm(3)·g(-1) for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti-6Al-4V, ~3.5 × 10(-6) cm(3)·g(-1), CP Ti and Ti-6Al-7Nb, ~3.0 × 10(-6) cm(3)·g(-1)), and one-sixth that of Co-Cr alloys (Co-Cr-Mo, ~7.7 × 10(-6) cm(3)·g(-1)). Among the Zr-Ru alloy series, Zr-1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr-Ru alloy system as therapeutic devices under MRI diagnostics environments.

Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility

PubMed Central

Li, H.F.; Zhou, F.Y.; Li, L.; Zheng, Y.F.

2016-01-01

In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co–Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10−6 cm3·g−1–1.29 × 10−6 cm3·g−1 for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti–6Al–4V, ~3.5 × 10−6 cm3·g−1, CP Ti and Ti–6Al–7Nb, ~3.0 × 10−6 cm3·g−1), and one-sixth that of Co–Cr alloys (Co–Cr–Mo, ~7.7 × 10−6 cm3·g−1). Among the Zr–Ru alloy series, Zr–1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr–Ru alloy system as therapeutic devices under MRI diagnostics environments. PMID:27090955

[Metallurgical differentiation of cobalt-chromium alloys for implants].

PubMed

Holzwarth, U; Thomas, P; Kachler, W; Göske, J; Schuh, A

2005-10-01

Cobalt Chromium alloys are used in cemented total hip or knee arthroplasty as well as in metal-on-metal bearings in total hip arthroplasty. An increasing number of publications report about (allergic) reactions to wear particles of Cobalt Chromium alloys. Reactions to nickel are more frequent in comparison to Cobalt or Chromium particles. It is well known that different kinds of Cobalt Chromium alloys contain different amounts of alloying elements; nevertheless. The aim of the current work was to compare the different Cobalt Chromium alloys according to ASTM F or ISO standards in respect to the different alloying elements. Co28Cr6Mo casting alloys according to ASTM F 75 or ISO 5832-4 as well as forging alloy types according to ASTM F 799 and ISO 5832 such as Co20Cr15W10Ni, Co35Ni20Cr, Fe40Co20Cr10Ni, Co20Cr20Ni, and Co28Cr6Mo were analyzed in respect to their element content of Co, Cr, Ni, Mo, Fe, W, and Mn. In 1935 the Cobalt based alloy "Vitallium" Co30Cr5Mo basically used in the aircraft industry was introduced into medicine. The chemical composition of this alloy based on Cobalt showed 30 wt.% Chromium and 5 wt.% Molybdenum. The differentiation using alloy names showed no Nickel information in single alloy names. The information given about different alloys can lead to an unprecise evaluation of histopathological findings in respect to alloys or alloying constituents. Therefore, implant manufacturers should give the exact information about the alloys used and adhere to European law, Euronorm 93/42/EWG.

Elemental Mercury Oxidation over Fe-Ti-Mn Spinel: Performance, Mechanism, and Reaction Kinetics.

PubMed

Xiong, Shangchao; Xiao, Xin; Huang, Nan; Dang, Hao; Liao, Yong; Zou, Sijie; Yang, Shijian

2017-01-03

The design of a high-performance catalyst for Hg 0 oxidation and predicting the extent of Hg 0 oxidation are both extremely limited due to the uncertainties of the reaction mechanism and the reaction kinetics. In this work, Fe-Ti-Mn spinel was developed as a high-performance catalyst for Hg 0 oxidation, and the reaction mechanism and the reaction kinetics of Hg 0 oxidation over Fe-Ti-Mn spinel were studied. The reaction orders of Hg 0 oxidation over Fe-Ti-Mn spinel with respect to gaseous Hg 0 concentration and gaseous HCl concentration were approximately 1 and 0, respectively. Therefore, Hg 0 oxidation over Fe-Ti-Mn spinel mainly followed the Eley-Rideal mechanism (i.e., the reaction of gaseous Hg 0 with adsorbed HCl), and the rate of Hg 0 oxidation mainly depended on Cl • concentration on the surface. As H 2 O, SO 2 , and NO not only inhibited Cl • formation on the surface but also interfered with the interface reaction between gaseous Hg 0 and Cl • on the surface, Hg 0 oxidation over Fe-Ti-Mn spinel was obviously inhibited in the presence of H 2 O, SO 2 , and NO. Furthermore, the extent of Hg 0 oxidation over Fe-Ti-Mn spinel can be predicted according to the kinetic parameter k E-R , and the predicted result was consistent with the experimental result.

Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts.

PubMed

Cheng, Fangyi; Shen, Jian; Peng, Bo; Pan, Yuede; Tao, Zhanliang; Chen, Jun

2011-01-01

Spinels can serve as alternative low-cost bifunctional electrocatalysts for oxygen reduction/evolution reactions (ORR/OER), which are the key barriers in various electrochemical devices such as metal-air batteries, fuel cells and electrolysers. However, conventional ceramic synthesis of crystalline spinels requires an elevated temperature, complicated procedures and prolonged heating time, and the resulting product exhibits limited electrocatalytic performance. It has been challenging to develop energy-saving, facile and rapid synthetic methodologies for highly active spinels. In this Article, we report the synthesis of nanocrystalline M(x)Mn(3-x)O(4) (M = divalent metals) spinels under ambient conditions and their electrocatalytic application. We show rapid and selective formation of tetragonal or cubic M(x)Mn(3-x)O(4) from the reduction of amorphous MnO(2) in aqueous M(2+) solution. The prepared Co(x)Mn(3-x)O(4) nanoparticles manifest considerable catalytic activity towards the ORR/OER as a result of their high surface areas and abundant defects. The newly discovered phase-dependent electrocatalytic ORR/OER characteristics of Co-Mn-O spinels are also interpreted by experiment and first-principle theoretical studies.

Preparation of Magnesium, Cobalt and Nickel Ferrite Nanoparticles from Metal Oxides using Deep Eutectic Solvents.

PubMed

Söldner, Anika; Zach, Julia; Iwanow, Melanie; Gärtner, Tobias; Schlosser, Marc; Pfitzner, Arno; König, Burkhard

2016-09-05

Natural deep eutectic solvents (DESs) dissolve simple metal oxides and are used as a reaction medium to synthesize spinel-type ferrite nanoparticles MFe2 O4 (M=Mg, Zn, Co, Ni). The best results for phase-pure spinel ferrites are obtained with the DES consisting of choline chloride (ChCl) and maleic acid. By employing DESs, the reactions proceed at much lower temperatures than usual for the respective solid-phase reactions of the metal oxides and at the same temperatures as synthesis with comparable calcination processes using metal salts. The method therefore reduces the overall required energy for the nanoparticle synthesis. Thermogravimetric analysis shows that the thermolysis process of the eutectic melts in air occurs in one major step. The phase-pure spinel-type ferrite particles are thoroughly characterized by X-ray diffraction, diffuse-reflectance UV/Vis spectroscopy, and scanning electron microscopy. The properties of the obtained nanoparticles are shown to be comparable to those obtained by other methods, illustrating the potential of natural DESs for processing metal oxides. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic modelling of the formation of zinc-manganese ferrite spinel in electric arc furnace dust.

PubMed

Pickles, C A

2010-07-15

Electric arc furnace dust is generated when automobile scrap, containing galvanized steel, is remelted in an electric arc furnace. This dust is considered as a hazardous waste in most countries. Zinc is a major component of the dust and can be of significant commercial value. Typically, the majority of the zinc exists as zinc oxide (ZnO) and as a zinc-manganese ferrite spinel ((Zn(x)Mn(y)Fe(1-x-y))Fe(2)O(4)). The recovery of the zinc from the dust in metal recycling and recovery processes, particularly in the hydrometallurgical extraction processes, is often hindered by the presence of the mixed ferrite spinel. However, there is a paucity of information available in the literature on the formation of this spinel. Therefore, in the present research, the equilibrium module of HSC Chemistry 6.1 was utilized to investigate the thermodynamics of the formation of the spinel and the effect of variables on the amount and the composition of the mixed ferrite spinel. It is proposed that the mixed ferrite spinel forms due to the reaction of iron-manganese particulates with both gaseous oxygen and zinc, at the high temperatures in the freeboard of the furnace above the steel melt. Based on the thermodynamic predictions, methods are proposed for minimizing the formation of the mixed ferrite spinel. 2010 Elsevier B.V. All rights reserved.

Towards a lattice-matching solid-state battery: synthesis of a new class of lithium-ion conductors with the spinel structure.

PubMed

Rosciano, Fabio; Pescarmona, Paolo P; Houthoofd, Kristof; Persoons, Andre; Bottke, Patrick; Wilkening, Martin

2013-04-28

Lithium ion batteries have conquered most of the portable electronics market and are now on the verge of deployment in large scale applications. To be competitive in the automotive and stationary sectors, however, they must be improved in the fields of safety and energy density (W h L(-1)). Solid-state batteries with a ceramic electrolyte offer the necessary advantages to significantly improve the current state-of-the-art technology. The major limit towards realizing a practical solid-state lithium-ion battery lies in the lack of viable ceramic ionic conductors. Only a few candidate materials are available, each carrying a difficult balance between advantages and drawbacks. Here we introduce a new class of possible solid-state lithium-ion conductors with the spinel structure. Such compounds could be coupled with spinel-type electrode materials to obtain a "lattice matching" solid device where low interfacial resistance could be achieved. Powders were prepared by wet chemistry, their structure was studied by means of diffraction techniques and magic angle spinning NMR, and Li(+) self-diffusion was estimated by static NMR line shape measurements. Profound differences in the Li(+) diffusion properties were observed depending on the composition, lithium content and cationic distribution. Local Li(+) hopping in the spinel materials is accompanied by a low activation energy of circa 0.35 eV being comparable with that of, e.g., LLZO-type garnets, which represent the current benchmark in this field. We propose these novel materials as a building block for a lattice-matching all-spinel solid-state battery with low interfacial resistance.

High magnesium mobility in ternary spinel chalcogenides

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

Canepa, Pieremanuele; Bo, Shou-Hang; Sai Gautam, Gopalakrishnan

Magnesium batteries appear a viable alternative to overcome the safety and energy density limitations faced by current lithium-ion technology. Furthermore, the development of a competitive magnesium battery is plagued by the existing notion of poor magnesium mobility in solids. We demonstrate by using ab initio calculations, nuclear magnetic resonance, and impedance spectroscopy measurements that substantial magnesium ion mobility can indeed be achieved in close-packed frameworks (~ 0.01-0.1 mS cm -1 at 298 K), specifically in the magnesium scandium selenide spinel. Our theoretical predictions also indicate that high magnesium ion mobility is possible in other chalcogenide spinels, opening the door formore » the realization of other magnesium solid ionic conductors and the eventual development of an all-solid-state magnesium battery.« less

High magnesium mobility in ternary spinel chalcogenides

DOE PAGES

Canepa, Pieremanuele; Bo, Shou-Hang; Sai Gautam, Gopalakrishnan; ...

2017-11-24

Magnesium batteries appear a viable alternative to overcome the safety and energy density limitations faced by current lithium-ion technology. Furthermore, the development of a competitive magnesium battery is plagued by the existing notion of poor magnesium mobility in solids. We demonstrate by using ab initio calculations, nuclear magnetic resonance, and impedance spectroscopy measurements that substantial magnesium ion mobility can indeed be achieved in close-packed frameworks (~ 0.01-0.1 mS cm -1 at 298 K), specifically in the magnesium scandium selenide spinel. Our theoretical predictions also indicate that high magnesium ion mobility is possible in other chalcogenide spinels, opening the door formore » the realization of other magnesium solid ionic conductors and the eventual development of an all-solid-state magnesium battery.« less

Mitigation of chromium poisoning of cathodes in solid oxide fuel cells employing CuMn1.8O4 spinel coating on metallic interconnect

NASA Astrophysics Data System (ADS)

Wang, Ruofan; Sun, Zhihao; Pal, Uday B.; Gopalan, Srikanth; Basu, Soumendra N.

2018-02-01

Chromium poisoning is one of the major reasons for cathode performance degradation in solid oxide fuel cells (SOFCs). To mitigate the effect of Cr-poisoning, a protective coating on the surface of interconnect for suppressing Cr vaporization is necessary. Among the various coating materials, Cu-Mn spinel coating is considered to be a potential candidate due to their good thermal compatibility, high stability and good electronic conductivity at high temperature. In this study, Crofer 22 H meshes with no protective coating, those with commercial CuMn2O4 spinel coating and the ones with lab-developed CuMn1.8O4 spinel coating were investigated. The lab-developed CuMn1.8O4 spinel coating were deposited on Crofer 22 H mesh by electrophoretic deposition and densified by a reduction and re-oxidation process. With these different Crofer 22 H meshes (bare, CuMn2O4-coated, and CuMn1.8O4-coated), anode-supported SOFCs with Sr-doped LaMnO3-based cathode were electrochemically tested at 800 °C for total durations of up to 288 h. Comparing the mitigating effects of the two types of Cu-Mn spinel coatings on Cr-poisoning, it was found that the performance of the denser lab-developed CuMn1.8O4 spinel coating was distinctly better, showing no degradation in the cell electrochemical performance and significantly less Cr deposition near the cathode/electrolyte interface after the test.

Cobalt phosphide based nanostructures as bifunctional electrocatalysts for low temperature alkaline water splitting

DOE PAGES

Lambert, Timothy N.; Vigil, Julian A.; Christensen, Ben

2016-08-22

Cobalt phosphide based thin films and nanoparticles were prepared by the thermal phosphidation of spinel Co 3O 4 precursor films and nanoparticles, respectively. CoP films were prepared with overall retention of the Co 3O 4 nanoplatelet morphology while the spherical/cubic Co 3O 4 and Ni 0.15Co 2.85O 4 nanoparticles were converted to nanorods or nanoparticles, respectively. The inclusion of nickel in the nanoparticles resulted in a 2.5 fold higher surface area leading to higher gravimetric performance. In each case high surface area structures were obtained with CoP as the primary phase. All materials were found to act as effective bifunctionalmore » electrocatalysts for both the HER and the OER and compared well to commercial precious metal benchmark materials in alkaline electrolyte. As a result, a symmetrical water electrolysis cell prepared from the CoP-based film operated at a low overpotential of 0.41-0.51 V.« less

Synthesis of surfactant-coated cobalt ferrite nanoparticles for adsorptive removal of acid blue 45 dye

NASA Astrophysics Data System (ADS)

Waheed Mushtaq, Muhammad; Kanwal, Farah; Imran, Muhammad; Ameen, Naila; Batool, Madeeha; Batool, Aisha; Bashir, Shahid; Mustansar Abbas, Syed; Rehman, Ata ur; Riaz, Saira; Naseem, Shahzad; Ullah, Zaka

2018-03-01

Cobalt ferrite (CoFe2O4) nanoparticles (NPs) are synthesized by wet chemical coprecipitation method using metal chlorides as precursors and potassium hydroxide (KOH) as a precipitant. The tergitol-1x (T-1x) and didecyldimethyl ammonium bromide (DDAB) are used as capping agents and their effect is investigated on particle size, size distribution and morphology of cobalt ferrite nanoparticles (CFNPs). The Fourier transform infrared spectroscopy confirms the synthesis of CFNPs and formation of metal-oxygen (M-O) bond. The spinel phase structure, morphology, polydispersity and magnetic properties of ferrite nanoparticles are investigated by x-ray diffraction, scanning electron microscopy, dynamic light scattering and vibrating sample magnetometry analyses, respectively. The addition of capping agents effects the secondary growth of CFNPs and reduces their particle size, as is investigated by dynamic light scattering and atomic force microscopy. The results evidence that the DDAB is more promising surfactant to control the particle size (∼13 nm), polydispersity and aggregation of CFNPs. The synthesized CFNPs, CFNPs/T-1x and CFNPs/DDAB are used to study their adsorption potential for removal of acid blue 45 dye, and a maximum adsorptive removal of 92.25% is recorded by 0.1 g of CFNPs/DDAB at pH 2.5 and temperature 20 ± 1 °C. The results show that the dye is physically adsorbed by magnetic NPs and follows the Langmuir isotherm model.

Iron-Induced Activation of Ordered Mesoporous Nickel Cobalt Oxide Electrocatalyst for the Oxygen Evolution Reaction.

PubMed

Deng, Xiaohui; Öztürk, Secil; Weidenthaler, Claudia; Tüysüz, Harun

2017-06-28

Herein, ordered mesoporous nickel cobalt oxides prepared by the nanocasting route are reported as highly active oxygen evolution reaction (OER) catalysts. By using the ordered mesoporous structure as a model system and afterward elevating the optimal catalysts composition, it is shown that, with a simple electrochemical activation step, the performance of nickel cobalt oxide can be significantly enhanced. The electrochemical impedance spectroscopy results indicated that charge transfer resistance increases for Co 3 O 4 spinel after an activation process, while this value drops for NiO and especially for CoNi mixed oxide significantly, which confirms the improvement of oxygen evolution kinetics. The catalyst with the optimal composition (Co/Ni 4/1) reaches a current density of 10 mA/cm 2 with an overpotential of a mere 336 mV and a Tafel slope of 36 mV/dec, outperforming benchmarked and other reported Ni/Co-based OER electrocatalysts. The catalyst also demonstrates outstanding durability for 14 h and maintained the ordered mesoporous structure. The cyclic voltammograms along with the electrochemical measurements in Fe-free KOH electrolyte suggest that the activity boost is attributed to the generation of surface Ni(OH) 2 species that incorporate Fe impurities from the electrolyte. The incorporation of Fe into the structure is also confirmed by inductively coupled plasma optical emission spectrometry.

A new approach to synthesize supported ruthenium phosphides for hydrodesulfurization

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

Wang, Qingfang; Key Laboratory of Advanced Energy Materials Chemistry; Wang, Zhiqiang

2016-02-15

Highlights: • We bring out a new method to synthesize noble metal phosphides at low temperature. • Both RuP and Ru{sub 2}P were synthesized using triphenylphosphine as phosphorus sources. • Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. • RuP/SiO{sub 2} prepared by new method had better HDS activity to that by TPR method. - Abstract: Supported noble metal ruthenium phosphides were synthesized by one-step H{sub 2}-thermal treatment method using triphenylphosphine (TPP) as phosphorus sources at low temperatures. Two phosphides RuP and Ru{sub 2}P can be prepared by this method via varying the molarmore » ratio of metal salt and TPP. The as-prepared phosphides were characterized by X-ray powder diffraction (XRD), low-temperature N{sub 2} adsorption, CO chemisorption and transmission electronic microscopy (TEM). The supported ruthenium phosphides prepared by new method and conventional method together with contradistinctive metallic ruthenium were evaluated in hydrodesulfurization (HDS) of dibenzothiophene (DBT). The catalytic results showed that metal-rich Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. Besides this, ruthenium phosphide catalyst prepared by new method exhibited superior HDS activity to that prepared by conventional method.« less

Enhancement of electrochemical performance by simultaneous substitution of Ni and Mn with Fe in Ni-Mn spinel cathodes for Li-ion batteries

NASA Astrophysics Data System (ADS)

Kiziltas-Yavuz, Nilüfer; Yavuz, Murat; Indris, Sylvio; Bramnik, Natalia N.; Knapp, Michael; Dolotko, Oleksandr; Das, Bijoy; Ehrenberg, Helmut; Bhaskar, Aiswarya

2016-09-01

LiNi0.5-xFe2xMn1.5-xO4 (x = 0, 0.1, 0.15, 0.2) spinel cathode materials are synthesized using citric acid-assisted sol-gel method with final calcination temperature of 1000 °C. The structure and morphology of the materials are characterized by using synchrotron and neutron powder diffraction as well as scanning electron microscopy. Different from the parent LiNi0.5Mn1.5O4 (LNMO) material, the Fe-doped spinels do not contain a rock-salt type impurity phase. However, they contain additional layered (C2/m) and spinel Fe3O4 (Fd 3 bar m) phases in small amounts. The substitution of Fe into the spinel structure has been confirmed by Mössbauer spectroscopy. The Fe-doped spinels exhibit improved cycling stability (with a C/2 charge-discharge rate) and rate capability compared to the parent LNMO at room temperature in a voltage range 3.5-5.0 V. Among all these samples, the composition LiNi0.4Fe0.2Mn1.4O4 shows the best room temperature cycling stability (capacity retention of 92% after 300 cycles) as well as the highest initial discharge capacity (134 mAh g-1). The delivered capacities at high C-rates (especially at 10C and 20C) with respect to the capacity delivered at C/2 are higher for all Fe-doped samples compared to the parent LNMO. Furthermore, Fe-doping improves the thermal stability of the Ni-Mn spinels in the delithiated state.

Spinel lithium manganese oxide nanoparticles: unique molten salt synthesis strategy and excellent electrochemical performances.

PubMed

Wang, Xiong; Zhu, Juanjuan; Liu, Yingjie

2009-11-01

As a promising candidate cathode material, spinel lithium manganese oxide nanoparticles were successfully synthesized through a novel molten salt synthesis route at relatively low temperature, using manganese dioxide nanowires as precursor. A variety of techniques were applied to characterize the spinel nanomaterial, including X-ray diffraction, transmission electron microscopy, field-emission scanning electron microscopy, and X-ray photoelectron spectroscopy. The average particle size of the resulting spinel nanoparticles was about 80 nm with narrow distribution. As cathode material for rechargeable lithium ion battery, the electrochemical properties were investigated. All the results show that the electrochemical performances of the homogeneous spinel nanoparticles were improved, which might be ascribed to large specific surface area, fairly narrow size distribution, and the unique synthesis strategy.

Sustainable synthesis of monodispersed spinel nano-ferrites

EPA Science Inventory

A sustainable approach for the synthesis of various monodispersed spinel ferrite nanoparticles has been developed that occurs at water-toluene interface under both conventional and microwave hydrothermal conditions. This general synthesis procedure utilizes readily available and ...

Textures in spinel peridotite mantle xenoliths using micro-CT scanning: Examples from Canary Islands and France

NASA Astrophysics Data System (ADS)

Bhanot, K. K.; Downes, H.; Petrone, C. M.; Humphreys-Williams, E.

2017-04-01

Spinel pyroxene-clusters, which are intergrowths of spinel, orthopyroxene and clinopyroxene in mantle xenoliths, have been investigated through the use of micro-CT (μ-CT) in this study. Samples have been studied from two different tectonic settings: (1) the northern Massif Central, France, an uplifted and rifted plateau on continental lithosphere and (2) Lanzarote in the Canary Islands, an intraplate volcanic island on old oceanic lithosphere. μ-CT analysis of samples from both locations has revealed a range of spinel textures from small < 2 mm microcrystals which can be either spatially concentrated or distributed more evenly throughout the rock with a lineation, to large 4-12 mm individual clusters with ellipsoidal complex vermicular textures in random orientation. Microprobe analyses of pyroxenes inside and outside the clusters show broadly similar compositions. Spinel-pyroxene clusters are the result of a transition of shallow lithospheric mantle from the garnet stability field to the spinel stability field. Both the northern Massif Central and Lanzarote are regions that have experienced significant lithospheric thinning. This process provides a mechanism where the sub-solidus reaction of olivine + garnet = orthopyroxene + clinopyroxene + spinel is satisfied by providing a pathway from garnet peridotite to spinel peridotite. We predict that such textures would only occur in the mantle beneath regions that show evidence of thinning of the lithospheric mantle. Metasomatic reactions are seen around spinel-pyroxene clusters in some Lanzarote xenoliths, so metasomatism post-dated cluster formation.

Challenges and approaches for high-voltage spinel lithium-ion batteries.

PubMed

Kim, Jung-Hyun; Pieczonka, Nicholas P W; Yang, Li

2014-07-21

Lithium-ion (Li-ion) batteries have been developed for electric vehicle (EV) applications, owing to their high energy density. Recent research and development efforts have been devoted to finding the next generation of cathode materials for Li-ion batteries to extend the driving distance of EVs and lower their cost. LiNi(0.5)Mn(1.5)O(4) (LNMO) high-voltage spinel is a promising candidate for a next-generation cathode material based on its high operating voltage (4.75 V vs. Li), potentially low material cost, and excellent rate capability. Over the last decade, much research effort has focused on achieving a fundamental understanding of the structure-property relationship in LNMO materials. Recent studies, however, demonstrated that the most critical barrier for the commercialization of high-voltage spinel Li-ion batteries is electrolyte decomposition and concurrent degradative reactions at electrode/electrolyte interfaces, which results in poor cycle life for LNMO/graphite full cells. Despite scattered reports addressing these processes in high-voltage spinel full cells, they have not been consolidated into a systematic review article. With this perspective, emphasis is placed herein on describing the challenges and the various approaches to mitigate electrolyte decomposition and other degradative reactions in high-voltage spinel cathodes in full cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure and Electrical Properties of Mn-Cu-O Spinels

NASA Astrophysics Data System (ADS)

Bobruk, M.; Durczak, K.; Dąbek, J.; Brylewski, T.

2017-04-01

The study presents the results of structural and electrical conductivity investigations of a Cu1.3Mn1.7O4 spinel obtained using EDTA gel processes. An amorphous gel was synthesized and calcinated for 5 h in air at temperatures of 673, 773, 873, and 973 K. When calcinating the gel at temperatures below 973 K, the obtained powders consisted of two phases—the regular Cu1.5Mn1.5O4 spinel and manganese(III) oxide. At 973 K, Mn2O3 was no longer observed, but a new Mn3O4 phase appeared in addition to the Cu1.5Mn1.5O4 spinel. Green bodies prepared from these powders were sintered for 2 h in air at 1393 K. The obtained sinters had a porosity of around 12% and were composed predominantly of the spinel phase, with minor amounts of Mn3O4 and, in the case of three of four sinters—CuO. Electrical conductivity measurements were taken over the temperature range of 300-1073 K. A change in the character of conductivity of the studied sinters was observed in the range of 400-430 K, and it was associated with an increase in activation energy from 0.20 to 0.56 eV. The electrical conductivity of the studied sinters ranged from 74.8 to 88.4 S cm-1, which makes the Cu1.3Mn1.7O4 material suitable for application as a protective-conducting coating in IT-SOFC ferritic stainless steel interconnects.

Structural and catalytic properties of some azo-rhodanine Ruthenium(III) complexes

NASA Astrophysics Data System (ADS)

Shoair, A. F.; El-Bindary, A. A.; Abd El-Kader, M. K.

2017-09-01

Novel azo-rhodanine ruthenium(III) complexes of the type trans-[Ru(Ln)2(AsPh3)2]Cl (Ln = monobasic bidentate anions of 5-(4‧-methoxyphenylazo)-3-phenylamino-2-thioxothiazolidin-4-one (HL1), 5-(phenylazo)-3-phenylamino-2-thioxothiazolidin-4-one (HL2) and 5-(4‧-chlorophenylazo)-3-phenylamino-2-thioxothiazolidin-4-one (HL3); AsPh3 = triphenylarsine) have been synthesized and characterized by elemental analysis, spectroscopic (IR, 1H NMR and UV-VIS), magnetic, X-ray diffraction, mass spectra and thermal analysis techniques. These techniques confirm the formation of octahedral ruthenium(III) complexes. The Ru(III) complexes were tested as a catalysts for the oxidation of benzyl alcohol to benzaldehyde with N-methylmorpholine-N-oxide as a co-oxidant. The effect of time, temperature, and solvent were also studied and the mechanism of this catalytic oxidation reaction is suggested. Molecular docking was used to predict the binding between azo rhodanine derivatives (HLn) with the receptor of 3qum- immune system receptor of human prostate specific antigen (PSA) in a Fab sandwich with a high affinity and a PCa selective antibody.

Ruthenium nanoparticles in ionic liquids: structural and stability effects of polar solutes.

PubMed

Salas, Gorka; Podgoršek, Ajda; Campbell, Paul S; Santini, Catherine C; Pádua, Agílio A H; Costa Gomes, Margarida F; Philippot, Karine; Chaudret, Bruno; Turmine, Mireille

2011-08-14

Ionic liquids are a stabilizing medium for the in situ synthesis of ruthenium nanoparticles. Herein we show that the addition of molecular polar solutes to the ionic liquid, even in low concentrations, eliminates the role of the ionic liquid 3D structure in controlling the size of ruthenium nanoparticles, and can induce their aggregation. We have performed the synthesis of ruthenium nanoparticles by decomposition of [Ru(COD)(COT)] in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(1)C(4)Im][NTf(2)], under H(2) in the presence of varying amounts of water or 1-octylamine. For water added during the synthesis of metallic nanoparticles, a decrease of the solubility in the ionic liquid was observed, showed by nanoparticles located at the interface between aqueous and ionic phases. When 1-octylamine is present during the synthesis, stable nanoparticles of a constant size are obtained. When 1-octylamine is added after the synthesis, aggregation of the ruthenium nanoparticles is observed. In order to explain these phenomena, we have explored the molecular interactions between the different species using (13)C-NMR and DOSY (Diffusional Order Spectroscopy) experiments, mixing calorimetry, surface tension measurements and molecular simulations. We conclude that the behaviour of the ruthenium nanoparticles in [C(1)C(4)Im][NTf(2)] in the presence of 1-octylamine depends on the interaction between the ligand and the nanoparticles in terms of the energetics but also of the structural arrangement of the amine at the nanoparticle's surface.

Complex of transferrin with ruthenium for medical applications

DOEpatents

Richards, P.; Srivastava, S.C.; Meinken, G.E.

1984-05-15

A novel ruthenium-transferrin complex is disclosed which is prepared by reacting iron-free human transferrin dissolved in a sodium acetate solution at pH 7 with ruthenium by heating at about 40 C for about 2 hours. The complex is purified by means of gel chromotography with pH 7 sodium acetate as eluent. The mono- or di-metal complex produced can be used in nuclear medicine in the diagnosis and/or treatment of tumors and abscesses. Comparative results with Ga-67-citrate, which is the most widely used tumor-localizing agent in nuclear medicine, indicate increased sensitivity of detection and greater tumor uptake with the Ru-transferrin complex. No Drawings

Ruthenium-Catalyzed Cascade C—H Functionalization of Phenylacetophenones**

PubMed Central

Mehta, Vaibhav P; García-López, José-Antonio; Greaney, Michael F

2014-01-01

Three orthogonal cascade C—H functionalization processes are described, based on ruthenium-catalyzed C—H alkenylation. 1-Indanones, indeno indenes, and indeno furanones were accessed through cascade pathways by using arylacetophenones as substrates under conditions of catalytic [{Ru(p-cymene)Cl2}2] and stoichiometric Cu(OAc)2. Each transformation uses C—H functionalization methods to form C—C bonds sequentially, with the indeno furanone synthesis featuring a C—O bond formation as the terminating step. This work demonstrates the power of ruthenium-catalyzed alkenylation as a platform reaction to develop more complex transformations, with multiple C—H functionalization steps taking place in a single operation to access novel carbocyclic structures. PMID:24453063

Ruthenium-Catalyzed Cascade Annulation of Indole with Propargyl Alcohols.

PubMed

Kaufmann, Julia; Jäckel, Elisabeth; Haak, Edgar

2018-05-14

Cascade transformations forming multiple bonds and one-pot procedures provide rapid access to natural-product-like scaffolds from simple precursors. These atom-economic processes are valuable tools in organic synthesis and drug discovery. Herein, we report on ruthenium-catalyzed cascade annulations of indole with readily available propargyl alcohols. These provide rapid access to diverse carbazoles, cyclohepta[b]indoles, and further fused polycycles with high selectivity. A bifunctional ruthenium complex featuring a redox-coupled cyclopentadienone ligand acts as a common catalyst for the different cascade processes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of cobalt precursor on pyrolyzed carbon-supported cobalt-polypyrrole as electrocatalyst toward oxygen reduction reaction

PubMed Central

2013-01-01

A series of non-precious metal electrocatalysts, namely pyrolyzed carbon-supported cobalt-polypyrrole, Co-PPy-TsOH/C, are synthesized with various cobalt precursors, including cobalt acetate, cobalt nitrate, cobalt oxalate, and cobalt chloride. The catalytic performance towards oxygen reduction reaction (ORR) is comparatively investigated with electrochemical techniques of cyclic voltammogram, rotating disk electrode and rotating ring-disk electrode. The results are analyzed and discussed employing physiochemical techniques of X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma, elemental analysis, and extended X-ray absorption fine structure. It shows that the cobalt precursor plays an essential role on the synthesis process as well as microstructure and performance of the Co-PPy-TsOH/C catalysts towards ORR. Among the studied Co-PPy-TsOH/C catalysts, that prepared with cobalt acetate exhibits the best ORR performance. The crystallite/particle size of cobalt and its distribution as well as the graphitization degree of carbon in the catalyst greatly affects the catalytic performance of Co-PPy-TsOH/C towards ORR. Metallic cobalt is the main component in the active site in Co-PPy-TsOH/C for catalyzing ORR, but some other elements such as nitrogen are probably involved, too. PMID:24229351

Restitic or not? Insights from trace element content and crystal - Structure of spinels in African mantle xenoliths

NASA Astrophysics Data System (ADS)

Lenaz, Davide; Musco, Maria Elena; Petrelli, Maurizio; Caldeira, Rita; De Min, Angelo; Marzoli, Andrea; Mata, Joao; Perugini, Diego; Princivalle, Francesco; Boumehdi, Moulay Ahmed; Bensaid, Idris Ali Ahmadi; Youbi, Nasrrddine

2017-05-01

The lithospheric architecture of Africa consists of several Archean cratons and smaller cratonic fragments, stitched together and flanked by polycyclic fold belts. Here we investigate the structure and chemistry of spinels from lithospheric mantle xenoliths from distinct tectonic settings, i.e. from the Saharan metacraton in Libya (Waw-En-Namus) which could show archaic chemical features, Cameroon (Barombi Koto and Nyos Lakes) where the Sub Continental Lithospheric Mantle was modified during the Pan-African event and fluxed by asthenospheric melts of the Tertiary Cameroon Volcanic Line and Morocco (Tafraoute, Bou-Ibalrhatene maars) in the Middle Atlas where different metasomatic events have been recorded. From a structural point of view it is to notice that the Libyan spinels can be divided into two groups having different oxygen positional parameter (u > 0.2632 and u < 0.2627, respectively), while those from Cameroon are in between those values as the Moroccan ones already studied by other authors. The intracrystalline closure temperature (Tc) of the here studied spinels is different among the different samples with one Libyan group (LB I) showing Tc in the range 490-640 °C and the other 680-950 °C (LB II). Cameroon and Morocco spinels show a Tc in the range 630-760 °C. About 150 different spinels have been studied for their trace element content and it can be seen that many of them are related to Cr content, while Zn and Co are not and clearly distinguish the occurrences. Differences in the trace element chemistry, in the structural parameters and in the intracrystalline closure temperatures suggest that a different history should be considered for Cameroon, Morocco and LB I and LB II spinels. Even if it was not considered for this purpose, we tentatively used the Fe2 +/Fe3 + vs. TiO2 diagram that discriminate between peridotitic and the so-called "magmatic" spinels, i.e. spinel crystallized from melts. LB I and LB II spinels plot in the peridotitic field

Spinel compounds as multivalent battery cathodes: A systematic evaluation based on ab initio calculations

DOE PAGES

Liu, Miao; Rong, Ziqin; Malik, Rahul; ...

2014-12-16

In this study, batteries that shuttle multivalent ions such as Mg 2+ and Ca 2+ ions are promising candidates for achieving higher energy density than available with current Li-ion technology. Finding electrode materials that reversibly store and release these multivalent cations is considered a major challenge for enabling such multivalent battery technology. In this paper, we use recent advances in high-throughput first-principles calculations to systematically evaluate the performance of compounds with the spinel structure as multivalent intercalation cathode materials, spanning a matrix of five different intercalating ions and seven transition metal redox active cations. We estimate the insertion voltage, capacity,more » thermodynamic stability of charged and discharged states, as well as the intercalating ion mobility and use these properties to evaluate promising directions. Our calculations indicate that the Mn 2O 4 spinel phase based on Mg and Ca are feasible cathode materials. In general, we find that multivalent cathodes exhibit lower voltages compared to Li cathodes; the voltages of Ca spinels are ~0.2 V higher than those of Mg compounds (versus their corresponding metals), and the voltages of Mg compounds are ~1.4 V higher than Zn compounds; consequently, Ca and Mg spinels exhibit the highest energy densities amongst all the multivalent cation species. The activation barrier for the Al³⁺ ion migration in the Mn₂O₄ spinel is very high (~1400 meV for Al 3+ in the dilute limit); thus, the use of an Al based Mn spinel intercalation cathode is unlikely. Amongst the choice of transition metals, Mn-based spinel structures rank highest when balancing all the considered properties.« less

Using ruthenium polypyridyl functionalized ZnO mesocrystals and gold nanoparticle dotted graphene composite for biological recognition and electrochemiluminescence biosensing

NASA Astrophysics Data System (ADS)

Liu, Suli; Zhang, Jinxing; Tu, Wenwen; Bao, Jianchun; Dai, Zhihui

2014-01-01

Using ruthenium polypyridyl functionalized ZnO mesocrystals as bionanolabels, a universal biological recognition and biosensing platform based on gold nanoparticle (AuNP) dotted reduced graphene oxide (rGO) composite was developed. AuNP-rGO accelerated electron transfer between the detection probe and the electrode, and increased the surface area of the working electrode to load greater amounts of the capture antibodies. The large surface area of ZnO mesocrystals was beneficial for loading a high content ruthenium polypyridyl complex, leading to an enhanced electrochemiluminescence signal. Using α-fetoprotein (AFP) as a model, a simple and sensitive sandwich-type electrochemiluminescence biosensor with tripropylamine (TPrA) as a coreactant for detection of AFP was constructed. The designed biosensor provided a good linear range from 0.04 to 500 ng mL-1 with a low detection limit of 0.031 ng mL-1 at a S/N of 3 for AFP determination. The proposed biological recognition and biosensing platform extended the application of ruthenium polypyridyl functionalized ZnO mesocrystals, which provided a new promising prospect.

Valence band-edge engineering of nickel oxide nanoparticles via cobalt doping for application in p-type dye-sensitized solar cells.

PubMed

Natu, Gayatri; Hasin, Panitat; Huang, Zhongjie; Ji, Zhiqiang; He, Mingfu; Wu, Yiying

2012-11-01

We have systematically studied the effects of substitutional doping of p-type nanoparticulate NiO with cobalt ions. Thin films of pure and Co-doped NiO nanoparticles with nominal compositions Co(x)Ni(1-x)O(y) (0 ≤ x ≤ 0.1) were fabricated using sol-gel method. X-ray photoelectron spectroscopy revealed a surface enrichment of divalent cobalt ions in the Co(x)Ni(1-x)O(y) nanoparticles. Mott-Schottky analysis in aqueous solutions was used to determine the space charge capacitance values of the films against aqueous electrolytes, which yielded acceptor state densities (N(A)) and apparent flat-band potentials (E(fb)). Both N(A) and E(fb) values of the doped NiO were found to gradually increase with increasing amount of doping; thus the Fermi energy level of the charge carriers decreased with Co-doping. The photovoltage of p-DSCs constructed using the Co(x)Ni(1-x)O(y) films increased with increasing amount of cobalt, as expected from the trend in the E(fb). Co-doping increased both carrier lifetimes within the p-DSCs and the carrier transport times within the nanoparticulate semiconductor network. The nominal composition of Co₀.₀₆Ni₀.₉₄O(y) was found to be optimal for use in p-DSCs.

Spinel and plagioclase peridotites of the Nain ophiolite (Central Iran): Evidence for the incipient stage of oceanic basin formation

NASA Astrophysics Data System (ADS)

Pirnia, Tahmineh; Saccani, Emilio; Arai, Shoji

2018-06-01

The Nain ophiolites crop out along the western border of the central East Iran Microcontinent (CEIM) and consist of an ophiolitic mélange in which pargasite-bearing spinel and plagioclase mantle lherzolites are largely represented. Whole-rock and mineral chemistry data suggest that these rocks record the complex history of the asthenospheric and lithospheric mantle evolution. The spinel lherzolites have experienced low-degree ( 5%) partial melting and contain clinopyroxenes with positive Eu anomalies (Eu/Eu* = 1.10-1.48) suggesting that the partial melting occurred under oxidized conditions (fayalite-magnetite-quartz -0.8 to +1.3). The pargasite and coexisting clinopyroxene in these rocks are depleted in light rare earth elements (LREE) (mean chondrite-normalized CeN/SmN = 0.045). The depleted chemistry of this amphibole reflects metasomatism during interaction with H2O-rich subalkaline mafic melts, most likely concurrently with or after the partial melting of the spinel lherzolites. The plagioclase lherzolites were subsequently formed by the subsolidus recrystallization of spinel lherzolites under plagioclase facies conditions as a result of mantle uprising, as evidenced by: (1) the development of plagioclase rims around the spinels; (2) plagioclase + orthopyroxene exsolution textures within some clinopyroxene grains; (3) an increase in plagioclase modal content coupled with an increase in modal olivine and a decrease in modal pyroxene and pargasite; (4) coincident decreases in Al, Mg, and Ni, and increases in Cr, Ti, and Fe in spinel, as well as decreases in Al and Ca, and increases in Cr and Ti in pyroxene and pargasite; and (5) the identical whole rock compositions of the spinel and plagioclase lherzolites, which rules out a magmatic origin for the plagioclase in these units. The Nain lherzolites have similar whole-rock and mineral geochemical compositions to subcontinental peridotites that are typically representative of Iberia-type rifted continental margins

Economics of food irradiation: Comparison between electron accelerators and cobalt-60

NASA Astrophysics Data System (ADS)

Morrison, R. M.

The Codex Alimentarius Commission's proposed international standard permits three types of ionizing radiation to be used on foods: gamma rays from radioactive cobalt-60 or cesium-137, high energy electrons, and x-rays. The latter two types of radiation are produced by electron accelerators powered by electricity. Unlike gamma rays and x-rays which can penetrate pallet loads of foods, electrons of the allowed energy levels only penetrate 1 to 3 inches when irradiated from one side. Thus, electrons are limited to treating the surface of foods or foods in thin packages or a shallow stream of grains, powders, or liquids. Average costs per kilogram (kg) of irradiating selected foods are similar for the electron accelerator and cobalt-60 irradiators analyzed in this study, but initial investment costs generally vary by U.S. $1 million. Irradiation treatment costs range from 1 to 15 U.S. cents per kg for the foods and annual volumes examined with larger volumes having lower treatment costs. Cobalt-60 is less expensive than electrons when annual volumes are below 23 million kgs. For radiation source requirements above the equivalent of about 1 million curies of cobalt-60, electrons become more economical. The largest differences in costs occur with the papaya irradiators where using x-rays to penetrate the fruit is more expensive than using cobalt-60.

A new powder production route for transparent spinel windows: powder synthesis and window properties

NASA Astrophysics Data System (ADS)

Cook, Ronald; Kochis, Michael; Reimanis, Ivar; Kleebe, Hans-Joachim

2005-05-01

Spinel powders for the production of transparent polycrystalline ceramic windows have been produced using a number of traditional ceramic and sol-gel methods. We have demonstrated that magnesium aluminate spinel powders produced from the reaction of organo-magnesium compounds with surface modified boehmite precursors can be used to produce high quality transparent spinel parts. The new powder production method allows fine control over the starting particle size, size distribution, purity and stoichiometry. The new process involves formation of a boehmite sol-gel from the hydrolysis of aluminum alkoxides followed by surface modification of the boehmite nanoparticles using carboxylic acids. The resulting surface modified boehmite nanoparticles can then be metal exchanged at room temperature with magnesium acetylacetonate to make a precursor powder that is readily transformed into pure phase spinel.

Implications of spinel compositions for the petrotectonic history of abyssal peridotite from Southwest Indian Ridge (SWIR)

NASA Astrophysics Data System (ADS)

Chen, T.; Jin, Z.; Wang, Y.; Tao, C.

2012-12-01

Abyssal peridotites generate at mid-ocean ridges. Lherzolite and harzburgite are the main rock types of peridotites in the uppermost mantle. The lherzolite subtype, less depleted and less common in ophiolites, characterizes mantle diapirs and slow-spreading ridges. Along the Earth's mid-ocean ridges, abyssal peridotites undergo hydration reactions to become serpentinite minerals, especially in slow to ultraslow spreading mid-ocean ridges. Spinel is common in small quantities in peridotites, and its compositions have often been used as petrogenetic indicators [1]. The Southwest Indian Ridge (SWIR) is one of the two ultraslow spreading ridges in the world. The studied serpentinized peridotite sample was collected by the 21st Voyage of the Chinese oceanic research ship Dayang Yihao (aka Ocean No. 1) from a hydrothermal field (63.5°E, 28.0°S, and 3660 m deep) in SWIR. The studied spinels in serpentinized lherzolite have four zones with different compositions: relic, unaltered core is magmatic Al-spinels; micro- to nano- sized ferrichromite zoned particles; narrow and discontinuous magnetite rim; and chlorite aureoles. The values Cr# of the primary Al-spinels indicate the range of melting for abyssal peridotites from SWIR extends from ~4% to ~7% [2]. The alteration rims of ferrichromite have a chemical composition characterized by Fe enrichment and Cr# increase indicating chromite altered under greenschist-amphibolite facies. Magnetites formed in syn- and post- serpentinization. Chlorite (clinochlore) formed at the boundary and crack of spinel indicating it had undergone with low-temperature MgO- and SiO2-rich hydrothermal fluids [3]. It suggests that serpentinized lherzolite from SWIR had undergone poly-stage hydration reactions with a wide range of temperature. Acknowledgments: EMPA experiment was carried out by Xihao Zhu and Shu Zheng in The Second Institute of Oceanography and China University of Geosciences, respectively. The work was supported by NSFC

Low-solubility particles and a Trojan-horse type mechanism of toxicity: the case of cobalt oxide on human lung cells

PubMed Central

2014-01-01

Background The mechanisms of toxicity of metal oxide particles towards lung cells are far from being understood. In particular, the relative contribution of intracellular particulate versus solubilized fractions is rarely considered as it is very challenging to assess, especially for low-solubility particles such as cobalt oxide (Co3O4). Methods This study was possible owing to two highly sensitive, independent, analytical techniques, based on single-cell analysis, using ion beam microanalysis, and on bulk analysis of cell lysates, using mass spectrometry. Results Our study shows that cobalt oxide particles, of very low solubility in the culture medium, are readily incorporated by BEAS-2B human lung cells through endocytosis via the clathrin-dependent pathway. They are partially solubilized at low pH within lysosomes, leading to cobalt ions release. Solubilized cobalt was detected within the cytoplasm and the nucleus. As expected from these low-solubility particles, the intracellular solubilized cobalt content is small compared with the intracellular particulate cobalt content, in the parts-per-thousand range or below. However, we were able to demonstrate that this minute fraction of intracellular solubilized cobalt is responsible for the overall toxicity. Conclusions Cobalt oxide particles are readily internalized by pulmonary cells via the endo-lysosomal pathway and can lead, through a Trojan-horse mechanism, to intracellular release of toxic metal ions over long periods of time, involving specific toxicity. PMID:24669904

Dielectric and impedance study of praseodymium substituted Mg-based spinel ferrites

NASA Astrophysics Data System (ADS)

Farid, Hafiz Muhammad Tahir; Ahmad, Ishtiaq; Ali, Irshad; Ramay, Shahid M.; Mahmood, Asif; Murtaza, G.

2017-07-01

Spinel ferrites with nominal composition MgPryFe2-yO4 (y = 0.00, 0.025, 0.05, 0.075, 0.10) were prepared by sol-gel method. Temperature dependent DC electrical conductivity and drift mobility were found in good agreement with each other, reflecting semiconducting behavior. The dielectric properties of all the samples as a function of frequency (1 MHz-3 GHz) were measured at room temperature. The dielectric constant and complex dielectric constant of these samples decreased with the increase of praseodymium concentration. In the present spinel ferrite, Cole-Cole plots were used to separate the grain and grain boundary's effects. The substitution of praseodymium ions in Mg-based spinel ferrites leads to a remarkable rise of grain boundary's resistance as compared to the grain's resistance. As both AC conductivity and Cole-Cole plots are the functions of concentration, they reveal the dominant contribution of grain boundaries in the conduction mechanism. AC activation energy was lower than dc activation energy. Temperature dependence normalized AC susceptibility of spinel ferrites reveals that MgFe2O4 exhibits multi domain (MD) structure with high Curie temperature while on substitution of praseodymium, MD to SD transitions occurs. The low values of conductivity and low dielectric loss make these materials best candidate for high frequency application.

Formation of vinyl halides via a ruthenium-catalyzed three-component coupling.

PubMed

Trost, Barry M; Pinkerton, Anthony B

2002-06-26

The ruthenium-catalyzed three-component coupling of an alkyne, an enone, and halide ion to form E- or Z-vinyl halides has been investigated. Through systematic optimization experiments, the conditions effecting the olefin selectivity were examined. In general, more polar solvents such as DMF favored the formation of the E-isomer, and less polar solvents such as acetone favored formation of the Z-isomer. The optimized conditions for the formation of E-vinyl chlorides were found to be the use of cyclopentadienyl ruthenium (II) cyclooctadiene chloride, stannic chloride pentahydrate as a cocatalyst, and for a chloride source, either ammonium chloride in DMF/water mixtures or tetramethylammonium chloride in DMF. A range of several other ruthenium (II) catalysts was also shown to be effective. A wide variety of vinyl chlorides could be formed under these conditions. Substrates with tethered alcohols or ketones either five or six carbons from the alkyne portion gave instead diketone or cyclohexenone products. For formation of vinyl bromides, a catalyst system involving the use of cyclopentadienylruthenium (II) tris(acetonitrile) hexafluorophosphate with stannic bromide as a cocatalyst was found to be most effective. The use of ammonium bromide in DMF/acetone mixtures was optimal for the synthesis of E-vinyl bromides, and the use of lithium bromide in acetone was optimal for formation of the corresponding Z-isomer. Under either set of conditions, a wide range of vinyl bromides could be formed. When alkynes with propargylic substituents are used, enhanced selectivity for formation of the Z-isomer is observed. When aryl acetylenes are used as the coupling partners, complete selectivity for the Z-isomer is obtained. A mechanism involving a cis or trans halometalation is invoked to explain formation of the observed products. The vinyl halides have been shown to be precursors to alpha-hydroxy ketones and cyclopentenones, and as coupling partners in Suzuki-type reactions.

Ruthenium on chitosan: A recyclable heterogeneous catalyst for aqueous hydration of nitriles to amides

EPA Science Inventory

Ruthenium has been immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with ruthenium chloride and has been utilized for the oxidation of nitriles to amides; the hydration of nitriles occurs in high yield and excellent selectivity, which procee...

Structural and magnetic characterization of Ti doped cobalt ferrite (CoFe2O4)

NASA Astrophysics Data System (ADS)

Pal, Jaswinder; Kumar, Sunil; Kaur, Randeep; Agrawal, P.; Singh, Mandeep; Singh, Anupinder

2018-05-01

Synthesis of Co1-xTixFe2O4 solid solutions for 0.1≤x≤0.4 using the solid-state-reaction rate has been done. The prepared samples were characterized by using XRD (X-ray diffraction) and SEM (Scanning Electron Microscopy). Magnetic studies have been done using Vibrating Sample Magnetometer (VSM). XRD confirmed that Cobalt Ferrite spinel cubic structure in all prepared samples. The lattice parameter `a' increases with increase in the concentration of Ti. SEM micrograph shows good grain growth in all samples. Magnetic Study reveals that the M-H curves of all the prepared samples taken at room temperature are very well saturated. The maximum value of remnant magnetization (Mr ˜13.9 emu/g) and saturation magnetization (Ms ˜74.4 emu/g) has been observed for x =0.2 sample. Coercivity does not show any regular variation with increase in the molar concentration of Ti in CoFe2O4 at A-site.

Structural, spectral, DFT and biological studies on macrocyclic mononuclear ruthenium (II) complexes

NASA Astrophysics Data System (ADS)

Muthukkumar, M.; Kamal, C.; Venkatesh, G.; Kaya, C.; Kaya, S.; Enoch, Israel V. M. V.; Vennila, P.; Rajavel, R.

2017-11-01

Macrocyclic mononuclear ruthenium (II) complexes have been synthesized by condensation method [Ru (L1, L2, L3) Cl2] L1 = (C36 H31 N9), L2= (C42H36N8), L3= (C32H32 N8)]. These ruthenium complexes have been established by elemental analyses and spectroscopic techniques (Fourier transform infrared spectroscopy (FT-IR), 1H- nuclear magnetic resonance (NMR), 13C- NMR and Electrospray ionization mass spectrometry (ESI-MS)). The coordination mode of the ligand has been confirmed and the octahedral geometry around the ruthenium ion has been revealed. Binding affinity and binding mode of ruthenium (II) complexes with Bovine serum Albumin (BSA) have been characterized by Emission spectra analysis. UV-Visible and fluorescence spectroscopic techniques have also been utilized to examine the interaction between ligand and its complexes L1, L2, & L3 with BSA. Chemical parameters and molecular structure of Ru (II) complexes L1H, L2H, & L3H have been determined by DFT coupled with B3LYP/6-311G** functional in both the gaseous and aqueous phases.

Radioactive cobalt removal from Salem liquid radwaste with cobalt selective media

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

Maza R.; Wilson, J.A.; Hetherington, R.

This paper reports results of benchtop tests using ion exchange material to selectively remove radioactive cobalt from high conductivity liquid radwaste at the Salem Nuclear Generating Station. The purpose of this test program is to reduce the number of curies in liquid releases without increasing the solid waste volume. These tests have identified two cobalt selective materials that together remove radioactive cobalt more effectively than the single component currently used. All test materials were preconditioned by conversion to the divalent calcium or sulfate form to simulate chemically exhausted media.

The Mystery of the Electronic Spectrum of Ruthenium Monophosphide

NASA Astrophysics Data System (ADS)

Adam, Allan G.; Christensen, Ryan M.; Dore, Jacob M.; Konder, Ricarda M.; Tokaryk, Dennis W.

2016-06-01

Using PH3 as a reactant gas and ruthenium as the target metal in the UNB laser ablation spectrometer, the ruthenium monophosphide molecule (RuP) has been detected. Dispersed fluorescence experiments have been performed to determine ground state vibrational frequencies and the presence of any low-lying electronic states. Rotationally resolved spectra of two vibrational bands at 577nm and 592nm have been taken; the bands have been identified as 1-0 and 0-0 bands based on isotopic shifts. Ruthenium has seven stable isotopes and rotational transitions have been observed for six of the RuP isotopologues. RuP is isoelectronic to RuN so it is expected that RuP will have a 2Σ+ ground state and low resolution spectra indicated a likely 2Σ+ - 2Σ+ electronic transition. Further investigation has led us to believe we are observing a 2Π - 2Σ+ transition but mysteriously some important rotational branches are missing. It is hoped that new data to be recorded on a second electronic system we have observed at 535nm will help shed light on this mystery.

Structural and ambient/sub-ambient temperature magnetic properties of Er-substituted cobalt-ferrites synthesized by sol-gel assisted auto-combustion method

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

Prathapani, Sateesh; Department of Metallurgical Engineering and Materials Science, IIT-Bombay, Mumbai 400076; Jayaraman, Tanjore V., E-mail: ddas@uohyd.ernet.in, E-mail: tvjayaraman@gmail.com

2014-07-14

Er-substituted cobalt-ferrites CoFe{sub 2−x}Er{sub x}O{sub 4} (0 ≤ x ≤ 0.04) were synthesized by sol-gel assisted auto-combustion method. The precursor powders were calcined at 673–873 K for 4 h, subsequently pressed into pellets and sintered at 1273 K for 4 h. X-ray diffraction (XRD) confirmed the presence of the spinel phase for all the compositions and, additional orthoferrite phase for higher compositions (x = 0.03 and 0.04). The XRD spectra and the Transmission Electron Microscopy micrographs indicate that the nanocrystalline particulates of the Er-substituted cobalt ferrites have crystallite size of ∼120–200 nm. The magnetization curves show an increase in saturation magnetization (M{sub S}) and coercivity (H{sub C}) for Er-substituted cobalt-ferrites atmore » sub-ambient temperatures. M{sub S} for CoFe{sub 2}O{sub 4}, CoFe{sub 0.99}Er{sub 0.01}O{sub 4}, CoFe{sub 0.98}Er{sub 0.02}O{sub 4}, and CoFe{sub 0.97}Er{sub 0.03}O{sub 4} peak at 89.7 Am{sup 2}/kg, 89.3 Am{sup 2}/kg, 88.8 Am{sup 2}/kg, and 87.1 Am{sup 2}/kg, respectively, at a sub-ambient temperature of ∼150 K. H{sub C} substantially increases with decrease in temperature for all the compositions, while it peaks at x = 0.01−0.02 at all temperatures. The combination of Er content—x ∼ 0.02 and the temperature—∼5 K provides the maximum H{sub C} ∼ 984 kA/m. Er-substituted cobalt-ferrites have higher cubic anisotropy constant, K{sub 1}, compared to pure cobalt-ferrite at ambient/sub-ambient temperatures. K{sub 1} gradually increases for all compositions in the temperature decreasing from 300 to 100 K. While K{sub 1} peaks at ∼150 K for pure cobalt-ferrite, it peaks at ∼50 K for CoFe{sub 0.99}Er{sub 0.01}O{sub 4}, CoFe{sub 0.98}Er{sub 0.02}O{sub 4}, and CoFe{sub 0.96}Er{sub 0.04}O{sub 4}. The M{sub S} (∼88.7 Am{sup 2}/kg), at 5 K, for Er substituted cobalt-ferrite is close to the highest values reported for Sm and Gd

Ruthenium on rutile catalyst, catalytic system, and method for aqueous phase hydrogenations

DOEpatents

Elliot, Douglas C.; Werpy, Todd A.; Wang, Yong; Frye, Jr., John G.

2001-01-01

An essentially nickel- and rhenium-free catalyst is described comprising ruthenium on a titania support where the titania is greater than 75% rutile. A catalytic system containing a nickel-free catalyst comprising ruthenium on a titania support where the titania is greater than 75% rutile, and a method using this catalyst in the hydrogenation of an organic compound in the aqueous phase is also described.

Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds

EPA Science Inventory

One-pot synthesis of ruthenium nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium nano particles immobilization; the hydration of nitriles and transfer hydrogenation of carbonyl compounds occurs in hi...

Thermoelectric Properties of Variants of Cu4Mn2Te4 with Spinel-Related Structure.

PubMed

Guo, Quansheng; Vaney, Jean-Baptiste; Virtudazo, Raymond; Minami, Ryunosuke; Michiue, Yuichi; Yamabe-Mitarai, Yoko; Mori, Takao

2018-05-07

Thermoelectric properties of Cu 4 Mn 2 Te 4 , which is antiferromagnetic with a Néel temperature T N = 50 K and crystallizes in a spinel-related structure, have been investigated comprehensively here. The phase transition occurring at temperatures 463 and 723 K is studied by high-temperature X-ray diffraction (XRD) and differential scanning calorimetry (DSC), and its effect on thermoelectric properties is examined. Hypothetically Cu 4 Mn 2 Te 4 is semiconducting according to the formula (Cu + ) 4 (Mn 2+ ) 2 (Te 2- ) 4 , while experimentally it shows p-type metallic conduction behavior, exhibiting electrical conductivity σ = 2500 Ω -1 cm -1 and Seebeck coefficient α = 20 μV K -1 at 325 K. Herein, we show that the carrier concentration and thus the thermoelectric transport properties could be further optimized through adding electron donors such as excess Mn. Discussions are made on the physical parameters contributing to the low thermal conductivity, including Debye temperature, speed of sound, and the Grüneisen parameter. As a result of simultaneously boosted power factor and reduced thermal conductivity, a moderately high zT = 0.65 at 680 K is obtained in an excess Mn\\In co-added sample, amounting to 5 times that of the pristine Cu 4 Mn 2 Te 4 . This value ( zT = 0.65) is the best result ever reported for spinel and spinel-related chalcogenides.

Morphology and composition of spinel in Pu'u 'O'o lava (1996-1998), Kilauea volcano, Hawaii

USGS Publications Warehouse

Roeder, P.L.; Thornber, C.; Poustovetov, Alexei; Grant, A.

2003-01-01

The morphology and composition of spinel in rapidly quenched Pu'u 'O'o vent and lava tube samples are described. These samples contain glass, olivine phenocrysts (3-5 vol.%) and microphenocrysts of spinel (~0.05 vol.%). The spinel surrounded by glass occurs as idiomorphic octahedra 5-50 μm in diameter and as chains of octahedra that are oriented with respect to each other. Spinel enclosed by olivine phenocrysts is sometimes rounded and does not generally form chains. The temperature before quenching was calculated from the MgO content of the glass and ranges from 1150oC to 1180oC. The oxygen fugacity before quenching was calculated by two independent methods and the log f O2 ranged from -9.2 to -9.9 (delta QFM=-1). The spinel in the Pu'u'O'o samples has a narrow range in composition with Cr/(Cr+Al)=0.61 to 0.73 and Fe2+/(Fe2++Mg) =0.46 to 0.56. The lower the calculated temperature for the samples, the higher the average Fe2+/(Fe2++Mg), Fe3+ and Ti in the spinel. Most zoned spinel crystals decrease in Cr/(Cr+Al) from core to rim and, in the chains, the Cr/(Cr+Al) is greater in the core of larger crystals than in the core of smaller crystals. The occurrence of chains and hopper crystals and the presence of Cr/(Cr+Al) zoning from core to rim of the spinel suggest diffusion-controlled growth of the crystals. Some of the spinel crystals may have grown rapidly under the turbulent conditions of the summit reservoir and in the flowing lava, and the crystals may have remained in suspension for a considerable period. The rapid growth may have caused very local (μm) gradients of Cr in the melt ahead of the spinel crystal faces. The crystals seem to have retained the Cr/(Cr+Al) ratio that developed during the original growth of the crystal, but the Fe2+/(Fe2++Mg) ratio may have equilibrated fairly rapidly with the changing melt composition due to olivine crystallization. Six of the samples were collected on the same day at various locations along a 10-km lava tube and the

The distribution of chromium among orthopyroxene, spinel and silicate liquid at atmospheric pressure

NASA Technical Reports Server (NTRS)

Barnes, S. J.

1986-01-01

The Cr distributions for a synthetic silicate melt equilibrated with bronzitic orthopyroxene and chromite spinel between 1334 and 1151 C over a range of oxygen fugacities between the nickel-nickel oxide and iron-wuestite buffers are studied. The occurrence, chemical composition, and structure of the orthopyroxene-silicate melt and the spinel-silicate melt are described. It is observed that the Cr content between bronzite and the melt increases with falling temperature along a given oxygen buffer and decreases with falling oxygen fugacity at a given temperature; however, the Cr content of the melt in equilibrium with spinel decreases with falling temperature and increases with lower oxygen fugacity.

Insights into electrode/electrolyte interfacial processes and the effect of nanostructured cobalt oxides loading on graphene-based hybrids by scanning electrochemical microscopy

NASA Astrophysics Data System (ADS)

Gupta, Sanju; Carrizosa, Sara B.

2016-12-01

Nanostructured cobalt oxide polymorphs (CoO and Co3O4) deposited via electrodeposition allowed optimal loading on supercapacitive graphene nanosheets producing a set of graphene-based hybrids namely, CoO/GO, CoO/ErGO, Co3O4/GO, Co3O4/rGO, and Co3O4/ErGO, as pseudocapacitive electrochemical electrodes. We gained fundamental insights into the complex physicochemical interfacial processes at electrode surfaces and electrode/electrolyte (or solid/liquid) interfaces by scanning electrochemical microscopy operating in the feedback probe approach and imaging modes while monitoring and mapping the redox probe (re)activity behavior. We determined the various experimental descriptors including diffusion coefficient, electron transfer rate, and electroactive site distribution on electrodes. We emphasize the interplay of (1) heterogeneous basal and edge plane active sites, (2) graphene surface functional moieties (conducting/semiconducting), and (3) crystalline spinel cobalt oxides (semiconducting/insulating) coated graphene, reinforcing the available electron density of states in the vicinity of the Fermi level contributing to higher electroactivity, faster interfacial diffusion, and shorter distances for electron transfer, facilitated through molecular and chemical bridges obtained by electrodeposition as compared with the physical deposition.

Catalytic water oxidation by ruthenium(II) quaterpyridine (qpy) complexes: evidence for ruthenium(III) qpy-N,N'''-dioxide as the real catalysts.

PubMed

Liu, Yingying; Ng, Siu-Mui; Yiu, Shek-Man; Lam, William W Y; Wei, Xi-Guang; Lau, Kai-Chung; Lau, Tai-Chu

2014-12-22

Polypyridyl and related ligands have been widely used for the development of water oxidation catalysts. Supposedly these ligands are oxidation-resistant and can stabilize high-oxidation-state intermediates. In this work a series of ruthenium(II) complexes [Ru(qpy)(L)2 ](2+) (qpy=2,2':6',2'':6'',2'''-quaterpyridine; L=substituted pyridine) have been synthesized and found to catalyze Ce(IV) -driven water oxidation, with turnover numbers of up to 2100. However, these ruthenium complexes are found to function only as precatalysts; first, they have to be oxidized to the qpy-N,N'''-dioxide (ONNO) complexes [Ru(ONNO)(L)2 ](3+) which are the real catalysts for water oxidation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cobalt metabolism and toxicology--a brief update.

PubMed

Simonsen, Lars Ole; Harbak, Henrik; Bennekou, Poul

2012-08-15

Cobalt metabolism and toxicology are summarized. The biological functions of cobalt are updated in the light of recent understanding of cobalt interference with the sensing in almost all animal cells of oxygen deficiency (hypoxia). Cobalt (Co(2+)) stabilizes the transcriptional activator hypoxia-inducible factor (HIF) and thus mimics hypoxia and stimulates erythropoietin (Epo) production, but probably also by the same mechanism induces a coordinated up-regulation of a number of adaptive responses to hypoxia, many with potential carcinogenic effects. This means on the other hand that cobalt (Co(2+)) also may have beneficial effects under conditions of tissue hypoxia, and possibly can represent an alternative to hypoxic preconditioning. Cobalt is acutely toxic in larger doses, and in mammalian in vitro test systems cobalt ions and cobalt metal are cytotoxic and induce apoptosis and at higher concentrations necrosis with inflammatory response. Cobalt metal and salts are also genotoxic, mainly caused by oxidative DNA damage by reactive oxygen species, perhaps combined with inhibition of DNA repair. Of note, the evidence for carcinogenicity of cobalt metal and cobalt sulfate is considered sufficient in experimental animals, but is as yet considered inadequate in humans. Interestingly, some of the toxic effects of cobalt (Co(2+)) have recently been proposed to be due to putative inhibition of Ca(2+) entry and Ca(2+)-signaling and competition with Ca(2+) for intracellular Ca(2+)-binding proteins. The tissue partitioning of cobalt (Co(2+)) and its time-dependence after administration of a single dose have been studied in man, but mainly in laboratory animals. Cobalt is accumulated primarily in liver, kidney, pancreas, and heart, with the relative content in skeleton and skeletal muscle increasing with time after cobalt administration. In man the renal excretion is initially rapid but decreasing over the first days, followed by a second, slow phase lasting several weeks

Origin of spinel lamella and/or inclusions in olivine of harzburgite form the Pauza ultramafic rocks from the Kurdistan region, northeastern Iraq

NASA Astrophysics Data System (ADS)

Mohammad, Y.; Maekawa, H.; Karim, K.

2009-04-01

Exsolution lamellae and octahedral inclusions of chromian spinel occur in olivine of harzburgite of the Pauza ultramafic rocks, Kurdistan region, northeastern Iraq. The lamella is up to 80μm long and up to 50 μm wide. The lamellae and octahedral inclusions of chromian spinel are distributed heterogeneously in the host olivine crystal. They are depleted in Al2O3 relative to the subhedral spinel grains in the matrix and spinel lamella in orthopyroxene. Olivine (Fo92 - 93) with spinel lamellae occurs as fine-grained crystals around orthopyroxene, whereas olivine (Fo90-91) free from spinel is found in matrix. Based on back-scattered images analyses, enrichments of both Cr # and Fe+3 in the chromian spinel lamella in olivine (replacive olivine) relative to that in adjacent orthopyroxene. As well as the compositions of chromian spinel lamellae host olivine are more Mg-rich than the matrix olivine. Furthermore the restriction of olivine with spinel lamellae and octahedral inclusions on around orthopyroxene, and the similarity of spinel lamella orientations in both olivine and adjacent orthopyroxene. This study concludes that the spinel inclusions in olivine are remnant (inherited from former orthopyroxene) spinel exsolution lamella in orthopyroxene, that has been formed in upper mantle conditions ( T = 1200 °C, P = 2.5 GPa ). Replacive olivine are formed by reaction of ascending silica poor melt and orthopyroxene in harzburgite as pressure decrease the solubility of silica-rich phase (orthopyroxene) in the system increase, therefore ascending melt dissolve pyroxene with spinel exsolution lamella and precipitate replacive olivine with spinel inclusions. We can conclude that the olivines with spinel lamella are not necessary to be original and presenting ultrahigh-pressure and/or ultra deep-mantle conditions as previously concluded. It has been formed by melting of orthopyroxene (orthopyroxene with spinel exsolution lamella = olivine with spinel lamellae and octahedral

Cosine (Cobalt Silicide Growth Through Nitrogen-Induced Epitaxy) Process For Epitaxial Cobalt Silicide Formation For High Performance Sha

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

Lim, Chong Wee; Shin, Chan Soo; Gall, Daniel

A method for forming an epitaxial cobalt silicide layer on a MOS device includes sputter depositing cobalt in an ambient to form a first layer of cobalt suicide on a gate and source/drain regions of the MOS device. Subsequently, cobalt is sputter deposited again in an ambient of argon to increase the thickness of the cobalt silicide layer to a second thickness.

Unraveling the Structure of Mn-Promoted Co/TiO2 Fischer-Tropsch Catalysts by In Situ X-Ray Absorption Spectroscopy

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

Grandjean, Didier; Morales, Fernando; Mens, Ad

2007-02-02

Combination of in situ X-ray absorption spectroscopy (XAFS) at the Co and Mn K-edges with electron microscopy (STEM-EELS) has allowed to unravel the complex structure of a series of unpromoted and Mn promoted TiO2-supported cobalt Fischer-Tropsch catalysts prepared by homogeneous deposition precipitation (HDP), both in their calcined and reduced states. After calcination the catalysts are generally composed of large Co3O4 aggregates (13-20 nm) and a MnO2-type phase that is either dispersed on the TiO2 surface or, for the major part, covering the Co3O4 particles. Additionally Mn is also forming a spinel-type Co3-xMnxO4 solid solution at the surface of the Co3O4more » particles. In pure Co or when small amount of this spinel-type phase are formed during calcination, reduction in H2 at 350 deg. C produces Co0 particles of variable sizes (3.5-15 nm) otherwise Co reduction is limited to the Co2+ state. Manganese that exists entirely in a Mn2+ state in the reduced catalysts is forming (1) a highly dispersed Ti2MnO4-type phase at the TiO2 surface, (2) a less dispersed MnO phase close to the cobalt particles that coexists with (3) a rock salt-type Mn1-xCoxO solid solution. Similarly, large amount of spinel solid solution in the calcined state favors the formation of Mn1-xCoxO-type solid solution during reduction showing that one of the main roles of the Mn promoter is to limit Co reducibility.« less

Nickel and cobalt release from jewellery and metal clothing items in Korea.

PubMed

Cheong, Seung Hyun; Choi, You Won; Choi, Hae Young; Byun, Ji Yeon

2014-01-01

In Korea, the prevalence of nickel allergy has shown a sharply increasing trend. Cobalt contact allergy is often associated with concomitant reactions to nickel, and is more common in Korea than in western countries. The aim of the present study was to investigate the prevalence of items that release nickel and cobalt on the Korean market. A total of 471 items that included 193 branded jewellery, 202 non-branded jewellery and 76 metal clothing items were sampled and studied with a dimethylglyoxime (DMG) test and a cobalt spot test to detect nickel and cobalt release, respectively. Nickel release was detected in 47.8% of the tested items. The positive rates in the DMG test were 12.4% for the branded jewellery, 70.8% for the non-branded jewellery, and 76.3% for the metal clothing items. Cobalt release was found in 6.2% of items. Among the types of jewellery, belts and hair pins showed higher positive rates in both the DMG test and the cobalt spot test. Our study shows that the prevalence of items that release nickel or cobalt among jewellery and metal clothing items is high in Korea. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

designer phase transitions in lithium-based spinels

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

Wouter Montfrooij

When electrons in a metal become correlated with each other, new cooperative behavior can arise. This correlation is magnified when the metal has magnetic ions embedded in it. These atomic magnets try to line up with each other, but in doing so actually create a correlation between the motions of conduction electrons. In turn, these correlated electron motions prevent the magnetic ions from aligning, even at zero Kelvin. When this competition is strongest (at the so-called quantum critical point-QCP) the response of the system can no longer be described using the text book theory for metals. In addition, a rangemore » of new phenomena has been seen to emerge in the vicinity of a QCP, such as heavy-fermion superconductivity, coexistence of magnetism and superconductivity and hyper-scaling. The main goal of our research is to try to unravel the details of the feedback mechanism between electron motion and magnetism that lies at the heart of this new physics. We have chosen lithium-based spinel structures as the most promising family of systems to achieve our goal. Known lithium-based spinels Li{sub x}M{sub 2}O{sub 4} [M=V, Ti and Mn] show a variety of ground states: heavy-fermion, superconducting, or geometrically frustrated local moment systems. Li{sub x}M{sub 2}O{sub 4} should be ideal systems for studying QCPs since their properties can easily be fine-tuned, simply by extracting some Li [which can be done without introducing disorder in the immediate surroundings of the magnetic ions]. The premise of the proposal was that since this Li-extraction can be done both in the metallic as well as in insulating compounds, that we can expand the types of quantum phase transitions that can be studied to beyond transitions in magnetic metals. The project called for developing a better understanding of quantum phase transitions by measuring all aspects of the electronic response of Li{sub x}M{sub 2}O{sub 4} by means of neutron scattering, giving microscopic information

Influence of rare earth ion doping (Ce and Dy) on electrical and magnetic properties of cobalt ferrites

NASA Astrophysics Data System (ADS)

Hashim, Mohd.; Raghasudha, M.; Meena, Sher Singh; Shah, Jyoti; Shirsath, Sagar E.; Kumar, Shalendra; Ravinder, D.; Bhatt, Pramod; Alimuddin; Kumar, Ravi; Kotnala, R. K.

2018-03-01

Ce and Dy substituted Cobalt ferrites with the chemical composition CoCexDyxFe2-2xO4 (x = 0, 0.01, 0.02, 0.03, 0.04, 0.05) were synthesized through the chemical route, citrate-gel auto-combustion method. The structural characterization was carried out with the help of XRD Rieveld analysis, SEM and EDAX analysis. Formation of spinel cubic structure of the ferrites was confirmed by XRD analysis. SEM and EDAX results show that the particles are homogeneous with slight agglomeration without any impurity pickup. The effect of RE ion doping (Ce and Dy) on the dielectric, magnetic and impedance studies was systematically investigated by LCR meter, Vibrating Sample Magnetometer and Impedance analyzer respectively at room temperature in the frequency range of 10 Hz-10 MHz. Various dielectric parameters viz., dielectric constant, dielectric loss and ac conductivity were measured. The dielectric constant of all the ferrite compositions shows normal dielectric dispersion of ferrites with frequency. Impedance analysis confirms that the conduction in present ferrites is majorly due to the grain boundary mechanism. Ferrite sample with x = 0.03 show high dielectric constant, low dielectric loss and hence can be utilized in high frequency electromagnetic devices. Magnetization measurements indicate that with increase in Ce and Dy content in cobalt ferrites, the magnetization values decreased and coercivity has increased.

Controlling the misuse of cobalt in horses.

PubMed

Ho, Emmie N M; Chan, George H M; Wan, Terence S M; Curl, Peter; Riggs, Christopher M; Hurley, Michael J; Sykes, David

2015-01-01

Cobalt is a well-established inducer of hypoxia-like responses, which can cause gene modulation at the hypoxia inducible factor pathway to induce erythropoietin transcription. Cobalt salts are orally active, inexpensive, and easily accessible. It is an attractive blood doping agent for enhancing aerobic performance. Indeed, recent intelligence and investigations have confirmed cobalt was being abused in equine sports. In this paper, population surveys of total cobalt in raceday samples were conducted using inductively coupled plasma mass spectrometry (ICP-MS). Urinary threshold of 75 ng/mL and plasma threshold of 2 ng/mL could be proposed for the control of cobalt misuse in raceday or in-competition samples. Results from administration trials with cobalt-containing supplements showed that common supplements could elevate urinary and plasma cobalt levels above the proposed thresholds within 24 h of administration. It would therefore be necessary to ban the use of cobalt-containing supplements on raceday as well as on the day before racing in order to implement and enforce the proposed thresholds. Since the abuse with huge quantities of cobalt salts can be done during training while the use of legitimate cobalt-containing supplements are also allowed, different urinary and plasma cobalt thresholds would be required to control cobalt abuse in non-raceday or out-of-competition samples. This could be achieved by setting the thresholds above the maximum urinary and plasma cobalt concentrations observed or anticipated from the normal use of legitimate cobalt-containing supplements. Urinary threshold of 2000 ng/mL and plasma threshold of 10 ng/mL were thus proposed for the control of cobalt abuse in non-raceday or out-of-competition samples. Copyright © 2014 John Wiley & Sons, Ltd.

Enhanced thermoelectric performance in ternary spinel Cu4Mn2Te4via the synergistic effect of tellurium deficiency and chlorine doping.

PubMed

Chen, Hong; Lin, Hua; Liu, Yi; Wu, Xin-Tao; Wu, Li-Ming

2017-11-07

The chemistry of copper-based chalcogenides has received considerable attention due to their diverse structures and potential applications in the area of thermoelectric (TE) materials. In this communication, a series of spinel-type Cu 4 Mn 2 Te 4 -based samples have been successfully prepared and their high TE performances are attributed to the enhanced power factor and low thermal conductivity via the synergistic effect of Te deficiency and Cl doping. Consequently, a maximum TE figure of merit (ZT) of ∼0.4 was achieved for the Cu 4 Mn 2 Te 3.93 Cl 0.03 sample at 700 K, which was about 100% enhanced in comparison with the undoped Cu 4 Mn 2 Te 4 sample and one of the highest ZT values reported for p-type spinel tellurides.

Determination of oxygen diffusion kinetics during thin film ruthenium oxidation

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

Coloma Ribera, R., E-mail: r.colomaribera@utwente.nl; Kruijs, R. W. E. van de; Yakshin, A. E.

2015-08-07

In situ X-ray reflectivity was used to reveal oxygen diffusion kinetics for thermal oxidation of polycrystalline ruthenium thin films and accurate determination of activation energies for this process. Diffusion rates in nanometer thin RuO{sub 2} films were found to show Arrhenius behaviour. However, a gradual decrease in diffusion rates was observed with oxide growth, with the activation energy increasing from about 2.1 to 2.4 eV. Further exploration of the Arrhenius pre-exponential factor for diffusion process revealed that oxidation of polycrystalline ruthenium joins the class of materials that obey the Meyer-Neldel rule.

Pentamethylcyclopentadienyl-ruthenium catalysts for regio- and enantioselective allylation of nucleophiles.

PubMed

Bruneau, Christian; Renaud, Jean-Luc; Demerseman, Bernard

2006-07-05

Ruthenium(II) complexes containing the pentamethylcyclopentadienyl ligand efficiently perform the activation of allylic carbonates and halides to generate cationic and dicationic ruthenium(IV) complexes. This activation has been transferred as a key step to the catalytic allylation of nucleophiles. The structural and electronic properties of the allylic moieties lead to the regioselective formation of chiral products resulting from nucleophilic addition to their most substituted terminus. The catalytic activity of various Ru(Cp*) precatalysts in several allylic substitutions by C and O nucleophiles will be presented. The enantioselective version that has been demonstrated by using optically pure bisoxazoline ligands will also be discussed.

Characterization of Self-Assembled Monolayers on a Ruthenium Surface

PubMed Central

2017-01-01

We have modified and stabilized the ruthenium surface by depositing a self-assembled monolayer (SAM) of 1-hexadecanethiol on a polycrystalline ruthenium thin film. The growth mechanism, dynamics, and stability of these monolayers were studied. SAMs, deposited under ambient conditions, on piranha-cleaned and piranha + H2SO4 cleaned substrates were compared to monolayers formed on H-radical-cleaned Ru surfaces. We found that alkanethiols on H-radical-cleaned Ru formed densely packed monolayers that remained stable when kept in a nitrogen atmosphere. X-ray photoelectron spectroscopy (XPS) shows a distinct sulfur peak (BE = 162.3 eV), corresponding to metal–sulfur bonding. When exposed to ambient conditions, the SAM decayed over a period of hours. PMID:28585831

Wrought cobalt- base superalloys

NASA Astrophysics Data System (ADS)

Klarstrom, D. L.

1993-08-01

Wrought cobalt-base superalloys are used extensively in gas turbine engines because of their excellent high-temperature creep and fatigue strengths and resistance to hot corrosion attack. In addition, the unique character of the oxide scales that form on some of the alloys provides outstanding resistance to high-temperature sliding wear. This article provides a review of the evolutionary development of wrought cobalt-base alloys in terms of alloy design and physical metallurgy. The topics include solid-so-lution strengthening, carbide precipitation characteristics, and attempts to introduce age hardening. The use of PHACOMP to enhance thermal stability characteristics and the incorporation of rare-earth ele-ments to improve oxidation resistance is also reviewed and discussed. The further development of cobalt-base superalloys has been severely hampered by past political events, which have accentuated the strategic vulnerability of cobalt as a base or as an alloying element. Consequently, alternative alloys have been developed that use little or no cobalt. One such alternative, Haynes® 230TMalloy, is discussed briefly.

Study on the energy band structure and photoelectrochemical performances of spinel Li{sub 4}Ti{sub 5}O{sub 12}

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

Ge, Hao; Tian, Hui; Song, Hua

2015-01-15

Highlights: • Spinel Li{sub 4}Ti{sub 5}O{sub 12} possesses more positive potential of valence band and wider band gap than TiO{sub 2}. • Spinel Li{sub 4}Ti{sub 5}O{sub 12} displays typical n-type semiconductor characteristic and excellent UV-excitateded photocatalysis activity. • Our preliminary study will open new perspectives in investigation of other lithium-based compounds for new photocatalysts. - Abstract: Energy band structure, photoelectrochemical performances and photocatalysis activity of spinel Li{sub 4}Ti{sub 5}O{sub 12} are investigated for the first time in this paper. Li{sub 4}Ti{sub 5}O{sub 12} possesses more positive valence band potential and wider band gap than TiO{sub 2} due to its valencemore » band consisting of Li{sub 1s} and Ti{sub 3d} orbitals mixed with O{sub 2p}. Li{sub 4}Ti{sub 5}O{sub 12} shows typical photocatalysis material characteristics and excellent photocatlytic activity under UV irradiation.« less

A ruthenium anticancer compound interacts with histones and impacts differently on epigenetic and death pathways compared to cisplatin

PubMed Central

Capuozzo, Antonelle; Ali, Moussa; Santamaria, Rita; Armant, Olivier; Delalande, Francois; Dorsselaer, Alain Van; Cianferani, Sarah; Spencer, John; Pfeffer, Michel; Mellitzer, Georg; Gaiddon, Christian

2017-01-01

Ruthenium complexes are considered as potential replacements for platinum compounds in oncotherapy. Their clinical development is handicapped by a lack of consensus on their mode of action. In this study, we identify three histones (H3.1, H2A, H2B) as possible targets for an anticancer redox organoruthenium compound (RDC11). Using purified histones, we confirmed an interaction between the ruthenium complex and histones that impacted on histone complex formation. A comparative study of the ruthenium complex versus cisplatin showed differential epigenetic modifications on histone H3 that correlated with differential expression of histone deacetylase (HDAC) genes. We then characterized the impact of these epigenetic modifications on signaling pathways employing a transcriptomic approach. Clustering analyses showed gene expression signatures specific for cisplatin (42%) and for the ruthenium complex (30%). Signaling pathway analyses pointed to specificities distinguishing the ruthenium complex from cisplatin. For instance, cisplatin triggered preferentially p53 and folate biosynthesis while the ruthenium complex induced endoplasmic reticulum stress and trans-sulfuration pathways. To further understand the role of HDACs in these regulations, we used suberanilohydroxamic acid (SAHA) and showed that it synergized with cisplatin cytotoxicity while antagonizing the ruthenium complex activity. This study provides critical information for the characterization of signaling pathways differentiating both compounds, in particular, by the identification of a non-DNA direct target for an organoruthenium complex. PMID:27935863

Synthesis and characterization of spinel type high-power cathode materials Li MxMn2-x O4 (M=Ni, Co, Cr)

NASA Astrophysics Data System (ADS)

Yoon, Y. K.; Park, C. W.; Ahn, H. Y.; Kim, D. H.; Lee, Y. S.; Kim, J.

2007-05-01

The transition metal-doped spinel cathode materials, LiM0.5Mn1.5O4 (M=Ni. Co, Cr) were prepared by solid-state reaction. The structure and morphology of the samples were investigated by X-ray diffraction, Rietveld refinement and scanning electron microscopy (SEM). The diffraction peaks of all the samples corresponded to a single phase of cubic spinel structure with a space group Fd3m. Field-emission SEM shows octahedron like shapes and the primary particles size was between 500 nm and 2 μm. Oxidation states of Ni, Co and Cr were found to be 2+, 2+ and 3+ as revealed by X-ray photoelectron spectroscopy. During discharging, LiNi0.5Mn1.5O4 and LiCo0.5Mn1.5O4 sample shows more than 130 mAh/g between 3.5 and 5.2 V at a current density of 0.65 mA/cm2 and well developed plateau around 5 V, respectively.

Detoxification and immobilization of chromite ore processing residue in spinel-based glass-ceramic.

PubMed

Liao, Chang-Zhong; Tang, Yuanyuan; Lee, Po-Heng; Liu, Chengshuai; Shih, Kaimin; Li, Fangbai

2017-01-05

A promising strategy for the detoxification and immobilization of chromite ore processing residue (COPR) in a spinel-based glass-ceramic matrix is reported in this study. In the search for a more chemically durable matrix for COPR, the most critical crystalline phase for Cr immobilization was found to be a spinel solid solution with a chemical composition of MgCr 1.32 Fe 0.19 Al 0.49 O 4 . Using Rietveld quantitative X-ray diffraction analysis, we identified this final product is with the phases of spinel (3.5wt.%), diopside (5.2wt.%), and some amorphous contents (91.2wt.%). The partitioning ratio of Cr reveals that about 77% of the Cr was incorporated into the more chemically durable spinel phase. The results of Cr K-edge X-ray absorption near-edge spectroscopy show that no Cr(VI) was observed after conversion of COPR into a glass-ceramic, which indicates successful detoxification of Cr(VI) into Cr(III) in the COPR-incorporated glass-ceramic. The leaching performances of Cr 2 O 3 and COPR-incorporated glass-ceramic were compared with a prolonged acid-leaching test, and the results demonstrate the superiority of the COPR-incorporated glass-ceramic matrix in the immobilization of Cr. The overall results suggest that the use of affordable additives has potential in more reliably immobilizing COPR with a spinel-based glass-ceramic for safer disposal of this hazardous waste. Copyright © 2016 Elsevier B.V. All rights reserved.

Pharmacokinetics of inorganic cobalt and a vitamin B12 supplement in the Thoroughbred horse: Differentiating cobalt abuse from supplementation.

PubMed

Hillyer, L L; Ridd, Z; Fenwick, S; Hincks, P; Paine, S W

2018-05-01

While cobalt is an essential micronutrient for vitamin B 12 synthesis in the horse, at supraphysiological concentrations, it has been shown to enhance performance in human subjects and rats, and there is evidence that its administration in high doses to horses poses a welfare threat. Animal sport regulators currently control cobalt abuse via international race day thresholds, but this work was initiated to explore means of potentially adding to application of those thresholds since cobalt may be present in physiological concentrations. To devise a scientific basis for differentiation between presence of cobalt from bona fide supplementation and cobalt doping through the use of ratios. Six Thoroughbred horses were given 10 mL vitamin B 12 /cobalt supplement (Hemo-15 ® ; Vetoquinol, Buckingham, Buckinghamshire, UK., 1.5 mg B 12 , 7 mg cobalt gluconate = 983 μg total Co) as an i.v. bolus then an i.v. infusion (15 min) of 100 mg cobalt chloride (45.39 mg Co) 6 weeks later. Pre-and post-administration plasma and urine samples were analysed for cobalt and vitamin B 12 . Urine and plasma samples were analysed for vitamin B 12 using an immunoassay and cobalt concentrations were measured via ICP-MS. Baseline concentrations of cobalt in urine and plasma for each horse were subtracted from their cobalt concentrations post-administration for the PK analysis. Compartmental analysis was used for the determination of plasma PK parameters for cobalt using commercially available software. On administration of a vitamin B 12 /cobalt supplement, the ratio of cobalt to vitamin B 12 in plasma rapidly increased to approximately 3 and then rapidly declined below a ratio of 1 and then back to near baseline over the next week. On administration of 100 mg cobalt chloride, the ratio initially exceeded 10 in plasma and then declined with the lower 95% confidence interval remaining above a ratio of 1 for 7 days. For two horses with extended sampling, the plasma ratio remained above one for

Physical properties and spin excitations in the lacunar spinels AV4S8(A =Ga, Ge)

NASA Astrophysics Data System (ADS)

Pokharel, Ganesh; Christianson, Andrew; Mandrus, David; Liusuo Wu Team; Mark Lumsden Collaboration; Rupam Mukherjee Collaboration; Matthew Stone Collaboration; Georg Ehlers Collaboration

In the lacunar spinels AV4S8 (A = Ga, Ge), the interplay of spin, charge, and orbital degrees of freedom results in a complex phase diagram which includes: ferroelectric, orbitally ordered, and Néel type skyrmion phases. Below 12.7 K GaV4S8 exhibits cycloidal and ferromagnetic order and the application of a magnetic field results in a Néel type skyrmion spin structure. On the other hand, GeV4S8 orders antiferromagentically below 18 K. To illuminate the underlying physics driving the formation of these novel phases, we have measured the magnetization, resistivity, thermal conductivity, and inelastic neutron scattering spectrum of these spinels. The inelastic neutron scattering data shows broadened spin excitations which extend to 6 meV within the magnetically order phases for both GaV4S8 and GeV4S8. The similarity of the spectra for ferromagnetic GaV4S8 and antiferromagnetic GeV4S8 reflects the close balance of ferromagnetic and antiferromagnetic interactions in these materials. This research is funded by the Gordon and Betty Moore Foundation's EPIQS Initiative through Grant GBMF4416.

Photoexpulsion of Surface-Grafted Ruthenium Complexes and Subsequent Release of Cytotoxic Cargos to Cancer Cells from Mesoporous Silica Nanoparticles

PubMed Central

Frasconi, Marco; Liu, Zhichang; Lei, Juying; Wu, Yilei; Strekalova, Elena; Malin, Dmitry; Ambrogio, Michael W.; Chen, Xinqi; Botros, Youssry Y.; Cryns, Vincent L.; Sauvage, Jean-Pierre; Stoddart, J. Fraser

2014-01-01

Ruthenium(II) polypyridyl complexes have emerged both as promising probes of DNA structure and as anticancer agents because of their unique photophysical and cytotoxic properties. A key consideration in the administration of those therapeutic agents is the optimization of their chemical reactivities to allow facile attack on the target sites, yet avoid unwanted side effects. Here, we present a drug delivery platform technology, obtained by grafting the surface of mesoporous silica nanoparticles (MSNPs) with ruthenium(II) dipyridophenazine (dppz) complexes. This hybrid nanomaterial displays enhanced luminescent properties relative to that of the ruthenium(II) dppz complex in a homogeneous phase. Since the coordination between the ruthenium(II) complex and a monodentate ligand linked covalently to the nanoparticles can be cleaved under irradiation with visible light, the ruthenium complex can be released from the surface of the nanoparticles by selective substitution of this ligand with a water molecule. Indeed, the modified MSNPs undergo rapid cellular uptake, and after activation with light, the release of an aqua ruthenium(II) complex is observed. We have delivered, in combination, the ruthenium(II) complex and paclitaxel, loaded in the mesoporous structure, to breast cancer cells. This hybrid material represents a promising candidate as one of the so-called theranostic agents that possess both diagnostic and therapeutic functions. PMID:23815127

Photoexpulsion of surface-grafted ruthenium complexes and subsequent release of cytotoxic cargos to cancer cells from mesoporous silica nanoparticles.

PubMed

Frasconi, Marco; Liu, Zhichang; Lei, Juying; Wu, Yilei; Strekalova, Elena; Malin, Dmitry; Ambrogio, Michael W; Chen, Xinqi; Botros, Youssry Y; Cryns, Vincent L; Sauvage, Jean-Pierre; Stoddart, J Fraser

2013-08-07

Ruthenium(II) polypyridyl complexes have emerged both as promising probes of DNA structure and as anticancer agents because of their unique photophysical and cytotoxic properties. A key consideration in the administration of those therapeutic agents is the optimization of their chemical reactivities to allow facile attack on the target sites, yet avoid unwanted side effects. Here, we present a drug delivery platform technology, obtained by grafting the surface of mesoporous silica nanoparticles (MSNPs) with ruthenium(II) dipyridophenazine (dppz) complexes. This hybrid nanomaterial displays enhanced luminescent properties relative to that of the ruthenium(II) dppz complex in a homogeneous phase. Since the coordination between the ruthenium(II) complex and a monodentate ligand linked covalently to the nanoparticles can be cleaved under irradiation with visible light, the ruthenium complex can be released from the surface of the nanoparticles by selective substitution of this ligand with a water molecule. Indeed, the modified MSNPs undergo rapid cellular uptake, and after activation with light, the release of an aqua ruthenium(II) complex is observed. We have delivered, in combination, the ruthenium(II) complex and paclitaxel, loaded in the mesoporous structure, to breast cancer cells. This hybrid material represents a promising candidate as one of the so-called theranostic agents that possess both diagnostic and therapeutic functions.

MgAl2O4 spinel refractory as containment liner for high-temperature alkali salt containing environments

DOEpatents

Peascoe-Meisner, Roberta A [Knoxville, TN; Keiser, James R [Oak Ridge, TN; Hemric, James G [Knoxville, TN; Hubbard, Camden R [Oak Ridge, TN; Gorog, J Peter [Kent, WA; Gupta, Amul [Jamestown, NY

2008-10-21

A method includes containing a high-temperature alkali salt containing environment using a refractory containment liner containing MgAl.sub.2O.sub.4 spinel. A method, includes forming a refractory brick containing MgAl.sub.2O.sub.4 spinel having an exterior chill zone defined by substantially columnar crystallization and an interior zone defined by substantially equiaxed crystallization; and removing at least a portion of the exterior chill zone from the refractory brick containing MgAl.sub.2O.sub.4 spinel by scalping the refractory brick containing MgAl.sub.2O.sub.4 spinel to define at least one outer surface having an area of substantially equiaxed crystallization. A product of manufacture includes a refractory brick containing MgAl.sub.2O.sub.4 spinel including an interior zone defined by substantially equiaxed crystallization; and at least one outer surface having an area of substantially equiaxed crystallization.

Cobalt(II) complexes with azole-pyridine type ligands for non-aqueous redox-flow batteries: Tunable electrochemistry via structural modification

NASA Astrophysics Data System (ADS)

Armstrong, Craig G.; Toghill, Kathryn E.

2017-05-01

A single species redox flow battery employing a new class of cobalt(II) complexes with 'tunable' tridentate azole-pyridine type ligands is reported. Four structures were synthesised and their electrochemical, physical and battery characteristics were investigated as a function of successive substitution of the ligand terminal pyridyl donors. The Co(II/I) and Co(III/II) couples are stable and quasi-reversible on gold and glassy carbon electrodes, however redox potentials are tunable allowing the cobalt potential difference to be preferentially increased from 1.07 to 1.91 V via pyridine substitution with weaker σ-donating/π-accepting 3,5-dimethylpyrazole groups. The charge-discharge properties of the system were evaluated using an H-type glass cell and graphite rod electrodes. The complexes delivered high Coulombic efficiencies of 89.7-99.8% and very good voltaic efficiencies of 70.3-81.0%. Consequently, energy efficiencies are high at 63.1-80.8%, marking an improvement on other similar non-aqueous systems. Modification of the ligands also improved solubility from 0.18 M to 0.50 M via pyridyl substitution with 3,5-dimethylpyrazole, though the low solubility of the complexes limits the overall energy capacity to between 2.58 and 12.80 W h L-1. Preliminary flow cell studies in a prototype flow cell are also demonstrated.

A preliminary evaluation of stream sediment sampling for the detection of cobalt mineralization in the Bou Azzer District, Morocco

USGS Publications Warehouse

Foose, M.P.

1983-01-01

Analyses of 28 stream sediment samples collected in the Bou Azzer district, Morocco, show that this sampling technique may be useful in locating the cobalt arsenide mineralization that exists in this area. The absence of exceptionally high values of cobalt and arsenic, the nearly lognormal distribution of cobalt values, and the lack of correlation between the highest values of cobalt and arsenic were unanticipated results that do not support the use of this sampling technique. However, highest values of several metals, including cobalt, were associated with an identified area of cobalt mineralization, and high cobalt was present near a second area in which cobalt mineralization is suspected. Although probably mostly reflecting the geochemistry of unexposed ultramafic rocks, the association of these metals with mineralization shows that this type of sampling can independently locate areas of known or potential cobalt mineralization.

Acetate- and thiol-capped monodisperse ruthenium nanoparticles: XPS, XAS, and HRTEM studies.

PubMed

Chakroune, Nassira; Viau, Guillaume; Ammar, Souad; Poul, Laurence; Veautier, Delphine; Chehimi, Mohamed M; Mangeney, Claire; Villain, Françoise; Fiévet, Fernand

2005-07-19

Monodisperse ruthenium nanoparticles were prepared by reduction of RuCl3 in 1,2-propanediol. The mean particle size was controlled by appropriate choice of the reduction temperature and the acetate ion concentration. Colloidal solutions in toluene were obtained by coating the metal particles with dodecanethiol. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XANES and EXAFS for the Ru K-absorption edge) were performed on particles of two different diameters, 2 and 4 nm, and in different environments, polyol/acetate or thiol. For particles stored in polyol/acetate XPS studies revealed superficial oxidation limited to one monolayer and a surface coating containing mostly acetate ions. Analysis of the EXAFS spectra showed both oxygen and ruthenium atoms around the ruthenium atoms with a Ru-Ru coordination number N smaller than the bulk value, as expected for fine particles. In the case of 2 nm acetate-capped particles N is consistent with particles made up of a metallic core and an oxidized monolayer. For 2 nm thiol-coated particles, a Ru-S bond was evidenced by XPS and XAS. For the 4 nm particles XANES and XPS studies showed that most of the ruthenium atoms are in the zerovalent state. Nevertheless, in both cases, when capped with thiol, the Ru-Ru coordination number inferred from EXAFS is much smaller than for particles of the same size stored in polyol. This is attributed to a structural disorganization of the particles by thiol chemisorption. HRTEM studies confirm the marked dependence of the structural properties of the ruthenium particles on their chemical environment; they show the acetate-coated particles to be single crystals, whereas the thiol-coated particles appear to be polycrystalline.

Specific heat of new perovskite-type cobaltates Pr{sub 1-x}Nd{sub x}CoO{sub 3}

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

Thakur, Rasna, E-mail: rasnarishu@gmail.com; Thakur, Rajesh K.; Gaur, N. K.

2016-05-23

Specific heat and Bulk modulus (B) of new perovskite-type cobaltates Pr{sub 1-x}Nd{sub x}CoO{sub 3} has been studied by means of a Modified Rigid Ion Model (MRIM) and Atoms in Molecules (AIM) theory in a wide temperature range (1 K ≤ T ≤1000 K). The effect of Nd doping on the elastic, cohesive and thermal properties of PrCoO{sub 3} have been studied probably for the first time by an atomistic approach. The computed results are in good agreement with the available experimental data.

Spinel cataclasites in 15445 and 72435 - Petrology and criteria for equilibrium

NASA Technical Reports Server (NTRS)

Baker, M. B.; Herzberg, C. T.

1980-01-01

The problem of establishing the existence of equilibrium among the coexisting phases in the rock is addressed by presenting petrographic and mineral chemistry data on a new spinel cataclasite from 15445 (clast H) and data more extensive than those previously available on two clasts in 72435. Criteria useful in reconstructing the original petrology of these and other spinel cataclasites are analyzed by considering equilibrium among the different phases, that is, the mono- or polymict nature of these cataclasized samples. Finally, the role of impact processes in disturbing the equilibria is discussed.

Rhenium and Iridium Partitioning in Silicate and Magmatic Spinels: Implications for Planetary Magmatism and Mantles

NASA Technical Reports Server (NTRS)

Righter, K.

2001-01-01

Highly siderophile elements Re, Ru and Ir partition strongly into spinel structures with large octahedral sites. New experimental results for both magmatic and silicate spinels will be presented with a few planetary implications. Additional information is contained in the original extended abstract.

Plasma-assisted oxide removal from ruthenium-coated EUV optics

NASA Astrophysics Data System (ADS)

Dolgov, A.; Lee, C. J.; Bijkerk, F.; Abrikosov, A.; Krivtsun, V. M.; Lopaev, D.; Yakushev, O.; van Kampen, M.

2018-04-01

An experimental study of oxide reduction at the surface of ruthenium layers on top of multilayer mirrors and thin Ru/Si films is presented. Oxidation and reduction processes were observed under conditions close to those relevant for extreme ultraviolet lithography. The oxidized ruthenium surface was exposed to a low-temperature hydrogen plasma, similar to the plasma induced by extreme ultraviolet radiation. The experiments show that hydrogen ions are the main reducing agent. Furthermore, the addition of hydrogen radicals increases the reduction rate beyond that expected from simple flux calculations. We show that low-temperature hydrogen plasmas can be effective for reducing oxidized top surfaces. Our proof-of-concept experiments show that an in situ, EUV-generated plasma cleaning technology is feasible.

Porous Mn-doped cobalt oxide@C nanocomposite: a stable anode material for Li-ion rechargeable batteries

NASA Astrophysics Data System (ADS)

Kalubarme, Ramchandra S.; Jadhav, Sarika M.; Kale, Bharat B.; Gosavi, Suresh W.; Terashima, Chiaki; Fujishima, Akira

2018-07-01

Cobalt oxide is a transition metal oxide, well studied as an electrode material for energy storage applications, especially in supercapacitors and rechargeable batteries, due to its high charge storage ability. However, it suffers from low conductivity, which effectively hampers its long-term stability. In the present work, a simple strategy to enhance the conductivity of cobalt oxide is adopted to achieve stable electrochemical performance by means of carbon coating and Mn doping, via a simple and controlled, urea-assisted glycine-nitrate combustion process. Structural analysis of carbon coated Mn-doped Co3O4 (Mn-Co3O4@C) confirms the formation of nanoparticles (∼50 nm) with connected morphology, exhibiting spinel structure. The Mn-Co3O4@C electrode displays superior electrochemical performance as a Li-ion battery anode, delivering a specific capacity of 1250 mAh g‑1. Mn-Co3O4@C demonstrates excellent performance in terms of long-term stability, keeping charge storage ability intact even at high current rates due to the synergistic effects of fast kinetics—provided by enriched electronic conductivity, which allows ions to move freely to active sites and electrons from reaction sites to substrate during redox reactions—and high surface area combined with mesoporous architecture. The fully assembled battery device using Mn-Co3O4@C and standard LiCoO2 electrode shows 90% capacity retention over 100 cycles.

Opposite correlations between cation disordering and amorphization resistance in spinels versus pyrochlores

DOE PAGES

Uberuaga, Blas Pedro; Tang, Ming; Jiang, Chao; ...

2015-10-29

Understanding and predicting radiation damage evolution in complex materials is crucial for developing next-generation nuclear energy sources. Here, using a combination of ion beam irradiation, transmission electron microscopy and X-ray diffraction, we show that, contrary to the behaviour observed in pyrochlores, the amorphization resistance of spinel compounds correlates directly with the energy to disorder the structure. Using a combination of atomistic simulation techniques, we ascribe this behaviour to structural defects on the cation sublattice that are present in spinel but not in pyrochlore. Specifically, because of these structural defects, there are kinetic pathways for the relaxation of disorder in spinelmore » that are absent in pyrochlore. This leads to a direct correlation between amorphization resistance and disordering energetics in spinel, the opposite of that observed in pyrochlores. Furthermore, these results provide new insight into the origins of amorphization resistance in complex oxides beyond fluorite derivatives.« less

Cobalt sorption onto anaerobic granular sludge: isotherm and spatial localization analysis.

PubMed

van Hullebusch, Eric D; Gieteling, Jarno; Zhang, Min; Zandvoort, Marcel H; Daele, Wim Van; Defrancq, Jacques; Lens, Piet N L

2006-01-24

This study investigated the effect of different feeding regimes on the cobalt sorption capacity of anaerobic granular sludge from a full-scale bioreactor treating paper mill wastewater. Adsorption experiments were done with non-fed granules in monometal (only Co) and competitive conditions (Co and Ni in equimolar concentrations). In order to modify the extracellular polymeric substances and sulfides content of the granules, the sludge was fed for 30 days with glucose (pH 7, 30 degrees C, organic loading rate=1.2 g glucose l(-1) day-1) in the presence (COD/SO4(2-)=1) or absence of sulfate. The partitioning of the sorbed cobalt between the exchangeable, carbonates, organic matter/sulfides and residual fractions was determined using a sequential extraction procedure (modified Tessier). Experimental equilibrium sorption data for cobalt were analysed by the Langmuir, Freundlich and Redlich-Peterson isotherm equations. The total Langmuir maximal sorption capacity of the sludge fed with glucose and sulfate loaded with cobalt alone displayed a significantly higher maximal cobalt sorption (Qmax =18.76 mg g-1 TSS) than the sludge fed with glucose alone (Qmax =13.21 mg g-1 TSS), essentially due to an increased sorption capacity of the exchangeable (30-107%) and organic/sulfides fractions (70-30%). Environmental scanning electron microscopy coupled with an energy dispersive X-ray analysis of granular cross-sections showed that mainly iron minerals (i.e. iron sulfides) were involved in the cobalt accumulation. Moreover, the sorbed cobalt was mainly located at the edge of the granules. The sorption characteristics of the exchangeable and carbonates fractions fitted well to the Redlich-Peterson model (intermediate multi-layer sorption behaviour), whereas the sorption characteristics of the organic matter/sulfides and residual fractions fitted well to the Langmuir model (monolayer sorption behaviour). The organic matter/sulfides fraction displayed the highest affinity for cobalt

Platinum-ruthenium nanotubes and platinum-ruthenium coated copper nanowires as efficient catalysts for electro-oxidation of methanol

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

Zheng, Jie; Cullen, David A.; Forest, Robert V.

2015-01-15

The sluggish kinetics of methanol oxidation reaction (MOR) is a major barrier to the commercialization of direct methanol fuel cells (DMFCs). In this study, we report a facile synthesis of platinum–ruthenium nanotubes (PtRuNTs) and platinum–ruthenium-coated copper nanowires (PtRu/CuNWs) by galvanic displacement reaction using copper nanowires as a template. The PtRu compositional effect on MOR is investigated; the optimum Pt/Ru bulk atomic ratio is about 4 and surface atomic ratio about 1 for both PtRuNTs and PtRu/CuNWs. Enhanced specific MOR activities are observed on both PtRuNTs and PtRu/CuNWs compared with the benchmark commercial carbon-supported PtRu catalyst (PtRu/C, Hispec 12100). Finally, x-raymore » photoelectron spectroscopy (XPS) reveals a larger extent of electron transfer from Ru to Pt on PtRu/CuNWs, which may lead to a modification of the d-band center of Pt and consequently a weaker bonding of CO (the poisoning intermediate) on Pt and a higher MOR activity on PtRu/CuNWs.« less

Physical and photoelectrochemical properties of the spinel LiMn2O4 and its application in photocatalysis

NASA Astrophysics Data System (ADS)

Douafer, S.; Lahmar, H.; Benamira, M.; Rekhila, G.; Trari, M.

2018-07-01

Nanocrystalline lithium manganese oxide (LiMn2O4), synthesized by the sol-gel method, crystallizes in the spinel structure. The physical, electrical, and photoelectrochemical properties were studied for the photocatalytic degradation of methyl orange, a toxic compound, under solar irradiation. The diffuse reflectance spectrum allowed the direct band gap (1.99 eV) to be calculated. The Fourier transform IR spectrum contained all the characteristic peaks of the spinel LiMn2O4, which exhibited n-type behavior. The thermal evolution of the electrical conductivity exhibited an Arrhenius-type behavior with an activation energy of 0.27 eV. The Mott-Schottky curve allowed the determination of the flat band potential (-0.24 V vs. the saturated calomel electrode) as well as the carrier density (1.78 × 1021 cm-3). The detoxification of water containing methyl orange with LiMn2O4 as a photocatalyst was successfully completed. Total degradation for an initial concentration of 10-4 M methyl orange at pH ∼3 and 25 °C was obtained in less than 5 h under solar irradiation. No adsorption was obtained in the dark in the presence of LiMn2O4.

Origin of Spinel Framboids in Calcium-Aluminum-Rich Inclusions

NASA Astrophysics Data System (ADS)

Yoshizaki, T.; Nakashima, D.; Nakamura, T.; Ishida, H.; Sakamoto, N.

2017-07-01

Mineralogical, petrological and O-isotopic study of a CV CAI suggests that spinel framboids in the CAI were originally mini-CAIs that condensed separately under different conditions and subsequently aggregated to form the inclusion.

Complete cobalt recovery from lithium cobalt oxide in self-driven microbial fuel cell - Microbial electrolysis cell systems

NASA Astrophysics Data System (ADS)

Huang, Liping; Yao, Binglin; Wu, Dan; Quan, Xie

2014-08-01

Complete cobalt recovery from lithium cobalt oxide requires to firstly leach cobalt from particles LiCoO2 and then recover cobalt from aqueous Co(II). A self-driven microbial fuel cell (MFC)-microbial electrolysis cell (MEC) system can completely carry out these two processes, in which Co(II) is firstly released from particles LiCoO2 on the cathodes of MFCs and then reduced on the cathodes of MECs which are powered by the cobalt leaching MFCs. A cobalt leaching rate of 46 ± 2 mg L-1 h-1 with yield of 1.5 ± 0.1 g Co g-1 COD (MFCs) and a Co(II) reduction rate of 7 ± 0 mg L-1 h-1 with yield of 0.8 ± 0.0 g Co g-1 COD (MECs), as well as a overall system cobalt yield of 0.15 ± 0.01 g Co g-1 Co can be achieved in this self-driven MFC-MEC system. Coulombic efficiencies reach 41 ± 1% (anodic MFCs), 75 ± 0% (anodic MECs), 100 ± 2% (cathodic MFCs), and 29 ± 1% (cathodic MECs) whereas overall system efficiency averages 34 ± 1%. These results provide a new process of linking MFCs to MECs for complete recovery of cobalt and recycle of spent lithium ion batteries with no external energy consumption.

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

PubMed

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

2013-05-21

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

Petrology of spinel lherzolite xenoliths from Youkou volcano, Adamawa Massif, Cameroon Volcanic Line: mineralogical and geochemical fingerprints of sub-rift mantle processes

NASA Astrophysics Data System (ADS)

Njombie, Merlin Patrick Wagsong; Temdjim, Robert; Foley, Stephen F.

2018-02-01

The basaltic maar of Youkou, situated in the Adamawa Volcanic Massif in the eastern branch of the continental segment of the Cameroon Volcanic Line, contains mantle-derived xenoliths of various types in pyroclastites. Spinel-bearing lherzolite xenoliths from the Youkou volcano generally exhibit protogranular textures with olivine (Fo89.4-90.5), enstatite (En89 - 91Fs8.7-9.8Wo0.82-1.13), clinopyroxene, spinel (Cr#Sp = 9.4-13.8), and in some cases amphibole (Mg# = 88.5-89.1). Mineral equilibration temperatures in the lherzolite xenoliths have been estimated from three-two pyroxene thermometers and range between 835 and 937 °C at pressures of 10-18 kbar, consistent with shallow mantle depths of around 32-58 km. Trends displayed by bulk-rock MgO correlate with Al2O3, indicating that the xenoliths are refractory mantle residues after partial melting. The degree of partial melting estimated from spinel compositions is less than 10%: evidences for much higher degrees of depletion are preserved in one sample, but overprinted by refertilization in others. Trace element compositions of the xenoliths are enriched in highly incompatible elements (LREE, Sr, Ba, and U), indicating that the spinel lherzolites underwent later cryptic metasomatic enrichment induced by plume-related hydrous silicate melts. The extreme fertility (Al2O3 = 6.07-6.56 wt% in clinopyroxene) and the low CaO/Al2O3 ratios in the spinel lherzolites suggest that they could not be a simple residue of partial melting of primitive mantle and must have experienced refertilization processes driven by the infiltration of carbonatite or carbonated silicate melts.

Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries

DOEpatents

Manthiram, Arumugam; Choi, Wongchang

2014-05-13

The present invention includes compositions and methods of making cation-substituted and fluorine-substituted spinel cathode compositions by firing a LiMn.sub.2-y-zLi.sub.yM.sub.zO.sub.4 oxide with NH.sub.4HF.sub.2 at low temperatures of between about 300 and 700.degree. C. for 2 to 8 hours and a .eta. of more than 0 and less than about 0.50, mixed two-phase compositions consisting of a spinel cathode and a layered oxide cathode, and coupling them with unmodified or surface modified graphite anodes in lithium ion cells.

All-spinel oxide Josephson junctions for high-efficiency spin filtering.

PubMed

Mesoraca, S; Knudde, S; Leitao, D C; Cardoso, S; Blamire, M G

2018-01-10

Obtaining high efficiency spin filtering at room temperature using spinel ferromagnetic tunnel barriers has been hampered by the formation of antiphase boundaries due to their difference in lattice parameters between barrier and electrodes. In this work we demonstrate the use of LiTi 2 O 4 thin films as electrodes in an all-spinel oxide CoFe 2 O 4 -based spin filter devices. These structures show nearly perfect epitaxy maintained throughout the structure and so minimise the potential for APBs formation. The LiTi 2 O 4 in these devices is superconducting and so measurements at low temperature have been used to explore details of the tunnelling and Josephson junction behaviour.

Rietveld refinement and electrical properties of Ni-Zn spinel ferrites

NASA Astrophysics Data System (ADS)

Hooda, Ashima; Sanghi, Sujata; Agarwal, Ashish; Khasa, Satish; Hooda, Bhawana

2017-05-01

NiFe2O4, ZnFe2O4, Ni0.5Zn0.5Fe2O4 spinel samples have been synthesized by conventional solid state reaction technique. Powder X-ray diffraction and Rietveld refinement revealed that the samples were single Spinel phase with space group fd3m. The average crystalline size (D), lattice constant (a), X-ray density (ρx), measured density (ρm) and Porosity (P) of prepared samples were determined from XRD data. The dc electrical resistivity (p) was measured as a function of temperature. The variations of ρ were explained on the basis of Verwey and de Bohr mechanism. The value of DC resistivity found to increase with increase Zn concentration.

Decarboxylation of cinnamic acids using a ruthenium sawhorse

USDA-ARS?s Scientific Manuscript database

The ruthenium sawhorse has proven effective in the conversion of trans-cinnamic acid, and substituted trans-cinnamic acids, giving an effective source of biobased styrene and styrene analogues. The reaction is especially versatile, as it achieves product without utilising co-reagents. However, the o...

Zoned Cr, Fe-spinel from the La Perouse layered gabbro, Fairweather Range, Alaska

USGS Publications Warehouse

Czamanske, G.K.; Himmelberg, G.R.; Goff, F.E.

1976-01-01

Zoned spinel of unusual composition and morphology has been found in massive pyrrhotite-chalcopyrite-pent-landite ore from the La Perouse layered gabbro intrusion in the Fairweather Range, southeastern Alaska. The spinel grains show continuous zoning from cores with up to 53 wt.% Cr2O3 to rims with less than 11 wt.% Cr2O3. Their composition is exceptional because they contain less than 0.32 wt.% MgO and less than 0.10 wt.% Al2O3 and TiO2. Also notable are the concentrations of MnO and V2O3, which reach 4.73 and 4.50 wt.%, respectively, in the cores. The spinel is thought to have crystallized at low oxygen fugacity and at temperatures above 900??C, directly from a sulfide melt that separated by immiscibility from the gabbroic parental magma. ?? 1976.

Detrital Cr-spinel in the Šambron-Kamenica Zone (Slovakia): evidence for an ocean-spreading zone in the Northern Vardar suture?

NASA Astrophysics Data System (ADS)

Lenaz, Davide; Mazzoli, Claudio; Spišiak, Jan; Princivalle, Francesco; Maritan, Lara

2009-03-01

The Šambron-Kamenica Zone is situated on the northern margin of the Levočské vrchy mountains and Šarišskà vrchovina Highland, where the Central Carpathian Paleogene joins the Pieniny Klippen Belt. Sandstone outcrops in this area. From Cretaceous to Late Oligocene in age, these sediments suggest transport directions from S and SE. The heavy mineral assemblages of this sandstone include Cr-spinel grains, mainly displaying types II and III alpine-peridotite affinities, and are representative of Ocean Island Basalt volcanism. A sample from Upper Eocene sediments at Vit’az shows a clear change in Cr-spinel composition, which turns out to have types I and II peridotite affinities, and to derive from arc and Middle Ocean Ridge Basalt volcanism, with sediment transport directions from SW and WSW. These data indicate major variations in the Upper Eocene tectonic setting, giving constraints to paleogeographic reconstruction of the Slovak Central Carpathians.

Layer-by-layer grown scalable redox-active ruthenium-based molecular multilayer thin films for electrochemical applications and beyond.

PubMed

Kaliginedi, Veerabhadrarao; Ozawa, Hiroaki; Kuzume, Akiyoshi; Maharajan, Sivarajakumar; Pobelov, Ilya V; Kwon, Nam Hee; Mohos, Miklos; Broekmann, Peter; Fromm, Katharina M; Haga, Masa-aki; Wandlowski, Thomas

2015-11-14

Here we report the first study on the electrochemical energy storage application of a surface-immobilized ruthenium complex multilayer thin film with anion storage capability. We employed a novel dinuclear ruthenium complex with tetrapodal anchoring groups to build well-ordered redox-active multilayer coatings on an indium tin oxide (ITO) surface using a layer-by-layer self-assembly process. Cyclic voltammetry (CV), UV-Visible (UV-Vis) and Raman spectroscopy showed a linear increase of peak current, absorbance and Raman intensities, respectively with the number of layers. These results indicate the formation of well-ordered multilayers of the ruthenium complex on ITO, which is further supported by the X-ray photoelectron spectroscopy analysis. The thickness of the layers can be controlled with nanometer precision. In particular, the thickest layer studied (65 molecular layers and approx. 120 nm thick) demonstrated fast electrochemical oxidation/reduction, indicating a very low attenuation of the charge transfer within the multilayer. In situ-UV-Vis and resonance Raman spectroscopy results demonstrated the reversible electrochromic/redox behavior of the ruthenium complex multilayered films on ITO with respect to the electrode potential, which is an ideal prerequisite for e.g. smart electrochemical energy storage applications. Galvanostatic charge-discharge experiments demonstrated a pseudocapacitor behavior of the multilayer film with a good specific capacitance of 92.2 F g(-1) at a current density of 10 μA cm(-2) and an excellent cycling stability. As demonstrated in our prototypical experiments, the fine control of physicochemical properties at nanometer scale, relatively good stability of layers under ambient conditions makes the multilayer coatings of this type an excellent material for e.g. electrochemical energy storage, as interlayers in inverted bulk heterojunction solar cell applications and as functional components in molecular electronics applications.

Interfacial microanalysis of rubber tyre-cord adhesion and the influence of cobalt

NASA Astrophysics Data System (ADS)

Fulton, W. Stephen; Smith, Graham C.; Titchener, Keith J.

2004-01-01

The effect of cobalt-containing adhesion promoters on the structure and morphology of rubber-brass and rubber-tyre-cord interfaces before and after ageing has been investigated by X-ray photoelectron spectroscopy (XPS) depth profiling, glancing incidence X-ray diffraction (XRD) and transmission electron microscopy (TEM). The effect the cobalt adhesion promoters had upon the interface morphology as they suppressed the growth of crystalline dendrites normally associated with the ageing process was imaged in TEM using samples prepared by the focused ion beam (FIB) milling technique. XPS depth profiling through the interfaces revealed that different types of adhesion promoter influenced the amount and distribution of cobalt ions in the bonding layer. XRD demonstrated the influence that cobalt had upon the structure of the interface and subsequent crystallinity, with a lesser degree of crystallinity being associated with better adhesion performance. From the results a model for the effect of the Co chemistry of the adhesion promotor has been developed.

A Comprehensive Study of Pristine, Fine-grained, Spinel-rich Inclusions from the Leoville and Efremovka CV3 Chondrites. 1; Petrology

NASA Technical Reports Server (NTRS)

MacPherson, G. J.; Krot, A. N.; Ulyanov, A. A.; Hicks, T.

2002-01-01

Fine-grained spinel-rich CAI from Efremovka and Leoville lack the overprint of Na and Fe metasomatism seen in Allende. They contain spinel, pyroxene, anorthite, and melilite; most have a zoned structure with spinel-rich cores, melilite-rich mantles. Additional information is contained in the original extended abstract.

Improvement of ruthenium based decarboxylation of carboxylic acids

USDA-ARS?s Scientific Manuscript database

The removal of oxygen atoms from biobased carboxylic acids is an attractive route to provide the drop in replacement feedstocks that industry needs to continue to provide high performance products. Through the use of ruthenium catalysis, an efficient method where this process can be accomplished on ...

Release of cobalt and chromium ions into the serum following implantation of the metal-on-metal Maverick-type artificial lumbar disc (Medtronic Sofamor Danek).

PubMed

Zeh, Alexander; Planert, Michael; Siegert, Gabriele; Lattke, Peter; Held, Andreas; Hein, Werner

2007-02-01

Cross-sectional study of 10 patients to measure the serum levels of cobalt and chromium after TDA. To investigate the release of cobalt and chromium ions into the serum following implantation of the metal-on-metal Maverick-type artificial lumbar disc. In total hip endoprosthetics and consequently for TDA (total disc arthroplasty), metal-on-metal combinations are used with the aim of reducing wear debris. In metal-on-metal TDA the release of metal ions has until now been secondary to the main discussion. We investigated the serum cobalt and chromium concentration following implantation of 15 Maverick TDAs (monosegmental L5-S1, n = 5; bisegmental L4-L5 and L5-S1, n = 5; average age, 36.5 years). Five healthy subjects (no metal implants) acted as a control group. The measurements of the metals were carried out using the HITACHI Z-8200 AAS polarized Zeeman atomic absorption spectrometer after an average of 14.8 months. The concentrations of cobalt and chromium ions in the serum amounted on average to 4.75 microg/L (SD, 2.71) for cobalt and 1.10 microg/L (SD, 1.24) for chromium. Compared with control group, both the chromium and cobalt levels in the serum showed significant increases (Mann-Whitney U test, P = 0.0120). At follow-up,the Oswestry Disability Score was on average significantly decreased by 24.4 points (L5-S1) (t test, P < 0.05) and by 26.8 points (L4-S1) (t test, P < 0.05). The improved clinical situation is also represented by a significant decrease of the Visual Analog Pain Scale of 42.2 points after the follow-up (t test, P < 0.05). Significant systemic release of Cr/Co was proven in the serum compared with the control group. The concentrations of Cr/Co measured in the serum are similar in terms of their level to the values measured in THA metal-on-metal combinations or exceed these values given in the literature. Long-term implication of this metal exposure is unknown and should be studied further.

Thermodynamic assessment of the rhodium-ruthenium-oxygen (Rh-Ru-O) system

NASA Astrophysics Data System (ADS)

Gossé, S.; Bordier, S.; Guéneau, C.; Brackx, E.; Domenger, R.; Rogez, J.

2018-03-01

Ruthenium (Ru) and rhodium (Rh) are abundant platinum-group metals formed during burn-up of nuclear fuels. Under normal operating conditions, Rh and Ru accumulate and predominantly form metallic precipitates with other fission products like Mo, Pd and Tc. In the framework of vitrification of high-level nuclear waste, these fission products are poorly soluble in molten glasses. They precipitate as metallic particles and oxide phases. Moreover, these Ru and Rh rich phases strongly depend on temperature and the oxygen fugacity of the glass melt. In case of severe accidental conditions with air ingress, oxidation of the Ru and Rh is possible. At low temperatures (T < 1422 K for rhodium sesquioxide and T < 1815 K for ruthenium dioxide), the formed oxides are relatively stable. On the other hand, at high temperatures (T > 1422 K for rhodium sesquioxide and T > 1815 K for ruthenium dioxide), they may decompose into (Rh)-FCC or (Ru)-HCP metallic phases and radiotoxic volatile gaseous species. A thermodynamic assessment of the Rh-Ru-O system will enable the prediction of: (1) the metallic and oxide phases that form during the vitrification of high-level nuclear wastes and (2) the release of volatile gaseous species during a severe accident. The Calphad method developed herein employs a thermodynamic approach in the investigation of the thermochemistry of rhodium and ruthenium at high temperatures. Current literature on the thermodynamic properties and phase diagram data enables preliminary thermodynamic assessments of the Rh-O and Ru-O systems. Additionally, select compositions in the ternary Rh-Ru-O system underwent experimental tests to complement data found in literature and to establish the phase equilibria in the ternary system.

Determination of ferrous and total iron in refractory spinels

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

Amonette, James E.; Matyas, Josef

2015-12-30

Accurate and precise determination of the redox state of iron (Fe) in spinels presents a significant challenge due to their refractory nature. The resultant extreme conditions needed to obtain complete dissolution generally oxidize some of the Fe(II) initially present and thus prevent the use of colorimetric methods for Fe(II) measurements. To overcome this challenge we developed a hybrid oxidimetric/colorimetric approach, using Ag(I) as the oxidimetric reagent for determination of Fe(II) and 1,10-phenanthroline as the colorimetric reagent for determination of total Fe. This approach, which allows determination of Fe(II) and total Fe on the same sample, was tested on a seriesmore » of four geochemical reference materials and then applied to the analysis of Fe(Ni) spinel crystals isolated from simulated high-level-waste (HLW) glass and of several reagent magnetites. Results for the reference materials were in excellent agreement with published values, with the exception of USGS BIR-1, for which higher Fe(II) values and lower total Fe values were obtained. The Fe(Ni) spinels showed Fe(II) values at the detection limit (ca. 0.05 wt% Fe) and total Fe values slightly higher than obtained by total elemental analysis. For the magnetite samples, total Fe values were in agreement with reference results, but a wide range in Fe(II) values was obtained indicating various degrees of conversion to maghemite.« less

Oriented conductive oxide electrodes on SiO2/Si and glass

DOEpatents

Jia, Quanxi; Arendt, Paul N.

2001-01-01

A thin film structure is provided including a silicon substrate with a layer of silicon dioxide on a surface thereof, and a layer of cubic oxide material deposited upon the layer of silicon dioxide by ion-beam-assisted-deposition, said layer of cubic oxide material characterized as biaxially oriented. Preferably, the cubic oxide material is yttria-stabilized zirconia. Additional thin layers of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide are deposited upon the layer of yttria-stabilized zirconia. An intermediate layer of cerium oxide is employed between the yttria-stabilized zirconia layer and the lanthanum strontium cobalt oxide layer. Also, a layer of barium strontium titanium oxide can be upon the layer of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide. Also, a method of forming such thin film structures, including a low temperature deposition of a layer of a biaxially oriented cubic oxide material upon the silicon dioxide surface of a silicon dioxide/silicon substrate is provided.

Regulation of the Cobalt/Nickel Efflux Operon dmeRF in Agrobacterium tumefaciens and a Link between the Iron-Sensing Regulator RirA and Cobalt/Nickel Resistance

PubMed Central

Dokpikul, Thanittra; Chaoprasid, Paweena; Saninjuk, Kritsakorn; Sirirakphaisarn, Sirin; Johnrod, Jaruwan; Nookabkaew, Sumontha; Mongkolsuk, Skorn

2016-01-01

ABSTRACT The Agrobacterium tumefaciens C58 genome harbors an operon containing the dmeR (Atu0890) and dmeF (Atu0891) genes, which encode a transcriptional regulatory protein belonging to the RcnR/CsoR family and a metal efflux protein belonging to the cation diffusion facilitator (CDF) family, respectively. The dmeRF operon is specifically induced by cobalt and nickel, with cobalt being the more potent inducer. Promoter-lacZ transcriptional fusion, an electrophoretic mobility shift assay, and DNase I footprinting assays revealed that DmeR represses dmeRF transcription through direct binding to the promoter region upstream of dmeR. A strain lacking dmeF showed increased accumulation of intracellular cobalt and nickel and exhibited hypersensitivity to these metals; however, this strain displayed full virulence, comparable to that of the wild-type strain, when infecting a Nicotiana benthamiana plant model under the tested conditions. Cobalt, but not nickel, increased the expression of many iron-responsive genes and reduced the induction of the SoxR-regulated gene sodBII. Furthermore, control of iron homeostasis via RirA is important for the ability of A. tumefaciens to cope with cobalt and nickel toxicity. IMPORTANCE The molecular mechanism of the regulation of dmeRF transcription by DmeR was demonstrated. This work provides evidence of a direct interaction of apo-DmeR with the corresponding DNA operator site in vitro. The recognition site for apo-DmeR consists of 10-bp AT-rich inverted repeats separated by six C bases (5′-ATATAGTATACCCCCCTATAGTATAT-3′). Cobalt and nickel cause DmeR to dissociate from the dmeRF promoter, which leads to expression of the metal efflux gene dmeF. This work also revealed a connection between iron homeostasis and cobalt/nickel resistance in A. tumefaciens. PMID:27235438

Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

NASA Astrophysics Data System (ADS)

Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.; Ketchum, Douglas R.; Ghodssi, Reza

2015-10-01

A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 with solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.

Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

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

Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.

A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 withmore » solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.« less

Cobalt-rhodium heterobimetallic nanoparticle-catalyzed reactions.

PubMed

Park, Ji Hoon; Chung, Young Keun

2008-05-14

Transition metal nanoparticles have attracted a great deal of attention. This review discusses the synthesis of heterobimetallic cobalt-rhodium nanoparticles and their use as catalysts in organic transformations. Co-Rh nanoparticles (Co2Rh2) with a fixed stoichiometry (2 : 2) were easily obtained from Co2Rh2(CO)12. These nanoparticles were quite effective catalysts for carbonylation reactions. Particularly, special focus is paid to the Pauson-Khand-type reaction.

Nitrogen-doped carbon-supported cobalt-iron oxygen reduction catalyst

DOEpatents

Zelenay, Piotr; Wu, Gang

2014-04-29

A Fe--Co hybrid catalyst for oxygen reaction reduction was prepared by a two part process. The first part involves reacting an ethyleneamine with a cobalt-containing precursor to form a cobalt-containing complex, combining the cobalt-containing complex with an electroconductive carbon supporting material, heating the cobalt-containing complex and carbon supporting material under conditions suitable to convert the cobalt-containing complex and carbon supporting material into a cobalt-containing catalyst support. The second part of the process involves polymerizing an aniline in the presence of said cobalt-containing catalyst support and an iron-containing compound under conditions suitable to form a supported, cobalt-containing, iron-bound polyaniline species, and subjecting said supported, cobalt-containing, iron bound polyaniline species to conditions suitable for producing a Fe--Co hybrid catalyst.

Influence of Bi(3+)-doping on the magnetic and Mössbauer properties of spinel cobalt ferrite.

PubMed

Gore, Shyam K; Mane, Rajaram S; Naushad, Mu; Jadhav, Santosh S; Zate, Manohar K; Alothman, Z A; Hui, Biz K N

2015-04-14

The influence of Bi(3+)-doping on the magnetic and Mössbauer properties of cobalt ferrite (CoFe2O4), wherein the Fe(3+) ions are replaced by the Bi(3+) ions to form CoBixFe2-xO4 ferrites, where x = 0.0, 0.05, 0.1, 0.15 or 0.2, has been investigated. The structural and morphological properties of undoped and doped ferrites, synthesized chemically through a self-igniting sol-gel method, are initially screened using X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy measurements. The changes in magnetic moment of ions, their coupling with neighboring ions and cation exchange interactions are confirmed from the Mössbauer spectroscopy analysis. The effect of Bi(3+)-doping on the magnetic properties of CoFe2O4 ferrite is examined from the vibrating sample magnetometry spectra. Saturation magnetization and coercivity values are increased initially and then decreased, as result of Bi(3+)-doping. The obtained results with improved saturation magnetization (from 26.36 to 44.96 emu g(-1)), coercivity (from 1457 to 1863 Oe) and remanence magnetization (from 14.48 to 24.63 emu g(-1)) on 0.1-0.15 mol Bi(3+)-doping of CoBixFe2-xO4 demonstrate the usefulness for magnetic recording and memory devices.

Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries

DOEpatents

Manthiram, Arumugam; Choi, Wonchang

2010-05-18

The present invention includes compositions and methods of making cation-substituted and fluorine-substituted spinel cathode compositions by firing a LiMn_2-y-zLi_yM_zO₄ oxide with NH₄HF₂ at low temperatures of between about 300 and 700.degree. C. for 2 to 8 hours and a .eta. of more than 0 and less than about 0.50, mixed two-phase compositions consisting of a spinel cathode and a layered oxide cathode, and coupling them with unmodified or surface modified graphite anodes in lithium ion cells.

Insertion of lattice strains into ordered LiNi0.5Mn1.5O4 spinel by mechanical stress: A comparison of perfect versus imperfect structures as a cathode for Li-ion batteries

NASA Astrophysics Data System (ADS)

Kozawa, Takahiro; Murakami, Takeshi; Naito, Makio

2016-07-01

The Ni-doped lithium manganese oxide, LiNi0.5Mn1.5O4, has received much attention as a cathode active material in high-energy lithium-ion batteries (LIBs). This active material has two different spinel structures depending on the ordering state of the Ni and Mn ions. The ordered LiNi0.5Mn1.5O4 spinel has an inferior cathode performance than the disordered phase because of its poor electronic conductivity. However, the ordered LiNi0.5Mn1.5O4 spinel possesses the potential advantage of avoiding dissolution of the Mn ion, which is an issue for the disordered spinel. The improvement of cathode performance is important for future applications. Here, we report a unique approach to improve the cathode performance of the ordered LiNi0.5Mn1.5O4 spinel. The mechanical treatment using an attrition-type mill successfully inserted lattice strains into the ordered LiNi0.5Mn1.5O4 spinel structure without a phase transformation to the disordered phase. The insertion of lattice strains by mechanical stresses provided an increased discharge capacity and a decreased charge transfer resistance. This limited crystal structure modification improved the cathode performance. The present work has the potential for application of the mechanically treated ordered LiNi0.5Mn1.5O4 spinel as a cathode for high-energy LIBs.

Petrogenesis and tectonic setting of the Bondla mafic-ultramafic complex, western India: Inferences from chromian spinel chemistry

NASA Astrophysics Data System (ADS)

Ishwar-Kumar, C.; Rajesh, V. J.; Windley, B. F.; Razakamanana, T.; Itaya, T.; Babu, E. V. S. S. K.; Sajeev, K.

2016-11-01

Crustal-scale shear/suture zones hold prime importance because they are one of the critical parameters used for paleogeographic configurations of supercontinental assemblies. The Kumta suture, located on the western margin of peninsular India, has been interpreted as the eastern extension of the Betsimisaraka suture zone of Madagascar. This suture separates the Karwar block (ca. 3200 Ma tonalite-trondhjemite-granodiorite (TTG) and amphibolite) in the west from a quartzite-dominated shelf that overlies ca. 2571 Ma quartzo-feldspathic gneisses of the Dharwar block in the east. The NW/SE-trending Bondla ultramafic-mafic complex, situated in the arc just west of the Kumta suture, comprises gabbro, troctolite, wehrlite, dunite, peridotite, pyroxenite, chromitite and chromian spinel-bearing serpentinite. In this paper, we study the chemistry of Cr-spinels in chromitites and serpentinites to help understand their paleo-tectonic environments. The Cr-spinel in Bondla chromitites and serpentinites shows variations in Cr# [Cr/(Cr + Al)] ranging from 0.54 to 0.58 and 0.56 to 0.64 respectively; also, the Mg# [Mg/(Mg + Fe)] varies from 0.56 to 0.67 and 0.41 to 0.63 respectively. The Cr-spinels in serpentinites have strong chemical zoning with distinctive ferrian chromite rims (Mg# 0.41-0.63), whereas the Cr-spinels in chromitites are generally homogeneous with only occasional weak zoning. The spinel-core crystallization temperature in the serpentinite is estimated to be above 600 °C (the spinel stability field was calculated for equilibrium with Fo90 olivine), which suggests the core composition is chemically unaltered. The Cr-spinels in all studied samples have low-Al2O3 (15-23 wt%) and moderate to high-Cr# (0.54-0.69), suggesting derivation from a supra-subduction zone arc setting. The chemistry of clinopyroxene in serpentinite indicates a wide range of crystallization temperatures from 969 °C to 1241 °C at 1.0 GPa. The calculated parental magma composition was similar to

Chromian spinels in highly altered ultramafic rocks from the Sartohay ophiolitic mélange, Xinjiang, NW China

NASA Astrophysics Data System (ADS)

Qiu, Tian; Zhu, Yongfeng

2018-06-01

The Sartohay ophiolitic mélange is located in western Junggar (Xinjiang province, NW China), which is a major component of the core part of the Central Asian Orogenic Belt (CAOB). Chromian spinels in serpentinite, talc schist, carbonate-talc schist and listwaenite in Sartohay ophiolitic mélange retain primary compositions with Cr# of 0.39-0.65, Mg# = 0.48-0.67, and Fe3+# < 0.08. Chromian spinels in deformed listwaenite were initially transformed into Fe2+-rich chromite during shearing deformation followed by Fe3+-rich chromite at shallow levels. The Cr# and Fe3+# of Fe2+-rich chromite (Cr# = 0.59-0.86, Fe3+# = 0.01-0.12, Mg# = 0.35-0.61) and Fe3+-rich chromite (Cr# = 0.85-1.00, Fe3+# = 0.17-0.38, Mg# < 0.29) increase with decrease of Mg#. We propose a model to illustrate the evolution of chromian spinels in highly altered ultramafic rocks from the Sartohay ophiolitic mélange. Chromian spinels in serpentinite and talc schist were rimmed by Cr-magnetite, which was dissolved completely during transformation from serpentinite/talc schist to listwaenite. Chromian spinels were then transformed into Fe2+-rich chromite in shear zones, which characterized by high fluid/rock ratios. This Fe2+-rich chromite and/or chromian spinels could then be transformed into Fe3+-rich chromite in oxidizing conditions at shallow levels.

New ruthenium carboxylate complexes having a 1-5-. eta. sup 5 -cyclooctadienyl ligand

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

Osakada, Kohtaro; Grohmann, A.; Yamamoto, Akio

1990-07-01

Reaction of 3-butenoic acid with Ru(cod)(cot) (cod) = 1-2-{eta}{sup 2}:5-6-{eta}{sup 2}-cyclooctadiene; cot = 1-6-{eta}{sup 6}-cyclooctatriene in the presence of PMe{sub 3} gives a new ruthenium(II) complex formulated as Ru(1-5-{eta}{sup 5}-C{sub 8}H{sub 11}){eta}{sup 1}(O),{eta}{sup 2}(C,C{prime}-OCOCH{sub 2}CH{double bond}CH{sub 2})(PMe{sub 3}) (1). X-ray crystallography revealed its structure as having a piano-stool coordination around the ruthenium center. Crystals of 1 are tetragonal, space group P4{sub 3}2{sub 1}2, with a = 12.559 (3) {angstrom}, c = 20.455 (4) {angstrom}, and Z = 8. {sup 1}H and {sup 13}C({sup 1}H) NMR spectra of 1 agree well for the structure with the allyl entity of the carboxylatemore » {pi}-bonded through the C{double bond}C double bond to ruthenium.« less

Isolation of genomic DNA using magnetic cobalt ferrite and silica particles.

PubMed

Prodelalová, Jana; Rittich, Bohuslav; Spanová, Alena; Petrová, Katerina; Benes, Milan J

2004-11-12

Adsorption separation techniques as an alternative to laborious traditional methods (e.g., based on phenol extraction procedure) have been applied for DNA purification. In this work we used two types of particles: silica and cobalt ferrite (unmodified or modified with a reagent containing weakly basic aminoethyl groups, aminophenyl groups, or alginic acid). DNA from chicken erythrocytes and DNA isolated from bacteria Lactococcus lactis were used for testing of adsorption/desorption properties of particles. The cobalt ferrite particles modified with different reagents were used for isolation of PCR-ready bacterial DNA from different dairy products.

Molecular Models of Ruthenium(II) Organometallic Complexes

ERIC Educational Resources Information Center

Coleman, William F.

2007-01-01

This article presents the featured molecules for the month of March, which appear in the paper by Ozerov, Fafard, and Hoffman, and which are related to the study of the reactions of a number of "piano stool" complexes of ruthenium(II). The synthesis of compound 2a offers students an alternative to the preparation of ferrocene if they are only…

Stretched-to-compressed-exponential crossover observed in the electrical degradation kinetics of some spinel-metallic screen-printed structures

NASA Astrophysics Data System (ADS)

Balitska, V.; Shpotyuk, O.; Brunner, M.; Hadzaman, I.

2018-02-01

Thermally-induced (170 °C) degradation-relaxation kinetics is examined in screen-printed structures composed of spinel Cu0.1Ni0.1Co1.6Mn1.2O4 ceramics with conductive Ag or Ag-Pd layered electrodes. Structural inhomogeneities due to Ag and Ag-Pd diffusants in spinel phase environment play a decisive role in non-exponential kinetics of negative relative resistance drift. If Ag migration in spinel is inhibited by Pd addition due to Ag-Pd alloy, the kinetics attains stretched exponential behavior with ∼0.58 exponent, typical for one-stage diffusion in structurally-dispersive media. Under deep Ag penetration into spinel ceramics, as for thick films with Ag-layered electrodes, the degradation kinetics drastically changes, attaining features of two-step diffusing process governed by compressed-exponential dependence with power index of ∼1.68. Crossover from stretched- to compressed-exponential kinetics in spinel-metallic structures is mapped on free energy landscape of non-barrier multi-well system under strong perturbation from equilibrium, showing transition with a character downhill scenario resulting in faster than exponential decaying.

Reaction of a (Salen)ruthenium(VI) nitrido complex with thiols. C-H bond activation by (Salen)ruthenium(IV) sulfilamido species.

PubMed

Man, Wai-Lun; Lam, William W Y; Kwong, Hoi-Ki; Peng, Shie-Ming; Wong, Wing-Tak; Lau, Tai-Chu

2010-01-04

The reaction of [Ru(VI)(N)(L)(MeOH)](PF(6)) [1; L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion] with a stoichiometric amount of RSH in CH(3)CN gives the corresponding (salen)ruthenium(IV) sulfilamido species [Ru(IV){N(H)SR}(L)(NCCH(3))](PF(6)) (2a, R = (t)Bu; 2b, R = Ph). Metathesis of 2a with NaN(3) in methanol affords [Ru(IV){N(H)S(t)Bu}(L)(N(3))] (2c). 2a undergoes further reaction with 1 equiv of RSH to afford a (salen)ruthenium(III) sulfilamine species, [Ru(III){N(H)(2)S(t)Bu}(L)(NCCH(3))](PF(6)) (3). On the other hand, 2b reacts with 2 equiv of PhSH to give a (salen)ruthenium(III) ammine species [Ru(III)(NH(3))(L)(NCCH(3))](PF(6)) (4); this species can also be prepared by treatment of 1 with 3 equiv of PhSH. The X-ray structures of 2c and 4 have been determined. Kinetic studies of the reaction of 1 with excess RSH indicate the following schemes: 1 --> 2a --> 3 (R = (t)Bu), 1 --> 2b --> 4 (R = Ph). The conversion of 1 to 2 probably involves nucleophilic attack of RSH at the nitrido ligand, followed by a proton shift. The conversions of 2a to 3 and 2b to 4 are proposed to involve rate-limiting H-atom abstraction from RSH by 2a or 2b. 2a and 2b are also able to abstract H atoms from hydrocarbons with weak C-H bonds. These reactions occur with large deuterium isotope effects; the kinetic isotope effect values for the oxidation of 9,10-dihydroanthracene, 1,4-cyclohexadiene, and fluorene by 2a are 51, 56, and 11, respectively.

Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise.

PubMed

Rapp, Teresa L; Phillips, Susan R; Dmochowski, Ivan J

2016-12-13

The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, light-driven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes that provide a sterically bulky, photolabile moiety for transiently "caging" biologically active molecules. Photouncaging involves the use of visible (1-photon) or near-IR (2-photon) light to break one or more bonds between ruthenium and coordinated ligand(s), which can occur on short time scales and in high quantum yields. In this work we demonstrate the use of a model "caged" acetonitrile complex, Ru(2,2'-bipyridine) 2 (acetonitrile) 2 , or RuMeCN in an advanced synthesis and physical chemistry laboratory. Students made RuMeCN in an advanced synthesis laboratory course and performed UV-vis spectroscopy and electrochemistry. The following semester students investigated RuMeCN photolysis kinetics in a physical chemistry laboratory. These two exercises may also be combined to create a 2-week module in an advanced undergraduate laboratory course.

Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise

PubMed Central

2016-01-01

The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, light-driven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes that provide a sterically bulky, photolabile moiety for transiently “caging” biologically active molecules. Photouncaging involves the use of visible (1-photon) or near-IR (2-photon) light to break one or more bonds between ruthenium and coordinated ligand(s), which can occur on short time scales and in high quantum yields. In this work we demonstrate the use of a model “caged” acetonitrile complex, Ru(2,2′-bipyridine)2(acetonitrile)2, or RuMeCN in an advanced synthesis and physical chemistry laboratory. Students made RuMeCN in an advanced synthesis laboratory course and performed UV–vis spectroscopy and electrochemistry. The following semester students investigated RuMeCN photolysis kinetics in a physical chemistry laboratory. These two exercises may also be combined to create a 2-week module in an advanced undergraduate laboratory course. PMID:28649139

Hydrogenation of Carbon Dioxide to Methane by Ruthenium Nanoparticles in Ionic Liquid.

PubMed

Melo, Catarina I; Szczepańska, Anna; Bogel-Łukasik, Ewa; Nunes da Ponte, Manuel; Branco, Luís C

2016-05-23

The efficient transformation of carbon dioxide into fuels can be an excellent alternative to sequestration. In this work, we describe CO2 hydrogenation to methane in imidazolium-based ionic liquid media, using ruthenium nanoparticles prepared in situ as catalyst. The best yield of methane (69 %) was achieved using 0.24 mol % ruthenium catalyst (in [omim][NTf2 ], 1-octyl-3-methylimidazolium bistrifluoromethanesulfonylimide, at 40 bar of hydrogen pressure plus 40 bar of CO2 pressure, and at 150 °C. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Luminescence Quenching of the Tris(2,2’-bipyrazine) Ruthenium(II) Cation, and Its Monoprotonated Complex.

DTIC Science & Technology

1984-01-01

10 ROA ENT. POCT ASK B.E REPMNGORNTIDOCUMEANDTDR RATIO PAGE UNI UES Yorkhniverity Chemistr Deparment . CNT OL IN OFaIC NAMEtle AND TYPE 2. REPORT &TE0...Alternatively, in view of the high negative charge on the quencher and high positive charge on the excited ruthenium species, some kind of exciplex may be...Southampton S09 5NH White Oak Laboratory United Kingdom Silver Spring, Maryland 20910 Dr. T. Katan Dr. Sam Perone Lockheed Missiles and Chemistry

Cobalt ferrite nano-composite coated on glass by Doctor Blade method for photo-catalytic degradation of an azo textile dye Reactive Red 4: XRD, FESEM and DRS investigations.

PubMed

Habibi, Mohammad Hossein; Parhizkar, Janan

2015-11-05

Cobalt ferrite nano-composite was prepared by hydrothermal route using cobalt nitrate, iron nitrate and ethylene glycol as chelating agent. The nano-composite was coated on glass by Doctor Blade method and annealed at 300 °C. The structural, optical, and photocatalytic properties have been studied by powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and UV-visible spectroscopy (UV-Vis DRS). Powder XRD analysis confirmed formation of CoFe2O4 spinel phase. The estimated particle size from FESEM data was 50 nm. The calculated energy band gaps, obtained by Tauc relation from UV-Vis absorption spectra was 1.3 eV. Photocatalytic degradation of Reactive Red 4 as an azo textile was investigated in aqueous solution under irradiation showed 68.0% degradation of the dye within 100 min. The experimental enhanced activity compare to pure Fe2O3 can be ascribed to the formation of composite, which was mainly attributable to the transfer of electron and hole to the surface of composite and hinder the electron hole recombination. Copyright © 2015 Elsevier B.V. All rights reserved.

Novel catalysts and photoelectrochemical system for solar fuel production

NASA Astrophysics Data System (ADS)

Zhang, Yan

Solar fuel production from abundant raw chemicals such as CO2 and water is highly desired as a clean renewable energy solution for the future. Developing photoelectrochemical cells is viewed as a promising approach to realize this energy conversion and storage process. Efficient and robust oxygen evolution catalyst made from non-precious materials remains a major challenge for such a system. This thesis basically consists of three parts of work, including studies on enhancing the photocatalytic oxygen evolution activity of cobalt-based spinel nanoparticles by manganese3+ substitution, in situ formation of cobalt oxide nanocubanes as highly active catalyst for photocatalytic oxygen evolution reaction, and development of a photoanode-driven photoelectrochemical cell for CO2 reduction with water. The first part of this thesis work devotes efforts in the development and study on cobalt and other transition metal oxide based oxygen evolution catalyst. Photocatalytic oxygen evolution is a critical step for solar fuel production from abundant sources. It poses a significant challenge because it requires an efficient catalyst to bridge the one-electron photon capture process with the four-electron oxygen reaction. Among all the metal oxides, Co3O4 spinel exhibits a high activity as an oxygen evolution catalyst. The results of this work demonstrate that the photocatalytic oxygen evolution activity of Co3O4 spinel can be further enhanced by substituting Co with Mn in the spinel structure. Using a facile hydrothermal approach, Co3O4 spinel nanoparticles as well as Mn-substituted and Ni-substituted Co3O4 spinel nanoparticles with a typical particle size of 5-7 nm were successfully synthesized. The morphology and crystal structures of the as-synthesized nanoparticle catalysts have been carefully examined using various structural characterization techniques, including powder x-ray diffraction (PXRD), transmission electron microscope (TEM), gas adsorption, and x-ray absorption

Syntheses and Characterization of Ruthenium(II) Tetrakis(pyridine)complexes: An Advanced Coordination Chemistry Experiment or Mini-Project

ERIC Educational Resources Information Center

Coe, Benjamin J.

2004-01-01

An experiment for third-year undergraduate a student is designed which provides synthetic experience and qualitative interpretation of the spectroscopic properties of the ruthenium complexes. It involves the syntheses and characterization of several coordination complexes of ruthenium, the element found directly beneath iron in the middle of the…

Lattice parameters and stability of the spinel compounds in relation to the ionic radii and electronegativities of constituting chemical elements.

PubMed

Brik, Mikhail G; Suchocki, Andrzej; Kamińska, Agata

2014-05-19

A thorough consideration of the relation between the lattice parameters of 185 binary and ternary spinel compounds, on one side, and ionic radii and electronegativities of the constituting ions, on the other side, allowed for establishing a simple empirical model and finding its linear equation, which links together the above-mentioned quantities. The derived equation gives good agreement between the experimental and modeled values of the lattice parameters in the considered group of spinels, with an average relative error of about 1% only. The proposed model was improved further by separate consideration of several groups of spinels, depending on the nature of the anion (oxygen, sulfur, selenium/tellurium, nitrogen). The developed approach can be efficiently used for prediction of lattice constants for new isostructural materials. In particular, the lattice constants of new hypothetic spinels ZnRE2O4, CdRE2S4, CdRE2Se4 (RE = rare earth elements) are predicted in the present Article. In addition, the upper and lower limits for the variation of the ionic radii, electronegativities, and their certain combinations were established, which can be considered as stability criteria for the spinel compounds. The findings of the present Article offer a systematic overview of the structural properties of spinels and can serve as helpful guides for synthesis of new spinel compounds.

Modification of Alumina and Spinel Inclusions by Calcium in Liquid Steel

NASA Astrophysics Data System (ADS)

Verma, Neerav

2011-12-01

Steel Cleanliness plays a crucial role in determining steel properties such as toughness, ductility, formability, corrosion resistance and surface quality. The production of clean steel often involves the elimination or chemical and morphological modification of oxide and sulfide inclusions. Along with deteriorating the steel properties, solid inclusions can affect steel castability through nozzle clogging. Nozzle clogging occurs when solid inclusions accumulate in the caster pouring system such as the ladle shroud or submerged entry nozzle (SEN). Thus, it is important to understand how to achieve desired inclusion characteristics (shape, size and chemistry) through the steelmaking process. Among the various practices adopted in industries to counteract the effect of solid inclusions, modification of solid inclusions to liquid or partially liquid state through calcium treatment is one of the methods. Calcium can be used because it has a strong ability to form oxides and sulfides. In Al-killed steels, the most common inclusions are alumina (Al2O3) inclusions, which are solid at steelmaking temperatures. On calcium treatment, solid alumina inclusions are converted to calcium aluminates, which have liquidus temperatures lower than steelmaking temperature (1600°C) [14]. It has been found that alumina inclusions may contain some MgO and such inclusions are termed alumina magnesia spinels (Al2O3.xMgO) [18]. These spinels are more stable than alumina and it has been suggested that they might be more difficult to modify [18]. But, some authors have proposed that MgO can actually help in the liquefaction of inclusions, and have demonstrated successful modification of spinels by Ca treatment [20, 21]. In the present research, the mechanism of transformation of alumina and spinel inclusions upon calcium treatment was studied by characterizing transient evolution of inclusions. A vacuum induction was used for melting, making additions (Al, Al-Mg and CaSi2) and sampling. The

Time-dependent release of cobalt and chromium ions into the serum following implantation of the metal-on-metal Maverick type artificial lumbar disc (Medtronic Sofamor Danek).

PubMed

Zeh, Alexander; Becker, Claudia; Planert, Michael; Lattke, Peter; Wohlrab, David

2009-06-01

In total hip endoprosthetics and consequently for TDA, metal-on-metal combinations are used with the aim of reducing wear debris. In metal-on-metal TDA the release of metal ions has until now been secondary to the main discussion. In order to investigate the ion release following the implantation of the metal-on-metal Maverick type artificial lumbar disc we measured the serum cobalt and chromium concentration following implantation of 15 Maverick TDAs (monosegmental L5/S1, n = 5; bisegmental L4/5 and L5/S1, n = 5; average age 36.5 years). Five healthy subjects (no metal implants) acted as a control group. The two measurements of the metals were carried out using the absorption spectrometry after an average of 14.8 and 36.7 months. In summary, the concentrations of cobalt and chromium ions in the serum at both follow-ups amounted on average to 3.3 microg/l (SD 2.6) for cobalt and 2.2 microg/l (SD 1.5) for chromium. These figures are similar to the figures shown in the literature following the implantation of metal-on-metal THA. After a comparison to the control group, both the chromium and cobalt levels in the serum showed visible increases regarding the first and the second follow-up. As there is still a significant release of cobalt and chromium into the serum after an average follow-up of 36.7 months a persistent release of these ions must be taken into consideration. Despite the evaluation of the systemic and local effects of the release of Cr/Co from orthopaedic implants has not yet been concluded, one should take into consideration an explanation given to patients scheduled for the implantation of a metal-on-metal TDA about these results and the benefits/risks of alternative combinations of gliding contact surfaces.

Mineral resource of the month: cobalt

USGS Publications Warehouse

Shedd, Kim B.

2009-01-01

Cobalt is a metal used in numerous commercial, industrial and military applications. On a global basis, the leading use of cobalt is in rechargeable lithium-ion, nickel-cadmium and nickel-metal hydride battery electrodes. Cobalt use has grown rapidly since the early 1990s, with the development of new battery technologies and an increase in demand for portable electronics such as cell phones, laptop computers and cordless power tools.

The Role of External Inputs and Internal Cycling in Shaping the Global Ocean Cobalt Distribution: Insights From the First Cobalt Biogeochemical Model

NASA Astrophysics Data System (ADS)

Tagliabue, Alessandro; Hawco, Nicholas J.; Bundy, Randelle M.; Landing, William M.; Milne, Angela; Morton, Peter L.; Saito, Mak A.

2018-04-01

Cobalt is an important micronutrient for ocean microbes as it is present in vitamin B12 and is a co-factor in various metalloenzymes that catalyze cellular processes. Moreover, when seawater availability of cobalt is compared to biological demands, cobalt emerges as being depleted in seawater, pointing to a potentially important limiting role. To properly account for the potential biological role for cobalt, there is therefore a need to understand the processes driving the biogeochemical cycling of cobalt and, in particular, the balance between external inputs and internal cycling. To do so, we developed the first cobalt model within a state-of-the-art three-dimensional global ocean biogeochemical model. Overall, our model does a good job in reproducing measurements with a correlation coefficient of >0.7 in the surface and >0.5 at depth. We find that continental margins are the dominant source of cobalt, with a crucial role played by supply under low bottom-water oxygen conditions. The basin-scale distribution of cobalt supplied from margins is facilitated by the activity of manganese-oxidizing bacteria being suppressed under low oxygen and low temperatures, which extends the residence time of cobalt. Overall, we find a residence time of 7 and 250 years in the upper 250 m and global ocean, respectively. Importantly, we find that the dominant internal resupply process switches from regeneration and recycling of particulate cobalt to dissolution of scavenged cobalt between the upper ocean and the ocean interior. Our model highlights key regions of the ocean where biological activity may be most sensitive to cobalt availability.

Potential Temperatures of Sources of MORB, OIB and LIPs Based on AL Partitioning Between Olivine and Spinel

NASA Astrophysics Data System (ADS)

Sobolev, A. V.; Batanova, V. G.; Krasheninnikov, S.; Borisov, A.; Arndt, N.; Kuzmin, D.; Krivolutskaya, N.; Sushevskaya, N.

2013-12-01

Knowledge of potential temperatures of convecting mantle is required for the understanding the global processes on the Earth [1]. The common way to estimate these is the reconstruction of primary melt compositions and liquidus temperatures based on the Fe-Mg partitioning between olivine and melt. This approach requires knowledge of the compositions of primitive melts in equilibrium with olivine alone as well as composition of olivine equilibrium with primary melts. This information is in most cases unavailable or of questionable quality. Here we report a new approach to obtain crystallization temperatures of primary melts based on the olivine-spinel Al-Cr geothermometer [2]. The advantages of this approach are: (1) low rate of diffusion of Al in the olivine, which promises to preserve high magmatic temperatures and (2) common presence of spinel in assemblage with high-Mg olivine. In order to decipher influence of elevated Ti concentrations in spinel we have run several experiments at high temperatures (1400-1200 degree C), atmospheric pressure and controled oxygen fugacity. We also analysed over two thousand spinel inclusions and high-Mg host olivines from different MORB, OIB, LIP and Archean komatiites on the JXA-8230 EPMA at ISTerre, Grenoble, France. Concentrations of Al, Ti, Na, P, Zn, Cr, Mn, Ca, Co, Ni were determined with a precision of 10 ppm (2 standard errors) using a newly developed protocol [3]. When available, we also analysed matrix glass and glass inclusions in olivine and found that temperature estimations from olivine-spinel (Al-Cr) and olivine-melt (Fe-Mg) [4] equilibrium match within (+/-30 degree C). The results show contrasting crystallization temperatures of Mg-rich olivine of the same Fo content from different types of mantle-derived magmas, from the lowest (down to 1220 degree C) for MORB to the highest (up to 1550 degree C) for komatiites and Siberian meimechites. These results match predictions from Fe-Mg olivine-melt equilibrium and

Ruthenium(III) catalyzed oxidation of sugar alcohols by dichloroisocyanuric acid—A kinetic study

NASA Astrophysics Data System (ADS)

Lakshman Kumar, Y.; Venkata Nadh, R.; Radhakrishnamurti, P. S.

2016-02-01

Kinetics of ruthenium(III) catalyzed oxidation of biologically important sugar alcohols (myo-inositol, D-sorbitol, and D-mannitol) by dichloroisocyanuric acid was carried out in aqueous acetic acid—perchloric medium. The reactions were found to be first order in case of oxidant and ruthenium(III). Zero order was observed with the concentrations of sorbitol and mannitol whereas, a positive fractional order was found in the case of inositol concentration. An inverse fractional order was observed with perchloric acid in oxidation of three substrates. Arrhenius parameters were calculated and a plausible mechanism was proposed.

Theoretical analysis of the influence of chelate-ring size and vicinal effects on electronic circular dichroism spectra of cobalt(III) EDDA-type complexes.

PubMed

Wang, Ai; Wang, Yuekui; Jia, Jie; Feng, Lixia; Zhang, Chunxia; Liu, Linlin

2013-06-20

To assess the contributions of configurational and vicinal effects as well as chelate-ring size to rotational strengths, the geometries of a series of cobalt(III) complexes [Co(EDDA-type)(L)](±) with the tetradentate EDDA-type ligands, EDDA (ethylenediamine-N,N'-diacetate), DMEDDA (N,N'-dimethylethylenediamine-N,N'-diacetate), DEEDDA (N,N'-diethylethylenediamine-N,N'-diacetate), and a bidentate ancillary ligand L (L = ethylenediamine, oxalate, carbonate, (S)-alanine, and malonate) in aqueous solution have been optimized at the DFT/B3LYP/6-311++G(2d,p) level of theory. Based on the optimized geometries, the excitation energies and oscillator and rotational strengths have been calculated using the time-dependent density functional theory (TDDFT) method with the same functional and basis set. The calculated circular dichroism (CD) curves are in excellent agreement with the observed ones except for some small red or blue shifts in peak wavelengths. For the influence of chelate-ring size of the bidentate ligands on the CD intensities, a qualitative analysis together with the quantitative TDDFT calculation reveal that it depends on the symmetry of the cobalt-EDDA backbone. For the s-cis-isomers, the influence is negligible due to the perturbation is symmetric. For the uns-cis-isomers, the perturbation is unsymmetric. Since a small ring size means a large perturbation, this leads to the integral CD intensities decreasing with increasing the chelate ring size. The vicinal effects of asymmetric nitrogens incorporate both the substitutent effects and conformational relaxation effects, with the former being dominant. By analyzing the contributions of chiral arrays to rotational strengths, we found that the part of contributions dominated by the S-type chiral nitrogens could be considered as a good measure for the vicinal effects of chiral nitrogens. In addition, we found that the twist form (δ/λ) of the backbone ethylenediamine ring (E-ring) of the coordinated EDDA-type

Phase control of Mn-based spinel films via pulsed laser deposition

DOE PAGES

Feng, Zhenxing; Chen, Xiao; Fister, Timothy T.; ...

2016-07-06

Phase transformations in battery cathode materials during electrochemical-insertion reactions lead to capacity fading and low cycle life. One solution is to keep the same phase of cathode materials during cation insertion-extraction processes. Here, we demonstrate a novel strategy to control the phase and composition of Mn-based spinel oxides for magnesium-ion battery applications through the growth of thin films on lattice-matched substrates using pulsed laser deposition. Materials at two extreme conditions are considered: fully discharged cathode MgMn 2O 4 and fully charged cathode Mn 2O 4. The tetragonal MgMn 2O 4 (MMO) phase is obtained on MgAl 2O 4 substrates, whilemore » the cubic MMO phase is obtained on MgO substrates. Similarly, growth of the empty Mn 2O 4 spinel in the cubic phase is obtained on an MgO substrate. These results demonstrate the ability to control separately the phase of spinel thin films (e.g., tetragonal vs. cubic MMO) at nominally fixed composition, and to maintain a fixed (cubic) phase while varying its composition (MgxMn 2O 4, for x = 0, 1). As a result, this capability provides a novel route to gain insights into the operation of battery electrodes for energy storage applications.« less

Phase control of Mn-based spinel films via pulsed laser deposition

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

Feng, Zhenxing; Chen, Xiao; Fister, Timothy T.

Phase transformations in battery cathode materials during electrochemical-insertion reactions lead to capacity fading and low cycle life. One solution is to keep the same phase of cathode materials during cation insertion-extraction processes. Here, we demonstrate a novel strategy to control the phase and composition of Mn-based spinel oxides for magnesium-ion battery applications through the growth of thin films on lattice-matched substrates using pulsed laser deposition. Materials at two extreme conditions are considered: fully discharged cathode MgMn 2O 4 and fully charged cathode Mn 2O 4. The tetragonal MgMn 2O 4 (MMO) phase is obtained on MgAl 2O 4 substrates, whilemore » the cubic MMO phase is obtained on MgO substrates. Similarly, growth of the empty Mn 2O 4 spinel in the cubic phase is obtained on an MgO substrate. These results demonstrate the ability to control separately the phase of spinel thin films (e.g., tetragonal vs. cubic MMO) at nominally fixed composition, and to maintain a fixed (cubic) phase while varying its composition (MgxMn 2O 4, for x = 0, 1). As a result, this capability provides a novel route to gain insights into the operation of battery electrodes for energy storage applications.« less

Parameters governing ruthenium sawhorse-based decarboxylation of oleic acid

USDA-ARS?s Scientific Manuscript database

Ruthenium-catalyzed decarboxylation of 9-cisoctadecenoic is a path to produce biobased olefins. Here, a mechanistic study of this reaction was undertaken utilizing a closed reaction system and a pressure reactor. The proposed mechanism of an isomerization followed by a decarboxylation reaction was c...

Correlation between structural, magnetic, and dielectric properties of manganese substituted cobalt ferrite

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

Ramana, C. V., E-mail: rvchintalapalle@utep.edu; Kolekar, Y. D.; Kamala Bharathi, K.

2013-11-14

Manganese (Mn) substituted cobalt ferrites (CoFe{sub 2−x}Mn{sub x}O{sub 4}, referred to CFMO) were synthesized and their structural, magnetic, and dielectric properties were evaluated. X-ray diffraction measurements coupled with Rietveld refinement indicate that the CFMO materials crystallize in the inverse cubic spinel phase. Temperature (T = 300 K and 10 K) dependent magnetization (M(H)) measurements indicate the long range ferromagnetic ordering in CoFe{sub 2−x}Mn{sub x}O{sub 4} (x = 0.00–0.15) ferrites. The cubic anisotropy constant (K{sub 1}(T)) and saturation magnetization (M{sub s}(T)) were derived by using the “law of approach” to saturation that describes the field dependence of M(H) for magnetic fields much higher than the coercive fieldmore » (H{sub c}). Saturation magnetization (M{sub s}), obtained from the model, decreases with increasing temperature. For CoFe{sub 2}O{sub 4}, M{sub s} decreases from 3.63 μ{sub B} per formula unit (f.u.) to 3.47 μ{sub B}/f.u. with increasing temperature from 10 to 300 K. CFMO (0.00–0.15) exhibit the similar trend while the magnitude of M{sub s} is dependent on Mn-concentration. M{sub s}-T functional relationship obeys the Bloch's law. The lattice parameter and magnetic moment calculated for CFMO reveals that Mn ions occupying the Fe and Co position at the octahedral site in the inverse cubic spinel phase. The structure and magnetism in CFMO are further corroborated by bond length and bond angle calculations. The dielectric constant dispersion of CFMO in the frequency range of 20 Hz–1 MHz fits to the modified Debye's function with more than one ion contributing to the relaxation. The relaxation time and spread factor derived from modeling the experimental data are ∼10{sup −4} s and ∼0.35(±0.05), respectively.« less

Palladium-cobalt particles as oxygen-reduction electrocatalysts

DOEpatents

Adzic, Radoslav [East Setauket, NY; Huang, Tao [Manorville, NY

2009-12-15

The present invention relates to palladium-cobalt particles useful as oxygen-reducing electrocatalysts. The invention also relates to oxygen-reducing cathodes and fuel cells containing these palladium-cobalt particles. The invention additionally relates to methods for the production of electrical energy by using the palladium-cobalt particles of the invention.

Mononuclear ruthenium polypyridine complexes that catalyze water oxidation

DOE PAGES

Tong, Lianpeng; Thummel, Randolph P.

2016-08-05

Over the past decade, significant advances have been made in the development of molecular water oxidation catalysts (WOCs) in the context of developing a system that would accomplish artificial photosynthesis. Mononuclear ruthenium complexes with polypyridine ligands have drawn considerable attention in this regard, due to their high catalytic activity and relatively simple structure. In this perspective review, we will discuss mononuclear Ru polypyridine WOCs by organizing them into four groups according to their ligand environments. Each group will be discussed with regard to three fundamental questions: first, how does the catalyst initiate O–O bond formation? Second, which step in themore » catalytic cycle is rate-determining? Third, how efficient is the catalyst according to the specific descriptors such as turnover frequency? All discussion is based on the high-valent ruthenium intermediates that are proposed in the catalytic cycle according to experimental observation and theoretical simulation. Two fundamental mechanisms are set forth. An acid–base mechanism that involves the attack of a water molecule on the oxo of a high valent Ru=O species to form the O–O bond. Subsequent steps lead to dissociation of O 2 and rehydration of the metal center. A second mechanism involves the formation of a Ru–O˙ radical species, two of which then couple to form a Ru–O–O–Ru species that can release O 2 afterwards. The acid–base mechanism appears to be more common and mechanistic differences could result from variation directly related to polypyridine ligand structures. Thus, understanding how electronic, steric, and conformational properties can effect catalyst performance will lead to the rational design of more effective WOCs with not only ruthenium but also other transition metals.« less

Synthesis of cobalt-containing mesoporous catalysts using the ultrasonic-assisted “pH-adjusting” method: Importance of cobalt species in styrene oxidation

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

Li, Baitao, E-mail: btli@scut.edu.cn; Zhu, Yanrun; Jin, Xiaojing

2015-01-15

Cobalt-containing SBA-15 and MCM-41 (Co-SBA-15 and Co-MCM-41) mesoporous catalysts were prepared via ultrasonic-assisted “pH-adjusting” technique in this study. Their physiochemical structures were comprehensively characterized and correlated with catalytic activity in oxidation of styrene. The nature of cobalt species depended on the type of mesoporous silica as well as pH values. The different catalytic performance between Co-SBA-15 and Co-MCM-41 catalysts originated from cobalt species. Cobalt species were homogenously incorporated into the siliceous framework of Co-SBA-15 in single-site Co(II) state, while Co{sub 3}O{sub 4} particles were loaded on Co-MCM-41 catalysts. The styrene oxidation tests showed that the single-site Co(II) state was moremore » beneficial to the catalytic oxidation of styrene. The higher styrene conversion and benzaldehyde selectivity over Co-SBA-15 catalysts were mainly attributed to single-site Co(II) state incorporated into the framework of SBA-15. The highest conversion of styrene (34.7%) with benzaldehyde selectivity of 88.2% was obtained over Co-SBA-15 catalyst prepared at pH of 7.5, at the mole ratio of 1:1 (styrene to H{sub 2}O{sub 2}) at 70 °C. - Graphical abstract: Cobalt-containing mesoporous silica catalysts were developed via ultrasonic-assisted “pH-adjusting” technique. Compared with Co{sub 3}O{sub 4} in Co-MCM-41, the single-site Co(II) state in Co-SBA-15 was more efficient for the styrene oxidation. - Highlights: • Fast and cost-effective ultrasonic technique for preparing mesoporous materials. • Incorporation of Co via ultrasonic irradiation and “pH-adjusting”. • Physicochemical comparison between Co-SBA-15 and Co-MCM-41. • Correlation of styrene oxidation activity and catalyst structural property.« less

A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: Aqueous hydration of nitriles to amides

EPA Science Inventory

One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this...

Self-diffusion of magnesium in spinel and in equilibrium melts - Constraints on flash heating of silicates

NASA Technical Reports Server (NTRS)

Sheng, Y. J.; Wasserburg, G. J.; Hutcheon, I. D.

1992-01-01

An isotopic tracer is used to measure Mg self-diffusion in spinel and coexisting melt at bulk chemical equilibrium. The diffusion coefficients were calculated from the measured isotope profiles using a model that includes the complementary diffusion of Mg-24, Mg-25, and Mg-26 in both phases with the constraint that the Mg content of each phase is constant. The activation energy and preexponential factor for Mg self-diffusion in spinel are, respectively, 384 +/- 7 kJ and 74.6 +/- 1.1 sq cm/s. These data indicate Mg diffusion in spinel is much slower than previous estimates. The activation energy for Mg self-diffusion in coexisting melt is 343 +/- 25 kJ and the preexponential factor is 7791.9 +/- 1.3 sq cm/s. These results are used to evaluate cooling rates of plagioclase-olivine inclusions (POIs) in the Allende meteorite. Given a maximum melting temperature for POIs of about 1500 C, these results show that a 1-micron radius spinel would equilibrate isotopically with a melt within about 60 min.

Spinel-structured metal oxide on a substrate and method of making same by molecular beam epitaxy

DOEpatents

Chambers, Scott A.

2006-02-21

A method of making a spinel-structured metal oxide on a substrate by molecular beam epitaxy, comprising the step of supplying activated oxygen, a first metal atom flux, and at least one other metal atom flux to the surface of the substrate, wherein the metal atom fluxes are individually controlled at the substrate so as to grow the spinel-structured metal oxide on the substrate and the metal oxide is substantially in a thermodynamically stable state during the growth of the metal oxide. A particular embodiment of the present invention encompasses a method of making a spinel-structured binary ferrite, including Co ferrite, without the need of a post-growth anneal to obtain the desired equilibrium state.

Half-sandwich ruthenium(II) biotin conjugates as biological vectors to cancer cells.

PubMed

Babak, Maria V; Plażuk, Damian; Meier, Samuel M; Arabshahi, Homayon John; Reynisson, Jóhannes; Rychlik, Błażej; Błauż, Andrzej; Szulc, Katarzyna; Hanif, Muhammad; Strobl, Sebastian; Roller, Alexander; Keppler, Bernhard K; Hartinger, Christian G

2015-03-23

Ruthenium(II)-arene complexes with biotin-containing ligands were prepared so that a novel drug delivery system based on tumor-specific vitamin-receptor mediated endocytosis could be developed. The complexes were characterized by spectroscopic methods and their in vitro anticancer activity in cancer cell lines with various levels of major biotin receptor (COLO205, HCT116 and SW620 cells) was tested in comparison with the ligands. In all cases, coordination of ruthenium resulted in significantly enhanced cytotoxicity. The affinity of Ru(II) -biotin complexes to avidin was investigated and was lower than that of unmodified biotin. Hill coefficients in the range 2.012-2.851 suggest strong positive cooperation between the complexes and avidin. To estimate the likelihood of binding to the biotin receptor/transporter, docking studies with avidin and streptavidin were conducted. These explain, to some extent, the in vitro anticancer activity results and support the conclusion that these novel half-sandwich ruthenium(II)-biotin conjugates may act as biological vectors to cancer cells, although no clear relationship between the cellular Ru content, the cytotoxicity, and the presence of the biotin moiety was observed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of thermobarometry for spinel lherzolite fragments in alkali basalts

NASA Astrophysics Data System (ADS)

Ozawa, Kazuhito; Youbi, Nasrrddine; Boumehdi, Moulay Ahmed; McKenzie, Dan; Nagahara, Hiroko

2017-04-01

Geothermobarometry of solid fragments in kimberlite and alkali basalts, generally called "xenoliths", provides information on thermal and chemical structure of lithospheric and asthenospheric mantle, based on which various chemical, thermal, and rheological models of lithosphere have been constructed (e.g., Griffin et al., 2003; McKenzie et al., 2005; Ave Lallemant et al., 1980). Geothermobarometry for spinel-bearing peridotite fragments, which are frequently sampled from Phanerozoic provinces in various tectonic environments (Nixon and Davies, 1987), has essential difficulties, and it is usually believed that appropriated barometers do not exist for them (O'Reilly et al., 1997; Medaris et al., 1999). Ozawa et al. (2016; EGU) proposed a method of geothermobarometry for spinel lherzolite fragments. They applied the method to mantle fragments in alkali basalts from Bou Ibalhatene maars in the Middle Atlas in Morocco (Raffone et al. 2009; El Azzouzi et al., 2010; Witting et al., 2010; El Messbahi et al., 2015). Ozawa et al. (2016) obtained 0.5GPa pressure difference (1.5-2.0GPa) for 100°C variation in temperatures (950-1050°C). However, it is imperative to verify the results on the basis of completely independent data. There are three types of independent information: (1) time scale of solid fragment extraction, which may be provided by kinetics of reactions induced by heating and/or decompression during their entrapment in the host magma and transportation to the Earth's surface (Smith, 1999), (2) depth of the host basalt formation, which may be provided by the petrological and geochemical studies of the host basalts, and (3) lithosphere-asthenosphere boundary depths, which may be estimated by geophysical observations. Among which, (3) is shown to be consistent with the result in Ozawa et al. (2016). We here present that the estimated thermal structure just before the fragment extraction is fully supported by the information of (1) and (2). Spera (1984) reviewed

Structural and magnetic properties of ytterbium substituted spinel ferrites

NASA Astrophysics Data System (ADS)

Alonizan, Norah H.; Qindeel, Rabia

2018-06-01

Chemical co-precipitation route adopted to synthesize the magnetic materials. In the present work, iron is replaced by ytterbium ion in manganese-based spinel ferrites. The yield chemically represented by MnYb x Fe2- x O4 ( x = 0.00, 0.025, 0.05, 0.075, 0.10) and its structural, magnetic and electrical properties were observed. The cubic structure of spinel ferrites was confirmed by X-ray diffraction analysis. Spherically shaped grains were perceived in SEM pictures and size lessened with the growth of ytterbium concentration. SEM profile also shows little irregularity in spherical particles. The substitution of ytterbium (Yb) results in the enhancement of electrical resistivity. The resistivity was reduced with the gradual increase in temperature from 303 to 693 K. The trend of activation energy was found to be similar to that of room temperature resistivity. The coercivity of samples was raised with Yb-ion substitution while saturation magnetization and remanence reduced.

Cobalt: for strength and color

USGS Publications Warehouse

Boland, Maeve A.; Kropschot, S.J.

2011-01-01

Cobalt is a shiny, gray, brittle metal that is best known for creating an intense blue color in glass and paints. It is frequently used in the manufacture of rechargeable batteries and to create alloys that maintain their strength at high temperatures. It is also one of the essential trace elements (or "micronutrients") that humans and many other living creatures require for good health. Cobalt is an important component in many aerospace, defense, and medical applications and is a key element in many clean energy technologies. The name cobalt comes from the German word kobold, meaning goblin. It was given this name by medieval miners who believed that troublesome goblins replaced the valuable metals in their ore with a substance that emitted poisonous fumes when smelted. The Swedish chemist Georg Brandt isolated metallic cobalt-the first new metal to be discovered since ancient times-in about 1735 and identified some of its valuable properties.

Evaluation of humidity sensing properties of TMBHPET thin film embedded with spinel cobalt ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Zafar, Qayyum; Azmer, Mohamad Izzat; Al-Sehemi, Abdullah G.; Al-Assiri, Mohammad S.; Kalam, Abul; Sulaiman, Khaulah

2016-07-01

In this study, we report the enhanced sensing parameters of previously reported TMBHPET-based humidity sensor. Significant improved sensing performance has been demonstrated by coupling of TMBHPET moisture sensing thin film with cobalt ferrite nanoparticles (synthesized by eco-benign ultrasonic method). The mean size of CoFe2O4 nanoparticles has been estimated to be 6.5 nm. It is assumed that the thin film of organic-ceramic hybrid matrix (TMBHPET:CoFe2O4) is a potential candidate for humidity sensing utility by virtue of its high specific surface area and porous surface morphology (as evident from TEM, FESEM, and AFM images). The hybrid suspension has been drop-cast onto the glass substrate with preliminary deposited coplanar aluminum electrodes separated by 40 µm distance. The influence of humidity on the capacitance of the hybrid humidity sensor (Al/TMBHPET:CoFe2O4/Al) has been investigated at three different frequencies of the AC applied voltage ( V rms 1 V): 100 Hz, 1 kHz, and 10 kHz. It has been observed that at 100 Hz, under a humidity of 99 % RH, the capacitance of the sensor increased by 2.61 times, with respect to 30 % RH condition. The proposed sensor exhibits significantly improved sensitivity 560 fF/ % RH at 100 Hz, which is nearly 7.5 times as high as that of pristine TMBHPET-based humidity sensor. Further, the capacitive sensor exhibits improved dynamic range (30-99 % RH), small hysteresis ( 2.3 %), and relatively quicker response and recovery times ( 12 s, 14 s, respectively). It is assumed that the humidity response of the sensor is associated with the diffusion kinetics of water vapors and doping of the semiconductor nanocomposite by water molecules.

Complex of transferrin with ruthenium for medical applications. [Ru 97, Ru 103

DOEpatents

Richards, P.; Srivastava, S.C.; Meinken, G.E.

1980-11-03

A novel Ruthenium-transferrin complex, prepared by reacting iron-free human transferrin dissolved in a sodium acetate solution at pH 7 with ruthenium by heating at about 40/sup 0/C for about 2 hours, and purifying said complex by means of gel chromatography with pH 7 sodium acetate as eluent. The mono- or di-metal complex produced can be used in nuclear medicine in the diagnosis and/or treatment of tumors and abscesses. Comparitive results with Ga-67-citrate, which is the most widely used tumor-localizing agent in nuclear medicine, indicate increased sensitivity of detection and greater tumor uptake with the Ru-transferrin complex.

Electrooxidative Ruthenium-Catalyzed C-H/O-H Annulation by Weak O-Coordination.

PubMed

Qiu, Youai; Tian, Cong; Massignan, Leonardo; Rogge, Torben; Ackermann, Lutz

2018-05-14

Electrocatalysis has been identified as a powerful strategy for organometallic catalysis, and yet electrocatalytic C-H activation is restricted to strongly N-coordinating directing groups. The first example of electrocatalytic C-H activation by weak O-coordination is presented, in which a versatile ruthenium(II) carboxylate catalyst enables electrooxidative C-H/O-H functionalization for alkyne annulations in the absence of metal oxidants; thereby exploiting sustainable electricity as the sole oxidant. Mechanistic insights provide strong support for a facile organometallic C-H ruthenation and an effective electrochemical reoxidation of the key ruthenium(0) intermediate. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coupled ferroelectric polarization and magnetization in spinel FeCr2S4

PubMed Central

Lin, L.; Zhu, H. X.; Jiang, X. M.; Wang, K. F.; Dong, S.; Yan, Z. B.; Yang, Z. R.; Wan, J. G.; Liu, J.-M.

2014-01-01

One of the core issues for multiferroicity is the strongly coupled ferroelectric polarization and magnetization, while so far most multiferroics have antiferromagnetic order with nearly zero magnetization. Magnetic spinel compounds with ferrimagnetic order may be alternative candidates offering large magnetization when ferroelectricity can be activated simultaneously. In this work, we investigate the ferroelectricity and magnetism of spinel FeCr2S4 in which the Fe2+ sublattice and Cr3+ sublattice are coupled in antiparallel alignment. Well defined ferroelectric transitions below the Fe2+ orbital ordering termperature Too = 8.5 K are demonstrated. The ferroelectric polarization has two components. One component arises mainly from the noncollinear conical spin order associated with the spin-orbit coupling, which is thus magnetic field sensitive. The other is probably attributed to the Jahn-Teller distortion induced lattice symmetry breaking, occuring below the orbital ordering of Fe2+. Furthermore, the coupled ferroelectric polarization and magnetization in response to magnetic field are observed. The present work suggests that spinel FeCr2S4 is a multiferroic offering both ferroelectricity and ferrimagnetism with large net magnetization. PMID:25284432

Frequency domain kinetic of positron-electron annihilation in the MgO-Al2O3 spinel-type ceramics

NASA Astrophysics Data System (ADS)

Fl'unt, Orest; Klym, Halyna; Ingram, Adam

2018-03-01

In this work, the kinetic of positron-electron annihilation in the MgO-Al2O3 spinel-type ceramics sintered at different temperatures (1100, 1200 and 1400 °C) has been calculated and analyzed in a frequency domain. The spectra of real (in-phase) and imaginary (quadrature) components of positron-electron annihilation kinetic have been obtained numerically from usual temporal characteristics using integral Fourier transform. The numerical calculations were carried out using cubic spline interpolation of the pulse characteristics of MgO-Al2O3 ceramics in time domain with following analytical calculations of integrals. The obtained spectra as real so imaginary part of MgO-Al2O3 ceramics in frequency domain almost good obey a Debye law denying correlation between elementary positron annihilation processes. Complex diagrams of frequency domain responses of as-prepared samples have a shape of semicircles with close characteristic frequencies. Some deviation on low-frequency side of the semicircles is observed confirming an availability of longer time kinetic processes. Sintering temperature dependencies of the relaxation times and characteristic frequencies of positron-electron annihilation processes have been obtained. It is shown that position of large maxima on the frequency dependencies of imaginary part corresponds to fast average relaxation lifetime representing the most intensive interaction process of positrons with small cavity traps in solids.

Platinum-ruthenium-palladium alloys for use as a fuel cell catalyst

DOEpatents

Gorer, Alexander

2002-01-01

A noble metal alloy composition for a fuel cell catalyst, a ternary alloy composition containing platinum, ruthenium and palladium. The alloy shows increased activity as compared to well-known catalysts.

Columnar-Structured Mg-Al-Spinel Thermal Barrier Coatings (TBCs) by Suspension Plasma Spraying (SPS)

NASA Astrophysics Data System (ADS)

Schlegel, N.; Ebert, S.; Mauer, G.; Vaßen, R.

2015-01-01

The suspension plasma spraying (SPS) process has been developed to permit the feeding of sub-micrometer-sized powder into the plasma plume. In contrast to electron beam-physical vapor deposition and plasma spray-physical vapor deposition, SPS enables the cost-efficient deposition of columnar-structured coatings. Due to their strain tolerance, these coatings play an important role in the field of thermal barrier coatings (TBCs). In addition to the cost-efficient process, attention was turned to the TBC material. Nowadays, yttria partially stabilized zirconia (YSZ) is used as standard TBC material. However, its long-term application at temperatures higher than 1200 °C is problematic. At these high temperatures, phase transitions and sintering effects lead to the degradation of the TBC system. To overcome those deficits of YSZ, Mg-Al-spinel was chosen as TBC material. Even though it has a lower melting point (~2135 °C) and a higher thermal conductivity (~2.5 W/m/K) than YSZ, Mg-Al-spinel provides phase stability at high temperatures in contrast to YSZ. The Mg-Al-spinel deposition by SPS resulted in columnar-structured coatings, which have been tested for their thermal cycling lifetime. Furthermore, the influence of substrate cooling during the spraying process on thermal cycling behavior, phase composition, and stoichiometry of the Mg-Al-spinel has been investigated.

Selected aspects of the action of cobalt ions in the human body.

PubMed

Czarnek, Katarzyna; Terpiłowska, Sylwia; Siwicki, Andrzej K

2015-01-01

Cobalt is widespread in the natural environment and can be formed as an effect of anthropogenic activity. This element is used in numerous industrial applications and nuclear power plants. Cobalt is an essential trace element for the human body and can occur in organic and inorganic forms. The organic form is a necessary component of vitamin B12 and plays a very important role in forming amino acids and some proteins in nerve cells, and in creating neurotransmitters that are indispensable for correct functioning of the organism. Its excess or deficiency will influence it unfavourably. Salts of cobalt have been applied in medicine in the treatment of anaemia, as well as in sport as an attractive alternative to traditional blood doping. Inorganic forms of cobalt present in ion form, are toxic to the human body, and the longer they are stored in the body, the more changes they cause in cells. Cobalt gets into the body in several ways: firstly, with food; secondly by the respiratory system; thirdly, by the skin; and finally, as a component of biomaterials. Cobalt and its alloys are fundamental components in orthopaedic implants and have been used for about 40 years. The corrosion of metal is the main problem in the construction of implants. These released metal ions may cause type IV inflammatory and hypersensitivity reactions, and alternations in bone modelling that lead to aseptic loosening and implant failure. The ions of cobalt released from the surface of the implant are absorbed by present macrophages, which are involved in many of the processes associated with phagocytose orthopaedic biomaterials particles and release pro-inflammatory mediators such as interleukin-1 (IL-1), interleukin-6 (IL-6), tumour necrosis factor α (TNF-α), and prostaglandin.

Selected aspects of the action of cobalt ions in the human body

PubMed Central

Terpiłowska, Sylwia; Siwicki, Andrzej K.

2015-01-01

Cobalt is widespread in the natural environment and can be formed as an effect of anthropogenic activity. This element is used in numerous industrial applications and nuclear power plants. Cobalt is an essential trace element for the human body and can occur in organic and inorganic forms. The organic form is a necessary component of vitamin B12 and plays a very important role in forming amino acids and some proteins in nerve cells, and in creating neurotransmitters that are indispensable for correct functioning of the organism. Its excess or deficiency will influence it unfavourably. Salts of cobalt have been applied in medicine in the treatment of anaemia, as well as in sport as an attractive alternative to traditional blood doping. Inorganic forms of cobalt present in ion form, are toxic to the human body, and the longer they are stored in the body, the more changes they cause in cells. Cobalt gets into the body in several ways: firstly, with food; secondly by the respiratory system; thirdly, by the skin; and finally, as a component of biomaterials. Cobalt and its alloys are fundamental components in orthopaedic implants and have been used for about 40 years. The corrosion of metal is the main problem in the construction of implants. These released metal ions may cause type IV inflammatory and hypersensitivity reactions, and alternations in bone modelling that lead to aseptic loosening and implant failure. The ions of cobalt released from the surface of the implant are absorbed by present macrophages, which are involved in many of the processes associated with phagocytose orthopaedic biomaterials particles and release pro-inflammatory mediators such as interleukin-1 (IL-1), interleukin-6 (IL-6), tumour necrosis factor α (TNF-α), and prostaglandin. PMID:26557039

Study on volatilization mechanism of ruthenium tetroxide from nitrosyl ruthenium nitrate by using mass spectrometer

NASA Astrophysics Data System (ADS)

Kato, Tetsuya; Usami, Tsuyoshi; Tsukada, Takeshi; Shibata, Yuki; Kodama, Takashi

2016-10-01

In a cooling malfunction accident of a high-level liquid waste (HLLW) tank, behavior of ruthenium (Ru) attracts much attention, since Ru could be oxidized to a volatile chemical form in the boiling and drying of HLLW, and part of radioactive Ru can potentially be released to the environment. In this study, nitrosyl Ru nitrate (Ru(NO)(NO3)3) dissolved in nitric acid (HNO3), which is commonly contained in a simulated HLLW, was dried and heated up to 723 K, and the evolved gas was introduced into a mass spectrometer. The well-known volatile species, ruthenium tetroxide (RuO4) was detected in a temperature range between 390 K and 500 K with the peak top around 440 K. Various gases such as HNO3, nitrogen dioxide (NO2), nitrogen monoxide (NO) also evolved due to evaporation of the nitric acid and decomposition of the nitrate ions. The ion current of RuO4 seems to increase with the increasing decomposition of nitrate, while the evaporation of HNO3 decreases. More volatilization of RuO4 was observed from the HNO3 solution containing not only Ru(NO)(NO3)3 but also cerium nitrate (Ce(NO3)3·6H2O) which was added for extra supply of nitrate ion, compared with that from the HNO3 solution containing only Ru(NO)(NO3)3. These experimental results suggest that Ru could be oxidized to form RuO4 by the nitrate ion as well as HNO3.

COMPLEX RUTHENIUM ACIDO-NITROS COMPOUNDS (in Russian)

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

Zvyagintsev, O.E.; Starostin, S.M.

1961-06-01

The chemical nature of the water in the complex ruthenium acidonitroso compounds is studied by measuring certain acid properties, reactions, and behaviors of the compounds in aqueous solution. The dependence of molecular electrical conductivity on time and dilution, variations of specific electroconductivity, the optical density, and the light absorption of the compounds at 200 to 800 m mu wave range were investigated and the dissociation constants were calculated. (R.V.J.)

Cobalt: A vital element in the aircraft engine industry

NASA Technical Reports Server (NTRS)

Stephens, J. R.

1981-01-01

Recent trends in the United States consumption of cobalt indicate that superalloys for aircraft engine manufacture require increasing amounts of this strategic element. Superalloys consume a lion's share of total U.S. cobalt usage which was about 16 million pounds in 1980. In excess of 90 percent of the cobalt used in this country was imported, principally from the African countries of Zaire and Zambia. Early studies on the roles of cobalt as an alloying element in high temperature alloys concentrated on the simple Ni-Cr and Nimonic alloy series. The role of cobalt in current complex nickel base superalloys is not well defined and indeed, the need for the high concentration of cobalt in widely used nickel base superalloys is not firmly established. The current cobalt situation is reviewed as it applies to superalloys and the opportunities for research to reduce the consumption of cobalt in the aircraft engine industry are described.

Characteristics of polyaniline cobalt supported catalysts for epoxidation reactions.

PubMed

Kowalski, Grzegorz; Pielichowski, Jan; Grzesik, Mirosław

2014-01-01

A study of polyaniline (PANI) doping with various cobalt compounds, that is, cobalt(II) chloride, cobalt(II) acetate, and cobalt(II) salen, is presented. The catalysts were prepared by depositing cobalt compounds onto the polymer surface. PANI powders containing cobalt ions were obtained by one- or two-step method suspending PANI in the following acetonitrile/acetic acid solution or acetonitrile and then acetic acid solution. Moreover different ratios of Co(II) : PANI were studied. Catalysts obtained with both methods and at all ratios were investigated using various techniques including AAS and XPS spectroscopy. The optimum conditions for preparation of PANI/Co catalysts were established. Catalytic activity of polyaniline cobalt(II) supported catalysts was tested in dec-1-ene epoxidation with molecular oxygen at room temperature. The relationship between the amount of cobalt species, measured with both AAS and XPS techniques, and the activity of PANI-Co catalysts has been established.

Characteristics of Polyaniline Cobalt Supported Catalysts for Epoxidation Reactions

PubMed Central

Kowalski, Grzegorz; Pielichowski, Jan; Grzesik, Mirosław

2014-01-01

A study of polyaniline (PANI) doping with various cobalt compounds, that is, cobalt(II) chloride, cobalt(II) acetate, and cobalt(II) salen, is presented. The catalysts were prepared by depositing cobalt compounds onto the polymer surface. PANI powders containing cobalt ions were obtained by one- or two-step method suspending PANI in the following acetonitrile/acetic acid solution or acetonitrile and then acetic acid solution. Moreover different ratios of Co(II) : PANI were studied. Catalysts obtained with both methods and at all ratios were investigated using various techniques including AAS and XPS spectroscopy. The optimum conditions for preparation of PANI/Co catalysts were established. Catalytic activity of polyaniline cobalt(II) supported catalysts was tested in dec-1-ene epoxidation with molecular oxygen at room temperature. The relationship between the amount of cobalt species, measured with both AAS and XPS techniques, and the activity of PANI-Co catalysts has been established. PMID:24701183

Spinel-Bearing, Al-Rich Chrondrules in the Unequilibrated Ordinary Chondrite NWA7402

NASA Technical Reports Server (NTRS)

Ross, D. K.; Simon, J. I.; Cato, M. J.

2017-01-01

Several Al-rich chondrules (ARCs) have been discovered in the unequilibrated ordinary chondrite NWA7402. Two of these three ARCs are spinel-bearing. Here we have characterized these unusual chondrules with respect to their mineralogy and bulk compositions. These objects will be targets for future O and Mg isotope analysis. NWA7402 is clearly unequilibrated, with wide ranges of olivine compositions in chondrules (Fo99-Fo70, excluding rims). Chromium-oxide contents in olivine, and Raman organic spectral parameters support the classification of this meteorite as petrologic type 3.1 [1]. NWA7402 is similar to, and could be paired with NWA5717, in that they both possess light and dark lithologies.

Endoresection with adjuvant ruthenium brachytherapy for selected uveal melanoma patients - the Tuebingen experience.

PubMed

Süsskind, Daniela; Dürr, Carina; Paulsen, Frank; Kaulich, Theodor; Bartz-Schmidt, Karl U

2017-12-01

To evaluate the treatment of selected patients with uveal melanoma with endoresection and adjuvant ruthenium brachytherapy. Thirty-five patients with uveal melanoma not suitable for ruthenium plaque monotherapy were treated with endoresection and adjuvant ruthenium brachytherapy between January 2001 and October 2013. Recurrence-free survival, globe retention, course of visual acuity (VA), occurrence of therapy-related complications and metastasis-free and overall survival were analysed retrospectively. Eight patients (22.9%) had a tumour recurrence after a median follow-up of 49.5 months (range: 21-134 months). Enucleation was necessary in eight patients. Thirty-two patients (91%) had a loss of VA with a median loss of nine lines (range: 0 to -39 lines); VA was stable in three patients and no patients had a gain in VA. Four patients (11.4%) developed radiation retinopathy. Metastases were detected in seven patients (20.0%) during follow-up. The occurrence of metastasis was significantly associated with monosomy 3 (p < 0.0001). Twenty-four patients (68.6%) were alive at the end of follow-up. Five patients (14.3%) died because of uveal melanoma (UM) metastasis. Endoresection with adjuvant ruthenium brachytherapy is an option for selected patients with UM who cannot be treated with brachytherapy as monotherapy. About two-thirds of eyes can be retained long term without recurrences. Visual acuity cannot be maintained in most cases, and may even decrease considerably. Radiation complications are comparatively rare and not a significant problem. © 2016 Acta Ophthalmologica Scandinavica Foundation. Published by John Wiley & Sons Ltd.

Characterization of dipole defects in MgAl2O4 spinel

NASA Astrophysics Data System (ADS)

Carvalhaes, R. P. M.; da Rocha, M. S. F.; de Souza, S. S.; Blak, A. R.

2005-01-01

Dipole defects in gamma-irradiated and thermal treated MgAl2O4 samples have been studied through thermally stimulated depolarisation currents(TSDC) technique and computer modelling methods. The presence of TSDC bands varies from sample to sample and some crystals do not present any band. The origin of these bands has been investigated in several different samples. In the spectra of spinels showing TSDC peaks, three bands at 130K, 160K and 320K are observed. The peaks at 130K and 160K have been attributed to dipole defects. After 1200kGy of gamma irradiation the broad band at 320K dislocates to 290K and increases ten times. Pulsed thermal treatments between 350K and 470K produce a progressive reduction of the peak area and a shift in the peak position back to 320K. A detailed analysis of the curve indicates the possibility of a superposition of peaks. Gamma irradiation restores the 320K TSDC peak. Taking into account optical absorption(OA) and electron paramagnetic resonance(EPR) results, the thermal reduction of the 320K TSDC band was attributed to V-type centres as a result of hole trapping at tetrahedral and octahedral cation vacancies. Computer modelling methods, based on lattice energy and defect minimisation, were applied to identify dipole defects that occur in these crystals. The calculations were made in normal and inverse spinel structures, doped with Cr, Co, Mn and Fe in order to justify the presence of dipole bands.

Spinel formation for stabilizing simulated nickel-laden sludge with aluminum-rich ceramic precursors.

PubMed

Shih, Kaimin; White, Tim; Leckie, James O

2006-08-15

The feasibility of stabilizing nickel-laden sludge from commonly available Al-rich ceramic precursors was investigated and accomplished with high nickel incorporation efficiency. To simulate the process, nickel oxide was mixed alternatively with gamma-alumina, corundum, kaolinite, and mullite and was sintered from 800 to 1480 degrees C. The nickel aluminate spinel (NiAl2O4) was confirmed as the stabilization phase for nickel and crystallized with efficiencies greater than 90% for all precursors above 1250 degrees C and 3-h sintering. The nickel-incorporation reaction pathways with these precursors were identified, and the microstructure and spinel yield were investigated as a function of sintering temperature with fixed sintering time. This study has demonstrated a promising process for forming nickel spinel to stabilize nickel-laden sludge from a wide range of inexpensive ceramic precursors, which may provide an avenue for economically blending waste metal sludges via the building industry processes to reduce the environmental hazards of toxic metals. The correlation of product textures and nickel incorporation efficiencies through selection of different precursors also provides the option of tailoring property-specific products.

Cations in Octahedral Sites: A Descriptor for Oxygen Electrocatalysis on Transition-Metal Spinels

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

Wei, Chao; Feng, Zhenxing; Scherer, Günther G.

2017-04-10

Exploring efficient and low-cost electrocatalysts for the oxygen-reduction reaction (ORR) and oxygen-evolution reaction (OER) is critical for developing renewable energy technologies such as fuel cells, metal–air batteries, and water electrolyzers. A rational design of a catalyst can be guided by identifying descriptors that determine its activity. Here, a descriptor study on the ORR/OER of spinel oxides is presented. With a series of MnCo2O4, the Mn in octahedral sites is identified as an active site. This finding is then applied to successfully explain the ORR/OER activities of other transition-metal spinels, including MnxCo3-xO4 (x = 2, 2.5, 3), LixMn2O4 (x = 0.7,more » 1), XCo2O4 (X = Co, Ni, Zn), and XFe2O4 (X = Mn, Co, Ni). A general principle is concluded that the eg occupancy of the active cation in the octahedral site is the activity descriptor for the ORR/OER of spinels, consolidating the role of electron orbital filling in metal oxide catalysis.« less

RHEED oscillations in spinel ferrite epitaxial films grown by conventional planar magnetron sputtering

NASA Astrophysics Data System (ADS)

Ojima, T.; Tainosho, T.; Sharmin, S.; Yanagihara, H.

2018-04-01

Real-time in situ reflection high energy electron diffraction (RHEED) observations of Fe3O4, γ-Fe2O3, and (Co,Fe)3O4 films on MgO(001) substrates grown by a conventional planar magnetron sputtering was studied. The change in periodical intensity of the specular reflection spot in the RHEED images of three different spinel ferrite compounds grown by two different sputtering systems was examined. The oscillation period was found to correspond to the 1/4 unit cell of each spinel ferrite, similar to that observed in molecular beam epitaxy (MBE) and pulsed laser deposition (PLD) experiments. This suggests that the layer-by-layer growth of spinel ferrite (001) films is general in most physical vapor deposition (PVD) processes. The surfaces of the films were as flat as the surface of the substrate, consistent with the observed layer-by-layer growth process. The observed RHEED oscillation indicates that even a conventional sputtering method can be used to control film thickness during atomic layer depositions.

Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis

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

Wan, Gang; Yang, Ce; Zhao, Wanpeng

The introduction of active transition metal sites (TMSs) in carbon enables the synthesis of noble-metal-free electrocatalysts for clean energy conversion applications, however, there are often multiple existing forms of TMSs, which are of different natures and catalytic models. Regulating the evolution of distinctive TMSs is highly desirable but remains challenging to date. Anions, as essential elements involved in the synthesis, have been totally neglected previously in the construction of TMSs. Herein, the effects of anions on the creation of different types of TMSs is investigated for the first time. It is found that the active cobalt-nitrogen sites tend to bemore » selectively constructed on the surface of N-doped carbon by using chloride, while metallic cobalt nanoparticles encased in protective graphite layers are the dominant forms of cobalt species with nitrate ions. The obtained catalysts demonstrate cobalt-sites-dependent activity for ORR and HER in acidic media. And the remarkably enhanced catalytic activities approaching that of benchmark Pt/C in acidic medium has been obtained on the catalyst dominated with cobalt-nitrogen sites, confirmed by the advanced spectroscopic . Our finding demonstrates a general paradigm of anion-regulated evolution of distinctive TMSs, providing a new pathway for enhancing performances of various targeted reactions related with TMSs.« less

The effect of calcination temperature on the formation and magnetic properties of ZnMn2O4 spinel

NASA Astrophysics Data System (ADS)

Hermanto, B.; Ciswandi; Afriani, F.; Aryanto, D.; Sudiro, T.

2018-03-01

The spinel based on transition-metal oxides has a typical composition of AB2O4. In this study, the ZnMn2O4 spinel was synthesized using a powder metallurgy technique. The Zn and Mn metallic powders with an atomic ratio of 1:2 were mechanically alloyed for 3 hours in aqueous solution. The mixed powder was then calcined in a muffle furnace at elevated temperature of 400, 500 and 600 °C. The X-ray Diffractometer (XRD) was used to evaluate the formation of a ZnMn2O4 spinel structure. The magnetic properties of the sample at varying calcination temperatures were characterized by a Vibrating Sample Magnetometer (VSM). The results show that the fraction of ZnMn2O4 spinel formation increases with the increase of calcination temperature. The calcination temperature also affects the magnetic properties of the samples.

Chemical, structural, and electrochemical characterization of 5 V spinel and complex layered oxide cathodes of lithium ion batteries

NASA Astrophysics Data System (ADS)

Tiruvannamalai Annamalai, Arun Kumar

2007-12-01

Lithium ion batteries have revolutionized the portable electronics market since their commercialization first by Sony Corporation in 1990. They are also being intensively pursued for electric and hybrid electric vehicle applications. Commercial lithium ion cells are currently made largely with the layered LiCoO 2 cathode. However, only 50% of the theoretical capacity of LiCoO 2 can be utilized in practical cells due to the chemical and structural instabilities at deep charge as well as safety concerns. These drawbacks together with the high cost and toxicity of Co have created enormous interest in alternative cathodes. In this regard, spinel LiMn2O4 has been investigated widely as Mn is inexpensive and environmentally benign. However, LiMn 2O4 exhibits severe capacity fade on cycling, particularly at elevated temperatures. With an aim to overcome the capacity fading problems, several cationic substitutions to give LiMn2-yMyO 4 (M = Cr, Fe, Co, Ni, and Cu) have been pursued in the literature. Among the cation-substituted systems, LiMn1.5Ni0.5O 4 has become attractive as it shows a high capacity of ˜ 130 mAh/g (theoretical capacity: 147 mAh/g) at around 4.7 V. With an aim to improve the electrochemical performance of the 5 V LiMn 1.5Ni0.5O4 spinel oxide, various cation-substituted LiMn1.5-yNi0.5-zMy+zO4 (M = Li, Mg, Fe, Co, and Zn) spinel oxides have been investigated by chemical lithium extraction. The cation-substituted LiMn1.5-yNi0.5-zM y+zO4 spinel oxides exhibit better cyclability and rate capability in the 5 V region compared to the unsubstituted LiMn1.5Ni 0.5O4 cathodes although the degree of manganese dissolution does not vary significantly. The better electrochemical properties of LiMn 1.5-yNi0.5-zMy+zO4 are found to be due to a smaller lattice parameter difference among the three cubic phases formed during the charge-discharge process. In addition, while the spinel Li1-xMn1.58Ni0.42O4 was chemically stable, the spinel Li1-xCo2O4 was found to exhibit both

Structural behavior of ZnCr 2S 4 spinel under pressure

DOE PAGES

Efthimiopoulos, I.; Lochbiler, T.; Tsurkan, V.; ...

2016-12-15

Here, the series of Cr-chalcogenide spinels ACr 2X 4 (A = Zn, Cd, Hg; X = S, Se) exhibits a rich phase diagram upon compression, as revealed by our recent investigations. There exist, however, some open questions regarding the role of cations in the observed structural transitions. In order to address these queries, we have performed X-ray diffraction and Raman spectroscopic studies on the ZnCr 2S 4 spinel up to 42 GPa, chosen mainly due to the similarity of the Zn 2+ and Cr 3+ cationic radii. Two reversible structural transitions were identified at 22 and 33 GPa, into a I4 1/ amd and an orthorhombic phase, respectively. Close comparison with the behavior of relevant Cr-spinels revealed that the structural transitions are mainly governed by the competition of the magnetic exchange interactions present in these systems, and not by steric effects. In addition, careful inspection of the starting Fdmore » $$\\bar{3}$$m phase revealed a previously unnoticed isostructural transition. The latter is intimately related to changes in the electronic properties of these systems, as evidenced by our Raman studies. Our results provide insights for tuning the physical and chemical properties of these materials, even under moderate compression, as well as promoting the understanding of similar pressure-induced effects in relevant systems.« less

Intolerability of cobalt salt as erythropoietic agent.

PubMed

Ebert, Bastian; Jelkmann, Wolfgang

2014-03-01

Unfair athletes seek ways to stimulate erythropoiesis, because the mass of haemoglobin is a critical factor in aerobic sports. Here, the potential misuse of cobalt deserves special attention. Cobalt ions (Co(2+) ) stabilize the hypoxia-inducible transcription factors (HIFs) that increase the expression of the erythropoietin (Epo) gene. Co(2+) is orally active, easy to obtain, and inexpensive. However, its intake can bear risks to health. To elaborate this issue, a review of the pertinent literature was retrieved by a search with the keywords 'anaemia', 'cobalt', 'cobalt chloride', 'erythropoiesis', 'erythropoietin', 'Epo', 'side-effects' and 'treatment', amongst others. In earlier years, cobalt chloride was administered at daily doses of 25 to 300 mg for use as an anti-anaemic agent. Co(2+) therapy proved effective in stimulating erythropoiesis in both non-renal and renal anaemia, yet there were also serious medical adverse effects. The intake of inorganic cobalt can cause severe organ damage, concerning primarily the gastrointestinal tract, the thyroid, the heart and the sensory systems. These insights should keep athletes off taking Co(2+) to stimulate erythropoiesis. Copyright © 2013 John Wiley & Sons, Ltd.

Unconventional magnetisation texture in graphene/cobalt hybrids

DOE PAGES

Vu, A. D.; Coraux, J.; Chen, G.; ...

2016-04-26

Magnetic domain structure and spin-dependent reflectivity measurements on cobalt thin films intercalated at the graphene/Ir(111) interface are investigated using spin-polarised low-energy electron microscopy. We find that graphene-covered cobalt films have surprising magnetic properties. Vectorial imaging of magnetic domains reveals an unusually gradual thickness-dependent spin reorientation transition, in which magnetisation rotates from out-of-the-film plane to the in-plane direction by less than 10° per cobalt monolayer. During this transition, cobalt films have a meandering spin texture, characterised by a complex, three-dimensional, wavy magnetisation pattern. In addition, spectroscopy measurements suggest that the electronic band structure of the unoccupied states is essentially spin-independent alreadymore » a few electron-Volts above the vacuum level. These properties strikingly differ from those of pristine cobalt films and could open new prospects in surface magnetism.« less

Consumer leather exposure: an unrecognized cause of cobalt sensitization.

PubMed

Thyssen, Jacob P; Johansen, Jeanne D; Jellesen, Morten S; Møller, Per; Sloth, Jens J; Zachariae, Claus; Menné, Torkil

2013-11-01

A patient who had suffered from persistent generalized dermatitis for 7 years was diagnosed with cobalt sensitization, and his leather couch was suspected as the culprit, owing to the clinical presentation mimicking allergic chromium dermatitis resulting from leather furniture exposure. The cobalt spot test, X-ray fluorescence, inductively coupled plasma mass spectrometry and scanning electron microscopy were used to determine cobalt content and release from the leather couch that caused the dermatitis and from 14 randomly collected samples of furniture leather. The sample from the patient's leather couch, but none of the 14 random leather samples, released cobalt in high concentrations. Dermatitis cleared when the patient stopped using his couch. Cobalt is used in the so-called pre-metallized dyeing of leather products. Repeated studies have found high levels of cobalt sensitization, but not nickel sensitization, in patients with foot dermatitis. We raise the possibility that cobalt may be widely released from leather items, and advise dermatologists to consider this in patients with positive cobalt patch test reactions. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

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

Kakade, S. G., E-mail: sundipkakade@gmail.com, E-mail: ydk@physics.unipune.ac.in; Department of Physics, Sir Parashurambhau College, Pune-411 030; Kambale, R. C.

Cobalt ferrite (CoFe{sub 2}O{sub 4}) shown to be promising candidate for applications such as high-density magnetic recording, enhanced memory storage, magnetic fluids and catalysts. Utility of ferrite nanoparticles depends on its size, dispersibility in solutions, and magnetic properties. We have investigated the structural properties of synthesized cobalt ferrite nanoparticles synthesized by sol gel auto combustion for uncontrolled, acidic, neutral and basic pH values. X-ray diffraction (XRD) study confirms the cubic spinel phase formation with lattice constant 8.38 Å. In this study, we have optimized the pH value to synthesize homogenous cobalt ferrite nanoparticles with enhanced magnetic behavior. The surface morphologymore » has been investigated by employing SEM images and the confirmation of spinel ferrite was also supported by using IR spectroscopy. Magnetic measurements for CoFe{sub 2}O{sub 4} compositions (with pH <1, pH = 3, 7, 10) were investigated using VSM measurements.« less

Position Assignment and Oxidation State Recognition of Fe and Co Centers in Heterometallic Mixed-Valent Molecular Precursors for the Low-Temperature Preparation of Target Spinel Oxide Materials

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

Lieberman, Craig M.; Barry, Matthew C.; Wei, Zheng

A series of mixed-valent, heterometallic (mixed-transition metal) diketonates that can be utilized as prospective volatile single-source precursors for the low-temperature preparation of M xM' 3–xO 4 spinel oxide materials is reported. Three iron–cobalt complexes with Fe/Co ratios of 1:1, 1:2, and 2:1 were synthesized by several methods using both solid-state and solution reactions. On the basis of nearly quantitative reaction yields, elemental analyses, and comparison of metal–oxygen bonds with those in homometallic analogues, heterometallic compounds were formulated as [Fe III(acac) 3][Co II(hfac) 2] (1), [Co II(hfac) 2][Fe III(acac) 3][Co II(hfac) 2] (2), and [Fe II(hfac) 2][Fe III(acac) 3][Co II(hfac) 2]more » (3). In the above heteroleptic complexes, the Lewis acidic, coordinatively unsaturated CoII/FeII centers chelated by two hexafluoroacetylacetonate (hfac) ligands maintain bridging interactions with oxygen atoms of acetylacetonate (acac) groups that chelate the neighboring Fe III metal ion. Preliminary assignment of Fe and Co positions/oxidation states in 1–3 drawn from X-ray structural investigation was corroborated by a number of complementary techniques. Single-crystal resonant synchrotron diffraction and neutron diffraction experiments unambiguously confirmed the location of Fe and Co sites in the molecules of dinuclear (1) and trinuclear (2) complexes, respectively. Direct analysis in real time mass spectrometry revealed the presence of Fe III- and Co II-based fragments in the gas phase upon evaporation of precursors 1 and 2 as well as of Fe III, Fe II, and Co II species for complex 3. Theoretical investigation of two possible “valent isomers”, [Fe III(acac) 3][Co II(hfac) 2] (1) and [Co III(acac) 3][Fe II(hfac) 2] (1'), provided an additional support for the metal site/oxidation state assignment giving a preference of 6.48 kcal/mol for the experimentally observed molecule 1. Magnetic susceptibility measurements data are in agreement

High-pressure behaviour of Cr-Fe-Mg-Al spinels: applications to diamond geobarometry

NASA Astrophysics Data System (ADS)

Periotto, Benedetta; Bruschini, Enrico; Nestola, Fabrizio; Lenaz, Davide; Princivalle, Francesco; Andreozzi, Giovanni B.; Bosi, Ferdinando

2014-05-01

Spinels belonging to the chromite - magnesiochromite - hercynite (FeCr2O4-MgCr2O4-FeAl2O4) system are among the most common inclusions found in diamonds (Stachel and Harris 2008). In particular, although FeCr2O4 and MgCr2O4 components sum to between 85 and 88% of spinels found in diamonds, hercynite FeAl2O4 plays a not negligible role in determining their thermo-elastic properties with concentrations reaching 7-9 % (other minor end-members like MgAl2O4, MgFe2O4 and Fe2O3 rarely reach 2-3% in total, see Lenaz et al. 2009). Recent studies were focused on the determination of the diamond formation pressure by the so-called "elastic method" (see for example Nestola et al. 2011 and references therein). It was demonstrated that accurate and precise thermo-elastic parameters are fundamental to minimize the uncertainty of formation pressure. In this work we have determined the equations of state at room temperature of three synthetic spinel end-members chromite - magnesiochromite - hercynite and one natural spinel crystal extracted from a diamond (from Udachnaya mine, Siberia, Russia) by single-crystal X-ray diffraction in situ at high-pressure. A diamond-anvil cell was mounted on a STADI IV diffractometer equipped with a point detector and motorized by SINGLE software (Angel and Finger 2011). The natural crystal was investigated to test (and possibly validate) the "empirical prediction model", capable to provide bulk modulus and its first pressure derivative only knowing the composition of the spinels found in diamonds. Such prediction model could be used to obtain pressure of formation for the diamond-spinel pair through the elastic method. Details and results will be discussed. The research was funded by the ERC Starting Grant to FN (grant agreement n° 307322). References Angel R.J., Finger L.W. (2011) SINGLE A program to control single-crystal diffractometers. Journal of Applied Crystallography, 44, 247-251. Lenaz D., Logvinova A.M., Princivalle F., Sobolev N. (2009

C-H functionalization of phenols using combined ruthenium and photoredox catalysis: in situ generation of the oxidant.

PubMed

Fabry, David C; Ronge, Meria A; Zoller, Jochen; Rueping, Magnus

2015-02-23

A combination of ruthenium and photoredox catalysis allowed the ortho olefination of phenols. Using visible light, the direct C-H functionalization of o-(2-pyridyl)phenols occurred, and diverse phenol ethers were obtained in good yields. The regeneration of the ruthenium catalyst was accomplished by a photoredox-catalyzed oxidative process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Compositional controls on spinel clouding and garnet formation in plagioclase of olivine metagabbros, Adirondack Mountains, New York

USGS Publications Warehouse

McLelland, J.M.; Whitney, P.R.

1980-01-01

Olivine metagabbros from the Adirondacks usually contain both clear and spinel-clouded plagioclase, as well as garnet. The latter occurs primarily as the outer rim of coronas surrounding olivine and pyroxene, and less commonly as lamellae or isolated grains within plagioclase. The formation of garnet and metamorphic spinel is dependent upon the anorthite content of the plagioclase. Plagioclase more sodic than An38??2 does not exhibit spinel clouding, and garnet rarely occurs in contact with plagioclase more albitic than An36??4. As a result of these compositional controls, the distribution of spinel and garnet mimics and visually enhances original igneous zoning in plagioclase. Most features of the arrangement of clear (unclouded) plagioclase, including the shells or moats of clear plagioclase which frequently occur inside the garnet rims of coronas, can be explained on the basis of igneous zoning. The form and distribution of the clear zones may also be affected by the metamorphic reactions which have produced the coronas, and by redistribution of plagioclase in response to local volume changes during metamorphism. ?? 1980 Springer-Verlag.

Chromium and Ruthenium-Doped Zinc Oxide Thin Films for Propane Sensing Applications

PubMed Central

Gómez-Pozos, Heberto; González-Vidal, José Luis; Torres, Gonzalo Alberto; Rodríguez-Baez, Jorge; Maldonado, Arturo; de la Luz Olvera, María; Acosta, Dwight Roberto; Avendaño-Alejo, Maximino; Castañeda, Luis

2013-01-01

Chromium and ruthenium-doped zinc oxide (ZnO:Cr) and (ZnO:Ru) thin solid films were deposited on soda-lime glass substrates by the sol-gel dip-coating method. A 0.6 M solution of zinc acetate dihydrate dissolved in 2-methoxyethanol and monoethanolamine was used as basic solution. Chromium (III) acetylacetonate and Ruthenium (III) trichloride were used as doping sources. The Ru incorporation and its distribution profile into the films were proved by the SIMS technique. The morphology and structure of the films were studied by SEM microscopy and X-ray diffraction measurements, respectively. The SEM images show porous surfaces covered by small grains with different grain size, depending on the doping element, and the immersions number into the doping solutions. The sensing properties of ZnO:Cr and ZnO:Ru films in a propane (C3H8) atmosphere, as a function of the immersions number in the doping solution, have been studied in the present work. The highest sensitivity values were obtained for films doped from five immersions, 5.8 and 900, for ZnO:Cr and ZnO:Ru films, respectively. In order to evidence the catalytic effect of the chromium (Cr) and ruthenium (Ru), the sensing characteristics of undoped ZnO films are reported as well. PMID:23482091

Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cell Stacks

NASA Technical Reports Server (NTRS)

Valdez, Thomas I.; Firdosy, S.; Koel, B. E.; Narayanan, S. R.

2005-01-01

Dissolution of ruthenium was observed in the 80-cell stack. Duration testing was performed in single cell MEAs to determine the pathway of cell degradation. EDAX analysis on each of the single cell MEAs has shown that the Johnson Matthey commercial catalyst is stable in DMFC operation for 250 hours, no ruthenium dissolution was observed. Changes in the hydrophobicity of the cathode backing papers was minimum. Electrode polarization analysis revealed that the MEA performance loss is attributed to changes in the cathode catalyst layer. Ruthenium migration does not seem to occur during cell operation but can occur when methanol is absent from the anode compartment, the cathode compartment has access to air, and the cells in the stack are electrically connected to a load (Shunt Currents). The open-to-air cathode stack design allowed for: a) The MEAs to have continual access to oxygen; and b) The stack to sustain shunt currents. Ruthenium dissolution in a DMFC stack can be prevented by: a) Developing an internally manifolded stacks that seal reactant compartments when not in operation; b) Bringing the cell voltages to zero quickly when not in operation; and c) Limiting the total number of cells to 25 in an effort to limit shunt currents.

Probing the structural evolution of ruthenium doped germanium clusters: Photoelectron spectroscopy and density functional theory calculations

PubMed Central

Jin, Yuanyuan; Lu, Shengjie; Hermann, Andreas; Kuang, Xiaoyu; Zhang, Chuanzhao; Lu, Cheng; Xu, Hongguang; Zheng, Weijun

2016-01-01

We present a combined experimental and theoretical study of ruthenium doped germanium clusters, RuGen− (n = 3–12), and their corresponding neutral species. Photoelectron spectra of RuGen− clusters are measured at 266 nm. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) are obtained. Unbiased CALYPSO structure searches confirm the low-lying structures of anionic and neutral ruthenium doped germanium clusters in the size range of 3 ≤ n ≤ 12. Subsequent geometry optimizations using density functional theory (DFT) at PW91/LANL2DZ level are carried out to determine the relative stability and electronic properties of ruthenium doped germanium clusters. It is found that most of the anionic and neutral clusters have very similar global features. Although the global minimum structures of the anionic and neutral clusters are different, their respective geometries are observed as the low-lying isomers in either case. In addition, for n > 8, the Ru atom in RuGen−/0 clusters is absorbed endohedrally in the Ge cage. The theoretically predicted vertical and adiabatic detachment energies are in good agreement with the experimental measurements. The excellent agreement between DFT calculations and experiment enables a comprehensive evaluation of the geometrical and electronic structures of ruthenium doped germanium clusters. PMID:27439955

Fe-Mg substitution in aluminate spinels: effects on elastic properties investigated by Brillouin scattering

NASA Astrophysics Data System (ADS)

Bruschini, Enrico; Speziale, Sergio; Bosi, Ferdinando; Andreozzi, Giovanni B.

2018-03-01

We investigated by a multi-analytical approach (Brillouin scattering, X-ray diffraction and electron microprobe) the dependence of the elastic properties on the chemical composition of six spinels in the series (Mg1-x ,Fe x )Al2O4 (0 ≤ x ≤ 0.5). With the exception of C 12, all the elastic moduli (C 11, C 44, K S0 and G) are insensitive to chemical composition for low iron concentration, while they decrease linearly for higher Fe2+ content. Only C 12 shows a continuous linear increase with increasing Fe2+ across the whole compositional range under investigation. The high cation disorder showed by the sample with x = 0.202 has little or no influence on the elastic parameters. The range 0.202 < x < 0.388 bounds the percolation threshold (p c) for nearest neighbor interaction of Fe in the cation sublattices of the spinel structure. Below x = 0.202, the iron atoms are diluted in the system and far from each other, and the elastic moduli are nearly constant. Above x = 0.388, Fe atoms form extended interconnected clusters and show a cooperative behavior thus affecting the single-crystal elastic moduli. The elastic anisotropy largely increases with the introduction of Fe2+ in substitution of magnesium in spinel. This behavior is different with respect to other spinels containing transition metals such as Mn2+ and Co2+.

A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: aqueous hydration of nitriles to amides.

PubMed

Baig, R B Nasir; Varma, Rajender S

2012-06-25

One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involves the in situ generation of magnetic silica (Fe(3)O(4)@SiO(2)) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this catalyst which proceeds exclusively in aqueous medium under neutral conditions.

Carboxylate-assisted ruthenium-catalyzed alkyne annulations by C-H/Het-H bond functionalizations.

PubMed

Ackermann, Lutz

2014-02-18

To improve the atom- and step-economy of organic syntheses, researchers would like to capitalize upon the chemistry of otherwise inert carbon-hydrogen (C-H) bonds. During the past decade, remarkable progress in organometallic chemistry has set the stage for the development of increasingly viable metal catalysts for C-H bond activation reactions. Among these methods, oxidative C-H bond functionalizations are particularly attractive because they avoid the use of prefunctionalized starting materials. For example, oxidative annulations that involve sequential C-H and heteroatom-H bond cleavages allow for the modular assembly of regioselectively decorated heterocycles. These structures serve as key scaffolds for natural products, functional materials, crop protecting agents, and drugs. While other researchers have devised rhodium or palladium complexes for oxidative alkyne annulations, my laboratory has focused on the application of significantly less expensive, yet highly selective ruthenium complexes. This Account summarizes the evolution of versatile ruthenium(II) complexes for annulations of alkynes via C-H/N-H, C-H/O-H, or C-H/N-O bond cleavages. To achieve selective C-H bond functionalizations, we needed to understand the detailed mechanism of the crucial C-H bond metalation with ruthenium(II) complexes and particularly the importance of carboxylate assistance in this process. As a consequence, our recent efforts have resulted in widely applicable methods for the versatile preparation of differently decorated arenes and heteroarenes, providing access to among others isoquinolones, 2-pyridones, isoquinolines, indoles, pyrroles, or α-pyrones. Most of these reactions used Cu(OAc)2·H2O, which not only acted as the oxidant but also served as the essential source of acetate for the carboxylate-assisted ruthenation manifold. Notably, the ruthenium(II)-catalyzed oxidative annulations also occurred under an ambient atmosphere of air with cocatalytic amounts of Cu(OAc)2�

Spectroelectrochemical studies of hole percolation on functionalised nanocrystalline TiO2 films: a comparison of two different ruthenium complexes.

PubMed

Li, Xiaoe; Nazeeruddin, Mohammad K; Thelakkat, Mukundan; Barnes, Piers R F; Vilar, Ramón; Durrant, James R

2011-01-28

We report the application of spectroelectrochemical techniques to compare the hole percolation dynamics of molecular networks of two ruthenium bipyridyl complexes adsorbed onto mesoporous, nanocrystalline TiO(2) films. The percolation dynamics of the ruthenium complex cis-di(thiocyanato)(2,2'-bipyridyl-4,4'-dicarboxylic acid)-(2,2'-bipyridyl-4,4'-tridecyl) ruthenium(II), N621, is compared with those observed for an analogous dye with an additional tri-phenyl amine (TPA) donor moiety, cis-di(thiocyanato)(2,2'-bipyridyl-4,4'-dicarboxylic acid)-(2,2'-bipyridyl-4,4'-bis(vinyltriphenylamine)) ruthenium(II), HW456. The in situ oxidation of these ruthenium complexes adsorbed to the TiO(2) films is monitored by cyclic voltammetry and voltabsorptometry, whilst the dynamics of hole (cation) percolation between adsorbed ruthenium complexes is monitored by potentiometric spectroelectrochemistry and chronoabsorptometry. The hole diffusion coefficient, D(eff), is shown to be dependent on the dye loading on the nanocrystalline TiO(2) film, with a threshold observed at ∼60% monolayer surface coverage for both dyes. The hole diffusion coefficient of HW456 is estimated to be 2.6 × 10(-8) cm(2)/s, 20-fold higher than that obtained for the control N621, attributed to stronger electronic coupling between the TPA moieties of HW456 accelerating the hole percolation dynamics. The presence of mercuric ions, previously shown to bind to the thiocyanates of analogous ruthenium complexes, resulted in a quenching of the hole percolation for N621/TiO(2) films and an enhancement for HW456/TiO(2) films. These results strongly suggest that the hole percolation pathway is along the overlapped neighbouring -NCS groups for the N621 molecules, whereas in HW456 molecules cation percolation proceeds between intermolecular TPA ligands. These results are discussed in the context of their relevance to the process of dye regeneration in dye sensitised solar cells, and to the molecular wiring of wide

Cobalt(II) and Cobalt(III) Coordination Compounds.

ERIC Educational Resources Information Center

Thomas, Nicholas C.; And Others

1989-01-01

Presents a laboratory experiment which illustrates the formation of tris(phenanthroline)cobalt complexes in the 2+ and 3+ oxidation states, the effect of coordination on reactions of the ligand, and the use of a ligand displacement reaction in recovering the transformed ligand. Uses IR, UV-VIS, conductivity, and NMR. (MVL)

21 CFR 73.1015 - Chromium-cobalt-aluminum oxide.

Code of Federal Regulations, 2010 CFR

2010-04-01

...) Identity. The color additive chromium-cobalt-aluminum oxide is a blue-green pigment obtained by calcining a... percent each) of oxides of barium, boron, silicon, and nickel. (b) Specifications. Chromium-cobalt... milliliters of 0.5 N hydrochloric acid. (c) Uses and restrictions. The color additive chromium-cobalt-aluminum...

Amphibole and hercynite spinel in Shergotty and Zagami Magmatic water, depth of crystallization, and metasomatism

NASA Technical Reports Server (NTRS)

Treiman, A. H.

1985-01-01

Amphibole and spinel occur in the Shergotty and Zagami meteorites only in magmatic inclusions in pigeonite. The trapped magma is essentially identical to the parental magmas for Shergotty and Zagami. The amphibole is a kaersutite with minimal halogen content; by inference, it must have been hydrous. If so, the Shergotty and Zagami melts contained at least 0.2 wt pct H2O and were probably H2O-undersaturated. Pressures in excess of 1 kilobar seem necessary for the formation of amphibole. Spinel replaces magnetite in the inclusions, and olivine replaces magnetite elsewhere in the meteorites. To stabilize spinel, the melt in the inclusions must have become enriched in Al during fractionation, possibly because the small volume of the inclusions made nucleation of plagioclase unlikely. Pervasive replacement of magnetite through reduction reactions suggests that Shergotty and Zagami interacted with hydrogen-rich fluids during their cooling.

Subsurface Optical Microscopy of Coarse Grain Spinels. Phase 1

DTIC Science & Technology

2013-12-01

A 456 nm LED line bar illuminated in figure 15 and a Xenon fiber optic bar illuminator is shown for figure 16. The optical in situ or subsurface ... imaging of coarse grain spinels and AlONs is optically more complex than expected. An overhead view of the side illumination field is shown in figure 20

Procedure for rapid determination of nickel, cobalt, and chromium in airborne particulate samples

NASA Technical Reports Server (NTRS)

Davis, W. F.; Graab, J. W.

1972-01-01

A rapid, selective procedure for the determination of 1 to 20 micrograms of nickel, chromium, and cobalt in airborne particulates is described. The method utilizes the combined techniques of low temperature ashing and atomic absorption spectroscopy. The airborne particulates are collected on analytical filter paper. The filter papers are ashed, and the residues are dissolved in hydrochloric acid. Nickel, chromium, and cobalt are determined directly with good precision and accuracy by means of atomic absorption. The effects of flame type, burner height, slit width, and lamp current on the atomic absorption measurements are reported.

Effect of cutting edge radius on surface roughness in diamond tool turning of transparent MgAl2O4 spinel ceramic

NASA Astrophysics Data System (ADS)

Yue, Xiaobin; Xu, Min; Du, Wenhao; Chu, Chong

2017-09-01

Transparent magnesium aluminate spinel (MgAl2O4) ceramic is one of an important optical materials. However, due to its pronounced hardness and brittleness, the optical machining of this material is very difficult. Diamond turning has advantages over the grinding process in flexibility and material removal rate. However, there is a lack of research that could support the use of diamond turning technology in the machining of MgAl2O4 spinel ceramic. Using brittle-ductile transition theory of brittle material machining, this work provides critical information that may help to realize ductile-regime turning of MgAl2O4 spinel ceramic. A characterization method of determination the cutting edge radius is introduced here. Suitable diamond tools were measured for sharpness and then chosen from a large number of candidate tools. The influence of rounded cutting edges on surface roughness of the MgAl2O4 spinel ceramic is also investigated. These results indicate that surface quality of MgAl2O4 spinel is relate to the radius of diamond tool's cutting edge, cutting speed, and feed rate. Sharp diamond tools (small radius of cutting edge) facilitated ductile-regime turning of MgAl2O4 spinel and shows great potential to reduce surface roughness and produce smoother final surface.

Osmium, tungsten, and chromium isotopes in sediments and in Ni-rich spinel at the K-T boundary: Signature of a chondritic impactor

NASA Astrophysics Data System (ADS)

Quitté, Ghylaine; Robin, Eric; Levasseur, Sylvain; Capmas, Françoise; Rocchia, Robert; Birck, Jean-Louis; Allègre, Claude Jean

It is now established that a large extraterrestrial object hit the Earth at the end of the Cretaceous period, about 65 Ma ago. We have investigated Re-Os, Hf-W, and Mn-Cr isotope systems in sediments from the Cretaceous and the Paleogene in order to characterize the type of impactor. Within the Cretaceous-Tertiary (K-T) boundary layer, extraterrestrial material is mixed with terrestrial material, causing a dilution of the extraterrestrial isotope signature that is difficult to quantify. A phase essentially composed of Ni-rich spinel, formed in the atmosphere mainly from melted projectile material, is likely to contain the extraterrestrial isotopic signature of the impactor. We show that the analysis of spinel is indeed the best approach to determine the initial isotope composition of the impactor, and that W and Cr isotopes confirm that the projectile was a carbonaceous chondrite.

Complete agreement of the post-spinel transition with the 660-km seismic discontinuity.

PubMed

Ishii, Takayuki; Huang, Rong; Fei, Hongzhan; Koemets, Iuliia; Liu, Zhaodong; Maeda, Fumiya; Yuan, Liang; Wang, Lin; Druzhbin, Dmitry; Yamamoto, Takafumi; Bhat, Shrikant; Farla, Robert; Kawazoe, Takaaki; Tsujino, Noriyoshi; Kulik, Eleonora; Higo, Yuji; Tange, Yoshinori; Katsura, Tomoo

2018-04-20

The 660-km seismic discontinuity, which is a significant structure in the Earth's mantle, is generally interpreted as the post-spinel transition, as indicated by the decomposition of ringwoodite to bridgmanite + ferropericlase. All precise high-pressure and high-temperature experiments nevertheless report 0.5-2 GPa lower transition pressures than those expected at the discontinuity depth (i.e. 23.4 GPa). These results are inconsistent with the post-spinel transition hypothesis and, therefore, do not support widely accepted models of mantle composition such as the pyrolite and CI chondrite models. Here, we present new experimental data showing post-spinel transition pressures in complete agreement with the 660-km discontinuity depth obtained by high-resolution in situ X-ray diffraction in a large-volume high-pressure apparatus with a tightly controlled sample pressure. These data affirm the applicability of the prevailing mantle models. We infer that the apparently lower pressures reported by previous studies are experimental artefacts due to the pressure drop upon heating. The present results indicate the necessity of reinvestigating the position of mantle mineral phase boundaries previously obtained by in situ X-ray diffraction in high-pressure-temperature apparatuses.

Chemistry of Bimetallic Linked Cyclopentadienyl Complexes: Progress Report, 1 December 1986 --30 November 1989

DOE R&D Accomplishments Database

Schrock, R. R.

1989-01-01

Research continued on the chemistry and preparation of bimetallic cyclopentadienyl complexes containing up to two tungsten or one tungsten and a cobalt, rhodium, or ruthenium. The general method for preparation and analysis of polyenes is also discussed. (CBS)

Fabrication of cobalt magnetic nanostructures using atomic force microscope lithography.

PubMed

Chu, Haena; Yun, Seonghun; Lee, Haiwon

2013-12-01

Cobalt nanopatterns are promising assemblies for patterned magnetic storage applications. The fabrication of cobalt magnetic nanostructures on n-tridecylamine x hydrochloride (TDA x HCl) self-assembled monolayer (SAM) modified silicon surfaces using direct writing atomic force microscope (AFM) lithography for localized electrochemical reduction of cobalt ions was demonstrated. The ions were reduced to form metal nanowires along the direction of the electricfield between the AFM tip and the substrate. In this lithography process, TDA x HCI SAMs play an important role in the lithography process for improving the resolution of cobalt nanopatterns by preventing nonspecific reduction of cobalt ions on the unwritten background. Cobalt nanowires and nanodots with width of 225 +/- 26 nm and diameter of 208 +/- 28 nm were successfully fabricated. Platinium-coated polydimethylsiloxane (PDMS) stamp was used fabricating bulk cobalt structures which can be detected by energy dispersive X-ray spectroscopy for element analysis and the physical and magnetic properties of these cobalt nanopatterns were characterized using AFM and magnetic force microscope.

Magnetic cobalt ferrite composite as an efficient catalyst for photocatalytic oxidation of carbamazepine.

PubMed

He, Yongzhen; Dai, Chaomeng; Zhou, Xuefei

2017-01-01

A magnetic spinel cobalt ferrite nanoparticle composite (CFO) was prepared via an ultrasonication-assisted co-precipitation method. The morphological structure and surface composition of CFO before and after reaction were investigated by using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray, and Fourier transform infrared spectroscopy, indicating the consumption of iron oxide during photodegradation. X-ray photoelectron spectroscopy and vibrating sample magnetometry confirm the preparation of the ferrite nanoparticle composite and its magnetic properties. The prepared CFO was then used for the photocatalytic degradation of carbamazepine (CBZ) as an example of pharmaceuticals and personal care products (PPCPs) from aqueous solution. The effects of the nanocomposite dosage, contact time, and solution pH on the photodegradation process were investigated. More than 96% of the CBZ was degraded within 100 min at 0.2 g·L -1 CFO in the presence of UV light. The reactive species for CBZ degradation in the CFO/UV system was identified as hydroxyl radicals by the methanol scavenging method. Combined with the detection of leached iron ions during the process, the CBZ degradation mechanism can be presumed to be heterogeneous and homogeneous photocatalytic degradation in the CFO/UV system. Furthermore, iminostilbene and acridine were detected as intermediate products by GC-MS.

Arsenate Adsorption On Ruthenium Oxides: A Spectroscopic And Kinetic Investigation

EPA Science Inventory

Arsenate adsorption on amorphous (RuO₂•1.1H₂O) and crystalline (RuO₂) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was ...

Stabilization of MgAl2O4 spinel surfaces via doping

NASA Astrophysics Data System (ADS)

Hasan, Md. M.; Dholabhai, Pratik P.; Castro, Ricardo H. R.; Uberuaga, Blas P.

2016-07-01

Surface structure of complex oxides plays a vital role in processes such as sintering, thin film growth, and catalysis, as well as being a critical factor determining the stability of nanoparticles. Here, we report atomistic calculations of the low-index stoichiometric magnesium aluminate spinel (MgAl2O4) surfaces, each with two different chemical terminations. High temperature annealing was used to explore the potential energy landscape and provide more stable surface structures. We find that the lowest energy surface is {100} while the highest energy surface is {111}. The surfaces were subsequently doped with three trivalent dopants (Y3+, Gd3+, La3+) and one tetravalent dopant (Zr4+) and both the surface segregation energies of the dopants and surface energies of the doped surface were determined. All of the dopants reduce the surface energy of spinel, though this reduction in energy depends on both the size and valence of the dopant. Dopants with larger ionic radius tend to segregate to the surface more strongly and reduce the surface energy to a greater extent. Furthermore, the ionic valence of the dopants seems to have a stronger influence on the segregation than does ionic size. For both undoped and doped spinel, the predicted crystal shape is dominated by {100} surfaces, but the relative fraction of the various surfaces changes with doping due to the unequal changes in energy, which has implications on equilibrium nanoparticle shapes and therefore on applications sensitive to surface properties.

Spinel and orthopyroxene exsolved from clinopyroxene in the Haladala pluton in the middle Tianshan (Xinjiang, China)

NASA Astrophysics Data System (ADS)

Zhu, Yongfeng; Chen, Jing; Xue, Yunxin; Feng, Wanyi; Jiang, Jiuyang

2017-12-01

The Haladala pluton, consisting of troctolite, olivine gabbro and gabbro with zircon SHRIMP U-Pb age of 309 ± 2 Ma (MSWD = 0.72), intruded the Devonian-Carboniferous arc segments in the middle Tianshan. Amphibole, coexisting with magnetite, amphibole, and phlogopite, crystallized in a magma chamber at depth of 20 km (6.9-7.4 kbar, 934-943 °C) based on various thermobaramoters. Two kinds of exsolution textures (spinel rods in clinopyroxene, orthopyroxene lamellae in clinopyroxene) occur in troctolite and olivine gabbro. We describe oriented spinel rods and orthopyroxene lamellae exsolved from the host clinopyroxene based on optical and high-resolution transmission electron microscope (HRTEM) observations. The spinel rods (100) are parallel to their host clinopyroxene (010). Orthopyroxene lamellae (010) are coherent and strictly parallel to their host clinopyroxene (010). Exsolution of spinel rods from the host clinopyroxene is controlled by the reaction of (Ca0.5M2+ 0.5)Fe3+[AlSiO6]in clinopyroxene → (Ca0.86-0.17M2+ 0.14-0.17)(M2 + 1.00-0.96Al0-0.04)[Al0.17-0.10Si1.83-1.90O6] + Fe3O4 + O2.

In Vitro Effects of Novel Ruthenium Complexes in Neospora caninum and Toxoplasma gondii Tachyzoites

PubMed Central

Barna, Fabienne; Debache, Karim; Küster, Tatiana

2013-01-01

Upon the screening of 16 antiproliferative compounds against Toxoplasma gondii and Neospora caninum, two hydrolytically stable ruthenium complexes (compounds 16 and 18) exhibited 50% inhibitory concentrations of 18.7 and 41.1 nM (T. gondii) and 6.7 and 11.3 nM (N. caninum). To achieve parasiticidal activity with compound 16, long-term treatment (22 to 27 days at 80 to 160 nM) was required. Transmission electron microscopy demonstrated the rapid impact on and ultrastructural alterations in both parasites. These preliminary findings suggest that the potential of ruthenium-based compounds should thus be further exploited. PMID:23979747

The role of cobalt on the creep of Waspaloy

NASA Technical Reports Server (NTRS)

Jarrett, R. N.; Chin, L.; Tien, J. K.

1984-01-01

Cobalt was systematically replaced with nickel in Waspaloy (which normally contains 13% Co) to determine the effects of cobalt on the creep behavior of this alloy. Effects of cobalt were found to be minimal on tensile strengths and microstructure. The creep resistance and the stress rupture resistance determined in the range from 704 to 760 C (1300 to 1400 C) were found to decrease as cobalt was removed from the standard alloy at all stresses and temperatures. Roughly a ten-fold drop in rupture life and a corresponding increase in minimum creep rate were found under all test conditions. Both the apparent creep activation energy and the matrix contribution to creep resistance were found to increase with cobalt. These creep effects are attributed to cobalt lowering the stacking fault energy of the alloy matrix. The creep resistance loss due to the removal of cobalt is shown to be restored by slightly increasing the gamma' volume fraction. Results are compared to a previous study on Udimet 700, a higher strength, higher gamma' volume fraction alloy with similar phase chemistry, in which cobalt did not affect creep resistance. An explanation for this difference in behavior based on interparticle spacing and cross-slip is presented.

Separation and Recovery of Cobalt from Copper Leach Solutions

NASA Astrophysics Data System (ADS)

Jeffers, T. H.

1985-01-01

Significant amounts of cobalt, a strategic and critical metal, are present in readily accessible copper recycling leach solutions. However, cost-effective technology is not available to separate and recover the cobalt from this low-grade domestic source. The Bureau of Mines has developed a procedure using a chelating ion-exchange resin from Dow Chemical Co. to successfully extract cobalt from a pH 3.0 copper recycling solution containing only 30 mg/1 cobalt. Cyclic tests with the commercial resin XFS-4195 in 4-ft-high by 1-in.-diameter columns gave an average cobalt extraction of 95% when 65 bed volumes of solution were processed at a flow rate of 4 gpm/ft.2 Elution of the cobalt using a 50 g/l H2SO4 solution yielded an eluate containing 0.5 gli Co. Selective elution of the loaded resin and solvent extraction procedures using di-2-ethylhexyl phosphoric acid (D2EHPA) and Cyanex 272 removed the impurities and produced a cobalt sulfate solution containing 25 g/l Co.

57Fe Mössbauer spectroscopy of mineral assemblages in mantle spinel lherzolites from Cenozoic alkali basalt, eastern China: Petrological applications

NASA Astrophysics Data System (ADS)

Hao, Xi-Luo; Li, Yi-Liang

2013-01-01

Mineral assemblages in spinel lherzolite xenoliths from the Cenozoic alkali basalt of eastern China were analyzed by 57Fe Mössbauer spectroscopy for Fe3+/ΣFe and distribution of Fe2+/Fe3+ in non-equivalent crystal cites. Orthopyroxene, clinopyroxene and spinel have 0.08-0.13, 0.19-0.31 and 0.13-0.23 Fe3+/ΣFe, respectively. The cation-exchange equilibrium temperatures, Fe3+ partition coefficient and oxygen fugacity of the upper mantle peridotites were calculated. The equilibrium temperatures are between 1103 K and 1405 K consistent with those reported elsewhere. The oxygen fugacities of spinel lherzolites calculated with olivine-orthopyroxene-spinel (ΔlogƒO2 from - 1.1 to 0) and clinopyroxene-olivine-orthopyroxene oxybarometers (ΔlogƒO2 from - 2.0 to 0.7) are consistent with previously reported upper mantle values.

Solution blow spun spinel ferrite and highly porous silica nanofibers

USDA-ARS?s Scientific Manuscript database

The novelty of this work is the production of nano- and submicrometric silica and spinel-ferrite fibers using the solution blow spinning (SBS) method. A pseudo-core-shell method for the production of large surface area silica fibers is also reported. Silica fibers present mean diameters and specific...

Synthesis and Catalytic Activity of Ruthenium-Indenylidene Complexes for Olefin Metathesis: Microscale Experiments for the Undergraduate Inorganic or Organometallic Laboratories

ERIC Educational Resources Information Center

Pappenfus, Ted M.; Hermanson, David L.; Ekerholm, Daniel P.; Lilliquist, Stacie L.; Mekoli, Megan L.

2007-01-01

A series of experiments for undergraduate laboratory courses (e.g., inorganic, organometallic or advanced organic) have been developed. These experiments focus on understanding the design and catalytic activity of ruthenium-indenylidene complexes for olefin metathesis. Included in the experiments are the syntheses of two ruthenium-indenylidene…

Sorption of copper, zinc and cobalt by oat and oat products.

PubMed

Górecka, Danuta; Stachowiak, Jadwiga

2002-04-01

We determined copper, zinc and cobalt sorption by oat and its products under variable pH conditions as well as the content of neutral dietary fiber (NDF) and its fractional composition. Adsorbents in a model sorption system were: oat, dehulled oat, oats bran and oats flakes. Three various buffers (pH 1.8, 6.6 and 8.7) were used as dispersing solutions. Results collected during this study indicate that copper, zinc and cobalt sorption is significantly affected by the type of cereal raw material. Zinc and copper ions are subjected to higher sorption than cobalt ions. Examined metal ions were subjected to high sorption under conditions corresponding to the duodenum environment (pH 8.7), regardless of the kind of adsorbent. A little lower sorption capacity is observed under conditions close to the neutral environment, while the lowest one is found in environment reflecting conditions of stomach juice (pH 1.8). Zinc ions are bound intensively by dehulled oat, while oats flakes bound mostly copper and cobalt, independently on environmental conditions. Contents of dietary fiber in oat, dehulled oat, oat bran and oat flakes were: 40.1, 19.3, 20.3 and 14.3%, respectively. The dominating fraction in all oat products was the fraction of hemicelluloses. The content of remaining fractions varies in dependence on the product.

Cobalt chloride attenuates hypobaric hypoxia induced vascular leakage in rat brain: Molecular mechanisms of action of cobalt chloride

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

Kalpana, S.; Dhananjay, S.; Anju, B.

2008-09-15

This study reports the efficacy of cobalt preconditioning in preventing hypobaric hypoxia induced vascular leakage (an indicator of cerebral edema) using male Sprague-Dawley rats as model system. Exposure of animals to hypobaric hypoxia led to a significant increase in vascular leakage, reactive oxygen species (ROS), nitric oxide (NO), and vascular endothelial growth factor (VEGF) levels. There was a marked increase in Nuclear Factor {kappa}B (NF{kappa}B) DNA binding activity and levels of pro-inflammatory cytokines such as Monocyte chemoattractant protein (MCP-1), Interferon-{gamma} (IFN-{gamma}), Interleukin-1 (IL-1), and Tumor Necrosis Factor-{alpha} (TNF-{alpha}) and cell adhesion molecules such as Vascular Cell Adhesion Molecule-1 (VCAM-1), andmore » P-selectin. Chemical preconditioning by cobalt for 7 days (12.5 mg Co/kg b.w., oral) significantly attenuated cerebral vascular leakage and the expression of inflammatory mediators induced by hypoxia. Administration of NF{kappa}B inhibitor, curcumin (50 mg/kg b.w.; i.p.) appreciably inhibited hypoxia induced vascular leakage indicating the involvement of NF{kappa}B in causing vascular leakage. Interestingly, cobalt when administered at 12.5 mg Co/kg b.w. (i.p.), 1 h before hypoxia could not prevent the vascular leakage indicating that cobalt per se did not have an effect on NF{kappa}B. The lower levels of NF{kappa}B observed in the brains of cobalt administered animals might be due to higher levels of antioxidant and anti-inflammatory proteins (hemeoxygenase-1 and metallothionein). To conclude cobalt preconditioning inhibited hypobaric hypoxia induced cerebral vascular leakage by lowering NF{kappa}B DNA binding activity and its regulated pro-inflammatory mediators. This is contemplated to be mediated by cobalt induced reduction in ROS/NO and increase in HO-1 and MT.« less

In vitro and in vivo antiproliferative and trypanocidal activities of ruthenium NO donors

PubMed Central

Silva, J J N; Osakabe, A L; Pavanelli, W R; Silva, J S; Franco, D W

2007-01-01

Background and purpose: Many compounds liberating NO (NO donors) have been used as therapeutic agents. Here we test two ruthenium nitrosyls, which release NO when activated by biological reducing agents, for their effects in vitro and in vivo against Trypanasoma cruzi, the agent responsible for the American trypanosomiasis (Chagas' disease). Experimental approach: Ruthenium NO donors were incubated with a partially drug-resistant strain of T. cruzi and the anti-proliferative and trypanocidal activities evaluated. In a mouse model of acute Chagas' disease, trypanocidal activity was evaluated by measuring parasitemia, survival rate of infected mice and elimination of amastigotes in myocardial tissue. Key results: In vitro, the observed anti-proliferative and trypanocidal activities of trans-[Ru(NO)(NH3)4isn](BF4)3 and trans-[Ru(NO)(NH3)4imN](BF4)3 were due to NO liberated upon reduction of these nitrosyls. Ru(NO)isn had a lower IC50epi (67 μM) than the NO donor, sodium nitroprusside (IC50epi=244 μM) and Ru(NO)imN (IC50try=52 μM) was more potent than gentian violet (IC50try=536 μM), currently used in the treatment of blood. Both ruthenium nitrosyls eliminated, in vivo, extracellular as well as intracellular forms of T. cruzi in the bloodstream and myocardial tissue and allowed survival of up to 80% of infected mice at a dose (100 nmol kg−1 day−1) much lower than the optimal dose for benznidazole (385 μmol kg−1 day−1). Conclusions and implications: Our data strongly suggest that NO liberated is responsible for the anti-proliferative and trypanocidal activities of the ruthenium NO donors and that these compounds are promising leads for novel and effective anti-parasitic drugs. PMID:17603548

Cobalt compounds as antidotes for hydrocyanic acid

PubMed Central

Evans, C. Lovatt

1964-01-01

The antidotal potency of a cobalt salt (acetate), of dicobalt edetate, of hydroxocobalamin and of cobinamide against hydrocyanic acid was examined mainly on mice and rabbits. All the compounds were active antidotes for up to twice the LD50; under some conditions for larger doses. The most successful was cobalt acetate for rabbits (5×LD50), which was effective at a molar cyanide/cobalt (CN/Co) ratio of 5, but had as a side-effect intense purgation. Hydroxocobalamin was irregular in action, but on the whole was most effective for mice (4.5×LD50 at a molar ratio of 1), and had no apparent side effects. Dicobalt edetate, at molar ratios of up to 2, was more effective for rabbits (3×LD50) than for mice (2×LD50), but had fewer side effects than cobalt acetate. The effect of thiosulphate was to augment the efficacy of dicobalt edetate and, in mice, that of hydroxocobalamin; but, apparently, in rabbits, to reduce that of hydroxocobalamin. Cobinamide, at a molar ratio of 1, was slightly more effective than hydroxocobalamin on rabbits and also less irregular in its action. Cobalt acetate by mouth was effective against orally administered hydrocyanic acid. The oxygen uptake of the body, reduced by cyanide, is rapidly reinstated when one of the cobalt antidotes has been successfully administered. PMID:14256807

COBALT COMPOUNDS AS ANTIDOTES FOR HYDROCYANIC ACID.

PubMed

EVANS, C L

1964-12-01

The antidotal potency of a cobalt salt (acetate), of dicobalt edetate, of hydroxocobalamin and of cobinamide against hydrocyanic acid was examined mainly on mice and rabbits. All the compounds were active antidotes for up to twice the LD50; under some conditions for larger doses. The most successful was cobalt acetate for rabbits (5xLD50), which was effective at a molar cyanide/cobalt (CN/Co) ratio of 5, but had as a side-effect intense purgation. Hydroxocobalamin was irregular in action, but on the whole was most effective for mice (4.5xLD50 at a molar ratio of 1), and had no apparent side effects. Dicobalt edetate, at molar ratios of up to 2, was more effective for rabbits (3xLD50) than for mice (2xLD50), but had fewer side effects than cobalt acetate. The effect of thiosulphate was to augment the efficacy of dicobalt edetate and, in mice, that of hydroxocobalamin; but, apparently, in rabbits, to reduce that of hydroxocobalamin. Cobinamide, at a molar ratio of 1, was slightly more effective than hydroxocobalamin on rabbits and also less irregular in its action. Cobalt acetate by mouth was effective against orally administered hydrocyanic acid. The oxygen uptake of the body, reduced by cyanide, is rapidly reinstated when one of the cobalt antidotes has been successfully administered.

Cobalt mineral exploration and supply from 1995 through 2013

USGS Publications Warehouse

Wilburn, David R.

2011-01-01

The global mining industry has invested a large amount of capital in mineral exploration and development over the past 15 years in an effort to ensure that sufficient resources are available to meet future increases in demand for minerals. Exploration data have been used to identify specific sites where this investment has led to a significant contribution in global mineral supply of cobalt or where a significant increase in cobalt production capacity is anticipated in the next 5 years. This report provides an overview of the cobalt industry, factors affecting mineral supply, and circumstances surrounding the development, or lack thereof, of key mineral properties with the potential to affect mineral supply. Of the 48 sites with an effective production capacity of at least 1,000 metric tons per year of cobalt considered for this study, 3 producing sites underwent significant expansion during the study period, 10 exploration sites commenced production from 1995 through 2008, and 16 sites were expected to begin production by 2013 if planned development schedules are met. Cobalt supply is influenced by economic, environmental, political, and technological factors affecting exploration for and production of copper, nickel, and other metals as well as factors affecting the cobalt industry. Cobalt-rich nickel laterite deposits were discovered and developed in Australia and the South Pacific and improvements in laterite processing technology took place during the 1990s and early in the first decade of the 21st century when mining of copper-cobalt deposits in Congo (Kinshasa) was restricted because of regional conflict and lack of investment in that country's mining sector. There was also increased exploration for and greater importance placed on cobalt as a byproduct of nickel mining in Australia and Canada. The emergence of China as a major refined cobalt producer and consumer since 2007 has changed the pattern of demand for cobalt, particularly from Africa and

Enhancement of Electrochemical Performance of LiMn2O4 Spinel Cathode Material by Synergetic Substitution with Ni and S

PubMed Central

Bakierska, Monika; Świętosławski, Michał; Gajewska, Marta; Kowalczyk, Andrzej; Piwowarska, Zofia; Chmielarz, Lucjan; Dziembaj, Roman; Molenda, Marcin

2016-01-01

Nickel and sulfur doped lithium manganese spinels with a nominal composition of LiMn2−xNixO4–ySy (0.1 ≤ x ≤ 0.5 and y = 0.01) were synthesized by a xerogel-type sol-gel method followed by subsequent calcinations at 300 and 650 °C in air. The samples were investigated in terms of physicochemical properties using X-ray powder diffraction (XRD), transmission electron microscopy (EDS-TEM), N2 adsorption-desorption measurements (N2-BET), differential scanning calorimetry (DSC), and electrical conductivity studies (EC). Electrochemical characteristics of Li/Li+/LiMn2−xNixO4–ySy cells were examined by galvanostatic charge/discharge tests (CELL TEST), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). The XRD showed that for samples calcined at 650 °C containing 0.1 and 0.2 mole of Ni single phase materials of Fd-3m group symmetry and nanoparticles size of around 50 nm were obtained. The energy dispersive X-ray spectroscopy (EDS) mapping confirmed homogenous distribution of nickel and sulfur in the obtained spinel materials. Moreover, it was revealed that the adverse phase transition at around room temperature typical for the stoichiometric spinel was successfully suppressed by Ni and S substitution. Electrochemical results indicated that slight substitution of nickel (x = 0.1) and sulfur (y = 0.01) in the LiMn2O4 enhances the electrochemical performance along with the rate capability and capacity retention. PMID:28773491

The Idaho cobalt belt

USGS Publications Warehouse

Bookstrom, Arthur A.

2013-01-01

The Idaho cobalt belt (ICB) is a northwest-trending belt of cobalt (Co) +/- copper (Cu)-bearing deposits and prospects in the Salmon River Mountains of east-central Idaho, U.S.A. The ICB is about 55 km long and 10 km long in its central part, which contains multiple strata-bound ore zones in the Blackbird mine area. The Black Pine and Iron Creek Co-Cu prospects are southeast of Blackbird, and the Tinkers Pride, Bonanza Copper, Elk Creek, and Salmon Canyon Copper prospects are northwest of Blackbird.

Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

DOEpatents

Pierantozzi, Ronald

1985-01-01

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

DOEpatents

Pierantozzi, R.

1985-04-09

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Ceria-supported ruthenium nanoparticles as highly active and long-lived catalysts in hydrogen generation from the hydrolysis of ammonia borane.

PubMed

Akbayrak, Serdar; Tonbul, Yalçın; Özkar, Saim

2016-07-05

Ruthenium(0) nanoparticles supported on ceria (Ru(0)/CeO2) were in situ generated from the reduction of ruthenium(iii) ions impregnated on ceria during the hydrolysis of ammonia borane. Ru(0)/CeO2 was isolated from the reaction solution by centrifugation and characterized by ICP-OES, BET, XRD, TEM, SEM-EDS and XPS techniques. All the results reveal that ruthenium(0) nanoparticles were successfully supported on ceria and the resulting Ru(0)/CeO2 is a highly active, reusable and long-lived catalyst for hydrogen generation from the hydrolysis of ammonia borane with a turnover frequency value of 361 min(-1). The reusability tests reveal that Ru(0)/CeO2 is still active in the subsequent runs of hydrolysis of ammonia borane preserving 60% of the initial catalytic activity even after the fifth run. Ru(0)/CeO2 provides a superior catalytic lifetime (TTO = 135 100) in hydrogen generation from the hydrolysis of ammonia borane at 25.0 ± 0.1 °C before deactivation. The work reported here includes the formation kinetics of ruthenium(0) nanoparticles. The rate constants for the slow nucleation and autocatalytic surface growth of ruthenium(0) nanoparticles were obtained using hydrogen evolution as a reporter reaction. An evaluation of rate constants at various temperatures enabled the estimation of activation energies for both the reactions, Ea = 60 ± 7 kJ mol(-1) for the nucleation and Ea = 47 ± 2 kJ mol(-1) for the autocatalytic surface growth of ruthenium(0) nanoparticles, as well as the activation energy of Ea = 51 ± 2 kJ mol(-1) for the catalytic hydrolysis of ammonia borane.

Superexchange Effects on Oxygen Reduction Activity of Edge-Sharing [Cox Mn1-x O6 ] Octahedra in Spinel Oxide.

PubMed

Zhou, Ye; Sun, Shengnan; Xi, Shibo; Duan, Yan; Sritharan, Thirumany; Du, Yonghua; Xu, Zhichuan J

2018-03-01

Mn-Co containing spinel oxides are promising, low-cost electrocatalysts for the oxygen reduction reaction (ORR). Most studies are devoted to the design of porous Mn-Co spinels or to strongly coupled hybrids (e.g., MnCo 2 O 4 /N-doped-rmGO) to maximize the mass efficiency. The lack of analyses by metal oxide intrinsic activity (activity normalized to catalysts' surface area) hinders the development of fundamental understanding of the physicochemical principles behind the catalytic activities. A systematic study on the composition dependence of ORR in ZnCo x Mn 2- x O 4 (x = 0.0-2.0) spinel is presented here with special attention to the role of edge sharing [Co x Mn 1- x O 6 ] octahedra in the spinel structure. The ORR specific activity of ZnCo x Mn 2- x O 4 spans across a potential window of 200 mV, indicating an activity difference of ≈3 orders of magnitude. The curve of composition-dependent ORR specific activity as a function of Co substitution exhibits a volcano shape with an optimum Mn/Co ratio of 0.43. It is revealed that the modulated e g occupancy of active Mn cations (0.3-0.9), as a consequence of the superexchange effect between edge sharing [CoO 6 ] and [MnO 6 ], reflects the ORR activity of edge sharing [Co x Mn 1- x O 6 ] octahedra in the ZnCo x Mn 2- x O 4 spinel oxide. These findings offer crucial insights in designing spinel oxide catalysts with fine-tuned e g occupancy for efficient catalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A series of spinel phase cathode materials prepared by a simple hydrothermal process for rechargeable lithium batteries

NASA Astrophysics Data System (ADS)

Liang, Yan-Yu; Bao, Shu-Juan; Li, Hu-Lin

2006-07-01

A series of spinel-structured materials have been prepared by a simple hydrothermal procedure in an aqueous medium. The new synthetic method is time and energy saving i.e., no further thermal treatment and extended grinding. The main experimental process involved the insertion of lithium into electrolytic manganese dioxide with glucose as a mild reductant in an autoclave. Both the hydrothermal temperature and the presence of glucose play the critical roles in determining the final spinel integrity. Particular electrochemical performance has also been systematically explored, and the results show that Al 3+, F - co-substituted spinels have the best combination of initial capacity and capacity retention among all these samples, exhibited the initial capacity of 115 mAh/g and maintained more than 90% of the initial value at the 50th cycle.

The cytotoxicity and genotoxicity of soluble and particulate cobalt in human lung fibroblast cells

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

Smith, Leah J.; Holmes, Amie L.; Maine Center for Environmental Toxicology and Health, University of Southern Maine, 96 Falmouth St., P.O. Box 9300, Portland, ME 04101-9300

Cobalt exposure is increasing as cobalt demand rises worldwide due to its use in enhancing rechargeable battery efficiency, super-alloys, and magnetic products. Cobalt is considered a possible human carcinogen with the lung being a primary target. However, few studies have considered cobalt-induced toxicity in human lung cells. Therefore, in this study, we sought to determine the cytotoxicity and genotoxicity of particulate and soluble cobalt in human lung cells. Cobalt oxide and cobalt chloride were used as representative particulate and soluble cobalt compounds, respectively. Exposure to both particulate and soluble cobalt induced a concentration-dependent increase in cytotoxicity, genotoxicity, and intracellular cobaltmore » ion levels. Based on intracellular cobalt ion levels, we found that soluble cobalt was more cytotoxic than particulate cobalt while particulate and soluble cobalt induced similar levels of genotoxicity. However, soluble cobalt induced cell cycle arrest indicated by the lack of metaphases at much lower intracellular cobalt concentrations compared to cobalt oxide. Accordingly, we investigated the role of particle internalization in cobalt oxide-induced toxicity and found that particle-cell contact was necessary to induce cytotoxicity and genotoxicity after cobalt exposure. These data indicate that cobalt compounds are cytotoxic and genotoxic to human lung fibroblasts, and solubility plays a key role in cobalt-induced lung toxicity. - Highlights: • Particulate and soluble cobalt are cytotoxic and genotoxic to human lung cells. • Soluble cobalt induces more cytotoxicity compared to particulate cobalt. • Soluble and particulate cobalt induce similar levels of genotoxicity. • Particle-cell contact is required for particulate cobalt-induced toxicity.« less

COBALT Flight Demonstrations Fuse Technologies

NASA Image and Video Library

2017-06-07

This 5-minute, 50-second video shows how the CoOperative Blending of Autonomous Landing Technologies (COBALT) system pairs new landing sensor technologies that promise to yield the highest precision navigation solution ever tested for NASA space landing applications. The technologies included a navigation doppler lidar (NDL), which provides ultra-precise velocity and line-of-sight range measurements, and the Lander Vision System (LVS), which provides terrain-relative navigation. Through flight campaigns conducted in March and April 2017 aboard Masten Space Systems' Xodiac, a rocket-powered vertical takeoff, vertical landing (VTVL) platform, the COBALT system was flight tested to collect sensor performance data for NDL and LVS and to check the integration and communication between COBALT and the rocket. The flight tests provided excellent performance data for both sensors, as well as valuable information on the integrated performance with the rocket that will be used for subsequent COBALT modifications prior to follow-on flight tests. Based at NASA’s Armstrong Flight Research Center in Edwards, CA, the Flight Opportunities program funds technology development flight tests on commercial suborbital space providers of which Masten is a vendor. The program has previously tested the LVS on the Masten rocket and validated the technology for the Mars 2020 rover.

Role of Mediator and Effects of Temperature on ortho-C-N Bond Fusion Reactions of Aniline Using Ruthenium Templates: Isolation and Characterization of New Ruthenium Complexes of the in-Situ-Generated Ligands.

PubMed

Roy, Suman K; Sengupta, Debabrata; Rath, Santi Prasad; Saha, Tanushri; Samanta, Subhas; Goswami, Sreebrata

2017-05-01

In this work, ortho-C-N bond fusion reactions of aniline are followed by the use of two different ruthenium mediators. Reaction of aniline with [Ru III (terpy)Cl 3 ] (terpy = 2,2':6',2″-terpyridine) resulted in a trans bis-aniline ruthenium(II) complex [1] + which upon oxidation with H 2 O 2 produced compound [2] + of a bidentate ligand, N-phenyl-1,2-benzoquinonediimine, due to an oxidative ortho-C-N bond fusion reaction. Complex [1] + and aniline (neat) at 185 °C produced a bis-chelated ruthenium complex (3). A previously reported complex [Ru II (N-phenyl-1,2-benzoquinonediimine)(aniline) 2 (Cl) 2 ] (5) undergoes similar oxidation by air at 185 °C to produce complex [3]. A separate chemical reaction between aniline and strongly oxidizing tetra-n-propylammonium perruthenate [(n-pr) 4 N] + [RuO 4 ] - in air produced a ruthenium complex [4] of a N 4 -tetraamidophenylmacrocycle ligand via multiple ortho-C-N bond fusion reaction. Notably, the yield of this product is low (5%) at 100 °C but increases to 25% in refluxing aniline. All these complexes are characterized fully by their physicochemical characterizations and X-ray structure determination. From their structural parameters and other spectroscopic studies, complex [2] + is assigned as [Ru II (terpy)(N-phenyl-1,2-benzoquinonediimine)(Cl)] + whereas complex [4] is described as a ruthenium(VI) complex comprised of a reduced deprotonated N-phenyl-1,2-diamidobenzene and N 4 -tetraamidophenylmacrocyclic ligand. Complex [2] + exhibits one reversible oxidation at 1.32 V and one reversible reduction at -0.75 V vs Ag/AgCl reference electrode. EPR of the electrogenerated complexes has revealed that the oxidized complex is a ruthenium(III) complex with an axial EPR spectrum at g av = 2.06. The reduced complex [2], on the other hand, shows a single-line EPR signal at g av = 1.998. In contrast, complex [4] shows two successive one-electron oxidation waves at 0.5 and 0.8 V and an irreversible reduction wave at -0.9 V. EPR

Ear piercing, and nickel and cobalt sensitization, in 520 young Swedish men doing compulsory military service.

PubMed

Meijer, C; Bredberg, M; Fischer, T; Widström, L

1995-03-01

Piercing the earlobes has increased in popularity among males in recent years. This habit would be expected to increase the incidence of nickel and cobalt sensitization. Patch testing with nickel sulfate and cobalt chloride was performed in 520 young Swedish men doing compulsory military service. The overall frequency of nickel/cobalt positive tests was 4.2%. The prevalence of nickel/cobalt positive tests was significantly higher (p < 0.05) in 152 men with pierced earlobes (7.9%) than in those 368 with unpierced earlobes (2.7%). A history of hand eczema (7/152 = 4.6%) or other types of eczema (22/152 = 14.5%) in individuals with pierced earlobes was no more common than in those with unpierced earlobes: 24/368 = 6.5% and 51/386 = 13.9%, respectively (n.s.). Hand eczema was no more common in sensitized (1/22 = 4.5%) than in nonsensitized individuals (32/498 = 6.4%) (n.s.).

Degradation of lithium ion batteries employing graphite negatives and nickel-cobalt-manganese oxide + spinel manganese oxide positives: Part 2, chemical-mechanical degradation model

NASA Astrophysics Data System (ADS)

Purewal, Justin; Wang, John; Graetz, Jason; Soukiazian, Souren; Tataria, Harshad; Verbrugge, Mark W.

2014-12-01

Capacity fade is reported for 1.5 Ah Li-ion batteries containing a mixture of Li-Ni-Co-Mn oxide (NCM) + Li-Mn oxide spinel (LMO) as positive electrode material and a graphite negative electrode. The batteries were cycled at a wide range of temperatures (10 °C-46 °C) and discharge currents (0.5C-6.5C). The measured capacity losses were fit to a simple physics-based model which calculates lithium inventory loss from two related mechanisms: (1) mechanical degradation at the graphite anode particle surface caused by diffusion-induced stresses (DIS) and (2) chemical degradation caused by lithium loss to continued growth of the solid-electrolyte interphase (SEI). These two mechanisms are coupled because lithium is consumed through SEI formation on newly exposed crack surfaces. The growth of crack surface area is modeled as a fatigue phenomenon due to the cyclic stresses generated by repeated lithium insertion and de-insertion of graphite particles. This coupled chemical-mechanical degradation model is consistent with the observed capacity loss features for the NCM + LMO/graphite cells.

Tracking the Oxygen Status in the Cell Nucleus with a Hoechst-Tagged Phosphorescent Ruthenium Complex.

PubMed

Hara, Daiki; Umehara, Yui; Son, Aoi; Asahi, Wataru; Misu, Sotaro; Kurihara, Ryohsuke; Kondo, Teruyuki; Tanabe, Kazuhito

2018-05-04

Molecular oxygen in living cells is distributed and consumed inhomogeneously, depending on the activity of each organelle. Therefore, tractable methods that can be used to monitor the oxygen status in each organelle are needed to understand cellular function. Here we report the design of a new oxygen-sensing probe for use in the cell nucleus. We prepared "Ru-Hoechsts", each consisting of a phosphorescent ruthenium complex linked to a Hoechst 33258 moiety, and characterized their properties as oxygen sensors. The Hoechst unit shows strong DNA-binding properties in the nucleus, and the ruthenium complex shows oxygen-dependent phosphorescence. Thus, Ru-Hoechsts accumulated in the cell nucleus and showed oxygen-dependent signals that could be monitored. Of the Ru-Hoechsts prepared in this study, Ru-Hoechst b, in which the ruthenium complex and the Hoechst unit were linked through a hexyl chain, showed the most suitable properties for monitoring the oxygen status. Ru-Hoechsts are probes with high potential for visualizing oxygen fluctuations in the nucleus. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Origin of Spinel Nanocheckerboards via First Principles

NASA Astrophysics Data System (ADS)

Kornbluth, Mordechai; Marianetti, Chris A.

2015-06-01

Self-organizing nanocheckerboards have been experimentally fabricated in Mn-based spinels but have not yet been explained with first principles. Using density-functional theory, we explain the phase diagram of the ZnMnxGa2 -xO4 system and the origin of nanocheckerboards. We predict total phase separation at zero temperature and then show the combination of kinetics, thermodynamics, and Jahn-Teller physics that generates the system's observed behavior. We find that the {011 } surfaces are strongly preferred energetically, which mandates checkerboard ordering by purely geometrical considerations.

PRECIPITATION OF ZIRCONIUM, NIOBIUM, AND RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Wilson, A.S.

1958-08-12

An improvement on the"head end process" for decontaminating dissolver solutions of their Zr, Ni. and Ru values. The process consists in adding a water soluble symmetrical dialkyl ketone. e.g. acetone, before the formation of the manganese dioxide precipitate. The effect is that upon digestion, the ruthenium oxide does not volatilize, but is carried on the manganese dioxide precipitate.

40 CFR 721.10201 - Cobalt lithium manganese nickel oxide.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Cobalt lithium manganese nickel oxide... Specific Chemical Substances § 721.10201 Cobalt lithium manganese nickel oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cobalt lithium manganese...

40 CFR 721.10201 - Cobalt lithium manganese nickel oxide.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Cobalt lithium manganese nickel oxide... Specific Chemical Substances § 721.10201 Cobalt lithium manganese nickel oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cobalt lithium manganese...

40 CFR 721.10201 - Cobalt lithium manganese nickel oxide.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Cobalt lithium manganese nickel oxide... Specific Chemical Substances § 721.10201 Cobalt lithium manganese nickel oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cobalt lithium manganese...

Ruthenium or osmium complexes and their uses as catalysts for water oxidation

DOEpatents

Corbea, Javier Jesus Concepcion; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L.; Hoertz, Paul; Meyer, Thomas J.

2013-09-03

The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

Ruthenium or osmium complexes and their uses as catalysts for water oxidation

DOEpatents

Concepcion Corbea, Javier Jesus; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L; Hoertz, Paul; Meyer, Thomas J

2014-10-28

The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

Strong competition between orbital ordering and itinerancy in a frustrated spinel vanadate

DOE PAGES

Ma, Jie; Lee, Jun Hee; Hahn, Steven E.; ...

2015-01-26

In this study, the crossover from localized to itinerant electron regimes in the geometrically frustrated spinel system Mn 1-xCo xV 2O 4 is explored by neutron-scattering measurements, first-principles calculations, and spin models. At low Co doping, the orbital ordering (OO) of the localized V 3+ spins suppresses magnetic frustration by triggering a tetragonal distortion. At high Co doping levels, however, electronic itinerancy melts the OO and lessens the structural and magnetic anisotropies, thus increasing the amount of geometric frustration for the V-site pyrochlore lattice. Contrary to the predicted paramagentism induced by chemical pressure, the measured noncollinear spin states in themore » Co-rich region of the phase diagram provide a unique platform where localized spins and electronic itinerancy compete in a geometrically frustrated spinel.« less

Antiproliferative effects of ruthenium-based nucleolipidic nanoaggregates in human models of breast cancer in vitro: insights into their mode of action

PubMed Central

Irace, Carlo; Misso, Gabriella; Capuozzo, Antonella; Piccolo, Marialuisa; Riccardi, Claudia; Luchini, Alessandra; Caraglia, Michele; Paduano, Luigi; Montesarchio, Daniela; Santamaria, Rita

2017-01-01

Looking for new metal-based anticancer treatments, in recent years many ruthenium complexes have been proposed as effective and safe potential drugs. In this context we have recently developed a novel approach for the in vivo delivery of Ru(III) complexes, preparing stable ruthenium-based nucleolipidic nanoaggregates endowed with significant antiproliferative activity. Herein we describe the cellular response to our ruthenium-containing formulations in selected models of human breast cancer. By in vitro bioscreens in the context of preclinical studies, we have focused on their ability to inhibit breast cancer cell proliferation by the activation of the intrinsic apoptotic pathway, possibly via mitochondrial perturbations involving Bcl-2 family members and predisposing to programmed cell death. In addition, the most efficient ruthenium-containing cationic nanoaggregates we have hitherto developed are able to elicit both extrinsic and intrinsic apoptosis, as well as autophagy. To limit chemoresistance and counteract uncontrolled proliferation, multiple cell death pathways activation by metal-based chemotherapeutics is a challenging, yet very promising strategy for targeted therapy development in aggressive cancer diseases, such as triple-negative breast cancer with limited treatment options. These outcomes provide valuable, original knowledge on ruthenium-based candidate drugs and new insights for future optimized cancer treatment protocols. PMID:28349991

Fluorination Induced the Surface Segregation of High Voltage Spinel on Lithium-Rich Layered Cathodes for Enhanced Rate Capability in Lithium Ion Batteries.

PubMed

Jin, Yi-Chun; Duh, Jenq-Gong

2016-02-17

This study is aimed to explore the effect of fluoride doping and the associated structural transformation on lithium-rich layered cathode materials. The polymeric fluoride source is first adopted for synthesizing lithium intercalated oxide through a newly developed organic precipitation process. A heterostructured spinel/layered composite cathode material is obtained after appreciable fluorination and a superior rate capability is successfully achieved. The fluoride dopant amount and the surface spinel phase are evidenced and systematically examined by various structural spectroscopy and electrochemical analysis. It appears the reversible Ni(2+/4+) redox couple at high voltage regime around 4.8 V because of the formation of spinel LiNi1/2Mn3/2O4 phase. The mechanism of "layer to spinel" phase transformation is discussed in detail.

Stabilization of MgAl 2O 4 spinel surfaces via doping

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

Hasan, Md. M.; Dholabhai, Pratik P.; Castro, Ricardo H. R.

Here, the surface structure of complex oxides plays a vital role in processes such as sintering, thin film growth, and catalysis, as well as being a critical factor determining the stability of nanoparticles. We report atomistic calculations of the low-index stoichiometric magnesium aluminate spinel (MgAl 2O 4) surfaces, each with two different chemical terminations. High temperature annealing was used to explore the potential energy landscape and provide more stable surface structures. We find that the lowest energy surface is {100} while the highest energy surface is {111}. The surfaces were subsequently doped with three trivalent dopants (Y 3+, Gd 3+,more » La 3+) and one tetravalent dopant (Zr 4+) and both the surface segregation energies of the dopants and surface energies of the doped surface were determined. All of the dopants reduce the surface energy of spinel, though this reduction in energy depends on both the size and valence of the dopant. Dopants with larger ionic radius tend to segregate to the surface more strongly and reduce the surface energy to a greater extent. Furthermore, the ionic valence of the dopants seems to have a stronger influence on the segregation than does ionic size. For both undoped and doped spinel, the predicted crystal shape is dominated by {100} surfaces, but the relative fraction of the various surfaces changes with doping due to the unequal changes in energy, which has implications on equilibrium nanoparticle shapes and therefore on applications sensitive to surface properties.« less

Stabilization of MgAl 2O 4 spinel surfaces via doping

DOE PAGES

Hasan, Md. M.; Dholabhai, Pratik P.; Castro, Ricardo H. R.; ...

2016-02-06

Here, the surface structure of complex oxides plays a vital role in processes such as sintering, thin film growth, and catalysis, as well as being a critical factor determining the stability of nanoparticles. We report atomistic calculations of the low-index stoichiometric magnesium aluminate spinel (MgAl 2O 4) surfaces, each with two different chemical terminations. High temperature annealing was used to explore the potential energy landscape and provide more stable surface structures. We find that the lowest energy surface is {100} while the highest energy surface is {111}. The surfaces were subsequently doped with three trivalent dopants (Y 3+, Gd 3+,more » La 3+) and one tetravalent dopant (Zr 4+) and both the surface segregation energies of the dopants and surface energies of the doped surface were determined. All of the dopants reduce the surface energy of spinel, though this reduction in energy depends on both the size and valence of the dopant. Dopants with larger ionic radius tend to segregate to the surface more strongly and reduce the surface energy to a greater extent. Furthermore, the ionic valence of the dopants seems to have a stronger influence on the segregation than does ionic size. For both undoped and doped spinel, the predicted crystal shape is dominated by {100} surfaces, but the relative fraction of the various surfaces changes with doping due to the unequal changes in energy, which has implications on equilibrium nanoparticle shapes and therefore on applications sensitive to surface properties.« less

Formation of polycyclic lactones through a ruthenium-catalyzed ring-closing metathesis/hetero-Pauson-Khand reaction sequence.

PubMed

Finnegan, David F; Snapper, Marc L

2011-05-20

Processes that form multiple carbon-carbon bonds in one operation can generate molecular complexity quickly and therefore be used to shorten syntheses of desirable molecules. We selected the hetero-Pauson-Khand (HPK) cycloaddition and ring-closing metathesis (RCM) as two unique carbon-carbon bond-forming reactions that could be united in a tandem ruthenium-catalyzed process. In doing so, complex polycyclic products can be obtained in one reaction vessel from acyclic precursors using a single ruthenium additive that can catalyze sequentially two mechanistically distinct transformations.

Spindly cobalt ferrite nanocrystals: preparation, characterization and magnetic properties.

PubMed

Cao, Xuebo; Gu, Li

2005-02-01

In this paper we describe the preparation of homogeneously needle-shaped cobalt ferrite (CoFe(2)O(4)) nanocrystals on a large scale through the smooth decomposition of urea and the resulting co-precipitation of Co(2+) and Fe(3+) in oleic acid micelles. Furthermore, we found that other ferrite nanocrystals with a needle-like shape, such as zinc ferrite (ZnFe(2)O(4)) and nickel ferrite (NiFe(2)O(4)), can be prepared by the same process. Needle-shaped CoFe(2)O(4) nanocrystals dispersed in an aqueous solution containing oleic acid exhibit excellent stability and the formed colloid does not produce any precipitations after two months, which is of prime importance if these materials are applied in magnetic fluids. X-ray diffraction (XRD) measurements were used to characterize the phase and component of the co-precipitation products, and demonstrate that they are spinel ferrite with a cubic symmetry. Transmission electron microscopy (TEM) observation showed that all the nanocrystals present a needle-like shape with a 22 nm short axis and an aspect ratio of around 6. Varying the concentration of oleic acid did not bring about any obvious influence on the size distribution and shapes of CoFe(2)O(4). The magnetic properties of the needle-shaped CoFe(2)O(4) nanocrystals were evaluated by using a vibrating sample magnetometer (VSM), electron paramagnetic resonance (EPR), and a Mössbauer spectrometer, and the results all demonstrated that CoFe(2)O(4) nanocrystals were superparamagnetic at room temperature.

Magnetic and magneto elastic properties of cobalt ferrite ceramic compacted through cold isostatic pressing

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

Indla, Srinivas; Das, Dibakar, E-mail: ddse@uohyd.ernet.in; Chelvane, Arout

2016-05-06

Nano crystalline CoFe{sub 2}O{sub 4} powder was prepared by combustion synthesis method. As synthesized powder was calcined at an appropriate condition to remove the impurities and to promote phase formation. Phase pure CoFe{sub 2}O{sub 4} powder was pressed into cylindrical rod at an applied pressure of 200 MPa using a cold isostatic pressing. Sintering of the green compact at 1350°c for 12 hrs resulted in sintered cylindrical rod with ~85% of the theoretical density. Single phase cubic spinel structure was observed in the powder x-ray diffraction pattern of the sintered pellet. Scanning electron micrographs (SEM) of the as sintered pelletmore » revealed the microstructure to be composed of ferrite grains of average size ~4 µm. Saturation magnetization of 72 emu/g and coercivity of 355 Oe were observed for cobalt ferrite sample. The magnetostriction was measured on a circular disc (12 mm diameter and 12 mm length) with the strain gauge (350 Ω) mounted on the flat surface of the circular disc. Magnetostriciton of 180 ppm and strain derivative of 1 × 10{sup −9} m/A were observed for the sintered CoFe{sub 2}O{sub 4} sample.« less

Structural, dielectric and gas sensing behavior of Mn substituted spinel MFe2O4 (M=Zn, Cu, Ni, and Co) ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Ranjith Kumar, E.; Siva Prasada Reddy, P.; Sarala Devi, G.; Sathiyaraj, S.

2016-01-01

Spinel ferrite (MnZnFe2O4, MnCuFe2O4, MnNiFe2O4 and MnCoFe2O4) nanoparticles have been prepared by evaporation method. The annealing temperature plays an important role on changing particle size of the spinel ferrite nanoparticles was found out by X-ray diffraction and transmission electron microscopy. The role of manganese substitution in the spinel ferrite nanoparticles were also analyzed for different annealing temperature. The substitution of Mn also creates a vital change in dielectric properties have been measured in the frequency range of 100 kHz to 5 MHz. These spinel ferrites are decomposed to α-Fe2O3 after annealing above 550 °C in air. Through the characterization of the prepared powder, the effect of annealing temperature, chemical composition and preparation technique on the microstructure, particle size and dielectric properties of the Mn substituted spinel ferrite nanoparticles are discussed. Furthermore, Conductance response of Mn substituted MFe2O4 ferrite nanoparticles were measured by exposing the materials to reducing gas like liquefied petroleum gas (LPG).

Semiconducting-metallic transition of singlecrystalline ferromagnetic Hf-doped CuCr2Se4 spinels

NASA Astrophysics Data System (ADS)

Maciążek, E.; Malicka, E.; Gągor, A.; Stokłosa, Z.; Groń, T.; Sawicki, B.; Duda, H.; Gudwański, A.

2017-09-01

Chalcogenide spinels show a variety of physical properties and are very good candidates for electronic and high-frequency applications. We report the measurements of magnetic susceptibility, magnetic isotherm, electrical conductivity, thermoelectric power and calculations of the superexchange and double-exchange integrals made for singlecrystalline Cu[CrxHfy]Se4 spinels. The results showed a ferromagnetic order of magnetic moments below the Curie temperatures of 390 K and, an increase in the splitting of the zero-field cooled and field cooled susceptibilities with increasing Hf-content below the room temperature suggesting a slight spin-frustration and a rapid transition from semiconducting to metallic state at room temperature. A quantitative evaluation of the exchange Hamiltonian showed that the total hopping integral rapidly decreased and the bandwidth of the 3d t2g band due to Cr3+ and Cr4+ ions strongly narrowed from 0.76 eV for y = 0 to 0.28 eV for y = 0.14. The narrowing of this band appears to be responsible for semiconducting properties of the Hf-doped CuCr2Se4 spinels below the room temperature.

Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

DOEpatents

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-07-12

A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

Quantifying cobalt in doping control urine samples--a pilot study.

PubMed

Krug, Oliver; Kutscher, Daniel; Piper, Thomas; Geyer, Hans; Schänzer, Wilhelm; Thevis, Mario

2014-01-01

Since first reports on the impact of metals such as manganese and cobalt on erythropoiesis were published in the late 1920s, cobaltous chloride became a viable though not widespread means for the treatment of anaemic conditions. Today, its use is de facto eliminated from clinical practice; however, its (mis)use in human as well as animal sport as an erythropoiesis-stimulating agent has been discussed frequently. In order to assess possible analytical options and to provide relevant information on the prevalence of cobalt use/misuse among athletes, urinary cobalt concentrations were determined by inductively coupled plasma-mass spectrometry (ICP-MS) from four groups of subjects. The cohorts consisted of (1) a reference population with specimens of 100 non-elite athletes (not being part of the doping control system), (2) a total of 96 doping control samples from endurance sport athletes, (3) elimination study urine samples collected from six individuals having ingested cobaltous chloride (500 µg/day) through dietary supplements, and (4) samples from people supplementing vitamin B12 (cobalamin) at 500 µg/day, accounting for approximately 22 µg of cobalt. The obtained results demonstrated that urinary cobalt concentrations of the reference population as well as the group of elite athletes were within normal ranges (0.1-2.2 ng/mL). A modest but significant difference between these two groups was observed (Wilcoxon rank sum test, p < 0.01) with the athletes' samples presenting slightly higher urinary cobalt levels. The elimination study urine specimens yielded cobalt concentrations between 40 and 318 ng/mL during the first 6 h post-administration, and levels remained elevated (>22 ng/mL) up to 33 h. Oral supplementation of 500 µg of cobalamin did not result in urinary cobalt concentrations > 2 ng/mL. Based on these pilot study data it is concluded that measuring the urinary concentration of cobalt can provide information indicating the use

Effects of long-time elevated temperature exposures on hot-isostatically-pressed power-metallurgy Udimet 700 alloys with reduced cobalt contents

NASA Technical Reports Server (NTRS)

Hart, F. H.

1984-01-01

Because almost the entire U.S. consumption of cobalt depends on imports, this metal has been designated "strategic'. The role and effectiveness of cobalt is being evaluated in commercial nickel-base superalloys. Udiment 700 type alloys in which the cobalt content was reduced from the normal 17% down to 12.7%, 8.5%, 4.3%, and 0% were prepared by standard powder metallurgy techniques and hot isostatically pressed into billets. Mechanical testing and microstructural investigations were performed. The mechanical properties of alloys with reduced cobalt contents which were heat-treated identically were equal or better than those of the standard alloy, except that creep rates tended to increase as cobalt was reduced. The effects of long time exposures at 760 C on mechanical properties and at 760 C and 845 C on microstructures were determined. Decreased tensile properties and shorter rupture lives with increased creep rates were observed in alloy modifications. The exposures caused gamma prime particle coarsening and formation of sigma phase in the alloys with higher cobalt contents. Exposure at 845 C also reduced the amount of MC carbides.

Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1995-01-17

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or [beta]-pyrrolic positions.

Nitrated metalloporphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1994-01-18

Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or [beta]-pyrrolic positions.

Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1993-05-18

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso- and/or [beta]-pyrrolic positions.

Nitrated metalloporphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1994-01-01

Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or .beta.-pyrrolic positions.

Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1993-01-01

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1995-01-01

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

Ultrathin spinel membrane-encapsulated layered lithium-rich cathode material for advanced Li-ion batteries.

PubMed

Wu, Feng; Li, Ning; Su, Yuefeng; Zhang, Linjing; Bao, Liying; Wang, Jing; Chen, Lai; Zheng, Yu; Dai, Liqin; Peng, Jingyuan; Chen, Shi

2014-06-11

Lack of high-performance cathode materials has become a technological bottleneck for the commercial development of advanced Li-ion batteries. We have proposed a biomimetic design and versatile synthesis of ultrathin spinel membrane-encapsulated layered lithium-rich cathode, a modification by nanocoating. The ultrathin spinel membrane is attributed to the superior high reversible capacity (over 290 mAh g(-1)), outstanding rate capability, and excellent cycling ability of this cathode, and even the stubborn illnesses of the layered lithium-rich cathode, such as voltage decay and thermal instability, are found to be relieved as well. This cathode is feasible to construct high-energy and high-power Li-ion batteries.

Homobimetallic Ruthenium-N-Heterocyclic Carbene Complexes For Olefin Metathesis

NASA Astrophysics Data System (ADS)

Sauvage, Xavier; Demonceau, Albert; Delaude, Lionel

In this chapter, the synthesis and catalytic activity towards olefin metathesis of homobimetallic ruthenium (Ru)-alkylidene, -cyclodiene or -arene complexes bearing phosphine or N-heterocyclic carbene (NHC) ligands are reviewed. Emphasis is placed on the last category of bimetallic compounds. Three representatives of this new type of molecular scaffold were investigated. Thus, [(p-cymene)Ru(m-Cl)3RuCl (h2-C2H4)(L)] complexes with L = PCy3 (15a), IMes (16a), or IMesCl2 (16b) were prepared. They served as catalyst precursors for cross-metathesis (CM) of various styrene derivatives. These experiments revealed the outstanding aptitude of complex 16a (and to a lesser extent of 16b) to catalyze olefin metathesis reactions. Contrary to monometallic Ru-arene complexes of the [RuCl2(p-cymene)(L)] type, the new homobimetallic species did not require the addition of a diazo compound nor visible light illumination to initiate the ring-opening metathesis of norbornene or cyclooctene. When diethyl 2,2-diallylmalonate and N,N-diallyltosylamide were exposed to 16a,b, a mixture of cycloisomerization and ring-closing metathesis (RCM) products was obtained in a nonselective way. Addition of phenylacetylene enhanced the metathetical activity while completely repressing the cycloisomerization process.

Characteristics of a promising new thermoelectric material - Ruthenium silicide

NASA Technical Reports Server (NTRS)

Ohta, Toshitaka; Vining, Cronin B.; Allevato, Camillo E.

1991-01-01

A preliminary study on arc-melted samples has indicated that ruthenium silicide has the potential to obtain figure-of-merit values four times higher than that of conventional silicon-germanium material. In order to realize the high figure-of-merit values, high-quality crystal from the melt is needed. A Bridgman-like method has been employed and has realized much better crystals than arc-melted ones.

Influences On The Oceanic Biogeochemical Cycling Of The Hybrid-Type Metals: Cobalt, Iron, And Manganese

DTIC Science & Technology

2012-02-01

have been possible. We also thank Scot Birdwhistell in the Woods Hole Oceanographic Institution (WHOI) inductively coupled plasma mass spectrometry...Cobalt, Iron, and Manganese MIT/WHOI Joint Program in Oceanography/ Applied Ocean Science and Engineering Massachusetts Institute of Technology Woods Hole...by Abigail Emery Noble Massachusetts Institute of Technology Cambridge, Massachusetts 02139 and Woods Hole Oceanographic Institution Woods Hole

Cobalt asthma in metalworkers from an automotive engine valve manufacturer.